第講演要旨集
Abstracts of the 47th Fullerenes-NanotubesGraphene General Symposium
September 3–5, 2014, IB Building, Nagoya University
主催

フラーレン・ナノチューブ・グラフェン学会
The Fullerenes, Nanoutubes and Graphene Research Society

共催

日本化学会

The Chemical Society of Japan

JST 戦略的国際共同研究プロジェクト IRENA
IRENA Project by JST-EC DG RTD, Strategic International
Collaborative Research Program, SICORP
協賛

The Physical Society of Japan

応用物理学会

The Japan Society of Applied Physics

高分子学会

The Society of Polymer Science, Japan

電気化学会

The Electrochemical Society of Japan

http://fullerene-jp.org

Research Society

IB

電子情報館

日本物理学会２０１４年９月３日︵水︶〜 ５日︵金︶ 名古屋大学

47

回 フラーレン・ナノチューブ・グラフェン総合シンポジウム

47

Abstract of the
47th Fullerenes-Nanotubes-Graphene General Symposium
Sponsored by: The Fullerenes, Nanotubes and Graphene Research Society
Co-Sponsored by: The Chemical Society of Japan

IRENA Project by JST-EC DG RTD, Strategic International
Collaborative Research Program, SICORP
Supported by: The Physical Society of JapanThe Japan Society of Applied Physics
The Society of Polymer Science, JapanThe Electrochemical Society of Japan
Date: September 3rd (Wed)–5th (Fri), 2014
Place: IB Building, Nagoya University

Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Presentation Time: Plenary Lecture (40 min presentation + 5 min discussion)Special Lecture (25 min presentation + 5 min discussion)Award Nominee Lecture (10 min presentation + 10 min discussion)
General Lecture (10 min presentation + 5 min discussion)
Poster Preview (1 min presentation without discussion)

第 47 回フラーレン・ナノチューブ・グラフェン総合シンポジウム
講演要旨集
主催：フラーレン・ナノチューブ・グラフェン学会
共催：日本化学会

JST 戦略的国際共同研究プロジェクト IRENA
協賛：日本物理学会、応用物理学会、高分子学会、電気化学会
日時：平成 26 年 9 月 3 日 (水)〜5 日 (金)場所：名古屋大学 IB 電子情報館〒 464-8603 名古屋市千種区不老町
発表時間：基調講演 (発表 40 分＋質疑応答 5 分)
特別講演 (発表 25 分＋質疑応答 5 分)
受賞対象者講演 (発表 10 分＋質疑応答 10 分)
一般講演 (発表 10 分＋質疑応答 5 分)
ポスタープレビュー（発表 1 分、質疑応答なし)

展示団体御芳名(五十音順、敬称略)

アイクストロン (株)(株) 島津製作所(株) セントラル科学貿易(株) 東陽テクニカ
ナカライテスク (株)ナノフォトン (株)日本電子 (株)(株) ニューメタルス エンド ケミカルス コーポレーション(株) 名城ナノカーボン
レニショー (株)(株) ワイエムシィ／ YMC テクノス (株)和光純薬工業 (株)広告掲載団体御芳名(五十音順、敬称略)

アイクストロン (株)(株) アド・サイエンス(株) コロナ社
ジェー・エー・ウーラム・ジャパン (株)(株) 島津製作所(株) セントラル科学貿易(株) 東陽テクニカ
ナカライテスク (株)日本エフイー・アイ (株)日本電子 (株)日本分析工業 (株)日立工機 (株)フロンティアカーボン (株)(株) 堀場製作所
レニショー (株)(株) ワイエムシィ／ YMC テクノス (株)WITec (株)Table of Contents
Session Time Table in Japanese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
English . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
Table of Chairpersons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
Scientific Program in Japanese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
English . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvi
Abstract of Plenary / Special Lectures . . . . . . . . . . . . . . . . . . . . . . . . . 1
General Lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Poster Presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

目次
プログラム早見表

和文 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
英文 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii

座長一覧表 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
講演プログラム

和文 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
英文 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvi

講演要旨

基調講演・特別講演 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
一般講演 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
ポスター発表 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

著者索引 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

プログラム早見表

FNTG-47@Nagoya, 2014

9月3日(水)
8:45
9:00
9:15

受付開始

8:45〜

講演開始

9:30〜

9:30
9:45
10:00
10:15
10:30
10:45
11:00
11:15
11:30
11:45
12:00
12:15

一般講演

5件

(グラフェンの物性と応用)
9:30〜10:45
休憩

10:45〜11:00

特別講演 (荒川 公平)
11:00〜11:30
一般講演 3件(ナノチューブの合成と応用)
11:30〜12:15

12:30
昼食
(幹事会)
12:15〜13:30

13:15
13:30
13:45
14:00
14:15
14:30
14:45
15:00
15:15
15:30
15:45
16:00
16:15
16:30
16:45
17:00

9:00

受付開始

8:45〜

講演開始

9:00〜

13:30〜14:00
一般講演 6件(フラーレン・ナノホーン・ナノ炭素)
14:00〜15:30
休憩

15:30〜15:45

特別講演 (山本 貴博)
15:45〜16:15
ポスタープレビュー(1P-1〜1P-41)
16:15〜17:00

17:15

9:00

受付開始

8:45〜

講演開始

9:00〜

一般講演

5件

一般講演 4件

9:15

9:30

(大澤賞受賞対象者講演・

9:30(グラフェンおよび2次元物質の9:45

飯島賞受賞対象者講演)

9:45

物性・金属内包フラーレン)

10:00

9:00〜10:20

10:00

9:00〜10:15

10:20

休憩

10:20〜10:35

10:35

10:15
10:30

10:45

基調講演 (齋藤 理一郎)

10:45

11:00

10:35〜11:20

11:00

11:20
11:30
11:45
12:05
12:15

一般講演

3件

(ナノチューブの応用)
11:20〜12:05
NT15の案内

11:15
11:30
11:45
12:00
12:15
12:30

休憩

10:15〜10:30

特別講演 (秋田 成司)
10:30〜11:00
特別講演 (Shulaker Max)
11:00〜11:30
一般講演

4件

(グラフェンおよび2次元物質の合成)
11:30〜12:30

12:45

昼食

12:45

13:00

12:15〜13:30

13:00

昼食

13:15

12:30〜13:45

13:15

特別講演 (Lu Xing)

9月5日(金)
8:45

9:15

12:30

12:45
13:00

9月4日(木)
8:45

13:30
13:45

若手奨励賞表彰式
総会

14:00
14:15
14:30
14:45
15:00
15:15
15:30
15:45
16:00
16:15
16:30

特別講演 (岩佐 義宏)
14:15〜14:45
一般講演 3件(グラフェンの合成)
14:45〜15:30
休憩

15:30〜15:45

ポスタープレビュー(2P-1〜2P-41)
15:45〜16:30

16:45

13:30
13:45
14:00

14:30

13:45〜14:45

14:45
15:00
15:15
15:30
15:45

【1F プレゼンスペース】

16:45

15:45〜17:15

17:15

16:30〜18:00【1F プレゼンスペース】

17:45

17:00〜18:30

18:00

18:15

18:15

18:30

18:30

移動

(3P-1〜3P-40)
15:00〜15:45

16:30【1F プレゼンスペース】

18:00

ポスタープレビュー

ポスターセッション

17:00

17:45

14:45〜15:00

16:15

ポスターセッション

17:30

休憩

16:00

17:15

ポスターセッション

4件(ナノチューブの物性)

17:00

17:30

一般講演

14:15

18:00〜18:30

18:45
19:00
19:15

懇親会

19:30

【レストラン花の木】

19:45

18:30〜20:30

20:00

基調講演：発表40分＋質疑5分【1件】
特別講演：発表25分＋質疑5分【6件】
賞対象者講演：発表10分＋質疑10分【4件】
一般講演：発表10分＋質疑5分【33件】

20:15

ポスタープレビュー：発表1分【122件】

20:30

–i–

Session Time Table

FNTG-47@Nagoya, 2014

September 3rd (Wed)
8:45
9:00
9:15

September 4th (Thu)
8:45

Registration starts at 8:45
Session starts at 9:30

9:00
9:15

9:30

9:30

9:45

9:45

10:00
10:15
10:30
10:45
11:00
11:15
11:30
11:45
12:00
12:15

General Lectures [5](Properties and Applications ofGraphene)
9:30〜10:45
Coffee Break 10:45〜11:00

Special Lecture (K. Arakawa)
11:00〜11:30
General Lectures [3](Synthesis and Applications ofNanotubes)
11:30〜12:15

12:30
12:45
13:00

Lunch
(Administrative Meeting)
12:15〜13:30

13:15
13:30
13:45

10:00
10:20
10:35
10:45
11:00

11:30
11:45
12:05

General Lectures [6](Fullerenes / Nanohorns /Nanocarbons)
14:00〜15:30

15:15

15:45
16:00

Special Lecture (T. Yamamoto)
15:45〜16:15

16:15

12:45
13:00

13:30
13:45

16:30
16:45

14:30

15:00

15:30
15:45
16:00

10:45
11:00

Announcement of NT15

Lunch
12:15〜13:30

11:45
12:00

General Meeting
Special Lecture (Y. Iwasa)
14:15〜14:45

13:00

Coffee Break 15:30〜15:45

Poster Preview(2P-1〜2P-41)
15:45〜16:30

17:30

Poster Session[Presentation Space at 1F]
16:30〜18:00

Coffee Break 10:15〜10:30

Special Lecture (S. Akita)
10:30〜11:00
Special Lecture (M. Shulaker)
11:00〜11:30
General Lectures [4](Synthesis of Graphene and
2D Materials)
11:30〜12:30

Lunch
12:30〜13:45

13:30
13:45
14:00
14:15
14:30
14:45

General Lectures [3](Synthesis of Graphene)
14:45〜15:30

General Lectures [5](Properties of Graphene and 2D
Materials / Endohedral
Metallofullerenes)
9:00〜10:15

12:45

13:15

Award Ceremony

Registration starts at 8:45
Session starts at 9:00

11:30

15:00
15:15
15:30

General Lectures [4](Properties of Nanotubes)
13:45〜14:45
Coffee Break 14:45〜15:00

Poster Preview(3P-1〜3P-40)
15:00〜15:45

15:45
16:00
16:15

16:45

17:15

18:00

10:30

16:45

17:15

Poster Session[Presentation Space at 1F]
17:00〜18:30

10:15

16:30

17:00

17:45

10:00

16:30

17:00

17:30

General Lectures [3](Application of Nanotubes)
11:20〜12:05

14:45

16:15

Poster Preview(1P-1〜1P-41)
16:15〜17:00

9:45

12:30

15:15
Coffee Break 15:30〜15:45

9:30

11:15

13:15

Special Lecture (X. Lu)
13:30〜14:00

9:15

12:30

14:15

15:30

Plenary Lecture (R. Saito)
10:35〜11:20

9:00

12:15

14:00

15:00

Coffee Break 10:20〜10:35

8:45

12:15

14:15

14:45

General Lectures [4](Lectures of Osawa Award and
Iijima Award Nominees)
9:00〜10:20

11:20

14:00

14:30

Registration starts at 8:45
Session starts at 9:00

September 5th (Fri)Poster Session[Presentation Space at 1F]
15:45〜17:15

17:00
17:15

17:45
18:00

18:15

18:15

18:30

18:30

Relocation 18:00〜18:30

18:45
19:00
19:15
19:30
19:45

Banquet[Restaurant HANANOKI]
18:30〜20:30

Plenary Lecture: 40 min + 5 min [1]Special Lecture: 25 min + 5 min [6]Award Nominee Lecture: 10 min + 10 min [4]20:00

General Lecture: 10 min + 5 min [33]

20:15

Poster Preview: 1 min + 0 min [122]20:30– ii –

FNTG-47@Nagoya, 2014

座長一覧 (Chairpersons)(敬称略)

9 月 3 日 (水)
セッション

時

間

座

長

一般講演

9:30∼10:45

松田 一成

特別講演 (荒川 公平)

11:00∼11:30

篠原 久典

一般講演

11:30∼12:15

千足 昇平

特別講演 (Xing Lu)

13:30∼14:00

赤阪 健

一般講演

14:00∼15:30

菅井 俊樹

特別講演 (山本 貴博)

15:45∼16:15

岡田 晋

ポスタープレビュー

16:15∼17:00

乗松 航
大町 遼

時

座

9 月 4 日 (木)セッション
大澤賞受賞対象者講演

間長

飯島賞受賞対象者講演

9:00∼9:20
9:20∼10:20

山本 貴博

基調講演 (齋藤 理一郎)

10:35∼11:20

丸山 茂夫

一般講演

11:20∼12:05

岡崎 俊也

特別講演 (岩佐 義宏)

14:15∼14:45

齋藤 理一郎

一般講演

14:45∼15:30

保田 諭

ポスタープレビュー

15:45∼16:30

坂本 裕俊
小鍋 哲

時

座

9 月 5 日 (金)
セッション

間

長

一般講演

9:00∼10:15

宮本 良之

特別講演 (秋田 成司)

10:30∼11:00

湯田坂 雅子特別講演 (Max Shulaker)

11:00∼11:30

大野 雄高

一般講演

11:30∼12:30

加藤 俊顕

一般講演

13:45∼14:45

宮内 雄平

ポスタープレビュー

15:00∼15:45

岸 直希
小林 慶太

– iii –

FNTG-47@Nagoya, 20149 月 3 日 (水)特別講演 : 発表 25 分＋質疑応答 5 分
一般講演 : 発表 10 分＋質疑応答 5 分
ポスタープレビュー : 発表 1 分、質疑応答なし

一般講演 (9:30–10:45)
グラフェンの物性と応用

1-1 「薄膜収縮を用いた歪みグラフェンの研究」
塩谷 広樹, クラチウン モニカ, ルッソ サヴェリオ, 山本 倫久, 樽茶 清悟 . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1-2 「角度分解光電子分光によるグラファイトのフォノンの分散関係の観測」
田中 慎一郎, 有田 将司, 島田 賢也 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1-3 「グラフェン／金属電極界面における接触抵抗の第一原理計算」
實宝 秀幸, 岡田 晋, 大淵 真理 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1-4 「ねじれ積層した２層グラフェンの超大規模な第一原理計算」
内田 和之, 岩田 潤一, 押山 淳 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1-5 「同位体を用いたグラフェンのバンド構造制御」
是常 隆, 斎藤 晋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13>>>>>>>> 休憩 (10:45–11:00) <<<<<<<<

特別講演 (11:00–11:30)
1S-1 「Industrialization Decision of Single-Walled Carbon-Nanotubes by Supergrowth-Method」
荒川 公平 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

一般講演 (11:30–12:15)
ナノチューブの合成と応用

1-6 「Selective Growth of (16,0) Carbon Nanotubes using Tungsten-Cobalt Catalyst」
LI Yan, YANG Feng, WANG Xiao, ZHANG Daqi, YANG Juan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1-7 「ナノチューブ成長のキラリティー選択におけるキャップ形成の役割」
阿知波 洋次, 児玉 健, 橋本 健朗, 城丸 春夫 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1-8 「カーボンナノチューブの内部空間を利用したダイヤモンド分子ポリマーの直接合成」
中西 勇介, 大町 遼, 北浦 良, FOKINA Natalie, SCHREINER Peter, DAHL Jeremy, CARLSON Robert,
篠原 久典 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16>>>>>>>> 昼食 (12:15–13:30) <<<<<<<<

特別講演 (13:30–14:00)
1S-2 「In-Depth Understanding of the Molecular Structures and Chemical Properties of Carbide Cluster
Metallofullerenes」
LU Xing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

一般講演 (14:00–15:30)
フラーレン

1-9 「Simulations of Dynamic C60 -Ih Self-Assembly Cut the Gordian Knot: Coexistence of Bottom-Up and
Top-Down Mechanisms」
QIANG Hu-Jun, WANG Ying, MOROKUMA Keiji, IRLE Stephan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1-10 「C60 -C70 ２成分フラーレンウィスカーの合成と構造解析」
今野 俊生, 若原 孝次, 宮澤 薫一 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1-11 「Li+ @C60 とシクロヘキサジエンの Diels–Alder 反応における内包 Li+ による反応加速効果」
上野 裕, 川上 裕貴, 中川 晃二, 岡田 洋史, 伊熊 直彦, 青柳 忍, 小久保 研, 松尾 豊, 大島 巧 . . . . . . . . . 19

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9 月 3 日 (水)FNTG-47@Nagoya, 2014

ナノホーン／ナノ炭素

1-12 「ナノホーンにおけるトポロジカルラマンバンドの理論」
佐々木 健一, 舘野 功太, 後藤 秀樹 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1-13 「ボウル型 π 共役系分子スマネン誘導体のレーザアニーリングによる含窒素グラファイト様炭素の合成」
稲田 雄飛, 雨夜 徹, 清水 康智, 佐伯 昭紀, 辻 良太郎, 大塚 岳夫, 関 修平, 平尾 俊一 . . . . . . . . . . . . . . . 21
1-14 「ホウ素、窒素を共ドープしたカーボンナノホーン集合体の構造と電気化学特性」
弓削 亮太, 眞子 隆志, 坂東 俊治, 湯田坂 雅子, 當山 清彦, 飯島 澄男, 田村 宜之 . . . . . . . . . . . . . . . . . . . 22>>>>>>>> 休憩 (15:30–15:45) <<<<<<<<

特別講演 (15:45–16:15)
1S-3 「Heat-Transport and Thermoelectric Properties of Carbon Nanotubes」
山本 貴博 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

ポスタープレビュー (16:15–17:00)
ポスターセッション (17:00–18:30)(☆: 若手奨励賞候補)ナノチューブの応用

1P-1 「単層カーボンナノチューブ透明導電膜の保護膜形成による安定性向上」
岸 直希, 鈴木 崇, 斎藤 毅, 曽我 哲夫 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
1P-2 「Nitrogen-Fe-Carbon Coated Carbon Nanotube Catalyst for Oxygen Reduction Reaction」
古谷 アトム, 村越 敬, 保田 諭 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1P-3 「Li Ion Storage Properties of Functional Molecules Encapsulated in SWCNTs」
TASHIRO Kosuke, SONG Hayong, NISHIWAKI Yoshiki, KAWASAKI Shinji . . . . . . . . . . . . . . . . . . . . . 49
1P-4 「Ion Size Dependency of Ion Adsorptions on Outer and Inner Surfaces of SWCNTs」
筒井 誠人, 竹内 裕, 川崎 晋司 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
1P-5 「Integration of Double Wall Carbon Nanotube Sensors on CMOS Platform」
SEICHEPINE Florent, ROTHE Jörg, DUDINA Alexandra, HIERLEMANN Andreas, FREY Urs . . . . 51
☆ 1P-6「Optical Properties of Quantum Dots Beaded to Multi-Walled Carbon Nanotube Forest (QD-Beaded
MWCNT Forest)」
ジャントーン ウドーン, SEKIYA Kazuki, FURUTA Hiroshi, HATTA Akimitsu . . . . . . . . . . . . . . . . . . . . 52

☆ 1P-7「高密度配向 pn 接合半導体カーボンナノチューブにおける光電特性」
赤間 俊紀, 加藤 俊顕, 安彦 嘉浩, 畠山 力三, 金子 俊郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

ナノチューブの合成と精製

1P-8 「界面活性剤 SDS による単層カーボンナノチューブ金属/半導体分離のための第一原理計算」
大淵 真理 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
1P-9 「ナノポーラステンプレート内での交互積層と炭素ナノ構造の作製」
佐田 貴生, 藤ヶ谷 剛彦, 中嶋 直敏 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
1P-10 「Oligofluorenes with Diﬀerent Main-Chain Lengths for Selective Sorting of Semiconducting
Single-Walled Carbon Nanotubes」
白木 智丈, 新留 頌一郎, 利光 史行, 藤ヶ谷 剛彦, 中嶋 直敏 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
1P-11 「キャップ構造解析プログラムの開発」
菅井 俊樹, 櫻井 英博 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57–v–

FNTG-47@Nagoya, 20149 月 3 日 (水)ナノチューブの物性☆ 1P-12「イオン液体を用いた電気二重層キャリア注入による半導体型単層カーボンナノチューブの熱電物性の制御」
大島 侑己, 北村 典雅, 神田 翔平, 河合 英輝, 中井 祐介, 真庭 豊, 柳 和宏 . . . . . . . . . . . . . . . . . . . . . . . . . . 58

1P-13 「交流電場を用いたポリマー中での単層カーボンナノチューブの配向」
木村 俊貴, 村上 俊也, 木曽田 賢治, 伊東 千尋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
1P-14 「Photo-Oxidation Reactivity of Individual Single-walled Carbon Nanotube in Local Enhanced
Electromagnetic Field」
吉井 孝拓, 高瀬 舞, 保田 諭, 村越 敬 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
☆ 1P-15「欠陥を有する CNT の電界下での電子物性」
石山 佑, 岡田 晋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

1P-16 「Brightening of Excitons in Ozone Doped Carbon Nanotubes」
JUHASZ Gergely, NIEHAUS Thomas, NAKASHIMA Naotoshi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
グラフェンの応用

1P-17 「Optimization of Graphene Transfer onto Rough Surfaces for Electrochemical Cell Applications」
RIUS Gemma, NAKAGOME Akito, ERYU Osamu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
1P-18 「Selective Detection of Immunoglobulin M Using Reduced Graphene Field-Eﬀect Transistors Modified
with Fragments」
TANIKAWA Sachiko, NEGISHI Ryota, MATSUZAKI Michihiro, OHNO Yasuhide,
MAEHASHI Kenzo, MATSUMOTO Kazuhiro, KOBAYASHI Yoshihiro . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
1P-19 「イオン照射された炭素材料への Pt 系ナノ粒子の合成と電極触媒活性評価」
早瀬 勝平, 吉竹 晴彦, 西村 智朗, 王 志朋, 緒方 啓典 .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .65
1P-20 「SiC 上グラフェンへの銅インターカレーション」
今井 雅人, 乗松 航, 楠 美智子 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
グラフェンの物性

1P-21 「Eﬀect of Water Molecules in Trapping Carbon Dioxide Molecules Inside the Interlayer Space ofGraphene Oxides」
YAMASAKI Ayumi, YUMURA Takashi, WAKASUGI Takashi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
1P-22 「Characterization and Photoluminescence of Individual Graphene Nanosheets by Electrochemical
Exfoliation of Graphite」
LIN Li-Hung, JUANG Tzong-Yuan, JHAN Sin-Rong, CHEN Chien-Jen . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
☆ 1P-23「電界によるグラフェンナノリボンへの自由電子注入」
山中 綾香, 岡田 晋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

☆ 1P-24「粉末 X 線回折を用いた多層グラフェンの精密構造解析」
布山 直樹, 客野 遥, 中井 祐介, 宮田 耕充, 真庭 豊 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70

1P-25 「Absence of Raman G’ Band by Ultraviolet Excitation in Monolayer Graphene Systems」
シレガール シヤハリル, ハスデオ エッドウイ, ヌグラハ アフマド, 齋藤 理一郎 . . . . . . . . . . . . . . . . . . 71
1P-26 「Polarization Dependence of ARPES Intensity in Graphene」
アイリャ ポウルヤ, ヌグラハ アフマド, ハスデオ エッドウイ, 齋藤 理一郎 . . . . . . . . . . . . . . . . . . . . . . 72
1P-27 「Propagation Properties of Graphene Surface Plasmon」
ウータリ ムハンマド ソフィ, ハスデオ エッドウイ, ヌグラハ アフマオ, 齋藤 理一郎 . . . . . . . . . . . . . 73
1P-28 「STM によるグラフェン/Au(111) の電気化学特性評価」
熊谷 諒太, 佐藤 志野, 保田 諭, 村越 敬 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
☆ 1P-29「薄膜流化法で合成した遷移金属ダイカルコゲナイドの光学特性」
犬飼 恵理, 小林 佑, 宮田 耕充, 真庭 豊, 篠原 久典 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

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FNTG-47@Nagoya, 20149 月 3 日 (水)フラーレンとその応用☆ 1P-30「C36 をユニットとした二次元新奇炭素結晶相の物質設計」
丸山 実那, 岡田 晋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

☆ 1P-31「1,3-Dipolar Addition of Triphenylmethyl to Sc2 C2 @C3v (8)-C82 」
CAI Wenting, XIE Yunpeng, LU Xing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

1P-32 「Morphology Control of C70 One-Dimensional Structures in Liquid-Liquid Interfacial Precipitation(LLIP) and their Electrochemical Properties」
ZHENG Shushu, JU Hui, LU Xing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
1P-33 「Control of Cell Growth and Morphology on Highly Oriented Fullerene Nanowhisker-Scaﬀold
Constructed by Mimicking a Method of LB Film」
粕谷 侑紀, 南 皓輔, 山崎 智彦, QINGMIN Ji, 中西 和嘉, 有賀 克彦, 酒井 秀樹 . . . . . . . . . . . . . . . . . . . . . 79
☆ 1P-34「５員環スピロアセタールを基本骨格として異なる付加基を有するフラーレン二付加体の太陽電池特性評価」
三木江 翼, 佐伯 昭紀, 増田 寛之, 伊熊 直彦, 小久保 研, 関 修平 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

1P-35 「金属/酸化物多層膜を電極として用いた半透明 PTB7:PC71 BM 有機薄膜太陽電池」
藤井 俊治郎, 田中 丈士, 片浦 弘道 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
1P-36 「光渦による C60 分子の重合化現象および光マニュピレーション」
穐山 航, 仲村 直人, 田中 悠, 宮本 克彦, 尾松 孝茂, , 落合 勇一, 青木 伸之 . . . . . . . . . . . . . . . . . . . . . . . . . 82
1P-37 「有機薄膜太陽電池における新規 [60] および [70]PCBM 類縁体を用いたデバイス特性」
九田 優樹, 林 達也, 阿部 海, LEE Haeseong, LEE Jae S., LEE Seung J., JANG Jin, PAC Chyongjin, 森
山 広思 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
1P-38 「添加剤を用いたバルクヘテロ接合型有機薄膜太陽電池の固体ＮＭＲ分光法による局所構造解析」
河野 紗希, 石川 紗代, 緒方 啓典 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
1P-39 「カルボン酸エステル含有フラーレン誘導体の合成および有機薄膜太陽電池特性」
井川 望月, 林 達也, 阿部 海, LEE Haeseong, LEE Jae S., LEE Seung Joo, JANG Jin, PAC Chyongjin, 森
山 広思 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
その他

1P-40 「導電性改良剤としてナノカーボンを用いた電気二重層キャパシタの特性評価」
水谷 彰孝, 岡部 雄太, 須田 善行, 滝川 浩史, 植 仁志, 清水 一樹, 梅田 良人 . . . . . . . . . . . . . . . . . . . . . . . . 86
1P-41 「Self-Organized Nano-Structured Field Emitter Fabricated by Field Emission Induced Growth」
ITO Shinichi, NAKAHARA Hitoshi, SAITO Yahachi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

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9 月 4 日 (木)FNTG-47@Nagoya, 2014

基調講演 : 発表 40 分＋質疑応答 5 分
特別講演 : 発表 25 分＋質疑応答 5 分
大澤賞・飯島賞対象者講演 : 発表 10 分＋質疑応答 10 分
一般講演 : 発表 10 分＋質疑応答 5 分
ポスタープレビュー : 発表 1 分、質疑応答なし

大澤賞受賞対象者講演 (9:00–9:20)
2-1 「Production, Purification and Electronic Properties of the Missing, Small-Bandgap Metallofullerenes」
王 志永, 中西 勇介, 野田 祥子, 丹羽 宏之, 張 錦英, 北浦 良, 篠原 久典 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

飯島賞受賞対象者講演 (9:20–10:20)
2-2 「カーボンナノチューブおよびグラフェンによる電流駆動・超高速・オンチップ発光素子」
牧 英之, 森 達也, 山内 陽平, 本多 敏 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2-3 「時空間生体刺激のための光機能化ナノモジュレーターの開発」
都 英次郎, リュシェ ジュリー, マウロ マテオ, セブリアン クリスティーナ, 八尾 寛, メナール-モワイ
ヨン セシリア, ハチソン ジェームス, 湯田坂 雅子, 飯島 澄男, デコラ ルイーザ, ビアンコ アルベルト. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2-4 「高純度 (9,4) および (10,3) 単層カーボンナノチューブのミリグラムスケール分離」
蓬田 陽平, 都築 真由美, 魏 小均, 平野 篤, 藤井 俊治郎, 田中 丈士, 片浦 弘道 . . . . . . . . . . . . . . . . . . . . . 26>>>>>>>> 休憩 (10:20–10:35) <<<<<<<<

基調講演 (10:35–11:20)
2S-4 「Graphene and Atomic Layer Semiconducting Materials」
齋藤 理一郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

一般講演 (11:20–12:05)
ナノチューブの応用

2-5 「Metal-Free Hydrogen Evolution from Water using Single-Walled Carbon Nanotubes」
KOHNO Naoki, OHKUBO Kei, FUKUZUMI Shunichi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2-6 「Breath Figure Directed Self-Assembly of Single-Walled Carbon Nanotubes for Solar Cells」
崔 可航, 千葉 孝昭, 項 栄, 千足 昇平, 丸山 茂夫 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2-7 「柔軟で高い熱伝導性を有する CNT/炭素繊維/ゴム複合材料」
阿多 誠介, 西澤 あゆみ, 山田 健郎, 畠 賢治 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

NT15 国際会議の案内 (12:05–12:15)>>>>>>>> 昼食 (12:15–13:30) <<<<<<<<

若手奨励賞表彰式 (13:30–13:45)

FNTG 学会総会 (13:45–14:15)
特別講演 (14:15–14:45)
2S-5 「Spin-Valley Functionalities in Transition Metal Dichalcogenide 2D Crystals」
岩佐 義宏 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5– viii –9 月 4 日 (木)FNTG-47@Nagoya, 2014

一般講演 (14:45–15:30)
グラフェンの合成

2-8 「Low Temperature Graphene Synthesis from PMMA by Microwave Plasma Treatment」
山田 貴壽, 沖川 侑揮, 石原 正統, 長谷川 雅考 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2-9 「Synthesis of Concavo-Convex Graphene by Using Copper NPs as Catalyst」
SUNAYAMA Yuki, MIYAMURA Hiroshi, CUYA Jhon, SATO Yoshinori, JEYADEVAN Balachandran. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2-10 「その場走査電子顕微鏡法による金属上のグラフェン成長の観察」
加藤 大樹, 高橋 惇郎, 籾内 雄太, 本間 芳和 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32>>>>>>>> 休憩 (15:30–15:45) <<<<<<<<

ポスタープレビュー (15:45–16:30)
ポスターセッション (16:30–18:00)(☆: 若手奨励賞候補)ナノチューブの応用

2P-1 「熱伝導体応用のための垂直配向カーボンナノチューブ薄膜の熱伝導特性の評価」
前田 健太, 瑞樹 永祐, 佐藤 英樹 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2P-2 「鉄内包カーボンナノチューブシートの作製と磁気特性評価」
久保中 伸雄, 佐藤 貴之, 佐藤 英樹, 藤原 裕司 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2P-3 「Application of Water-Dispersible Multiwalled Carbon Nanotubes to Obtain Electroconductive Cotton
Textile for Flexible Heater」
RAHMAN Mohammad Jellur, MIENO Tetsu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2P-4 「Electronic Properties Measurement for Inner Tubes of DWCNTs」
SAKO Yusuke, TSUBOI Mika, OMACHI Haruka, SHINOHARA Hisanori, KITAURA Ryo . . . . . . . . . 91
ナノチューブの合成と精製☆ 2P-5「オーバーローディングと段階溶出による SWCNT の高純度単一構造分離」
魏 小均, 都築 真由美, 平川 琢也, 蓬田 陽平, 平野 篤, 藤井 俊治郎, 田中 丈士, 片浦 弘道 . . . . . . . . . . . 92

2P-6 「ゲルカラムクロマトグラフィーによる Nano-C 単層 CNT の金属半導体分離」
片浦 弘道, 久保田 真理子, 都築 真由美, 平野 篤, 藤井 俊治郎, 田中 丈士 . . . . . . . . . . . . . . . . . . . . . . . . . 93
☆ 2P-7「SiC 上カーボンナノチューブフォレスト向け高温マスクパターニング」
稲葉 優文, 李 智宇, 鈴木 和真, 渋谷 恵, 平野 優, 明道 三穂, 平岩 篤, 乗松 航, 楠 美智子, 川原田 洋 . 94

2P-8 「分子ノギスによる 2 層カーボンナノチューブの構造分離」
劉 剛, 木村 隆英, 小松 直樹 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2P-9 「新規の数珠状構造をもつカーボンナノチューブの合成」
横井 裕之, 畠山 一翔, 上田 茉子, 松本 正吾, 谷口 貴章, 鯉沼 陸央, 松本 泰道 . . . . . . . . . . . . . . . . . . . . . 96
2P-10 「解離可能な超分子可溶化剤による半導体性単層カーボンナノチューブの精製」
利光 史行, 中嶋 直敏 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
☆ 2P-11「パルスプラズマ CVD による高純度（6,4）単層カーボンナノチューブの大量合成」
許 斌, 加藤 俊顕, 金子 俊郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

ナノチューブの物性

2P-12 「Soft X-ray Spectroscopic Study on Horizontally Aligned Multi-walled Carbon Nanotube Films
Irradiated by Ar Ions」
TAMURA Ryosuke, TSUKAGOSHI Akira, HONDA Shinichi, NIIBE Masahito, TERASAWA Mititaka,
HIRASE Ryuji, YOSHIOKA Hideki, IZUMI Hirokazu, NIWASE Keisuke, TAGUSHI Eiji,
OURA Masaki . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2P-13 「単層カーボンナノチューブにおけるコヒーレント G バンドとコヒーレント RBM フォノン」
ヌグラハ アフマド, ハスデオ エッドウィ, 齋藤 理一郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100– ix –

FNTG-47@Nagoya, 20149 月 4 日 (木)2P-14 「単層カーボンナノチューブの X 線照射後熱アニーリングによるナノ構造の形成」
松田 充晃, 村上 俊也, 木曽田 賢治, 伊東 千尋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101☆ 2P-15「高い吸収係数を持つ CNT フォレストのラマン散乱」
石本 光輝, 関家 一樹, 小路 紘史, 古田 寛, 八田 章光 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

2P-16 「Open-End for Cloning from Zigzag-Type Aligned Carbon Nanotubes」
SHIBUYA Megumi, INABA Masafumi, SUZUKI Kazuma, HIRANO Yu, KUSUNOKI Michiko,
KAWARADA Hiroshi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
グラフェンの物性

2P-17 「グラフェンプラズモン伝搬に対する電荷遮蔽効果」
佐々木 健一, 熊田 倫雄 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2P-18 「Electronic Structure of Graphene Wrinkles Induced by Ni Substrate」
CUONG Nguyen Thanh, OTANI Minoru, OKADA Susumu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
グラフェンの合成☆ 2P-19「Electrical and Heat Transport of Isotopically-Modified Graphene Heterojunctions」
安野 裕貴, 竹井 邦晴, 秋田 成司, 有江 隆之 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

2P-20 「ノズル照射型 CVD 法を用いたグラフェン成長における基板温度依存性」
松浦 佑介, 佐藤 英樹, 三宅 秀人, 平松 和政 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2P-21 「Au キャップ層、Al2 O3 バリア層を用いたグラフェン析出法における核形成制御」
山田 純平, 鈴木 学, 上田 悠貴, 成塚 重弥, 丸山 隆浩 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2P-22 「太陽炉を用いた酸化グラフェン超高温処理による構造修復」
石田 俊, 宮田 雄一朗, 山元 克真, 楠本 太郎, 篠田 佳彦, 小林 慶裕 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109☆ 2P-23「急速加熱プラズマ CVD による Ni ナノバーを用いた高密度グラフェンナノリボンアレイの合成」
鈴木 弘朗, 加藤 俊顕, 金子 俊郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

2P-24 「単層カーボンナノチューブから生成したグラフェン量子ドット」
高橋 未咲, 陣内 涼太, 菅井 俊樹 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2P-25 「銅箔上での mm スケール単結晶グラフェンのアルコール CVD 成長」
津島 幸平, 曽田 将来, 陳 嘯, 金 成眞, 千足 昇平, 丸山 茂夫 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2P-26 「Synthesis of Multi-Layer Graphene for Wiring Application by Precipitation Method using Hybrid
Diﬀusion Barrier Layer」
SUZUKI Manabu, YAMADA Jumpei, UEDA Yuki, NARITSUKA Shigeya, MARUYAMA Takahiro. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113☆ 2P-27「Graphene Growth on Wide Terraces of SiC (0001) in Ar Atmosphere」
WANG Chenxing, NAKAHARA Hitoshi, ASAKA Koji, SAITO Yahachi . . . . . . . . . . . . . . . . . . . . . . . . . 114

2P-28 「Fabrication of Bottom-Up Graphene Rings on Si-Terminated 6H-SiC (0001) by Thermal
Decomposition in Argon Gas Atmosphere」
RUAMMAITREE Akkawat, NAKAHARA Hitoshi, SAITO Yahachi . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
フラーレンとその化学☆ 2P-29「ナノサターン：新奇 C60 包摂系の物質設計」
木暮 聖太, 岡田 晋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116☆ 2P-30「十重付加体 C60 鎖の磁性状態」
成田 康平, 岡田 晋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

2P-31 「C60 (Fc)2 ナノシートの圧力誘起相転移」
嘉藤 恭平, 小薗江 佳菜, 宮澤 薫一, 橘 勝 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
2P-32 「多層交流アークプラズマでのフラーレンの合成効率の向上」
竹内 雅則, 佐野 弘, 芦原 将彰, 真木 教雄, 真柄 宏之, 上野 幹広, 森下 和幸 . . . . . . . . . . . . . . . . . . . . . . 119–x–

FNTG-47@Nagoya, 20149 月 4 日 (木)2P-33 「Photoinduced Charge Transfer Properties of TTF-Triphenylamine C60 Donor-Acceptor Conjugate」
LU Xing, CHEN Muqing, SAHA Avishek, GULDI Dirk M. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
内包ナノチューブ／ナノホーン／ナノワイヤー／ナノ炭素／その他

2P-34 「フラーレンでキャップした単層カーボンナノチューブに内包された Xe ガスの分析透過電子顕微鏡観察」
小林 慶太, 保田 英洋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2P-35 「Ultrastructural Localization of Intravenously Injected Carbon Nanohorns in Tumor」
MATSUMURA Sachiko, YUGE Ryota, SATO Shigeo, TOMIDA Akihiro, ICHIHASHI Toshinari,
IRIE Hiroshi, IIJIMA Sumio, SHIBA Kiyotaka, YUDASAKA Masako . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2P-36 「Development of Measurement System for Electrical Properties of Carbon Nanocoil and Relationship ofResistivity with the Coil Shapes」
NAKAMURA Yasushi, KUNIMOTO Ryuji, SUDA Yoshiyuki, TAKIKAWA Hirofumi, UE Hitoshi,
SHIMIZU Kazuki, UMEDA Yoshito . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
2P-37 「Investigation of Catalytic Layer Formation and Optimization of Spin Coat Velocity for High-Yield
Synthesis of Carbon Nanocoil by using Fe2 O3 Fine Powder」
IIDA Tetsuo, MARUYAMA Koji, SUDA Yoshiyuki, TAKIKAWA Hirofumi, UE Hitoshi,
SHIMIZU Kazuki, UMEDA Yoshito . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2P-38 「電着法により Pt ナノ粒子を担持させた炭素材料の電極触媒特性評価」
吉竹 晴彦, 早瀬 勝平, 王 志朋, 緒方 啓典 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2P-39 「直流反転アーク放電法による LaC2 内包カーボンナノカプセルの高収率生成」
山本 和典, 山口 憲司, 社本 真一, 赤阪 健 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2P-40 「Relationship between the Structure and the Character of Starfish Nanocarbon」
NAMBA Natsuki, TAKADA Yukihiro, NAKADA Kyoko . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127☆ 2P-41「Low-Pressure Chemical Vapor Deposition of Multi-Walled Carbon Nanocoils with a Fiber Diameter of
7.5 nm」
清水 慶明, 須田 善行, 滝川 浩史, 植 仁志, 清水 一樹, 梅田 良人 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

懇親会 (18:30–20:30)(於 レストラン花の木)– xi –

9 月 5 日 (金)FNTG-47@Nagoya, 2014

特別講演 : 発表 25 分＋質疑応答 5 分
一般講演 : 発表 10 分＋質疑応答 5 分
ポスタープレビュー : 発表 1 分、質疑応答なし

一般講演 (9:00–10:15)
グラフェンおよび 2 次元物質の物性

3-1 「単層二硫化タングステンにおける結合励起子」
加藤 俊顕, 金子 俊郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3-2 「Photo-Induced Anomalous Nernst Eﬀects in Transition Metal Dichalcogenides」
小鍋 哲, 山本 貴博 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3-3 「MoS2 の CVD 合成とその太陽電池応用」
壷井 佑夏, 小澤 大知, 王 飛久, 宮内 雄平, 毛利 真一郎, 松田 一成 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3-4 「Vertical Transport in Graphene/Ultrathin h-BN/Graphene van der Waals Heterostructures」
森川 生, 増渕 覚, 山口 健洋, 守谷 頼, 井上 義久, 渡邊 賢司, 谷口 尚, 町田 友樹 . . . . . . . . . . . . . . . . . . . . 36
金属内包フラーレン

3-5 「Sc2 @C66 Revisited: An Endohedral Fullerene with Scandium Ions Nestled within Two Unsaturated
Linear Triquinanes」
山田 道夫, 栗原 広樹, 鈴木 光明, GUO Jing Dong, WAELCHLI Markus, OLMSTEAD Marilyn M.,
BALCH Alan L., 永瀬 茂, 前田 優, 長谷川 正, LU Xing, 赤阪 健 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37>>>>>>>> 休憩 (10:15–10:30) <<<<<<<<

特別講演 (10:30–11:00)
3S-6 「Carbon Nanotube Nanoelectromechanical Systems with Resonance Vibration」
秋田 成司 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

特別講演 (11:00–11:30)
3S-7 「CNT Computer: Demonstrating Robust Carbon Nanotube Digital Systems」
SHULAKER Max, HILLS Gage, CHEN Hong-Yu, WONG H.-S. Philip, MITRA Subhasish . . . . . . . . . . 7

一般講演 (11:30–12:30)
グラフェンおよび 2 次元物質の合成

3-6 「ラジカル重合型化学気相成長法によるアームチェア端をもつ sub-1nm グラフェンナノリボンの表
面合成」
中江 隆博, 矢野 真葵, 小島 崇寛, 坂口 浩司 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3-7 「Nitrogen-Induced Interface Improvement in Epitaxial Graphene on SiC」
NORIMATSU Wataru, MASUDA Yoshiho, KUSUNOKI Michiko . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3-8 「hBN 基板上への硫化タングステン (IV) 原子層の直接合成」
岡田 光博, 澤崎 拓実, 渡邊 賢司, 谷口 尚, 日比野 浩樹, 篠原 久典, 北浦 良 . . . . . . . . . . . . . . . . . . . . . . . . 40
3-9 「Electronic Structures of Carbon Flakes in Hexagonal Boron-Nitride Layers」
FUJIMOTO Yoshitaka, SAITO Susumu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41>>>>>>>> 昼食 (12:30–13:45) <<<<<<<<– xii –

9 月 5 日 (金)FNTG-47@Nagoya, 2014

一般講演 (13:45–14:45)
ナノチューブの物性

3-10 「内層引き抜き現象を利用した多層カーボンナノチューブの層間抵抗の測定」
四ノ宮 悠司, 安坂 幸師, 中原 仁, 齋藤 弥八 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3-11 「One-Dimensional Plasmon Excitation in Far-Infrared Region」
MORIMOTO Takahiro, JOUNG Soon-Kil, SAITO Takeshi, FUTABA Don N., HATA Kenji,
OKAZAKI Toshiya . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3-12 「単層カーボンナノチューブにおける X 線照射欠陥の直径依存性」
村上 俊也, 磯崎 哲, 松田 充晃, 木曽田 賢治, 伊東 千尋 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3-13 「Studies on the Relationship between SWNTs and Fe Catalyst Nanoparticles during Floating Catalyst
CVD from CO」
JIANG Hua, KASKELA Antti, MUSTONEN Kimmo, NASIBULIN Albert G., KAUPPINEN Esko I. .45>>>>>>>> 休憩 (14:45–15:00) <<<<<<<<

ポスタープレビュー (15:00–15:45)
ポスターセッション (15:45–17:15)(☆: 若手奨励賞候補)ナノチューブの応用☆ 3P-1「高効率な単層カーボンナノチューブ有機太陽電池：酸化モリブデンのドーピングおよび電子ブ
ロック機能」
田 日, CUI Kehang, NASIBULIN Albert, KAUPPINEN Esko, 丸山 茂夫, 松尾 豊 . . . . . . . . . . . . . . . . . 129☆ 3P-2「Threshold Voltage Distribution of Chemically Doped n-Type Carbon Nanotube Thin-Tilm Transistors」
YASUNISHI Tomohiro, KISHIMOTO Shigeru, OHNO Yutaka . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130☆ 3P-3「Design and Preparation of Pt Nanoclusters on Polybenzoimidazole-Wrapped Carbon Nanotubes andtheir use in Energy Applications」
HAMASAKI Yuki, FUJIGAYA Tsuyohiko, NAKASHIMA Naotoshi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

3P-4 「Flexible Microelectrode Based on CNT Thin Film for Electrochemical Sensor Applications」
NGUYEN Xuan Viet, KISHIMOTO Shigeru, OHNO Yutaka . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132☆ 3P-5「トップコンタクト電極を用いた CNT/SiC 界面の接触抵抗及び Schottky 障壁高さの評価」
鈴木 和真, 稲葉 優文, 渋谷 恵, 李 智宇, 明道 三穂, 平野 優, 平岩 篤, 乗松 航, 楠 美智子, 川原田 洋 .133

3P-6 「単層カーボンナノチューブを電極および正孔輸送材料として用いたペロブスカイト太陽電池」
千葉 孝昭, 坂口 貴寛, アルバート ナシブリン, エスコ カウピネン, 項 榮, 千足 昇平, 丸山 茂夫 . . . 134
3P-7 「カーボンナノチューブ薄膜の有機発光ダイオードにおける電子注入」
山田 竜也, 岸本 茂, 大野 雄高 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135☆ 3P-8「tert-Butoxide Mediated Arylation of Single-Wall Carbon Nanotubes with Iodoarenes」
TSUBOI Mika, OMACHI Haruka, KITAURA Ryo, SHINOHARA Hisanori . . . . . . . . . . . . . . . . . . . . . . 136

ナノチューブの合成と精製

3P-9 「単層カーボンナノチューブのネットワーク構造制御のための操作方法」
井ノ上 泰輝, 大塚 慶吾, 千足 昇平, 丸山 茂夫 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3P-10 「極薄ナノダイヤモンド層からの単層カーボンナノチューブ成長」
椎名 諒, 林 明生, 根岸 良太, 有福 達治, 清柳 典子, 小林 慶裕 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
3P-11 「FT-ICR 質量分析器を用いたサイズ選別コバルトクラスターと酸素との反応解析」
戸張 雄太, 小笠原 一樹, 佐藤 仁紀, 斎藤 真琴, 千足 昇平, 丸山 茂夫, 菅井 俊樹 . . . . . . . . . . . . . . . . . . 139
3P-12 「FT-ICR 質量分析装置を用いたコバルトクラスターとエタノールの化学反応に関する研究」
佐藤 仁紀, 小笠原 一樹, 戸張 雄太, 斎藤 真琴, 千足 昇平, 菅井 俊樹, 丸山 茂夫 . . . . . . . . . . . . . . . . . . 140– xiii –FNTG-47@Nagoya, 20149 月 5 日 (金)3P-13 「Synthesis and Properties of π-Extended Carbon Nanorings」
YAGI Akiko, VENKATARAMANA Gandikota, SEGAWA Yasutomo, ITAMI Kenichiro . . . . . . . . . . . 141
ナノチューブの物性

3P-14 「X 線回折実験によるカーボンナノチューブの精密構造とカイラリティ分布の研究」
光山 遼, 田寺 真, 客野 遥, 鈴木 亮輔, 石井 広義, 中井 祐介, 宮田 耕充, 柳 和宏, 片浦 弘道, 真庭 豊 .142
3P-15 「[6] シクロパラフェニレンカチオンラジカルのスピン密度符号の動的な交替」
加藤 立久, 香山 貴彦, 亀岡 優一郎, 茅原 栄一, 山子 茂, 佐藤 徹, 田中 一義 . . . . . . . . . . . . . . . . . . . . . . 143
3P-16 「Electronic and Structural Properties of B-Doped Carbon-Nanotube Film on SiC」
NORIMATSU Wataru, ODA Koji, FUJITA Hayato, KUSUNOKI Michiko . . . . . . . . . . . . . . . . . . . . . . . 144
グラフェンの応用と物性

3P-17 「表面官能基で開始される、カチオンおよびアニオン重合によるグラフェンオキサイドへのポリ
マーのグラフト反応」
永田 和寛, 河原 崇史, 橋本 久美, 藤木 一浩, 為末 真吾, 山内 健, 坪川 紀夫 . . . . . . . . . . . . . . . . . . . . . . 145
3P-18 「シリセンのエッジエネルギーと構造再構成」
斎藤 晋, 是常 隆 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
グラフェンの合成☆ 3P-19「薄膜硫化法による遷移金属ダイカルコゲナイドヘテロ構造の一段階合成」
小林 佑, 森 勝平, 真庭 豊, 宮田 耕充 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147

3P-20 「アンジップされたカーボンナノチューブ上のグラフェン層成長による多層グラフェンナノリボンの形成」
北川 治樹, 根岸 良太, 田中 啓文, 福森 稔, 小川 琢治, 小林 慶裕 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3P-21 「Graphitic Carbon Synthesis via Electrochemical Reduction Reactions」
金 制憲, 保田 諭, 村越 敬 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
3P-22 「触媒を用いたアモルファスカーボンの熱処理による SiO2 上へのグラフェンの成長」
長谷部 洋平, 中原 仁, 安坂 幸師, 齋藤 弥八 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3P-23 「拡散バリアと 2 段階熱処理を用いた析出法による高品質多層グラフェンの成長」
上田 悠貴, 鈴木 学, 山田 純平, 丸山 隆浩, 成塚 重弥 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
3P-24 「TiC マスクをした SiC 基板の表面分解によるグラフェン形成」
宮本 玄生, 乗松 航, 楠 美智子 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3P-25 「CH4 を用いたマイクロ波表面波プラズマ CVD によるグラフェン合成」
市村 進, 内田 秀雄, 脇田 紘一, 林 靖彦, 梅野 正義 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3P-26 「Plasma CVD Growth of Good Quality Graphene Film using Camphor Precursor」
ARYAL Hare, GHIMIRE Dilip, ADHIKARI Sudip, UCHIDA Hideo, WAKITA Koichi,
UMENO Masayoshi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
2 次元物質の応用と物性
3P-27 「赤外レーザーによるヘキサゴナルボロンナイトライドの層間相互作用の変調」
宮本 良之 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3P-28 「単層 MoS2 における励起子衝突を介したトリオン生成」
毛利 真一郎, 宮内 雄平, 松田 一成 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156☆ 3P-29「反転対称性の破れた遷移金属カルコゲナイドバルク結晶におけるスピン/バレー分極観察」
鈴木 龍二, 坂野 昌人, 張 奕勁, 明石 遼介, 森川 大輔, 原沢 あゆみ, 矢治 光一郎, 黒田 健太, 宮本 幸治,
奥田 太一, 石坂 香子, 有田 亮太郎, 岩佐 義宏 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157☆ 3P-30「遷移金属ダイカルコゲナイドの合成とマイルドプラズマによる機能化」
高橋 智之, 加藤 俊顕, 金子 俊郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158

3P-31 「カーボンナノリング・シクロパラフェニレン (CPP) のガス・蒸気吸着」
坂本 裕俊, 藤森 利彦, 李 暁琳, 金子 克美, KAN Kai, 伊丹 健一郎 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159– xiv –

FNTG-47@Nagoya, 20149 月 5 日 (金)フラーレンの応用と化学☆ 3P-32「siRNA Delivery Targeting to the Lung via Agglutination-Induced Accumulation and Clearance of
Cationic Tetraamino Fullerene」
南 皓輔, 岡本 好司, 土井 研人, 原野 幸治, 野入 英世, 中村 栄一 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160

3P-33 「フラーレンナノウィスカーの成長に及ぼす溶液体積の影響」
宮澤 薫一, 平田 千佳, 若原 孝次 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3P-34 「臭素化フラーレンの置換反応による新規八重付加型フラーレンの付加位置選択的合成」
渡邉 敬太, 内山 幸也, 与座 健治, 森山 広思 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
3P-35 「ジフェニルジアゾメタンと [Li+ @C60 ] の反応」
岡田 洋史, 川上 裕貴, 松尾 豊 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
3P-36 「固体 NMR による水酸化フラーレンをベースとした複合体のプロトンダイナミクス」
佐野 喜章, 緒方 啓典 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
金属内包フラーレン☆ 3P-37「コラニュレンとリチウムイオン内包フラーレンの電荷移動錯体形成と光誘起電子移動反応」
山田 美穂子, 大久保 敬, 塩谷 光彦, 福住 俊一 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165

3P-38 「Syntheses, Structural Determination, and Characterization of Electronic Properties of Bis-Germylated
Sc3 N@Ih -C80 and Lu3 N@Ih -C80 」
MIYABE Kyosuke, KAKO Masahiro, SATO Kumiko, SUZUKI Mitsuaki, MIZOROGI Naomi,
MAEDA Yutaka, OLMSTEAD Marilyn M., BALCH Alan L., WANG Wei-Wei, NAGASE Shigeru,
AKASAKA Takeshi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
3P-39 「7 Li 固体 NMR によるリチウム-C60 フラーレンクラスター構造の解明」
遠藤 智明, 吉田 慎一郎, 河地 和男, 笠間 泰彦, 權 垠相 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
3P-40 「リチウムイオン内包フラーレン (Li+ @C60 ·NTf−2 ) の高効率合成」
小針 良仁, 岡田 洋史, 中野 博人, 河地 和彦, 笠間 泰彦, 權 垠相, 松尾 豊 . . . . . . . . . . . . . . . . . . . . . . . . . 168– xv –

September 3rd, Wed.

FNTG-47@Nagoya, 2014

Special Lecture : 25 min + 5 min discussion
General Lecture : 10 min + 5 min discussion
Poster Preview : 1 min without discussion

General Lectures (9:30–10:45)
Properties and Applications of Graphene
1-1 “Studies of Strained Graphene with Thin Film Shrinkage Methods”
Hiroki SHIOYA, Monica CRACIUN, Saverio RUSSO, Michihisa YAMAMOTO, Seigo TARUCHA . . . 9
1-2 “Probing of the Phonon Dispersion in Graphite by using the Angle-Resolved Photoelectron Spectroscopy”
Shin-ichiro TANAKA, Masashi ARITA, Kenya SHIMADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1-3 “First-Principles Study on the Contact Resistance in the Graphene/Metal Interface”
Hideyuki JIPPO, Susumu OKADA, Mari OHFUCHI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1-4 “Ultra-large Scale DFT Calculations for Twisted Bilayer Graphene”
Kazuyuki UCHIDA, Jun-Ichi IWATA, Atsushi OSHIYAMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1-5 “Band Structure Engineering in Graphene using Isotope Eﬀect”
Takashi KORETSUNE, Susumu SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13>>>>>>>> Coﬀee Break (10:45–11:00) <<<<<<<<

Special Lecture (11:00–11:30)
1S-1 “Industrialization Decision of Single-Walled Carbon-Nanotubes by Supergrowth-Method”
Kohei ARAKAWA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

General Lectures (11:30–12:15)
Synthesis and Applications of Nanotubes
1-6 “Selective Growth of (16,0) Carbon Nanotubes using Tungsten-Cobalt Catalyst”
Yan LI, Feng YANG, Xiao WANG, Daqi ZHANG, Juan YANG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1-7 “The Role of “cap” Stabilities on the Chirality Selection in the Nanotube Growth”
Yohji ACHIBA, Takeshi KODAMA, Kenro HASHIMOTO, Haruo SHIROMARU . . . . . . . . . . . . . . . . . . 15
1-8 “Direct Synthesis of Diamantane Polymers inside Carbon Nanotubes from Halogenated Diamondoids”
Yusuke NAKANISHI, Haruka OMACHI, Ryo KITAURA, Natalie A. FOKINA, Peter R. SCHREINER,
Jeremy E. P. DAHL, Robert M. K. CARLSON, Hisanori SHINOAHRA . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16>>>>>>>> Lunch Time (12:15–13:30) <<<<<<<<

Special Lecture (13:30–14:00)
1S-2 “In-Depth Understanding of the Molecular Structures and Chemical Properties of Carbide Cluster
Metallofullerenes”
Xing LU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

General Lectures (14:00–15:30)
Fullerenes
1-9 “Simulations of Dynamic C60 -Ih Self-Assembly Cut the Gordian Knot: Coexistence of Bottom-Up and
Top-Down Mechanisms”
Hu-Jun QIANG, Ying WANG, Keiji MOROKUMA, Stephan IRLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1-10 “Synthesis and Structural Analysis of C60 -C70 Two-Component Fullerene Whiskers”
Toshio KONNO, Takatsugu WAKAHARA, Kun’ichi MIYAZAWA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1-11 “Reaction Rate Enhancement by Encapsulated Li+ on Diels–Alder Reaction of Li+ @C60 with
Cyclohexadiene”
Hiroshi UENO, Hiroki KAWAKAMI, Koji NAKAGAWA, Hiroshi OKADA, Naohiko IKUMA,
Shinobu AOYAGI, Ken KOKUBO, Yutaka MATSUO, Takumi OSHIMA . . . . . . . . . . . . . . . . . . . . . . . . . . 19
– xvi –

September 3rd, Wed.

FNTG-47@Nagoya, 2014

Nanohorns/Nanocarbons
1-12 “Theory of Topological Raman Band in the Carbon Nanohorn”
Kenichi SASAKI, Kouta TATENO, Hideki GOTOH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1-13 “Synthesis of Nitrogen-Doped Graphitic Carbon through Laser Annealing of Bowl-Shaped π-Conjugated
Molecule Sumanene Derivative”
Yuhi INADA, Toru AMAYA, Yasutomo SHIMIZU, Akinori SAEKI, Ryotaro TSUJI, Takeo OTSUKA,
Shu SEKI, Toshikazu HIRAO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1-14 “Structure and Electrochemical Properties of Boron- and Nitrogen-Doped Carbon Nanohorn Aggregates”
Ryota YUGE, Takashi MANAKO, Shunji BANDOW, Masako YUDASAKA, Kiyohiko TOYAMA,
Sumio IIJIMA, Noriyuki TAMURA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22>>>>>>>> Coﬀee Break (15:30–15:45) <<<<<<<<

Special Lecture (15:45–16:15)
1S-3 “Heat-Transport and Thermoelectric Properties of Carbon Nanotubes”
Takahiro YAMAMOTO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

Poster Previews (16:15–17:00)
Poster Session (17:00–18:30)(☆: Candidates for the Young Scientist Poster Award)

Application of Nanotubes
1P-1 “Stability Improvement of Transparent Conductive Thin Films of Single-Wall Carbon Nanotubes by
Forming Protective Thin Layer”
Naoki KISHI, Takashi SUZUKI, Takeshi SAITO, Tetsuo SOGA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
1P-2 “Nitrogen-Fe-Carbon Coated Carbon Nanotube Catalyst for Oxygen Reduction Reaction”
Atom FURUYA, Kei MURAKOSHI, Satoshi YASUDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1P-3 “Li Ion Storage Properties of Functional Molecules Encapsulated in SWCNTs”
Kosuke TASHIRO, Hayong SONG, Yoshiki NISHIWAKI, Shinji KAWASAKI . . . . . . . . . . . . . . . . . . . . . 49
1P-4 “Ion Size Dependency of Ion Adsorptions on Outer and Inner Surfaces of SWCNTs”
Masato TSUTSUI, Yu TAKEUCHI, Shinji KAWASAKI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
1P-5 “Integration of Double Wall Carbon Nanotube Sensors on CMOS Platform”
Florent SEICHEPINE, Jörg ROTHE, Alexandra DUDINA, Andreas HIERLEMANN, Urs FREY . . . . 51
☆ 1P-6“Optical Properties of Quantum Dots Beaded to Multi-Walled Carbon Nanotube Forest (QD-Beaded
MWCNT Forest)”
Udorn JUNTHORN, Kazuki SEKIYA, Hiroshi FURUTA, Akimitsu HATTA . . . . . . . . . . . . . . . . . . . . . . . 52

☆ 1P-7“Photovoltaic Features of Densely-Aligned pn Junction Semiconducting Single-Walled Carbon Nanotube
Films”
Toshiki AKAMA, Toshiaki KATO, Yoshihiro ABIKO, Rikizo HATAKEYAMA, Toshiro KANEKO . . 53

Synthesis and Purification of Nanotubes
1P-8 “Ab initio Study for Metal/Semiconductor Separation of Single-Wall Carbon Nanotubes using Surfactant
Sodium Dodecyl Sulfate”
Mari OHFUCHI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
1P-9 “Layer-by-Layer Assembly in Nanoporous Template and Fabrication of Carbon Nanoarchitecture”
Takao SADA, Tsuyohiko FUJIGAYA, Naotoshi NAKASHIMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
1P-10 “Oligofluorenes with Diﬀerent Main-Chain Lengths for Selective Sorting of Semiconducting
Single-Walled Carbon Nanotubes”
Tomohiro SHIRAKI, Shoichiro SHINDOME, Fumiyuki TOSHIMITSU, Tsuyohiko FUJIGAYA,
Naotoshi NAKASHIMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

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September 3rd, Wed.

1P-11 “Development of Cap Structure Analysis Program”
Toshiki SUGAI, Hidehiro SAKURAI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Properties of Nanotubes☆ 1P-12“Control of Thermo-Electric Properties of Semiconducting Single Wall Carbon Nanotubes by Electric
Double Layer Techniques Using an Ionic Liquid”
Yuki OSHIMA, Yoshimasa KITAMURA, Shouhei KANDA, Hideki KAWAI, Yusuke NAKAI,
Yutaka MANIWA, Kazuhiro YANAGI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

1P-13 “Alignment of Single-Walled Carbon Nanotubes in Polymer Matrix using Alternating Electric Field”
Toshiki KIMURA, Toshiya MURAKAMI, Kenji KISODA, Chihiro ITOH . . . . . . . . . . . . . . . . . . . . . . . . . 59
1P-14 “Photo-Oxidation Reactivity of Individual Single-walled Carbon Nanotube in Local Enhanced
Electromagnetic Field”
Takahiro YOSHII, Mai TAKASE, Satoshi YASUDA, Kei MURAKOSHI . . . . . . . . . . . . . . . . . . . . . . . . . . 60
☆ 1P-15“Electronic Structure of Carbon Nanotubes with Various Defects under an Electric Field”
U ISHIYAMA, Susumu OKDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

1P-16 “Brightening of Excitons in Ozone Doped Carbon Nanotubes”
Gergely JUHASZ, Thomas NIEHAUS, Naotoshi NAKASHIMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Application of Graphene
1P-17 “Optimization of Graphene Transfer onto Rough Surfaces for Electrochemical Cell Applications”
Gemma RIUS, Akito NAKAGOME, Osamu ERYU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
1P-18 “Selective Detection of Immunoglobulin M Using Reduced Graphene Field-Eﬀect Transistors Modified
with Fragments”
Sachiko TANIKAWA, Ryota NEGISHI, Michihiro MATSUZAKI, Yasuhide OHNO,
Kenzo MAEHASHI, Kazuhiro MATSUMOTO, Yoshihiro KOBAYASHI . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
1P-19 “Synthesis and Electrocatalytic Activities of Pt-Based Nanoparticles Supported on Ion-Irradiated Carbon
Materials”
Shohei HAYASE, Haruhiko YOSHITAKE, Tomoaki NISHIMURA, Zhipeng WANG, Hironori OGATA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
1P-20 “Coper Intercalation in Graphene on SiC(0001)”
Masato IMAI, Wataru NORIMATSU, Michiko KUSUNOKI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Properties of Graphene
1P-21 “Eﬀect of Water Molecules in Trapping Carbon Dioxide Molecules Inside the Interlayer Space ofGraphene Oxides”
Ayumi YAMASAKI, Takashi YUMURA, Takashi WAKASUGI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
1P-22 “Characterization and Photoluminescence of Individual Graphene Nanosheets by Electrochemical
Exfoliation of Graphite”
Li-Hung LIN, Tzong-Yuan JUANG, Sin-Rong JHAN, Chien-Jen CHEN . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
☆ 1P-23“Free-Electron Carriers Outside Graphene Nanoribbon by an Electric Field”
Ayaka YAMANAKA, Susumu OKADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

☆ 1P-24“Structure Analysis of Multilayer Graphene using X-Ray Diﬀraction”
Naoki NUNOYAMA, Haruka KYAKUNO, Yusuke NAKAI, Yasumitsu MIYATA, Yutaka MANIWA . 70

1P-25 “Absence of Raman G’ Band by Ultraviolet Excitation in Monolayer Graphene Systems”
Syahril SIREGAR, Eddwi HASDEO, Ahmad R.T. NUGRAHA, Riichiro SAITO . . . . . . . . . . . . . . . . . . . 71
1P-26 “Polarization Dependence of ARPES Intensity in Graphene”
Pourya AYRIA, Ahmad R.T. NUGRAHA, Eddwi HASDEO, Riichiro SAITO . . . . . . . . . . . . . . . . . . . . . . 72
1P-27 “Propagation Properties of Graphene Surface Plasmon”
Muhammad Shoufie UKHTARY, Eddwi H. HASDEO, Ahmad R.T. NUGRAHA, Riichiro SAITO . . 73
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September 3rd, Wed.

1P-28 “Electrochemical Characteristic Evaluation of Graphene/Au(111) by STM”
Ryota KUMAGAI, Shino SATO, Satoshi YASUDA, Kei MURAKOSHI . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
☆ 1P-29“Optical Properties of Transition Metal Dichalcogenides”
Eri INUKAI, Yu KOBAYASHI, Yasumitsu MIYATA, Yutaka MANIWA, Hisanori SHINOHARA . . . . 75

Fullerenes and its Applications☆ 1P-30“Electronic and Geometric Structures of Novel Two-dimensional Materials Consisting of C36 ”
Mina MARUYAMA, Susumu OKADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

☆ 1P-31“1,3-Dipolar Addition of Triphenylmethyl to Sc2 C2 @C3v (8)-C82 ”
Wenting CAI, Yunpeng XIE, Xing LU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

1P-32 “Morphology Control of C70 One-Dimensional Structures in Liquid-Liquid Interfacial Precipitation(LLIP) and their Electrochemical Properties”
Shushu ZHENG, Hui JU, Xing LU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
1P-33 “Control of Cell Growth and Morphology on Highly Oriented Fullerene Nanowhisker-Scaﬀold
Constructed by Mimicking a Method of LB Film”
Yuki KASUYA, Kosuke MINAMI, Tomohiko YAMAZAKI, Qingmin JI, Waka NAKANISHI,
Katsuhiko ARIGA, Hideki SAKAI .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
☆ 1P-34“Secondary Addition of 5-Membered Acetalized Ring to Methanofullerenes Leads to Enhancement of
Polymer Solar Cells”
Tsubasa MIKIE, Akinori SAEKI, Hiroyuki MASUDA, Naohiko IKUMA, Ken KOKUBO, Shu SEKI
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

1P-35 “Semitransparent PTB7:PC71 BM Solar Cells using an Oxide/Metal/Oxide Transparent Anode”
Shunjiro FUJII, Takeshi TANAKA, Hiromichi KATAURA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
1P-36 “Polymerization with Optical Manipulation of C60 Molecules by Optical Vortex Irradiation”
Wataru AKIYAMA, Naoto NAKAMURA, Yu TANAKA, Katsuhiko MIYAMOTO,
Takashige OMATSU, Jonathan BIRD, Yuichi OCHIAI, Nobuyuki AOKI . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
1P-37 “Device Characteristics using Novel [60] and [70]PCBM Analogues in Organic Photovoltaic Devices”
Yuki KUDA, Tatsuya HAYASHI, Kai ABE, Haeseong LEE, Jae S. LEE, Seung Joo LEE, Jin JANG,
Chyongjin PAC, Hiroshi MORIYAMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
1P-38 “Solid-State NMR Studies on the Aggregated Structures of Organic Bulk Heterojunction Solar Cells with
Solvent Additives”
Saki KAWANO, Sayo ISHIKAWA, Hironori OGATA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
1P-39 “Synthesis and Characterization of Fullerene Derivatives with Carboxylic Acid Ester in Organic
Photovoltaic Devices”
Mizuki IGAWA, Tatsuya HAYASHI, Kai ABE, Haeseong LEE, Jae S. LEE, Seung Joo LEE, Jin JANG,
Chyongjin PAC, Hiroshi MORIYAMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Other Topics
1P-40 “Improving Electric Double Layer Capacitor Property by Adding Nanocarbon Materials”
Akitaka MIZUTANI, Yuta OKABE, Yoshiyuki SUDA, Hirofumi TAKIKAWA, Hitoshi UE,
Kazuki SHIMIZU, Yoshito UMEDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
1P-41 “Self-Organized Nano-Structured Field Emitter Fabricated by Field Emission Induced Growth”
Shinichi ITO, Hitoshi NAKAHARA, Yahachi SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

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September 4th, Thu.

FNTG-47@Nagoya, 2014

Plenary Lecture : 40 min + 5 min discussion
Special Lecture : 25 min + 5 min discussion
Award Nominee Lecture : 10 min + 10 min discussion
General Lecture : 10 min + 5 min discussion
Poster Preview : 1 min without discussion

Osawa Award Nominee Lecture (9:00–9:20)
2-1 “Production, Purification and Electronic Properties of the Missing, Small-Bandgap Metallofullerenes”
Zhiyong WANG, Yusuke NAKANISHI, Shoko NODA, Hiroyuki NIWA, Jinying ZHANG,
Ryo KITAURA, Hisanori SHINOHARA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

Iijima Award Nominee Lectures (9:20–10:20)
2-2 “An Electrically-Driven, Ultra-High-Speed, On-Chip Light Emitter Based on Carbon Nanotubes andGraphene”
Hideyuki MAKI, Tatsuya MORI, Yohei YAMAUCHI, Satoshi HONDA . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2-3 “Photofunctional Nanomodulators for Spatiotemporal Bioexcitation”
Eijiro MIYAKO, Julie RUSSIER, Matteo MAURO, Cristina CEBRIAN, Hiromu YAWO,
Cécilia MÉNARD-MOYON, James HUTCHISON, Masako YUDASAKA, Sumio IIJIMA,
Luisa DE COLA, Alberto BIANCO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2-4 “Milligram-Scale Separation of High-Purity (9,4) and (10,3) SWCNTs”
Yohei YOMOGIDA, Mayumi TSUZUKI, Xiaojun WEI, Atsushi HIRANO, Shunjiro FUJII,
Takeshi TANAKA, Hiromichi KATAURA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26>>>>>>>> Coﬀee Break (10:20–10:35) <<<<<<<<Plenary Lecture (10:35–11:20)
2S-4 “Graphene and Atomic Layer Semiconducting Materials”
Riichiro SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

General Lectures (11:20–12:05)
Application of Nanotubes
2-5 “Metal-Free Hydrogen Evolution from Water using Single-Walled Carbon Nanotubes”
Naoki KOHNO, Kei OHKUBO, Shunichi FUKUZUMI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2-6 “Breath Figure Directed Self-Assembly of Single-Walled Carbon Nanotubes for Solar Cells”
Kehang CUI, Takaaki CHIBA, Rong XIANG, Shohei CHIASHI, Shigeo MARUYAMA . . . . . . . . . . . . . 28
2-7 “Highly Thermal Conductive yet Rubbery Material with CNT/Carbon Fiber/Rubber”
Seisuke ATA, Ayumi NISHIZAWA, Takeo YAMADA, Kenji HATA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

Announcement of NT15 International Conference (12:05–12:15)>>>>>>>> Lunch Time (12:15–13:30) <<<<<<<<

Award Ceremony (13:30–13:45)
General Meeting of the FNTG Society (13:45–14:15)
Special Lecture (14:15–14:45)
2S-5 “Spin-Valley Functionalities in Transition Metal Dichalcogenide 2D Crystals”
Yoshihiro IWASA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5– xx –

September 4th, Thu.

FNTG-47@Nagoya, 2014

General Lectures (14:45–15:30)
Synthesis of Graphene
2-8 “Low Temperature Graphene Synthesis from PMMA by Microwave Plasma Treatment”
Takatoshi YAMADA, Yuki OKIGAWA, Masatou ISHIHARA, Masataka HASEGAWA . . . . . . . . . . . . . 30
2-9 “Synthesis of Concavo-Convex Graphene by Using Copper NPs as Catalyst”
Yuki SUNAYAMA, Hiroshi MIYAMURA, Jhon CUYA, Yoshinori SATO, Balachandran JEYADEVAN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2-10 “In situ Scanning Electron Microscopy of Graphene Growth on Metal Surfaces”
Hiroki KATO, Junro TAKAHASHI, Yuta MOMIUCHI, Yoshikazu HOMMA . . . . . . . . . . . . . . . . . . . . . . 32>>>>>>>> Coﬀee Break (15:30–15:45) <<<<<<<<

Poster Previews (15:45–16:30)
Poster Session (16:30–18:00)(☆: Candidates for the Young Scientist Poster Award)

Applications of Nanotubes
2P-1 “Evaluation of Heat Conduction Property of Vertically Aligned Carbon Nanotube Films for ThermalInterface Material Application”
Kenta MAEDA, Eisuke TAMAKI, Hideki SATO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2P-2 “Fabrication of Carbon Nanotube Sheet using Carbon Nanotubes Filled with Iron Nanowires andCharacterization of its Magnetic Property”
Nobuo KUBONAKA, Takayuki SATO, Hideki SATO, Yuji FUJIWARA . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2P-3 “Application of Water-Dispersible Multiwalled Carbon Nanotubes to Obtain Electroconductive Cotton
Textile for Flexible Heater”
Mohammad Jellur RAHMAN, Tetsu MIENO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2P-4 “Electronic Properties Measurement for Inner Tubes of DWCNTs”
Yusuke SAKO, Mika TSUBOI, Haruka OMACHI, Hisanori SHINOHARA, Ryo KITAURA . . . . . . . . . 91
Synthesis and Purification of Nanotubes☆ 2P-5“High-Purity Single-Chirality Separation of SWCNTs using Overloading Selective Adsorption andStepwise Elution Chromatography”
Xiaojun WEI, Mayumi TSUZUKI, Takuya HIRAKAWA, Yohei YOMOGIDA, Atsushi HIRANO,
Shunjiro FUJII, Takeshi TANAKA, Hiromichi KATAURA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

2P-6 “Metal/Semiconductor Separation of Nano-C SWCNTs using Gel Column Chromatography”
Hiromichi KATAURA, Mariko KUBOTA, Mayumi TSUZUKI, Atsushi HIRANO, Shunjiro FUJII,
Takeshi TANAKA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
☆ 2P-7“Mask Patterning at Very High Temperature for Carbon Nanotube Forest on Silicon Carbide”
Masafumi INABA, Chih-Yu LEE, Kazuma SUZUKI, Megumi SHIBUYA, Yu HIRANO, Miho MYODO,
Atsushi HIRAIWA, Wataru NORIMATSU, Michiko KUSUNOKI, Hiroshi KAWARADA . . . . . . . . . . . . 94

2P-8 “Structural Discrimination of Double-Walled Carbon Nanotubes by Chiral Diporphyrin Nanocalipers
with a Larger Cavity”
Gang LIU, Takahide KIMURA, Naoki KOMATSU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2P-9 “Synthesis of Carbon Nanotube with an Unconventional Beaded Structure”
Hiroyuki YOKOI, Kazuto HATAKEYAMA, Mako UEDA, Shogo MATSUMOTO,
Takaaki TANIGUCHI, Michio KOINUMA, Yasumichi MATSUMOTO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
2P-10 “Facile Sorting of Surfactant-Free Semiconducting Single-Walled Carbon Nanotubes using
Supramolecular Solubilizers”
Fumiyuki TOSHIMITSU, Naotoshi NAKASHIMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
☆ 2P-11“High Yield Synthesis of (6,4) Single-Walled Carbon Nanotube by Pulse Plasma CVD”
Bin XU, Toshiaki KATO, Toshiro KANEKO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

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September 4th, Thu.

Properties of Nanotubes
2P-12 “Soft X-ray Spectroscopic Study on Horizontally Aligned Multi-Walled Carbon Nanotube Films
Irradiated by Ar Ions”
Ryosuke TAMURA, Akira TSUKAGOSHI, Shinichi HONDA, Masahito NIIBE, Mititaka TERASAWA,
Ryuji HIRASE, Hideki YOSHIOKA, Hirokazu IZUMI, Keisuke NIWASE, Eiji TAGUSHI,
Masaki OURA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2P-13 “Coherent G-band and RBM Phonons in Single Wall Carbon Nanotubes”
Ahmad R.T. NUGRAHA, Eddwi HASDEO, Riichiro SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2P-14 “A Nanostructure Grown in Single-Walled Carbon Nanotubes by X-ray Irradiation and the Following
Thermal Annealing”
Mitsuaki MATSUDA, Toshiya MURAKAMI, Kenji KISODA, Chihiro ITOH . . . . . . . . . . . . . . . . . . . . . 101☆ 2P-15“Raman Scattering from Aligned CNT Forests of High Absorption Coeﬃcient”
Kouki ISHIMOTO, Kazuki SEKIYA, Hirofumi KOJI, Hiroshi FURUTA, Akimitsu HATTA . . . . . . . . 102

2P-16 “Open-End for Cloning from Zigzag-Type Aligned Carbon Nanotubes”
Megumi SHIBUYA, Masafumi INABA, Kazuma SUZUKI, Yu HIRANO, Michiko KUSUNOKI,
Hiroshi KAWARADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Properties of Graphene
2P-17 “Eﬀects of Screening on Plasmon Transport in Graphene”
Kenichi SASAKI, Norio KUMADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2P-18 “Electronic Structure of Graphene Wrinkles Induced by Ni Substrate”
Nguyen Thanh CUONG, Minoru OTANI, Susumu OKADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Synthesis of Graphene☆ 2P-19“Electrical and Heat Transport of Isotopically-Modified Graphene Heterojunctions”
Yuki ANNO, Kuniharu TAKEI, Seiji AKITA, Takayuki ARIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

2P-20 “Influence of Growth Temperature on Formation of Graphene using Nozzle Injection Chemical Vapor
Deposition Method”
Yusuke MATSUURA, Hideki SATO, Hideto MIYAKE, Kazumasa HIRAMATSU . . . . . . . . . . . . . . . . . 107
2P-21 “Nucleation Control of Graphene in Precipitation Method by the use of Al2 O3 Barrier and Au Capping
Layers”
Jumpei YAMADA, Manabu SUZUKI, Yuki UEDA, Shigeya NARITSUKA, Takahiro MARUYAMA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2P-22 “Ultrahigh Temperature Process of Graphene Oxides using Solar Furnace for their Structural Restoration”
T. ISHIDA, Y. MIYATA, K. YAMAMOTO, T. KUSUSMOTO, Y. SHINODA, Y. KOBAYASHI . . . . . 109☆ 2P-23“Growth of Densely-Aligned Graphene Nanoribbons Array from Nickel Nanobar by Rapid Heating
Plasma CVD”
Hiroo SUZUKI, Toshiaki KATO, Toshiro KANEKO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

2P-24 “Production of Graphene Quantum Dots from Single-walled Carbon Nanotubes”
Misaki TAKAHASHI, Ryota JINNOUCHI, Toshiki SUGAI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2P-25 “Alcohol CVD Growth of Millimeter Scale Single-Crystal Graphene on Copper Foils”
Kohei TSUSHIMA, Masaki SOTA, Xiao CHEN, Sungjin KIM, Shohei CHIASHI,
Shigeo MARUYAMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2P-26 “Synthesis of Multi-Layer Graphene for Wiring Application by Precipitation Method using Hybrid
Diﬀusion Barrier Layer”
Manabu SUZUKI, Jumpei YAMADA, Yuki UEDA, Shigeya NARITSUKA, Takahiro MARUYAMA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113☆ 2P-27“Graphene Growth on Wide Terraces of SiC (0001) in Ar Atmosphere”
Chenxing WANG, Hitoshi NAKAHARA, Koji ASAKA, Yahachi SAITO . . . . . . . . . . . . . . . . . . . . . . . . . 114– xxii –FNTG-47@Nagoya, 2014

September 4th, Thu.

2P-28 “Fabrication of Bottom-Up Graphene Rings on Si-Terminated 6H-SiC (0001) by Thermal Decomposition
in Argon Gas Atmosphere”
Akkawat RUAMMAITREE, Hitoshi NAKAHARA, Yahachi SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Fullerenes and its Chemistry☆ 2P-29“Nano-Saturn : Theoretical Design of New C60 Inclusion Compounds”
Shota KIGURE, Susumu OKADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116☆ 2P-30“Magnetic Properties of Decamethyl C60 Chain”
Kohei NARITA, Susumu OKADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

2P-31 “Pressure-Induced Phase Transition of C60 (Fc)2 Nanosheet”
Kyohei KATO, Kana OSONOE, Kun’ichi MIYAZAWA, Masaru TACHIBANA . . . . . . . . . . . . . . . . . . . 118
2P-32 “Improving Eﬃciency in Synthesis of Fullerenes in Multi-Phase AC Arc Plasma”
Masanori TAKEUCHI, Hiroshi SANO, Masaaki ASHIHARA, Norio MAKI, Hiroyuki MAKARA,
Mikihiro UENO, Kazuyuki MORISHITA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
2P-33 “Photoinduced Charge Transfer Properties of TTF-Triphenylamine C60 Donor-Acceptor Conjugate”
Xing LU, Muqing CHEN, Avishek SAHA, Dirk M. GULDI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
Endohedral Nanotubes / Nanohorns / Nanowires / Nanocarbons / Others
2P-34 “Analytical Transmission Electron Microscopy of Xe Gas Encapsulated within the Inner Space ofFullerene-Capped Single-Wall Carbon Nanotube”
Keita KOBAYASHI, Hidehiro YASUDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2P-35 “Ultrastructural Localization of Intravenously Injected Carbon Nanohorns in Tumor”
Sachiko MATSUMURA, Ryota YUGE, Shigeo SATO, Akihiro TOMIDA, Toshinari ICHIHASHI,
Hiroshi IRIE, Sumio IIJIMA, Kiyotaka SHIBA, Masako YUDASAKA . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2P-36 “Development of Measurement System for Electrical Properties of Carbon Nanocoil and Relationship ofResistivity with the Coil Shapes”
Yasushi NAKAMURA, Ryuji KUNIMOTO, Yoshiyuki SUDA, Hirofumi TAKIKAWA, Hitoshi UE,
Kazuki SHIMIZU, Yoshito UMEDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
2P-37 “Investigation of Catalytic Layer Formation and Optimization of Spin Coat Velocity for High-Yield
Synthesis of Carbon Nanocoil by using Fe2 O3 Fine Powder”
Tetsuo IIDA, Koji MARUYAMA, Yoshiyuki SUDA, Hirofumi TAKIKAWA, Hitoshi UE,
Kazuki SHIMIZU, Yoshito UMEDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2P-38 “Electrocatalytic Properties of Pt-Based Nanoparticles Supported on Carbon Materials by One-Step
Electrodeposition”
Haruhiko YOSHITAKE, Shohei HAYASE, Zhipeng WANG, Hironori OGATA . . . . . . . . . . . . . . . . . . . 125
2P-39 “High Yield Synthesis of LaC2 Encapsulated Carbon Nanocapsules by Inverse DC Arc Discharge”
Kazunori YAMAMOTO, Kenji YAMAGUCHI, Shin-ichi SHAMOTO, Takeshi AKASAKA . . . . . . . 126
2P-40 “Relationship between the Structure and the Character of Starfish Nanocarbon”
Natsuki NAMBA, Yukihiro TAKADA, Kyoko NAKADA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127☆ 2P-41“Low-Pressure Chemical Vapor Deposition of Multi-Walled Carbon Nanocoils with a Fiber Diameter of
7.5 nm”
Yoshiaki SHIMIZU, Yoshiyuki SUDA, Hirofumi TAKIKAWA, Hitoshi UE, Kazuki SHIMIZU,
Yoshito UMEDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

Banquet (18:30–20:30)(at Retaurant HANANOKI)– xxiii –September 5th, Fri.

FNTG-47@Nagoya, 2014

Special Lecture : 25 min + 5 min discussion
General Lecture : 10 min + 5 min discussion
Poster Preview : 1 min without discussion

General Lectures (9:00–10:15)
Properties of Graphene and 2D Materials
3-1 “Bound Excitons in Monolayer Tungsten Disulfide”
Toshiaki KATO, Toshiro KANEKO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3-2 “Photo-Induced Anomalous Nernst Eﬀects in Transition Metal Dichalcogenides”
Satoru KONABE, Takahiro YAMAMOTO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3-3 “Synthesis of MoS2 by Chemical Vapor Deposition and its Application for Solar Cell”
Yuka TSUBOI, Daichi KOZAWA, Feijiu WANG, Yuhei MIYAUCHI, Shinichiro MOURI,
Kazunari MATSUDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3-4 “Vertical Transport in Graphene/Ultrathin h-BN/Graphene van der Waals Heterostructures”
Sei MORIKAWA, Satoru MASUBUCHI, Takehiro YAMAGUCHI, Rai MORIYA, Yoshihisa INOUE,
Kenji WATANABE, Takashi TANIGUCHI, Tomoki MACHIDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Endohedral Metallofullerenes
3-5 “Sc2 @C66 Revisited: An Endohedral Fullerene with Scandium Ions Nestled within Two Unsaturated
Linear Triquinanes”
Michio YAMADA, Hiroki KURIHARA, Mitsuaki SUZUKI, Jing Dong GUO, Markus WAELCHLI,
Marilyn M. OLMSTEAD, Alan L. BALCH, Shigeru NAGASE, Yutaka MAEDA, Tadashi HASEGAWA,
Xing LU, Takeshi AKASAKA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37>>>>>>>> Coﬀee Break (10:15–10:30) <<<<<<<<

Special Lecture (10:30–11:00)
3S-6 “Carbon Nanotube Nanoelectromechanical Systems with Resonance Vibration”
Seiji AKITA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Special Lecture (11:00–11:30)
3S-7 “CNT Computer: Demonstrating Robust Carbon Nanotube Digital Systems”
Max SHULAKER, Gage HILLS, Hong-Yu CHEN, H.-S. Philip WONG, Subhasish MITRA . . . . . . . . . . 7

General Lectures (11:30–12:30)
Synthesis of Graphene and 2D Materials
3-6 “Fabrication of Sub-1 nm Graphene Nanoribbons with Armchair Edges by Radical
Polymerization-Chemical Vapor Deposition”
Takahiro NAKAE, Maki YANO, Takahiro KOJIMA, Hiroshi SAKAGUCHI . . . . . . . . . . . . . . . . . . . . . . . 38
3-7 “Nitrogen-Induced Interface Improvement in Epitaxial Graphene on SiC”
Wataru NORIMATSU, Yoshiho MASUDA, Michiko KUSUNOKI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3-8 “Direct CVD Synthesis of Atomic Layered WS2 on hBN Substrates”
Mitsuhiro OKADA, Takumi SAWAZAKI, Kenji WATANABE, Takashi TANIGUCHI, Hiroki HIBINO,
Hisanori SHINOHARA, Ryo KITAURA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3-9 “Electronic Structures of Carbon Flakes in Hexagonal Boron-Nitride Layers”
Yoshitaka FUJIMOTO, Susumu SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41>>>>>>>> Lunch Time (12:30–13:45) <<<<<<<<– xxiv –September 5th, Fri.

FNTG-47@Nagoya, 2014

General Lectures (13:45–14:45)
Properties of Nanotubes
3-10 “Inter-Shell Resistance in a Multiwall Carbon Nanotube Measured by Utilizing Inner-Shell Retraction
Phenomena”
Yuji SHINOMIYA, Koji ASAKA, Hitoshi NAKAHARA, Yahachi SAITO . . . . . . . . . . . . . . . . . . . . . . . . . 42
3-11 “One-Dimensional Plasmon Excitation in Far-Infrared Region”
Takahiro MORIMOTO, Soon-Kil JOUNG, Takeshi SAITO, Don N. FUTABA, Kenji HATA,
Toshiya OKAZAKI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3-12 “Diameter Dependence of X-ray Irradiated Defect in Single-Walled Carbon Nanotubes”
Toshiya MURAKAMI, Satoshi ISOZAKI, Mitsuaki MATSUDA, Kenji KISODA, Chihiro ITOH . . . . 44
3-13 “Studies on the Relationship between SWNTs and Fe Catalyst Nanoparticles during Floating Catalyst
CVD from CO”
Hua JIANG, Antti KASKELA, Kimmo MUSTONEN, Albert G. NASIBULIN, Esko I. KAUPPINEN .45>>>>>>>> Coﬀee Break (14:45–15:00) <<<<<<<<

Poster Previews (15:00–15:45)
Poster Session (15:45–17:15)(☆: Candidates for the Young Scientist Poster Award)

Applications of Nanotubes☆ 3P-1“Eﬃcient SWCNT OSCs: Doping and Electron Blocking Functions of MoO x ”
Il JEON, Kehang CUI, Albert NASIBULIN, Esko KAUPPINEN, Shigeo MARUYAMA,
Yutaka MATSUO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129☆ 3P-2“Threshold Voltage Distribution of Chemically Doped n-Type Carbon Nanotube Thin-Tilm Transistors”
Tomohiro YASUNISHI, Shigeru KISHIMOTO, Yutaka OHNO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130☆ 3P-3“Design and Preparation of Pt Nanoclusters on Polybenzoimidazole-Wrapped Carbon Nanotubes andtheir use in Energy Applications”
Yuki HAMASAKI, Tsuyohiko FUJIGAYA, Naotoshi NAKASHIMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

3P-4 “Flexible Microelectrode Based on CNT Thin Film for Electrochemical Sensor Applications”
Xuan Viet NGUYEN, Shigeru KISHIMOTO, Yutaka OHNO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132☆ 3P-5“Estimation of the Contact Resistivity and Schottky Barrier Height at CNT/SiC Interface by Top Contact
Electrode”
Kazuma SUZUKI, Masafumi INABA, Megumi SHIBUYA, Chih-Yu LEE, Miho MYODO,
Yu HIRANO, Atsushi HIRAIWA, Wataru NORIMATSU, Michiko KUSUNOKI, Hiroshi KAWARADA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133

3P-6 “Perovskite Solar Cells with Single-Walled Carbon Nanotubes as Electrodes and Hole Conductors”
Takaaki CHIBA, Takahiro SAKAGUCHI, Albert G. NASIBLIN, Esko I. KAUPPINEN, Rong XIANG,
Shohei CHIASHI, Shigeo MARUYAMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
3P-7 “Electron Injection in Organic Light-Emitting Diodes by Carbon Nanotube Thin Film”
Tatsuya YAMADA, Shigeru KISHIMOTO, Yutaka OHNO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135☆ 3P-8“tert-Butoxide Mediated Arylation of Single-Wall Carbon Nanotubes with Iodoarenes”
Mika TSUBOI, Haruka OMACHI, Ryo KITAURA, Hisanori SHINOHARA . . . . . . . . . . . . . . . . . . . . . . 136

Synthesis and Purification of Nanotubes
3P-9 “Manipulation Method for Controlling Network Structures of Single-Walled Carbon Nanotubes”
Taiki INOUE, Keigo OTSUKA, Shohei CHIASHI, Shigeo MARUYAMA . . . . . . . . . . . . . . . . . . . . . . . . 137
3P-10 “Carbon Nanotube Synthesis from Very Thin Nanodiamond Layers”
Ryo SHIINA, Akio HAYASHI, Ryota NEGISHI, Michiharu ARIFUKU, Noriko KIYOYANAGI,
Yoshihiro KOBAYASHI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138– xxv –

FNTG-47@Nagoya, 2014

September 5th, Fri.

3P-11 “Reaction Analysis of Isolated Cobalt Cluster with O2 by Using FT-ICR Mass Spectrometer”
Yuta TOBARI, Kazuki OGASAWARA, Yoshinori SATO, Makoto SAITO, Shohei CHIASHI,
Shigeo MARUYAMA, Toshiki SUGAI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3P-12 “FT-ICR Study of Chemical Reaction of Cobalt Clusters with Ethanol”
Yoshinori SATO, Kazuki OGASAWARA, Yuta TOBARI, Makoto SAITO, Shohei CHIASHI,
Toshiki SUGAI, Shigeo MARUYAMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3P-13 “Synthesis and Properties of π-Extended Carbon Nanorings”
Akiko YAGI, Gandikota VENKATARAMANA, Yasutomo SEGAWA, Kenichiro ITAMI . . . . . . . . . . . 141
Properties of Nanotubes
3P-14 “Chirality Fingerprinting and Geometrical Determination of Single-Walled Carbon Nanotubes: Analysisof Fine Structure of X-ray Diﬀraction Pattern”
Ryo MITSUYAMA, Shin TADERA, Haruka KYAKUNO, Ryosuke SUZUKI, Hiroyoshi ISHII,
Yusuke NAKAI, Yasumitsu MIYATA, Kazuhiro YANAGI, Hiromichi KATAURA, Yutaka MANIWA .142
3P-15 “Dynamic Alternation of Sign in Spin Density of [6]Cycloparaphenylene Radical Cation”
Tatsuhisa KATO, Takahiko KOUYAMA, Yuichiro KAMEOKA, Eiichi KAYAHARA,
Shigeru YAMAGO, Tohru SATO, Kazuyoshi TANAKA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3P-16 “Electronic and Structural Properties of B-Doped Carbon-Nanotube Film on SiC”
Wataru NORIMATSU, Koji ODA, Hayato FUJITA, Michiko KUSUNOKI . . . . . . . . . . . . . . . . . . . . . . . 144
Applications and Properties of Graphene
3P-17 “Grafting of Polymers onto Graphene Oxide by Cationic and Anionic Polymerization Initiated by the
Surface Functional Groups”
Kazuhiro NAGATA, Takashi KAWAHARA, Kumi HASHIMOTO, Kazuhiro FUJIKI,
Shingo TAMESUE, Takeshi YAMAUCHI, Norio TSUBOKAWA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3P-18 “Edge Energy and Reconstruction of Silicene”
Susumu SAITO, Takashi KORETSUNE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
Synthesis of Graphene☆ 3P-19“One-Step Synthesis of Heterostructures Based on Transition Metal Dichalcogenides by Thin-Film
Sulfurization”
Yu KOBAYASHI, Shohei MORI, Yutaka MANIWA, Yasumitsu MIYATA . . . . . . . . . . . . . . . . . . . . . . . . . 147

3P-20 “Multilayer Graphene Nanoribbons Fabricated by Graphene Over-Layer Growth on Unzipped Carbon
Nanotubes”
Haruki KITAKAWA, Ryota NEGISHI, Hirofumi TANAKA, Minoru FUKUMORI, Takuji OGAWA,
Yoshihiro KOBAYASHI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3P-21 “Graphitic Carbon Synthesis via Electrochemical Reduction Reactions”
Jeheon KIM, Satoshi YASUDA, Kei MURAKOSHI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
3P-22 “Growth of Graphene on SiO2 by Catalyst-Assisted Heat Treatment of Amorphous Carbon”
Yohei HASEBE, Hitoshi NAKAHARA, Koji ASAKA, Yahachi SAITO . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3P-23 “Growth of High-Quality Multi-Layer Graphene by Precipitation Method using Diﬀusion Barrier and
Two Step Annealing”
Yuki UEDA, Manabu SUZUKI, Jumpei YAMADA, Takahiro MARUYAMA, Shigeya NARITSUKA .151
3P-24 “Graphene Formed by Surface Decomposition of TiC-Masked SiC Substrate”
Genki MIYAMOTO, Wataru NORIMATSU, Michiko KUSUNOKI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3P-25 “Synthesis of graphene using CH4 by Microwave Surface Wave Plasma Chemical Vapor Deposition”
Susumu ICHIMURA, Hideo UCHIDA, Koichi WAKITA, Yasuhiko HAYASHI, Masayoshi UMENO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153– xxvi –FNTG-47@Nagoya, 2014

September 5th, Fri.

3P-26 “Plasma CVD Growth of Good Quality Graphene Film using Camphor Precursor”
Hare ARYAL, Dilip GHIMIRE, Sudip ADHIKARI, Hideo UCHIDA, Koichi WAKITA,
Masayoshi UMENO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Applications and Properties of 2D Materials
3P-27 “Modifying Inter-Layer Interaction of Hexagonal Boron Nitride by Infrared Laser”
Yoshiyuki MIYAMOTO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3P-28 “Trion Generation via Exciton Collision in Monolayer MoS2 ”
Shinichiro MOURI, Yuhei MIYAUCHI, Kazunari MATSUDA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156☆ 3P-29“Valley-Dependent Spin Polarization in Bulk MoS2 with Broken Inversion Symmetry”
Ryuji SUZUKI, Masato SAKANO, Yijin ZHANG, Ryosuke AKASHI, Daisuke MORIKAWA,
Ayumi HARASAWA, Koichiro YAJI, Kenta KURODA, Koji MIYAMOTO, Taichi OKUDA,
Kyoko ISHIZAKA, Ryotaro ARITA, Iwasa YOSHIHIRO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157☆ 3P-30“Growth and Mild Plasma Functionalization of Transition Metal Dichalcogenides”
Tomoyuki TAKAHASHI, Toshiaki KATO, Toshiro KANEKO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158

3P-31 “Gas/Vapor Adsorption Behaviors of Carbon Nanorings of Cycloparaphenylenes (CPPs)”
Hirotoshi SAKAMOTO, Toshihiko FUJIMORI, Xiaolin LI, Katsumi KANEKO, Kai KAN,
Kenichiro ITAMI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Applications and Chemistry of Fullerenes☆ 3P-32“siRNA Delivery Targeting to the Lung via Agglutination-Induced Accumulation and Clearance of
Cationic Tetraamino Fullerene”
Kosuke MINAMI, Koji OKAMOTO, Kent DOI, Koji HARANO, Eisei NOIRI, Eiichi NAKAHMURA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160

3P-33 “Influence of the Solution Volume on the Growth of Fullerene Nanowhiskers”
Kun’ichi MIYAZAWA, Chika HIRATA, Takatsugu WAKAHARA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3P-34 “Regioselective Synthesis of Novel Octasubstituted Fullerenes by a Substitution Reaction of
Octabromofullerene C60 Br8 ”
Keita WATANABE, Kouya UCHIYAMA, Kenzi YOZA, Hiroshi MORIYAMA . . . . . . . . . . . . . . . . . . . 162
3P-35 “Reaction of [Li+ @C60 ] with Diphenyldiazomethane”
Hiroshi OKADA, Hiroki KAWAKAMI, Yutaka MATSUO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
3P-36 “Solid State NMR Studies of Proton Dynamics in Fullerenol-Based Composites”
Yoshiaki SANO, Hironori OGATA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Endohedral Metallofullerenes☆ 3P-37“Charge-Transfer Complexation and Photoinduced Electron Transfer between Corannulene and Lithium
Ion-Encapsulated [60]Fullerene”
Mihoko YAMADA, Kei OHKUBO, Mitsuhiko SHIONOYA, Shunichi FUKUZUMI . . . . . . . . . . . . . . . 165

3P-38 “Syntheses, Structural Determination, and Characterization of Electronic Properties of Bis-Germylated
Sc3 N@Ih -C80 and Lu3 N@Ih -C80 ”
Kyosuke MIYABE, Masahiro KAKO, Kumiko SATO, Mitsuaki SUZUKI, Naomi MIZOROGI,
Yutaka MAEDA, Marilyn M. OLMSTEAD, Alan L. BALCH, Wei-Wei WANG, Shigeru NAGASE,
Takeshi AKASAKA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
3P-39 “Elucidation of Lithium and C60 Fullerene Cluster Structures using 7 Li Solid-State NMR Strudies”
Tomoaki ENDO, Shin-ichiro YOSHIDA, Kazuo KAWACHI, Yasuhiko KASAMA, Eunsang KWON .167
3P-40 “An Eﬃcient Isolation Method for Lithium-Ion Endohedral Metallofullerene, Li+ @C60 ·NTf−2 ”
Yoshihito KOHARI, Hiroshi OKADA, Hiroto NAKANO, Kazuhiko KAWACHI, Yasuhiko KASAMA,
Eunsang KWON, Yutaka MATSUO .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .168

– xxvii –基調講演・特別講演
Plenary & Special Lectures

1S-1 ∼ 1S-3
2S-4 ∼ 2S-5
3S-6 ∼ 3S-7

1S-1

FNTG-47, 2014

Industrialization decision of single-walled carbon-nanotubes
by Supergrowth-method○Kohei Arakawa1
1

Zeon Corporation, 1-6-2Marunouchi,Chiyoda-ku,Tokyo, Japan

In 2004, a new water-assisted highly efficient synthetic approach of impurity-freesingle-walled carbon nanotubes was announced by Kenji.Hata of National Institute ofAdvanced Industrial Science and Technology (AIST). The feature of the method is that a verysmall amount of water to maintain catalytic activity at the time of CNT synthesis is added.
The Supergrowth method can provide very fast growth rate, high specific surface area andhigh aspect ratio . Zeon Corporation was concerned with development of carbon nanotube forthe first time by participating in Carbon Nanotube Capacitor Development Projectcommissioned by the New Energy and Industrial technology Development Organization(NEDO) in 2006. A consecutive mass production process was developed in the project by thecollaborative research with AIST . The productivity of the process was more than 1000 times
by original one developed in 2004. Impurity-free single-walled carbon nanotubes bySupergrowth-method will become industrial material soon.
As for the carbon nanotube, many uses are expected, but the most uses are realized by thecomposition with other materials. For basic technology construction to make carbon nanotube
composites with other materials and to provide a method for separating semiconductor carbon
nanotubes and metallic ones and so on, Technology research Association for Single-walled
Carbon nanotube (TASC) was established in 2010.
In the technology research association (TASC), there were many results of research. For
example, high thermal conductivity of 90W/m-K was provided in a composite material withfluorine-based rubber and carbon fibers and single-walled carbon nanotubes bySupergrowth-method. The conductivity is almost equal to iron. These materials are used as
the heat management in a semiconductor industry and so on. Electrical properties of acomposite with cupper and single-walled carbon nanotube by Supergrowth-method were
ampacity of approximately 100 times and almost equal conductivity, in comparison withcupper. The composite with cupper will be used the electric equipment industry andautomotive field and so on.
In April 2014, an investment of the mass production factory of Super-Growth single-walledcarbon nanotubes was approved. We are going to start production to support market needs in
October 2015.

–1–

1S-2

FNTG-47, 2014

In-Depth Understanding of the Molecular Structures andChemical Properties of Carbide Cluster Metallofullerenes
Xing Lu
School of Materials Science and Engineering,
Huzahong University of Science and Technology (HUST), China
When a metal carbide cluster such as Sc2C2 or Sc3C2 is encapsulated inside fullerenes,
the resultant species are difficult to distinguish from conventional metallofullerenes(Sc2@C2n+2). 1 Thus it results a fact that the molecular structures of many carbide cluster
metallofullerenes (Sc2C2@C2n) have been erroneously assigned in previous studies.2
In addition to provide unambiguous structural information from both NMR
spectroscopic and single crystal XRD crystallographic perspectives, we focusedparticularly on the chemical properties of some typical species such as Sc2C2@C2v(5)-C80,
Sc2C2@Cs(6)-C82, Sc2C2@C2v(9)-C82, Sc2C2@C3v(8)-C82, and Sc3C2@Ih(7)-C80 indifferent reactions like 1,3-dipolar addition, carbene cycloaddition or radical reaction.
New results and new rules governing the chemical reactivity of the cage carbons by theinternal carbide clusters have been obtained.3
References:
1.

X. Lu, T. Akasaka, S. Nagase, Acc. Chem. Res. 2013, 47, 1627-1635.

2.

(a) X. Lu, L. Feng, T. Akasaka, S. Nagase, Chem. Soc. Rev. 2012, 41, 7723-7760. (b) H.
Cong, B. Yu, T. Akasaka, X. Lu, Coord. Chem. Rev. 2013, 257, 2880-2898.

3.

(a) X. Lu, K. Nakajima, Y. Iiduka, H. Nikawa, N. Mizorogi, Z. Slanina, T. Tsuchiya, S.
Nagase, T. Akasaka, J. Am. Chem. Soc. 2011, 133, 19553-19558. (b) H. Kurihara, X. Lu, Y.
Iiduka, N. Mizorogi, Z. Slanina, T. Tsuchiya, T. Akasaka, S. Nagase, J. Am. Chem. Soc. 2011,
133, 2382-2385. (c) H. Kurihara, X. Lu, Y. Iiduka, M. Hachiya, H. Nikawa, N. Mizorogi, Z.
Slanina, T. Tsuchiya, S. Nagase, T. Akasaka, J. Am. Chem. Soc. 2012, 134, 3139-3144. (d) X.
Lu, K. Nakajima, Y. Iiduka, H. Nikawa, T. Tsuchiya, N. Mizorogi, Z. Slanina, S. Nagase, T.
Akasaka, J. Am. Chem. Soc. 2012, 51, 5889-5892. (e) H. Fang, H. Cong, M. Suzuki, P. Bao,
B. Yu, Y. Xie, N. Mizorogi, M. M. Olmstead, A. L. Balch, S. Nagase, T. Akasaka, X. Lu, J.
Am. Chem. Soc. 2014, DOI: 10.1021/ja505858y. (f) W. Cai, M. Chen, L. Bao, Y. Xie, X. Lu,
Angew. Chem. Int. Ed. submitted.
Tel & Fax: +86-2787559404; E-mail: lux@hust.edu.cn

–2–

1S-3

FNTG-47, 2014

Heat-Transport and Thermoelectric Properties of Carbon Nanotubes○Takahiro Yamamoto1,2
1
2

Department of Liberal Arts (Physics), Tokyo University of Science, Tokyo 125-8585, Japan
Department of Electrical Engineering, Tokyo University of Science, Tokyo 125-8585, Japan

Great attention has been paid to carbon nanotubes (CNTs) as potential candidates for heatremoval materials because of their extremely high thermal conductivity. Besides its practicalimportance in heat-device applications, the phonon transport in CNTs is the subject ofacademic interest because it exhibits various interesting phenomena originating from thecoherency of phonons in quasi-one-dimensional systems. In this talk, we present recent
development of research on the heat-transport in single-walled CNTs (SWNTs), such as thequantization of thermal conductance due to ballistic phonon transport [1,2], the non-linear
length dependence of thermal conductance due to crossover from ballistic to diffusive phonontransport [3], and the effect of defects [4,5] and mechanical bending [6].
On the other hand, a semiconducting SWNT (s-SWNT) is a promising candidate for aubiquitous thermoelectric material with large thermoelectric power factor (TE-PF). Because
the low thermal conductance is favorable to the high-performance thermoelectric materials in
addition to large TE-PF, the high thermal conductance of s-SWNT has to be reduced without
decreasing the large thermoelectric TE-PF. In this talk, we propose that 13C-disordereds-SWNT is a potential candidate for realizing high thermoelectric performance [7], and wereport that the thermal conductance decreases by nearly 80% when 13C concentration is morethan 20%.
A semiconducting SWNT film would be suitable for a bulk thermoelectric material. In fact,
recent experiments reported a giant thermoelectric power (TEP) in s-SWNT films, which iscomparable to that of commercial Bi2Te3 alloys [8]. In this talk, we present the first-principles
simulation (based on the NEGF+DFT method) on the TEP of a minimal model for s-SWNT
film in which two s-SWNTs are laterally contacted. The obtained results are as follows: (i)TEPs exhibit larger values (~170µV/K) at the room temperature, (ii) The sign of TEP canchange at the low temperature, (iii) The temperature dependence of TEP is sensitive to smallchanges of the chemical potential. These results are in good agreements with experimental
results. Thus, we conclude that the unusual behavior of thermoelectric power of an s-SWNT
film originates from tube-tube contacts.
[1] T. Yamamoto, S. Watanabe, K. Watanabe, Phys. Rev. Lett. 92, 075502 (2004).
[2] T. Yamamoto, S. Watanabe, K. Watanabe, Phys. Rev. Lett. 96, 255503 (2006).
[3] T. Yamamoto, S. Konabe, S. Shiomi, S. Maruyama, Appl. Phys. Express 2, 095003 (2009).
[4] N. Kondo, T. Yamamoto, K. Watanabe, Jpn. J. Appl. Phys. 45, L963 (2006).
[5] T. Yamamoto, Y. Nakazawa, K. Watanabe, New J. Phys. 9, 245 (2007).
[6] F. Nishimura, T. Takahashi, K. Watanabe, T. Yamamoto, Appl. Phys. Express 2, 035003(2009).
[7] T. Yamamoto, K. Sasaoka, S. Watanabe, Phys. Rev. Lett. 106, 215503 (2011).
[8] Y. Nakai, et al., Appl. Phys. Express 7, 025103(2014).
Corresponding Author: Takahiro Yamamoto
Tel: +81-3-5876-1486, Fax: +81-3-5876-1486,
E-mail: takahiro@rs.tus.ac.jp

–3–

2S-4

FNTG-47, 2014

Graphene and Atomic Layer Semiconducting Materials○Riichiro Saito1
1

Department of Physics, Tohoku University, Sendai 980-8578, Japan

Graphene and new atomic layer semiconducting materials such as MoS2, MoTe2, WS2 etc. haveprovided a huge and active field in the world for fundamental and applied physics, chemistry, andsemiconducting engineering [1]. In this presentation, starting from a general introduction of graphene
physics and engineering, we briefly introduce our recent project of Ministry of Education (MEXT)
grant in Japan, Science of Atomic Layers which starts in 2013 till 2017 [2] by overviewing the recent
interesting subjects which direct the potential activity in the near future.
Then we will focus the talk on our recent research activity of resonance Raman spectroscopy forcharacterizing graphene and some atomic layer systems [3,4]. We will present some recent
experimental results of Raman spectroscopy of single, double [5] and triple layer graphene [6] samples
with commensurate stacking orders by applying the gate voltage [7, 8], strain [9] or magnetic fields[10] which is combined with our theoretical study. We also present unpublished Raman spectra of
MoTe2 atomic layer. Finally, we list up the current problems of the graphene field and discuss thepossible direction of the future electronics [11].

References:[1] A. K. Geim and K. S. Novoselov, Nat. Mater. 6, 183 (2007).
[2] Web: http://flex.phys.tohoku.ac.jp/satl/index.html Face book: SATL
[3] R. Saito et al., Adv. in Phys 60, 413-550 (2011).
[4] A. Jorio, M. S. Dresselhaus, R. Saito, G. Dresselhaus, “Raman spectroscopy in Graphene
related systems” , Wiley-VCH, (2011).
[5] K. Sato et al., Phys. Rev. B, 86, 125414 (2012).
[6] C. Cong et al., ACS Nano 5, 8760 (2011).
[7] R. Saito et al., Solid Stat. Comm. 175-176, 18-34 (2013).
[8] P. T. Araujo et al., Sci. Rep. 2, 1017 (2013).
[9] M. A. Bissett et al., ACS Nano 6, 10229 (2012).
[10] C. Qiu et al., Phys. Rev. B, 88, 165407 (2013).
[11] R. Saito, “Nanotube and Grapene”, Butsurikagaku-no-Saizensen in Japanese, Kyoritu,(2014).
Corresponding Author: Riichiro Saito
Tel: +81-22-795-7754, Fax: +81-22-795-6447,
E-mail: rsaito@flex.phys.tohoku.ac.jp
Web: http://flex.phys.tohoku.ac.jp

–4–

2S-5

FNTG-47, 2014

Spin-valley functionalities in Transition Metal Dichalcogenide 2D Crystals○Yoshihiro Iwasa1,2
1

QPEC & Department of Applied Physics, University of Tokyo, Tokyo 113-8656, Japan
2
RIKEN Center for Emergent Matter Science, Wako 351-0198, Japan

Transition metal dichalcogenide (TMD) attracts growing interest as two dimensional(2D) crystals beyond graphene. Of particular importance is its strong spin-valley couplingthrough the spin-orbit interactions and related optoelectronic functionality, both of whichmake TMD a quite unique system. In this presentation, we review our latest achievements on
spin-valley physics and FET functionalities in TMD materials, with particular focus on theproperties which are not expected in graphene.
The electronic structure of themonolayer TMD is predicted as shownin Fig. 1. In addition to the gap opening,spin polarization at the valence band top
at the edge of the Brilloin zone ispredicted due to the momentum
Fig.1, Theoretical model of the electronic
dependent Berry curvature [1]. Weband structure of TMD monolayer [1]started with the experimental proof ofthis theory by utilizing spin- and angle resolved-photoemission spectroscopy [2]. This became
possible by choosing bulk crystals with broken inversion symmetry. Photoluminescencecircular dichroism also proved that noncentrosymmetric MoS2 crystals are useful materials forthe future valleytronics.
Field effect transistor (FET) plays crucial roles in the control of spin-valley degrees
of freedom. We demonstrate FET related new functionalities, including electrically induced
Zeeman-type spin splitting [3], an ambipolar FET [4], an electrically switchable chiral lightsource [5], and electric field induced superconductivity [6]. These results indicate that TMD
based 2D crystals have rich functionalities covering spintronics, optoelectronics, andsuperconductivity, all of which make TMD unique among 2D crystals.
References [1] D. Xiao et al., Phys. Rev. Lett. 108, 196802 (2012). [2] R. Suzuki et al., Nat.
Nanotech. in press. [3] H. T. Yuan et al., Nat. Phys. 9, 563 (2013). [4] Y. J. Zhang et al., Nano
Lett. 12, 1136 (2012), ibid. 13, 3023 (2013). [5] Y. J. Zhang et al., Science 344, 725 (2014).
[6] J. T. Ye et al., Science 338, 1193 (2012).
Corresponding Author: Y. Iwasa,
Tel: +81-3-58541-6828, Fax: +81-3-5841-6822,
E-mail: iwasa@ap.t.u-tokyo.ac.jp,–5–

FNTG-47, 2014

3S-6

Carbon nanotube nanoelectromechanical systems with resonance vibration○Seiji Akita
1

Department of Physics and Electronics, Osaka Prefecture University, Sakai 599-8531,
Japan

Nanocarbons such as carbon nanotubes (CNTs) are appropriate for nanoscale
electro-mechanical system (NEMS) because of their light weight, high aspect ratio, andextraordinary mechanical properties. In this presentation, the NEMS consisting of CNTs suchas nano-switches[1] or highly sensitive mass and force sensors[2] will be introduced.
For the nano-mechanical switch application, a "stuck" of nano-switch arm induced byvan-der-Waals force is one of serious problems for practical applications. Recently, wedemonstrated the release of the stuck CNT cantilever beam in nanorelay applications. Even
with strong adhesion induced by electrostatic attraction that is 100 times stronger than the vander Waals interaction, successful release of a nanotube arm from a stuck state was realized by
the application of a resonant vibration to the stuck CNT arm. Furthermore, nonvolatile
operation of the nanotube nanorelay was demonstrated by the application of the resonant
vibration to the stuck CNT arm.
Recently, we have measured successfully the resonant properties of CNTs in viscous
fluids such as air[2] or liquid[3] by using an optical detection method. In ambient air, theresonance frequency of the CNT resonator depends on the humidity of the air, because of theadsorption of water molecules on the CNT or viscosity change of the air depending on thehumidity.[4] In water, the resonance frequency of the CNT resonator decreased with lowering
the water temperature corresponding to the natural phenomenon by which liquid viscosity
tends to increase at lower temperatures.[3] These imply that the CNT cantilever is applicableto the nanospace viscosity sensor of surrounding viscous media.
To achieve higher force sensitivity, we also realized sustained mechanicalself-oscillation of the CNT resonators by using PLL with an opt-mechanical heterodyne[2] invacuum and air. Mass sensitivities less than 100 zg were easily achieved in vacuum for longterm (~ 100 s) deviation and even in air for short term (~ 1 s) deviation. This highly sensitive
mechanical resonator is applicable to the highly sensitive calorimeter. Small heat capacity due
to the small volume of CNTs enables us to measure the minute heat in the order of 100
aJ/K.[5]Acknowledgement: This work was partially supported by JSPS KAKENHI Grant Number
25286010, by the Osaka Prefectural Government and by the Iketani Science and Technology
Foundation.
[1] T. Kagota, A. Nagataki, K. Takei, T. Arie, and S. Akita, Appl. Phys. Lett. 103, 203504 (2013).
[2] A. Yoshinaka, T. Arie, and S. Akita, Appl. Phys. Lett., 98, 133103 (2011).
[3] S. Sawano, T. Arie, and S. Akita, Nano Lett., 10, 3395 (2010).
[4] T. Kuroyanagi, Y.Terada, K. Takei, S. Akita, and T. Arie, Appl. Phys. Lett., 104, 193104 (2014).
[5] S. Hiroshima, A. Yoshinaka, T. Arie, and S. Akita, Jpn. J. Appl. Phys. 52, 06GH02 (2013).
Corresponding Author: S. Akita
Tel&Fax: +81-72-254-9261
E-mail: akita@pe.osakafu-u.ac.jp–6–

FNTG-47, 2014

3S-7

CNT Computer: Demonstrating Robust Carbon Nanotube Digital Systems
Max Shulaker1, Gage Hills1, Hong-Yu Chen1, H.-S. Philip Wong1, Subhasish Mitra1,2
1

Dept. Electrical Engineering, 2 Dept. Computer Science, Stanford University, USA

Carbon nanotube (CNT)-based FETs are an exciting emerging nanotechnology, promising highperformance and highly energy-efficient future digital systems. Compared to traditional
silicon-based FETs, carbon nanotube FETs (CNFETs) are projected to achieve a 10-foldimprovement in energy-delay product, a metric of energy efficiency1. However, substantial
imperfections inherent to CNTs have prohibited the realization of larger-scale CNFET digitalsystems:
1) Mis-positioned CNTs, which cause stray conducting paths that can lead to incorrect logic
functionality.
2) Metallic CNTs, which due to their diameter and chirality have little or no band-gap, result in
CNFETs with increased leakage current, and can lead to incorrect logic functionality.
The imperfection-immune paradigm2, a combination of design and processing techniques,
overcomes these substantial CNT imperfections, allowing for larger-scale CNFET digital systems
to be realized. To overcome mis-positioned CNTs, we use mis-positioned CNT-immune design,
which guarantees correct logic functionality in the presence of any mis-positioned CNTs3. To
overcome metallic CNTs, we employ VLSI-compatible Metallic CNT Removal (VMR)4. VMR isa design and processing technique which allows electrical breakdown to be performed at the chipscale, selectively removing >99.99% of all metallic CNTs while inadvertently removing <4% of
the semiconducting CNTs. Importantly, both mis-positioned CNT-immune design and VMR
incur minimal area and energy cost, and are encapsulated within the standard cells so there is nodie-specific customization2. The entire imperfection-immune paradigm is therefore compatible
with VLSI processing and design flows.
The imperfection-immune paradigm has enabled larger-scale circuit demonstrations, such as thefirst CNT computer5. The CNT computer implements the SUBNEG instruction (subtract andbranch if negative), and is therefore Turing-complete. Thus any arbitrary program from any
instruction set can be re-encoded and executed with the CNT computer, given enough memory andexecution time. As an operating system, the processor implements non-preemptive multitasking,in which each program executes a self-interrupt and voluntarily gives control to another task; as ademonstration, the CNT computer performs both integer counting and integer sorting concurrently
in an interleaved fashion. Importantly, the CNT computer includes 7 stages of cascaded
combinational and sequential logic, thus demonstrating that any arbitrary digital system can berealized using CNFETs.
a) Schematic of the CNT computer, entirely implemented with
CNFETs. b) Scanning electron microscopy (SEM) image of the
CNT computer. c) Microscopy image of a wafer, containing
195 dies, with each die containing 5 full CNT computers. d)
SEM of a single CNFET, with CNTs bridging the channel.
[1]  Chang,  L.,  et  al.,  “IEDM  Short  Court,”  IEDM, 2012.
[2]   Zhang,   J.,   et   al.,   “Carbon   Nanotube   Robust   Digital   VLSI,”  TCAD, 2012.
[3]   Patil,   N.,   et   al.,   “Design   Methods   for   Misaligned   and  Mispositioned Carbon-Nanotube Immune Circuits,”  TCAD, 2008.
[4]   Patil,   N.,   et   al.,   “VMR:   VLSI-compatible Metallic Carbon
Nanotube Removal for Imperfection-Immune Cascaded
Multi-Stage  Digital  Logic  Circuits  Using  Carbon  Nanotube  FETs,”  IEDM, 2009.
[5] Shulaker, M., et   al.,   “Carbon   Nanotube   Computer,”   Nature,2013.
Corr. Auth.: Max Shulaker, 6502744987, maxms@stanford.edu

–7–

一般講演
General Lectures

1-1 ∼ 1-14
2-1 ∼ 2-10
3-1 ∼ 3-13

FNTG-47, 2014

1-1

Studies of strained graphene with thin film shrinkage methods○Hiroki Shioya1, Monica F. Craciun2, Saverio Russo2, Michihisa Yamamoto1, Seigo Tarucha1
12

Department of Applied Physics, University of Tokyo, Tokyo 113-8656, Japan
Centre for Graphene Science, University Exeter, Exeter Devon EX4 4QL, England

Theoretical works on strained graphene suggest the possibility and usefulness of strainengineering of graphene, by predicting remarkable and extraordinary properties, such as Diraccone merging, bandgap opening and pseudo magnetic field generation, causing zero filed
quantum Hall effect [1]. However, most of these predictions have not yet been confirmed
because it is experimentally difficult to control the magnitude and type (e.g. uniaxial, biaxial,
etc…) of strain in graphene devices via bending the substrate [2]. In this presentation wereport two novel methods to apply strain without bending the substrate. We employ thin filmsof evaporated metal and organic insulator deposited on graphene, which shrink after electron
beam irradiation or heat application. These methods make it possible to apply both biaxial
strain and in-plane isotropic compressive strain in a well-controlled manner. Raman
spectroscopy measurements show a clear splitting of the degenerate states of the G-band in
the case of biaxial strain, and G-band blue shift without splitting in the case of in-plane
isotropic compressive strain. In the case of biaxial strain application we find out the ratio of
the strain component perpendicular to the stretching direction is at least three times larger
than what was previously observed, indicating that shrinkage of the metal or organic insulator
deposited on graphene induces both tensile and compressive strain in this atomically thinmaterial. Our studies present for the first time a viable way to apply strain to graphene
without the need to bend the substrate. The methods demonstrated in this study hold thepromise for the development of strain engineering of graphene and help explore novel physics
in strained graphene. Moreover, these techniques can also be used for other two-dimensional
crystals, such as atomically thin metal dichalcogenides.

(Left) Schematic diagram for applying biaxial strain on bilayer graphene by electron beam irradiation on themetal thin films. (Right) Electron beam dose dependence of the G-band peak of the Raman spectrum. [3][1] V.M. Pereira et al. Phys. Rev. Lett. 103 046801-046804 (2009); G. Montambaux et al. Phys. Rev. B 80
153412-153415 (2009); F. Guinea et al. Nat. Phys. 6 30-33 (2009)[2] T. M. G. Mohiuddin et al. Phys. Rev. B 79 205433-205440 (2009)[3] H. Shioya et al. Nano Letters 14, 1158-1163 (2014)
Corresponding Author: H. Shioya
Tel: +81-3-5841-6822, Fax: +81-3-5841-6822,
E-mail: shioya@meso.t.u-tokyo.ac.jp

–9–

1-2

FNTG-47, 2014

Probing of the phonon dispersion in graphite by using theangle-resolved photoelectron spectroscopy○Shin-ichiro Tanaka1, Masashi Arita2, Kenya Shimada2
1

Institute for Industrial and Scientific Research, Osaka University, 567-0047 Ibaraki, Japan
2
Hiroshima Synchrotron Radiation Center, Hiroshima University, 739-0046
Higashihiroshima, Japan[1] S. Tanaka et al., Sci. Rep. 3, 3031 (2013).
[2] P. Venezue et al., Phys. Rev. B
0354336(2011).

//

-1

-1

-1

0.0 A-1

Phonon Energy (meV)

Photoelectron Intensity (Arb. Units)

The electron-phonon coupling (EPC) plays one of the most important roles in the solidstate physics. For the carbon-related materials, the Raman spectroscopy has been mainly used
for investigating the EPC. Here we present an investigation of the EPC in graphite by using
the angle-resolved photoelectron spectroscopy (ARPES). The main advantage of thistechnique is that both the momenta of the electrons and phonons are directly determined.
When the photon energy is tuned at ~6eV or ~11eV, an indirect photoexcitationaccompanying with the electron-phonon scattering, from the Fermi level at the K-point of the-band to the point near the -point, resonantly occurs and the scattered electrons can bedetected by the electron analyzer [1]. The step structures around 160meV observed in the
ARPES curves taken at h=11.1eV shown in the left panel of Fig.1 are results of theenergy-conservation rule during the EPC. The energy-shift of the step from the Fermi-edgecorresponds to the phonon energy which scatters the electron. Since there are two equivalentFermi-points in the Brillouin zone, the phonon dispersion along K- and K-M-K lines areprobed when the ARPES along -K lines are measured. The dispersion relation of the phonon
derived from the ARPES is plotted in the right panel of Fig.1 According to comparisons to thetheoretical calculation[2], only the TO-phonon branch calculated in the scheme of the
DFT+GW approximation agrees with the experiments. This clearly demonstrates that the EPC
coupling efficiency is much stronger in the TO-branch, that is the origin of the ‘D-band’ in the
Raman spectra of graphite, than LO or LA branches in the process of the indirect
photoexcitation at h=11.1eV. On illuminating with photons of 7.1-eV, only the ZA and ZO
phonons are observed around 70meV, and it
shows a clear linear-polarization dependence;h=11.1eV
185
GW-TO
both the ZO and ZA phonons are observedLO
180
for the s-polarized light but only the ZO
175
GW-TO
k (-K)
phonon is observed for the p-polarized light
170
0.6 A
(not shown here). The detailed discussion
165
TO
0.30 A160
about the excitation processes andLO
155
DFT+GW : Along K- line
0.18 A
comparison of the ARPES results with theLA
DFT: Along K- line
150
Raman spectroscopy will be presented.
DFT+GW : Along K- line
145

LA

DFT

: Along K- line

140

84,

0
100 200 300
Binding Energy (meV)

0.0

K
K

0.3

0.6

0.9

1.2

M

Fig. 1 ARPES spectra of graphite atvarious parallel momentum of thephotoelectron (left) and the phonon
dispersion relation derived by the stepenergy in the ARPES spectra (right).

Corresponding Author: Shin-ichiro Tanaka
Tel:+81-6-6879-8491, Fax:+81-6-6879-8494
E-mail: stanaka@sanken.osaka-u.ac.jp– 10 –FNTG-47, 2014

1-3

First-principles study on the contact resistance in the graphene/metalinterface○Hideyuki Jippo1,2, Susumu Okada2, Mari Ohfuchi1
1

Fujitsu Labs. Ltd., 10-1 Morinosato-wakamiya, Atsugi, Kanagawa 243-0197, Japan2
Univ. of Tsukuba,1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577, Japan

Electronic properties of armchair graphene nanoribbons (AGNRs) strongly depend on the
ribbon width within families of 3m, 3m+1, or 3m+2, where m is an integer. The fact implies
that the transport properties of graphene nanoribbons bridging two electrodes also depend on
the width of nanoribbons. In this work, we perform first-principles electronic transport
calculations of AGNRs bridging between two metal electrodes with respect to the ribbon
width to give theoretical insight for designing the electronic devices comprising AGNRs.
Figure 1 shows a structural model in our transport
calculations. The AGNRs with their width N are
bridged between two Au electrodes with the contact
length Lcon. The electrodes are modeled by slabs with
(111) surfaces of fcc Au comprising four atomic layers.
The Au electrode was chosen as a typical material
having weak interaction with graphene [1]. Theinterlayer distance is found to be 0.37 nm. By forming
the complex, the Dirac point of graphene is shifted
Fig.1: (a) Top and (b) side views for the
upward by 0.4 eV, indicating p-type doping by the Au model of the AGNR with the width N =electrodes.
39 bridged between two Au electrodes.
We calculate currents I at a bias voltage Vb = 0.1 V The dotted rectangles indicate the unit
between the two electrodes using the nonequilibrium cells of leads. The contact length of Lcon
Green’s function method. The current I is obtained by was fixed to be 0.86 nm.
integrating the transmission over the energy region
between the chemical potentials of the left and rightleads. Figure 2 shows the total resistivity ρtot evaluatedby (Vb/I)Ly, where Ly is the unit cell length along they-direction. We find that the ρtot strongly depends on
the ribbon width: The resistivity is classified as thefamily pattern of the ribbon width because of thefamily pattern dependence of the wave function
distribution of the ribbon. Higher resistivity in the
ribbons with 3m+2 is ascribed to the absence of thetransmission peak within the integral region, while thetransmission peaks decrease the resistivity for the Fig.2: Total resistivity for the models ofribbon whose width are 3m and 3m+1. Thus, we found the AGNR with Au electrodes at a bias
voltage Vb = 0.1 V. The AGNRs for N =that the contact resistance of AGNR/Au interfaces also 3m (circle),
3m+1 (square), 3m+2
depends on the ribbon width families of AGNRs.
(triangle) were investigated.
[1] P. A. Khomyakov et al. Phys. Rev. B 79, 195425 (2009).
Corresponding Author: H. Jippo
Tel: +81-46-250-8843, Fax: +81-46-250-8274, E-mail: jippo.hideyuki@jp.fujitsu.com– 11 –

1-4

FNTG-47, 2014

Ultra-large Scale DFT Calculations for Twisted Bilayer Graphene○Kazuyuki Uchida, Jun-Ichi Iwata, and Atsushi Oshiyama
Department of Applied Physics, University of Tokyo, Hongo 7-3-1, Tokyo, Japan
A twisted bilayer graphene (tBLG) is composed of two graphene layers. They are stacked
and twisted to each other in their basal planes. Moiré patterns appear in the atomic
arrangement, and become more prominent as the twist angle θ becomes smaller. The purposeof this work is to clarify how the Moiré patterns are reflected on the atomic and electronic
structures of tBLGs from first-principles.
We have performed ultra-large scale DFT calculations for a series of twisted bilayer
graphenes. The number of C atoms in the unit cell is 22708 for θ = 0.76°, which is the largest
system we have calculated in this work. We have found that the graphene layers arecorrugated reflecting the Moiré pattern for θ < ~10°: The inter-layer distance is largest at the
locally AA stacking region, and is shortest at the locally AB-stacking region [Fig. 1 (a)]. We
have also found that the Fermi velocity vF also shows a drastic change as a function of θ [Fig.
1 (b)]: the vF is essentially the same as that in single layer ghraphene for θ ~ 30°, and issubstantially reduced toward zero for θ < ~5°. The results show that the sensitivities to the
Moiré pattern of the atomic structure and of the electron wave are different. The reduction in
the Fermi velocity vF is not monotonic: We have found that the vF vanishes for θ ~ 1.08°, andslightly increases for the smaller twist angle [inset of Fig. 1 (b)].

D ǉ＝0.99°, Natom/cell=13468

(b)
1

1.8

0

x (ư)

40

80

-80

-40

0

40

80

y (ư)

-1.68
-1.72

z (ư) -1.76
-1.8

-80

-40

0

x (ư)

40

80

-80

-40

0

40

0.1

0.6

0.08

F

0.4
0.2
0

0.06

Natom=22708

0.04

ƧM

0.02
0

Ƨe~5°

80

y (ư)

0
F

)
0
F

-40

experiment [1]/-80Fermi velocity ( F /1.68

DFT calculation (this work)

0.8

F

1.76

z (ư) 1.72

0

5

10

0.8

15

1

Ƨ (°)

20

F

1.2

25

1.4

30

twist angle Ƨ (°)

Fig. 1: (a) Corrugated atomic structure of a tBLG (twisted bilayer grphene) with the twist angle θ of
0.99°. (b) Fermi velocity normalized to that in single-layer graphene is plotted as a function of thetwist angle θ.
[1] A. Luican, et al., PRL 106, 126802 (2011).
Corresponding Author: Kazuyuki Uchida
Tel: +81-3-5841-6812,
E-mail: kuchida@ap.t.u-tokyo.ac.jp– 12 –

1-5

FNTG-47, 2014

Band structure engineering in graphene using isotope effect○Takashi Koretsune1, Susumu Saito2
1

2

RIKEN CEMS, Saitama 351-0198, Japan
Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551 Japan

Band structure engineering in graphene is an important issue for the practical use ofgraphene. In fact, there are many suggestions to modify the band structure of graphene suchas the adsorption of adatoms on graphene, periodic structure engineering, graphene
nanoribbons, and the strain effect. In addition to these structure modifications, theelectron-phonon couplings can affect the band structure. For example, it is known that theband gap of diamond is substantially reduced due to electron-phonon couplings and it ispredicted that the Fermi velocity of graphene is also affected[1]. Thus, we discuss thepossibility of band structure engineering in graphene using electron-phonon couplings andisotope effect.
First, we consider the band structure difference between pure 12C graphene and pure 13Cgraphene. By calculating the effect of electron-phonon couplings using frozen phonon methodon the basis of density functional theory, we evaluate the isotope dependence of the depth of
the so-called Dirac point, that is, the work function of graphene. Interestingly, it is found that
there is a slight difference in the work function indicating that it is possible to shift the depthof the Dirac point locally without using the gate voltage.
Next, we consider the possibility of band gap opening using isotope effect. Particularly, we
calculate the case of periodic isotope modifications and evaluate the band gap. We will also
discuss the theoretical reason for the isotope effect.

[1] C.-H. Park et al., Phys. Rev. Lett. 99, 086804 (2007).
Corresponding Author: T. Koretsune
E-mail: takashi.koretsune@riken.jp– 13 –

1-6

FNTG-47, 2014

Selective growth of (16,0) carbon nanotubes using tungsten-cobalt catalystsżYan Li, Feng Yang, Xiao Wang, Daqi Zhang, and Juan Yang
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Single-walled carbon nanotubes (SWNTs) have shown great potentials in various fields
attributing to their unique structure-dependent properties, therefore, the structure-controlled
preparation of SWNTs is a crucial issue for their advanced applications (e.g. carbon-based
nanoelectronics) and has been a great challenge for about two decades. Recently, we realized
the selective growth of (12,6) SWNTs at the content of >92% by using the catalysts withwell-defined structures. However, the selective growth of zigzag SWNTs, which are
kinetically unfavorable, is much more difficult than other types of tubes. Here, we show that
SWNTs of a single zigzag structure, (16,0), can be produced directly with an abundance of
82% by using tungsten-based bimetallic alloy catalyst. The catalyst nanoparticles are able tomaintain their solid state structure during the SWNT CVD growth and thus the well-designed
catalyst structure determines the chirality of the resultant SWNTs.

Fig. 1 (a) Radical-breathing-mode (RBM) region Raman spectra of (16,0)-SWNTs. (b) Relative
abundance of various chiralities from Raman measurements denoted in the SWNT chiral map.

Further study on the effects of the growth condition verifies the kinetically unfavorable
property of zigzag tubes.

[1] F. Yang et al. Nature 510, 522-524 (2014)[2] F. Ding et al. Proc. Natl. Acad. Sci., 106, 2506 (2009).
Corresponding Author: Y. Li
Tel & Fax: +86-10-6275-6773
E-mail: yanli@pku.edu.cn– 14 –

1-7

FNTG-47, 2014

The role of “cap” stabilities on the chirality selection in the nanotube
growth○Yohji Achiba, Takeshi Kodama, Kenro Hashimoto and Haruo Shiromaru
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
A semispherical cap structure (a half fullerene)

has generally been believed toplay an essential role on the formation of nano-structured carbons. Actually, the chiralityof carbon nanotubes is totally dependent on the cap structures formed at the very earlystage in the tube growth. Furthermore, among many chiral candidates, the tube structure
so called “near armchair” is known to be the most abundant (n,m) species. What is thereason why such a particular structure is chosen?
Although the experimental evidence whether the cap is really present or not as a
growth-reaction intermediate is still unclear, in the present work, we intended to clarify
the properties of these hypothetical structures on the basis of theoretical calculations.
For the purpose of clarifying the selectivity of specific cap structures, we performed thecalculations of the “cap stability” on many kinds of isomeric forms with different sizes
by means of several different kinds of theoretical approaches such as AM1, HF/3-21G
and B3LYP/6-31G. Since the high selectivity of the near armchair was experimentallyfound to be particularly prominent at the lower reaction temperature, the heat offormations of the different cap structures were theoretically examined as shown in the
figure. The results suggest that the size-dependent thermodynamics of each structure isimportant in the initial cap formation prior to the subsequent tube-growth process. For
example, the cap (named as “bared caps” inthe figure) with (6,6) or (7,5) is about 0.1
eV/atom more stable at the size range of Cn =50-60 than the one with (10,2) or (11,1).
These evidences strongly suggest that in theearly growth process, the caps possessing
many armchairs at their edge is prominently
produced, particularly at the lower reaction
temperature, leading to the near armchair
enriched chirality distributions.
Corresponding Author: Yohji Achiba

Figure: Heat of formations of cap structures

E-mail: achiba-yohji@tmu.ac.jp、Tel:+81-42-677-2534, Fax:+81-42-677-2525– 15 –

1-8

FNTG-47, 2014

Direct Synthesis of Diamantane Polymers inside Carbon Nanotubes from
Halogenated Diamondoids
Yusuke Nakanishi,1 Haruka Omachi,1 Ryo Kitaura,1 Natalie A. Fokina,2 Peter R. Schreiner,2 Jeremy
E. P. Dahl,3 Robert M. K. Carlson,3 and Hisanori Shinohara1
1

Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan.
Institute of Organic Chemistry, Justus-Liebig University Heinrich-Buff-Ring 58, 35392
Giessen, Germany.
3
Institute for Materials and Energy Science, Stanford University, Stanford, California 94305,
United State.
2

Carbon nanotubes (CNTs), nano-scale cylinders composed of curved graphene sheets,
provide an ideal space for creating one-dimensional (1D) nanostructures. To date, various 1D
nanomaterials, such as metal atomic nanowires[1] and ultrathin boron-nitride nanotubes[2],have been fabricated within the inner space of CNTs. These 1D nanomaterials exhibit entirely
new electronic and magnetic properties that are different from those of their bulk counterparts.
As a part of our exploration of novel 1D nanomaterials, we have recently initiated synthetic
studies toward 1D diamond crystalline.[3,4] Studies on this new form of diamond may shedmuch light on understanding of the unique properties of diamond materials.
Here we report the direct synthesis method of diamantane polymers inside CNTs. We
employed halogen-functionalized diamondoids as a precursor, which are regarded as nano-
sized diamond fragments. Specific di-halogenated diamantane molecules are inserted into
CNTs by the vapor-phase doping method. At the same time, the dehalogenation and new C-C
bonds formation between each molecule may take place to produce rosary-like diamondpolymers. Transmission electron microscope and ab initio calculation provide clear evidence
for the fabrication of diamantane polymers. Furthermore, optical measurements suggest thatthe polymer formation occurs via dehalogenation and coupling of the precursors.

Figure. Model structures of a diamantane polymer in a DWCNT.
[1] R. Kitaura et al. Nano Lett., 8, 693, (2008). [2] R. Nakanishi et al. Sci. Rep, 3, 1385, (2013). [3] J. Zhang etal. ACS Nano, 6, 8674, (2012). [4] J. Zhang et al. Angew. Chem. Int. Ed., 125, 3805, (2013).
Corresponding Author: Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442
E-mail: author@domain.jp– 16 –

1-9

FNTG-47, 2014

Simulations of dynamic C60-Ih self-assembly cut the Gordian Knot:
Coexistence of bottom-up and top-down mechanisms
Hu-Jun Qiang,1,2 Ying Wang,1 Keiji Morokuma,3 ○Stephan Irle1
1

2

Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical
Chemistry, Jilin University, Changchun 130021, China
3
Fukui Institute of Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan

In
this
talk
we
present
density-functional tight-binding (DFTB)
based, non-equilibrium quantum chemicalmolecular
dynamics(QM/MD)
simulationsof dynamic
fullerene
self-assembly from carbon vapor in ahelium atmosphere at a temperature of2500 Kelvin. In some trajectories,
buckminsterfullerene C60-Ih self-assembles
from ensembles of C2 molecules on thetimescale of several nanoseconds by abottom-up pathway resembling Heath’s
fullerene road [1] as reported in ourprevious
constant
carbondensitysimulations [2] and in experiment[3,4]. In other trajectories, larger Fig.1: Trajectory showing growth, shrinking, andfullerene cages shrink in a carbon-assisted annealing of a carbon cluster to finally yield
annealing process, eventually producing buckminsterfullerene C60-Ih.
the famous C60-Ih cage in a top-down
pathway as earlier shown in the "shrinking hot giant" road of fullerene formation [2,5] and inexperiment [6]. Thus, the present simulations cut a Gordian Knot puzzling someexperimentalists: Buckminsterfullerene C60-Ih self-assemble both via the bottom-up and the
top-down mechanism [2].
[1] J. R. Heath, In: Fullerenes; G. Hammond et al. (eds.), ACS Symp. Ser. Washington, DC (1992). DOI:
10.1021/bk-1992-0481.ch001[2] B. Saha et al. J. Phys. Chem. C 115, 22707 (2011).
[3] T. Ogata et al. Carbon 47, 683 (2009).
[4] P. Dunk et al. Nat. Commun. 3, 855 (2012).
[5] S. Irle et al. J. Phys. Chem. B 110, 15431 (2006).
[6] J. Y. Huang et al. Phys. Rev. Lett. 99, 175503 (2007).
Corresponding Author: S. Irle
Tel & Fax: +81-52-747-6397
E-mail: sirle@chem.nagoya-u.ac.jp– 17 –

1-10

FNTG-47, 2014

Synthesis and Structural Analysis of C60-C70 Two-Component Fullerene
Whiskers○Toshio Konno, Takatsugu Wakahara, Kun’ichi Miyazawa
Fullerene Engineering Group, Materials Processing Unit, National Institute for Materials
Science, Tsukuba, Ibaraki, 305-0044, Japan
Fullerene whiskers, needle-like crystals comprising fullerene molecules, are synthesized by
the liquid-liquid interfacial precipitation method[1]. Fullerene molecules can be reused byredissolving fullerene whiskers into organic solvents. For this recyclability of fullerene
whiskers, fullerene whiskers have a variety of material applications.
We attempt to synthesize and analyze C60-C70 two-component fullerene whiskers, since thesehave absorption bands of both C60 and C70 and these are available as new uniquesemiconductors with a wide wavelength range of light absorption.
We synthesized C60-C70 two-component fullerene whiskers by the liquid-liquid interfacial
precipitation method[1] at 288 K with toluene as a good solvent for fullerene and isopropyl
alcohol as a poor solvent for fullerene, changing the ratio of C70 to C60. We conducted chemicalcomposition analyses on precipitations by high-performance liquid chromatography. Figure 1
shows the measured values and theoretical values of chemical compositions of the
precipitations. The theoretical values give the close agreement with the measured values except
for case that the C70 content of mother solution is 64 mass%. When the C70 content of mothersolution is 64 mass%, the degree of super saturation of C60 is assumed to be 0. We consider that
the C70 seed crystals promote the precipitation of C60 by co-precipitation. Figure 2 shows thechemical composition of fracture surfaces of a C60-C70 needle like crystal. The chemicalcomposition of the fracture surfaces seems not to be uniform but sinusoidally modulated.
Spinodal decomposition is a phenomenon that biphasic separation spontaneously progresses
and a sinusoidally-modulated structure occurs after a finite time. We consider that themodulated structure of the fracture surfaces of the C60-C70 needle like crystal results from thespinodal decomposition.
100
100

5

Measured
value

50
50

00
00

50
50

30
20

100
100

C70 content of mother solutions(mass%)
mass%)(
Fig.1. Measured
values and theoretical values of thechemical composition of precipitations.

040

Theoretical
value

0

20
10
Distance (㎛)

Fig.2. Chemical composition of the fracture surfaces
inside of red lines of a C60-C70 needle like crystal.

[1] K. Miyazawa, Y. Kuwasaki, A. Obayashi, and M. Kuwabara, J. Mater. Res., 17, 83-88(2002).
Corresponding Author: K. Miyazawa
Tel: +81-(0)29-860-4528, Fax: +81-(0)29-860-4667
E-mail: miyazawa.kunichi@nims.go.jp– 18 –

FNTG-47, 2014

1-11

Reaction rate enhancement by encapsulated Li+ on Diels–Alder reaction of
Li+@C60 with cyclohexadiene
Hiroshi Ueno1, Hiroki Kawakami2, Koji Nakagawa1, Hiroshi Okada2, Naohiko Ikuma1,
Shinobu Aoyagi3, ○Ken Kokubo1*, Yutaka Matsuo2*, Takumi Oshima1
1

Division of Applied Chemistry, Graduate School of Engineering, Osaka University,
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
2
Department of Chemistry, School of Science, The University of Tokyo,
Bunkyo-ku, Tokyo 113-0033, Japan3
Department of Information and Biological Sciences, Nagoya City University,
Nagoya 467-8501, JapanThe Diels–Alder (DA) reaction of fullerene is one of the successful strategies tosynthesize fullerene-based n-type materials for organic photovoltaics. However, the inherent
equilibrium between the DA and retro-DA reactions lowers the yield and limits the scope ofdienes. Considering the Lewis acid activation of dienophiles, we have focused on the DA
reaction of lithium-ion-encapsulated [60]fullerene Li+@C60 [1]. Comparing C60 with Li+@C60,
it is emphasized that the steric effects can be ignored on the kinetics and thermodynamics.
In this study, we kinetically and computationally investigated the DA reaction of+[Li @C60](PF6–) with 1,3-cyclohexadiene (C6H8) to precisely determine the kinetic
parameters such as Ea ΔH‡, ΔS‡, and ΔG‡ through the reaction rate measurement [2]. The
product was fully characterized by spectroscopic and single crystal X-ray analyses. Comparedwith empty C60, Li+@C60 reacted 2400-fold faster at 303 K, a rate enhancement that
corresponds to lowering the activation energy by 24.2 kJ mol–1. The result was well explained
by DFT calculation at the M06-2X/6-31G(d) level of theory considering the reactant complex
with dispersion corrections as well as by the frontier molecular orbital theory. This is the firstdetailed report on the kinetics of a DA reaction catalyzed by “an intramolecularly
encapsulated catalyst” without coordination to a heteroatom in the dienophile.

[1] Kawakami, H.; Okada, H.; Matsuo, Y. Org. Lett. 2013, 15, 4466.
[2] Ueno, H.; Kawakami, H.; Nakagawa, K.; Okada, H.; Ikuma, N.; Aoyagi, S.; Kokubo, K.; Matsuo,
Y.; Oshima, T. J. Am. Chem. Soc. 2014, 136, in press. DOI: 10.1021/ja505952y.
Corresponding Authors: K. Kokubo and Y. Matsuo
Tel: +81-6-6879-4592, Fax: +81-6-6879-4593, E-mail: kokubo@chem.eng.osaka-u.ac.jp
Tel & Fax: +81-3-5841-1476, E-mail: matsuo@chem.s.u-tokyo.ac.jp– 19 –

1-12

FNTG-47, 2014

Theory of topological Raman band in the carbon nanohorn○Ken-ichi Sasaki, Kouta Tateno, Hideki Gotoh
NTT Basic Research Laboratories, NTT Corporation, 3-1 Morinosato Wakamiya, Atsugi,
Kanagawa 243-0198, Japan
In the Raman spectrum measured at the edge of graphene, the D band appears as aprominent peak. The edge D band is useful in the characterization of the armchair edge
because it is a result of an intervalley scattering of the electron by the armchair edge [1]. Theintervalley scattering is not unique to the armchair edge, but common to topological defects,
such as pentagons and heptagons [2]. Since topological defects are found throughout thehoneycomb network of carbon, the characterization is an important issue.
Based on our recent work on the activation mechanism of the edge D band [3], we found anovel type of the D band induced by a topological defect, which we call a topological D band(see Figure) [4]. A photo-excited carrier with a non-zero winding number is the key toactivating a topological D band. A topological D band can be distinguished from theconventional edge D band by its peak position and non-dispersive nature, because theselection rules for electron-phonon matrix elements are altered in an essential way by thepresence of the topological defect.

Figure (Left) Process exciting a topological D band in a nanohorn. (Right) A pathwith a zero winding number does not contribute to the D band.
[1] L.G. Cancado et al., Phys. Rev. Lett. 93, 247401 (2004).
[2] S. Iijima et al., Nature 356, 776 (1992); R. Tamura and M. Tsukada, Phys. Rev. B 49, 7697 (1994); H.
Matsumura and T. Ando, J. Phys. Soc. Jpn. 67, 3542 (1998); P. E. Lammert et al., Phys. Rev. Lett. 85, 5190
(2000).
[3] K. Sasaki et al., Crystals 3(1) 120 (2013).
[4] K. Sasaki et al., Phys. Rev. Lett. 111, 116801 (2013).
Corresponding Author: K. Sasaki
Tel: +81-46-240-3033, Fax: +81-46-270-2361,
E-mail: sasaki.kenichi@lab.ntt.co.jp– 20 –

1-13

FNTG-47, 2014

Synthesis of Nitrogen-doped Graphitic Carbon through Laser Annealingof Bowl-shaped -Conjugated Molecule Sumanene Derivative○Yuhi Inada1, Toru Amaya1, Yasutomo Shimizu1, Akinori Saeki1, Ryotaro Tsuji2,
Takeo Otsuka2, Shu Seki1, Toshikazu Hirao1,3
1

2

Department of Applied Chemistry, Osaka University, Osaka 565-0871, JapanKANEKA Fundamental Technology Research Alliance Laboratories, Osaka University,
Osaka 565-0871, Japan
3
JST, ACT-C, Saitama 332-0012, Japan

Intensity (a.u.)

Intensity (a.u.)

Nitrogen-doped graphitic carbons have attracted much interests due to their catalytic andelectrical properties. On the other hand, the chemistry of sumanene, a bowl-shaped
-conjugated molecule has been studied in our laboratory (Fig.1a).[1, 2] Here, we describe thesynthesis of nitrogen-doped graphitic carbon by laser annealing of sumanene derivatives,
which have an imino group as a nitrogen source.[3, 4]
A thin film of imine 1 wasannealed by pulsed laser (Nd:YAG,
355
nm)
to
give
the
nitrogen-doped graphitic carbon,
whose conductivity was ~4 S/cm
(Fig.1b). The typical Raman
spectrum (Fig.2a) has two
signature bands. The broad D band
Fig.1: (a) Sumanene. (b) Synthesis of nitrogen-doped graphitic
at ~1335 cm-1 and G band at
carbon through laser annealing of imine 1.
~1590 cm-1 are attributed to
(a)
(b)
G
disordered carbon arisen fromD
structural defects and sp3-bonded
carbon, and sp2-bonded graphitic
carbon, respectively. The XPS
measurements revealed that thenitrogen-doped graphitic carbon is
1800
1600
1400
1200
1000
405
400
395
mainly composed of carbon (N/C
Raman shift (cm )Binding energy (eV)ratio: 0.0373). Nitrogen atoms are
doped into graphitic lattice with
Fig.2: (a) Raman spectrum and (b) N 1s XPS spectrum of thevarious bonding patterns (Fig.2b).
laser-annealed imine 1.
−1[1] Sakurai, H.; Daiko, T.; Hirao, T. Science 2003, 301, 1878.
[2] Amaya, T.; Hirao, T. Chem. Commun. 2011, 47, 10524-10535.
[3] Inada, Y.; Amaya, T.; Shimizu, Y.; Saeki, A.; Otsuka, T.; Tsuji, R.; Seki, S.; Hirao, T. Chem. Asian J. 2013, 8,
2569-2574.
[4] Amaya, T.; Inada, Y.; Shimizu, Y.; Saeki, A.; Tsuji, R.; Seki, S.; Hirao, T. Chem. Asian J. 2014, in press.
Corresponding Author: T. Hirao
Tel: +81-6-6879-7413, Fax: +81-6-6879-7415,
E-mail: hirao@chem.eng.osaka-u.ac.jp– 21 –

FNTG-47, 2014

1-14

Structure and electrochemical properties of boron- and nitrogen-dopedcarbon nanohorn aggregates○Ryota Yuge1, Takashi Manako1, Shunji Bandow2, Masako Yudasaka3, Kiyohiko Toyama1,
Sumio Iijima4, and Noriyuki Tamura1
1

Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan2
Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan
3
Nanotube Research Center, National Institute of Advanced Science and Technology (AIST),
Tsukuba, 305-8565, Japan
4
Faculty of Science & Technology, Meijo University, Nagoya 468-8502, Japan
Single-wall carbon nanohorns (SWNHs) [1] are a kind of nano-carbon materials including
carbon nanotubes and graphenes, which are attractive due to their excellent properties.
Recently, it has been reported that non-metallic nitrogen- and boron-doped carbon nanotubes
have the intrinsic catalytic properties for oxygen reduction reaction (ORR) [2-3]. Thesematerials achieve not only the potentially low cost as they are noble metal free but also thebetter stability toward CO poisoning compared to traditional platinum catalysts [2]. Here, we
doped nitrogen and/or boron in SWNHs and investigated their electrochemical oxygen
reduction activity.
SWNHs were prepared by the CO2 laser ablation, which was operated at 3.5 kW at room
temperature. The graphite target with or without boron was used. The buffer gases were Ar
and N2. The gas flow rate and pressure were 10 L/min and 760 Torr, respectively. The boron-,nitrogen-, and boron/nitrogen-implanted SWNHs are denoted as B-, N-, and BN-SWNHs,
respectively.
BN- and B-SWNHs had larger specific surface area than SWNHs, because they had holes
accessible to inside of tubules. The appearance of the pore-size of 1 to 10 nm for BN- and
B-SWNHs indicated the possibility of the formation of large-diameter SWNH and/or new
pores. XPS analysis indicated that the several carbon atoms in lattice of SWNHs could besubstituted for boron, nitrogen and BN. In oxygen-saturated 0.1 molar potassium hydroxide
solution, electro-catalytic activities of BN-, B-, and N-SWNHs were superior to that of
SWNHs, indicating that boron and nitrogen atoms incorporated in graphene network act as
active catalytic sites of ORR. The details will be shown in the presentation.
[1] S. Iijima et al. Chem. Phys. Lett. 309, 165 (1999).
[2] K. Gong et al. Science 323, 760 (2009).
[3] Y. Zhao et al. J. Am. Chem. Soc. 135, 1201 (2013).
Corresponding Author: R. Yuge
Tel: +81-29-850-1566, Fax: +81-29-856-6137
E-mail: r-yuge@bk.jp.nec.com– 22 –

FNTG-47, 2014

2-1

Production, Purification and Electronic Properties of the Missing,
Small-Bandgap Metallofullerenes○Zhiyong Wang, Yusuke Nakanishi, Shoko Noda, Hiroyuki Niwa, Jinying Zhang, Ryo
Kitaura, Hisanori Shinohara
Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan
Solvent-extraction of the missing metallofullerenes, such as M@C60 and M@C70 (M = Sc,
Y, or lanthanides), has been a long-standing challenge ever since the first mass production of
metallofullerenes in 1991 [1]. C60 and C70 have a triple- or nearly triple-degenerate lowest
unoccupied molecular orbital. When a metal atom is entrapped inside, it transfers formally
two or three electrons to the fullerene cage, leading to an unstable open-shell configuration ora small band gap. This causes M@C60 and M@C70 to behave like highly reactive radicals,
forming polymers or oligomers in arc-discharge soot, which are insoluble in toluene andcarbon disulfide. They are, thus, called the “missing metallofullerenes”. Besides M@C60 and
M@C70, there are some other missing metallofullerenes, which includes M@C72, M@C74,
M@C76, etc.
Herein, we report an in-situ functionalization
method for the stabilization and extraction ofalmost all of these missing metallofullerenes.
Polytetrafluoroethene (PTFE) were added to theconventional
arc-dischargechambertoexohedrally functionalize these metallofullerenes[2]. A large number of metallofullerene
derivatives, M@C2n(CF3)m (2n = 60, 70, 72, 74
or 76, m = 1 or 3), are produced efficiently.
Unlike the pristine metallofullerenes, M@C2n,thesefunctionalized
metallofullerenes,
M@C2n(CF3)m, are found to be greatly soluble
and stable in organic solvents. A series of thesemissing metallofullerenes has been isolated byhigh performance liquid chromatography. In
particular, M@C60 and M@C70 have been
purified, for the first time since 1991, in forms of
trifluoromethyl derivatives, M@C60(CF3)3 and
M@C70(CF3)3 (M = Y or La) (Fig. 1).

Fig. 1. (a) Molecular structural models of
M@C60 and M@C70. (b, c) Matrix-assisted laser
desorption/ionization time of flight mass spectraof La@C60(CF3)3 and Y@C70(CF3)3.

Density functional calculations suggest that the missing metallofullerenes are stabilized asa result of the bandgap enlargement upon –CF3 functionalization. Some interesting opticaland magnetic properties have been found for those derivatives of the missing
metallofullerenes.
References: [1] Y. Chai et al. J. Phys. Chem. 95, 7564-7568 (1991). [2] Z. Y. Wang et al. Angew. Chem. Int. Ed.
52, 11770-11774 (2013).
Corresponding Author: H. Shinohara; Fax: +81-52-747-6442; E-mail: noris@nagoya-u.jp.

– 23 –

2-2

FNTG-47, 2014

An electrically-driven, ultra-high-speed, on-chip light emitter
based on carbon nanotubes and graphene○Hideyuki Maki1, Tatsuya Mori1, Yohei Yamauchi1, Satoshi Honda1
1

Department of Applied Physics and Physico-Informatics, Keio University,
Yokohama 223-8522, Japan

Electrically driven high-speed light emitters are widely used in the areas of opticalcommunication, time-resolved spectroscopy, etc. However, because of their large footprints, thelow crystallinity of the compound semiconductors grown directly on Si wafers, these emittersface significant challenges with respect to their integration with silicon-based platforms. On theother hand, carbon nanomaterials, such as carbon nanotubes (CNTs) and graphene. are an
attractive material for optical and optoelectronic applications. Electrically driven carbon-based
emitters, which can be based on electron-hole recombination or blackbody radiation, haveseveral advantages: (i) a small footprint emitter can easily be obtained due to its simple
fabrication process, (ii) carbon nanomaterials can be prepared directly on a Si wafer. In thisstudy, we report the first electrically driven, ultra-high-speed light emitter based on carbon
nanotubes and graphene [1-3].
A schematic structure of the CNT-based light emitter is illustrated in Fig. 1(a). CNT films
were formed on a SiO2/Si substrate, and metal electrodes were deposited as the source and drainelectrodes. For time-resolved emission measurements, the electrodes were designed as 50-
coplanar transmission lines. The emission from the CNT blackbody emitter was highly
localized at the position of the nanotube film [Fig. 1(b)]. The light emissions exhibit very broad
emission spectra, whose spectra can be fitted with Planck’s law, indicating the blackbody
radiation generated by Joule heating. To investigate the dynamic response of this emitter, we
carried out time-resolved emission measurements under applied rectangular bias voltages (Fig.
2). The rise and fall times are < 0.4 ns, which correspond to the (a)response speed of > 1 GHz. We also theoretically elucidate themechanisms of this high-speed response, which is dominated by
the high heat dissipation to the substrate. In addition, we
demonstrated 140-ps-width pulsed light generation, experimental
1-Gbps and theoretical 10-Gbps modulation and experimental (b)Signal line
1-Mbps optical communication. Furthermore, we also developed
the high-speed CNT-EL emitter and the graphene-based planar
blackbody emitter. These light emitters with the advantages ofEmission
ultrafast response speeds, a small footprint, and integration on
Ground line
silicon can enable novel architectures for optical interconnects, Fig.1: CNT blackbody emitter
optoelectronic integrated circuits, compact transient spectroscopy
systems with an ultrafast white light source, and so forth.
This work was partially supported by the A-STEP from JST,
Grants-in-Aid for the Encouragement of Young Scientists (A)from MEXT, and the SCOPE from MIC, Japan.
High-speed
emission

Input
signal

CNT film[1] T. Mori, Y. Yamauchi, S. Honda, H. Maki, Nano Lett. in press.
Fig.2: High-speed emission from
[2] M. Fujiwara, D. Tsuya, H. Maki, Appl. Phys. Lett., 103, 143122 (2013).
[3] N. Hibino, S. Suzuki, H. Wakahara, Y. Kobayashi, T. Sato, H. Maki, ACS
the CNT emitter.
Nano, 5, 1215 (2011).
Corresponding Author: H. Maki, Tel: +81-45-566-1643, Fax: +81-45-566-1587, E-mail: maki@appi.keio.ac.jp– 24 –

FNTG-47, 2014

2-3

Photofunctional nanomodulators for spatiotemporal bioexcitationżEijiro Miyako1*, Julie Russier2, Matteo Mauro3, Cristina Cebrian3, Hiromu Yawo4,
Cécilia Ménard-Moyon2, James A Hutchison3, Masako Yudasaka1,
Sumio Iijima1, Luisa De Cola3, Alberto Bianco2
1

Nanotube Research Center (NTRC), National Institute of Advanced Industrial Science andTechnology (AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan
2
CNRS, Institut de Biologie Moléculaire et Cellulaire, Laboratoire d’Immunopathologie et
Chimie Thérapeutique, 67000 Strasbourg, France
3
Laboratoire de Chimie et des Biomatériaux Supramoléculaires, Institut de Science etd'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg and CNRS UMR 7006,
67000 Strasbourg, France
4
Department of Developmental Biology and Neuroscience, Tohoku University, Graduate
School of Life Sciences, Sendai, Miyagi 980-8577, Japan

Comprehensive
controlandanalysis of molecular biologicalinformation at the single-cell level are
required to understand biological
functions in an integrated manner. In
the present study, we show that a new
type of light-driven nanomodulator
comprising chemically functionalized
carbon nanohorns generates heat andreactive oxygen species (ROS) whencells containing them are subjected tonear-infrared (NIR) laser irradiation.
Intercellular calcium ion flux andmembrane currents were successfully
controlled at the single-cell level by
opticalmodulationofthechemico-physical properties of thenanohorns (Fig. 1). Furthermore, thenanomodulator allowed the remote
excitation of physiological tissue
exposed to NIR laser irradiation. This
study provides a powerful tool forsingle-cell analysis and open the doors
to the development of innovative celltherapies.

(a)

NIRlight

Process(2)ROS

NIRlight

S O 3NaS O 3Ͳ

NaO 3SON+NS O 3NaHNOONIRlight

Process(1)
Heat

NH

eͲ

O

Process(3)Heat

Dye–CNHnanomodulator(b)(c) (i)

NIRlaserirradiation(ii)
808nmlaser
irradiation

(iii)

204mW(104PW/Pm2)
100Pm(iv)
100Pm200pA1sec

Fig.1: (a) Schematic illustration of the photofunctional nanomodulator. (b)Calcium imaging in Mouse leukemic monocyte macrophage (RAW264.7)
cells detected by laser-induced emission of fluorescence by nanomodulator.
The red circle indicates the irradiated site. (c) Analysis of rat dorsal root
ganglion (DRG) cell-membrane current using a cell patch clamp under 785[1] E. Miyako et al. Nature. Commun. 3, 1226
nm laser irradiation: (i) 42 mW, (ii) 168 mW, (iii) 294 mW, and (iv) 378(2012).
mW.
[2] E. Miyako et al. Proc. Natl. Acad. Sci.
USA 109, 7523-7528 (2012).
[3] E. Miyako et al. Angew. Chem. Int. Ed. 50, 12266-12270 (2011).
*Corresponding Author: E. Miyako
Tel: +81-87-869-3574, Fax: +81-29-861-6290, E-mail: e-miyako@aist.go.jp– 25 –

FNTG-47, 2014

2-4

Milligram-scale separation of high-purity (9,4) and (10,3) SWCNTs○Yohei Yomogida, Mayumi Tsuzuki, Xiaojun Wei, Atsushi Hirano, Shunjiro Fujii,
Takeshi Tanaka, and Hiromichi Kataura
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8562, Japan
Large scale structure sorting technique is highly desired for investigating chiralitydependent physical properties and for developing further applications of single-wall carbon
nanotubes (SWCNTs). Various separation methods have been developed to date but most ofthem still have difficulties in getting milligram-scale single chirality SWCNTs within a day.
Previously, we reported a multicolumn gel chromatography method that realized a separationof 13 single-chirality SWCNTs where we used selective adsorption of SWCNT to the gel [1].
In this work, we have improved this method especially in a scalability by combining selective
adsorption and selective desorption using stepwise elution chromatography. We havedemonstrated 1 mg separation of (9,4) and (10,3) single chirality SWCNTs per day.
Chirality-selective adsorption of SWCNTs to the gel was realized by mixed surfactant of
sodium dodecyl sulfate (SDS) and sodium cholate (SC). Although the selectivity in theadsorption process was not enough to get single chirality, following stepwise elution could
select single chirality species. Here, the stepwise elution was performed by changing
concentration of sodium deoxycholate (DOC) in the SC/SDS/DOC mixed surfactant system.
Chirality distribution analysis for the solution obtained from each process revealed that theadsorption process selected the chiral angle and the elution process selected diameter range.
In this work, we used HiPco (NanoIntegris) for starting SWCNT in which the diameter
distribution was centered at 1 nm. High-performance liquid chromatography (HPLC) with
400 ml gel column was used for separation. The column was filled with Sephacryl S-200 (GEHealthcare). Starting with 200 mg raw HiPco SWCNT, about 1 mg of (9,4) and (10,3) wereobtained. Because these spices are main
components in HiPco SWCNT, large scale
separation was easier than the separation of(6,5) that is minor component of HiPco. Figure
1 shows the optical absorption spectra of (9,4)
and (10,3) single chirality SWCNTs obtained inthis work. Well defined absorption spectra
clearly show that the purities are much higher
than those obtained by multicolumn method[1].
This work was supported by KAKENHI No.
25220602.
[1] H. Liu et al. Nat. Commun. 2, 309 (2011).
Corresponding Author: Hiromichi Kataura,
Tel: +81-29-861-2551, Fax: +81-29-861-2786
E-mail: h-kataura@aist.go.jp

Fig. 1.
Opticalaqueous solutions
SWCNTs obtained
concentrations forindicated.

– 26 –

absorption spectra ofof (9,4) and (10,3)in this work. DOC
stepwise elution are

2-5

FNTG-47, 2014

Metal-free hydrogen evolution from waterusing single-walled carbon nanotubes○Naoki Kohno, Kei Ohkubo, Shunichi Fukuzumi
Department of Material and Life Science, Graduate School of Engineering, Osaka University,
ALCA, Japan Science and Technology Agency, Osaka 565-0871, Japan

Evolved hydrogen, µmol

Despite single-walled carbon nanotubes (SWNTs) have much attention in the field of
nanotechnology and material science, they have not been well explored as an active
componentinsensitizinghydrogenevolutionfromwater.
Recently,
SWNTs/fullerodendron/SiO2 nanohybrid have been reported to be used for a photocatalytichydrogenevolutionsysteminthepresenceofmethylviologen,
1-benzyl-1,4-dihydronicotinamide and Pt composite [1]. In this system, however, precious Pt
was used as a hydrogen evolution catalyst. There is no report on metal-free photocatalytichydrogen evolution from water using only SWNTs. We report herein the use of SWNTs as ahydrogen evolution photocatalyst from water by laser irradiation.
Hydrogen evolution occurred in a deaerated water (2.5 mL) containing SWNTs (2.0 mg)
under laser irradiation (λ =532 nm, 600 mW, 10 Hz). The amount of hydrogen evolved
reached to 9.7 µmol by laser irradiation for 1 h (Figure 1). When water was replaced bydeuterated water (D2O), HD and D2 were evolved efficiently. The deuterium kinetic isotope
effect was determined to be 1.9. These10
results suggest that the hydrogen source iswater used as a solvent. No water oxidation
8
to form dioxygen or hydrogen peroxide wasin H2Oin D2Oobserved under the present reaction
conditions.
6
TEM images of SWNTs after laser
photoirradiation for 5 h show tubular4morphology, indicating high stability of
SWNTs in the catalytic hydrogen evolution.
2
The comparison of IR spectra of SWNTs
before and after laser photoirradiationsuggests that SWNTs were hydroxylated to
0
0
0.25
0.5
0.75
1.0
exhibit O–H stretching vibrations at
–1
Time,
h
3200–3600 cm . Thus, the hydrogen
evolution is initiated by the two-electron
Figure 1. Plots of hydrogen evolved in H2O (solidoxidation of SWNTs to attach two OHline) and D2O (broken line) (2.5 mL) containing
groups. The stoichiometry of the
SWNTs (2.0 mg) by laser irradiation (λ = 532 nm,
laser-induced hydrogen evolution with
600 mW) vs time.
SWNTs in water is given by Scheme 1.
Scheme 1[1] T. Tajima. et al. Adv. Mater. 23, 5750 (2011).
Corresponding Author: S. Fukuzumi
Tel: +81-6-6879-7369, Fax: +81-6-6879-7370,
E-mail: fukuzumi@chem.eng.osaka-u.ac.jp

2H2O + SWNTs
Laser irradiation

λ = 532 nm, 600 mW– 27 –

H2 + SWNTs(OH)2

2-6

FNTG-47, 2014

Breath Figure Directed Self-Assembly of Single-Walled Carbon Nanotubes
for Solar Cells
ż Kehang Cui1, Takaaki Chiba1, Rong Xiang1, Shohei Chiashi1, Shigeo Maruyama1
1

Department of Mechanical Engineering, The University of Tokyo, Bunkyo 113-8656, JapanFor solar cell applications SWNTs have superiorities in terms of the wide spectrum ofabsorption ranging from near-infrared to visible wavelength, high electrical conduc-tivity athigh transparency as well as the possibility multiple exciton generation. Combined with earth
abundance and chemical stability, the SWNT is supposed to be a promising candidate fornext-generation solar cells. In this study, we are trying to control the diameter of SWNTs andtheir microscale assembly for the applications of SWNT-Si solar cells.
Highly transparent-conductive SWNT films from controlled bundle-diameter and long
bundle length were synthesized by the thermal decomposition of ferrocene vapor in a carbon
monoxide atmosphere, with the average diameter of approx. 2 nm. The SWNT films with asheet resistance of 134 ȍVTDWWKHWUDQVPLWWDQFHRI81.5 % over the AM1.5G spectrum were
dry-transferred onto Si substrate to form a diode. The power conversion efficiency of the solar
cell is 11% and is stable after 1 year, which is attributed to the high purity pristine SWNTs.
Moreover, the solar cell performance under different light intensities is investigated toevaluate both the series and shunt resistance of the device. The interfacial oxide layer between
the SWNT film and the Si substrate is also discussed [1].
A water-vapor treatment is proposed to build up SWNTs to a self-assembled
microhoneycomb network for the application of solar cells [2]. The micro-honeycomb
network consists of vertical aggregated SWNT walls and a buckypaper bottom. Thishierarchical structure exhibits lower sheet resistance and higher optical transmittancecompared with the buckypaper (Fig. 1). The heterojunction solar cell was fabricated by dry
depositing the SWNT film to the 3 mm by
3 mm n-type silicon substrate. The pristine
(a)
(b)
+
SWNT-Si heterojunction solar cell shows a+++record-high fill factor of 72 % as well as a+
+ + + +
power conversion efficiency (PCE) of 6 %+++without tuning the diameter or height of
+ +
+
+
+
original vertically aligned SWNTs [2]. The+
5 ȝm
PCE remains stable for months in ambientcondition. A PCE exceeding 10 % is
Fig.1: (a) Mechanisms of improvement byachieved in the dry state after dilute nitrichoneycomb structure and (b) comparison of FF
acid treatment.
and series resistance.
Micro-honeycomb SWNT/Si solar cell
Random-oriented SWNT/Si solar cell[1] K. Cui et al, J. Mater. Chem. A, 2 (2014) 11311.
[2] K. Cui et al, J. Phys. Chem. Lett., 4 (2013) 2571.
Corresponding Author: S. Maruyama
Tel: +81-3-123-4567, Fax: +81-3-123-4567,

E-mail: maruyama@photon.t.u-tokyo.ac.jp– 28 –

2-7

FNTG-47, 2014

Highly thermal conductive yet rubbery material with CNT/carbon
fiber/rubber○Seisuke Ata1, Ayummi Nishizawa2 Takeo Yamada1 and Kenji Hata1
1

Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565, Japan
2
Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba,
305-8565, JapanIn AIST, Hata et al. developed the super-growth chemical vapor deposition technique tosynthesis high-purity, long and exclusively single walled CNTs. The growth efficiency of thistechnique is superior to other SWNTs enabling industrial mass production (in ton-scale), an
aspect which will soon become reality. Furthermore, the single wall carbon nanotubes
synthesized using this technique, it was given a name to SG-SWNT, exhibits several uniqueproperties such as high aspect ratio, high surface area, high purity and good dispersibility,
making them one of the best available conductive fillers for the development of composites.
These properties were utilized for the development of a highly conductive rubber-likecomposite by mixing long single wall-nanotubes (SWNTs), an ionic liquid, and a fluoridated
co-polymer.
We investigated the various factors critical for achieving SG-SWNT/polymer with superior
electrical and mechanical properties, such as dispersion method, evaluation of CNT in
solution (for process control), compounding. These investigations have culminated in thedevelopment of SG-SWNT/polymer composite with excellent electrical and thermal
conductivity, high durability and environmental resistance.
In this presentation, we would like to report the high thermal conductive CNT/carbon
fiber/polymer composite. Thermal conductivity of our composite is about 100 W/mK, thisvalue is almost same as that of iron or brass. This high thermal conductivity is achieved byincreasing of thermal transfer efficiency between carbon fiber with CNTs. This high thermal
conductive yet rubbery material could be applied for thermal transfer materials, such as
thermal interface material (TIM).
Corresponding Author: S.Ata
Tel: +81-22-861-4654, Fax: +81-22-861-4851,
E-mail: ata-s@aist.go.jp– 29 –

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FNTG-47, 2014

Low temperature graphene synthesis from PMMAby microwave plasma treatment○Takatoshi Yamada, Yuki Okigawa, Masatou Ishihara, Masataka Hasegawa
Nanotube Research Center, National Institute of Advanced Industrial Science and Technology,
Tsukuba 305-8565, Japan
Although graphene synthesis at temperature less than 320ºC using microwave
plasma CVD was reported [1], sheet resistance of graphene synthesized at low temperature
are not enough to use for electrical applications [2]. Therefore, it is necessary to improve
electrical properties of graphene synthesized at low temperature. It was reported that
decreasing of temperatures of graphene synthesizes by thermal process using solid carbon
sources compared to vapor carbon sources [3, 4]. The obtained graphene synthesized fromsolid carbon source show high qualities. Combination of the plasma process and the solidcarbon sources is expected for high quality graphene synthesis technology at low temperaturein short periods. In this paper, we report about graphene synthesis by surface wave microwave
plasma treatment of PMMA [5] and discuss characteristics of the obtained graphene.
Graphene synthesis process in this study was as follows. At first, about 50 nm thickness
of PMMA was spin-coated polycrystalline Cu foils and then surface wave microwave plasma
treatments were carried out on PMMA/Cu foils in a slot antenna-type microwave plasma
CVD system.
It was confirmed, by means of XTEM and Raman spectroscopy, the obtainedgraphene consisted of small size of graphene flakes and each flake connected to form
continuous graphene film. In Hall effect measurements at room temperature, the highest holemobility was 560 cm2/Vs and the lowest sheet resistance was 1000Ω/sq.
[1] T. Yamada et al., J. Phys. D 46 (2013) 063001.
[2] Y. Okigawa et al., Appl. Phys. Lett. 103 (2013) 153106.
[3] Z. Sun et al., Nature 468 (2010) 549.
[4] M. X. Zheng et al, Appl. Phys. Lett. 96 (2010) 063110.
[5] T. Yamada et al., Appl. Phys. Exp. 6 (2013)115102.
Corresponding Author: T. Yamada
Tel: +81-29-1861-3851, Fax: +81-29-681-4522,
E-mail: takatoshi-yamada@aist.go.jp– 30 –

2-9

FNTG-47, 2014

Synthesis of Concavo-Convex Graphene by Using Copper NPs as Catalyst
ż<XNL6XQD\DPD1, Hiroshi Miyamura1,
Jhon Cuya1, Yoshinori Sato2 Balachandran Jeyadevan1,
1

Department of Material Science, University of Shiga Prefecture, Hikone 522-8533, Japan
2
Tohoku University, Sendai 980-8577, Japan

Graphene having a single atomic layer structure consisting of sp2 bonded carbon is attracting
researchers with its unique properties such as mechanical strength and ultrahigh electron
mobility. Graphene, which is generally used in the applications of FET and catalyst aresynthesized by Chemical Vapor Deposition method and has a flat-six-membered ring
structures [1].
In this study, we report the results of graphene synthesized by using not only copper foil but
also copper nanoparticles as catalyst. This newly synthesized rugged surfaced graphene has an
optical property different to the conventional graphene.
The rugged surface graphene is synthesized
as follows: Cu2O nanoparticles are
self-assembled on Cu foil and heat-treated at1050 ºC in Ar, H2 atmosphere (Fig. 1(a)).
Then, methane gas was flowed as carbon
ȝP
ȝP
source. After the synthesis, we etched Cu (a)(b)
NPs/Cu foil catalyst away by using FeCl3 andtransfered the graphene on arbitrary substrate[2]. The resulted graphene sheet was curved
taking the shape of the particles and had amonodispersed asperity with the size of about
49 ± 9 nm (Fig. 1(b)). In addition, this(d)(c)
particle-shape influenced structure did notdisappear even after the etching and Fig. 1. (a) SEM and TEM images of Cu NPs/Cu foil. (b)transferring processes (Fig. 1(c)). It became AFM image of Graphene/Cu NPs/Cu foil, 3D-AFM images
obvious that this new graphene does not of (c) concavo-convex and (d) flat graphene.
require the support of the substrate and retains the rugged surface structure on any substrate.
Typically, graphene is nearly transparent because it has only 2.3% universal opticalabsorption per layer [3]. However, in the case of this new graphene with rugged surface, thetransmission is 14% lower than that of flat-graphene due to its concavo-convex shape thateasily scatters the light. The electrical and optical characteristics of this concavo-convex
shaped graphene will also be reported.
[1] Y. Zhu et al., Adv. Mater. 22, 3906 (2010)

Corresponding Author: Y. Sunayama[2] W. Regan et al., Appl. Phys. Lett. 96, 113102 (2010)

TEL: +81-749-28-8352(ext.4302)[3] R. R. Nair et al., Science 320, 1308 (2008)

E-mail: zn21ysunayama@ec.usp.ac.jp– 31 –

2-10

FNTG-47, 2014

In situ scanning electron microscopy of graphene growth on metal surfaces○Hiroki Kato1, Junro Takahashi1, Yuta Momiuchi1, Yoshikazu Homma11

Department of Physics,Tokyo University of Science,Tokyo 162-8601, Japan

Segregation of graphene from carbon atoms dissolved in specific metal such as Ni, Co, Pd,
etc. can form large single monolayer domain due to its low nucleation probability. Once
nucleation on surface occurs, the graphene expands rapidly with the speed of several tens
micrometers per second. Since the graphene fronts pass a field of view at once, observation ofeither nucleation or graphene fronts is hard by conventional low energy electron microscopy(LEEM). In this presentation, we show the feasibility of in situ scanning electron microscopy(SEM) for monitoring monolayer graphene segregation process [1]. SEM has an enough wide
field of view up to a few millimeters. The nucleation and surface dynamics of graphene
growth on metal is discussed.
It was found that edge of monolayer graphene has a distinct feature in contrast observed byin-lens detector. The crater-like contrast, which we named as edge contrast (EC), is observed
at only monolayer graphene but not at multilayer one. Following the findings, it was verified
that segregated monolayer graphene on Co and Pd also has EC. We also checked EC withtemperatures. By repeating cycles of cooling and heating, EC of monolayer graphene wasdiminished and recovered at the temperature of ~400°C.
Preferential Ni surface domain for graphene segregation were observed by in situ SEM.
Subsequent analysis by electron backscatter diffraction (EBSD) showed that Ni(111) has
highernucleation
probability.
Furthermore, the some points ofnucleation were coincident when
repeating the cycles of dissolution andsegregation. The region was observedby atomic force microscopy (AFM).
The topography clearly shows thatstep-bunched region has higher
nucleation probability than others. In
situ SEM images showed the graphene
expands more rapidly along the stepthan perpendicular to the step. These
nucleation and growth mechanism are Fig. 1. In situ SEM images of monolayer graphene on Ni
simply explained by surface diffusivity surface observed at (a) room temperature and (b) ~400°C.
of segregated carbon adatoms.
Arrows indicate monolayer graphene domains segregated.
[1] K. Takahashi et al. Surf. Sci. 606, 728 (2012).
Corresponding Author: H. Kato
Tel: +81-3-3260-4271, Fax: +81-3-5261-1023
E-mail: h_kato@rs.kagu.tus.ac.jp– 32 –

3-1

FNTG-47, 2014

Bound excitons in monolayer tungsten disulfide○Toshiaki Kato and Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Transition metal dichalcogenide (TMD) is known as a true two-dimensional (2D)
material with excellent semiconducting properties. In spite of its potential, however,there are still remained lots of issues for the practical applications of TMD-based
optoelectrical devices. In particular, the large area growth, defect free growth, andcontrollable carrier doping are regarded as crucial issues in their production stage.
Understanding the optical features of TMD is also important issue for future
optoelectrical applications. In this study we have carried out detailed
photoluminescence (PL) study for monolayer tungsten disulfide (WS2) grown by achemical vapor deposition (CVD) method [1-6]. Novel PL peak has been observed at
the grain boundary of WS2. Detailed atomic force microscopy and PL intensity mapping
measurements show the novel peak appears only from the grain boundary region.
Temperature dependent PL measurements also revealed that the novel peak can bedivided into two types (type 1 and type 2) as a difference of peak energy and these canbe assigned as peak of neutral excitons weakly and strongly bounded at the grainboundaries, respectively. This finding is important for the future optoelectricalapplications of 2D atomic sheet with grain boundary engineering, which is one of thegeometrical standpoints of 2D atomic sheet materials.

[1] T. Kato and R. Hatakeyama, J. Am. Chem. Soc. 130, 8101 (2008).
[2] T. Kato and R. Hatakeyama, ACS Nano 4, 7395 (2010).
[3] Z. Ghorannevis, T. Kato, T. Kaneko, and R. Hatakeyama, J. Am. Chem. Soc. 132, 9570 (2010).
[4] T. Kato, L. Jiao, X. Wang, H. Wang, X. Li, L. Zhang, R. Hatakeyama, and H. Dai, Small 7, 574(2011).
[5] T. Kato and R. Hatakeyama, ACS Nano 6, 8508 (2012).
[6] T. Kato and R. Hatakeyama, Nat. Nanotechnol. 7, 651 (2012).
Corresponding Author: T. Kato
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: kato12@ ecei.tohoku.ac.jp– 33 –

3-2

FNTG-47, 2014

Photo-induced anomalous Nernst effects in transition metal dichalcogenides○Satoru Konabe1 and Takahiro Yamamoto2
1Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki

305-8571, Japan
2Department of Liberal Arts (Physics), Tokyo University of Science, Katsushika, Tokyo

125-8585, Japan

Monolayer transition metal dichalcogenides (TMDCs) such as MoS2, MoSe2, WS2
and WSe2 are quasi-two-dimensional semiconducting alternatives to graphene that haverecently attracted much attention due to their remarkable electronic and optoelectronic
properties [1]. The lack of inversion symmetry in TMDCs, in contrast to graphene, gives rise
to nontrivial quantum phenomena [2,3] rooted in the topological nature of the Blochelectrons. In addition, valley-spin coupled physics [2] emerges in TMDCs from broken
inversion symmetry and strong spin-orbit interaction, making TMDCs intriguing candidates
for spintronic and valleytronic applications.
Thermoelectric effects ubiquitously appear in materials under a thermal gradient.
These can provide microscopic insight into the electronic structure and the dynamics ofelectronic transport and optical excitations. Indeed, spontaneous photocurrent generation in
MoS2 under laser illumination was reported most recently and was interpreted in terms of aphoto-thermoelectric effect with an unusually large Seebeck coefficient [4].
In this presentation, we theoretically investigate the thermoelectric response of
TMDCs under light illumination using semiclassical transport theory [5]. Our findings showthat monolayer TMDCs subjected to circular polarized light exhibit intriguing thermoelectric
properties due to strong spin-orbit interaction, which breaks electron-hole symmetry, andbroken inversion symmetry, which induces a finite Berry curvature. Surprisingly, TMDCs
display a large anomalous Nernst signal of the order of sub-microvolts per Kelvin, despite theabsence of an external magnetic field and magnetic moments. This anomalous Nernst effectrequires the broken inversion symmetry, which induces a finite Berry curvature, in addition to
spin-orbit coupling, electron-hole asymmetry and valley degeneracy breaking (throughphotoexcitations). Hence, the valley Nernst effect is a unique feature of TMDC, which isabsent in graphene.
References:[1] A. Splendiani et al. Nano Lett. 10, 1271 (2010), K. F. Mak et al. Phys. Rev. Lett. 105, 136805 (2010),
Q. H. Wang et al. Nat. Nanotechnol. 7, 699 (2012), M. Chhowalla et al., Nature Chem. 5, 263 (2013).
[2] D. Xiao, et al., Phys. Rev. Lett. 108, 196802 (2012).
[3] T. Cao, et al., Nat. Commun. 3, 887 (2012).
[4] M. Buscema, et al., Nano Lett. 13, 358 (2013).
[5] S. Konabe and T. Yamamoto, submitted.
Corresponding Author: Satoru Konabe
E-mail: konabe@comas.frsc.tsukuba.ac.jp
Tel: +81-2-9853-5600 ext.8233– 34 –

3-3

FNTG-47, 2014

Synthesis of MoS2 by chemical vapor deposition andits application for solar cell○Yuka Tsuboi1, Daichi Kozawa1, Feijiu Wang1, Yuhei Miyauchi1, 2,

Shinichiro Mouri1, and Kazunari Matsuda1
1Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
2
Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya
464-8602, Japan
Since rising of graphene studies, the atomically-thin layered two-dimensional
materials (2D) have been widely and intensively studied. Molybdenum disulfide (MoS2)
is one of the 2D layered materials, which can be thinned down to atomic scale thickness.
Furthermore, few-layers MoS2 shows prominent light absorption in spite of such an
ultrathin structure [1,2]. Thus, the MoS2 has potential application for optoelectronic
devices. Here, we studied the photovoltaic properties of solar cell based on the 2D
materials of MoS2.
The MoS2 thin films were synthesized by chemical vapor deposition (CVD)methods. The MoS2/n-Si heterojunction solar cell was fabricated using CVD grown
MoS2 thin film. Figure 1a shows the current density-voltage (J-V) curves of MoS2/n-Si

2

Current density [mA/cm ]2

Current density [mA/cm ]solar cell under dark and light conditions, where the single layer graphene was used to
improve the photovoltaic properties. The photovoltaic conversion efficiency isevaluated as 4.9% from the J-V curve under light conditions. Figure 1b shows
comparison of J-V curves of MoS2/n-Si and MoS2/p-Si under light conditions. The
experimental results show the large difference between MoS2/n-Si and MoS2/p-Si
20
20
solar cells. We will discuss
(a)
(b)
Light
n-Si
the
detailphotovoltaic
15
Dark15p-Si
conversion
process
in
10
10
MoS2/Si solar cells.
55[1] M. Bernardi, M. Palummo, and J.
00
Grossman, Nano Lett. 13, 3664
(2013).
−5−5[2] D. Kozawa, K. Matsuda, G. Eda,
0
0.2
0.4
0.6
0
0.2
0.4
0.6
et al., Nature Com. in press
Voltage [V]Voltage [V]Corresponding Author: Y. Tsuboi
Fig. 1 (a) J-V curves of MoS2/n-Si solar cell under dark andTel: +81-774-38-3465
light conditions. (b) J-V curves of MoS2/n-Si and MoS2/p-Si
Fax: +81-774-38-3467
E-mail: tsuboi.yuka.72w@st.kyoto-u.ac.jp solar cells.

– 35 –

3-4

FNTG-47, 2014

Vertical transport in graphene/ultrathin h-BN/graphene
van der Waals heterostructures○Sei Morikawa1, Satoru Masubuchi1, 2, Takehiro Yamaguchi1, Rai Moriya1,
Yoshihisa Inoue1, Kenji Watanabe3, Takashi Taniguchi3, Tomoki Machida1, 2
1Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, Japan
2
Institute of Nano Quantum Information Electronics,
The University of Tokyo, Tokyo 153-8505, Japan
3
National Institute for Material Science, Tsukuba 305-0044, Japan

Based on the recent technology of the van der Waals heterostructures, we fabricated agraphene/ultrathin h-BN/graphene/h-BN heterostructures and measured the tunnel current
between two graphene sheets through the ultrathin h-BN [Fig. 1(a)]. In zero magnetic fields,
the fine structures of tunnel conductance Gt = dIt/dVsd as a function of Vsd [Fig. 1(b)] can be
assigned to the peaks and dips of electronic density of states (DOS) in the respective graphenesheet [Fig. 1(c)]. These results represent the realization of the DOS spectroscopy simply bymeasuring vertical transport between graphene sheets through the h-BN tunnel barrier.
In high magnetic fields, the tunneling spectra developed sharp peaks as a function of Vsd
and B [Fig. 1(d)], indicating the distinct quantization of DOS. Considering the band diagramsof two graphene sheets and the quantum capacitance between them, these peaks can be
assigned to the Landau levels of the lower graphene. In addition, we found the anomalous
structures of the tunneling spectra such as the splitting of the Landau levels away from theFermi level. We will discuss the possible origin of these results.

(a)

(c)

(d)

(b)
(i)

(ii)
(iii)

(iv)

Fig. 1. (a) The schematic of our graphene vertical tunnel junction. (b) The tunneling conductance Gt as afunction of Vsd. (c) The band diagrams of two graphene sheets which can be assigned to the dips (i, ii) and peaks(iii, iv) in (b). (d) Gray scale plot of Gt in high magnetic fields, as a function of Vsd and B.
Corresponding Author: S. Morikawa
Tel: +81-3-5452-6158, Fax: +81-3-5452-6157
E-mail: morikawa@iis.u-tokyo.ac.jp– 36 –

FNTG-47, 2014

3-5

Sc2@C66 Revisited: An Endohedral Fullerene with Scandium Ions Nestledwithin Two Unsaturated Linear Triquinanes○Michio Yamada1, Hiroki Kurihara1,2, Mitsuaki Suzuki1,2,3, Jing Dong Guo4,
Markus Waelchli5, Marilyn M. Olmstead6, Alan L. Balch6, Shigeru Nagase7, Yutaka Maeda1,
Tadashi Hasegawa1, Xing Lu8, Takeshi Akasaka1,2,3,8
1

2

Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki
305-8577, Japan
3
Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
4
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
5
Bruker Biospin K.K., Yokohama, Kanagawa 221-0022, Japan
6
Department of Chemistry, University of California, Davis, California 95616, United States
7
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
8
School of Materials Science and Engineering, Huazhong University of Science andTechnology, Hubei 430074, China

The geometries of fullerenes are governed by the isolated pentagon rule (IPR), which statesthat stable fullerenes have each of their 12 pentagons surrounded by five hexagons.1,2 At thedawn of fullerene science, it was widely believed that the IPR would also be applicable forendohedral fullerenes. In 2000, that idea was altered by the discovery of the first non-IPR
fullerenes, Sc2@C663 and Sc3N@C68.4 The molecular structure of Sc2@C66 was examinedusing 13C NMR spectroscopy and MEM/Rietveld analysis with powder diffraction data.3,5
The results were interpreted to indicate that Sc2@C66 possessed a C2v(4348)-C66 cage that
contained two sets of double fused pentagons (see Fig. 1a). Additionally, two scandium
atoms were encaged as a dimer with a Sc–Sc distance of 2.87(9) Å. However, that structure
has remained a long-standing mystery, since it is thermodynamically unfavorable.6
Here, we demonstrate definitively that Sc2@C66 does not have the structure that was long
believed to be but a brand new type (see Fig. 1b). 2D NMR spectroscopic and single-crystal
X-ray analyses disclose that Sc2@C66 has a
C2v(4059)-C66 cage containing two sets of
unsaturated linear triquinanes (ULTs), in
which three pentagons abut one another andtwo scandium ions are located within thefolds of each of the ULT units.7[1] H. W. Kroto, Nature 329, 529 (1987).
Fig. 1: a, Long-believed structure of Sc2@C66[2] T. G. Schmalz et al., J. Am. Chem. Soc. 110, 1113
(erroneously assigned). b, Single-crystal X-ray(1988).
structure of Sc2@C66.
[3] C.-R. Wang et al., Nature 408, 426 (2000).
[4] S. Stevenson et al., Nature 408, 427 (2000).
[5] M. Takata et al., Chem. Phys. Lett. 372, 512 (2003).
[6] K. Kobayashi & S. Nagase, Chem. Phys. Lett. 362, 373 (2002).
[7] M. Yamada et al., J. Am. Chem. Soc. 136, 7611 (2014).
Corresponding Author: T. Akasaka
E-mail: akasaka@tara.tsukuba.ac.jp– 37 –

FNTG-47, 2014

3-6

Fabrication of sub-1 nm graphene nanoribbons with armchair edges
by radical polymerization-chemical vapor depositionżTakahiro Nakae, Maki Yano, Takahiro Kojima, Hiroshi Sakaguchi
Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan
Graphene nanoribbon (GNR), which is a one-dimensional carbon structure, exhibits
semiconductor properties, whereas graphene is a two-dimensional carbon sheet withpseudo-metal, zero band gap characteristics.[1] The methods of GNR synthesis can beclassified into top-down or bottom-up approaches. Although top-down methods haveadvantages for producing GNRs with micrometer length,[2] the edge structures are usually
undefined and the width of the ribbon can be larger than the molecular dimensions. In contrast,
bottom-up techniques can produce GNRs with a defined edge-structure and narrow widths,
less than 1 nm. The bottom-up approaches reported to date provide GNRs with a defined edge
structure, however suffer from the systematic synthesis of GNR having different width atlarger scales because of the low solubility of GNRs and the need for special environments andinstruments.[3] Therefore, a simple bottom-up synthetic method for large-scale production of
GNR is eagerly sought not only for complete characterization of the material but also for use
in bulk-film devices such as transistors and photovoltaic cells.
Here, we demonstrated large-scale growthof all types of armchair-edged GNRs (3p, 3p+1,
and 3p+2; p is defined as the number of carbon
atoms along the width) [4] on Au(111) even in
extremely low-vacuum conditions using our
newly developed method, radical-polymerizedchemical vapor deposition (RP-CVD) (Figure1)[5]. Using this technique, a systematicsynthesis of a multilayered high-density array Figure 1. a) Experimental setup of RP-CVD withof width-controlled sub-1 nm GNRs on a metal an illustration of the presumed GNR growthsurface, with width-dependent band gap, is mechanism when using 10,10ƍ-dibromo-9,9ƍbianthryl as a monomer. b) STM image ofmade possible. GNR films transferred onto polyperianthracene.
insulating substrates behave as an excellent
photoconductor.
[1] L. Chen, Y. Hernandez, X. Feng, K. Mullen, Angew. Chem. Int. Ed. 51, 7640 (2012).
[2] (a) L. Jiao et al. Nature 458, 877 (2009). (b) D. B. Kosynskin et al. Nature 458, 872 (2012). (c) X. Wang, H.
Dai Nat. Chem. 2, 661 (2010). (d) T. Kato, R. Hatakeyama Nat. Nanotech. 7, 651 (2012).
[3] (a) A. Chuvilin et al. Nat. Mater. 10, 687 (2011). (b) A. V. Talyzin, et al. Nano Lett. 11, 4352 (2011). (c) J.
Cai et al. Nature 466, 470 (2010). (d) L. Lafferentz et al. Nat. Chem. 4, 215 (2012). (e) C. Bronner et al. Angew.
Chem. Int. Ed. 52, 4422 (2013).
[4] X. Zhu, H. Su J. Phys. Chem. A 115, 11998 (2011).
[5] H. Sakaguchi, Y. Kawagoe, Y. Hirano, T. Iruka, M. Yano, T. Nakae, Adv. Mater., 26, 4134 (2014).
Corresponding Author: H. Sakaguchi
Tel: +81-774-38-3505, Fax: +81-774-38-3508,
E-mail: nakae@iae.kyoto-u.ac.jp, sakaguchi@iae.kyoto-u.ac.jp– 38 –

FNTG-47, 2014

3-7

Nitrogen-induced interface improvement in epitaxial graphene on SiC○Wataru Norimatsu1, Yoshiho Masuda1, Michiko Kusunoki2
1

Department of Applied Chemistry, Nagoya University, Nagoya 464-8603, Japan
2
EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan

Graphene can be grown by thermal decomposition of silicon carbide. This
technique enables us to grow wafer-scale graphene on the semi-insulating substrate. It is
widely known that the carrier mobility in graphene strongly depends on the interface between
graphene and the substrate [1]. In epitaxial graphene on SiC (0001), there is a 6√3×6√
3R30 reconstructed layer consisting of the honeycomb carbon structure [2]. Graphene lieson this layer, and this layer is called a buffer layer, which dominantly scatter the electricalcarriers in graphene on SiC. In this study, in order to improve the mobility in epitaxial
graphene, we tried to modify the interface between graphene and the substrate, andinvestigated its crystallographic and electronic properties.
New-type interface was obtained by heating the 6H-SiC single-crystal substrate at
1350~1800 ºC under N2 or N2/Ar mixed atmosphere. After this treatment, graphene wasgrown by further heating under Ar atmosphere. The obtained interface was directly
observed by a Topcon EM-002B transmission electron microscope (TEM) and an aberration
corrected JEOL-ARM200F TEM. Hall-effect measurements were also carried out tocharacterize the electronic property.
Figure 1 shows the high-resolution
TEM images of graphene grown under (a) N2/Ar
atmosphere, and (b) Ar atmosphere. In theimage in (a), there are periodic contrasts in thegraphene/SiC interface. The period of thiscontrast is about 5.4 Å. These features were
never observed in the graphene grown under Aror vacuum conditions, suggesting the new-typeof interface including nitrogen. Our carefulanalysis revealed the possible presence of thesilicon-nitride layer under the buffer layer. Our
Hall-effect measurement showed the differencein the substrate effect in the electronic propertyof graphene grown in the N2/Ar and the Ar
atmospheres.
Fig. 1 HRTEM images of graphene (a) on
Si-N layer on SiC, and (b) on SiC.

References[1] A. J. M. Giesbers et al., Phys. Rev. B, 87, 195405 (2013).

[2] W. Norimatsu and M. Kusunoki, Chem. Phys. Lett., 468, 52 (2009).
Corresponding Author: W. Norimatsu, Tel/Fax: +81-52-789-5859,
E-mail: w_norimatsu@esi.nagoyau-u.ac.jp– 39 –

3-8

FNTG-47, 2014

Direct CVD synthesis of atomic layered WS2 on hBN substrates○Mitsuhiro Okada1, Takumi Sawazaki1, Kenji Watanabe2, Takashi Taniguchi2, Hiroki
Hibino3, Hisanori Shinohara1, Ryo Kitaura1
1

Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
2
National Institute for Materials Science, Tsukuba 305-0044, Japan
3
NTT Basic Research Laboratories, NTT Corporation, Atsugi 243-0198, Japan
Transition metal dichalcogenides (TMDCs) have recently attracted a great deal of attention.
More than 40 different kinds of TMDCs with layered structures have been known to exist,
providing wide-spread platform to explore physics and chemistry of the two-dimensional
materials. Group VI TMDCs (M = Mo, W, X = S, Se, Te, Fig.1) have been extensively studied
recently because they possess direct band gaps and high carrier mobilities. In addition,
TMDCs have characteristic electronic structures with the coupled spin and valley degrees of
freedom, which can lead to a new type of electronics called valleytronics. To explore suchpossibility of TMDCs, the preparation of high-quality TMDC samples is indispensable.
Recent studies have shown that substrates oftentimes alter intrinsic electronic properties ofatomic layers of TMDCs. Hexagonal boron nitride (hBN) has been proven to be one of thebest substrates to observe intrinsic properties of the atomic layers. hBN is an insulator with alarge bandgap of 6.4 eV, providing atomically flat surface without dangling bonds andcharged impurities. TMDCs on hBN are thus the key structure to investigate intrinsic
properties of TMDCs. Here, we have focused on chemical vapor deposition (CVD) growth of
TMDC (WS2) directly onto hBN substrates (Fig. 2).
Figure 3 shows typical SEM images of WS 2 grown on hBN. The large white contrast andtriangular dark contrasts correspond to a flake of hBN and CVD-grown WS2 crystals,
respectively. The typical size of the WS2 crystals is about 1 ~ 3 m, and the triangle shape of
the WS2 indicates that the present WS2 crystals have zigzag edges. Raman spectroscopy andphotoluminescence spectroscopy show the efficient growth of monolayer WS2. The electronbackscattering diffraction and low-energy electron diffraction of the present WS2 show theexistence of a strict crystallographic relation between WS2 and hBN, which leads to formationof moiré superstructure with a periodicity 4~5 times larger than that of the original crystal.
Corresponding Author: R.Kitaura and H.Shinohara
Tel: +81-52-789-2477, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp and noris@nagoya-u.jp

Fig.1: Model of WS2. Dark ballis tungsten, and bright ball issulfur.

Fig.2: Image of WS2 on hBN.
Hexagonal sheet under WS2 ishBN.

– 40 –

Fig.3: SEM image of WS2 on
hBN. White flake is hBN, andtriangle crystal on it is WS2.

FNTG-47, 2014

3-9

Electronic Structures of Carbon Flakes in Hexagonal Boron-Nitride Layers
ż<RVKLWDND)XMLPRWR1 and Susumu Saito1,2,3
1

Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551, Japan
International Research Center for Nanoscience and Quantum Physics, Tokyo Institute ofTechnology, Tokyo 152-8551, Japan
3
Materials Research Center for Element Strategy, Tokyo Institute of Technology, Kanagawa
226-8503, Japan
2

Since a graphene sheet was fabricated, two-dimensional atomic-layer sheets haveattracted much interest from the viewpoint of nanoscience and nanotechnology. Among them,hexagonal boron nitride (h-BN) atomic-layer sheets are also regarded as an important material
since they show several superior properties analogous to a graphene sheet. In the aspect of theelectronic structures, two materials exhibit considerably different features; graphene is azero-gap material, whereas h-BN monolayer is a wide-gap semiconductor [1]. Recently, h-BN
layered sheets have been fabricated successfully, and creation of triangular-shaped atomic
vacancies and doping with carbon impurities into it have been performed as well [2, 3]. Such
defects in h-BN monolayer are expected to lead to the novel electronic properties and/or tune
their properties. For example, substitution of a single carbon atom in h-BN monolayer sheet
can induce impurity states in the band gap. It is also reported that the energy band gap ofh-BN monolayer sheet is controllable under applying strains [4, 5]. Therefore, the existence ofthe multi-vacancies and the carbon-atoms flake could give rise to further rich electronic
properties.
Here, we investigate electronic structures of multi-vacancies and carbon-atoms flakes
embedded in the h-BN layered sheet using a first-principles density-functional calculation(Fig.1). We will discuss about the origin of defect states induced by multi-vacancies andcarbon flakes.

B atom
N atom
C atomFigure 1. Atomic structure of h-BN monolayer with C-atoms flake.
[1] K. Watanabe, T. Taniguchi, and H. Kanda, Nature Mater. 3 (2004) 404.
[2] C. Jin, F. Lin, K. Suenaga, and S. Iijima, Phys. Rev. Lett. 102 (2009) 195505.
[3] X. Wei, M. Wang, Y. Band, and D. Golberg, ACS Nano 5 (2011) 2916.
[4] Y. Fujimoto, T. Koretsune, and S. Saito, JPS Conf. Proc. 1 (2014) 012066.
[5] Y. Fujimoto, T. Koretsune, and S. Saito, J. Ceram. Soc. Jpn. 122 (2014) 346.
Corresponding Author: Yoshitaka Fujimoto
TEL: +81-3-5734-2368, FAX: +81-3-5734-2368, E-mail: fujimoto@stat.phys.titech.ac.jp– 41 –

3-10

FNTG-47, 2014

Inter-shell resistance in a multiwall carbon nanotube measured
by utilizing inner-shell retraction phenomenażYuji Shinomiya1, Koji Asaka1, Hitoshi Nakahara1, Yahachi Saito1
1

Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan

Multiwall carbon nonotubes (MCNT) are expected to be applied to various nanoscale
electronic devices. However, inter-shell resistance in a MWCNT is not clear. We found thatelectrical resistance of a MWCNT increased as inner-shells were retracted to a Mo electrodeby in-situ transmission electron microscopy (TEM). In this study, we investigated theinter-shell resistance in a MWCNT by utilizing the phenomena of inner-shell retraction.
MWCNTs were attached to an edge of an Au plate, and a tip of the MWCNT was brought
into contact with a Mo electrode inside a TEM. Structural changes in the MWCNT
contacted with the Mo electrode were observed by in-situ TEM, and applied current andvoltage to the MWCNT were simultaneously
measured.
Figs. 1 (a) - (d) show a series of TEM
images of structural changes of MWCNT. The
length of the MWCNT bridged between the Au
plate and the Mo electrode is 240 nm, and thenumber of graphene layers comprising the
MWCNT is 26. When the bias voltage wasincreased to 2.37 V, the current increased to
5.47 kȍ
160 µA. At that time, the MWCNT tip wasinserted into the Mo electrode (Fig. 1 (a)).
While keeping the voltage 2.00V, the innermost
7 layers of the MWCNT were retracted to the
Mo electrode (Fig. 1 (b)), and then two sets of
3 layers were successively retracted (Figs .1 (c),6.32 kȍ(d)). The arrows in Fig. 1 show the end of theinner-shells being retracted. During theinner-shell retraction, the total resistanceincreased from 5.47 kȍ (Fig. 1 (b)) to 7.85 kȍ(Fig. 1 (d)). These results show that the
inner-shells contribute to the electrical
7.85 kȍ
conduction in the MWCNT. Under theassumption that the increase of the total
resistance results from the change of inter-shellresistance between the inner-shells being
retracted and the outer-shell adjacent to these, Fig. 1 A series of TEM images of the process
the inter-shell conductance is estimated to [0.3- when inner-shells of the MWCNT were
0.5 kȍ]-1/µm2.
retracted to the Mo electrode.
Corresponding Author: Yuji Shinomiya
E-mail: Shinomiya@surf.nuqe.nagoya-u.ac.jp, Tel: +81-52-789-3714, Fax: +81-52-789-3703– 42 –

FNTG-47, 2014

3-11

One-Dimensional Plasmon Excitation in Far-Infrared Region○Takahiro Morimoto1, Soon-Kil Joung1, Takeshi Saito2,1, Don N. Futaba2,1,
Kenji Hata2,1, and Toshiya Okazaki 2,1
1

Technology Research Association for Single Wall Carbon Nanotubes (TASC),
Tsukuba 305-8565, Japan
2
Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565, Japan[1] A. Ugawa et al., et al., PRB, 60, R11305, (1999).
[2] A. Pekker and K. Kamaras, PRB, 84, 075475 (2011).
[3] Qi Zhang et al., Nano Lett, 13, 5991, (2013).
[4] Takahiro Morimoto et al., ACS Nano, submitted (2014).

– 43 –-log(TCNT/T0) (arb.u)

1.4

856nm

1.2
1.0

743nm

0.8

656nm

0.6
0.4

551nm

0.2
0.0
10

100

1000

Wavenumber (cm-1)

Fig.1 The length dependence of the FIR

FIR absorption position (cm-1)

absorption of the Arc-CNTs samples.
400●e-DIPS▲HiPCo
■Arc

300

200

100

0
0

2

4

6

Wave Vector q (m-1)

Fig.2 The dispersion relationship of the 1D
plasmonic wave vector and peak positions.
Four Probe Resistance ()The Far-infrared (FIR) and Terahertz (THz) absorption is
one important topic for optical properties of carbon nanotubes(CNTs) [1]. The many experimental and theoretical works [2,3] were reported based on two different mechanisms, themini-gap and plasmonic excitation. The mini-gap induced bycurvature effect has a few ten meV, and this value is similar tothe photon energy of FIR and THz frequency region. On theother hand, the one dimensional plasmonic resonance is related
to their tube length, not a diameter. Therefore, it is important toconfirm the relationship between FIR absorption and tube
length with constant diameter samples.
We measured carefully prepared CNT film samples forwide range optical transmission properties from Near-infrared
to THz frequency [4]. These samples have different tube lengthand constant diameter. Figure.1 shows the typical results of the
FIR absorption of different CNT length samples. The FIR
absorption peak features are clearly shifted to higher frequency
region by decreasing CNT length. The inter-band absorption,
however, is constant while these measurement as shown inright side of Fig.1. Figure.2 shows the dispersion relationshipof the one dimensional plasmon and FIR absorption peak
positions. The long (low damage) tubes show good agreementwith theoretical prediction curve (black solid line in Fig.2).
The defect inducements by sample preparation process areshown as displacement from theoretical value in this figure.
Figure.3 shows the four probe resistance with same film
thickness samples. The FIR absorptions have linearly
dependence to their four probe resistance. This strongly
indicates that the FIR absorptions are directly related to theirtube length. These all results are consistent with the theoreticalmodel of the one dimensional plasmonic excitation induced in
CNTs current channels.
This presentation is based on results obtained from a projectcommissioned by the New Energy and Industrial Technology
Development Organization (NEDO).

2000

1500

●e-DIPS▲HiPCo
■Arc

1000

500

0
100

200

300

FIR absorption position (cm-1)

Fig.3 The four probe resistance of same
thickness CNTs films.

Corresponding Author: T. Okazaki
E-mail: toshi.okazaki@aist.go.jp

FNTG-47, 2014

3-12

Diameter dependence of X-ray irradiated defect in single-walledcarbon nanotubes○Toshiya Murakami1, Satoshi Isozaki1, Mitsuaki Matsuda1, Kenji Kisoda2, Chihiro Itoh1
1

Department of Materials Science and Chemistry, Wakayama University, Wakayama
640-8510, Japan2
Department of Physics, Wakayama University, Wakayama 640-8510, Japan

Structural modification of single-walled carbon nanotubes (SWNTs) by ionizing radiation
is a candidate of a tool to modify their properties. We have shown that X-ray irradiation
forms intrinsic defects, which is the vacancy-interstitial pairs (Frenkel defects), in SWNTs
and changes their geometric structures.[1,2] The structural change was shown to change theelectronic property of SWNTs.[3] The structure and thermal stability of the X-ray-induced
defects are presumably dependent on the chirality and diameter of tubes. In this report, wehave compared the thermal stability of the X-ray-induced defects in SWNTs having a several
diameters.
The samples used in the present study were commercially supplied SWNTs made byarc-discharge technique and CoMoCAT-CVD method. The average diameters (d) of these
SWNTs are ~1.4 and 0.9 nm, respectively. The samples were irradiated with X-ray (K lineof Mg) in vacuum and subsequently annealed in inert gas. The pristine, irradiated andannealed SWNTs were measured by Raman scattering spectroscopy with the probe laser of
532 nm wavelength.
Figure 1 shows the Raman spectra of the pristine, X-ray irradiated and annealed (600ºC)
SWNTs. The insets are radial breathing modes (RBMs) of the pristine samples. The
X-ray-induced enhancement of D band was reduced by the post-irradiation annealing. The
annealing temperature dependences of ∆D/G (the change of the intensity ratio of D band to Gband) are shown in Fig. 2. The temperature of the half reduction in ∆D/G of the thin
SWNTs (d~0.9) was higher than that of the thick SWNTs (d~1.4), indicating that the
X-ray-induced defects in thinner SWNTs have higher thermal stability. Furthermore, thereactions eliminating the X-ray-induced defects were not simulated using 2nd order reaction
model. We concluded from these results that the X-ray-induced defects have complex
structures.
α Fig. 1: Raman spectra of pristine, irradiated and annealed     Fig. 2: ΔD/G of SWNTs, depended
 (600ºC) SWNTs.
   on annealing temperature[1] C. Itoh et al. Nucl. Instrum. Methods Phys. Res. B 266, 2772 (2008). [2] T. Murakmai et al. J. Appl. Phys.
114, 114311 (2013). [3] T. Murakami et al. Jpn. J. Appl. Phys. 53, 05FC03 (2014).
Corresponding Author: T. Murakami, Tel: +81-73-457-8532, E-mail: murakami@sys.wakayama-u.ac.jp– 44 –

FNTG-47, 2014

3-13

Studies on the relationship between SWNTs and Fe catalyst nanoparticles
during floating catalyst CVD synthesis from CO○ 1 Hua Jiang, 1 Antti Kaskela, 1 Kimmo Mustonen, 1,2 Albert G. Nasibulin, 1 Esko I.
Kauppinen
1

2

Department of Applied Physics, Aalto University School of Science, Aalto, Espoo, Finland
Skolkovo Institute of Science and Technology, 100 Novaya st., Skolkovo, Odintsovsky district,
Moscow Region, 143025, RUSSIA

Single-walled carbon nanotubes (SWCNTs) nucleate and grow on catalytic nanoparticles
and the size and crystal structure of the nanoparticles play a key role in determining thechirality of the produced SWCNTs. However, it is often observed that not all nanoparticles
actively catalyze growth of SWCNTs in a chemical vapor deposition (CVD) process though
they appear to have similar size and structure as active nanoparticles. In addition, thecorrelation between the nanotube properties and that of active nanoparticles remains underdiscussion.
In this contribution, we have performed a comprehensive statistical analysis of morphology,
size and chemical compositions of a large number of nanoparticles, including both
catalytically active and inactive ones, by means of aberration-corrected high-resolution
transmission electron microscopy. SWCNTs were produced by a novel floating-catalyst CVD
process with Fe nanoparticles serving as catalysts for CO-disproportionation reaction. It isdisclosed that active and inactive nanoparticles show no essential difference in morphology
and size distribution. Though the average diameter of active nanoparticles (~3.3 nm) is overthree times larger than that of SWCNTs (~1.1 nm), our results have shown that the ratio of acertain SWCNT diameter to that of an active catalyst nanoparticle varies dramatically,
ranging from 1:2.2 to 1:4.3. Importantly, we discriminate at least two species of Fe
nanoparticles, i.e. oxidized Fe nanoparticles and metallic BCC Fe nanoparticles. It is foundthat no oxidized Fe nanoparticles, but only BCC Fe nanoparticles are catalytically active for
SWCNT growth. Electron diffraction analysis indicates a biased chiral distribution of
SWCNTs towards high chiral angles, but no significant preference to a specific chirality isobserved. The fraction of semiconducting tubes is about 75 %. Also, we will present highly
conductive flexible, transparent films and high mobility TFT-FETs made from these SWNTs.

– 45 –

ポスター発表
Poster Presentations

1P-1 ∼ 1P-41
2P-1 ∼ 2P-41
3P-1 ∼ 3P-40

1P-1

FNTG-47, 2014

Stability improvement of transparent conductive thin films of single-wallcarbon nanotubes by forming protective thin layer○

Naoki Kishi1, Takashi Suzuki1, Takeshi Saito2, Tetsuo Soga1

1

Department of Frontier Materials, Nagoya Institute of Technology,
Nagoya 466-8555, Japan
2
Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565, Japan
Single-wall carbon nanotube (SWCNT) thin films have attracted much attention inrecent years as transparent conductive electrodes for plastic electronic devices. Transparent
conductive ﬁlms   of   SWCNTs   provide   high   ﬂexibility   and   ease   of   processing   at   low  temperatures. In addition to electric conductivity, stability is also important property toemploy SWCNT thin ﬁlms   for   practical   applications. Jackson et al. reported that electricalconductivity of doped SWCNT films can be stabilized by coating polymer[1]. However,further studies on improvement of durability are required for practical use of transparent
conductive thin films of SWCNTs.
In this study, we report stability improvement of SWCNT transparent conductive
films by forming protective thin layer of conductive polymer materials. Coating conductive
polymer materials such as poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) andpolyaniline improves stability of electrical conductivity of SWCNT thin films in air. We also
found that electrical conductivity of SWCNT films are enhanced by carrier doping fromcoated polymer thin layer. The details will be discussed in our presentation.
[1] R. Jackson et al., Adv. Funct. Mater., 18 (2008) 2548.
Corresponding Author: Naoki Kishi
TEL/FAX: +81-52-735-5147
E-mail: kishi.naoki@nitech.ac.jp– 47 –

1P-2

FNTG-47, 2014

Nitrogen-Fe-Carbon Coated Carbon Nanotube Catalyst
for Oxygen Reduction Reaction○Atom Furuya1, Kei Murakoshi 1, Satoshi Yasuda 1,2
1

Department of Chemistry, Faculty of science, Hokkaido University,
Sapporo 060-0810, Japan
2
JST-PRESTO, Kawaguchi, Saitama 332-0012, Japan

H2O2 yield / %Development of low-cost, abundant and durable catalysts for oxygen reduction reaction(ORR) without use of precious metals such as Pt has been hot topics in Polymer electrolyte
fuel cells (PEFC) field. Among the various Pt replaced candidates, nitrogen-metal-carbon(N-M-C) catalyst produced by pyrolysis of various nitrogen, inexpensive transition metals
such as iron and cobalt, and carbon precursors, have been attracted much attention due to their
ORR activities in both alkali and acid solution. However, in spite of numerous studies, theORR activity is still low in acid condition compared to conventional Pt catalyst, probably
arising from the loss of electrical conductivity by structural distortion of the carbon inducedby catalytic sites (Fe-Nx structure) doping and low amount support of the catalytic site formedon the carbon surface. In this study, to resolve these issues, core-shell structured N-Fe-C/CNT
hybrid system was fabricated by pyrolysis of CNTs wrapped in iron(II) phthalocyanine (FePc)
molecules. Carbon nanotubes have a feature of high electrical conductivity and high specificsurface area. Beside, FePc molecule contains Fe-N structure which works as ORR active site.
Graphitization of FePc molecules on the CNT is expected to avoid destruction of the carbon
structure by the doping and support a lot of the catalytic sites on the CNT surface.
FePc/CNT composite was fabricated by mixing CNT and FePc dispersed solution. To
obtain N-Fe-C/CNT catalyst, the composites were annealed at 900 Co under Ar to graphitize
adsorbed FePc molecules. Ring rotating disk electrode (RRDE) voltammetry in oxygen
saturated 0.5 M H2SO4 solution was performed to evaluate ORR activities (Fig. 1). RRDE
measurements showed that a half-wave potential and H2O2 yield were 0.77 V versus RHE and
5 % at all potentials, resulting in one the highest ORR activity in previously reported N-Fe-C
carbon composites. These results indicate that our fabrication technique will provide high
ORR active catalysis and will serve development of CNT ORR electrocatalyst.
TEL & FAX: +81-(0)11-706-4811
E-mail: satoshi-yasuda@sci.hokudai.ac.jp

10
5
0
0.2

0.4

0.6

0.8

1.0

Potential / V vs RHE

Current density / A/cm

2

0
-1

-2
-3
-4

-5x10

-3

0.2

0.4

0.6

0.8

1.0

Potential / V vs RHE

Scheme. Schematic illustration of the fabrication of
N-Fe-C/CNT composite.

Fig. 1 RRDE polarization curves and peroxide yield
N-Fe-C/CNT in an O2-saturated 0.5 M H2SO4
solution. (The rotating electrode rate : 1600 rpm, scanrate : 10 mV/s)– 48 –

1P-3

FNTG-47, 2014

Li ion storage properties of functional molecules encapsulated in SWCNTs○Kosuke Tashiro, Hayong Song, Yoshiki Nishiwaki, Kento Hosoe, Shinji Kawasaki*
Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan
Recently, higher capacity and lower cost rechargeable batteries are strongly demanded.
Among them, lithium-sulfur batteries using elemental sulfur and lithium ion batteries usingorganic materials like quinones have attracted much attention. However, the batteries basedon these materials suffer from poor cycle performance because of the dissolution ofpolysulfide and quinone ions into electrolytes. In this work, we tried to encapsulate these
active materials into single-walled carbon nanotubes (SWCNTs) in order to prevent the
dissolution into the electrolytes.
We encapsulated anthraquinone (AQ) and 9, 10-phenanthrenequinone (PhQ) molecules into
SWCNTs by vacuum sublimation method. Charge-discharge profiles were measured using
these encapsulated molecules as working electrode and, lithium metal as counter andreference electrodes. 1 M LiClO4/Ethylenecarbonate:Diethylcarbonate was used as electrolyte.
Fig.1(b) shows the charge-discharge curves of PhQ@SWCNTs at a current density of 100 mA
g-1, while Fig.1(a) was obtained for bulk PhQ sample. By the encapsulation treatment, thecapacity fading was greatly diminished during charge and discharge processes. Detailed
discussion will be presented at the conference.

3

(b)

+

Potential (V vs Li/Li )(a)+

Potential (V vs Li/Li )

3

2

0

100

200

300

Capacity (mAh/g)

2

0

100

200

Capacity (mAh/g)

Fig.1 Charge-discharge curves of (a) a mix of PhQ powder
sample and SWCNTs, and (b) PhQ@SWCNTs*

Corresponding Author: S. Kawasaki

E-mail: Kawasaki.shinji@.nitech.ac.jp– 49 –

300

1P-4

FNTG-47, 2014

Ion size dependency of ion adsorptions onouter and inner surfaces of SWCNTs○Masato Tsutsui, Yu Takeuchi, Shinji Kawasaki
Department of Materials Schience and Engineering, Nagoya Institute of Technology,
Nagoya 466-8555, Japan
Single-walled carbon nanotubes (SWCNTs) are promised electrode materials of electric
double layer capacitor (EDLC) because they exhibit exceptional properties such as highelectrical conductivity, high theoretical specific surface area, and so on. Although thereported EDLC capacity values of SWCNT electrodes are not very high probably due to thedecrease of the effective outer surface area by the formation of bundles, the EDLC
capacitance per unit area of SWCNTs is much higher than those of ordinary carbon materials
such as activated carbons. Therefore, the ion adsorption on SWCNTs is somehow different
from that on the ordinary carbon surface. The unique tube structure and electronic structureof SWCNTs might contribute to the high unit area capacitance. In fact, we revealed that thecharacteristic electronic density of states of SWCNTs affect the shape of cyclic
voltammogram (CV).[1, 2] However, it is not understood well how the unique tube structure
affects the ion adsorption property. In order to clarify the structural effect, we prepared openand closed-end SWCNT samples and measured their EDLC properties with several kinds ofadsorption ions having different sizes. We performed CV and charge-discharge
measurements with several electrolytes (LiCl, NaCl, KCl, CsCl, MgCl2, CaCl2 aqueous
solution and triethylmethylammonium tetrafluorobrate (TEMABF4) in propyrene carbonate(PC)). Detailed discussion is presented at the conference.

100

(A)

100

(B)

inner surface

Capacitance (F/g)

Capacitance (F/g)

inner surface

00

Closed−end
−100

−100

Open−end
−1000

−500

0

Closed−end
Open−end

500

−500

+

Potential (mV vs. Ag/AgCl)

Potential (mV vs. Ag/Ag )0

Fig. Cyclicvoltammograms of open- and closed-end SWCNTs in(A)1M TEMABF4/PC (B)1M LiCl aqueous solution.
[1] A. Al-zubaidi et al, J. Phys. Chem. C, 2012, 116, 7681-7686[2] A. Al-zubaidi et al, Phys. Chem. Chem. Phys., 2012, 14, 16055-16061
Corresponding Author: S. Kawasaki
Tel: +81-52-735-5221
E-mail: kawasaki.shinji@nitech.ac.jp– 50 –

500

1000

FNTG-47, 2014

1P-5

Integration of Double Wall Carbon Nanotube Sensors on CMOS Platform○Florent Seichepine1, Jörg Rothe2, Alexandra Dudina1,2, Andreas Hierlemann2, Urs Frey1,212Frey Initiative Research Unit, RIKEN QBiC, Kobe, Hyogo 650-0047, JAPANBio Engineering Laboratory, D-BSSE, ETH Zurich, Basel CH-4058, SWITZERLAND

We present a dielectrophoretic (DEP) manipulation technique to integrate
double-walled CNT (DWNT) onto of CMOS circuits for sensing applications. The main
target is the parallel integration of a controlled number of CNTs on a large number ofindividual sensor sites within a sensor array. The use of a post-synthesis integration techniqueallows for control of the nature of the integrated CNTs (e.g. the use of pre-functionalizedCNTs) in a room temperature process, which prevents damage to the CMOS circuits that has
been observed, e.g., for high-temperature CVD growth of CNTs.
A versatile CMOS based system has been designed that features current readout of1024 pixels via 32 channels [1]. Each pixel is connected to a CNT device sharing a common
electrode connected to a controlled voltage source. The CNTs were assembled from asuspension of catalytically CVD-grown DWNTs [2]in water with carboxymethyl cellulose as
surfactant. The DEP was performed between two interdigitated electrodes. To obtain
independent sensor sites a part of the electrode is made of Cr and this part is selectively
etched away after the assembly. A final metallization step connects the CNTs to the CMOS
circuits. The current flowing through each CNT sensor can then be independently controlled.
Fig.1 shows SEM pictures of the CNT assembly. The local field applied during
dielectrophoresis creates a self-limiting assembly process leading to the integration of a large
number of single CNTs (or small bundles) (about 12%). The resistance of the obtained single
CNT connections ranges from 0.2 to 8 MΩ. Fig.2 presents the resistance mapping of all CNT
devices of a selected chip.
With this platform, we aim to develop a versatile tool for local detection ofbiochemical substances and for highly sensitive multiplexed sensing.

Fig.1: SEM picture of a subset of CNT connections
integrated on a CMOS platform (Scale bar 5µm).

[1]J. Rothe, O. Frey, A. Stettler, Y. Chen, and A. Hierlemann,

Fig.2: Resistance map of a CNT sensor
array. Inset: Corresponding I-V plots.
2012 IEEE Sensors, pp. 1–4, Oct. 2012.

[2]E. Flahaut, R. Bacsa, A. Peigney, and C. Laurent, Chem. Comm.., no. 12, pp. 1442–1443, 2003.
Corresponding Author: Florent Seichepine
Frey Initiative Research Unit, RIKEN QBiC, Kobe Institute2-2-3 Minatojima-minamimachi, Chuo-ku, Kobe,
Hyogo 650-0047, JAPANe-mail: f.seichepine@riken.jp– 51 –

FNTG-47, 2014

1P-6

Optical properties of quantum dots beaded to multi-walled carbon
nanotube forest (QD-beaded MWCNT forest)○Junthorn Udorn1, Kazuki Sekiya 1, Hiroshi Furuta 1, Akimitsu Hatta 1
1

Electronic and Photonic Systems Engineering, Kochi University of Technology,
Kochi 782-0003, Japan
Carbon nanotubes (CNTs) have received widespread attention since they provide uniquestructure of mechanical, chemical, and electronic properties [1]. Moreover, the verticallyaligned carbon nanotubes (VACNTs) have a high absorption coefficient in the visible region[2,3]. Also, polarized light is dominated to absorption of short length VACNTs [4]. The major
challenge of significantly improving optical characteristics of QDs is a modification of CNTs
structures with semiconductor nanoparticles [5]. Recently, there has been much interest in theuse of quantum dots (QD) for the enhancement of light harvest in photovoltaic efficiency[6-8]. The optical absorption of QDs such as CdS [9] and CdSe [10] in the broad range of UV
throughout near-infrared spectra is intrinsically tunable due to the band gap of selectedparticle size. In this study, the optical reflectance comparison of MWCNT forest beaded
with/without CdSe/ZnS (core/shell) QD-beaded
MWCNT forest is revealed. In addition, aproperty of QDs assembled with MWCNT
forest and Si is investigated. Figure 1 illustrates
optical reflectance peaks of QD-beaded
MWCNTs and QD-coated Si compared withtypical Si peaks. At the wavelength range of
320 – 360 nm in UV region, increasing curves
of QD-beaded MWCNT forest and QD-coatedFig.1: Reflectance spectra at the
Si are significantly noticeable compared withwavelength of UV-visible region of
QD-beaded
MWCNT
forestandthat of Si curve. The optical reflectance of the
QD-coated Si compared with typical Si
QD-beaded MWCNT forest is higher thanand MWCNT forest.
MWCNT forest in UV spectra region whereas
significantly remain steady at the visible region. Further investigations on Raman
spectroscopy and PL will be discussed in presentation.
This work was supported by Japan Government (MONBUKAGAKUSHO) scholarship(No. 132308) and JSPS KAKENHI Grant (No.24560050).
[1] Iijima, S. Nature 354, 56(1991). [2] Yang, Z. P.; et al. Nano Lett. 8, 446(2008). [3] Mizuno, K.; et al. Proc.
Natl. Acad. Sci. 106(15), 6044(2009). [4] Muraki Y.;et al.Carbon.43(13), 2664(2005). [5] Hickey, S. G.; et al. J.
Phys. Chem. B 104, 7623(2000). [6] Péchy, P.; et al. J. Am. Chem. Soc. 123(8), 1613(2001). [7] Barve, A. V; etal. Appl. Phys. Lett. 100(19), (2012). [8] Mar, J. D.; et al. J. Appl. Phys. 110(5), (2011).
Nanoscale 4(3), 742(2012). [10] Tian, J.; et al. Nanoscale 5(3), 936(2013).
Corresponding Authors: J. Udorn, H. Furuta Tel: +81-887-57-2211,
E-mail: 178002a@gs.kochi-tech.ac.jp, furuta.hiroshi@kochi-tech.ac.jp– 52 –[9] Yu, K.; et al.

FNTG-47, 2014

1P-7

Photovoltaic features of densely-aligned pn junction semiconducting
single-walled carbon nanotube films○Toshiki Akama, Toshiaki Kato, Yoshihiro Abiko, Rikizo Hatakeyama, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Single-walled carbon nanotube (SWNT) is one of the most attractive material for futurehigh performance solar cells [1] due to their flexible filament-like structure, high carrier
mobility, and tunable bandgap energy by controlling the diameter. In addition, multiple
exciton generation (MEG) in SWNT has also been demonstrated experimentally andtheoretically [2, 3]. For the fabrication of pn homo-junction based SWNTs thin film, it isnecessary to fabricate both p- and n-type SWNTs thin film. It is well known that pristine
SWNTs shows p-type transport property. Recently, we have demonstrated very stable n-type
SWNTs-thin film transistors (TFTs) by Cs encapsulation into SWNTs by a plasma ion
irradiation method [4].
Here we report the photovoltaic features of pn homo-junction SWNTs film fabricated byposition selective Cs encapsulation. Densely-aligned semiconducting SWNTs are utilized as astarting material. The half channel area of a pristine SWNTs-TFT fabricated by a conventional
photolithography technique is covered with polymer to prevent Cs plasma irradiation andposition selective Cs encapsulation is realized. Cs
encapsulation is carried out by the plasma ion
irradiation method. Finally, Cs irradiated SWNTs thinfilm is rinsed by purified water to remove the Cs atoms
adsorbing on the outside of SWNTs. In this study, theelectrical transport properties are investigated withoutor with light illumination using a solar simulator.
It is found that the clear rectifying drain-source
current (IDS) vs. drain-source voltage (VDS)
characteristics can be observed after the position
selective Cs encapsulation into SWNTs thin film.
Furthermore, a short-circuit current and an open-circuit
voltage can be detected under light illumination using asolar simulator as shown in Fig. 1. This indicates thatpn homo-junction based on SWNTs thin film can be Fig.1: IDS-VDS characteristics of position
applicable to solar cells. Our finding is important as a selective Cs encapsulated SWNTs thin
crucial step for the fabrication of high performance film without and with light illumination.
SWNTs solar cells.
[1] R. Hatakeyama, Y. F. Li, T. Y. Kato, and T. Kaneko, Appl. Phys. Lett. 97, 013104 (2010).
[2] S. Konabe and S. Okada, Phys. Rev. Lett. 108, 227401 (2012).
[3] N. M. Gabor et al., Science 325, 1367 (2009).
[4] Y. Abiko, T. Kato, R. Hatakeyama, and T. Kaneko, J. Phys.: Conf. Ser. 518, 012013 (2014).
Corresponding Author: T. Akama
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: akama13@ecei.tohoku.ac.jp– 53 –

FNTG-47, 2014

1P-8

Ab initio study for metal/semiconductor separation of single-wall carbon
nanotubes using surfactant sodium dodecyl sulfate○Mari Ohfuchi
Fujitsu Labs., Atsugi 243-0197, Japan
Metal/semiconductor separation of single-wall carbon nanotubes (SWCNTs) is an essential
way to realize their electronic applications. One of the promising techniques for large-scaleindustrial use is hydrogel-based separation using surfactant sodium dodecyl sulfate (SDS) [1].
Nevertheless the origin causing the difference between metallic (M-) and semiconducting(S-)SWCNTs in the adsorption with SDS surfactants is still not clear. In this study, we
perform density functional theory (DFT) calculations [2] to address this issue.
The models of metallic (5, 5) and semiconducting (8, 0) nanotubes adsorbed by an SDS
anion are shown in Fig. 1. It is well known that the basis set superposition error (BSSE) is
unavoidable when localized orbital basis set is employed to describe non-covalent adsorption.
The adsorption energy with BSSE correction was obtained to be 0.198 and 0.170 eV for the(5, 5) and (8, 0) nanotubes, respectively. Considering kT  0.026 eV (k is the Boltzmann
constant and the temperature T = 300 K), the difference of 0.028 eV results in three times theaggregation number of SDS on M-SWCNTs. The energy band structures for the models are
given in Fig. 2. The flat bands derived from the SDS anion just below the chemical potential(set to zero) means some charge is transferred from the SDS anion to SWCNTs. The
transferred charge was also calculated with the BSSE correction. We could find a remarkabledifference in neither the amount nor the spatial distribution of the charge. This means there isno difference in the electron-electron interaction energy. On the other hand, we found that thedifference in the integral of the band energy occupied with the transferred charge into
SWCNTs (Fig. 3) almost agrees with the difference in the adsorption energy. Thus, we canconclude that the difference in the adsorption of SDS to M- and S-SWCNTs is attributed tothe difference in the energy band structure of SWCNTs.

Fig.1: Models for (a) (5, 5)
and (b) (8, 0) CNTs adsorbed
by an SDS anion. The gray,white, black, and light grayspheres represent C, H, O,
and S atoms, respectively.

Fig.2: Energy band structures for themodels in Fig. 1.

Fig.3: Difference in the band energy
occupied with the charge transferredfrom the SDS anion to SWCNTs.
The thick curves represent theoccupied band. The broken lines
represent   the   chemical   potential   μ,  which was set to zero in Fig. 2.

[1] T. Tanaka, Y. Urabe, D. Nishide, and H. Kataura, Appl. Phys. Express 2, 125002 (2009).
[2] T. Ozaki, Phys. Rev. B 67, 155108 (2003); http://www.openmx-square.org/.
Corresponding Author: M. Ohfuchi
Tel: +81-46-250-8194, Fax: +81-46-250-8274, E-mail: mari.ohfuti@jp.fujitsu.com– 54 –

1P-9

FNTG-47, 2014

Layer-by-layer assembly in nanoporous template andfabrication of carbon nanoarchitecture
Takao Sada1, ○Tsuyohiko Fujigaya1,2, Naotoshi Nakashima 1,2,3
1 Department of Applied Chemistry, Graduate School of Engineering, Kyushu University

Motooka, Fukuoka 819-0395, Japan, 2WPI-I2CNER, Kyushu University,
3JST-CREST,5 Sanbancho, Chiyoda-ku, Tokyo, 102-0075, Japan
Layer-by-layer (LbL) assembly is widely recognized as a versatile and simple technique
for the fabrication of the well-controlled ultrathin film onto the surface of flat substrates by
the alternate deposition of polyanion and polycation. Recently, the LbL assembly onto
non-flat surface especially inside porous materials such as anodic aluminum oxide (AAO)
membrane have received great attentions [1]. However, controlled LbL-assembly onto theinterior of nonporous template is still challenging since the extended conformation of thecharged polymers in an aqueous solution limit the diffusion into such a confined nanospace,which often resulted in the filling of the pore entrance upon LbL-assembly. Herein, we
demonstrate, for the first time, the utility of trivalent ions as the positive charged species for
the LbL assembly in AAO membrane with 35 nm in diameter and synthesized the carbon
nanoarchitecture from the LbL film.
Fig. 1a shows the monitoring of the weight of the AAO (pore diameter = 35 nm) as afunction of the number of LbL layers. LbL assembly formation was carried out using theaqueous solutions of polyacrylic acid (PAA) as the polyanion and poly(allylaminehydrochloride) (PAH) or FeCl3 as the polycation, respectively. The weight was found to
linearly increase only using Fe 3+ as the polycation, suggesting facile diffusion of the Fe3+ into
the pores of the AAO. In addition, after annealing the LbL film, we observed the tubular
structures (Fig. 1b), which suggested that the successful coating of the pore interior. The
present LbL-assembly fabrication inside the small nanopores is applicable to many otherporous materials and allows us to fabricate well-controlled carbon nanoarchitecture.

Weight Change (mg)

(a)

(b)
0.8
0.6
0.4
0.2

100 nm0

0

2

4

6 8 10 12 14 16
LbL Layers

Fig. 1 (a) Plots of the weight change of AAO membrane with 35 nm in diameter after dipping into
PAA solutions as negative charged species and Fe3+ (red line) and PAH (black line) solutions as
positive charged species. (b) STEM images of carbonaceous nanotubes after heating and dissolving the
AAO membrane after the LbL assembly of PAA/Fe.
[1] K. Ariga, Q. Ji, J. P. Hill and A. Vinu, Soft Matter, 2009, 5, 3562.
Corresponding Author: N. Nakashima
Tel: +81-92-802-2840, Fax: +881-92-802-2840,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp– 55 –

FNTG-47, 2014

1P-10

Oligofluorenes with different main-chain lengths for selective sorting ofsemiconducting single-walled carbon nanotubes○Tomohiro Shiraki1,2, Shoichiro Shindome1, Fumiyuki Toshimitsu1,
Tsuyohiko Fujigaya1,2 , Naotoshi Nakashima1,2,3
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744
Motooka, Nishi-ku Fukuoka 819-0395, Japan,
2International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu
University, Fukuoka 819-0395, Japan,
3
JST-CREST, 5 Sanbancho, Chiyoda-ku, Tokyo 102-0075, Japan

Polyfluorene derivatives have been remarked as
fascinating dispersants for single-walled carbon nanotubes
because they solubilize only semiconducting single-walledcarbon nanotubes (sem-SWNTs).[1] The selective
extraction mechanism, however, is still unclear. Thus,
further experimental and theoretical examinations areneeded to understand the details, which leads to the designof a better selective sem-SWNT-sorting dispersant. Here,
we report the synthesis of 11 fluorene oligomers withdifferent main chain lengths, and their SWNT
solubilization behaviors.
Eleven oligofluorenes (Fig. 1) were synthesized
through conventional coupling reactions. Sonication of
SWNTs (Hipco) with the synthesized oligofluorenes intoluene provided SWNT dispersions when the chain
length was longer than n=12 (12 mer). Interestingly, as
shown in the Raman spectra (Fig. 2), the selective
sem-SWNT extraction was recognized when longer
oligofluorenes (n  18mer) were used. The selectivity
was further investigated by vis/NIR absorption andphotoluminescence spectroscopies, which revealed thatthe chiralites of the extracted SWNTs were different whenusing poly(9,9’-di-n-octylfluorene) (PFO) and the longer
oligofluorenes; that is, (9, 7) SWNT was extracted
together with (7, 5), (7, 6), (8, 6), and (8, 7) SWNTs by
PFO, although the SWNT dispersions using theoligofluorenes did not contain (9, 7) SWNT. The present
study indicates importance of the main-chain length ofoligofluorenes on sem-SWNT selectivity.
[1] A. Nish et al. Nat. Nanotechnol. 2, 640 (2007).
Corresponding Author: N. Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp– 56 –

Fig.1: Chemical structure ofsynthesized oligofluorenes (FO).

Fig.2: Raman spectra of SWNTs
wrapped by oligofluorenes
and PFO. ex= 633 nm.

FNTG-47, 2014

1P-11

Development of Cap Structure Analysis ProgramżToshiki Sugai1 and Hidehiro Sakurai2
1

1

Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Research Center of Integrative Molecular Systems, Institute for Molecular Science, Myodaiji,
Okazaki 444-8787, JapanA hemispherical or conical carbon aromatic molecule so called “cap” is considered as a tipof carbon nanotubes (CNT) which defines whole CNT structures. Chirally selective CNT cangrow from these caps by adding carbon atoms as hexagonal rings. The structures of the cap
are characterized usually by the location of six pentagons. A semi-spherical C60 cap for (5, 5)nanotube has recently been mass produced with sophisticated organic synthesis[1]. For thedesign of the cap for any target CNT, we need to know correspondence between cap and CNT,
which is difficult intuitively for a cap and a CNT with lower symmetry. The corresponding
algorithms have been reported so far such as a pentagonal defect on graphen sheet[2] andPetrie path[3] both of which are neither based on the molecular structure nor familiar withmost of synthetic chemists. In this study, we present a cap structure analysis program whichclarifies the correspondence of a given
cap to a CNT and that of a given CNT
to any possible cap structures byhandling molecular structures of thecap.
Figure 1 shows the correspondence
between an acute cap with Cs symmetry
and a (5, 5) CNT. The cap has fiveconnected pentagons out of the whole 6
pentagons forming the tip and the one
rest pentagon located on the rim of thecap. The correspondence is obtained byanalyzing the locations of the tip and Fig. 1 Cap and CNT corresponding between an
the rim. The details of the system will acute cap and (5,5) CNT.
be presented.
[1]L. T. Scott, E.A. Jackson, Q. Zhang, B. D. Steinberg, M. Bancu, and B. Li, J. Am. Chem. Soc. 134, 107 (2012)[2]G. Brinkmann, P. W. Fowler, D. E. Manolopoulos, and A. H. R. Palser, Chem. Phys. Lett. 315, 335 (1999).
[3]S. Reich, L. Li, and J. Robertson, Phys. Rev. B 72, 165423 (2005).
TEL: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp– 57 –

FNTG-47, 2014

1P-12

Control of Thermo-Electric Properties of
Semiconducting Single Wall Carbon Nanotubes
by Electric Double Layer Techniques Using an Ionic Liquid○Yuki Oshima, Yoshimasa Kitamura, Shouhei Kanda, Hideki Kawai, Yusuke Nakai,
Yutaka Maniwa, Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Minami-Osawa 192-0397, Japan
Development of high performance thermo-electric devices is of great importance for
efficiently converting waste heat into electric power. To improve the thermo-electricperformance, it is promising to use low-dimensional materials, and to correctly tune theirFermi level. Doping using chemical reagents is a general approach to tune the Fermi level.
However, precise tuning by this approach is rather difficult. Single wall carbon nanotubes(SWCNTs) are one of one-dimensional materials, and recently we have revealed that thesemiconducting SWCNTs networks show very large Seebeck coefficient. [1] To understand thephysical background, it is very important to clarify the relationships between the Seebeckcoefficients and the Fermi level. We have controlled various physical properties of SWCNTs
by tuning the Fermi level through carrier injections caused by electric double layers using anionic liquid.[2],[3] Therefore, in this study, we tried to control the Seebeck coefficient ofsemiconducting SWCNT networks by electric double layer transistor (EDLT) setups, and toreveal the relationships between the Seebeck effect and the Fermi level.
In this study, the semiconducting SWCNTs with diameter of 1.4nm were prepared by using
density gradient centrifugations. The ionic liquid (TMPA-TFSI) was used to form electric
double layers, and then the thermo-electric voltages were measured as a function of appliedchannel voltage.
Figure 1 shows the Seebeck coefficient of the semiconducting SWCNTs as a function ofchannel voltages. As shown here, the Seebeck coefficients were continuously changed, andeven the polarities were changed by the shift of the channel voltage. We found that thisbehavior can be theoretically explained by the Mott’s formula. As a result of analyses, thepeak positions of the Seebeck coefficient well corresponded to the first van-Hove singularitiesof this sample, reflecting the one-dimensional
nature of the semiconducting SWCNTs. Our results
suggest that the EDLT techniques are quite usefulto reveal the relationship between the Seebeckcoefficient and the Fermi level of low-dimensional
materials. The EDLT techniques will be an
essential technique for obtaining the highest
thermo-electric performance from low-dimensional
materials.
[1] Y.Nakai et al. Appl. Phys. Express 7, 025103 (2014).
[2] K.Yanagi et al. Adv. Mater 23, 2811 (2011).
[3] K.Yanagi et al. Phys. Rev. Lett. 110, 086801 (2013).

Corresponding Author: K.Yanagi
Tel: +81-42-677-2494, Fax: +81-42-677-2483,
E-mail: yanagi-kazuhiro@tmu.ac.jp– 58 –

Fig.1: Seebeck coefficient of the
Semiconducting SWCNT networks asa function of Channel voltage

1P-13

FNTG-47, 2014

Alignment of single-walled carbon nanotubes in polymer matrix
using alternating electric field!

○Toshiki Kimura1, Toshiya Murakami 1, Kenji Kisoda2 and Chihiro Itoh1
1 Department of Materials Science and Chemistry, Wakayama University, Wakayama
640-8510, Japan
2 Department of Physics, Wakayama University, Wakayama 640-8510, Japan!

Recently, the conductive polymer films with characteristic properties, like transparent or
anisotropic, are required for developing advanced feature devices. The composites consistingof single-walled carbon nanotubes (SWNTs) and polymers were developed for conducting
film, and it was found that the composites had higher conductivity than that containing carbon
black.[1] However, the SWNTs in the composite are randomly orientated, and hence theproperties attributed to the high aspect ratio of SWNT are not fully utilized. In order to utilize
the anisotropic properties of SWNTs in the composite, the alignment of SWNTs are highly
required. In this paper, we demonstrate that SWNTs are highly aligned in polymer matrix byapplying alternating current (AC) electric field.
SWNTs were grown by chemical vapor deposition using ethanol as the carbon source. The
catalysts and supports attached to the as-grown SWNTs were removed with H2O2/HCl. The
fraction of treated SWNTs was dispersed in a 10 wt% solution of polymethylmethacrylate intoluene. Then, the AC electric field of 280 Vrms at 550 Hz was applied to the SWNT-dispersed solution. After the solution was dried, a plastic film was obtained. The obtained films
were measured by Raman scattering spectroscopy with a probe laser of 532 nm wavelength.
In order to check the SWNT alignment in the polymer matrix, polarized Raman intensity was
discussed.
Figure 1 shows the picture of the polymer film containing aligned SWNTs obtained in thepresent study. The direction of aligned SWNTs is corresponding to that of the applied AC
electric field in SWNT-dispersed solution. Polarized Raman spectra of SWNTs in polymer
matrix are shown in Fig. 2. The G band (1594 cm-1) clearly dependedt on θ, the angle between the direction of the electric vector of the probe laser and that of the applied AC electricfield. The inset in Fig. 2 shows the dependence of the G band intensities on θ. The experimental points were well explained by the function of f(θ)=A+Bcos2θ, where A and B are constants, which indicates that the SWNTs were highly aligned in the polymer matrix.

!
!
!
!
!
!
!
!

Fig.1 SWNT-polymer composite[1] J. Sandler et. al. Polymer. 40 (1999) 5967.
Corresponding Author: T. Kimura, Tel: +81-73-457-8532,
E-mail: s153025@center.wakayama-u.ac.jp– 59 –

Fig.2 Polarized Raman spectra

1P-14

FNTG-47, 2014

Photo-oxidation Reactivity of Individual Single-walled Carbon Nanotube in
Local Enhanced Electromagnetic Field○Takahiro Yoshii1, Mai Takase1, Satoshi Yasuda1,2, Kei Murakoshi1
1Department of Chemistry, Hokkaido University, Sapporo 060-8603, Japan
2
JST-PRESTO, Kawaguchi, Saitama 332-0012, Japan

Utilization of localized electromagnetic field, which is induced by photo-illumination at a
vicinity of plasmon active metal nano-structure, has been attractive attention for photonano-processing field. SWNT is the one of fascinating materials appropriate for novel
nano electric and optical devices 1. In this study, to investigate the possibility of photonano-process of SWNT using localized electromagnetic field, photo reactivity of an isolated
SWNT at local electromagnetic field was studied bysurface-enhanced Raman scattering (SERS) measurement.
The well-defined plasmon active Au nanodimer arrays were
fabricated, and isolated SWNT was supported at the vicinity of the
Au nanodimers. This system allows us to not only provide highly
localized electromagnetic field, but also probe localized optical
200nm
response for an isolated SWNT via SERS measurement (Fig. 1) 2.
SERS measurements were conducted in the N2 saturated and O2 Figure. 1 AFM image ofsaturated 0.5 M H2SO4 solution for metal and semiconductor plasmon active Au
nanodimer arrays.
SWNT (m-SWNT and s-SWNT, respectively). Fig. 2
shows SERS spectra of (a) m-SWNT (b) s-SWNT in O2 (a)D-bandRBM
G-bandsaturated solution at each laser power. With an increase ×0.2
in laser power, the D-band intensity of s-SWNT was
significantly increased, while no apparent change of
0.2 m W
Raman spectra was observed for m-SWNT. In N2
saturated solution, SERS spectra showed no increment
1.0 m Win D-band intensity depending on laser power for both
SWNT. These results strongly indicate that,photo-induced defective structures are produced in-1
Raman shift / cm
s-SWNT under O2 saturated solution. In consideration (b)of previous reports3, it is strongly suggested that×10
0.2 m Ws-SWNTs selectively produce singlet oxygen (1O2) bylocalized electromagnetic field, producing defectstructures by 1O2 reaction with s- SWNT. These results
1.0 m W
implies that selective nano-processing of SWNT is
possible by photochemical reaction induced by theenhanced electromagnetic field, leading to new pathway-1
for nanoscale fabrication of SWNT.
Raman shift / cm
[1] M. Takase et al., Phys. Chem. Chem. Phys., 15 4270 (2013).
[2] M. Takase et al., Nature Photon., 7,550 (2013).
[3] G. Dukovic et al., J. Am. Chem. Soc., 126, 15269 (2004).

Figure. 2 SERS spectra of RBM, D-band
and G-band at 0.2 and 1.0 mW
excitation power for (a) (15, 6)
m-SWNT and (b) (11,7) s-SWNT in O2
saturated solution.

Corresponding Author: K. Murakoshi, Tel: +81-11-706-2704, E-mail: kei@sci.hokudai.ac.jp– 60 –

FNTG-47, 2014

1P-15

Electronic structure of carbon nanotubes with various defects under anelectric field○U Ishiyama and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba
305-8577, Japan
Carbon nanotubes (CNTs) are attracting much attention because of it unique geometricand electronic structures those allow them being an emerging material for semiconductor
electronic devices in the next generation. It has been shown experimentally that CNTs work
as a conducting channel of field-effect transistors (FETs). However, the fundamental
properties of CNTs with hybrid structures under an electric field are not fully understood. In
particular, it is still unclear how the defects introduced into CNT affect the electronic
properties and charge accumulation into CNT under an electric field being one of important
issues for designing the CNT-based electronic devices. In this work, we aim to elucidate thefundamental electronic properties of CNT with various defects under the external electricfield that inject electrons/holes into CNTs.
All calculations are performed by using the density functional theory with local density
approximation. To express the exchange correlation potential among interacting electrons, weapply the local density approximation. We use an ultrasoft pseudopotential to describe theinteraction between valence electrons and ions. The effective screening medium (ESM)
method is applied to investigate electronic properties of CNT with carriers under the electricfield in the framework of the first-principles calculations. Here, we consider (10,0), (11,0),and (12,0) CNTs with the divacancy, C2 adatom, and Stone-Wales defect per triple
periodicities of CNT along their axis. To simulate the CNT-FET device, we consider themodel system in which CNT is located above the planar electrode simulated by the effective
screening medium.
Figure 1 shows the number of accumulated
carriers in (10,0) CNT with divacancy as a functionof the gate electric field. We find that the thresholdgate voltage for accumulating electrons and holes
strongly depends on the relative position of thedefects of nanotubes with respect to the electrode.
Internal electric field in the nanotubes induced by
defects causes the threshold gate voltage variation
for the carrier accumulation.

Corresponding Author: U Ishiyama
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: yishiyama@comas.frsc.tsukuba.ac.jp– 61 –

Fig. 1: The number of accumulated
carriers in (10,0) CNT with the divacancy
as a function of the external electric field.
Circles, triangles, and squares denote thedefect arrangements of θ =0˚, θ =90˚,θ =180˚, respectively.

FNTG-47, 2014

1P-16

Brightening of excitons in ozone doped carbon nanotubes○Gergely Juhasz1, Thomas Niehaus2, Naotoshi Nakashima1
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
Fukuoka 819-0395, Japan
2
Theoretical Physics, Department of Physics, University of Regensburg, D-93040
Regensburg, Germany

Carbon nanotubes have unique luminescent properties, including sharp, well defined
emitting peaks in the NIR region. However, the weak luminescent intensity is a major
disadvantage practical applications. Covalent functionalization of nanotubes often induces
drastic changes in the optical properties. Gosh et al. have reported [1] an ozonization methodthat leads to oxygen doped CNTs with red-shifted, bright peaks in their luminescence
spectrum [2]. This brighter luminescence can have a great practical importance for industry.
For a theoretical investigation of electronic and optical properties of oxygen doped
nanotubes, calculation were performed using Density Functional based Tight Binding (DFTB)
and corresponding TD-DFTB method on infinite (periodic) and finite models of SWCNTs.
This method is capable to handle systems of several hundreds of atoms. In this study weprimarily focused on pristine nanotubes, and nanotubes with ether-like oxygen dopants, whichwere suspected to be responsible for the bright luminescent emission.
A comparison the energetics of different dopant positions has confirmed that in most cases
the ether-like doping is the most stable one, especially at high θ angles. A closer inspection of
DOS and PDOS around bandgap has confirmed that energy levels can shift upon O doping,
however the calculated energy shift-values are significantly lower than the experimentallyobserved red-shift. Such change in the DOS/PDOS profile is also dependent on theconcentration of the O-dopant, which contradicts the observed sharp emission lines.
A deeper analysis of the optical properties using TD-DFTB pointed out a significant
difference between the pristine and tube models. In pristine tubes, there are a handful of low
energy transitions, however the lowest energy ones are optically forbidden. This is inagreement with the presence of dark excitons.
However, in doped nanotubes the transition
correspondingtothelowestenergy(“HOMO-LUMO transition”) become opticallyallowed, which means that the corresponding
dark-exciton brightens up. This mechanism canclearly explain the large red-shift, the observedbrightening and the sharpness of theluminescence peaks at E11*.
[1] S. Ghosh et al. Science. 330, 1656 (2010).
[2] Y. Miyauchi et al. Nature Photonics 7, 715 (2013).
Corresponding Author: N. Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp– 62 –

Fig.1: Proposed mechanism of luminescencein O-doped carbon nanotubes.

FNTG-47, 2014

1P-17

Optimization of graphene transfer onto rough surfaces
for electrochemical cell applications
Gemma Rius, ○Akito Nakagome, Osamu Eryu
Nagoya Institute of Technology, Gokiso, Nagoya 466-8555, Japan
While chemical vapor deposition (CVD) is undoubtedly the most reliable synthetic method
for high-quality, scalable production of graphene, the applications based on CVD-graphene
are often constraint by the necessity to place graphene onto the desired (functional) substrate.
Common graphene transfer route is based on a PMMA layer, as etching-resistant and flexible
media, followed by wet etching of PMMA after graphene relocation. The technique has
indeed demonstrated good capability, in spite of being time and material-consuming.
Additional drawbacks include, for example, that the success of CVD-graphene transfer
based on PMMA-media is often limited by substrate topology, hydrophobicity, etc.
Particularly, wet removal of PMMA in acetone can take away not only PMMA but often takes
graphene too, especially when it consists in small size flakes. This is due to the fact that,
although the bend-ability of both PMMA and graphene is remarkable, full contact ofPMMA-graphene with the support is not completely guaranteed due manipulation.
In this communication we present a
dramatic increase of the throughput of
CVD-graphene transfer onto metal foils,
such as Ti. We apply the methodology
presented by Ruoff’s group [1]. Transfer of
CVD-grapheneonto
microstructured
surfaces was improved by applying athermal treatment before PMMA removal.
Fig.1: (Left) Concept of increasing adhesion ofUsing a temperature higher the melting PMMA-graphene film to Ti foil by means of a heat treatment.
temperature (Tg~125C) of the polymer, (Right) ~50% increase of the EC capacitance of Ti foil
e.g. 180C, better contact of the electrode, by the use of graphene flakes functionalization.
PMMA-graphene layer with the microfabricated substrate could be achieved, which improved
both transfer throughput and graphene planarity. In our case, we have applied a similar
strategy to allow the PMMA-graphene layer to accommodate to a rough metal foil substrate(Fig. 1, left). The introduction of an intermediate thermal treatment in the conventionaltransfer process sequence brought us an increase of the Ti surface covered by (transferred)graphene from <20% to 95% success, as understood by Raman spectroscopy.
Hybrid graphene-metal materials can be used as electrode materials for electrochemical(EC) cell applications. For instance, in-plane graphene-Ti substrates showed higher electrical
capacitance with respect to bare Ti foils (Fig. 1, right) [2] while not substantially increasing
the weight and volume of the electrode. Transferred graphene not only implies an increase of
surface area, towards higher-performance supercapacitors, but may provide corrosion
protection to the structural metal electrodes or specificity for sensing.
[1] J. W. Suk et al. ACS Nano 5, 6916–6924 (2011).
[2] G. Rius et al. J. Nanomaterials (Under rev. 2014).
Corresponding Author: A. Nakagome
Tel: +81-52-735-5909
E-mail: cix14090@stn.nitech.ac.jp– 63 –

1P-18

FNTG-47, 2014

Selective Detection of Immunoglobulin M
Using Reduced Graphene Field-Effect Transistors
Modified with Fragments○Sachiko  Tanikawa1, Ryota Negishi1, Michihiro Matsuzaki1,
Yasuhide Ohno2, Kenzo Maehashi2, Kazuhiro Matsumoto2 and Yoshihiro Kobayashi1
1Department of Applied Physics, Osaka University, Suita, 567-0871, Japan
2
ISIR, Osaka Univeersity, Ibaraki, 567-0047, Japan

Reduced graphene oxide (rGO) has attracted considerable interest by virtue of the relative
ease to synthesise wafer-scale graphene thin films and thereby apply to scalable integration offield-effect transistor (FET) biosensors. Our previous work has demonstrated that it ispossible to selectively detect immunoglobulin E (IgE) using rGO FETs functionalised withaptamers [1]. Alongside aptamers, antibodies are known to bind antigens with specificity andaffinity and are in general use due to their versatility to bind various antigens. However,antibodies themselves, which are typically larger than the Debye length, cannot be exploited
due to the effect of counter-ion shielding. This work demonstrates that this problem can besurmounted by the use of antibody fragments and presents the selective detection of IgM
using rGO FETs.
The Debye length and the size of anti-IgM fragments are approximately 5 nm and 3 nm
respectively. Therefore, the adsorption of IgM is expected to occur within the Debye length,
which corresponds to the effective distance from the surface for analytes to be detected. rGO
FETs were fabricated by conventional lithography method. Anti-IgM fragments were
immobilised onto the rGO channels in order toPotentiostat
achieve selective detection. The data was acquired
CERE
WE: Ag/AgCl
by measuring the current across the source anddrain (Isd) over time. Throughout the measurement～5 nm
the gate voltage was kept constant using abipotentiostat and Ag/AgCl reference electrode as
SourceDrain
Grapheneelectrodeelectrode
SiO2/Si
shown in Figure 1.
CE
RE
ＷE
The result shows no change in Isd when bovine
Potentiostat
serum albumin (BSA) is injected and a decrease
IgM
Antibody fragments
when 1  μM  and 100 nM IgM is added (see Figure 2).
Not only does this demonstrate the selectivity Figure 1: Experimental setup showing
against IgM, this also indicates that IgM are bound IgM bound to anti-IgM fragments within
the Debye length.
within the Debye length.
The detection of IgM using rGO FETs is presented
that utilise antibody fragments for selective IgM
capture. The use of antibody fragments is probably
effective for the selective detection of various
proteins including IgM. Frthermore, rGO can beextended to large areas. The result presented here
implicates potential for FET arrays that enable
simultaneous detection of many different analytes.
[1] Matsuzaki, M. et al.. The 74st Autumn Meeting ofJapan Society of Applied Physics and Related Societies.
16p-B1-8 (2013)
Corresponding author: Sachiko Tanikawa
E-mail: tanikawa@ap.eng.osaka-u.ac.jp– 64 –

Figure 2: Isd versus time showing
non-specific (BSA) and specific (IgM)
adsorption.

1P-19FNTG-47, 2014

Synthesis and electrocatalytic activities of Pt-based nanoparticles supported
on ion-irradiated carbon materials○1Shohei Hayase, 1Haruhiko Yoshitake, 2Tomoaki Nishimura, 4Wang Zhipeng
and 1,2,3Hironori Ogata
1

Graduate School of Science and Engineering, Hosei University Koganei 184-8584, Japan
2
Research Center of Ion Beam Technology Hosei University Koganei 184-8584, Japan
3
Research Center for Micro-Nano Technology,Hosei University,Koganei 184-0003,Japan
4
Institute of Carbon Science and Technology, Shinshu University, Nagano 380-8553, Japan
Pt nanoparticles supported on the carbon materials are known to exhibit high methanoloxidation activity and it is expected use as an anode materials of direct methanol fuel cell
(DMFC). As is well-known, the highly dispersed Pt-based alloys on carbon supports as wellas catalyst particle size and shape plays a dominant role in the electrochemical performancefor fuel cells. We have explored the carbon nanomaterials with different microstructures,
including Carbon nanosheets(CNSs), Single-Walled Carbon Nanotubes(SWNTs) and HOPG
as a catalyst support for Pt-based nanoparticles by one-step electrodeposition and revealed
their methanol oxidation activites. In this study, the effects of surface modification by
ion-irradiation of carbon materials on their support properties of Pt-based nanoparticles andtheir methanol oxidation activites were investigated to clarify the relationship between themethanol oxidation activities and their local structures. The ion beam accelerated withcarbon ion source with 200 keV were irradiated to the carbon materials with 1 ×1013, 1 ×1014, 1 × 1015 ions/cm2. Figure.1 shows the ion irradiation dose dependence of the CV
responses of Pt/HOPG in (a)H2SO4 solution and (b)CH3OH+H2SO4 aqueous solutions.
Table.1 shows their electrochemical characteristics of methanol oxidation. The detailed
results on the relationship between the condition of electrodeposition, the chemicalcompositon of Pt nanoparticles and their electrocatalytic performances will be presented.
12Without irradiation
  1×1013 ions/cm2
  1×1014 ions/cm2
  1×1015 ions/cm2

10
6

1
0

4
2
0
-2
-4
-6
-8

-1
-2
-3
-4
-5
-6
-7

-10
-0.4

Without irradiation
1×1013 ions/cm2
1×1014 ions/cm2
1×1015 ions/cm2

2

Current density
2[mA/cm ]Current density
2[mA/cm ]

8

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

-8
0.0

Potential [V,vs Ag/AgCl]

0.2

0.4

0.6

0.8

1.0

Potential [V,vs Ag/AgCl]

Figure 1. CV responses of Pt/HOPG in (a)H2SO4 solution and (b)CH3OH+H2SO4 aqueous
solutions.
Table.1 Electrochemical characteristics of methanol oxidation

1) Zhipeng Wang, Mao Shoji and Hironori Ogata, Appl. Surf. Sci.259(2012)219-224.
Corresponding Author: Hironori Ogata,Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp– 65 –

1P-20FNTG-47, 2014

Copper intercalation in graphene on SiC(0001)°M. Imai1, W. Norimatsu1, M. Kusunoki1, 2
1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University,
Nagoya 464-8603, Japan
2. EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan
Graphene is expected to be one of the next-generation electronic materials because of itsvery high carrier mobility and mechanical properties. Graphene can be grown by SiC surface
decomposition. It is widely known that graphene on SiC has lower carrier mobility than the
exfoliated graphene because of the carrier scattering by the interface layer, called a buffer
layer. Then, the carrier mobility would be improved by the interface modification, such as
intercalation of other elements between the buffer layer and the SiC. In past reports,
intercalation of hydrogen, germanium, silicon, gold, and copper, was reported, which was
confirmed by LEED and ARPES experiments [1]. However, the direct observation ofintercalation has not yet carried out, so we tried to directly observe the copper intercalation bya transmission electron microscope (TEM).
Graphene was prepared by heating the SiC substrate at 1575℃ for 30 min, in Ar 6 atm. Cu
nano-particles were deposited on graphene/SiC by evaporation method. After copper
deposition, the substrate was annealed at 450℃    for 3 hr. Atmosphere during annealing wasthree patterns, (1) in a high vacuum (10-4~10-5 Torr), (2) under Ar flow (2.0L/min), and (3)under Ar+H2 flow (2.0 L/min). The obtained samples were analyzed by TEM, XPS, andRaman spectroscopy.
Figure 1 shows TEM images and Raman spectra of the sample after annealing at 450℃  for3 h under Ar flow. As can be seen in the image, the distance between SiC and graphene was
6.05Å.Which is significantly larger than the one of typical graphene on SiC. In addition, we
can find the obscure periodic contrast with an averaged distance of 4.07Å, as shown byarrows in the image in (b). These results strongly suggest that copper atoms are intercalated
between graphene and SiC. The appearance of the strong 2D peak in the Raman spectrum
after annealing also indicates that the buffer layer converted to graphene by copper
intercalation.
(a)graphene

10 nm

SiC

(c)

(b)
graphene

SiC

1 nm

Fig. 1 (a) TEM images of graphene with Cu after heating at 450℃×3 h in Ar flow. (b) Enlarged view of (a).
(c) Raman spectra of graphene with Cu nano-particle.
[1] C. Riedl, et al., Phys. Rev. Lett., 103, 246804 (2009), K. Emtsev, et al., Phys. Rev. B 84, 125423 (2011), C.
Xia, et al., Phys. Rev. B 85, 045418 (2012), I. Gierz, et al., Phys. Rev. B 81, 235408 (2010), K.Yagyu, et al.,Appl. Phys. Lett., 104, 053115(2014).
Corresponding Auther: M. Imai
Tel: 052-789-5859, Fax: 052-789-5859,
Email: imai.masato@a.mbox.nagoya-u.ac.jp– 66 –

FNTG-47, 2014

1P-21

Effect of water molecules in trapping carbon dioxide molecules inside theinterlayer space of graphene oxides○Ayumi Yamasaki1, Takashi Yumura1, Takashi Wakasugi1
1

Department of Chemistry and Materials Technology, Kyoto Institute of Technology,
Matsugasaki, Sakyo-ku, Kyoto, 606-8585, Japan.

Graphene oxide (GO) have a potential to trap carbon dioxides, according to recent
experimental studies[1]. We are interested in how a CO2 molecule is trapped between GO
layers. We employed PBE DFT calculations under periodic boundary conditions to investigate
the energetics of CO2 migration within hydrated or anhydrous GOs. Our supercell contains 64
carbon atoms attached by some epoxy and hydroxyl groups plus intercalated water molecules,
abbreviated by C64O4(OH)16•nH2O. When anhydrous GO structures contain a CO2 molecule,the CO2 interacts repulsively with the GO layers to increase the interlayer spacing. The
repulsive electrostatic interactions are reduced by the insertion of water molecules into
CO2-containing GO structures due to the occurrence of attractive water–layer interactions
through hydrogen bonding. Consequently, the interlayer spacings in CO2-containing hydrated
structures are shortened compared with the anhydrous cases. The results indicate that theintercalated water molecules have the ability to connect the GO layers in the presence of CO 2.
Furthermore, the DFT calculations indicated that the GO interlayer spacings control CO2
migration within the layers. The importance of the interlayer spacings on the migration of
CO2 arises from the occurrence of repulsive interactions between CO2 and oxygen-containing
groups on the graphene sheets. We calculated the energetics of CO2 migration within hydrated
or anhydrous in GOs layers. We obtained the transition states of the CO2@C64O4(OH)16•
nH2O structures, respectively. The activation energy for CO2 migration is sensitive to thenumber of water molecules. The energy values decrease from 44.0 to 8.4 kcal/mol when ndecreases from 2 to 0 (Fig.1). The results can be understand as follow. When the GOinterlayer spacings are short due to the presence of intercalated water molecules, the repulsive
interactions between CO2 and the GO layers are strong enough to prevent CO2 from migratingfrom its original position. Such repulsive interactions do not occur during the migration of
50
CO2 within anhydrous structures because of therelatively longer interlayer spacing. Accordingly, CO240
migrates within anhydrous GO with a less significant
barrier, indicating that CO2 molecules are easily
30
released from the GO. In the repulsive interactions
during CO2 migration, water molecules play two roles.
20
One role is that water molecules directly repel CO2
n=2
10
through electrostatic interactions. The other role isn=1that water molecules connect the two GO layers
n=00
through hydrogen bonds. The two layers being
0
1
2
3
4
closely separated strongly repel CO2.
Fig.1: Energy profiles of the migration of CO2
within the C64O4(OH)16•nH2O structures.

[1] S. Eigler et al. Chem. Mater. 24, 1276-1282 (2012).
[2] T. Yumura, A. Yamasaki. Phys. Chem. Chem. Phys. 16, 9656-9666 (2014).
Corresponding Author: T. Yumura
Tel: +81-75-724-7571, Fax: +81-75-724-758, E-mail: yumura@chem.kit.ac.jp– 67 –

1P-22

FNTG-47, 2014

Characterization and photoluminescence of individual graphenenanosheets by electrochemical exfoliation of graphite○Li-Hung Lin1, Tzong-Yuan Juang2, Sin-Rong Jhan1, Chien-Jen Chen1
1

2

Dep. of Electrophysics, National Chiayi University, Chiayi 60004, Taiwan
Dep. of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan

Graphene shows much uniqueness in many ways in its characteristics, including its
quantum transport in magnetic conductivity. Although graphene sample preparation
can be done by pure mechanical methods in laboratories, suitable mass-productive
methods for graphene sheet are necessary for applications. It has been shown thatgraphene sheet prepared by chemical methods still showed quantum transportcharacteristics at low temperature [1].
We studied the possibility of a facile and novel electrolysis method to prepare highquality graphene sheets through graphite interlayers, thereby exfoliating the layer
spacing. The exfoliation mechanism of graphite cathode into individual graphenenanosheets through exfoliate processes will be revealed. First, we use an electrolysis
approach, involving direct molecular exfoliation of graphite stacked layers, to obtain
individual graphene platelets under various cell voltage with appropriate surfactants.
Varying the cell voltage (12 V, 8 V and 4 V) versus time curve of an electrolysis
experiment allowed us to determine the exfoliate behavior from morphologicalobservations made using TEM, XRD, X-ray photoelectron spectroscopy (XPS), andRaman spectroscopy (Fig. 1). Next, the photoluminescence properties andnanostructure of resulting well-dispersion graphene nanosheet, such as carbon
nanostructure and basal spacing have be thoroughly investigated. Under the four cellvoltages, the resulting graphene nanosheets possess less defects structure by Raman
spectropscopy. XPS also indicated the less oxidic layer under lower electric voltage.
TEM image indicated that our graphenenanosheets in water to form an ultrathin
nanoplatelets with a diameter ranging from
2 to 10 µm. The resulting graphenenanosheets were soluble in water anddimethylformamide. It is interesting thatthe strong fluorescence emission wasobserved at 450 nm in aqueous media forresulting graphene nanosheets. Thissolution-phase methodology, throughelectrolytic exfoliation approach, provides
the way toward obtaining individual
nanosheets, opening up opportunities for ,Fig.,1.,Raman,spectroum,for,graphene,
platelet-like nanographene materials in
prepared,at,various,cell voltages.,semiconductor industry and drug delivery
systems.
[1] C. Chuang et al., Appl. Phys. Lett. 103, 043117 (2013).
Corresponding,Author:,L.4H.,Lin,
Tel:,+8864542717410,,Fax:,+8864542717909,
E4mail:,lihung@mail.ncyu.edu.tw,– 68 –

1P-23

FNTG-47, 2014

Free-electron carriers outside graphene nanoribbon by an electric field○Ayaka Yamanaka, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba
305-8577, Japan
Electric field occasionally affects the electronic structure of graphene and graphite. In thecase of bilayer graphene under the normal electric field, the metal-semiconductor-metaltransition occurs with increasing the electric field. Similar electronic structure modulation
also found in the graphene nanoribbon under the lateral electric field. In the case, we foundthat the lateral electric field basically opens or increases the energy gap of the ribbons [1].
However, it is still unclear how the electronic structure of the ribbons is further modulated by
the strong lateral electric field. Thus, in this work, we study the electronic structure ofgraphene nanoribbons under the lateral electric field to investigate the possibility for injectionof free carriers outside the ribbons based on the density functional theory with combining
the effective screening medium method.
We applied the lateral electric field to the graphene nanoribbons with armchair and zigzag
edges and analyzed the electronic structure to uncover how the electric field affects on theelectronic structure. As shown in Fig. 1, we found that the quadric dispersion band at the point in the conduction band shifts downward withincreasing the electric field. The state possesses
unusual feature: The wave function of this state is
distributed in the vacuum region outside the grapheneribbon (Fig. 2). Thus, this state possesses similarfeature to the nearly free electron (NFE) state ofgraphene which is distributed above the graphene
layer. Moreover, with further increasing the electricfield, we find that NFE state crosses Fermi levelindicating the electron injection into this peculiar freeelectrons state in graphene nanoribbons.

Fig.2: Wave function distribution of NFE state located at thevacuum region next to the graphene edges.
[1] A. Yamanaka, in preparation.
Corresponding Author: A. Yamanaka
Tel: +81-29-853-5600 (ext. 8233),
Fax: +81-29-853-5924,
E-mail: ayamanaka@comas.frsc.tsukuba.ac.jp– 69 –

Fig.1: Electronic structure of graphene
nanoribbon with zigzag edges. The
gray line indicates the NFE state.

1P-24

FNTG-47, 2014

Structure Analysis of Multilayer Graphene using X-ray Diffraction○Naoki Nunoyama1, Haruka Kyakuno1, Yusuke Nakai1, Yasumitsu Miyata1,2,
and Yutaka maniwa1,
1

Department of Physics, Faculty of Science, Tokyo Metropolitan University, Hachioji, Tokyo
192-0397, Japan
2
JST, PRESTO, Kawaguchi, Saitama, 332-0012, Japan

It has been reported that physical properties of multilayer graphene are sensitive to thenumber of graphene layers (N) [1], as well as interlayer spacing and stacking sequences.
Therefore, it is important to establish a method to clarify the structure of the multilayer
graphene. N, which is not larger than five, can be estimated by Confocal Raman spectroscopy[1]. There are also reports in which N can be estimated using conventional X-ray diffraction(XRD) method [2], based on Bragg’s law and Sherrer’s equation. In this study, we examinedfurther the possibility of powder XRD method to obtain detailed structures of multilayer
graphene.
We performed XRD measurements at KEK-PF, BL8B. The obtained patterns are shown in
Fig. 1 and were simulated for model multilayer graphenes using the Debye formula [3],
! ! =

!! !!

!"# !!!"!"!"!.

Figure 2 shows the simulated patterns as a function of N at a fixed interlayer distance of
d002=3.3555 Å. The (002) peaks around Q=1.8 Å -1 represent multilayer structure for modelgraphenes with N ≥ 2 . The (002) peak becomes broader, and shifted toward the lower Q
region with decreasing N even though the d002 was fixed. The calculated results show that the(002) peak structures depend on N and d002. We performed structure analysis by comparing
the (002) peak of the observed and simulated patterns. As a result, we found the most suitable
N and d002 for the present sample as shown in Fig.1. Thus, we believe that powder XRD canbe applied to multilayer graphene to obtain their detailed structural information.

Intensity (arb. units)

Intensity (arb. units)

10

0

1

2

3

4

5

6

8
6

1

0.8

7

1

1.2

2

1.4

4
3

1.6

1.8

2

2.2

2.4

Q (1/Å)Q (1/Å)Fig. 1 Observed and simulated patterns.
Solid line: observed. Dashed line: simulated
pattern with N = 5 and d002=3.4700

Fig. 2 Simulated powder patterns with N = 1,
2, 3, 4, 6, 8, 10 and d002=3.3555

[1] Ferrari AC et al. Phys. Rev. Lett. 97, 187401(1-4) (1996).
[2] Huh SH. Physics and Applications of Graphene-Experiments. Chap. 5. INTECH. (2011).
[3] Kittel C. Introduction to solid state physics. 8th ed. john Wiley & Sons. Inc. (2005).
Corresponding Author: Yutaka Maniwa, Tel: +81-42-677-2490, E-mail: maniwa@phys.se.tmu.ac.jp– 70 –

FNTG-47, 2014

1P-25

Absence of Raman G' Band by Ultraviolet Excitation in
Monolayer Graphene Systems○ Syahril Siregar, Eddwi H. Hasdeo, Ahmad. R. T. Nugraha, and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
In this work, we investigate the G band and G' band Raman spectra of single layer graphene
theoretically for several laser excitation energies (EL), from ultraviolet to long-wavelength
visible light region, such as 266 nm, 355 nm, 532 nm, and 785 nm. To calculate the Raman
spectra utilize phonon dispersion obtained from a force constant model considering up totwentieth nearest neighbor [1] and the electron-photon with electron-phonon matrix elements
obtained within the extended tight binding model [2]. The G band (G' band) here is calculated
by considering resonance (double resonance) Raman process.
We find that the integrated intensity result of G band is proportional to EL 4. This results
agrees with the experimental results [3], however the integrated intensity of G' band isinversely proportional to the EL, which leads to the absence of the G' band in the high EL. In
this case, there is no G' band peak in the ultraviolet region, i.e. the 266 nm EL. This result is
consistent with the experimental result which also shows the absence of G' band [4]. We
expect that the absence of the G' band in the ultraviolet region is not caused by theelectron-phonon matrix elements, but the contribution from the electron-photon matrix
elements. In the Raman intensity formula, the electron-photon matrix elements consist of two
terms; emission and absorption. The Emission and absorption electron–photon matrix
elements might cancel each other when we increase EL. Therefore, by studying the G' band ofgraphene in the ultraviolet region we can understand more the double resonance Ramanprocess.
[1] G. Samsonidze, Photophysics of Carbon Nanotubes, M.I.T Ph.D. thesis (2007).
[2] K. Sato et al., Chem. Phys. Lett. 427, 117 (2006).
[3] L. G. Cancado, A. Jorio, and M.A. Pimenta, Phys. Rev. B 76, 064304 (2007).
[4] Hsiang Lin Liu et al., unpublished (2014).
Corresponding Author: Syahril Siregar
TEL: +81-22-795-5719, FAX: +81-22-795-6447
E-mail: siregar@flex.phys.tohoku.ac.jp– 71 –

FNTG-47, 2014

1P-26

Polarization dependence of ARPES intensity in graphene○  Pourya Ayria, Ahmad R. T. Nugraha, Eddwi H. Hasdeo and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
In this work, we report the light polarization dependence of angle resolved photoemission
spectroscopy (ARPES) in graphene based on a first-principles calculation [1]. In ARPES, If theenergy of photo-excited electrons surpasses the work function of the sample, the electrons are
emitted from surface. The electron kinetic energy and momentum parallel to the surface areobserved by the analyzer from which we directly get information of electron energy dispersion as
a function of wave vector [2]. The polarization dependence of ARPES intensity comes from thematrix elements of electron-photon interaction. The matrix elements effects can be separated into,(1) a polarization factor and (2) an interference term which relates to crystal structure [3,4]. Ingraphene, the in-plane light polarization can determine the electronic chirality, the Berry phases
and hopping integrals between nonequivalent orbitals, in ARPES intensity [5,6].
However, most of the pervious works have discussed the in-plane polarization dependences. In
our study, we found that the ARPES intensity shows a strong dependence of polarization
perpendicular to graphene plane which it can be important due to, not only determining thesymmetry of the electronic states but also identifying the π and σ   bands because of different
intensity respect to these two polarizations. The study of ARPES intensity distribution of thevalence bands with these different light polarization presents that the initial state has even or odd
symmetry with related to the mirror symmetry plane for π and σ bands respectively. The intensityof π band decreases dramatically by employing light polarization perpendicular to surface, while
the intensity of σ  bands increase. In addition, the electron dispersion relation of graphene up to 70
eV is calculated in order to consider the effects of final states of excited electron in this opticaltransition process. The calculated results of polarization dependence as a function of incident
light energy near Dirac point are directly compared with recent experiments [5,6].
[1] Paolo Giannozzi et al., J. Phys.: Condens. Matter 21 395502 (2009)[2] A. Damascelli, Rev. Mod. Phys 75, 155414, 473 (2003)[3] E. L. Shirley et al. Phys. Rev. B 51 , 13614 (1995).
[4] I. Gierz et al. Phys. Rev. B 83, 121408 (2011).
[5] Y. Liu et al., Phys. Rev. Lett. 107, 166803 (2011)[6] C. Hwang et al., Phys. Rev. B 84, 125422 (2011).
Corresponding Author: P. Ayria
TEL: +81-22-795-6442, FAX: +81-22-795-6447,
E-mail: pouryaayria@flex.phys.tohoku.ac.jp– 72 –

FNTG-47, 2014

1P-27

Propagation Properties of Graphene Surface Plasmon○  Muhammad  Shoufie  Ukhtary,  Eddwi  H.  Hasdeo,  Ahmad  R.T.  Nugraha,  and  Riichiro  Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan

In this work, we discuss the propagation behavior of graphene surface plasmon by considering a
distributed circuit model. It is known that doped graphene can sustain surface plasmon whose
frequency can be in range of infrared and terahertz [1]. This graphene surface plasmon cantransmit signal from source to a device in which the signal will be used [2]. This mechanism
enables graphene to behave just like transmission lines. The properties of graphene surface
plasmon can be described by its frequency dispersion and velocity of transmission. Calculating
the plasmon dispersion and its velocity is very important to design plasmonic devices based ongraphene. Kumada et al has shown the behaviour of plasmon velocity with a metal gate
attachment on graphene [5]. However, their observed values are different to the theoreticalresults done by Sasaki et al [3].
Here, we employ the distributed circuit model, which is usually used to explain the signaltransmission in transmission lines, to explain the propagation of graphene surface plasmon.
Energy propagation, signal frequency dispersion, group velocity and losses can be obtained bythis model [4]. The model basically treats each component of system as circuit component
𝐿, 𝑅, 𝐶 and the current-voltage relationship   can   be  acquired  from   Kirchoff’s law. We consider
the graphene system to consist of a series of resistor R , magnetic inductance L , kinetic
inductance L , and then paralleled to quantum capacitor C [2]. At a high signal frequency, we
expect no loss on the circuit, and the velocity of propagation will be constant. It means that all
the frequency component of signal travels at the same speed. The losses appear at low signal
frequency due to ohmic loss on R, and the velocity of propagation is no longer constant, but
frequency-dependent [2]. Kumada et al show that frequency and velocity are tuned by adding a
metal gate and changing the voltage [5]. The circuit model then should also include thegeometrical capacitor C . We show that the circuit model can explain the group velocity
difference with and without metal and it can explain the experimental results in which theobserved group velocity is much slower than the theoretical values.

[1] Y. V. Bludov et al., Int.J.of Mod.Phys B Vol. 27, No. 10 341001(2013).
[2] H.-S.P.Wong et al., “ Carbon Nanotube and Graphene Device Physics”, Cambridge
University Press (2011).
[3] Sasaki et al., arXiv:1404.2763v1 (2014).
[4] S. Ramo et al., “ Fields and Waves in Communication Electronics”, Wiley (1994).
[5] N. Kumada et al., New Journal of Physics 16 063055 (2014).
Corresponding Author: Muhammad Shoufie Ukhtary
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail:shoufie@flex.phys.tohoku.ac.jp– 73 –

1P-28

FNTG-47, 2014

Electrochemical Characteristic Evaluation of Graphene/Au(111) by STM○Ryota Kumagai1, Shino Sato1, Satoshi Yasuda1, 2, Kei Murakoshi1
1Department of Chemistry, Hokkaido University, Sapporo 060-8603, Japan
2
JST-PRESTO, Kawaguchi, Saitama 332-0012, Japan

Introduction
Graphene, a two dimensional carbon material, has recently attracted attention as support
material on metal catalysts due to high conductivity and high affinity with the metal catalyst.
To further develop and improve the catalytic activity supported graphene, fundamental
research related to an electronic and surface structure of graphene/metal is one of thesignificant issues. In this study, we synthesized single monolayer graphene on Au(111) bychemical vapor deposition (CVD) technique and investigated the surface structure ofgraphene/Au(111) by using electrochemical STM (EC-STM).
Experiment
The Au(111) facet formed on a single crystal bead was prepared by the Clavilier method.
Graphene grown on the Au(111) by CVD using methane as carbon source. Synthesizedgraphene was characterized by raman spectroscopy using a 532 nm excitation laser. Surface
structure of the sample was investigated by EC-STM in 0.1M H2SO4 solution.
Results and Discussioin
Fig.1 shows representative Raman spectra for agraphene/Au(111). Three Raman features of graphene
were clearly observed, and 2D/G ratio and FWHM of
2D band were approximately 2 and 30 cm-1, indicatingthat produced graphene is single monolayer.
EC-STM of graphene/Au(111) was conducted toinvestigate electrochemical feature. Fig.2 is typical
EC-STM image of graphene/Au(111) in 0.1M H2SO4
solution with an electrode potential held at Esample = +1.09 V (vs Ag/AgCl). EC-STM measurement revealed
that single monolayer graphene is produced on areconstructed Au(111) structure. Additionally,
potential sweep measurement demonstrated that unlikebare reconstructed Au(111) surface, the graphene
covered reconstructed structure stabilized at wide
electrochemical potential range. These results strongly
indicate that coverage of graphene on metal surface
dramatically change the electrochemical response of
the metal and will have high potential the creation ofnovel electrochemical reaction on metal surface.
Corresponding Author: K. Murakoshi
TEL & FAX: +81-(0)11-706-2704
E-mail: kei@sci.hokudai.ac.jp– 74 –

Figure.1 Typical Raman spectra
for a graphene/Au(111).

Figure.2 STM image of agraphene/Au(111) (It: 2.0 nA, Etip: 0.02 V, Esample: + 1.09 V vs. Ag /AgCl). Inset : higher magnification
STM image (It: 2.5 nA, Etip: - 0.02
V, Esample: + 0.43 V vs. Ag / AgCl).

1P-29FNTG-47, 2014

Optical properties of transition metal dichalcogenides
grown by thin-film sulfurization○Eri Inukai1, Yu Kobayashi2, Yasumitsu Miyata2,3,*, Yutaka Maniwa2, Hisanori Shinohara1,*
1

2

Department of Chemistry, Nagoya University, Nagoya, 464-860
Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397
3
JST, PRESTO, Kawaguchi, 332-0012

Atomically-thin transition-metal dichalcogenides (TMDCs) have attracted much attention
because of their tunable electronic properties and unique spin-valley physics. Recently,
TMDC samples can be prepared by various methods such as mechanical exfoliation, chemical
vapor deposition, and thin-film sulfurization. However, in many cases, the quality of thesesamples is unclear even though its importance in various applications. This is mainly causedby the lack of a quantitative method to check sample quality. To evaluate the quality, we focus
our attention to a photoluminescence (PL) peak derived from localized exciton states, because
this peak is suggested to relate to defects and/or impurities [1].
In this study, we have investigated the low-temperature PL spectra of monolayer MoS2
and WS2 synthesized by thin-film sulfurization. The monolayer MoS2 and WS2 weresynthesized through the thermal annealing of oxide films on Si substrates under argon/sulfur
atmosphere as reported previously [2]. Photoluminescence spectra of the samples were
measured for 79 ~ 473 K under vacuum. At around room temperature, both the samples show
PL peaks derived from free excitons,
while, under 200 K, the broad, boundexciton peak appears at lower energy
only for MoS2, (Fig.1A). Interestingly,
the present peak can be seen at higher
temperature compared with theprevious report [1]. This result suggeststhat these PL peaks reflect the sample
quality, and could provide an insight tocontrol such localized exciton state for
future optical applications.

Fig.1 Photoluminescence spectra of (a) MoS2 and (b) WS2
for different temperatures.

[1] T. Korn, et al., Appl. Phys. Lett. 99 (2014) 102109.,[2] S. Mori, et al., The 46th Fullerenes-Nanotubes-Graphene General Symposium.
Corresponding Authors: Yasumitsu Miyata, Hisanori Shinohara,
Tel: 042-677-2508, 052-789-2482, E-mail: ymiyata@tmu.ac.jp, noris@nagoya-u.jp– 75 –

1P-30FNTG-47, 2014

Electronic and Geometric Structures of Novel Two-dimensional Materials
Consisting of C36○Mina Maruyama and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8571, Japan
Fullerenes are known to form various condensed phases in which the fullerenes act as abuilding block with/without morphological changes. The electronic structure of thesecondensed phases strongly depends on dimensionality and network topologies. For instance,
under ambient condition, C60 are weakly bound to its adjacent molecules leading to aface-centered cubic (fcc) phase. Besides the fcc phase, polymeric phases of C60 have beensynthesized by applying the high pressure under the elevated temperature and irradiating rightto fcc C60. In the polymeric phases, C atoms form one-, two-, and three-dimensional covalent
networks those result in interesting structural and electronic properties which are totallydifferent from those in fcc C60 solid. Here, we focus on small fullerenes solid which are
expected to inherently have a polymeric or clathrated structure due to its remarkable chemical
reactivity. We study the geometric and electronic structures of the novel two-dimensional
covalent network consisting of a C36 polygon based on the density functional theory (DFT)with local density approximation (LDA).
Figure1 shows optimized structures of polymerized C36. We find three stable structures ofwhich lattice parameters are 4.6 A, 5.2 A, and 6.0 A. Under the lattice parameter of 4.6 A,
polymerized C36 is a semiconductor with indirect band gap of 3.5 eV. Under the lattice
parameter of 5.2 A, the
(b)
(c)
(a)
polymerized C36 is asemiconductor
withindirect band gap of 2.0
eV. In contrast to thesetwo phases, under thelattice parameter of 6.0
A, polymerized C36 is ametal. The geometricstructures of these threephases are tunable byapplying lateral strain
leadingtothemetal-semiconductortransition.
Figure 1: Geometric structures of polymerized C36. (a) Optimized
lattice parameter a = 4.6 A, (b) 5.2 A, and (c) 6.0 A.
Corresponding Author: Mina Maruyama
E-mail: mmaruyama@comas.frsc.tsukuba.ac.jp
Tel: +81-29-853-5600(ext: 8233)– 76 –

FNTG-47, 2014

1P-31

1,3-Dipolar Addition of Triphenylmethyl to Sc2C2@C3v(8)-C82○Wenting Cai, Yunpeng Xie, Xing Lu*
State Key Laboratory of Materials Processing and Die & Mould Technology, School ofMaterials Science and Engineering, Huazhong University of Science and Technology, 1037
Luoyu Road, Wuhan 430074, China
Functionalized endohedral metallofullerenes (EMFs), which bear more amazing properties
than the pristine ones and hollow fullerenes, has stirred plenty of interest and has been
extensively investigated. To date, according to the relatively high production yield, mostresearches focus on conventional EMFs and metal nitride cluster EMFs so that their chemical
properties has blossomed to afford many meaningful results related to the dictation effect of
the internal cluster on the cage carbons. However, severely limited results about the chemical
properties of carbide cluster metallofullerenes (CCMFs) have been reported.[1]Herein, we presented the first 1,3-dipolar reaction of the most abundant scandium carbide
EMFs Sc2C2@C3v(8)-C82 with 3-triphenylmethyl-5-oxazolidinone (1). Only one monoadduct
Sc2C2@C3v(8)-C82(CH2)2NTrt (2) was obtained and successfully isolated for various
measurements. Single-crystal X-ray crystallographic results of 2 reveal that the substituent
group is linked to a [6,6]-bond junction of the cage, which is far from either of the two Sc
atoms. Thus, the addition shows neglectable influence on the position and orientation of the
carbide cluster relative to the cage. Electronic and electrochemical results confirm that 2 ismore stable than pristine Sc2C2@C3v(8)-C82 as a result of a larger HOMO-LUMO gap. On thebasis of theoretical calculations, it is worth noting that an unexpected reactivity concentrated
hexagon is found on Sc2C2@C3v(8)-C82 due to the overlap of high POAV angels and large
LUMO coefficients. What is more important is that this region would not be detected on
C3v(8)-C82 in the absence of the carbide cluster. Considering the cluster orientation, we
concluded that this feature is expected to be a general phenomenon in the chemical propertiesof carbide EMFs.

Fig.1: Addition positions of three Sc2C2@C3v(8)-C82 derivatives. Only the predominant Sc atoms are shown forclarity;(a)
Sc2C2@C3v(8)-C82Ad;[2](b)(μ-H)3Re3(CO)9(η2,η2,η2-Sc2C2@C3v(8)-C82;[3](c)Sc2C2@C3v(8)-C82(CH2)2NTrt. The reactivity concentrated hexagon on the cage of Sc2C2@C3v(8)-C82 isindicated by an arrow.
[1] X. Lu, T. Akasaka, S. Nagase. Acc.Chem.Res. 1627-1635, 47 (2013).
[2] Y. Iiduka et al. Angew. Chem. Int. Ed. 5562-5564, 46 (2007).
[3] C. H. Chen et al. Angew. Chem. Int. Ed. 13046-13049, 51 (2012).
Corresponding Author: Prof. Dr. X. Lu
Tel & Fax: +86-2787559404
E-mail: lux@hust.edu.cn– 77 –

FNTG-47, 2014

1P-32

Morphology Control of C70 One-dimensional Structures in Liquid-liquidInterfacial Precipitation (LLIP) and Their Electrochemical Properties○Shushu Zheng, Hui Ju, Xing Lu*
State Key Laboratory of Materials Processing and Die & Mould Technology, School ofMaterial Science and Engineering, Huazhong University of Science and Technology, 1037
Luoyu Road, Wuhan 430074, China
Liquid-liquid interfacial precipitation (LLIP) has been an effective way in building
ordered structures of fullerenes.[1] Numerous C60 nano/microstructures ranging fromone-dimensional(1D) to three-dimensional(3D) have been successfully obtained from
LLIP,[2,3] but little is discussed about C70 nano/microstructures. Moreover, fully
understanding of the formation process and the solvent effect is still not that clear.
In this representation, 1D structures of C70 (Figure 1) have been readily preparedusing three kinds of xylenes (m-xylene, p-xylne, o-xylene) as good solvent andisopropyl alcohol as poor solvent with LLIP method. Size distributions of these C70 1D
structures differ from each other and they have distinct internal structures. The XRD
pattern of as-prepared structures is hcp, orthorhombic, hcp for applying o-xylene,
m-xylene and p-xylene as the good solvent, respectively. Moreover, nanorods preparedfrom m-xylene as solvent will evolve to fcc structure under heating treatment, while
the other 1D structures retain unchanged in high temperatures. Electrochemical
properties of C70 1D structures are discussed and are determined to relate to the
crystalline types (Figure 2), the electrochemical capacitance increases in the order of
hcp > fcc > orthorhombic.

Figure 1．SEM of C70 1D structures prepared in different solventswith LLIP. (a) o-xylene, (b) m-xylene, (c) p-xylene. Inset:
High-magnification SEM images of C70 microstructures.

[1] S. S. Babu et al. Chem. Soc. Rev. 39, 4021(2010).
[2] L. K. Shrestha et al. J. Am. Chem. Soc. 135, 586(2013).
[3] J. Jeong et al. J. Phys. Chem. C 114, 12976(2010).
Corresponding Author: Prof. Dr. Xing Lu
Tel & Fax: +86-2787559404,
E-mail: lux@hust.edu.cn– 78 –

Figure 2．GCD curves of C70 powder andC70 1D structures of different XRD
patterns at the current density of 0.1 A/g

FNTG-47, 2014

1P-33

Control of Cell Growth and Morphology on Highly Oriented Fullerene
Nanowhisker-Scaffold Constructed by Mimicking a Method of LB Film
○Yuki Kasuya1, 2, Kosuke Minami2, Tomohiko Yamazaki2,
Qingmin Ji2, Waka Nakanishi2, Katsuhiko Ariga2, Hideki Sakai1
1

Department of Pure and Applied Chemistry, Tokyo University of Science, Chiba 278-8510,
Japan
2
International Center for Materials Nanarchitectonics, National Institute for Materials
Science, Ibaraki 305-0044, JapanThe carbon clusters have gained significant
attention as a cell scaffold in tissue engineering
due to their chemical, physicochemical andelectrochemical properties [1, 2]. To engineer
tissue-like structures, cells must organize
themselves into 2-dimentional (2-D) to 3-Dstructures. However, the scaffolds fabricatedFig. 1: FNW as a cell scaffold.
with carbon nanotubes or graphens are difficult to control cellular morphology because of theirnanoscale structures. Fullerene nanowhisker (FNW), which is 1-D fullerene crystals withrelatively large size (submicrometer in diameter and submilimeter in length) [3] as well as with
their biocompatibility [4], provide a potential platform of the patterned surface for directing
cells into biomimetic tissue architectures in vitro (Fig. 1). In this presentation, we report on theapplication of FNW as a scaffold for cell adhesion and growth as well as the cell morphologicalcontrol. We successfully fabricated highly oriented FNW scaffolds on a glass slide bymimicking a method of Langmuir-Blodgett film (Fig. 2).

Fig. 2: Preparation of aligned FNW substrate by mimicking method of LB film.

By using this aligned FNW substrate, mouse myoblast cells(C2C12) adhered and grew on the FNW with low cytotoxicity.
Moreover, the cells cultured on the aligned FNW substrate grew
1-dimentionally along with FNW and elongated in the directionof FNW alignment (Fig. 3). Our results indicate that the sub-msized ridges with the 1-D alignment of FNW enabled to control
Fig. 3: C2C12 cells cultured
both the growth direction and morphology of cells.
on aligned FNW substrate.

[1] Ku, S. H.; Park, C. B. Biomaterials, 2013, 34, 2017－2023[2] Abdullah, C. A. C. et al. Nanotechnology, 2011, 22, 205102[3] Miyazawa, K. et al. J. Mater. Res. 2002, 17, 83－88.
[4] Nudejima, S.; Miyazawa, K. Adv. Biomed. Res. 2010, 89－94.
Corresponding Author: H. Sakai and K. Ariga
H. Sakai: Tel & fax: +81-4-7121-2439. E-mail: hisakai@rs.noda.tus.ac.jp
K. Ariga: Tel & fax: +81-29-860-4597. Email: ARIGA.Kstsuhiko@nims.go.jp– 79 –

1P-34

FNTG-47, 2014

Secondary addition of 5-membered acetalized ring to methanofullerenes
leads to enhancement of polymer solar cells○Tsubasa Mikie, Akinori Saeki, Hiroyuki Masuda, Naohiko Ikuma, Ken Kokubo, Shu Seki
Department of Applied Chemistry, Graduate School of Engineering, Osaka University,
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
An effective way to concurrently achieve highcurrent density (Jsc) and open circuit voltage (Voc) inorganic photovoltaic devices is an introduction oftightly-packed fullerene phases with its shrunken
-electron system, so that the fullerene has a highelectron mobility and a raised LUMO level. As suchthe rationalized strategy is a multiple addition ofsubstituents.
With an use of time-resolved microwave
conductivity (TRMC) technique, we found that a
pristine film of C60 mono-adduct of 5-memberedspiro-acetalized

unit

showedmuchlargerphotoconductivity than that of PCBM. The result
suggests that the compound have high electron
mobility probably due to their compact packing.
However, the compound blended with P3HT
resulted in an extremely-low power conversion
efficiency (PCE) due to its poor solubility and

Figure 1. A structure of fullerenes 1a-4b(upper side). LUMO and HOMO energy
level (eV) of fullerenes evaluated by cyclic
voltammetry and the absorption edge of
UV-vis spectra (bottom side).

miscibility with P3HT. Here we report thesecondary addition of spiro-acetalized unit to the representative 58-fullerene derivatives toenhance both solubility and Voc with preserving high Jsc (Figure 1).
Compounds 1-4 were synthesized by the previous method[1] via TiCl4-mediated acetalization of
cyclohexanone-fused fullerenes 1a-4a in excellent yields. Adding a cyclohexanone group tomethanoC60 (58) raised the LUMO level by 0.08 eV due to the shrinkage of fullerene -system (56),and acetalization of 2a further lifted up LUMO level by 0.04 eV due to electron-donating nature ofalkoxy group. Compound 3b showed the highest PCE of 4.43% with Voc of 0.80 V, Jsc of 8.84 mAcm-2,
and fill factor of 0.63.
[1] Kokubo, K.; Masuda, H.; Ikuma, N.; Mikie, T.; Oshima, T. Tetrahedron Lett., 2013, 54, 3510.
*Corresponding Author: Shu Seki
Tel: +81-6-6879-4586, Fax: +81-6-6879-4586, E-mail: seki@chem.eng.osaka-u.ac.jp– 80 –

1P-35

FNTG-47, 2014

Semitransparent PTB7:PC71BM solar cells using an oxide/metal/oxidetransparent anodeżShunjiro Fujii1, Takeshi Tanaka1, and Hiromichi Kataura1
1

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8562, Japan
Organic solar cells (OSCs) are of special interest owing to the advantages of low-costand solution-processable fabrications. Previously, we reported performance enhancementof bulk-heterojunction solar cell based on a benzodithiophene polymer of PTB7* andphenyl-C71-butyric-acid-methyl-ester (PC71BM) by inserting LiF buffer layer [1]. One
simple approach for further improvement of the performance is to fabricate
semitransparent OSCs and to use a tandem structure, in which two or more cells withdifferent optical absorption are stacked. On the other hand, semitransparent OSCs arealso interesting for other applications, such as energy-generating windows.
In this work we fabricated semitransparent inverted PTB7:PC71BM solar cells on
ITO/glass substrate. For the transparent anode, we utilize oxide/thin metal/oxide
multilayer structure due to its favorable optical and electric properties [2]. The device
structure was Glass/ITO/PFN**/PTB7:PC71BM/MoO3/Au/MoO3 (Figure 1). Figure 2
shows the current density-voltage (J-V) curves for the semitransparent solar cell withlight illuminated from ITO or Au/MoO3 side. The power conversion efficiencies
extracted from the J-V curves were 2.8% and 2.3%, respectively. The detailed device
characteristics will be discussed.

MoO3

Au

MoO3

PTB7:PC71BMPFN

ITO/Glass2

Current Density (mA/cm )*PTB7;apoly[[4,8-bis[(2-ethylhexyl)oxy]benzo**PFN;apoly[(9,9-bis(3'-(N,N-dimethylamino)[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2propyl)-2,7-fluorene)-alt-2,7-(9,9–dioctylfluorene)[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl]
-4

0
2
4
6
8

Figure 1 Schematic illustration ofsemitransparent solar cell.
[1] S. Fujii et al., The 45th FNTG General
symposium 2013, 1p-34[2] S. Y. Ryu et al., Appl. Phys. Letts. 92 (2008)023306‫ە‬ITO side‫ۑ‬Au/MoO3 side

-2

0

0.2
0.4
Voltage (V)

0.6

0.8

Figure 2 J-V characteristics under AM 1.5G
(100ௗmW/cm2) illuminated from two transparent
electrodes (ITO and Au/MoO3).
Corresponding Author: Hiromichi Kataura
E-mail: h-kataura@aist.go.jp– 81 –

1P-36

FNTG-47, 2014

Polymerization with optical manipulation of C60 moleculesby optical vortex irradiation○Wataru Akiyama1, Naoto Nakamura1, Yu Tanaka1,
Katsuhiko Miyamoto1, Takashige Omatsu1,2, Jonathan P. Bird3,
Yuichi Ochiai1, and Nobuyuki Aoki1,41

Graduate School of Advanced Integration Science, Chiba University,
Chiba, 263-8522 Japan
2
JST-CREST, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan3
Department of Electrical Engineering, University at Buffalo, SUNY, Buffalo, NY
14260-1920, USA
4
JST-PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan
Recently, a state of the art photo-polymerization of a C60 thin film has been realizedby irradiation of topological laser beam namely optical vortex (OV). Since the beam has
a helical wavefront and a torque appears along the tangential direction, a confinement
force can be expected along the peripheral direction of the beam and the polymerization
takes a progress with a compressive photon-pressure under a high-beam-power density.
Therefore, it can be expected to achieve unique photo-polymerization regime in a C60
thin film. Moreover, combining with circular polarization, total angular momentum oflight can be controlled [1].
In our study, thermally evaporated C60 thin film was deposited 10 nm on Si3N4
membrane grids for a transmission electron microscope (TEM) observation. A
continuous-wave laser beam (λ = 532 nm) was used for the optical source. The OV wasproduced by using a spiral phase plate and irradiated onto the sample through an
objective lens. The photo-polymerization was done at high-vacuum condition.
In the observation of the surface of the C60 thin film by atomic force microscope andTEM, very thin layers having a thickness of ~5 nm covering the surface of C60 grains
after the OV irradiation. The layers cover also the surface of the substrate surrounded by
the grains. It suggests that the thin layer is formed affected not only by aphoto-polymerization regime but also by an optical manipulation of C60 molecules by
the OV irradiation. Taking care of the fact and our previous studies including in-situ
transport measurements, the thin-surface layer has different transport properties fromthat in the bulk region.
[1] T. Omatsu et al., Opt. Express 18 (2010) 17967.
Corresponding Author: W. Akiyama
Tel: +81-43-290-3430, Fax: +81-43-290-3427,
E-mail: adsa3781@chiba-u.jp– 82 –

1P-37

FNTG-47, 2014

Device characteristics using novel [60] and [70]PCBM analogues
in organic photovoltaic devices†○Yuki Kuda1, Tatsuya Hayashi1, Kai Abe1, Haeseong Lee2,3, Jae S. Lee2, Seung J. Lee4,
Jin Jang4,Chyongjin Pac1,5, and Hiroshi Moriyama1
1

Department of Chemistry, Toho University, Miyama2-2-1, Funabashi 274-8510, Japan
Takoma Technology Co. Ltd., 178, Doosa-ri, Nonsan-city, Chungnam 320-922, Korea
3
Department of Advanced Materials Jeonju University, Wansangu Jeonju 560-759, Korea
4
Department of Information Display, Kyung Hee University, Dongdaemun-ku Seoul 130-171, Korea
5
Department of Materials Chemistry, Korea University, Sejong Jochiwon, Chung-Nam 339-700, Korea
2

Bulk heterojunction (BHJ)-type organic photovoltaic cells (OPVs) have attracted attention
because of their light weight, flexibility and solution-process construction. One of the mostrepresentative OPVs is based on poly(3-hexyl thiophene) (P3HT) as a donor andphenyl-C61-butyric acid methyl ester (PCBM) [1] as an acceptor. Recently, C70 derivatives of
PCBM were developed and showed a high power conversion efficiency (PCE) of 7.4 % with
(PTB7) [2] as the donor. In our ongoing work in preparing a series of the PCBM analogues,
we prepared Methyl-C61-phenyl carboxylic acid methyl ester (MPCM) as well as its C70
derivatives and fabricated OPV devices with P3HT as the donor. The performance of devices
with [60]MPCM and [70]MPCM was compared, [70]MPCM showing a higher PCE than[60]MPCM.
O

SO2NHNH2

O
O

O
OH

O

O

pyridine, CH3ONa
C70 / ODCB

CH3OH

CH3OH, H2SO4
O

O
O
NNHTs
2

1

3

Table 1. OPV parameterssample

JSC

VOC
2

FF

PCE

(mA/cm )

(V)

(%)

PCBM

7.61

0.587

0.603

2.69

[70]MPCM

6.75

0.602

0.468

1.90

[60]MPCM

5.72

0.538

0.492

1.51

Fig. 1. J-V characteristics[1][2]

J. C. Hummelen, B. W. Knight, F. LePeq, F. Wudl, J. Yao, C. L. Wilkins, J. Org. Chem., 1995, 60, 532-538.
Y. Liang, Z. Xu, J. Xia, S. Tsai, Y. Wu, G. Li, C. Ray, L. Yu, Adv. Mater., 2010, 22, E135-E138.

†   This work was supported by the Bilateral International Collaborative R&D Program (Project number:
GT-2009-CL-OT-0058, Ministry of Knowledge Economy, Republic of Korea and the MEXT-Supported Program for theStrategic Research Foundation at Private Universities, Japan.
Corresponding Author : Hiroshi Moriyama

TEL : +81-47-472-1211, FAX : +81-47-472-1188 E mail : moriyama@chem.sci.toho-u.ac.jp– 83 –

FNTG-47, 2014

1P-38

Solid-State NMR Studies on the Aggregated Structures of Organic Bulk
Heterojunction Solar Cells with Solvent Additives○Saki Kawano1, Sayo Ishikawa1 and Hironori Ogata1,2
1Department of Chemical Science and Technology,Hosei University Koganei 184-8584
Japan
3
Research Center for Micro-Nano Technology,Hosei University,Koganei 184-0003,Japan
Bulk heterojunction (BHJ) organic solar cells are an emerging technology that has thepotential to provide a low cost photovoltaic devices. It is well known that thenanomorphology of the polymer:fullerene BHJ is a critical factor which affects the solar cell
performance. The addition of processing additives is widely used approach to increase power
conversion efficiencies for many organic solar cells. Among them, the influence of additives,
such as 1,8-diiodooctane (DIO), 1,8-Octanedithiol and so forth on the performance of
P3HT/PCBM BHJ solar cells were widely investigated. Solid-state NMR spectroscopy offers
several techniques for the investigation of the morphological, structural, and dynamics
properties of BHJ organic solar cells. In this study, we investigated the change in the
crystallinity, morphology, and the properties of molecular motions of P3HT/PCBM BHJ filmby adding solvent additives by using 13C and 1H solid-state NMR spectroscopy.
Mixed solution of P3HT/PCB of 1:1(w/w) was prepared by mixing P3HT and PCBM into
chlorobenzene at a concentration of 1 wt% for 50 hrs in a glove box under argon atmosphere.
A 3% by volume of additive DIO was then dropped into the solution and then stirred for 1 hr.
The   solution   was   filtered   using   0.45μm   filter   before   making   films   to   remove   undissolved  materials. P3HT/PCBM BHJ films were prepared by dropping the solution in a glass plateand dried in a glove box under argon atmosphere for 40 hrs and then put in the vacuum for
24hrs. Dried film were removed from the glassplate and sealed into 4 mm zirconia NMR rotor.
Solid-state NMR spectra were collected on Bruker AVANCE300 spectrometer.
13
C-CP/MAS NMR spectra of P3HT/PCBM BHJ films showed that the width of the peaks
assigned both P3HT and PCBM is narrowed by the addition of DIO. The detailed results ofthe change of morphology and the properties of molecular motions of P3HT/PCBM BHJ filmby the addition of DIO and anather additives will be presented.

[1] Cuiying Yang, Jerry G. Hu, and Alan J. Heeger, J.Am.Chem.Soc., vol.128, no.36, pp.12007–12013, 2006.
[2] Jae Kwan Lee, Wan Li Ma, Christoph J. Brabec, Jonathan Yuen, Ji Sun Moon, Jin Young Kim, Kwanghee
Lee, Guillermo C. Bazan , and Alan J. Heeger, J. Am. Chem. Soc., vol.130 no.11, pp.3619–3623, 2008.
Corresponding Author: H. Ogata
Tel: +81-42-387-6229, Fax: +81-42-387-6229,
E-mail: hogata@hosei.ac.jp– 84 –

1P-39FNTG-47, 2014

Synthesis and characterization of fullerene derivatives withcarboxylic acid ester in organic photovoltaic devices†○Mizuki Igawa1, Tatsuya Hayashi1, Kai Abe1, Haeseong Lee2,3, Jae S Lee2, Seung Joo Lee4,
Jin Jang4,Chyongjin Pac1,5, and Hiroshi Moriyama1
1 Department of Chemistry, Toho University, Miyama 2-2-1, Funabashi 274-8510, Japan
2 Takoma Technology Co. Ltd., 178, Doosa-ri, Nonsan-city, Chungnam 320-922, Korea
3Department of Advanced Materials Jeonju Univ.Wansang Jeonju 560-759, Korea

4Department of Information Display, Kyung Hee University, Dongdaemun-ku Seoul 130-171, Korea
5Department of Materials Chemistry, Korea University, Sejong Jochiwon Chung-Nam 339-700, Korea

Lightweight, low-cost and flexible organic photovoltaic devices (OPVs) have attracted muchattention. OPVs have a bulk heterojunction (BHJ) structure with mixed electron acceptor anddonor in the active layer. Currently, [6,6]-phenyl C61-butylic acid methyl ester (PCBM)[1] iswidely used in OPVs as an electron acceptor.
In this study, we synthesized novel fullerene derivatives with a different carboxylic acid ester,e.g., hexyl ester, MPCH. These derivatives have good solubility because of their long alkyl
chain, and are easy to synthesize. We fabricated an OPV device using this fullerene derivative
as an electron acceptor and poly(3-hexylthiophene) (P3HT) as an electron donor. MPCH
showed power conversion efficiency (PCE) that is almost the same as that of PCBM. It is tobe noted that the current density is rather high. Furthermore, we synthesized [70]MPCH,
whose PCE is now under investigation.
O
OH

O

C6H13OH, H2SO4

O

O

O

O

C6H13

O

NH2NHTs
NNHTs

O

3

2

1

pyridine, CH3ONa
C60 / o-DCB

CH3OH
O

C6H13

4

Current density / mA/cm2

9
8

Table 1. OPV characteristics using novel C60 derivative.

7
6

JSC (mA/cm2)

VOC (V)FF

PCE (%)

PCBM

7.61

0.587

0.603

2.69

MPCH

7.90

0.568

0.593

2.66

5
4
3

MPCH

2

PCBM

1
0
0

0.2

0.4

0.6

Voltage / V

Figure 1. J-V characteristics of OPV devices.
[1] J. C. Hummelen, B. W. Knight, F. LePeq, F. Wudl, J. Yao, C. L. Wilkins, J. Org. Chem. 1995, 60, 532–538.
† This work was supported by the Bilateral International Collaborative R&D Program (Project number:
GT-2009-CL-OT-0058, Ministry of Knowledge Economy, Republic of Korea and the MEXT-Supported Program for theStrategic Research Foundation at Private Universities, Japan.
Corresponding Author : Hiroshi Moriyama
TEL: +81-47-472-1211, FAX: +81-47-472-1188,

E-mail: moriyama@chem.sci.toho-u.ac.jp– 85 –C6H13

FNTG-47, 2014

1P-40

Improving electric double layer capacitor property
by adding nanocarbon materials○A. Mizutani1, Y. Okabe1, Y. Suda1, H. Takikawa1, H. Ue2, K. Shimizu3, Y. Umeda4
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon Co.,Ltd., Oyama, Sizuoka 410-1431, Japan
3
Development Department, Shonan Plastic Mfg. Co.,Ltd., Hiratsuka, Kanagawa 254-0807, Japan
4
Toho Gas Co.,Ltd., Nagoya, Aichi 456-8511, Japan

Specific capacitance (F/g)

1. Introduction
Electric double layer capacitor (EDLC) is an energy device. When EDLC charges anddischarges, ions in electrolyte adsorb and desorb on electrode surface. EDLC has advantages
that provide higher charge/discharge rate and perform longer cycle life compared withrechargeable batteries, because chemical reaction does not occur such as redox reaction. In
this study, EDLC performance was evaluated by using nanocarbon materials as electric
conductor of activated carbon (AC) elctrodes.
2. Experimental
Arc black (AcB) was prepared using a twin-torch arc discharge apparatus. AcB contains
dominantly cocoon-shaped carbon particles and includes an amorphous ingredient mostly.
CNB was synthesized by heat treatment of AcB at 2600 C in Ar gas. Particle shape of CNB
is hollow. CNB is graphitic and has high conductivity. Oxidized CNB (Ox-CNB) was
prepared by heat treatment of CNB in the air using an electrical furnace. Ox-CNB has a large
specific surface area [1]. AC electrodes were prepared by mixing 10 wt.% nanocarbon
materials as electric conductor. The specific capacitance of EDLC was estimated fromelectrochemical measurement. The electrodes were compared to AC electrode and AC
electrode mixing ketjen black (KB).
3. Results
100
Fig. 1 shows the specific capacitance obtained
80
from the galvanostatic charge/discharge curves.
AC+Ox-CNB60
AC electrode obtained the highest specific40
capacitance at a current density of 0.1 A/g. But,
AC+KB
20
AC electrode with Ox-CNB obtained the highest
AC
specific capacitance at current density of 0.5 A/g
0
0.0
0.5
1.0
1.5
2.0
and more. So the specific capacitance of EDLC
Current density (A/g)
was increased by Ox-CNB when using at a highFig.1. Specific capacitance of EDLCs atcharge/discharge. Ox-CNB can be used as andifferent current densities.
electric conductor.
This work has been partly supported by the EIIRIS Project from Toyohashi University ofTechnology (TUT); JSPS KAKENHI Grant Number 24360108 and 25630110.
[1] Y. Okabe et al. Electrochim. Acta. 131, 207 (2014).
Corresponding Author: A. Mizutani
Tel: +81-532-44-1228,
E-mail: mizutani.akitaka@pes.ee.tut.ac.jp– 86 –

FNTG-47, 2014

1P-41

Self-Organized Nano-Structured Field Emitter Fabricatedby Field Emission Induced Growth
Shinichi Ito, Hitoshi Nakahara, Yahachi Saito
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
Currently, single crystalline tungsten is used as a high brightness emitter.
Recently, some studies reveal that single atom emitters or carbon nanotube emittershave potential to replace the single crystalline tungsten emitter. Nano emitter, which ismade by field emission induced growth (FEIG) method, is focused in this report. FEIG
is a method that high negative voltage is applied to a tungsten tip under a source gas
atmosphere (methane in our case), and the ions generated by field-emitted electrons are
attracted and deposited onto the tip of tungsten needle. It was already reported [1, 2]
that the FEIG nano emitter has potential to use as an emitter of scanning electron
microscope (SEM).
(a)

(b)

(c)

5
80

4

Applied Voltage [kV]Emission Current [µA]

In this report, we focused on
analyzing growth-destruction cycle
during FEIG. Figure 1 shows applied
voltage and emission current during
growth of an emitter. Between 230 s and400 s, applied voltage was constant
while emission current increased whichindicates the emitter was growing at thisregion. At about 400 s, emission current
became rapidly to zero because thegrown emitter destructed itself. For
further increase of applied voltage,
emission current started to increaseagain, which is the second growth cycle

60

3

40

2

20

1
0

0

200

400
Growth Time [s]

600

0
800

of the emitter. At about 590 s, it was Fig. 1. Growth time vs applied voltage, emission
destructed again, and the third cycle current and FEM patterns during FEIG
started. FEM patterns (a-c) in the figure
are snapshots at dashed lines. These patterns are taken from the same area of the FEM
screen. As shown by arrows in the FEM patterns, the sizes of bright area became narrowcycle by cycle. Narrowness of bright area shows narrowness of emission angle caused
by decrease of field concentration at the tip of tungsten needle. Namely, averagecurvature radius of tungsten needle became large cycle by cycle. In addition,
appearance of different bright area at each cycle indicates changes in surface
morphology of tungsten tip.
[1] H. Nakahara, S. Ichikawa, T. Ochiai, Y. Kusano and Y. Saito: e-J. Surf. Sci. Nanotech. 9 (2011) 400.
[2] H. Nakahara, S. Ito, S. Ichikawa and Y. Saito: e-J. Surf. Sci. Nanotech. 12 (2014) 192.

– 87 –

FNTG-47, 2014

2P-1

Evaluation of heat conduction property of vertically aligned carbon
nanotube films for thermal interface material application
Kenta Maeda, Eisuke Tamaki, Hideki Sato
Graduate School of Engineering, Mie University, Tsu 514-8507 , Japan
Carbon nanotubes (CNTs) possess remarkably high thermal conductivity that exceeds thatof diamond (~2,000 W/mK) [1]. Thus it is expected that CNT can be applied to a flexible andhigh-performance thermal interface material (TIM). It is considered that a CNT film, which
consists of densely grown vertically aligned CNTs, is suitable for this application. For
realization of such application, characterization of heat conduction property of CNT film withvarious growth morphologies (i.e., diameter, growth density, number of CNT layer and so on)
is indispensable. In this study, we are aiming at examining and clarifying the heat conduction
property of vertically aligned CNT film with various growth morphologies.
Vertically aligned MWCNT films grown on P-type Si(100) wafers by thermal chemical
vapor deposition method using acetylene as a precursor were used as samples for heat
conduction measurements. The thickness of the CNT film was 114 µm. Thermal conduction
properties of the CNT films were evaluated using the experimental setup shown in Fig 1. A
ceramic heater was used as a heat source. The heater was attached to one side of a flat surface
of a metal rod (SUS304; 5 mm in diameter and 5 mm in length). The other side of the flat
surface is contacted to the CNT film. Heat flow from the heater to the base gives rise totemperature gradient, which is measured by thermocouples attached to the metal rod and Si
substrate.
Ceramic
The heat flux at the arbitrary positions between the heater
heaterT
Metal rodand the base is given by Fourier's law,
ThermoT couple
CNT film
q = -λgradT(1)
Si substrateT
where q is the heat flux, λ is thermal conductivity, and T is Base
the temperature. In general, evaluation of λ of the CNT film
Fig 1 Experimental setup of thermal
is difficult because of its small thickness. However, the conduction measurements.
qualitative evaluation of the thermal conduction property of120
the CNT film is possible by measuring the temperature
differences among three different points. Fig 2 shows the100
Slope : 0.91
temperature difference ΔT (=T1-T3) as a function of heat flux
80
q. In this graph, the slope is proportional to thermal
resistivity of the CNT film, which is reciprocal of the60
Slope : 0.51
thermal conductivity. The slope of the CNT film/Si sample
40
is smaller than (0.56 times of) that without CNT film,
indicating that the CNT film promotes the thermal
CNT film/Si
20
Si (w/o CNT film)
conduction between the SUS/Si interface. It is expected that0
optimization of the growth morphology of CNT film
0
50
100
150
200
q (W/mm2)
enhances thermal conductivity.
This study was partly supported by Tanikawa Fund Fig 2 Temperature differences ΔT
Promotion of Thermal Technology.
(=T1-T3) plotted as a function of
1 mm

1

3 mm
1 mm

2

ΔT (˚C)3

heat flux q.

[1] D. Kim, L. Zhu, C. Han, J. Kim, S. Baik, Langmuir, 27, 14532 (2011).
Corresponding Author: H. Sato Tel/FAX: +81-59-231-9404
E-mail: sato@elec.mie-u.ac.jp– 88 –

FNTG-47, 2014

2P-2

Fabrication of carbon nanotube sheet using carbon nanotubes filled withiron nanowires and characterization of its magnetic property○Nobuo Kubonaka, Takayuki Sato, Hideki Sato, Yuji Fujiwara
Graduate School of Engineering, Mie-University, Tsu, 514-8507, Japan
Carbon nanotubes filled with iron nanowires (Fe@CNTs) show shape anisotropy owing tohaving the high-aspect ratio of magnetic nanowires, and high coercivity (>1.0 kOe) at room
temperature[1]. Because of this characteristic, Fe@CNTs are promising material for various
magnetic applications such as magnetic shields, electromagnetic wave absorbers,
sheet-shaped magnets and so on. For these applications, it is important to fabricate flexible
sheets with Fe@CNTs and to examine those magnetic properties. In this study, we have madeCNT sheets from Fe@CNTs grown on the substrate and investigated those magnetic
properties.
A procedure for synthesis of Fe@CNTs is same as our previous work[1]. Vertically grown
Fe@CNTs on Si substrate were pressed by a cylindrical metal bar for the purpose of pushing
the CNTs down to a certain direction and arranging the orientation of the CNT axes.
Commercially available adhesive agent was then applied
all over the surface and was cured for 24 hours at room
temperature. Finally, the Fe@CNTs sheets were peeled
off from the substrate with tweezers. The magnetic
property of the Fe@CNTs sheet was measured by avibrating sample magnetometer.
(a)(b)
Figures 1 (a) and (b) show a top surface SEM imageof Fe@CNT film after the press and a photograph of Fig. 1 (a) SEM image of Fe@CNT
film after pushing down. (b) Photograph
Fe@CNT sheet peeled off from the substrate,of Fe@CNT sheet peeled off from therespectively. The arrow in Fig. 1(a) indicates the substrate.
direction of pushing the CNTs down. After peeling off
the CNT sheet, no CNT remained on the substrate.
Figure 2 shows the magnetization curve of (a) as-grown
Fe@CNT film on the Si substrate and (b) Fe@CNT
sheet peeled off from the Si substrate. Coercivities of
the as-grown Fe@CNT film are different between theperpendicular (0.92 kOe) and parallel directions (0.49
kOe) [Fig. 2(a)]. On the other hand, the coercivities of
the Fe@CNT sheet are nearly identical for theperpendicular and the parallel directions to the sheet(0.76-0.86 kOe). It is considered that these differencesreflect the orientations of the CNT axes in the sheet.
These results indicate that the magnetic anisotropy of
the Fe@CNTs can be controlled by selecting the press
condition of the vertically aligned Fe@CNT film.
This work was supported by JSPS KAKENHI No.
25390030.
[1] H. Sato et al, Jpn. J. Appl. Phys. 52, 11NL03 (2013).
Corresponding Author: H. Sato
Tel/FAX: +81-59-231-9404
E-mail: sato@elec.mie-u.ac.jp– 89 –

Fig. 2 Magnetization curves of(a) as-grown and (b) Fe@CNT sheet.

FNTG-47, 2014

2P-3

Application of water-dispersible multiwalled carbon nanotubes to obtainelectroconductive cotton textile for flexible heater○Mohammad Jellur Rahman1, Tetsu Mieno1,2
1

Graduate School of Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan2
Department of Physics, Shizuoka University, Shizuoka 422-8529, Japan

Interests on the production of lightweight and flexible electrothermal materials have been
increased for their importance in the advanced technologies particularly for the aviation andaerospace industries, microreactor technology, and different kinetic systems [1-3]. In thisstudy, electroconductive cotton textile has been prepared by a simple dipping-drying coating
technique using water-dispersible multiwalled carbon nanotubes (MWNTs). For this, pristine
MWNTs (p-MWNTs) are at first functionalized by a safe and new method of
citric-acid-assisted RF (13.56 MHz) oxygen plasma developed in our laboratory [4], which isless destructive to the CNT structure. The oxygen-containing surface groups on thefunctionalized MWNTs (f-MWNTs) enable them to stably disperse in water to produce
MWNT ink, which subsequently are incorporated in the 100 % cotton textile by repeatedly
dipping the textile into it and dried at room temperature.
(a)

(b)

Fig. 1: Application of the f-MWNTs to produce electroconductive f-MWNTs/cotton textile for heating element.

Owing to the surface functional groups, the f-MWNTs become strongly attached with thecotton fibers forming network armors on their surfaces. After several cycle of dipping the
f-MWNTs uniformly cover the individual cotton fibers, and the textile becomes conductive
enough to be used as wire in lighting up an LED. The conductivity of the textiles becomes
more than 0.20 S/m depending on the loaded content of f-MWNTs. Their thermal conductivity
is enhanced by ca. 70%, and the thermal stability and flame retardancy are also improved. Asa demonstration of practical use, the textile is shown as a conductive textile heater designedwith parallel electrodes. The temperature of the f-MWNTs/cotton textile can be increased
homogeneously to ca. 80 C within ca. 5 min by applying an electric power of ca. 0.1 W/cm2,
which is much less than the power required for conventional wired heater. Our proposed
textile can be a material for the light-weight and flexible heating-unit applications.
[1] L. B. Hu et al. Nano Lett. 10, 708 (2010). [2] P. Lukowicz et al. Meth. Inf. Med. 43, 232 (2004).
[3] D. Negru et al. Fibres Text. East. Eur. 20, 53 (2012). [4] M. J. Rahman, T. Mieno, J. Nanomater. 2014, 508192 (2014).
Corresponding Author: T. Mieno, Tel. and Fax: + 81-54-238-4750, E-mail: sptmien@ipc.shizuoka.ac.jp– 90 –

2P-4

FNTG-47, 2014

Electronic property measurements for inner tubes of DWCNTs○Yusuke  Sako, Mika Tsuboi, Haruka Omachi, Hisanori Shinohara, Ryo Kitaura
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
Atomic wires have attracted a wide range of attention due to their interesting properties thatare distinctly different from those of bulk materials. Although TEM-based characterizations ofatomic wires have been performed[1], studies on physical properties of the atomic wires haveso far been limited due to their instability. Encapsulation into 1D hollow space of CNTs canstabilize the atomic wires, providing various stable atomic wires that can be treated underatmospheric conditions [2]. To investigate physical properties of atomic wires in CNTs, one
has to remove the contribution from CNTs per se. To address this issue, we have performed
functionalization of surrounding CNTs to make the CNTs insulator, thus enabling us toinvestigate the intrinsic properties of atomic wires. In this work, we have focused on
double-wall CNTs (DWCNTs) as a model system to check the validity of our approach.
We used DWCNT with an average diameter of about 0.8 and 1.5 nm for inner and outer
CNT, respectively. Figure 2 shows temperature dependence in conductance of a pristine
DWCNT and a functionalized DWCNT. In this experiment, we have made 2-terminal devices
of individual DWCNTs, and after conductance measurements of the devices, functionalization
have been done onto the devices. Arrhenius plots at the high-temperature region are linear,providing bandgaps[3] of the functionalized DWCNT (1.15 eV). Larger bandgaps observed in
the functionalized DWCNT indicates successful measurement of electronic properties of innertubes.

Fig . 1: DWCNT and functionalized DWCNT

Fig . 2: Temperature dependence in conductance offunctionalized DWCNT[1] H. Ohnishi et al., Nature, 395, 780 (1998). [2] R. Kitaura et al., Angew. Chem. Int. Ed., 48, 8298 (2009).
[3] Y. Asada et al., Adv. Mater., 23, 4631 (2011).
Corresponding Author: Kitaura, R., Shinohara, H.
Tel: +81-52-789-2477, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp, noris@nagoya-u.jp– 91 –

FNTG-47, 2014

2P-5

High-Purity Single-Chirality Separation of SWCNTs using Overloading
Selective Adsorption and Stepwise Elution Chromatography○Xiaojun Wei, Mayumi Tsuzuki, Takuya Hirakawa, Yohei Yomogida, Atsushi Hirano,
Shunjiro Fujii, Takeshi Tanaka and Hiromichi Kataura
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8562, Japan

Absorbance (arb. unit)

Single-wall carbon nanotubes (SWCNTs) have a wide range of electronic properties, due tovarieties in allowed structures defined as (n, m). A number of advanced applications,
including high-performance field effect transistors (FETs), nanoscale sensors and laser source
based on single-chirality SWCNTs, require SWCNTs with an identical physical property.
Therefore, high-purity single-chirality SWCNT is necessary to achieve various advanced
applications.
For this purpose, we developed a new
chromatography method by combining the
E22
E11
overloading selective adsorption [1] and stepwise
elution. As the first separation step, as reported
96%
previously, the overloading chromatography(6,4)
limited the chirality distributions to a narrow90%
range scaled by the largest C-C bond curvature in(8,3)
SWCNTs [1] using sodium dodecyl sulfate (SDS).
97%
SWCNTs were collected by sodium cholate (SC)(6,5)
solution for the second step separation. As thesecond level separation, stepwise elution
92%
chromatography was performed to the samples(7,3)
obtained from the first step using deoxycholate
88%(DOC), SC and SDS mixed surfactant. Individual(7,5)
chirality species could be eluted out by stepwise
91%
increasing the concentration of DOC. As a result,(9,4)
seven kinds of high-purity single-chirality
93%
SWCNTs were obtained. Optical absorption(7,6)
spectra are shown in Fig. 1. Each spectrum
exhibits sharp absorption peaks corresponding to400 600 800 1000 1200
E11, E22 and E33 transitions, indicating almost no
Wavelength (nm)other chirality SWCNTs are in these samples. The
Figure 1. Optical absorption spectra ofpurities of single-chirality SWCNTs obtained inseven sorted (n, m) semiconducting species
this study are estimated much higher than that of(ranked according to the measured E11
previous reports [1, 2].
absorption wavelength).
This work was supported by KAKENHI No.
25220602.
[1] H. Liu et al. Nat. Commun. 2, 309 (2011).
[2] H. Liu et al. Nano Lett. 13, 1996 (2013).
Corresponding Author: H. Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786, E-mail: h-kataura@aist.go.jp– 92 –

FNTG-47, 2014

2P-6

Metal / Semiconductor Separation of Nano-C SWCNTs using Gel Column
Chromatography○Hiromichi Kataura, Mariko Kubota, Mayumi Tsuzuki, Atsushi Hirano, Shunjiro Fujii, andTakeshi Tanaka
Nanosystem Research Institute, AIST, C4, 1-1-1 Higashi, Tsukuba, 305-8562, Japan

AbsorbanceFor the practical use of single-wall carbon nanotubes (SWCNTs) to the electronic devices,
preparation of semiconductor enriched SWCNT is necessary. At the present, selective growthof semiconducting (s-) SWCNT is succeeded but the production rate is quite limited and thus
the large scale production of s-SWCNT is performed only by the separation work. We havebeen working on the metal/semiconductor separation of SWCNTs using gel column
chromatography. This method is applicable for the large scale separation but we have toslightly modify the separation parameters, if the target SWCNT is changed, because thedetailed properties of SWCNT are highly depending on the production way and following
purification process. In this report, we show some results on the separation of Nano-C
SWCNTs that is produced by combustion method. Because the combustion method requires
much lower production cost than that of HiPco, the price is 5 times lower than HiPco. In thismeaning, separation of Nano-C SWCNTs is interesting for the large scale production ofs-SWCNTs.
Figure 1 shows optical absorption
1
spectraofmetallic
andsemiconducting APT-200 SWCNTs
Nano-C APT200(Nano-C) separated by gel column
0.8chromatography.
Althoughthe
S11
diameter distribution of APT-200 is
0.6
quite similar to HiPco, we had toslightly change separation parameterfrom that of HiPco. Each spectrum in
0.4
M11 S22
Fig. 1 resembles to that of HiPco
except slightly narrower diameter
0.2
distribution of APT-200 than that of
HiPco.
The
narrow
diameter*
distribution
is
good
for
0
single-chirality separation. Actually,
400
600
800
1000 1200
without selective adsorption process,Wavelength (nm)we
could
obtainalmostsingle-chirality
SWCNTsusing Figure 1. Optical absorption spectra of metallic (dottedcurve) and semiconducting (solid curve) SWCNTs
stepwise elution chromatography.
This work was supported by separated from APT-200 SWCNTs (Nano-C).
KAKENHI No. 25220602.
Corresponding Author: Hiromichi Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786,
E-mail: h-kataura@aist.go.jp– 93 –

FNTG-47, 2014

2P-7

Mask patterning at very high temperature for carbon nanotube forest on
silicon carbide○Masafumi Inaba1, Chih-Yu Lee1, Kazuma Suzuki1, Megumi Shibuya1,
Yu Hirano1, Miho Myodo1, Atsushi Hiraiwa1, Wataru Norimatsu2,
Michiko Kusunoki2, Hiroshi Kawarada1
1
Graduate School of Advanced Science and Engineering, Waseda University, Tokyo
169-8555, Japan2
Eco Topia Science Institute, Nagoya University, Aichi 464-8603, Japan
Carbon nanotube forest formed by silicon carbide surface decomposition method (CNTs on
SiC) consists of nearly ideally close-packed CNTs with a surface density of ~3x1012 cm-2[1].
Kusunoki et al firstly reports CNTs on SiC patterning using Si3N4 deposition [2] and Cambaz etal exhibited patterning by carbon deposition [3]. However, these methods have difficulty inremoving the masks. Si3N4 etching needs concentrated phosphorus acid treatment, anddeposited carbon has no etching selectivity to CNTs. Here we report new patterning method
for CNTs on SiC by double-layered mask with little damage to CNTs.
We used zinc oxide (ZnO) and carbon as
double-layered mask. Fig. 1 shows the schematic image
SiC Substrateof this patterning method. First, ZnO layer was
deposited on bulk SiC substrate with the thickness of
Deposit ZnO/C mask layers~1m. Next, carbon layer was deposited as the ZnO
Carboncover layer. Then, the substrate was annealed in vacuum
ZnO
at ~1600 oC. CNTs were formed at no mask area. Lastly,
ZnO/C mask layer was easily removed by several
SiC Substratesecond hydrochloric acid treatment. There is small
number of higher melting point material than the
CNT formation at 1600 oC in vacuum
temperature of carbon nanotube formation (~1600 oC).
Some metals can endure the temperature, but most ofthem form carbide or silicide at relatively low
temperature. In thin film case, the actual melting point
decreases and the film sublimate at lower temperature.
SiC Substrate
Although melting point of Si3N4 is ~1900 oC, higher
Lift-off mask layer by HCl solution
than the CNT formation temperature, the mask
[2]
decreases after CNT formation . Actually that of ZnO
in air is ~2000 oC, ZnO mask without carbon layer
sublimated. Carbon (melting point: ~3600 oC) layer
SiC Substratesuppress ZnO sublimation. Since ZnO is an amphotericFig. 1 Schematic image of ZnO/C
oxide, it is easily dissolved to acids. HCl solution gives high temperature mask
less damage to CNTs than other strong acids. Thus, HClsolution is suitable to ZnO/C mask lift-off. Fig. 2 shows
the result of this process captured by optical microscope.
The white square is no CNT area (masked area). There
were no raman peaks at masked area.
This research is partially granted by JSPS(No. 26630136)[1] M. Kusunoki et al. Appl. Suef. Sci. 254, 257 (2007).
[2] M. Kusunoki et al. Jpn. J. Appl. Phys. 42, L1486 (2003).
[3] Z. Goknur Cambaz et al. Carbon 46, 841 (2008) 841–849.
Corresponding Author: M. Inaba
Tel&Fax: +81-3-5286-3391 E-mail: inaba-ma@ruri.waseda.jp– 94 –

50m
Fig. 2 Optical microscope image ofpatterned no-CNT area (white) and CNT
area (black)FNTG-47, 2014

2P-8

Structural Discrimination of Double-Walled Carbon Nanotubes by Chiral
Diporphyrin Nanocalipers with a Larger Cavity
Gang Liu, Takahide Kimura, ○Naoki Komatsu
Department of Chemistry, Shiga University of Medical Science, Otsu 520-2192, Japan.
We have been developing host-guest
methodology for separation of single-walledcarbon nanotubes (SWNTs) according to thehandedness, diameter, and even metallicity byuse of diporphyrin and dipyrene nanotweezers
and nanocalipers [1-3]. Herein, we reportstructural separation of double-walled carbon
nanotubes (DWNTs) by chiral diporphyrin
nanocalipers (1 in Fig. 1) with a larger cavity [4]than that of the previous ones [5].
The HR-TEM analysis of 81 extracted CNTs
allowed us to determine the distribution in thenumber of walls and the diameters of DWNTs(Fig. 2). After the extraction, triple-walledcarbon nanotunes (TWNTs) disappers toincrease the content of DWNTs and SWNTs
slightly (Fig. 2a). As for the diameter of
DWNTs, the wide diameter range from 0.75 –2.75 nm was significantly narrowed to 1.25 –1.75 nm as shown in Fig. 2b. This diameter
range of the enriched DWNTs is also supportedby the Raman spectroscopies. In addition, The
DWNTs extracted with (R)- and (S)-1 exhibit
almost symmetrical CD peaks (Fig. 3),
indicating that the extracted DWNTs are
optically active.
[1] G. Liu, F. Wang, N. Komatsu, in Handbook of
Carbon Nano Materials, World Scientific, 2012; Vol.
3, p 203.
[2] G. Liu, N. Komatsu, Chem. Eur. J., 2013, 19,16221.
[3] G. Liu, N. Komatsu, J. Am. Chem. Soc. 2013, 135,
4805.
[4] G. Liu, N. Komatsu, to be submitted.
[5] F. Wang, N. Komatsu, J. Am. Chem. Soc. 2010, 132,10876.

Fig. 1 Structure of chiral diporphyrin nanocalipersabFig. 2 Abundance of SWNTs, DWNTs, and
TWNTs (a) and diameter distribution of DWNTs(b) before and after extraction.

Fig. 3 CD spectra of CNTs extracted with (R)and (S)-1.

Corresponding Author: Naoki Komatsu
Tel: +81-77-548-2102, Fax: +81-77-548-2405, E-mail: nkomatsu@belle.shiga-med.ac.jp– 95 –

FNTG-47, 2014

2P-9

Synthesis of carbon nanotube with an unconventionalbeaded structureżHiroyuki Yokoi1,2, Kazuto Hatakeyama1,2, Mako Ueda3, Shogo Matsumoto3,
Takaaki Taniguchi1,2, Michio Koinuma1,2, Yasumiti Matsumoto1,2
1

Graduate School of Science and Technology, Kumamoto University, Kumamoto 860-8555,
Japan
2
JST, CREST, K’s Gobancho 6F, 7 Gobancho, Chiyoda-ku, Tokyo, 102-0076, Japan
3
Faculty of Engineering, Kumamoto University, Kumamoto 860-8555, Japan

Various types of nanostructures are known for carbon nanotube(CNT), including thebamboo-type[1], the cup-stacked-type[2], the beaded-type[3], the necklace-type[4] andcoiled[5] as well as the tubular-type[6]. As physical and chemical properties of nanocarbon
materials are related strongly to their microscopic structures, CNTs with unconventional
structures are expected to have peculiar properties that are not prominent for the conventional
tubular CNTs. For example, the cup-stacked CNT has many edges on the inner and the outersurfaces of the tube wall, which favors the application of the CNTs to material supporting
catalysts[7].
In this paper, we report on the development of a new type of beaded CNTs. This material
was synthesized with the submarine-style CVD method developed originally. In the synthesis,
graphene oxide-supported cobalt-iron catalyst was heated in a small chamber submerged in
2-propanol. The bottom of the chamber was opened and the inner space of the chamber was
filled with argon. Alcohol vapor was supplied to the heated catalyst as a carbon source fromthe liquid surface exposed at the bottom of the chamber. The substrate temperature waselevated to 1110-1120 K for 10 minutes.
In FE-SEM observation, we have found that large part of thus synthesized CNTs havebeaded structures (Fig. 1). TEM analysis has revealed that the beaded fibers are consisted of aseries of elongated nanobells[8]. The typical size of the nanobell is 20-40 nm in diameter,
100-200 nm in length while the length-to-diameter ratio of the conventional nanobells is 1-2.
Recently, a work of corking carbon nanobells with gold nanoparticles was reported to findpotential applications to nanoscale reaction containers or drag delivery vehicles[9]. The
hybrid nanocarbon material of nanobell and short CNT could provide another approach to
new applications of the nanospace.
[1] Y. Saito and T. Yoshikawa, J. Cryst. Growth, 134,
154 (1993).
[2] M. Endo et al., Appl. Phys. Lett., 80, 1267 (2002).
[3] J.-M. Ting and J.B.C. Lan, Appl. Phys. Lett., 75,
3309 (1999).
[4] H. Okuno et al., Carbon, 42, 2543 (2004).
[5] X. Chen et al., Nano Lett. 3, 1299 (2003).
[6] S. Iijima, Nature, 354, 56 (1991).
[7] C. Kim et al., J. Appl. Phys., 96, 5903 (2004).
[8] X. Ma et al., appl. Phys. Lett., 77, 4136 (2000).
[9] Y. Zhao et al., ACS Nano, 6, 6912 (2012).
Corresponding Author: H. Yokoi
Tel: +81-96-342-3727, Fax: +81-96-342-3710,
E-mail: yokoihr@kumamoto-u.ac.jp– 96 –

Fig.1: FE-SEM image of synthesized CNTs.
Most tubes observed in this frame exhibit thefeature of beaded fiber.

FNTG-47, 2014

2P-10

Facile sorting of surfactant-free semiconducting single-walled carbon
nanotubes using supramolecular solubilizers○Fumiyuki Toshimitsu1, Naotoshi Nakashima1, 2, 3
1

Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University, Fukuoka 819-0395, Japan
3
JST-CREST, Chiyoda-ku, Tokyo 102-0075, Japan

Highly purified single-walled carbon nanotubes (SWNTs) are essential for fundamental studies
and applications toward next-generation nanotechnology1. Especially, unique optical and electricalproperties of semiconducting-SWNTs (sem-SWNTs) would be fully utilized only when they areseparated from poisoning metallic-tubes2. Despite several technical methods have been reported
for the separation, the development of a new powerful separation method is still a greatchallenge. We have previously reported polymer wrapping techniques which efficiently
solubilize/extract only sem-SWNTs with high chiral-selectivity by developing polyfluorene
derivatives (PFOs)3, 4, 5. However, there are serious problems when using these solubilizing
methods; that is, difficulty in the removal of the wrapping surfactants or polymers as well as their
low extraction yields.
In order to solve these problems simultaneously, here weNNNN
developed a newly designed, detachable solubilizer system using
meta-coordination bonding or hydrogen-bonding. Based on suchsupramolecular approach, three solubilizers were newly
designed and sysnthesized (Fig. 1). Thanks to the introduction of
H N
NH
N
N
weak coordination bonds into conventional PFOs, the newpolymers not only recognize semiconducting chirality but also
are removable from the sem-SWNT surfaces. The extracted
sem-SWNTs
wereanalyzedusing
UV-Vis-NIR,
two-dimensional photoluminescence and the Raman
HOOC
COOH
spectroscopies. The solubilized sem-SWNTs could be further
purified by removing the wrapping polymers, in which they
were washed in acid or strong sonication conditions. The
Figure 1. Chemical structures
quantitative elimination of solubilizers were confirmed byof solubilizers in this work.
spectroscopies including X-ray photoelectron spectroscopy. The
details of this study will be presented at the meeting.
2

2

Referneces[1] H. J. Dai, Acc. Chem. Res. 35, 1035 (2002).
[2] Cao, Q. & Rogers, J. A., Adv. Mat. 21, 29–53 (2009).
[3] H. Ozawa, N. Ide, T. Fujigaya, Y. Niidome, and N. Nakashima, Chem. Lett. 40, 239 (2011).
[4] K. Akazaki, F. Toshimitsu, H. Ozawa, T. Fujigaya, and N. Nakashima, J. Am. Chem. Soc., 134, 12700 (2012).
[5] T. Fukumaru, F. Toshimitsu, T. Fujigaya & N. Nakashima, Nanoscale 6, 5879–86 (2014).
Corresponding Author: N. Nakashima
Tel: +81-92-802-2845, Fax: +81-92-802-2845
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp– 97 –

2P-11FNTG-47, 2014

High yield synthesis of (6,4) single-walled carbon nanotube
by pulse plasma CVD○Bin Xu, Toshiaki Kato, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Single-walled carbon nanotubes (SWNTs) are regarded as promising materials in many
fields because of their excellent properties such as high mechanical strength, high carrier
mobility, and high current density. Despite all these merits, the application of SWNTs are still
remained as a big challenge, especially in the electrical devices fields. Since the chirality of
SWNTs plays an important role in deciding the electronic and optical properties of SWNTs, it
is important to realize the chirality-controlled synthesis of SWNTs. Plasma chemical vapor
deposition (CVD) is known as a powerful tool for the structural-controlled growth of nanocarbon materials [1,2]. Up to now, we have realized synthesis of SWNTs withnarrow-chirality distribution by advanced plasma processing such as time-programmed
plasma CVD, Au-catalyzed plasma CVD, and pulse plasma CVD [3-6].
In this study, we have improved the pulse plasma CVD though the precise adjustment ofgrowth conditions such as growth temperature, gaspressure, and plasma off time. The distribution ofchirality species can be suppressed up to three kinds((6,4), (6,5), (7,3)) under the suitable conditions.
Interestingly, photoluminescence intensity of (6,4)
SWNTs is higher than that of (6,5) SWNTs, which
can not be seen in other growth methods.
Furthermore, it is found that the growth of (6,4)
SWNTs can be selectively suppressed by adding
small amount of hydrogen during pulse plasma CVD.
This can be explained by the different stability ofcap structures.
[1] T. Kato and R. Hatakeyama, ASC Nano 6, 8508 (2012).
[2] T. Kato and R. Hatakeyama, Nature Nanotechnology 7, 651(2012).

Fig. 1: Photoluminescence-excitation
mapping of SWNTs synthesized bypulse plasma CVD.

[3] T. Kato and R. Hatakeyama, ACS Nano 4, 7395 (2010).
[4] Z. Ghorannevis, T. Kato, T. Kaneko, and R. Hatakeyama, J. Am. Chem. Soc. 132, 9570 (2010).
[5] B. Xu, T. Kato, K. Murakoshi, and T. Kaneko, The 47th Fullerenes-Nanotubes-Graphene General
Symposium, 1P-17 (2014).
[6] B. Xu, T. Kato, K. Murakoshi, and T. Kaneko, Plasma Fusion Res. 9, 1206075 (2014).
Corresponding Author: B. Xu
Tel: 022-795-7046, Fax: 022-263-9225,
E-mail: xu12@ecei.tohoku.ac.jp– 98 –

FNTG-47, 2014

2P-12

Soft X-ray Spectroscopic Study on Horizontally Aligned
Multi-walled Carbon Nanotube Films Irradiated by Ar Ions
○R. Tamura1,5, A. Tsukagoshi1,5, S. Honda 1,5, M. Niibe1, M. Terasawa1,5, R. Hirase2,
H. Yoshioka2, H. Izumi2, K. Niwase3, E. Taguchi4 , M. Oura5
1University of Hyogo, Himeji, Hyogo 671-2280, Japan
2Hyogo Prefectural Institute of Technology, Kobe 654-0037, Japan
3Hyogo University of Teacher Education, Kato, Hyogo 673-1494, Japan
4Osaka University, Ibaraki, Osaka 567-0047, Japan
5RIKEN SPring-8 Center, Sayo, Hyogo 679-5148, Japan

Intensity (a.u.)

Nanostructured carbon materials such as carbon nanotubes (CNTs) and graphenes havebeen extensively studied toward realization of potential nanodevice applications. The
morphology of the CNTs strongly relates to the device performance. For example,
horizontally aligned multi-walled CNTs (MWCNTs) have been demonstrated to be applicableto the nanodevices such as sensors, and LSI interconnects. On the other hand, irradiating
nanostructured carbon materials with energetic charged particles is thought to be capable oftailoring their structure and properties, and can be applied to process of nanodevice
fabrication [1]. It was reported that the electrical transport properties and structural propertiesof the individual CNT were modified by the electron irradiation [2]. Thus, many researches
were focused on the charged particle irradiated individual CNT. However effects of ion
irradiation on the structural properties of ensembles of horizontally aligned MWCNT films
have not been fully understood.
In this study, low energy Ar ions were irradiated to horizontally aligned MWCNT films(thickness: 35 m) using an electron cyclotron resonance ion source at BL17SU of SPring-8.
The structural properties of the irradiated MWCNT films were characterized by scanningelectron microscopy (SEM), Raman spectroscopy and transmission electron microscopy(TEM). In addition, soft X-ray photoelectronh = 700 eV
spectroscopy (XPS) and soft X-ray absorption
spectroscopy(XAS)
measurements
were
HOPG
performed to characterize electronic states of theirradiated MWCNT films at BL17SU of Spring-8
and BL09 of NewSUBARU, respectively. The
1×1015 ions/cm2
energy was calibrated with the standard sample. It
was found that as-grown MWCNT films presented
the same trend as highly oriented pyrolytic
as-grown
graphite (HOPG). Moreover, additional peaks in
XPS spectra of the valence bands of the MWCNT
films at 700 eV photon energy were recognized
after Ar ion irradiation (Fig. 1).
0[1] A. V. Krasheninnikov and K. Nordlund, J. Appl. Phys.
107, 071301 (2010).
[2] S. Suzuki et al., Jpn. J. Appl. Phys. 43, L1118 (2004).
Corresponding Author: S. Honda
Tel: +81-79-267-4922, Fax: +81-79-267-4922,
E-mail: s-honda@eng.u-hyogo.ac.jp– 99 –

10

20

30

40

50

60

Binding Energy (eV)Fig.1: XPS spectra of the valence bands of the
MWCNT films as-grown and irradiated by Ar
ions with HOPG as a reference.

FNTG-47, 2014

2P-13

Coherent G-band and RBM phonons in single wall carbon nanotubes○  Ahmad  R.T.  Nugraha, Eddwi H. Hasdeo, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
In the pump-probe spectroscopy, optical properties like differential transmittance (ΔT/T)  are  vibrating at phonon frequencies because the phonon modes in are vibrating in phase, which
are known as coherent phonons. For a single wall carbon nanotube (SWNT), Fouriertransform  of  ΔT/T  as  a  function  of  phonon  frequency  show  several peaks that correspond tothe  SWNT’s  coherent  phonon  modes,  such  as  the  radial  breathing  mode  (RBM)  and  G-band.
For the RBM of a SWNT, the coherent phonon signal has been understood to originate fromthe modulated diameter-dependent energy gaps due to the coherent RBM phonon oscillations[1-4]. On the other hand, while the G-band   phonons   can   also   modify   ΔT/T   of   SWNTs,   a  previous   theoretical   calculation   predicted   that   the   modulations   of   ΔT/T   due   to   G-band
phonons are much smaller than those caused by the RBM [5]. However, experimental
measurements showed that the coherent G-band signal is comparable to the RBM signal [6].
This fact indicates that coherent G-band phonons have a different generation mechanism. In
this study, we expect that the modulations of electron-photon interaction as a function of timeshould be responsible for the coherent G-band intensity instead of the energy gap modulations
as in RBM. The coherent G-band vibration cause larger change in the optical matrix elements
than the RBM vibration, in which the time-dependence of optical matrix elements was notnecessary. We also consider parameters like SWNT chirality and laser pulse width anddiscuss their effects to the coherent phonon spectra.
[1] A. Gambetta et al., Nat. Phys. 2, 515-520 (2006).
[2] Y.-S. Lim et al., Nano Lett. 6, 2696-2700 (2006).
[3] J.-H. Kim et al., Phys. Rev. Lett. 102, 037402 (2009).
[4] A. R. T. Nugraha et al., Phys. Rev. B 84, 174302 (2011).
[5] G. D. Sanders et al., Phys. Rev. B 79, 205434 (2009).
[6] J.-H. Kim et al, Phys. Rev. B 86, 161415 (2012).
Corresponding Author: A. R. T. Nugraha
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: nugraha@flex.phys.tohoku.ac.jp– 100 –

FNTG-47, 2014

2P-14

A nanostructure grown in single-walled carbon nanotubes by X-ray
irradiation and the following thermal annealing1‫ۑ‬Mitsuaki Matsuda1, Toshiya Murakami1, Kenji Kisoda2, and Chihiro Itoh1
Department of Materials Science and Chemistry, Wakayama University, Wakayama
640-8510, Japan2
Department of Physics, Wakayama University, Wakayama 640-8510, Japan

In single-walled carbon nanotubes (SWCNTs), X-ray irradiation forms pairsof interstitial carbon atoms and vacancies and leads to change of tube structure.
Thermal annealing gives rise to diffusion of the interstitial carbon atoms, and anumber of the interstitials recombine with vacancies.[1] In this presentation, we
demonstrate that a nanostructure grew after annealing the X-ray irradiated
SWCNTs. The nanostructure is presumably ascribed to the structure composedfrom the interstitial atoms.
SWCNTs grown by chemical vapor deposition were irradiated with X-ray(1254 eV), and subsequently annealed at 100-700 ºC in Ar atmosphere. The
pristine, irradiated and annealed samples were measured by Raman scattering
spectroscopy with an excitation wavelength of 532 nm.
Figure 1 shows Raman spectra of the pristine, X-ray irradiated and annealed
SWCNTs. The Raman intensities were normalized with respect to G bands.
Thermal annealing of the irradiated SWCNTs reduced the intensity of the X-ray
enhanced D band, indicating the X-ray induced defects were eliminated. Besides
the intensity reduction of the D band, we found a formation of a new peak around
1870 cm-1. The peak intensity started to grow around 350 ºC. The intensity has apeak around 450 ºC, and then decreased byraising the annealing temperature.
Thefrequency of this peak was independent of theprobe-laser wavelength, which indicates the newpeak is presumably ascribed to a nanostructure
but not to the double-resonance-related peaks of
SWCNTs. The similar Raman peaks werepreviously attributed to carbon chains in
multi-walled carbon nanotubes.[2] From theseresults, we suggest that the carbon chains wereformed in the X-ray irradiated SWCNTs. By
thermal annealing.
[1] M. Matsuda et al. 45th FNTG symposium, 2P-16.
[2] X. Zhao et al. Phys. Rev. Lett. 90, 187401 (2003).
CorrespondingAuthor:M.Matsuda,Tel:+81-73-457-8532
E-mail:s143052@center.wakayama-u.ac.jp– 101 –

Fig.1 Raman spectra of thepristine, X-ray irradiatedand annealed SWCNTs.

FNTG-47, 2014

2P-15

Raman scattering from aligned CNT forests of high absorption coefficient○Kouki  ISHIMOTO1, Kazuki SEKIYA1, Hirofumi KOJI1,
Hiroshi FURUTA1,2, Akimitsu HATTA1,2
Kochi Univ. Technol. 1, Research Inst., Kochi Univ. Technol. 2
E-mail: k.ishimoto0122@gmail.com, furuta.hiroshi@kochi-tech.ac.jp

Carbon Nanotubes (CNTs) are much attractive attention as a material in various application
fields because of their superior electrical conductivity and large surface area. High densityand vertically aligned CNT structures (CNT forest) show unique optical absorption behaviors[1, 2]. Blackbody-like absorption in CNT forests was explained as the recursive reflection andabsorption to the CNT body [2] and absorption coefficients of CNT forests are dependent on
the vertical alignment of CNT axis to the incident light [1]. We reported depth profiles ofRaman spectra of CNT forests by mean of confocal Raman spectrometer [3], which indicates
the G-Peak intensity are derived from the density, and also the apparent absorption coefficientof the forests. In this report, we obtained the apparent absorption coefficient from UV-VIS
spectra [4] and compared with Raman scattering.
CNT forests for the optical observations were prepared by a catalytic thermal CVD method
on Fe/Al (=2/3 nm) deposited by electron beam and Fe/AlO (=2/30 nm) catalyst deposited bymagnetron sputtering on a Si substrate. A thermal CVD process was operated at thetemperature of 730 degree with a carbon gas source of acetylene (C2H2) for 20 second. Inorder to perform annealing, samples were kept in a CVD chamber for 3.5 min at high vacuum,
before introducing C2H2 gas of 10 sccm flow rate, and pressure 0.8 Pa. For CNT forest Raman
measurements, confocal micro-Raman spectrometer was used. Raman measurements were
performed  with  1μm  step,  starting  from  a substrate surface, which was set as a reference state.
In addition, specular reflectance of CNT forests [4] using the UV-VIS spectra was measured.
During the experiments, synthetic conditions were unified; however grown CNT forests
showed different structures. We performed Raman spectroscopy measurement and totalreflection measurement using different structure CNT forest. Figure 1 shows plot of apparent
absorption coefficient measured by Raman spectroscopy (wavelength 532nm) vs. specularreflectance. The CNT apparent absorption coefficient values were obtained from Raman
spectra, through a logarithmic approximation of the decreasing slope of maximum G peakintensity. Apparent absorption coefficient values obtained from specular reflectance were also
increase, so we can derive the apparent absorption coefficient by Raman spectroscopy
measurement from the top surface. Figure 2 shows Raman spectra of CNT forests grown bydifferent Fe catalyst thicknesses. Further study will be needed to the same experiment by
these CNT forests, and to confirm the influence to Raman spectrum.
Acknowledgements: This work was supported by JSPS KAKENHI Grant Number 24560050.

Figure 1. Plot of absorption coefficient measured
Figure 2. Plot of Raman spectrum of different Fe
by catalyst Raman vs. total reflectancethickness[1] Y. Murakami et al., Carbon. 43(13) (2005) 2664-2676[2] K.Sekiya et al., JSAP(The Japan Society of Applied Physics) (2012) 17-076[3] K.Ishimoto et al., JSAP(The Japan Society of Applied Physics) (2014) 17-140[4] K. Sekiya*, H. Koji, H. Furuta, and A. Hatta, AVS60, Oct. 27 – Nov. 1, 2013, Long Beach, California, USA)– 102 –

FNTG-47, 2014

2P-16

Open-end for cloning from zigzag-type aligned carbon nanotubes○Megumi Shibuya1, Masafumi Inaba1, Kazuma Suzuki1, Yu Hirano1,
Michiko Kusunoki2, Hiroshi Kawarada1
1 Department of Nanoengineerging, Waseda University, Tokyo 169-8555, Japan
2 Eco topia Science Institute, Nagoya University, Nagoya 464-8603, Japan

1. Cloning from zigzag-type aligned carbon nanotubes
Carbon nanotube forest synthesized with silicon carbide surface decomposition
method (CNT on SiC)[1] are mostly zigzag-type[2] and exhibits the most densely packed
CNT forest (~1013 cm-2). It is attractive as non-catalyst substrate for the growth of CNTs.
It is necessary for re-growth to open their caps. In this work, we investigated surface
bonding before and after open-end treatment using X-ray Photoelectron
Spectroscopy(XPS).
2. Open-end treatment with H2O2
Carbon nanotubes were heated to 1600 ℃ in a vacuum of ~10-3 Pa for 3 h. They
were open-ended under mild oxidative conditions using dilute aqueous H2O2
solutions[3].
3. Transformation of surface bonding through open-end treatment
XPS spectra before and after open-end treatment shows that carbon nanotubes wereoxidized (Fig1,2). The results shows that carbon nanotubes were open-ended because of
the presence of -COO bond. We use zigzag-type aligned carbon nanotubes as template
for the growth of CNTs in the future.

Fig.1 XPS spectrum (wide scan) of zigzag typealigned carbon nanotubes

Fig.2 XPS spectrum (narrow scan) of zigzag typealigned carbon nanotubes

This research is partially granted by JSPS(No. 26630136)[1] M. Kusunoki et al., Appl. Phys. Lett.77, 531 (2000)[2] M. Kusunoki et al., Chem. Phys. Lett. 366, 458-462 (2002)[3] R. Marega et al.,Carbon 47, 675-682 (2009)
Tel: +81-3-5286-3391, Fax: +81-3-5286-3391,
E-mail: seal_1030@fuji.waseda.jp– 103 –

FNTG-47, 2014

2P-17

Effects of screening on propagation of graphene surface plasmons○Ken-ichi Sasaki and Norio Kumada
NTT Basic Research Laboratories, NTT Corporation, 3-1 Morinosato Wakamiya, Atsugi,
Kanagawa 243-0198, Japan
Plasmons, which consist of carriers and electromagnetic fields, are the principal elementsof excited states in solids. When carriers are confined in a two-dimensional layer, surface
plasmons can exist. The electromagnetic fields appear outside the layer and can be sensitive
to the screening effect provided, for example, by a metallic plate that is a part of a device,
which is not so obvious for other excited states in solids, such as electrons and phonons. A
device composed of graphene, provides a great opportunity to study this sensitivity of surface
plasmons, as was demonstrated by a recent time-resolved experiment [1], which we review
below.
Figure (a) is the schematic of a transport experiment performed by Kumada et al. ongraphene grown by SiC sublimation. After applying a current pulse with a frequency of a few
GHz at the injection gate on epitaxial graphene, they observed the current induced at thedetection gate located approximately 220 um from the injection gate. Figure (b) shows anexample of the current observed as a function of time. The waveform has a peak structure at
1.5 ns, which enabled the authors to define the propagation velocity of a pulse as the
propagation distance divided by the peak time, i.e., 220 um/1.5 ns ~ 150 km/s. The details of a
waveform, such as peak time, depend on the Fermi energy position EF, which was controlledusing a metal top gate in their experiment. As a result, they were able to find the EF
dependence of the velocity shown by the solid curve in Figure (c). The velocity decreases as
the Fermi energy approaches the Dirac point. For a wide range of EF the velocity is one orderof magnitude smaller than the Fermi velocity. The velocity in a device without a top gate wasobserved to be one
or two order ofmagnitudelarger
than
the
Fermi
velocity suggestingthat
thepresence/absence ofthe gate strongly
affects the plasmontransport.
We investigated the propagation velocity of surface plasmons in graphene, while paying
particular attention to the effect of a metal gate on the transport properties [2]. We will showthat in the absence of a metal gate, plasmons propagate faster than the electrons. In thepresence of a metal gate, the propagation velocity is much slower than Fermi velocity when
the screening effect provided by interface states is taken into account. Furthermore,slow-moving surface plasmons undergo a strong diffusion when EF is near the Dirac point,
which explains the drop at EF ~ 0.1 eV seen in Figure (c).
[1] N. Kumada et al., New J. Phys. 16, 063055 (2014).
[2] K. Sasaki and N. Kumada, Phys. Rev. B, accepted (2014).
Corresponding Author: K. Sasaki
Tel: +81-46-240-3033, Fax: +81-46-270-2361, E-mail: sasaki.kenichi@lab.ntt.co.jp– 104 –

2P-18

FNTG-47, 2014

Electronic Structure of Graphene Wrinkles Induced by Ni Substrate○Nguyen Thanh Cuong1,3, Minoru Otani1,3, Susumu Okada2,3
1

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8568, Japan
2
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
3
Japan Science and Technology Agency, CREST, Tokyo 102-0076, Japan

Energy (eV)Graphene is now attracting a lot of research interests because of its peculiar geometric andelectronic structures: it has a honeycomb atomic network and perfectly planar structure withatom thickness, so that they possess two linear dispersion bands at the Fermi energy. However,the unique electronic properties of graphene are highly sensitive to the network topology andinteraction with the underlying substrates. Furthermore, epitaxial graphene on metal
substrates usually possesses the non-planar structures such as: wrinkle or ripple structure [1].
These structural distortions are expected to modulate electronic properties of pristinegraphene, but microscopic understanding on the electronic structure modulation is not
sufficiently addressed yet. Therefore, in this work, based on first-principles calculations weinvestigate the geometry and electronic structure of graphene wrinkles on Ni surface. We findthat the strong interaction between
Graphene wrinkle/Ni(111)PDOS of C atomgraphene and Ni substrate results in a4
confined graphene wrinkle at nanoscale3
width. Our projected density of state2
W=1.01 nm
analyses showed that the carbon atoms
1
situated in this wrinkle region exhibit the0
gap
semiconducting property with band-gap of−1
1 eV, as shown in Fig. 1. This result is−2
however sharp contrast with the metallic−3
behavior of isolated graphene wrinkles [2],−4−0.15 00.15
indicating that the graphene wrinkle on Ni
DOS (state/eV)
surface could act as a graphene Fig.1: Side view of optimized geometry of graphene
nanoribbon. Furthermore, we also findwrinkle on Ni(111) surface and projected density ofthat the band-gap of C atoms in graphenewrinkle on Ni substrate also strongly state (PDOS) of C atoms at the center of wrinkle.
depends on the width of graphene wrinkle. These findings provide news insights into
understanding the transport properties of graphene wrinkle on metal substrates.
[1] W. Zhu et al., Nano Lett. 12, 3431-3436 (2012)[2] S. Okada, T, Kawai, Jpn. J. Appl. Phys. 51, 02BN05 (2012)
Corresponding Author: Nguyen Thanh Cuong
Tel: +81-29-861-6067, Fax: +81-29-861-3171,
E-mail: cuong-nguyen@aist.go.jp– 105 –

FNTG-47, 2014

2P-19

Electrical and heat transport of isotopically-modified
graphene heterojunctions○Yuki Anno, Kuniharu Takei, Seiji Akita and Takayuki Arie
Department of Physics and Electronics, Osaka Prefecture University, Osaka 599-8531, Japan
Graphene randomly containing carbon isotopes has already been synthesized using two
carbon isotopes, and shows limited phonon propagation and reduced thermal conductivity
because the main heat carrier in graphene is phonon [1]. However, the synthesis forcontrolling the region of isotopically modified graphene has not been performed. In this study,
we performed artificially controlled synthesis of isotopically modified graphene
heterostructures by chemical vapor deposition (CVD) and clarified the electrical and thermal
properties of the graphene heterojunction for device application.
12
C-graphene and 13C-graphene were synthesized by low-pressure CVD. First,
13
C-graphene synthesized with 13CH4 was directly patterned on a copper foil by conventional
photolithography and O2 plasma etching. Immediately after removing photoresist,
12
C-graphene was synthesized with 12CH4 by CVD. Heterostructured graphene wastransferred onto an SiO2(300nm)/Si substrate and evaluatedby Raman spectroscopy. To measure the thermal property,
heterostructured graphene was suspended to estimate thetemperature profile by the peak shifts of Raman G band.
Figure 1 shows the composed image of an optical
micrograph and Raman 2D band mapping of
12 13
C/ C-graphene. 12C/13C-graphene heterostructures weresuccessfully synthesized in the same plane as monolayer
Fig.1 Raman mapping image ofwith a few defects. Double 2D peaks in the Ramangraphene heterostructures.
spectrum at the junction indicate that the heterojunction has
2D
a clear boundary (Fig. 2). Electrical measurement across theC-graphene
heterojunction showed that the mobility was estimated as405.4 cm2V-1s-1. The mobility of the 12C- and 13C-graphene
C/ C junction
were 385.4 cm2V-1s-1 and 547.9 cm2V-1s-1, respectively. No
C-graphene
2D
remarkably reduction in the mobility across theheterojunction suggests that graphene heterostructures areelectrically well connected. Figure 3 shows the temperature
1200
1600
2000
2400
2800
Raman shift [cm-1]
profile across the suspended graphene heterostructure
2 Raman spectra from 12C- anddetermined by peak shifts of Raman G band, indicating that Fig.
13
C-graphene and their junction.
the thermal conduction at the junction was drasticallyreduced with high thermal resistance (11.8 K/μW per 1 μm
of boundary length). Our proposed technique could control
the electrical and heat transport independently and will becapable of fabricating new functional graphene devices.
Intensity [arb.unit.]

12[1] S. Chen, Q. Wu, et al. Nature Mater, 11, 203-207 (2012).
[2] Y. Anno, K. Takei, S. Akita, T. Arie. Phys. Status Solidi RRL.,in press.
Corresponding Author: T. Arie
Tel: +81-72-254-9265, Fax: +81-72-254-9265,
E-mail: arie@pe.osakafu-u.ac.jp– 106 –

12

12

13

13

13

Fig.3 Temperature profile ofgraphene heterostructures.

FNTG-47, 2014

2P-20

Influence of growth temperature on formation of graphene using nozzle
injection chemical vapor deposition method○Yusuke Matsuura, Hideki Sato, Hideto Miyake, Kazumasa Hiramatsu
Graduate School of Engineering, Mie University, Tsu 514-8507, Japan
Graphene has attracted much attention owing to its many unique properties and potential
applications [1]. It is considered that a chemical vapor deposition (CVD) method is apromising for production of graphene. In this study, we have examined growth temperature ofgraphene by means of a low-pressure alcohol catalytic CVD (LP-ACCVD) method [2]. Here
we have adopted nozzle injection method to supply carbon source gas to a substrate. Thismethod enables efficient supply of carbon source gas
(b)
(a)
(c)
to a substrate for the growth of graphene. Therefore,
we can expect efficient growths and lowering of thegrowth temperature of graphene.
P-type Si (100) wafers with SiO2 layer (300 nm inthickness) were used as substrate for the graphene(d)(e)
growth. Fe film was used as a catalyst layer. The film
was deposited onto the substrate by a vacuum
evaporation method (60 nm in thickness). The
substrate was introduced into a high vacuum chamber(base pressure: <1x10-4 Pa) and then the substrate was Fig.1: OM images of substrates after CVD
heated to the growth temperature (600-800˚C). processes. Growth temperatures are (a)Ethanol gas was then introduced into the chamber via 600˚C, (b) 650˚C, (c) 700˚C, (d) 750˚C andthe nozzle (0.50 mm inner diameter). The irradiation (e) 800˚C. The scale bars are 20 μm.
of ethanol gas to the substrate was carried out in apressure of 0.5 Pa for 30 min. After the irradiation, thetemperature of the substrate was lowered with aconstant cooling rate (50℃/min).
Figures 1 (a)-(e) show optical microscope (OM)
images of the surfaces of substrates after CVD at thetemperature between 600-800˚C. These indicate thatthe higher growth temperature gives the larger domain
1200
1700
2200
2700
size. Figure 2 is representative Raman spectra for the
Raman shift (cm-1)
surfaces of the substrate shown in Fig.1 (a)-(e). Raman
Fig.2: Raman spectra on surfaces ofspectra of ≦650˚C show that 2D/G peak intensity substrates shown in Fig.1 (a)-(e).
ratios decreases as the growth temperature lowers. Excitation wavelength is 532 nm.
These results indicate that the domain size and thenumber of layer of graphene change at the growthtemperature between 700 and 750˚C, which corresponds to the eutectoid temperature of iron(723˚C).
G

Intensity(a.u.)

D

2D

600℃

650℃

700℃

750℃
800℃

[1] F. Shedin et al. Nat. Mater. 6, 652 (2007).
[2] D. Sawaguchi et al. J. of Appl. Phy. 51, 01AH03 (2012)
Corresponding Author: H. Sato Tel: +81-59-231-9404, Fax: +81-59-231-9404,
E-mail: sato@elec.mie-u.ac.jp– 107 –

2P-21FNTG-47, 2014

Nucleation control of graphene in precipitation methodby the use of Al2O3 barrier and Au capping layers○

Jnmpei Yamada, Manabu Suzuki, Yuki Ueda, Shigeya Naritsuka, and Takahiro Maruyama
Dept. Mat. Sci. & Eng., Meijo Univ., Nagoya 468-8502, Japan[Introduction] Graphene is a two-dimensional material having monolayer of carbon atoms
in a honeycomb lattice. Its superior electrical, mechanical, and chemical properties are
expected to apply in various fields. In order to improve the quality, the enlargement of thedomain structure is mandatory. The use of Al 2O3 barrier and/or Au capping layers is
effective to improve the quality in the precipitation method [1]. In this paper, the effect of
Al2O3 barrier layer and/or Au capping layer is studied in the precipitation method bysystematically comparing the characteristics of graphene grown with/without the barrier andcapping layers.
[Experimental Methods] Al2O3, Ni, amorphous carbon (a-C) and Au layers were deposited
on a sapphire substrate using electron beam evaporation. Four types of samples wereprepared to compare the qualities of grown graphene; Ni(300nm) / a-C(40nm) / sapphire
substrate (sample A), Ni(300nm) / Al2O3(2nm) / a-C(40nm) / sapphire substrate (sample B),
Au(20nm) / Ni(300nm) / a-C(40nm) / sapphire substrate (sample C), and Au(20nm) /Ni(300nm) / Al2O3 (2nm) / a-C(40nm) / sapphire substrate (sample D). The samples wereannealed at 800oC, for 120 minutes, in a vacuum to precipitate graphene. Raman spectro
scopy, and X-ray photoelectron spectroscopy (XPS) were used to characterize the samples.
[Results and discussion] Figure 1 shows the Raman spectra of each sample. G’/G   ratio  shows that the sample C is possibly monolayer while others are multilayer. The thickness ofeach sample increases in the order, sample C, D, B, and A. The D/G ratio of the sample D as
small as 0.1 indicates a high-quality graphene was grown by the method. Fig.2 shows XPS
spectra of the samples. The sample D has not only a highest carbon peak but also low andobscure Ni and Au peaks. This indicates that the coverage of the graphene is large anduniform. Al2O3 barrier layer plus Au capping layer structure (sample D) is found most useful
to suppress the excess precipitation and, consequently, to grow a uniform and smoothgraphene with large domains.
C1s
Ni2p
Ni3p,sNi LMM
Au4f

Fig.1 Raman spectra

Au4d

Au4p

Fig.2 XPS spectra

Reference: [1] R. S. Weatherup et al., Nano Lett., 13 (2013) 4624.
Acknowledgement: This work was partly supported by Grant-in-Aid for Specially Promoted Research(No.25000011) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
Corresponding Author: J.Yamada
Tel: +81-52-838-2387
E-mail: 100425324@ccalumni.meijo-u.ac.jp– 108 –

FNTG-47, 20142P-22

Ultrahigh temperature process of graphene oxides using solar furnace
for their structural restoration
żT. Ishida1, Y. Miyata1, T. Kusumoto1, K. Yamamoto1, Y. Shinoda2 and Y. Kobayashi1
1Department of Applied Physics, Osaka University, Suita 565-0871, Japan
2
Wakasawan Energy Research Center, Tsuruga 914-0192, Japan
Graphene oxides (GOs) are a promising material for large scale applications of graphene
because of their mass-production feature due to efficient chemical exfoliation of graphite.
However, defects such as oxygen-containing groups and lattice vacancies are formed during
their synthesis process and the restoration of the defects is a crucial issue for their practicaluse as the graphene. It has been reported that GO restoration significantly proceeds at hightemperature under vacuum and inert gas conditions. But even if the GO is annealed at 1000 ºC,
the temperature often used in typical CVD processes, the crystallinity of the obtained GO is
not sufficient and process at much higher temperatures should be required [1]. Solar furnace isvery suitable for this purpose since it is very handy system and can heat specific position ofsamples at around 2000 ºC. In this work, we applied the solar furnace to heat the GO under N2
environment and examined the effect of ultrahigh temperature annealing to the structural
restoration of the GO.
Sunlight
Figure 1 shows schematic setup of the ultrahightemperature process system used in this study. Sapphire,
Fresnel lenszirconia, and graphite were used as the materials of (100 cm
x140 cm)Concentrated
Quartz tube
crucibles and substrates. Commercially available GO
x~10000
Grapheneflakes and sheets (Graphene Laboratories Inc., NiSiNa
Substratematerials Co. Ltd.) were dispersed on a substrate (5 mm
Crucible
1cm䕕
Thermal insulator
x 5 mm), and were treated at high temperature by
Sample stage
irradiating concentrated sunlight focusing to the sample Water-cooled
flangeVacuumgage
area (1 cm x 1 cm) under N2 gas environment at
atmospheric and reduced (100~500 Pa) pressures. Gas inlet
Gas exhaust(Pumping)
Sample temperature was regularly monitored by optical (Flow regulated)
pyrometer, and was verified by observing melting Fig.1: Schematics of ultrahigh temperaturepoints of various metals. Raman spectra observed from process system using solar furnaceannealed GOs are shown in Fig. 2. Relative intensities ofAnnealed at reduced pressure(N , 430 Pa) for 10 min
D- and 2D-bands to G-bands, which are helpful guideline
for the GO restoration, were remarkably improved
compared with those of the previous processes at 1000 ºC
Pristine GO
under ethanol environment [1], indicating superiority of
Annealed at atmosphericthis process. The process condition of reduced pressurepressure (N ) for 5 min
gives rise to significantly better feature in the Raman
spectra than that of atmospheric one. This result suggeststhat impurities containing in carrier N2 gas (99.999 %) are
Pristine GO
not negligible and attack GO surface to induce
1000
1500
2000
2500
3000
considerable defects in the high temperature process.
Intensity [a.u.]2

2

Raman shift [cm-1][1] R. Negishi et al., The 66th JSAP spring meeting,
18p-E2-11 (Tokyo, 2014)
Corresponding Author: Y. Kobayashi,
E-mail: kobayashi@ap.eng.osaka-u.ac.jp

Fig.2: Raman spectra observed from graphenesamples processed at around 1700 ºC under N2
environments of reduced and atmospheric pressure.
Excitation wavelength is 532 nm.

– 109 –

2P-23

FNTG-47, 2014

Growth of densely-aligned graphene nanoribbons arrayfrom nickel nanobar by rapid heating plasma CVD○Hiroo Suzuki, Toshiaki Kato, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Graphene nanoribbons (GNRs) combine the unique electronic and spin properties ofgraphene with a transport gap that arises from quantum confinement and edge effects. This
makes them an attractive candidate material for the channels of next-generation transistors.
Although GNRs can be made in a variety of ways, the reliable site and alignment control of
GNRs with high on/off current ratios remains a challenge. Plasma chemical vapor deposition(CVD) is known as fruitful method for the structural-controlled growth and damage-freefunctionalization of nano carbon materials such as carbon nanotubes [1-3] and graphene [4-6].
We have developed a new, simple, scalable method based on the advanced plasma CVD
method for directly fabricating narrow (~23 nm) GNRs devices with a clear transport gap(58.5 meV) and a high on/off ratio (>104) [7]. In spite of the outstanding advantages of thismethod, further improvement of growth yield is
required to realize the integration of GNRs device inlarge scale. Understanding the growth mechanism isimportant to solve this problem. In this study, we
attempted to reveal the growth mechanism of GNRs
aiming for the improvement of growth yield. Basedon the systematic investigations, we found that thecorrelation between evaporation rate of Ni andamount of carbon supply to Ni strongly affects theyield of GNRs growth. Through the precise
adjustment of amount of carbon supply during
plasma CVD, the yield of GNRs growth can be
drastically improved. Based on this result,fabrication of densely-aligned GNRs were carriedout under the suitable conditions, resulting in the Fig.1: (a) Typical scanning electron microscopy
image and (b) G-band Raman mapping image
successful integration of high density GNRs array of high density GNRs array.
(4/μm) in large scale by our method.
[1] T. Kato and R. Hatakeyama, J. Am. Chem. Soc. 130, 8101 (2008).
[2] T. Kato and R. Hatakeyama, ACS Nano 4, 7395 (2010).
[3] Z. Ghorannevis, T. Kato, T. Kaneko, and R. Hatakeyama, J. Am. Chem. Soc. 132, 9570 (2010).
[4] T. Kato, L. Jiao, X. Wang, H. Wang, X. Li, L. Zhang, R. Hatakeyama, and H. Dai, Small 7, 574 (2011).
[5] T. Kato and R. Hatakeyama, ACS Nano 6, 8508 (2012).
[6] H. Suzuki, T. Kato and T. Kaneko, Plasma and Fusion Res. 9, 1206079 (2014).
[7] T. Kato and R. Hatakeyama, Nat. Nano. 7, 651 (2012).
Corresponding Author: H. Suzuki
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: suzuki12@ecei.tohoku.ac.jp– 110 –

2P-24

FNTG-47, 2014

Production of Graphene Quantum Dots fromSingle-walled Carbon Nanotubes○Misaki Takahashi, Ryota Jinnouchi, Toshiki Sugai
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Graphene quantum dots (GQDs) are nanometer-size graphene fragments. They arepromising materials for many fields because of their unique electronic and optical property
due to quantum confinement (size) and edge effects. They have been produced from various
carbonaceous materials such as carbon fibers [1], double-wall carbon nanotubes [2],single-wall carbon nanotubes (SWNTs) with a diameter less than 2 nm [3], and Glucose [4]through mainly oxidation processes. Their size and morphology are controlled by the reaction
conditions [4]. To produce smaller GQD in particular, narrow SWNTs would be one of thebest materials considering the nano ribbons derived from them [5]. Here we try to productionof smaller GQDs by chemical oxidation of CoMoCAT SWNTs with a diameter of 0.7-1.3 nm.
CoMoCAT (Sigma-Aldrich) were added into a mixture of concentrated H2SO4 and HNO3
followed by sonication for 24 hours. The oxidized mixture was diluted with deionized (DI)water and then centrifuged at 10000 rpm for 20 min to separate GQDs and SWNTs. Collectedsupernatant containing GQDs were neutralized with NaOH followed by re-crystallization toeliminate by-produced salt. The produced GQDs were characterized by TEM, absorption, andphotoluminescence (PL) observation.
Fig.1 shows a TEM image of highly crystalized GQDs with a lattice parameter of 0.33 nm
and diameter of ~10 nm revealing the stacked graphite like structure and size distribution,
both of which agree well with previous reports [2]. The optical properties, especially PL, aresimilar to those of the GQDs produced from othermaterials. Those almost the same GQDs fromvarious carbonaceous materials show that the size
control should be performed with the intensity ofthe oxidation and suggests that they are produced
not from the major components of the starting
materials but from minor ones.
[1] J. Peng et al. Nano Lett. 12, 844 (2012).
[2] F. Li et al NPG Asia Materials 5 e60 (2013).
[3] Y. Dong et al. Carbon. 64, 245 (2013).
[4] Tang et al ACS Nano 6 5102 (2012).
[5] J. M. Tour et al Nature 458 872 (2009).
Corresponding Author: T. Sugai
Tel: 047-472-4406
E-mail: sugai@chem.sci.toho-u.ac.jp

Fig.1 TEM image of CoMoCAT-derived GQDs

– 111 –

2P-25

FNTG-47, 2014

Alcohol CVD Growth of Millimeter Scale Single-Crystal Graphene on
Copper Foils○Kohei Tsushima, Masaki Sota, Xiao Chen, Sungjin Kim, Shohei Chiashi, Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Graphene, for its one-atom-thick two-dimensional structure, is one of the most expectedmaterials for its superior properties in mechanical strength, carrier mobility, and thermal
conductivity. While mechanically exfoliated graphene is high-quality single-crystal, it isdifficult to obtain large-scale flake [1]. On the other hand, the chemical vapor deposition(CVD) method produces graphene with large sizes, but it is often polycrystalline [2].
Therefore, a method for the growth of large single-crystal, high-quality graphene has been
extensively explored. Here, we report the alcohol CVD technique for the growth of millimeterscale single-crystal graphene on commercially available copper foils.
A typical CVD growth procedure is as following: 80  μm  thick copper foils are cleaned by
10% HCl for 40 min, then are immersed in DI water and 2-propanol for 5 min, respectively.
Afterwards, it is oxidized at 240 °C for 60 min in air. The pocket structure is formed byfolding the copper foil [3]. After being loaded into a quartz tube the Cu foil is heated to1065 °C, and exposed to low pressure ethanol with Ar/H2 buffer gas for 20 hours.
An optical image of the copper-foil surface after CVD is shown in Fig. 1. It was oxidized
in air for direct observation of graphene. Several 5 mm-sized graphene with hexagonal shape
are observed. Raman spectroscopy shown in Fig. 2 is measured after the graphene wastransferred to Si/SiO2 substrates. The D-band intensity is negligible, suggesting the low defectlevel and large grain size. The intensity ratio of 2D band to G band is about 2, which is asignature for single-layer graphene. Combined with the pre-oxidation of copper substrate,alcohol CVD is proved to be very useful for the synthesis of millimeter-size single-crystal
graphene.
[1] K. Novoselov, et al. Science, 306, 666 (2004).
[2] X. Li, et al. Science, 324, 1312 (2009).
[3] X. Li, et al. J. Am. Chem. Soc. 133, 2816 (2011).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp

Fig.1: Optical image of graphene on the copper

Fig.2: Raman spectrum of graphene after transferred to afoil.

Si/SiO2 substrate.

– 112 –

2P-26

FNTG-47, 2014

Synthesis of Multi-layer Graphene for Wiring Application
by Precipitation Method using Hybrid Diffusion Barrier Layer
Manabu Suzuki, Jumpei Yamada, Yuki Ueda,
Takahiro Maruyama, and Shigeya Naritsuka
Fac. Sci. & Tech., Meijo University, Nagoya 468-8502
Graphene attracts much attention due to its excellent properties, such asmechanical strength, high carrier mobility, surface sensitivity, and atomic-scale
thickness. Multi-layer graphene is also tried to apply electrical wiring systems from its
great endurance for the current. However, it is difficult to achieve uniform multi-layer
graphene with large domains, which are mandatory for the application. Weatherup et al.
reported that carbon diffusion barriers are useful to fabricate a uniform, high-quality
graphene in the precipitation method [1]. In this study, the method is developed toprovide multi-layer graphene with large domains with increasing the amount of the
precipitating carbons by increasing both the annealing time and temperature.
After depositing Au (20nm)/ Ni (300nm)/ Al2O3 (2nm)/ a-C (40nm) on asapphire substrate using electron beam deposition, the samples were annealed in a
vacuum at 900oC for 5, 30, 60min, respectively.
The coverage and the number of the graphene layers were found to increase
with the annealing time from the observation of the morphology (not shown). After thegraphene started to cover the surface of the catalysts, the nucleation of grapheneoccurred under the layer. The size of the islands reached to 15m in the diameter after
the annealing for 60min, as shown in Fig.1. From the Raman spectra in Fig.2 withstrong, sharp G and tiny D peaks (D/G ratios of less than 0.01), the qualities of thegraphene  are  found  become  excellent.  The  G’/G  ratios  of  the  position  (a),  (b)  and  (c),indicated in Fig.1, suggest the unique resulted structure of the layer, which consists of 2
or 3 ML-thick graphene islands and an overlaid 1ML-thick uniform graphene.

(ｂ)
(c)

(a)

Intensity[a.u.]

G
G'

D

(a)
(b)
(c)

1000

1500

2000

Raman Shift[cmFig.1 Surface morphology

2500

-1

3000

]

Fig.2 Raman spectra

Reference: [1] R. S. Weatherup et al., Nano Lett., 13 (2013) 4624.
Acknowledgement: This work was partly supported by Grant-in-Aid for Specially Promoted Research(No.25000011) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

– 113 –

2P-27

FNTG-47, 2014

Graphene growth on wide terraces of SiC (0001) in Ar atmosphere○Chenxing  Wang,  Hitoshi  Nakahara,  Koji  Asaka,  and  Yahachi  Saito
Department of Quantum Engineering, Nagoya University, Furo-cho, Nagoya 464-8603, Japan

High quality epitaxial graphene have been formed by thermal decomposition of SiC due
to sublimation of Si atoms during heat treatment. However, surface steps on single-crystalline
SiC substrates prevent graphene from continuously growing across SiC surfaces. Therefore,
step-free SiC surfaces or wide terraces were needed for preparing uniform graphene.
Nevertheless, as a matter of fact, the step edges play an important role of providing
carbon atoms for the graphene growth. For the stepped surfaces, graphene grows from thestep edges as shown in figure 1a; while, for the center of wide terraces, graphene also grow on
the terraces by forming pits (figure 1b) because of the lack of carbon source. The formation ofpits prevents graphene from being formed uniformly on wide terraces.
In this report, considering that the sublimation of Si atoms is much easier from step edges
than from terraces at a high pressure of argon atmosphere, we aim to grow graphene only
from the step edges by controlling the graphene growth temperature. Figure 2 shows a SEM
image of graphene grown on a 5-μm-wide of SiC by annealing sample at 1550ºC for 20min in
1atm of Ar atmosphere. Buffer layer with stripped pattern, which are commonly observed
together with step-edge grown graphene, remained across the whole terrace, indicating that all
the monolayer graphene on this terrace was grown from the step edge. It is expected thatfurther annealing will decrease the stripy buffer layer areas.

Fig. 1 two processes of graphene growth on SiC(0001): (a) from step edges; (b) on step-free surfaces
or center of wide terraces.

Corresponding Author: Chenxing Wang
Tel: +81-52-789-3714, Fax: +81-52-789-3703,
E-mail: cx-wang@surf.nuqe.nagoya-u.ac.jp

Fig. 2 SEM image of graphene grown on 5-μm-wide
terrace of SiC surface. Stripy monolayer graphene areas(gray regions) and buffer layer areas (bright regions)formed on this terrace.

– 114 –

FNTG-47, 2014



2P-28

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E\WKHUPDOGHFRPSRVLWLRQLQDUJRQJDVDWPRVSKHUH
ż$NNDZDW5XDPPDLWUHH+LWRVKL1DNDKDUD<DKDFKL6DLWR
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan

2SWLFDO DQWHQQDV DUH GHYLFHV WKDW HIILFLHQWO\ FRQYHUW WKH HQHUJ\ RI IUHH SURSDJDWLQJUDGLDWLRQ LQWR ORFDOL]HG HQHUJ\ DQG YLFH YHUVD 7KH GHYHORSPHQW RI RSWLFDO DQWHQQDV FDQLPSURYH WKH HIILFLHQF\ RI VHQVLQJ SKRWRGHWHFWLRQ OLJKW HPLVVLRQ VSHFWURVFRS\ DQG VR RQ*UDSKHQHULQJVDUHSURPLVLQJPDWHULDOIRUGHYHORSLQJRSWLFDODQWHQQDVEHFDXVHLWVSODVPRQVKDYHPRUHHOHFWURPDJQHWLFFRQILQHPHQWWKDQPHWDOOLFSODVPRQV (SLWD[LDO JUDSKHQH ZDV IDEULFDWHG E\ HPSOR\LQJ 1W\SH 6LWHUPLQDWHG +6L& VXEVWUDWHV7KH6L&VXEVWUDWHZDVILUVWFOHDQHGE\XOWUDVRQLFSUHFOHDQLQJZLWKDFHWRQH
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SUHVVXUHRIDWP)LJ D VKRZVDQ$)0WRSRJUDSKLFLPDJH)LJ E LVDQ$)0SKDVHLPDJH PHDVXUHG DW WKH VDPH SRVLWLRQ DQG WLPH DV )LJ  D  GLVSOD\LQJ WKHUH DUH PDQ\JUDSKHQHULQJVRQWKH6L&VXEVWUDWH WKHEULJKWUHJLRQVLQGLFDWHJUDSKHQHUHJLRQV )LJ F 
VKRZV D WRSRJUDSKLF LPDJH IRFXVLQJ RQ JUDSKHQH ULQJ :H DOVR WU\ WR DQQHDO WKH 6L&
VXEVWUDWHVXQGHUGLIIHUHQW$USUHVVXUHVXFKDV8+9DQG$USUHVVXUHRIDWP7KHUHLVQRDQ\JUDSKHQHULQJRQERWKFRQGLWLRQV)LJ$)0PRUSKRORJ\ DDQGF DQGSKDVH E LPDJHVRIWKHVDPSOHZKLFKDQQHDOHGXQGHU$USUHVVXUHRI
DWP – 115 –

2P-29FNTG-47, 2014

Nano-Saturn : Theoretical Design of New C60 Inclusion Compounds○Shota Kigure and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
Structural hierarchy of nanocarbon materials allows us to design the novel
complexes which possess unusual geometric and electronic properties. Indeed, recently,
such complexes comprising C60 and cyclic hydrocarbon molecules have beensynthesized experimentally. These complexes have the shortest peapod structure inwhich C60 is included within the cyclic hydrocarbon molecules, such as
cycloparaphenylene and cyclochrysenylene. Electronic structure of such complexes is
not the simple sum of those of constituents because of the substantial interaction
between them. In the present work, we theoretically design novel inclusion compounds
based on density functional theory (DFT) with local density approximation.
Figure 1 shows an optimized geometric structure of a novel inclusioncompound which consist of C60 and hexa-p-(m-biphenyl).

The compound is Saturn inthe nano-world. Our DFT calculations show that the formation reaction of thenanosaturn is exothermic with the energy gain of 0.7 eV. Under the optimum structure,
the saturn’s ring is slightly dislodged from the equator of C60 leading to two metastableconformations, because the pore of the ring is insufficient to accommodate C60.
Moreover, the structural hindrance leads to the other nanosatrurn structure in which thephenyl groups in the ring is tilted
each other to accommodate C60.
Corresponding author: Shota Kigure
Email:
skigure@comas.frsc.tsukuba.ac.jp
TEX/FAX: 029-853-5600(8233) /029-853-5924

Figure 1 Optimized structure of C60 included within
hexa-p-(m-biphenylene)– 116 –

FNTG-47, 2014

2P-30

Magnetic Properties of Decamethyl C60 Chain○Kohei Narita and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
Hollow-cage carbon clusters, fullerenes, are known to form condensed phases in which
fullerenes act as an atom-like constituent unit with the structural hierarchy. Besides the
structural hierarchy, the electronic structure of fullerene solids also reflects that of its
constituent unit. According to both structural and electronic hierarchies, the solid phases offullerene induce interesting derivatives and compounds those possess unusual electronic
properties. Pentaorgano C60, fullerene shuttlecocks, also forms a condensed phase as in thecase of pristine C60. In the case, because of its conical structure, the molecules form
one-dimensional columnar structure in which the shuttlecock is stacked in head-to-tail manneras in the case of badminton shuttlecock [1]. Following the synthesis of pentaorgano C60,
decaorgano C60 have been also synthesized [2]. By analogy with the pentaorgano C60,
decaorgano C60 also form condensed phase being expected to exhibit interesting variation in
their electronic properties. Thus, in the present work, we theoretically investigate theenergetics and electronic structures of one-dimensional column of decaorgano C60 based on
the density functional theory with local spin density approximation.
The most stable intermolecular distance of decamethyl C60 is found to be 11.11 Å which is
10% larger than that of the pristine C60 because of the ten methyl groups attached to bothsides of C60. Since the isolated decamethyl C60 possesses two spin states as their metastablestate, i.e. singlet and triplet states, we find that the one-dimensional decamethyl C60 chainpossesses five metastable spin states under the optimum lattice parameter. Among them,
antiferromagnetic spin ordering not only in intra but also in inter molecule is found to be theground state, while the remaining state possess higher total energy by a few tens meV. The
spin ordering is ascribed to the flat deispersion bands associated with the radical spins on themolecules.

Fig. 1 Geometric structure of deca-methyl C60 chain
Fig. 2 Total energy of decamethyl C60 chain. Theenergies are measured from total energy of thedecamethyl C60 in an isolated system.

References[1] Y. matsuo, et al. J. Am. Chem. Soc. 126 (2004) 432[2] E. Nakamura, et al. J. Am. Chem. Soc. 125 (2003) 2834.
Corresponding Author: K. Narita
Tel: +81-29-853-5921, Fax: +81-29-853-5924
E-mail: sokada@comas.frsc.tsukuba.ac.jp– 117 –

2P-31FNTG-47, 2014

Pressure-induced phase transition of C60(Fc)2 nanosheet○Kyohei Kato1, Kana Osonoe1, Kun’ichi Miyazawa2, Masaru Tachibana1
1

Department of Nanosystem Science, Yokohama City University, Yokohama 236-0027,
Japan
2
National Institute for Materials Science, Ibaraki 305-0044, Japan High-pressure studies on fullerene crystals have led to various interest phases such as
polymer [1], amorphous and super-hard [2]. Recently, solvated fullerene micro- or nanocrystals grown by solution method have attracted much interest for their unique shapes,
structures, and properties. Thus, high-pressure studies on such solvated fullerene nanocrystals are of very interest for the production of polymerizations and new materials. In
this paper, we report the structural change of C60(Fc)2 nanosheets obtained by LiquidLiquid Interfacial Precipitation (LLIP) method under high pressure, where Fc is Ferrocene.
 The C60(Fc)2 nanosheets were prepared by the LLIP method [3], in which an interface
was formed between isopropyl alcohol (IPA) and toluene. For high-pressure studies, thepressure was generated by a diamond anvil cell (DAC) and ruby luminescence method wasused for pressure determination. Samples and ruby powder were loaded into a 300 µm
diameter hole in a stainless-steel gasket. Silicone oil was used as pressure medium. Raman
experiments were carried out at room temperature using a Raman spectrometer (NRS
1000) with a 532 nm green laser line as excitation. The highest pressure reached in thisstudy is about 5.0 GPa.
 Two clear transitions are observed in the pressure dependence of Raman peaks of
C60(Fc)2. Generally the peak frequency monotonically increases with increasing pressure.
The slope of the peak frequency with pressure discontinuously changes at around 0.7-1.3
GPa. The corresponding change is also observed as the splitting of another peaks. The
other transition is observed at around 2.8 GPa. This exhibits the splitting of Ag(2) mode of
C60 at 1468 cm-1 and the appearance of new peaks at 637 and 957 cm-1. These origins of
two transitions will be discussed in the light of the polymerization [4] and orientation
disorder-order transition [5].
[1] Y. Iwasa et al., Science 264, 1570 (1994).
[2] L. Wang et al., Science 337, 825 (2012).
[3] T. Wakahara et al., J. Am. Chem. Soc. 131, 9940 (2009).
[4] A. M. Rao et al., Phys. Rev. B 55, 4766 (1997).
[5] K. Meletov et al., Phys. Rev. B 55, 10090 (1995).
Corresponding Author: M. Tachibana
Tel & Fax: +81-45-787-2307
E-mail: tachiban@yokohama-cu.ac.jp– 118 –

FNTG-47, 2014

2P-32

Improving efficiency in synthesis of fullerenes in multi-phase ac arc plasma○Masanori Takeuchi, Hiroshi Sano, Masaaki Ashihara, Norio Maki,
Hiroyuki Makara, Mikihiro Ueno, and Kazuyuki Morishita
Industrial Technology Center of Fukui Prefecture, Fukui 910-0102, JapanThe multi-phase ac arc plasma processing has been investigated as an efficient method forsynthesizing fullerenes [1]. The yields of fullerenes from soot could be improved bypermuting phase order of the carbon electrodes in six- and twelve-phase plasma.

Fig.1. The normal six-phase electrodes from in
ac arc plasma reactor. (After the discharge)

Fig.2. The permuted six-phase electrodes form in
ac arc plasma reactor. (After the discharge)

Yield of fullerenes (%)

The carbon electrodes in the ac arc plasma reactor that were discharged by a normal
six-phase and by the permuted six-phase are shown in Figure 1 and 2 respectively. And then
the normal and permuted phases of these electrodes are indicated in table 1. As shown here
every phase difference between adjacent
Table 1. Phase orders of electrodes.
electrodes in the normal is 60°. On the other
NormalPermutedNo.
hand, it should be noticed that these differences
phase diff. phase diff.
in the permuted phase are appeared as 60° and
1
0°
60°
0°
60°
180° alternately.
2
60°
60°
180°
180°
The influence of these phase orders on yield
3
120°
60°
240°
60°
of fullerenes in six-phase ac arc electrodes is
4
180°
60°
60°
180°
shown in Figure 3. The highest yield of
5
240°
60°
120°
60°
6
300°
60°
300°
180°
fullerene by the permuted phase order was
remarkably attained to more than 33% on the40
upper side wall in the plasma reactor.
normal35
permuted
The synthesis of fullerene by multi-phase ac
30
arc system involves no other chemical solvents
25
e.g. benzene and is relatively easy. Therefore,
20
this method is considered that it can be suitable
15
for the efficient production of fullerenes.
[1] H. Sano et al. The 45th FNTG General Symposium,
2P-10 (2013).
Corresponding Author: H. Sano
Tel: +81-776-55-0664, Fax: +81-776-55-0665,
E-mail: sano@fklab.fukui.fukui.jp– 119 –

1050Upper lid

Upper sidewall

Others

Total

Fig.3. Influence of the electrode phase orders onyield of fullerenes in six-phase ac arc electrodes.

FNTG-47, 20142P-33

                                         !"      #$%
 & '($##%()*+ , ),  ,   -  ./0 .!1  .2     $   ! "# " $" %%&' %( #' )%* +  
,  #" -  * "   " "    !.%*   !.%* .   !.%* .  ,  "   ( )"  +  (  " )%/&  , -" + 
"' .  " ",("   '  ' "% "# $ " "" 
 !.%* . !.%* .)%/&+   #"  "" 0($ ,#,  "" $"  !!(%  '  $   , '( ""$"   " " '%* ""  # "    ,(" ",  " ( )%%&+   "     "  " "  ,"  ""'  )(,,# "1, "" "'#" "" ' "$ 1"  #   "'  #  "# "+& % #" - "  ",("( "),  . +," ( '"  ( "#)2!'+%/& ( " 3*4% 5&6378 .989::;2!24<.'36= " 

– 120 –

FNTG-47, 2014

2P-34

Analytical transmission electron microscopy of Xe gas encapsulated within
the inner space of fullerene-capped single-wall carbon nanotubesżKeita Kobayashi1, Hidehiro Yasuda1,2
1Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, Ibaraki,
Osaka 567-0047, Japan
2
Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka
University, Suita, Osaka 565-0871, Japan
Although the size effect on the solid-state properties of nanomaterials has been alreadydiscovered by several macroscopic analysis methods, further clarifying the effect and its
mechanism requires separate analysis of isolated nanomaterials by microscopic methods.
Analytical transmission electron microscopy (TEM) can be used to separately analyze thestructure and electronic state of isolated nanomaterials, making it a powerful method for
elucidating the details of the unique structure and properties of nano-sized specimens.
However, because the specimen must be held under high-vacuum conditions during
TEM observation, experimentally studying the size effect for highly volatile specimens byanalytical TEM remains a challenge. At the 46th Fullerenes-Nanotubes-Graphene General
Symposium, we reported analytical TEM of Xe gas that was encapsulated within the innerspace of carbon nanotubes (CNTs) whose openings were covered with ionic liquid to prevent
diffusion of the Xe gas into TEM specimen chamber. Strong Xe L-lines and Xe M-edges,
respectively, were observed by energy-dispersive X-ray spectroscopy (EDX) and electronenergy-loss spectroscopy (EELS) of the Xe-encapsulating CNTs on an analytical TEM
system[1]. These results show that Xe gas was held within the inner space of the CNTs evenunder high-vacuum conditions, suggesting that analytical TEM of highly volatile specimens
can be performed by this method.
However, since ionic liquid covered the entire CNT, clear TEM observation of
encapsulated Xe was problematic. Also, additional peaks due to the ionic liquid prevented
accurate analysis of EDX and EELS spectra of the specimen.
Against this background, we aimed to hold Xe gas within the inner space of
single-wall (SW) CNTs by capping their openings with fullerenes during TEM observation.
As a result, we confirmed that Xe gas could be held in the SWCNTs during TEM observation
using EDX. In this presentation, the details of the method will be introduced and the uniquebehavior of Xe gas confined within nanospaces will be discussed.
This work was supported by KAKENHI (#25790003) from JSPS.
[1] K. Kobayashi et al. Abst. 46th Full. Nanotub. Graphen General Symp. 79 (2014).
Corresponding Author: K. Kobayashi
Tel: +81-6-6879-7941, Fax: +81-6-6879-7942,
E-mail: kobayashi-z@uhvem.osaka-u.ac.jp– 121 –

FNTG-47, 20142P-35

Ultrastructural Localization of Intravenously Injected Carbon Nanohorns
in Tumor
Sachiko Matsumura,1 Ryota Yuge,2 Shigeo Sato,3 Akihiro Tomida,3 Toshinari Ichihashi,2
Hiroshi Irie,4 Sumio Iijima,2,5,6 Kiyotaka Shiba,1 ○Masako Yudasaka6
1

Cancer Institute, Japanese Foundation for Cancer Research, 3-8-31 Ariake, Koto, Tokyo,
135-8550
2
Smart Energy Research Laboratories, NEC Corporation Miyukigaoka, Tsukuba, 305-8501
3
Cancer Chemotherapy Center, Japanese Foundation for Cancer Research, 3-8-31 Ariake,
Koto, Tokyo, 135-8550
4
Teikyo University School of Medicine, 2-11-1 Kaga, Itabashi, Tokyo, 173-8605
5Faculty of Scienec and Technology, Meijo University, Tenpaku, Nagoya, 468-8502
6
Nanotube Research Center, National Institute of Advanced Industrial Science and Technology,
1-1-1 Higashi, Tsukuba, 305-8565
Various potential applications of nanocarbons are presented in biological fields. One of themost interesting potential applications is the delivery of drugs or imaging agents to the tumor
sites. It is generally expected that the nanocarbons intravenously injected in the bodyselectively accumulate in tumors because the tumor vessel walls are not perfectly constructed,
therefore leaky, and the particles with nanometer sizes move outside of the vessels and stay intumors tissues where lymphatic drainage routes are poorly developed (EPR effect). Actually,
successes of the high level accumulation of carbon nanotubes at tumors are confirmed inanimal experiments. In such studies, where in the tumor tissues the nanocarbons exist has notbeen well clarified. This subject should be addressed because the effect of the delivered drugs
depended on where they are in tumor sites.
Thus we observed the tumor tissues of a mouse in which the carbon nanohorns (CNHs)
coated with phospholipid PEG were intravenously injected. The tumors were transplanted inmice subcutaneously. The tissue observation showed that CNHs were captured bymacrophages inside the tumor vessels and the extravasation of CNHs was not obviously seen.
On the other hand, the extravasation of CNH occurred in normal skin capillary vessels, which
are leakier than the tumor vessel walls. Thus, the extravasation of CNHs could occur also in
the tumor vessels; however, to make extravasation really occur in tumor, the size of CNHs or
surface functionalization should be optimized.
Corresponding Author: K. Shiba, M. Yudasaka,E-mail: kshiba@jfcr.or.jp, m-yudasaka@aist.go.jp– 122 –

2P-36

FNTG-47, 2014

Development of measurement system for electrical properties of carbon
nanocoil and relationship of resistivity with the coil shapes.
○Yasushi Nakamura 1, Ryuji Kunimoto 1, Yoshiyuki Suda 1,
Hirofumi Takikawa 1, Hitoshi Ue 2, Kazuki Shimizu 3, Yoshito Umeda 4
1

Department of Electrical and Electronic Information Engineering,
Toyohashi University of Technology, Toyohashi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon Co., Ltd., Oyama 410-1431, Japan
3
Development Department, Shonan Plastic Mfg. Co., Ltd., Hiratsuka 254-0807, Japan
4
Toho Gas Co.,Ltd., Nagoya, Aichi 456-8511, Japan
Carbon nanocoil (CNC) is a carbon nanofiber (CNF) with
Au thin film
(1)
Pt
helical shape. Carbon microcoil (CMC)
that is in micro size(2)
SiO2
is expected to be a micro-inductor . We have targeted thePtmeasurement of inductance of the CNC. For the measurement,
the construction of measurement system is needed. In addition,
evaluation of electrical resistivity that is the basic electricalcharacteristics is important. In this study, we constructed
Fig. 1 SEM micrograph of
CNC fixed to the Au film
measurement system to measure electrical resistance for single
10
CNC and evaluated electrical resistivity of single CNC.
CNCs are synthesized by catalytic chemical vapor
10
deposition (3). Fig. 1 shows the SEM image of a preparedsample. Au-film was deposited on Si/SiO2-substrate using ion
coater. 5μm square of this thin film was removed using
10
focussed ion beam (FIB). We bridged CNC between there.
0 500
1000
1500
Coil diameter [nm]
CNC was fixed at both ends using Pt-deposition using FIB.
Fig. 2 Relationship ofOne end of the CNC was separated from Au as the independent
resistivity with coilelectrode by FIB. Silver paste was used to bond the Au film
diameterwith a stage of SEM. The stage of SEM was connected to the manipulator tip through asource meter. We approached the manipulator tip to the CNC and measured the electricalresistance of CNC.
Fig.2 shows relationship of resistivity with coil diameter. Resistivity of CNC was in therange from 1.06×10-3 Ω•cm to 8.0×10-2 Ω•cm. Resistivity was increased by the coildiameter. In adittion, We investigated relationship between resistivity and shapes of carbon
nanofiber (CNF). Resistivities of 4 CNF were 1.6×10-2 Ω•cm. There was no change inresistivity by shape. From the result, there is a possibility to have a unique properties.
This work has been partly supported by the EIIRIS Project from Toyohashi University ofTechnology (TUT); JSPS KAKENHI Grant Number 24360108 and 25630110.
Resistivity [cm]

-1

-2

-3

[1] S. Motojima, et al: Diamond and Related Materials 13, 1989 (2004)[2] Y. Kato, et al: Japanese Journal of Applied Physics, 45, 4A, 2695 (2006)[3] M. Yokota, et al: The Journal of Nanoscience and Nanotechnology 11, pp.2344-2348 (2011)
Corresponding Author: Yoshiyuki Suda
Tel: +81-532-44-6726, Fax: +81-532-44-6757, E-mail: suda@ee.tut.ac.jp– 123 –

FNTG-47, 2014

2P-37

Investigation of catalytic layer formation and optimization of spin coat velocity
for high-yield synthesis of carbon nanocoil by using Fe2O3 fine powder○T. Iida1, K. Maruyama1, Y. Suda1, H. Takikawa1, H. Ue2, K. Shimizu3, Y. Umeda4
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon Co.,Ltd., Oyama, Sizuoka 410-1431, Japan
3
Development Department, Shonan Plastic Mfg. Co.,Ltd., Hiratsuka, Kanagawa 254-0807, Japan
4
Toho Gas Co.,Ltd., Nagoya, Aichi 456-8511, Japan
Carbon nanocoil (CNC) is a carbon nanofiber (CNF) with helical shape. CNC is applied toelectron field emitters, electromagnetic wave absorption material. Therefore it is necessary forhigh-yield synthesis of CNC. CNC is synthesized by catalytic chemical vapor deposition(CVD) using Fe-Sn composite metal catalyst. In our study, CNC has been synthesized using
the Fe powder (1, 3-5μm) and SnO2 solution [1]. In this method, the purity of CNC on surfaceof carbon product was about 100%. But, when the cross-section of carbon product wasobserved, CNC was not synthesized inside of carbon product and CNC purity of entire
product was from 20 to 55%. In this study, we intended to improve purity of entire product byinvestigating new method of synthesis. We aimed to reduce the thickness of carbon layer byusing Fe2O3 fine powder (20 nm) and change from drop-coat to spin-coat.
Si plate was used as substrate. As catalyst, Fe2O3 fine powder (Nilaco, 224050) was
dissolved in ethanol with Fe density of 0.1 mol/l, and SnO2 solution (Kojundo chemicallaboratory, 235061, S) with a density of 0.13 mol/l was prepared. The Solution was dropped
onto the substrate placed in spin coater. The substrate was then rotated at 1000-2500 rpm.
Fe2O3 and SnO2 catalytic layers were formed separately. After coating, the substrate wastransferred immediately onto a hotplate and was heated at 80C for 5 min. The effect ofdifference on catalytic layer formation was considered. The three types of catalytic layers (1)Fe/Sn, (2) Sn/Fe, and (3) Sn/Fe/Sn were prepared. The substrate which supported catalyst was
set in CVD equipment and annealed by N2 gas with a flow rate of 1400 sccm at 780C for 5
min. After that, N2 gas was supplied with a flow rate of 1400 sccm and C2H2 gas with a flowrate of 250 sccm at 780C for 10 min to grow CNCs. Products were observed using ascanning electron microscope (SEM).
Sheeted carbon products were observed on substrate. When the catalytic layer was Fe/Sn
that was coated at 1000 rpm, the CNC
purity on surface of product was about
100% and the CNC purity of entire productwas about 71%. When the catalytic layer
was Sn/Fe/Sn that was coated at 1000 rpm,
the carbon layer of product was thinnerthan the carbon layer grown from Fe/Sn
catalytic layer. The CNC purity of entire
Fig. 1 CVD products using a Sn/Fe/Sn catalytic layer
product was about 83% as shown in Fig. 1.
This work has been partly supported by the EIIRIS Project from Toyohashi University ofTechnology (TUT); JSPS KAKENHI Grant Number 24360108 and 25630110.
[1] M.Yokota et al. J. Nanosci. Nanotechnol., 10(6), 3910-3914 (2010).
Corresponding Author: Yoshiyuki. Suda
Tel: +81-0532-44-6726, Fax: +81-532-44-6757, E-mail: suda@ee.tut.ac.jp– 124 –

2P-38

FNTG-47, 2014

Electrocatalytic properties of Pt-based nanoparticles supported on carbon
materials by one-step electrodeposition○1 Haruhiko Yoshitake, 1 Shohei Hayase , 2Wang Zhipeng and 1,3Hironori Ogata
1

2

Graduate School of Science and Engineering, Hosei University Koganei 184-8584, Japan
Institute of Carbon Science and Technology, Shinshu University, Nagano 380-8553, Japan
3
Research Center for Micro-Nano Technology,Hosei University,Koganei 184-0003,Japan

Direct methanol fuel cells (DMFCs) are one of the most promising transportable powersources which can be used in mobiles, laptops, and small power generation. The basic
operation principle of DMFCs involves methanol oxidation and oxygen reduction on the
precious metal catalysts, which are loaded on the support surfaces. As is well-known, thedispersion of Pt-based alloys on carbon supports as well as catalyst particle size and shapeplays a dominant role in the electrochemical performance for fuel cells. In this study, we
explore electrocatalytic properties of Pt-based nanoparticles supported on the carbon materials,
carbon nanosheets (CNS), Single walled Carbon Nanotubes(SWNTs) or highly orderedpyrolytic graphite(HOPG) by one-step electrodeposition. Figure.1 shows the one example ofthe temperature dependence of CV responses of Pt/HOPG in CH3OH+H2SO4 aqueous
solution and Table.1 shows their electrochemical characteristics of methanol oxidation. The
detailed results on the relationship between the temperature of methanol solution, and theirelectrocatalytic performance for methanol oxidation will be presented.

288K
293K
298K
303K
308K
313K
318K

5

Current density(mA/cm2)

0
-5
-10
-15
-20
0.0

0.2

0.4

0.6

0.8

1.0

Potential(V , vs Ag/AgCl)

Figure 1. CV responses of Pt/HOPG
in CH3OH+H2SO4 aqueous solution.

Table.1 Temperature dependence of theelectrochemical characteristics of methanoloxidation.

References:(1)J.M.Sieben et al., J. Appl. Electrochem.38(2008)483-490.
(2)Zhipeng Wang, Mao Shoji and Hironori Ogata, Appl. Surf. Sci.259(2012)219-224.
Corresponding Author: Hironori Ogata,Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp– 125 –

FNTG-47, 2014

2P-39

High yield synthesis of LaC2 encapsulated carbon nanocapsules by inverse
DC arc discharge○Kazunori Yamamoto1, Kenji Yamaguchi1, Shin-ichi Shamoto1, Takeshi Akasaka2
1

Nano-Structure Synthesis Research Group, Quantum Beam Science Directorate,
Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195, Japan
2
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki
305-8577, JapanThe discovery of endohedral fullerenes [1,2] has triggered a new exciting field of research,where a variety of new endohedral carbon nanostructures, such as nanocapsules [3,4] andnanotubes [5] have been produced. Several materials such as pure metals, alloys, and carbides
have been nanoencapsulated in carbon. Although these “carbon nanoencapsulates” are very
important compounds due to their potential application for the disposal of radioactive waste
metals, such as rare earth and actinide [6], they are still laboratory materials, and their very
low conversion efficiency from starting metal/carbon mixtures to the carbon nanoencapsulates,
resulting from the present synthetic technology, is certainly one of the main explanations ofpresent status. Attempts to increase productivity of “carbon nanoencapsulates” were notsuccessful, therefore, nearly 30 years after their discovery, no real large-scale industrial
application of carbon nanoencapsulates has yet started.
The encapsulation of metals in fullerenes and carbon nanocapsules is normally performedby conventional arc discharge of a composite rod made from a metal oxide and carbon
powder in He atmosphere [1-5]. In the case of many endohedral fullerene syntheses, thecomposite rods are normally subjected to heat treatment at a temperature of about 1000 oC in
vacuum prior to arc discharge [7]. In the heat treatment, it is believed that gaseouscomponents such as H2O are removed from the composite rod. Moreover, it is also believedthat part of the metal oxide in the composite rod changes to the metal carbide. When
LaC2-enriched composite carbon rods were used, instead of hydrooxidized or oxidized
lanthanum composite rods, the yield of lanthanofullerene increased by a factor of 10 or more[7]. However, there has been no systematic study on the influence of anode composition upon
the generation of endohedral carbon nanocapsules.
In this study, we present an enhanced approach to synthesize endohedral carbon
nanocapsules by “inverse DC arc discharge” method. In the first step, a lanthanum-graphite
composite rod (Toyo Tanso Co. Ltd., KM-20LA) was evaporated by DC arc discharge under
50 Torr He, then, long rod-like deposit was generated on cathode (so called, cathode deposit).
In the second step, the catode deposit was re-evaporated by DC arc discharge by changing DC
electric polarity, and the second cathode deposit was generated. The yield is characterized bypowder X-ray diffraction. We have found that the yield of LaC2 encapsulated carbon
nanocapsules was increased in the second cathode deposit, which may be caused by thecomplete removal of gaseous compound from anode.
[1] J.R. Heath et al., J. Am. Chem. Soc., 107, 7779 (1985). [2] Y. Chai et al., J. Phys. Chem., 95, 7561(1991).
[3] R.S. Ruoff et al., Science, 259, 336(1993). [4] M. Tomita et al., Jpn. J. Appl. Phys., 32, L280(1993).
[5] S. Seraphin et al., Appl. Phys. Lett., 63, 2073(1993). [6] K. Yamamoto et al., Prog. Nucl. Energy, 47, 616(2005). [7] S. Bandow et al., J. Phys. Chem., 97, 6101(1993).
Corresponding Author: K. Yamamoto, Tel: +81-29-282-6474,
E-mail: yamamoto.kazunori@jaea.go.jp– 126 –

FNTG-47, 2014

2P-40

Relationships between the Structure and the Characterof Starfish Nanocarbon〇Natsuki Namba, Yukihiro Takada and Kyoko Nakada
College of Science and Engineering, Aoyama Gakuin University,
5-10-1, Fuchinobe, Chuo-ku Sagamihara 252-5258, Japan
PurposeThe electronic states of sp2 carbon materials depend on their structures. The objective of
this study is to clarify the rule to predict the characteristic from the structure of new sp2
carbon material. To achieve this objective, we proposed   new   structures   named   “starfish
nanocarbon”  and  analyzed  the  relationships between their structures and electronic states.
Methodology
Starfish nanocarbons are defined by the structure satisfying all following conditions. 1.
They are composed of 6-membered rings and 7-membered rings. 2. Their axis is composed oftwelve 7-membered rings and twenty four 6-membered rings centered. 3. They have 6 equalarms. The arms are zigzag-tube or armchair-tube. We calculated the electronic states ofvarious types of starfish nanocarbons by Hückel method.
Results & Discussion
Structure
The conditions 1 and 2 allow each of four rings A to D (Fig.1) to be a 6- or
7-membered ring. The number of placement methods is therefore 16. Twelve of those satisfied
condition 3. They have four 7-membered rings per arm. However they are distinguished by aconfiguration of 7-membered rings. The shape of the arm is determined by this method and 12
starfish nanocarbons are divided into 3 groups by this. (a) zigzag-even : Arms of this structure
connect to (2n,0) tube. (b) zigzag-odd : Arms of this structure connect to ((2n+1),0) tube. (c)armchair : Arms of this structure connect to (n,n) tube.
Calculation We focused on following three points and 12 starfish nanocarbons are divided
into 3 groups by this. (1) Whether there are 6‐fold degeneration at E=0 or not. (2)Characteristic of HOMO-LUMO gap. (3) The location of DOS peak((a)E=±1 ,(b)E=0,(c)nopeak). Comparing structures with calculation results, correspondents between both results
were seen. (a) zigzag-even : there are 6-fold degeneration at E=0 and DOS peak at E=±1 .
(b) zigzag-odd  :  there  aren’t  6-fold degeneration at E=0 and DOS peak at E=0. (c) armchair :there  aren’t  6-fold degeneration at E=0 and HOMO-LUMO gap shows triple periodicity withthe length of the arm. From above, the structure and electronic states of starfish nanocarbons
are corresponding and divided into 3 groups decided by these characters.

Fig. 1: Name of the parts of starfish nanocarbon.

Corresponding Author: K. Nakada
Tel: +81-42-759-6219 Fax: +81-42-759-6493 E-mail: nakada@chem.aoyama.ac.jp– 127 –

2P-41FNTG-47, 2014

Low-pressure chemical vapor deposition of multi-walled carbon nanocoilswith a fiber diameter of 7.5 nm○Yoshiaki Shimizu1, Yoshiyuki Suda1, Hirofumi Takikawa1,
Hitoshi Ue 2, Kazuki Shimizu 3, Yoshito Umeda4
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon Co., Ltd., Oyama, Shizuoka 410-1431, Japan
3
Development Department, Shonan Plastic Mfg. Co., Ltd., Hiratsuka, Kanagawa 254-0807, Japan
4
Toho Gas Co., Ltd., Nagoya, Aichi 456-8511, Japan
Multi-walled carbon nanocoils (MWCNCs) are nano-carbon materials with helicalstructure composed of multi-walled carbon nanotube (MWCNTs) with diameters of 5−20
nm. Generally, MWCNC is synthesized from composite catalysts including Fe-Sn.
MWCNCs with a multi-walled graphitic structure have a higher Young’s modulus (0.7
TPa) than CNCs (1). Pan et al. reported that MWCNCs have higher electric field emission
efficiency than MWCNTs because of their three-dimensional structure (2). In our previous
study, MWCNCs were grown from a Fe/Sn-supported mesoporous material such as zeolite,
by chemical vapor deposition (CVD) at C2H2/N2 gas pressure of 5 Torr (3). The averagefiber diameters of the MWCNCs were reduced from 20 nm to 10 nm. In this study, weinvestigated the reduction in the fiber diameter of MWCNCs by reducing C 2H2/N2 gaspressure to 1 Torr. The MWCNCs were observed by transmission electron microscopy(TEM) and the average fiber diameters of the MWCNCs was 7.5 nm.
Fe2O3/zeolite was prepared by mixing Y-type zeolite (Tosoh HSZ-390HUA) in an ironacetate mass fraction of 5 %. Then, the mixture was calcined at 100◦C for 20 h. To produce
the Fe/Sn catalyst on zeolite, Sn was evaporated onto the surface of Fe2O3/zeolite undervacuum. Fe/Sn−catalyst−supported zeolite was placed on a ceramic boat and inserted into
the center of tubular electric furnace. N2 and C2H2 gases were supplied to the apparatus for
10 min to grow MWCNCs while temperature at 700◦C. The N2 and C2H2 flow rates were1000 and 50 sccm, respectively. Products were observed using a TEM.
TEM images of the MWCNCs grown at various C2H2/N2 gas pressures are shown in
Fig. 1. The fiber diameter of the MWCNCs decreased as C2H2/N2 gas pressure was reduced
from 760 Torr to 1 Torr. The fiber diameters were approximately 7.5 nm at 1 Torr. This
result suggests that when the C2H2/N2 gas pressure is reduced, the number of C2H2
molecules adsorbed on catalyst nanoparticles reduced and there was only small amount ofresidual gases(4).
This work has been partly supported by the EIIRIS Project from Toyohashi Universityof Technology (TUT); JSPS KAKENHI Grant Number 24360108 and 25630110.
[1] A. Volodin, et al: Nano Lett., 4 (2004) 1775-1779[2] L. Pan, et al: Jpn. J. Appl. Phys., 44 (2005) 1652-1654[3] S. L. Lim, et al: Jpn. J. Appl. Phys., 52 (2013) 11NL04-07[4] T. Maruyama, et al: Dia. Relat. Mater., 17 (2008) 589-593
Corresponding Author: Y. Suda
Tel: +81 532 44 6726, Fax: +81 532 44 6757,
E-mail: suda@ee.tut.ac.jp

Fig. 1. TEM images of MWCNCs synthesized withpressures of (a)1 Torr and (b) 760 Torr

– 128 –

3P-1

FNTG-47, 2014

Efficient SWCNT OSCs: Doping and Electron Blocking Functions of MoOx
○Il Jeon1, Kehang Cui2, Albert G. Nasibulin3, Esko I. Kauppinen3, Shigeo Maruyama2,
Yutaka Matsuo1,*
1

2

Department of Chemistry, The University of Tokyo, Hongo 113-0033, Japan
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Applied Physics, Aalto University, Espoo 15100, Finland

Cathodee-Hole Blocking Layer!
Organic Photo Active Layer !

h+

PTB7!

Electron transfer from CNT to MoOx (doping)!
and Electron blocking!
MoOx doped CNT Network!

5 um !

MoOx!

Flexible Substrate

Current Density (mA cm-2)

As an alternative path to Indium based organic solar cells (OSCs), carbon nanotube (CNT)
and graphene based OSCs have emerged as next generation solar cells. In addition to avoiding
finite and harmful Indium usage, superior flexibility with more facile preparation is the main
forte of CNT OSCs.[1] Despite such advantages, its inferior conductivity and transparency
have been the bottleneck. Solution to this problem involves using dopant HNO3.[2] However,this method has serious limitations; HNO3 is corrosive, explosive and produces notorious
toxic gas, NO2, as well as its effect lasting for less than few hours.[3] Z. Bao and hercolleagues recently have found a more stable and innocuous method of doping CNT.[4] In theperspective of OSC application, stability is the most vital factor. Therefore, this MoOx doping
is surmised to be the most suited methodology for our work. So, we aim to achieve the mosteffectively composed CNT OSC by adopting and studying each component that are state of
the art in their science. At the center of this work, we have exploited MoOx’s dual functions
as both p-dopants and electron blocking layer. We have also produced free standing CNT film
which are strong and durable even at its thinnest state via Aerosol CVD technique.[5] This
CNTs with 90% transparency and 85 Ω/ resistance.[6] Furthermore, we have used low band
gap polymers which have greater absorption in longer wavelength. Harnessing the fact that
CNT possess a higher transmittance at longer wavelength in the visible region, this novel
approach has allowed us to transcend the previous works by obtaining the World Record
Efficiency of 5.77% (Jsc=18.9mA/cm2, Voc=0.72V,
20
ITO Ref PTB 7 Light
FF=0.42). (Fig. 1, 2)
ITO Ref PTB 7 Dark
SWCNT MoOx dual anneal no Pedot LightSWCNT MoOx dual anneal no pedot Dark
SWCNT MoOx dual anneal w/ pedot LightSWCNT MoOx dual anneal w/ pedot Dark

10

0

-10

-20

CNT!

-0.5

Fig.1: Illustration of CNT OSC structure we used to study
and converge the highest technologies into one system

0

0.5

1

Applied Bias Voltage (V)Fig.2: I-V curve of CNT OSC with PTB7

[1] J. Du et al. Adv. Mater. 26, 1958 (2014) [2] D. J. Lipomi et al. Nat. Nanotechnol. 6, 788 (2011) [3] D. W.
Shin et al. Nanotechnology 20, 475703 (2009) [4] Nano Lett. 12, 3574 (2012) [5] A. G. Nasibulin et al. ACS
Nano 5, 3214 (2011) [6] Z. Wu et al. Science 305, 1273 (2004)
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-1476, Fax: +81-3-5841-1476, E-mail: matsuo@chem.s.u-tokyo.ac.jp– 129 –

3P-2

FNTG-47, 2014

Threshold voltage distribution of chemically dopedn-type carbon nanotube thin-film transistors○T.  Yasunishi,  S.  Kishimoto,  and  Y.  Ohno
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, JapanThe carbon nanotube thin-film transistor (CNT TFT) is attracting much attention as
high-mobility active device for flexible electronics. For controlling conduction type of CNT
TFTs, the chemical doping technique with polyethyleneimine (PEI) is often used [1]. In theprevious work, we realized air-stable, high-mobility n-type CNT TFTs on plastic film [2, 3]
with the chemical doping technique. The next challenge would be the control of thresholdvoltage (Vth) which is important to realize integrated circuit. In this work, we investigate theVth distribution of chemically-doped n-type CNT TFTs. We also reduce Vth distribution by
mixing PEI with a polymer.
We fabricated bottom-gate CNT TFTs on a polyethylenenaphthalate (PEN) substrate as
shown in Fig. 1. The CNT film was formed by transfer technique based on the
floating-catalyst CVD technique [4]. For n-type doping, we used two types of dopantmaterial; #1: PEI dissolved in methanol and #2: a mixture of PEI and polyvinylalcohol (PVA)
in water.
Both devices show n-type characteristics. Distributions of Vth are shown in the histogram ofFig. 2. In the case of only PEI, an average of Vth<Vth> was -0.66 V and the standard deviation (Vth)was 0.50 V. On the other hand, when PEI was mixed
with PVA, <Vth> = -0.31 V and (Vth) = 0.18 V. The
variation of Vth was reduced by using the dopant
Fig.1: Schematic of device structure.
material of a mixture of PEI and PVA.
16

Acknowledgments: This work was partially
supported by JST/SICORP and Grant-in-Aid of
JSPS.

10
8
6
4
2
0
-2

Corresponding Author: Y. Ohno
Tel & Fax: +81-052-789-5387,
E-mail: yohno@nagoya-u.jp

PEI + PVA
PEI

12

Count

[1] M. Shim et al., J. Am. Chem. Soc. 123, 11512 (2001).
[2] T. Yasunishi et al., Phys. Stat. Sol. C 10, 1612 (2013).
[3] T. Yasunishi et al., Jpn. J. Appl. Phys. 53, 05FD01 (2014).
[4] D.-M. Sun et al., Nature Nanotech. 6 156 (2011).

14

-1

0

1

Vth (V)

Fig.2: Distributions of threshold voltage.

– 130 –

2

FNTG-47, 2014

3P-3

Design and preparation of Pt nanoclusters on polybenzoimidazole-wrappedcarbon nanotubes and their use in energy applications○Yuki Hamasaki1,2, Tsuyohiko Fujigaya1,2,3, Naotoshi Nakashima1,2,4
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
744 Motooka, Fukuoka 819-0395, Japan22
WPI I CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan
3
ALCA, 7 Gobancho, Chiyoda-ku, Tokyo 102-0076, Japan
4
JST-CREST, 5 Sanbancho, Chiyoda-ku, Tokyo, 102-0075, JapanThe commercialization of proton exchange membrane fuel cells (PEFC) can help tomitigate global warming and reduce our dependence on fossil fuels. The eﬃcient cathodic
electrocatalysts for oxygen reduction are largely unavailable, so fundamental progress in thedesign of these catalysts is highly needed. Recently, Pt clusters provide a promising approachto reduce Pt usage and enhance Pt catalysis toward oxygen reduction reaction (ORR) [1].
In this study, we designed and fabricated Pt nanoclusters immobilized on the surfaces ofpolymer-wrapped carbon nanotubes. In this study, we used multi-walled carbon nanotubes(MWNTs) and PBI as the carbon support and the polymer, respectively, because they haveunique physical and chemical properties when using in PEFC electrocatalysts as previousl
reported [2-11]. The use of polyelectrolyte as an anchoring unit is advantageous in view of thepractical applications in PEFCs.
The PBI/MWNTs composites were added to methanol, then dispersed by sonication, towhich a methanol solution of H2PtCl6·6H2O was added. After stirring at room temperature,
the composite solution was washed by methanol to remove any excess Pt ions, and then added
NaBH4. After stirring, the solid was collected by filtration, and then dried under vacuum. The
obtained solid material was characterized using the X-ray photoelectron spectroscopy (XPS),
thermogravimetric analyses (TGA), scanning transmission electron microscope (STEM) andelectrochemical measurements. The results will be reported at the meeting.

[1] K. Yamamoto et al., Nat. Chem. 1, 397 (2009).
[2] Okamoto et al., Adv. Funct. Mater. 18,1776 (2008).
[3] Okamoto et al., Small. 5, 735 (2009).
[4] Fujigaya et al., Carbon 47, 3227 (2009).
[5] T. Fujigaya et al., Chem. Cat. Chem. 5, 1701 (2013).
[6] T. Fujigaya et al., Poly. J. 45, 356 (2013).
[7] T. Fujigaya and N. Nakashima, Adv. Mater. 25, 1666 (2013).
[8] M. R. Berber et al., Sci. Rep. 3, art. no. 1764 (2013).
[9] T. Fujigya et al., J. Mater. Chem. A 2, 3888 (2014).
[10] T. Fujigya et al., Chem. Plus. Chem. 79, 400 (2014).
[11] M. R. Berber et al., Chem. Cat. Chem. 6, 567 (2014).
Corresponding Author: Naotoshi Nakashima
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp
Tel&Fax: +81-92-802-2840– 131 –

3P-4

FNTG-47, 2014

Flexible microelectrode based on CNT thin film for electrochemical sensor
applications○Nguyen Xuan Viet, Shigeru Kishimoto, and Yutaka Ohno
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
Carbon nanotubes have shown promising properties as electrochemical electrodes such as
the rapid electron transfer kinetics, wide potential window, high sensitivity, biocompatibility,
and manufacturing versatility [1]. CNT-based flexible devices have been investigatedextensively for varieties of application in gas sensors [2], electronics devices, andelectrochemical sensors (chemical and bio sensors) [3-7]. However, the conventional
solution-based process to form CNT thin film may degrade the performance and theuniformity in electrochemical activity on the electrode surface due to the contamination
associated with dispersal substances. In this study, we demonstrate high-performance flexible
microelectrodes based on a CNT thin film for electrochemical biosensor applications, andapply them to detect dopamine, an importantneurotransmitter.
The CNT microelectrodes were fabricated on a PEN
substrate by the dry transfer method [8] and standard
microfabrication process. In the electrode structure, only
CNT surface is exposed to electrolyte and performs
electrochemical reaction. To minimize the contamination of
CNT surface due to photoresists, the CNT surface wascovered with an oxide film during the fabrication process
Photo of CNT thin film based[9]. An array of 35 microelectrodes (Fig.1) was fabricated Fig.1:flexible
microelectrodeson the PEN substrate in size of 10×15 mm2.
The electrochemical properties of CNT microelectrodes were characterized by cyclic
voltammetry with K4[Fe(CN)6]. The results showed the well-defined sigmoidal voltammetriccurves, the steady-state characteristic of ultramicroelectrode, and reversible properties withthe difference in quartile potentials |E3/4 – E1/4| ~ 60 mV, close to the ideal value (59 mV).
This means that the fabricated CNT microelectrodes have high electron transfer rate.
Electrodeposition of gold nanoparticles on electrode confirmed the uniformity inelectrochemical activity of the CNT surface, especially after an activation process. These
CNT microelectrodes also exhibited high sensitivity in detection of dopamine.
[1] J.J. Gooding, Electrochimica Acta, 50 (2005) 3049-3060.
[2] Y. Sun, H.H. Wang, Advanced Materials, 19 (2007) 2818-2823.
[3] D. Lee, T. Cui, Biosensors and Bioelectronics, 25 (2010) 2259-2264.
[4] X.B. Yan, et al., Electrochemistry communications, 9 (2007) 1269-1275.
[5] J.-Y. Lee, et al., Thin Solid Films, 517 (2009) 3883-3887.
[6] M.-P.N. Bui, et al., Sensors and Actuators B: Chemical, 150 (2010) 436-441.
[7] M.-P. Ngoc Bui, et al., Chemical Communications, (2009) 5549-5551.
[8] A. Kaskela, et al., Nano letters, 10 (2010) 4349-4355.
[9] N.X. Viet, et al., Talanta, 91 (2012) 88-94.
Corresponding Author: Y. Ohno
Tel: +81-52-789-5387, Fax: +81-52-789-5387,
E-mail: yohno@nagoya-u.jp– 132 –

FNTG-47, 2014

3P-5

Estimation of the contact resistivity and Schottky barrier height at
CNT/SiC interface by top contact electrode○Kazuma Suzuki1, Masafumi Inaba1, Megumi Shibuya1, Chih-Yu Lee1, Miho Myodo1,
Yu Hirano1, Atsushi Hiraiwa1, Wataru Norimatsu2, Michiko Kusunoki2, Hiroshi Kawarada1
School of Science and Engineering, Waseda University, Tokyo 169-8555, Japan2
Eco topia Science Institute, Nagoya University, Aichi 464-8603, Japan

Fig.1 Schematic image ofcurrent paths in CNT/SiC system
7
Dopant Density (cm-3)
Nd=3  1016
Nd=5  1017
Nd=3 1018

Resistance R (k)

6
5
4
3
2

2

2

2

-2

1 / Sisland (cm )Fig.2 Relationship between reciprocal
contact area and total resistancenot deposite
deposite electrodeΦ b = 0.7 eV ……… 1.3eV
Φ b = 0.6 eV010Φ b = 0.55 eV
Φ b = 0.5 eV-210Φ b = 0.45 eV
Φ b = 0.4 eV-410Φ b = 0.35 eV
Φ b = 0.3 eV

-6

10

16

10

17

10

18

19

10

10
-3

Dopant density Nd (cm )Fig.3 Relationship of the dopant
density and the contact resistivity[1] M. Kusunoki et al., Appl. Phys. Lett.77, 531 (2000)[2] M. Kusunoki et al., Appl. Phys. Lett. 87, 103105 (2005)
Corresponding Author: K. Suzuki
Tel: +81-3-5286-3391, Fax: +81-3-5286-3391, E-mail: gloria-274@asagi.waseda.jp– 133 –

2

8x8 m15x15 m
10x10 m
1 20x20 m
5
6
6
6
0.0
5.0x101.0x101.5x102.0x102

1. CNT on SiC
Carbon nanotube forest synthesized with silicon carbide
surface decomposition method (CNT on SiC)[1][2] exhibits themost densely packed CNT forest (~3×1012 cm-2) and is suitablefor electrodes with high current density durability. CNTs can beimportant material for SiC, which is promising materials of
power semiconductors, in cooperation with its high thermal
conductivity. It is necessary for application as electrodes toevaluate the contact resistivity.
2. The contact resistivity at CNT/SiC interface
Lateral conduction also coexists in the CNT on SiC becauseof its high tube density. However, the lateral resistance is large,
and makes it difficult to evaluate the contact resistivity. In
order to exclude the lateral resistance, Ti (10 nm) / Au (100nm) was deposited on CNTs on SiC as the top contact
electrode. To restrict the contact area of CNT forest on SiC,
electrically isolated areas were formed with focused ion beam.
The electric properties of isolated areas with different size were
measured by conductive AFM to obtain size dependence of
total resistance composed of top and bottom contact
resistances and CNT intrinsic resistance. Since the contact
resistance of CNT/SiC interface is inversely proportional tothe contact area, the slope of the graph corresponds to thecontact resistivity. Evaluation of the slope can be more detailsince R-intercept, corresponding to the resistance of theexternal, becomes smaller.(Fig.2)
3. Schottky barrier height at CNT/SiC interface
Fig. 3 shows the results of plotting the contact resistivity ofthe each donor density (3×1016 cm-3, 5×1017 cm-3, 3×1018
cm-3) SiC. Each curve is the theoretical relationship between
donor density and contact resistivity of the metal and 4H-SiC
when Schottky barrier height varies from 0.3 to 1.3 eV. By
removing the lateral resistance of the CNT, small contact
resistance is obtained. Schottky barrier height of the CNT /SiC interface was estimated to be 0.40 ~ 0.45 eV. This value isequivalent to NiSix, which is the most major ohmic contact to
SiC. Therefore, this Schottky barrier height is very low for
SiC and CNTs on SiC can be desirable electrode for SiC
power devices.

Contact resistivity (cm )

1

3P-6

FNTG-47, 2014

Perovskite Solar Cells with Single-Walled Carbon Nanotubes
as Electrodes and Hole Conductors○Takaaki Chiba1, Takahiro Sakaguchi1, Albert G. Nasiblin2, 3, Esko I. Kauppinen2,
Rong Xiang1, Shohei Chiashi1 and Shigeo Maruyama1
1

Department of Mechanical Engineering, The University of Tokyo, Hongo 113-8656, Japan
Department of Applied Physics, Aalto University School of Science, Espoo 15100, Finland
3
Skolkovo Institute of Science and Technology, 100 Novaya str., Skolkovo, Moscow Region,
143025, Russia

2

Organic-inorganic metal halide perovskite solar cells, which were invented by Miyasaka groupin 2009 [1], have been attracting much attention because of their high power conversion
efficiency (PCE) and low production cost. Conventional perovskite solar cells are composed oftransparent conductive substrate (FTO), dense TiO2 layer, mesoporous TiO2 layer, perovskite
absorption layer (CH3NH3PbI3), hole transport material (HTM) and Au electrode (Fig. 1(a)).
Even though the reported highest PCE of the perovskite solar cells exceeds 15 % [2], they needsome improvements. For example, vacuum deposited Au electrode is costly. So, for further low
production cost and bulk production, it is anticipated to replace Au to inexpensive and printablematerials. In addition, organic semiconductors such as spiro-MeOTAD or PTAA, which areused as HTM, are unstable under high temperature and ultraviolet light. Hence, it is desired tobe replaced with more stable material. Single-walled carbon nanotube (SWNT) film is
considered as one of the alternatives for both Au and HTM because SWNT film can have good
conductivity, superior stability and p-type characteristics.
In this study, we have fabricated perovskite solar cells with SWNTs as electrodes and hole
conductors. Figure 1(b) shows the structure of perovskite solar cells with SWNTs. In these solar
cells, vertically aligned SWNT (VA-SWNT) [3] and SWNT film synthesized by aerosol CVD
method [4] are employed. The preliminary J-V characteristics of these cells are measured underAM1.5G conditions (Fig. 2). The PCE of perovskite solar cells with VA-SWNTs and SWNT
film was 1.24 % and 0.67 % respectively, compared to 3.87 % of conventional solar cells with
Au/HTM. Even though the preliminary PCE of perovskite solar cells with SWNTs was still
lower, it is shown that SWNTs work as both electrodes and hole conductors.
Au/HTM
VA−SWNTSWNT film

2

Current Density (mA/cm )10Fig. 1 Schematic images of (a) conventional perovskite solar cell and

PCE=3.87%
5

PCE=1.24%00

PCE=0.67%
0.5
Voltage (V)1Fig. 2 J-V characteristics of the(b) perovskite solar cell with SWNTs.

perovskite solar cells.
[1] A. Kojima et al. JACS 131, 6050 (2009). [2] J. Burschka et al. Nature 499, 316 (2012).
[3] Y. Murakami et al. Chem. Phys. Lett. 385, 298 (2004). [4] A. G. Nasibulin et al. ACS Nano 5, 3214 (2011).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421, E-mail: maruyama@photon.t.u-tokyo.ac.jp– 134 –

FNTG-47, 2014

3P-7

Electron injection in organic light-emitting diodes
by carbon nanotube thin film
○Tatsuya Yamada, Shigeru Kishimoto, and Yutaka Ohno
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
A transparent cathode enables to realize top-emitting organic light-emitting diodes(OLEDs) and transparent OLEDs [1]. Conventionally, ultrathin layers of LiF/Al/Ag or
Mg/Ag/ITO have been used as a transparent cathode, but they suffer from high reflectivity or
instability in air [2]. Carbon nanotube transparent conductive films (CNT-TCFs) haveattractive advantages such as low refractive index and chemical stability. Although CNT has ahigh work function (~4.8 eV [3]) for cathode, a work function of CNT can be changed bydoping. Furthermore, in the previous work, we showed a possibility to enhance hole injection
from a CNT anode in OLEDs by utilizing field concentration effect. Therefore, CNT-TCFs
would be usable as cathode of OLED. In this work, we have investigated the possibility ofelectron injection from CNT cathode to an OLED by means of device simulation.
We simulated an OLED structure that consists of double layers of Alq3 (electron transportand emission layer) and -NPD (hole transport layer). Figure 1 shows the device structureand energy band diagram [4]. We assumed a CNT to be a metal wire with a diameter of 1 nm
as cathode. For comparison, we also simulated for the case of LiF/Al as a conventional planarcathode, forming a Schottky barrier of Schottky barrier height (SBH) of 0.5 eV for an electron[5]. The other simulation parameters were determined based on literatures [4-6].
Figure 2 shows the electron current injected from CNTs to Alq3 as a function of spacing
between CNTs () for various SBH at a bias voltage of 5 V. Horizontal line corresponds tothe case of LiF/Al. First, we examined for a work function of 4.8 eV for CNT, i.e. non-doped
CNT, forming a Schottky barrier of 1.7 eV for an electron. The electron current increased
with , and maximum current was in the same order as that for LiF/Al, even for a high SBHof 1.7 eV. This is due to field concentration effect toCathode (CNT)
(a)

0
x
CNTs. Then, we varied the SBH formed at the
Alq
60
nm
interface between CNT and Alq3,. i.e., electron-doped - NPD
120 nmCNTs were assumed. When SBH was 1.1 eV,
Anodeymaximum current exceeded that of LiF/Al cathode.
(b)
2.4 eV
3.1 eVThis result shows the potential of CNT films as a
ITO (4.8 eV )3.1 ev(planar)cathode of OLEDs utilizing field concentration effect
2.6 eV
0.7 eV
CNT(~4.8 eV )and doping.
α-NPD
3

[6]

[6]

[5]

[6]

[6]

[3]

Alq3

10-2

Electron current (A/cm2)[1] B. Tian, et al., J.Appl. Phys. 110, 104507 (2011)[2] G. L. Ma, et al., Appl. Surf. Sci. 252, 3580 (2006)[3] S. Suzuki, et al., Appl. Phys. Lett. 76, 4007 (2000).
[4] A. Hepp, et. al., Synth. Met. 146, 11 (2004).
[5] B. Masenelli, et. al., Appl. Phys. Lett. 79, 4438 (2001).
[6] J. Staudigel, et. al., J. Appl. Phys. 86, 3895 (1999).
Corresponding Author: Y. Ohno
Tel: +81-52-789-5387, Fax: +81-52-789-5387,
E-mail: yohno@nagoya-u.jp

Fig. 1 (a) Device structure and (b) energy
band diagram examined in simulation.
LiF/Al10-3
V = 5V

10-4

10-5

SBH = 1.7 eV
SBH = 1.5 eV
SBH = 1.3 eV
SBH = 1.1 eV

050

100 150 200 250 300 350

 (nm)

Fig. 2 Calculated electron current versus at 5 V.

– 135 –

3P-8

FNTG-47, 2014

tert-Butoxide Mediated Arylation of Single-Wall Carbon Nanotubes with
Iodoarenes○Mika Tsuboi, Haruka Omachi, Ryo Kitaura,1 and Hisanori Shinohara*,1

Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan.
Single-wall carbon nanotubes (SWCNTs) have attracted significant attention from almost
all areas of science and technology. Especially, the introduction of functional groups onto the
SWCNT sidewall is extremely interesting because the groups affect not only the increase ofsolubility but also the change of electronic properties of SWCNTs.[1] Although diazonium
chemistry is the most widely used method for the side-wall arylation of SWCNTs, [2,3] it isrequired to prepare the desired diazonium salts from aniline precursors freshly due to its
instability and potential hazard.
Here, we report a new arylation method of SWCNTs promoted by tert-butoxide. After thetreatment with aryl radical species generated from iodoarenes and potassium tert-butoxide,
aryl groups were introduced onto the sidewalls of SWCNTs (Figure 1a). Raman spectra show
strong D-band intensity because of increased sp3-carbon with functionalized sidewalls of
SWCNTs. (Figure 1b). Importantly, the degree of the functionalization can be controlled by
the reaction times and temperature. We also confirmed the efficient functionalization of
SWCNTs by other spectroscopic and microscopic measurements.

(a)

(b)

FunctionalizedAr

I

Intensity /a.u.

PristineAr

KO t-Bu

Ar

1100

1200

1300

1400

1500

1600

1700

Raman shift /cm–1

Figure 1. (a) Sidewall arylation of SWCNTs with aryl iodides and potassium tert-butoxide. (b) Raman
spectra of SWCNTs before (gray line) and after (black line) the functionalization.
[1] N. Karousis et al. Chem. Rev., 110, 5366 (2010).
[2] M. S. Strano et al. Science., 301, 1519 (2003).
[3] Y. Piao et al. Nat. Chem., 5, 840 (2013).
Corresponding Author: H. Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442,
E-mail: noris@nagoya-u.jp– 136 –

3P-9

FNTG-47, 2014

Manipulation Method for Controlling Network Structures ofSingle-Walled Carbon Nanotubes○Taiki Inoue, Keigo Otsuka, Shohei Chiashi, Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
In addition to atomic structures of individual single-walled carbon nanotubes (SWCNTs),
network structures of SWCNTs also affect the performance of SWCNT devices. For example,
thin film transistors using randomly oriented SWCNT networks show semiconducting
behavior (high on/off ratio) even with a mixture of semiconducting and metallic SWCNTs aslong as the density of metallic SWCNTs is lower than the percolation threshold [1].
Additionally, it is suggested that Y-junction (partially bundled SWCNTs) is effective to reduce
the junction resistance compared to X-junction (crossed SWCNTs) [2]. While functionaltransistors are obtained by controlling overall density of random SWCNT networks, further
controllability of junction positions, junction types, and alignment would realize moresophisticated configurations for devices with higher current densities and smaller channel
sizes.
In this study, we demonstrate a scalable manipulation method to fabricate thesite-selectively bundled structures of SWCNTs using aligned SWCNT arrays as the starting
configuration. This method is based on a transfer process using a poly(methyl methacrylate)(PMMA) film [3] together with a photoresist as a sacrificial layer to make selected parts of
SWCNTs to be freely suspended over trenches of the PMMA film. Firstly, by standard
photolithography process, a photoresist was patterned to partially cover horizontally aligned
SWCNTs grown on a crystal quartz substrate. Then the substrate was fully covered with a
PMMA film by spin coating. The PMMA film with the SWCNTs and the photoresist patterns
was peeled off from the substrate, and the photoresist was dissolved to give partiallysuspended SWCNTs over the trenched PMMA film. During this process, evaporation of liquid
induced neighboring suspended SWCNTs to contact each other, resulting in partially bundled
structures. Finally, the film was placed on a target substrate, and the PMMA was dissolved
away to leave the manipulated SWCNTs. A scanning electron microscopy (SEM) image of apartially bundled structure of SWCNTs fabricated by this method is shown in Fig. 1(a). We
also fabricated radially-densified arrays of SWCNTs in a similar manner (Fig. 1(b)). Because
the proposed method is a type of a batch process which enables us to manipulate multiple
SWCNTs on a substrate all at once, it could beapplicable to large scale fabrication of devices
with controlled SWCNT networks.

[1] E. Snow et al., Appl. Phys. Lett. 82, 2145 (2003).
[2] P.N. Nirmalraj et al., Nano Lett. 9, 3890 (2009).
[3] L. Jiao et al., J. Phys. Chem. C 112, 9963 (2008).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp

Fig.1: SEM images of (a) partially bundled SWCNTs
and (b) densified SWCNTs. Insets show schematic
images of SWCNT structures.

– 137 –

3P-10FNTG-47, 2014

Carbon nanotube synthesis from very thin nanodiamond layers○R. Shiina1, A. Hayashi1, R. Negishi1, M. Arifuku2, N. Kiyoyanagi2, Y. Kobayashi 1
1

Department of Applied Physics, Osaka University, Suita 565-0871, Japan
2
Nippon Kayaku Co., Ltd, Tokyo 115-8588, Japan

Single walled carbon nanotubes (SWCNTs) have been synthesized by chemical vapor
deposition (CVD) process using nanodiamond (ND) particles as the growth nuclei [1].
Pre-heating treatments in air at typically 600-700 ºC is indispensable for SWCNT growthfrom ND to remove residual carbonaceous impurities and reduce ND particle size into
suitable size for the growth. The “growth window”, or range of the SWCNT growth condition,
for the ND particles, is much narrower than that for conventional metal catalysts since ND do
not have any catalytic effects to decompose carbon feedstock gas. The growth window should
be significantly sensitive to ND structures after the heating treatments. In the previous works,
very thick (~200 layers) ND layers were required since the ND layer structure should be verybroad for satisfying the narrow growth window and obtaining sufficient amount of SWCNTs.
However, only very small portion of the ND particles was activated by chance for the
SWCNT growth and consequently the growth efficiency is extremely low. Therefore,
SWCNT synthesis from a few layers of ND is a crucial issue for applying the ND tostructure-controlled growth of SWCNT from non-metallic crystalline particles. In this work,
we carefully re-examined the growth conditions including the pre-heating process in air, andfound that SWCNTs can be grown from a few layers of ND.
SWNTs were synthesized by thermal CVD from ND particles dispersed on SiO2/Si
substrates. Diluted acetylene and ethanol were used as carbon feedstock gases. SEM images
observed from the samples grown under various conditions are summarized in Fig. 1. In thecase of acetylene, SWCNT growth is very efficient for thicker ND layers, but become
drastically inactive for thinner ones. Using ethanol, on the other hand, SWNT can be growneven for only one layer of ND after optimizing ND dispersion on substrates, pre-heating in air
and gas phase condition during CVD growth. We can observe grown SWCNTs by AFM forthe first time and confirm that their typical diameters are between 1.2-1.6 nm (Fig. 2). AFM
analysis (not shown) indicates that diameter distribution of the ND particles after pre-heatingin air is very broad in the range of 0.8 -35 nm for thicker ND layers, maybe due to cohesion of
ND particles, and is much narrower in the range of 0.8-10 nm for thinner (~1 layer) ND.
These results suggest that the growth window is much wider for ethanol than acetylene, andmust be closely related to nucleation and growth mechanism of SWCNT from ND particles.
[1] D. Takagi, Y. Kobayashi and Y. Homma, J. Am. Chem. Soc. 131(2009)6922.
Corresponding Author: Y. Kobayashi, E-mail: kobayashi@ap.eng.osaka-u.ac.jp
1 layer

10 layers

200 layers

Acetylene

2 m

1 m

1 m

5 m

10 m

1 m

Ethanol

1 m
Fig.1: SEM images from samples with various thicknesses of ND Fig.2:AFM image of a CVD-grownlayers grown using acetylene and ethanol as carbon feedstock gases
sample with 1 layer of ND.

– 138 –

3P-11FNTG-47, 2014

Reaction Analysis of Isolated Cobalt Cluster with O2
by Using FT-ICR Mass Spectrometer○Yuta Tobari1, Kazuki Ogasawara2, Yoshinori Sato2, Makoto Saito2, Shohei Chiashi2,
Shigeo Maruyama2, Toshiki Sugai1
1

2

Department of Chemistry, Toho University, Funabashi 274-8510, Japan
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan

(15,6)(16,4)(17,2)(14,6)(15,4)(13,8)

Intensity / arb. units

Transition metal nano particles and clusters are
Number of Cobalt Atoms
14
16
18
20
popular catalyst for production of carbon nanotubes(a)(CNT). The production of CNT as well as the catalyst+
Pristine Co17
particle itself are performed through oxidation andreduction processes [1]. However, details of theprocesses of nano particles are not well understoodespecially on the size effect and the structure effect.
(b)+O2 (1~4)
Here we present studies on oxidation process of Co−8
910 Torr, 6 sclusters with O2 by Fourier transform ion cyclotron
1.6 collision / sresonance mass spectrometer (FT-ICR).
Details of experimental apparatus and techniques
have been described elsewhere [2]. Co clusters were−7(c)5.410 Torr, 1 s
produced by a laser vaporization cluster beam source
9.3 collision / s
and were trapped for seconds to be thermalized in a+
CoxOy = (x,y)
cell under a homogeneous magnetic field of 6 T. The
trapped clusters were isolated by SWIFT (Stored
Waveform Inverse Fourier Transform) technique and
800
900
1000
1100
1200
then were exposed to oxygen followed by mass
Mass (m/z)
analyses. The reactions were performed in two Fig. 1: Mass spectra of pristine Co17+ and Co
oxide ion clusters.
conditions where the number of collisions between
the clusters and oxygen were kept constant but indifferent frequencies both of which were controlled by the oxygen gas pressure and theexposed periods: the lower pressure and the longer period of 9.0×10-8 Torr and 6 s, and thehigher pressure and the shorter period of 5.4×10-7 Torr and 1 s, respectively.
Figure 1 shows mass spectra of isolated Co17+ cluster (Fig. 1a) and Co oxide clusters (1band 1c). In the low collision frequency condition (Fig. 1b), dominant product ions were
oxygen adducts of Co17O2m+ (m = 1-4) and weakly metal dissociated oxide of Co16O2m+ (m =1-4). On the other hand, in the higher frequency condition (Fig. 1c), highly metal dissociatedoxide of Co17-nO2m+ (n = 0-4, m = 1-4) with Co13O8+ [3] as the most prominent one wereobserved. These salient differences are interpreted that the highly exothermic cluster oxidation
leads to the dissociation and the thermal relaxation induced by non-reactive collision andblack-body radiation [4]. We have controlled the branching ratio between the two paths withthe pressure.
[1] K. Hata, et al. Science 306, 1362 (2004).
.[2] S. Maruyama, et al. Rev. Sci. Instrum. 61, 3686 (1990).
[3] Q. Sun, et al. Phys. Rev. B 62, 8500 (2000). [4] M. L. Anderson, et al. J. Chem. Phys. 130, 064305 (2009).
Corresponding Author: T. Sugai
Tel: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp– 139 –

FNTG-47, 2014

3P-12

FT-ICR Study of Chemical Reaction of Cobalt Clusters with Ethanol○Yoshinori Sato1, Kazuki Ogasawara1, Yuta Tobari2, Makoto Saito1, Shohei Chiashi1,
Toshiki Sugai2, and Shigeo Maruyama1
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan2
Department of Chemistry, Toho University, Funabashi 274-8510, Japan

Intensity / arb. units

The chemical vapor deposition (CVD) is one of the most popular growth methods of single
walled carbon nanotubes (SWNTs). In CVD processes, carbon source molecules were
supplied to nanoscale catalytic metal particles, and SWNTs were grown from the catalyst
particles. Chemical reaction of carbon source molecules and the metal particles are criticallyimportant for understanding the growth mechanism of SWNTs, however they are still unclear.
We have reported [1] the size dependency in the reaction of cobalt clusters with ethanol at
1×10-8 Torr; chemisorption of one ethanol molecule for Con+ (n < 12, n > 17); and bothchemisorption and dehydrogenation at Con+ (12 ≤ n ≤ 17).
In this study, we observed the reactions of cobalt clusters with ethanol at higher pressure inorder to investigate the further reaction of Co clusters with ethanol by Fourier transform ion
cyclotron resonance (FT-ICR) mass spectrometer with direct-injection laser-vaporization
cluster beam source [2]. Cobalt clusters were trapped within the FT-ICR cell, andsubsequently ethanol vapor was introduced. The ethanol vapor pressure was 8×10-6 Torr,
which was about 800 times higher than that of the previous experiments [1]. Figure 1(a)(a) Pristine Coshows the mass spectrum of pristine cobalt
clusters. Three types of reaction pattern
Number of Co Atoms
16
18
20
22
depending on cluster size were observed. In the+case of Con (n > 18), both chemisorption of(a) Pristine Co
one and two ethanol molecules were observed
as shown in Figure 1(b) and 1(c), which show
the reaction products from Co16-22+ clusters
exposed to ethanol for 0.1 s and 0.2 s
respectively. There is no specific peak derived
from Con (9 < n < 18). It was suggested that Co(b) 0.1 s
Co18-22+C2H5OH
clusters dissociated by extensive thermalenergy induced by chemisorption of ethanol.
Co18-22+2C2H5OH
These two types of reaction pattern are distinct
from results of previous study [1]. In the case(c) 0.2 sof Con+ (n < 9), only the chemisorption
Co18-22+C2H5OH(Con+C2H5OH) was observed, which was
Co18-22+2C2H5OH
consistent with our previous study [1] at lower
pressure of ethanol.
[1] S. Inoue and S. Maruyama, Jpn. J. Appl. Phys. 47,
1931 (2008).
[2] S. Maruyama et al. Rev. Sci. Instrum. 61, 3686
(1990).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983
E-mail: maruyama@photon.t.u-tokyo.ac.jp– 140 –

1000

1200

1400

Mass (amu)
Fig.1: Chemical reactions of cobalt clusters withethanol. (a) Mass spectrum of pristine Co clusters
and reaction products from Co clusters exposedto ethanol for (b) 0.1 s and (c) 0.2 s.

3P-13

FNTG-47, 2014

Synthesis and Properties of π-Extended Carbon Nanorings○Akiko Yagi1, Gandikota Venkataramana1, Yasutomo Segawa1,2, Kenichiro Itami1,2,3
1

Graduate School of Science, Nagoya University, JapanJST ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Japan
3
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Japan
2

Recently, several research groups including our own have synthesized cycloparaphenylene(CPP), which is a carbon nanoring consisting of solely para-linkaged benzenes.[1] Since then,further research has revealed a number of interesting properties of CPP and has produced
several kinds of CPP derivatives. Herein, we report the first synthesis of π-extended carbon
nanorings, [9]cyclo-1,4-naphthylene ([9]CN) and cyclo[12]paraphenylene-[2]2,7-pyrenylene([12,2]CPPyr).[2,3] For example, a nickel-mediated “shotgun” macrocyclization of L-shaped
dihydronaphthalene unit provided an excellent way to prepare the macrocycle, which wastransformed to [9]CN by reductive aromatization (Scheme 1). Careful structure-property
analysis uncovered unique features of [9]CN that are quite different from those of [9]CPP.
Stepwise cross-coupling macrocyclization of pyrene and diphenylcyclohexane units by Pd
and Ni catalysts, followed by aromatization of cyclohexane moieties afforded [12,2]CPPyr insix steps from commercially available compounds (Scheme 2). The UV-vis absorption andfluorescence spectra as well as TD-DFT calculations clarified the unique photophysical andelectronic properties of [12,2]CPPyr.
OMe
Br

Br
Br

Ni-mediated"Shotgun"
Macrocyclization

Br

MeO

Reductive
Aromatization

OMe

+
O

MeO

O

OMe

OMe

L-shaped Unit

MeO

[9]Cyclo-1,4-naphthylene([9]CN)

OMe

Cyclic Trimer

Scheme 1. Synthesis of [9]CN.
(pin)BMOMO

Pd- and Nicatalyzed
coupling
Br

OMOM

MOMO

OMOM

Oxidative
Aromatization

B(pin)

MOMO

MOMO

Br
MOMO

OMOM
MOMO

OMOM

Cyclo[12]paraphenylene-[2]2,7-pyrenylene([12,2]CPPyr)Scheme 2. Synthesis of [12,2]CPPyr.
[1] Review: H. Omachi et al. Acc. Chem. Res. 2012, 45, 1378.
[2] A. Yagi et al. J. Am. Chem. Soc. 2012, 134, 2962.
[3] A. Yagi et al. Chem. Commun. 2014, 50, 957.
Corresponding Author: K. Itami
Tel: +81-52-789-6097, Fax: +81-52-789-6098, E-mail: itami@chem.nagoya-u.ac.jp– 141 –

3P-14

FNTG-47, 2014

Chirality Fingerprinting and Geometrical Determination ofSingle-Walled Carbon Nanotubes: Analysis of Fine Structure of X-ray
Diffraction Pattern
Ryo Mitsuyama 1 , Shin Tadera 1 , ○Haruka Kyakuno 1 , Ryosuke Suzuki 1 , Hiroyoshi Ishii 1 ,Yusuke Nakai 1 , Yasumitsu Miyata 1,3 , Kazuhiro Yanagi 1 , Hiromichi Kataura 2 ,and Yutaka Maniwa 1,*
1

Department of Physics, Tokyo Metropolitan University, Hachioji Tokyo, 192-0397, Japan
2
Nanosystem Research Institute (NRI), AIST, Tsukuba, Ibaraki, 305-8562, Japan
3
JST, PRESTO, Kawaguchi, Saitama 332-0012, Japan
Single-walled carbon nanotubes (SWCNTs) are seamless cylindrical tubes consistingof carbon atoms with diameters ranging from less than one nanometer to a few nanometers.
The arrangement of carbon atoms in an SWCNT is uniquely specified by using a pair of
integers (n,m) referred to as the chiral indices. While the detailed structures, such as acarbon-carbon bond length, should be important, they have not been fully clarified yet. In
this work [1], we examined the possibility of powder X-ray diffraction (XRD) method tocharacterize structures of SWCNTs. We found that
(1) The

XRD

is

a

usefultool

to“fingerprint”   the   chiral   indices   of  bulk SWCNT samples. (see Fig. 1)(2) Information on the detailed structure
within an SWCNT can be obtained
from the XRD pattern.
(3) Theapplication

toaFigure 1 Calculated XRD patterns for graphene,(6,6) SWCNT, and (10,0) SWCNT from upper tobottom, respectively.

highlyconcentrated SWCNTs clarifies thatthe (6, 5) SWCNT is expanded by
0.9±0.3% along the radial direction
compared to that of ideal rolling up
structure of graphene with a single
bond length, with a negligible change
along the tube axis. (see Fig. 2)[1] R. Mitsuyama et al., Carbon 75 (2014)299-306*

Corresponding author: Y. Maniwa
E-mail address: maniwa@phys.se.tmu.ac.jp

Figure 2 Schematic structure of (6,5) SWCNT
expanded by 1% along the radial direction.
θ 12 =119.05, θ 23 =119.58, and θ 31 =118.70. In thedefault structure, d 1 =1.409 Å, d 2 =1.418 Å,
d 3 =1.417 Å, and θ 12 =118.86, θ 23 =120.08,θ 31 =118.41. Here, θ ij is the angle between bonds iand j.

– 142 –

FNTG-47, 2014

3P-15

Dynamic Alternation of Sign in Spin Density of [6]Cycloparaphenylene
Radical Cation○Tatsuhisa Kato 1, 2, Takahiko Koyama1, Yuichiro Kameoka 3, Eiichi Kayahara 4, Shigeru
Yamago 4, Tohru Sato 3, and Kazuyoshi Tanaka 3
1
Department of Interdisciplinary Environment, Graduate School of Human andEnvironmental Studies, Kyoto University, Kyoto 606-8501, Japan
2
Institute For Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan3
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University,
Kyoto 615-8510, Japan
4
Institute for Chemical research, Kyoto University, Uji 611-0011, Japan
A cycloparaphenylele (CPP) is the molecule with thesimplest structure unit of carbon nanotube, as shown in Fig. 1.
CPP exhibits the torsional structure around the bond of adjacentphenylene rings [1], which is explained by the pseudo
Jahn-Teller effect. The instability of the cylindrical D6hstructure is driven by the vibronic couplings of the deformation
mode between occupied and unoccupied orbitals [2].
A radical cation of [6]CPP was prepared by chemical
oxidation by SbCl5 [3]. Its electronic structure was investigatedby electron spin resonance (ESR) and electron nuclear double
resonance (ENDOR) measurements. The dynamics with respect
to the torsional deformation were reflected in ENDOR spectra.
One special multiple resonance method, electron–nuclear-nuclear triple resonance (TRIPLE), was applied to the radical
cation of [6]CPP. The 13C-TRIPLE
spectrum in Fig.2 shows relative
signs of hyper fine coupling (HFC)interactions. As a result, thedynamic
alternation
betweenpositive and negative spin density
were experimentally confirmed.

Fig.1: Molecular model ofcycloparaphenylene[1] B. M. Wong, J. Chem. Phys. C 113,
21921 (2009).
[2] Y. Kameoka et al., Chem. Phys. Lett.
598, 69 (2014).
[3] E. Kayahara et al., Angew. Chem. Int.
Ed. 52, 13722 (2013).
Corresponding Author: T. Kato
Tel: +81-75-753-6695,
Fax: +81-75-753-6695,
E-mail: kato.tatsuhisa.6e@kyoto-u.ac.jp

Fig.2: 13C-TRIPLE spectrum of [6]CPP radical cation.

– 143 –

3P-16

FNTG-47, 2014

Electronic and structural properties of B-doped carbon-nanotube film on SiC○Wataru Norimatsu1, Koji Oda1, Hayato Fujita1, and Michiko Kusunoki2
1

Department of Applied Chemistry, Nagoya University, Nagoya 464-8603, Japan
2
EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan

Carbon nanotube (CNT) has attractive electronic properties due to its
one-dimensionality. We have been investigated the structural features of closely-packed
CNTs film grown by surface decomposition of silicon carbide. In this method, annealing
SiC in a vacuum leads to sublimation of silicon atoms from the surface, and the remaining
carbon atoms form CNTs on SiC. Features of CNTs formed by thermal decomposition of
SiC are high purity without any catalyst metals, high orientation, strong adhesion to the SiC
surface at the atomic-scale, mostly zigzag-typed with the diameter ranging from two to fivenanometers, and high density of more than 3×1010 /mm2. If we succeeded doping into CNTs,
further transport control would be achieved. In this study, we attempted B-doping into theclosely-packed zigzag CNTs film, and performed their transport measurements.
_

Carbon nanotube samples were obtained by heating 6H-SiC (0001) single crystal
substrates at 1600 ºC for an hour in a high-vacuum of 1×10-4 Torr. Under this condition,
CNTs with about 120 nm are grown closely-packed covering over the SiC surface. After
B-doping, structural features of the obtained samples were examined using transmission
electron microscopes (TEMs). Hall-effect measurement was carried out in the temperature
range of 20 and 300 K.
Figure 1 (a) and (b) show TEM images of CNT films after the B-doping reaction at 1600
˚C. As is seen in the figure, configuration of CNTs was mostly maintained (Figure 1 (a)),
but a part of SiC substrates was decomposed further and boron carbide crystals were formed
there. Figure 2 shows B element mapping in the same area of CNT films by EELS. This B
elemental mapping image confirmed the presence of boron carbide crystal in the brightest
region and also exhibited bright striation contrast along CNTs. These results indicated thepossibility that a little amount of B atoms were doped into the CNT films.
(a)

(b)

(c)

Figure 1 TEM image of (a) CNTs film on SiC (000-1), (b) Boron-doped CNTs film together with (c) boron elemental
mapping image.

Corresponding Author: W. Norimatsu, Tel/Fax: +81-52-789-5859,
E-mail: w_norimatsu@esi.nagoyau-u.ac.jp– 144 –

FNTG-47, 2014

3P-17

Grafting of polymers onto graphene oxide by cationic and anionicpolymerization initiated by the surface functional groups
Kazuhiro Nagata1, ○Takashi Kawahara2, Kumi Hashimoto1, Kazuhiro Fujiki3,
Shingo Tamesue1, Takeshi Yamauchi1, Norio Tsubokawa1
1
2

Graduate School of Science and Technology, Niigata University, Niigata 950-2181, Japan
Center for Fostering Innovative Leadership, Niigata University, Niigata 950-2181, Japan3
Department of Environmental Science, Niigata Institute of Technology,
Niigata 945-1195, Japan

We have pointed outthat carboxyl (COOH)
groups on nanocarbons
have an ability toinitiate the cationicpolymerization of vinyl
monomers [1]. In addi-tion, we have reported
the anionic ring-open-
Scheme 1: Cationic and anionic polymerization initiated by GO
ing alternating copoly-merizetion of epoxides and cyclic acid anhydrides initiated by potassium carboxylate(COOK) groups of nanocarbon surface [2].
In this paper, we investigated the conventional grafting of several polymers onto graphene
oxide (GO) by two processes: (1) cationic polymerization initiated by surface COOH groupsof GO and (2) grafting of polyesters by anionic ring-opening alternating copolymerization
initiated by COOK groups of GO as shown in Scheme 1.
The cationic polymerizations of isobutyl vinyl ether and N-vinylcarbazole weresuccessfully initiated by COOH groups of GO to give the corresponding polymer-grafted GO.
The cationic polymerization was considered to be initiated by proton addition from COOH
groups to monomer and propagation of polymer cation proceeds with carboxylate anion as acounter anion. It was found that the corresponding polymers were successfully grafted onto
GO based on the termination reaction of growing polymer cation and surface countercarboxylate anion.
In addition, the anionic ring-opening alternating copolymerization of epoxide and cyclicacid anhydrides were also initiated by COOK groups, which were previously introduced onto
GO by the neutralization of COOH groups with KOH, and the corresponding polyesters weregrafted onto GO, based on the propagation of polyester from COOK groups. The grafting ofpolyester onto GO was confirmed by thermal decomposition GC-MS.
The dispersibility of GO in organic solvents was remarkably improved by the grafting ofthese polymers.
[1] N. Tsbokawa et al. Polym. J. 13, 1093 (1981).
[2] N. Tsbokawa et al. Polym. J. 16, 333 (1984).
Corresponding Author: N. Tsubokawa
Tel: +81-25-262-6779, Fax: +81-25-262-6779,
E-mail: ntsuboka@eng.niigata-u.ac.jp– 145 –

3P-18

FNTG-47, 2014

Edge energy and reconstruction of siliceneżSusumu Saito1,2,3, Takashi Koretsune1,41

Department of Physics, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
2
International Research Center for Nanoscience and Quantum Physics,
Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
3
Materials Research Center for Element Strategy, Tokyo Institute of Technology,
Midori-ku, Yokohama, Kanagawa 226-8503, Japan
4
Center for Emergent Matter Science, Institute of Physical and Chemical Research (RIKEN),
Wako, Saitama 351-0198, Japan
Graphene, a single-layer graphite sheet, has been studied theoretically for more than adecade as two-dimensional carbon network material which can host periodically thenanostructured carbon units to realize new electronic properties [1], and for more than two
decades as an atomic-layer sheet which can be used to construct new materials by alternative
stacking with the other two-dimensional layer [2]. The experimental realization of graphene
about a decade ago triggered the extensive study of graphene and other atomic-layer materials.
Among them, silicene, the atomic-layer Si sheet, is of high importance and interest because
the material can be considered as the “thinnest Si wafer” and many methodologies andtechniques used in the present field of the Si semiconductor technology could be used forsilicene as well.
We have studied the stabilities of neutral and charged silicene layers and the composite
layers of silicene and graphene and silicene and hexagonal BN layers. In the present work westudy the energetics and the geometrical reconstruction of silicene edge in the framework of
the density functional theory. It is found that the reconstruction of the so-called armchair edge
is relatively large with considerable stabilization energy. In the case of zigzag edge, thereconstruction is also found to take place (Fig. 1) unlike graphene, while its energy gain due
to the reconstruction of zigzag edge is smaller than that of the armchair edge.

Figure 1 Reconstruction of zigzag edge (upper and lower sides) in silicene ribbon[1] “Geometric and Electronic Structure of New Carbon-Network Materials: Nanotube Array on Graphite Sheet”,
T. Matsumoto and S. Saito, J. Phys. Soc. Jpn. 71, 2765 (2002).
[2] “Design of C60-graphite cointercalation compounds”,
S. Saito and A. Oshiyama, Phys. Rev. B 49, 17413 (1994).
Corresponding Author: S. Saito
E-mail: saito@stat.phys.titech.ac.jp– 146 –

3P-19FNTG-47, 2014

One-step synthesis of heterostructures based ontransition metal dichalcogenides by thin-film sulfurization○Yu Kobayashi1, Shohei Mori1, Yutaka Maniwa1, and Yasumitsu Miyata1,2,*
1

Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
JST, PRESTO, Kawaguchi, 332-0012, Japan

Development of a facile preparation method of the heterostructures in two-dimensional
materials is one of the most important topics for the use of their potential in electronics andoptics. So far, several groups, including ours, have reported the synthesis of metal-insulator
junction consisting of graphene and hexagonal boron nitride by using two-step chemical vapor
deposition [1-3]. Recently, our group also have demonstrated the formation of semiconductor
heterostructures of transition metal dichalcogenides (TMDCs) via two-step thin-film
sulfurization [4]. The previous work suggests that TMDC-based heterostructures can be formedby the difference in growth rate between MoS2 and WS2 even by single-step sulfurization.
Here, we report the one-step synthesis of the heterostructures consisting of atomic layer
MoxW1-xS2 by controlling the growth rates of MoS2 and WS2. To control the growth rates, we
use patterned WO3 and MoO3 thin films on SiO2/Si substrates and optimize their sulfurization
temperature. Figure 1 shows a False-color Raman image of a crystal obtained after thesulfurization, which reveals that WS2 mainly forms around MoS2. Furthermore, thecomposition ratio of W and Mo is found to vary depending the position in the crystal as shownin photoluminescence spectra (Fig.1b).
These results indicate that MoS2 hashigher growth rate than WS2, leading
to the formation of MoxW1-xS2–based
heterostructures. The present finding
provides a fast, effective way toprepare the heterostructure based on
atomic layer TMDC alloys.
Fig.1 (a) False-color Raman image of an Mo W S
1-x

x 2

heterostructure. Bright (middle dark) part corresponds to the[1] Y. Miyata, et al., Appl. Phys. Express 5(2012) 085102., [2] M. Levendorf et al.,Nature, 488 (2012) 627., [3] P. Sutter et al.,E2g mode intensity of WS2 (MoS2). (b) Photoluminescence
spectra taken at different points of the crystal. Asterisks
indicate the spectra of pure WS2 and MoS2.

Nano Lett., 12 (2012) 4869. [4] S. Mori, et al.,The 46th Fullerenes-Nanotubes-Graphene General Symposium.
Corresponding Author: Yasumitsu Miyata, Tel: +81-42-677-2508, E-mail: ymiyata@tmu.ac.jp– 147 –

FNTG-47, 2014

3P-20

Multilayer graphene nanoribbons fabricated by graphene over-layer
growth on unzipped carbon nanotubes○H. Kitakawa1, R. Negishi1, H. Tanaka2, M. Fukumori2, T. Ogawa2, Y. Kobayashi1
1Department of applied physics, Osaka University, Suita 565-0871, Japan2
Department of Chemistry, Osaka University, Toyonaka 560-0043, Japan

References: [1] Y. Ouyang, et al. Nano Research 3, 8 (2010) [2] R.
Negishi et al. Thin Solid Films 519, 6447 (2011) [3] L. Jiao et al. Nat.
Nanotech. 5, 321 (2011)
Acknowledgement: Authors would like to thank Prof. K. Matsumoto(Osaka Univ.) for supporting AFM measurements.
Corresponding Author: H. Kitakawa(kitakawa@ap.eng.osaka-u.ac.jp)– 148 –

Grown layer thickness of
GNR(nm)Height(nm)Multilayer graphene nanoribbons (M-GNRs) with weak interlayer coupling like a turbostratic
structure are desired for high-performance GNR field effect transistors (GNRFETs) becauseof their electronic properties such as high on/off ratio and band gap opening in theoretical
calculations [1]. However, it is difficult to synthesize narrow M-GNRs with controlled layer
number. We recently found that graphene layers were synthesized over mechanicallyexfoliated graphene by ethanol chemical vapor deposition (CVD) and grown layers haveturbostratic structure [2]. In this work, we report the M-GNRs synthesis by graphene
over-layer growth on bilayer GNRs with several nanometers width, which are prepared byunzipping double-wall carbon nanotubes (DWCNTs).
GNRs as growth templates were obtained from unzipping DWCNTs [3]. Graphene layers
were grown by ethanol CVD using a furnace with three temperature zones, in which
temperatures for carbon feedstock decomposition and graphene growth can be controlledindividually [2]. The temperatures used for thermal decomposition and graphene growth were
900 ºC and 720-735 ºC, respectively. Thickness of the grown graphene was evaluated byatomic force microscopy (AFM).
Figure 1 shows the AFM images obtained from the GNR (a) before and (b) after CVD
growth, and (c) height profiles of the GNR along L-L'. Before the growth, the thickness of
GNR estimated from the height profiles was ~1.0 nm, which corresponds to bilayer. The
thickness of the GNR increased by ~1.4 nm after growth. This result indicates that themultilayer GNR with 3~4 layer was additionally formed by
the growth. For the grown M-GNR, we examined Raman
(a)
(b)
L’
spectroscopy measurements of the 2D band profiles which
L’
L
L
reflect the stacking structure of the graphene layers. The 2D
L’Lband profile can be fitted using a single Lorentzian (not
200nm
200nm
shown here), and this indicates that grown layers haveturbostratic structure. Figure 2 shows the comparison of
4
Before(c)grown layer thickness of the GNRs with several nanometer3
Afterwidths and mechanically exfoliated graphene with the size of2LL’several micrometers. Growth rates of graphene layers on the
10
GNRs and the graphene are independent of terrace sizes,
0
100
200
where precursors are nucleated at the initial growth stage.
Distance(nm)This indicates that the growth of graphene layers on the Fig. 1 AFM images of the GNR
GNR proceeds by multiple nucleation. This also indicates (a) before and (b) after growth.
that the nucleation at the edge sites of GNR does not (c) Height profiles of along L-L’.     3contribute to the growth of graphene layers on GNRs. In
summary, we could synthesize M-GNRs and reveal that they2
have turbostratic structure. These results are significant for
application to high performance GNRFETs.
1
0
0
1
2
3
Grown layer thickness ofgraphene(nm)Fig. 2 Grown layer thickness of GNR
compared with that of graphene.

3P-21FNTG-47, 2014

Graphitic Carbon Synthesis via Electrochemical Reduction Reactions○Jeheon Kim1, Satoshi Yasuda2, Kei Murakoshi1
1Department of Chemistry, Hokkaido University, Sapporo, 060-0810, Japan
2

JST-PREST, Kawaguchi, Saitama, 332-0012, Japan.

Graphene has been come into spotlight for various applications due to its exceptional
physical, electrical, chemical, and mechanical properties [1]. Conventional synthesis ofgraphene is based on chemical vapor deposition (CVD) technique at high temperature
condition, and its process enables to produce high quality graphene on a large scale. However,in spite of numerous studies, development of low temperature growth of graphene has been
still challenging in the viewpoint of realization of flexible plastic electric systems. Recently,
we have succeeded in synthesizing carbon nanotube by electrochemical technique [1]. In thisstudy, we studied an attempt on graphene synthesis by employing electrochemical reductionof halogenated carbon at room temperature.
In the experimental, the three electrodecell was employed as electrochemical deposition
system. TMPA-TFSI which is ionic liquid (IL),
was adopted as electrolyte due to facilitate thewide reductive electrochemical window. Besides,
halogenated carbon such as tetrabromo methane(CBr4) was used as carbon source because of its
electrochemical activity. Ni, Pt sheet, and Ag/Ag+
electrode, were used as working, counter and Fig 1 Cyclic voltammogram for IL (solidreference electrodes, respectively.
lines) and CBr4 in IL (dotted lines).
Cyclic voltammogram (CVs) was plottedfor each sample in Fig. 1. In case of IL electrolyte(b)(solid lines), no reduction peaks was observed. (a)However, IL electrolyte contained CBr4 (dashedlines) was reduced below – 2.0 V, arising fromelectrochemical reduction of CBr4. After thedeposition for 30 min at – 2.5 V, Raman
2.5 μmspectroscopy analysis revealed that the depositedmaterial possesses clear D- and G-bands (Fig 2(a)) features, showing the synthesis of graphitic Fig 2 (a) Raman spectra for each deposited
carbon. Typical D / G ratio was obtained about
0.6, indicating that the deposited material consists material in IL (solid lines) and CBr4 + IL onof nano-size graphene. In addition, nano-size Ni substrate. (b) AFM image on graphitic
graphene structures were covered over the carbon for CBr4 + IL deposition.
substrate (Fig. 2(b)). These results strongly
indicate that nano-size graphene is successfully synthesized by electrochemical reduction of
halogenated carbon in IL at room temperature, and the technique will serve as thedevelopment of fabrication of novel flexible electric devices.
Reference[1] A.Shawky, S.Yasuda, K.Murakoshi, Carbon, 50, 4184-4191 (2012)– 149 –

3P-22

FNTG-47, 2014

Growth of Graphene on SiO2 by Catalyst-Assisted
Heat Treatment of Amorphous Carbon
ż<RKHL+DVHEH+LWRVKL1DNDKDUD.RML$VDNDDQG<DKDFKL6DLWR
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
Graphene has attracted considerable attention
because of its outstanding electrical, mechanical andchemical properties. In this study, an amorphous
carbon (a-C) layer was sandwiched between an
metal layer and SiO2/Si substrate, and then graphene
layers were synthesized on SiO2 directly by heat
treatment.
As shown in Fig. 1(a), SiO2, a-C and metal
catalyst films were formed on a Si substrate throughelectron beam vapor deposition within the samechamber. Iron (Fe), nickel (Ni) and copper (Cu) wereused as catalytic metal. The thickness of catalyst anda-C was varied from 20 nm to 200 nm and from 1
nm to 20 nm, respectively. The films were heat
treated to graphitize in vacuum by an annularelectronic furnace at temperatures ranging from 973
to 1173 K (Fig. 1(b)). After heat treatment, the films
were investigated by cross-sectional transmission
electronmicroscopy
(TEM)
and
Raman
spectroscopy.
Figure 2 shows a cross-sectional TEM image ofthe film with Fe (60 nm) / a-C (10 nm) / SiO2 (30nm) / Si after the heat treatment at 1173 K.
Multilayer graphene was formed at the interface
between Fe and SiO2 layers.
Figure 3 shows the Raman spectra of this sample
before and after heat treatment. After the heat
treatment, clear G and 2D peaks are obtained.
Existence of multilayer graphene is suggested fromthese intensity ratios. This result is in agreementwith the result of the cross-sectional TEM image.
Corresponding Author: Y. Hasebe
Tel&Fax: +81-52-789-3714, +81-52-789-3703
E-mail:hasebe@surf.nuqe.nagoya-u.ac.jp

(a)
metal
a-C
SiO2
Si
(b)
graphene

Fig. 1. (a) SiO2, a-C and Fe layers aredeposited on a Si by electron-beamdeposition. (b) The films are heat treated tographitize.

Fe

0.34 nm

SiO2
Fig. 2. Cross-sectional TEM image of theinterface between Fe and SiO2 layers.
Multilayer graphene is indicated by anarrow.

as deposite
2DG
1173 KD

Fig. 3. Raman spectra of carbon films.

– 150 –

3P-23

FNTG-47, 2014

Growth of high-quality multi-layer graphene by precipitation method
using diffusion barrier and two step annealing○Yuki  Ueda,  Manabu  Suzuki,  Jumpei Yamada, Takahiro Maruyama, and Shigeya Naritsuka
Dept. of Mat. Sci. and Eng., Meijo Univ., Nagoya 468-8502, Japan
Graphene is two-dimensional materials with honeycomb structure of carbon atoms.
Precipitation method is one of the prospective methods to grow high-quality graphene [1-2].
In this paper, the effect of diffusion barrier plus two-step annealing is investigated to improve
the quality of the multi-layer graphene grown by the precipitation method.
The sample used in the experiment has Au (20nm) / Ni (300nm) / Al2O3 (2nm) / a-C(40nm) structure, which were deposited on a (0001) sapphire substrate using electron beam
deposition. The sample was annealed to precipitate graphene at 900oC for 60min after the
pre-annealing of 700oC for 30min. The cooling rate of 10oC/min was used in the cool-down
process after annealing. The properties of the grown layers were characterized using optical
microscope and Raman spectroscopy.
Figure 1 shows an optical microscope image of thesample surface after annealing. A lot of dark-color islands areobserved, which correspond to the thicker areas. Raman
spectra in Fig.2 were taken from each point, indicated A, B,
and C in Fig. 1. It is found from the figure that the graphenefully covers the whole surface including the bright part in the
background in Fig.1. D/G ratio of less than 0.06 and small
G’/G  ratio  indicate  that  high-quality multi-layer graphene weregrown by the method. The pre-annealing of 700oC might

Fig.1 Optical microscope image

suppress the residual nucleation of graphene and helps thegraphene smoothly cover the surface. In addition, the quality ofgraphene was thought to improve during the high-temperatureannealing at 900oC. The 2D nuclei of graphene are thought tooccur after the first graphene covers the whole surface.
Fig.2 Raman spectra[1] R. S. Weatherup et al., Nano Lett., 13 (2013) 4624.
[2] M. Suzuki et al., 61st JSAP Spring Meeting (2014) 17a-E2-16.
Corresponding Author: Shigeya Naritsuka
Tel: +81-52-838-2386, Fax: +81-52-832-1172,
E-mail: narit@meijo-u.ac.jp

Acknowledgement: This work was partly supported by Grant-in-Aid forSpecially Promoted Research (No.25000011) from the Ministry of
Education, Culture, Sports, Science and Technology of Japan.

– 151 –

3P-24

FNTG-47, 2014

Uniform graphene formed by surface decomposition of TiC-masked SiC substrate°G. Miyamoto1, W. Norimatsu1, M. Kusunoki1, 2
1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University,
Nagoya 464-8603, Japan
2. EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan
Epitaxial graphene on a SiC(0001) Si-face formed by thermal decomposition is high quality, so
hoped to be applied to the field effect transistor. Graphene formed on the SiC(000-1) C- face has highcarrier mobility, however, it is difficult to form uniform mono layer graphene. Titanium carbide (TiC)
is NaCl-type structure and has high thermostability, highly electrically conductivity, and high degree of
hardness. The lattice distance of the TiC(111) has the same values as the one of SiC {0001} plane,
which enabled to succeed in forming a uniform epitaxial TiC film of 0.75 nm thick on the surface of
SiC substrate [1]. We have reported that in graphitization, the TiC film played a role of mask, and as aresult, 4 or 5 layers of graphene were formed homogeneously in a large area. In this time, we tried tocontrol the layer number of graphene on the C-face by changing the condition of the heat treatment.
6H-SiC(000-1) substrates were heated to 1500-1550°C for 0.5 hour in a vacuum of 4.0 × 10-5 Torrwith a SiC, TiO2 and C powders, to grow the epitaxial TiC film. After forming TiC film, making anenvironment in semi-closed system with a lid, the substrates were annealed at 1600°C for 0.5 hour Ar
atmosphere of 6 atm pressure for surface graphitization. We observed the formed samples using Raman
spectroscopy, AFM, and TEM (EM-002B : Topcon).
Fig. 1 shows the Raman spectrum of graphene derived from TiC/SiC. The obtained weak D peak at
1362 cm-1, sharp G peak at 1602 cm-1, and very sharp 2D peak at 2705 cm-1 revealed the formation ofhigh quality graphene in a large area. Full width half maximum of 2D peak is 31 cm-1 and I2D/IG ratio is
2.11. This result strongly indicates formation of mono-layer graphene. Fig. 2(a) and (b) shows AFM
topographic and phase images. Fig. 2(a) shows keeping of a step-terrace structure, and Fig. 2(b) shows
the formation of uniform layer number of graphene in the area of 10 micrometer order squares.
4.7nm

(a)

(b)

G
D
4  μm

4  μm
0 nm
Fig. 1 Raman spectrum for the graphene

Fig. 2 AFM images of the graphene-layered SiC (a) thelayers formed by the surface decomposition

topographic image and (b) the phase image.

of the TiC/SiC substrate.
[1] K. Kimura, K. Shoji, Y. Yamamoto, W. Norimatsu and M. Kusunoki, Phys. Rev. B 87, 075431 (2013).
Corresponding Auther: M. Kusunoki
Tel: 052-789-5859, Fax: 052-789-5859
Email: miyamoto.genki@h.mbox.nagoya-u.ac.jp– 152 –

3P-25

FNTG-47, 2014

Synthesis of graphene using CH4 by Microwave Surface Wave Plasma
Chemical Vapor Deposition○Susumu Ichimura1 2, Hideo Uchida1, Koichi Wakita1,
Yasuhiko Hayashi2, Masayoshi Umeno1
1

Institute for General Research of Science, Chubu University, Kasugai 487-8501, Japan2
Department of Natural science, Okayama University, Okayama 700-8530, Japan

Recently, graphene has attracted attention as atransparent conductive film [1]. From the viewpoint ofa large area, we are researching by focusing on
Microwave Surface Wave Plasma CVD. Microwave
Surface Wave Plasma CVD is known as a film forming
method without damage. However, damage has
occurred in the graphene growth.
Plasma damage is divided into ultraviolet light or
charged particles [2]. In order to investigate theinfluence, experiments were carried out using a grid
(two pieces). Fig. 1 shows the setup for the
grid-inserted Microwave Surface Wave
Plasma CVD. Fig.2 shows the Raman
spectrum of the grid presence or absence. It
was confirmed that it is possible to reduce thedisordered peak by grid-inserted. In addition,
it was graphene grown by applying a DC
voltage to the grid, but no damaging reduced.
The synthesis graphene were characterized
by Raman, SEM, AFM and TEM. Fig. 3
shows cross section HR-TEM image, it isgraphene that was prepared by grid-inserted.

Fig.1: Setup for grid-inserted
Microwave Surface Wave Plasma
CVD

Fig.2: Raman spectrum[1] Kemal Celebi et al. NANO LETTERS 13,
967-974 (2013)[2] Yoshihiro Kojima et al. Jpn. J. Appl. Phys. 44,
2600-2603(2005)
Corresponding Author: S. Ichimura
Tel: +81-568-51-1111 Ext. 4226,
Fax: +81-568-51-9056,
E-mail: ichimura@isc.chubu.ac.jp

Fig.3: HR-TEM image of graphenegrown by grid-inserted– 153 –

3P-26

FNTG-47, 2014

Plasma CVD growth of good quality graphene film using camphor
precursor○Hare Ram Aryal1, 2, Dilip Chandra Ghimire1, 2, Sudip Adhikari1, 2,
3

2

Uchida , Koichi Wakita , and Masayoshi Umeno

Hideo

1

1

Institute for General Research of Science, Chubu University, Japan2
Department of Clinical Engineering, Chubu University, Japan3
Department of Electronics and information Engineering, Chubu University, Japan
This technique has been widely used in recent days. Plasma CVD growth of graphene isappropriate to grow large area graphene film and also is advantageous for significant energy
savings. However, improving the quality of the film is still a challenge while comparing withthermal CVD grown films. Rapid growth leads to the formation of nano-crystalline graphenefilms which degrades overall quality of the film.
In this work, we have employed microwave surface wave plasma CVD to grow graphenefilm at low temperature. We believe that ion bombardment and UV radiation create defects on
the sp2 bonding of graphene. We avoid direct exposure of substrates to the plasma and preferslow growth process for quality improvement of the film. Fig. 1 shows Raman spectrum of atypical graphene film grown at 550 ℃. Reduced defect related peak intensity reveals goodquality of the film.

Fig. 1 Raman signal of as grown graphene at 550 ℃

Corresponding author:
H. R. Aryal
Tel: 0568-51-1111 (Ext: 4218)
E-mail: aryal_hareram@yahoo.com– 154 –

FNTG-47, 2014

3P-27

Modifying Inter-layer Interaction of Hexagonal Boron Nitride by Infrared
Laser
Yoshiyuki Miyamoto
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Central 2, 1-1-1, Umezono, Tsukuba 305-8568, Japan
We theoretically demonstrated that optical excitation can enhance the weak attraction likeas van der Waals interaction [1]. The mechanism is understood by induction of dynamical
dipole by optical excitation that causes attractive forces among atoms and molecules.
We apply this idea for modifying weak interaction acting between atomic layers ofhexagonal born nitride (hBN) by illuminating infrared (IR) laser. By performing a molecular
dynamics (MD) simulation of bi-layer hBN under intense laser beam whose frequency is inresonance with the optical out-of-plane mode (A2umode), we observed considerable contraction of theinter-layer distance by 0.2 Å. We have performed
first-principles MD simulation based on thetime-dependent
densityfunctional
theory(TDDFT)[2] treating electron-ion dynamics underillumination of the IR laser. The numerical scheme[3,4] was applied for the simulation
The mechanisms of the contraction can beunderstood by increase of the dipole-dipole
interaction upon lattice vibration due to IR laser, as
illustrated in Fig. 1. When polarization vector of
Fig.1: (a) Stable structure of bi-layer
the optical electric field (E-field) is normal to eachhexagonal born nitride (hBN). (b)Snapshot of the structure of the bi-layer
layer of hBN, born and nitrogen atoms are forced tohBNunder illumination of infrared laser
move in opposite directions normal to the layers
light.
that induces dynamical dipole moments attracting
these two layers. The TDDFT simulation (including
electron dynamics) also suggests a side-effect of electron excitation coming from intense laser
beside induction of lattice vibration. In a poster presentation, we will discuss detailed
condition of IR illumination and mechanisms of modification of the inter-layer interaction.
This work was done in collaboration with Dr. Takehide Miyazaki (AIST), Prof. Hong
Zhang (Sichuan University), and Prof. Angel Rubio (ETSF and FHI).
[1] Y. Miyamoto, T. Miyazaki, A. Rubio and H. Zhang, Appl. Phys. Lett 104, 201107 (2014).
[2] E. Runge and E. K. U. Gross, Phys. Rev. Lett 52, 997 (1984)[3] O. Sugino and Y. Miyamoto, Phys. Rev. B59, 2579 (1999).
[4] Y. Miyamoto and H. Zhang, Phys. Rev. B77, 165123 (2008).
Corresponding Author: Y. Miyamoto
Tel: +81-28-849-1498, Fax: +81-29-861-3171,
E-mail: yoshi-miyamoto@aist.go.jp– 155 –

3P-28

FNTG-47, 2014

Trion Generation via Exciton Collision in Monolayer MoS2
○Shinichiro Mouri1, Yuhei Miyauchi1,2,3 and Kazunari Matsuda1
1Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
2
Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama
332-0012, Japan
3
Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8601, Japan
Monolayer transition metal dichalcogenides including molybdenum disulfide (MoS2)
have attracted much attention as a novel two-dimensional direct band gap
semiconductor, and also are promising candidate to realize the future optoelectric
devices [1-3]. Control of the many-body interactions among optically generated carries
is necessary to achieve the high performance optoelectric devices. In this study, we
examined the many-body carrier dynamics in monolayer MoS2 (1L-MoS2) via
photoluminescence (PL) spectroscopy.
Figure 1(a) shows the PL spectra of F4TCNQ-doped 1L-MoS2 measured at different
excitation power density. The F4TCNQ doping treatment is effective to reduce theexcess electrons in the spontaneously n-doped 1L-MoS2 [4]. The exciton PL (X: ~1.88eV) is dominant at weak excitation region and the trion PL (X-: ~1.84 eV) component
increases with increasing excitation power density. Figure 1(b) shows the PL intensities
of excitons and trions as functions of excitation power density. The exciton PL intensity
is saturated at high excitation power density while the trion PL intensity is almost
linearly increased. This strong PL saturation behaviour suggests that the excitonexciton collision becomes remarkable in the strong excitation region and additional
carriers generated via exciton-exciton collsion give rise to the linear increase of trion
PL intensity. The detailed mechanism of exciton and trion decay will be discussed in
the presentation.
(b)

PL Intensity (Arb. Units)

F4TCNQ-doped 1L-MoS2
12 J/cm
4
2
0.8

1.70

2

-

X

X

1.75
1.80
1.85
1.90
Photon Energy (eV)F4TCNQ-doped 1L-MoS2

PL Intensity (Arb. Units)

(a)

1.95

-

Trion (X )Exciton (X)

0

4

8

12
2

Excitation Power Density (J/cm )Figure 1 (a) Excitation power dependence of PL of F4TCNQ-doped 1L MoS2. (b) PL
intensity of trion (squares) and exciton (circles) at each excitation power density.
[1] K. F. Mak et al. Phys. Rev. Lett. 105, 136805 (2012).
[2] Q. H. Wang et al. Nat. Nanotechnol. 7, 699 (2012).
[3] X. Xu et al. Nat. Physics 10, 343 (2014).
[4] S. Mouri et al. Nano Lett. 14, 5944 (2013).
Corresponding Author: S. Mouri
Tel: +81-774-38-3463, Fax: +81-774-38-4567,
E-mail: iguchan@iae.kyoto-u.ac.jp– 156 –

FNTG-47, 2014

3P-29

Valley-dependent spin polarization in bulk MoS2
with broken inversion symmetry○Ryuji Suzuki1,2, Masato Sakano2, Yijin Zhang1,2, Ryosuke Akashi3, Daisuke Morikawa3,
Ayumi Harasawa4, Koichiro Yaji4, Kenta Kuroda5, Koji Miyamoto6, Taichi Okuda6, Kyoko
Ishizaka2, Ryotaro Arita3, Yoshihiro Iwasa1,2,3
1

Quantum-Phase Electronics Centre (QPEC), University of Tokyo, Tokyo 113-8656, Japan2
Department of Applied Physics, University of Tokyo, Tokyo 113-8656, Japan
3
RIKEN CEMS, Wako 3351-0198, Japan
4
Institute for Solid State Physics, University of Tokyo, Kashiwa, 277-8581, Japan
5
Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
6
Hiroshima Synchrotron Radiation Centre, Hiroshima University, Higashi-Hiroshima
739-0046, Japan

Recently, transition metal dichalcogenide (TMD) is attracting many interests as a candidatefor beyond-graphene 2D materials.   In   addition   to   “high   mobility”[1], TMD exhibits richproperties
and functions
including“ambipolar-transistor”[2],   “field   induced  superconductivity”[3],  “Zeeman-type spin splitting”[4] and  “selection  rule  of  band  excitation  with circular polarized light (valley polarization)”[5]. In the study of spin and valley related
functionalities so far, only monolayer TMD, (Fig. 1 Left), has been a target material, becauseof its broken inversion symmetry. The well-known bulk 2H-polytype crystal(Fig. 1 Centre) is
centrosymmetric, and thus the peculiar nature originating from broken inversion symmetry
disappears. Based on this background, we focus on 3R bulk crystal (Fig. 1 Right), in which
each layer stacks so as to keep the non-centrosymmetry and therefore the 3R crystal should
retain the same spin/valley properties as monolayer.
In this presentation, we report
direct observation of the valley
dependent spin polarized band in
3R-MoS2
throughspinandangle-resolve
photoemission
spectroscopy (SARPES) [6]. Moreover,through the experiment of layer
number dependence of circularpolarized
photoluminescence,
we
confirmedthatthemulti-layer
3R-MoS2 has the same valley
polarization as that in monolayer. The
Fig. 1: Crystal structures of monolayer, 2H- andpresent results revealed that 3R-MoS2
3R-polytypes of MoS2
is a new plat form of expanding valley
physics.
[1] B. Radisavljevic et al., Nature Nanotech. 6, 147 (2011) . [2] Y. J. Zhang et al., Nano Lett. 12,1136 (2012).
[3] J. T. Ye et al., Science 338, 1193 (2012). [4] D. Xiao et al,. Phys. Rev. Lett. 108, 196802 (2012). [5] K. F.
Mak et al., Nature Nanotech. 7, 494 (2012). [6] R. Suzuki and M. Sakano et al., Nature Nanotech. in press.
Corresponding Author: R. Suzuki
Tel: +81-3-5841-6822, Fax: +81-3-5841-6822, E-mail: ryujisuzuki@mp.t.u-tokyo.ac.jp– 157 –

3P-30FNTG-47, 2014

Growth and mild plasma functionalizationof transition metal dichalcogenides○Tomoyuki Takahashi, Toshiaki Kato, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Atomic scale two dimensional sheets attract intense attention due to their superior electrical,
mechanical, and optical features. Graphene including high carrier mobility and high opticaltransmittance is one of the promising candidates for the fabrication of next generation highperformance electrical devises [1,2]. Since there is no band gap in graphene, however, it isdifficult to apply graphene for the semiconducting device fields. Layered transition metal
dichalcogenide (TMD) (Fig. 1) is known as other true two-dimensional (2D) material withexcellent semiconducting properties. In spite of its potential, there are still remained lots ofissues for the practical applications of TMD-based optoelectrical devices. In particular, thelarge area growth, defect free growth, and controllable carrier doping are regarded as crucial
issues in their production stage.
In this study, we have demonstrated the high quality single crystal growth of MoS2 andWS2 (Fig. 2). The effects of catalysts and growth conditions on the structure of MoS2 and WS2
were also investigated. Furthermore, mild plasma treatment [3-6] was also carried out aiming
for the controllable functionalization of these TMDs. Photoluminescence (PL) intensity of
MoS2 and WS2 can be changed by N2, H2, and O2 plasma treatments. In particular, N2 plasma
treatment can enhance the PL intensity of MoS2 higher than that of untreated one. This isbecause that trions (charged excitons) can change to neutral excitons due to the hole dopingby N2 plasma irradiation.

1 mFig. 1: Schematic illustration of TMD structure.

Fig. 2: Typical scanning electron microscope image of WS2.

[1] T. Kato and R. Hatakeyama, ACS Nano 6, 8508 (2012).
[2] T. Kato and R. Hatakeyama, Nature Nanotechnology 7, 651 (2012).
[3] T. Kato and R. Hatakeyama, J. Am. Chem. Soc. 130, 8101 (2008).
[4] T. Kato and R. Hatakeyama, ACS Nano 4, 7395 (2010).
[5] Z. Ghorannevis, T. Kato, T. Kaneko and R. Hatakeyama, J. Am. Chem. Soc. 132, 9570 (2010).
[6] T. Kato, L. Jiao, X. Wang, H. Wang, X. Li, L. Zhang, R. Hatakeyama, and H. Dai, Small 7, 574 (2011).
Corresponding Author: T. Takahashi
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: takahashi13@ecei.tohoku.ac.jp– 158 –

3P-31FNTG-47, 2014

Gas/vapor adsorption behaviors of carbon nanorings ofcycloparaphenylenes (CPPs)○Hirotoshi Sakamoto1, Toshihiko Fujimori2, Xiaolin Li2, Katsumi Kaneko2, Kai Kan1,
Kenichiro Itami1,3
1

JST-ERATO Itami Molecular Nanocarbon Project, Graduate School of Science,
Nagoya University, Nagoya 464-8601, Japan
2
Research Center for Exotic Nanocarbons/Center for Energy and Environmental Science,
Shinshu University, Nagano 380-8553, Japan
3
WPI-Institute of Transformative Bio-Molecules (ITbM),
Nagoya University, Nagoya 464-8601, Japan
Introduction
Complexity of the pore structures has been a matter of concern in developing porous
carbons. Then, much effort has been made to design and control of the pore structures
precisely in order to enhance the performance of porous carbons.
Cycloparaphenylenes (CPPs), recently developed through organic syntheses, could be an
ultimate solution to the problem. Their structures are the shortest segments of armchair carbon
nanotubes (CNTs), therefore, they are also called “carbon nanorings”. CPPs have hollow
structures intrinsically, which we consider as nanospace for guest accomodation, and they canbe obtained highly pure crystals with uniform molecular packing. Then CPP can be said to bea “crystalline porous carbon with well-defined uniform structures”, which is definitely
valuable to investigate as quite a new porous material.
Experimental Section
We investigated into the possibility of [12]CPP (CPP of 12 benzene rings, see Figure) as aporous crystalline adsorbent through the experiments of adsorption isotherm, in situ powder
X-ray diffraction (XRD) and IR spectroscopy.
Results and Discussion
We have found that [12]CPP shows unique stepwise adsorption isotherms depending on
the chemical properties of the guest molecules. These steps reflect “structural flexibility” ofthe host in response to the stimuli of guest molecules, which were confirmed by in situ XRD
and IR. These behaviors are considered to be based on the “molecular crystallinity”, and havenever seen in the other previous porous carbons.
Corresponding Author: H. Sakamoto
Tel/Fax: +81-52-789-5916
E-mail: sakamotoh@nagoya-u.jp– 159 –

FNTG-47, 2014

3P-32

siRNA delivery targeting to the lung via agglutination-induced
accumulation and clearance of cationic tetraamino fullerene○Kosuke Minami1,†, Koji Okamoto2, Kent Doi2, Koji Harano1, Eisei Noiri2, Eiichi Nakamura1
1

2

Department of Chemistry, The University of Tokyo, Tokyo 113-0033, Japan
Department of Hemodialysis and Apheresis, University Hospital, The University of Tokyo,
Tokyo 113-0033, JapanThe efficient treatment of lung diseases requires lung-selective drug delivery. Because they
are the narrowest capillaries in the body, alveolar capillaries serve as target sites for thelung-selective delivery using drug-carrying microspheres. However, the lung-selective
delivery is difficult because the accumulation of micrometer-sized carriers in the lung often
induces inflammation and embolization-related toxicity. Recently, another strategy for thepassive pulmonary targeting via a simultaneous aggregation and dissolution in the bloodstream has gained much attention. Cationic lipid-based carriers are widely investigated,
however, the lipid-based carriers tend to interact and aggregate with erythrocytes throughboth membrane fusion and electrostatic interaction, which often causes toxic effect in lung.
Fullerene is both hydrophobic and lipophobic, and thus the fullerene-based carriers do not
fuse with lipophilic erythrocyte membrane but prefer to aggregate with plasma proteins. In
light of the diverse aggregation behavior of fullerenes in water, and their ability of in vivo
gene delivery [1], we hypothesized that the a cationic fullerene could serve as a carrier for thedelivery of small interfering RNA (siRNA) for RNA interference therapeutics in vivo. In thispresentation, we report on the lung-specific siRNA delivery using a cationic fullerene,
Tetra(piperazino)fullerene epoxide (TPFE) by agglutination-induced accumulation andclearance in vivo (Fig.1) [2]. This delivering agent agglutinated with siRNA and plasma(1) Formation of TPFE-siRNA complex
proteins in the blood stream to form Preparation
H N
NH
ternary microsphere, which selectively
NN
accumulated in the lung capillaries.
+N
O N NH~100 nm
H N
The self-assembled scaffold of the
4•CF CO
three-component complex enables the
TPFE
siRNA
dissociation into small particles
Blood vessel
suitable for the cellular uptake as well Size control
as the clearance of TPFE. Finally, the(2) Agglutination with plasma
proteins in bloodstream
therapeutic potential of the new
Plasma proteins
Delivery
protocol was demonstrated throughthe successful delivery of siRNA andBlood vessel
knockdown of target gene expression,(3) Clogging in lungcapillaryindicating the clinical applicability of
TPFE-siRNA
Lung capillarycomplexfullerene-basedsiRNA
delivery(~6 µm)(4) Release & delivery
systems.
Plasma proteins
2

2

2

2

3

2

–

> 6 µmFig. 1: The rationale for lung-specific siRNA delivery by TPFE.
[1] R. Maeda-Mamiya et al. Proc. Natl. Acad. Sci. U.S.A. 107, 5339 (2010)[2] K. Minami et al. Sci. Rep. 4, 4916 (2014).
Corresponding Author: E. Nakamura and E. Noiri
E. Nakamura: Tel: +81-3-5841-4356. E-mail: nakamura@chem.s.u-tokyo.ac.jp
E. Noiri:
Tel: +81-3-3815-5411. Email: noiri-tky@umin.ac.jp†
Present address: International Center for Materials Nanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba 305-0044, Japan– 160 –

FNTG-47, 2014

3P-33

Influence of the solution volume on the growth of fullerene nanowhiskers
żKun’ichi Miyazawa, Chika Hirata, Takatsugu Wakahara
Fullerene Engineering Group, Materials Processing Unit,
National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan
A variety of applications of C60 nanowhiskers (C60NWs) have been investigated up to now
in the fields such as solar cells, field effect transistors, biosensors, catalysts, superconductors,
and so forth. It has been shown that the composites of C60NWs and ZnO ceramics exhibit anexcellent photocatalytic activity [1]. Shorter and thinner C60NWs are necessary for thephotocatalytic application in order to obtain the larger surface arias for the higher
photocatalytic activities and the better dispersive ability.
It has been known that the growth of C60NWs is influenced by temperature, light, the ratioof poor solvent vs good solvent for C60, and concentration of water. The diameter of
C60NWs was shown to be a linear function of the area of the liquid-liquid interface when the
total volume of solvent is constant, while the inner diameter of glass bottle changes [2]. Thistime, however, it will be demonstrated how the length and diameter of C60NWs change
depending on the bottle size and the solution volume.
A modified liquid-liquid interfacial precipitation method was used to synthesize the
C60NWs [3]. Five different sizes of transparent glass bottles were used. For the LLIP method,a C60-saturated toluene solution was poured into a glass bottle and an equal amount of
isopropyl alcohol was layered onto the C60-saturated toluene solution. The glass bottle wascapped and manually mixed by shaking the bottle 30 times and the bottles were stored in an
incubator at 15 qC for 8 days [3]. The synthesis of C60NWs was repeated three times for eachsize of glass bottle. Fig.1 and Fig.2 show the relationships between the size (length anddiameter) of C60NWs and the solution volume. Using the intercepts of the vertical axes ofFigs. 1 and 2, the minimum mean size of C60NWs is estimated to be 5.02 Pm in length and
387 nm in diameter.
On the otherh an d , t he s i z eof C60NWs
a s ym p t o t i c a l l yapproaches the
maximum size of
16.6 Pm in lengthand 784 nm indiameter withincreasing theFig.1: Relationship between the Fig. 2: Relationship between thesolution volume.
solution volume and the mean solution volume and the mean
length of C60NWs.
diameter of C60NWs.
[1] B. H. Cho, K. B. Lee, K. Miyazawa and W. B. Ko, Asian J. Chem. 25,8027(2013).
[2] T. Wakahara, Y. Nemoto, M. Xu, K. Miyazawa, D. Fujita, Carbon 48, 3359(2010).
[3] K. Miyazawa and K. Hotta, J. Cryst. Growth 312, 2764(2010).
Corresponding Author: K. Miyazawa
Tel: +81-29-860-4528, Fax: +81-29-860-4667,
E-mail: miyazawa.kunichi@nims.go.jp– 161 –

3P-34

FNTG-47, 2014

Regioselective synthesis of novel octasubstituted fullerenes by a substitution

reaction of octabromofullerene C60Br8○Keita Watanabe 1, Kouya Uchiyama 1, Kenji Yoza 2, Hiroshi Moriyama1
1

Department of Chemistry, Toho University, Funabashi, 274-8510, Japan
2
Bruker AXS, Yokohama, 221-0022, Japan

It is well known that multifunctionalized fullerenes have unique properties derived fromtheir contracted π  system as well as addends attached to the fullerene skeleton. However, it isdifficult regioselectively to synthesize them, therefore regioselective synthesis of fullerene
derivatives with multiaddends has attracted much attention in the field of organic electronic
devices and life sciences. We have noted that octabromofullerene, C60Br8 [1], has a uniquewell-characterized structure suitable for a starting material [2]. The substitution reaction of
C60Br8 can be a powerful tool for the regioselective synthesis of multifunctionalized
fullerenes; furthermore, the reaction can easily change the chemical properties depending on
the substituents.
Here, we report the synthesis of novel octaalkoxyfullerenes and octaarylfullerenes withlonger alkyl chains, C60(OR)8 (R = n-C9H19, n-C10H21) in addition to the aliphatic chains R =CnH2n+1 (n = 1－8), and C60(4-C6H4OR)8. (R = CH3, C2H5). Furthermore, we succeeded in thesynthesis of the 2,2,2-trifluoroethanol derivatives of fullerene, C60(OCH2CF3)8. These
compounds were fully characterized by 1H, 13C, and 19F NMR spectroscopy. In addition, the
X-ray single-crystal structure of these octaalkoxyfullerenes C60(OR)8 (R = CH3, C2H5)
demonstrated that there are unique isolated,almost nonconjugated, double bonds at the
ROH
center of the C60 skeleton. (1.32 Å (OMe) and1.34 Å (OEt) for the central C=C, which areAg+shorter than that of C=C for the 6–6 junction,
while the C–C bonds for the 6–5 junction are
both
1.45
Å).
Cyclicvoltammetry
CF3CH2OH
measurements of these compounds showedAg+that their electron-accepting properties were
notably different because of the substituent
effects of the addends. In particular, it was
ROC6H5found that C60 (OCH2CF3)8 had a lower
Ag+
LUMO level (－4.10 eV) than that of C60,
which should be caused by the strong
electron-withdrawing
abilityofthe
Scheme 1.
trifluoroethyl groups, although the π system of
the fullerene moiety was contracted from 60π to42π.
[1] P. R. Birkett, P. B. Hitchcock, H.W. Kroto, R. Taylor, D. R. M. Walton, Nature 1992, 357, 479–481.
[2] H. Moriyama, K. Uchiyama, Japanese Patent Application No.2012-194209 (特開 2014-047204).
K. Uchiyama, H. Moriyama, K. Yoza, 45th FNTG Symposium Abstract 3-5 (2013).
Corresponding author: Hiroshi. Moriyama
TEL: +81-47-472-1211, FAX: +81-47-472-1188

E-mail: moriyama@chem.sci.toho-u.ac.jp– 162 –

3P-35

FNTG-47, 2014

Reaction of [Li+@C60] with Diphenyldiazomethane○Hiroshi Okada, Hiroki Kawakami, Yutaka Matsuo
Department of Chemistry, School of Science, The University of Tokyo,
Tokyo, 113-0033, Japan
Methano (methanediyl) groups (R2C=) have acted as important part in fullerene chemistry.
Deprotonated bromomalonic ester attacks fullerene nucleophilically to give thethree-membered-ring followed by bromide elimination, which called as Bingel reaction [1].
Our group developed a new method to obtain non-substituted methanofullerene(dihydromethanofullerene, C61H2). Silylmethyl fullerenyl anion can be oxidized by Cu(II) andthe silyl group was removed by chloride anion to form the CH2-capped fullerene [2]. Somemodified dihydromethano fullerenes were applied to organic photovoltaics with good power
conversion efficiency [3].
Methanofullerenes are also synthesized by using diazoalkanes, such as diazomethane [4]anddiphenyldiazomethane
[5].
The
most
commonfullerene
derivative,[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was synthesized with a diazoalkane
generated by thermolysis of tosylhydrazone [6].
In this study, we investigated the reaction of [Li+@C60] with diphenyldiazomethane. The
reaction of [Li+@C60](NTf2–) [7] and diphenyldiazomethane (Ph2CN2) in dichloromethane
was performed. Ph2CN2 added on the fullerene cage smoothly at room temperature. We report
the characterization of the products, their properties, and comparison of the reactivities oflithium-ion-endohedral fullerene and empty fullerene to Ph2CN2.
[1] C. Bingel et al. Chem. Ber. 1993, 126, 1957–1959.
[2] Y. Zhang et al. J. Am. Chem. Soc. 2011, 133, 8086–8089.
[3] Y. Matsuo et al. Adv. Mater. 2013, 25, 6266–6269.
[4] T. Suzuki et al. J. Am. Chem. Soc. 1992, 114, 7301– 7302.
[5] T. Suzuki et al. Science 1991, 254, 1186–1188.
[6] J. C. Hummelen et al. J. Org. Chem. 1995, 60, 532–538.
[7] H. Okada et al. Fullerenes, Nanotubes and Carbon Nanostructures 2014, 22, 262–268.
Corresponding Author: H. Okada
Tel: +81-3-5841-1371, Fax: +81-3-5841-1371
E-mail: h_okada@chem.s.u-tokyo.ac.jp– 163 –

FNTG-47, 2014

3P-36

Solid State NMR Studies of Proton Dynamics in fullerenol-based
composites○Yoshiaki Sano1 and Hironori Ogata 1,2
1
Graduate School of Engineering, Hosei University, Koganei, Tokyo 184-8584, Japan
2
Research Center for Micro-Nano Technology, Hosei University, Koganei, Tokyo,
184-0003,Japan
Fullerenols(Polyhydroxylated Fullerenes: C60(OH)x) have a structure with introductionof hydroxyl groups on fullerene (C60) cage, and their solids possess 3-dimensionalhydrogen-bonding networks. So, it have been thought to have potential applications in
proton conductors. We previously reported proton dynamics in fullerenols solids bytemperature dependence of both wide line 1H-NMR and1H-T1 measurements[1,2]. In thisstudy, we fabricated the several kinds of fullerenol based composites and investigatedtheir proton dynamics by using 1H-NMR spectroscopy.
Detailed results on the relationship between the composition of fullerenol-based
composites and the properties of proton motions will be presented.

Fig. 1 Temperature dependence of 1H-T1 for fullerenol solids

References:[1] K. Baba et al., Proc.of the 44th Fullerene-Nanotubes-Graphene General Symposium (1-5)[2] Y. Sano et al., Proc.of the 46th Fullerene-Nanotubes-Graphene General Symposium (2P-1)[3] K. Hinokuma et al., Chem. Phys. Lett., 341, 442 (2001)[4] L. Y. Chiang et al., Org. Chem. 59, 3960 (1994)
Corresponding Author: H. Ogata
Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp– 164 –

FNTG-47, 2014

3P-37

Charge-Transfer Complexation and Photoinduced Electron Transfer
between Corannulene and Lithium Ion-Encapsulated [60]Fullerene○Mihoko Yamada1, Kei Ohkubo1, Mitsuhiko Shionoya2, Shunichi Fukuzumi1
1

Department of Material and Life Science, Graduate School of Engineering, Osaka
University, ALCA, Japan Science and Technology Agency, Osaka 565-0871, Japan2
Department of Chemistry, Graduate School of Science, The University of Tokyo, Tokyo
113-0033, JapanOne of the simplest non-covalent electron donor-acceptor systems can be constructed witha charge-transfer (CT) interaction which is enhanced with increasing the orbital overlap
between the HOMO of an electron donor and the LUMO of an electron acceptor in the groundstate.[1] Corannulene (C20H10) has attracted great attention as a buckyball catcher due to its
well-fitted curved π-surface with the surface of C60.[2] Thus, we studied the construction of anelectron donor-acceptor CT system composed of corannulene and Li+@C60, withconcave-convex π-π CT interactions between the two curved π-surfaces.
UV-vis-NIR absorption spectrum of Li+@C60•–*
in benzonitrile at 298 K was changed upon
Electron transfer
addition of C20H10. An additional broad+
K = 1.3 10 M
absorption band in the vis-NIR region exhibits•+
formation of a CT complex C20H10/Li+@C60.
(Li @C )*C H(C H/Li @C)The formation constant of the CT complex in the
triplet CS state
Photoexcitation hν
ground state (KG) was determined to be 1.9 × 10
M–1 from the UV-vis absorption spectroscopic
titration (Scheme 1). Femtosecond laser+
K = 1.9 10 M
excitation of the CT complex produced thesinglet CS state 1(C20H10•+/Li+@C60•–) (τ = 1.4
Li @C
C H
C H /Li @Cns) as indicated by a shoulder absorption at 1035
CT complex+•–
nm due to Li @C60 . On the other hand, Scheme 1. Formation of a CT complex andnanosecond laser excitation generated a radical photoinduced ET between C20H10 and Li+@C60.
ion pair C20H10•+ and Li+@C60•– depending on
10
4 μs
the concentration of C20H10, which indicated
750 nm3(Li+@C60)*
20 μs
intermolecular ET from C20H10 to the triplet excited state
8
200 μsof Li+@C60 [3(Li+@C60)*] to form a CS state (Figure 1).
400-600 nm
6
The spin state of the resulting CS state was revealed to be
C20H10•+
triplet by a triplet signal at g = 4 detected by EPR at 4 K.
1035 nm4
Li+@C60•–
The formation constant of the triplet CS state (KT) was
determined to be 1.3 × 103 M–1. The triplet CS state2
decayed to the ground state via intramolecular charge
recombination with a long lifetime of 240 µs.
0
Li +

Li +

T

3

20 10

+

×

3

–1

60

3

20 10

•+

+

•–
60

Li +

Li +

G

+

20 10

×

–1

60

+

60

103ΔAbsorbance

20 10

400

600

800

1000

1200

Wavelength / nm

[1] R. S. Mulliken, J. Am. Chem. Soc. 1952, 74, 811.
[2] L. N. Dawe et al. Chem. Commun. 2012, 48, 5563.
Corresponding Author: S. Fukuzumi
Tel: +81-6-6879-7369, Fax: +81-6-6879-7370,
E-mail: fukuzumi@chem.eng.osaka-u.ac.jp– 165 –

Figure 1. Transient absorption
spectra after nanosecond laser
excitation at 355 nm of Li+@C60 (0.1mM) and C20H10 (3.5 mM) in
deaerated PhCN at 298 K.

3P-38

FNTG-47, 2014

Syntheses, Structural Determination, and Characterization of Electronic
Properties of Bis-Germylated Sc3N@Ih-C80 and Lu3N@Ih-C80○Kyosuke Miyabe1, Masahiro Kako*,1, Kumiko Sato2, Mitsuaki Suzuki3, Naomi Mizorogi2,
Yutaka Maeda3, Marilyn M. Olmstead4, Alan L. Balch4, Wei-Wei Wang5,
Shigeru Nagase5, Takeshi Akasaka2,3,6
1

Department of Engineering Science, The University of Electro-Communications, Chofu,
Tokyo 182-8585, Japan
2
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan3
Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
4
Department of Chemistry, University of California, Davis, California 95616, United States
5
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
6
Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
Endohedral metallofullerenes (EMFs) have attracted much attention from physical andchemical viewpoints because of their unique electronic structures. Exohedral functionalization
have been developed as powerful tools to modify the physical and chemical properties of
EMFs and hollow fullerenes. In particular, introduction of heteroatoms such as electropositive
silicon onto fullerene surfaces has been recognized to perturb the electronic characteristics offullerenes. In fact, it is confirmed that HOMO/LUMO levels of silylated EMFs and hollow
fullerenes are higher than those of parent fullerenes based on the electrochemical analyses andtheoretical calculations. In addition, it is also demonstrated that the positions and dynamic
behaviors of the metal atoms encapsulated in EMF cages are affected by exohedral chemicalfunctionalization. These derivatizations of fullerenes are expected to contribute to theapplication of fullerenes as functional materials.
In this context, we are investigating the functionalization of trimetallic nitride template
endohedral metallofullerenes (TNT EMFs) using reactive organosilicon compounds. The
reactions of Lu3N@Ih-C80 with thermally generated diarylsilylene afforded the corresponding[6,6]-silacyclopropane and [5,6]-silafulleroid derivatives [1]. More recently, the preliminary
results of bis-silylation of Lu3N@Ih-C80 using disiliranes has been also reported [2]. To obtain
more insight into the effects of organometallic functional groups on EMFs, we investigatedbis-germylation of Lu3N@Ih-C80 using digermirane 1 (Scheme 1). Herein we report the detailsof syntheses, structural determination, and characterization of the electronic properties of thebis-silylated and bis-germylated M3N@Ih-C80 (M = Sc, Lu) derivatives, based on X-ray
crystallography, electrochemical analyses, and theoretical calculations.
Scheme 1.
Dep
Dep
Dep Ge Ge Dep
Dep2GeM3N@Ih-C80(M = Sc, Lu)

GeDep2

Dep = 2,6-diethylphenyl
1h!
2: M = Sc
3: M = Lu[1] K. Sato et al. J. Am. Chem. Soc. 134, 16033–16039 (2012).
[2] K. Sato et al. Org. Lett. 14, 5908-5911 (2012).
Corresponding Author: Masahiro Kako Tel: +81-42-442-5570  E-mail: kako@e-one.uec.ac.jp– 166 –

3P-39FNTG-47, 2014

Elucidation of Lithium and C60 Fullerene Cluster Structureusing 7Li Solid-State NMR Studies○Tomoaki Endo1, Shin-ichiro Yoshida2, Kazuhiko Kawachi3,
Yasuhiko Kasama3, Eunsang Kwon 2
1

Sendai National College of Technology, Natori 981-1239, Japan

2

Ｒｅｓｅａｒｃｈ and Analytical center for Giant Molecules, Graduate School of Science,
Tohoku University, Sendai 980-8578, Japan
Idea International Co. Ltd., Sendai 981-0922, Japan

3

Lithium clusters circumscribed by fullerene would be shaped during the formation processof the lithium ion-encapsulated fullerene (Li+@C60) by the low energy ion bombardment
method [1]. Recently, applying to the lithium plasma radiation to vaporized fullerene, it ispossible to produce a large scale production of Li +@C60 [2] and it was prepared to Li+@C60
salt using chemical treatment. We need to elucidate that the cluster not only form the view
point of scientific research but also aspects of engineering. In this study, we investigate thelithium clusters using 7Li solid state NMR spectroscopy.
The chemical shifts of lithium clusters circumscribed by fullerene have four different
values at under LiCl standard. To elucidate the lithium and fullerene cluster structure
corresponding to those chemical shifts, we have to understand the basic nature of chemical
shifts of lithium nuclei, which the case means lithium atom exist in the outside of fullerene
cage or inside of fullerene cage and how the lithium atom attached with fullerene.
In the case of lithium ion-encapsulated fullerene, the chemical shift of lithium nuclei wasobserved high field shift (about 10ppm) [3]. On the other hands, the chemical shifts of lithium
nuclei of simple complex of lithium and fullerene have not made clear. To measure suchchemical shifts, we synthesized lithium and fullerene complexes to fix the ratio of lithium. To
compare those chemical shifts, it is become a complete elucidation of lithium clusters
circumscribed by fullerene, those of knowledge may become an important key to prepare alarge scale Li+@C60 preparation. A part of the results are showed in Fig.1.

Fig.1 7 Li Solid-NMR spectra of [Li+@C60]・PF6 (left) and LiC60 (right)[1] "Production and LDMS characterisation of endohedral alkali-fullerene films", E.E.B. Campbell, R.
Tellgmann, N. Krawez, I.V. Hertel, J. of Phys. and Chem. of Solids, 58, 1763-1769 (1997).
[2] S. Aoyagi et al. Nature. Chem. 2, 678 (2010).
[3] E.Kwon et al. FNTG-43 予稿集 (2013).
[4] S. N. Titova et al. Physics of the Solid State. 123, 456 (2011).
Corresponding Author: T. Endo
Tel: +81-22-291-7410, Fax: +81-22-291-7410,
E-mail: tendo@sendai-nct.ac.jp– 167 –

FNTG-47, 2014

3P-40

An Efficient Isolation Method for Lithium-Ion Endohedral
Metallofullerene, Li+@C60•NTf2○Yoshihito Kohari1, Hiroshi Okada2, Hiroto Nakano1, Kazuhiko Kawachi3,
Yasuhiko Kasama3, Eunsang Kwon4, Yutaka Matsuo2
1

Department of Bioengineering, Graduate School of Engineering, Muroran Institute ofTechnology, Muroran 050-8585, Japan2
Department of Chemistry, School of Science, The University of Tokyo, Tokyo 113-0033,
Japan, Japan
3
Idea International Co., Ltd, Sendai 981-0922, Japan
4
Research and Analytical center for Giant Molecules, Graduate School of Science, Tohoku
University, Sendai 980-8578, Japan
Since the synthesis and characterization of lithium cation endohedral metallofullerene (licfullerene) [1], several investigations have been performed on the application of the “licfullerene” to the functional materials [2]. However, the solubility limit of the “lic fullerene”
such as Li+@C60  PF6- in common organic
solvents has brought restrictions to decrease 
diversity of their applications. Thus, wepreviously reported an anion-exchange method
to improve their solubility [3], which was a
stepwise process of the anion exchanged from
PF6- to a large anion such as OTf-, NTf2- and
TFPB-. In the present work, we investigated an








efficient isolation method for the Li+@C60 salt,
Li+@C60  NTf2- (1), having high solubility in 
Li+@C60NTf2various organic solvents such as dichlorometaane,
chlorobenzene and o-dichlorobenzene.
Successful isolation of 1 was achieved
without employing the exchange of the PF6-. The
isolation yield of 1 was 0.4%, which was thesimilar as the result of the stepwise process as
Li+NTf2described above. 1 was easily obtained in highpurity as determined by NMR spectroscopy (Fig.,
ca. 98% from 19F NMR analysis) using a simple               
reprecipitation with o-dichlorobenzene as a good Fig. NMR Spectra of Li+@C60  NTf2- insolvent and hexane as a poor solvent.
o-DCB. (a) 7Li NMR spectrum; (b) 19F NMR
In addition, 1 was found to be soluble in ionic spectrum.
liquid such as 1-ethyl-3-methylimidazolium  bis(trifluoromethylsulfonyl)imide, and thesolution appears to be purple-violet in color. The experimental details of the isolation and theproperties of the ionic liquid solution of 1 will also be presented.
[1] S. Aoyagi et al., Nature Chemistry, 2, 678 (2010). [2] For recent reports, see: K. Ohkubo et al., Chem.
Commun., 49, 7376 (2013); K. Kokubo et al. Nanoscale, 5, 2317 (2013); K. Ohkubo et al. Chemical Science, 4,1451 (2013). [3] H. Okada and Y. Matsuo, Fullerenes, Nanotubes and Carbon Nanostructures, 22, 1 (2014).
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-1476 Fax: +81-3-5841-1476, E-mail: matsuo@chem.s.u-tokyo.ac.jp– 168 –

著者索引
Author Index

Author Index

FNTG-47@Nagoya, 2014

A

Bold number: Speaker

D

ABE, Kai . . . . . . . . . . . . . . . . . . . . . . . 1P-37, 1P-39

DAHL, Jeremy E. P. . . . . . . . . . . . . . 1-8

ABIKO, Yoshihiro . . . . . . . . . . . . . . . 1P-7

DE COLA, Luisa . . . . . . . . . . . . . . . . 2-3

ACHIBA, Yohji . . . . . . . . . . . . . . . . . 1-7

DOI, Kent . . . . . . . . . . . . . . . . . . . . . . 3P-32

ADHIKARI, Sudip . . . . . . . . . . . . . . 3P-26

DUDINA, Alexandra . . . . . . . . . . . . 1P-5

AKAMA, Toshiki . . . . . . . . . . . . . . . 1P-7

E

AKASAKA, Takeshi. . . . . . . . . . . . . 2P-39, 3-5, 3P-38
AKASHI, Ryosuke . . . . . . . . . . . . . . 3P-29

ENDO, Tomoaki . . . . . . . . . . . . . . . . 3P-39

AKITA, Seiji . . . . . . . . . . . . . . . . . . . . 2P-19, 3S-6

ERYU, Osamu . . . . . . . . . . . . . . . . . . 1P-17

AKIYAMA, Wataru . . . . . . . . . . . . . 1P-36
AMAYA, Toru . . . . . . . . . . . . . . . . . . 1-13
ANNO, Yuki . . . . . . . . . . . . . . . . . . . . 2P-19
AOKI, Nobuyuki . . . . . . . . . . . . . . . . 1P-36
AOYAGI, Shinobu . . . . . . . . . . . . . . . 1-11
ARAKAWA, Kohei . . . . . . . . . . . . . . 1S-1
ARIE, Takayuki. . . . . . . . . . . . . . . . . 2P-19
ARIFUKU, Michiharu . . . . . . . . . . 3P-10
ARIGA, Katsuhiko . . . . . . . . . . . . . . 1P-33
ARITA, Masashi . . . . . . . . . . . . . . . . 1-2
ARITA, Ryotaro . . . . . . . . . . . . . . . . 3P-29
ARYAL, Hare . . . . . . . . . . . . . . . . . . . 3P-26
ASAKA, Koji . . . . . . . . . . . . . . . . . . . 2P-27, 3-10, 3P-22
ASHIHARA, Masaaki . . . . . . . . . . . 2P-32
ATA, Seisuke . . . . . . . . . . . . . . . . . . . . 2-7
AYRIA, Pourya . . . . . . . . . . . . . . . . . 1P-26

F
FOKINA, Natalie A. . . . . . . . . . . . . . 1-8
FREY, Urs . . . . . . . . . . . . . . . . . . . . . . 1P-5
FUJIGAYA, Tsuyohiko . . . . . . . . . . 1P-9, 1P-10, 3P-3
FUJII, Shunjiro . . . . . . . . . . . . . . . . . 1P-35, 2-4, 2P-5,
2P-6
FUJIKI, Kazuhiro . . . . . . . . . . . . . . 3P-17
FUJIMORI, Toshihiko . . . . . . . . . . 3P-31
FUJIMOTO, Yoshitaka . . . . . . . . . . 3-9
FUJITA, Hayato . . . . . . . . . . . . . . . . 3P-16
FUJIWARA, Yuji . . . . . . . . . . . . . . . 2P-2
FUKUMORI, Minoru . . . . . . . . . . . 3P-20
FUKUZUMI, Shunichi . . . . . . . . . . 2-5, 3P-37
FURUTA, Hiroshi . . . . . . . . . . . . . . . 1P-6, 2P-15
FURUYA, Atom . . . . . . . . . . . . . . . . . 1P-2
FUTABA, Don N. . . . . . . . . . . . . . . . 3-11

B
G

BALCH, Alan L. . . . . . . . . . . . . . . . . 3-5, 3P-38
BANDOW, Shunji . . . . . . . . . . . . . . . 1-14

GHIMIRE, Dilip . . . . . . . . . . . . . . . . 3P-26

BIANCO, Alberto . . . . . . . . . . . . . . . 2-3

GOTOH, Hideki . . . . . . . . . . . . . . . . 1-12

BIRD, Jonathan . . . . . . . . . . . . . . . . . 1P-36

GULDI, Dirk M. . . . . . . . . . . . . . . . . 2P-33

C

GUO, Jing Dong . . . . . . . . . . . . . . . . 3-5

CAI, Wenting . . . . . . . . . . . . . . . . . . . 1P-31

H

CARLSON, Robert M. K. . . . . . . . 1-8

HAMASAKI, Yuki . . . . . . . . . . . . . . 3P-3

CEBRIAN, Cristina . . . . . . . . . . . . . 2-3

HARANO, Koji . . . . . . . . . . . . . . . . . 3P-32

CHEN, Chien-Jen . . . . . . . . . . . . . . . 1P-22

HARASAWA, Ayumi . . . . . . . . . . . . 3P-29

CHEN, Hong-Yu . . . . . . . . . . . . . . . . 3S-7

HASDEO, Eddwi . . . . . . . . . . . . . . . 1P-25, 1P-26, 2P-13

CHEN, Muqing . . . . . . . . . . . . . . . . . 2P-33
CHEN, Xiao . . . . . . . . . . . . . . . . . . . . 2P-25
CHIASHI, Shohei . . . . . . . . . . . . . . . 2-6, 2P-25, 3P-6,
3P-9, 3P-11, 3P-12
CHIBA, Takaaki . . . . . . . . . . . . . . . . 2-6, 3P-6
CRACIUN, Monica . . . . . . . . . . . . . 1-1

HASDEO, Eddwi H. . . . . . . . . . . . . . 1P-27
HASEBE, Yohei . . . . . . . . . . . . . . . . . 3P-22
HASEGAWA, Masataka . . . . . . . . . 2-8
HASEGAWA, Tadashi . . . . . . . . . . . 3-5
HASHIMOTO, Kenro . . . . . . . . . . . 1-7

CUI, Kehang . . . . . . . . . . . . . . . . . . . . 2-6, 3P-1

HASHIMOTO, Kumi . . . . . . . . . . . 3P-17

CUONG, Nguyen Thanh . . . . . . . . 2P-18

HATA, Kenji . . . . . . . . . . . . . . . . . . . . 2-7, 3-11

CUYA, Jhon . . . . . . . . . . . . . . . . . . . . 2-9

HATAKEYAMA, Kazuto . . . . . . . . 2P-9
HATAKEYAMA, Rikizo . . . . . . . . . 1P-7
– 169 –

Author Index

FNTG-47@Nagoya, 2014

Bold number: Speaker

HATTA, Akimitsu . . . . . . . . . . . . . . . 1P-6, 2P-15

ITOH, Chihiro . . . . . . . . . . . . . . . . . . 1P-13, 2P-14, 3-12

HAYASE, Shohei . . . . . . . . . . . . . . . . 1P-19, 2P-38

IWASA, Yoshihiro . . . . . . . . . . . . . . . 2S-5

HAYASHI, Akio . . . . . . . . . . . . . . . . . 3P-10

IWATA, Jun-Ichi . . . . . . . . . . . . . . . . 1-4

HAYASHI, Tatsuya . . . . . . . . . . . . . . 1P-37, 1P-39

IZUMI, Hirokazu . . . . . . . . . . . . . . . 2P-12

HAYASHI, Yasuhiko . . . . . . . . . . . . 3P-25

J

HIBINO, Hiroki . . . . . . . . . . . . . . . . 3-8
HIERLEMANN, Andreas . . . . . . . 1P-5

JANG, Jin . . . . . . . . . . . . . . . . . . . . . . 1P-37, 1P-39

HILLS, Gage . . . . . . . . . . . . . . . . . . . 3S-7

JEON, Il . . . . . . . . . . . . . . . . . . . . . . . . 3P-1

HIRAIWA, Atsushi . . . . . . . . . . . . . . 2P-7, 3P-5

JEYADEVAN, Balachandran . . . . 2-9

HIRAKAWA, Takuya . . . . . . . . . . . 2P-5

JHAN, Sin-Rong . . . . . . . . . . . . . . . . 1P-22

HIRAMATSU, Kazumasa . . . . . . . 2P-20

JI, Qingmin . . . . . . . . . . . . . . . . . . . . . 1P-33

HIRANO, Atsushi . . . . . . . . . . . . . . . 2-4, 2P-5, 2P-6

JIANG, Hua . . . . . . . . . . . . . . . . . . . . 3-13

HIRANO, Yu . . . . . . . . . . . . . . . . . . . 2P-7, 2P-16, 3P-5

JINNOUCHI, Ryota . . . . . . . . . . . . . 2P-24

HIRAO, Toshikazu . . . . . . . . . . . . . . 1-13

JIPPO, Hideyuki . . . . . . . . . . . . . . . . 1-3

HIRASE, Ryuji . . . . . . . . . . . . . . . . . 2P-12

JOUNG, Soon-Kil . . . . . . . . . . . . . . . 3-11

HIRATA, Chika . . . . . . . . . . . . . . . . . 3P-33

JU, Hui . . . . . . . . . . . . . . . . . . . . . . . . . 1P-32

HOMMA, Yoshikazu . . . . . . . . . . . . 2-10

JUANG, Tzong-Yuan . . . . . . . . . . . . 1P-22

HONDA, Satoshi . . . . . . . . . . . . . . . . 2-2

JUHASZ, Gergely . . . . . . . . . . . . . . . 1P-16

HONDA, Shinichi . . . . . . . . . . . . . . . 2P-12

JUNTHORN, Udorn . . . . . . . . . . . . 1P-6

HUTCHISON, James . . . . . . . . . . . 2-3

I

K
KAKO, Masahiro . . . . . . . . . . . . . . . 3P-38

ICHIHASHI, Toshinari . . . . . . . . . . 2P-35

KAMEOKA, Yuichiro . . . . . . . . . . . 3P-15

ICHIMURA, Susumu . . . . . . . . . . . 3P-25

KAN, Kai . . . . . . . . . . . . . . . . . . . . . . . 3P-31

IGAWA, Mizuki . . . . . . . . . . . . . . . . . 1P-39

KANDA, Shouhei . . . . . . . . . . . . . . . 1P-12

IIDA, Tetsuo . . . . . . . . . . . . . . . . . . . . 2P-37

KANEKO, Katsumi . . . . . . . . . . . . . 3P-31

IIJIMA, Sumio . . . . . . . . . . . . . . . . . . 1-14, 2-3, 2P-35

KANEKO, Toshiro . . . . . . . . . . . . . . 1P-7, 2P-11, 2P-23,
3-1, 3P-30

IKUMA, Naohiko . . . . . . . . . . . . . . . 1-11, 1P-34
IMAI, Masato . . . . . . . . . . . . . . . . . . . 1P-20
INABA, Masafumi . . . . . . . . . . . . . . 2P-7, 2P-16, 3P-5
INADA, Yuhi . . . . . . . . . . . . . . . . . . . 1-13

KASAMA, Yasuhiko . . . . . . . . . . . . 3P-39, 3P-40
KASKELA, Antti . . . . . . . . . . . . . . . 3-13
KASUYA, Yuki . . . . . . . . . . . . . . . . . 1P-33

INOUE, Taiki . . . . . . . . . . . . . . . . . . . 3P-9

KATAURA, Hiromichi . . . . . . . . . . 1P-35, 2-4, 2P-5,
2P-6, 3P-14

INOUE, Yoshihisa . . . . . . . . . . . . . . . 3-4

KATO, Hiroki. . . . . . . . . . . . . . . . . . . 2-10

INUKAI, Eri . . . . . . . . . . . . . . . . . . . . 1P-29

KATO, Kyohei . . . . . . . . . . . . . . . . . . 2P-31

IRIE, Hiroshi . . . . . . . . . . . . . . . . . . . 2P-35

KATO, Tatsuhisa . . . . . . . . . . . . . . . . 3P-15

IRLE, Stephan . . . . . . . . . . . . . . . . . . 1-9
ISHIDA, T. . . . . . . . . . . . . . . . . . . . . . 2P-22

KATO, Toshiaki . . . . . . . . . . . . . . . . . 1P-7, 2P-11, 2P-23,
3-1, 3P-30

ISHIHARA, Masatou . . . . . . . . . . . 2-8

KAUPPINEN, Esko . . . . . . . . . . . . . 3P-1

ISHII, Hiroyoshi . . . . . . . . . . . . . . . . 3P-14

KAUPPINEN, Esko I. . . . . . . . . . . . 3-13, 3P-6

ISHIKAWA, Sayo . . . . . . . . . . . . . . . 1P-38

KAWACHI, Kazuhiko . . . . . . . . . . . 3P-40

ISHIMOTO, Kouki . . . . . . . . . . . . . 2P-15

KAWACHI, Kazuo . . . . . . . . . . . . . . 3P-39

ISHIYAMA, U . . . . . . . . . . . . . . . . . . 1P-15

KAWAHARA, Takashi . . . . . . . . . . 3P-17

ISHIZAKA, Kyoko . . . . . . . . . . . . . . 3P-29

KAWAI, Hideki . . . . . . . . . . . . . . . . . 1P-12

ISOZAKI, Satoshi . . . . . . . . . . . . . . . 3-12

KAWAKAMI, Hiroki . . . . . . . . . . . . 1-11, 3P-35

ITAMI, Kenichiro . . . . . . . . . . . . . . . 3P-13, 3P-31

KAWANO, Saki . . . . . . . . . . . . . . . . . 1P-38

ITO, Shinichi . . . . . . . . . . . . . . . . . . . 1P-41

KAWARADA, Hiroshi . . . . . . . . . . . 2P-7, 2P-16, 3P-5
– 170 –

FNTG-47@Nagoya, 2014

Author Index

KAWASAKI, Shinji . . . . . . . . . . . . . 1P-3, 1P-4

Bold number: Speaker

L

KAYAHARA, Eiichi . . . . . . . . . . . . . 3P-15

LEE, Chih-Yu . . . . . . . . . . . . . . . . . . . 2P-7, 3P-5

KIGURE, Shota . . . . . . . . . . . . . . . . . 2P-29

LEE, Haeseong . . . . . . . . . . . . . . . . . 1P-37, 1P-39

KIM, Jeheon . . . . . . . . . . . . . . . . . . . . 3P-21

LEE, Jae S. . . . . . . . . . . . . . . . . . . . . . 1P-37, 1P-39

KIM, Sungjin . . . . . . . . . . . . . . . . . . . 2P-25

LEE, Seung Joo . . . . . . . . . . . . . . . . . 1P-37, 1P-39

KIMURA, Takahide . . . . . . . . . . . . . 2P-8

LI, Xiaolin . . . . . . . . . . . . . . . . . . . . . . 3P-31

KIMURA, Toshiki. . . . . . . . . . . . . . . 1P-13

LI, Yan . . . . . . . . . . . . . . . . . . . . . . . . . 1-6

KISHI, Naoki . . . . . . . . . . . . . . . . . . . 1P-1

LIN, Li-Hung . . . . . . . . . . . . . . . . . . . 1P-22

KISHIMOTO, Shigeru . . . . . . . . . . 3P-2, 3P-4, 3P-7

LIU, Gang . . . . . . . . . . . . . . . . . . . . . . 2P-8

KISODA, Kenji . . . . . . . . . . . . . . . . . 1P-13, 2P-14, 3-12

LU, Xing . . . . . . . . . . . . . . . . . . . . . . . . 1S-2, 1P-31, 1P-32,
2P-33, 3-5

KITAKAWA, Haruki . . . . . . . . . . . . 3P-20
KITAMURA, Yoshimasa . . . . . . . . 1P-12

M

KITAURA, Ryo . . . . . . . . . . . . . . . . . 1-8, 2-1, 2P-4, 3-8,
3P-8

MACHIDA, Tomoki . . . . . . . . . . . . . 3-4

KIYOYANAGI, Noriko . . . . . . . . . . 3P-10

MAEDA, Kenta . . . . . . . . . . . . . . . . . 2P-1

KOBAYASHI, Keita . . . . . . . . . . . . . 2P-34

MAEDA, Yutaka . . . . . . . . . . . . . . . . 3-5, 3P-38

KOBAYASHI, Y. . . . . . . . . . . . . . . . . 2P-22

MAEHASHI, Kenzo . . . . . . . . . . . . . 1P-18

KOBAYASHI, Yoshihiro . . . . . . . . . 1P-18, 3P-10, 3P-20

MAKARA, Hiroyuki . . . . . . . . . . . . 2P-32

KOBAYASHI, Yu . . . . . . . . . . . . . . . 1P-29, 3P-19

MAKI, Hideyuki . . . . . . . . . . . . . . . . 2-2

KODAMA, Takeshi . . . . . . . . . . . . . 1-7

MAKI, Norio . . . . . . . . . . . . . . . . . . . 2P-32

KOHARI, Yoshihito . . . . . . . . . . . . . 3P-40

MANAKO, Takashi . . . . . . . . . . . . . 1-14

KOHNO, Naoki . . . . . . . . . . . . . . . . . 2-5
KOINUMA, Michio . . . . . . . . . . . . . 2P-9

MANIWA, Yutaka . . . . . . . . . . . . . . 1P-12, 1P-24, 1P-29,
3P-14, 3P-19

KOJI, Hirofumi . . . . . . . . . . . . . . . . . 2P-15

MARUYAMA, Koji . . . . . . . . . . . . . 2P-37

KOJIMA, Takahiro . . . . . . . . . . . . . 3-6

MARUYAMA, Mina . . . . . . . . . . . . 1P-30

KOKUBO, Ken . . . . . . . . . . . . . . . . . 1-11, 1P-34
KOMATSU, Naoki . . . . . . . . . . . . . . 2P-8

MARUYAMA, Shigeo . . . . . . . . . . . 2-6, 2P-25, 3P-1,
3P-6, 3P-9, 3P-11,
3P-12

KONABE, Satoru . . . . . . . . . . . . . . . 3-2

MARUYAMA, Takahiro . . . . . . . . . 2P-21, 2P-26, 3P-23

KONNO, Toshio . . . . . . . . . . . . . . . . 1-10
KORETSUNE, Takashi. . . . . . . . . . 1-5, 3P-18
KOUYAMA, Takahiko . . . . . . . . . . 3P-15
KOZAWA, Daichi . . . . . . . . . . . . . . . 3-3
KUBONAKA, Nobuo . . . . . . . . . . . . 2P-2
KUBOTA, Mariko . . . . . . . . . . . . . . 2P-6
KUDA, Yuki . . . . . . . . . . . . . . . . . . . . 1P-37
KUMADA, Norio . . . . . . . . . . . . . . . 2P-17
KUMAGAI, Ryota . . . . . . . . . . . . . . 1P-28
KUNIMOTO, Ryuji . . . . . . . . . . . . . 2P-36

MASUBUCHI, Satoru . . . . . . . . . . . 3-4
MASUDA, Hiroyuki . . . . . . . . . . . . . 1P-34
MASUDA, Yoshiho . . . . . . . . . . . . . . 3-7
MATSUDA, Kazunari . . . . . . . . . . . 3-3, 3P-28
MATSUDA, Mitsuaki . . . . . . . . . . . 2P-14, 3-12
MATSUMOTO, Kazuhiro . . . . . . . 1P-18
MATSUMOTO, Shogo . . . . . . . . . . 2P-9
MATSUMOTO, Yasumichi . . . . . . 2P-9
MATSUMURA, Sachiko . . . . . . . . . 2P-35

KURIHARA, Hiroki . . . . . . . . . . . . 3-5

MATSUO, Yutaka . . . . . . . . . . . . . . . 1-11, 3P-1, 3P-35,
3P-40

KURODA, Kenta. . . . . . . . . . . . . . . . 3P-29

MATSUURA, Yusuke . . . . . . . . . . . 2P-20

KUSUNOKI, Michiko . . . . . . . . . . . 1P-20, 2P-7, 2P-16,
3-7, 3P-5, 3P-16,
3P-24

MATSUZAKI, Michihiro . . . . . . . . 1P-18

KUSUSMOTO, T. . . . . . . . . . . . . . . . 2P-22

MÉNARD-MOYON, Cécilia . . . . . 2-3

KWON, Eunsang . . . . . . . . . . . . . . . 3P-39, 3P-40

MIENO, Tetsu . . . . . . . . . . . . . . . . . . 2P-3

KYAKUNO, Haruka . . . . . . . . . . . . 1P-24, 3P-14

MIKIE, Tsubasa . . . . . . . . . . . . . . . . 1P-34

MAURO, Matteo . . . . . . . . . . . . . . . . 2-3

MINAMI, Kosuke . . . . . . . . . . . . . . . 1P-33, 3P-32– 171 –

Author Index

FNTG-47@Nagoya, 2014

Bold number: Speaker

MITRA, Subhasish . . . . . . . . . . . . . . 3S-7

NAKANISHI, Waka . . . . . . . . . . . . . 1P-33

MITSUYAMA, Ryo . . . . . . . . . . . . . 3P-14

NAKANISHI, Yusuke . . . . . . . . . . . 1-8, 2-1

MIYABE, Kyosuke . . . . . . . . . . . . . . 3P-38

NAKANO, Hiroto . . . . . . . . . . . . . . . 3P-40

MIYAKE, Hideto . . . . . . . . . . . . . . . 2P-20
MIYAKO, Eijiro . . . . . . . . . . . . . . . . 2-3

NAKASHIMA, Naotoshi . . . . . . . . 1P-9, 1P-10, 1P-16,
2P-10, 3P-3

MIYAMOTO, Genki . . . . . . . . . . . . 3P-24

NAMBA, Natsuki . . . . . . . . . . . . . . . 2P-40

MIYAMOTO, Katsuhiko . . . . . . . . 1P-36

NARITA, Kohei . . . . . . . . . . . . . . . . . 2P-30

MIYAMOTO, Koji . . . . . . . . . . . . . . 3P-29

NARITSUKA, Shigeya . . . . . . . . . . 2P-21, 2P-26, 3P-23

MIYAMOTO, Yoshiyuki . . . . . . . . . 3P-27

NASIBLIN, Albert G. . . . . . . . . . . . 3P-6

MIYAMURA, Hiroshi . . . . . . . . . . . 2-9

NASIBULIN, Albert . . . . . . . . . . . . 3P-1

MIYATA, Y. . . . . . . . . . . . . . . . . . . . . . 2P-22

NASIBULIN, Albert G. . . . . . . . . . . 3-13

MIYATA, Yasumitsu . . . . . . . . . . . . 1P-24, 1P-29, 3P-14,
3P-19

NEGISHI, Ryota . . . . . . . . . . . . . . . . 1P-18, 3P-10, 3P-20

MIYAUCHI, Yuhei . . . . . . . . . . . . . . 3-3, 3P-28

NIEHAUS, Thomas . . . . . . . . . . . . . 1P-16

MIYAZAWA, Kun’ichi . . . . . . . . . . 1-10, 2P-31, 3P-33

NIIBE, Masahito . . . . . . . . . . . . . . . . 2P-12

MIZOROGI, Naomi . . . . . . . . . . . . . 3P-38

NISHIMURA, Tomoaki . . . . . . . . . 1P-19

MIZUTANI, Akitaka . . . . . . . . . . . . 1P-40

NISHIWAKI, Yoshiki . . . . . . . . . . . 1P-3

MOMIUCHI, Yuta . . . . . . . . . . . . . . 2-10

NISHIZAWA, Ayumi . . . . . . . . . . . . 2-7

MORI, Shohei . . . . . . . . . . . . . . . . . . 3P-19

NIWA, Hiroyuki . . . . . . . . . . . . . . . . 2-1

MORI, Tatsuya . . . . . . . . . . . . . . . . . 2-2

NIWASE, Keisuke . . . . . . . . . . . . . . . 2P-12

MORIKAWA, Daisuke . . . . . . . . . . 3P-29

NODA, Shoko . . . . . . . . . . . . . . . . . . . 2-1

MORIKAWA, Sei . . . . . . . . . . . . . . . 3-4

NOIRI, Eisei . . . . . . . . . . . . . . . . . . . . 3P-32

MORIMOTO, Takahiro . . . . . . . . . 3-11

NORIMATSU, Wataru . . . . . . . . . . 1P-20, 2P-7, 3-7,
3P-5, 3P-16, 3P-24

MORISHITA, Kazuyuki . . . . . . . . . 2P-32

NGUYEN, Xuan Viet . . . . . . . . . . . . 3P-4

MORIYAMA, Hiroshi . . . . . . . . . . . 1P-37, 1P-39, 3P-34

NUGRAHA, Ahmad R.T. . . . . . . . . 1P-25, 1P-26, 1P-27,
2P-13

MOROKUMA, Keiji . . . . . . . . . . . . 1-9

NUNOYAMA, Naoki . . . . . . . . . . . . 1P-24

MORIYA, Rai . . . . . . . . . . . . . . . . . . 3-4

MOURI, Shinichiro . . . . . . . . . . . . . 3-3, 3P-28

O

MURAKAMI, Toshiya . . . . . . . . . . 1P-13, 2P-14, 3-12

OCHIAI, Yuichi . . . . . . . . . . . . . . . . . 1P-36

MURAKOSHI, Kei . . . . . . . . . . . . . . 1P-2, 1P-14, 1P-28,
3P-21

ODA, Koji . . . . . . . . . . . . . . . . . . . . . . 3P-16
OGASAWARA, Kazuki . . . . . . . . . . 3P-11, 3P-12

MUSTONEN, Kimmo . . . . . . . . . . . 3-13

OGATA, Hironori . . . . . . . . . . . . . . . 1P-19, 1P-38, 2P-38,
3P-36

MYODO, Miho . . . . . . . . . . . . . . . . . 2P-7, 3P-5

OGAWA, Takuji . . . . . . . . . . . . . . . . 3P-20

N
NAGASE, Shigeru . . . . . . . . . . . . . . 3-5, 3P-38

OHFUCHI, Mari . . . . . . . . . . . . . . . . 1-3, 1P-8

NAGATA, Kazuhiro . . . . . . . . . . . . . 3P-17

OHKUBO, Kei . . . . . . . . . . . . . . . . . . 2-5, 3P-37

NAKADA, Kyoko . . . . . . . . . . . . . . . 2P-40

OHNO, Yasuhide . . . . . . . . . . . . . . . 1P-18

NAKAE, Takahiro . . . . . . . . . . . . . . 3-6

OHNO, Yutaka . . . . . . . . . . . . . . . . . 3P-2, 3P-4, 3P-7

NAKAGAWA, Koji . . . . . . . . . . . . . . 1-11

OKABE, Yuta . . . . . . . . . . . . . . . . . . . 1P-40

NAKAGOME, Akito . . . . . . . . . . . . 1P-17

OKADA, Hiroshi . . . . . . . . . . . . . . . . 1-11, 3P-35, 3P-40

NAKAHARA, Hitoshi . . . . . . . . . . . 1P-41, 2P-27, 2P-28,
3-10, 3P-22

OKADA, Mitsuhiro . . . . . . . . . . . . . 3-8

NAKAHMURA, Eiichi . . . . . . . . . . 3P-32

OKADA, Susumu . . . . . . . . . . . . . . . 1-3, 1P-23, 1P-30,
2P-18, 2P-29, 2P-30

NAKAI, Yusuke . . . . . . . . . . . . . . . . . 1P-12, 1P-24, 3P-14

OKAMOTO, Koji . . . . . . . . . . . . . . . 3P-32

NAKAMURA, Naoto . . . . . . . . . . . . 1P-36

OKAZAKI, Toshiya . . . . . . . . . . . . . 3-11

NAKAMURA, Yasushi . . . . . . . . . . 2P-36

OKDA, Susumu . . . . . . . . . . . . . . . . . 1P-15– 172 –

Author Index

FNTG-47@Nagoya, 2014

Bold number: Speaker

OKIGAWA, Yuki . . . . . . . . . . . . . . . . 2-8

SASAKI, Kenichi . . . . . . . . . . . . . . . 1-12, 2P-17

OKUDA, Taichi . . . . . . . . . . . . . . . . . 3P-29

SATO, Hideki . . . . . . . . . . . . . . . . . . . 2P-1, 2P-2, 2P-20

OLMSTEAD, Marilyn M. . . . . . . . 3-5, 3P-38

SATO, Kumiko. . . . . . . . . . . . . . . . . . 3P-38

OMACHI, Haruka . . . . . . . . . . . . . . 1-8, 2P-4, 3P-8

SATO, Shigeo . . . . . . . . . . . . . . . . . . . 2P-35

OMATSU, Takashige . . . . . . . . . . . . 1P-36

SATO, Shino . . . . . . . . . . . . . . . . . . . . 1P-28

OSHIMA, Takumi . . . . . . . . . . . . . . 1-11

SATO, Takayuki . . . . . . . . . . . . . . . . 2P-2

OSHIMA, Yuki . . . . . . . . . . . . . . . . . 1P-12

SATO, Tohru . . . . . . . . . . . . . . . . . . . 3P-15

OSHIYAMA, Atsushi. . . . . . . . . . . . 1-4

SATO, Yoshinori . . . . . . . . . . . . . . . . 2-9, 3P-11, 3P-12

OSONOE, Kana . . . . . . . . . . . . . . . . 2P-31

SAWAZAKI, Takumi . . . . . . . . . . . . 3-8

OTANI, Minoru . . . . . . . . . . . . . . . . . 2P-18

SCHREINER, Peter R. . . . . . . . . . . 1-8

OTSUKA, Keigo . . . . . . . . . . . . . . . . 3P-9

SEGAWA, Yasutomo . . . . . . . . . . . . 3P-13

OTSUKA, Takeo . . . . . . . . . . . . . . . . 1-13

SEICHEPINE, Florent . . . . . . . . . . 1P-5

OURA, Masaki . . . . . . . . . . . . . . . . . 2P-12

SEKI, Shu . . . . . . . . . . . . . . . . . . . . . . 1-13, 1P-34
SEKIYA, Kazuki . . . . . . . . . . . . . . . . 1P-6, 2P-15

P

SHAMOTO, Shin-ichi . . . . . . . . . . . 2P-39

PAC, Chyongjin . . . . . . . . . . . . . . . . . 1P-37, 1P-39

SHIBA, Kiyotaka . . . . . . . . . . . . . . . 2P-35

Q

SHIBUYA, Megumi . . . . . . . . . . . . . 2P-7, 2P-16, 3P-5

QIANG, Hu-Jun . . . . . . . . . . . . . . . . 1-9

SHIINA, Ryo . . . . . . . . . . . . . . . . . . . 3P-10
SHIMADA, Kenya . . . . . . . . . . . . . . 1-2

R

SHIMIZU, Kazuki . . . . . . . . . . . . . . 1P-40, 2P-36, 2P-37,
2P-41

RAHMAN, Mohammad Jellur . . . 2P-3
RIUS, Gemma . . . . . . . . . . . . . . . . . . 1P-17

SHIMIZU, Yasutomo . . . . . . . . . . . . 1-13

ROTHE, Jörg . . . . . . . . . . . . . . . . . . . 1P-5

SHIMIZU, Yoshiaki . . . . . . . . . . . . . 2P-41

RUAMMAITREE, Akkawat . . . . . 2P-28

SHINDOME, Shoichiro . . . . . . . . . 1P-10

RUSSIER, Julie . . . . . . . . . . . . . . . . . 2-3

SHINOAHRA, Hisanori . . . . . . . . . 1-8

RUSSO, Saverio . . . . . . . . . . . . . . . . . 1-1

SHINODA, Y. . . . . . . . . . . . . . . . . . . . 2P-22
SHINOHARA, Hisanori . . . . . . . . . 1P-29, 2-1, 2P-4,
3-8, 3P-8

SSADA, Takao . . . . . . . . . . . . . . . . . . . 1P-9

SHINOMIYA, Yuji . . . . . . . . . . . . . . 3-10

SAEKI, Akinori . . . . . . . . . . . . . . . . . 1-13, 1P-34
SAHA, Avishek . . . . . . . . . . . . . . . . . 2P-33

SHIONOYA, Mitsuhiko . . . . . . . . . 3P-37

SAITO, Makoto . . . . . . . . . . . . . . . . . 3P-11, 3P-12

SHIOYA, Hiroki . . . . . . . . . . . . . . . . 1-1

SAITO, Riichiro . . . . . . . . . . . . . . . . 1P-25, 1P-26, 1P-27,
2S-4, 2P-13

SHIRAKI, Tomohiro . . . . . . . . . . . . 1P-10

SAITO, Susumu . . . . . . . . . . . . . . . . 1-5, 3-9, 3P-18

SHULAKER, Max . . . . . . . . . . . . . . 3S-7

SAITO, Takeshi . . . . . . . . . . . . . . . . . 1P-1, 3-11

SIREGAR, Syahril . . . . . . . . . . . . . . 1P-25

SAITO, Yahachi . . . . . . . . . . . . . . . . 1P-41, 2P-27, 2P-28,
3-10, 3P-22

SOGA, Tetsuo . . . . . . . . . . . . . . . . . . . 1P-1

SAKAGUCHI, Hiroshi . . . . . . . . . . 3-6
SAKAGUCHI, Takahiro . . . . . . . . . 3P-6
SAKAI, Hideki . . . . . . . . . . . . . . . . . . 1P-33
SAKAMOTO, Hirotoshi . . . . . . . . . 3P-31

SHIROMARU, Haruo . . . . . . . . . . . 1-7

SONG, Hayong . . . . . . . . . . . . . . . . . 1P-3
SOTA, Masaki . . . . . . . . . . . . . . . . . . 2P-25
SUDA, Yoshiyuki . . . . . . . . . . . . . . . . 1P-40, 2P-36, 2P-37,
2P-41

SAKANO, Masato . . . . . . . . . . . . . . 3P-29

SUGAI, Toshiki . . . . . . . . . . . . . . . . . 1P-11, 2P-24, 3P-11,
3P-12

SAKO, Yusuke . . . . . . . . . . . . . . . . . . 2P-4

SUNAYAMA, Yuki . . . . . . . . . . . . . . 2-9

SAKURAI, Hidehiro . . . . . . . . . . . . 1P-11

SUZUKI, Hiroo . . . . . . . . . . . . . . . . . 2P-23

SANO, Hiroshi . . . . . . . . . . . . . . . . . . 2P-32

SUZUKI, Kazuma . . . . . . . . . . . . . . 2P-7, 2P-16, 3P-5

SANO, Yoshiaki . . . . . . . . . . . . . . . . . 3P-36

SUZUKI, Manabu . . . . . . . . . . . . . . 2P-21, 2P-26, 3P-23– 173 –

Author Index

FNTG-47@Nagoya, 2014

SUZUKI, Mitsuaki . . . . . . . . . . . . . . 3-5, 3P-38

Bold number: SpeakerU

SUZUKI, Ryosuke . . . . . . . . . . . . . . 3P-14

UCHIDA, Hideo . . . . . . . . . . . . . . . . 3P-25, 3P-26

SUZUKI, Ryuji . . . . . . . . . . . . . . . . . 3P-29

UCHIDA, Kazuyuki . . . . . . . . . . . . . 1-4

SUZUKI, Takashi . . . . . . . . . . . . . . . 1P-1

UCHIYAMA, Kouya . . . . . . . . . . . . 3P-34

T

UE, Hitoshi . . . . . . . . . . . . . . . . . . . . . 1P-40, 2P-36, 2P-37,
2P-41

TACHIBANA, Masaru . . . . . . . . . . 2P-31
TADERA, Shin . . . . . . . . . . . . . . . . . . 3P-14
TAGUSHI, Eiji . . . . . . . . . . . . . . . . . . 2P-12

UEDA, Mako . . . . . . . . . . . . . . . . . . . 2P-9

TAKADA, Yukihiro . . . . . . . . . . . . . 2P-40

UEDA, Yuki . . . . . . . . . . . . . . . . . . . . 2P-21, 2P-26, 3P-23

TAKAHASHI, Junro . . . . . . . . . . . . 2-10

UENO, Hiroshi . . . . . . . . . . . . . . . . . 1-11

TAKAHASHI, Misaki . . . . . . . . . . . 2P-24

UENO, Mikihiro . . . . . . . . . . . . . . . . 2P-32

TAKAHASHI, Tomoyuki . . . . . . . . 3P-30
TAKASE, Mai . . . . . . . . . . . . . . . . . . 1P-14

UKHTARY, Muhammad Shoufie 1P-27

TAKEI, Kuniharu . . . . . . . . . . . . . . . 2P-19
TAKEUCHI, Masanori . . . . . . . . . . 2P-32

UMEDA, Yoshito . . . . . . . . . . . . . . . . 1P-40, 2P-36, 2P-37,
2P-41

TAKEUCHI, Yu . . . . . . . . . . . . . . . . 1P-4

UMENO, Masayoshi . . . . . . . . . . . . 3P-25, 3P-26

TAKIKAWA, Hirofumi . . . . . . . . . . 1P-40, 2P-36, 2P-37,
2P-41

V

TAMAKI, Eisuke . . . . . . . . . . . . . . . 2P-1
TAMESUE, Shingo . . . . . . . . . . . . . . 3P-17

VENKATARAMANA, Gandikota 3P-13

TAMURA, Noriyuki . . . . . . . . . . . . . 1-14

W

TAMURA, Ryosuke . . . . . . . . . . . . . 2P-12
TANAKA, Hirofumi . . . . . . . . . . . . . 3P-20

WAELCHLI, Markus . . . . . . . . . . . 3-5

TANAKA, Kazuyoshi . . . . . . . . . . . . 3P-15

WAKAHARA, Takatsugu . . . . . . . 1-10, 3P-33

TANAKA, Shin-ichiro . . . . . . . . . . . 1-2

WAKASUGI, Takashi . . . . . . . . . . . 1P-21

TANAKA, Takeshi . . . . . . . . . . . . . . 1P-35, 2-4, 2P-5,
2P-6

WAKITA, Koichi . . . . . . . . . . . . . . . . 3P-25, 3P-26

TANAKA, Yu . . . . . . . . . . . . . . . . . . . 1P-36

WANG, Chenxing . . . . . . . . . . . . . . . 2P-27

TANIGUCHI, Takaaki . . . . . . . . . . 2P-9

WANG, Feijiu . . . . . . . . . . . . . . . . . . . 3-3

TANIGUCHI, Takashi . . . . . . . . . . . 3-4, 3-8
TANIKAWA, Sachiko . . . . . . . . . . . 1P-18

WANG, Wei-Wei . . . . . . . . . . . . . . . . 3P-38

TARUCHA, Seigo . . . . . . . . . . . . . . . 1-1

WANG, Xiao . . . . . . . . . . . . . . . . . . . . 1-6

TASHIRO, Kosuke . . . . . . . . . . . . . . 1P-3

WANG, Ying . . . . . . . . . . . . . . . . . . . . 1-9

TATENO, Kouta . . . . . . . . . . . . . . . . 1-12

WANG, Zhipeng . . . . . . . . . . . . . . . . 1P-19, 2P-38

TERASAWA, Mititaka . . . . . . . . . . 2P-12
TOBARI, Yuta . . . . . . . . . . . . . . . . . . 3P-11, 3P-12

WANG, Zhiyong . . . . . . . . . . . . . . . . 2-1

TOMIDA, Akihiro . . . . . . . . . . . . . . 2P-35

WATANABE, Keita . . . . . . . . . . . . . 3P-34

TOSHIMITSU, Fumiyuki . . . . . . . 1P-10, 2P-10

WATANABE, Kenji . . . . . . . . . . . . . 3-4, 3-8

TOYAMA, Kiyohiko. . . . . . . . . . . . . 1-14
TSUBOI, Mika . . . . . . . . . . . . . . . . . . 2P-4, 3P-8
TSUBOI, Yuka . . . . . . . . . . . . . . . . . . 3-3

WEI, Xiaojun . . . . . . . . . . . . . . . . . . . 2-4, 2P-5
WONG, H.-S. Philip . . . . . . . . . . . . . 3S-7

TSUBOKAWA, Norio . . . . . . . . . . . 3P-17

X

TSUJI, Ryotaro . . . . . . . . . . . . . . . . . 1-13
TSUKAGOSHI, Akira. . . . . . . . . . . 2P-12

XIANG, Rong . . . . . . . . . . . . . . . . . . . 2-6, 3P-6

TSUSHIMA, Kohei . . . . . . . . . . . . . 2P-25

XIE, Yunpeng . . . . . . . . . . . . . . . . . . . 1P-31

TSUTSUI, Masato . . . . . . . . . . . . . . 1P-4
TSUZUKI, Mayumi . . . . . . . . . . . . . 2-4, 2P-5, 2P-6

XU, Bin . . . . . . . . . . . . . . . . . . . . . . . . . 2P-11– 174 –

Author Index

FNTG-47@Nagoya, 2014Y
YAGI, Akiko . . . . . . . . . . . . . . . . . . . . 3P-13
YAJI, Koichiro . . . . . . . . . . . . . . . . . . 3P-29
YAMADA, Jumpei . . . . . . . . . . . . . . 2P-21, 2P-26, 3P-23
YAMADA, Michio. . . . . . . . . . . . . . . 3-5
YAMADA, Mihoko . . . . . . . . . . . . . . 3P-37
YAMADA, Takatoshi . . . . . . . . . . . . 2-8
YAMADA, Takeo . . . . . . . . . . . . . . . 2-7
YAMADA, Tatsuya . . . . . . . . . . . . . . 3P-7
YAMAGO, Shigeru . . . . . . . . . . . . . . 3P-15
YAMAGUCHI, Kenji . . . . . . . . . . . . 2P-39
YAMAGUCHI, Takehiro . . . . . . . . 3-4
YAMAMOTO, K. . . . . . . . . . . . . . . . 2P-22
YAMAMOTO, Kazunori . . . . . . . . 2P-39
YAMAMOTO, Michihisa . . . . . . . . 1-1
YAMAMOTO, Takahiro . . . . . . . . . 1S-3, 3-2
YAMANAKA, Ayaka . . . . . . . . . . . . 1P-23
YAMASAKI, Ayumi . . . . . . . . . . . . . 1P-21
YAMAUCHI, Takeshi . . . . . . . . . . . 3P-17
YAMAUCHI, Yohei . . . . . . . . . . . . . 2-2
YAMAZAKI, Tomohiko . . . . . . . . . 1P-33
YANAGI, Kazuhiro . . . . . . . . . . . . . 1P-12, 3P-14
YANG, Feng . . . . . . . . . . . . . . . . . . . . 1-6
YANG, Juan . . . . . . . . . . . . . . . . . . . . 1-6
YANO, Maki . . . . . . . . . . . . . . . . . . . . 3-6
YASUDA, Hidehiro . . . . . . . . . . . . . . 2P-34
YASUDA, Satoshi . . . . . . . . . . . . . . . 1P-2, 1P-14, 1P-28,
3P-21
YASUNISHI, Tomohiro . . . . . . . . . 3P-2
YAWO, Hiromu . . . . . . . . . . . . . . . . . 2-3
YOKOI, Hiroyuki . . . . . . . . . . . . . . . 2P-9
YOMOGIDA, Yohei . . . . . . . . . . . . . 2-4, 2P-5
YOSHIDA, Shin-ichiro . . . . . . . . . . 3P-39
YOSHIHIRO, Iwasa . . . . . . . . . . . . 3P-29
YOSHII, Takahiro . . . . . . . . . . . . . . 1P-14
YOSHIOKA, Hideki . . . . . . . . . . . . 2P-12
YOSHITAKE, Haruhiko . . . . . . . . 1P-19, 2P-38
YOZA, Kenzi . . . . . . . . . . . . . . . . . . . 3P-34
YUDASAKA, Masako . . . . . . . . . . . 1-14, 2-3, 2P-35
YUGE, Ryota . . . . . . . . . . . . . . . . . . . 1-14, 2P-35
YUMURA, Takashi . . . . . . . . . . . . . 1P-21

Z
ZHANG, Daqi . . . . . . . . . . . . . . . . . . 1-6
ZHANG, Jinying . . . . . . . . . . . . . . . . 2-1
ZHANG, Yijin . . . . . . . . . . . . . . . . . . 3P-29
ZHENG, Shushu . . . . . . . . . . . . . . . . 1P-32– 175 –

Bold number: Speaker複写をご希望の方へ
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2014 年 9 月 3 日 発行

第 47 回フラーレン・ナノチューブ・グラフェン総合シンポジウム
講演要旨集
hhh フラーレン・ナノチューブ・グラフェン学会 iii〒 113-8656 東京都文京区本郷 7-3-1
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ダウンストリーム式

プラズマアッシャー【GV１０ｘ】

有機系コンタ ミネーション
予防・除去ツール
GV10xはプラズマアッシングにより、コンタミネーションの原因となる炭化水素(ﾊｲﾄﾞﾛｶｰﾎﾞﾝ)を灰化除去する
ことが可能で、コンタミレスな観察・分析を実現します。

2Way■ in-situクリーーニング [左図 –左]
試料チャン
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■ ex-situクリーニング [左図 –右]
プラズマソースを接続した卓上チャンバー内に試料やホルダをセットし、これらを前処理(予防)します。
試料に付着してしまったコンタミのの除去(クリーニング)や、試料の表面改質・親水化処理にも有効です。

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JEOLの最新表面分析装置

マイクロからナノスケール領域の観察・分析に！

Surface Analysis

原子分解能分析電子顕微鏡

Cold
新 たな 扉を開く鍵……
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誘導体化フラーレン用HPLCカラム

COSMOSIL Buckyprep-D
R● 誘導体化フラーレン用HPLCカラム● トルエン移動相中で誘導体化フラーレンが分離可能■C60インデン付加体の分析例
C60インデンは誘導体化フラーレンの一種であり、有機薄膜太陽電池のn型半導体材料として注目されている化合物です。
コスモシール Buckyprep-Dを用いることにより高い分離性能が得られます。

COSMOSIL Application Data
Buckyprep

Buckyprep-D

Column:Column size: 4.6mmI.D.-250mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30qC
Detection:
UV 325nm
Sample:Inj.Vol.:

C60 [Indene]2 (1.0mg/ml)
1.0Pl

NACALAI TESQUE, INC

Data courtesy of Yusuke Tajima, Dr. Sci.
Organic Optoelectronics Laboratory, RIKEN (Institute of Physics and Chemistry)■Buckyprepシリーズの用途

フラーレン分離のスタンダードカラム

COSMOSIL Buckyprep

誘導体化フラーレンの分離

COSMOSIL Buckyprep-D

金属内包フラーレンの分離

COSMOSIL Buckyprep-M・誘導体化フラーレン (Buckyprep-D)

・金属内包フラーレン (Buckyprep-M)

COSMOSIL Application DataCOSMOSIL Application Data

Column:Buckyprep-D
Column size: 4.6mmI.D.-50mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30qC
Detection:
UV325nmColumn:Buckyprep-M
Column size: 4.6mmI.D.-250mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30qC
Detection:
UV312nmSample:Inj.Vol.

C86(0.125mg/ml)
1; C602; C70(0.250mg/ml)
3; [6,6]-Phenyl-C61 Butyric Acid Methyl Ester[PCBM](0.125mg/ml)
4; [6,6]-Phenyl-C71 Butyric Acid Methyl Ester[ [70]PCBM ](0.375mg/ml)
1.0Pl
NACALAI TESQUE, INC

Sc
Sc2@C76(I)Sample:Sc2@C76(I)Sc2@C78
Sc2@C80(I)C86

Sample courtesy of Prof. H.Shinohara,
Department of chemistry, Nagoya University

C84
C84

Sc2@C78
Sc2@C80(I)NACALAI TESQUE, INC

詳しい情報はWeb siteをご覧ください。

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LC-9110ⅡNEXT 10
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溶液中の粒子のナノチューブや粒子の分散・微細化に！
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超高圧 湿式微粒化装置（湿式ジェットミル）

卓上型

超高圧 湿式微粒化装置（ラボ型

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吉田工業（株）製
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相互作用
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床置型実験機ノズルからの噴出排出＊特許登録済高圧・超高圧でエネルギーを与えられた被処理流体はノズルより噴出され過流と卓上型実験機なります。複数の過流は相互に干渉しながらキャビテーションが誘起されます。

5L/h：最大圧力 140MPa

過流の相互干渉とキャビテーションの相互作用により、瞬時に微粒化が完了します。

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------------------------------------------------------

AFM- ラマン装置
AFM- ラマンの用途

Applications of AFM-Raman①AFM/ラマン同一領域測定②TERS分析■ AFM： 形状、電気・磁気的性質、機械特性、熱特性などの可視化■ 回折限界を超える測定空間分解能（数 10 nm〜）によるラマン測定■ ラマン： 有機物、無機化合物、結晶性などの化学情報※TERS： Tip Enhancement Raman
Spectroscopy

AFM- ラマンの特長・仕様

Advantages and Specifications■ 仕様・特長
1. ラマン光に干渉しない IR AFM ダイオード
2. ヘッドの移動を必要としないチップ交換
3. カンチレバーのオートアライメント
4. TERS 用 高 NA 対物レンズ（0.7 NA）
Smart SPM + XploRA

アプリケーション例

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■ ナノワイヤ■ ポリマー■ SERS 基板■ 半導体

Data courtesy of Prof. Hiroshi Ujii of K.U. Leuven

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フロンティアカーボンのフラーレン製品
銘

純度(HPLC面積％、代表値）
内容他

最低数量
（ｇ）
10
2
2
1
1

ST

99
99.5
99.5/ 昇華精製品
99.9/ 昇華精製品
99.9/ 昇華精製/ 単結晶品
97

SU

98/ 昇華精製品

0.5ST

C60,C70, その他高次フラーレンの混合物

50

分子構造

柄
ST
TL
SU
SUH
SC

nanom purple
フラーレン C60

nanom orange
フラーレン C70

nanom mix
混合フラーレン※微粒化品（ ST-F）もありますOnanom spectra[60]PCBM(phenyl C61-butyric acid methyl
ester)

E100

99

1

E100H

99.5

1

E102

99.9

0.5

98/ 異性体トータル

1

O

nanom spectra E400
bis[60]PCBM※位置異性体の混合物(bis-phenyl C61-butyric acid methyl ester)Onanom spectra E124

OO

O

[60,70]PCBM[60]PCBM、[70]PCBMの混合物

199/ 異性体トータル

0.5

Onanom spectra

E110(phenyl C71-butyric acid methyl
ester)

E112[70]PCBM

1O※位置異性体の混合物

主成分

99.5/異性体トータル※位置異性体の混合物

0.5nanom spectra Q100

99

0.5

nanom spectra Q40 0

99/ 異性体トータル

1[60]インデン付加体[60]インデン２付加体※位置異性体の混合物

HO

nanom spectra D100

HO

水酸化フラーレン

n/2

C60OHn n=10を主成分とする混合物(n = ca.10)

12
H

nanom spectra A100n/2
H

水素化フラーレン

C60Hn n=30を主成分とする混合物(n = ca. 30)※銘柄、取扱数量等は予告無く変更する場合がございます。 ※試験研究用途向けです。

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