第回 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

48
44

平成

年３月 日〜 日

27
25

２

21
11

13
23

F NTG

Research Society

第 48 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

The 48th Fullerenes-Nanotubes-Graphene General Symposium

講演要旨集
Abstracts2015 年 2 月 21 日（土）～ 23 日（月）東京大学 伊藤国際学術研究センター
The University of Tokyo, ITO INTERNATIONAL RESEARCH CENTER
主催 フラーレン・ナノチューブ・グラフェン学会
The Fullerenes, Nanotubes and Graphene Research Society
共催
社会構想マネジメントを先導するグロ－バルリーダー養成プログラム（GSDM）「社会構想構築のためのナノテクノロジー科学技術シンポジウム」
Global Leader Program for Social Design and Management (GSDM)“Nanotechnology Symposium for Social Design and Management”
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
東京大学 GMSI The University of Tokyo
Graduate Program for Mechanical Systems Innovation (GMSI)
協賛
日本物理学会
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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

nanom spectra[60]PCBM(phenyl C61-butyric acid methyl
ester)※微粒化品（ ST-F）もあります

O

99

1

E100H

99.5

1

E102

99.9

0.5

98/ 異性体トータル

1

E100

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

O

nanom spectra

E110(phenyl C71-butyric acid methyl
ester)

E112[70]PCBM

1O[60]PCBM、[70]PCBMの混合物

199/ 異性体トータル

0.5※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

物

nanom spectra A100

H

n/2
(n = ca. 30)

1

H

2

水素化フラーレン

C60OHn n=10を主成分とする混合(n = ca.10)

C60Hn n=30を主成分とする混合物※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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1

Abstract of
The 48th Fullerenes-Nanotubes-Graphene General Symposium
Sponsored by : The Fullerenes, Nanotubes and Graphene Research Society
Co-Sponsored by : Global Leader Program for Social Design and Management (GSDM)“Nanotechnology Symposium for Social Design and Management”

The Chemical Society of Japan
IRENA Project by JST-EC DG RTD,

Strategic International Collaborative Research Program, SICORPThe University of Tokyo

Graduate Program for Mechanical Systems Innovation (GMSI)

Supported by : The Physical Society of JapanThe Japan Society of Applied Physics
The Society of Polymer Science, JapanThe Electrochemical Society of Japan

Date : February 21st (Sat) – 23rd (Mon), 2015
Place : The University of Tokyo, ITO INTERNATIONAL RESEARCH CENTER

7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656

Presentation Time : Special Lecture ( 25 min presentation + 5 min discussion)

General Lecture ( 10 min presentation + 5 min discussion)
Poster Preview ( 1 min presentation without discussion)

第 48 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 : 社会構想マネジメントを先導するグロ－バルリーダー養成プログラム (GSDM)「社会構想構築のためのナノテクノロジー科学技術シンポジウム」
日本化学会
JST 戦略的国際共同研究プロジェクト IRENA
東京大学大学院工学系研究科「機械システム･イノベーション」プログラム (GMSI)
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 27 年 2 月 21 日(土)～23 日(月)場所 : 東京大学 伊藤国際学術研究センター〒113-8656 東京都文京区本郷 7-3-1

伊藤謝恩ホール（発表 25 分 + 質疑応答 5 分）
発表時間 : 特別講演
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）アド・サイエンス
オックスフォード・インストゥルメンツ（株）
QuantumWise Japan（株）
共立出版（株）
サイバネットシステム（株）
シグマ アルドリッチ ジャパン(同）（株）島津製作所
東京ダイレック(株）ナカライテスク（株）
ナノフォトン（株）
日本カンタム・デザイン（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
日立工機（株）(株）堀場製作所(株）名城ナノカーボン
レニショー(株）ワケンビーテック(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)WITec(株）エクセルソフト（株)（株）エリオニクス
共立出版（株）(株）コロナ社
サーモフィッシャーサイエンティフィック（株）
ナカライテスク（株）
フロンティアカーボン（株）(株）堀場製作所

Contents
Time Table ・・・・・・・・・・・・・・・・・・ i
Chairperson ・・・・・・・・・・・・・・・・・iii
ProgramJapanese ・・・・・・・・・・・・ iv
English ・・・・・・・・・・・・ xix
Abstracts
Special Lecture ・・・・・・・・・・ 1
General Lecture ・・・・・・・・・ 11
Poster Preview ・・・・・・・・・・45
Author Index ・・・・・・・・・・・・・・・・177

目次
早見表 ・・・・・・・・・・・・・・・・・・・ i
座長一覧・・・・・・・・・・・・・・・・・・・iii
プログラム 和文・・・・・・・・・・・・・・・ iv
英文・・・・・・・・・・・・・・ xix
講演予稿
特別講演・・・・・・・・・・・・・ 1
一般講演・・・・・・・・・・・・・11
ポスター発表・・・・・・・・・・・45
発表索引・・・・・・・・・・・・・・・・・・ 177

プログラム早見表
２月２１日 （土）

２月２２日 （日）２月２３日 （月）受付開始 ８：３０～

受付開始 ８：３０～
講演開始 ９：００～

受付開始 ８：３０～
講演開始 ９：００～

講演開始 ９：３０～
9:30
10:00

特別講演 （Yan Li）
9:30-10:00
一般講演 2件 10:00-10:30（ﾅﾉﾁｭｰﾌﾞの生成と精製・内包ﾅﾉﾁｭｰﾌﾞ)

10:30
10:45
11:15

休憩 10:30-10:45
特別講演 (今津直樹)
10:45-11:15
一般講演 3件

9:00 特別講演（Esko I. Kauppinen）
9:00-9:30
9:30
一般講演 3件(ナノチューブの生成と精製・
ナノチューブの応用) 9:30-10:15

10:15
10:30
11:00

(フラーレンの化学・金属内包フラーレン・フラーレン)(ナノチューブの生成と精製・
ナノチューブの応用) 11:15-12:00

12:00

昼食
（幹事会）
12:00-13:15

13:15

特別講演 (斉木幸一朗)
13:15-13:45
13:45
一般講演 4件(グラフェンの応用・
ナノホーン・ナノ炭素粒子)
13:45-14:45
14:45
ポスタープレビュー( 1P-1 ～ 1P-44 )14:45-15:45
15:45

休憩 10:15-10:30
特別講演 (山田容子)
10:30-11:00
一般講演 4件

12:00

11:00-12:00
昼食
12:00-13:15

13:15

授賞式
13:15-14:00

14:00

ポスタープレビュー( 2P-1 ～ 2P-44 )14:00-15:00

15:00

9:00

特別講演 (長汐晃輔)
9:00-9:30
9:30
一般講演 4件(グラフェンの物性・その他）
9:30-10:30

10:30
10:45

休憩 10:30-10:45
特別講演 (松田一成)
10:45-11:15
11:15
一般講演 3件(グラフェンの物性・その他）
11:15-12:00
12:00
昼食
12:00-13:15

13:15

ポスタープレビュー( 3P-1 ～ 3P-43 )13:15-14:15

14:15

ポスターセッション（多目的スペース）
14:15-16:00

16:00

特別講演 （北浦 良）
16:00-16:30
一般講演 4件(グラフェン生成・その他・
グラフェンの応用）
16:30-17:30

ポスターセッション（多目的スペース）
15:00-16:45

ポスターセッション（多目的スペース）
15:45-17:30

16:30
16:45
17:15
17:30

休憩 17:30-18:00

18:00

チュートリアル講師： 末永和知
産業技術総合研究所（伊藤謝恩ホール）
18:00-19:30

18:45

特別講演 （加藤雄一郎）
16:45-17:15
一般講演 6件(ナノチューブの物性)
17:15-18:45

17:30

懇親会
（多目的スペース）
18:45-20:45

19:30
特別講演 発表２５分・質疑５分
一般講演 発表１０分・質疑５分
ﾎﾟｽﾀｰﾌﾟﾚﾋﾞｭｰ 発表１分・質疑なし
20:45

i

Time table
February 21 (Sat.)
Registration begins at 8:30

Lectures begin at 9:30
9:30
10:00

Special Lecture(Yan Li) 9:30-10:00
General Lectures [2](Formation and purification of nanotubes ・Endohedral nanotubes) 10:00-10:30

10:30
10:45
11:15

Coffee Break 10:30-10:45
Special Lecture(Naoki Imazu) 10:45-11:15
General Lectures [3]

13:15

Special Lecture(Koichiro Saiki) 13:15-13:45
13:45
General Lectures [4](Applications of graphene ・Carbon nanoparticles ・Nanohorns) 13:45-14:45
14:45
Poster Preview( 1P-1 through 1P-44 )14:45-15:45
15:45

Lectures begin at 9:00

Lectures begin at 9:00

Special Lecture(Esko I. Kauppinen) 9:00-9:30
9:30
General Lectures [3](Applications of nanotubes ・ Formation

10:15
10:30
11:00

Coffee Break 10:15-10:30
Special Lecture(Hiroko Yamada) 10:30-11:00
General Lectures [4](Chemistry of fullerenes ・Endohedral metallofullerenes ・Fullerenes) 11:00-12:00

12:00

Lunch
12:00-13:15

13:15

Award Ceremony
13:15-14:00

14:00

Poster Preview( 2P-1 through 2P-44 )14:00-15:00

15:00

Poster Session(Event Space)
15:45-17:30

18:00

Coffee Break 17:30-18:00

Special Lecture(Kosuke Nagashio) 9:00-9:30
9:30
General Lectures [4](Properties of graphene ・
Other topics)

9:30-10:30
10:30 Coffee Break 10:30-10:45
10:45
Special Lecture(Kazunari Matsuda) 10:45-11:15
11:15
General Lectures [3](Properties of graphene ・
Other topics) 11:15-12:00
12:00
Lunch
12:00-13:15

13:15

Poster Preview( 3P-1 through 3P-43 )13:15-14:15

14:15

Poster Session(Event Space)
14:15-16:00

Poster Session(Event Space)
15:00-16:45
16:00

16:45

17:30

9:00

and purification of nanotubes) 9:30-10:15

Applications of nanotubes） 11:15-12:00

Lunch(Administrative meeting)
12:00-13:15

February 23 (Mon.)
Registration begins at 8:30

9:00

（Formation and purification of nanotubes ・

12:00

February 22 (Sun.)
Registration begins at 8:30

Special Lecture（Yuichiro K. Kato） 16:45-17:15
17:15
General Lectures [6](Properties of nanotubes)
17:15-18:45

Special Lecture(Ryo Kitaura) 16:00-16:30
16:30
General Lectures [4](Graphene synthesis ・Applications of graphene ・
Other topics) 16:30-17:30
17:30

Tutorial
Lecturer: Kazutomo Suenaga

AIST(Ito Hall)
18:00-19:30

18:45

Banquet(Event Space)
18:45-20:45

19:30
20:45
Special Lecture: 25 min (Presentation) + 5 min (Discussion)
General Lecture: 10 min (Presentation) + 5 min (Discussion)
Poster Preview: 1 min (Presentation)ii

座長一覧 (Chairpersons)
2月21日(土）
セッション
特別講演(Yan Li）
一般講演
特別講演(今津 直樹）
一般講演
特別講演(斉木 幸一朗）
一般講演
ポスタープレビュー時
間
9:30 ～10:00
10:00 ～10:30
10:45 ～ 11:15
11:15 ～ 12:00
13:15 ～ 13:45
13:45 ～ 14:45
14:45 ～ 15:45

チュートリアル(末永 和知）

18:00 ～ 19:30

2月22日（日）セッション
特別講演(Esko I.Kauppinen）
一般講演
特別講演(山田 容子）
一般講演
ポスタープレビュー時
間
9:00 ～ 9:30
9:30 ～10:15
10:30 ～11:00
11:00 ～ 12:00
14:00 ～ 15:00

特別講演(加藤 雄一郎）
一般講演

16:45 ～ 17:15
17:15 ～ 18:45

2月23日（月）セッション
特別講演(長汐 晃輔）
一般講演
特別講演(松田 一成）
一般講演
ポスタープレビュー時
間
9:00 ～ 9:30
9:30 ～ 10:30
10:45 ～ 11:15
11:15 ～ 12:00
13:15 ～ 14:15

特別講演(北浦 良）
一般講演

16:00 ～ 16:30
16:30 ～ 17:30

(敬称略）

iii

座
長
丸山 茂夫
野田 優
中嶋 直敏
大野 雄高
吾郷 浩樹
菅井 俊樹
長谷川 馨
小林 慶太
丸山 茂夫

座
長
篠原 久典
岡崎 俊也
長汐 晃輔
松尾 豊
宮田 耕充
項 榮
松田 一成
小鍋 哲

座
長
山本 貴博
高井 和之
加藤 雄一郎
北浦 良
宮内 雄平
井ノ上 泰輝齋藤 弥八
斎藤 晋２月２１日 （土）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
特別講演 ( 9:30-10:00 )1S-1

What we know about chirality-controlled growth of single-walled carbon nanotubes* Yan Li1

一般講演 ( 10:00-10:30 )ナノチューブの生成と精製 ・ 内包ナノチューブ
1-1

Rh/Pd触媒下で共存する二つのチューブ成長メカニズム* 阿知波 洋次 , 児玉 拓也 , 兒玉 健 , 橋本 健朗 , 城丸 春夫

11

1-2

Ionic atomic chains inside carbon nanotubes* 千賀 亮典 , 末永 和知

12＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜特別講演 ( 10:45-11:15 )1S-2

次世代フレキシブルデバイス向け２層カーボンナノチューブ透明導電フィルム* 今津 直樹 , 大井 亮 , 西野 秀和 , 佐藤 謙一 , 渡邊 修 , 本田 史郎 , 鈴木 基之

2

一般講演 ( 11:15-12:00 )ナノチューブの生成と精製 ・ ナノチューブの応用
1-3

Selective Separation of Semiconducting Single-Walled Carbon Nanotubes Using Flavin
Compounds* 福澤 将史 , 利光 史行 , 加藤 雄一 , 中嶋 直敏

13

1-4

単層カーボンナノチューブの構造選択におけるコール酸塩の役割* 蓬田 陽平 , 都築 真由美 , 魏 小均 , 平野 篤 , 藤井 俊治郎 , 田中 丈士 ,

14

片浦 弘道
1-5

コバルトセン内包CNTを用いた熱電材料の開発* 藤ヶ谷 剛彦 , 福丸 貴弘 , 中嶋 直敏

15＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜特別講演 ( 13:15-13:45 )1S-3

熱放射顕微法によるグラフェン成長のリアルタイム観察* 斉木 幸一朗 , 寺澤 知潮 , 加藤 頌

3

一般講演 ( 13:45-14:45 )グラフェンの応用 ・ ナノホーン ・ ナノ炭素粒子
1-6

イオン照射による炭素材料の局所的な構造の制御およびワンステップ電着法によるPtナノ粒
子の担持特性* 早瀬 勝平 , 吉竹 晴彦 , 西村 智朗 , 王 志朋 , 緒方 啓典

iv

16

２月２１日 （土）1-7

中性子線捕捉療法のためのBNナノホーンの作製* 飯泉 陽子 , 岡崎 俊也 , 張 民芳 , 弓削 亮太 , 市橋 鋭也 , 中村 真紀 , 池原 譲 ,飯島 澄男 , 湯田坂 雅子

17

1-8

ガン療法のための多機能性カーボンナノホーン複合体の開発* Eijiro Miyako, Svetlana Chechetka, Benoit Pichon, Minfang Zhang, Masako Yudasaka,
Sylvie Bégin-Colin, Alberto Bianco

18

1-9

爆轟法および太陽系外起源炭素隕石中ナノダイヤのLDI比較分析* 田中 利彦 , 山野井 亮子 , 大澤 映二

19

ポスタープレビュー ( 14:45-15:45 )ポスターセッション ( 15:45-17:30 )
その他
1P-1

（☆） 若手奨励賞候補

移動度測定による粒子帯電量の解析* 菅井 俊樹 , 廣芝 泰祐 , 松林 広延 , 三室 和暉 , 陣内 涼太

45

ナノ環境と安全評価
1P-2

Exciton-photon interaction in tip enhanced Raman spectroscopy of single wall carbon
nanotubes* Thomas Czank, Pourya Airya, Riichiro Saito

46

ナノチューブの物性
1P-3(5,4)(6,4)(6,5)(8,6)カーボンナノチューブ酸化過程の第一原理計算* 大淵 真理

47

1P-4
☆

Bias-voltage induced absorption peaks in individual suspended carbon nanotubes* Takushi Uda, Masahiro Yoshida, Akihiro Ishii, Yuichiro K. Kato

48

1P-5

Photoluminescence studies on individual small-diameter carbon nanotubes* Shun Aota, Naoto Akizuki, Shinichiro Mouri, Xiaojun Wei, Takeshi Tanaka,
Hiromichi Kataura, Kazunari Matsuda, Yuhei Miyauchi

49

1P-6

Assigning (n,m ) of Random Single-Walled Carbon Nanotubes on Silicon Substrates by
Resonant Raman Spectroscopy* Daqi Zhang, Feng Yang, Yan Li, Juan Yang

50

1P-7

Trions in individual air-suspended carbon nanotubes* Alexander Popert, Masahiro Yoshida, Yuichiro K. Kato

51

1P-8
☆

電界下におけるCNT薄膜の電子物性* 石山 佑 , 岡田 晋

52

ナノチューブの応用
1P-9

高密度CNTフォレストの面内伝導による隣接CNTの電気的接触評価* 稲葉 優文 , 李 智宇 , 鈴木 和真 , 平野 優 , 渋谷 恵 , 明道 三穂 , 乗松 航 ,楠 美智子 , 川原田 洋

v53

２月２１日 （土）Overcoming the Quality-Quantity Trade-Off in Printing Carbon Nanotubes by Repetitive
Dispersion-Extraction Process* Hiroyuki Shirae, Dong Young Kim, Kei Hasegawa, Taishi Takenobu, Yutaka Ohno,
Suguru Noda

54

1P-11

基板上の単層カーボンナノチューブナノギャップの制御形成と電界放出* 大塚 慶吾 , 下村 勇貴 , 井ノ上 泰輝 , 千足 昇平 , 丸山 茂夫

55

1P-12

ベンジル誘導体からの光誘起ラジカル生成を利用したカーボンナノチューブの表面修飾* 高田 知哉 , 阿部 薫明

56

1P-13

ナノプレミキサーを利用したCNT, VGCFの新しい分散法* 生田 太郎 , 高塚 隆之

57

1P-10
☆

ナノチューブの生成と精製
1P-14☆

単一構造単層カーボンナノチューブ光学異性体の光学特性* 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

58

1P-15
☆

サブミリメータ長カーボンナノチューブの小粒径セラミックス担体上での流動層合成* 川端 孝祐 , 陳 忠明 , 長谷川 馨 , 大沢 利男 , 野田 優

59

1P-16

Controlled Growth of Single-Walled Carbon Nanotubes Using W-Co Catalyst at Different
Temperatures and Carbon Feedings* Feng Yang, Xiao Wang, Daqi Zhang, Juan Yang, Yan Li

60

1P-17

アセチレンブラック粒子上でのカーボンナノチューブ合成による複合化と、秒スケールでの反 61
応制御* 栗谷 匡明 , 長谷川 馨 , 原田 祐作 , 野田 優

☆
1P-18

FT-ICRによるエタノール分子およびアセトニトリル分子と遷移金属クラスターの反応分析* 小笠原 一樹 , 戸張 雄太 , 佐藤 仁紀 , 斎藤 真琴 , 千足 昇平 , 菅井 俊樹 ,

62

丸山 茂夫
1P-19
☆

単層カーボンナノチューブの火炎合成と、温度場・反応制御* 山口 麻衣 , 長谷川 馨 , 大沢 利男 , 野田 優

63

1P-20

An Effective Method for the Production of Single Walled Carbon Nanotubes by the Bipolar
Pulsed Arc Discharge Method* Kazi Hanium Maria, Tetsu Mieno

64

グラフェン生成1P-21☆

SiO2上h-BNの上面および周囲への数層～多層グラフェンの選択的析出* 山口 航太郎 , 長谷川 馨 , 野田 優

65

1P-22
☆

WS2/MoS2ヘテロ構造の二段階成長と評価* 森 勝平 , 真庭 豊 , 宮田 耕充

66

1P-23

分子蛍光性を持つグラフェン量子ドットの生成* 高橋 未咲 , 菅井 俊樹

67vi

２月２１日 （土）1P-24☆

2層グラフェンの作製及び電気特性* 星野 崚 , 木村 諒也 , 今井 健太郎 , 林 佑太郎 , 永田 知子 , 岩田 展幸 , 山本 寛

68

1P-25
☆

WドープNbS2原子層の成長と評価* 佐々木 将悟 , 真庭 豊 , 宮田 耕充

69

グラフェンの応用
1P-26

パイ共役高分子マイクロ球体の酸化グラフェンによる被覆* 愛敬 雄介 , 田畑 顕一 , 櫛田 創 , ダニエル ブラーム , 桑原 純平 , 神原 貴樹 ,近藤 剛弘 , 中村 潤児 , タン ダオ デュイ , 石井 智 , 長尾 忠昭 , アクセル ロルケ ,

70

山本 洋平
1P-27
☆

Direct and real-time TEM observation of aqueous solution sandwiched by graphene layers* Yuki Sasaki, Ryo Kitaura, Hisanori Shinohara

71

1P-28

グラフェンの近接効果における基板表面構造の影響
泉山 彰里 , * 高井 和之

72

グラフェンの物性
1P-29

単層遷移金属カルコゲナイドで構成されるファンデルワールスヘテロ構造の発光特性* 毛利 真一郎 , 小澤 大知 , 江田 剛輝 , 宮内 雄平 , 松田 一成

73

1P-30

Crossover between Localization and Delocalization in Edge-Disordered Graphene
Nanoribbons* 高島 健悟 , 山本 貴博

74

G* band Raman spectra of single layer graphene revisited* シレガール シヤハリル , ハスデオ ヘスキ , ヌグラハ アフマド , リウ ハシアン ,

75

☆
1P-31

齋藤 理一郎1P-32☆

コランニュレンポリマーの構造と電子構造* 成田 康平 , 岡田 晋

76

1P-33

微量水素終端したグラフェンにおけるスピン軌道相互作用と電子波位相破壊の抑制
上條 潤一 , * 片桐 勇人 , 加藤 建彰 , 中村 壮智 , 勝本 信吾 , 江澤 雅彦 ,Barbaros Özyilmaz, 春山 純志

77

1P-34

黒リン単原子層の特異な電子物性
片桐 勇人 , 牧野 竜也 , * 大畠 智佳 , 中村 壮智 , 勝本 信吾 , 江澤 雅彦 ,篠原 久典 , 春山 純志

78

1P-35

黒リン単原子層のエッジ磁性* 中西 雄大 , 大畠 智佳 , 岩城 稜磨 , 野村 くみ子 , 江澤 雅彦 , 篠原 久典 ,

79

その他

春山 純志

ナノチューブの物性
1P-36

イオン化ゲルゲートを配した金属伝導カーボンナノチューブ膜の電子物性* 本間 友大 , 菊地 涼 , 山田 俊矢 , 大畠 智佳 , 小谷田 美保 , 春山 純志 ,Apparao Rao

vii

80

２月２１日 （土）ナノ炭素粒子
1P-37

カーボンナノポットの生成に対する酸化グラフェンの光還元効果* 横井 裕之 , 畠山 一翔 , 松本 正吾 , 上田 茉子 , 谷口 貴章 , 鯉沼 陸央 ,

81

松本 泰道
1P-38
☆

ナノダイヤモンドの電子物性と構造及びそのフッ素化効果* 黄金 健太 , 東原 秀和 , 服部 義之 , 高井 和之

82

1P-39

自己摩耗法によるミクロダイヤモンドの球形化:予備的結果* 山野井 亮子 , 大澤 映二

83

1P-40

The Topological Stracture of Starfish Nanocarbon* Natsuki Namba, Yukihiro Takada, Kyoko Nakada

84

1P-41

Double resonance Raman modes in mono- and few-layer MoTe2* Huaihong Guo, Teng Yang, Mahito Yamamoto, Lin Zhou, Ryo Ishikawa, Keiji Ueno,
Kazuhito Tsukagoshi, Zhidong Zhang, M. S. Dresselhaus, R. Saito

85

1P-42

Improving the property of electric double layer capacitor by using activated carbon
nanoballoon* Akitaka Mizutani, Yoshiyuki Suda, Hirofumi Takikawa, Hitoshi Ue, Kazuki Shimizu,
Yoshito Umeda

86

1P-43

Spontaneous antiferromagmetism in the α-graphyne single layer* Teng Yang, Baojuan Dong, Huaihong Guo, R. Saito, Zhidong Zhang

87

1P-44

亜鉛をドープした酸化鉄ナノチューブと有機金属ハライドぺロブスカイト複合膜の分光感度
特性* 小杉 優太 , 楠田 寛之 , 斉木 彩乃 , 坂東 俊治

88

その他

＞＞＞＞＞＞＞ 休憩 ( 17:30-18:00 ) ＜＜＜＜＜＜＜チュートリアル ( 18:00-19:30 )電子顕微鏡によるナノカーボン構造評価* 末永 和知viii

２月２２日 （日）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
特別講演 ( 9:00-9:30 )2S-4

STUDIES ON SWNT BUNDLING* Esko I. Kauppinen

4

一般講演 ( 9:30-10:15 )ナノチューブの応用 ・ ナノチューブの生成と精製
2-1

フレキシブル有機太陽電池のための電子ブロック透明電極としての酸化モリブデンでドープした直接・乾式堆積による単層カーボンナノチューブ膜* 田 日 , Kehang Cui, 千葉 孝昭 , Anton Anisimove, Albert Nasibulin, Esko Kauppinen,
丸山 茂夫 , 松尾 豊

20

2-2

単層カーボンナノチューブカソードを用いたペロブスカイト型太陽電池の評価* 千葉 孝昭 , 坂口 貴寛 , Nasiblin Albert, Kauppinen Esko, 項 榮 , 千足 昇平 ,

21

丸山 茂夫
2-3

SiC表面分解法により形成した カーボンナノチューブフォレストからの無触媒CVD成長* 平野 優 , 稲葉 優文 , 渋谷 恵 , 鈴木 和真 , 李 智宇 , 明道 三穂 , 平岩 篤 ,乗松 航 , 楠 美智子 , 川原田 洋

22＞＞＞＞＞＞＞ 休憩 ( 10:15-10:30 ) ＜＜＜＜＜＜＜特別講演 ( 10:30-11:00 )2S-5

グラフェンナノリボンの戦略的 ボトムアップ合成への提案* 山田 容子 , 林 宏暢

5

一般講演 ( 11:00-12:00 )フラーレンの化学 ・ 金属内包フラーレン ・ フラーレン
2-4分子性フラーライド塩[lucigenin]C60の構造と電子状態

23* 森山 広思 , 山本 翔平 , 森 初果 , 与座 健治 , 原 英之
2-5

電子ドナー性物質および極性溶媒を用いた金属内包フラーレン分離法* 千葉 和喜 , 秋山 和彦 , 久冨木 志郎

24

2-6

C60への多段階環化付加反応の振電相互作用密度解析* 春田 直毅 , 佐藤 徹 , 田中 一義

25

2-7

レーザー蒸発条件下における直線炭素分子からフラーレンまで* 若林 知成 , 和田 資子 , 森澤 勇介 , 遠藤 瞳 , 田口 裕貴 , 松本 淳 , 兒玉 健 ,阿知波 洋次 , 城丸 春夫

26＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜
大澤賞・飯島賞・若手奨励賞の授賞式 ( 13:15-14:00 )ix

２月２２日 （日）ポスタープレビュー ( 14:00-15:00 )ポスターセッション ( 15:00-16:45 )フラーレンの化学（☆） 若手奨励賞候補

2P-1+(5,6)-および(6,6)-[Li @C61Ph2]NTf2–のそれぞれの異性体についての単離とキャラクタリゼー 89
ション* 岡田 洋史 , 川上 裕貴 , 青柳 忍 , 松尾 豊

2P-2

オキサゾリノ[70]フラーレン誘導体の構造変化を利用した有機太陽電池における開放電圧向 90
上へのアプローチ* 松尾 豊 , Shu-Hui Li, Zong-Jun Li, 中川 貴文 , James Ryan, Xiang Gao

2P-3

1
固体 H-NMR分光法による水酸化フラーレン固体のプロトンダイナミクスに与える水分子の影 91
響* 佐野 喜章 , 緒方 啓典

金属内包フラーレン
2P-4
☆

2P-5

+

Photoinduced Electron Transfer from Anionic Phthalocyanines to Li @C60 and Light-Energy
Conversion* Yuki Kawashima, Kei Ohkubo, Vicente Manuel Blas-Ferrando, Hayato Sakai,
Enrique Font-Sanchis, Javier Ortíz, Fernando Fernández-Lázaro, Taku Hasobe,Ángela Sastre-Santos, Shunichi Fukuzumi

92

Addition Reactions of Trimetallic Nitride Template Endohedral Metallofullerenes with
Disilirane and Digermirane* 宮部 恭輔 , 加固 昌寛 , 佐藤 久美子 , 鈴木 光明 , 溝呂木 直美 ,Marilyn M. Olmstead, Alan L. Balch, Wei-Wei Wang, 永瀬 茂 , 赤阪 健

93

フラーレン
2P-6
☆

ナノサターンのエネルギー論* 木暮 聖太 , 大町 遼 , 篠原 久典 , 岡田 晋

94

2P-7

電場下における水内包フラーレンのエネルギー論* 反町 純也 , 岡田 晋

95

2P-8
☆

Absolute yield of fullerene formed by graphite laser ablation at room temperature* Hitomi Endo, Yuki Taguchi, Jun Matsumoto, Tomonari Wakabayashi, Takeshi Kodama,
Yohji Achiba, Haruo Shiromaru

96

ナノチューブの物性
2P-9

カイラリティ分離したDNA修飾ナノチューブを用いた薄膜トランジスタの作製と評価* 桑原 有紀 , 二瓶 史行 , 大森 滋和 , 斎藤 毅

97

2P-10

潰れたカーボンナノチューブの安定性と電子構造* 西川 潤平 , 斎藤 晋

98

2P-11
☆

単層カーボンナノチューブの化学修飾による電子準位への影響(1) ： 実験による解明* 白石 智也 , 秋月 直人 , 宮内 雄平 , 松田 一成 , 中嶋 直敏

99x２月２２日 （日）2P-12

Effect of Chemical Doping on the Electronic States of Single-Walled Carbon Nanotubes:
Theory* Gergely Juhasz, 白石 智也 , 中嶋 直敏

100

2P-13

Ab initio calculation for electronic bands of CNT in which the chain of sulphur is inserted* Yuhei Natsume101

ナノチューブの応用
2P-14

電気二重層キャリア注入により極性制御された半導体型単層カーボンナノチューブ熱電デバイスの作製* 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

102

2P-15
☆

医療応用にむけた単層カーボンナノチューブの水溶化と細胞毒性評価* 中村 圭祐 , 趙 利 , 秦 紅梅 , 青沼 秀児 , 木村 隆英 , 小松 直樹

103

2P-16

Gate-controlled generation of optical pulse trains using individual carbon nanotubes
Ming Jiang, Yusuke Kumamoto, * Akihiro Ishii, Masahiro Yoshida, Takashi Shimada,Yuichiro K. Kato

104

2P-17

Electroluminescence from individual air-suspended carbon nanotubes within split-gatestructures* Noriyuki Higashide, Ming Jiang, Takushi Uda, Masahiro Yoshida, Akihiro Ishii,
Yuichiro K. Kato

105

ナノチューブの生成と精製
2P-18ゲルを用いた単層カーボンナノチューブの分離における酸化剤の効果* 平野 篤 , 田中 丈士 , 片浦 弘道

106

2P-19

Optimization of the synthesis parameters of Carbon Nanotube (CNT) forest using the
Taguchi Method* パンダー アダム , 古田 寛 , 八田 章光

107

木質バイオエタノールからの単層カーボンナノチューブの合成* 荒木 拓馬 , 本田 淳 , 薮下 侑平 , 村上 俊也 , 木曽田 賢治 , 山口 真範 ,

108

☆
2P-20

伊東 千尋
2P-21
☆

Nitrogen doping of single-walled carbon nanotubes prepared from fluorinated SWCNTs using 109
ammonia gas* Koji Yokoyama, Yoshinori Sato, Kazutaka Hirano, Kenichi Motomiya, Kazuyuki Tohji,
Yoshinori Sato2P-22

欠陥のない単層カーボンナノチューブ成長の分子動力学シミュレーション* 吉川 亮 , 高木 勇海 , 千足 昇平 , 丸山 茂夫

110

2P-23

Automatic Gradient Elution Gel Filtration for Separation of Metal and Semiconducting
Single-Wall Carbon Nanotubes* Boanerges Thendie, Haruka Omachi, Ryo Kitaura, Yasumitsu Miyata, Hisanori Shinohara

111

超分子ポリマーによる半導体性カーボンナノチューブの選択的かつ可逆的抽出* 利光 史行 , 中嶋 直敏

112

☆
2P-24

xi

２月２２日 （日）内包ナノチューブ
2P-25

Structural transformation of tellurium encapsulated in the inner space of carbon nanotubes
depending on tube diameter* 小林 慶太 , 保田 英洋

113

2P-26
☆

カーボンナノチューブの内部空間を鋳型にしたダイヤモンド分子鎖の合成* 中西 勇介 , 大町 遼 , Fokina Natalie A., 北浦 良 , Schreiner Peter R.,
Dahl Jeremy E. P., Carlson Robert M. K., 篠原 久典

114

2P-27

カーボンナノチューブに内包された複数パイ共役系オリゴマーの特性に関する量子化学
計算* 湯村 尚史 , 山下 裕生

115

グラフェン生成2P-28☆

エピタキシャル銅表面における単層グラフェン成長のダイナミクス* 太田 勇二郎 , 水野 清義 , 日比野 浩樹 , 河原 憲治 , 滝沢 里奈 , 辻 正治 ,

116

吾郷 浩樹
2P-29

微小酸化グラフェンの作製とそのバイオ分野への応用可能性* 張 民芳 , 岡崎 俊也 , 飯泉 陽子 , 都 英二郎 , 飯島 澄男 , 湯田坂 雅子

117

2P-30
☆

金属融解によるCVDグラフェンの絶縁性基板上への直接転写* 井上 凌介 , 真庭 豊 , 宮田 耕充

118

2P-31

反応性指標としての振電相互作用密度: グラフェンフラグメントのDiels-Alder反応への応用
春田 直毅 , * 佐藤 徹 , 田中 一義

119

2P-32
☆

グラファイト上における高品質単層WS2の成長* 小林 佑 , 佐々木 将悟 , 森 勝平 , 日比野 浩樹 , 渡邊 賢司 , 谷口 尚 , 真庭 豊 ,

120

宮田 耕充

グラフェンの物性
2P-33

アームチェア型グラフェンナノリボンによる光電場振幅変調：第一原理計算による研究* Yoshiyuki Miyamoto, Hong Zhang

121

2P-34

Spectroscopic studies of single layer molybdenum ditelluride* Sandhaya Koirala, Daichi Kozawa, Shinichiro Mouri, Yuhei Miyauchi, Kazunari Matsuda

122

2P-35

単層遷移金属ダイカルコゲナイドのゼーベック効果* 金橋 魁利 , 蒲 江 , Nguyen Thanh Cuoug, Lain-Jong Li, 岡田 晋 , 太田 裕道 ,

123

竹延 大志
2P-36

金属電極間に架橋されたグラフェンの電気伝導特性* 實宝 秀幸 , 岡田 晋 , 大淵 真理

124

2P-37

グラフェンにおけるフォノンの非調和性と熱伝導* 水野 将志 , 齋藤 理一郎

125

2P-38

エピタキシャルグラフェンの構造と電子物性および分子吸着効果* 中本 圭亮 , 赤津 隆 , 高井 和之

126

xii

２月２２日 （日）2P-39

欠陥グラフェン吸着によるグラフェンのバンドギャップ形成* 岸本 健 , 岡田 晋

127

2P-40

Fabrication and In-situ TEM Characterization of Freestanding Graphene Nanoribbons
Devices* Qing Wang, Ryo Kitaura, Shoji Suzuki, Hisanori Shinohara

128

☆

その他
2P-41

グラファイト面に垂直なガスフローによって運ばれるグラファイトレーザーアブレーション生成 129
物* 田口 裕貴 , 遠藤 瞳 , 阿部 百合香 , 松本 淳 , 若林 知成 , 兒玉 健 ,阿知波 洋次 , 城丸 春夫

2P-42
☆

二次元結晶の相転移制御と新機能* 吉田 将郎 , 張 奕勁 , 叶 劍挺 , 鈴木 龍二 , 今井 康彦 , 木村 滋 , 藤原 明比古 ,

130

岩佐 義宏
2P-43

Structure and Spectra of Polyyne-Iodine Complex* 長島 大 , 佐藤 徹 , 岩原 直也 , 田中 一義 , 和田 資子 , 若林 知成

131

2P-44

Ambipolar transistor and superconductivity in transition metal dichalcogenides* Wu Shi, Jianting Ye, Yijing Zhang, Ryuji Suzuki, Masaro Yoshida, Naoko Inoue, Yu Saito,
Yoshihiro Iwasa

132

特別講演 ( 16:45-17:15 )2S-6

Single carbon-nanotube photonics and optoelectronics* 加藤 雄一郎

6

一般講演 ( 17:15-18:45 )ナノチューブの物性
2-8

単層カーボンナノチューブの光学遷移における塩基配列に依存したDNAの吸着効果* 伊藤 雅浩 , 伊藤 悠介 , 加藤 大樹 , 梅村 和夫 , 本間 芳和

27

2-9

ドープされた原子層物質における電子構造と極性* 斎藤 晋 , 是常 隆 , 藤本 義隆

28

2-10

Electronic States of Flattened Carbon Nanotubes: Effects of tube chirality and displacement* 中西 毅 , 安藤 恒也

29

2-11

Coherent and squeezed phonons in single wall carbon nanotubes* ヌグラハ アフマド , ハスデオ エッドウィ , 齋藤 理一郎

30

2-12

Stark effect of excitons in individual air-suspended carbon nanotubes* Masahiro Yoshida, Yusuke Kumamoto, Akihiro Ishii, Akio Yokoyama, Yuichiro K. Kato

31

2-13

Exciton diffusion, end quenching, and exciton-exciton annihilation in individual air-suspended 32
carbon nanotubes* Akihiro Ishii, Masahiro Yoshida, Yuichiro K. Katoxiii

２月２３日 （月）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
特別講演 ( 9:00-9:30 )3S-7

グラフェン電界効果トランジスタ ―コンダクタンス法によるギャップ内準位解析―* 長汐 晃輔

7

一般講演 ( 9:30-10:30 )グラフェンの物性 ・ その他
3-1電極接合に起因する二層グラフェンのバンドギャップ* 野内 亮33

3-2

還元した酸化グラフェン薄膜のバンドライク伝導* 根岸 良太 , 赤堀 誠志 , 山田 省二 , 伊藤 孝寛 , 渡辺 義夫 , 小林 慶裕

34

3-3

Circularly polarized luminescence from lateral TMD p-i-n junctions* Yijin Zhang, Masaru Onga, Yoshihiro Iwasa

35

3-4

Mechanical exfoliation and van der Waals assembly of layered ferromagnetic dichalcogenide
FexTaS2* 荒井 美穂 , 守谷 頼 , 矢吹 直人 , 増渕 覚 , 上野 啓司 , 町田 友樹

36＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜特別講演 ( 10:45-11:15 )3S-8

ナノカーボン物質・原子層物質のナノ光科学とその応用* 松田 一成

8

一般講演 ( 11:15-12:00 )グラフェンの物性 ・ その他
3-5

単層黒リン”phosphorene”の光学特性* 中村 隆 , 小澤 大知 , 毛利 真一郎 , 松田 一成

37

3-6

遷移金属ダイカルコゲナイドにおけるバレー分極緩和の理論的研究* 小鍋 哲 , 岡田 晋

38

3-7

3R-MoS2の励起子* 鈴木 龍二 , Sandor Bordacs, 明石 遼介 , 越智 正之 , 有田 亮太郎 , 十倉 好紀 ,

39

岩佐 義宏

＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜xiv

２月２３日 （月）ポスタープレビュー ( 13:15-14:15 )ポスターセッション ( 14:15-16:00 )フラーレンの応用（☆） 若手奨励賞候補

3P-1

Solid-State NMR Studies on the Aggregated Structures of Organic Bulk Heterojunction Solar 133
Cells with Solvent Additives(II)* Saki Kawano, Hironori Ogata

3P-2

低いLUMO準位を有するスピロ-1,3-ジオキソラノフラーレンの開発とローバンドギャップポリ
マーを用いた有機薄膜太陽電池への応用* 三木江 翼 , 佐伯 昭紀 , 伊熊 直彦 , 小久保 研 , 関 修平

134

スタック構造を用いた半透明タンデム有機薄膜太陽電池の作製* 藤井 俊治郎 , 田中 丈士 , 片浦 弘道

135

☆
3P-3

金属内包フラーレン
3P-4[5,6]-pyrrolidino-Sc3N@I h -C80ジアステレオマーの単離とキャラクタリゼイション

136* 前田 優 , 木村 仁士 , 上田 ちひろ , 鈴木 光明 , 山田 道夫 , Nikolaos Karousis,
Nikos Tagmatarichis, Marilyn M Olmstead, Alan L Balch, Wei-Wei Wang, 永瀬 茂 ,

赤阪 健
3P-5

Reactions of Trimetallic Nitride Template Endohedral Metallofullerenes with
Silacyclopropanes* 南 和也 , 杉浦 健 , 加固 昌寛 , 佐藤 久美子 , 永瀬 茂 , 赤阪 健

137

3P-6

Ionic Donor-Acceptor Supramolecules: Complexation of Molecular Nanocarbons with
Cationic Li+@C60* Hiroshi Ueno, Taishi Nishihara, Katsuma Matsui, Yasutomo Segawa, Kenichiro Itami

138

ナノチューブの物性
3P-7

単層カーボンナノチューブの特性に対する純度の量的重要性* 松本 尚之 , Chen Guohai , 湯村 守雄 , フタバ ドン , 畠 賢治

139

3P-8
☆

バンドルしたSWNTのRBM周波数に関する分子動力学計算* 紅谷 篤史 , 本間 直樹 , 千足 昇平 , 本間 芳和 , 山本 貴博

140

3P-9

Molecular structure of chalcogen encapsulated in single-walled carbon nanotubes studied bymolecular dynamics simulations* Yutaka Sato, Yosuke Kataoka, Hironori Ogata

141

3P-10

分子動力学シミュレーションによる単層カーボンナノチューブに内包されたアルカリハライドの局所構造と特性* 横倉 瑛太 , 片岡 洋右 , 緒方 啓典

142

ナノチューブの応用
3P-11

Ultralow mode-volume photonic crystal nanobeam cavities for high-efficiency coupling toindividual carbon nanotube emitters* Hidenori Machiya, Ryohei Miura, Saneyuki Imamura, Ryuichi Ohta, Akihiro Ishii,
Xuqing Liu, Takashi Shimada, Satoshi Iwamoto, Yasuhiko Arakawa, Yuichiro K. Kato

xv

143

２月２３日 （月）Characteristic variation of thin-film transistors based on purified semiconducting carbon
nanotubes* Jun Hirotani, Ryotaro Matsui, Shigeru Kishimoto, Yutaka Ohno

144

3P-13

Thermoelectric power of carbon nanotubes from first principles* グエン タン フン , 齋藤 理一郎

145

3P-14

Effect of TiO2 coating on field emission properties of carbon nanotube by in-situ transmission 146
electron microscopy* 松田 薫洋 , 中原 仁 , 安坂 幸師 , 齋藤 弥八

3P-12
☆

☆
3P-15

Light-emitting Electrochemical Cell with Few-Walled Carbon-Nanotube Electrodes* 中山 航 , 白江 宏之 , 野田 優 , 坂上 知 , 竹延 大志

147

ナノチューブの生成と精製
3P-16

高真空アルコールガスソース法によるRh触媒からの単層カーボンナノチューブ成長* 小澤 顕成 , 才田 隆広 , 成塚 重弥 , 丸山 隆浩

3P-17

Relationship between Chirality Control of Single-Walled Carbon Nanotube and Wavelength of 149
the Irradiated Free Electron Laser* 吉田 圭佑 , 津田 悠作 , 川口 大貴 , 永田 知子 , 岩田 展幸 , 山本 寛

☆

148

3P-18

Synthesis of single walled carbon nanotubes by using sputtered Co/Cu and Co/W as catalyst* Hua An, Kehang Cui, Rong Xiang, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama

3P-19

ホットウォール型化学気相成長装置と自由電子レーザーを用いた単層カーボンナノチューブ 151
カーボンの面内配向成長とカイラリティ制御* 川口 大貴 , 吉田 圭介 , 永田 知子 , 岩田 展幸 , 山本 寛

☆
3P-20

FT-ICR質量分析器によるH2Oとの反応におけるコバルトクラスター上の水素原子の効果の解析* 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 ,

150

152

菅井 俊樹
3P-21
☆

Synthesis of carbon nanotubes by means of “molecular template epitaxial growth” approach* Liu Hong, Akira Takakura, Lawrence Scott, Yuhei Miyauchi, Kenichiro Itami

153

3P-22

フラーレンを有するカルバゾール−フルオレン共重合体による半導体性単層カーボンナノ
チューブの可溶化および複合化* 利光 史行 , 小澤 寛晃 , 中嶋 直敏

154

ナノホーン
3P-23

Cytotoxicity of Carbon Nanohorns Enhanced by Too Much PLPEG* Maki Nakamura, Yoshio Tahara, Shinsuke Fukata, Minfang Zhang, Sumio Iijima,
Masako Yudasaka

155

3P-24

ホウ素と窒素をドープしたカーボンナノホーン集合体の電気化学特性* 弓削 亮太 , 坂東 俊治 , 湯田坂 雅子 , 當山 清彦 , 飯島 澄男 , 田村 宜之 ,

156

眞子 隆志

xvi

２月２３日 （月）グラフェン生成3P-25☆

グラフェンの亀裂におけるジグザグ端の選択的な形成* 藤原 美帆 , 井上 凌介 , 真庭 豊 , 篠原 久典 , 宮田 耕充

157

3P-26

炭素含有ガス不使用の熱CVD法によるグラフェン生成法* 森迫 詩陽 , 辻本 茉里奈 , 橘 勝

158

3P-27
☆

Cu-Ni合金薄膜上における非常に均一な二層グラフェン* 竹崎 悠一郎 , 日比野 浩樹 , 辻 正治 , 吾郷 浩樹

159

3P-28

Al2O3バリア層、Auキャップ層を用いた高品質多層グラフェンの析出法におけるアニール
温度依存性* 山田 純平 , 鈴木 学 , 上田 悠貴 , 丸山 隆浩 , 成塚 重弥

160

グラフェンの応用
3P-29☆

酸化グラフェン / ナノグラフェンにおける磁気的評価* 山科 智貴 , 井坂 琢也 , 井上 和美 , 松尾 吉晃 , 高井 和之

161

3P-30

水溶液中でシリコン酸化膜上グラフェンの不要ひずみとドーピングを抑える前処理法
増田 祥也 , * 佐野 正人

162

3P-31
☆

単層WSe2を用いた電気二重層発光ダイオード* 蒲 江 , 藤本 太陽 , Huang Jing-Kai, Li Lain-Jong, 坂上 知 , 竹延 大志

163

グラフェンの物性
3P-32

グラフェンＦＥＴにおけるヒドラジン分子吸着効果* 梅原 太一 , 高井 和之

164

3P-33

Kohn anomaly meets Fano resonance in G and G’ bands Raman spectra of graphene* ハスデオ エツドウイ , ヌグラハ アフマド , 齋藤 理一郎

165

3P-34

Surface plasmon excitations in graphene* Shoufie Ukhtary, Eddwi Hasdeo, Ahmad Nugraha, Riichiro Saito

166

3P-35
☆

Interlayer exciton in atomically thin heterostructures of transition metal dichalcogenides* Daichi Kozawa, Ivan Verzhbitskiy, Alexandra Carvalho, A. H. Castro Neto,
Kazunari Matsuda, Goki Eda

167

3P-36

Optical characteristic of CVD grown monolayer WSe2 under high-density carrier doping* 松木 啓一郎 , Jiang Pu, 松田 一成 , Lain-Jong Li, 竹延 大志

168

3P-37

Photon energy dependence of angle resolved photoemission spectroscopy in graphene* アイリヤ ポウルヤ , ハスデオ ヘスキ , ヌグラハ アフマド , 田中 慎一郎 ,169

齋藤 理一郎3P-38☆

グラフェンナノリボンのNFE状態に対する局所電界効果* 山中 綾香 , 岡田 晋

xvii

170

２月２３日 （月）Evaluation of Graphene Quality by Raman Rapid Chemical Imaging
Mamoru Komatsu, Kaori Umeyama, * Noriaki Nishikawa, Mark Wall

171

3P-40

ヘテロ積層デバイスを目指した高品質h-BNシートのCVD成長* 内田 勇気 , 祝迫 佑 , 辻 正治 , 吾郷 浩樹

172

3P-41
☆

WSe2における熱電特性の電界制御* 飯塚 貴彦 , 吉田 将郎 , 清水 直 , 岩佐 義宏

173

3P-42

CVD合成された多層MoS2・WS2薄膜の光電気化学特性* 本間 光太郎 , 河合 英輝 , 柳 和宏

174

3P-39

その他

ナノ環境と安全評価
3P-43

Preparation of Nb2O5- Graphene Nanocomposites and Kinetics for Photocatalytic Degradation 175
of Organic Dyes
Hae Soo Park, * Jeong Won Ko, Weon Bae Ko

特別講演 ( 16:00-16:30 )3S-9

9

高品質原子層のCVD成長と機能開拓* 北浦 良一般講演 ( 16:30-17:30 )グラフェン生成 ・ その他 ・ グラフェンの応用
3-8

CVD synthesis of single-crystal single-layer graphene and bi-layer graphene from ethanol* Xiao Chen, Kohei Tsushima, Masaki Sota, Rong Xiang, Shohei Chiashi, Shigeo Maruyama

40

3-9

Magnetic Ordering of Two-dimensional Networks of Fused C36 Polyhedra under an Electric
Field* 丸山 実那 , 岡田 晋

41

3-10

炭素材料へのPt-Ru金属ナノ粒子の担持および電着条件の違いにおける電極触媒特性の評価* 吉竹 晴彦 , 早瀬 勝平 , 王 志朋 , 緒方 啓典

42

3-11

Hexahydroxytriphenylene and its derivetives for graphene exfoliation in aqueous and organicmedia* 劉 剛 , 木村 隆英 , 小松 直樹

43

xviii

February 21st, Sat.
Special Lecture : 25 min (Presentation) + 5 min (Discussion)
General Lecture : 10 min (Presentation) + 5 min (Discussion)
Poster Preview : 1 min (Presentation)
Special Lecture ( 9:30-10:00 )1S-1

What we know about chirality-controlled growth of single-walled carbon nanotubes* Yan Li

1

General Lecture ( 10:00-10:30 )Formation and purification of nanotubes ・ Endohedral nanotubes
1-1

Co-existence of two tube-growth processes by Rh/Pd catalyst* Yohji Achiba, Takuya Kodama, Takeshi Kodama, Kenro Hashimoto, Haruo Shiromaru

11

1-2

Ionic atomic chains inside carbon nanotubes* Ryosuke Senga, Kazu Suenaga

12＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Special Lecture ( 10:45-11:15 )1S-2

Double-walled carbon nanotube transparent conductive film for next generation flexible
device* Naoki Imazu, Takashi Oi, Hidekazu Nishino, Kenichi Sato, Osamu Watanabe,
Shiro Honda, Motoyuki Suzuki

2

General Lecture ( 11:15-12:00 )Formation and purification of nanotubes ・ Applications of nanotubes
1-3

Selective Separation of Semiconducting Single-Walled Carbon Nanotubes Using Flavin
Compounds* Masashi Fukuzawa, Fumiyuki Toshimitsu, Yuichi Kato, Naotoshi Nakashima

13

1-4

Role of cholate for chirality selection of SWCNTs* Yohei Yomogida, Mayumi Tsuzuki, Xiaojun Wei, Atsushi Hirano, Shunjiro Fujii,
Takeshi Tanaka, Hiromichi Kataura

14

1-5

Development of thermoelectric device using cobaltocene-encapsulated carbon nanotubes* Tsuyohiko Fujigaya, Takahiro Fukumaru, Naotoshi Nakashima

15＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜Special Lecture ( 13:15-13:45 )1S-3

Real-time observation of graphene growth by thermal emission microscopy* Koichiro Saiki, Tomo-o Terasawa, Sho Katoxix

3

February 21st, Sat.
General Lecture ( 13:45-14:45 )Applications of graphene ・ Nanohorns ・ Carbon nanoparticles
1-6

Modification of the local structure of carbon materials by ion irradiation and the support
properties of Pt nanoparticles by one-step electro deposition method* Shohei Hayase, Haruhiko Yoshitake, Tomoaki Nishimura, Wang Zhipeng, Hironori Ogata

16

1-7

Preparation of Boron Nitride Containing Carbon Nanohorn for Boron Neutron Capture
Therapy* Yoko Iizumi, Toshiya Okazaki, Minfanf Zhang, Ryota Yuge, Toshinari Ichihashi,
Maki Nakamura, Yuzuru Ikehara, Sumio Iijima, Masako Yudasaka

17

1-8

Multifunctional carbon nanohorn complexes for cancer treatment* Eijiro Miyako, Svetlana Chechetka, Benoit Pichon, Minfang Zhang, Masako Yudasaka,
Sylvie Bégin-Colin, Alberto Bianco

18

1-9

Comparative LDI analysis of nanodiamonds from detonation synthesis and pre-solar
carbonaceous meteorites* Toshihiko Tanaka, Ryoko Yamanoi, Eiji Osawa

19

Poster Preview ( 14:45-15:45 )Poster Session ( 15:45-17:30 ) （☆）Candidates for the Young Scientist Poster Award
Other topics
1P-1

Charge analyses on particles by Ion Mobility Measurement* Toshiki Sugai, Yasuhiro Hiroshiba, Matsubayashi Hironobu, Kazuki Mimuro,
Ryota Jinnouchi

45

Environmental/Safety characterization of nanomaterials
1P-2

Exciton-photon interaction in tip enhanced Raman spectroscopy of single wall carbon
nanotubes* Thomas Czank, Pourya Airya, Riichiro Saito

46

Properties of nanotubes
1P-3

Ab Initio Study on Oxidation of (5,4), (6,4), (6,5), and (8,6) Carbon Nanotubes* Mari Ohfuchi

47

1P-4
☆

Bias-voltage induced absorption peaks in individual suspended carbon nanotubes* Takushi Uda, Masahiro Yoshida, Akihiro Ishii, Yuichiro K. Kato

48

1P-5

Photoluminescence studies on individual small-diameter carbon nanotubes* Shun Aota, Naoto Akizuki, Shinichiro Mouri, Xiaojun Wei, Takeshi Tanaka,
Hiromichi Kataura, Kazunari Matsuda, Yuhei Miyauchi

49

1P-6

Assigning (n,m ) of Random Single-Walled Carbon Nanotubes on Silicon Substrates by
Resonant Raman Spectroscopy* Daqi Zhang, Feng Yang, Yan Li, Juan Yang

50

1P-7

Trions in individual air-suspended carbon nanotubes* Alexander Popert, Masahiro Yoshida, Yuichiro K. Kato

51

xx

February 21st, Sat.
1P-8☆

Electronic properties of CNT thin films under an electric field* U Ishiyama, Susumu Okada

52

Applications of nanotubes
1P-9

Electrical contact of parallel adjacent CNTs estimated from in-plane conductivity of dense
CNT forest on silicon carbide* Masafumi Inaba, Chih-Yu Lee, Kazuma Suzuki, Yu Hirano, Megumi Shibuya,
Miho Myodo, Wataru Norimatsu, Michiko Kusunoki, Hiroshi Kawarada

53

1P-10

Overcoming the Quality-Quantity Trade-Off in Printing Carbon Nanotubes by Repetitive
Dispersion-Extraction Process* Hiroyuki Shirae, Dong Young Kim, Kei Hasegawa, Taishi Takenobu, Yutaka Ohno,
Suguru Noda

54

1P-11

Controlled formation of nanogaps of single-walled carbon nanotubes on substrates and fieldemission from the nanogaps* Keigo Otsuka, Yuuki Shimomura, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama

55

1P-12

Surface modification of carbon nanotubes utilizing photo-induced radical formation frombenzyl derivatives* Tomoya Takada, Shigeaki Abe

56

1P-13

The new method for CNT and VGCF dispersion by Nano Premixer* Taro Ikuta, Takayuki Takatsuka

57☆

Formation and purification of nanotubes
1P-14☆

Optical Properties of Optical Isomer of Single-Chirality SWCNTs* Xiaojun Wei, Mayumi Tsuzuki, Takuya Hirakawa, Yohei Yomogida, Atsushi Hirano,
Shunjiro Fujii, Takeshi Tanaka, Hiromichi Kataura

58

1P-15

Synthesis of Submillimeter-Long Carbon Nanotubes on Small Ceramic Powders by Fluidized
Bed* Kosuke Kawabata, Zhongming Chen, Kei Hasegawa, Toshio Osawa, Suguru Noda

59

1P-16

Controlled Growth of Single-Walled Carbon Nanotubes Using W-Co Catalyst at Different
Temperatures and Carbon Feedings* Feng Yang, Xiao Wang, Daqi Zhang, Juan Yang, Yan Li

60

1P-17

Growing carbon nanotubes on acetylene black particles to form their hybrid and controlling
the reaction on a few second time scale* Masaaki Kuriya, Kei Hasegawa, Yusaku Harada, Suguru Noda

61

FT-ICR study of chemical reaction of ethanol and acetonitrile molecules on transition metalclusters* Kazuki Ogasawara, Yuta Tobari, Yoshinori Sato, Makoto Saito, Shohei Chiashi,
Toshiki Sugai, Shigeo Maruyama

62

☆

☆
1P-18

xxi

February 21st, Sat.
1P-19
☆
1P-20

Flame Synthesis of Single-Wall Carbon Nanotube and Control over the Temperature Field
and Reactions* Mai Yamaguchi, Kei Hasegawa, Toshio Osawa, Suguru Noda

63

An Effective Method for the Production of Single Walled Carbon Nanotubes by the Bipolar
Pulsed Arc Discharge Method* Kazi Hanium Maria, Tetsu Mieno

64

Graphene synthesis
Selective precipitation of few/multi-layer graphene on/around h-BN on SiO2 from metalcarbon films* Kohtaro Yamaguchi, Kei Hasegawa, Suguru Noda

65

1P-22
☆

Two-step growth and characterization of WS2/MoS2 heterostructures* Shohei Mori, Yutaka Maniwa, Yasumitu Miyata

66

1P-23

Production of graphene quantum dots with molecule-like fluorescence* Misaki Takahashi, Toshiki Sugai

67

1P-24
☆

Growth of bilayer graphene and its electric property* Ryo Hoshino, Ryoya Kimura, Kentaro Imai, Yutaro Hayashi, Tomoko Nagata,
Nobuyuki Iwata, Hiroshi Yamamoto

68

1P-25
☆

Growth and characterization of W-doped NbS2 atomic layers* Shogo Sasaki, Yutaka Maniwa, Yasumitsu Miyata

69

1P-21
☆

Applications of graphene
1P-26

π-Conjugated Polymer Microspheres Covered by Graphene Oxide* Yusuke Aikyo, Kenichi Tabata, Soh Kushida, Daniel Braam, Junpei Kuwabara,
Takaki Kanbara, Takahiro Kondo, Junji Nakamura, Thang Dao Duy, Satoshi Ishii,
Tadaaki Nagao, Axel Lorke, Yohei Yamamoto

70

1P-27
☆

Direct and real-time TEM observation of aqueous solution sandwiched by graphene layers* Yuki Sasaki, Ryo Kitaura, Hisanori Shinohara

71

1P-28

Influence of the surface structure of substrate for proximity effect on Graphene
Akinori Izumiyama, * Kazuyuki Takai

72

Properties of graphene
1P-29

Photoluminescence Properties of van der Waals Hetero Structure Composed of Monolayer
Transition Metal Dichalcogenides* Shinichiro Mouri, Daichi Kozawa, Goki Eda, Yuhei Miyauchi, Kazunari Matsuda

73

1P-30

Crossover between Localization and Delocalization in Edge-Disordered Graphene
Nanoribbons* Kengo Takashima, Takahiro Yamamoto

74

☆

xxii

February 21st, Sat.
*

1P-31

G band Raman spectra of single layer graphene revisited* Syahril Siregar, Hesky Hasdeo, Ahmad Nugraha, Hsiang Liu, Riichiro Saito

75

1P-32
☆

Geometric and Electronic Structures of Corannulene Polymers* Kohei Narita, Susumu Okada

76

1P-33

Electron-wave dephasing suppressed by spin–orbit interaction in slightly hydrogenatedgraphene within a topological insulating regime
Junichi Kamijo, * Yuto Katagiri, Tateaki Kato, Taketomo Nakamura, Shingo Katumoto,Motohiko Ezawa, Barbaros Özyilmaz, Junji Haruyama

77

Other topics
1P-34

Anomalous electronic properties of mono-atomic layer of black phosphorus
Yoto Katagiri, Tatuya Makino, * Tika Ohata, Taketomo Nakamura, Shingo Katumoto,Motohiko Ezawa, Hisanori Shinohara, Junji Haruyama

78

1P-35

Magnetism of Edges of single-layer black phosphorus* Yudai Nakanishi, Tika Ohata, Ryoma Iwaki, Kumiko Nomura, Motohiko Ezawa,
Hisanori Shinohara, Junji Haruyama

79

Properties of nanotubes
1P-36

Electronic properties of thin films of all-metallic carbon nanotubes with ionized gel-gate* Tomohiro Honma, Ryo Kikuchi, Syunya Yamada, Chika Ohata, MIho Koyata,
Junji Haruyama, Apparao Rao

80

Carbon nanoparticles
1P-37

Photo-reduction of graphene oxide for improvement of the purity of carbon nanopot* HIroyuki Yokoi, Kazuto Hatakeyama, Shogo Matsumoto, Mako Ueda, Takaaki Taniguchi,
Michio Koinuma, Yasumichi Matsumoto

81

1P-38
☆

Structure and electronic properties of nanodiamond and its fluorination effect* Kennta Kogane, Hidekazu Touhara, Yoshiyuki Hattori, Kazuyuki Takai

82

1P-39

Spheroidization of microdiamond by self-ablation: preliminary results* Ryoko Yamanoi, Eiji Ōsawa

83

Other topics
1P-40

The Topological Stracture of Starfish Nanocarbon* Natsuki Namba, Yukihiro Takada, Kyoko Nakada

84

1P-41

Double resonance Raman modes in mono- and few-layer MoTe2* Huaihong Guo, Teng Yang, Mahito Yamamoto, Lin Zhou, Ryo Ishikawa, Keiji Ueno,
Kazuhito Tsukagoshi, Zhidong Zhang, M. S. Dresselhaus, R. Saito

85

xxiii

February 21st, Sat.
1P-42

Improving the property of electric double layer capacitor by using activated carbon
nanoballoon* Akitaka Mizutani, Yoshiyuki Suda, Hirofumi Takikawa, Hitoshi Ue, Kazuki Shimizu,
Yoshito Umeda

86

1P-43

Spontaneous antiferromagmetism in the α-graphyne single layer* Teng Yang, Baojuan Dong, Huaihong Guo, R. Saito, Zhidong Zhang

87

1P-44

Characteristc of spectral sensitivity for the composite film of Zn doped iron oxide nanotubes
and organometal halide perovskite* Yuta Kosugi, Hiroyuki Kusuda, Ayano Saiki, Shunji Bandow

88＞＞＞＞＞＞＞ Coffee Break ( 17:30-18:00 ) ＜＜＜＜＜＜＜Tutorial ( 18:00-19:30 )TEM characterization of carbon nanomaterials* Kazutomo Suenagaxxiv

February 22nd, Sun.
Special Lecture : 25 min (Presentation) + 5 min (Discussion)
General Lecture : 10 min (Presentation) + 5 min (Discussion)
Poster Preview : 1 min (Presentation)
Special Lecture ( 9:00-9:30 )2S-4

STUDIES ON SWNT BUNDLING* Esko I. Kauppinen

4

General Lecture ( 9:30-10:15 )Applications of nanotubes ・ Formation and purification of nanotubes
2-1

Direct- and Dry-Deposited Single-Walled Carbon Nanotube Films Doped with MoOx as
Electron-Blocking Transparent Electrodes for Efficient Flexible Organic Solar Cells

20* Il Jeon, Kehang Cui, Takaaki Chiba, Anton Anisimove, Albert Nasibulin,
Esko Kauppinen, Shigeo Maruyama, Yutaka Matsuo
2-2

Evaluation of perovskite solar cells with single-walled carbon nanotube cathodes* Takaaki Chiba, Takahiro Sakaguchi, Albert G. Nasiblin, Esko I. Kauppinen, Rong Xiang,
Shohei Chiashi, Shigeo Maruyama

21

2-3

Non-catalytic CVD growth from carbon nanotube forest formed by SiC surface
decomposition* Yu HIRANO, Masafumi INABA, Megumi SHIBUYA, Kazuma SUZUKI, Chih-Yu LEE,
Miho MYODO, Atsushi HIRAIWA, Wataru NORIMATSU, Michiko KUSUNOKI,
Hiroshi KAWARADA

22＞＞＞＞＞＞＞ Coffee Break ( 10:15-10:30 ) ＜＜＜＜＜＜＜Special Lecture ( 10:30-11:00 )2S-5

A Proposal of New Strategy for Bottom-up Synthesis of Graphene Nanoribbons* Hiroko Yamada, Hironobu Hayashi

5

General Lecture ( 11:00-12:00 )Chemistry of fullerenes ・ Endohedral metallofullerenes ・ Fullerenes
2-4Structure and electronic state of [lucigenin]C 60 molecular fulleride salt
* Hiroshi Moriyama, Shohei Yamamoto, Hatsumi Mori, Kenji Yoza, Hideyuki Hara

23

2-5

Method of Separating Endohedral Metallofullerenes using Electron Donor and Polar Solvent* Kazuki Chiba, Kazuhiko Akiyama, Shiro Kubuki

24

2-6

Vibronic Coupling Density Analysis for Multiple Cycloadditions to C 60
* Naoki Haruta, Tohru Sato, Kazuyoshi Tanaka

25

2-7

From linear carbon molecules to fullerenes under laser vaporization* Tomonari Wakabayashi, Yoriko Wada, Yusuke Morisawa, Hitomi Endo, Yuki Taguchi,
Jun Matsumoto, Takeshi Kodama, Yohji Achiba, Haruo Shiromaru

26＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜xxvFebruary 22nd, Sun.
Awards Ceremony ( 13:15-14:00 )Poster Preview ( 14:00-15:00 )Poster Session ( 15:00-16:45 ) （☆）Candidates for the Young Scientist Poster Award
Chemistry of fullerenes
2P-1

Isolation and Characterization for Each Isomer of (5,6)- and (6,6)-[Li+@C61Ph2]NTf2–* Hiroshi Okada, Hiroki Kawakami, Shinobu Aoyagi, Yutaka Matsuo

89

2P-2

Approach to High Open-circuit Voltage in Organic Solar Cells Utilizing Structural Change ofOxazolino-C70 Derivative* Yutaka Matsuo, Shu-Hui Li, Zong-Jun Li, Takafumi Nakagawa, James Ryan, Xiang Gao

90

2P-3

Effects of water molecules on the proton dynamics in fullerenol solids investigated bysolid-state 1H NMR* Yoshiaki Sano, Hironori Ogata

91

Endohedral metallofullerenes
2P-4
☆

2P-5

Photoinduced Electron Transfer from Anionic Phthalocyanines to Li +@C60 and Light-Energy
Conversion* Yuki Kawashima, Kei Ohkubo, Vicente Manuel Blas-Ferrando, Hayato Sakai,
Enrique Font-Sanchis, Javier Ortíz, Fernando Fernández-Lázaro, Taku Hasobe,Ángela Sastre-Santos, Shunichi Fukuzumi

92

Addition Reactions of Trimetallic Nitride Template Endohedral Metallofullerenes with
Disilirane and Digermirane* Kyosuke Miyabe, Masahiro Kako, Kumiko Sato, Mitsuaki Suzuki, Naomi Mizorogi,
Marilyn M. Olmstead, Alan L. Balch, Wei-Wei Wang, Shigeru Nagase, Takeshi Akasaka

93

Fullerenes
2P-6☆

Energetics of the Nano-Saturn* Shota Kigure, Haruka Omachi, Hisanori Shinohara, Susumu Okada

94

2P-7

Enegetics of H2O encapsulated in fullerenes under an electric field* Jun-ya Sorimachi, Susumu Okada

95

2P-8
☆

Absolute yield of fullerene formed by graphite laser ablation at room temperature* Hitomi Endo, Yuki Taguchi, Jun Matsumoto, Tomonari Wakabayashi, Takeshi Kodama,
Yohji Achiba, Haruo Shiromaru

96

Properties of nanotubes
2P-9

Fabrication and characterization of SWCNT-TFTs using chirality separated DNA-wrapped
SWCNTs* Yuki Kuwahara, Fumiyuki Nihey, Shigekazu Ohmori, Takeshi Saito

97

2P-10

Energetics and electronic structure of deformed carbon nanotubes* Jumpei Nishikawa, Susumu Saito

98

xxvi

February 22nd, Sun.
Effect of Chemical Doping on the Electronic States of Single-Walled Carbon Nanotubes (1) :Experiment* Tomonari Shiraishi, Naoto Akizuki, Yuhei Miyauchi, Kazunari Matsuda,
Naotoshi Nakashima

99

2P-12

Effect of Chemical Doping on the Electronic States of Single-Walled Carbon Nanotubes:
Theory* Gergely Juhasz, Tomonari Shiraishi, Naotoshi Nakashima

100

2P-13

Ab initio calculation for electronic bands of CNT in which the chain of sulphur is inserted* Yuhei Natsume

101

2P-11
☆

Applications of nanotubes
2P-14

Fabrication of Thermoelectric Device using P- and N-Type Controlled Single Wall Carbon
Nanotubes by Electric Double Layer Carrier Injections* Yuki Oshima, Yoshimasa Kitamura, Shouhei Kanda, Hideki Kawai, Yusuke Nakai,
Yutaka Maniwa, Kazuhiro Yanagi

102

2P-15

Polyglycerol-functionalized SWNTs: size separation, toxicological study and biomedical
application* Keisuke Nakamura, Li Zhao, Hongmei Qin, Shuji Aonuma, Takahide Kimura,
Naoki Komatsu

103

2P-16

Gate-controlled generation of optical pulse trains using individual carbon nanotubes
Ming Jiang, Yusuke Kumamoto, * Akihiro Ishii, Masahiro Yoshida, Takashi Shimada,Yuichiro K. Kato

104

2P-17

Electroluminescence from individual air-suspended carbon nanotubes within split-gatestructures* Noriyuki Higashide, Ming Jiang, Takushi Uda, Masahiro Yoshida, Akihiro Ishii,
Yuichiro K. Kato

105☆

Formation and purification of nanotubes
2P-18

Redox-dependent separation of single-wall carbon nanotubes in hydrogels* Atsushi Hirano, Takeshi Tanaka, Hiromichi Kataura

106

2P-19

Optimization of the synthesis parameters of Carbon Nanotube (CNT) forest using the
Taguchi Method* Adam Pander, Hiroshi Furuta, Akimitsu Hatta

107

2P-20

Synthesis of single-walled carbon nanotubes from woody bioethanol* Takuma Araki, Atsushi Honda, Yuhei Yabushita, Toshiya Murakami, Kenji Kisoda,
Masanori Yamaguchi, Chihiro Itoh

108

2P-21

Nitrogen doping of single-walled carbon nanotubes prepared from fluorinated SWCNTs
using ammonia gas* Koji Yokoyama, Yoshinori Sato, Kazutaka Hirano, Kenichi Motomiya, Kazuyuki Tohji,
Yoshinori Sato

109

☆

☆

xxvii

February 22nd, Sun.
2P-22

Molecular Dynamic Simulation of Defect Free Growth of Single-Walled Carbon Nanotube* Ryo Yoshikawa, Yukai Takagi, Shohei Chiashi, Shigeo Maruyama

110

2P-23

Automatic Gradient Elution Gel Filtration for Separation of Metal and Semiconducting
Single-Wall Carbon Nanotubes* Boanerges Thendie, Haruka Omachi, Ryo Kitaura, Yasumitsu Miyata, Hisanori Shinohara

111

Facile sorting and release of semiconducting single-walled carbon nanotubes based on
dynamic formation of supramolecular polymers* Fumiyuki Toshimitsu, Naotoshi Nakashima

112

☆
2P-24

Endohedral nanotubes
2P-25

Structural transformation of tellurium encapsulated in the inner space of carbon nanotubes
depending on tube diameter* Keita Kobayashi, Hidehiro Yasuda

113

2P-26

Synthesis of Diamantane Chains inside Carbon Nanotubes from Bridgehead-halogenatedDiamantanes* Yusuke Nakanishi, Haruka Omachi, Natalie A. Fokina, Ryo Kitaura, Peter R. Schreiner,
Jeremy E. P. Dahl, Robert M. K. Carlson, Hisanori Shinohara

114

A Computational Study on Properties of Multimeric Pi Conjugated Oligomers inside Carbon
Nanotubes* Takashi Yumura, Hiroki Yamashita

115

☆

2P-27

Graphene synthesis
2P-28☆

Growth Dynamics of Single-Layer Graphene on Epitaxial Cu surfaces* Yujiro Ohta, Seigi Mizuno, Hiroki Hibino, Kenji Kawahara, Rina Takizawa,
Masaharu Tsuji, Hiroki Ago

116

2P-29

Preparation of Small-Sized Nano-Graphene Oxide for Biological Application* Minfang Zhang, Toshiya Okazaki, Yoho Iizumi, Eijiro Miyako, Sumio Iijima,
Masako Yudasaka

117

2P-30
☆

Direct transfer of CVD graphene to insulating substrates by metal melting* Ryosuke Inoue, Yutaka Maniwa, Yasumitsu Miyata

118

2P-31

Vibronic Coupling Density as a Reactivity Index: Applications for Diels-Alder Reactions ofGraphene Fragments
Naoki Haruta, * Tohru Sato, Kazuyoshi Tanaka

119

2P-32
☆

Growth of high-quality monolayer WS2 on graphite* Yu Kobayashi, Shogo Sasaki, Shohei Mori, Hiroki Hibino, Kenji Watanabe,
Takashi Taniguchi, Yutaka Maniwa, Yasumitsu Miyata

120

Properties of graphene
2P-33

Amplitude modulation of optical field by arm-chair graphene nanoribbons:A First-principles
Study* Yoshiyuki Miyamoto, Hong Zhang

xxviii121

February 22nd, Sun.
2P-34

Spectroscopic studies of single layer molybdenum ditelluride* Sandhaya Koirala, Daichi Kozawa, Shinichiro Mouri, Yuhei Miyauchi, Kazunari Matsuda

122

2P-35

Seebeck effect of monolayer transition metal dichalcogenides* Kaito Kanahashi, Jiang Pu, Nguyen Thanh Cuoug, Lain-Jong Li, Susumu Okada,
Hiromichi Ohta, Taishi Takenobu

123

2P-36

Electronic transport properties of graphene between metal electrode* Hideyuki Jippo, Susumu Okada, Mari Ohfuchi

124

2P-37

Anharmonicity of Phonons and Thermal Conduction in Graphene* Masashi Mizuno, Riichiro Saito

125

2P-38

Structure and electronic properties of epitaxial graphene and its molecular adsorption effect* Keisuke Nakamoto, Takashi Akatsu, Kazuyuki Takai

126

2P-39

Bandgap Opening in Graphene Adsorbed on Defective Graphene* Ken Kishimoto, Susumu Okada

127

2P-40

Fabrication and In-situ TEM Characterization of Freestanding Graphene Nanoribbons
Devices* Qing Wang, Ryo Kitaura, Shoji Suzuki, Hisanori Shinohara

128☆

Other topics
2P-41

Graphite laser ablation products carried by coaxial gas flow
* Yuuki Taguchi, Hitomi Endo, Yurika Abe, Jun Matsumoto, Tomonari Wakabayashi,
Takeshi Kodama, Yohji Achiba, Haruo Shiromaru

129

2P-42
☆

Controlling and functionalizing phase transitions in two-dimensional crystals* Masaro Yoshida, Yijin Zhang, Jianting Ye, Ryuji Suzuki, Yasuhiko Imai, Shigeru Kimura,
Akihiko Fujiwara, Yoshihiro Iwasa

130

2P-43

Structure and Spectra of Polyyne-Iodine Complex* Dai Nagashima, Tohru Sato, Naoya Iwahara, Kazuyoshi Tanaka, Yoriko Wada,
Tomonari Wakabayashi

131

2P-44

Ambipolar transistor and superconductivity in transition metal dichalcogenides* Wu Shi, Jianting Ye, Yijing Zhang, Ryuji Suzuki, Masaro Yoshida, Naoko Inoue, Yu Saito,
Yoshihiro Iwasa

132

xxix

February 22nd, Sun.
Special Lecture ( 16:45-17:15 )2S-6

Single carbon-nanotube photonics and optoelectronics* Yuichiro K. Kato

6

General Lecture ( 17:15-18:45 )Properties of nanotubes
2-8

The effect of DNA adsorption on optical transitions in single-walled carbon nanotube
depending on base sequence* Masahiro Ito, Yusuke Ito, Hiroki Kato, Kazuo Umemura, Yoshikazu Homma

27

2-9

Electronic properties and polarities of atomic-layer materials: Doped graphene, hexagonal
BN layers, and carbon nanotubes* Susumu Saito, Takashi Koretsune, Yoshitaka Fujimoto

28

2-10

Electronic States of Flattened Carbon Nanotubes: Effects of tube chirality and displacement* Takeshi Nakanishi, Tsuneya Ando

29

2-11

Coherent and squeezed phonons in single wall carbon nanotubes* Ahmad R. T. Nugraha, Eddwi H. Hasdeo, Riichiro Saito

30

2-12

Stark effect of excitons in individual air-suspended carbon nanotubes* Masahiro Yoshida, Yusuke Kumamoto, Akihiro Ishii, Akio Yokoyama, Yuichiro K. Kato

31

2-13

Exciton diffusion, end quenching, and exciton-exciton annihilation in individual airsuspended carbon nanotubes* Akihiro Ishii, Masahiro Yoshida, Yuichiro K. Kato

32

xxx

February 23rd, Mon.
Special Lecture : 25 min (Presentation) + 5 min (Discussion)
General Lecture : 10 min (Presentation) + 5 min (Discussion)
Poster Preview : 1 min (Presentation)
Special Lecture ( 9:00-9:30 )3S-7

Graphene field-effect transistors -Analysis on gap states by conductance method* Kosuke Nagashio

7

General Lecture ( 9:30-10:30 )Properties of graphene ・ Other topics
3-1

Bandgap opening in bilayer graphene at metal contacts* Ryo Nouchi

33

3-2

Band-like transport in reduced graphene oxide films* Ryota Negishi, Masashi Akabori, Shoji Yamada, Takahiro Ito, Yoshio Watanabe,
Yoshihiro Kobayashi

34

3-3

Circularly polarized luminescence from lateral TMD p-i-n junctions* Yijin Zhang, Masaru Onga, Yoshihiro Iwasa

35

3-4

Mechanical exfoliation and van der Waals assembly of layered ferromagnetic dichalcogenide
FexTaS2* Miho Arai, Rai Moriya, Naoto Yabuki, Satoru Masubuchi, Keiji Ueno, Tomoki Machida36＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Special Lecture ( 10:45-11:15 )3S-8

Nano-optical science and application of nano-carbon materials and atomically thin layeredmaterials* Kazunari Matsuda

8

General Lecture ( 11:15-12:00 )Properties of graphene ・ Other topics
3-5

Optical Properties of Single-layer Black Phosphorus,“Phosphorene”* Takashi Nakamura, Daichi Kozawa, Shinichiro Mouri, Kazunari Matsuda

37

3-6

Relaxation of Valley Polarization in Transition Metal Dichalcogenides* Satoru Konabe, Susumu Okada

38

3-7

Exciton spectroscopy of 3R-MoS2* Ryuji Suzuki, Sandor Bordacs, Ryosuke Akashi, Masayuki Ochi, Ryotaro Arita,
Yoshinori Tokura, Yoshihiro Iwasa

39＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜xxxiFebruary 23rd, Mon.
Poster Preview ( 13:15-14:15 )Poster Session ( 14:15-16:00 ) （☆）Candidates for the Young Scientist Poster Award
Applications of fullerenes
3P-1

Solid-State NMR Studies on the Aggregated Structures of Organic Bulk Heterojunction Solar 133
Cells with Solvent Additives(II)* Saki Kawano, Hironori Ogata

3P-2

Application of spiro-1, 3-dioxolanofullerenes with low-lying LUMO level to low bandgap
polymer based organic photovoltaic cell
* Tsubasa Mikie, Akinori Saeki, Naohiko Ikuma, Ken Kokubo, Shu Seki

134

Fabrication of semitransparent tandem organic solar cells using multiple-device stacked
structure* Shunjiro Fujii, Takeshi Tanaka, Hiromichi Kataura

135

☆
3P-3

Endohedral metallofullerenes
3P-4

Isolation and characterization of [5,6]-pyrrolidino-Sc3N@I h -C80 diastereomers* Yutaka Maeda, Masato Kimura, Chihiro Ueda, Mitsuaki Suzuki, Michio Yamada,
Nikolaos Karousis, Nikos Tagmatarichis, Marilyn M Olmstead, Alan L Balch,
Wei-Wei Wang, Shigeru Nagase, Takeshi Akasaka

136

3P-5

Reactions of Trimetallic Nitride Template Endohedral Metallofullerenes with
Silacyclopropanes* Kazuya Minami, Takeshi Sugiura, Masahiro Kako, Kumiko Sato, Shigeru Nagase,
Takeshi Akasaka

137

3P-6

Ionic Donor-Acceptor Supramolecules: Complexation of Molecular Nanocarbons with
Cationic Li+@C60* Hiroshi Ueno, Taishi Nishihara, Katsuma Matsui, Yasutomo Segawa, Kenichiro Itami

138

Properties of nanotubes
3P-7

The Quantitative Importance of Purity on the Properties of Single Wall Carbon Nanotubes* Naoyuki Matsumoto, Guohai Chen, Motoo Yumura, Don Futaba, Kenji Hata

139

3P-8
☆

MD simulation on RBM frequency of bundled SWNTs* Atsushi Beniya, Naoki Homma, Shohei Chiashi, Yoshikazu Homma, Takahiro Yamamoto

140

3P-9

Molecular structure of chalcogen encapsulated in single-walled carbon nanotubes studied bymolecular dynamics simulations* Yutaka Sato, Yosuke Kataoka, Hironori Ogata

141

3P-10

Local structure and properties of the alkali halides encapsulated in single-walled carbon
nanotubes studied by molecular dynamics simulations* Eita Yokokura, Yousuke Kataoka, Hironori Ogata

142

Applications of nanotubes
3P-11

Ultralow mode-volume photonic crystal nanobeam cavities for high-efficiency coupling toindividual carbon nanotube emitters* Hidenori Machiya, Ryohei Miura, Saneyuki Imamura, Ryuichi Ohta, Akihiro Ishii,
Xuqing Liu, Takashi Shimada, Satoshi Iwamoto, Yasuhiko Arakawa, Yuichiro K. Kato

xxxii

143

February 23rd, Mon.
Characteristic variation of thin-film transistors based on purified semiconducting carbon
nanotubes* Jun Hirotani, Ryotaro Matsui, Shigeru Kishimoto, Yutaka Ohno

144

3P-13

Thermoelectric power of carbon nanotubes from first principles* Nguyen Tuan Hung, Riichiro Saito

145

3P-14

Effect of TiO2 coating on field emission properties of carbon nanotube by in-situ
transmission electron microscopy* Masahiro Matsuda, Hitosi Nakahara, Koji Asaka, Yahachi Saito

146

Light-emitting Electrochemical Cell with Few-Walled Carbon-Nanotube Electrodes* Ko Nakayama, Hiroyuki Shirae, Suguru Noda, Tomo Sakanoue, Taishi Takenobu

147

3P-12
☆

☆
3P-15

Formation and purification of nanotubes
3P-16

Synthesis of Single-Walled Carbon Nanotubes from Rh Catalysts by Alcohol Gas Source
Method in high Vacuum* Akinari Kozawa, Takahiro Saida, Shigeya Naritsuka, Takahiro Maruyama

148

3P-17

Relationship between Chirality Control of Single-Walled Carbon Nanotube and Wavelengthof the Irradiated Free Electron Laser* Keisuke Yoshida, Yusaku Tsuda, Daiki Kawaguchi, Tomoko Nagata, Nobuyuki Iwata,
Hiroshi Yamamoto

149

3P-18

Synthesis of single walled carbon nanotubes by using sputtered Co/Cu and Co/W as catalyst* Hua An, Kehang Cui, Rong Xiang, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama

150

3P-19

Control of In-Plane Orientation and Chirality of Single-Walled Carbon Nanotubes using HotWalled Chemical Vapor Deposition Method and Free Electron Laser* Daiki Kawaguchi, Keisuke Yoshida, Tomoko Nagata, Nobuyuki Iwata, Hiroshi Yamamoto

151

3P-20

The Effects of Hydrogen Atom on Cobalt Clusters in the Reaction with H 2O Investigated by
FT-ICR Mass Spectrometer* Yuta Tobari, Kazuki Ogasawara, Yoshinori Sato, Makoto Saito, Shohei Chiashi,
Shigeo Maruyama, Toshiki Sugai

152

3P-21
☆

Synthesis of carbon nanotubes by means of “molecular template epitaxial growth” approach* Liu Hong, Akira Takakura, Lawrence Scott, Yuhei Miyauchi, Kenichiro Itami

153

3P-22

Hybridization of Semiconducting-Single-Walled Carbon Nanotubes and Fullerene-Carrying
Carbazole-Fluorene Copolymers* Fumiyuki Toshimitsu, Hiroaki Ozawa, Naotoshi Nakashima

154

☆

☆

Nanohorns
3P-23

Cytotoxicity of Carbon Nanohorns Enhanced by Too Much PLPEG* Maki Nakamura, Yoshio Tahara, Shinsuke Fukata, Minfang Zhang, Sumio Iijima,
Masako Yudasaka

xxxiii155

February 23rd, Mon.
3P-24

Electrochemical properties of boron- and nitrogen-doped carbon nanohorn aggregates* Ryota Yuge, Shunji Bandow, Masako Yudasaka, Kiyohiko Toyama, Sumio Iijima,
Noriyuki Tamura, Takashi Manako

156

Graphene synthesis
3P-25☆

Selective formation of zigzag edges in graphene cracks* Miho Fujihara, Ryosuke Inoue, Yutaka Maniwa, Hisanori Shinohara, Yasumitsu Miyata

157

3P-26

The synthesis of graphene by thermal CVD process without flowing gas containing carbon* Shiyo Morisako, Marina Tsujimoto, Masaru Tachibana

158

3P-27
☆

Highly Uniform Bilayer Graphene on Cu-Ni Alloy Films* Yuichiro Takesaki, Hiroki Hibino, Masaharu Tsuji, Hiroki Ago

159

3P-28

Annealing time dependence of precipitation of high-quality multilayer graphene using Al2O3
barrier and Au capping layers* Jumpei Yamada, Manabu Suzuki, Yuki Ueda, Takahiro Maruyama, Shigeya Naritsuka

160

Applications of graphene
3P-29☆

Evaluation of magnetism of chemically active sites in graphene oxide / nanographene* Tomoki Yamashina, Takuya Isaka, Kadumi Inoue, Yoshiaki Matsuo, Kazuyuki Takai

161

3P-30

Acid-treatment minimizes unintentional strain and doping of single-layer graphene on SiO2
substrate in aqueous environments
Katsuya Masuda, * Masahito Sano

162

3P-31
☆

Electric Double Layer Light-emitting Diodes of Monolayer WSe2
* Jiang Pu, Taiyo Fujimoto, Jing-Kai Huang, Lain-Jong Li, Tomo Sakanoue,
Taishi Takenobu

163

Properties of graphene
3P-32

Effect of hydrazine adsorption on Graphene FET characteristic* Taichi Umehara, Kazuyuki Takai

164

3P-33

Kohn anomaly meets Fano resonance in G and G’ bands Raman spectra of graphene* Eddwi Hasdeo, Ahmad Nugraha, Riichiro Saito

165

3P-34

Surface plasmon excitations in graphene* Shoufie Ukhtary, Eddwi Hasdeo, Ahmad Nugraha, Riichiro Saito

166

3P-35
☆

Interlayer exciton in atomically thin heterostructures of transition metal dichalcogenides* Daichi Kozawa, Ivan Verzhbitskiy, Alexandra Carvalho, A. H. Castro Neto,
Kazunari Matsuda, Goki Eda

167

3P-36

Optical characteristic of CVD grown monolayer WSe2 under high-density carrier doping* Keiichiro Matsuki, Jiang Pu, Kazunari Matsuda, Lain-Jong Li, Taishi Takenobu

168

xxxiv

February 23rd, Mon.
3P-37

Photon energy dependence of angle resolved photoemission spectroscopy in graphene* Pourya Ayria, Hesky Hasdeo, Ahmad Nugraha, Shin-Ichiro Tanaka, Riichiro Saito

169

3P-38
☆

Local electric field effects on nearly free electron states of graphene nanoribbons* Ayaka Yamanaka, Susumu Okada

170

3P-39

Evaluation of Graphene Quality by Raman Rapid Chemical Imaging
Mamoru Komatsu, Kaori Umeyama, * Noriaki Nishikawa, Mark Wall

171

Other topics
3P-40

CVD synthesis of high-quality h-BN films for heterostructure devices* Yuki Uchida, Tasuku Iwaizako, Masaharu Tsuji, Hiroki Ago

172

3P-41

Electric field control of thermoelectric properties in WSe 2

173

☆
3P-42

* Takahiko Iizuka, Masaro Yoshida, Sunao Shimizu, Yoshihiro Iwasa
Influence of Electric Double Layer Carrier Injections on Optical Absorption Spectra of CVD
synthesized Multi-layered MoS2 and WS2 thin films* Kotaro Homma, Hideki Kawai, Kazuhiro Yanagi

174

Environmental/Safety characterization of nanomaterials
3P-43

Preparation of Nb2O5- Graphene Nanocomposites and Kinetics for Photocatalytic
Degradation of Organic Dyes
Hae Soo Park, * Jeong Won Ko, Weon Bae Ko

175

Special Lecture ( 16:00-16:30 )3S-9

Characterization of CVD-grown high-quality atomic layers* Ryo Kitaura

9

General Lecture ( 16:30-17:30 )Graphene synthesis ・ Other topics ・ Applications of graphene
3-8

CVD synthesis of single-crystal single-layer graphene and bi-layer graphene from ethanol* Xiao Chen, Kohei Tsushima, Masaki Sota, Rong Xiang, Shohei Chiashi,
Shigeo Maruyama

40

3-9

Magnetic Ordering of Two-dimensional Networks of Fused C36 Polyhedra under an Electric
Field* Mina Maruyama, Susumu Okada

41

3-10

Effects of electrodeposition conditions on the states of Pt-Ru nanoparticles on carbon
materials and their electrocatalytic properties toward methanol oxidation* Haruhiko Yoshitake, Shohei Hayase, Zhipeng Wang , Hironori Ogata

42

3-11

Hexahydroxytriphenylene and its derivetives for graphene exfoliation in aqueous and organic
media* Gang Liu, Takahide Kimura, Naoki Komatsu

43

xxxv

特別講演
Special Lecture

1S – 1 ～ 1S – 3
2S – 4 ～ 2S – 6
3S – 7 ～ 3S – 9

1S-1
What we know about chirality-controlled growth of single-walled carbon
nanotubes○Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
The chirality-controlled synthesis of single-walled carbon nanotubes (SWNTs) SWNTs is a
crucial issue for their advanced applications (e.g. carbon-based nanoelectronics) and has beena great challenge for about two decades. Recently, we realized the selective growth of (12,6)
SWNTs at the content of >92%, and also showed the selective growth of (14,4) and (16,0)
tubes. In this talk, I will start from our understanding on catalyzed growth of SWNTs inchemical vapor deposition (CVD), then discuss the important factors on the chirality control,
and finally explain our design on the catalysts composition and structure as well as the CVD
conditions.

[1] F. Yang et al. Nature 510, 522-524 (2014).
[2] Y. Li et al., Adv. Mater 22, ,1508-1515 (2010)..
Corresponding Author: Y. Li
Tel & Fax: +86-10-6275-6773
E-mail: yanli@pku.edu.cn

-1-

1S-2
Double-walled carbon nanotube transparent conductive film for next
generation flexible device○Naoki Imazu1, Takashi Oi1, Hidekazu Nishino2, Kenichi Sato2, Osamu Watanabe1, Shiro
Honda2, Motoyuki Suzuki1
1

Film products development center, Toray Industries, Inc., Shiga 520-8558, Japan
Chemicals research laboratories, Toray Industries, Inc., Aichi 455-8502, Japan2

We have developed double-walled carbon nanotube (DWCNT) transparent conductive
film (TCF). Our DWCNT TCF has very high transparent conductivity, which are currently
among the top in the world. And it has great characteristics such as high flexibility (bending
and stretching durability) and high environmental stability.
In order to improve transparent conductivity, we
focus on DWCNT, and developed flexible, hightransparent conductive DWCNT TCF. We alreadyhave established mass production system [1].
Combining this CNT dispersion and our fine wet
coating technology, we have developed DWCNT
TCF. Picture of our DWCNT TCF roll is shown in
Fig. 1. We also have established mass production rollto roll technology for this DWCNT TCF. The widthof mass production DWCNT TCF is over 1000 mm.
One
exampleof
our
DWCNT TCF
Fig.1 Toray DWCNT TCF roll sample
commercialized product is shown in Fig. 2. This
figure is twist-ball type e-paper display. DWCNT
TCF is used as upper transparent conductive
electrode. DWCNT TCF’s neutral color and highlight transmittance contribute to showing clear
image. And as this figure, large screen digital
signage is realized using our DWCNT TCF.
Flexible touch screen using patterned Toray
Fig.2 Commercialized product of E-paper
DWCNT TCF are shown in Fig. 3. Even if theseusing Toray DWCNT TCF
devices are under bended situation, both worknormally. Especially, touch screen
detected the multi position across thefolding line. These demonstrations are
significant for future flexible device
realization.
[1] Toray Industries, Inc., “Mass production
technology development of CNT transparent
conductive film for EPD” 9 February 2012,<http://www.toray.co.jp/news/rd/nr120209.html>(19 August 2012)
Corresponding Author: M. Suzuki
Tel: +81-77-533-8254, Fax: +81-77-533-8461,
E-mail: Motoyuki_Suzuki@nts.toray.co.jp

Fig.3 Flexible touch screen using patterned TorayDWCNT TCF (Prototype)

-2-

1S-3
Real-time observation of graphene growth by thermal emission microscopy○Koichiro Saiki1,2, Tomo-o Terasawa2, and Sho Kato 1
1
2

Department of Complexity Science & Engineering,The University of Tokyo
Department of Chemistry, The University of Tokyo,Chiba 277-8561, Japan

Scalable synthesis of a large-area, high-quality graphene is indispensable to use theexcellent nature of graphene for various industrial applications. Chemical vapor deposition(CVD) is considered the most promising synthesis method for that purpose and a large
number of works on CVD growth of graphene have been carried out worldwide. Nevertheless,the property of CVD graphene has not yet reached that of exfoliated one. The optimization of
CVD growth parameters has been done mostly based on the post-synthesis characterization byuse of scanning electron microscopy, Raman spectroscopy, etc. If the intermediate state during
the growth can be observed in situ and in real time, it will help to elucidate the growthmechanism and to optimize the growth parameters. In the case of CVD growth on Cu, themost popular substrate, however, conventional electron microscopy could not be used during
the growth under gas ambience and at high temperatures.
Recently we have proved that the graphene could be distinguished optically from the metal
substrate at elevated temperatures. The large difference in thermal emissivity between carbon
materials and a certain kind of metal gives rise to the contrast between graphene and the metal
substrate. By using optical microscopy we can observe the growing graphene from outside thefurnace even under the gaseous condition of several thousand Pa. The spatial and time
resolution was 1800 nm and 1 sec, respectively.[1]Using this observation method we succeeded in analyzing the growth mechanism ofgraphene on the metal substrate. In the case of CVD growth of graphene on Cu, we evaluatedthe saturation nucleation density and growth rate for various methane flow rates and substratetemperatures. Both the growth rate and saturation nucleation density increased with thesubstrate temperature, indicating that the production on surface and attachment to grapheneedge of growth precursors were enhanced at the substrate temperatures between 900 and1000 °C. After the methane supply was stopped, the graphene started to shrink and finallydisappeared. The shrinkage rate also depended on the substrate temperature, suggesting theenhanced detachment of C atoms from graphene edge.[1]The effect of vapor phase oxygen on the CVD growth of graphene on Cu was studied.
Oxygen has been found to decrease the saturation nucleation density and the growth rate. In
the low partial pressure region, however, the growth rate increased with oxygen partialpressure. This increase might be ascribed to the decrease in the energy barrier for theattachment of precursor to the graphene edge by the surface oxygen.[2]The graphene growth on Pd from graphene oxide was also observed by thermal emission
microscopy. The graphene appeared at the boundary between Pd grains at high temperatures,
while it also segregated from the center of Pd grains by decreasing the substrate temperature.
Thermal emission microscopy proved to be a powerful tool to observe the growth featurein the CVD condition and optimize the growth parameters.
[1] T. Terasawa and K. Saiki, submitted.
[2] T. Terasawa and K. Saiki, submitted.
Corresponding Author: K. Saiki
Tel: +81-4-7136-5526, Fax: +81-4-7136-3903,
E-mail: saiki@k.u-tokyo.ac.jp

-3-

2S-4
STUDIES ON SWNT BUNDLING
Esko I. Kauppinen
Department of Applied Physics, Aalto University School of Science
Puumiehenkuja 2, P.O. Box 16100, FI-00076 Aalto, FINLAND

esko.kauppinen@aalto.fi
SWNTs have the tendency to form bundles during the growth processes. However,much of the research on SWNT optical and transport properties has been focused on theindividual tubes, i.e. the effect of bundling has received relatively minor efforts. In this paper, we
discuss our recent work on the effect on SWNT bundling on the conductivity of SWNT thin filmtransparent conductors (TCF) as well as on the thin film field effect transistors (TFT-FET). In
addition, we also explore how the bundling affects both the Raman as well as the opticalabsorption spectra of SWNTs.
To control the fraction of the bundled tubes formed during the floating catalyst CVD
synthesis, we have developed a novel iron catalyst particle production method via physical vapor
deposition, based on arc discharge between two electrodes i.e. the spark generator. This method
allows us to control separately both the catalyst particle size and concentration when fed into thefloating catalyst SWCNT synthesis reactor using CO as the carbon source gas. Our results showthat when reducing the catalyst particle gas phase number concentration, the fraction of thebundled tubes can be reduced down to 20 %. When allowing the individual tubes toagglomerate i.e. form bundles in the gas phase downstream the reactor but prior thin film
deposition, we form bundles in controlled manner from the individual primary tubes with given
length distribution. The sheet resistance of TCF increases significantly with the bundling of theindividual tubes with the very same length distribution. Similarly, the on-off ratio of TFT-FETs
is reduced. We also explore the effect of bundling on the Raman and optical absorption spectraof SWNT thin films with varying degree of the tube bundling.

-4-

2S-5
A Proposal of New Strategy for Bottom-up Synthesis of Graphene
Nanoribbons○Hiroko Yamada1,2, Hironobu Hayashi1
1Graduate School of Materials Science, Nara Institute of Science and Technology, Nara
630-0192, Japan
2
CREST, JST, Saitama 102-0075, JapanThe electronic structure of graphene nanoribbon (GNR) is known to depend on the edge
structures. Zigzag edge GNR is expected to be metallic while armchair edge GNR can besemiconducting. Therefore the bottom-up synthesis of armchair GNR with a fixed width has
been sought widely. Cai et al. have reported the in-situ synthesis of anthracene nanoribbon byheating 9,10-dibromoanthracene at 400 ºC in vacuo via radical coupling of anthracenes at
9,10-positions followed by the annelation [1]. However the synthesis of nanoribbons withhigher acenes are difficult because higher acenes are insoluble and unstable to prepare
dibromoacenes as starting materials and the reaction points of radical elongation will bedisordered.
We
havedeveloped
thermalandO
photochemical precursor methods, whereO
RRhνacenes can be prepared from the correspondingRRR
precursors by heating or photoirradiation R-2COR
R
quantitatively (Figure 1). The diketoneBrBrprecursors can be converted to acenes inheating
solution, film, and solid states by-4C 2H 4
photoirradiation [2]. Bicyclo[2.2.2]octadiene
Br(BCOD)-fused precursors can be converted toBracenes in film and solid by heating [3]. Using Fig. 1 Photoconversion from the precursor tothis technique we have prepared organic pentacene (upper) and thermal conversion fromsemiconducting materials for solution process, the precursor to pentacene dimer (lower).
employing the difference of solubility between
precursors and acenes. These precursor methods are promising for the synthesis ofnonoribbons of higher acenes. Here we will report the synthesis of the acene unit compounds
for the bottom-up synthesis of GNRs.
[1] J. Cai, P. Ruffieux et al., Nature 466, 470 (2010)[2] M. Suzuki, H. Nakano, K. Nakayama, H. Yamada et al. J. Photochem. Photobiol. C, Photochem. Rev. 18, 50(2014).
[3] H. Yamada et al., RSC Adv. 3, 15310 (2013)
Corresponding Author: H. Yamada
Tel: +81-743-72-6041, Fax: +81-743-72-6042
E-mail: hyamada@ms.naist.jp

-5-

2S-6
Single carbon-nanotube photonics and optoelectronics
Yuichiro K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
Single-walled carbon nanotubes have unique optical properties as a result of their
one-dimensional structure. Not only do they exhibit strong polarization for both absorption
and emission, large exciton binding energies allow for room-temperature excitonic
luminescence. Furthermore, their emission is in the telecom-wavelengths and they can bedirectly synthesized on silicon substrates, providing new opportunities for nanoscale
photonics and optoelectronics.
Here we discuss the use of individual single-walled carbon nanotubes for generation,
manipulation, and detection of light on a chip. Their emission properties can be controlled bycoupling to silicon photonic structures such as photonic crystal microcavities [1] andmicrodisk resonators [2]. Simultaneous photoluminescence and photocurrent measurements
show that excitons can dissociate spontaneously [3], enabling photodetection at low bias
voltages despite the large binding energies. More recently, we have found that alternatinggate-voltages can generate optical pulse trains from individual nanotubes [4]. Ultimately,
these results may be combined to achieve further control over photons at the nanoscale.
Work supported by KAKENHI (24340066, 24654084, 26610080, 26870167), SCOPE, The
Canon Foundation, The Asahi Glass Foundation, KDDI Foundation, and JSPS Open
Partnership Joint Projects, as well as Project for Developing Innovation Systems, theNanotechnology Platform, and Photon Frontier Network Program of MEXT, Japan.
[1] R. Miura, S. Imamura, R. Ohta, A. Ishii, X. Liu, T. Shimada, S. Iwamoto, Y. Arakawa, Y. K. Kato, Nature
Commun. 5, 5580 (2014).
[2] S. Imamura, R. Watahiki, R. Miura, T. Shimada, Y. K. Kato, Appl. Phys. Lett. 102, 161102 (2013).
[3] Y. Kumamoto, M. Yoshida, A. Ishii, A. Yokoyama, T. Shimada, Y. K. Kato, Phys. Rev. Lett. 112, 117401(2014).
[4] M. Jiang, Y. Kumamoto, A. Ishii, M. Yoshida, T. Shimada, Y. K. Kato, arXiv:1407.7086.
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp

-6-

3S-7
Graphene field-effect transistors-Analysis on gap states by conductance methodK. Nagashio 1,2
1

Department of Materials Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
PRESTO-JST

The perspective to overcome the short channel effect based on the scaling length () [1] attracts
great attention to 2D layered channels. This is due to their rigidly-controllable few atomic thickness aswell as low dielectric constant (~4) for 2D layered channel. Although old-but-new 2D channels suchas transition metal dichalcogenides are intensively investigated [2], bilayer graphene has stilladvantage for high performance device from the viewpoint of mobility due to the smaller effective
mass (mBLG=~0.037 and mMoS2=~0.5).
The targeted issue for bilayer graphene is low Ion/Ioff at the room temperature, which is explainedby the variable range hopping in “gap states” [3]. However, as the zero-order approximation, there will
be intrinsically no interface states in bilayer graphene because there is no dangling bonds on the basal
plane, compared with Pb centers in SiO2/Si system. The origin for the gap states is still open question.
In spite of this, the detailed measurements on Dit and time constant for gap states have not beenreported yet. One of reasons could be the leakage current through the top gate insulator since robust
methodology is not established.
Recently, we demonstrated a considerable suppression of the low-field leakage as well as theultra-high displacement of ~8 V/nm (n = ~4×1013 cm-2) in bilayer graphene by applying thehigh-pressure O2 annealing to Y2O3 top gate insulator [4,5]. The reliable Y2O3 top gate insulator
provides the access to the carrier response issue in the largely-opened band gap. In this talk, we focus
on the conductance measurements for bilayer graphene to extract Dit and time constant. Based on thesemeasurements, two possible origins for the gap states, (i) border traps at the edge of Y2O3 and (ii) the
local breakdown of A-B stacking in bilayer graphene, are discussed.
Acknowledges
The Kish graphite was provided from Covalent Materials Corporation. This work was partly supported by aGrant-in-Aid for Scientific Research on Innovative Areas.
References[1] I. Ferain, C. A. Colinge, and J.-P. Colinge, Nature, 2011, 479, 310.
[2] R. Radisavljevic, A. Radenovic, J. Brivio, V. Giacometti, and A. Kis, Nature nanotech. 2011, 6, 147.
[3] J. B. Oostinga, H. B. Heersche, X. Liu, A. F. Morpurgo, and L. M. K. Vandersypen, Nature Mater. 2008, 7,
151.
[4] K. Nagashio, K. Kanayama, T. Nishimura, and A. Toriumi, IEDM Tech. Dig. 2013, 503.
[5] K. Kanayama, K. Nagashio, T. Nishimura, and A. Troiumi, APL, 2014, 104, 083519.
Corresponding Author: K. Nagashio
Tel&Fax: +81-3-5841-7161
E-mail: nagashio@material.t.u-tokyo.ac.jp

-7-

3S-8
Nano-optical science and application of nano-carbon
materials and atomically thin layered materials○Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Recently, nano-carbon materials (carbon nanotube, and graphene) and atomically thinlayered materials (transition metal dichalcogenides) have attracted a great deal of attention
from viewpoint of fundamental physics [1-7] and optical device application [8]. In
nano-carbon materials, the single-walled carbon nanotubes have novel electronic properties,
because of their degenerated band structures and enhanced Coulomb interaction with a
1-dimensional (1D) cylindrical structure. The enhanced Coulomb interaction in carbon
nanotubes leads to the formation of stable excitons (bound electron-hole pairs) with extremely
large binding energies of about several hundred meV by the optical excitation. It is anticipatedthat the excitons and exciton-complexes in carbon nanotubes show various interesting
physical aspects such as mesoscopic quantum phenomena, efficient light-exciton conversion
and so on. We studied the excitonic properties of carrier-doped carbon nanotubes [3-5] andfound the positive and negative charged excitons (trions) at room temperature in the carbon
nanotubes [3,5]. This is the first observation of room temperature stable trion (charged
exciton) among various semiconductors, which will open the door to realize the spin
manipulation in carbon based materials. We successfully improved the photoluminescencequantum efficiency of carbon nanotubes using 0D-1D hybrid nanostructure [6]. In atomicallythin layered transition metal dichalcogenides such MoS2, is also a promising platform to study
the novel excitonic properties and optical applications [9,10]. The transition-metal
dichalcogenides shows the strong light absorption (5-10%) even in an atomically thin material[10], which suggests the characteristics excitonic properties in the atomically-thin layeredmaterials. We will discuss the novel optical properties of nano-carbon materials andatomically thin layered materials.
[1] H. Hirori, K. Matsuda et al., Phys. Rev. Lett. 97, 257401 (2006).
[2] R. Matsunaga, K. Matsuda et al., Phys. Rev. Lett. 101, 147404 (2008).
[3] R. Matsunaga, K. Matsuda et al., Phys. Rev. Lett. 106, 037404 (2011).:Physics Viewpoint; Physics 4, 5(2011).
[4] S. Konabe, K. Matsuda, and S. Okada, Phys. Rev. Lett. 109, 187403 (2012).
[5] J. S. Park, N. Nakashima, K. Matsuda et al., J. Am. Chem. Soc. 134, 14461 (2012).
[6] Y. Miyauchi, K. Matsuda et al., Nature Photonics 7, 715 (2013).
[7] M. Iwamura, Y. Miyauchi, K. Matsuda et al., ACS Nano 8, 11254 (2014).
[8] F. Wang, K. Matsuda et al., submitted for publication[9] S. Mouri, K. Matsuda et al., Nano Lett. 13, 5944 (2013).
[10] D. Kozawa, K. Matsuda, G. Eda et al., Nature Commun. 5, 4543 (2014).
Corresponding Author: Kazunari Matsuda
Tel: +81-774-38-3460
Fax: +81-774-38-3460
E-mail: matsuda@iae.kyoto-u.ac.jp

-8-

3S-9
Characterization of CVD-grown high-quality atomic layers
Ryo Kitaura
Department of Chemistry, Nagoya University, Nagoya 464-8602, JapanThe discovery of graphene has attracted significant research attention, leading to creation of
the research field of atomic layer material[1]. The family of atomic layers, including graphene,
hexagonal boron nitrides (hBN, Fig. 1a) and transition metal dichalcogenides (TMDCs, Fig1b), provides fundamental and wide-spread platform to explore materials science in
two-dimensional (2D) systems. To explore this fascinating new field, preparation ofhigh-quality sample to observe intrinsic properties of 2D atomic layers is essential. In addition
to the high-crystallinity, the environmental effect is one of the most important factors todetermine quality of sample. Recent studies have shown that environment such as substrates
alter intrinsic properties of atomic layers. For example, carrier mobility of graphene is about
10 times smaller than that of graphene on hBN[2].
For preparation of high-quality atomic layers, we have focused on chemical vapor deposition(CVD) method with various substrates, realizing successful growth of high-quality atomic
layers including graphene, hBN and TMDCs. In this presentation, I would like to show ourrecent results on CVD growth and characterization of high-quality atomic layers: TMDCs onhBN (WS2 grown on hBN, for example (Fig. 2)), large-area hBN etc.
(a)

(b)

Fig.1 Structure representations of structure of (a) hexagonal boron nitrideand (b) transition metal dichalcogenides.
[1] K. S. Novoselov et al., Nature 438, 197 (2005).
[2] C. R. Dean et al., Nat Nanotechnol 5, 722 (2010).
Corresponding Author: R. Kitaura
Tel: +81-52-789-2482, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp-9-Fig.2 A SEM image of WS2
grown on hBN

一般講演
General Lecture

1–1 ～ 1–9
2 – 1 ～ 2 – 13
3 – 1 ～ 3 – 11

1-1
Co-existence of two tube-growth processes by Rh/Pd catalyst-What we learned about growth mechanism from Pd addition experiments-○Yohji Achiba, Takuya Kodama, Takeshi Kodama, Kenro Hashimoto and Haruo
Shiromaru
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
Metal nanoparticles definitely play an important role on controlling size andchirality distributions of carbon nanotubes, and thus a variety of atomic elements haveso far been examined not only to establish an industrial scale production of carbon
nanotubes but also to develop a selective generation of specific nanotubes with a single
chirality. Particularly, for realizing the latter aim, so called “CoMoCAT” has beendeveloped for a CVD tube production and Rh/Pd (1:1) bimetallic alloy for a laser
vaporization method. Here, in the present work, we will show the experimental details
of Rh/Pd system by placing an emphasis on how the difference in the concentration of
Pd in the Rh/Pd alloy system give an effect on the yields as well as on the size andchirality distributions of the nanotubes and will discuss how the Pd catalyst plays a keyrole on the large enhancement in the formation of the tubes with a specific chirality.
Typical examples of the Pd effect on the yield of the tubes with specific (n,m)
species are shown in Figure (a) and (b), where the Rh concentration to the carbon source
was kept constant 1.2% (atomic ratio), while the amount of Pd was systematicallychanged from 0 to 4.8%. The furnace temperature of the laser vaporization method was
also systematically changed from 900 to 1150℃. The resulting bimodal distribution of
the tube-growth curves strongly suggests the presence of two different growthmechanisms governed by two parameters, temperature and Pd concentration.

Figure: (a) the relative yield of (6,5) tubes prepared at different furnace temperature and different Pd
concentration. (b) the same for (7,6) tubes.
Corresponding Author: Yohji Achiba
E-mail: achiba-yohji@tmu.ac.jp、Tel:+81-42-677-2534, Fax:+81-42-677-2525- 11 -

1-2
Ionic atomic chains inside carbon nanotubes○Ryosuke Senga1, Kazu Suenaga1
1

Nanotube research center, AIST, Tsukuba 305-8565, Japan

Low-dimensional materials are attracting a wide range of interests in many research fields
as their unique properties induced by their confined size and reduced dimensionality. The
field of two-dimensional materials such as graphene, hexagonal boron nitride and transition
metal dichalcogenides have been widely spread and deeply progressed over the past years.
However the study of one-dimensional materials has been still limited and remained as
scientific challenges. Especially, one-dimensional ionic crystals have not been well discussed
because of the difficulties in their fabrication and assessment, even though more intriguing
physical properties can be expected in such a diatomic linear lattice. Herein, we describe thesuccessful synthesis of ionic atomic chains inside carbon nanotubes (CNTs) and their atomic
structural analysis, based on scanning transmission electron microscopy (STEM) and electronenergy loss spectroscopy (EELS) [1].
Figure 1(a) shows an annular dark-field (ADF) image of a CsI atomic chain encapsulated
in a double walled CNT. From the EELS chemical maps (Fig.1 (b) and (c)), it is clear that two
chemical elements, one being a cation (Cs+) and the other an anion (I-), align alternately inside
the CNT as shown in Fig. 1(d). One of the unique phenomena of the CsI atomic chain is
non-equivalent atomic vibrations for different atoms corresponding to the interactions of theatoms with the CNT. We have also found monovacancies at both Cs and I sites. They are ofgreat importance because the properties of the atomic chains are strongly governed by suchinterrupted periodicities. Indeed, the theoretical studies show that these vacancy sites
contribute as donor or acceptor states depending on the missing elements. These properties
can be obviously distinguished from three-dimensional bulk structures and have a huge
potential for future applications.
Fig. 1 The elemental analysis
for a CsI atomic chain [1].
(a) An ADF image of a CsI
atomic chain inside a double
walled CNT. (b), (c) EELS
chemical maps of Cs and I,
respectively, corresponding to
the ADF image as shown in(a). (d) A schematic model of
the CsI atomic chain.

[1] R. Senga et al. Nature Mat. 13, 1050 (2014).
Corresponding Author: R. Senga
Tel: +81-29-862-6518
E-mail: ryosuke-senga@aist.go.jp- 12 -

1-3
Selective Separation of Single-Walled Carbon Nanotubes
Using Flavin Compounds○Masashi Fukuzawa1, Fumiyuki Toshimitsu1, Yuichi Kato1, 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

Single-walled carbon nanotubes (SWNTs) are classified into metallic or semiconducting
tubes according to their chirality. These tubes coexist in the raw SWNT materials; thus theseparation of metallic or semiconducting SWNTs is quite important for use of the materials inmany applications. One of the key techniques for the chirality-sorting is a utilization of
conjugated polymers such as poly(9,9-dialkylfluorene-2,7-diyl).[1, 2] Selective extraction of thesemiconducting SWNTs (s-SWNTs) using such polymers is simple and powerful; however,removal of the used adsorbents from the polymer/SWNT composites is difficult due to thestrong interaction between the polymers and the SWNTs. In addition, the preparation of thesesynthetic polymers is complicated. Therefore, it is eagerly demanded to develop an s-SWNTselective solubilizer having features, such as facile preparation, efficient solubilizing ability anddetachability from the SWNT surfaces.
We have found that a flavin compound (1,[3] Fig. 1a) can selectively solubilize s-SWNTs
with ~99% purity from raw SWNTs.[4] In a systematical exploration for the efficient solubilizers,
we here synthesized various flavin derivatives (Fig. 1), and examined their s-SWNT
solubilization abilities. The absorption spectra of the HiPco-SWNTs dissolved in toluene using
these compounds revelaed that 1, 2 and 3 are able to solubilize the s-SWNTs selectively. On theother hand, 4 and 5 did not solubilize any SWNTs. The selective extraction of s-SWNTs with
1, 2 and 3 is also confirmed by Raman spectroscopy. These results strongly suggested that theimidyl hydrogen and methyl group(s) on the aromatic rings are essential for selective extractionof s-SWNTs. The use of such small molecules for the SWNT solubilization has an advantage
not only in its preparation but also in post-processing after the SWNT solubilization. We
examined the removal of these compounds from s-SWNTs after the selective solubilization,and found that just washing with chloroform take flavin compounds off from the s-SWNT
surfaces. A possible mechanism for such selective separation will be presented at the meeting.
R1, R2, R3, R4 =a) Me, Me, C12H25, H (1)b) Me, Me, C18H37, H (2)c) H, Me, C12H25, H (3)d) H, H, C12H25, H (4)e) Me, Me, C12H25, Me (5)Fig. 1 Chemical structures of flavin derivatives.
[1] F. Chen, et al., Nano Lett. 2007, 7, 3013.
[2] A. Nish, et al., Nat. Nanotech. 2007, 2, 640.
[3] S. Y. Ju, et al., Science 2009, 323, 1319.
[4] Y. Kato et al., Chem. Lett., submitted.
Corresponding Author: N. Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840;
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 13 -

1-4
Role of cholate for chirality selection of SWCNTs○Yohei Yomogida, Xiaojun Wei, Atsushi Hirano, Shunjiro Fujii, Takeshi Tanaka, andHiromichi Kataura
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8562, Japan- 14 -

Absorbance (a.u.)

DOC as eluent
S11
S22

400

600 800 1000 1200
Wavelength (nm)Absorbance (a.u.)

SC as eluent
S11
S22

SC Concentration[1] Y. Yomogida et al. 47th FNTG General Symposium[2] H. Liu et al. Nat. Commun. 2, 309 (2011).

Fig.1 Molecular structure of cholate
derivatives

DOC Concentration

Chirality separation is highly desired to knowchirality-dependent physical properties of single-wallcarbon nanotubes (SWCNTs). Previously, we
reported a milligram-scale separation of single
chirality SWCNTs using a gel column and mixed
surfactants of sodium dodecyl sulfate (SDS), sodium
cholate (SC), and sodium deoxycholate (DOC) [1].
In the separation, chirality species have different
affinities to the gel and are collected in the order of
their affinities. We found that their affinities could bechanged by introducing cholates and thus wedemonstrated more efficient separation than that insingle system of SDS [2] by using suitable cholate
for the separation of specific species. However, therole of cholate in mixed surfactant system is still not
well known.
In this work, we applied several cholate
derivatives with different structure in the number,position, and orientation of hydroxyl groups to thecolumn separation (Fig. 1). Their selectivities were
evaluated by the elution order of chiral species in theseparation. SWCNTs adsorbed to the gel in SC/SDS
system were eluted by stepwise increase of theconcentration of each derivative in the fixed
concentration of SC/SDS. In this method, the species
with low affinity to the gel are eluted first with low
concentration of eluent. We observed that elution
orders were strongly dependent on the used cholate
derivatives. For example, the order eluted by DOC
showed the trend from smaller diameter species tolarger diameter species (Fig. 2, top), while the ordereluted by SC showed countertrend (Fig. 2, bottom).
Finally, we found that these different elution orders
correlate with their hydrophobic/hydrophilic balance.
This work was supported by KAKENHI No.
25220602.

400

600 800 1000 1200
Wavelength (nm)Fig.2 Optical absorption spectra of eluted
SWCNTs with increasing DOC (top) andSC (bottom) concentration

1-5
Development of thermoelectric device using cobaltocene-encapsulated
carbon nanotubes○Tsuyohiko Fujigaya1,2, Takahiro Fukumaru1 and Naotoshi Nakashima1,2,
1 Department of Applied Chemistry, Graduate School of Engineering.
Kyushu University, 744, Motooka Nishi-ku Fukuoka, 819-0395, Japan
2 WPI I2CNER. Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan
Thermoelectric conversion is one of the key technologies to realize a sustainable society sincelarge quantities of energy have been wasted as heat. A number of semiconducting materials especially,
inorganic materials, such as Bi2Te3, Si/Ge and PbTe, have been intensively studied due to their highpower factors originated from large Seebeck coefficients and high carrier conductivity. Recently,
carbon nanotubes have attracted much attention as substitutes due to their lower cost, ease of
fabrication, flexibility and light weight. Very recently, Maniwa et al. reported that a sorted
semiconducting single-walled carbon nanotubes (s-SWNTs) film shows a very large Seebeckcoefficient (170 V K-1 at 300 K) [1]. Whilet SWNTs are promising p-type organic thermoelectricmaterials, the development of the flexible n-type thermoelectric materials is still challenging even atpresent, because n-type semiconducting organic materials are inherently unstable in air due tooxidation.
In this study, in order to tune the SWNTs to the n-type, we chose cobaltocene (CoCp2) as the
dopant for the encapsulation due to its strong reducibility (Fig. 1). Among the variety of doping
approach, we focused on encapsulation of the dopant molecules inside the SWNTs, which show asuperior doping stability due to the molecular shielding effect compared to the doping on the outside
the tubes. Then, the SWNTs encapsulated with CoCp2 (CoCp2@SWNTs) were used to fabricate a p-nconnected thermoelectric device without any air protective coating.
We prepared cobaltocene-encapsulated SWNTs (denoted
CoCp2@SWNTs) by evapolating the CoCp2 under heating in
the presence of the open-capped SWNTs. It was revealed that
CoCp2
CoCp2@SWNTs
showedanegative-type(n-type)semiconducting behaviour (Seebeck coefficient: -41.8 V K-1
at 320 K). The CoCp2@SWNT film was found to show a high Fig. 1 Structure of CoCp2@SWNT
electrical conductivity (43,200 S m-1 at 320 K) and large
power factor (75.4 W m-1 K-2) and the performance was remarkably stable under atmosphericconditions over a wide range of temperatures. The thermoelectric figure of merit (ZT) value of the
CoCp2@SWNT film (0.157 at 320 K) was highest among the reported n-type organic thermoelectricmaterials due to the large power factor and low thermal conductivity (0.15 W m -1 K-1). These
characteristics of the n-type CoCp2@SWNTs allowed us to fabricate a p-n type thermoelectric device
by combination with an empty SWNT-based p-type film. The fabricated device exhibited a highly
efficient power generation close to the calculated values even without any air-protective coating due tothe high stability of the SWNT-based materials under atmospheric conditions.[2][1] Y. Nakai, et al.. Appl. Phys. Express 7, 025103, (2014).
[2] T. Fukumaru, et al. Sci. Rep., in press.

- 15 -

1-6
Modification of the local structure of carbon materials by ion irradiationand the support properties of Pt nanoparticles by one-step electro
deposition method○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 anode materials of direct methanol fuel cell
(DMFC). As is well-known, the highly dispersed Pt on carbon supports as well as catalyst
particle size and shape plays a dominant role in the electrochemical performance for fuelcells1). We have explored the effects of ion-irradiation of carbon materials with different
microstructures, including Carbon nanosheets(CNSs), Single-Walled Carbon Nanotubes(SWNTs) and HOPG on their support properties of Pt nanoparticles by one-step electro
deposition method2) and reported the improvement of the electrocatalytic activities by ion
irradiation. In this study we investigated more detailed local structures of ion irradiatedcarbon materials and relationship between the local structures of carbon materials, the shapeand dispersion state of Pt nanoparticles and the methanol oxidation activities. The ion beam
accelerated with carbon ion source with 200 keV and 400keV were irradiated to the carbon
materials with 1 ×1013, 1 × 1014, 1 × 1015 ions/cm2. Figure.1 shows the one example of TEM
images of HOPG before and after ion irradiation. The detailed results will be presented.

Figure. 1.
ions/cm2)

TEM images (a) pristine of HOPG and (b) ion irradiated HOPG (400 keV, 1×1014

1) Zhipeng Wang, Mao Shoji and Hironori Ogata, Appl. Surf. Sci.259(2012)219-224.
2) S.Hayase et al., Abstract of the 47th Fullerenes-Nanotubes-Graphene General Symposium(1P-19).
Corresponding Author: Hironori Ogata,Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 16 -

1-7
Preparation of Boron Nitride Containing Carbon Nanohorn for Boron
Neutron Capture Therapy○Yoko Iizumi1, Toshiya Okazaki1, Minfang Zhang1, Ryota Yuge2, Toshinari Ichihashi2, Maki
Nakamura1, Yuzuru Ikehara1, Sumio Iijima1,2,3, Masako Yudasaka1
1

Nanotube Research Center, National Institute of Advanced Science and Technology (AIST),
Tsukuba, 305-8565, Japan
2
Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
3
Faculty of Science & Technology, Meijo University, Nagoya 468-8502, Japan
Boron neutron capture therapy (BNCT) has been tried to establish as a novel treatment for amalignant tumor of Brain, glioblastoma. The nuclear reaction between boron and low energy
neutrons generate  beam and 7Li, which have short trajectory, about 10 micrometer,
comparable to the cell sizes. When the boron compounds exist only in the tumor cells but notin the normal cells, the neutron beam can kill the tumor cells, while harmless to the normal
cells. In other words, BNCT is feasible to use for the control of not only glioblastoma, butalso the other solid tumors with dissemination, and massive invasion and metastasis if theboron compounds are properly delivered to cancer cells.
Various types of boron compounds and carriers have been studied to increase the BNCT
efficacies, though the high and selective accumulation of boron compounds at tumor cells has
not been well achieved. In this context, we have prepared the BN loaded single-walled carbon
nanohorns aggregate (CNH) using a method of Nakanishi et al [1] modified for our purpose.
And the obtained BN-CNH was functionalized with tumor targeting molecule, folic acid (FA).
Ammonia borane (H3N-BH3) and CNHs were sealed in a quartz glass ampoule, and heatedat various temperatures (550-850 oC). An optimum production temperature was 800 oC in
terms of the large BN quantities and stable BN structures. The XPS analysis showed that a
number ratio of C:B:N was 5:2:2 in BN-CNH prepared at 800 oC. The BN had layer
morphology, therefore they were hexagonal BN, which was confirmed also by EELS
measurements. The BN sheets were found on the outside and inside of nanohorn tubule walls.
The BN sheets were also deposited on the thin graphite sheets as confirmed by TEM
observations and XRD measurements. Here, the thin graphite sheets mean those constructing
CNHs together with nanohorn tubules.
Further, purposing the selective accumulation of BN-CNHs in tumor cells, BN-CNHs were
coated with phospholipid polyethylene glycol having FA (BN-CNH/PLPEG-FA). The in vitro
cell experiments indicated that BN-CNH/PLPEG-FA was selectively ingested by humantumor KB cells but not by human normal FHs 173We cells. BN-CNH/PLPEG (without FA)
did not show such tumor cell selective uptake tendency. Thus BN-CNH is concluded to havehigh potential for BNCT application.
[1] R. Nakanishi, et al. Sci. Report. DOI:10.1038/srep01385.
Contact: t-okazaki@aist.go.jp, m-yudasaka@aist.go.jp- 17 -

1-8
Multifunctional carbon nanohorn complexes for cancer treatment○Eijiro Miyako1, Svetlana A. Chechetka1, Benoit Pichon2, Minfang Zhang1,
Masako Yudasaka1, Sylvie Bégin-Colin2, Alberto Bianco3
1

Nanotube Research Center (NTRC), National Institute of Advanced Industrial Science andTechnology (AIST), Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Japan
2
Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504
(CNRS-UdS-ECPM) 23, rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France
3
CNRS, Institut de Biologie Moléculaire et Cellulaire, Immunopathologie et Chimie
Thérapeutique, 15 Rue René Descartes, 67084 Strasbourg Cedex, France

Multifunctional carbon nanohorn (CNH) complexes were synthesized using oxidized CNH,
magnetite (MAG) nanoparticles, and polyethyleneimine (PEI). The ferromagnetic MAG
nanoparticles were loaded onto CNH (MAG–CNH) using iron (II) acetate and a subsequent
heat treatment. Chemical functionalization of the MAG–CNH complexes with PEI improved
their water-dispersibility and allowed further conjugation with a fluorophore. The applicationof an external magnetic field significantly intensified the targeted vectorization of CNH
complexes into human cervical cancer (HeLa) cells. Following cell uptake, laser irradiation of
the cells showed a significant enhancement in the photothermal effects of CNHs leading tocell death. We have confirmed that the photothermal property and ferromagnetic
characteristics of CNH complexes exhibit an efficient cell elimination. The present study is an
essential step toward the development of an innovative cancer therapy and a highly sensitive
detection of cancer cells at the single-cell level.

Fig. 1 Concept of the cancer treatment using multifunctional CNHs.
[1] E. Miyako et al. Angew. Chem. Int. Ed. 53, 13121 (2014).
[2] E. Miyako et al. Nature Communications 3, 1226 (2012).
[3] E. Miyako et al. Proc. Natl. Acad. Sci. USA 109, 7523 (2012).
[4] E. Miyako et al. Angew. Chem. Int. Ed. 50, 12266 (2011).
Corresponding Author: E. Miyako
Tel: +81-87-869-3574, Fax: +81-29-861-6290,
E-mail: e-miyako@aist.go.jp- 18 -

1-9Comparative LDI analysis of nanodiamonds from detonation
synthesis and pre-solar carbonaceous meteorites○Toshihiko Tanaka,1 Ryoko Yamanoi2 and Eiji Ōsawa2*
1

Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, Iwaki, Fukushima 970-8034, Japan.
2
NanoCarbon Research Institute, AREC, Faculty of Fiber Science and Technology, Shinshu
University, Ueda, Nagano 386-8567, Japan. *osawa@nano-carbon.jp, Tel: +81-268-75-8381
Primary particles of detonation nanodiamond (PPDND) are the smallest known artificial
diamond (diameter of 2.8〜3nm), available in macroscopic quantities and well-studied1. On
the other hand, the smallest known natural diamonds, isolated from several pre-solar
carbonaceous chondrites of Allende, Murchison and a few other meteorites, have been shownto have comparative sizes (2.4〜2.8nm)2,3. We recently found that LDI (Laser desorption
ionization) MS of these two kinds of nanodiamond gave identical features as well regarding
position and abnormal width of core diamond peak (Fig. 1). The purpose of this work is toanalyze origin of the similarities.
10792
2996

a

ca 13000b

Fig. 1 (a) LDI MS of our primary particles of disperseddetonation nanodiamond. (b) MALDI MS Nanodiamond isolated
from Allende meteorite, copied from ref. 2.

According to our modeling with SCC-DFTB level of theory, the 3nm PPDND is a bucky
diamond having 2012 carbon atoms (24,144 Dalton) with the morphology of doubly truncatedoctahedron (inserted in the upper right corner)4. However, the observed LDI spectra showmajor diamond peak at ca11,000 Dalton (Fig. 1a), nearly one-half of the expected mass. One
likely explanation for this observation would be to invoke the well-known macle formation
process,5 which produced a pair of equal divisions during high-energy of laser desorption, but
the two halves drifted apart while undergoing extensive fragmentation by excess energy.
Nanodiamond from Allende meteorite is considered consisting of ca 1,000 carbon atoms
based on MALDI spectra (Fig. 1b), but this mass contradicts with the size of ca 2.8nm
obtained by visual analysis of TEM images and comparable to that of PPDND!2 Confusion isaggravated by very low reported density (2.22g/cm3)3, too low for a diamond crystal. We will
present a comprehensive picture for the nanodiamonds based on information from detonation
nanodiamond.
[1] A. Barnard, N. Mchedlov-Petrossyan, E. Ōsawa et al. manuscript in preparation. [2] I. C. Lyon, Meteorit.
Planet. Sci. 40, 981 (2005). [3]R. S. Lewis et al. Nature, 326, 160 (1987). [4] A. S. Barnard, E. Ōsawa,
Nanoscale, 6, 1188 (2014). [5] R. Tappert & M. Tappert, ‘Diamond in Nature’, Springer, Berlin, 2011, p. 32.

- 19 -

2-1
Direct- and Dry-Deposited Single-Walled Carbon Nanotube Films Dopedwith MoOx as Electron-Blocking Transparent Electrodes for Efficient
Flexible Organic Solar Cells○ Il Jeon1, Kehang Cui2, Takaaki Chiba2, Anton Anisimov3, Albert G. Nasibulin4,5, Esko I.
Kauppinen4, Shigeo Maruyama2*, and Yutaka Matsuo1*
12

Department of Chemistry, The University of Tokyo, Tokyo 113-0033, Japan
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
3
Canatu Ltd., Konalankuja 5, FI-00390 Helsinki, Finland4
Department of Applied Physics, Aalto University School of Science, Aalto, Finland
5
Skolkovo Institute of Science and Technology, Moscow, 143025, Russia

As an alternative path to indium based organic solar cells (OSCs), carbon nanotubes (CNTs)
and graphene with excellent mechanical flexibility and earth abundance have emerged as thenext generation electrode1. Single-walled CNTs (SWCNTs) have advantages in terms ofstretchability2, easier synthesis, direct roll-to-roll deposition onto substrates, and accordingly
lower costs. There has been a vigorous research on SWCNTs and its application astransparent conductive film in photovoltaics to date.3 Here, we propose the most effectively
composed ITO-free OSC and its flexible application by applying technologies that arestate-of-the-art. Firstly, high quality direct- and dry-deposited aerosol SWCNT was used as
anode for the first time. Secondly, MoOx with poly-(3,4-ethylenedioxythiophene)-polystyrenesulfonic (PEDOT:PSS) on top functioning as both dopant and hole-transporting
layer (HTL) was discovered and applied. Thirdly, using thieno[3,4-b]thiophene/
benzodithiophene (PTB7), which is highly performing photoactive material with no annealing
requirement, flexible application on films are demonstrated. Our record high SWCNT OSC
shows a power conversion efficiency (PCE) of 6.04%, which is 83% to its ITO based
counterpart with a PCE of 7.48%. (Fig. 1) We anticipate the methodology presented here is
not only limited to OSCs but extends to other photovoltaic applications such as emerging
perovskite solar cells too. Our finding paves toward fully carbon flexible solar cells by using afacile and stable process.
[1] D. Volder et al. Science 339, 535 (2013).
[2] S. Won et al. Nanoscale 6, 6057 (2014).
[3] J. Du et al. Adv. Mater. 26, 1958 (2014).
Corresponding Author: S. Maruyama and Y. Matsuo
Tel: +81-3-123-4567, Fax: +81-3-123-4567,
E-mail: matsuo@chem.s.u-tokyo.ac.jp

OR

S

eh+

Al

F

LiF!
PTB7:PC71BM:DIO!

RO

MoOx-doped SWCNT Network and+! PEDOT capping!

+!

+!

+!

+!

+!

Glass/Flexible Substrate

S
O

OR

R = 2-ethylhexyl

PTB7!
5 μm !

MoOx!
SWCNT!
Aerosol!
SWCNT!

Fig.1 The schematics of our optimized device.

- 20 -

S
n

S

2-2
Evaluation of perovskite solar cellswith single-walled carbon nanotube cathodes○Takaaki Chiba 1, Takahiro Sakaguchi 1, Albert G. Nasiblin 2, 3, Esko I. Kauppinen 2,
Rong Xiang 1, Shohei Chiashi 1 and Shigeo Maruyama 1
1

Department of Mechanical Engineering,The University of Tokyo, Tokyo 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 in 2009 [1], havebeen attracting much attention because of their high power conversion efficiency (PCE). Onlyin these 5 years, the PCE of perovskite solar cells has increased from 3.8 % to about 20 %.
Beside this promising aspects, the stability is still a concern. As cathodes, hole transportmaterial (HTM), usually spiro-OMeTAD, and gold electrode are used in conventional
perovskite solar cells. The spiro-OMeTAD is expensive and gradually deteriorates. The gold
electrode is also expensive, moreover, vacuum deposition process hinders the cost-effective
manufacturing. Hence, for further low cost bulk production, it is desired to replace HTM andgold electrode to inexpensive and stable materials, which can be fabricated in ambient condition.
Single-walled carbon nanotubes (SWNTs) are considered to be one of the promising candidates
for the cathode, and there are a few reports on perovskite solar cells with SWNTs [2].
In this study, we employed vertically aligned-SWNT (VA-SWNT)/FTO cathodes andfabricated perovskite solar cells (Fig. 1). Perovskite crystals were prepared from PbI2 and PbCl2
in ambient conditions. The J-V characteristics show that the PCE of solar cells with SWNT/FTO
from PbI2 and PbCl2 are 5.4 % and 4.0 %, respectively, while the PCE with HTM/Au are 8.9 %and 10.1 % (Fig. 2). Figure 3 shows the SEM images of perovskite crystal (a) from PbI2 and(b) from PbCl2. The surface coverage of perovskite crystal from PbI2 is larger than that ofperovskite crystal from PbCl2, which indicates the surface coverage has significant effect. The
solar cell system using the SWNT transparent conductive film by dry deposition process [3] will
also be discussed.
[1] A. Kojima et al. JACS 131, 6050 (2009). [2] Z. Li et al. ACS Nano 8, 6797 (2014).
[3] 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

2

Current Density (mA/cm )PbI2 HTM/Au
PbI2 VA−SWNT
PbCl2 HTM/Au
PbCl2 VA−SWNT

20

10

0
0

Fig. 1 Schematic image of perovskite
solar cells with VA-SWNT.

0.4
Voltage (V)0.8

Fig. 2 J-V characteristics ofperovskite solar cells.

- 21 -

Fig. 3 SEM images ofperovskite crystal (a) from
PbI2 and (b) PbCl2.

2-3
Non-catalytic CVD growth from carbon nanotube forest
formed by SiC surface decomposition
Yu Hirano1, Masafumi Inaba1, Megumi Shibuya1, Kazuma Suzuki1,Chih-Yu Lee1,
Miho Myodo1, Atsushi Hiraiwa1, Wataru Norimatsu2, Michiko Kusunoki2, Hiroshi Kawarada1○

1

School of Science and Engineering, Waseda University, Tokyo 169-8555, Japan2
Eco Topia Science Institute, Nagoya University, Aichi 464-8603, Japan

We report the non-catalytic synthesis of carbon nanotubes by thermal CVD method from
uncapped carbon nanotube forest as template . The uncapped CNT forest was formed by SiC
surface decomposition (CNT forest on SiC) [1]. CNT forest on SiC consists of nearly ideallyclose-packed, well-aligned, and catalyst-free CNTs. We also report analysis of the synthesized
CNTs by using Raman spectroscopy and SEM, and investigation of the chirality and thegrowth model.
CNT forest was formed on the C-face () of n-type 4H-SiC substrate with SiC surface
decomposition method. The length of CNT forest was about 30 nm. Then, this CNT forest
was treated to uncap CNTs by mild oxidation with 15 wt%, 100°C H2O2 solution [2]. CNTs
were grown from uncapped CNT surface by thermal CVD method with CH4 and H2 as sourcegases.Fig.1 shows the schematic image of this experimental.

Fig.1 Process image of this experimental

Fig.2 The SEM image after
CVD (CH4 40%, 1000°C, 1h)

We explored the optimal proportion of these gases and temperature condition for growth. In
thermal CVD method, CNTs were grown under wide range conditions; at 1000°C, CH4
proportion of 10~100% (H2 dilution, total flow 50 sccm). The best condition of these gases
for non-catalytic CVD growth was CH4 ratio of 40%, 1000°C. The CNT forest thickness
increased homogeneously from 30 nm to about 100 nm in this condition, various diameters
CNTs grew rapidly from the surface of CNT forest. The ratio of the rapidly grown CNTs wasestimated to be about 1/1000 of uncapped CNT surface.
Raman spectra after uncap, CVD 1h, and CVD 4h (thetreatment conditions were the same as the above) are shown in
Fig.3. As the CVD growth time got longer, the intensity of
G-band increased and G/D ratio became higher. Non-catalytic
CNTs growth in CVD continued for a long period. Also, we cansee enhanced RBM spectra after 4h CVD growth indicating highquality CNTs were of synthesized.

Fig.3 Raman spectra after[1] M. Kusunoki et al., Appl. Phys. Lett. 87, 103105 (2005)
uncap, CVD 1h, and 4h[2] R. Marega et al., Carbon 47, 675 (2009).
Corresponding Author: Y. Hirano/Tel: 03-5286-3391, Fax: 03-5286-3391, E-mail: yu.-855@ruri.waseda.jp- 22 -

2-4
Structure and electronic state of [lucigenin]C60 molecularfulleride salt
○Hiroshi Moriyama1, Shohei Yamamoto1, Hatsumi Mori2, Kenji Yoza3, Hideyuki Hara4
1

2

Department of Chemistry, Toho University, Miyama 2-2-1, Funabashi 274-8510, Japan
Institute for Solid State Physics, The University of Tokyo, Kashiwanoha 5-1-1, Kashiwa, 277-8581, Japan
3
Bruker AXS, Moriyacho 3-9, Yokohama, 221-0022, Japan
4
Bruker Biospin, Moriyacho 3-9, Yokohama, 221-0022, Japan

Fullerene C60 has high electron affinity, and is easily
R
reduced to form fulleride anion radicals by accepting an electron.
N
Electrocrystallization of C60 in the presence of appropriate countercations affords relatively stable single crystals of radical salts. In
2NO
this study, we used lucigenin (Fig. 1) as a counter cation for the
preparation of fulleride salts because lucigenin has an intriguingNcharge state (+2, +1, 0) and its fulleride salts are obtained by
R = -CHR-CH CH-CH C H
electrocrystallization. We determined the crystal structure by
Figure 1. Lucigenin and analogues.
Fig. 1 Lucigenin and analogues
single-crystal X-ray diffraction analysis and investigated theelectronic state of the fulleride salt by ESR measurements.
Single-crystal X-ray analysis of the crystal structure
revealed that in [lucigenin]C60 the ratio of lucigenin:C60 is 1:1(Fig. 2). A columnar structure of C60 moieties was observedwith a C60−C60 distance of 9.993 Å (Fig. 2), within van der
Waals interaction. Jahn−Teller distortion of the C60 cage wasclearly observed; thus there was descent in symmetry of the C60
moiety from Ih to S6. The Jahn−Teller distortion causes orbital
Fig. 2 ORTEP diagram of [lucigenin]C60
splitting of t1u. Therefore, it was expected that the t1u orbital
would be split into eu and au orbitals.
An ESR spectrum showed a weak signal assignable to a trace amount of [C120O]n－,but there was no broad signal characteristic of C60－●. This result implies that the charge stateof C60 was further reduced to C602－from C601－ and the lucigenin cation remains 2+. It should
be noted that the spin state of C602－ is not the degenerated spin−parallel triplet state (Fig. 3,left), but the singlet state (spin paired) of the au state caused by Jahn−Teller distortion.
Therefore, the au orbital is occupied by
Jahn−Teller
two electrons, and hence the charge state
Jahn-Teller splitting
splittingeuof the salt was found to be ESR-silent[lucigenin]2+(C60)2−.
However, spin
ΔEST
singlet−triplet conversion should easily
occur to give the triplet state, ESR-active
t1u
auparallel spins on the eu orbital, because
Fig.Figure.
3 Singlet−triplet
splittingsplitting
model model.
3 Singlet-triplet∆EST (the singlet−triplet energy gap) was
found to be rather small.
+

3

+

3

2
2

Corresponding Author : Hiroshi Moriyama

TEL: +81-47-472-1211, FAX: +81-47-472-1188, E-mail: moriyama@chem.sci.toho-u.ac.jp- 23 -

3

6

5

2-5
Method of Separating Endohedral Metallofullerenes using Electron Donorand Polar Solvent○Kazuki Chiba, Kazuhiko Akiyama, and Shiro Kubuki
Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Various methods for the separation of endohedral metallofullerene (EMF) have beendeveloped and reported so far. One of the most efficient way is electrochemical separation
making use of the difference in the redox potential between EMF and empty fullerene. In
2012, a method for the separation with TiCl4 was reported [1]. EMF in fullerene crude extract
is selectively oxidized with TiCl4, and efficiently separated as the precipitate. So theformation of precipitate composed of EMF-TiCl4 aggregate and their particle size are found tobe the most important parameters, this separation method could be effectively applied for the
separation of the large amount of EMFs [2]. However, this method is not suitable for the
separation of trace amount of EMF, such as carrier-free radioactive EMFs applicable for the
nuclear medicine, because the formation of aggregate and their size are expected to be
insufficient. Herein, we report a newly developed separation method without aggregation of
EMFs using electron donor and polar solvent.
Fullerene crude extract was prepared by arc-discharge method using porous carbon rod
containing La and radio-tracer of 139Ce. Fivefold volume of 0.3 M triethylamine (TEA)/
acetonitrile solution was added to the CS2 solution of the fullerene crude extract for the
reduction of EMF and to remove the empty fullerenes as a precipitate. After the shaking it for5 minutes, this suspended solution was filtered. The filtrate was treated with dichloroacetic
acid (DCA) to oxidize EMF to its neutral form and then analyzed with high performanceliquid chromatography (HPLC). Figure 1(a)C60
C70
shows the HPLC chromatogram of thefiltrate after removal of DCA. For the
C84
comparison, the chromatograms of the EMF
rich fraction separated with TiCl4 (b) andLa@C82
fullerene crude extract (c) are also indicated.
The peak intensity of La@C82 was almost(c)same as those in crude extract and fraction
separated with TiCl4. On the other hand, the(b)intensities of C60 and C70 were decreased
drastically compared to those in crude
extract, though those of higher fullerenes(a)such as C78 and C84 were still remained. The
separation rate, which was defined as thepercentage of the amount of EMF afterFig.1 HPLC chromatograms of (a) filtrate of theseparation to before, was determined from 
separation with TEA, (b) EMF rich fraction
139
separated with TiCl4 and (c) fullerene crude extract.
ray measurement using
Ce-EMF as a(column:
5PYE, eluent: chlorobenzene)
radio-tracer and was found to be 93±2%.
[1] K. Akiyama et al., J. Am. Chem. Soc., 134, 9762-9767, (2012).
[2] K. Chiba et al., 5th Asia-Pacific Symposium on Radiochemistry, 271p-24-APP-04 (Kanazawa, 2013).
Corresponding Author: K. Akiyama
Tel: +81-42-677-2525 (Ext. 3587), E-mail: kakiyama@tmu.ac.jp- 24 -

2-6
Vibronic Coupling Density Analysis for Multiple Cycloadditions to C60◦ Naoki Haruta1 , Tohru Sato1,2 , Kazuyoshi Tanaka1
1 Department of Molecular Engineering, Graduate School of Engineering,

Kyoto University, Kyoto, 615-8510, Japan
2 Unit of Elements Strategy Initiative for Catalysts & Batteries, Kyoto University,

Nishikyo-ku, Kyoto 615-8510, Japan
Much attention has been attracted to functionalizations of fullerenes because fullerene derivatives such as PCBMs have been used in the ﬁeld of material chemistry. Theoretical prediction
for the regioselectivity of fullerenes and their derivatives would therefore be helpful to develop
novel fullerene-based materials.
The frontier orbital theory is such a theory. However, the conventional frontier orbital theory
sometimes fails to predict the regioselectivities of fullerenes because their frontier orbitals arestrongly delocalized due to the large molecular size and high symmetry. To overcome thisdiﬃculty, we have proposed vibronic coupling density (VCD) as a reactivity index [1,2]. It canbe formulated in the framework of Parr and Yang’s conceptual density functional theory [3]. The
VCD theory takes into consideration not only electronic states but also molecular deformations.
This is in contrast to the frontier orbital theory, in which only the electronic states (frontier
orbitals) are considered.
In our previous studies, we have explained the reactive sites of C60 [2], C70 [4], and La2 @C80
[5] on the basis of the VCD theory. We found their reactive sites to have almost the same
VCD distributions as a dienophile, ethylene (Fig. 1). This is consistent with experimental
observations that fullerenes act like dienophiles in Diels–Alder reactions. The VCD analysis
enabled us to extract a picture of the functional group, ethylene.
In this study, we applied the VCD theory to
successive multiple cycloadditions of butadienes
Reactive site
to C60 [6]. C60 n-adducts (n = 1, · · · , 6) were experimentally reported to be synthesized [7-9]. We
calculated the VCDs of C60 adducts with n butadienes (n = 1, · · · , 5) and analyzed their reactivities. Just like C60 , all the calculated C60 multiadducts were found to have ethylene-like VCD
distributions at their reactive sites. This is conC60
C60 pentakisadductsistent with experimental observations that C60 Ethylene
multiadducts behave as dienophiles in multiple
cycloadditions. Furthermore, the VCD theory Fig. 1: VCDs of ethylene, C60 , and C60 penpredicted that the hexakisadduct with a six-fold takisadduct for their eﬀective modes in nuaxis can be ﬁnally obtained, which is also consis- cleophilic cycloadditions.
tent with experimental ﬁndings [8,9].
[1] T. Sato et al, J. Phys. Chem. A 112, 758 (2008). [2] T. Sato et al, Chem. Phys. Lett. 531, 257 (2012). [3]R. G. Parr and W. J. Yang, J. Am. Chem. Soc. 106, 4049 (1984). [4] N. Haruta et al, J. Org. Chem. 77, 9702
(2012). [5] N. Haruta et al, J. Org. Chem. 80, 141 (2015). [6] N. Haruta et al, Tetrahedron 70, 3510 (2014). [7]A. Hirsch et al, Angew. Chem., Int. Ed. Engl. 33, 437 (1994). [8] A. Hirsch et al, J. Am. Chem. Soc. 116, 9385
(1994). [9] B. Kräutler and J. Maynollo, Angew. Chem., Int. Ed. Engl. 34, 87 (1995).
Corresponding Author: T. Sato
Tel: +81-75-383-2803, Fax: +81-75-383-2555
E-mail: tsato@moleng.kyoto-u.ac.jp- 25 -

2-7
From linear carbon molecules to fullerenes under laser vaporization- Growth, annealing, and quenching ○Tomonari Wakabayashi1, Yoriko Wada2, Yusuke Morisawa1, Hitomi Endo2, Yuki Taguchi2,
Jun Matsumoto2, Takeshi Kodama2, Yohji Achiba2, Haruo Shiromaru2
1

2

Department of Chemistry, Kinki University, Higashi-Osaka 577-8502, Japan
Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan

Laser vaporization of graphite has opened a wide variety of synthetic routes to novel
carbon nanostructures, i.e., linear carbon molecules [1], monocyclic rings [2], fullerenes [3],and nanotubes [4]. It is essentially a high-temperature process, instantaneously heating target
materials above 4,000 K, followed by ablation of layered carbons, which eventually fragment
into scrambling small carbon molecules of sp hybridization. The sticky carbon molecules
agglomerate rapidly, growing into spheroidal nanoparticles through self-annealing by latent
heat of isomerization from sp to sp2 as well as by heat of formation of chemical bonds [5].
When the cooling process is accompanied by subsidy annealing by the heat of an externalsource like a furnace, keeping the ambient temperature above ~800°C for more than amillisecond, the molecular carbon aggregates are efficiently converted to perfect symmetry of
hollow, closed carbon cages of fullerenes [6]. Assisted by the presence of appropriate metal
catalysts, carbon vapor molecules condense into a nano-sized metal particle then crystalize on
the surface into nanotubes. Both, fullerenes and nanotubes, are based on sp2 hybridization andthermodynamically stable allotropic forms of carbon at standard conditions.
Another form of carbon, amongst those appeared in the context of allotropy of carbon,
naturally be a linearly organized solid form of sp carbon atoms, namely carbyne. A number ofattempts have been made but thwarted in characterizing the material in a crystallographic
sense [7]. It is in one part by metastable nature in thermodynamics and in another by highly
reactive nature of unsaturated chemical bonds in the sp form of carbon. Again, under thecondition of laser vaporization, such a transient species of sp carbon atoms can be quenchedchemically as hydrogen-end-capped linear carbon molecules, namely polyynes [8,9], or as aself-terminated monocyclic ring of carbon, cyclic-C10 [10]. In a balance of competitive
reactions between growth and quenching, possibly with annealing, polyynes and fullerenes
are formed simultaneously under laboratory conditions. We discuss our recent finding on theprocess of laser vaporization forming polyynes, fullerenes, and monocyclic carbon rings.
[1] J. R. Heath et al. J. Am. Chem. Soc. 109, 359 (1987).
[2] S. Yang et al. Chem. Phys. Lett. 144, 431 (1988).
[3] H. W. Kroto et al. Nature 318, 162 (1985).
[4] S. Iijima et al. Nature 363, 603 (1993).
[5] T. Wakabayashi et al. J. Phys. Chem. B 108, 3686 (2004).
[6] R. E. Haufler et al. Proc. Mat. Res. Soc. Symp. 206, 627 (1991).
[7] F. Diederich et al. Acetylene Chemistry, Wiley, Chap. 9 (2005).
[8] M. Tsuji et al. Chem. Phys. Lett. 355, 101 (2002).
[9] H. Tabata et al. Carbon. 44, 522 (2006).
[10] Y. Kato et al. Chem. Phys. Lett. 386, 279 (2004).
Corresponding Author: T. Wakabayashi
Tel: +81-6-4307-3408, Fax: +81-6-6723-2721,
E-mail: wakaba@chem.kindai.ac.jp
Fig. 1. Spectrum of blackbody radiation of laser
ablated carbon particles in hexane (~4100 K).

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2-8
The effect of DNA adsorption on optical transitions in single-walled carbon
nanotube depending on base sequence○Masahiro Ito, Yusuke Ito, Hiroki Kato, Kazuo Umemura, Yoshikazu Homma
Department of Physics, Tokyo University of Science, Tokyo 152-8601, Japan
DNA-SWNT hybrids emit photoluminescence (PL) not only in solution [1], but also on asubstrate under the dry condition [2]. PL spectra can be used to analyze the adsorption state of
DNA on SWNT. However, it is difficult to evaluate purely the effect of DNA adsorption from
DNA-SWNTs in solution or their ensembles on a substrate. In this study, we prepared low
density DNA-SWNTs on the SiO2 substrate to detect a mono-dispersed DNA-SWNT in thelaser spot. Single-stranded DNA (ssDNA): (dT)30, (dA)30, (dC)30 and (dG)30 were used andtheir effect on PL was investigated.
In the case of DNA-SWNT in solution, the difference in PL spectra did not appear
specifically, although PL spectra from (dT)30-SWNT showed blue-shifts relative to other
ssDNA. In contrast, PL from mono-dispersed DNA-SWNT exhibited different peaks
depended on the base sequence of DNA, as shown in Fig. 1 for (9,4) SWNT. The dependenceof the energy shift on the DNA type is almost the same for different charalities. PL emission
peaks from each type of ssDNA-SWNT are listed in Table 1. The PL energy ofmono-dispersed DNA-SWNT shifted in the order (dT)30, (dA)30, (dC)30 and (dG)30.
PL shifts cannot be explained only by the difference in the number of π-π stacking. If wetake into account the number of n-π stacking, the tendency of red shift should be T < A < C <G. PL spectra reflect the interaction between SWNT and DNA base.
[1] M. Zheng et al. Nature, 2, 338 (2003)[2] M. Ito et al. Appl. Phys. Lett. 104, 043102 (2014)
Corresponding Author: M. Ito
Tel: +81-3260-4271-, Fax: +81-3-5261-1023,
E-mail: m-ito@rs.tus.ac.jp
Table 1. PL emission peaks from each type of
DNA-SWNT under the dry condition.
Emission wavelength (nm)chirality(dT)30(dA)30(dC)30(dG)30(10,2)

1067

1072

1078

1083

(9,4)

1119

1123

1124

1131

(8,6)

1185

1186

1202

1202

(8,7)

1278

1282

1290

1303

Fig 1. PL peaks from various mono-dispersed DNA-SWNTs.

- 27 -

2-9
Electronic properties and polarities of atomic-layer materials:
Doped graphene, hexagonal BN layers, and carbon nanotubes○Susumu Saito1,3,4, Takashi Koretsune2, and Yoshitaka Fujimoto1
1

Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551, Japan
2
RIKEN Center for Emergent Matter Science, Saitama 351-0198, Japan
3
International Research Center for Nanoscience and Quantum Physics,
Tokyo Institute of Technology, Tokyo 152-8551, Japan
4
Materials Research cener for Element Strategy, Tokyo Institute of Technology,
Kanagawa 226-8503, JapanFor more than a decade, we have theoretically studied the electronic properties of a variety
of doped and structurally modified atomic-layer materials including graphene, hexagonal BN
layers, and carbon nantoubes using the predictive density-functional methods [1-10]. It has
been demonstrated that the doping as well as the structural modification can give rise to thedefect states which should govern the polarity and the electronic transport properties of thesystem. In addition, it has been also shown that the adsorption of hydrogen atoms around theimpurity site can further modify the electronic properties. In the low-dimensional
atomic-layer materials the adsorption of hydrogen and other molecules around the impurity
site should take place more easily than in the ordinary bulk materials and therefore the effectsof their adsorption on the electronic properties are to be of high importance in the future
device applications of the atomic-layer materials.
In this presentation we first review the above-mentioned interesting and important
modifications of electronic properties in atomic-layer materials including monolayer graphene,
bilayer graphene, monolayer and bilayer hexagonal BN, and carbon nanotubes. Next we
propose a rather simple theory to predict the electronic polarities of the doped atomic-layermaterials.
[1] T. Matsumoto and S. Saito, J. Phys. Soc. Japan 71, 2765 (2002).
[2] T. Koretsune and S. Saito, Physical Review B 77, 165417 (2008).
[3] N. Murata, J. Haruyama, J. Reppert, A.M. Rao, T. Koretsune, S. Saito, M. Matsudaira and Y. Yagi,
Phys. Rev. Lett. 101, 027002 (2008).
[4] T. Koretsune and S. Saito, Sci. Technol. Adv. Mater. 9 044203 (2008) .
[5] Y. Fujimoto and S. Saito, Physica E 43, 677-680 (2011).
[6] Y. Fujimoto, and S. Saito, J. Phys: Conf. Ser. 302, 012006 (2011).
[7] Y. Fujimoto and S. Saito, Phys. Rev. B 84, 245446 (2011).
[8] Y. Fujimoto and S. Saito, J. Appl. Phys. 115, 153701 (2014).
[9] Y. Fujimoto and S. Saito, JPS Conf. Proc. 1, 012066 (2014).
[10] Y. Fujimoto and S. Saito, Surface Science (in press).
Corresponding Author: Susumu Saito
E-mail: saito@stat.phys.titech.ac.jp- 28 -

2-10
Electronic States of Flattened Carbon Nanotubes:
Effects of tube chirality and displacement◦ Takeshi Nakanishi1 , and Tsuneya Ando2
1

2

Nanosystem Research Institute, AIST, Japan
Department of Physics, Tokyo Institute of Technology, Japan

We theoretically study effects of inter-wall interaction in flattened carbon nanotubes, first
directly calculating effective inter-wall interaction within an effective-mass scheme and second
regarding flattened tubes as ribbons of bilayer graphene with closed edges described by boundary
conditions explicitly derived.
Within the effective-mass scheme, effects of inter-wall interactions are shown to be importantin non-chiral nanotubes such as zigzag and armchair. In fact, with the increase in the width of
the flattened region, the band structure approaches that of a bilayer ribbon in which the electron
motion in the ribbon-width direction is discritized. In chiral nanotubes, inter-wall interaction canessentially be neglected except in the vicinity of non-chiral tubes. Inter-wall interactions diminish
rapidly when chiral angle deviates from zigzag or armchair, although the decay is slower in thevicinity of the armchair tube. When the flattened region has the structure of AA and AB stacked
bilayer graphene, the same results can be derived by calculating boundary conditions corresponding
to the closed-edge structure in which the top and bottom layers are smoothly connected througha monolayer graphene.

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2-11
Coherent and squeezed phonons in single wall carbon nanotubes○ Ahmad R.T. Nugraha, Eddwi H. Hasdeo, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Ultrashort laser pulses with duration less than a typical phonon period given to a single wall carbon
nanotube (SWNT) sample may generate lattice oscillations coherently, or called as the coherent
phonons. Quantum mechanically, these oscillations can be treated using the concept of coherent states,in which the amplitude-phase uncertainty reach its minimum value [1-3]. In general, we may increase
the uncertainty in the amplitude and at the same time decrease the uncertainty in the phase, or viceversa, while still holding the minimum uncertainty principle. These states are refered to as thesqueezed states. The squeezed phonons in solid state systems have been previously reported to exist insome materials having strong electron-phonon coupling, such as CdZnTe and ZnTe [4]. Recently,
there is also a possibility to generate squeezed phonons in SWNTs via ultrafast spectroscopy using
less than 10-fs pulses, in which the coherent oscillations of G’ bands involving second-order(two-phonon) process may be relevant as a particular example [5-6].
In this work, we calculate the squeezed phonon amplitude of G’ band for a given SWNT and compare
it with the coherent phonon amplitude of G band. The squeezed phonon amplitude for the G’ band isdefined by taking an average of the coherent states of the two phonons generated in the second orderprocess with nonzero wavevectors. By using these phonon amplitudes, we find that the ratio between
the G’ band and G band intensity (IG’/IG) in ultrafast spectroscopy can be adjusted depending on someparameters such as the laser energy, laser pulse width, and SWNT chirality (electron-phonon
coupling). This result might be useful for understanding the coherent control of phonon excitations, i.e.
we may be able to selectively excite a certain phonon mode by adjusting some physical parameters. It
is also very interesting to see that the coherent states and squeezed states of phonons can be excited
simultaneously in an individual SWNT.
[1] J.-H. Kim et al., Chem. Phys. 413, 55-80 (2013).
[2] A. R. T. Nugraha et al., Phys. Rev. B 84, 174302 (2011).
[3] A. R. T. Nugraha et al., Phys. Rev. B 88, 075440 (2013).
[4] Y.-S. Lim et al., Phys. Rev. B 68, 153308 (2003).
[5] Y.-S. Lim et al., Nano Lett. 14, 1426-1432 (2014).
[6] K. Sato et al., Conference on Lasers and Electro-Optics, QELS JTh 2A (2013).
Corresponding Author: A.R.T. Nugraha
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: nugraha@flex.phys.tohoku.ac.jp- 30 -

2-12
Stark effect of excitons in individual air-suspended carbon nanotubes○M. Yoshida, Y. Kumamoto, A. Ishii, A. Yokoyama, Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
We investigate electric-field induced redshifts of photoluminescence from individual
single-walled carbon nanotubes [1]. Photoluminescence spectra of air-suspended nanotubes
within field-effect transistor structures are collected under an application of symmetric bias
voltages on source and drain contacts [2]. We find that redshifts scale quadratically with field,
while measurements with different excitation powers and energies show that effects fromheating and relaxation pathways are small. We attribute the shifts to the Stark effect, andcharacterize nanotubes with different chiralities. By taking into account exciton binding
energies for air-suspended tubes, we find that theoretical predictions are in quantitative
agreement.
Work supported by KAKENHI, the Canon Foundation, Asahi Glass Foundation, and KDDI
Foundation, as well as the Photon Frontier Network Program of MEXT, Japan. M.Y. is
supported by ALPS, and A.I. is supported by MERIT and JSPS Research Fellowship.
[1] M. Yoshida, Y. Kumamoto, A. Ishii, A. Yokoyama, and Y. K. Kato, Appl. Phys. Lett. 105, 161104 (2014).
[2] Y. Kumamoto, M. Yoshida, A. Ishii, A. Yokoyama, T. Shimada, and Y. K. Kato, Phys. Rev. Lett. 112, 117401(2014).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 31 -

2-13
Exciton diffusion, end quenching, and exciton-exciton annihilation
in individual air-suspended carbon nanotubes○A. Ishii, M. Yoshida, and Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
Luminescence properties of carbon nanotubes are strongly affected by exciton diffusion,
which plays an important role in various nonradiative decay processes [1]. Here we perform
photoluminescence microscopy on hundreds of individual air-suspended carbon nanotubes to
elucidate the interplay between exciton diffusion, end quenching, and exciton-exciton
annihilation processes [2]. A model derived from random-walk theory as well as Monte Carlosimulations are utilized to analyze nanotube length dependence and excitation power
dependence of emission intensity. We have obtained the values of exciton diffusion length andabsorption cross section for different chiralities, and diameter-dependent photoluminescencequantum yield have been observed. The simulations have also revealed the nature of aone-dimensional coalescence process, and an analytical expression for the power dependenceof emission intensity is given.
Work supported by KAKENHI (23104704, 24340066, 24654084, 26610080), The CanonFoundation, Asahi Glass Foundation, KDDI Foundation, and the Photon Frontier Network
Program of MEXT, Japan. The samples were fabricated at the Center for Nano Lithography &Analysis at The University of Tokyo. A.I. is supported by MERIT and JSPS Research
Fellowship, and M.Y. is supported by ALPS.
[1] S. Moritsubo, T. Murai, T. Shimada, Y. Murakami, S. Chiashi, S. Maruyama, and Y. K. Kato, Phys. Rev.
Lett. 104, 247402 (2010).
[2] A. Ishii, M. Yoshida, and Y. K. Kato, arXiv:1412.7622 (2014).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 32 -

3-1
○Ryo Nouchi1
1

Nanoscience and Nanotechnology Research Center, Osaka Prefecture University, Sakai,
Osaka 5998570, Japan

Bilayer graphene (BLG) possesses a finite bandgap when a potential difference isintroduced between the two constituent graphene layers. The potential difference can begenerated by applying a perpendicular electric field [1] and by introducing a difference in the
carrier concentration between the two graphene layers by means of surface charge transferfrom the adsorbed layers [2]. As a possible source for the latter mechanism, in addition toforeign molecules/atoms unintentionally adsorbed on the surface of the BLG, the metal
contacts must be taken into account. Finite charges are transferred through the contacts due tothe Fermi level alignment between the metallic electrodes and the BLG. Thus, it is expectedthat a finite bandgap exists at the metal contacts. In this presentation, an experimental
signature of the bandgap opening in BLG at the metal contacts will be discussed [3].

0.2
0.1

0.4

4T

0.2

2T

VG > VNP
0.0
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.0
Vinner (V)VG > VNP
1.0 2.0 3.0
Vouter (V)(dID/dVouter) (mS)

ID (mA)

0.3

VG < VNP

0.6) (mS)
(dID/dVinner) (mS)VG < VNP

0.4

(c)

(b)

0.8

0.5

ID (mA)

(a)

0.15
0.10
0.05
0.00

0.05

4T

40
0
40
VG – VNP (V)

Metal

0.10

Metal

Substrate

0.05
0.00

BLG

2T
40
0
40
VG – VNP (V)VG > VNP
EF

Fig.1 (a) Currentvoltage characteristics measured with 4T and 2T configurations. The maximum voltage waschosen to equalize the electric field strength. (b) Gatevoltage dependence of the degree of the nonlinearity
extracted from (a). (c) Expected band diagram for the positivelygated region.

BLG flakes were formed on a Si/SiO2 substrate by mechanical exfoliation from a graphite
crystal. The source/drain electrodes made of Cr/Au were formed on the flakes byelectronbeam lithography processes. A 300nmthick SiO2 layer acted as the gate insulator.
Figure 1a shows highfield transport characteristics of the fabricated BLG fieldeffecttransistor measured with four (4T) and twoterminal (2T) configurations. A difference in thefirstorder derivative of ID at the maximum voltage and 0 V, (dID/dV), is employed as anindicator of nonlinearity of the currentvoltage characteristics, which becomes positive(negative) for superlinear (sublinear) curves. Figure 1b shows the gatevoltage dependence of
the indicator of the nonlinearity. The positive values around the charge neutrality point, VNP,
in the 4T plot can be understood by multiple carrier tunneling processes through the bandgap
induced by charge puddles. The increase in the indicator in the positivelygated region of the
2T plots and its absence in the 4T data coincides with the carrier tunneling through thebandgap at the two pn junctions formed in the BLG channel (Fig. 1c). The opening of abandgap at the metalBLG contacts is an additional source of electrodecontact resistance.
[1] Y. Zhang et al. Nature , 820 (2009).
[2] T. Ohta, A. Bostwick, T. Seyller, K. Horn, and E. Rotenberg, Science , 951 (2006).
[3] R. Nouchi, Appl. Phys. Lett. , 223106 (2014).
Corresponding Author: R. Nouchi
Tel: +81722548394, Fax: +81722548394,
Email: rnouchi@21c.osakafuu.ac.jp- 33 -

3-2
Band-like transport in reduced graphene oxide filmsln (σ)ln (σ)

Absorption intensity (arb. units)○R. Negishi1, M. Akabori2, S. Yamada2, T. Ito3, Y. Watanabe4, Y. Kobayashi1
1Department of Applied Physics, Osaka University, Suita 565-0871, Japan
2
Center for Nano Materials and Technology, JAIST, Nomi 923-1292, Japan
3
Synchrotron Radiation Research Center, Nagoya University, Nagoya 464-8603, Japan
4
Aichi Synchrotron Research Center, Seto, 489-0965, Japan
Utilizing carrier transport that reflects intrinsic graphene band structure is essential for the
excellent electrical performance of the graphene-based transistors. The reduced graphene
oxide (rGO) film is one of promising materials for large area synthesis of graphene. However
electrical performance of the rGO is insufficient, since electrical transport properties of rGO
are described by the 2-dimensional variable range hopping (VRH) model through thelocalization states [1-3] because of many defects still remaining in the rGO. In this study, we
found that the high temperature process above 1100 ºC in ethanol environment (hereafter“ethanol treatment”) enables us to overcome this issue from the analysis of X-lay absorption
fine structure (XAFS) spectra and conductivity of the rGO films.
π* σ* C 1s θ = 45º
The ethanol treatment of the GO films was carried out using thechemical vapor deposition apparatus with a furnace. The
unoccupied π* and σ* states of the rGO are evaluated from XAFS
H2/Ar 1130 °C
spectra using synchrotron radiation. The conductivity of the rGO
Ethanol 900 °C
films were measured by Hall-effect measurements using van der1000 °C
Pauw method.
1130 °C
Figure 1 shows XAFS spectra observed from the rGO films after
ethanol treatment at 900, 1000, and 1130 °C, thermal annealing in
HOPG
H2/Ar at 1130 °C and highly oriented pyrolytic graphite (HOPG).
282
292
302
312
The unoccupied π* and σ* states are clearly observed at photon
Photon Energy (eV)energy of 285.4 and 292 eV. The π* peak intensity as shown by Fig. 1 XAFS spectra observed
double head arrow becomes stronger for ethanol treatment at from the rGO.
1130 °C compared to the other treatments. This means that highT (K)temperature above 1100 °C in ethanol treatment leads to significant
50 20 10300
-1.94
expansion of conjugated π-electron system in the rGO films. The
VRH+TA-1.98
expansion of π system is also confirmed by prominent emergence ofVRH
2D bands in Raman spectra observed from the rGO samples.
-2.02
EthanolTemperature dependences of conductivity in the rGO films after
1100 ºC-2.06
ethanol treatment are shown in Fig. 2. The conductivity can be fitted
by only the VHR for 900 °C, and by the sum of VRH and thermally-2.10
activated (TA) conduction (σTA exp(-Ea/2kBT)) for 1100 °C as
indicated by dots and solid lines. The activation energy (Ea) of 13
VRH
-10.0
meV estimated from fitting analysis is smaller than thermal energy
Ethanolat room temperature. This means that the carrier transport around-10.5
900 ºCroom temperature for the rGO films after ethanol treatment of-11.0
1100 °C shows band-like transport due to decreasing barrier heightenergy between localization states by expansion of conjugated-11.5
π-electron system. This result indicates that high temperature-12.0
process above 1100 °C in ethanol environment is indispensable to
0.6
0
0.4
0.2
derive intrinsic electrical properties of graphene from GO.
T-1/3 (K-1/3)[1] A. B. Kaiser et al. Nano Lett. 9, 1787 (2009). [2] G. Eda, et al., Adv. Mater. 22,505 (2009). [3] R. Negishi and Y. Kobayashi, Appl. Phys. Lett., 105 253502(2014). Corresponding Author: R. Negishi, E-mail: negishi@ap.eng.osaka-u.ac.jp- 34 -

Fig. 2 Temperaturedependence of conductivity
in rGO samples.

3-3
Circularly polarized luminescence from lateral TMD p-i-n junctions○Yijin Zhang1, Masaru Onga1, Yoshihiro Iwasa1
1

Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan

Transition-metal dichalcogenides (TMDs), ones of the most popular layered materials, arerecently attracting growing interests over the world both for device application and for novel
peculiar optical physics. Semiconducting members has been proved to be a good transistor
channel materials possessing ambipolar high ON/OFF ratio [1], transparency and flexibility[2], possibility of miniaturization[3]. Novel optical properties of TMDs, on the other hand,originate from their unique multi valley band structure in which Fermi pockets exist at theedge (K and –K points) of the Brillouin zone. The innate lack of inversion symmetry inmonolayer limit (Fig. 1) lead to inherent valley circular dichroism: optical interband
transitions at K and –K are only allowed with σ+ and σ- circularly polarized light, respectively[4]. Such a valley dichroic optical selection rule exalts TMDs to potential materials for
opto-valleytronics.
In order to merge these two distinct research directions,
optoelectronic devices with electrical controllability of valley
degree of freedom have been sought. Simple optoelectronic
devices can be easily realised by forming lateral (in-plane)
p-i-n junction inside TMD channel using ambipolar nature of
TMD transistors [5]. We observed electroluminescence fromlateral p-i-n junction embedded in WSe2, a member of TMDs.
Interestingly, the luminescence was circularly polarized
without valley polarization [6]. Additionally, the degree ofpolarization changes its sign when the current direction isflipped, indicating the realisation of electrically switchable Fig.1 Crystal structure of TMDs
circularly polarized light source.
The electrical control of circularly polarized light is likely mediated by the band dispersion.
In addition to the inversion asymmetry, three-fold rotational symmetry also inheres inmonolayer TMDs, which gives rise to anisotropic band dispersion; trigonal warping. The
warping is much effective for valence band, while the conduction band is less affected [7].
Therefore, luminescence intensity from a single valley under finite electric field depends onthe field direction. Particularly, the intensity differs under rotating field direction by 180° due
to the three-fold rotational symmetry.
[1] V. Podzorov et al. Appl. Phys. Lett. 95, 3301 (2004).
[2] J. Pu et al. Appl. Phys. Lett. 103, 023505 (2013).
[3] B. Radisavljević et al. Nat. Nanotechnol. 6, 147 (2011).
[4] D. Xiao et al. Phys. Rev. Lett. 108, 196802 (2012).
[5] Y. J. Zhang et al. Nano Lett. 13, 3023 (2013).
[6] Y. J. Zhang et al. Science 344, 725 (2014).
[7] A. Kormányos et al. Phys. Rev. B 8, 045416 (2013).
Corresponding Author: Y. J. Zhang
Tel&Fax: +81-3-5841-6822,
E-mail: yzhang@mp.t.u-tokyo.ac.jp- 35 -

3-4
Mechanical exfoliation and vanv der Waals assembly oflayered ferromagnetic dichalcogenide FexTaS2
ji Ueno2,○Miho Arai1, Rai Moriya1, Naoto Yabuki1, Satoru Masubuchi1,3, Keiji
1, 3
and Tomoki Machida
1

Institute of Industrial Science, University of Tokyo,
Tokyo Tokyo 153-8505,, JJapan
Department of Chemistry,
Chemistry Saitama University, Saitama 338-8507, Japan
3
Institute for Nano Quantum Information Electronics, University of Tokyo,
Tokyo Tokyo 153-8505,
Japan
2

Recently, two-dimensional (2D) materials and their van der Waals (vdW) heterostructures
are received considerable attention for fundamental physics and electronics applications.
Previously discovered 2D materials exhibited variety
riety of electronic properties such as metal,
semiconductor, insulator, and superconductor. However, ferromagnetic 2D material and its
vdW heterostructure are still a missing piece in this field and these are strongly demanded forthe purpose of spintronicss with 2D materials and vdW heterostructures.
heterostructure
Here we report the mechanical exfoliation and vdW assembly of ferromagnetic layered
dichalcogenide FexTaS2. The FexTaS2 has a unique crystal structure; allll the Fe atoms
intercalate the vdW gap of layered TaS2 and form ordered structure as illustrated Fig. 1(a) [1].
This material is known to show giant perpendicular magnetic anisotropy below its Tc of 160 K
in its bulk form. By using Scotch
cotch tape method, we demonstrated the mechanical exfoliation of
few tens of nm-thick Fe0.25TaS2 flake on SiO2/Si substrate [Fig. 1(b)]. M
Magnetic fielddependence of Hall and sheet resistance was measured at 2 K and results are show
hown in Fig.1(c). Clear anomalous
nomalous Hall effect and anisotropic magnetoresistance were observed
observed. The
results
esults indicate that the magnetic property of the single crystal Fe0.25TaS2 is still conserved in
the exfoliated flakes. In addition, we
w demonstrated vdW assembly of two different
erent Fe0.25TaS2
flakes by using dry transfer technique to make it perform as spin valve device [Fig. 2].
Fabricated vdW junction exhibited tunnel magnetoresistance effect.
(a)

TaS2 layer

M

(c)

T=2K

Fe atom

(d)
B

(b)

Sub.

Fe0.25TaS2

Fig.1 (a) The crystal structure of FexTaS2. (b) Illustration of
fabricated Fe0.25TaS2 devices. (c,d)) Magnetic dependence of (c) Hall
resistance (Rxy) and (d) Sheet resistance (Rxx).
[1] J. Checkelsky et al ., Phys. Rev. B 77,
77 014433 (2008).
Corresponding Author: M. Arai5452-6157
Tel: +81-3-5452-6158, Fax: +81-3-5452
E-mail: marai@iis.u-tokyo.ac.jp- 36 -

Fig.2 Photograph of
Fe0.25TaS2/ Fe0.25TaS2 vdW junction.

3-5
Optical properties of a few layers black phosphorus,“Phosphorene”○Takashi Nakamura, Daichi Kozawa, Shinichiro Mouri, Yuhei Miyauchi,
and Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Kyoto, Japan
Recently atomically thin layered two-dimensional (2D) materials, graphene, and MoS2,
have attracted much interest from the viewpoints of fundamental physics and applications.
The black phosphorus is also capable of being mechanically exfoliated to single or several
atomic layers, which are called as “phosphorene”. Although the phosphorene is spotlighted as
the new material for 2D semiconductor [1], the detail electronic and optical properties havenot been fully understood. Thus, we studied single- and multi-layer black phosphorene byusing optical spectroscopy, Raman, photoluminescence (PL), and differential reflectivity tounderstand their characteristic optical and electronic properties.
The inset of Figure 2 shows optical image of a few layers black phosphorene on SiO2/Si
substrate, where the layer number of black phosphorene is confirmed from the optical contrast
and Raman spectra [2]. Figure 1 shows the linearly polarized differential reflectivity spectra
corresponding to absorption spectrum of black phosphorene on quartz substrate with different
thickness. The differential reflectivity spectrum of thick phosphorene (7layers) shows thepeak at 0.37 eV, which is almost consistent with the previously reported value of bulk
phosphorus [3]. In contrast, the differential reflectivity spectrum of 4layers thin phosphorene
shows a peak at 0.42 eV. The
observed peak of a few layers
black phosphorene at 0.42 eV is
assigned as the exciton absorption
peak. Moreover, the linearlypolarized differential reflectivity
spectrum in Fig. 2 shows thestrong anisotropic features in theabsorption
spectrum,whichsuggest the anisotropic electronic
structures of black phosphorene.
We will discuss the detail opticaland electronic properties of a few
Fig, 1: Differential reflectivity
Fig ,2: Polarized differential
layers black phosphorene based
spectrum of phosphorene
reflectivity spectrum
on the experimental results ofRaman and PL spectroscopy.
[1] Likai Li et al., Nature Nanotech. 9, 372–377 (2014)..
[2] Wanglin Lu et al, Nano Research 7, 853-859 (2014).
[3] Han Liu et al, ACS Nano 8, 4033–4041 (2014).
Corresponding Author: Takashi Nakamura
Tel: +81-774-38-3463,
Fax: +81-774-38-4567,
E-mail: nakamura.takashi.23z@st.kyoto-u.ac.jp- 37 -

3-6
Relaxation of Valley Polarization in Transition Metal Dichalcogenides○Satoru Konabe and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 3058571, Japan

Valley Relaxation Time (psec)

Monolayer transition metal dichalcogenides (TMDCs) such as MoS2, MoSe2, WS2
and WSe2 have recently attracted much attention because of their remarkable electronic andoptoelectronic properties [1]. The lack of inversion symmetry with a strong spin-orbit
interaction gives rise to nontrivial valley-spin coupled physics [2], which enables us to control
the valley degrees of freedom using the polarized light [3]. For valleytronics application, it is
crucial to keep a specific valley state as long as possible by suppressing a valley relaxation[4]. To achieve this, we have to identify the microscopic mechanism of the valley relaxation.
However, despite intensive theoretical and experimental works, it is still unclear [5].
In this study, we theoretically investigate the valley relaxation mechanism inmonolayer TMDCs by solving the Bloch equation of a valley pseudo spin associated with an
exciton. We find that the exchange interaction between an electron and a hole is essential for
determining the valley relaxation time. We also find that the relaxation process exhibits acrossover from the collisional-broadening region at low temperature to the thermalbroadening region at high temperature; the crossover occurs at around the temperaturecorresponding to the homogeneous broadening that is related to the exciton momentumrelaxation time (Fig. 1). Furthermore, we elucidate the screening effect due to doping on therelaxation process, which drastically changes the temperature dependence of the valley
relaxation both qualitatively and quantitatively compared with the non doped case.
5.0

τ=66 fsec

4.0

τ=33 fsec
τ=15 fsec

3.0
2.0
1.0
0.0

0

20

40

60

80

100

Temperature (K)120

Fig. 1 Temperature dependence of the valley
relaxation time for WSe2 with the carrier densityof 1012 cm-2. τ is the exciton momentum
relaxation time. The dashed lines indicate therelaxation time where the collisional broadening
is dominant for the exciton distribution.

140

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] H. Zeng et al, Nature Nanotech. 7, 490 (2012), K. F. Mak, et al. Nature Nanotech. 7, 494 (2012).
[4] X. Xu et al, Nature Physics 10, 343 (2014), K. F. Mak et al, Science 344, 1489 (2014).
[5] T. Cao et al, Nature Commun. 3, 887(2012), D. Lagarde et al, Phys. Rev. Lett. 112, 047401(2014).
Corresponding Author: Satoru Konabe
E-mail: konabe@comas.frsc.tsukuba.ac.jp
Tel: +81-2-9853-5600 ext.8233- 38 -

3-7
Exciton spectroscopy in 3R-MoS2○Suzuki Ryuji1, Sandor Bordacs2, Ryosuke Akashi3, Masayuki Ochi4, Ryotaro Arita4,
Yoshinori Tokura1,4, Yoshihiro Iwasa1,41Quantum-phase electronic centre and Department of Applied Physics, Faculty ofEngineering, The University of Tokyo, Tokyo 113-8656, Japan2
Budapest University of Technology and Economics, H-1521 Budapest, Hungary
3
Department of Physics, School of science, The University of Tokyo, Tokyo 113-0033, Japan
4
Center for Emergent Matter Science, RIKEN, Saitama 351-0198, Japan
Transition-metal dichalcogenides (TMDs) are attracting a great deal of interest as beyond
graphene materials because of their rich physical properties[1-3]. The key of the monolayer
TMDs in contrast to the bulk is the broken inversion symmetry (Fig. 1), which results in novel
valley properties, coupled with spins through their strong spin-orbit interaction [4]. On theother hand, 3R-MoS2 is known to keep the broken inversion symmetry and thus strong valley
polarization in PL spectra even in multilayers, providing new opportunities to investigate
properties of monolayers with use of bulk materials and the stacking dependent properties
between the 2H (centrosymmetric) and 3R (non-centrosymmetric) [5].
In this presentation, we reportcomparative studies of 2H- and 3R-MoS2
on dimensionality of the excitons, withreflectivity measurement (Fig. 2). We
found energy differences of 3R-MoS2
between A exciton (appeared as the sharp
peaks around 1.9 eV) and that excitedstates (indicated by arrow) is much larger
than 2H-MoS2. This indicates that theexciton binding energies of both polytype
Fig. 1: Crystal structures of monolayer, 2H- andare different from each other, and that
3R-polytypes of MoS2
dimensionality of excitons depends on its
way of stacking. The present result reveals
that the dimension engineering can berealized just by manipulating stacking, a newtechnique to control the novel properties of
2D materials.
[1] B. Radisavljevic et al., Nature Nanotech. 6, 147(2011). [2] K. F. Mak et al., Nature Nanotech. 7, 494(2012). [3] J. T. Ye et al., Science 338, 1193 (2012).
[4] D. Xiao et al., Phys. Rev. Lett. 108, 196802(2012). [5] R. Suzuki, M. Sakano et al., Nature
Nanotech. 9, 611 (2014).
Corresponding Author: R. Suzuki
Tel: +81-3-5841-6822, Fax: +81-3-5841-6822,
E-mail: ryujisuzuki@mp.t.u-tokyo.ac.jp

Fig. 2: Reflectivity spectra of 2H- and3R-MoS2- 39 -

3-8
CVD synthesis of single-crystal single-layer graphene and bi-layer graphenefrom ethanol○Xiao Chen, Kohei Tsushima, Masaki Sota, Rong Xiang, Shohei Chiashi, Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Graphene synthesis using chemical vapor deposition (CVD) on metal substrates has been
intensively investigated in the past few years. Recently, the growth of single-crystal graphene
has drawn most attention for that graphene films without grain boundaries show superior
electrical and mechanical properties. Several strategies toward such purpose were developed,
including inducing surface oxygen on Cu foils, using single-crystal substrates, etc.
We’ve shown that both self-limited growth of
single-layer graphene and self-limited growthbi-layer graphene can be realized using ethanol as the
carbon source [1, 2]. Here, we show that by tuning
the CVD conditions, graphene single crystals as large
as 5 mm can be synthesized on poly-crystal Cu
substrates (Fig. 1-a). Cu foils were oxidized on a hot
plate at 250 ˚ prior to the CVD reaction, andan extremely low flow rate of ethanol vapor (0.03
scccm) was employed during the growth. The
single-crystal nature of the resultant large graphene
flakes was confirmed by selected area electron
diffraction. Furthermore, by controlling the CVDparameters, after the full coverage of single-layer
graphene, large single-crystal bi-layer graphene canbe synthesized (Fig. 1-b). Raman spectroscopy
confirmed that more than 90% of the bi-layer regions
were AB-staked. These results demonstrate great
potential of ethanol as a carbon source for theFig.1 a. Graphene single crystals on asynthesis of high-quality graphene. Especially, theCu foil. b. Image of single-layer
large-grain AB-stacked bi-layer graphene could begraphene and bi-layer graphenevery important for applications such as field effecttransferred to a Si/SiO2 substrate.
transistors.
[1] P. Zhao, et al. J. Phys. Chem. C. 117, 10755(2013).
[2] P. Zhao, et al. ACS. Nano. 8, 11631(2014)
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6408, Fax: +81-3-5841-6408,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 40 -

3-9
Magnetic Ordering of Two-dimensional Networks of Fused C36 Polyhedra
under an Electric Field○Mina Maruyama and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8571, Japan
Electronic structures of layered materials with internal atomic structures are known todepend on the external electric field. It has been reported that bilayer graphene exhibits themetal-insulator-metal transition under the perpendicular electric filed. In our previous work,
we theoretically designed two-dimensional networks consisting of fused C36 polyhedra as apossible semiconducting layered materials with nanometer thickness. In this work, we study
electronic structures of the 2D networks of C36 polyhedron under the perpendicular electricfield using the density functional theory (DFT) with combining the effective screening
medium (ESM) method to investigate the possibility of magnetic ordering on all carbon
materials. To express the exchange-correlation potential among the interacting electrons, we
use the local spin density approximation (LSDA). We adopt the ultrasoft pseudopotential for
describing electron-ion interactions. The valence wave function is expanded in terms of plane
wave basis set with cutoff energy of 25 Ry.
Our DFT-ESM calculations show that the C36 network exhibit the magnetic ordering underhole doping by the perpendicular electric field, in which the polarized electron spin is primary
localized on the hexagonal ring situated at the top of the C36 covalent network and isferromagnetically aligned throughout the sheet [Figs 1(a) and 1(b)]. Calculated magnetic
moments are 1.74 and 2.22 µB/nm2 for the cases of dual gate and single gate, respectively. In
addition, in the case of thedual gate, we also find that(a)(b)
the nearly free electron
(NFE)
state
shiftsdownward and crosses the
Fermi level with spinpolarized
electrons.
Therefore, by applying theperpendicular filed on the
C36 sheet, we indicate thepossibility of peculiar spin
systems in which thepolarized spins coexist on
the atomic network and at
the vacuum region, being Fig.1: Isosurfaces of spin densities of C36 sheet under the electric field byexpectedtoexhibit (a) the dual gate electrodes and (b) by the single gate electrode.
unusual spin properties.
Corresponding Author: Mina Maruyama
E-mail: mmaruyama@comas.frsc.tsukuba.ac.jp
Tel: +81-29-853-5600(ext: 8233)- 41 -

3-10
Effects of electrodeposition conditions on the states of Pt-Ru nanoparticles
on carbon materials and their electrocatalytic properties
toward methanol oxidation○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. We have explored theelectrocatalytic properties of Pt-based nanoparticles supported on the carbon materials by
one-step electrodeposition. In this study, we investigated the effects of electrodeposition
conditions on the shape and dispersion state and electrocatalytic properties of Pt-based
nanoparticles supported on the carbon materials, Single walled Carbon Nanotubes(SWNTs) or
highly ordered pyrolytic graphite(HOPG). Figure 1 shows the TEM image of Pt-Ru
nanoparticles deposited on SWNTs at constant voltage of -1.36V for 5 sec. and table.1
summarizes their electrochemical characteristics of methanol oxidation. The detailed resultson the relationship between the deposition conditions, the shape and dispersion state of Pt-Ru
nanoparticles and their electrocatalytic performance for methanol oxidation will be presented.

Supported
Carbon

SWMTs

Figure 1. TEM image of Pt-Ru particles
deposited on SWNTs at -1.36V for 5s.

Table 1.

References:

Active area

Jf

2

2

[mA/cm ]2

4.49

of SPt [cm ]9.58×10

Vf
[V]

1.69

Electrochemical characteristics
of methanol oxidation.

(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.
(3)M.Tsai et al., ElectroChemistry. Communication 8(2006)1445-1452.
(4)S.H.Ahn et al., Chem. Eng .J. , (2012)181-182 , 276-280.
Corresponding Author: Hironori Ogata,Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 42 -

If/Ib

0.64

3-11
Hexahydroxytriphenylene and its derivetives for graphene exfoliation
in aqueous and organic media○Gang Liu, Takahide Kimura, Naoki Komatsu
Department of Chemistry, Shiga University of Medical Science, Seta, Otsu, 520-2192, Japan
Liquid-phase exfoliation of graphite to graphene has received extensive interest because ofa facile and inexpensive way for preparation of a large quantity of graphene [1]. The graphene
dispersion prepared by this method can be easily processed by drop-casting, filtration, or
spin-coating, and the techniques have been widely used in thin film electronic device [2].
Therefore, this method has been considered as one of the most promising routes in mass
production of graphene. Herein, we report a simple and scalable preparation of graphene
dispersion through direct exfoliation of graphite in the presence of triphenylene derivative (1,2 or 3 in Fig. 1). The advantages of the exfoliation process reported here are; 1) commerciallyavailable exfoliants are employed; 2) highly concentrated and high-quality graphene
dispersion is obtained in a facile way; 3)
THF can be used as low boiling point
medium in addition to water as green
medium; 4) the dried graphene solid
can be easily redispersed as highly
concentrated and stable dispersion; and5) exfoliants are removed in a facile
way without causing any damage to the Fig. 1 Chemical structures of hexahydroxytriphenylene (1)and its derivatives (2 and 3)
structure of graphene [3].
The graphene dispersion was
prepared by bath-sonication of thesuspension of graphite powder andtriphenylene in water or THF, followedby centrifugation at 1029g. Scanningtransmission
electronmicroscope(STEM, Fig. 2) images indicate that
almost all the materials observed are Fig. 2 Typical STEM images of the exfoliated graphene
the plates with high transparency,
implying thin graphene sheets. The
exfoliation was further confirmed by
the Raman, XRD (Fig. 3), and AFM.
Through heat treatment at 440 °C for 3
min under air, the exfoliants arethoroughly removed without disturbing
Fig. 3 Raman spectra (left) and XRD patterns (right) of
the structure of graphene.
graphite and exfoliated graphene before and after
treatment at 440 °C for 3 min under air[1] A. Ciesielski, P. Samori, Chem. Soc. Rev.
43, 381 (2014).
[2] D. W. Chang, H.-J. Choi, A. Filer, J.-B. Baek, J. Mater. Chem. A, 2, 12136 (2014).
[3] G. Liu, T. Kimura, N. Komatsu, to be submitted.
Corresponding Author: G. Liu
Tel: +81-77-548-2102, Fax: +81-77-548-2405, E-mail: gliu@belle.shiga-med.ac.jp- 43 -

ポスター発表
Poster Preview

1P – 1 ～ 1P – 44
2P – 1 ～ 2P – 44
3P – 1 ～ 3P – 43

1P-1
Charge analyses on particles by Ion Mobility Measurement○Toshiki Sugai, Yasuhiro Hiroshiba, Hironobu Matsubayashi, Kazuki Mimuro,and Ryota Jinnouchi
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Ion mobility measurements have revealed varieties of novel information on nanomaterials. Structures of metallofullerenes show significant dependence on the number ofmetal atoms and the cage size and their novel structures have been also clarified[1]. Our
newly developed ion trap mobility measurement system can hold the ionized particles formore than 2 hours realizing observations on long term transitions with high accuracy.
However those measurements mainly performed on a single particle to study relative
structural changes. To apply these measurements to larger nano systems and to have statisticalinformation, charge state should be analyzed because the mobility depends not only on the
structures but also on the amount of charge. Here we present the analyses on the charge statemeasured by the ion mobility.
The system consists of a laser ionization source for polystyrene particles and anelectrospray ionization source for salt solution, and electrodes for the trap. The produced
ionized particles were trapped and moved in air for several minutes. The movement of every
particle was observed and recorded by a microscope to evaluate its mobility. The amount ofcharge was analyzed from the obtained mobility.
Figure 1 shows the observed
dependence of the amount of charges on
the particles on their diameters. In bothparticles, the amount of charge increases as
the diameter and the amount anddependence are quite similar despite of thetotally different ionization methods. The
difference between the polystyrene and salt
solution, the amount of charge ofpolystyrene
particles
more
rapidlyFig. 1 Charge analyses on particles.
decreases as the diameter decreases.
[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
TEL: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 45 -

1P-2
Exciton-photon interaction in tip enhanced Raman spectroscopy ofsingle wall carbon nanotubes○ T.R. Czank, P. Ayria, R. Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Raman spectroscopy is based on the inelastic scattering of light which can be extensively used
to analyze nanomaterials. However, when the wavelengths used to probe samples havereached the diffraction limit for given sample size, it is not possible to get higher resolution
than those of the probing wavelength. To overcome this limitation, tip enhanced Raman spectroscopy (TERS) is often used by putting an additional metallic tip above the sample to utilize
the near field effect, enhancing the Raman intensity. Using this technique, for example, thespatial resolution for a single wall carbon nanotube (SWNT) sample can be increased fromthe order of µm to nm [1]. Understanding the mechanism behind TERS is thus very importantto further improve development of this spectroscopy technique.
In this work, we propose that the interaction between excitons generated in the SWNT sample
and near field generated by the metallic tip, is the origin of the intensity enhancement in
TERS. To justify this hypothesis, we calculate the exciton-photon interaction in armchair
SWNTs in the presence of metallic tip. Within this approach, the near field factor can not be
considered as constant as previously considered in the conventional Raman spectroscopy, because the amplitude of the near field factor is already comparable to the exciton wavefunctions [2]. The calculated matrix elements for the armchair SWNTs reveals that, the intensity isenhanced near the K points. Nevertheless, the symmetry breaks [3] because of the near field
factor, which gives rise to the chirality-dependence of the exciton photon matrix element withthe presence of the metallic tip.
[1] L G Cançado, et al, Phys. Rev. Lett. 103, 186101 (2009)[2] P. Tapsanit, Near field enhancement of optical transitions carbon nanotubes, Tohoku University, (2012)[3] H. Ajiki, et al, Nat. Phot. 7, 550-554 (2013)
Author: Czank T. R., TEL: +81-080-3339-8149, E-mail: thomas@flex.phys.tohoku.ac.jp- 46 -

1P-3
Ab Initio Study on Oxidation of (5,4), (6,4), (6,5), and (8,6) Carbon
Nanotubes○Mari Ohfuchi1
1

Fujitsu Laboratories Ltd., Atsugi 243-0197, Japan

Oxidation of single-wall carbon nanotubes (SWCNTs) has attracted attention because of
their greater luminescence quantum yield than that of pristine CNTs [1]. Oxygen-doped CNTs
are prepared by exposure of SWCNTs to ozone and light, whereas the luminescenceoriginating from oxygen doping of SWCNTs has also been observed for thin CNTs separated
into single chirality without a particular oxidation treatment [2]. Density functional theory(DFT) has been used to study the adsorption of oxygen molecules (O2) onto SWCNTs,
however the calculations have been limited to zigzag or armchair CNTs with comparatively
small unit cells. In this study, we performed DFT calculations of the adsorption of O2 on torealistic (5,4), (6,4), (6,5), and (8,6) nanotubes.
The O2 molecules approaching SWCNTs physisorb onto the surface at a distance ofapproximately 0.31 nm. As shown in Fig. 1, the adsorption energies for the physisorption aresmall negative values and do not appear to depend either on the adsorption sites or on thechirality of the SWCNTs. When the O2 molecules move closer to the SWCNTs, the firstchemisorption occurs at an O–C distance of approximately 0.15 nm. Although the adsorptionenergy appears to be affected by the chiral angle of the SWCNTs, in general it increases as the
SWCNTs become thicker. We found that the reaction barrier between the physisorption andthe chemisorption corresponds approximately to the energy difference between them. Theenergy difference and the corresponding reaction rate are summarized in Table 1. This isconsistent with the experimental results related to chirality-separated CNTs.
Table 1. Energy difference E and reaction rate R.

Chirality
(5,4)
(6,4)
(6,5)

Fig. 1. Adsorption energies of oxygen molecules oncarbon nanotubes. The adsorption sites a and b are on
the bonds nearly perpendicular and parallel to thenanotube axis, respectively.

(8,6)

Site

E (kcal/mol)

R (s-1)*a

11.31

6.5×104

b

17.81

1.3

a

16.68

8.4

b

15.60

51

a

19.22

0.12

b

22.65

4.0×10-4a26.23

1.0×10-6b24.87

1.0×10-5

The prefactor was assumed to be a standard value of1013 s–1.

*[1] Y. Miyauchi et al. Nature Photon. 7, 715 (2013).
[2] H. Liu et al. Nat. Commun. 2, 309 (2011).
Corresponding Author: M. Ohfuchi
Tel: +81-46-250-8194, Fax: +81-46-250-8274, E-mail: mari.ohfuti@jp.fujitsu.com- 47 -

1P-4
Bias-voltage induced absorption peaks in individual suspended carbon
nanotubes
T. Uda, M. Yoshida, A. Ishii, Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
We investigate longitudinal electric-field effects on photocurrent and photoluminescence
excitation spectra of individual air-suspended carbon nanotubes. To apply electric fields on
nanotubes, we have fabricated field effect transistors with carbon nanotubes [1-3]. We havealso constructed a system which can perform simultaneous photocurrent andphotoluminescence spectroscopy [1,2]. A wavelength-tunable continuous wave Ti:sapphirelaser is used to excite the nanotubes, and a lock-in amplifier and an InGaAs photodiode arrayare used to detect photocurrent and photoluminescence, respectively. We find new peaks inthe spectra when a bias voltage is applied.
Work supported by KAKENHI (24340066, 24654084, 26610080), the Canon Foundation,
Asahi Glass Foundation, and KDDI Foundation, as well as the Photon Frontier Network
Program of MEXT, Japan. The devices were fabricated at the Center for Nano Lithography &Analysis at The University of Tokyo. A.I. is supported by MERIT and JSPS Research
Fellowship, and M.Y. is supported by ALPS.
[1] Y. Kumamoto, M. Yoshida, A. Ishii, A. Yokoyama, T. Shimada, and Y. K. Kato, Phys. Rev. Lett. 112, 117401(2014).
[2] M. Yoshida, Y. Kumamoto, A. Ishii, A. Yokoyama, and Y. K. Kato, Appl. Phys. Lett. 105, 161104 (2014).
[3] S. Yasukochi, T. Murai, S. Moritsubo, T. Shimada, S. Chiashi, S. Maruyama, and Y. K. Kato, Phys. Rev. B
84, 121409(R) (2011).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 48 -

1P-5
Photoluminescence studies on individual small-diameter carbon nanotubes○Shun Aota 1, Naoto Akizuki 1, Shinichiro Mouri 1, Xiaojun Wei 2, Takeshi Tanaka 2,
Hiromichi Kataura 2, Kazunari Matsuda 1, and Yuhei Miyauchi 1
1

Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
2
Nanosystem Research Institute, AIST, Tsukuba, Ibaraki 305-8562, Japan

Single-walled carbon nanotubes (SWNTs) show distinctive physical properties originatingfrom their one-dimensional (1D) nature. In addition, zero-dimension (0D)-like local states in
SWNTs have recently attracted increasing attention because of their potential usefulness in
optoelectronics, bioimaging and quantum information fields [1,2]. In this context, we havebeen exploring optical properties of localized exciton states prepared by means of chemicaltreatments. The previous studies have revealed that SWNTs with chemically-derived local
states can be viewed as unique 0D-1D hybrid low-dimensional systems that show novel
exciton photophysics such as brightening of excitons [1] and enhanced photoluminescence(PL) nonlinearity [2]In this study, we performed optical measurements on individual small-diameter (5,4) SWNTs
that exhibit a low energy PL feature attributable to localized exciton states. The high purity(5,4) SWNTs were prepared using the multicolumn gel chromatography method [3]. The
isolated SWNTs were dispersed in an agarose gel matrix to immobilize them. The
measurements were performed in the ambient air.
Figure 1 shows a PL image observed with an
excitation photon energy of 1.49 eV that corresponds
to the E11 resonance of (5,4) SWNTs. Each bright spot
in Fig. 1 corresponds to PL from an individual (5,4)
SWNT. The inset of Fig. 1 shows a PL spectrum taken
for one of the bright spot observed in the PL image. A
characteristic low energy PL feature was observed at~1.26 eV, indicating the existence of localized states in
the SWNTs. Detailed photophysics of the localizedstates in the separated individual (5,4) SWNTs will be
discussed in the conference.

Fig. 1. PL image of separated(5,4) SWNTs dispersed in agarose
gel matrix. The excitation photon
energy of 1.49 eV was used. Inset
shows a PL spectrum taken for
one of the bright spots.

[1] Y. Miyauchi et al., Nat. Photonics 6, 715 (2013)[2] M. Iwamura et al., ACS Nano 8, 11254 (2014)[3] H. Liu et al., Nat. Commun. 2, 309 (2011)
Corresponding Author: S. Aota
Tel: +81-774-38-3465,
E-mail: aota.shun.23z@st.kyoto-u.ac.jp- 49 -

1P-6
Assigning (n,m) of Random Single-Walled Carbon Nanotubes on Silicon
Substrates by Resonant Raman Spectroscopy○Daqi Zhang, Feng Yang, Juan Yang, Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
The application of single-walled carbon nanotube (SWNT) based devices requires anexperimental method to assign the (n,m) of SWNTs on standard silicon substrates. Various
spectroscopic methods have been developed to assign (n,m), including resonant Raman,absorption, photoluminescence, and Rayleigh scattering [1]. For as-grown SWNTs on silicon
substrate, resonant Raman is the most widely used and accepted way to obtain (n,m) [2],while other spectroscopic methods are limited due to the substrate.
In this work, we use resonant Raman spectroscopy with two excitation lasers (i.e., 532 nm
and 633 nm) to assign (n,m) for our random SWNTs on silicon substrates catalyzed by Ni, Co,
and Fe. Based on 28 different chiralities assigned in the diameter range of 1.2-2.1 nm, we
propose an equation of ωRBM=235.9/dt+5.5 as the best fit for our random SWNT samples onsilicon substrates (Fig. 1). No significant catalyst-specified effects on the ωRBM-dt relation isobserved. The assignments are further verified by electron diffraction pattern and somestructure-dependent Raman features (e.g., G band shape [3] and the intermediate frequency
mode features [4]). This method is further applied to assign our chirality-specific SWNT
samples [5].

[1] D. Zhang, J. Yang, Y. Li, Small 9, 1284 (2013).
[2] A. Jorio, et al., Phys. Rev. Lett. 86, 1118 (2001).
[3] T. Michel, et al., Phys. Rev. B 80, 245416 (2009).
[4] J. Wang, Y. Li, et al., J. Phys. Chem. C 116, 23826(2012).
[5] F. Yang, Y. Li, et al., Nature, 510, 522 (2014).
Fig. 1 Linear fit of ωRBM with respect to 1/dt. The
fitting line gives ωRBM=235.9/dt+5.5.
Inset: difference between calculated dt and theactual dt with respect to cos2 3θ for both S- (dots)
and M-SWNTs (squares).

Corresponding Author: Y. Li
Tel: +86-10-62756773 Fax: +86-10-62756773
E-mail: yanli@pku.edu.cn- 50 -

1P-7
Trions in individual air-suspended carbon nanotubes○A. Popert, M. Yoshida, Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
We perform photoluminescence measurements on individual air-suspended single-walledcarbon nanotubes at room temperature and under high vacuum, using field-effect transistor
structures [1,2]. Upon application of gate voltage, the bright exciton peak quenches [3], and a
new redshifted peak appears. The diameter dependent energy separation from the bright
exciton peak shows that the gate-induced peak originates from trions. We perform statisticalanalysis of the trion binding energies for a diameter range of 0.9 to 1.3 nm, and they are foundto be 20-40 meV higher than previous values reported for solution-based carbon nanotubes.
We attribute the difference to the absence of dielectric screening when using air-suspended
carbon nanotubes. We further observe blueshifts in the trion emission at high gate electricfields.
Work supported by KAKENHI (24340066, 24654084, 26610080), the Canon Foundation,
Asahi Glass Foundation, and KDDI Foundation, as well as the Photon Frontier Network
Program of MEXT, Japan. The devices were fabricated at the Center for Nano Lithography &Analysis at The University of Tokyo. M.Y. is supported by ALPS and A.P. is supported by
JASSO.
[1] M. Yoshida, Y. Kumamoto, A. Ishii, A. Yokoyama, and Y. K. Kato, Appl. Phys. Lett. 105, 161104 (2014).
[2] Y. Kumamoto, M. Yoshida, A. Ishii, A. Yokoyama, T. Shimada, and Y. K. Kato, Phys. Rev. Lett. 112, 117401(2014).
[3] S. Yasukochi, T. Murai, S. Moritsubo, T. Shimada, S. Chiashi, S. Maruyama, and Y. K. Kato, Phys. Rev. B
84, 121409(R) (2011).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 51 -

1P-8
Electronic properties of CNT thin films under an electric 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 geometric andelectronic 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), in which the CNTs form a mat
structure with nano-scale interfaces among these CNTs. However, the fundamental propertiesof these CNT-CNT interfaces under an electric field are not fully understood. In this work, we
aim to elucidate the electronic properties of the CNT thin films, which consist of the double
layer of CNTs, under the external electric field which injects electrons/holes into these CNT
thin films.
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 thin films of
CNTs consisting of (11,0), (12,0), (13,0), (14,0), and (15,0) CNTs forming CNT double layers.
To simulate the CNT-FET device, we consider the model system shown in Fig.1.
Figure 2 shows the electrostatic potential of a CNT thin film consisting of (12,0) and (11,0)
CNTs without electric field. As shown in Fig.2, intrinsic electric field occurs in the interface
between these CNTs because of their different workfunctions. According to the electric field,
carrier accumulations depend on the mutual arrangement of CNTs with respect to theelectrode.

Fig.1
films

A structural model of CNT thin

Fig.2

Electrostatic potential of a CNT thin film

without external field.

Corresponding Author: U Ishiyama
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: yishiyama@comas.frsc.tsukuba.ac.jp- 52 -

1P-9
Electrical contact of parallel adjacent CNTs
estimated from in-plane conductivity of dense CNT forest on silicon carbide○Masafumi Inaba1, Chih-Yu Lee1, Kazuma Suzuki1, Yu Hirano1, Megumi Shibuya1,
Miho Myodo1, 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

Sheet conductivity (S/sq)

We have reported the in-plane conductivity ofdense carbon nanotube forest on silicon carbide substrate
Point probe(a)(CNT forest on SiC).[1] Here we additionally discuss the(b)contact conductivity estimation of parallel adjacent CNTs CNT caps
Conductance Gcap
yielded from the in-plane conductivity.
CNT
The experimental setup is the same as the previous
bulk
report.[1] On-axis C-face (000-1) of semi-insulating SiC
GCNT
-8
o
CNT/SiC
substrates (< 10 S/cm) were annealed at 1600 C in vacuum
interfaceGi/f(~10-2 Pa). The in-plane conductivity was measured by van
Semi-insulating SiC
SiC bulk
der Pauw method. Fig.1 shows (a) the schematic image of
GSiC(<10-8 S/cm)
sheet conductivity measurement and (b) its equivalent circuit.
By changing the CNT length or CNT film thickness, there
Fig. 1 (a) Schematic image of sheet conductivity
were constant part and CNT length dependent part as shown
measurement and (b) its equivalent circuitin Fig. 2. As a result, the contributive in-plane conduction-3
3x10
parts were CNT top region and CNT bulk region.
In CNT bulk region, where in-plane conductivity
was 50 S/cm, CNT should be parallel adjacent to each other.
We assumed three approximations to conduct the contact-3
2x10
resistivity. First, CNTs have the same diameter and aredensely packed with the hexagonal pattern. Second,
CNT/CNT contact conductivity is the same for CNTs with
CNT bulk conduction
the same diameter. Third, CNT conductivity is much higher-3
1x10~ 50 S/cm
than the CNT/CNT contact conductivity. With theseapproximations, CNT forest is described as the net-like
CNT cap conduction
circuit in Fig.3, where each wire corresponds to the~ 7×10-4 S/sq (~1.4×103 S/cm)
CNT/CNT contact conductive path and each node0
corresponds to CNT. With brief calculations, the contact
0
100
200
300
400
conductivity normalized by CNT contact length was written
CNT length (nm)as  C ,CNT / CNT   S / 3t .  S t is the slope of Fig. 2. Thus
Fig. 2 Relationship between CNT sheet
the CNT/CNT contact conductivity is yielded as ~30 S/cm conductivity and CNT length(contact resistivity: ~3×10-2 cm).
Only a few groups reported the CNT-CNT
Imaginary electrodejunction electrical properties in dispersed CNT network.
Znidarsic et al[2] reports the CNT/CNT contact resistance
CNT
range of 200 k for X-type connection and 60 k for
Y-type connection. In X-type contact, the CNTs arepoint-contacted with each other and in Y-type case CNTs areparallel-contacted with each other in a part. In CNT forest on
SiC case, CNTs should be considered as metallic due to theirwlarge diameters. Even though the chirality is semiconducting,the bandgap should be even smaller for larger diameter
CNTs. The contact resistivity of semiconducting/semiconducting or semiconducting/metallic contact should
be higher than that of metallic/metallic. The Y-type contact
resistance of 60 k corresponds to the contact length of 5
nm in case the contact type is metallic/metallic, which is
calculated as the method of Lan et al.[3] We will discuss thedetail in this presentation.
l lThis study was supported by JSPS (No. 26630136)
RT  RS[1] Inaba et al., The 47th Fullerenes-Nanotubes-Graphene
Fig. 3 Upside view of approximatedelectricalw
General Symposium, 2P-7
circuit of dense carbon nanotube forest.
[2] A. Znidarsic et al., J. Phys. Chem. C 117, 25 (2013).
[3] C. Lan et al., Nanotechnology 19, 12 (2008).
Corresponding Author: M. Inaba
Tel&Fax: +81-3-5286-3391 E-mail: inaba-ma@ruri.waseda.jp- 53 -

1P-10Overcoming the Quality-Quantity Trade-Off in Printing Carbon Nanotubes
by Repetitive Dispersion-Extraction Process○Hiroyuki Shirae1, Dong Young Kim1, Kei Hasegawa1, Taishi Takenobu2, Yutaka Ohno3, andSuguru Noda1,*
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Department of Applied Physics, Waseda University, Tokyo 169-8555, Japan3
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603 Japan
1

2

Carbon nanotubes (CNTs) are an attractive candidate material for electrodes and wirings inflexible electronic devices owing to their fair electric conductivity, excellent stability inambient, flexibility, and compatibility with printing processes. Their uniform films withexcellent conductivities have been realized through mild dispersion followed bycentrifugation and printing, however a significant fraction of expensive CNTs are wasted
during centrifugation. Moreover, in the fabrication of patterned electrodes/wirings, photo- orelectron-beam lithography is often applied to the uniform films, which causes additional lossof CNTs. Toward the practical application of CNTs to flexible electronics, simple andloss-free printing of conductive CNT films is highly demanded.
In this work, we propose and examine a repetitive dispersion-centrifugation process, which
minimize the damage to CNTs via mild dispersion and the material loss of CNTs via reuse ofundispersed CNTs. We also propose and examine a filtration process using a metal mask witha membrane filter, which yields patterned CNT films with minimal material loss.
We used as-produced CNTs synthesized via floating-catalyst CVD, the so-called eDIPS
method [1] (MEIJO eDIPS, EC grade; Meijo Nano Carbon Co., Ltd.). CNTs were added at
0.01 wt% to the 0.5 wt% aqueous solution of sodium dodecylbenzenesulfonate (SDBS). The
solution was sonicated at 30 W, 45 kHz for a set time, and then centrifuged at 3500 rpm for
20-30 min. The supernatant (3/4 of the solution) was taken out and used for printing while thesediment was used for next cycle of dispersion with adding SDBS aq. at the same amount(Fig. 1). The amount of dispersed CNTs was determined by UV-Vis absorption spectroscopy
for each cycle. CNTs lines were formed by vacuum filtration through a membrane filter with ametal mask (slit widths of 88−215 μm), washed with hot water, and then transferred to PET
films (Fig. 2). These processes were repeated until the CNTs were mostly dispersed (≥90%).
90% of the CNT aggregates were converted into conductive CNTs films within 13 cycles(39 min), demonstrating the improved conductivity and reduced energy/time requirements forultrasonication. CNTs lines with a high conductivity of 1400−2300 S cm−1 were obtained
without doping. Lengths and crystallinities of dispersed CNTs will be discussed.

Fig.1 The repetitive
dispersion-extraction process

Fig. 2 The CNT
lines on PET

Fig. 3 Dispersion ratio and conductivity of the
CNT lines prepared at different cycles.

[1] T. Saito et al. J. Phys. Chem. B 110, 5849 (2006).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 54 -

1P-11
Controlled formation of nanogaps of single-walled carbon nanotubes
on substrates and field emission from the nanogaps○Keigo Otsuka, Yuuki Shimomura, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Nanogaps of single-walled carbon nanotubes (SWNTs) formed by electrical breakdown areuseful as true nanoscale electrodes contacting with nanocrystals, phase-change materials [1],and so on. Controlling the nanogap size for the electrode applications is necessary for reliable
and efficient device performance. Although the gap size can be somehow decreased by using
Ar gas flow or short SWNTs [1], the mechanisms which determine the gap size remain unclear.
Here, we report that field emission occurs at the nanogaps of SWNTs lying on substrates andplays an important role in the formation/growth of the nanogaps during/after the breakdown.
Horizontally aligned SWNT arrays were grown on r-cut crystal quartz and transferred onto
silicon substrates with 100-nm-thick oxide and photolithographically-patterned electrodes.
After plasma etching of unwanted SWNTs, nanogaps were fabricated by electrical breakdown.
Typical I-V curves for single nanogap devices with two gap sizes taken in vacuum andcorresponding Fowler-Nordheim (FN) plots are shown in Fig. 1, indicating the occurrence offield emission. Field enhancement factors are estimated to be 6×107 and 2×107 m-1 for the 30
and 300 nm gaps, respectively, from the slope of the FN plots, which agrees with a previous
report [2] despite the difference of device configurations. We also extended the nanogaps in air
by applying various voltages on SWNT array devices after nanogap formation. The nanogap
sizes after the process showed linear increase with the applied voltage as shown in Fig. 2.
Interestingly, only anodic SWNTs were gradually etched by increasing voltage as shown in Fig.
3, probably due to electron-stimulated oxidation.
This field emission-induced gap growth explains the nanogap size dependence on original
SWNT length by electrical breakdown [1]; since the voltage needed to initiate SWNT
breakdown is proportional to the SWNT length [3], the gap size just after the breakdown
depends on the SWNT length.

0.02
1/V

0.03

1000

Gap Size (nm)

2

0.01

nm

ln(I/V )= 30

Current (nA)

L gap

−35
5

300 nmLgap = 30 nm

L gap =

−30

10

Lgap = 6.35V

500

Lgap = 300 nm

0
0

50

Voltage (V)100

Fig. 1 I-V curves for single nanogap
devices. FN plots are given in the inset.
Measurements were conducted in vacuum.

0
0

50
100
Applied Voltage (V)Fig. 2 Extended gap sizes vs applied
voltage. Experiments were performed
in air.

[1] F. Xiong et al., Science 332, 568 (2011).
[2] J.-M. Bonard et al., Phys. Rev. Lett. 89, 197602 (2002).
[3] E. Pop, Nanotechnology 19, 295202 (2008).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421 Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 55 -

Fig. 3 SEM images of thegap growth for an
identical SWNT after
various voltages wereapplied. Scale bars are 500nm.

1P-12
Surface modification of carbon nanotubes utilizing
photo-induced radical formation from benzyl derivatives○Tomoya Takada1, Shigeaki Abe 2
1

Department of Bio- and Material Photonics, Chitose Institute of Science and Technology,
Chitose 066-8655, Japan
2
Graduate School of Dental Medicine, Hokkaido University, Sapporo 060-8586, Japan

Surface modification of carbon nanotubes (CNTs) is an essential subject for their industrial
application, since homogeneous dispersion of CNTs in solvents are effectively enhanced byappropriate surface modification. In addition, functional groups introduced by surface
modification of CNTs act as reaction sites for subsequent bond formation with, for example,
other organic molecules and polymers. Many methods for the surface modification have beenreported previously. However, modification methods employing photochemical reactions
have been scarcely studied. In this work, a simple method for the surface modification of
CNTs with radicals formed by photo-irradiation was developed. We reported the surface
modification of CNTs with photochemicaly
generated benzyl radical derivatives last year. Here,some additional results on the mechanism of thephoto-induced surface modification are shown.
As a radical source, 4-(bromomethyl)benzoic
acid (4-BMBA, Wako Pure Chemicals, Co. Ltd.)was used in this work. BMBA and multi-walledcarbon nanotubes (MWCNTs, diameter 10-30 nm,
Wako Pure Chemicals, Co. Ltd.) were added into
Fig. 1 Scheme of the surface modification
dimethylformamide (DMF) and then dispersed bysonication. Light from an Xe lamp (wavelength in this work.
≥300nm) was irradiated to the mixture at 30 ºC for
24 hours. During the irradiation, oxygen in the mixture solution was purged with Ar gas.
MWCNTs after the irradiation were filtered, washed and dried in the air. Amount of the
4-carboxybenzyl radicals introduced on the MWCNTs surface was determined byconventional acid-base back titration; carboxyl groups attached on MWCNTs were
neutralized with sodium hydrogen carbonate (NaHCO3) aqueous solution, and the amount ofresidual NaHCO3 was then measured by titration with hydrochloric acid (HCl). In addition,
dark control experiment (i.e. the similar procedure without the light irradiation) was also
carried out.
On the basis of the back titration results, partial neutralization of NaHCO3 aqueous solution
caused by carboxybenzyl groups introduced on MWCNTs was confirmed. In addition,
dispersibility in water of the MWCNTs modified with light irradiation was drastically
improved compared to those of pristine MWCNTs and dark control sample. These results
indicate that carboxybenzyl groups generated by photo-induced C-Br bond cleavages are
successfully attached to the MWCNTs surface through chemical bonds. This work has been
supported by JSPS KAKENHI (Grant-in-Aid for Scientific Research (C)) No. 25420814.
Corresponding Author: T. Takada
Tel/Fax: +81-123-27-6056, E-mail: t-takada@photon.chitose.ac.jp- 56 -

1P-13The new method for CNT and VGCF dispersion by Nano Premixer○Taro Ikuta, Takayuki Takatsuka,
Thinky Corporation,3-21-5 Kandasakuma-cho Chiyoda-ku, Tokyo 101-0025, Japan
In this study, multi-wall carbon nanotube (Elicarb) and vapor grown carbon fiber(VGCF-H) were dispersed by dual ultrasonic with rotation mixer; Nano Premixer, ultrasonicbath and homogenizer (Fig.1). To be compared with conventional type of ultrasonicinstruments, nano premixer has superior in dispersion, uniformity, and usability. The surface
resistivity was measured by low resistivity meter. After mixing MWNT by nano premixer, thesurface resistivity of it (5wt%) was lower than ultrasonic bath (Fig.2). Dispersion state of
MWNT and VGCF-H were evaluated by TEM, SEM. Nano Premixer can disperse MWNT
and VGCF-H well without cutting them. These results shows that it can loosen aggregated
MWNT by ultrasonic and mix them uniformly by rotate motion.

Fig.1 Nano Premixer

Fig.2 Surface resistivity of multi-wall nanotube

Fig.3 TEM micrographs of dispersed multi-wall nanotube (Left: ultrasonic bath, Right: Nano Premixer)

Fig.4 SEM micrographs of vapor grown carbon fiber VGCF-H (Left: Original Bulk, Right: Nano Premixer)
Corresponding Author: T.Takatsuka
Tel: +81-3-5821-7401, Fax: +81-3-5821-7422,
E-mail:takatsuka@thinky.co.jp- 57 -

1P-14
Optical Properties of Optical Isomer of Single-Chirality SWCNTs○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
Single-wall carbon nanotubes (SWCNTs) show narrow optical absorption peaks
corresponding to Ei,i transitions between i-th one-dimensional van Hove singularities forparallel polarization of electric filed to nanotube axis. From a selection rule, we expect opticalabsorption of Ei,i+1 transitions for the cross polarization, but a strong local field effect smears
out such absorptions. This makes difficult to analyze energy band structure of SWCNTs by
optical absorption. Recently, however, Castillo and Noguez theoretically demonstrated thatcircular dichroism (CD) spectrum clearly shows both Ei,i and Ei,i+1 transitions equally [1].
This means that CD spectrum of single-chirality optical isomer SWCNT enables detailed
analysis of band structure.
Very recently, we developed a new
separation method by combining theoverloading
andstepwiseelutionchromatography [2]. This method can sort out
single-chirality
andopticalisomers
simultaneously. In this work, we preparedhigh-purity optical isomers of nine distinct (n,m) species and measured CD spectra. Figure
1 shows CD (up) and absorption spectra(down) of M- and P- (6, 5) SWCNT isomers.
Here, CD intensity was normalized by E2,2
absorption intensity. Twice large intensity of
CD signal compared with the previous work
[3] suggests extremely high-purity opticalisomer separation. Furthermore, in the CD
spectra, in addition to Ei,i transitions, someother peaks are also observed. These
additional peaks can be assigned to Ei,i+1transitions. For example, CD peaks at 640,
441 and 272 nm are assigned to E1,2, E2,3 andE4,5 transitions, respectively. Detailed analysis
Figure 1. The normalized CD spectra (up) andwill be given in the presentation.
absorption spectra of separated M- and P- (6, 5)This work was supported by KAKENHI No.
isomers.
25220602.
[1] A. Sánchez-Castillo and C. Noguez, J. Phys. Chem. C 114, 9640-9644 (2010).
[2] X. Wei et al. 47th FNTG 2P-5, p.92 (2014).
[3] S. Ghosh et al. Nat. Nanotechnol. 5, 443-450 (2010).
Corresponding Author: H. Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786, E-mail: h-kataura@aist.go.jp- 58 -

1P-15Synthesis of Submillimeter-Long Carbon Nanotubes on Small Ceramic
Powders by Fluidized Bed○Kosuke Kawabata, Zhongming Chen, Kei Hasegawa, Toshio Osawa and Suguru Noda*
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Fluidized bed chemical vapor deposition (FBCVD) has realized mass production ofcarbon nanotubes (CNTs) [1]. The resulting CNTs are, however, aggregated with porous
catalyst-support particles and less conductive. We previously realized sub-millimeter-long
CNTs growing vertically from large Al2O3 beads (0.5 mm) with smooth surface by FBCVD[2,3]. Such CNTs can be easily separated from the beads by gas-flow, yielding highly pure
CNTs (C content  99.6 wt% [3]) with fair conductivity. Moreover, semi-continuous
production was realized by switching the gas; catalyst deposition from metal-organic vapors,
CNT growth from C2H2, and separation and collection of CNTs by carrier gas, in a single
reactor at a fixed temperature. Highly reactive C2H2 enables its efficient conversion to CNTs
at a yield ~ 70% in a residence time ~0.3 s [2], however needs be fed at a low concentration~
1 vol% with a large amount of carrier gas to avoid catalyst deactivation by carbonization [4].
In this work, we use less reactive C2H4 as a carbon source, which can be fed at muchhigher concentration with much less carrier gas. We need a different design principle;
converting C2H4 to CNTs in a longer residence time but with a retained volumetricproductivity due to its high feed concentration. Smaller gas feed rate enables the use of small
catalyst support particles, which provide larger surface and promote the reaction of C2H4.
Small particles with smooth surface will still yield sub-millimeter-long CNTs in verticallyaligned arrays, possibly enabling the collection of particles with CNTs by gas-flow. The
particles and CNTs will be separated from each other outside the FBCVD reactor and theparticles will be fed again to the FBCVD reactor. Aiming at this (semi-)continuous process,we studied the catalyst deposition and CNT growth processes separately using two reactors
and inexpensive small Al2O3 abrasive powder (~0.2 mm) as catalyst supports.
Al2O3 powder was washed with ~7 wt% HCl aq, filtrated, and dried at 150 oC for 2 h toremove the impurities on the surface. Treated abrasives were set in the catalyst deposition
reactor, heated in a N2 flow to and calcined in 4 vol% O2/N2 for 10 min at 800 oC. AlOx
support layer and Fe catalyst were successively deposited by CVD from aluminum
isopropoxide and ferrocene, respectively. The catalyst-supported powders were then filled in
the CVD reactor, heated to and kept for 10 min
at 800 oC in 10 vol% H2/N2. CVD was thencarried out by switching the gas to 0.7 vol%C2H2/1.5 vol% CO2/10 vol% H2/N2 for 20 min.
By this process, VA-CNTs grew on Al2O3
powder with a length ~150 µm (Fig. 1). CNT
growth from C2H4 will also be discussed.
Fig. 1 CNTs on Al2O3 abrasive powder.
[1] Q. Zhang, et al., ChemSusChem 4, 864 (2011).
[2] D.Y. Kim, et al., Carbon 49, 1972 (2011).
[3] Z. Chen, et al., Carbon 80, 339 (2014).
[4] K. Hasegawa, et al., Carbon 49, 4497 (2011)
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 59 -

1P-16
Controlled Growth of Single-Walled Carbon Nanotubes Using W-Co
Catalyst at Different Temperatures and Carbon Feedings○Feng Yang, Xiao Wang, Daqi Zhang, Juan Yang, Yan Li
Beijing National Laboratory for Molecular Science, Key Laboratory for the Physics andChemistry of Nanodevices, State Key Laboratory of Rare Earth Materials Chemistry andApplications, College of Chemistry and Molecular Engineering, Peking University, Beijing
100871, China
The structure-controlled synthesis of single-walled carbon nanotubes (SWNTs) is a
crucial issue for their advanced applications in nanoelectronics. The catalysts play an essential
role in controlling the structure of the SWNTs [1,2]. Recently, employing tungsten-based
alloy catalyst with high melting points and consequently are able to maintain their specificcrystal structure during the chemical vapor deposition (CVD) process, which regulates thechirality of the grown SWNTs [3]. Here we further systematic study the effects of CVD
conditions (e.g., temperature and carbon feeding) on the selective growth of the chiral
SWNTs.
Using the specific structure of theW6Co7 alloy, we are able to grow the highabundance of the (12,6) and (14,4) SWNTs,
respectively,atdifferent
growthtemperatures by altering the carbon feedings(Fig. 1). We find that CVD conditions
during the growth process play key role incontrolled growth of the single chiral
SWNTs.

[1] L. Yan et al. Adv. Mater. 22, 1508 (2010).
[2] Y. Chen et al. Carbon 81, 1 (2015)[3] F. Yang, X. Wang, D. Zhang, L. Yan et al.
Nature. 510, 522 (2014).
Corresponding Author: Yan Li
Tel: +86-010-62756773, Fax: +86-010-62756773,
E-mail: yanli@pku.edu.cn

Fig. 1 The Raman spectra of SWNTs grown at
different processes. a-c, Schemes showing thedifferent growth processes. d-f, The Raman spectra of
the corresponding SWNTs samples. Regions in which(14,4) tubes are located are indicated with frame(excitation wavelength, 532 nm).

- 60 -

1P-17Growing carbon nanotubes on acetylene black particles to form theirhybrid and controlling the reaction on a few second time scale○Masaaki Kuriya 1, Kei Hasegawa 1, Yusaku Harada 2, Suguru Noda 1
1

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
2
Denki Kagaku Kogyo Kabushiki Kaisha, Tokyo 103-8338, Japan

Acetylene black (AB) and carbon nanotubes (CNTs) are representative conductive fillers
for Li ion batteries and resin compounds. Their hybrid was developed by growing CNTs on
AB particles by fixed-bed chemical vapor deposition (CVD), which effectively enhanced the
conductivity of resin compounds due to their easy dispersability [1]. Aiming at higher
productivity, higher crystallinity, and smaller CNT diameters, we propose the production ofsuch hybrid in the AB production furnace. AB is currently produced at ~2000 °C and several
second time scale. If ferrocene is fed, Fe particles will form on AB and CNTs will grow as thegas cools down to 1000−1400 °C at the downstream. Such short process time will minimize
the aggregation of Fe particles on AB and yield small Fe particles and small-diameter CNTs.
As a first step, we fixed AB particles on Si substrates and applied the “pulse current heating
method [2]” to basically understand such high-temperature, short-time process.
Fig. 1a shows the experimental apparatus. AB was supported on Ti/SiO2/Si and thesubstrate was set in a reaction tube and connected to electrodes. The substrate was resistively
heated to a target temperature with the gas flow being changed; ferrocene vapor/2 vol%CO2/17 vol% H2/Ar for supporting catalyst, 3 vol% CO2/27 vol% H2/ Ar for annealing, and
0.5 vol% C2H2/3 vol% CO2/26 vol% H2/Ar for CVD.
First, we examined the reactions at a fixed temperature of 1100 °C; 1 s for catalyst
deposition from ferrocene, 9 s for annealing, and 10 s for CVD. Multiple Fe particles formedon each primary AB particle (Fig. 1b) and grew CNTs but with a rather large diameter of ~20
nm (Fig. 1c) and wavy morphology (Fig. 1d).
Next we applied the different temperature history mimicking the target process; 1400 °C
for 1 s for decomposition of ferrocene into Fe vapor, 1100oC for 1 s for deposition of Fe
particle from Fe vapor, and 1100 °C for 5 s for CVD. CNTs grew much densely, much longer,
and much more straightly (Fig. 1e). High temperature process actually forms Fe particles and
CNTs on AB in a few seconds.

Fig.1 (a) Schematic diagram of the apparatus. STEM image before CVD (b) and STEM (c) and SEM (d) images
after CVD for the fixed 1100 °C process. (e) SEM images for the cooling process from 1400 to 1100 °C.
[1] Y. Harada et al. the Carbon Society of Japan, 3A04 (2012). [2] K. Sekiguchi et al. Carbon, 50, 2110 (2012).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 61 -

1P-18FT-ICR study of chemical reactionof ethanol and acetonitrile molecules on transition metal clusters○Kazuki Ogasawara1, Yuta Tobari2, Yoshinori Sato1, 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. unit)

Chemical vapor deposition (CVD) method is one of the most common techniques for
production of single walled carbon nanotubes (SWNTs). During the CVD process, SWNTs
grow with carbon atoms decomposed from molecules such as CO, CH4 or ethanol on catalytic
metal particles at high temperature. Even though the surface chemical reaction on metal
particles is critically important, little is known due to the complexity in properties of thesenanoparticles. Moreover, Thurakitseree et al. [1] reported that changing the carbon feedstockfrom pure ethanol to a few % mixture of acetonitrile (CH3CN) in ethanol during CVD
drastically reduces the average diameter of the SWNTs, and this diameter-modification isreversible and repeatable. It is suggested that the nitrogen atoms in acetonitrile molecules
temporally impeded the formation of larger diameter SWNTs on the surface of catalytic
particles. However, the detailed mechanism of this reaction is still not clear.
In this study, the chemical reactions of transition metal (Fe, Ni, and Co) cluster cations withethanol and acetonitrile was observed by Fourier transform ion cyclotron resonance (FT-ICR)
mass spectrometer with direct injection laser vaporization cluster beam source [2]. Metal
clusters were trapped within the FT-ICR cell, subsequently the reactant molecules wasintroduced. Figure 1 shows the typical mass spectrum of the reaction products from Co13+
clusters. We can observe the dehydrogenated chemisorption such as +HCCN or +(CCN)2.
Figure 2 shows the schematic diagram of the reaction products. These reactions drasticallydepended on cluster size and the species of metals or reactant molecules in respect to thechange of simple / dehydrogenatechemisorption ratio and reaction rate
+HCCN
constants.
+(CCN)2(HCCN)+
Co13+(CCN)2

- 4H2

- 3H2
+(HCCN)2

C
C
N
0

50
100
Relative Mass (amu)

Fig.1 Mass spectra of isolated Co13+ clusters
after reaction with CH3CN.

C

Co13

C

C

N

+

N

C

C

C

Co13+

C
N

N

Fig.2 Schematic diagram of [Co13(CCN)2]+ and[Co13(CCN)2(HCCN)]+ clusters.

[1] T. Thurakitseree et al., ACS Nano, 7 (2013) 2205.
[2] S. Maruyama et al., Rev. Sci. Instrum., 61 (1990) 3686.
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 62 -

1P-19Flame Synthesis of Single-Wall Carbon Nanotubes and Control over theTemperature Field and Reactions○Mai Yamaguchi, Kei Hasegawa, Toshio Osawa, Suguru Noda
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Floating catalyst chemical vapor deposition (FCCVD) has realized mass-production ofmulti-wall carbon nanotubes (MWCNTs) at ~100 tons annually per plant. It also enabledcontinuous production of high-quality single-wall CNTs (SWCNTs), however at much smallerscales. Because single SWCNT of 1 nm in diameter weighs only 1/10,000 of single MWCNT
of 100 nm in diameter at the same length, small catalyst particles needs be fed at much higher
density. Such particles, however, quickly aggregates in the reactor at second time-scale of
FCCVD. We previously proposed to use a flame as a solution; ferrocene decomposes andyields Fe vapor in the premixed flame at ~3000 K, Fe vapor mixes with CVD gas, cools down
and forms Fe nanoparticles. All processes can occur in millisecond time-scales, possibly
yielding Fe nanoparticles at high density. Using a small burner (1 mm in diameter), highly
crystalline SWCNTs were produced, but at a small amount [1].
This time, we aim to enhance the productivity of SWCNTs via more careful control over
the temperature field. Mixing of hot flame gas with cold CVD gas enabled rapid cooling of Fe
vapor and formation of small catalyst particles, while the mixed gas continued to cool down,
resulting in a short CVD time [1]. Thus we applied a furnace to keep the temperature suitablefor CVD at second time scale, the internal preheater for the CVD gas, and additional Ar gas
line for cooling the flame gas and nucleating Fe nanoparticles (Fig. 1).
We introduce three parameters for temperatures; Tflame at the premixed flame, Tcat at the
mixing point of the flame gas with Ar cooling gas, and TCVD at the furnace. We calculate Tflame
and Tcat values by dividing the heat by the heat capacity of the gas, but actual temperature islower due to the decomposition of gas molecules and heat loss.
Fig. 2 shows the SWCNTs produced
under the current optimum condition.
C2H4/O2/Ar with ferrocene and sulfur
vapors is fed to the inner tube andferrocene is decomposed quickly in thepremixed flame at Tflame = 3700 °C. The
1 μm
flame gas is mixed with Ar and cooled
down to Tcat = 1100 °C to nucleate Fe
nanoparticles. CH4 is preheated and fed
radially to mix and start CVD at TCVD =900 °C. Products were collected by amembrane filter and analyzed by scanningelectron microscopy (SEM) and Raman
spectroscopy. SWCNTs with 1 nm
diameter was obtained but still at a small
amount.
Fig.1 Experimental
Fig.2 SEM image and[1] J. Oshima et al. 42nd FNTG Symposium,
1P-11 (2012).

apparatus

Raman spectrum

Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, Email: noda@waseda.jp- 63 -

1P-20An Effective Method for the Production of Single Walled Carbon
Nanotubes by the Bipolar Pulsed Arc Discharge Method
11Kazi Hanium Maria, 1Tetsu Mieno

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

Single-walled carbon nanotubes (SWNTs) are synthesized by an innovative low-frequency bipolar
pulsed arc discharge method using a newly developed bipolar pulsed current circuit with constantcurrent and constant pulse duration. In this set-up, the arc is produced between two graphite electrodes
containing a metal catalyst (Ni+Y), and both electrodes will sublimate carbon alternately roughly at asame rate as shown in Fig.1. In this case, all the sublimated carbon becomes soot containing
single-walled nanotubes [1, 2] and there is no deposition on the electrodes. The carbon sublimation rate
and the deposition rate of the bipolar pulsed arc discharge method are compared with those of the DC,
and the AC arc discharge methods, as listed in Table 1. TEM micrograph reveals that the bipolar pulsed
arc discharge has a tendency to produce thicker bundles of SWNTs as shown in Fig.2. The average
numbers of SWNTs in a bundle are 3 to 4 and the tube diameters are approximately 1.0-1.5 nm. This
diameters result is in good agreement with the results obtained from the Raman experiment. The
intensity ratio ID/IG in the Raman measurement varies from 0.021 to 0.026 with the frequency whichindicates the good quality of SWNTs.
Table 1. Comparison between the different arc discharge methods
Type
Current (A)Frequency (Hz)DC55
0AC 50(effective current) 60
Bipolar55
2

Sublimation Rate (mg/min)
25.40
4.19
18.08

Fig.1 Variation of sublimation rates,
Welectrode, from the two electrodes.

Deposition Rate (mg/min)
8.92
no deposit
no deposit

Fig.2 TEM image (× 100000) of the soot synthesized by the
bipolar pulsed arc discharges of frequency f = 0.05 Hz.

[1] M. J. Rahman, T. Mieno. Jpn. J Appl. Phys. 52, 056201 (2013).
[2] K. H. Maria, T. Mieno. Vacuum. 112, In Press, (2015).
Corresponding Author: T. Mieno
Tel & Fax: +81-54-238-4750, E-mail: sptmien@ipc.shizuoka.ac.jp- 64 -

1P-21
Selective precipitation of few/multi-layer graphene on/around h-BN on SiO2
from metal-carbon films○Kohtaro Yamaguchi, Kei Hasegawa, and Suguru Noda*
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Direct synthesis of graphene on dielectric/insulator substrates is important for simple
fabrication of graphene-based devices. Some studies have reported such growth [1,2],
however there are still many issues to be solved for practical fabrication of graphene.
Graphene on h-BN is gathering great interests due to the enhanced mobility in graphene [3].
In this work, we target at direct growth of graphene on h-BN.
We used metal-carbon (M-C) mixed/bilayer films as a starting material for graphene. Upon
heating, carbon precipitates to form graphene if the carbon concentration is higher than thesolubility at the heating temperature. For M-C films with a free surface, graphene selectively
precipitates not at the film/substrate interface but at the free surface to minimize the freeenergy of the system. Thus we used a cap layer to make the cap/M-C film interface morestable than the M-C film/substrate interface to precipitate graphene at the substrate side.
First we worked on precipitating graphene on SiO2 using SiO2 (500 nm)/Ni (300 nm)/a-C(30 nm) multilayer sputter-deposited on a quartz glass substrate. The sample was annealed ina tubular furnace for 10 min at 1000 °C under Ar atmosphere to precipitate graphene. SiO2
and metal layers were then removed using hydrofluoric acid and iron (III) chloride aqueous
solutions, respectively. With a SiO2 cap-layer, many graphite islands precipitated at theinterface between quartz glass substrate and Ni film. Without a cap layer, on the other hand,
precipitation occurred only at the Ni surface.
We then studied graphene precipitation on h-BN (Fig. 1a). First, h-BN flakes wereprepared on a quartz glass substrate by mechanical exfoliation using Kapton® tapes. Cu isused as a cap layer on Fe-C films because of the minimal solubilities of C and Fe in it. Cu(500 nm)/Fe-C (300 nm) was sputter-deposited on the substrate. The sample was annealed andmetals were then removed as mentioned above. Fig. 1b shows the optical and Raman mapping
images of the two typical h-BN flakes after removing the metal layers. Few/multi-layer
graphene precipitated on the h-BN surface and/or at the edge. Factors contributing to various
precipitation modes will be discussed.
(b) Optical images(a)
Depositing
layersh-BN flakes

-10
-8
-6

-10

h-BN peak

5 000
4 500
4 000

-4

Cu 500 nm

3 500

-2

3 000

0

2 500

2

Fe 300 nm
Quartz glass
Annealing
1000℃
Removing
layers

2 000

4

10 µm

1 500

6

10 µm

8
10
-10

-5

0

1 000

1 ƒÊm

0
5

-6

-15

G peak

4 500
4 000
3 500

-4
3 000

-2

2 500

0

2 000

2

1 500

4
6

1 000

10 µm

8
10
-10

10

-5

10 000 -15

0
Ê

1 ƒÊm

5

8 000
7 000

-5

500

10

3 500

9 000
-10

-10

3 000

-5

2 500

6 000
0

Multi-layer
graphene

500

-8

5 000

2 000

0

4 000
5

10 µm

3 000
2 000

10 µm

10

15
-10

0

2 ƒÊm

1 500
5
1 000

10 µm

10

1 000
0

10

15
-10

0

2 ƒÊm

500

10

Fig. 1(a) Process flow diagram. (b) Optical and Raman mapping images of h-BN and G peaks on h-BN flakes.
[1] K. Hirano et al. Nanoscale 4, 7791 (2012). [2] M. Kosaka et al. Carbon 82, 254 (2015). [3] C. R. Dean et al.
Nat. Nanotechnol. 5, 722 (2010).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 65 -

1P-22
Two-step growth and characterization of WS2/MoS2 heterostructures○

1

Shohei Mori1, Yutaka Maniwa1, Yasumitsu Miyata1,2
Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
JST, PRESTO, Kawaguchi, 332-0012, JapanThe heterostructures of two-dimensional semiconductors have attracted muchattention for their potential applications in electronics and optoelectronic. Recently,
several groups have reported the vapor-phase growth of lateral and stacked
heterostructures based on typical semiconductor transition metal dichalcogenides(TMDCs) such as MoS2, MoSe2, and WS2 [1-3]. These studies basically use thecontinuous feeding of two precursors for the growth of two different TMDCs withoutchanging reaction chambers. This process often leads to the alloying of heterojunction
interfaces and/or secondary-grown materials because of the contamination of theremaining first precursors in the chambers. To avoid the contamination, it is highly
desired to develop a two-step growth technique of the heterostructures with clean
reaction chambers.
Here, we report the two-step growth of WS2/MoS2 heterostructures by using suchclean environment. First, WS2 monolayers were formed on a SiO2/Si substrate by thesulfurization of WO3 thin films. Then, the samples were put on another quartz tube to
avoid the contamination of WO3 during MoS2 growth. The MoS2 atomic layers weregrown from sulfur and MoO3 by chemical vapor deposition. This process leads to theformation of triangle-shaped MoS2 grains on the WS2 as shown in the AFM image andRaman spectra (Fig. 1). In the poster, the details of sample preparation andcharacterization will be presented.

Fig.1 (a) AFM image and (b) Raman spectra of the WS2/MoS2 heterostructures.
[1] Y. Gong, et al. Nat. Mater. 13, 1135 (2014)., [2] X. Duan, et al. Nat. Nanotechnol, 9, 1024 (2014).,[3] C. Huang, et al. Nat. Mater. 13, 1096 (2014).
Corresponding Author: Yasumitsu Miyata, TEL:+81-42- 677-2508, E-mail: ymiyata@tmu.ac.jp- 66 -

1P-23
Production of graphene quantum dots with molecule-like fluorescence○Misaki Takahashi, Toshiki Sugai
Department of Chemistry, Toho University, Miyama 2-2-1 Chiba, 274-8510, Japan
Graphene quantum dots (GQDs) are nanometer-size graphene fragments. They arepromising materials because of their unique electronic and optical properties originating inquantum size and edge effects. In particular, their fluorescence should be constant likefluorescent molecules even if the excitation wavelength is changed for the applications suchas biomarkers. However, the emission wavelength of GQDs, especially derived from bulk
carbon such as carbon fibers, depend on excitation wavelength, which may come from theirdefects [1]. Although there have been a few reports on the GQDs with molecule-likefluorescence [2,3], emission wavelength cannot be controlled by changing the size of GQDswith keeping molecule-like fluorescence properties. Here we present production and size
control of GQDs with molecule-like fluorescence by chemical oxidation of single-walledcarbon nanotubes (SWNTs) in various conditions without any post-processing.
GQDs were prepared from CoMoCAT-SWNTs (Sigma-Aldrich) by oxidation in a mixture ofconcentrated H2SO4 and HNO3. The solution was sonicated for 24 hours and/or sonicated forfurther purification and separation such as dialysis
and size exclusion chromatography. The results
show that the starting material is crucial to theemission properties. Furthermore, the emission
wavelength and the size of GQDs were controlled
by the reaction conditions with keeping theproperties of molecular-like fluorescence.

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two hours and refluxed for 24 hours at temperatures from 70 to 150 °C. The oxidized mixture
was diluted with deionized water followed by centrifugation at 10000 rpm for 20 min to
separate GQDs and residue SWNTs. The produced GQDs were characterized by TEM,
absorption, and photoluminescence (PL) observations.
Fig.1 shows PL spectra of the GQDs prepared at temperature of 100°C. The emission
wavelength of 520 nm, which have been reported
QP
QP
QP
as one of the major emission wavelengths, doesQP
not depend on the excitation wavelength without
QPQP
QP
QP
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Fig.1 PL spectra of the GQDs prepared reaction
temperature at 100°C[1] J. Peng et al. Nano Lett. 12, 844 (2012). [2] M. Zhang et al J. Mater. Chem. 22, 7461 (2012).
[3] Y. Dong et al. Carbon. 64, 245 (2013).
Corresponding Author: T. Sugai
Tel: 047-472-4406 E-mail: sugai@chem.sci.toho-u.ac.jp- 67 -

:DYHOHQJWKQP

1P-24Growth of bilayer graphene and its electric property○Ryo Hoshino, Ryoya Kimura, Kentaro Imai, Yutaro Hayashi, Tomoko Nagata,
Nobuyuki Iwata, Hiroshi Yamamoto
College of Science &Technology, Nihon University, 7-24-1 Narashinodai, Funabashi-shi,
Chiba 2748501
In order to realize superconductivity at room temperature, we fabricate metal intercalated
bilayer graphene. The electron-exciton coupling is expected to generate high temperature
superconductivity [1]. In this study, we report the growth of bilayer graphene and its electric
property.
The bilayer graphene was fabricated by stacking two single-layered graphene sheets. The
single layered graphene was prepared by chemical vapor deposition (CVD) method on Cu foil
and transferred on SiO2/Si substrate. For the transport, poly methyl methacrylate (PMMA) wasused as a tentative protection film. Cu foil and PMMA film were removed after the transport
using soaking the specimen in an Fe(NO)3 aqueous solution and acetic acid solution. The
removal conditions were optimized to obtain high purity graphene.
Figure1 shows the Raman spectrum of graphene on SiO2/Si substrate prepared using
optimized removal conditions. The G- and G’- peaks were observed at 1591.5 cm-1 and 2689.2
cm-1, respectively. The ratio of G/G’ peak intensity and sift of the G’-peak indicate the growthof single-layered graphene sheet.
The electric properties of bilayer graphene fabricated by stacking this single-layered
graphene sheets and details for removal conditions will be discussed.

㻌

1000
800
700
600
500

㻌

Intensity [ a.u. ]

900

400
300
200
100

[1] Akimitsu. Parity. MARUZEN. 05, 6-12 (2008).

0
1200

Corresponding Author: Nobuyuki Iwata
Tel: +81-47-469-5457
E-mail: iwata.nobuyuki@nihon-u.ac.jp

1500

1800

2100

2400
-1

Wavenumber [ cm ]Fig.1 Raman spectrum of graphene- 68 -

2700

3000

1P-25Growth and characterization of W-doped NbS2 atomic layers○Shogo Sasaki1, Yutaka Maniwa1, Yasumitsu Miyata1,2
1Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
2
JST, PRESTO, Kawaguchi 332-0012, Japan

Atomic-layer transition metal dichalcogenides (TMDCs) are attractive two-dimensional
materials because of their tunable electronic properties and unique spin-valley physics. To
date, there have been many reports on the growth of semiconducting monolayer TMDCs suchas MoS2 and WS2 [1]. In contrast, very few synthesis studies have been reported for metallic
TMDCs such as NbS2 nanosheets [2]. It is, therefore, still highly desired to prepare highquality, large area metallic TMDC atomic layers for unraveling their unique electronic phases
including charge-density wave and superconductivity in the two-dimensional limit.
In this presentation, we report the growth and characterization of metallic W-doped NbS2
atomic layers. For the crystal growth, stacked WO3 and Nb films were prepared on various
substrates including sapphire and graphite by electron beam deposition. These films were
sulfurized by annealing at 1200℃ under hydrogen/sulfur/argon atmosphere. We found thatthe addition of W atoms effectively prompts the growth of Nb-based TMDC crystals. Figure
1a shows atomic force microscope (AFM) image of a typical hexagonal-shaped crystal of
W-doped NbS2. The thickness of such crystals ranges from 4.2 to 70 nm. High-resolution
AFM and FFT images reveal the honeycomb lattice of samples with lattice constant of 3.2 Å(Fig. 1b). These crystals have two characteristic Raman peaks at 360 cm-1 and 392 cm-1,
which can be assigned to WS2 E2g and NbS2 A1 modes, respectively (Fig. 1c). The resistivityof samples is around 10-5 ·m, which is comparable to that of bulk NbS2 (~10-6 ·m). These
results strongly suggest that the present approach provides atomic layer W-doped NbS2
crystals with metallic properties.

Fig 1 (a) AFM image of a typical W-doped NbS2 crystal. (b) High-resolution AFM and FFT images of thecrystal surface. (c) Raman spectra of monolayer WS2, bulk NbS2 and W-doped NbS2.
[1] M. Chhowalla, et al. Nat. Chem. 5 (2013) 263.
[2] W. Ge, et al. Nanoscale, 5 (2013) 5773.
Corresponding Author: Yasumitsu Miyata
TEL:+81-42- 677-2508, FAX:+81- 42-677-2483
E-mail: ymiyata@tmu.ac.jp- 69 -

1P-26π-Conjugated Polymer Microspheres Covered by Graphene Oxide○Yusuke Aikyo1, Kenichi Tabata2, Soh Kushida2, Daniel Braam3, Junpei Kuwabara2,
Takaki Kanbara2, Takahiro Kondo2, Junji Nakamura2, Dao Duy Thang4, Satoshi Ishii4,
Tadaaki Nagao4, Axel Lorke3, Yohei Yamamoto2
1

College of Science Engineering, University of Tsukuba, Ibaraki 305-8573, Japan
Graduate School of Pure and Applied Sciences and TIMS, University of Tsukuba,
Ibaraki 305-8573, Japan3
Department of Physics, University of Duisburg-Essen, Duisburg D47048, Germany
4
National Institute for Materials Science (NIMS), Ibaraki 305-0044, Japan
2

Carbon materials are studied for application in electronic and optoelectronic devices.
Recently, we reported that π-conjugated polymers self-assemble to form
microspheres[1,2], which exhibited whispering gallery mode (WGM) photoemission
upon laser irradiation to single spheres.[3] Here, we attempt covering the polymer
microspheres with 2D carbon materials such as graphene and graphene oxide (GO).
π-Conjugated polymer spheres were prepared by vapor diffusion of MeOH into a
CHCl3 solution of P1 (Fig. 1a). The resultant suspension of the polymer microspheres
was then dropped into
an aqueous solution of
GO. Figure 1b showsa SEM micrograph ofthe obtained precipitate,
where the surface of thepolymer microspherewas covered by GO.
µ-PL measurements ofthesinglesphere Fig. 1 (a) Molecular structure of P1, and SEM and XSTEM
showed clear WGM micrographs of self-assembled microspheres of P1. (b) SEM
photoemission
with micrograph of the microsphere of P1 covered with GO. (c) WGM
photoemission from the microspheres with and without GO covering.
periodic and sharp lines(Fig. 1c).
[1] T. Adachi et al. J. Am. Chem. Soc. 2013, 135, 870–876.
[2] L. Tong et al. Polym. Chem. 2014, 5, 3583–3587.
[3] K. Tabata et al. Sci. Rep. 2014, 4, 5902/1–5.
Corresponding Author: Y. Yamamoto
Tel: +81-29-853-5030, Fax: +81-29-853-4490.

e-mail: yamamoto@ims.tsukuba.ac.jp- 70 -

1P-27
Direct and real-time TEM observation of aqueous solution sandwiched bygraphene layers○Yuki Sasaki, Ryo Kitaura and Hisanori Shinohara
Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan
High-resolution transmission electron microscopy (HRTEM) observations provide
real-time atomic-level structural information on nanomaterials [1]-[3]. If we can apply HRTEM
for observation of liquids and solutions, that will be a great impact on physical chemistry of
liquids and solutions. One of the biggest problems of HRTEM observations of liquids is thatliquid samples have to be placed under a high vacuum
condition, the liquid samples being lost spontaneously byvaporization. To overcome this problem, we have here
focused on development of a new method for HRTEM
observationsofliquids
byusinggraphenesandwiched-type environmental cell. The environmental
cell has been successfully applied to observe water atvarious temperature and dynamics of aqueous solution ofiron nitrate.
Figure 1 and figure 2 shows a typical HRTEM image ofFe nitrate aqueous solution and a corresponding electronenergy loss spectrum, respectively. EELS peaks arisingfrom oxygen and iron have been clearly observed which

Fig.1 Typical HRTEM image ofthe graphene pocket, shown bydashed line.
Black circle shows iron nitrate.

respectively originates from oxygen in water molecules
and iron in iron nitrate. A contrast marked by the circle inFig. 1 probably corresponds to precipitated iron nitrate,
which moves rapidly and blinks during the observation. In
this poster, details of sample preparation and detailed
results of TEM observations are addressed.
[1] J. C. Meyer, et al. Nature 454, 319 (2008).
[2] R. Kitaura, et al. Nano. Lett. 8, 693 (2008).
[3] R. Kitaura, et al. Angew. Chem., Int. Ed. 48, 8298 (2009).
Corresponding Author: Ryo Kitaura and Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp and noris@nagoya-u.ac.jp- 71 -

Fig.2 Electron energy-loss spectrumof Fe(NO3)3 aqueous solution
encapsulated
insidegraphenepockets.
K-edge peak of oxygen and iron
were observed.

1P-28
Influence of the surface structure of substrate
for proximity effect on Graphene
Akinori Izumiyama1, ○Kazuyuki Takai1, 2
1
2

Department of Chemical Science and Technology, Hosei University, Tokyo 184-8584, Japan
Research Center for Micro-Nano Technology, Hosei University, Tokyo 184-0003, Japan

Atomic membrane system like graphene is intrinsically sensitive to chemical environment,
where all atoms possess surface. Indeed we have demonstrated a proximity effect on theelectronic properties of graphene on SiO2 substrate on which surface a large polarization is
introduced by modification with self-assemble monolayer (SAM) of polar molecules [1, 2].
However, the observed shift of the Fermi energy EF by the SAM-induced proximity effect isalmost half of that estimated by a simple band calculation [1]. This is attributed to the lesspolarization caused by poor packing of SAM on the SiO2 substrate. In this study, the surfaceof SiO2 is chemically treated for improvement of the structure of over-layer SAM, which isevaluated by XPS and the contact angle measurement. The SiO2 / Si substrate was treated bya piranha solution to make more hydrophilic surface by introduce of the hydroxyl functionalgroups. SAM fabrication was performed by dipping substrates into the solution of SAM
molecule ( CF3(CF2)5(CH2)2Si(OCH3) 3 ) with hexane solvent. XPS measurement was carried

Intensity (a.u.)out by using Al K excitation beam. Fig. 1 shows XPS C1s sepctra for SAM on SiO2
substrate with / without hydrophilic treatment. SAM without hydrophilic treatment exhibits
the peak for C-O in addition to the large contribution
C-C
CF2 Hydrophilic
CF3
C-O Substrateof the peak for C-C, indicating the presence of thetotallarge amount of SAM molecules without any
chemical bonding to the substrate. On the other hand,the peaks for C-C and C-O significantly reduced in
the hydrophilic substrate, suggesting the wellformation of the silane-coupling between the SAM
Non-Hydrophilicmolecules and hydroxyl functional groups on the
Substrate
substrate. The contact angle measurement also
supports the well hydrophilic nature of the substrate
treated by piranha solution.
[1] Y. Yokota, K. Takai, and T. Enoki, Nano. Lett. 11,
3669-3675 (2011)
281
285
289
293
Binding energy (eV)[2] K. Yokota, K. Takai, Y. Kudo, Y. Sato and T. Enoki,Phys. Chem. Chem.Phys. 16, 4313-4319 (2014)
Corresponding Author: Kazuyuki Takai,Fig. 1 XPS C1s spectra for SAM on SiO2
Tel: +81-42-387-6138, Fax: +81-42-387-7002,
substrate with / without hydrophilic treatment
E-mail: takai@hosei.ac.jp- 72 -

1P-29Photoluminescence Properties of Van der Waals Hetero Structure
Composed of Monolayer Transition Metal Dichalcogenides○Shinichiro Mouri1, Daichi Kozawa1, Goki Eda2, Yuhei Miyauchi1
and Kazunari Matsuda1
1Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan2
Department of Physics, National University of Singapore, Singapore
Monolayer transition metal dichalcogenides (1L-TMDs) have attracted muchattention as a novel two-dimensional semiconductor, and also are promising candidate
for the future optoelectric devices [1,2]. Van der Waals hetero-structures composed of
1L-TMDs can be suitable platform to realize functional semiconductor devices suchas high performance solar cell [3]. In this study, we studied photoluminescence (PL)properties of Van der Waals hetero-structures building from three 1L-TMDs.
Bold black line in Fig.1 shows the PL spectrum of 1L-WSe2/1L-MoSe2/1L-MoS2
hetero-structure. Glay lines in Fig. 1 show the PL spectra of 1L-WSe2 (Peak X: 1.66eV), 1L-MoS2 (Peak Y: 1.83 eV) and 1L-MoSe2 (Peak Z: 1.56 eV). In the PL
spectrum of the hetero-structure, these peaks were quenched and new PL peak (Peak
W: 1.58 eV) was appeared. In the Van der Waals hetero-structures building from two
1L-TMDs (1L-WSe2/1L-MoS2), the photo-generated carriers are spatially separated
and formed interlayer excitons [4,5]. The PL peak energy of
1L-WSe2/1L-MoSe2/1L-MoS2 hetero-structure is almost same as that of interlayer
excitons in 1L-WSe2/1L-MoS2 hetero-structure (1.5 eV ~ 1.65 eV [4,5]). This result
suggests that photo-generated carriers in 1L-WSe2/1L-MoSe2/1L-MoS2
hetero-structure might be separated
spatially as shown in the inset of Fig. 1
and form interlayer excitons. The detailed
MoS2 MoSe2WSe2
PL properties including valley polalizationeeffects and many-body effects will behdiscussed in the presentation.
[1] K. F. Mak et al. Phys. Rev. Lett. 105, 136805(2012).
[2] S. Mouri et al. Nano Lett. 14, 5944 (2013).
[3] A. K. Geim et al. Nature 499, 419 (2013).
[4] H. Fang et al. PNAS 111, 6198 (2014).
[5] M. H. Chiu et al. ACS Nano 8, 9649 (2014).
Corresponding Author: S. Mouri
Tel: +81-774-38-3463,
Fax: +81-774-38-4567,
E-mail: iguchan@iae.kyoto-u.ac.jp

Figure 1 PL spectra of 1L-MoS2, 1L-MoSe2,
1L-WSe2 and their Van der Waals
hetero-structure.

- 73 -

1P-30
Crossover between Localization and Delocalization in
Edge-Disordered Graphene Nanoribbons○Kengo Takashima1 and TakahiroYamamoto1,2
1

Department of Electrical Engineering, Tokyo University of Science, Tokyo 162-8601, Japan2
Department of Liberal Arts, Tokyo University of Science, Tokyo 162-8601, Japan

Graphene is expected to be a channel material of field effect transistors (FETs) because of its
high carrier mobility. However no band gap of the graphene is a serious problem for its FET
application. One possible way to overcome the gap-opening problem is to process it in theform of a nanometer width ribbon, referred as graphene nanoribbons (GNRs). They have beensuccessfully applied to FETs with high on-off ratio. A recent experiment reported that theresistance of GNRs increases exponentially with their length even at the room temperature [1].
This non-Ohmic behavior is due to the edge vacancy of GNRs. The effects of edge vacancy
become more remarkable when the ribbon width becomes narrower in the future. However
the electronic transport properties of such narrow GNRs have not been clarified yet.
In this study, we have investigated the coherent electronic transport in edge-disorderedarmchair GNRs (ED-AGNRs) using the nonequilibrium Green’s function method combinedwith a tight-binding model. In our simulation model, the edge vacancy is modeled by adding
or removing pairs of carbon atoms at the armchair-type edges. We calculated electricalconductances of various ED-AGNRs by changing the amount of edge vacancies from 4% to
50% and the ribbon-width from 0.74nm to 2.95nm. We confirmed that the electricalconductances G of ED-AGNRs decrease exponentially with their lengths L, i.e., G∝exp(-L/ξ),where ξ is the localization length [2]. Moreover, we numerically determined (i) the
vacancy-concentration dependence of ξ and (ii) the ribbon-width dependence of ξ. In addition,
we gave a physical interpretation of (i) and (ii) through theoretical analysis based on theperturbation theory. This result provides a guideline for developing GNR-based FETs.

References:[1] G. Xu et al., Nano Lett. 11, 1082 (2011).
[2] K. Takashima and T. Yamamoto., Appl. Phys. Lett., 104, 093105 (2014).
Corresponding Author: Takahiro Yamamoto
Tel: +81-3-5876-1486, Fax: +81-3-5876-1486,
E-mail: takahiro@rs.tus.ac.jp- 74 -

1P-31
G* band Raman spectra of single layer graphene revisited○ S. Siregar1, E.H. Hasdeo1, A.R.T. Nugraha1, H.-L. Liu2, and R. Saito1
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Department of Physics, National Taiwan Normal University, Taipei 11677, Taiwan
Weak Raman band existing around 2400 cm-1 in graphene, called as the G* band, is studied
theoretically for several laser excitation energies (EL), from infrared to long-frequency visible
light region, such as 355 nm, 532 nm, and 785 nm wavelengths. This study is especiallystimulated by a recent observation of G* band in single layer graphene by Liu et al., in which
the peak position of G* band is found to be sensitive to the EL [1]. An early attempt to explain
the G* band by Shimada et al [2] assigned three possibilities for the G* band based on the
double resonance Raman process: (1) q = 0, LO overtone phonon mode, (2) q = 0 LO and iTA
combination phonon mode, and (3) q = 2k, iTO and LA combination phonon mode, where q is
the phonon wavevector and k is the electron measured from the K point.
However, by calculating the Raman intensity directly in this work, we propose that the G*band might corresponds to the q = 2k, iTO and LA combination (iTOLA) phonon mode [3].
The combination phonon mode means that the excited electron emits the phonon twice, firstly
by emitting an iTO phonon and secondly by emitting an LA phonon, as can be seen in Fig. 1.
In the calculation of the Raman spectra, we use the phonon dispersion obtained from the force
constant model considering up to twentieth nearest neighbor [4] and the electron-photon
together with electron-phonon matrix elements obtained within the extended tight binding
model [5]. Our calculated Raman spectra of the G* band for the different laser excitationenergies are in good agreement with the experimental results by Liu et al. when we consider
the q = 2k iTOLA phonon mode and thus ruling out the other possible assignments. Thismight be because of the much stronger electron-phonon interaction
for the iTOLA compared to the other modes. It is expected that theG* band of single layer graphene could also be a unique signatureof the single layer graphene and thus enrich the possibility tocharacterize different graphene-related materials.
[1] H.-L. Liu, S. Siregar et al., Carbon 81, 807-813 (2015).
[2] T. Shimada et al., Carbon 43, 1049-1054 (2005).
[3] R. Saito et al., Solid State Communications 175-176, 18-34 (2013)[4] R. Saito et al., J. Phys.:Condens. Matter 22, 334203 (2010).
[5] K. Sato et al., Chem. Phys. Lett. 427, 117 (2006).
Corresponding Author: Syahril Siregar
TEL: +81-22-795-5719, FAX: +81-22-795-6447
E-mail: siregar@flex.phys.tohoku.ac.jp- 75 -

Figure 1: G* band schematic
double-resonance process

1P-32
Geometric and Electronic Structures of Corannulene Polymers○Kohei Narita and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
Graphene nanoribbons (GNR) has unique electronic properties depending on theiredge shape and width. It has been pointed out that the GNRs with armchair edges aremetals or semiconductors because of the discretization condition imposed on thetwo-dimensional hexagonal Brilluin zone of graphene where the conduction andvalence bands touch each other with linear dispersion at K point. In this work, we focus
on one-dimensional sp2 networks with curvatures, since the curvature in sp2 networks
occasionally induces the peculiar electronic structure near the Fermi level. We study thegeometric and electronic structures of one-dimensionally polymerized corannulene
which possesses the corrugated structure arising from the dish-like shape of theconstituent molecule based on the density functional theory with local density
approximation.
We investigate two possible chain structures of polymerized corranulene molecules,a 55-polymer and a 46-polymer: Corannulene is connected with its adjacent ones byforming five-membered rings (the 55-polymer) while it is connected via four- andsix-membered rings (46-polymer) (Fig. 1). The total energy of the 46-polymer is foundto be higher by 867 meV than that of the 55-polymer because of the four-memberedring possessing large strain around the atoms connecting the molecules. Electronic
structures of these polymers are semiconductor with direct energy gaps of 0.97 and 0.51
eV for 55- and 46-polymers, respectively, with the relatively small dispersion bands
near the fundamental gap (Fig. 2). Detailed analysis on the eneregetics of the dimerized
corranulene molecules unravels the relative stability of the corranulene polymers.

Fig. 1 Geometric structures of (a) the 55-polymer
and (b) 46-polymer.

Fig. 2 Electronic structures of (a)55-polymer and (b) 46-polymer. HO
denote the HOMO band.

Corresponding Author: K.	
  Narita
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 76 -

1P-33
Electron-wave dephasing suppressed by spin–orbit interaction in slightly
hydrogenated graphene within a topological insulating regime
J. Kamijo, ○Y. Katagiri, T. Kato, T. Nakamura1, S. Katsumoto1, M. Ezawa2, B. Ozyilmaz3,J. Haruyama
Faculty of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
1
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa,
Chiba277-8581, Japan2
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
3
Graphene Research Center, National University of Singapore, Singapore 119077
The small mass of carbon atoms has prevented the experimental introduction of intrinsic spin–orbit
interaction (SOI) into graphene, which produces various interesting phenomena such as topologicalinsulating states and the spin Hall effect (SHE) [1]. However, it was recently reported that the controlled
addition of small amounts of covalently bonded hydrogen atoms (e.g., NH < 0.1%) can introduce a colossal
enhancement of the SOI as a result of out-of-plane symmetry breaking (i.e., Rashba-type SOI) [2].
Oh the other hand, phase interference of electron spin waves in two-dimensional (2D) materials is one of
the attractive quantum effects within a diffusive carrier transport regime, and is highly valuable for
spintronics. In conventional 2D materials, SOI causes spin flipping and transforms weak localization(WL；a constructive phase interference) to anti-localization (AL; a destructive phase interference) through a phase shift9,10. Phenomena arising from phase interference have also been reported in SOI-absent
graphene containing a large amount of adatoms (foreign atoms or defects) and ripples in the substrate [3].
For instance, a large magnitude of WL has been reported.
However, none has experimentally revealed how SOI affects phase interference in graphene except for
few theories [4], because the realization of the coexistence of SOI with phase interference in graphene isdifficult. Precise control and optimization of a small amount of NH is crucial to produce the crossover NH
regime between the SOI and phase interference regimes.
Here, we report that Rashba-type SOI, which was introduced by precise slight-hydrogenation (NH <0.1%) of graphene using specified EB resist (i.e., HSQ resist) and EB irradiation, can strongly suppressdephasing in interference phenomena (e.g., causing no spin flipping and no transformation of WL to AL) ingraphene with out-of-plane symmetrical SOI, in contradiction to that in other 2D materials [5]. This implies
that the SOI-suppressed dephasing in topological insulating graphene are highly useful for future spintronic
devices because spin coherence can be maintained much more effectively, despite the presence of SOI andone can control spin through the SOI by applying electric fields. This opens the door to novel carbon
spintronics manifested by spin interference with SOI as a topological insulator.
[1] S. Murakami, N. Nagaosa, and S. C. Zhang Science 301, 1348 (2003).
[2] A. H. Castro Neto, B. Özyilmaz et al., Nature Physics 9, 284 (2013).
[3] M. B. Lundeberg, R. Yang, J. Renard, and J. A. Folk, Phys. Rev. Lett. 110, 156601 (2013)[4] E. McCann and V. I. Fal’ko, Phys. Rev. Lett. 108, 166606 (2012).
[5] J. Kamijyo, T. Nakamura, J. Haruyama et al., Science In-depth-review(http://www.ee.aoyama.ac.jp/haru-lab/)
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 77 -

1P-34
Anomalous electronic properties of mono(few)-atomic layers of
black phosphorous
Y. Katagiri, T. Makino, ○C. Ohata, T. Nakamura1, S. Katsumoto1, M. Ezawa2, H. Shinohara3,
J. Haruyama ,Faculty of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
1
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa,
Chiba277-8581, Japan2
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Chemistry, Nagoya University, Nagoya, 464-8602, Japan
Physics and applications of two-dimensional atomic layers of various materials are
attracting significant attention (e.g., graphene, h-BN, MoS2, WSe2). Among those,mono-atomic layer and few layers of black phosphorus are highly important and interestingfrom the following theoretical reasons [1-4]; e.g., (1) They provide energy band gaps (i.e., Eg
of 0.4  1 eV) existing at the position between Eg of graphene and chalcogenide compounds(e.g., MoS2), depending on layer number. (2) They also have an in-plane anisotropic atomic
and physical structure. Individual layers are buckled, with two in-plane, mutuallyperpendicular directions having armchair and zigzag edges. For example, it leads to theanisotropic electron effective mass, which is several times lighter in the armchair direction
than in the zigzag direction. Thus, it is crucial to reveal such physical properties,
experimentally.
Here, we report on observation of various unique electronic behaviors of mono(few)-layersof black phosphorus. The samples were fabricated by mechanical exfoliation of bulk black
phosphorous and the thickness was confirmed by optical micro scope, Raman spectroscopy,
and AFM observation. Anomalous quantum Hall effect linearly depending on B2/3, hole
doping by oxidation, and PN junction spontaneously formed by partial oxidation etc. will beshown. Details will be presented at poster.

(a)

(c)

Fig. 1: (a)(b) AFM image of folded

(b)
1.6nm

mono-atomic layer of black phosphorus.

(c) Two Hall-bar patterns formed on (a).

[1] L. Li et al., Nature Nanotech. 9, 372 (2014)[2] P.-J. Herrero et al., Nature Nanotech. 9, 330 (2014)[3] S. Kenig, A Neto et al., Appl. Phys. Lett. 104, 103106 (2014)[4] A. –C. Gomez et al., 2D Materials 1, 25001 (2014)
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 78 -

Fig. 2: Rxy as a function of perpendicularmagnetic field B2/3 in Hall effectmeasurement of few-layer black phosphorus.
Three plateaus are observed as shown by
three horizontal dotted lines. The trend of Rxyback ground exhibits a linear relationship on
B2/3. This originates from in-plane anisotropic
electronic structures (i.e., Dirac andconventional
Fermion)uniquetoatomic-layered black phosphorous.

1P-35Magnetism arising from edges of nanomesh of mono(few)-atomic layered
black phosphorous○Y. Nakanishi, C. Ohata, R. Iwaki. k. Nomura1, M. Ezawa1, H. Shinohara2, J. Haruyama
Faculty of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan1
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan2
Department of Chemistry, Nagoya University, Nagoya, 464-8602, JapanM (x 10-4 emu/100m2)

Physics and applications of mono(few) atomic layers of various materials are attracting
large attention (e.g., graphene, h-BN, MoS2, WSe2). Among those, mono(few)-atomic layer ofblack phosphorus (BP) are highly important and interesting because (1) they provide energy
band gaps (i.e., Eg of 0.4  1 eV) existing at the position between Eg of graphene andchalcogenide compounds (e.g., MoS2) and (2) they also have an in-plane anisotropic atomic
structure, resulting in anisotropic physical behaviors [1, 2]. With respect to magnetism
driven from edge states [4, 5], the latters is very important.
In the case of graphene, flat band ferromagnetism arising from edges state of zigzag
atomic-structure edges were theoretically well known and we experimentally observed it inhydrogenated graphene nanomesh, which has honeycomb like array of hexagonal nanoporeswith zigzag pore edges [3]. In mono-atomic layers of BP, individual layers are buckled, with
two in-plane, mutually perpendicular directions having armchair and zigzag edges. Thus, thisinduces possibility of formation of zigzag pore edges when one form the abovementioned
nanomesh consisting of hexagonal nanopores on the BP.
Following the method employed to graphene nanomesh [3], we formed similar nanomeshon few-layer BP, which was fabricated by mechanical exfoliation of bulk BP. As shown in
Fig. 1, indeed, we can observe ferromagnetism approximately 10 – 100 times greater (10-4
emu/100m2) than those in graphene nanomesh, in the BP nanomesh. Various dependence(e.g., on temperature, strong oxidation, hydrogen termination, degradation) will be presented
at poster.
1

Fig. 1: Magnetization curve of oxidized

nanomesh formed on few-layer black
phosphorus for different temperatures. The
magnetization values are 100 times
greater than those in hydrogenatedgraphene nanomesh. This is attributed toin-plane anisotropic edge atomic structure
unique to few-layered BP.

0
-1
-400

0
Magnetic field B (Oe)400

[1] L. Li et al., Nature Nanotech. 9, 372 (2014)[2] P.-J. Herrero et al., Nature Nanotech. 9, 330 (2014)[3] J. Haruyama et al., Appl. Phys. Lett. 104, 252410 and 105, 183111 (2014)[4] X. Peng et al., Appl. Phys. Lett. 116, 144301 (2014)[5] Z. Zhu et al., Appl. Phys. Lett. 105, 113105 (2014)
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 79 -

1P-36
Electronic properties of thin films of all-metallic carbon nanotubes
with ionic gel-gate
T. Honma, R. Kikuchi, S. Yamada, C. Ohata, M. Koyata, J. Haruyama, A. Rao1
Faculty of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
1Nanomaterials Center, Clemson University, 81 Technology Drive, Suite 200
Anderson, SC 29625, USA
High-transition temperature (Tc) superconductivity (SC) of carbon nanotubes (CNTs) iseagerly expected for next breakthrough for physics and applications of CNTs [1]. Althoughpreviously some groups reported on it, the Tc was below 12K with poor reproducibility. Ourgroup also reported on SC with Tc = 12K in the following two-different type CNTs; (1) Arrayof entirely end-bonded multi-walled CNTs [2] and (2) Thin films consisting of slightly
boron-doped single-walled CNTs (SWNTs) [3]. The former was attributed to elimination ofTomonaga -Luttinger liquid, while the latter originated from alignment of Fermi level to van
Hove singularity. However, they had problems similar to others. Thus, other method shouldbe employed to realize high-Tc and highly reproducible SC in CNTs.
Recently, SC realized by using ionic liquid(gel) gate is attracting considerable attention.
Bias voltages applied to the gate collects extremely high two-dimensional electronic densityof states on the sample surface by field effect, resulting in appearance of SC in various
materials. In the present experiment, we formed LiClO4 and KClO4 as ionic gel on thin film
consisting of SWNTs with only metallic behaviors (Fig. 1) and explored SC by changing gel
and SWNT-film conditions.
Figure 2(a) shows typical relationships of drain current (Id) vs. LiClO4-ionic-gel gate
voltage (Vig) and two drain voltages (Vd) of Fig.1-sample. Leakage current (i.e., at Vd = 0) is
reduced, while Id shows no significant increase on Vig increase. Figure 2(b) shows two-probe
measurement result of resistance as a function of temperature. Resistance drop due to SC
cannot be confirmed. To date, SC has not been observed in this type samples.
Gel gate(b)
Vig = 3V

SWNT
Film

Fig.

1:

Top-view
photomicroscope image of anionic-gel gate FET consistingof LiClO4 gel gate on ametallic SWNT thin film.

(a)

(c)

Vig (V)

Fig. 2: (a) Id as a function of Vig and Vd of Fig. 1-sample. (b) Resistance as afunction of temperature at Vig = 3V in (a). Measurement was carried out three times at
each temperature.

[1] J. Haruyama, Book of Carbon-based Superconductors: Towards High-Tc Superconductivity, ISBN
9814303305 (Pan Stanford Publishing 2014)[2] I. Takesue, J. Haruyama et al., Phys.Rev.Lett. 96, 057001 (2006)[3] N. Murata, J. Haruyama et al., Phys.Rev.Lett. 101, 027002 (2008)
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 80 -

1P-37
Photo-reduction of graphene oxide for improvement of
the purity of carbon nanopot○Hiroyuki Yokoi1,2, Kazuto Hatakeyama1,2, Shogo Matsumoto3, Mako Ueda3,
Takaaki Taniguchi1,2 , Michio Koinuma1,2 , Yasumichi 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

In the previous symposium, we reported on the creation of novel nanocarbon named‘carbon nanopot’[1]. Carbon nanopot is a pot-like shaped material composed withmulti-layered graphene sheets and is produced in series to form fibers (nanopot fibers). Its
typical size is 20-40 in diameter and 100-200 nm in length. The length-to-diameter ratio ofcarbon nanopot is much larger than that of conventional nanoball, which suggests higher
potential of carbon nanopot for the application to drug delivery vehicles[2]. In addition,
carbon nanopot consists of fanwise hollow pourer, multi-walled-nanotube like hollow neck,tapering hollow belly, and thick multi-walled dead-end bottom. This complex structure could
allow one to classify carbon nanopot into higher-ordered nanomaterial.
In the formation of the complex structure, the wettability between catalyst metal andgraphene oxide (GO) utilized as catalyst support could be one of the key factors. In order toclarify the contribution of the wettability of GO, we have investigated the effect ofphoto-reduction of GO on the production of carbon nanopot. We have aimed at modifying
wettability of GO through controlling the oxidation degree of GO.
In the experiments, we used mixture of iron acetate and cobalt acetate as catalyst, andprepared aqueous suspension of GO following modified Hummers method. The metal
acetates are mixed with the GO suspension to obtain GO supported catalyst. The catalyst was
dropped and dried on silicon substrates. Some substrates were used as prepared in thesynthesis and the others were photo-reduced in the atmosphere of oxygen for three hours. In
the synthesis, the in-liquid chemical vapor deposition methodwas employed. 2-Propanol wasused as the carbon source. The temperature and time of synthesis were 1100-1110 K and 10
minutes, respectively.
After the synthesis, deposited materials were investigated with FE-SEM. As shown in Fig.
1, some nanoball-type nanofibers were observed among nanopot fibers in the deposit for
non-photoreduced catalysts, whereas almost all fibers were nanopot fibers for photoreduced
ones. Though the above difference seems small, thetendency supports our hypothesis that the
wettability between catalyst metal and GO is one of
key factors to select productions from nanopot andnanoball.
[1] H. Yokoi et al., in Abstracts of the 47th FNTG General
Symposium (Sept. 2014), p.96.
[2] 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- 81 -

Fig.1: Carbon nanofibers deposited for
non-photoreduced catalyst.

1P-38Structure and electronic properties of nanodiamond andits fluorination effect1

2

2○Kenta Kogane ・Hidekazu Touhara ・Yoshiyuki Hattori ・Kazuyuki Takai

1, 3, 41

Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
2
Faculty of Textile Science and Technology, Shinshu University,
Nagano 386-8567, Japan
3
Faculty of Bioscience and Applied Chemistry, Hosei University, Tokyo 184-8584, Japan
4
Hosei University, Research Center for Micro-nano Technology, Tokyo 184-0003, Japan
Nanodiamond (ND) is featured with the large surface area as well as many excellent
properties of bulk diamond, although it has a problem of aggregation [1]. Fluorination of ND
is expected not only to stabilize the surface structure for disaggregation, but also to introducefunctional groups on the surface, the conduction carriers, and so on [2]. In this study, weevaluate the structure and magnetic properties of ND and fluorinated nanodiamond (FND) in
order to consider the change in the electronic state and the surface structure by fluorination byusing X-ray diffractometer (; XRD, Mo K), X-ray photoelectron spectroscopy (; XPS, AlK), and electron spin resonance (; ESR, X-band).
FND was synthesized by the direct reaction between detonation nanodiamond and 1 atm offluorine gas at the temperature of 623 K, 773 K and 873 K for 3 days. For the sample reacted
at 873 K, re-fluorination at 873 K was carried out for 7 days after annealing under vacuum.
Hereafter, each sample is labeled as FND623K, FND733K, and FND873K according to the
maximum temperature during synthesis, while Non-fluorinated one is referred to as ND.
Sharp peaks observed in XRD for ND and FND623K was associated with the diamondlattice constant (a = 3.567 Å [3]). Also, average crystalline sizes of both ND and FND623K
are estimated from FWHM of their peaks by using the Scherrer equation as 3 ~ 4 nm. Thesesuggest that fluorination modifies only the surface structure without affecting the crystal
structure of the core of ND. The F1s peaks of XPS for FNDs does not appear at the position
for physisorbed fluorine, and additional shoulder peak appears at the higher energy side of theC1s peak, suggesting the presence of the some chemical bonding between C and F in FND.
ESR linewidth for FNDs indicates the increasing in the spin relaxation in comparison withND (Fig. 1). However, the spin relaxation was enhanced also in ND heat-treated under thesame condition as FND873K. Therefore, effects of
1.3
fluorination of ND on the magnetism should be
examined taking the influence of the structural
1.2
relaxation by heat-treatment into consideration [4].
[1]Eiji Osawa, Journal of the surface science society of japan,
30, 258-266 (2009).
[2] Hidekazu Touhara, Akiko Yonemoto, Nanocarbon
Handbook, part3, chapter 4 (2007).
[3] S.V. Kidalov, Diamond & Related Materials, 19, 976–980(2010).
[4] J.W. Park, Current Applied Physics, 6, 188–193 (2006).

ΔHPP / mT

1.1

1

ND
ND873KFND623K
FND773K
FND873K

0.9
0.8
0.7

0

50

100

150

Power / mW

200

Fig. 1 Power dependence of ESR linewidth
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002, E-mail: takai@hosei.ac.jp- 82 -

1P-39Spheroidization of microdiamond by self-ablation: preliminary results
Ryoko Yamanoi and Eiji sawa
NanoCarbon Research Institute, AREC, Faculty of Fiber Science and Technology, Shinshu
University, Ueda, Nagano 386-8567, Japan
Natural diamonds show remarkably rich polymorphism1, which can be adequatelyinterpreted as the results of etching apexes and edges surface asperities like truncation anddual operations2. Final products of such surface metamorphosis are novel spherical diamonds,
and they are indeed found in nature on rare occasions3. Recently Moseler4 proposed atomistic
mechanism of the metamorphosis in diamond by using MD simulation as amorphization by
self-ablasion among diamond followed by the formation of graphitic fragments underpressure, which will finally drop off to effect wear.
We attempt here to bring diamond spheroidization into reality by combining three essential
feature of the Moseler mechanism into one set-up: rolling, self-ablation of diamond crystals,
under pressure. We used commercial microdiamond as the starting material and modified
electric Chinese ink-stick grinder to the self-ablation of microdiamond under pressure androlling (SAUPR)（Photo. 1）
Total sample size
=119 particles

After 6h

Photo 1. Left: original, Right: modified
Fig.1. Circularity distribution before and after treatments
Distribution of circularity among
Tab. 1. Application of F- and t-test statistical methods
randomly selected 119 crystals
Cirularity index Heywood diameterincreased (Fig 1), and that of(std dev), %(std dev), μm
diameter decreased. F-test on
Initial78(10)
29.15(5.65)
the both data-sets indicatedAfter 6 hours
82(9)26.73(5.67)
equal variance. Subsequent
Variance
equal
equal
t-test confirmed significant
t-testincrease in circularity by 4% ast(freedom)
3.316(236)
3.286(236)p<0.05well as significant decrease in
p
0.001
0.001
(both sides)
diameter by 8.3% (Tab 1). We
Judgement
Significant
Significant
are now improving the SAUPR
machine for more precise control of operation conditions. The surfaces in contact withmicrodiamond layers will be lined with CVD diamond films.
[1] V. M. Goldschmidt, “Atlas der Krystallformen”, Band III, Diamant, Tafeln 27-48, Fig. 1-364, Carl Winters
Universitätsbuchhandlung, Heidelberg, 1916. [2] E. sawa, A. Barnard, manuscript in preparation. [3] E. A.
Skalwold, Gems & Gemology, Summer issue, 128 (2012). [4]L. Pastewka et al. Nature Mater. 10, 34 (2011).
Corresponding Author: E. sawa
Tel: +81-268-75-8381 Fax: +81-268-75-8551 E-mail: Osawa@nano-carbon.jp- 83 -

1P-40The Topological Structure of 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
We proposed new structures named “starfish nanocarbon” (SFNC, Fig.1) and analyzed therelationships between their structures and electronic states. The structures and electronic
states of 12 SFNCs are determined by the configuration of four 7-membered rings per arm.
We now report two findings on the structure of SFNCs.
(1) The following formula is attested by a topological consideration for all SFNCs with N
arms:(Fig.2).
( the total number of 7-membered rings ) = N × 6.
(2) Two or more different SFNCs are able to combine and make chimera.12 SFNCs are
divided into 2 groups depending on whether the structure has 7-membered rings at thesites B (GroupB7) or not (GroupB6). Both groups have 6 different structures as whole
SFNCs, and 4 different tube types as the arms. SFCNs in the same group are able to be
combined and make chimera. We can decide freely configuration of tubes and theresultant chimera has many different types of structures. We show 3 examples (Fig.3).
The number of kind of chimera1/2, chimera1/3, chimera1/6 is 60, 80, 240, respectively.
SFNC is therefore a potential junction that connects different types of NTs.

Fig. 1 : Name of the parts of SFNC.

Fig. 2 : Topological structure of SFNC.

Fig. 3 : 3types of chimera.

Corresponding Author: K. Nakada
Tel: +81-42-759-6219 Fax: +81-42-759-6493

E-mail: nakada@chem.aoyama.ac.jp- 84 -

1P-41
Double resonance Raman modes in mono- and few-layer MoTe2
Huaihong Guo1, Teng Yang2, Mahito Yamamoto3, Lin Zhou4, Ryo Ishikawa5, Keiji Ueno6,
Kazuhito Tsukagoshi3, Zhidong Zhang2, M. S. Dresselhaus4, and R. Saito 1
Department of Physics, Tohoku University, Sendai, Miyagi 980-8578, Japan,
Institute of Metal Research, CAS, Shenyang 110016, China
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan
Department of Electrical Engineering and Computer Science, Massachusetts Institute ofTechnology,Cambridge, Massachusetts 02139-4037, USA,
Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts
02139-4307, USA
Department of Functional Materials Science, Graduate School of Science and Engineering,
Saitama University, Saitama 338-8570, Japan
Department of Chemistry, Graduate School of Science and Engineering, Saitama University,
Saitama 338-8570, Japan
We study the second-order Raman process of mono- and few-layer MoTe2, by combining ab
initio density functional perturbation calculations with experimental Raman spectroscopy at
1.58 eV, 1.96 eV and 2.33 eV laser excitation energies. The calculated electronic band
structure and the density of states show that the electron-photon resonance process occurs at
the high-symmetry M point in the Brillouin zone, where a strong optical absorption occurs by
a logarithmic Van-Hove singularity. Double resonance Raman scattering with inter-valley
electron-phonon coupling connects two of the three inequivalent M points in the Brillouinzone, giving rise to second-order Raman peaks due to the M point phonons. The predictedfrequencies of the second-order Raman peaks agree withthe observed peak positions that cannot be assigned interms of a first-order process. Our study attempts to
supply a basic understanding of the second-order Ramanprocess occurring in transition metal di-chalcogenides(TMDs) and may provide additional information both on
the lattice dynamics and optical processes especially for
TMDs with small energy band gaps such as MoTe2 or athigh laser excitation energy.

Fig.1 Raman spectrum of MoTe2.

Corresponding Author: Huaihong Guo
Tel: +81-22-795-5717, Fax: +81-22-795-6447

E-mail: hhguo@flex.phys.tohoku.ac.jp- 85 -

1P-42
Improving the property of electric double layer capacitor
by using activated carbon nanoballoon○A. Mizutani1, 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 respectively adsorb and desorb on the electrode surface. EDLC
has advantages that provide higher charge/discharge rate capability and perform longer cycle
life than rechargeable batteries, because chemical reaction such as redox reaction does notoccur during the charge and discharge. In this study, the performance of the EDLC using
carbon nanoballoon was evaluated.
2. Experimental
According to our previous research, carbon nanoballoon (CNB) was synthesized by heat
treatment of arc black at 2600 C in Ar gas [1]. The particle shape of CNB is hollow. CNB isgraphitic and has high conductivity. In this study, we prepared CNB from carbon black. It ishereinafter referred to as CNB-CB. In addition, activated CNB-CB (ACNB-CB) was preparedthrough the potassium hydroxide (KOH) activation. We prepared the electrode of EDLC using
ACNB-CB. The specific capacitance of EDLC was measured from the electrochemicalmeasurement. The electrodes were compared to the activated carbon (AC) electrode.
3. Results
Fig. 1 shows the specific capacitance obtained from20
the galvanostatic charge/discharge curves. The ACelectrode showed the highest specific capacitance at
15
ACNB-CBcurrent densities between 0.1 and 0.5 A/g. But, the
CNB-CB10
CNB electrodes showed higher specific capacitancethan the AC electrode at a current density of 1.0 A/g
CNB
5
and more. In addition, the CNB-CB electrode showedAChigher specific capacitance than the CNB electrode,
0
0.0
0.5
1.0
1.5
2.0
and the ACNB-CB electrode showed highest specific
Current
density(A/g)
capacitance. So the specific capacitance of EDLC was
Fig.1. Specific capacitance of EDLCs
increased by ACNB-CB when using at a highat different current densities.
charge/discharge rate.
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 -

1P-43
Spontaneous antiferromagmetism in the α-graphyne single layer

Teng Yang1, Baojuan Dong1, Huaihong Guo2, R. Saito2, and Zhidong Zhang1
Shenyang National Laboratory for Materials Science, Institute of Metal Research,
Chinese Academy of Sciences, Shenyang 110016, China
Department of Physics, Tohoku University, Sendai, Miyagi 980-8578, Japan,
We study the electronic structure of α-graphyne based on Density functional
calculations using hybrid functionals of GGA and Hatree Fock (so-called HSE). Thisnew type of carbon structure can be derived from graphene by inserting one carbon
pair between each two nearest carbon atoms in graphene. Interestingly, we found thata spontaneous antiferromagnetic (AFM) order forms in α-graphyne withmagnetization of 0.1 µB on each site, which is concurrent with a band gap of
approximately 0.5 eV. A tensile biaxial strain tends to increase both band gap andmagnetization, while the compressive strain has an opposite effect and even gives rise
to a K-point Dirac cone once the band gap is closed. This spontaneous AFM orderingand non-zero band gap at zero strain can be understood based on the Hubbard model.
The effective hopping parameter, which can be derived from a renormalization
method, is found to be much smaller than that in graphene. Value of U/t (U: Coulombinteraction, t: hopping integral) in α-graphyne is therefore larger than the critical one
required for the Mott-Hubbard transition, giving rise to a spontaneous AFM
semiconductor of carbon planar structure.
Corresponding Author: Teng Yang
Tel: +86-24-23971136, +86-24-23891320 (FAX)
E-mail: yangteng@imr.ac.cn- 87 -

1P-44Characteristic of spectral sensitivity for the composite film of Zn doped
iron oxide nanotubes and organometal halide perovskite○ Yuta Kosugi1, Hiroyuki Kusuda1, Ayano Saiki1, Shunji Bandow2
Department of Materials Science & Engineering1 and of Applied Chemistry2,
Meijo University, Nagoya 468-8502, JapanThe nanotube (NT) synthesis involves the polycondensation of iron nitric nonahydrate and zinc
nitric hexahydrate in 1-propanol including surfactant of a Pluronic F-127 at 45 ̊C.

After 5 days

reaction, a gel obtained is heated up to 120 ̊C at a rate of 1 ̊C/min in order to scroll up gel to form
tubular structure. Detail of the nanotube preparation is in the reference [1]. Regarding thesample preparation, stoichiometric ratio of Zn/Fe is easily controllable by changing the amount ofzinc nitrate hexahydrate (0~10 wt%).

According to the analyses of TEM, XRD, XPS and opticalabsorption spectra, we find the nanotube (outer diameter of
4-10 nm and inner one of 2-6 nm, and the length of ~50nm) is represented by ZnxFe3-xO4 and the band gap isdecreased upon low level Zn doping.

Fig. 1 is the Zn/Fe

atomic ratio dependence of the bad gap evaluated by the
Tauc plot method [2-4]. From this figure, we can see thatnon doped Fe3O4 NTs have a band gap of ~2.4 eV and theband gap indicates a minimum of ~2.0 eV for Zn0.27Fe2.73O4
NTs. Hence, we selected this sample and non-doped one
for the evaluation of spectral sensitivity.

Fig. 1. Zn/Fe atomic ratio dependenceof the bad gap.

Cell for the spectral sensitivity measurement was assembled by coating the dense layer of ironoxide on FTO and then the NT sample was stacked as a porous layer. Next the organometal
halide perovskite of CH3NH3PbI3 was spin coated, and finally the Au electrode was vacuum
deposited.

Optical power monitored band

pass filtered light from a Xe arc lamp was
irradiated on the cell and the photo induced
current was measured. Results are in Fig. 2.
IPCE (incident photon to current conversion
efficiency) of NT based samples have higher
efficiency than that of NP (nanopowder) at
long wavelength region. In addition Zn doped
NTs have better IPCE than non-doped one atshort wavelength region.

Fig. 2. IPCE of iron oxide based NTs andnanopowder (NP, d < ~50 nm).

[1] Y. Kosugi, S. Bandow, J. Inorg. Organomet.
Polym. 24, 933 (2014). [2] K. Wongsaprom et al., Appl. Phys. A 114, 373 (2014). [3] S.S. Kumar et al., Inter.
Nano Lett. 3, 30 (2013). [4] V. Džimbeg-Malčić et al., Technical Gazette 18, 117 (2011).
Corresponding Author: S. Bandow, Tel: +81-52-838-2404, E-mail: bandow@meijo-u.ac.jp- 88 -

2P-1
Isolation and Characterization for Each Isomer of(5,6)- and (6,6)-[Li+@C61Ph2]NTf2–○Hiroshi Okada,1 Hiroki Kawakami,1 Shinobu Aoyagi,2 Yutaka Matsuo1
1

Department of Chemistry, School of Science, The University of Tokyo,
Tokyo, 113-0033, Japan2
Department of Information and Biological Sciences, Nagoya City University,
Nagoya 467-8501, JapanThe reaction of fullerene and diazoalkane is representative methodology for synthesizing
various methanofullerene derivatives.[1] 1,3-Dipole cycloaddition on (6,6)-bond of C60,
followed by elimination of nitrogen molecule, affords fulleroid as a major product, which isthermally or photochemically converted to methanofullerene (Scheme 1). In the reaction
obtaining fulleroid, methanofullerene is also generated as a minor product.
Scheme 1

– N2
minor
R

R'
N2

N

N

(R')R

R
R'
– N2
major

R'

! or h"fulleroid(5,6)-isomer

fulleropyrazoline

R

R'(R)

metanofullerene(6,6)-isomer

Recently, we reported synthesis of lithium-ion-encapsulated diphenylmethanofullerene,[Li+@C61Ph2]NTf2–, by the reaction of [Li+@C60]NTf2– and diphenyldiazomethane.[2] In theprevious report, we obtained a mixture of (5,6)-fulleroid and (6,6)-methanofullerene isomers,
and isolated pure (6,6)-isomer by thermolysis of this mixture.
Herein, we report the isolation of (5,6)-isomer.
Separation from the mixture was performed with HPLC
using ion-exchange column (Inertsil CX, GLscience).
Analytical HPLC and 7Li NMR confirmed absence of(6,6)-isomer. We will also present properties of bothisomers as well as structural analysis. The crystal structureof (6,6)-isomer revealed by SR-XRD single crystal
structure analysis at SPring-8 is shown in Figure 1. The
Ph2C= moiety bounded on (6,6)-bond with inside Li+ wasclearly shown with this study[1] M. Yamada et al., Chem. Rev. 2013, 113, 7209–7264.
[2] H. Okada et al. 47th Fullerene Nanotubes-Graphene General
Symposium, 3P-35.
Corresponding Author: H. Okada and Y. Matsuo
Tel: +81-3-5841-1476, Fax: +81-3-5841-1476
E-mail: h_okada@chem.s.u-tokyo.ac.jp; matsuo@chem.s.u-tokyo.ac.jp- 89 -

Figure 1. Crystal structure of(6,6)-[Li+@C61Ph2]NTf2–(ODCB).
Counter anion and crystal solvent areomitted for clarity.

2P-2
Approach to High Open-circuit Voltage in Organic Solar Cells Utilizing
Structural Change of Oxazolino-C70 Derivative○Yutaka Matsuo1, Shu-Hui Li,2 Zong-Jun Li,2 Takafumi Nakagawa,1 James W. Ryan,1 andXiang Gao2
1

Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan
2
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied
Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 5625
Renmin Street Changchun, Jilin 130022, China
Reaction of 2,5-Bn2C70 (Bn = CH2Ph) with hydroxide and ArCN (Ar = Ph, m-ClPh)followed by reaction with I2 and BnBr afforded dibenzylated (1a,b) and tetrabenzylated
oxazolino[70]fullerenes (2a,b), respectively. The latter has a novel structural configuration,
where the addends are positioned from the polar to the transequatorial region. A key structuralfeature of this compound was the oxygen atom of the oxazoline ring is bound to the equatorial
belt region of C70, giving structural change in its reduced state. This enables stabilization of
the reduced state, suppresses charge recombination dynamics in organic solar cells to givehigh open-circuit voltage (0.85, 0.93, and 1.11 V in devices using P3HT, PTB7, andDPP(TBFu)2, respectively).

[1] S.-H. Li, Z.-J. Li, T. Nakagawa, J. W. Ryan, Y. Matsuo, X. Gao, Chem. Eur. J., in press. [DOI:
10.1002/chem.201405890]
Corresponding Author: Y. Matsuo and X. Gao
Tel: +81-3-5841-1476, Fax: +81-3-5841-1476
E-mail: matsuo@chem.s.u-tokyo.ac.jp- 90 -

2P-3
Effects of water molecules on the proton dynamics in fullerenol solids
investigated by solid-state 1H NMR○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 structures with addition ofhydroxyl groups on fullerene (C60) cage and their solids possess 3-dimensionalhydrogen-bonding networks. It have been thought to have potential applications in
proton conductive materials. It has been reported that C60(OH)12 solids have proton
conductivity in a dry atmosphere and that On the other hands, C60(OH)24 solids did
not show ionic conductivity at all [1]. However, detailed proton conduction mechanismof fullerenol solids have not been fully elucidated. We previously reported proton
dynamics in fullerenols solids by solid-state 1H NMR[2-3]. In this study, we investigatedeffects of water molecules on their proton dynamics in fullerenol solids by using
1
H-NMR spectroscopy. We synthesized the methods reported by Chiang et al.[4] andprepared two types of C60(OH)12 samples: one was dried in air after synthesis(driedsample), the other was dried using a vacuum pump after dehydration withacetonitrile(thoroughly dried sample).Figure 1(a) and (b) shows the NMR spectrum of
the dried and thoroughly dried C60(OH)12 solids at room temperature, respectively.
Detailed results on the relationship between the composition of fullerenol-based
composites and the properties of proton motions will be presented.

Figure 1 1HNMR spectra (a) as synthesis (b) dry fullerenol solids (r.t.)
References:[1] K. Hinokuma et al., Chem. Phys. Lett., 341, 442 (2001)[2] K. Baba et al., Proc.of the 44th Fullerene-Nanotubes-Graphene General Symposium (1-5)[3] Y. Sano et al., Proc.of the 46th Fullerene-Nanotubes-Graphene General Symposium (2P-1)[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- 91 -

2P-4
Photoinduced Electron Transfer from Anionic Phthalocyanines to Li+@C60
and Light-Energy Conversion○Yuki Kawashima1, Kei Ohkubo1, Vicente Manuel Blas-Ferrando2, Hayato Sakai3,
Enrique Font-Sanchis2, Javier Ortíz2, Fernando Fernández-Lázaro2, Taku Hasobe3,Ángela Sastre-Santos2, Shunichi Fukuzumi1
1
Department of Material and Life Science, Graduate School of Engineering, Osaka
University, ALCA, Japan Science and Technology Agency, Osaka 565-0871, Japan
2
División de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández,
Edificio Vinalopó, Avda. Universidad s/n, Elche, E-03202, Spain
3
Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama,223-8522, Japan
Supramolecular complexes composed of fullerenes and porphyrinoids have been widely
synthesized because they are suitable electron donor and acceptor for the formation of
long-lived charge separated (CS) state.[1] When a nonpolar solvent is used to form a
supramolecular complex with strong binding, photoinduced electron transfer does not occur
efficiently due to the higher energy of the CS state than the triplet excited energies offullerene and porphyrinoid. In contrast, a polar solvent can afford the long-lived CS state,
however the supramolecular binding between the donor and acceptor moieties is normallyweak due to the solvent polarization. We report herein formation of strong supramolecularcomplexes of cationic lithium-ion encapsulated C60 (Li+@C60)[2] with anionicphthalocyanines (Figure 1) and photoinduced charge separation in a polar mixed solvent.
Two phthalocyanines possessing carboxylate groups (H2Pc¥14− and H2Pc¥24−) form 1:2
supramolecular complexes with Li+@C60 [H2Pc¥14−/(Li+@C60)2 and H2Pc¥24−/(Li+@C60)2] ina polar mixed solvent. From the UV-Vis spectralchanges, the binding constants (K) were estimatedas ca. 1012 M−2. Upon the photoexcitation of
constructedsupramolecularcomplexes,
photoinduced electron transfer occurred to form
the CS state. The lifetime of the CS state was
H2Pc¥14–
H2Pc¥24–
determined to be 1.2 ms for H2Pc¥24−/(Li+@C60)2,
which is the longest CS lifetime among theporphyrinoid/fullerene supramolecular complexes.
H2Pc¥14−/(Li+@C60)2 also afforded the long-lived
CS state of 1.0 ms. The reorganization energy (λ)
and the electronic coupling term were determined
to be λ = 1.70 eV, V = 0.15 cm−1. Supramolecular
ZnPc¥44– complex of zinc anionic phthalocyanine with
H2Pc¥38–
+
Li @C60 was also prepared and investigated. The Figure 1. Chemical structure of phthalocyanines.
ZnPc¥44−/Li+@C60 supramolecular nanoclusters
were assembled on the optically transparent electrode of nanostructured SnO2 (OTE/SnO2) toconstruct the dye-sensitized solar cell. The IPCE (incident photon-to-photocurrent efficiency)
values of OTE/SnO2/(ZnPc¥44−/Li+@C60)n were much higher than the sum of the two IPCE
values of the individual systems OTE/SnO2/(Li+@C60)n and OTE/SnO2/(ZnPc¥44−)n, covering
the near-infrared region.
COO

OOC

OOC

O

O

COO

N

NH

N

N

N

N

HN

N

NH

N

N

HN

N

N

N

OOC

N

O

O

OOC

COO

COO

COO

OOC

O

O

OOC

O

NH

N

N

HN

O

OOC

COO–

N

N

N

N

O

N

N

COO

O

N

Zn

N

N

O

OOC

N

N

OOC

COO

O

N

–OOC

COO

[1] Fukuzumi, S.; Ohkubo, K.; Suenobu, T. Acc. Chem. Res. 2014, 47, 1455-1464.
[2] Kawashima, Y.; Ohkubo, K.; Fukuzumi, S. Chem. Asian J. 2015, 10, 44–54.
Corresponding Author: S. Fukuzumi, Tel: +81-6-6879-7369, E-mail: fukuzumi@chem.eng.osaka-u.ac.jp- 92 -COO–

2P-5
Addition Reactions of Trimetallic Nitride Template Endohedral
Metallofullerenes with Disilirane and Digermirane○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 been of great interest because of their uniqueelectronic properties due to the efficient electron-transfer from the encapsulated metal atoms
to the fullerene cages. To date, a number of studies have been carried out to develop
exohedral functionalization of EMFs, which will open up various applications such as organic
photovoltaics and biological diagnostic agents. It has been demonstrated that functionalizationof EMFs with electron-donating silyl groups alters the electronic characteristics of EMFs
significantly. Such exohedral silylation also affects the positions and dynamic behaviors ofthe metal atoms encapsulated in EMF cages, which is a potential strategy for preparation ofelectronically functional materials. However, the examples of heteroatoms introduced onto
the cages of EMFs have been hitherto limited to those of oxygen, nitrogen, silicon,
germanium, and some transition elements [1]. To expand the fields of potential applicationsof EMFs, it is important to develop efficient methods to derivatize EMFs with heteroatom
functional groups.
Previously, we reported the bis-germylation of trimetallic nitride template endohedral
metallofullerenes (TNT EMFs) using digermirane [2]. Preliminary results show that
introduction of germyl groups alter the oxidation potentials more cathodically than silylgroups do while the reduction potentials did not differ between 5 and 6. Meanwhile, thephotoreaction of digermirane 3 proceeded more efficiently than disilirane 2 probably due tothe structural and electronic advantages of 3. Herein we report the details of investigation of
structural and electronic properties of bis-silylated and bis-germylated TNT EMFs, as well as
the relative reactivities of disiliranes and digermirane toward TNT EMFs.
Scheme 1.

[1] L. Dunsch et al. Chem. Rev. 134, 5989–6113 (2013).
[2] M. Kako et al. The 47th Fullerenes-Nanotubes-Graphene General Symposium, 3P-38 (2014).
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 93 -

2P-6
Energetics of the Nano-Saturn○Shota Kigure1, Haruka Omachi2, Hisanori Shinohara2, and Susumu Okada1
1

Graduate School of Pure and Applied Science, University of Tsukuba,
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan2

Department of Chemistry, Graduate School of Science, Nagoya University, Furo,
Chikusa, Nagoya 464-8602, Japan

Structural hierarchy of nanocarbon materials allows us to design and synthesize newinclusion complexes which exhibit unusual geometric and electronic structures. For
example, C60 encapsulated into oligoarene molecules with a nanohoop structure, such as
cycloparaphenylene (CPP) and cyclochrysenylene, leading to the carbon inclusion
complexes with a unique geometric structure. In the present work, we study theenergetics and dynamical properties of C60 included into cyclohexabiphenylene(nano-Satrun) based on the density functional theory (DFT) with local density
approximation.
Our calculations showed that the nano-Saturn is energetically stable compared with theother known inclusion compounds consisting of C60 and CPP. Furthermore, theinclusion reaction of C60 is exothermic without any energy barriers during the reaction.
Furthermore, C60 oscillates with the frequency of about 1 THz around its equilibrium
position while hardly rotates inside the cyclohexabiphenylene ring due to the large
energy barrier of 0.1 eV.
Corresponding author:
S. Kigure and S. Okada
Email:
skigure@comas.frsc.tsukuba.ac.jp
sokada@comas.frsc.tsukuba.ac.jp
TEL/FAX:029-853-5600(8233)/029-853-5924

Figure. 1 (a) An energy potential surface during the reaction
intocoordinateof
inclusion
processof
C60
cyclohexabiphenylene. (b) Relative total energy of thenano-Saturn as a function of the mutual arrange of C60.

- 94 -

2P-7
Enegetics of H2O encapsulated in fullerenes under an electric field○Jun-ya Sorimachi, Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Fullerenes can encapsulate atoms or molecules inside their C-C networks because of their
hollow-cage structures with nanometer diameters. Recently, single H2O molecule has been
encapsulated into inner space of C60 by using the molecular surgery technique. Because of themoderate reactivity of the other higher fullerenes, similar complexes are expected to besynthesized using the same experimental technique. According to the dipole moment of H2O
inside the fullerene cages, the water-encapsulated fullerenes under the external electric field
exhibit unusual properties depending on the cage size, cage geometry, and the mutual
arrangement of H2O. In this work, we investigate the energetics of H2O molecule
encapsulated into fullerenes, C60~C80, with respect to the mutual direction of its dipole
moment against the external electric field, in which the dipole has parallel, antiparallel, andperpendicular directions to the field, to elucidate the screening effect of the fullerene cage. To
investigate the electronic structures and(a)(b)
energetics of H2O inside the fullerene cages
under an electric field, we use thedensity



functional theory (DFT) with the effective
screening medium method (ESM).
Our DFT-ESM calculations show that thescreening effect of the fullerene cages on the
dipole moment of water strongly depends on
the size, symmetry, and mutual arrangementof fullerene cages. We also find that a
particular dipole direction is energeticallyfavored (Fig. 1(a)) because of double cuspsof the electrostatic potential inside somefullerene cages (Fig. 1(b)). In the case of theC74, the relative energies of dipole withparallel and antiparallel to the field exhibit
asymmetric nature that is unusual for thebare dipole under the electric field. Thosefacts indicates that the π electrons on
fullerene cages strongly affect the screening
against the external electric field being
Fig. 1;(a) Dipole energy of H2O inside C74 with respect toexpected to lead unusual conformations of
the dipole direction. (b) A contour plot of
encapsulated
molecules
with
dipoleelectrostatic potential of the empty C74.
moments.

!
!

Corresponding Author: J. Sorimachi
Tel: +81-29-853-5600(ext.; 8233)
E-mail: jsorimachi@comas.frsc.tsukuba.ac.jp- 95 -

2P-8
Absolute yield of fullerene
formed by graphite laser ablation at room temperature○Hitomi Endo,1 Yuki Taguchi,1 Jun Matsumoto,1 Tomonari Wakabayashi,2
Takeshi Kodama,1 Yohji Achiba,1 and Haruo Shiromaru1
1

Department of Chemistry, Tokyo Metropolitan University, Tokyo, 192-0397, Japan2
Department of Chemistry, Kindai University, Osaka, 577-8502, Japan

Since the appearance of epoch making mass spectra (MS) of C60 in 1985 [1], many
attempts to obtain a macroscopic amount of C60 by laser vaporization (ablation) had all failed,until it was come to know that a high temperature condition was indispensable to C60
formation [2]. The striking MS [1] undoubtedly opened up a new field of nanocarbon science,but a simple question still remains, “how many C60 molecules were really formed by laser
ablation without heating devices in 1985?” At the FNTG46, we reported that the laser ablation(300 mJ/pulse, 10 Hz, 30 min) without heating devices yields perceptible amount of C60 [3]. It
is likely to be due to higher local temperature of the graphite surface irradiated by laser. In thepresent study, we repeated the laser ablation under the same conditions and measured theabsolute yield of C60, to examine whether the yield is consistent with a tacit consensus that it
might be very few but high enough to be detected by MS.
The temperature of the graphite surface under laser irradiation was measured to be about
200 C, by a thermocouple pasted on the surface and a pyrometer. The soluble ablation
products, which were carried by Ar gas flow, were analyzed by HPLC and UV absorption,and the amount of C60 was evaluated to be 6×10-10 mol (4×10-4 mg), namely 2×1010
molecules per laser shot. The C60 attached to the wall
200μm
were about 1×10-3 mg. Therefore, although typical laser
600μm
vaporization cluster source yields much smaller ablation
products, MS-detectable amount of C60 should be
included in the cluster beam.
Total amount of the vaporized carbon was evaluated to Fig. 1 The cross-section SEM image
be about 10 mg from a SEM image (Fig. 1). The C60 around the ablation area. The solid line
yield, the ratio (wt%) of C60 (gas-carried + wall-attached indicates the surface position, which isinterpolated from the intact surface. Theones) to the total, is shown in Fig. 2 together with those carbons in the area surrounded by thepreviously obtained by the laser ablation in a heated cell solid line and black dashed line are lost
so-called “laser-furnace experiment” [4]. The fullerene by ablation. The area above the whiteyield is not significantly deviate from the extrapolation of dashed line is filled by cone-shaped
pillars, where the space occupancy rate
the high-temperature values. Such a low yield suggests
is roughly assumed to be 0.5.
that the signal of synthesized C60 may be easily hidden
by artificial enhancement of C60+ due to dissociative
ionization of larger clusters, especially if multiphoton
ionization is employed.
[1] H. W. Kroto et al., Nature, 318 162 (1985). [2] R. E. Haufler
et al., Proc. Mat. Res. Soc. Symp., 206, 627 (1991). [3] Y. Abe etal., FNTG46, 141 (2014). [4] D. Kasuya et al., Eur. Phys. J. D, 9
355 (1999).
Corresponding Author:H. Endo, Tel: +81-42-677-1111, Fax:
+81-42-677-2525, E-mail:endo-hitomi@ed.tmu.ac.jp- 96 -

Fig. 2 C60 yield vs. temperature graph.
○: “Laser-furnace” [4] ■: present study

2P-9
Fabrication and characterization of SWCNT-TFTs
using chirality separated DNA-wrapped SWCNTs○Yuki Kuwahara 1,2, Fumiyuki Nihey 2,3, Shigekazu Ohmori 2, Takeshi Saito 1,2
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, Japan
3
NEC Corporation, Tsukuba, Ibaraki 305-8501, JapanThe thin film transistors (TFTs) using SWCNTs as a semiconducting material have beenstudied. Recently, progresses in various techniques for the separation of SWCNTs by theirelectric structures enable us to produce highly purified semiconducting SWCNTs, which have
improved the device performance of SWCNT-TFTs extremely. Using such highly purified
semiconducting SWCNTs can increase the density of SWCNT networks in TFT channel
preserving the better device performances in both on/off ratio and carrier mobility. Therefore
highly purified semiconducting SWCNTs are crucial for fabricating the SWCNT-TFTs of highperformances with their uniformity.
Previously, we reported the effective way to fabricate SWCNT-TFTs by preparing
homogeneous network of DNA wrapped SWCNTs (DNA-SWCNTs) [1]. However, theelectronic structure of SWCNTs was still uncontrolled, which resulted in the low device
performance of SWCNT-TFTs due to the presence of metallic SWCNTs pathway in thechannel. Here in this study, we have separated DNA-SWCNTs by their electronic structuresusing ion exchange chromatography (IEX) method
reported by Tu et al. [2], and fabricated
SWCNT-TFTs with the enriched fraction ofsemiconducting DNA-SWCNTs.
Figure 1 plots the device performances of
SWCNT-TFTs using DNA-SWCNTs before and after
IEX. Comparing their on/off ratios at the same
mobility, SWCNT-TFTs after IEX possess higher
values (104–7) than that before IEX. This result
indicates that IEX method sufficiently improves theperformance of SWCNT-TFTs, probably due to the
reductionofmetallic
SWCNTspathway. Fig.1On/off ratio as a function of carrier
SWCNT-TFTs with the on/off ratio of around 106
mobility (Lch = 40 μm) measured fromwas successfully obtained by IEX processedtransfer characteristics (VDS = −1 V).
DNA-SWCNTs.
Acknowledgment: This work was supported by Iketani Science and Technology Foundation.
A part of this work was conducted at the Nano-Processing Facility, supported by IBEC
Innovation Platform, AIST and "Nanotechnology Network Japan" of the Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan.
References: [1] Y. Asada et al., Adv. Mater. 23, 4631 (2011). [2] X. Tu et al., Nature. 460, 250 (2009).
Corresponding Author: T. Saito, Tel: +81-29-861-4863, Fax: +81-29-861-4413, E-mail: takeshi-saito@aito.go.jp- 97 -

2P-10
Energetics and electronic structures of deformed carbon nanotubes○Jumpei Nishikawa, Susumu Saito
Department of Physics, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
Because of its unique proparties, carbon nanotube (CNT) has been intensively studied invarious fields since its discovery by S. Iijima in 1991 [1]. Cylindrical structure is known as astable structure of CNTs, but it is also found experimentally that flatly deformed CNTs arestable in the case of large diameter CNTs [2]. Moreover, electronic-structure change with thisdeformation is theoretically reported [3].
To discuss the energetics of deformed CNTs, we calculate the total energy using thetight-binding model which can deal with interlayer interactions between sp2 layers [4]. To
discuss the electronic structure of these CNTs, we use Hamada-Sawada tight-binding model
which can reproduce the first-principles electronic structure of CNTs very well [5]. We also
use the first-principles density functional calculation. In this study, we report the change ofstability and electronic structure of cylindrical and deformed CNTs.
As a result, we find the critical diameters where deformed structure appears as one ofstable structures and those where the deformed geometry becomes more stable than acylindrical structure. As for the electronic structure, we discuss the energy-gap change withthe deformation, and we also discuss the differences with prior works [6,7].

Fig.1 Fully optimized deformed (36,0) CNT.
[1] S. Iijima. Nature. 354,56 (1991).
[2] Y. Miyata,M. Suzuki,M. Fujihara,Y. Asada,R. Kitaura and H. Shinohara. ACS nano 4,5807 (2010).
[3] K. Nishidate and M.Hasegawa. Phys. Rev. B. 81,125414(2010).
[4] Y. Omata,Y. Yamagami,K. Tadano,T. Miyake and S. Saito. Physica.E 29,454 (2005).
[5] N. Hamada,S. Sawada and A. Oshiyama:Phys. Rev. Lett. 68, 1579 (1992).
[6] S. Zhang et al. Phys. Rev. B 73, 075423 (2006).
[7] G. Gao et al. Nanotechnology. 9, 184 (1998).
Corresponding Author: Jumpei Nishikawa
E-mail: nishikawa.j.aa@m.titech.ac.jp- 98 -

2P-11
Effect of Chemical Doping on the Electronic States ofSingle-Walled Carbon Nanotubes (1) : Experiment
Tomonari Shiraishi1, Naoto Akizuki2, Yuhei Miyauchi2, Kazunari Matsuda2,
Naotoshi Nakashima1,4,5
1Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
2Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
3WPI-I2CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan

4JST-CREST, Japan Science and Technology Agency, 5 Sanbancho, Chiyoda-ku,

Tokyo 102-0075, Japan

Local luminescent states in single-walled carbon nanotubes (SWNTs) have been of greatinterest due to the bright photoluminescence (PL) from such states promising for theirapplications in optoelectronics and bioimaging. Recently, Miyauchi et al. [1] and Piao et al. [2]have reported the extraordinary exciton brightening in such local states generated by chemical
doping and clarified the mechanism of the PL enhancement induced by dimensionality
modification of excitons. However, detailed electronic structure of the local states has been still
unclear. To investigate the origin of the local states, it is important to evaluate the electron
potentials in conduction and valence bands of the chemical doped SWNTs. We have reported
that electronic potentials of (n,m)SWNTs can be determined based on in situ PL
spectroelectrochemistry [3]. Here, we used this method to determine the electronic potentialsof the chemical doped SWNTs dispersed in a carboxymethylcellulose (CMC) film.
Chemical doped SWNTs in a sodium dodecyl benzene sulfonate (SDBS) solution wereprepared according to the previous paper [1] and [2], and the SDBS molecules were replacedwith CMC. A CMC film containing the chemical doped SWNTs was formed on an ITO plate
and used for the PL spectroelectrochmical measurements in an aqueous solution.
Fig. 1 shows a 2D-PL map obtained from the chemical doped SWNTs in the CMC film. The
clear spot at around 1000 nm is the PL from the (6,5)SWNTs. We clearly observe a new spot ataround 1150-1200 nm is the new band generated by the chemical doping that is attributed tothe chemical doped (6,5)SWNTs. The PL intensitiesof the new band were found to change by applying theelectrochemical potentials to the ITO electrode; thus
the oxidation and reduction potentials of the local
states in the chemical doped SWNTs were
determined. We will provide detailed results on theelectronic states of the chemical doped SWNTs at themeeting.
[1] Y. Miyauchi et al. Nat. Photonics, 7, 715 (2013).
[2] Y. Piao et al. Nat. Chem, 5, 840 (2013).
[3] N. Nakashima et al. Angew. Chem. Int. Ed. 48, 7655 (2009); Fig. 1. 2D-PL mapping of a film of the
N. Nakashima et al. Sci. Rep, 3, art no. 2959 (2013).
chemical doped SWNTs on an ITO electrode.
Corresponding Author: Naotoshi Nakashima
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 99 -

2P-12
Effect of Chemical Doping on the Electronic States of Single-Walled Carbon
Nanotubes: Theory○Gergely Juhász,1 Tomonari Shiraishi,1 Naotoshi Nakashima1
1

Department of Applied Chemistry, Kyushu University, Fukuoka 81-0395,Japan

Covalent doping of single-walled carbon nanotubes (SWCNTs) can potentially control andtune the band structure of the nanotubes. This control allow tuning electochemical and opticalproperties, therefore it has a major importance. Such covalent modifications are often
quenches the photoluminescence in semi-conducting the SWCNTs. A very important counterexample was reported by Piao et al. [1]: sp3 doping with a controlled number aryl groups can
produce a new photoluminescence peak, substantially brighter than that of the pristine tubes.
To explain the optical effect a better understanding of electronic structure in sp3 doped
nanotubes is needed. We performed DFTB and TD-DFTB-based calculations on short models
of semiconducting (6,5) SWNT. We focused on single and double dopant scenarios, using H
and aryl groups as dopants. The analysis of the orbital structure revealed a significant radical
character in tubes with single doping sites. A double radical character was also observed intubes with two doping sites, when the dopant
positions were distant. Moreover the calculated
orbital energies, and therefore the energy of theaoptical transitions are very sensitive to the position of
the dopants (see Fig. 1). On the other hand no
experimental evidence of unpaired electrons havebeen reported so far. The relatively large
experimental bandgap and the observed sharp
photoluminestence transitions also exclude thepossibility of such electronic structures.
b
Such contradiction can be explained if the doping
reaction is selective and leads to geometries withweak radical character. The analysis of frontier
orbitals and large stability difference between
different doping configurations suggest that indeed
such selectivity can be an important factor during thedoping reaction. If so, the mild reaction conditions
can actually support such a selectivity, andFig.1 Calculated intensity of opticalexperimental photoluminescence spectrum istransitions and excitation energies
dominated by a handful of doping products.
(bellow) for tubes two doping
configurations: close (a) and distant
doping sites (b).

[1] Piao et al. Nature Chem. 5,840 (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- 100 -

2P-13
Ab initio calculation for electronic bands of CNT in which the chain ofsulphur is inserted○Yuhei Natsume1
1

A

P

Q

Chiba University, chiba 263-8522, Japan
We discuss electronic band structures in the linear chain ofsulphur encapsulated by single-walled CNT. The calculation ismade on the basis of DFT method [1]. Experimental work has
been reported by research group of Shinshu University[2]. Theyemphasize the stabilization of one-dimensional system of sulphurin CNT in relation with conducting characters. ■ In the present
work, sulphur atoms are set at the center axis of CNT in whichchiral number (n,m) is (5,5), as shown in Fig.A. The three unit
cells of pure CNT are contained in the unit cell, which isconstructed by four atoms of sulphur. The distance between
atoms of sulphur in the chain is 1.845Å. In calculation, theoptimization is made in consideration of properties of CNT
systems [3] under this condition of periodicity. The obtained
result is represented in right figure, where bands incorresponding BZ for above-mentioned unit cell are expressed.
Here, the dotted line
indicates Fermi level.
We can find several
crossings of bands at
Fermi surface (line).
As for these bands,------------------------------------------------EF
Bolch
statesareillustrated in Figs.
  
P,Q,R. Though the --------------------------------------overall electron density↑!
suggests that the chain EF
and CNT are coupled
by week van der Waals!!!!!!!!Rinteraction, significant
mixing between the
chain and CNT is foundonly for Fermi level.

PQ
↓
↓

ș

! ! !

ș

R

2pσ

■[1]Atomistix ToolKit version 13.8, QuantumWise A/S(www.quantumwise.com). M. Brandbyge, J.-L. Mozos, P.
Ordejo'n, J. Taylor, and K. Stokbro, Phys. Rev. B 65, 165401(2002). <http://dx.doi.org/10.1103/PhysRevB.65.165401>■[2]T.Fujimori, A.Morelos-Gomez, Z.Zhu, H.Muramatsu,
Electronic energy band structure to the direction of
R.Futamura, K.Urita, M.Terrones, T.Hayashi, M.Endo,
S.Y.Hong, Y.C.Choi, D.Tomanek & K. Kaneko, ”Conducting
the axis for CNT.
linear chains of sulphur inside carbon nanotubes”, Nature Commun. 4:2162 (2013) doi 10.10381/ncomms
3162. <http://www.nature.com/ncomms/index.html>■[3]Y.Natsume, “Numerical study of electronic
states in double-walled carbon nanotubes---Formation of metallic bands by covalent bridge between tubes---”3P-11, The 46th Fullerenes Nanotubes Graphene General Symposium, 3-5 Mar. 2014, Tokyo University, Hongo.

- 101 -

2P-14Fabrication of Thermoelectric Device using P- and N-Type Controlled
Single Wall Carbon Nanotubes by Electric Double Layer Carrier Injections○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 thermoelectric devices is of great importance for
efficiently converting waste heat into electric power. To understand the physical background,
it is very important to clarify the relationships between the Seebeck coefficients and the Fermi
level. We have controlled various physical properties of Single Wall Carbon Nanotube(SWCNTs) by tuning the Fermi level through carrier injections caused by electric double
layers using an ionic liquid.[1],[2] Recently, we have revealed that the semiconducting SWCNT
networks show very large Seebeck coefficient.[3] Furthermore, we have controlled theSeebeck coefficient of semiconducting SWCNT networks by electric double layer transistor(EDLT) setups.[4]In this study, we fabricated thermoelectric device using P and N-type controlled SWCNTs.
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. The schematic device structure is shown in the inset of Figure 1. The channel voltage
was applied to one of the semiconducting SWCNT thin film, and another thin film was kept
p-type, which was initial state. After the channel voltage was applied, we fixed the doped state
by freezing the ionic liquid for the precise data collection. Then, the thermoelectric voltages
were measured as a function of applied channel voltage.
Figure 1 shows the thermoelectric power of the device as a function of channel voltage. As
shown here, the thermoelectric powers, and even polarities, were changed by the shift ofchannel voltage, and the values of the thermoelectric power were controlled. Thus, we could
fabricate the tunable thermoelectric
device by EDLT setups using an ionicliquid. Our results suggest that the EDLT
techniques are quite useful to develop thehigh performance thermoelectric devices.
[1] K.Yanagi et al. Adv. Mater 23, 2811
(2011).
[2] K.Yanagi et al. Phys. Rev. Lett. 110,086801 (2013).
[3] Y.Nakai et al. Appl. Phys. Express 7,025103 (2014).
[4] K.Yanagi et al. Nano Lett. 14, 6437
(2014).

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

Fig.1: Thermoelectric power of the device as afunction of Channel voltage (Inset: Schematic
device structure)- 102 -

2P-15
Polyglycerol-functionalized SWNTs: size separation, toxicological study
and biomedical application○Keisuke Nakamura1,2, Li Zhao1, Hongmei Qin1, Shuji Aonuma2, Takahide Kimura1,
Naoki Komatsu1
1
Department of Chemistry, Shiga University of Medical Science, Otsu, 520-2192, Japan2
Department of Materials Chemistry, Osaka Electro-Communication University, Osaka,
572-8530, JapanFor biomedical in vivo applications of nanocarbons as an imaging probe and a drug carrier,they have to be solubilized in a physiological environment. Recently, we have found that
surface functionalization with polyglycerol (PG) affords very good hydrophilicity to various
nanocarbons (nanodiamond [1] and graphene [2]) as well as metal oxides (ZnO [3] and Fe3O4[4]). In this paper, we will report solubilization, chromatographic separation, toxicologicalstudy and biomedical application of PG-functionalized SWNTs. After cutting SWNTs(c-SWNTs) under ultrasonic irradiation in mixed acid for 48 h, c-SWNTs were functionalizedwith PG through ring opening polymerization of glycidol [1]. The solubility of the resulting
PG-functionalized SWNTs (c-SWNT-PG) was >10 mg/mL in pure water and >8.5 mg/mL in

Cell viability (%)

phosphate buffer. Since these solutions were very stable without any precipitation for morethan one month, they were subjected to size separation by size-exclusion chromatography [1]and evaluation of cytotoxicity. After incubating HeLa cells in the presence of c-SWNTs withor without PG for 24 h, cell viability
100
was measured by use of cell counting
80
kit-8. The result shown in Fig. 1
60
c-SWNT-PG
indicates that PG coating efficiently
40
c-SWNTs
reduce the cytotoxicity of c-SWNTs
20
probably because of stealth effect of
0
0.00

0.02

0.04
0.06
0.08
Concentration (mg/mL)

0.10

0.12

Fig.1 Cytotoxicity of c-SWNT-PG and c-SWNTs

PG [5]. Application of c-SWNT-PG tophotodynamic therapy is now inprogress.

[1] L. Zhao, N. Komatsu, et al. Angew. Chem. Int, Ed., 50, 1388 (2011)[2] T. Yasuda, N. Komatsu, et al. The 43rd Fullerenes-Nanotubes-Graphene General Symposium, 1-14
[3] L. Zhao, N. Komatsu, et al. J. Indian Chem. Soc., 88, December, 1787 (2011)[4] L. Zhao, N. Komatsu, et al. Adv. Funct. Mater., 22, 5107 (2012).
[5] L. Zhao, N. Komatsu, et al. Adv. Funct. Mater., 24, 5348 (2014).
Corresponding Author: Naoki Komatsu
Tel: +81-77-548-2102, Fax: +81-77-548-2405, E-mail: nkomatsu@shiga-med.ac.jp- 103 -

2P-16Gate-controlled generation of optical pulse trainsusing individual carbon nanotubes
M. Jiang, Y. Kumamoto, ○A. Ishii, M. Yoshida, T. Shimada, and Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
We report on optical pulse-train generation from individual air-suspended carbon
nanotubes under an application of square-wave gate voltages [1]. Electrostatically-induced
carrier accumulation quenches photoluminescence [2], while a voltage sign reversal purges
those carriers, resetting the nanotubes to become luminescent temporarily. Frequency domain
measurements reveal photoluminescence recovery with characteristic frequencies that
increase with excitation laser power, showing that photoexcited carriers quench the emission
in a self-limiting manner. Time-resolved measurements directly confirm the presence of an
optical pulse train synchronized to the gate voltage signal, and flexible control over pulse
timing and duration is demonstrated.
Work supported by KAKENHI (24340066, 24654084, 26610080, 26870167), SCOPE,
Canon Foundation, Asahi Glass Foundation, and KDDI Foundation, as well as the
Nanotechnology Platform and Photon Frontier Network Program of MEXT, Japan. A.I. is
supported by MERIT and JSPS Research Fellowship, and M.Y. is supported by ALPS.
[1] M. Jiang, Y. Kumamoto, A. Ishii, M. Yoshida, T. Shimada, and Y. K. Kato, arXiv:1407.7086 (2014).
[2] S. Yasukochi, T. Murai, S. Moritsubo, T. Shimada, S. Chiashi, S.Maruyama, and Y. K. Kato, Phys. Rev. B
84, 121409(R) (2011).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 104 -

2P-17
Electroluminescence from individual air-suspended carbon nanotubes
within split-gate structures○N. Higashide, M. Jiang, T. Uda, M. Yoshida, A. Ishii and Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
Electrically induced light emission from chirality-identified single-walled carbon
nanotubes are investigated by utilizing split-gate field-effect devices fabricated on
silicon-on-insulator substrates. We begin by etching trenches through the top silicon layer into
the buried oxide, and the silicon layer is thermally oxidized for use as local gates [1]. We
partially remove the oxide and form gate electrodes, then we attach electrodes on both sidesof the trench for contacting nanotubes. Catalyst particles are placed on the electrodes, andnanotubes are grown over the trench by chemical vapor deposition. We use
photoluminescence microscopy to locate the nanotubes and perform excitation spectroscopy
to identify their chirality [2]. By applying opposite polarity voltages on the split-gates, p-njunctions can be formed along the length of the nanotubes. Electroluminescence is observed
under forward bias, whose spectral shape is similar to that of photoluminescence. We find thatthe dependence of electroluminescence intensity on the two gate voltages is consistent withemission from a split-gate p-n diode.
Work supported by KAKENHI, The Canon Foundation, and The Asahi Glass Foundation,
as well as the Nanotechnology Platform and Photon Frontier Network Program of MEXT,
Japan.
[1] M. Jiang, Y. Kumamoto, A. Ishii, M. Yoshida, T. Shimada, Y. K. Kato, arXiv 1407.7086 (2014)[2] S. Moritsubo, T. Murai, T. Shimada, Y. Murakami, S. Chiashi, S. Maruyama, and Y. K. Kato, Phys. Rev.
Lett. 104, 247402 (2010).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 105 -

2P-18
Redox-dependent separation of single-wall carbon nanotubes in hydrogels○Atsushi Hirano, Takeshi Tanaka, Hiromichi Kataura
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8562, Japan
It has been reported that single-wall carbon nanotubes (SWCNTs) dispersed in sodium
dodecyl sulfate (SDS) solutions are separated into metallic and semiconducting species byhydrogel columns such as agarose [1] and Sephacryl columns. Our previous study suggested
that the separations are accounted for by the oxidation of SWCNTs with an O2/H2O redox
couple; specifically, metallic SWCNTs that are readily oxidized flow through the columns,
whereas semiconducting ones are retained in the columns [2]. In this study, various oxidants
for the SWCNTs were used for the separation to support the above suggestion.
K2IrCl6 and NaClO have been reported to oxidize SWCNTs [3,4]. Such oxidation was also
observed in the present study. Figure 1 shows the absorption spectra of the SWCNTs
dispersed in SDS solutions, which correspond to their S11 bands. The absorbances decreased
with increasing concentration of the oxidants. The oxidation effects were more pronounced
for K2IrCl6 than NaClO. After the injection of the SWCNTs into Sephacryl columns in theabsence of the oxidants, the retained semiconducting SWCNTs in the columns were eluted
using these oxidants. Figure 2 shows the amount of eluted semiconducting SWCNTs from thecolumns. It was found that the semiconducting SWCNTs were effectively eluted in thepresence of the oxidants at 1 mM; the elution effect was more pronounced for K2IrCl6 than
NaClO. Importantly, K3IrCl6 had less effect on the elution. Similar results were obtained with
one of the SDS analogs, sodium 1-undecanesulfonate. Oxidation of SWCNTs is thus
demonstrated to be a contributory factor in the interaction of the SWCNTs with the hydrogels.
Oxidized SWCNTs are positively charged, which enhances electrostatic attraction between
the SWCNT and the negatively charged surfactants. Condensation of the surfactants on the
SWCNTs through the attractive interaction should lead to the enhanced elution of the
SWCNTs from the columns.

Fig.1 Absorption spectra of the SWCNTs dispersed SDS in thepresence of K2IrCl6 or NaClO at different concentrations.
[1] T. Tanaka et al. Appl. Phys. Express 2, 125002 (2009)[2] A. Hirano et al. ACS Nano 7, 10285 (2013)[3] F. J. Knorr et al. Langmuir 25, 10417 (2009)[4] M. Zheng et al. J Am Chem Soc 126, 15490 (2004)
Corresponding Author: T. Tanaka
Tel: +81-29-861-2903, Fax: +81-29-861-2786,
E-mail: tanaka-t@aist.go.jp- 106 -

Fig.2 Amount of eluted semiconducting
SWCNTs from the hydrogel in thepresence of three oxidants at 1 mM.

2P-19Optimization of the synthesis parameters of Carbon Nanotube (CNT) forest
using the Taguchi Method○Adam PANDER1, Hiroshi FURUTA1,2, Akimitsu HATTA1,2
Kochi Univ. Technol. 1, Research Inst., Kochi Univ. Technol. 2
E-mail: 186001x@gs.kochi-tech.ac.jp, furuta.hiroshi@kochi-tech.ac.jp

Carbon Nanotubes (CNT), since their discovery by IIjima in 19911, has attracted much attention for various
applications due to their extraordinary electrical, thermal and physical properties. A CNT forest with high density
and alignment may provide uniform CNTs with desirable length, diameter and structure. It is known, thatphysical properties of CNTs influence directly their thermal, electrical and mechanical properties2. Currently
many various methods of CNTs synthesis are available, among which Chemical Vapor Deposition (CVD) is themost popular due to low cost, high production yield and ease in modifications3.
The growth of CNT forest may cause many difficulties related to the large number of parameters influencing the
growth during synthesis process. Choosing the proper parameters of the growth can be long lasting process, andeven that may not give the optimal growth values. One of the possible solutions to decrease the number of theexperiments is to apply optimization methods to the design the experiment parameter matrix4.
In this work, optimization of the parameters of the Carbon Nanotubes synthesis process was studied using
Taguchi Method. This method was applied for development of the plan of the experiments and elaboration ofobtained experimental results. The aim of Taguchi Method is to minimize the changes of the product properties
in dependence on noise factor (N – noise) and maximize the changes in dependence on signal factors (S – signal).
In Taguchi method statistic coefficient called signal-to-noise (S/N) ratio is used. S/N ratio allows to evaluate theinfluence of process parameters on the properties of the product. Taguchi Method provides data that consist
statistically significant factors of the process and allow to find optimum level of the parameters, using S/N ratio
analysis and experimental data analysis5,6. The Taguchi Method utilize 3 main optimization problems: the smaller
the better; the bigger the better and nominal value.
In this paper the growth parameters were: (a) thickness of iron catalyst, (b) hydrogen flow during annealing, (c)annealing time, (d) process temperature and (e) acetylene flow during growth stage. For each parameter, four
values were tested. Fig. 1. shows the table of the CNTs growth experiments. The results of the optimization wereverified by the diameter, height and density of CNTs forest. Fig. 2. shows S/N ratios of diameter of CNTs for
optimized parameters. As shown, according to Taguchi statistical analysis, the biggest influence on the diameterof CNTs has annealing time, where parameter 3 (5 min) is the most optimal value.
In future, Taguchi Method would provide optimal route from catalysts to growth of CNTs with desirable
properties (like diameter, length, waviness and etc.) through the Taguchi growth parameters with minimum trials
among huge number of possible growth condition matrix.
Exp. No.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.

a
0.5
0.5
0.5
0.5
1.0
1.0
1.0
1.0
1.5
1.5
1.5
1.5
2.0
2.0
2.0
2.0

Taguchi, L16
b
c
0
3
25
5
50
7
75
9
0
5
25
3
50
9
75
7
0
7
25
9
50
3
75
5
0
9
25
7
50
5
75
3

d
700
730
760
790
760
790
700
730
790
760
730
700
730
700
790
760

e
10
15
20
25
25
20
15
10
15
10
25
20
20
25
10
15

Fig 1. Plan of the experiments according to
Taguchi’s orthogonal table L16

Fig 2. The influence of selected process parameters used in the experiments on
CNTs diameter.(a) thickness of iron catalyst, (b) hydrogen flow during
annealing, (c) annealing time, (d) process temperature and (e) acetylene flow
during growth stage.

[1] S. Iijima, Nature 354, 56 (1991), [2 ]H. Furuta et al. App. Phys. Exp. 3 (2010), [3] M. Kumar, J. Nano. Sci. Tech. 10 (2010), [4] S. Porro, etal., Phys. E 37 (2007), [5] M. Pancielejko, A. Pander, et al., Arch. Mat. Sci. Eng. 54 (2012), [6] J. Walkowicz, et al., J. Mat. Sci. Perf. 22(2) (2013)- 107 -

2P-20Synthesis of single-walled carbon nanotubes from woody bioethanol○Takuma Araki1, Atsushi Honda1, Yuhei Yabushita2, Toshiya Murakami1, Kenji Kisoda2,
Masanori Yamaguchi2, and Chihiro Itoh1
1

Department of Materials Science and Chemistry, Wakayama University, Wakayama
640-8510, Japan
2
Faculity of Education, Wakayama University, Wakayama 640-8510, Japan

While properties of single-walled carbon nanotubes (SWNTs), the synthesis of SWNT
involves consumption of fossil fuels and emission of large amount of carbon dioxide. Thisis one of the reasons of high cost of SWNTs. One of the ideas to resolve these problems is
use of bioethanol as a carbon source. In this report, we have demonstrated the synthesis of
SWNT from woody bioethanol and characterized the woody SWNTs by Raman scattering
spectroscopy.
The woody bioethanol was produced by hydrolysis of wood chips using sulfuric acid, andsubsequent fermentation of glucose.[1] The bioethanol thus obtained had an ethanol
concentration of 5 vol%. Chemical vapor deposition (CVD) of SWNT was carried out using
the as-synthesized bioethanol as the carbon source with Co/a-SiO2 catalysts. We alsosynthesized SWNT by typical CVD using high-grade ethanol and 5 vol%-ethanol aqueous
solution for comparison.
The samples were characterized by Raman measurement with aprobe laser of 532 nm.
In Fig. 1, we show the Raman spectra of the SWNT obtained from woody bioethanol,
together with the spectra of SWNTs obtained from high-grade ethanol and its 5% aqueous
solution. The spectrum of the woody bioethanol clearly shows G band and Radial breathingmode (RBM), indicating that SWNTs were grown by woody bioethanol. The low S/N
spectrum indicates SWNT yield was low. The relative intensity of G band to D band, which
is a measure of the quality of SWNT, was ~15. Based on the analysis of RBM frequency,
we showed that most of the woody SWNTs obtained in the present study had the diameter of
0.9 nm. This characteristic is similar to the tubes grown with 5%-ethanol solution, in
contrast to the SWNT obtained by CVD
with high-grade ethanol where the dominant
tube had the diameter of 1.1 nm. The
diameter reduction of the SWNT isconceivably attributed to water vapor
etching of tubes during the CVD process.
In detail, the distribution of RBM of thewoody SWNT is different from SWNTs
obtained from 5%-ethanol solution. Thisdifference may be ascribed to the effects byimpurities in refined woody bioethanol.
The impurity originated from wood has apossibility of changing SWNT properties,
so further detail analyses are required.
[1] M.Yamaguchi, et. al., Society of Japan Science Teaching, Kinki branch (Kyoto), P-2, 2010.
Corresponding Author: T. Araki, Tel: +81-73-457-8532, E-mail: s143001@center.wakayama-u.ac.jp- 108 -

2P-21
Nitrogen doping of single-walled carbon nanotubes prepared fromfluorinated SWCNTs using ammonia gas○Koji Yokoyama1, Yoshinori Sato2, Kazutaka Hirano2, Kenichi Motomiya1, Kazuyuki Tohji1,
Yoshinori Sato1,3,*
1

Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan
Stella Chemifa Co., Osaka 595-0075, Japan
3
Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research,
Shinshu University, Matsumoto 390-8621, Japan
2

Nitrogen doping of single-walled carbon nanotubes (SWCNTs) plays a significant role as ameans to control their electronic density of states and carrier transport properties. The
methods of nitrogen doping are classified into two categories: “direct-synthesis doping” and“post-synthesis doping”. Although a number of direct-synthesis nitrogen doping methods for
SWCNTs have hitherto been studied, it is difficult to control the number of nitrogen atoms
and retain the crystallinity of nanotube framework. In contrast, little post-synthesis doping has
been reported until now. In addition, these methods require high temperature (>1000 K), andthe nitrogen contents of the resulting samples were low (<1.0 at.%). These are considered tobe due to the low reactivity of SWCNT surface. Here, we report a new facile method forsynthesizing nitrogen doped SWCNTs by the reaction of fluorinated SWCNTs (F-SWCNTs)
with ammonia gas.
We prepared F-SWCNTs by fluorination of highly crystalline SWCNTs (hc-SWCNTs)
synthesized by a direct current arc discharge, using a mixture of F2 (20%) and N2 (80%). 10
mg of F-SWCNTs placed into a reactor tube reacted with flowing a mixture of NH3 (1%) andN2 (99%) at the temperature range of 298-873 K for 30 min. The resulting samples werecharacterized using X-ray photoelectron
spectroscopy(XPS),
high-resolution
transmission electron microscopy (HRTEM),
and Raman scattering spectroscopy.
The XPS survey spectra of the samples
after ammonia gas reaction revealed that
nitrogen atoms were introduced into the
SWCNTs at all reaction temperatures, andthe maximum nitrogen content wasestimated to be 3.0 at.% at 673 K (Fig. 1).
The XPS spectra of N1s region showed the
SWCNTs had pyridinic, pyrrolic, andFig. 1 Nitrogen contents and composition of thegraphitic nitrogen atoms. We will report the
samples reacted at various reaction temperatures
detailed characterization in this presentation.
measured by XPS.
*Corresponding Author: Yoshinori Sato
Tel: +81-22-795-3215, Fax: +81-22-795-3215,
E-mail: hige@ncsimd.kankyo.tohoku.ac.jp- 109 -

2P-22
Molecular Dynamic Simulation of Defect Free Growth of Single-Walled
Carbon Nanotube○Ryo Yoshikawa, Yukai Takagi, Shohei Chiashi and Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Good atomic scale simulation is anticipated for understanding the growth mechanism of
single-walled carbon nanotubes (SWNTs). Often molecular dynamics (MD) simulations are
employed [1]. However, it has been difficult to simulate the growth of SWNTs whosechirality can be clearly assigned. The high-quality (defect-free) SWNTs in MD simulation aredesired for analyzing the relation between detailed SWNT structures and simulation
conditions (temperature, gas carbon density, and catalyst metal species).
We prepared cobalt cluster with 40-60 atoms in a periodic cell (10×10×10 nm3, 1300-1600K), and carbon atoms were supplied to the cell keeping one free carbon atom which are notconnected to other carbon atoms or metal atoms. The interaction between carbon and metal
atoms is expressed by our home-made Tersoff-type potentials [2].
After carefully adjusting growth parameters, defect-free SWNT was successfully obtained.
Figure 1(a) shows image of a defect-free SWNT, whose chirality is assigned to (14, 1). In
order to investigate the growth process in detail, we made unwrapped projection view of thegrown SWNT (Fig. 1(b)). The pentagonal and heptagonal rings appeared just only on the cap
part, and the atomic structure of the side wall part is fully composed of hexagonal rings.
Whole edge part of the SWNT connecting with the catalyst was found to be zigzag structure
except for a one kink. There are several carbon chains connected to zigzag tops. The carbon
chains formed hexagonal rings and then the SWNT grew up. In addition to the growthmechanism based on the time evolution of hexagonal ring generation, cap formation
mechanism in the earlier stage will be discussed.
(a)(b)
pentagonal ring

heptagonal ring

Fig. 1(a) Structure of SWNT grown from Co60 catalyst, which has (14, 1) chirality.
(b) Developed diagram view of the (14, 1) SWNT.
[1] Y. Shibuta and S. Maruyama, Chem. Phys. Lett., 382 (2003) 381.
[2] T. Matsuo et al., to be submitted.
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 110 -

2P-23
Automatic Gradient Elution Gel Filtration for Separation of Metal andSemiconducting Single-Wall Carbon Nanotubes○Boanerges Thendie1, Haruka Omachi1, Ryo Kitaura1, Yasumitsu Miyata2,3,and Hisanori Shinohara1
1

Department of Chemistry and Institute of Advanced Research, Nagoya University, Nagoya,464-8602, Japan2
Department of Physics, Tokyo Metropolitan University, Tokyo, 192-0397, Japan
3
JST, PRESTO, Tokyo, 102-0075, Japan

Semiconducting single wall carbon nanotubes (s-SWCNTs) are attractive materials forelectronic devices. However, conventional as-grown carbon nanotubes contain mixture ofmetallic (m-SWCNTs) and s-SWCNTs. Hence, separation is required to attain high purity sSWCNTs. In the past 5 years, our group have developed recycling gel filtration to obtain highpurity s-SWCNTs [1]. We have also demonstrated that simultaneous electronic-type and lengthbased separation of s-SWCNTs can be attained by a simple fractionation method [2].
In the present work, we introduce “automatic gradient elution” (AGE) of gel filtration.
In AGE system, two different solution of surfactant: sodium dodecyl sulfate (SDS) and sodium
cholate (SC) are mixed to obtain different elution composition over time. Gradual change ofthe elution composition allows remaining m- and s-SWCNTs to be eluted separately, increasing
the purity of s-SWCNTs. We also observed diameter-based separation by using AGE system.

Fig. 1 (a) schematic of the AGE system: SC and SDS are mixed in chamber II before entering column. Absorbanceof m- and s-SWCNTs vs elution order for gel filtration (b) without AGE and (c) with AGE. Without AGE,
remaining m- and s-SWCNTs eluted concurrently while in the AGE system, m- and s-SWCNTs eluted separately.
[1] Y. Miyata et al. Nano Res. 4, 963 (2011)[2] B. Thendie et al. Appl. Phys. Express 6, 065101 (2013)
Corresponding author: Hisanori Shinohara
Tel: (+81) 52-789-2482, Fax: (+81) 52-747-6442, E-mail: noris@nagoya-u.jp- 111 -

2P-24
Facile sorting and release of semiconducting single-walled carbon
nanotubes based on dynamic formation of supramolecular polymers
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, however, they are produced as mixtures of semiconducting- and metallic-SWNTs.
Full utilization of the unique optical and electrical properties of semiconducting-SWNTs(sem-SWNTs) would be exhibited only when they are separated from poisoning metallic-tubes.
One of the key techniques for SWNT-chirality sorting is wrapping method by conjugatedpolymers such as polyfluorenes.[1, 2] Selective extraction of the sem-SWNTs using suchpolymers is simple and powerful, however, removal of them from the extracted sem-SWNT
surfaces is difficult due to the strong multi-point interactions between the polymers and the
SWNTs. In addition, the preparation of these synthetic polymers is usually complicated.
In order to address these problems simultaneously, we have developed detachable
solubilizer systems based on a supramolecular approach. We have previously reported thatcoordination polymers of phenanthroline-capped fluorene (Fig. 1, 1) and various metal ions
extracted sem-SWNTs selectively.[1] We here report that the alternative non-covalent bondformation, hydrogen-bond polymerization using various conjugated monomers (Fig. 1, 2-6)
are examined for the solubilization/separation of sem-SWNTs. All the used compounds are
confirmed to form one-dimensional polymers just by mixing with each complementary, which
was confirmed using NMR technique. Solubilization of SWNTs by using these polymers
were screened by atomic force microscopy, photoluminescence, and Vis-NIR absorption and
Raman spectroscopic analysis, and was found that only the polymers of 2 and 3 acted as
sem-SWNT solubilizers, in which both components possess fluorene moiety.
Molecular-mechanics calculations was employed to visualize the difference of interactions
between these suplamolecular polymers and sem-SWNTs. Furthermore, the reversible bondformation and depolymerization by an outer stimulus, such as an addition of acid, change inpH or temperature was examined to remove the polymers from sem-SWNTs, resulting thefinding that even a simple washing with solvents worked.
N

H2N

N

N

N

1

NH2

N

HOOC

COOH

N

2

3

O

O

HN

NH

O

O

4

HOOC

HOOC

[2] A. Nish, et al., Nat. Nanotech. 2007, 2, 640.

[3] F. Toshimitsu, N. Nakashima, Nat. Commun. 2014, 5, 5041.
Corresponding Author: N. Nakashima
Tel: +81-92-802-2845, Fax: +81-92-802-2845;
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 112 -COOH

5

Fig. 1. Chemical structures of supramolecular polymer components.

[1] F. Chen, et al., Nano Lett. 2007, 7, 3013.

N

COOH

6

2P-25Structural transformation of tellurium encapsulated in the inner space ofcarbon nanotubes depending on tube diameter○Keita Kobayashi1, Hidehiro Yasuda 1,2
1

Research 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
Some materials encapsulated in the confined inner space of carbon nanotubes (CNTs) show
anomalous structures compared with their bulk phases. For example, some chalcogens (sulfur
and selenium) encapsulated in CNTs with a diameter of ~1 nm show linear, zigzag, andhelical structures [1, 2]. Moreover, the anomalous structures tend to depend on the innerdiameter of the CNTs. Because anomalous structures can produce novel physical properties,
determining the relationship between the size of the confined nanospace and structure of thematerial is important for developing novel nano devices.
In this study, we aimed to clarify the relation between CNT diameter and the structure ofencapsulated chalcogens by analyzing tellurium encapsulated in CNTs of various innerdiameters.
Transmission electron microscopy showed that tellurium adopts a double helix structure in
CNTs of less than ~2 nm in diameter (Fig. 1). The tellurium structure was also confirmed byelectron diffractometry of a bundle of CNTs and by Raman spectroscopy. In contrast, thetellurium in CNTs with a diameter greater than ~2 nm had an ordinary crystal structure.
According to previous theoretical studies [3], guest materials encapsulated in CNTs tend tobe located off center near the CNT wall because of the interaction between the guest material
and CNT wall [3]. The interaction decreases as theinner diameter of CNTs increases; therefore, theguest materials encapsulated in larger diameter
CNTs tend to aggregate in the center of the innerspace.
Based on our experimental results and previous
theoretical studies, we conclude that the structureof tellurium encapsulated in CNTs is determinedby competition between the interaction and latticeenergy of tellurium aggregated in the center.
Although the details of the formation mechanism
for the double helix structure remains unclear, our Fig.1 (a) Typical TEM images of Te encapsulated in(DW) CNTs. Arrow heads indicate crossing
hypothesis well explains the diameter dependency double-wall
section of Te chain attributed to double-helix structure. (b)of the structure of tellurium encapsulated in Cross section TEM image of Te encapsulated in DWCNTs.
CNTs.
[1] T. Fujimori et al., Nature Commun. 4, 2162 (2013).
[2] T. Fujimori et al., ACS Nano 7, 5607 (2013).
[3] M. Wilson, Chem. Phys. Lett. 366, 504 (2002).
Corresponding Author: K. Kobayashi
Tel: +81-6-6879-7941, Fax: +81-6-6879-7942, E-mail: kobayashi-z@uhvem.osaka-u.ac.jp- 113 -

2P-26
Synthesis of Diamantane Chains inside Carbon Nanotubes from
Bridgehead-halogenated Diamantane○Yusuke Nakanishi,1 Haruka Omachi,1 Natalie A. Fokina,2 Ryo Kitaura,1 Peter R. Schreiner,2Jeremy 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.
2Over the past decade, we have developed a synthetic methodology for onedimensional (1D) nanomaterials utilizing the cavities of carbon nanotubes (CNTs), in
which encapsulated species are molded into 1D nanostructure via thermal annealing.
To date, various kinds of 1D nanomaterials have been synthesized, including metal
atomic wires,1 ultrathin boron-nitride nanotubes,2 and well-defined CNTs,3 which
exhibit different properties from those of their bulk counterparts. As part of our
exploring for novel 1D nanomaterials, we have studied the synthesis of 1D diamondshaped materials from diamondoids, the molecules in the diamond configuration.4,5Here we report the synthesis of diamondoid
chains from bridgehead-halogenated diamantane (akind of diamondoids) within the inner spaces of CNTs.
The sublimed precursors undergo dehalogenation toform the diamantane radicals, which subsequently link
up to produce the polymer chains. Using experimental
and theoretical techniques, we revealed that the
diamantane skeletons were linked with each otherinside CNTs. Our synthesis of this new class of
diamond nanomaterials might offer a new direction for
the nano-diamond research as well as a new strategy
for the design and synthesis of 1D nanomaterials.
[1] R. Kitaura et al. Nano Lett., 8, 693, (2008).
[2] R. Nakanishi et al. Sci. Rep., 3, 1385, (2013).
[3] H. E. Lim et al. Nat. Commun., 4, 2548, (2013).
[4] J. Zhang et al. ACS Nano, 6, 8674, (2012).
[5] J. Zhang et al. Angew. Chem. Int. Ed., 125, 3805, (2013).
Corresponding Author: H. Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442,
E-mail: noris@nagoya-u.ac.jp- 114 -

Fig.1 Structural model of a diamantane chain
formed inside double-walled CNTs.

2P-27A Computational Study on Properties of Multimeric  Conjugated
Oligomers inside Carbon Nanotubes○Takashi Yumura1, Hiroki Yamashita 1
1

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

We have investigated the arrangements of  conjugated oligomers inside a nanotube byusing density functional theory (DFT) including dispersion corrections (B97D functional).
Previously, we discussed methyl-terminated ter-thiophene oligomers inside a nanotube, andfound that nanotube confinement has a strong impact on determining arrangements of theinner ter-thiophene chains [1]. Recently, oligofurans with various chain lengths have beensuccessfully synthesized [2]. However, the oligofurans readily degrade when they are exposed
to a combination of light and dioxygen. If oligofurans can be encapsulated into a nanotube,
similar to the thiophene oligomer cases [3], inner oligomers would be stable due to preventing
dioxygen from attacking them. Along our expectation, we extended our DFT studies to focus
on multimeric oligofuran chains inside a nanotube. The current study aims at obtaining
electronic properties of multimeric oligofuran inside a nanotube whose diameter ranges from
10.9 to 13.7 Å, and then we compared the results with the thiophene cases. DFT calculations
indicated a variety of arrangements of multimeric ter-furan chains, depending on host-tube
diameters and the number of chains. In terms of stacking fashions, we found a difference
between the inner furan and thiophene oligomers as shown in Figure 1 displaying 
conjugated dimer inside a nanotube with a diameter of 10.9 Å. In fact, the inner oligofurans
slide significantly along the long chain axis as well as along the short chain axis, whereas theinner oligothiophenes slightly slide along the long chain axis. Because of the different innerarrangements, the oligomer chains interact differently. The interchain interactions, which split
frontier orbitals of the multimeric chains, are responsible for changing electronic properties of
inner  conjugated oligomers. Therefore, our DFT calculations found that nanotubes havepower to modulate the electronic properties of inner  conjugated oligomers, depending ontypes of oligomer.

Fig. 1

B97D-optimized structures for tubes containing (a) oligofuran dimer and (b) oligothiophene[1] (a) H. Yamashita et al., J. Phys. Chem. C 116, 9681 (2012). (b) T. Yumura et al., J. Phys. Chem. C 118, 5510
(2014).
[2] (a) O. Gidron et al., J. Am. Chem. Soc. 132, 2148 (2010). (b) O. Gidron et al., Angew. Chem. Int. Ed. 53,
2546 (2014).
[3] (a) M. A. Loi et al., Adv. Mater. 22, 1635 (2010). (b) L. Alvarez et al., J. Phys. Chem. C 115, 11898 (2011).
Corresponding Author: Takashi Yumura
Tel: +81-75-724-7571, Fax: +81-75-724-7571, E-mail: yumura@kit.ac.jp- 115 -

2P-28Growth Dynamics of Single-Layer Graphene on Epitaxial Cu Surfaces○Y. Ohta,1 S. Mizuno,1 H. Hibino,3 K. Kawahara,1 R. Takizawa,1 M. Tsuji,1,2 and H. Ago1,2,4

Graduate School of Engineering Sciences, Kyushu University, Fukuoka 816-8580, Japan
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8580, Japan
3
NTT Basic Research Laboratory, NTT Corporation, Kanagawa 243-0198, Japan
4
PRESTO, Japan Science and Technology Agency, Saitama 332-0012, Japan
1

2

Graphene has attracted a great deal of interest because of its unique properties, which
promise applications in electronics and related fields. Recently, chemical vapor deposition(CVD) using Cu catalyst is widely used to grow large-area, single-layer graphene (SLG) due toself-limiting mechanism [1]. Considering relatively low melting temperature of Cu (1083 ºC),
it is interesting to investigate the growth dynamics of graphene at typical CVD temperatures,
1000-1075 ºC [2-5], which are close to the Cu melting temperature. As the large singlecrystalline graphene domains are grown at high temperatures, it also helps us to develop amethod to grow giant graphene domains on Cu surface.
In this work, we report a systematic study on the domain structure and the orientation of
SLG grown on epitaxial Cu(111) surface. We obtained hexagonal graphene domains with thelateral size of 10-100 m, which increases with increasing the CVD temperature (Ea =~4.5 eV),while the domain density decreased with the temperature. These results suggest that higher
CVD temperature enhances surface diffusion of carbon intermediate on the Cu(111) surface
and also promotes the catalytic decomposition of CH4 feedstock. The orientations of graphenesheets were studied by low-energy electron diffraction (LEED). When SLG was synthesized at900~1020 ºC, six sharp diffraction spots were observed, as shown in Fig. 1a, consistent with
our previous work [2-4]. However, when we increased the temperature to 1050 ºC, thediffraction spots were rotated by 2-3º from the original spots (Fig. 1b). Higher CVD temperature(1070 ºC) resulted in a ring-like streak pattern together with six diffraction spots (Fig. 1c),indicating mis-orientation of graphene domain due to thermal fluctuation of the surface Cu(111)
lattice. Such effect was more clearly observed for the epitaxial Cu(100) film. We will alsopresent transport properties of the SLG sheets having different domain sizes and orientations
grown on Cu(111) and Cu(100) films.
(d)Figure 1 LEED patterns of SLG/Cu(111) at 1000 (a), 1050 (b), and 1070 ºC (c). (d): Atomic model of hexagonalgraphene domains grown on the Cu(111) surface at 1000 ºC.
References: [1] X. Li et al., Science, 324, 1312 (2009). [2] H. Hu et al., Carbon, 50, 57 (2012). [3] C. M. Orofeo
et al., Carbon 50, 2189 (2012). [4] Y. Ogawa et al., J. Phys. Chem. Lett., 3, 219 (2012). [5] H. Ago et al., Appl.
Phys. Exp., 6, 75101 (2013).
Corresponding Author: Hiroki Ago (Tel & Fax: +81-92-583-7817, E-mail: ago@cm.kyushu-u.ac.jp)- 116 -

2P-29Preparation of Small-Sized Nano-Graphene Oxide
for Biological Application○Minfang Zhang1, Toshiya Okazaki1, Yoko Iizumi1, Eijiro Miyako1, Sumio Iijima1, 2, Masako
Yudasaka1
1
2

Nanotube Research Center, National Institute of Advanced Science and Technology (AIST),
Faculty of Science & Technology, Meijo University

Because of their interesting electronic, thermal, mechanical and optical properties,
graphene and graphene oxide (GO) have been considered to be useful in various fields, suchas advanced electronics, membranes engineering, and medicines, for example, drug delivery
system and cellular imaging [1]. Recently, the small sized graphene-sheets (GS) with
polyethylene glycol coating showed ultrahigh in vivo tumor uptake and high efficiency ofphoto-thermal therapy [2]. However, GS and GO samples obtained so far are typically
microns or larger in size which limited their developments in biological applications.
Although the small-sized GS or GO can be obtained by size-separation using density gradientcentrifugation [1-2], preparation of the small-sized GS or GO with large quantity is still achallenge.
To get small-sized GO, we used carbon nanohorns (CNHs) as start materials, and prepared
GO (CNH-GO) by an oxidation exfoliation method similar to the Hummers method [3] inwhich graphite is commonly used. The obtained CNH-GO had unique characteristics
comparing with those so far obtained. They had uniformly small sizes of about 10 nm, highsolubility in aqueous solutions and in most of the organic solvents, and strong fluorescence.
They had abundant oxygenated functional groups on the surface, therefore easily modified. It
should be especially emphasized that CNH-GO could be prepared in a large quantity without
using any surfactant for separation. All these superior characteristics suggest that CNH-GO isa promising material for biological and medicine applications. As an example, we have used
CNH-GO to conjugate with immunoglobulin G (IgG) antibodies for an immunoassay. The
results showed that CNH-GO conjugated IgG was successfully immunoprecipitated withprotein G-attached magnetic beads. The CNH-GO conjugates eluted from beads also hadstrong fluorescence, indicating their potential as fluorescence labels in immunoassay.
[1]. X. Sun, Z. Liu, K. Welsher, J. Robinson, A. Goodwin, S. Zaric, H. Dai. Nano Res. 1, 203(2008).
[2]. K. Yang, S. Zhang, G. Zhang, X. Sun, S. Lee, Z. Liu. Nano Lett. 10, 3318 (2010).
[3]. W. S. Hummers, R. E. Offeman. J. Am. Chem. Sci. 80, 1339 (1958)
Corresponding Authors: M. Zhang, M. Yudasaka
E-mail: m-zhang@aist.go.jp, m-yudasaka@aist.go.jp- 117 -

2P-30
Direct transfer of CVD graphene to insulating substrates by metal melting○Ryosuke Inoue1, Yutaka Maniwa1, Yasumitsu Miyata1,2
1Department of Physics, Tokyo Metropolitan University, Hachioji,192-0397, Japan
2
JST, PRESTO, Kawaguchi,332-0012, Japan

Chemical vapor deposition (CVD) has been a widely used technique for the growth oflarge-area, uniform monolayer graphene films. Generally, CVD graphene is grown on metal
substrates such as Cu and Ni foil, and thus requires a post-growth transfer process of graphenefilms from metal substrates to insulating substrates for electronics applications [1].
Conventional transfer process includes polymer coating to support graphene films during
etching Cu foil, and polymer washing by organic solvent. In this process, however, there areseveral issues such as remaining polymer and time-consuming multiple processes. Therefore,
the development of polymer-free, direct transfer process is still highly desired for improving
the processes and properties of CVD graphene.
Here, we report a facile, direct transfer process of CVD graphene using metal melting. First,
Cu foil was put on insulating substrates such as SiO2 and sapphire, and then graphene wasgrown by atmospheric CVD with methane at 1075 ℃. After the growth, the furnace
temperature was increased to 1150 ℃ to melt Cu foil on the substrates. During the melting,graphene films were directly transferred to the substrates. Optical microscopy image andRaman spectrum clearly show the presence of hexagonal-shaped graphene with negligible
D-band intensity on the substrate (Figs. 1a,b). Moreover, typical ambipolar behaviors areobserved in a graphene-based electrical double-layer transistors (EDLT) (Fig. 1c). In theposter, the details of the direct transfer process and properties of graphene will be presented.

Fig.1 (a) Optical microscope image and (b) Raman spectrum of a hexagonal-shaped graphene single
crystal on a quartz substrate. (c) Id-Vgs curve of a graphene-based EDLT.
[1] X. Li, et al., Science 324, 1312 (2009).
Corresponding Author: Yasumitsu Miyata
TEL:+81-42-677-2508,FAX:+81-42-677-2483,
E-mail: ymiyata@tmu.ac.jp- 118 -

2P-31
Vibronic Coupling Density as a Reactivity Index: Applications forDiels-Alder Reactions of Graphene Fragments
Naoki Haruta1 , ◦ Tohru Sato1,2 , Kazuyoshi Tanaka1
1 Department of Molecular Engineering, Graduate School of Engineering,

Kyoto University, Kyoto, 615-8510, Japan
2 Unit of Elements Strategy Initiative for Catalysts & Batteries, Kyoto University,

Nishikyo-ku, Kyoto 615-8510, Japan
Graphene fragments with diﬀerent structures have been extensively studied because of theirapplications in the ﬁeld of material chemistry [1,2]. To develop novel graphene fragments,
theoretical prediction of the reactivities would be helpful. The frontier orbital theory is one of
the most successful theories for such a theoretical prediction. However, it sometimes fails to
predict the regioselectivities of large molecules because frontier orbitals tend to be delocalized.
Recently we have proposed the concept of vibronic coupling density (VCD) as a reactivity index[3,4]. The VCD theory is based on not only electronic states but also molecular deformations.
This is in contrast to the frontier orbital theory in which only electronic states are considered.
The VCD theory has succeeded in explaining the regioselectivities of fullerenes whose frontier
orbitals are delocalized[4-6].
In this study, we investigated theregioselectivities of perylene (C20 H12 ), Perylene
bisanthene (C28 H14 ), and tribenzoperylene (C30 H16 ) with the VCD theory=×[7]. According to experimental works byClar et al. [8,9], Diels–Alder reactions Bisanthene Reactive Bay Regions
Butadieneof maleic anhydride to perylene, bisanthene, and tribenzoperylene yield larger=
×graphene fragments, coronene (C24 H12 ),ovalene (C32 H14 ), and dibenzocoronene(C32 H16 ). The VCD analysis clearlyΔρvsηsshows that the reactive sites of pery- Electronic Factor Vibrational Factor Vibronic Coupling Density
lene and bisanthene, which are thebay regions with arm-chair edges, have Fig. 1: Vibronic coupling density analyses for perylene
butadiene-like VCD distributions. This (C20 H12 ) and bisanthene (C28 H14 ).
is consistent with experimental observations that perylene and bisanthene, just like butadiene, react with dienophiles. We will present
the VCD analyses for the consecutive cycloadditions to perylene and bisanthene as well. In
addition, tribenzoperylene will be also discussed. Since it has four diﬀerent types of bay regions,
its regioselectivity is of interest.
[1] J. Wu et al, Chem. Rev. 107, 718 (2007). [2] O. V. Yazyev et al, Rep. Prog. Phys. 73, 056501 (2010). [3]T. Sato et al, J. Phys. Chem. A 112, 758 (2008). [4] T. Sato et al, Chem. Phys. Lett. 531, 257 (2012). [5] N.
Haruta et al, J. Org. Chem. 77, 9702 (2012). [6] N. Haruta et al, J. Org. Chem. 80, 141 (2015). [7] N. Haruta
et al, Tetrahedron Lett. 56, 590 (2015). [8] E. Clar and M. J. Zander, J. Chem. Soc. 4616 (1957). [9] E. Clar,
Nature 161, 238 (1948).
Corresponding Author: T. Sato
Tel: +81-75-383-2803, Fax: +81-75-383-2555
E-mail: tsato@moleng.kyoto-u.ac.jp- 119 -

2P-32Growth of high-quality monolayer WS2 on graphite○Yu Kobayashi1, Shogo Sasaki, Shohei Mori1, Hibino Hiroki2, Kenji Watanabe3,
Takashi Taniguchi3, Yutaka Maniwa1, and Yasumitsu Miyata1,4,*
1Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
NTT Basic Research Laboratories, NTT Corporation, Atsugi, Kanagawa 243-0198, Japan
3
National Institute for Materials Science, Tsukuba, Ibaraki 305-0044, Japan
4
JST, PRESTO, Kawaguchi, 332-0012, Japan
Atomic-layer transition metal dichalcogenides (TMDCs) have attracted appreciable interest
due to their tunable bandgap, spin-valley physics, and potential device applications. In recent
years, many studies have been reported for the growth of high-quality TMDCs, mainly usingchemical vapor deposition (CVD) and metal-film sulfurization.[1-3] Monolayer WS2 grown by
CVD on hexagonal boron nitride (hBN) was very recently reported to exhibit aphotoluminescence (PL) peak with a relatively narrow full width at half maximum (FWHM) of
26 meV and a weak asymmetric profile.[1] Considering monolayer growth on commonly-usedsubstrates such as SiO2/Si and sapphire, this clearly indicates that the growth substrate is oneof the essential factors for reducing charged impurities and structural defects.
Here, we report on the CVD growth of high-quality, monolayer WS2 onto exfoliatedgraphite. Unlike commonly-used substrates such as SiO2/Si and sapphire, monolayer WS2
grown on graphite presents a uniform, single excitonic PL peak with a Lorentzian profile and avery small full-width at half maximum (FWHM) of 8 meV, whereas WS2 grown on SiO2/Si has
a broad FWHM of 48 meV at 79 K (Fig.1).
Furthermore, no additional peaks areobserved for charged and/or bound excitons,
even at low temperature. These results
indicate that the cleaved graphite surface isan ideal substrate for the growth of highquality, non-doped TMDCs, and such
samples will be essential for revealing
intrinsic physical properties and for futureapplications.
[1] M. Okada, et al., ACS Nano 8 (2014) 8273.
[2] Y. -H. Lee et al., Adv. Mater., 24 (2012) 2320.

Fig.1 (a) Structure model and (b) optical image of
WS2 grown on graphite. (c) PL spectra of WS2 ongraphite and SiO2/Si substrates at 79 K.

[3] C. M. Orofeo et al., Appl. Phys. Lett., 105 (2014) 083112.
Corresponding Author: Yasumitsu Miyata, Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 120 -

2P-33
Amplitude modulation of optical field by arm-chair graphene nanoribbons:
A First-principles Study○Yoshiyuki Miyamoto1, Hong Zhang2
1

Nanosystem Institute of National Institute of Advanced Industrial Science and Technology(AIST), Central 2, Umezono 1-1-1, Tsukuba 305-8568, Japan
2
College of Physical Science and Technology, Sichuan University, Chengdu 610065, China
We present modulation of optical field by graphene nano-ribbon. We have chosen
semiconducting arm-chair graphene nano-ribbons as our test-cases. We here present N=7, N=9graphene nano-ribbons with the definition of Ref. 1, which have energy gaps of 1.62 eV and
0.78 eV, respectively. Although the band-gap are so different, the optical absorption spectrumof these ribbons become similar when optical polarization vector is perpendicular to theribbon edge and parallel to the ribbon plane as displayed in Figure 1.
We have performed real-time electron dynamics
simulation of graphene nano-ribbons by using theframework of the time-dependent density functional
theory[2]. We used a code [3,4] for the real-time
propagation of electrons under alternating electricfield that mimics optical field. Then we monitored
electric field 3.34 Å above the center-line of grapheneribbon, dot-dashed line of Fig. 1. When the frequency
of applied field was in UV region corresponding toabsorption peak with an E-field polarization shown in
Fig.1, a significant enhancement of optical field was
Fig.1
Structure of an arm-chairgraphene nano-ribbon (N=7) underobserved which modulated in a period of 10 THZ, see
optical field..
Fig. 2.
In this presentation, we will discuss the origin of
the modulation and possible applications.
.
[1] Y.-W. Son, M. L. Cohen, and S. G. Louie, Phys. Rev. Lett 97,
216803 (2006).
[2] E. Runge, and E. K. U. Gross, Phys. Rev. Lerr. 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: +81-29-849-1498, Fax: +81-29-861-3171,
E-mail: yoshi-miyamoto@aist.go.jp- 121 -

Fig. 2 Computed electric field withseveral optical frequencies, 3.34 Å above
the central line (dot-dashed line in Fig. 1)
of graphene nano-ribbon.

2P-34

Spectroscopic studies of single layer molybdenum ditelluride (MoTe2)○Sandhaya Koirala, Daichi Kozawa, Shinichiro Mouri, Yuhei Miyauchi, Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Kyoto, Japan
Recently, atomically-thin layered materials, transition-metal dichalcogenides (MX2;M=Mo,
W, X=Se, S,) have attracted much interests from the viewpoints of fundamental physics andpotential applications. The studies of transition-metal dichalcogenide (TMDs) are mainly
focused on the model system of MoS2. In contrast, molybdenum ditelluride (MoTe2) is amember of TMDs, which shows emerging research interest due to perspective of novel opticalproperties. MoTe2 is a newly studied material with a bandgap energy at 1.09 eV in the spectral
range of near-infrared region [1]. However, the detail optical properties of this material have
not reported so far.
In this study, we have investigated the optical properties of monolayer molybdenum
ditelluride (MoTe2) by spectroscopic studies of Raman, photoluminescence (PL) anddifferential reflectivity measurements. We exfoliated the monolayer and multilayers MoTe2 on
Si and quartz substrate. Figure 1(a) shows the Raman spectra of MoTe2 with various layer
thicknesses. The layer number of MoTe2 was confirmed from Raman spectra. Figure 1(b)shows temperature dependence of PL spectra of monolayer MoTe2. The PL spectra at room
temperature (300 K) show the peak at 1.09 eV. With decreasing temperature, the PL peak isshifted towards higher energy side, shown in Fig. 1(c). Moreover, two clear peaks (1.16 and1.19 eV) are observed at low temperature (<40 K), which are assigned as the radiative
recombination of free-excitons and charged excitons (trion), respectively. We will discuss thedetail information of exciton relaxation dynamics and valley-polarization dynamics of MoTe2
during the presentation. Obtained results provide us important insights of this material.

FIG.1 (a) Raman spectra of MoTe2 with various thicknesses. (b) PL spectrum of monolayer MoTe2. (c)Temperature dependence of PL spectra of monolayer MoTe2.
[1] Claudia Ruppert et al. Nano. Lett. 14 (20149 6231-6236.
Corresponding Author: Sandhaya Koirala,
Tel: +81-774-38-3463,
Fax: +81-774-38-4567,
E-mail: sandhaya@iae.kyoto-u.ac.jp- 122 -

2P-35Seebeck effect of monolayer transition metal dichalcogenides○Kaito Kanahashi1, Jiang Pu2, Nguyen Thanh Cuoug3, Lain-Jong Li4,
Susumu Okada3, Hiromichi Ohta5, Taishi Takenobu1,2,6
1

Department of Applied Physics, Waseda University, Shinjyuku 169-8555, Japan
Department of Advanced Science and Engineering, Waseda Univ., Tokyo 169-8555, Japan
3
Graduate School of Pure and Applied Sciences, University of Tsukuba, Japan4
Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
5
Research Insutute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan
6
Kagami Memorial Laboratory, Waseda University, Tokyo 169-0051, Japan

2

Transition metal dichalcogenides (TMDC) monolayers, such as MoS2 and WSe2, haveattracted attention due to their graphene like structure and spin-valley coupled system.
Recently, the thermoelectric properties of TMDC monolayers were measured and theextremely huge Seebeck coefficient (> 1 mV/K) was observed in single-crystal samples [1, 2].
Although CVD-grown large-area samples are suitable for future application, thethermoelectric properties of large-area TMDC monolayers have not yet been investigated. In
particularly, because Seebeck coefficient correlates directly with material conductivity,
carrier-density dependence is very important. Therefore, in this paper, we tried to measure theSeebeck coefficient of large-area TMDC monolayers with modulating their carrier density byelectric double layer transistors (EDLTs), in which one can accumulate extremely highdensity carriers (> 1013/cm2) [3, 4].
Figure 1 shows the device structure of EDLTs. As the gate dielectric, we selected the iongel, which is the mixture of ionic liquid (EMIM-TFSI) and organic polymer (PS-PMMA-PS).
As shown in Fig. 2, we successfully accumulated hole and electron carriers in p-type WSe2
and n-type MoS2, respectively. Finally, we measured the Seebeck coefficient of TMDC
EDLTs at room temperature. The sign of Seebeck coefficient agrees with the carrier type ofeach material (positive for p-type WSe2 and negative for n-type MoS2) and it reasonably
controlled by EDL gating, suggesting the solid success of the thermoelectric measurements.

Fig.1. Schematic of Seebeck measurement

Fig.2. Seebeck coefficient and sheet conductivity of TMDCs[1] M. Busceme et al., Nano Lett. 13, 358 (2013), [2] J. Wu et al., Nano Lett. 14, 2730 (2014)[3] J. K.Huang, T. Takenobu et al., ACS Nano. 8. 923 (2014), [4] J. Pu et al., Nano Lett. 12, 4013 (2012)
Corresponding Author: Taishi Takenobu, Tel&Fax: +81-3-5286-2981, E-mail: takenobu@waseda.jp- 123 -

2P-36
Electronic transport properties of graphene between metal electrodes○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

High contact resistance between graphene and metal electrodes is one of major problems
for realizing graphene-based electronic devices. It has been reported that the contact
resistance depend on the metal species. In this work, we perform first-principles electronictransport calculations of armchair graphene nanoribbons (AGNRs) bridging between Ti
electrodes. The results are compared with our previous data for Au electrodes [1], to discuss
the dependence of the transport properties on metal species.
Figure 1 shows a structural model in ourtransport calculations. Two Ti electrodes arebridged by the AGNRs with a channel length Lchof about 10 nm. The equilibrium spacing
between the graphene and metal surface wasfound to be 0.20 nm (cf. 0.37 nm for Au)
indicating that the strong π-d orbital interaction
between them. The contact length was fixed toFig. 1: (a) Top and (b) side views of a structural
be 0.86 nm. We calculated current densities I at a model. The AGNR with the width N = 95
bias voltage Vb = (μL-μR)/e = 0.1 V, where μL bridges two Ti electrodes. The solid and dotted(μR) is the chemical potential of the left (right) rectangles indicate the unit cells of the model
lead, using the nonequilibrium Green’s function and leads, respectively.
method. Fig. 2 shows I as a function of thechannel length Lch. We found that the current densities for Ti are about 10 times as large as
those for Au all Lch (i.e. N) studied here. As shown in Fig. 3(a), the transmission occurs at awide range of the energy eigenvalues E and the wave number along ribbon ky around those of
the AGNR (Fig. 3(b)) arising from the strong π-d coupling that substantially enhances theelectron transfer through the Ti-graphene contact. The fact indicates that the contact resistance
between graphene and metal electrodes decisively depends on the amount of the hybridization
between them.

Fig. 2: Current densities I for AGNRs
with N = 95 (triangle), 97 (square),and 99 (circle).

Fig. 3: (a) Transmission spectra T(ky, E) for the AGNR with N =95 bridging two Ti electrodes. The color bar of the value from 0 to
2 of the transmission is shown. The μL is set to 0 eV. (b) Band
structure of the isolated AGNR with N = 95.

[1] H. Jippo et al., FNTG 47, 1-3 (2014).
Corresponding Author: H. Jippo, Tel: +81-46-250-8843, E-mail: jippo.hideyuki@jp.fujitsu.com- 124 -

2P-37
Anharmonicity of Phonons and Thermal Conduction in Graphene○Masashi Mizuno1, Riichiro Saito1
1

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

Graphene and other low-dimensional carbon materials have a lot of potential for various
applications because of their outstanding physical properties [1]. We focused on the thermal
conductivity of graphene (~ 3,000 – 5,000 W / m K), which is about ten times larger than purecopper [2-4].
In graphene, phonons are the dominant carrier of heat and thermal conductivity isdetermined by the phonon mean free path (MFP). And the most intrinsic cause of phonon
scattering is the anharmonicity (cubic or higher order terms) of lattice potential. The main
purpose of our study is to understand how anharmonicity effects on thermal conductivity ingraphene. We also studied how thermal conductivity continues from diffusive transport toballistic transport which occurs when MFP is larger than the sample size of graphene.
Anharmonicity can be calculated by ab initio calculation [6] or from empirical inter-atomic
potentials [7,8]. However, the former is too complicated to study the basic relationships
between anharmonicity and thermal conductivity. Also, we never had very suitable empiricalinter-atomic potentials for calculation of anharmonicity. We have therefore integrated simple
formed cubic-anharmonic terms into the harmonic force constant model which is welloptimized to experimental data [9]. And we optimized the coefficients for anharmonic
potential to ab initio calculation or measured thermal conductivity.
We have found that anharmonic scatterings involving one in-plane phonon and twoout-of-plane phonons have an strong effect on thermal conductivity. This is because, ingraphene, ZA phonons and low-frequency TA and LA phonons carry the main part of heat andthese scattering processes affects the lifetime of these phonons.
We also found that, at room temperature or lower, MFPs of some phonons are comparable
to or larger than typical size of graphene sample (1 µm). In this case, ballistic transport ofphonons should occur and thermal conductivity depends on the sample size of graphene. We
will show the estimation of this dependency in the poster.
[1] R. Saito, et al., Physical Properties of Carbon Nanotubes, Imperial College Press, London (1998).
[2] A. A. Balandin, Nat. Mater. 10, 569 (2011).
[3] E. Pop, et al., MRS Bull. 37, 1273 (2012).
[4] S. Chen, et al., Nat. Mater. 11, 203 (2012).
[5] G. P. Srivastava, The Physics of Phonons. (CRC Press, UK, 1990).
[6] L. Paulatto, et al., Phys. Rev. B. 87, 214303 (2013).
[7] L. Lindsay, et al., Phys. Rev. B. 81, 205441 (2010).
[8] V. K. Tewary, et al., Phys. Rev. B. 79, 075442 (2009).
[9] M. Furukawa, unpublished (2009).
Corresponding Author: M. Mizuno
E-mail: mizuno@flex.phys.tohoku.ac.jp- 125 -

2P-38Structure and electronic properties of epitaxial graphene
and its molecular adsorption effectKeisuke Nakamoto1 , Takashi Akatsu2 , Kazuyuki Takai1,3,4

1

Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
Material and structures laboratory, Tokyo Institute of Technology, Tokyo 226-8503, Japan3
Department of Chemical Science and Technology, Hosei University, Tokyo 184 -8584, Japan
4
Research Center for Micro-Nano Technology, Hosei University, Tokyo 184-0003, Japan
2

Exfoliated graphene has been extensively investigated mainly on the transport study toward theelectronics application. Recently graphene research has been extended to studies for spectroscopy
and reactivity with other chemical species where large-area and high quality sample is necessary. In
this study, we examined the structure and the electronics structure of epitaxial graphene (EG) grown
on a SiC substrate as a typical large-area high quality graphene sample, and its effect of theadsorption of guest chemical substance by XPS (Al Kα), Raman spectroscopy (wavelength 532nm).
EG was grown by annealing SiC at 1750 °С for 5 minutes under Ar atmosphere. Molecularadsorption was performed by immersing EG in hydrazine hydrate (N2 H2 •H2 O) for 12 hours anddried (Hydrazine-EG).
Fig.1 shows XPS spectra for EG and hydrazine-EG. Emerging of N1s peak in hydrazine-EG
indicates the successful introduction of hydrazine in EG. However, N1s peak position suggests thepresence of C-N bonding. Fig.2 shows Si2p spectra for EG and hydrazine-EG. Peak intensity for the
buffer layer (102 eV) decreases after hydrazine introduction, suggesting hydrazine hydrate isintercalated and decouples the buffer layer and the SiC substrate as reported for hydrogen adsorption[1]. In Raman spectroscopy, the G-band position for hydrazine-EG shifts toward a higher energy side
as compared with EG. Hydrazine-EG might be electron-doped by the influence of the introduction of

Hydrazine-EG

1000

Bufferlayer-SiC

EG

EG

Intensity (arb. unit)

Intensity (arb. unit)

hydrazine hydrate.

N1s

500
Binding energy (eV)0

Fig.1 XPS spectra for EG and hydrazine-EG

BulkSiC

Hydrazine-EG

104

101
Binding energy (eV)98

Fig.2 Si2p spectra for EG and hydrazine-EG[1]C. Riedl, C.Coletti, T. Iwasaki, A.A.Zakharov, and U.starke, PRL 103, 246804 (2009)
Corresponding Author : Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002, E-mail:takai@hosei.ac.jp- 126 -

2P-39Bandgap Opening in Graphene Adsorbed on Defective Graphene○Ken Kishimoto and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Electronic structures of graphene sensitively depend on imperfections such as atomic
defects, topological defects, and edges. It has been demonstrated that graphene with defects iseither a metal or a semiconductor depending on the defect structure and arrangement. In
addition to the atomic imperfections, the interlayer stacking arrangements of graphene thinfilms also lead to the interesting variations in their electronic structures because of thesubstantial interlayer -interactions. These facts imply that the electronic structure ofpristine graphene is modulated by adsorbing the defective graphene due to the interlayerinteraction. In this work, we aim to study the electronic structure of bilayer graphene
consisting of pristine and defective graphene layers using the density functional theory (DFT)with the effective screening medium (ESM) method.
Our DFT-ESM calculations show that all bilayer graphene are semiconductors with finite
energy gap of about a few hundred meV irrespective of the defect structures and mutual
stacking arrangements (Fig. 1). Detailed analysis on the electronic structures unraveled thatthe defects on one of graphene layers causes inhomogeneous electrostatic potential on pristinegraphene layer leading to the finite energy gap between  and  states (Fig. 2). The results
indicate the possible procedure for realizing semiconducting bilayer graphene by modulating
the atomic arrangements of one of two layers.

Fig.1, Electronic energy band of bilayer
graphene consisting of pristine and defective
graphene layers.

Fig. 2, A contour plot of the electrostatic
potential on the pristine layer of bilayer
graphene.

.
Corresponding Author: K. Kishimoto
Tel: +81-29-853-5600(ext.; 8233)
E-mail: kkishimoto@comas.frsc.tsukuba.ac.jp- 127 -

2P-40Fabrication and In-situ TEM Characterization of Freestanding Graphene
Nanoribbons Devices○Qing Wang, Ryo Kitaura*, Shoji Suzuki, Hisanori Shinohara*
Department of Chemistry & Institute for Advanced Research, Nagoya University,
Nagoya 464-8602, Japan
Size and shape can strongly affect properties of nanomaterials. Graphene nanoribbons(GNRs) have recently attracted intensive interests because electronic structure of GNR,
including bandgap and localized edge states, strongly depends on their width and edge
structure: width-dependent bandgap and gapless edge states arising from zigzag edges. The
combination of precise structural characterization and electronic property measurement istherefore essential to fully understand the intrinsic properties of GNRs. For this purpose, a
new experimental technique using freestanding GNR devices has been developed, leading to
the simultaneous characterization of electronic properties and atomic structure of GNRs.
High quality graphene was transferred onto a Si substrate with an open slit covered by a
SiO2 layer. To fabricate a freestanding structure, we first made electronic contacts on isolated
graphene ribbons by Cr/Au, and then SiO2 membrane underneath the graphene ribbons was
etched away by buffered hydrogen fluoride acid. The so-prepared freestanding graphenedevice was assembled to a home-made transmission electron microscopy (TEM) holder for
in-situ characterization. The freestanding
graphene was sculpted by a focused electron
beam in TEM, purified and narrowed by Joule
heating down to several nanometers width.
Structure-dependent electronic properties were
investigated in TEM. We have observed
significant increase in resistance and found that
semiconducting behavior became more
dominant with decreasing width of GNR. The
detailsofdevicepreparation
andcharacterization of GNRs devices will be
addressed in the presentation.
Fig.1 Schematic diagram of the freestanding structure[1] J. Huang, et al. PNAS 106, 10103, (2009).
[2] Han et. al. PRL 104, 056801 (2010)
Corresponding Author: Ryo Kitaura and Hisanori Shinohara
TEL: (+81) 52-789-2482, FAX: (+81) 52-789-6442,
E-mails: r.kitaura@nagoya-u.jp and noris@ nagoya-u.jp- 128 -

2P-41Graphite laser ablation products
carried by coaxial gas flow
○Yuki Taguchi,1 Hitomi Endo,1 Yurika Abe,1 Jun Matsumoto,1Tomonari Wakabayashi,2
Takeshi Kodama,1 Yohji Achiba1and Haruo Shiromaru1
1

Department of chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan2
Department of Chemistry, Kindai University, Osaka 577-8502, Japan

Previously we have shown that hydrogen-terminated polyynes (HC2nH, hereafter merely
polyynes) are effectively produced by laser ablation of graphite in argon/propane gas flow,
and information on the polyyne-formation reactions would be obtained from the yields as afunction of the ratio of propane gas (R = fp/(fa+fp), where fa and fp are the flow rates of Ar andpropane, respectively) [1]. In that experiment, ablation products were emitted 45 degrees
toward the wall and only those successfully carried by the gas flow were detected. Thus, highvelocity products were not detected causing a bias in the measured yields. In the present study,
laser ablation was conducted in a new apparatus (Fig. 1) to improve the collection efficiency.
A graphite disk with small through-holes was set as shown in the inset, so as to make the gas
flow (50 mL/min) and ejected carbon clusters to be directed coaxially to the exit. A pulsed
Nd: YAG laser with the power of 150 mJ/pulse wasirradiated to the graphite for 60 seconds. After laser ablation,
the soluble products were analyzed by UV absorption. The
yields were commonly several times higher than those by
the old setup.
The R-dependence of the yields of the polyynes isshown in Fig. 2, which well reproduces our previous
measurements [1]. It follows that the limited collection
efficiency does not cause a serious bias. As can be seen in
the figure, the yields increase with the increase of the R Fig. 1 Schematic drawing of thevalues. At high R values, the yields of C6H2 and C8H2
laser ablation setup.
become to be almost a plateau, while those of C12H2
and C14H2 still continue to increase. A reasonable
explanation for the chain-size dependence of the yield
curves is that the precursors, bared carbon clusters of
C6 and C8, are nearly exhausted at around R = 0.5. On
the other hand, such the saturation effect is notobserved for the longer polyynes, probably due to thelower reactivity of the longer bared carbon clusters.
The enhancement of the longer polyynes at large R
indicates that the hydrogen termination occurs after thesize distribution of the chain-form carbon clusters isfixed.
[1] Y. Abe et al. FNTG 46, 141 (2014).
Corresponding Author: H. Shiromaru, Tel: +81-42-677-1111, Fax:
+81-42-677-2525, E-mail: shiromaru-haruo@tmu.ac.jp- 129 -

Fig. 2 Plots of relative yields of thepolyynes, (a) - (d) for C6H2, C8H2, C12H2
and C14H2, respectively. The yields arenormalized at R = 1. The error bars are
standard deviation of four independentlots.

2P-42Controlling and functionalizing phase transitions
in two-dimensional crystals○Masaro Yoshida1, Yijin Zhang1, Jianting Ye2, Ryuji Suzuki1, Yasuhiko Imai3,
Shigeru Kimura3, Akihiko Fujiwara3, Yoshihiro Iwasa1,41Quantum-Phase Electronics Center (QPEC) and Department of Applied Physics,
The University of Tokyo, Tokyo, 113-8656, Japan
2
Zernike Institute for Advanced Materials (ZIAM), University of Groningen, Nijenborgh 4,9747 AG, Groningen, the Netherland
3
Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, Hyogo 679-5198, Japan
4
RIKEN, Center for Emergent Matter Science (CEMS), Wako, 351-0198, Japan
Two-dimensional (2D) crystals, including graphene and transition metal dichalcogenides[1], provide an ideal platform for exotic electronic band structures in mono- or multi-layer
forms. The thinning to nanoscale may also affect collective phenomena in interacting electron
systems and can lead to unconventional states that are dramatically different from those inbulk. Here, we show the systematic control of charge density wave (CDW) transitions bychanging thickness and cooling rate in nano-thick crystals of 1T-type tantalum disulfide(1T-TaS2) [2]. First, we discovered asupercooled nearly commensurate CDW state,
which has never been observed in bulk crystals.
We also performed quasi in situ microbeam
X-ray diffraction measurement at SPring-8 andsucceeded in the direct observation ofsystematic change in lattice constant as afunction of thickness, which may be the originof the novel supercooled state. Furthermore, we
achieved current-induced switching between
various CDW states. The current-voltage
characteristic reminds us that of phase-change
memory (PCM) or memristor [3]. The glassy
behavior and non-linear response, possibly due
to the reduced dimensionality, manifest the
emergent complex nature and potentialfunctionalities of correlated electrons in 2D
crystals with nanometer thickness.
[1] K. S. Novoselov et al. PNAS 102, 10451 (2005).
[2] M. Yoshida et al. Sci. Rep. 4, 7302 (2014).
[3] M. Yoshida et al. in preparation.
Corresponding Author: M. Yoshida
Tel: +81-3-5841-6822, Fax: +81-3-5841-6822,
E-mail: masaro-yoshida@mp.t.u-tokyo.ac.jp

Fig.1 Resistivity-temperature (3D-T) curvesof a 1T-TaS2 nano-thick crystal at different
cooling rates, demonstrating that thesuper-cooled conducting state is realized by
rapid cooling. Inset is the cooling ratedependence of Hall coefficient (RH), showingthat a large number of carriers are mobile inthe supercooled state.

- 130 -

2P-43Structure and Spectra of Polyyne-Iodine Complex○ Dai Nagashima1 , Tohru Sato1,2 , Naoya Iwahara1 , Kazuyoshi Tanaka1 , Yoriko Wada3 ,Tomonari Wakabayashi3
1

Department of Molecular Engineering, Graduate School of Engineering, Kyoto University,
Kyoto 615-8510, Japan
2
Unit of Elements Strategy Initiative for Catalysts and Batteries, Kyoto University,
Kyoto 615-8510, Japan3
Department of Chemistry, Graduate School of Science and Engineering, Kinki University,
Osaka 577-8502 Japan

Polyynes,C2n H2 , are highly conjugated linear carbon chains which are synthesized by thelaser ablation of graphite and isolated size-selectively[1]. For C2n H2 (n = 5, · · · , 9), it has
been reported that the mixtures of polyyne and iodine in a non-polar solvent such as hexane
drastically changes in the UV/vis absorption spectra by the irradiation of visible light[2]. It
was found that the stoichiometries are C2n H2 I6 , and they have at least one C2 symmetry
axis[2] from the experimental observations including NMR. However, the molecular structures and formation mechanism of these complexes are still open.
In this study, we assigned the IR, UV/vis and NMR spectra of C10 H2 I6 by using the density functional theory (DFT) and time-dependent DFT (TD-DFT) to clarify the molecular
structure of the complex. All calculations were performed with the Zeroth-Order RegularApproximation (ZORA) Hamiltonian[3] using the Amsterdam Density Functional (ADF)
package. Prior to the calculations, we performed benchmark calculations for C10 H2 . We
employed the PBE/TZP, B3LYP*/TZP, KT2/TZP level of the theory for the IR spectra,
UV/vis spectra, and NMR spectra, respectively. We also simulate the observed vibronic
progressions in the UV/vis spectrum to obtain the vibronic coupling constant.
As shown in Fig.1, we presumed eight C10 H2 I6 isomers with a C2 symmetry axis. According to the results of the DFT calculations for the ground states, (a.1) isomer is themost stable structure among them as shown in Fig.2. Fig.3 shows the comparison of thecalculated IR spectrum of (a.1) with the experimental one[4]. We found that the simulated
IR, UV/vis, and NMR spectra for (a.1) reproduce the experimental ones well.
(a.1)

(a.2)

(b.1)

(b.2)

(c.1)

(c.2)

(d.1)

(d.2)

Figure 1: Calculated C10 H2 I6 isomers.

Figure 2: Relative energy of the isomers at the
PBE/TZP level of the theory.
[1] H. Tabata et al., Carbon 44, 3168(2006).
[2] Y. Wada et al., J. Phys. Chem. B. 115, 8439(2011).
[3] E. van Lenthe et al., J. Phys. Chem. 99, 4597(1993).
[4] Y. Wada et al., Chem. Phys. Lett. 541, 54(2012).
Corresponding Author: Tohru Sato
Tel: +81-75-383-2803, Fax: +81-75-383-2555,
E-mail: tsato@moleng.kyoto-u.ac.jp- 131 -

Figure 3: Experimental (solid line) and calculated(dotted line) IR spectra of (a.1) isomer.

2P-44
Ambipolar Transistor and Superconductivity in Transition Metal
Dichalcogenides
1

1,2

1

1

1

○Wu Shi , Jianting Ye , Yijing Zhang , Ryuji Suzuki , Masaro Yoshida ,Naoko Inoue1, Yu Saito1, and Yoshihiro Iwasa1,31Quantum-Phase Electronics Center and Department of Applied Physics, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan
2
Zernike Institute for Advanced Materials, University of Groningen, The Netherlands
3
Center for Emergent Matter Science, RIKEN, Hirosawa 2-1, Wako 351-0198, Japan

Two-dimensional materials such as transition metal dichalcogenides (TMDs) have attracted
substantial interest since the discovery of graphene. By mechanical cleavage, atomically flat andchemically stable thin flakes of TMDs can be readily obtained from bulk crystals and employed as
ideal channel materials for field effect transistor (FET) devices. Recently, coupling with novel
functioned ionic liquid (IL) dielectrics, TMD thin flakes have exhibited new functionalities suchas superconductivity and opto-valleytronics [1, 2] in the form of electrical double layer transistors(EDLTs) due to the extremely large electric field created at the EDL interface. In this work, wereport systematic evolution of field effect properties and gate-induced superconductivity in MoX2
(X = S, Se, and Te) utilizing the EDLT configuration. The ambipolar transistor characteristics ofMoX2 were nicely explained by the interface energy alignment between ionic liquids (ILs) andMoX2. As a consequence of decreasing efficiency in electron accumulation, gate-induced
superconductivity (GIS) was found in MoSe2
but not in MoTe2. Further experiments byreplacing IL with KClO4/polyethylene glycol(PEG) electrolyte significantly reduced electron
injection barrier and amplified transistor
performance, leading to the emergence ofsuperconductivity in MoTe2. The present result
reveals the correlation between transistor
operation and superconductivity, providing animportant guidance to systematically induce
superconductivity using an EDLT technique.
Figure 1. Superconductivity of 2H-type MoS 2,
MoSe2 and MoTe2 by ionic gating using ionic liquid(IL) and polymer electrolyte (PE), respectively.

[1] J. T. Ye, Y. J. Zhang, R. Akashi, M. S. Bahramy, R. Arita, Y. Iwasa, Science 338, 1193 (2012)[2] Y. J. Zhang, T. Oka, R. Suzuki, J. T. Ye, Y. Iwasa, Science 344, 725 (2014).
Corresponding Author: W. Shi
Tel: +81-3-5841-6822, Fax: +81-3-5841-6822
E-mail: shiwu@ap.t.u-tokyo.ac.jp- 132 -

3P-1
Solid-State NMR Studies on the Aggregated Structures of Organic Bulk
Heterojunction Solar Cells with Solvent Additives(II)○Saki Kawano1 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 such as 1,8-diiodooctane (DIO) is widelyused approach to increase power conversion efficiencies for many organic solar cells[1-2].
Solid-state NMR spectroscopy offers several techniques for the investigation of themorphological, structural, and dynamics properties of BHJ organic solar cells.
We have explored the effects of DIO addition of P3HT/PCBM BHJ films on the local
crystallinity and morphology by using solid-state NMR spectroscopy. In this study, weinvestigated the change in the crystallinity, morphology, and the properties of molecularmotions of P3HT/PCBM BHJ film by adding another solvent additives(1,8-Octanedithiol(ODT)) and also effects of annealing 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 ODT 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 plate and 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. Figure 1. shows
the 13C-DD/MAS NMR spectra of P3HT/PCBM BHJ films (a)with and (b)without ODTadditive.

Figure 1. 13C DD/MAS NMR spectra of P3HT/PCBM BHJ films with and without ODTadditive
The detailed results of the change of the crystallinity and morphology of P3HT/PCBM BHJ
film by the addition of ODT and comparison with other additives will be presented
References:[1] Cuiying Yang et al. J.Am.Chem.Soc., vol.128, no.36, pp.12007–12013, 2006.
[2] Jae Kwan Lee et al., J. Am. Chem. Soc., vol.130 no.11, pp.3619–3623, 2008.
[3] S. Kawano, S. Ishikawa and H. Ogata, Abstract of the 47th Fullerenes-Nanotubes-Graphene General
Symposium (1P-38)
Corresponding Author: H. Ogata, Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 133 -

3P-2
Application of spiro-1, 3-dioxolanofullerenes with low-lying LUMO levelto low bandgap polymer based organic photovoltaic cell
○Tsubasa Mikie, Akinori Saeki, Naohiko Ikuma, Ken Kokubo, Shu Seki
Department of Applied Chemistry, Graduate School of Engineering, Osaka University,
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Bulkheterojunction

(BHJ)

type

organic

photovoltaic (OPV) cell is one of the promisingtechnologies because of its low-cost scalable solution
process on a light-weight flexible substrate. Since
low bandgap polymers (LBP) have been developed,
the power conversion efficiency (PCE) of single cell
LBP:[6,6]-phenyl-C61(71)-butylic acid methyl ester

Scheme 1. Synthesis of SDOFns.
2

there has been little alternative of PCBM suitable for0

LBP. A general molecular design of LBP is to narrow
the band gap with keeping a deep HOMO level.
Therefore, some of LBPs lead to small offset in the
LUMO levels between LBP and fullerenes, whichmight inhibit an efficient charge separation.
Herein,wereportspiro-1,3-dioxolano[60]fullerene (SDOFn) bearing six, seven, eight, andtwelve-membered rings (n = 6, 7, 8, 12) (Scheme 1)[2]. This molecular design is followed by our recent
study on spiro-(thio)acetalized [60]fullerenes (SAFn

Current density / mAcm-2(PCBM and PC71BM) reached 9-10% [1]. However,

PTB7

-2
-4
-6
-8
-10

2d
Normal: 4.43%

-12
-14
-0.2

SDOF12Inverted: 5.39%
0

0.2

0.4

0.6

0.8

Voltage / V

Figure 1. J-V curves of PTB7: SDOF12(dashed line: normal cell, solid line:
inverted cell) under 100 mWcm-2 AM1.5G.

and STAFn, n = 5-7), which revealed 4.0% PCE for
the poly(3-hexylthiophene), P3HT blend (P3HT:SAF7) comparable to P3HT:PCBM [3]. Unlike SAFn
and STAFn, electron-withdrawing spiro-dioxolano unit of SDOFn is directly attached to the fullerene
core, so that their LUMO levels become shallower than those of SAFn. The blend film of SDOF12 andbenchmark LBP (PTB7) showed the good PCEs of 4.43 and 5.39% for normal (ITO/PEDOT:PSS/BHJ/Ca/Al) and inverted (ITO/ZnO/BHJ/MoOx/Ag) devices, respectively (Figure 1),
suggesting high potentials of SDOFs as the fullerene alternatives in BHJ-OPV systems.
[1] J. Kong, I.-W. Hwang, K. Lee, Adv. Mater. 2014, 26, 6275.
[2] T. Mikie, A. Saeki, N. Ikuma, K. Kokubo, S. Seki, Chem. Lett. DOI:10.1246/cl.141008.
[3] T. Mikie, A. Saeki, H. Masuda, N. Ikuma, K. Kokubo, S. Seki, J. Mater. Chem. A. 2015, 3, 1152-1157.
*Corresponding Author: Shu Seki
Tel: +81-6-6879-4586, Fax: +81-6-6879-4586, E-mail: seki@chem.eng.osaka-u.ac.jp- 134 -

3P-3
Fabrication of semitransparent tandem organic solar cells using
multiple-device stacked structure○Shunjiro 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-cost and solution-processable fabrications. Previously, we reported semitransparent
bulk-heterojunction OSCs based on a benzodithiophene polymer of PTB7*[1] andphenyl-C71-butyric-acid-methyl-ester (PC71BM) utilizing an oxide/metal/oxidetransparent anode [2]. However, the photocurrents of the semitransparent OSCs remained
low due to the optical loss through the semitransparent electrode. In this work wefabricated stacking structure of two separated OSCs to harvest an increased amount ofphotons which enhanced the power conversion efficiency (PCE).
The device structure was Glass/ITO/PFN**/PTB7:PC71BM/MoO3/Au/MoO3(Figure 1). Two identical semitransparent OSCs were stacked on top of each other andconnected in series or in parallel to form a tandem structure. Figure 2 shows the current
density-voltage (J-V) curves for the single and stacked cells connected in series and inparallel, respectively. The PCEs extracted from the J-V curves were 2.7%, 2.6% and3.3%, respectively. The stacked cells in parallel connection showed improved PCE
compared to a single cell. The detailed device characteristics will be discussed.
Semitransparent anode

MoO3
PTB7:PC71BMPFN
ITO/Glass*PTB7;apoly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl]**PFN;apoly[(9,9-bis(3'-(N,N-dimethylamino)
propyl)-2,7-fluorene)-alt-2,7-(9,9–dioctylfluorene)]-4

Figure 1 Schematic illustration of thestacked semitransparent solar cells.
[1] Y. Liang et al., Adv. Mater, 22 (2010) E135
[2] S. Fujii et al., The 47th FNTG General
symposium 2014, 1p-35

2

MoO3
PTB7:PC71BMPFN
ITO/GlassCurrent Density (mA/cm )-2
Semitransparent anode

0
2
4
6

□Single cell△Series○Parallel

81012Corresponding Author: Hiromichi Kataura
E-mail: h-kataura@aist.go.jp

0

0.2

0.4
0.6
0.8
Voltage (V)1

1.2

Figure 2 J-V characteristics under AM 1.5G.

- 135 -

3P-4
Isolation and characterization of [5,6]-pyrrolidino-Sc3N@Ih-C80
diastereomers○Yutaka Maeda1, Masato Kimura,2 Chihiro Ueda,1 Mitsuaki Suzuki,1 Michio Yamada,1
Nikolaos Karousis,3 Nikos Tagmatarichis,3 Marilyn M Olmstead,4 Alan L Balch,4 Wei-Wei
Wang,5 Shigeru Nagase,5 Takeshi Akasaka2
1

2

Department of Chemistry, Tokyo Gakugei University,Koganei, Tokyo 184-8501, Japan
Life Science center of Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba,
Ibaraki 305-8577, Japan
3
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48
Vassileos Constantinou Avenue, Athens 11635, Greece
4
Department of Chemistry, University of California at Davis, One Shields Ave, Davis, CA
95616, USA
5
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan

Recent developments in the chemistry of endohedral metallofullerenes (EMFs) have led toincreasing efforts to elucidate how the chemical reactivity and selectivity of empty fullerenes
are changed by endohedral metal doping and how the electronic properties ofmetallofullerenes affect chemical functionalization. The preparation and isolation oftrimetallic nitride template endohedral metallofullerenes (TNT-EMFs) in macroscopic
quantities have facilitated the study of their structures, properties, and chemical reactivities.
For practical application, such as organic photovoltaic cells, it is essential to control its
solubility or electronic properties by chemical modification. As practical reagents for thefunctionalization of TNT-EMFs, we focus on a azirizine, precursor of azomethyne ylide.1
Since custom-synthesized aziridines, carrying groups with advanced functionality, can beprepared from commercially available reagents in high yields through only a few steps.
Herein, we report the synthesis of [5,6]-pyrrolidino-Sc3N@Ih-C80 from Sc3N@Ih-C80 andaziridine derivatives. In addition, isolated pyrrolidino-Sc3N@Ih-C80 diastereomers werecharacterized by electronic absorption, NMR, and single-crystal X-ray crystallography.2[1] M. Prato et al. J. Am. Chem. Soc. 129, 14580 (2007).
[2] Y. Maeda et al. Chem. Commun. 50, 12552 (2014).
Corresponding Author: Y. Maeda
Tel: +81-42-329-7512, Fax: +81-42-329-7512, E-mail: ymaeda@u-gakugei.ac.jp- 136 -

3P-5
Reactions of Trimetallic Nitride Template Endohedral
Metallofullerenes with Silacyclopropanes○Kazuya Minami1, Takeshi Sugiura1, Masahiro Kako*,1, Kumiko Sato2,
Shigeru Nagase3, Takeshi Akasaka2,4,5
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, Japan
3
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
4
Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
5
Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
Endohedral metallofullerenes (EMFs) have been the focus of extensive researchbecause of their remarkable structures and properties. During the past decade, exohedral
functionalization of EMFs has been exploited intensively as crucial methods to modify
the physical and chemical properties of EMFs, which will expand the range of potential
applications in molecular electronics, nanomaterials sciences, and biochemistry [1]. Asa method for heteroatom functionalization, silylation using reactive silicon compounds
has been reported to induce remarkable changes of the characteristics of EMFs. For
example, the silylated fullerene derivatives possess more electronegative charge on thecage than parent fullerenes. Moreover, it has been also demonstrated that the movementof the encapsulated metal atom are affected by the introduction of silyl groups on thefullerene cages [2].
As a part of our continuing study of silylation of EMFs, we now report the reactionsof silacycropropanes 1 and 2 with trimetallic nitride template EMFs, M3N@Ih-C80 (M =Sc, Lu). The thermal reaction of Lu3N@Ih-C80 with 1 at 150°C afforded an adduct 3 byaddition of silylene (Dmt2Si). On the basis of the NMR and visible-near-infrared(vis-NIR) spectra, the silylene addition was occurred at the [6,6] ring junction of
Lu3N@Ih-C80. Meanwhile, when the Sc3N@Ih-C80 was photoirradiated with 2, threeadducts 4, 5, and 6 were obtained as carbosilylated Sc3N@Ih-C80. The NMR andvis-NIR spectra indicate that the structures of 4 and 5 are adducts at the [5,6] ringjunctions of Sc3N@Ih-C80, while 6 is an isomer derivatized at the [6,6] junction. The
structural and electronic properties of these silylated derivatives will be discussed basedon electrochemical and theoretical studies.
Scheme 1.

Scheme 2.

[1] M. Yamada, T. Akasaka Bull. Chem. Soc. Jpn. 87, 1289–1314 (2014).
[2] K. Sato et al. J. Am. Chem. Soc. 134, 16033–16039 (2012).
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 137 -

3P-6
Ionic Donor-Acceptor Supramolecules: Complexation of Molecular
Nanocarbons with Cationic Li+@C60○Hiroshi Ueno 1,2, Taishi Nishihara 1,2, Katsuma Matsui 2,
Yasutomo Segawa 1,2, Kenichiro Itami 1,2,3
1

JST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University,
Nagoya 464-8602, Japan
2
Graduate school of Science, Nagoya University, Nagoya 464-8602, Japan
3
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University,
Nagoya 464-8602, Japan
It is well known that cycloparaphenylenes (CPPs),[1] ring-shaped-conjugated molecules,
selectively encapsulate fullerenes. For example, [10]CPP encapsulates C60 to form a shortest
fullerene peapod.[2] On the other hand, lithium-ion-encapsulated fullerene (Li+@C60)[3] has
attracted much attention owing to its strong electron acceptability and unique ionicproperties,[4] and it has almost the same diameter as empty C60. Here, we report the synthesis
and characterization of ionic supramolecule Li+@C60[10]CPP salt, and its notable properties
induced by the specific intermolecular interaction between Li+@C60 and [10]CPP.
The complex Li+@C60[10]CPP was immediately formed when Li+@C60 and [10]CPP
were mixed in dichloromethane. The 1:1 complex of [10]CPP with Li+@C60 was
unambiguously characterized by NMR, ESI-MS, UV-vis titration as well as X-ray crystal
structure analysis (Figure 1). The complexation modulates the electronic state of [10]CPP and
Li+@C60. UV-vis-NIR spectrum showed new absorption band due to the charge transfer
interaction between Li+@C60 and[10]CPP.
In
addition,the+complexation renders Li @C60 lessreducible, which indicates theincrease of electron density of
Li+@C60 induced by the electrontransfer

interaction.

In

the

presentation, other interesting
results such as photophysicalproperty of the ionic complex will
also be discussed.

Figure 1. X-ray structure of Li+@C60[10]CPP cation.
Side view (left) and top view (right).

[1] Omachi, H. et al. Acc. Chem. Res. 2012, 45, 1378. [2] Iwamoto, T. et al. Angew. Chem. Int. Ed. 2011, 123, 8492.
[3] Aoyagi, S. et al. Nature Chem. 2010, 2, 678. [4] Ueno, H. et al. Chem. Commun. 2013, 49, 7376.
Corresponding Author: K. Itami
Tel and Fax: +81-52-789-5916, E-mail: itami@chem.nagoya-u.ac.jp- 138 -

3P-7
The Quantitative Importance of Purity on the Properties of Single Wall
Carbon Nanotubes○Naoyuki Matsumoto1,2, Guohai Chen1, Motoo Yumura1,2, Don N. Futaba1,2, Kenji Hata1,2
1Technology Research Association for Single Wall Carbon Nanotubes (TASC), Central 5,
1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
2
National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1
Higashi, Tsukuba, Ibaraki 305-8565, Japan
No doubt surrounds the unique and exceptional properties of single-walled carbon
nanotubes (SWCNTs); however, these properties pertain to the pristine SWCNTs, when intruth SWCNTs are never free from carbonaceous impurities. These impurities, both
amorphous (sp3) and graphitic (sp2) in structure, are easily adsorbed to the outer surface of the
SWCNTs during the synthesis process [1]. Fundamentally, through both theoretical andexperimental reports, the clear understanding has been developed on the interaction of these
impurities on SWCNTs to degrade these unique properties, such as electronic and thermal
conductivity [2, 3]. These reports demonstrate that purity is undoubtedly important. However,question remains, how important? To date, due to our inability to quantify purity and ourinability to develop purification processes that do not induce damage, the quantitative
importance of carbonaceous impurities on the properties of SWCNTs remains unclear.
We quantitatively investigated the importance of purity on the application of SWCNTs byexamining their effects on the electrical, thermal, mechanical, and dispersion properties forboth the as-grown SWCNT forest, dispersion, and processed buckypaper. In contrast to
previous reports, rather than using purification processes, we fabricated a family of SWCNT
forests by the water-assisted (Super-growth) CVD method varying only in purity through post
synthetic carbon deposition from nearly ideally pure (97%) to exceptionally dirty (38%). Our
results showed that not only did nearly every property at every stage, from the as-grown
SWCNT forest, dispersion, to the processed buckypaper, decrease, they decreased nonlinearlywith the greatest fractional decrease (25-75%) occurring within the first 15% decrease inpurity. For example, the SWCNT forest thermal diffusivity, the dispersabilty, and the
buckypaper breaking strength decreased by 65, 45, 50%, respectively within this span. To add
perspective on these results, SWCNTs with a purity of 85% (15% drop from ideal) would still
possess a specific surface area of over 800 m2/g.
Furthermore, as SWCNT the synthetic structural control further advances, these results
demonstrate that purity is as important as crystallinity, length, and diameter, on improving
properties and should not be neglected as it can offset any improvement due to other structural
improvements.
[1] S. Yasuda et al. Nano Lett. 9, 2585 (2009)[2] P. R. Bandaru J. Nanosci. Nanotech. 7, 1 (2007)[3] J. Hone et al. J. Phys. Chem. B, 59, R2514 (1999)
Corresponding Author: Don N. Futaba
Tel/Fax: +81-29-861-4851
E-mail: d-futaba@aist.go.jp- 139 -

3P-8
MD simulation on RBM frequency of bundled SWNTs○A. Beniya1, N. Homma1, S. Chiashi2, Y. Homma1, T. Yamamoto3
Department of Physics, Tokyo University of Science, Tokyo 162-8601, Japan
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Liberal Arts, Tokyo University of Science, Tokyo 162-8601, Japan
1

2

Radial Breathing Mode (RBM) is one of the most important vibrational modes ofsingle-walled carbon nanotubes (SWNT), because the measurement of RBM frequency
𝜔𝜔RBM allows us to uniquely assign the chirality to an individual SWNT by resonant
Ramman scatting. It is known that 𝜔𝜔RBM responds sensitively to surrounding
environment around an SWNT. Recently, we showed both experimentally andtheoretically that 𝜔𝜔RBM of an individual SWNT is up-shifted when the SWNT is
exposed to water vapor [1]. On the other hand, an SWNT embedded in bundled SWNTs
is not exposed to ambient air, but it receives van der Waals force from the surrounding

SWNTs. Thus, we can expect that 𝜔𝜔RBM of bundled SWNTs is also up-shifted incomparison to that of an SWNT in vacuum. In this paper, we quantitatively analyze theup-shift of 𝜔𝜔RBM of bundled SWNTs using molecular dynamics (MD) simulation.
In order to estimate 𝜔𝜔RBM of bundled SWNTs, we prepare an SWNT bundle
consisting of six (13,0) SWNTs as shown in Fig.1, andcalculate the vibrational spectrum of an SWNT locatedat the core of bundled SWNTs. The obtained 𝜔𝜔RBM was〜228 cm-1 and it is 〜6 cm-1 higher than 𝜔𝜔RBM of anindividual SWNT in vacuum. This 𝜔𝜔RBM shift iscomparable to the shift in the case of an individual (13,0)
SWNT in water vapor we previously obtained [1]. In
this symposium, we present MD simulation results of𝜔𝜔RBM for various chirality types of bundled SWNTs, anddiscuss the diameter dependence of 𝜔𝜔RBM shift.
Reference[1] Y. Homma, et al, Phys. Rev. Lett. 110, 157402-1-4 (2013)
Corresponding Author: Takahiro Yamamoto
Tel: +81-3-5876-1486, Fax: +81-3-5876-1486,
E-mail: takahiro@rs.tus.ac.jp- 140 -

Fig.1: Bundled SWNTs

3P-9
Molecular structure of chalcogen encapsulated in single-walled carbon
nanotubes studied by molecular dynamics simulations○1Yutaka Sato, 2Yosuke Kataoka, and 1,2,3Hironori Ogata
1

Graduate School of Science and Engineering, Hosei University, Koganei 184-8584, Japan
Department of Faculty of Bioscience and Applied Chemistry, Hosei University, Koganei,
184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, Koganei 184-0003, Japan
2

Single-walled carbon nanotubes(SWNTs) have a hollow space in the nanometer size that canbe encapsulated various functional molecules. The conﬁned environments of nanotubes
permit the formation of various kinds of unique encapsulated low dimensional structures withunusual properties compared with the bulk materuials. Recently, synthesis of sulfer
encapsulated SWNTs(DWNTs) and one-dimensional sulfer structures have been reported by
Fujimori et al. [1]. They also reported that these one-dimensional sulphur chains show theconducting character under ambient pressure. In this study, we report the effects of chirality
and tube diameter of SWNTs on the local structure of the sulfur and selenium by using
molecular dynamics(MD) simulations.
MD simulations were conducted by using SCIGRESSVer2.3.0(Fujitsu). We used the GEAR
method of the fifth order in the numerical integration and the speed scaling method in thetemperature control. One SWNT and arbitrary number of sulfur atoms were set in arectangular cell. First, the relaxation calculation were conducted at 1K with the NVT
ensemble for the encapsulation of sulfer. Stable structure at 297 K was calculated after therelaxation calculation at 800 K.
Figure1 shows one example of the structure of sulfur encapsulated in (6 , 6) SWNT at 297K.
Sulfur encapsulated in SWNT took one-dimensional chain structure. The detailed systematic
results will be presented.

Figure 1. The structure of S@SWNT at 297K

[1] Toshihiko Fujimori et al. Nature Commun.4(2013)2162.
[2]Frank H.Stillinger et al. J.Phys.Chem.,85(1986)6460.
[3]Frank H.Stillinger et al. J.Phys.Chem.1987, 91 (19), pp4899-4907- 141 -

3P-10Local structure and properties of the alkali halides encapsulated insingle-walled carbon nanotubes studied by molecular dynamics simulations○Eita Yokokura 1, Yosuke Kataoka 2 and Hironori Ogata1,2,3
1

Department of Faculty of Bioscience and Applied Chemistry, Hosei University, Koganei,
184-8584, Japan
2
Graduate School of Engineering, Hosei University, Koganei, 184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, Koganei, 184-0003, Japan
Single-walled carbon nanotubes (SWNTs) have a hollow space in the nanometer size thatcan be encapsulated various functional molecules. The conﬁned environments of nanotubes
permit the formation of various kinds of unique encapsulated low dimensional structures withunusual properties compared with the bulk. Synthesis of alkali halide encapsulated SWNTs
and their structures have been reported[1-2]. However, the systematic studies on the local
structure and some properties(ion conductivity, melting point etc.) encapsulated in SWNTs
with different diameters and chirality have not been reported. In this study, we report theeffects of the diameter and chirality of SWNTs on the local structure and melting point of theencapsulated alkali halides by using molecular dynamics (MD) simulations.
In our MD simulations, we used the Born-Mayer-Huggins-Tosi-Fumi intermolecularpotential between the alkali halide ions and the Dreiding potential between carbon atoms in
SWNT. One SWNT and any number of alkali halide ions around SWNT were set in arectangular cell as initial configuration. Stable structure at 298 K was calculated with the
NVT ensemble after the relaxation calculation at 1100 K. The relaxation calculation was
conducted after temperature was increased by 10 K from 298K.
Figure 1 shows the local structures of the potassium iodide (KI) encapsulated in (a)(8, 8)
tube and (b)(10, 10) tube at 298 K. KI are oriented in units of 2x2 crystallites in verticalalong the longitudinal axis of the tube. The detailed systematic results will be presented.
(a)

(b)

Figure1.Local structure of KI crystals encapsulated in (a),(b)(8,8) and (10,10) SWNT.
References[1] J. Sloan, M. C. Novotny, S. R. Bailey et al., Chem. Phys. Lett. 329(2000)61.
[2] R. R. Meyer, J. Sloan, R. E. Dunin-Borkowski, A. I. Kirkland, M. C. Novotny, S. R. Bailey, J. L. Hutchison,and M. L. H. Green, Science 289(2000) 1324.
Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 142 -

3P-11
Ultralow mode-volume photonic crystal nanobeam cavities forhigh-efficiency coupling to individual carbon nanotube emitters○H. Machiya1, R. Miura1, R. Ohta2 , S. Imamura1, A. Ishii1, X. Liu1, T. Shimada1,
S. Iwamoto2, Y. Arakawa2, Y. K. Kato1
1

Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
2
Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, JapanThe unique emission properties of single-walled carbon nanotubes are attractive for achieving
increased functionality in integrated photonics. In addition to being room-temperaturetelecom-band emitters that can be directly grown on silicon, they are ideal for coupling tonanoscale photonic structures. Here we discuss high-efficiency coupling of individual
air-suspended carbon nanotubes to silicon photonic crystal nanobeam cavities [1].
Photoluminescence images of dielectric- and air-mode cavities reflect their distinctly differentmode profiles and show that fields in the air are important for coupling. We find that the
air-mode cavities couple more efficiently, and estimated spontaneous emission coupling
factors reach a value as high as 0.85. We also describe our recent efforts on optimizing thedesigns of air-mode cavities and their fabrication processes. Our results demonstrateadvantages of ultralow mode-volumes in air-mode cavities for coupling to low-dimensional
nanoscale emitters.
This work was supported by SCOPE, KAKENHI (24340066, 24654084, 26610080,
26870167), Asahi Glass Foundation, Canon Foundation, KDDI Foundation, as well as the
Project for Developing Innovation Systems and the Photon Frontier Network Program of
MEXT, Japan. A.I. is supported by MERIT and JSPS Research Fellowship. The devices were
fabricated at the Center for Nano Lithography & Analysis at The University of Tokyo.
[1] R. Miura, S. Imamura, R. Ohta, A. Ishii, X. Liu, T. Shimada, S. Iwamoto, Y. Arakawa, Y. K. Kato, Nature
Commun. 5, 5580 (2014).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 143 -

3P-12
Characteristic variation of thin-film transistors
based on purified semiconducting carbon nanotubes○Jun Hirotani1, Ryotaro Matsui1, Shigeru Kishimoto1, and Yutaka Ohno1,2
1

Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
2
EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan

Carbon nanotubes (CNTs) provide great potential for high-performance flexible devices[1,2] because of exceptional intrinsic electrical, mechanical, and thermal properties. Though
great efforts have been made to achieve high-performance CNT thin-film transistors (TFTs),
one of critical issues for practical applications is device-to-device variation in their electricalcharacteristics [3]. Characteristic variation of CNT TFTs depends on the uniformity of CNT
networks which can be improved by increasing number density of CNTs but also affected byfabrication process. Though theoretical [4] and experimental [5] studies have been conducted,
further investigations are necessary both for reducing the variation and for enhancing theyield of devices.
In this work, we have investigated electrical performance and characteristic variation of
CNT TFTs as changing number density of CNTs in the channel. We used high-purity (~95%)
semiconducting single-walled CNTs to avoid a formation of short paths of metallic SWNTs ina high-density CNT film. The CNT film was formed on a SiO2/Si substrate by the vacuum
filtration and transfer method. An SEM image of the CNT film and schematic structure of
back-gate CNT TFT are shown in the insets of Figure. The channel length and width are 100m.
More than a hundred CNT TFTs were measured for each CNT densities, and Figure showstransfer characteristics for a CNT density. The typical on/off ratio was 105 ~ 106, andON-current variation was ~20% in terms of a standard derivation divided by average
ON-current. Our results show that as the CNT
density increases, the variation in ON-current
tend to be eliminated, while the variation isstill larger than predicted by simulation.
Acknowledgements: The semiconducting
SWNTs were provided by TASC. This work
was partially supported by Grant-in-Aid by
MEXT, JST/SICORP, and JST/ALCA.
[1] Q. Cao et al., Nature 454, 495 (2008).
[2] D.-M. Sun et al., Nature Nanotechnol. 6, 156(2011).
[3] A. E. Islam, Electronics 2, 332 (2013).
[4] N. Pimparkar et al., IEEE Trans. Electron Devices
54, 637 (2007).
[5] M. Shimizu et al., Appl. Phys. Exp. 6, 105103(2013).

Figure. Transfer characteristics of 124 CNT TFTs.
Insets: schematic device structure and an SEM
image of channel.

Corresponding Author: Yutaka Ohno, Tel & Fax: +81-52-789-5387, E-mail: yohno@nagoya-u.jp- 144 -

3P-13
Thermoelectric power of carbon nanotubes from first principles○ N. T. Hung, R. Saito
Department of Physics,Tohoku University, Sendai 980-8578, Japan
Carbon nanotubes as one-dimensional (1-D) structures can have either semiconducting or
metallic properties dependent on their chiral vectors, which are denoted by two integers (n, m)[1]. This opens up a promising candidate for high-performance thermoelectricity with large
thermoelectric power (TEP). In this work, the TEP of a series of semiconducting
single-walled carbon nanotubes (s-SWNTs) is investigated from first principles calculations
by using the density functional theory (DFT) [2, 3] and the Boltzmann transport equation. The
Wannier function-based interpolation (Wannier90 code) [4] techniques are applied to computeall the ultra-dense electronic structure. We did not use the constant relaxation time
approximation commonly practiced in the literature because it cannot explain the transport
properties of s-SWNTs [5]. Instead, we calculate the relaxation time directly fromelectron-phonon interaction. Since the large number of atoms in the s-SWNTs is expensive tocalculate full phonon dispersions within the DFT framework, here we utilize the extended
tight-binding model (ETB) [5, 6] based on the DFT to obtain the electron-phonon matrix
elements. The Seebeck coefficients are found to be in good agreement with recent theoreticalstudies using non-equilibrium Green’s function method [7, 8]. A comparison with theexperimental TEP of the s-SWCNTs films samples [9] is also provided. The results show that
the TEP is strongly dependent on the band-gap and temperature. In other words, thethermoelectricity of CNTs can be controlled by their geometrical structure.
References:[1] R. Saito, G. Dresselhaus, M. S. Dresselhaus, “Physical properties of carbon nanotubes”, Imperial collegepress (1998).
[2] P. Hohenberg et al., Phys. Rev. 136, B864 (1964).
[3] W. Kohn et al., Phys. Rev. A 140, A1133 (1965).
[4] N. Marzari et al., Rev. Mod. Phys. 84, 1419 (2012).
[5] J. Jiang et al. Phys. Rev. 71, 045417 (2005).
[6] J. Jiang et al. Phys. Rev. 72, 235408 (2005).
[7] X. Tan et al., Nanoscale Research Lett. 7, 116 (2012).
[8] J. W. Jiang et al., J. Appl. Phys. 109, 014326 (2011).
[9] K. Yanagi et al. Nano Lett. 14, 6437 (2014).
Corresponding Author: Nguyen Tuan Hung
TEL: +81-22-795-6442, FAX: +81-22-795-6447
E-mail: nguyen@flex.phys.tohoku.ac.jp- 145 -

3P-14
Effect of TiO2 coating on field emission properties of carbon nanotube byin-situ transmission electron microscopy
Masahiro Matsuda, Hitoshi Nakahara, Koji Asaka and Yahachi Saito
Department of Quantum Engineering, Nagoya University, Furo-cho, Nagoya 464-8603
Field emission characteristics from a multiwall carbon nanotube (MWNT) are influenced bytheir tip structures and materials deposited on its surface. In order to clarify the role of TiO2
deposition on MWNT, we studied field emission properties of TiO2-coated MWNT emitters byin-situ transmission electron microscopy (TEM).
Amorphous TiO2 was deposited on MWNTs attached to an edge of a gold plate by electron
beam deposition, as shown in Fig.1. A gold-coated tungsten tip was used as an anode.
Emission current - electric field characteristics and emission stability of TiO2-coated emitter
were measured in an electron microscope.
(b)(a)
Fig. 2 shows thickness vs threshold fieldand emission area. The distance between
the anode and a MWNT emitter was 300
nm. When thickness of TiO2 was 0.3 nm,
the threshold field (field required to give acurrent of 10 nA) was the lowest (271 Fig.1 before (a) and after (b) 0.5nm TiO2 coatingV/µm). Possible reasons for the decrease in on MWNT
the threshold field are the decrease in work
function 4.0 eV for TiO2, 4.5 eV for MWNT
and enlargement of the emission area (from 7.6
nm2 without TiO2 to 1696.4 nm2 for 0.3 nm
TiO2 derived from Fowler-Nordheim plots).
Further increase in TiO2 thickness made thethreshold field higher than that in the uncoated
MWNT. This may be caused by the decrease in Fig.2 thickness – threshold field andthe electric field concentration due to the emission area
increase in tip radius.
Emission fluctuation, which is defined by standard deviation divided by average current, isemployed to evaluate emission stability. The fluctuation values were 0.46 and 0.19 for
uncoated and 1.6 nm TiO2-coated MWNT, respectively, showing that the TiO2 coating
improves emission stability. It is considered that adsorption and desorption of residual gases
may be suppressed by TiO2 and the enlarged emission area averages out the local instabilities.

- 146 -

3P-15Light-emitting Electrochemical Cellwith Few-Walled Carbon-Nanotube Electrodes

1○Ko Nakayama1, Hiroyuki Shirae2, Suguru Noda2, Tomo Sakanoue1,
Taishi Takenobu1,3,4

Department of Applied Physics, Waseda University, Tokyo 169-8555, Japan
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan3
Department of Advanced Science and Engineering, Waseda Univ., Tokyo 169-8555, Japan
4
Kagami Memorial Laboratory, Waseda University, Tokyo 169-0051, Japan
2

Recently, touch screens become core components of mobile terminal devices andtransparent conductive films of ITO (indium tin oxide) are inevitable for device fabrication.
However, due to their rarity and inflexibility, flexible transparent conductive films without
rare materials have been strongly required for the next generation flexible electronics.
Although carbon-nanotube film is expected to be one of the candidates for flexible
transparent conductive films, the demonstration of flexible device is still seriously limited.
Therefore, in this paper, we tried to apply few-walled carbon-nanotube (FWCNT) films into
electrodes of light-emitting devices.
For this purpose, we fabricated thelight-emitting electrochemical cell (LEC), which
has very simple layered structures [1]. As shownin Fig.1, firstly, we prepared few-walledcarbon-nanotube films on flexible PET(polyethylene
terephthalate)films.
The
light-emitting layer of LEC is the mixture offluorescent organic polymer and electrolyte, and,in this research, we selected Super Yellow(PDY-132)

and

ionic

liquid(P88812BF4),

respectively. The mixture with weight ratio of 4

Fig.1. Device structure of LEC(polymer) : 1 (ionic liquid) was spin-coated on
flexible FWCNT films. Finally, the aluminumelectrode was thermally deposited. The fabricateddevices emitted yellow light and the luminancereached 1300 cd/m2 at 10V with the efficiency of
5.36 cd/A, which is higher than that of similar
Fig.2. Photo of LEC with FWCNT
LECs with ITO electrodes (1.09 cd/A). This
result shows the potential high performance of nanotube films as flexible conductive films.
[1] T. Sakanoue, T.T et al., APL, 100, 263301 (2012)
Corresponding Author: T. Takenobu

Tel/Fax:+81-3-5286-2981, E-mail:takenobu@waseda.jp- 147 -

3P-16
Synthesis of Single-Walled Carbon Nanotubes from Rh Catalysts
by Alcohol Gas Source Method in high Vacuum○Akinari Kozawa1, Takahiro Saida 2, Shigeya Naritsuka 1, Takahiro Maruyama 1,2
1

Department of Materials Science and Engineering, Meijo Univ., 1-501 Shiogamaguchi,
Tempaku, Nagoya 468-8502, Japan
2 Department of Applied Chemistry, Meijo Univ., 1-501 Shiogamaguchi, Tempaku, Nagoya
468-8502, Japan[1] T. Maruyama et al. Mater. Express 1 (2011) 267.
[2] H. Kondo et al. Jpn. J. Appl. Phys. 52 (2013) 06GD02.
Corresponding Author: T. Maruyama
Tel: +81-52-838-2386, Fax: +81-52-832-1179,
E-mail: takamaru@meijo-u.ac.jp

Intensity (a.u.)

Intensity (a.u.)Single-walled carbon nanotubes (SWNTs) have been anticipated for application in a lot of
future nanodevices. To fabricate SWNT devices, it is important to grow SWNTs with uniformchirality and diameter. So far, we have been reporting SWNT growth using Pt catalysts by
CVD under a low ethanol pressure and succeeded in obtaining SWNTs with small diameters
below 1.2 nm [1]. This suggests that metal catalysts with a high-melting point are effective togrow SWNTs with small and uniform diameters. In this study, we attempted to grow SWNTs
using Rh as catalysts since the melting point of Rh (1966°C) is higher than Pt, and it might
have advantage to form SWNTs with narrow chirality.
Using Rh catalysts, SWNTs were grown on SiO2/Si substrates by the alcohol gas source
method in the UHV chamber, a type of cold-wall CVD equipment [2]. The growthtemperature was set between 500 and 700°C, and the ethanol pressure was varied between 1
×10-5 and 1×10-2 Pa. The grown SWNTs were characterized by FE-SEM and Raman
spectroscopy.
(a)ex:633nm
Fig. 1 shows the Raman spectra of SWNTs grown
-3
700°C
110
Pa
from Rh catalysts on SiO2/Si substrates. The growthG-bandtemperature and ethanol pressure were 700°C and 1×10-3
Pa, respectively. A sharp G-band and RBM peaks wereobserved, indicating that SWNTs were grown from Rh
D-bandcatalysts. It should be noted that D band intensity wasvery weak and that G/D ratio was more than 20, showing
1200
1400
1600
1800
that the quality of SWNTs were fairly good. Our results
-1
Raman
shift
(cm
)
showed that Rh is a useful catalyst to grow high-quality
SWNTs. We will also discuss the difference between Rh(b)
ex:633nm
and Pt catalysts in the SWNT growth.
-3
700°C 110 Pa

100

Si

200

300

-1

Raman shift (cm )400

Fig.1 (a) High-frequency regionand (b) RBM region of Raman
spectra of SWNTs grown at 700ºC.

- 148 -

3P-17
Relationship between Chirality Control of Single-Walled Carbon Nanotube
and Wavelength of the Irradiated Free Electron Laser○Keisuke Yoshida, Yusaku Tsuda, Daiki Kawaguchi, Tomoko Nagata,
Nobuyuki Iwata and Hiroshi Yamamoto
Department of Electronic Engineering, College of Science & Technology, Nihon University,
7-24-1 Narashinodai, Funabashi, Chiba 274-8501 Japan
Single-walled carbon nanotube (SWNT) is one of the candidates for future applications in
nanoelectronic devices due to its high mobility and high current-carrying capacities. As theelectric properties of SWNTs are metallic or semiconducting depending on their chirality, thechirality control is required. We have succeeded in growing chirality controlled SWNTs byirradiating 800 nm free electron laser (FEL) during growth process using cold-wall chemical
vapor deposition (CVD) method1). All grown SWNTs were semiconductor having 1.12 nm indiameter, which was revealed from multi excited laser Raman analysis. In this study wereport chirality control as the wavelength of the FEL is varied. The process of chirality
control is as follows: i) investigation of optimized CVD condition to grow SWNTs withspecific diameter, ii) selection of resonantly absorbed wavelength of the FEL, iii) selective
growth of SWNTs with specific chirality.
The SWNTs were prepared by alcohol CVD method. The SWNTs were grown at 650ºC
for 10 min under ethanol flow at 2kPa with Co/Mo catalysts deposited by dipping technique.
FEL was irradiated during the growth.
Figure 1 shows the Raman spectraof the SWNTs grown with or without
700 nm FEL irradiation. The SWNTs
diameters were 0.90 nm and 1.08 nm
with FEL, while only 1.08 nm
diameter SWNTs grew without FEL.
As the chirality of SWNTs depends on
the band gap, Raman spectra indicatethat FEL irradiation enhance the
SWNTs growth having the specificchirality. We expect that various
chirality is selectively grown using
various wavelength of the FEL. Moredetailed results will be discussed.
[1] K.Sakai, et al., IEICE TRANS. Electron,
E94-C (2011) 1861.

Fig.1 Raman spectra of the SWNTs grown with the
700 nm FEL.
Used excitation laser was 532 nm.

- 149 -

3P-18Synthesis of single walled carbon nanotubes by using
sputtered Co/Cu and Co/W as catalyst○Hua An, Kehang Cui, Rong Xiang, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Ever since their discovery, single walled carbon nanotubes (SWNTs) have attracted
intensive attention because of their special electronic properties and potential applications.
Unfortunately, the as-grown SWNTs are always a mixture of various chiralities, which limits
their application in nanoelectronics. Since the chirality determines the structure of SWNTs,
diameter control and chirality control are the prerequisite to obtain SWNTs withhomogeneous properties. Extensive researches have focused on the diameter-control andchirality-control growth of SWNTs. However, it is a critical challenge to grow single-chirality
SWNTs. Recently, tungsten-based bimetallic nano-clusters have been used as catalysts togrow SWNTs with a single chirality of (12, 6), resulting in an abundance higher than 92%[1].
In this study, we used two exotic bimetallic combinations Co/Cu and Co/W as catalysts togrow SWNTs by alcohol catalytic chemical vapor deposition (ACCVD) [2]. The catalysts
were prepared on silicon substrates by a simple sputtering method. The SWNTs werecharacterized by scanning electron microscopy (SEM), Raman spectroscopy, opticalabsorption spectroscopy and transmission electron microscopy (TEM). We found that
SWNTs obtained from Co/Cu catalyst have much smaller diameter than those grown fromconventional Co or Co/Mo [3]. Temperature-dependent studies clearly proved that the
introduction of copper facilitated the growth of small-diameter SWNTs at low temperatures.
Meanwhile, high-quality and uniform SWNTs were obtained when we used Co/W to grow
SWNTs. The chirality distribution and growth mechanism will be presented.
[1] F. Yang et al., Nature 510, 522 (2014).
[2] S. Maruyama et al., Chem. Phys. Lett. 360, 229 (2002).
[3] R. Xiang et al., ACS Nano 6, 7472 (2012).

Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 150 -

3P-19Control of In-Plane Orientation and Chirality of Single-Walled Carbon
Nanotubes using Hot-Walled Chemical Vapor Deposition Method
and Free Electron Laser○Daiki Kawaguchi1, Keisuke Yoshida1, Yusaku Tsuda1
Tomoko Nagata1, Nobuyuki Iwata1 and Hiroshi Yamamoto1
1

Department of Electronics & Computer Science,College of Science & Technology, Nihon
University, 7-24-1 Narashinodai, Funabashi, Chiba 274-8501 Japan

Single-walled carbon nanotube (SWNT) has many advantages for application, such as highconductance, maximum allowable current density and mechanical strength. However,
SWNTs can be both metal and semiconductor, depending on their chirality. Thus the controlof the chirality is required. The in-plane orientation of the SWNTs are also essential for theelectric devices.
We have succeeded in controlling the chirality and obtained all semiconductive SWNTs byirradiation of free electron laser (FEL) during growing process on SiO2/Si substrate [1]. The
irradiation of FEL may enhance the growth of SWNTs having specific bandgap, whichcorresponds to the photon energy of the FEL. We also succeeded in growth of in-planealigned SWNTs on crystal quartz. In this study, we report the simultaneous control of thechirality and in-plane orientation.
The SWNTs were grown by alcohol catalyst chemical vapor deposition (ACCVD) method
on ST-cut quartz substrate for the in-plane orientation. The catalyst was evaporated Co/Fe
nano-particles.
Fig. 1(a) shows the dynamic force microscope (DFM) image.
Well-oriented SWNTs were observed. Fig. 1(b) shows the Raman spectrum. Radial
breathing mode (RBM) signals indicates the growth of SWNTs having 1.00 nm and 1.06 nm
diameters.
The simultaneous control of the chirality and in-plane orientation will be reported in thepresentation.
(a)Fig. 1(b)(a) DFM image and (b) Raman spectra. Open circles indicate the peak arising from the substrate.

[1] K. Sakai et al. IEICE Trans. Electron. E94-C, 1861 (2011)
Corresponding Author: N. Iwata
Tel: +81-47-469-5457, Fax: +81-47-469-5457,
E-mail: iwata.nobuyuki@nihon-u.ac.jp- 151 -

3P-20The Effects of Hydrogen Atom on Cobalt Clusters in the Reaction
with H2O Investigated by 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

In the carbon nanotube growth, reduction processes with H2 on Co-related materials havebeen widely used to prepare catalysts or Co clusters. However after the preparation of thecatalysts, H2 have not been thought to play crucial roles on Co clusters but to react with nascentnanotube precursors directly. Here, we present salient differences between cobalt clusters, Con+,and hydrogenated cobalt clusters, ConH+, in the reaction with H2O, which was performed by
Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer.
The details of the experiment have been described elsewhere [1]. Con+ and ConH+ were
produced by a laser vaporization cluster source with a Co metal plate and a supersonic He jet.
These precursor clusters were trapped within an ICR cell and were then exposed to H2O at
1.2×10-4 Pa and at room temperature for 4 s. The product ions were mass analyzed after the
exposure.
Figure 1 shows the mass spectra of the precursor and the product ions. The intensity ratio
between Con+ and ConH+ was almost constant in the entire size range (Fig. 1a). After the
exposure to H2O, all Con+ were mainly converted into simple adsorption products of Con(H2O)+
without any size dependence (Fig. 1b). On the other hand, ConH+ were converted into Con(OH)+in the smaller size range (9 ≤ n ≤ 13) indicating that the hydrogen on the Co clusters act as apromoter to break H2O. The larger ConH+ clusters (13 ≤ n ≤ 18) were converted into simple
adsorption products of ConH(H2O)+. This enhancement effect of a hydrogen atom on Co
clusters has also been reported in the reaction with NO [2]. The observed salient difference
between Con+ and ConH+ suggests that the role of hydrogen should be investigated not as simple
hydrogen gas but as the catalyst system with Co clusters.
(a) before reactions with H 2O(b) after reactions with H 2O
+
Con

+

Con

+

Intensity / arb. units

ConH

Intensity / arb. units

Con(H2O)n= 9

n = 13+Con(OH)+n= 9
ConH(H2O)+n = 13+ConH
n = 17
−3

−2

−1
0
1
2
Relative Mass (m/z)

n = 17
3

−3

−2

−1

0

1

2
16
17
Relative Mass (m/z)

18

19

20

21

Fig. 1 High-resolution mass spectra of Con+ and ConH+ (a) before and (b) after reactions with H2O.
Horizontal axes show mass difference between Con+ and product ions.
[1] S. Maruyama, et al. Rev. Sci. Instrum. 61, 3686 (1990).
[2] T. Hanmura, et al. J. Phys. Chem. A, 111, 422 (2007).
Corresponding Author: T. Sugai, Tel: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 152 -

3P-21Synthesis of carbon nanotubes
by means of “molecular template epitaxial growth” approach○Liu Hong1,2, Akira Takakura1,2, Lawrence T. Scott3, Yuhei Miyauchi1,2,4, Kenichiro Itami1,2,5
1Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
2
JST-ERATO Itami Molecular Nanocarbon Project, Nagoya University,
Nagoya 464-8601, Japan
3
Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA
4
Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan
5
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University,
Nagoya 464-8602, Japan
Carbon nanotubes have been considered as promising nanomaterials in various fields
including chemistry, electronics, photonics and biologic science. The past two decades haveseen a rapid development in the production strategy of carbon nanotube, which includes arc
discharge, laser ablation and chemical vapor deposition (CVD), etc. Though mass productionof carbon nanotubes has been realized, several
shortcomings are still required to be overcome. First,
metal catalysts are normally needed. Second, hightemperature is necessary. Third, control of diameter andchirality of synthesized carbon nanotube is difficult. How
to synthesize structure-controlled carbon nanotubes withmetal-free processes at low temperature remains achallenge.
Here, we report our progress on “growth from
template” approach, namely molecular template epitaxial
growth (MTEG), in producing carbon nanotubes without Fig.1 Chemical structure of [9]CPP
using any metal catalyst. The template molecules used in and C50H10
this study are carbon nanoring ([9]cycloparaphenylene,[9]CPP) and molecular end-cap of nanotube (C50H10),
both of which have been seen as precursors of carbon
nanotube (Fig.1).[1,2] Template molecules were dispersed
on c-plane sapphire by spin-casting, and ethanol wasused as carbon source gas in the CVD process. In thecase of [9]CPP, the temperature of reaction could be as
low as 450 °C, which offered carbon nanotubes with adiameter range of 0.8-2 nm (estimated from radial
breathing mode of Raman spectra, Fig.2). As a contrast,
we found that C50H10-synthesized nanotubes owned
much less distribution of chirality and diameter range.
Details of the results will be discussed in the conference.
Fig.2 Raman spectra (excitation

wavelength:
532
nm)
of
[1] H. Omachi et al. Nat. Chem. 5, 572 (2013)[9]CPP-synthesized carbon nanotubes[2] L. T. Scott et al. J. Am. Chem. Soc. 134, 107 (2012)
measured at different locations. Inset:
radial breathing mode region.
Corresponding Author: K. Itami, Y. Miyauchi
Tel/Fax: +81-052-788-6098 (K. I) +81-052-789-5916 (Y. M)
E-mail: itami@chem.nagoya-u.ac.jp (K. I) miyauchi.yuhei@d.mbox.nagoya-u.ac.jp (Y. M)- 153 -

3P-22Hybridization of Semiconducting-Single-Walled Carbon Nanotubes andFullerene-Carrying Carbazole-Fluorene Copolymers○Fumiyuki Toshimitsu 1, Hiroaki Ozawa 1, Naotoshi Nakashima 1, 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, JapanThe combination of single-walled carbon nanotubes (SWNTs) and fullerenes is one of themost desirable systems for the development of nanotube-based electronics, such as organic
photovoltaic and optoelectronic devices. Highly purified semiconducting-SWNTs(sem-SWNTs) are suitable for such applications, because the efficiency of the
sem-SWNT-based optoelectronic devices has been limited due to the coexistence of themetallic-SWNTs. In addition, random molecular orientations between the sem-SWNTs andacceptors prevent the formation of efficient conducting pathways. Although hybrid materialsof covalently modified SWNTs and fullerenes with high power conversion efficiencies (PCE)have been developed,[1] the covalent nanotube modification lowers the intrinsic properties of
the SWNTs, thus leading to lower efficiency than the theoretical value. Recent reports on
hybridizing such components using bulk-hetero-junction method[2] address the sem-SWNT
purity and homogeneous composition issues simultaneously, yet the interaction between
fullerenes and the SWNTs is only a Van-der-Waals interaction, which is too weak to fix themolecular orientation of the fullerene moieties on the surfaces of the SWNTs for the better
performance of this class of composites.
Strategically developed conjugated polymers are one of the key techniques to enhance
sem-SWNT properties. Here we report the design and synthesis of new copolymers 1–3 thatare composed of fullerene-carrying carbazole and fluorene units with fluorene/carbazole
composition ratios of 1:1, 5:1, and 10:1 (for 1–3,
respectively; Fig. 1). Solubilization of SWNTs byusing these copolymers was examined by using
atomic force microscopy (AFM), photoluminescence(PL), and Vis-NIR absorption and Raman
spectroscopic analysis, and was found that 1) all these
copolymers acted as sem-SWNT solubilizers and 2)
the amount of the solubilized sem-SWNTs depended
on the copolymer composition ratios. Furthermore,
we propose optimized molecular structures andorientations between the fullerene moieties,
copolymer main chains, and the sem-SWNTs basedon molecular-mechanics calculations.
Figure 1. Chemical structures of copolymers 1–3.
[1] T. Umeyama, et al., Adv. Mater. 2010, 22, 1767–70.
[2] D. J. Bindl, et al., Nano Lett. 2011, 11, 455–60.
Corresponding Author: N. Nakashima
Tel: +81-92-802-2845, Fax: +81-92-802-2845,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 154 -

3P-23
Cytotoxicity of Carbon Nanohorns Enhanced by Too Much PLPEG○Maki Nakamura 1, Yoshio Tahara 1*, Shinsuke Fukata 1, Minfang Zhang 1, Sumio Iijima 1,2,
Masako Yudasaka 1
1

National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi,
Tsukuba 305-8565, Japan
2
Meijo University, 1-501 Shiogamaguchi, Nagoya 468-8502, Japan(*Current address: Torii Pharmaceutical Co., LTD. Sakura, Chiba 285-0808, Japan)

In biological studies of nanocarbons, their dispersion in the aqueous solution is requisite.
Various dispersants have been tested for nanocarbons, in which phospholipid polyethylene
glycol (PLPEG) is one of the good and non-toxic dispersants, having been used in theapplication studies of nanacarbons to therapy and diagnosis. The coverage of PLPEG
molecules on single-walled carbon nanohorn (CNH) surface is saturated at the monolayer
level as estimated from the PLPEG quantities adsorbed on CNHs and size measurements withdynamic light scattering method [1]. Under the mono-coverage condition, CNH cytotoxicity
is low [1]. On the other hand, it was found that cytotoxicity increased when the excess amountof PLPEG was used [2]. In this report, we discuss the reason for this abnormal toxicity resultscaused by the excess dose of PLPEG.
The CNHs were dispersed in phosphate buffer saline (PBS) with PLPEG(1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethylene glycol) 2000](ammonium salt)). PLPEG: CNH quantity ratios were 0.25, 0.5, 1, 2, and 3. These dispersion
solutions were added in dishes where RAW264.7 macrophage was cultured at 37 oC in air
contacting CO2 (5%). The dispersion solution and cell culture medium were mixed by rollingthe dishes. The final concentrations of CNHs were 0.01, 0.03, 0.1 and 0.3 mg/mL. To discuss
the toxicity mechanism, the quantities of CNHs engulfed by RAW264.7 were estimated bymeasuring 700-nm light transmittance of the cell lysates. The cells were lysed with CelLytic
M in the presence of protease inhibitor. After the centrifuge, aliquot of the supernatant wasused for the protein assay to estimate the cell numbers, and the remaining lysate wassonicated with a surfactant, Triton X. The obtained dispersion solutions were subjected to the
700-nm light transmittance, and the CNH quantities were estimated by using
absorbance-quantity calibration line. The particle sizes of CNHs remained in the cell culture
medium were measured with dynamic light scattering.
The results showed that when PLPEG : CNH = 2 or 3, the macrophage uptake quantity of
PLPEG-CNH was enhanced, leading to the decrease of cell viability. The mechanism of
higher uptake of PLPEG-CNH in larger PLPEG quantity could be ascribed to the
PLPEG-CNH agglomeration sizes in the cell culture medium increased at PLPEG : CNH = 3.
The reason for this agglomeration size increase will be discussed in the presentation.
[1] M. Yang, M. Wada, M. Zhang, K. Kostarelos, R. Yuge, S. Iijima, M. Masuda, M. Yudasaka. Acta
Biomaterialia, 9 (2013) 4744–4753.
[2] M. Nakamura, Y. Tahara, S. Iijima, M. Yudasaka, 1P-43, 42nd F-NT-G Symposium, 2012.
Corresponding Authors: M. Nakamura, M. Yudasaka, Tel: +81-29-861-6290, Fax: +81-29-861-6290,
E-mail: ma-ki-nakamura@aist.go.jp, m-yudasaka@aist.go.jp- 155 -

3P-24
Electrochemical properties of boron- and nitrogen-doped carbon nanohorn
aggregates○Ryota Yuge1, Shunji Bandow2, Masako Yudasaka3, Kiyohiko Toyama1, Sumio Iijima4,
Noriyuki Tamura1, and Takashi Manako1
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 type of nano-carbon materials such ascarbon nanotubes and graphenes, which are attractive having the high electrical conductivity,
high dispersibility, and large specific surface area. Recently, it has been reported thatnanocarbons and nitrogen- and/or boron-doped nanocarbons indicate the good performance aselectrocatalysts for oxygen reduction reaction (ORR) [2-4]. These are potentially low cost
catalysts for the fuel cell application because noble metals are not contained [2]. In this study
we prepared the nitrogen and/or boron doped SWNHs and controlled the doping
concentrations. We also investigated their electrochemical oxygen reduction activity.
SWNHs were prepared by CO2 laser ablation of a graphite and/or boron-contained graphitetarget at room temperature in the continuous-wave mode. The gas pressure in the growthchamber was sustained at 760 Torr by controlling the evacuation rate while the flow rate of
buffer gas of N2 or Ar was kept at 10 L/min. Boron and nitrogen doping concentrations were
controlled by adjusting the boron quantities contained in target and the flow rate ratio of Ar
and N2 buffer gases. The boron-, nitrogen-, and boron/nitrogen-doped SWNHs are denoted as
B-, N-, and BN-SWNHs, respectively. The non-doped SWNHs are denoted as Ar-SWNHs.
Ar-SWNHs and N-SWNHs indicated the aggregate structure with dahlia type morphology.
On the other hand, B-, and BN-SWNHs indicated the petal-dahlia type aggregate structure.
The amount of petals (= thin graphene sheets) increased in B- and BN-SWNHs, probably
because the boron acted as the graphite formation catalyst. In oxygen-saturated 0.1 molar
potassium hydroxide solution, electro-catalytic activity of BN-, B-, and N-SWNHs weresuperior to that of Ar-SWNHs. Their electrocatalyst activities were also compared with thoseof the conventional carbon materials. 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. Li, et al. Nature Nanotech. 7, 394 (2012).
[4] 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- 156 -

3P-25
Selective formation of zigzag-edges in graphene cracks○Miho Fujihara1, Ryosuke Inoue2,
Yutaka Maniwa2, Hisanori Shinohara1, Yasumitsu Miyata2, 3
1

2

Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan
3
JST, PRESTO, Kawaguchi, 332-0012, Japan

Graphene edges have attracted much attention due to their unique electrical and magnetic
properties. To understand these properties, it is highly desired to prepare clean, smooth, andstructure-controlled edges. Recently, such clean and smooth edges with armchair and zigzag
structure were realized by tearing suspended graphene under electron beam irradiation [1].
However, structure selective preparation of zigzag or armchair edges has not been achieved
yet. In contrast, molecular dynamics (MD) simulations has predicted that uniaxial in-planestress selectively produces the cracks with zigzag edges [2].
Here, we report the selective formation of graphene edges aligned in the zigzag orientation
by cleavage with thermally-assisted tensile stress (Fig. 1a). Graphene grains were grown frommethane on copper foil by using chemical vapor deposition at 1075 ºC. After cooling to room
temperature, we occasionally observed zigzag-shaped cracks in graphene (Fig. 1b).
Considering the grain edges which have the zigzag face, these cracks are found to propagate
parallel to the zigzag edges. Statistical analysis of the crack direction suggests that uniaxial
tension is applied to the notched of graphene grains around Cu grain boundary (Fig. 1c). The
origin of tension is probably due to the non-uniform lattice strain of graphene induced bythermal shrinking of Cu substrates as supported by Raman strain mapping. Furthermore, we
demonstrate the carrier tuning around graphene edges by applying the electric field to thecracks (Fig. 1d). Our findings pave the way for the fabrication and applications of smooth,long zigzag edges of graphene and other two dimensional materials.

Fig.1 (a) Schematic illustration of tearing graphene during the post-growth cooling process. (b) Opticalimage of graphene with zigzag-shaped cracks on Cu foil. (c) Histogram of angles between the crack direction
and Cu grain edges. Inset: optical image of graphene on Cu foil. (d) ID-VGS curve of a side gate field-effecttransistor (FET) using the graphene with a straight crack. Inset: optical image of the side gate FET.
[1] K. Kim et al. Nature Commun. 4, 2723 (2013).
[2] B. Zhang et al., Appl. Phys. Lett. 101, 121915 (2012)
Corresponding Authors: Y. Miyata, H. Shinohara
Tel: +81-42-677-2508, +81-52-789-2482, E-mail: ymiyata@tmu.ac.jp, noris@nagoya-u.jp- 157 -

3P-26The synthesis of graphene by thermal CVD process
without flowing gas containing carbon○Shiyo Morisako , Marina Tsujimoto , Masaru Tachibana
Department of Materials System Science, Yokohama City University,
Yokohama 236-0027, Japan
Graphene is one of the nano-carbon materials and has two-dimensional sheet structure ofSp2 carbon. Many studies have shown high career mobility and transmittance of graphene.
Because of such properties, graphene is expected to use as thin-film electrodes such as Indium
Tin Oxide (ITO). One of the most useful synthesis of graphene is Chemical Vapor Deposition(CVD), which needs high temperature and carbon sources like methane [1] or ethanol [2,3].
Using this synthesis, it is expected that a large amount of graphene used for industrial fields
can be provided easily.
We synthesized graphene by using simple alcohol CVD process which use ethanol as carbon
sources. As a result, we succeeded to synthesize mono or few layer graphene efficiently on
copper foils. Interestingly, graphene was also synthesized without ethanol. It seem that thereason of formation of graphene is remaining vapor of alcohol in CVD chamber or dissolving
carbon in a copper foil essentially as impurity. To investigate the factor of formation ofgraphene, we applied to two methods. At first, we annealed a copper foil substrate for an hour
without ethanol after cleaning inside of chamber by flowing argon gas (900 sccm) to remove
remaining absorbates. Subsequently, we washed the substrate and then annealed it again to
investigate the effect of dissolving carbon. At all experiments, the formation of graphene wasobserved by Raman spectroscopy.
Recently, similar results were reported in H2 plasma treatment without carbon sources [4].
The origin of synthesis might be also similar to that in our synthesis as mentioned above. In
this work, we determined the main factor of segregation of graphene by annealing without
ethanol. In addition, we measured optical property of graphene synthesized by annealing
without ethanol.
[1] Xuesong Li et al. Science. 324 (2009) 1312-1314[2] H Shinohara et al. Appl. Phys. Lett. 96 (2010) 263105[3] A. Omukai. Trans. Mater. Res. Soc. Jpn. 36(3) (2011) 359-362[4] R. Kato et al. Carbon. 77 (2014) 832-828
Corresponding Author: M. Tachibana
Tel: +81-45-787-2307
E-mail : tachiban@yokohama-cu.ac.jp- 158 -

3P-27Highly Uniform Bilayer Graphene on Cu-Ni Alloy Films○Yuichiro Takesaki1, Hiroki Hibino2, Masaharu Tsuji1,3, Hiroki Ago1,3,4
1

Graduate School of Engineering. Sciences, Kyushu University, Fukuoka 816-8580, Japan
2
NTT Basic Research Laboratory, NTT cooperation, Kanagawa 243-0198, Japan
3
Institute for Materials Chemistry Engineering, Kyushu University, Fukuoka 816-8580, Japan
4
PRESTO, Japan Science and Technology Agency, Saitama 332-0012, Japan

Controlling the number of layers is important for future applications of graphene, because
the number of layers strongly influences the electrical and thermal conductivities as well asmechanical strength of graphene. In particular, for semiconductor applications, bilayer
graphene (BLG) is more promising than monolayer graphene, because the tunable bandgap isrealized by applying a vertical electric field to BLG [1]. Recently, chemical vapor deposition(CVD) using a Cu catalyst has been widely used for the growth of monolayer graphene due to
its low carbon solubility. On the other hand, in order to synthesize few-layer graphene, atransition metal with high carbon solubility, such as Ni and Co, is added to Cu catalyst [2-4].
However, BLG grown by CVD are generally not uniform, and the growth mechanism and thestacking order are not well understood.
Here, we studied the growth of highly uniform BLG by ambient pressure CVD using
Cu-Ni binary metal films sputtered on c-plane sapphire substrates. Effects of the CVD
temperature, cooling profile, CH4 and H2 concentrations, and Cu-Ni ratio were thoroughly
investigated. We succeeded in growing highly uniform BLG (93% coverage), as shown in Fig.
1. In particular, the CVD temperature profile was found to increase the BLG area. From thelow-energy electron microscope (LEEM) analysis, we clarified that the second layer grows
underneath the first layer. We think that the first layer is catalyzed by the Cu-rich metal
surface, while the second layer segregates from the bulk Cu-Ni alloy (Fig. 2). Moreover, theLEEM revealed that there are four types of orientations in our BLG. We will also discuss on
the stacking order of BLG and its electrical property. Our work is expected to contribute tofuture development of graphene-based electronic devices.
Transmittance (%)

Wavelength (nm)
97
96
95
94
93
92
91

400

500

600

700

800

(a)

(b)

2L
50 μm
Fig. 1 Optical micrograph of transferredgraphene mainly consisting of BLG. Inset
shows the optical transmittance.

C

Cu

Ni

Fig. 2 Growth mechanism of BLG. (a) The first layer isgrown on Cu-rich surfaces. (b) The second layer issegregated from the Cu-Ni below the first layer.

[1] Y. Zhang et al., Nature, 459, 820 (2009). [2] Y. Wu et al., ACS Nano, 6, 7731 (2012).
[3] Z. Sun et al., ACS Nano, 6, 9790 (2012). [4] W. Liu et al., Chem. Mater., 26, 907 (2014).
Corresponding Author: Hiroki Ago, Tel&Fax: +81-92-583-7817, E-mail: ago@cm.kyushu-u.ac.jp- 159 -

3P-28Annealing time dependence of precipitation of high-quality multilayer
graphene using Al2O3 barrier and Au capping layers○Jumpei Yamada1, Manabu Suzuki1, Yuki Ueda1, Takahiro Maruyama2, and Shigeya Naritsuka1
1

Department of Materials Science and Engineering, Meijo University,
Nagoya 468-8502, Japan2
Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan

Electrical wire is one of the prospective applications of graphene, whose property isthought to be improved by the use of graphene. To realize excellent graphene-wire, it isimportant to grow a high-quality graphene with large domains. However, the growth ofgraphene with large-domain is still challenging in the state-of-the-art growth technique.
Multilayer graphene is necessary to flow a large current. The use of Al2O3 barrier and Au
capping layers was helpful to improve the quality of multilayer graphene grown by
precipitation method [1]. In this paper, the annealing time is varied to study the precipitation
mechanism of multilayer graphene in the precipitation method.
Au(20nm) / Ni(300nm) / Al2O3 (2nm) / a-C(5nm) layers were deposited on a sapphire using
electron-beam deposition for preparing the samples. The annealing time was varied from 30
to 60 minutes during the precipitation at 900oC in vacuum.
 It is found from Fig.1 that multilayer graphene with very low D peak was successfullygrown by the precipitation method. As shown in Fig.2, the thickness of the grapheneincreased with increasing the annealing time. While the proportion of 2-layers graphene was
80% at the annealing time of 30 min, 5-layers graphene occupied 60% of the whole surface atthe time of 60 min. In addition, the D/G ratio improved with the thickness, and it finallyreached to the excellent value of 0.024 on the sample annealed for 60 min. The precipitation
mechanism of multilayer graphene using both Al2O3 barrier and Au capping layers will be
discussed on the conference site.

Fig.1 Surface optical microscope images and, Raman
spectra of precipitated graphenes annealed for 30
and 60 minutes.

Fig.2 Layer distribution of precipitated graphenes
annealed for 30 and 60 minutes.

Reference: [1] M. Suzuki et al., 2014 MRS Fall Meeting & Exhibit, Boston, MA, USA, Nov. 31st-Dec. 5 (2014) K20.28.
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 and JSPS Grand-in-Aid for Scientific Research on
Innovative Areas (No.26105002).
Corresponding Author: J.Yamada Tel: +81-52-838-2387 E-mail: 100425324@ccalumni.meijo-u.ac.jp- 160 -

3P-29Evaluation of magnetism of chemically active sites
in graphene oxide / nanographene○Tomoki Yamashina1, Takuya Isaka2, Kadumi Inoue2, Yoshiaki Matsuo3, Kazuyuki Takai1,2,4
1

2

Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
Department of Chemical Science and Technology, Hosei University, Tokyo 184-8584, Japan
3
Graduate School of Engineering, University of Hyogo, Hyogo 671-2280, Japan
4
Research Center for Micro-Nano Technology, Hosei University, Tokyo 184-0003, Japan
The introduction of functional groups, edges, defects or strain is typical method for giving

chemical activity to graphene. For example, the edge structure gives graphene the half-fillededge states with a large density of states near the Fermi level, where the spin magnetism andchemically activity emerge as the singly occupied molecular orbital (SOMO) of aromatic
molecules. The oxygen-containing functional groups also give graphene a catalytic activity invarious reaction systems [1], where the stabilized radical states take an important role. In thisstudy, the correlation between the spin magnetism and chemical activity for graphene oxide(GO) and activated carbon fibers (ACFs) which is assembly of nanographene with a lot ofedges was investigated by the XRD, XPS, the magnetic susceptibility and GC-MS.
GO samples were synthesized by Brodie [2] and Hummers [3] methods. An oxidation
reaction from benzyl alcohol to benzaldehyde was carried out by using ACFs and GO as
catalyst to evaluate their chemical activities. The results of magnetic susceptibility are shownin Table 1, where Nspin, and const. are the spin density, and the temperature-independent term,
respectively. The smaller const. for Hummers GO (HGO) and Brodie GO (BGO) than that of
ACFs indicates the vanishment of -electron by oxidation. HGO exhibits extremely large Nspinin spite of tiny spin magnetism of BGO, suggesting the artifact by the contribution of the Mn
impurity originating from oxidant reagent. Judging from the Nspin, ACFs should contain thelarger amount of the chemically active sites than that of BGO. This is supported by the larger
GC-MS yield for oxidation of benzaldehyde by using ACFs than that by BGO. However, thereaction by using HGO catalyst results in even larger yield for benzyl alcohol than those with
ACFs and BGO, where dibenzyl ether appears as major product, and benzaldehyde is obtained
as byproduct. Thus, the presence of Mn impurity also significantly influences both themagnetism and the chemical activity of GO.

Table 1 Parameters of spin magnetism[1] C.Su, M.Acik, K.Takai et al, Nat. Commun., 3, 1298 (2012)[2] B. C. Brodie, Phil. Trans. R .Soc. Lond., 149, 249-259 (1859)[3] D. C. Marcano et al, ACS Nano, 4, 8, 4806–4814 (2010)

SampleNspin (g-1)

const. (emu∙g-1)

BGO

2.1 × 1018

−4.6 × 10−7

3.9 × 1019

−1.0 × 10−6

HGO

Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002,
E-mail: takai@hosei.ac.jp

ACFs- 161 -

6.5 × 1020

−3.3 × 10−7

3P-30Acid-treatment minimizes unintentional strain and doping of single-layer
graphene on SiO2 substrate in aqueous environments
Katsuya Masuda and ○Masahito Sano
Department of Polymer Science and Engineering, Yamagata University
Yonezawa, Yamagata, 992-8510, Japan
Graphene is a zero band gap semiconductor which can be electron- and hole-doped easily
due to a linear band dispersion at the Dirac point. It also has an atomically flat, planar surface
that is chemically stable in air and liquid. These properties make graphene a very attractive
material as a platform for electrochemical- and bio-sensing applications.
On the other hand, the same properties cause a problem that the electronic properties ofgraphene are easily affected by supporting substrates. It is well known that graphene on
SiO2/Si is unintentionally strained and hole-doped in air. Stain and doping levels differ fromsample to sample as well as position within a single graphene flake. It is also important thatthe liquid environment does not affect the electronic properties. Various amine compounds are
known to act as electron donors against single-walled carbon nanotubes. In particular,tris(hydroxymethyl)aminomethane (Tris), a compound that commonly used as buffer inbiochemical studies, is shown to reduce proteins by electron transfer through nanotubes [1].
For stable and reliable operation of graphene electronic devices, minimization of
unintentional strain and doping caused by both substrates and liquid is highly desirable.
In this study, we show that simply dipping the graphene on SiO2/Si in either acid or alkali
solution beforehand reduces the sample variation, improves stability against Tris, and brings
the graphene close to the state of freestanding using Raman microscopy.
(a)

(b)

1588

1588
1586

1584

G (cm-1)

G (cm-1)

1586

1582
1580
1578

1584
1582
1580

air

water 0.001 0.01
0.1
Tris (mol/L)

1578

1

air

water 0.001 0.01
0.1
Tris (mol/L)

Fig. 1. The G center frequency in air, water and various Tris concentrations for (a) the untreated samples, (b)the acid- and alkali-treated samples with rinsing (filled marks) and without rinsing (empty marks). The blackand red dashed line correspond to the values of graphite and freestanding graphene, respectively.
[1] T. Nakashima, M. Sano J. Phys. Chem. C 115, 20931 (2011).
Corresponding Author: M. Sano
Tel: +81-238-26-3072 E-mail: mass@yz.yamagata-u.ac..jp- 162 -

1

3P-31
Electric Double Layer Light-emitting Diodes of Monolayer WSe2
○Jiang Pu 1, Taiyo Fujimoto 2, Jing-Kai Huang 3, Lain-Jong Li 3,
Tomo Sakanoue 1, Taishi Takenobu 1,2,4
1

Department of Advanced Science and Engineering, Waseda Univ., Tokyo 169-8555, Japan2
Department of Applied Physics, Waseda University, Tokyo 169-8555, Japan3
Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
4
Kagami Memorial Laboratory, Waseda University, Tokyo 169-0051, Japan

Monolayer transition metal dichalcogenides (TMDCs) have emerged as potential candidates
for optoelectronic applications because of their unique optical properties [1]. Owing to theirspin-valley coupled system, TMDCs exhibited circular polarized photoluminescence andelectroluminescence (EL), which provide possibilities for realizing novel functionalities.
Recently, light-emitting diodes/transistors based on monolayer WSe2 have demonstrated [2,3].
Although these devices enable EL capabilities, they typically need split-gate architecture oroperate at lower temperature to obtain EL. Therefore, exploring new types of device
configuration which can commonly generate excitonic EL is highly required for further
advances. In order to achieve this goal, both formation of p-n junction and injection of highcurrent density need to be realized simultaneously at room temperature. In this paper, we
propose unique light-emitting structure, electric double layer light-emitting diodes (EDLEDs),
fabricated with WSe2 monolayers. The EDLEDs can self-organize dynamic p-n junction atroom temperature due to ion alignment when we applied lateral electric field to materials.
The large-area WSe2 films were synthesized on sapphire substrates through chemical vapor
deposition [4]. The gold electrodes were patterned on film surface, and then ion gels, gelationof ionic liquids, were spin-coated to form EDLEDs. When we applied the lateral potential
gradient which is larger than bandgap of WSe2, the p-n junction is electrostatically formed inchannel, which consequently yielded clear EL spectrum from fabricated WSe2 EDLEDs (Fig.
1). In addition, we can inject high current density (>10 kA/cm2) into these devices at room
temperature, resulting in direct observation of EL image from WSe2 channel. Our proposed
EDLEDs offer significant advantages for future TMDC-based optoelectronic devices.

Fig. 1 The schematic depiction (left) and EL spectrum (right) of a WSe2 EDLED[1] Q. H. Wang, et al. Nat. Nanotechnol. 7, 699 (2012).
[2] J. S. Ross, et al. Nat. Nanotechnol. 9, 268 (2014)..
[3] Y. J. Zhang, et al. Science. 344, 725 (2014)..
[4] J. K. Huang, J. Pu, et al. ACS. Nano. 8, 923 (2014).

- 163 -

Corresponding Author: T. Takenobu
Tel/Fax: +81-3-5286-2981
E-mail: takenobu@waseda.jp

3P-32
Effect of hydrazine adsorption on Graphene FET characteristic○Taichi Umehara1, Kazuyuki Takai1, 2, 3
1

2

Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
Department of Chemical Science and Technology, Hosei University, Tokyo 184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, Tokyo 184-0003, Japan

The introduction of guest species to graphene has been extensively studied, since theelectronic properties of atomic membrane are easily modulated by the surface adsorption [1].
Especially, molecular materials are promising adsorbate to modify graphene because of its
capability in material design in comparison with metal adsorbate. Hole doping has beenachieved by oxygen adsorption as a consequence of complex electrochemical processes,
resulting in novel gate-tunable kinetics of the charge injection to graphene [2]. However,electron doping is poorly studied in the field of molecule adsorption of graphene. In this study,
effect of the adsorption of hydrazine having electron-donating nature on graphene isinvestigated in terms of the transport properties.
Hydrazine monohydrate (N2H4͌H2O) was dropped to the channel region of graphene field
effect transistor prepared by exfoliation on SiO2 substrate, followed by drying under ambientcondition.
The gate voltage dependence of the electrical conductivity for graphene before and after
N2H4͌H2O adsorption is shown in Fig. 1. Before N2H4͌H2O adsorption, a p-type conduction
caused by resist residue and ambient gases appears without hysteresis. After N2H4͌H2O
adsorption, a n-type conduction is clearly shown with a large hysteresis. The reducing

remains even after drying process. N2H4 ͌ H2O isliquid phase in bulk with higher vapor pressure(boiling point 387 K) compared to molecules often
used in carrier doping (TCNQ etc.). It is suggested
that hydrazine is not bonded to graphene with form ofphysisorption by simple van der Waals forces but
chemisorption including the ionic bonding.

Conductivity σ (10-3 Ω-1)

natureof hydrazine successfully induces the charge transfer to graphene in spite of hysteresisby the presence of water having large electric dipole.
4Interestingly, the large amount of electron doping
3
2
1
0
-60

-30
0
30
Gate Vg (V)60[1] S. Xiao et al, Phys. Rev. B 82, 041406 (2010)[2] Y.Sato, K.Takai, T.Enoki, Nano Lett. 11 3468 (2011)

Fig. 1

Corresponding Author: Kazuyuki Takai,
Tel: +81-42-387-6138, Fax: +81-42-387-7002,
E-mail: takai@hosei.ac.jp

circles denote data under ambient condition,

Backgate-voltage dependence ofthe conductivity. Closed circles and open
and after hydrazine treatment, respectively.

- 164 -

3P-33
Kohn anomaly meets Fano resonance in G and G’ bands
Raman spectra of graphene○ Eddwi H. Hasdeo, Ahmad R.T. Nugraha, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
The interplay between electron-phonon and electron-electron interactions in graphene for the G band(~1600 cm-1) and G’ band (~2600 cm-1) is investigated theoretically. Around these phonon frequencies,
the presence of gapless linear energy bands (Dirac cones) in graphene strongly affects the phonon
energies, spectral broadening factors, and spectral lineshapes. One of the related phenomena is theKohn anomaly, in which the phonon energy (lifetime) becomes lower (shorter) due to the interaction
between a phonon and an electron-hole pair in the linear energy band [1]. Another importantphenomenon is the appearance of the asymmetric spectral lineshape of the phonon spectra, known as
the Fano resonance, which has long been observed in metallic nanotubes [2] and recently is observedin graphene as a function of Fermi energy [3]. The detailed mechanism behind those two phenomena
have been a long standing question for more than a decade.
Here we show that the Fano resonance in graphene originates from the interference between thephonon spectra and the electronic Raman scattering (ERS) spectra [4,5]. Furthermore, the Kohn
anomaly and the ERS should correspond to the same electron-hole pair excitation in the Dirac cones ofgraphene. Taking both effects into account, we are able to reproduce the experimentally observed
Fermi energy dependence of frequency shift, spectral linewidth, and spectral asymmetry of the G band
Raman spectra [5]. We extend this theory for the G’ band of graphene and we expect to explain the
behavior of frequency shift and spectral linewidth as a function of Fermi energy for the G’ band,
which is opposite to that of the G band.
[1] A. Jorio et al., “Raman spectroscopy in graphene related systems”, Wiley (2011).
[2] S. D. M. Brown et al., Phys. Rev. B 63, 155414 (2001).
[3] D. Yoon et al., Carbon 61, 373-378 (2013).
[4] E. H. Hasdeo et al., Phys. Rev. B 88, 115107 (2013).
[5] E. H. Hasdeo et al., Phys. Rev. B 90, 245140 (2014).
Corresponding Author: E. H. Hasdeo
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: hasdeo@flex.phys.tohoku.ac.jp- 165 -

3P-34
Surface plasmon excitations in graphene○ M. Shoufie Ukhtary, Eddwi H. Hasdeo, Ahmad R.T. Nugraha, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Collective oscillations of electrons can be excited on the surface of metal and these oscillations are
known as surface plasmons (SPs). The existence of SPs can be depicted by their dispersion relation
showing the relation between the plasmon frequency and wavevector. This relation can be obtained bysolving Maxwell’s equation on the surface (semiclassical model) or by using random phaseapproximation (RPA) of quantum mechanics. In the case of graphene, the SP dispersion for doped
graphene has been studied by some researchers using both the semiclassical model [1] and also the
RPA method [2], and these prove that doped graphene can sustain the SPs. However, to take anadvantage of the SP properties of graphene, we have to design a realistic system consisting ofgraphene and layered dielectric materials so that the SPs have a possibility to be excited.
Excitation of SPs can be realised by applying light with a certain frequency onto the designed system.
The wavevector of the light needs to match the SP wavevector of in order to have SPs excited, whichmight be achieved by utilizing total internal reflection of light [3]. A special arrangement of grapheneand the dielectric materials is necessary to create the total internal reflection. Analysis of the excitation
process is done by the transfer matrix method to obtain the electric field profile across the system andthen we can extract the absorption or reflection spectra from the field profile. By considering several
layer arrangements, we find that a much larger absorption of light by graphene could be obtained
rather than the famous 2.3% absorption of light, especially when we apply THz radiation to the system.
This phenomenon seems to depend on the doping level or Fermi energy of doped graphene and thus
the light absorption in graphene might be controllable.
[1] X. Luo et al., Material Science and Engineering R 74 (2013).
[2] E. H. Hwang and S. Das Sarma, Physical Review B 75 205418 (2007).
[3] S. A. Maier. Plasmonics. Springer (2007).
Corresponding Author: M. Shoufie Ukhtary
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: shoufie@flex.phys.tohoku.ac.jp- 166 -

3P-35Interlayer exciton in atomically thin heterostructures of transition metal
dichalcogenides○Daichi Kozawa1, Ivan Verzhbitskiy2, Alexandra Carvalho2, A.  H. Castro Neto2,
Kazunari Matsuda1, Goki Eda2
1

Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
2
National University of Singapore, 2 Science Drive 3, 117542, Singapore

Heterostructure of monolayer transition metal dichalcogenides (TMDs) possesses
atomically sharp interface between the two layers and forms intrinsic p-n junction.
Photoexcited electron-hole pairs spontaneously separate into the two layers, resulting information of interlayer exciton (Fig. 1a and b). This charge transfer is extremely fast processthat take place within 50 fs[1]. The TMD-based heterostructures are promising particularly in
optoelectronics such as photo sensing and photovoltaic applications taking advantage of theefficient charge transfer and strong light-matter interactions[2]. Here, we report photocarrier
relaxation in the heterostructures using photoluminescence (PL) and PL excitation
spectroscopy.
Heterostructure MoSe2/WS2 bilayer was fabricated on a quartz substrate using dry transfer
process of upper layer onto the bottom layer with PDMS elastic polymer. In PL spectra of
MoSe2/WS2 heterostructure (Fig. 1c), PL peak of the interlayer exciton lies below the bandedge emission of isolated MoSe2 by ~ 35 meV because of the intrinsic band offset (Figure 1b).
The redshift of the PL peak and smaller PL intensity suggest the observation of the interlayer
exciton. We further conduct PL excitation spectroscopy for the heterostructure to examine therelaxation of the interlayer exciton. We will discuss the detailed mechanism of thephotocarrier relaxation in the heterostructures.

Fig.1 a,b, Schematic atomic structure and energy diagram of the MoSe2/WS2 heterostructures withinterlayer exciton. c, PL spectra of MoSe2/WS2 heterostructure measured at room temperature. PL spectraof isolated monolayers MoSe2 and WS 2 are also shown for comparison.
[1] X. Hong et al., Nat. Nanotechnol. 9, 682 (2014).
[2] D. Kozawa et al., Nat. Commun. 5, 4543 (2014).
Corresponding Author: D. Kozawa
Tel: +81-774-38-3465
E-mail: d-kozawa@iae.kyoto-u.ac.jp- 167 -

3P-36
Optical characteristic of CVD grown monolayer WSe2
under high-density carrier doping○Keiichiro Matsuki1, Jiang Pu2, Kazunari Matsuda3, Lain-Jong Li 4, Taishi Takenobu1,2,5
12Department of Applied Physics, Waseda University, Shinjuku 169-8555, Japan
Department of Advanced Science and Engineering, Waseda Univ., Tokyo 169-8555, Japan
3
Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan4
Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
5
Kagami Memorial Laboratory, Waseda University, Tokyo 169-0051, Japan

Monolayer transition-metal dichalcogenides (TMDCs), such as MoS2 and WSe2, areattracting interest due to their direct band gap in monolayers, large binding energy of exciton,and spin-valley coupled system. Although their optical properties have been already reported
well, the effect of high-density carrier doping, which might lead to many-body effects, has not
yet been investigated. Recently, we have succeeded in the CVD-growth of large-area samples
and their application into the electric double layer transistors (EDLTs), in which one canaccumulate extremely high density carriers (> 1020/cm3) [1-4]. Therefore, in this research, we
tried to measure optical properties of WSe2 monolayers under high-density carrier doping.
Figure 1 shows the device structure of WSe2 EDLTs. Large-area monolayer WSe2 wassynthesized by CVD method on a sapphire substrate and Au/Ni electrodes were thermallydeposited on it. As the electrolyte, we selected the ion gel, which is the mixture of ionic liquid([EMIM][TFSI]) and organic polymer (PS-PMMA-PS). As shown in Fig. 2, we successfully
accumulated both hole and electron carriers, and controlled the resistance of WSe2 monolayer
by gate voltage application, which is the signature of carrier doping and estimated highest
carrier density is approximately 2 × 1020/cm3.
For optical characteristics, we used 532-nm incident light and collected photoluminescence(PL) spectra at room temperature in vacuum. The spectra were measured under both hole andelectron carrier accumulation. Figure 3 reveals PL spectra at different gate voltages and we
observed clear spectral changes under high-density carrier accumulation. However, these PL
peaks are not simply explained by exciton or charged exciton. The mechanism will be
discussed at the meeting.

Fig.1. Device structure

Fig.2. Transister characteristics Fig.3. PL characteristics[1] A. M. Jones et al., Nature Nanotech. 8, 634 (2013), [2] K. F. Mak et al., Nature Nanotech. 12, 207 (2013)[3] J. K. Huang et al. ACS Nano. 8, 923(2014), [4] J. Pu et al., Nano Lett. 12, 4013(2012)
Corresponding Author: Taishi Takenobu, Tel&Fax: +81-3-5286-2981, E-mail: takenobu@waseda.jp- 168 -

3P-37
Photon energy dependence of angle resolved photoemission
spectroscopy in graphene○ Pourya Ayria1, Eddwi H. Hasdeo1, Ahmad R.T. Nugraha1, Shin-ichiro Tanaka2 and Riichiro Saito1
12

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

The institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka
567-0047, JapanThe dependencies of angle-resolved photoemission spectroscopy (ARPES) for different photon
energies and light polarization near Dirac point of graphene are studied theoretically. Recently, Tanaka
et al. showed an interesting ARPES results in which polarization dependent on ARPES intensitychanges its character as a function of photon energy [1]. Near the 𝐾𝐾 point of graphene, along of the𝛤𝛤 − 𝐾𝐾 direction 𝜋𝜋 ∗ band is brightened by s-polarized light (s-branch), while along the 𝐾𝐾 − 𝑀𝑀 direction
𝜋𝜋 ∗ band is brighten by p-polarized light (p-branch) due to the interference between carbon atom A andB wavefunctions [2]. The experimental observation reveals that the intensity of p-branch comparedwith s-branch becomes dominant for specific photon energy even though for various linear lightpolarizations. The origin of this dependency in ARPES can be explained by the concept of electronphoton matrix elements effect in which the final state of photoelectron has the crucial impact onobservation ARPES intensity [3].
Therefore, in this work, we study the electron-photon matrix elements effect in ARPES of graphene
theoretically. In order to find out the impact of the matrix elements, the final states energy andwavefunction of the excited electron are expanded by the first principle calculation [4]. Changing
incident photon energy allows us to access different final state energy. However, electron-photon
dipole selection rule imposes that transition to some final states are allowed and some are not.
Therefore, by considering these conditions, the theoretical calculation reproduces the experimental
observation. Moreover, the calculation of the electron-photon dipole vector for various final energies
clarifies the origin of the dramatic increase of ARPES intensity in the p-branch. We find that the
number of the final states which results in dipole vector in y direction along the 𝛤𝛤 − 𝐾𝐾 direction for the𝜋𝜋 ∗ band is less than the number of the final states with x direction along the 𝐾𝐾 − 𝑀𝑀 direction
particularly for a specific region of band energy. Hence, the contribution of dipole vector in x direction
compared with y direction at this region in ARPES intensity has crucial effect on increasing ARPES
intensity of the p-branch.
[1] Shin.ichiro.Tanaka et al., [private communication][2] C. Hwang et al., Phys. Rev. B. 84, 125422 (2011).
[3] A. Damascelli et al., Rev. Mod. Phys. 75, 155414, 473 (2003).
[4] Paolo Giannozzi et al., J. Phys. Cond. Matt. 21, 395502 (2009).
Corresponding Author: P. Ayria
TEL: +81-22-795-5719, FAX: +81-22-795-5719, E-mail: pourya@flex.phys.tohoku.ac.jp- 169 -

3P-38
Local electric field effects on nearly free electron states of graphene
nanoribbons○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].
Moreover, under the strong lateral electric field, we found that the nearly free electron (NFE)
state shifts downward and crosses Fermi level [2]. In this work, we study the detailed
electric-field dependence of NFE state of graphene nanoribbons based on the density
functional theory with combining the effective screening medium method.
We consider the graphene nanoribbons under parallel(degree) to perpendicular (degree) electricfield as shown in Fig. 1. Figure 2 shows the eigen valueof NFE states of graphene nanoribbons as a function of
the external electric field. In the parallel electric field,
NFE state at the ribbon side rapidly shift downward withincreasing the electric field, while the NFE state
distributed above and below the ribbon is insensitive tothe field. In the normal electric field, both NFE states are Fig.1 Structural model of rotatednanoribbons under an electric field.
insensitive to the electric field. These results imply thatthe electric field concentration around the ribbon edges enhances the decrease the electrostatic
potential around the edge atomic site. Thus, the mutual arrangement and shapes of graphene
nanoribbons with respect to the electric field is important to control the energy of NFE states.
(a) Parallel electric field (=0)(b) Normal electric field (=90)

Fig.2 Eigen value of NFE state of graphene nanoribbons[1] A. Yamanaka and S. Okada, Jpn. J. of Appl. Phys. 53, 06JD05 (2014).
[2] A. Yamanaka and S. Okada, Appl. Phys. Express 7, 125103 (2014).
Corresponding Author: A. Yamanaka
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: ayamanaka@comas.frsc.tsukuba.ac.jp- 170 -

3P-39Evaluation of Graphene Quality by Raman Rapid Chemical Imaging
Mamoru Komatsu, Kaori Umeyama, Noriaki Nishikawa, Mark H. Wall*
Thermo Fisher Scientific K.K., Chemical Analysis Division, Yokohama 221-0022, Japan
Graphene holds great potential for use in a variety important areas that include electronics,
energy storage, high strength composites and sensing technologies, to name a few. Graphene
has demonstrated exceptional barrier properties, being impenetrable to even helium. Coupledwith the fact that the material is also optically transparent this behavior has attracted intenseinterest in the material science area towards using graphene as a barrier layer in a variety of
applications. In this poster, we show how Raman imaging can be used to gain important
insight with respect to critical parameters and mechanisms that govern the nucleation andgrowth of graphene via chemical vapor deposition (CVD) (Fig 2 & 3). This poster alsopresents preliminary work investigating theprotective capabilities of graphene employing theuse of rapid Raman imaging (Fig 4-6).
Additionally, this poster introduces the latest tool
available to obtain Raman imaging of grapheme,
the Thermo Scientific™ DXR™xi Raman imaging
Fig 1. DXRxi Raman Imaging Microscope
microscope(Fig 1).
Raman chemical imaging of graphene samples
G bandSiO2/Si

2D bandSingle-layer
GrapheneFig 2: Raman chemical
image of island growth ofmonolayer graphene grownon Cu and transferred to
SiO2/Si. Peak-height-ratio
was used to generate theimage. Red regions
represent 2D band peak
(2700-2800cm-1), and theblue regions represent Gband peak (1580-1590cm-1).
- 50 × 50 micron area
- 10 co-addition scans- Collection time: 16.7
minutes.

Fig 3: Figure 3: Raman
chemical image of hexagonalgraphene islands that has beentransferred to SiO2/Si. MCR
was applied to generate theimage.Red regions are
single-layer graphene and theblue regions are SiO2/Si.
- 175 × 175 micron area
- 10 co-addition scans- Collection time: 3.4hours.

*Corresponding Author: Dr. Mark H. Wall
Thermo Fisher Scientific, Madison, WI, U.S.A.
E-mail: mark.wall@thermofisher.com

Fig 4: Optical image of single
layer graphene coated Cu

Fig 5: Raman chemical image ofintensity scale associated with
642cm-1 band of CuOX

Fig 6: Raman chemical image ofintensity scale associated with
1370cm-1 band (D band)- 171 -

3P-40
CVD synthesis of high-quality h-BN films for heterostructure devices
Yuki Uchida,1 Tasuku Iwaizako,1 Masaharu Tsuji,1,2 and Hiroki Ago1,2,3
Graduate School of Engineering Sciences, Kyushu University, Fukuoka 816-8580, Japan
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8580, Japan
3
PRESTO, Japan Science and Technology Agency, Saitama 332-0012, Japan
1

2

Recently, heterostructures of various layered materials have attracted a great deal of interest
due to their unique properties and promising applications in electronics and photonics. Amongthem, hexagonal boron nitride (h-BN), a honeycomb lattice of boron and nitrogen atoms, is a goodcandidate as an atomically thin insulating material. Its atomically smooth structure, the absence of
charge impurities, and large band gap (5.9 eV) make h-BN a promising material for heterostructuredevices. It has been demonstrated that in graphene field-effect transistors (FETs) the insertion ofan exfoliated h-BN flake in the interface between single-layer graphene and SiO2 dramaticallyincreases the carrier mobility of the graphene [1,2]. However, for practical applications,development of large-area growth of h-BN sheets is essential. Here, we present our study on
chemical vapor deposition (CVD) growth of large h-BN sheets on heteroepitaxial Cu(111) films.
A thin film of Cu(111) was sputtered onto c-plane sapphire substrate at 250 ºC to improve theCu crystallinity. h-BN was then grown on the Cu surface by ambient pressure CVD at 1050 ºC
using ammonia borane (NH3BH3) as a precursor in the flow of H2 and Ar gasses. Figure 1 shows
optical microscope images of the Cu surface reacted with ammonia borane for 50 min. The film ofh-BN completely covered the center of the Cu surface, while isolated triangular h-BN domains canbe seen at the edges of the Cu surface. We found that that the triangular h-BN domains areoriented in two directions (Figure 1C), suggesting the epitaxial growth of h-BN on the Cu(111)
surface. When increasing the CVD time to 60 min, the whole Cu surface (1 cm2) was fully
covered with h-BN. Comparison of graphene FETs measured with and without h-BN sheet will bealso shown at the Symposium.

Fig. 1 Optical micrographs of the Cu surface taken at three positions. To visualize h-BN sheets, the Cu
substrate was baked in air which makes clear contrast due to slight oxidation of the Cu surface.
[1] J. B. Oostiga et al., Nat. Mater., 7, 151 (2008). [2] C. R. Dean et al., Nat. Nanotech., 5, 722 (2010).
Corresponding Author: Hiroki Ago, Tel&Fax: +81-92-583-7818, Email: ago@cm.kyushu-u.ac.jp- 172 -

3P-41
Electric field control of thermoelectric properties in WSe2
○Takahiko Iizuka 1, Masaro Yoshida 1, Sunao Shimizu 2, Yoshihiro Iwasa 1, 2
1Quantum-Phase Electronics Center (QPEC) and Department of Applied Physics,
The University of Tokyo, Tokyo 113-8656, Japan
2
RIKEN Center for Emergent Matter Science (CEMS), Wako 351-0198, Japan

Layered transition metal dichalcogenides (TMDs) have attracted growing interest in
remarkable electric transport and optical properties. However, the experimental researches ofthermoelectric properties are limited although theoretical predictions imply highthermoelectric performance especially in mono or few-layer systems [1-3].
Thermoelectric figure of merit (ZT) is expressed as S2/ρκ, where ρ, S, κ are the electricalresistivity, the Seebeck coefficient, and the thermal conductivity. These are in a relation of
trade-off as a function of carrier density and thus the optimization against the carrier density isdesired for all materials. In this sense field effect carrier control, in particular, using
electric-double-layer transistors (EDLTs) offers a powerful means for this purpose, because it
enables us the continuous tuning of carrier density simply changing gate voltages.
In this presentation, we report the electric field control of thermoelectric properties in
Tungsten diselenide (WSe2), which is an archetypal member of semiconducting TMDs. Single
crystals of WSe2 can be easily mechanically exfoliated and the atomically flat surface is oneof the ideal platforms for EDLT technique [4]. We
made a micro EDLT-device of exfoliated WSe2 thinflake and measured its gate voltage dependence of
the Seebeck coefficient S and the electrical resistivity
ρ. For the Seebeck coefficient measurement, anelectrode separated from the flake is used as a heater
creating a temperature gradient. Two electrodes
attached to the flake are used as local resistancethermometers with four-terminal method. Thoseelectrodes are also used as voltage probes while they
are used as source and drain terminals for theelectrical conductivity measurement.
Fig.1 An optical microscope image of a
We observed the ambipolar FET operation and WSe
2 EDLT-device
large evolution of the Seebeck coefficient including
the sign change. This is the first observation of the Seebeck coefficient in the electron doped
WSe2 thin flake. We also estimated the power factor P = S2/ρ, which is crucial forthermoelectric performance, and found peaks as a function of gate voltage both for electronand hole-doping. The optimized power factor reached 2000 μW/mK2, implying that WSe2 is apromising thermoelectric material.
[1] J. Wu et al., Nano Lett. 14, 2730–4 (2014).
[2] D. Wickramaratne et al., J. Chem. Phys. 140, 124710 (2014)[3] W. Huang et al., Phys. Chem. Chem. Phys. 16, 10866–74 (2014)[4] Y. Zhang et al., Science 344, 725–8 (2014)
Corresponding Author: T. Iizuka
Tel: +81-3-5841-6822, Fax: +81-3-5841-6822,
E-mail: iizuka@mp.t.u-tokyo.ac.jp- 173 -

3P-42
Influence of Electric Double Layer Carrier Injections on Optical
Absorption Spectra of CVD synthesized Multi-layered MoS2 and WS2 thin
films
○Kotaro Homma, Hideki Kawai, Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Minami-Osawa 192-0397, Japan
Transition metal dichalcogenides (TMDCs) are atomically thin two dimensional
semiconducting crystals. TMDCs have a strong spin-orbit coupling originated from the dorbitals of the heavy metal atoms, which is distinct characteristic from graphene and carbon
nanotubes.1 The conduction and valence-band edges are located at the K points of the 2D
hexagonal Brillouin zone, and the strong spin-orbit coupling induces the spin splitting at thevalence band top. In the case of their monolayer and 3R phase crystals2, the inversion
symmetry is broken in the samples. As a result, spin and valley are coupled, leading various
approaches to manipulate the valley degree of freedom of carriers.1
For the manipulation of electronic states of TMDCs, electric double layer carrier injection
techniques are widely used, and various physical properties have been manipulated, such as
superconducting states and circular polarized light emissions.3 However, whether the carrier
injection can selectively inject holes on the one of the splitting electronic states has not beenclarified yet. Such selective carrier injection will contribute to the valleytronic applications.
Previously we have tuned optical absorption and thermoelectric properties of single-wallcarbon nanotubes using electric double layer carrier injections. 4 To clarify the above question,in this study, we investigated the influence of electric carrier injections on optical absorption
spectra, especially A and B exciton optical absorption bands, which are caused by the spin
splitting, of multi-layered MoS2 and WS2 thin films, which were synthesized by chemical
vapor deposition methods.
Figure 1 shows the optical absorption spectra of multi-layered MoS2 thin films as afunction of potential shift. As shown in the figure, the A and B exciton optical absorption
bands are clearly identified. When the electrons are injected to the bottom of conduction
bands, we found that the A and B exciton bands are disappeared at the same time, which inagreement with the electronic structures. However, although we tried to extract electrons fromthe top of the valence bands, as shown in the figure, nothing has changed in the opticalabsorption spectra. The result indicates thatelectrons cannot be extracted from our CVD
grown MoS2 due to the presence of defects,
suggesting importance to prepare a film withhigh crystallinity.

Reference: [1] Xiao et al., PRL 108 196802(2012), [2] Suzuki et al., Nat. Nanotech. 9, 611
2014, [3] Zhang et al., Science 344 725 (2014),
Zhang et al., Nano Lett. 12 1136 2012, Ye et al.,Science 338 1193 (2012) [4] Yanagi et al., Adv.
Mater. 23 2811 (2011), PRL 110 86801 (2013),
Nano Lett. 14 6437 (2014)

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

Fig. 1 Influence of Electrochemical doping
on optical absorption spectra of CVD grownmultilayered MoS2 thin film.

- 174 -

3P-43
Preparation of Nb2O5-Graphene Nanocomposites and Kinetics for
Photocatalytic Degradation of Organic Dyes
Hae Soo Park, ○Jeong Won Ko and Weon Bae Ko
Department of Chemistry, Sahmyook University, Seoul 139-742, South Korea
Niobium pentoxide (Nb2O5) nanoparticles were synthesized using niobium (V) chloride andpluronic F108NF as the precursor and templating agent, respectively. The Nb2O5-graphene
nanocomposites were placed in an electric furnace at 700 °C and calcined under Ar
atmosphere for 2 h. The morphology, crystallinity, and photocatalytic degradation activity ofthe samples were characterized by X-ray diffraction, transmission electron microscopy,
scanning electron microscopy, and UV-vis spectroscopy. The Nb2O5-graphene
nanocomposites were worked as a photocatalyst in the photocatalytic degradation of organicdyes under 254 nm UV light; the organic dyes used were methylene blue (MB), methyl
orange (MO), rhodamine B (RhB), and brilliant green (BG). The photocatalytic degradation
kinetics for the aforesaid dyes were determined in the presence of the Nb2O5-graphene
nanocomposites.

Fig.1 Kinetics of the degradation of (a) MB, (b) MO, (c) RhB and (d) BG with the synthesized
Nb2O5-graphene nanocomposites[1] F. Hashemzadeh, R. Rahimi and A. Ghaffarinejad, Ceram. Int., 40, 9817 (2014).
[2] S. K. Hong, J. H. Lee and W. B. Ko, J. Nanosci. Nanotechnol., 11, 6049 (2011).
Corresponding Author: Weon Bae Ko
Tel: +82-2-3399-1700, Fax:, +82-2-979-5318
E-mail: kowb@syu.ac.kr- 175 -

発表索引
Author Index

Author Index<A>
Abe, Shigeaki
Abe, Yurika
Achiba, Yohji
Ago, Hiroki
Aikyo, Yusuke
Airya, Pourya
Akabori, Masashi
Akasaka, Takeshi
Akashi, Ryosuke
Akatsu, Takashi
Akiyama, Kazuhiko
Akizuki, Naoto
An, HuaAndo, Tsuneya
Anisimove, Anton
Aonuma, Shuji
Aota, Shun
Aoyagi, Shinobu
Arai, Miho
Arakawa, Yasuhiko
Araki, Takuma
Arita, Ryotaro
Asaka, Koji
Ayria, Pourya

1P-12
2P-41
1-1, 2-7, 2P-8,
2P-41
2P-28, 3P-27, 3P-40
1P-26
1P-2
3-2
2P-5, 3P-4, 3P-5
3-7
2P-38
2-5
1P-5, 2P-11
3P-18
2-10
2-1
2P-15
1P-5
2P-1
3-4
3P-11
2P-20
3-7
3P-14
3P-37

<B>
Balch, Alan L.
Bandow, Shunji
Bégin-Colin, Sylvie
Beniya, Atsushi
Bianco, Alberto
Bordacs, Sandor
Braam, Daniel

2P-5, 3P-4
1P-44, 3P-24
1-8
3P-8
1-8
3-7
1P-26

<C>
Carlson, Robert M. K.
Carvalho Alexandra
Castro Neto, A. H.
Chechetka, Svetlana
Chen, GuohaiChen, Xiao
Chen, Zhongming
Chiashi, Shohei
Chiba, Kazuki

Chiba, Takaaki
Cui, Kehang
Cuoug, Nguyen Thanh
Czank, Thomas

2-1, 2-2
2-1, 3P-18
2P-35
1P-2

<D>
Dahl, Jeremy E. P.
Dao Duy, Thang
Dong, Baojuan
Dresselhaus, M. S.

2P-26
1P-26
1P-43
1P-41

<E>
Eda, Goki
Endo, Hitomi
Ezawa, Motohiko

1P-29, 3P-35
2-7, 2P-8, 2P-41
1P-33, 1P-34, 1P-35<F>
Fernández-Lázaro, Fernando 2P-4
2P-26
Fokina, Natalie A.
2P-4
Font-Sanchis, Enrique
1-5
Fujigaya, Tsuyohiko
3P-25
Fujihara, Miho
1-4, 1P-14, 3P-3
Fujii, Shunjiro
3P-31
Fujimoto, Taiyo
2-9
Fujimoto, Yoshitaka
2P-42
Fujiwara, Akihiko
3P-23
Fukata, Shinsuke
1-5
Fukumaru, Takahiro
1-3
Fukuzawa, Masashi
2P-4
Fukuzumi, Shunichi
2P-19
Furuta, Hiroshi
3P-7
Futaba, Don<G>
Gao, Xiang
Guo, Huaihong

2P-26
3P-35
3P-35
1-8
3P-7
3-8
1P-15
1P-11, 1P-18, 2-2,
2P-22, 3-8, 3P-8,
3P-18, 3P-20
2-5- 177 -

<H>
Hara, Hideyuki
Harada, Yusaku
Haruta, Naoki
Haruyama, Junji
Hasdeo, Eddwi H.
Hasdeo, Hesky
Hasegawa, Kei
Hashimoto, Kenro

2P-2
1P-41, 1P-43

2-4
1P-17
2-6, 2P-31
1P-33, 1P-34, 1P-35,
1P-36
2-11, 3P-33, 3P-34
1P-31, 3P-37
1P-10, 1P-15, 1P-17,
1P-19, 1P-21
1-1

Hasobe, Taku
Hata, Kenji
Hatakeyama, Kazuto
Hatta, Akimitsu
Hattori, Yoshiyuki
Hayase, Shohei
Hayashi, Hironobu
Hayashi, Yutaro
Hibino, Hiroki
Higashide, Noriyuki
Hiraiwa, Atsushi
Hirakawa, Takuya
Hirano, Atsushi
Hirano, Kazutaka
Hirano, Yu
Hiroshiba, Yasuhiro
Hirotani, Jun
Homma, Kotaro
Homma, Naoki
Homma, Yoshikazu
Honda, Atsushi
Honda, Shiro
Hong, Liu
Honma, Tomohiro
Hoshino, Ryo
Huang, Jing-Kai<I>
Ichihashi, Toshinari
Iijima, Sumio
Iizuka, Takahiko
Iizumi, Yoko
Ikehara, Yuzuru
Ikuma, Naohiko
Ikuta, Taro
Imai, Kentaro
Imai, Yasuhiko
Imamura, Saneyuki
Imazu, Naoki
Inaba, Masafumi
Inoue, Kadumi
Inoue, Naoko
Inoue, Ryosuke
Inoue, Taiki
Isaka, Takuya
Ishii, Akihiro
Ishii, Satoshi
Ishikawa, Ryo

2P-4
3P-7
1P-37
2P-19
1P-38
1-6, 3-10
2S-5
1P-24
2P-28, 2P-32, 3P-27
2P-17
2-3
1P-14
1-4, 1P-14, 2P-18
2P-21
1P-9, 2-3
1P-1
3P-12
3P-42
3P-8
2-8, 3P-8
2P-20
1S-2
3P-21
1P-36
1P-24
3P-31

1-7
1-7, 2P-29, 3P-23,
3P-24
3P-41
1-7, 2P-29
1-7
3P-2
1P-13
1P-24
2P-42
3P-11
1S-2
1P-9, 2-3
3P-29
2P-44
2P-30, 3P-25
1P-11, 3P-18
3P-29
1P-4, 2-12, 2-13,
2P-16, 2P-17, 3P-11
1P-26
1P-41

- 178 -

Iwata, Nobuyuki
Izumiyama, Akinori

1P-8
3P-6, 3P-21
2-8
3-2
2-8
2P-20
2P-43
3P-40
1P-35
3P-11
2P-42, 2P-44, 3-3,
3-7, 3P-41
1P-24, 3P-17, 3P-19
1P-28

<J>
Jeon, Il
Jiang, Ming
Jinnouchi, Ryota
Jippo, Hideyuki
Juhasz, Gergely

2-1
2P-16, 2P-17
1P-1
2P-36
2P-12

Ishiyama, U
Itami, Kenichiro
Ito, MasahiroIto, TakahiroIto, Yusuke
Itoh, Chihiro
Iwahara, Naoya
Iwaizako, Tasuku
Iwaki, Ryoma
Iwamoto, Satoshi
Iwasa, Yoshihiro<K>
Kako, Masahiro
Kamijo, Junichi
Kanahashi, Kaito
Kanbara, Takaki
Kanda, Shouhei
Karousis, Nikolaos
Katagiri, Yoto
Katagiri, Yuto
Kataoka, Yosuke
Kataoka, Yousuke
Kataura, Hiromichi
Kato, Hiroki
Kato, Sho
Kato, Tateaki
Kato, Yuichi
Kato, Yuichiro K.
Katumoto, Shingo
Kauppinen, Esko I.
Kawabata, Kosuke
Kawaguchi, Daiki
Kawahara, Kenji
Kawai, Hideki
Kawakami, Hiroki
Kawano, Saki

2P-5, 3P-5
1P-33
2P-35
1P-26
2P-14
3P-4
1P-34
1P-33
3P-9
3P-10
1-4, 1P-5, 1P-14,
2P-18, 3P-3
2-8
1S-3
1P-33
1-3
1P-4, 1P-7, 2S-6,
2-12, 2-13, 2P-16,
2P-17, 3P-11
1P-33, 1P-34
2S-4, 2-1, 2-2
1P-15
3P-17, 3P-19
2P-28
2P-14, 3P-42
2P-1
3P-1

Kubuki, Shiro
Kumamoto, Yusuke
Kuriya, Masaaki
Kushida, Soh
Kusuda, Hiroyuki
Kusunoki, MichikoKuwabara, Junpei
Kuwahara, Yuki

1P-9, 2-3
2P-4
2P-6
1P-36
1P-10
3P-4
1P-24
2P-42
2P-15, 3-11
2P-39
3P-12
2P-20
2P-14
1P-27, 2P-23, 2P-26,
2P-40, 3S-9
3P-43
3P-43
2P-25
3-2
2P-32
1-1, 2-7, 2P-8,
2P-41
1-1
1P-38
1P-37
2P-34
3P-2
3P-39
2P-15, 3-11
3-6
1P-26
2-9
1P-44
1P-36
3P-16
1P-29, 2P-34, 3-5,
3P-35
2-5
2-12, 2P-16
1P-17
1P-26
1P-44
1P-9, 2-3
1P-26
2P-9

<L>
Lee, Chih-Yu
Li, Lain-Jong
Li, Shu-Hui

1P-9, 2-3
2P-35, 3P-31, 3P-36
2P-2

Kawarada, Hiroshi
Kawashima, Yuki
Kigure, Shota
Kikuchi, Ryo
Kim, Dong Young
Kimura, Masato
Kimura, Ryoya
Kimura, Shigeru
Kimura, Takahide
Kishimoto, Ken
Kishimoto, Shigeru
Kisoda, Kenji
Kitamura, Yoshimasa
Kitaura, Ryo
Ko, Jeong Won
Ko, Weon Bae
Kobayashi, Keita
Kobayashi, Yoshihiro
Kobayashi, Yu
Kodama, Takeshi
Kodama, Takuya
Kogane, Kennta
Koinuma, Michio
Koirala, Sandhaya
Kokubo, Ken
Komatsu, Mamoru
Komatsu, Naoki
Konabe, Satoru,
Kondo, Takahiro
Koretsune, Takashi
Kosugi, Yuta,
Koyata, Miho
Kozawa, Akinari
Kozawa, Daichi- 179 -

Li, Yan
Li, Zong-Jun
Liu, Gang
Liu, Hsiang
Liu, Xuqing
Lorke, Axel
<M>
Machida, Tomoki
Machiya, Hidenori
Maeda, Yutaka
Makino, Tatuya
Manako, Takashi
Maniwa, Yutaka

1S-1, 1P-6, 1P-16
2P-2
3-11
1P-31
3P-11
1P-26

3-4
3P-11
3P-4
1P-34
3P-24
1P-22, 1P-25, 2P-14,
2P-30, 2P-32, 3P-25
Manuel Blas-Ferrando, Vicent 2P-4
1P-20
Maria, Kazi Hanium
3-9
Maruyama, Mina
1P-11, 1P-18, 2-1,
Maruyama, Shigeo
2-2, 2P-22, 3-8,
3P-18, 3P-20
3P-16, 3P-28
Maruyama, Takahiro
3-4
Masubuchi, Satoru
3P-30
Masuda, Katsuya
1P-1
Matsubayashi, Hironobu
1P-5, 1P-29, 2P-11,
Matsuda, Kazunari
2P-34, 3S-8, 3-5,
3P-35, 3P-36
3P-14
Matsuda, Masahiro
3P-6
Matsui, Katsuma
3P-12
Matsui, Ryotaro
3P-36
Matsuki, Keiichiro
2-7, 2P-8, 2P-41
Matsumoto, Jun
3P-7
Matsumoto, Naoyuki
1P-37
Matsumoto, Shogo
1P-37
Matsumoto, Yasumichi
3P-29
Matsuo, Yoshiaki
2-1, 2P-1, 2P-2
Matsuo, Yutaka
1P-20
Mieno, Tetsu
3P-2
Mikie, Tsubasa
1P-1
Mimuro, Kazuki
3P-5
Minami, Kazuya
3P-11
Miura, Ryohei
2P-5
Miyabe, Kyosuke
1-8, 2P-29
Miyako, Eijiro
2P-33
Miyamoto, Yoshiyuki
1P-22, 1P-25, 2P-23,
Miyata, Yasumitsu
2P-30, 2P-32, 3P-25
1P-5, 1P-29, 2P-11,
Miyauchi, Yuhei
2P-34, 3P-21

Mizorogi, Naomi
Mizuno, Masashi
Mizuno, Seigi
Mizutani, AkitakaMori, Hatsumi
Mori, Shohei
Morisako, Shiyo
Morisawa, Yusuke
Moriya, Rai
Moriyama, Hiroshi
Motomiya, Kenichi
Mouri, Shinichiro
Murakami, Toshiya
Myodo, Miho
<N>
Nagao, Tadaaki
Nagase, Shigeru
Nagashima, Dai
Nagashio, Kosuke
Nagata, Tomoko
Nakada, Kyoko
Nakagawa, Takafumi
Nakahara, Hitosi
Nakai, Yusuke
Nakamoto, Keisuke
Nakamura, Junji
Nakamura, Keisuke
Nakamura, Maki
Nakamura, Takashi
Nakamura, Taketomo
Nakanishi, Takeshi
Nakanishi, Yudai
Nakanishi, Yusuke
Nakashima, Naotoshi
Nakayama, Ko
Namba, Natsuki
Narita, Kohei
Naritsuka, Shigeya
Nasiblin, Albert G.
Nasibulin, Albert
Natsume, Yuhei
Negishi, Ryota
Nihey, Fumiyuki
Nishihara, Taishi
Nishikawa, Jumpei
Nishikawa, Noriaki
Nishimura, Tomoaki

2P-5
2P-37
2P-28
1P-42
2-4
1P-22, 2P-32
3P-26
2-7
3-4
2-4
2P-21
1P-5, 1P-29, 2P-34,
3-5
2P-20
1P-9, 2-3

1P-26
2P-5, 3P-4, 3P-5
2P-43
3S-7
1P-24, 3P-17, 3P-19
1P-40
2P-2
3P-14
2P-14
2P-38
1P-26
2P-15
1-7, 3P-23
3-5
1P-33, 1P-34
2-10
1P-35
2P-26
1-3, 1-5, 2P-11,
2P-12, 2P-24, 3P-22
3P-15
1P-40
1P-32
3P-16, 3P-28
2-2
2-1
2P-13
3-2
2P-9
3P-6
2P-10
3P-39
1-6

- 180 -

Nishino, Hidekazu
Noda, Suguru
Nomura, Kumiko
Norimatsu, Wataru
Nouchi, Ryo
Nugraha, Ahmad R. T.
<O>
Ochi, Masayuki
Ogasawara, Kazuki
Ogata, Hironori

1S-2
1P-10, 1P-15, 1P-17,
1P-19, 1P-21, 3P-15
1P-35
1P-9, 2-3
3-1
1P-31, 2-11, 3P-33,
3P-34, 3P-37

Okazaki, Toshiya
Olmstead, Marilyn M.
Omachi, Haruka
Onga, Masaru
Ortíz, JavierŌsawa, Eiji
Osawa, Toshio
Oshima, Yuki
Otsuka, Keigo
Ozawa, HiroakiÖzyilmaz, Barbaros

3-7
1P-18, 3P-20
1-6, 2P-3, 3-10,
3P-1, 3P-9, 3P-10
1P-34, 1P-35, 1P-36
1P-3, 2P-36
2P-4
2P-9
1P-10, 3P-12
2P-35
3P-11
2P-28
1S-2
2P-1
1P-8, 1P-32, 2P-6,
2P-7, 2P-35, 2P-36,
2P-39, 3-6, 3-9,
3P-38
1-7, 2P-29
2P-5, 3P-4
2P-6, 2P-23, 2P-26
3-3
2P-4
1-9, 1P-39
1P-15, 1P-19
2P-14
1P-11
3P-22
1P-33

<P>
Pander, Adam
Park, Hae Soo
Pichon, Benoit
Popert, AlexanderPu, Jiang

2P-19
3P-43
1-8
1P-7
2P-35, 3P-31, 3P-36<Q>
Qin, Hongmei

2P-15

Ohata, Chika
Ohfuchi, Mari
Ohkubo, Kei
Ohmori, Shigekazu
Ohno, Yutaka
Ohta, Hiromichi
Ohta, Ryuichi
Ohta, Yujiro
Oi, Takashi
Okada, Hiroshi
Okada, Susumu

<R>
Rao, Apparao
Ryan, James<S>
Saeki, Akinori
Saida, Takahiro
Saiki, Ayano
Saiki, Koichiro
Saito, Makoto
Saito, Riichiro

Saito, Susumu
Saito, Takeshi
Saito, Yahachi
Saito, Yu
Sakaguchi, Takahiro
Sakai, Hayato
Sakanoue, Tomo
Sano, Masahito
Sano, Yoshiaki
Sasaki, Shogo
Sasaki, Yuki
Sastre-Santos, Ángela
Sato, Kenichi
Sato, KumikoSato, Tohru
Sato, Yoshinori
Sato, Yutaka
Schreiner, Peter R.
Scott, Lawrence
Segawa, Yasutomo
Seki, Shu
Senga, Ryosuke
Shi, Wu
Shibuya, Megumi
Shimada, Takashi
Shimizu, Kazuki
Shimizu, Sunao
Shimomura, Yuuki
Shinohara, Hisanori
Shirae, Hiroyuki
Shiraishi, Tomonari
Shiromaru, Haruo
Siregar, Syahril

1P-36
2P-2

3P-2
3P-16
1P-44
1S-3
1P-18, 3P-20
1P-2, 1P-31, 1P-41,
1P-43, 2-11, 2P-37,
3P-13, 3P-33, 3P-34,
3P-37
2-9, 2P-10
2P-9
3P-14
2P-44
2-2
2P-4
3P-15, 3P-31
3P-30
2P-3
1P-25, 2P-32
1P-27
2P-4
1S-2
2P-5, 3P-5
2-6, 2P-31, 2P-43
1P-18, 2P-21, 3P-20
3P-9
2P-26
3P-21
3P-6
3P-2
1-2
2P-44
1P-9, 2-3
2P-16, 3P-11
1P-42
3P-41
1P-11
1P-27, 1P-34, 1P-35,
2P-6, 2P-23, 2P-26,
2P-40, 3P-25
1P-10, 3P-15
2P-11, 2P-12
1-1, 2-7, 2P-8,
2P-41
1P-31

- 181 -

Sorimachi, Jun-ya
Sota, Masaki
Suda, Yoshiyuki
Suenaga, Kazu
Sugai, Toshiki
Sugiura, Takeshi
Suzuki, Kazuma
Suzuki, Manabu
Suzuki, Mitsuaki
Suzuki, Motoyuki
Suzuki, Ryuji
Suzuki, Shoji<T>
Tabata, Kenichi
Tachibana, Masaru
Tagmatarichis, Nikos
Taguchi, Yuki
Tahara, Yoshio
Takada, Tomoya
Takada, Yukihiro
Takagi, Yukai
Takahashi, Misaki
Takai, Kazuyuki
Takakura, Akira
Takashima, Kengo
Takatsuka, Takayuki
Takenobu, Taishi
Takesaki, Yuichiro
Takikawa, Hirofumi
Takizawa, Rina
Tamura, Noriyuki
Tanaka, Kazuyoshi
Tanaka, Shin-Ichiro
Tanaka, Takeshi
Tanaka, Toshihiko
Taniguchi, Takaaki
Taniguchi, Takashi
Terasawa, Tomo-oThendie, Boanerges
Tobari, Yuta
Tohji, Kazuyuki
Tokura, Yoshinori
Toshimitsu, Fumiyuki
Touhara, Hidekazu
Toyama, Kiyohiko

2P-7
3-8
1P-42
1-2
1P-1, 1P-18, 1P-23,
3P-20
3P-5
1P-9, 2-3
3P-28
2P-5, 3P-4
1S-2
2P-42, 2P-44, 3-7
2P-40

1P-26
3P-26
3P-4
2-7, 2P-8, 2P-41
3P-23
1P-12
1P-40
2P-22
1P-23
1P-28, 1P-38, 2P-38,
3P-29, 3P-32
3P-21
1P-30
1P-13
1P-10, 2P-35, 3P-15,
3P-31, 3P-36
3P-27
1P-42
2P-28
3P-24
2-6, 2P-31, 2P-43
3P-37
1-4, 1P-5, 1P-14,
2P-18, 3P-3
1-9
1P-37
2P-32
1S-3
2P-23
1P-18, 3P-20
2P-21
3-7
1-3, 2P-24, 3P-22
1P-38
3P-24

Tsuda, Yusaku
Tsuji, Masaharu
Tsujimoto, Marina
Tsukagoshi, Kazuhito
Tsushima, Kohei
Tsuzuki, Mayumi
Tuan Hung, Nguyen

3P-17
2P-28, 3P-27, 3P-40
3P-26
1P-41
3-8
1-4, 1P-14
3P-13

<U>
Uchida, Yuki
Uda, Takushi
Ue, Hitoshi
Ueda, Chihiro
Ueda, Mako
Ueda, Yuki
Ueno, Hiroshi
Ueno, Keiji
Ukhtary, Shoufie
Umeda, Yoshito
Umehara, Taichi
Umemura, Kazuo
Umeyama, Kaori

3P-40
1P-4, 2P-17
1P-42
3P-4
1P-37
3P-28
3P-6
1P-41, 3-4
3P-34
1P-42
3P-32
2-8
3P-39

<V>
Verzhbitskiy, Ivan

3P-35

<W>
Wada, Yoriko
Wakabayashi, Tomonari
Wall, MarkWang, Qing
Wang, Wei-Wei
Wang, Xiao
Wang, Zhipeng
Watanabe, Kenji
Watanabe, Osamu
Watanabe, Yoshio
Wei, Xiaojun

2-7, 2P-43
2-7, 2P-8, 2P-41,
2P-43
3P-39
2P-40
2P-5, 3P-4
1P-16
1-6, 3-10
2P-32
1S-2
3-2
1-4, 1P-5, 1P-14<X>
Xiang, Rong

2-2,

<Y>
Yabuki, Naoto
Yabushita, Yuhei
Yamada, Hiroko
Yamada, Jumpei
Yamada, Michio
Yamada, Shoji

3-4
2P-20
2S-5
3P-28
3P-4
3-2

3-8,

3P-18

- 182 -

Yamada, Syunya
Yamaguchi, Kohtaro
Yamaguchi, Mai
Yamaguchi, Masanori
Yamamoto, Hiroshi
Yamamoto, Mahito
Yamamoto, Shohei
Yamamoto, Takahiro
Yamamoto, Yohei
Yamanaka, Ayaka
Yamanoi, Ryoko
Yamashina, Tomoki
Yamashita, Hiroki
Yanagi, Kazuhiro
Yang, FengYang, Juan
Yang, Teng
Yasuda, Hidehiro
Ye, Jianting
Yokoi, Hiroyuki
Yokokura, Eita
Yokoyama, Akio
Yokoyama, Koji
Yomogida, Yohei
Yoshida, Keisuke
Yoshida, Masahiro
Yoshida, Masaro
Yoshikawa, Ryo
Yoshitake, HaruhikoYoza, Kenji
Yudasaka, Masako
Yuge, Ryota
Yumura, Motoo
Yumura, Takashi<Z>
Zhang, Daqi
Zhang, Hong
Zhang, Minfang
Zhang, Yijin
Zhang, Zhidong
Zhao, Li
Zhou, Lin

1P-36
1P-21
1P-19
2P-20
1P-24, 3P-17, 3P-19
1P-41
2-4
1P-30, 3P-8
1P-26
3P-38
1-9, 1P-39
3P-29
2P-27
2P-14, 3P-42
1P-6, 1P-16
1P-6, 1P-16
1P-41, 1P-43
2P-25
2P-42, 2P-44
1P-37
3P-10
2-12
2P-21
1-4, 1P-14
3P-17, 3P-19
1P-4, 1P-7, 2-12,
2-13, 2P-16, 2P-17
2P-42, 2P-44, 3P-41
2P-22
1-6, 3-10
2-4
1-7, 1-8, 2P-29,
3P-23, 3P-24
1-7, 3P-24
3P-7
2P-27

1P-6, 1P-16
2P-33
1-7, 1-8, 2P-29,
3P-23
2P-42, 2P-44, 3-3
1P-41, 1P-43
2P-15
1P-41

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2015 年 2 月 21 日発行

第 48 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≪フラーレン・ナノチューブ・グラフェン学会≫〒113-8656 東京都文京区本郷 7-3-1
東京大学大学院工学系研究科 機械工学専攻
丸山研究室内Phone/Fax：03-3830-4848
E-mail：fntg@photon.t.u-tokyo.ac.jp
URL：http://fullerene-jp.org
印刷 / 製本 （株）創志企画

1C×1P（180×260mm）

アイクストロン社
カーボンナノチューブ＆グラフェン成長用CVD装置

Black Magic

Dense CNT

Horizontal SWCNT■ 装置導入後、スピーディに希望のCNTやグラフェンを成長可能

Graphene■ オリジナルレシピ付き「Thermal CVDとPlasma CVDの2モードに対応」（シングルCNT用、ダブルCNT用、マルチCNT用、グラフェン用、横方向CNT用、低圧力プロセス用、
高速成長CNT用など）■ あらゆる基板サイズに対応（研究用2 、4 、6 モデルから量産用最大300mmモデルまで）■ プラズマによる簡単なクリーニングと高メンテナンス性■ 世界中の大学・研究所・企業へ多数納入実績あり

アイクストロン株式会社 www.aixtron.com

販売代理店： 丸文株式会社

www.marubun.co.jp〒140-0001 東京都品川区北品川1-8-11 Daiwa品川Northビル 9F
E-mail: JAPANINFO@aixtron.com〒103-8577 東京都中央区日本橋大伝馬町8番1号
E-mail: kagaku@marubun.co.jp

Tel: 03-5781-0931 Fax: 03-5781-0940

Tel: 03-3639-1336 Fax: 03-3662-1349

Cover moreground, easily
ナノサイエンスや地質学、バイオなど、ラマン分光の技術をもっと活用できる分野は多岐にわたります。Thermo Scientific TM DXR TMxi イメージング顕微ラマンは、高度な性能を視覚的に操作することにより、初心者から熟練者まで分析業務をとてもシンプルにすることができるケミカルイメージング装置です。これであなたもラマンのエキスパート。広大なエリ
アを秒単位で探索し、確実にターゲットを捉えます。

革新的ラマンイメージング• www.thermoscientific.jp/DXRxi/

DXRxi イメージング顕微ラマン
一体型・高性能ラマン
イメージングシステム

Thermo Scientific OMNICTMxi
ラマンイメージングソフトウェア
一体型・高性能ラマン
イメージングシステム

サーモフィッシャーサイエンティフィック株式会社
サーモフィッシャーサイエンティフィック株式会社- 753 - 670- 753 - 671- 753 - 671
TEL.0120
FAX.0120
TEL.0120753 - 670
FAX.0120〒 221-0022
横浜市神奈川区守屋町
3-9〒 221- 0022
横浜市神奈川区守屋町
3-9
Analyze.jp@thermofisher.com www.thermoscientific.jp

Analyze.jp@thermofisher.com www.thermoscientific.jp□□□□【□□□□□月号広告】□□/□□□□□□□□□□/データ納品

須藤彰三・岡 真 監修

《基本法則から読み解く物理学最前線 ❺》フラーレン ･
ナノチューブ ･グラフェンの科学
齋藤理一郎 著

ナノカーボンの世界

・本書は，ナノカーボンという新しい炭素材料を紹介した本である。ナノカーボンとは，グラフェン，フラーレン，カー
ボンナノチューブという新物質をまとめて呼ぶ名前であり，いずれも新素材として注目を集めている。
この本の使命は，ナノカーボンの科学がどんなものである
かを物理学の研究者が紹介する本であり，必要な知識が詳細に書かれた教科書ではない。またいろいろな知識が整理されたハンドブックでもない。異国の地（ナノカーボンの世界）へ案内する旅のガイドブックである。
本書は高校生から大学院生，研究者，一般へと幅広い読者を想定した，式のあまりない本である。他の分野の人も予備知識なしで理解できるように専門用語の説明を加えている。
ナノカーボンについて，あらかた知っている中堅の研究者にも気楽に読める本である。

【A5判・並製本・180頁・本体2,000円(税別)】

主要目次
第１章 ナノカーボンの世界
第２章 ナノカーボンの発見
第３章 ナノカーボンの形
第４章 ナノカーボンの合成
第５章 ナノカーボンの応用
第６章 ナノカーボンの電子状態
第７章 ディラックコーンの性質
第８章 グラフェンとナノチューブのラマン分光
第９章 未来への課題

ナノ構造の科学とナノテクノロジー―量子デバイスの基礎を学ぶために―

Edward L. Wolf 著・吉村雅満・目良 裕・重川美咲子・重川秀実訳 海外で評価の高いテキス
ト『Nanophysics and Nanotechnology：An Introduction to Modern Concepts in Nanoscience2/e』の翻訳書。ナノ物理の基礎から工学への応用まで幅広い分野を網羅し，学生，研究者，
B5判・並製本・294頁・本体6,000円(税別)
技術者に向けての最適な内容構成としている。

ナノの本質 ―ナノサイエンスからナノテクノロジーまで―

T. Pradeep 著・木村啓作・八尾浩史・佐藤井一訳 本書はナノサイエンス，ナノテクノロジー
について数式を排除し，多くの図と写真で理解できるよう工夫された『NANO：The Essentials』の翻訳書。業界用語・専門用語もできるだけ日常語で表現する，化学式を用いずに化合物名で表わすなど，そこかしこに細かい工夫がみられる。この分野に出てくる必要な実験技法を網羅しており，本書一冊で完結する記述となっている。巻末にはナノ関連の用語集がついており，ナノ関連のハンドブックとしても有用である。
菊判・上製本・534頁・本体6,500円(税別)〒112-0006 東京都文京区小日向4-6-19
TEL.03-3947-2511／FAX.03-3947-2539

共立出版

http://www.kyoritsu-pub.co.jp/

f https://www.facebook.com/kyoritsu.pub

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: 30°C
Detection:
UV 325nm
Sample:Inj.Vol.:

C60 [Indene]2 (1.0mg/ml)
1.0µl

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: 30°C
Detection:
UV325nmColumn:Buckyprep-M
Column size: 4.6mmI.D.-250mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30°C
Detection:
UV312nmSample:Inj.Vol.

(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)
1.0µl
NACALAI TESQUE, INC

Sample:Sc2@C76(I)Sc2@C78
Sc2@C80(I)C86

Sample courtesy of Prof. H.Shinohara,
Department of chemistry, Nagoya University

C86

Sc
Sc2@C76(I)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。

ナカライテスク株式会社〒604-0855

京都市中京区二条通烏丸西入東玉屋町498

価格 ・ 納期のご照会 フリーダイヤル 0120-489-552
製品に関するご照会 TEL : 075-211-2746 FAX : 075-211-2710

Web site :http://www.nacalai.co. jp

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

Combiscope + XploRA INVApplication Examples■ 主なアプリケーション■ カーボンナノチューブ■ 生物構造■ グラフェン
■ 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

株式会社 堀場製作所

本社 〒601-8510京都市南区吉祥院宮の東町２番地

TEL：
（075）
313-8121 http://www.horiba.com/jp/scientiﬁc/

●東京
（03）
6206-4717 ●名古屋
（０５２）
９３６-5781 ●大阪（０６）-６３９０-８０１１ ●福岡（０９２）
292-3593

インテル®

Parallel Studio XE
2015

シミュレーションを高速化

バージョン 2015 より、インテル® Composer XE、インテル® Parallel Studio XE、インテル® Cluster Studio XE が統一され、『インテル® Parallel Studio XE』ブランドとして生まれ変わりました。

開発のニーズにあわせて、3 種類のエディションを提供します。
コンパイラー
ライブラリーComposer Edition

解析

Professional Edition

MPI(旧名称 : インテル® Composer XE )(旧名称 : インテル® Parallel Studio XE )Cluster Edition(旧名称 : インテル® Cluster Studio XE )・ 最新プロセッサーの性能を最大限に引き出せるように、最適化されたバイナリーを自動生成する Fortran、C/C++ コンパイラー
・ 最適化されたパフォーマンス・ライブラリーと並列化モデル
Composer Edition の機能に加え、パフォーマンス分析、マルチスレッド化のアドバイス、高度なメモリー / スレッド・エラー・チェック機能を提供

Professional Edition の機能に加え、最適化された MPI ライブラリー、
MPI アプリケーションのエラーチェックおよびチューニング機能を提供

インテル® Parallel Studio XE 2015 の主な新機能
・ 新しい標準規格に対応 (C++11、Fortran 2003/2008、MPI-3.0、OpenMP 4.0)
・ インテル® グラフィックス・テクノロジーの解析に対応
・ メモリー使用量の増減を解析しグラフ表示
・ インテル® Xeon Phi™ コプロセッサーに対応した並列化アドバイスツール
システム 構 成 : ハ ードウェア : イン テル® Core™ i7-4770K プ ロセッサ ー @3.50GHz, ハイパースレッディング無効 , 16 GB RAM; ソフトウェア : インテル®
Fortran コ ン パ イ ラ ー 15.0, Absoft*14.0.3, PGI* Fortran* 14.7, Open64*,
gFortran* 4.9.0; Linux* OS: Red Hat* Enterprise Linux* Server release 6.4(Santiago), カ ー ネ ル 2.6.32-358.el6.x86_64; Windows* OS: Windows* 7
Enterprise SP 1; Polyhedron Fortran ベンチマーク (www.polyhedron.com)
性能に関するテストに使用されるソフトウェアとワークロードは、性能がインテル ® マイクロプロセッサー用に最適化されていることがあります。SYSmark* や
MobileMark* などの性能テストは、特定のコンピューター・システム、コンポー
ネント、ソフトウェア、操作、機能に基づいて行ったものです。結果はこれらの要因によって異なります。製品の購入を検討される場合は、他の製品と組み合わせた場合の本製品の性能など、ほかの情報や性能テストも参考にして、パフォー
マンスを総合的に評価することをお勧めします。 * その他の社名、製品名などは、
一般に各社の表示、商標または登録商標です。 ベンチマークの出典 : インテル
コーポレーション
最適化に関する注意事項 : インテル® コンパイラーは、互換マイクロプロセッサー
向けには、インテル製マイクロプロセッサー向けと同等レベルの最適化が行われない可能性があります。これには、インテル® ストリーミング SIMD 拡張命令 2 ( インテル® SSE2)、インテル® ストリーミング SIMD 拡張命令 3 (インテル® SSE3)、ス
トリーミング SIMD 拡張命令 3 補足命令 (SSSE3) 命令セットに関連する最適化およびその他の最適化が含まれます。インテルでは、インテル製ではないマイクロプ
ロセッサーに対して、最適化の提供、機能、効果を保証していません。本製品のマイクロプロセッサー固有の最適化は、インテル製マイクロプロセッサーでの使用を目的としています。インテル® マイクロアーキテクチャーに非固有の特定の最適化は、インテル製マイクロプロセッサー向けに予約されています。この注意事項で対象としている特定の命令セットに関する詳細は、該当製品のユーザーズガイド
またはリファレンス・ガイドを参照してください。改訂 #20110804

無料評価版はこちら

http://www.xlsoft.com/intel

製品の詳細に関するお問い合わせ先 :〒 108-0073 東京都港区三田 3-9-9 森伝ビル 6F
Tel: 03-5440-7875 Fax: 03-5440-7876 E-mail: intel@xlsoft.com
インテル® ソフトウェア製品のパフォーマンス / 最適化に関する詳細は、http://software.intel.com/en-us/articles/optimization-notice/#opt-jp を参照してください。

Intel、インテル、Intel ロゴ、Intel Xeon Phi、VTune は、アメリカ合衆国および / またはその他の国における Intel Corporation の商標です。* その他の社名、製品名などは、一般に各社の表示、商標または登録商標です。
Ⓒ 2015 Intel Corporation. 無断での引用、転載を禁じます。
XLsoft のロゴ、XLsoft は XLsoft Corporation の商標です。Copyright Ⓒ 2015 XLsoft Corporation.