F NTG

Research Society

第 50 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 50th Fullerenes-Nanotubes-Graphene General Symposium

講演要旨集
Abstracts2016 年 2 月 19 日（金） ～ 22 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
東京大学工学系研究科 School of Engineering, The University of Tokyo
東京大学 CIAiS Consortium for Innovation of Advanced Integrated Science (UTokyo)
東京大学 GMSI Graduate Program for Mechanical Systems Innovation (UTokyo)
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, SICORP
協賛
日本物理学会
応用物理学会
高分子学会
電気化学会

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

Abstract of
The 50th Fullerenes-Nanotubes-Graphene General Symposium
Sponsored by : The Fullerenes, Nanotubes and Graphene Research Society
Co-Sponsored by : School of Engineering, The University of Tokyo

Consortium for Innovation of Advanced Integrated Science(UTokyo)
Graduate Program for Mechanical Systems Innovation(UTokyo)
The Chemical Society of Japan
IRENA Project by JST-EC DG RTD, SICORP

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

Date : February 19th (Fri.) – 22nd (Mon.), 2016
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 + 5min discussion)

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

第 50 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 : 東京大学大学院工学系研究科
東京大学 CIAiS東京大学 GMSI
日本化学会
JST 戦略的国際共同研究プロジェクト IRENA
協賛 : 日本物理学会、応用物理学会、高分子学会、電気化学会
日時 : 平成 28 年 2 月 19 日(金) ～ 22 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

発表時間 : 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）

展示団体御芳名 (五十音順、 敬称略）
アイクストロン（株）
IOP英国物理学会出版局
QuantumWise Japan（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（株）セントラル科学貿易
東京ダイレック(株）ナカライテスク（株）
ナノフォトン（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）
フリッチュ・ジャパン（株）(株）堀場製作所（株）三ツワフロンテック（株）名城ナノカーボン

広告掲載団体御芳名 (五十音順、 敬称略）
アイクストロン(株)エクセルソフト（株）（株) コロナ社（株）セントラル科学貿易
ナカライテスク（株）
日本電子（株）
フロンティアカーボン（株）（株）三ツワフロンテック

Contents
Time Table ・・・・・・・・・・・・・・・・・・ i
Chairperson ・・・・・・・・・・・・・・・・・iii
ProgramJapanese ・・・・・・・・・・・・ iv
English ・・・・・・・・・・・・ xxi
Abstracts
Special Lecture ・・・・・・・・・・ 1
General Lecture ・・・・・・・・・ 13
Poster Preview ・・・・・・・・・・41
Author Index ・・・・・・・・・・・・・・・・187

目次
早見表 ・・・・・・・・・・・・・・・・・・・ i
座長一覧・・・・・・・・・・・・・・・・・・・iii
プログラム 和文・・・・・・・・・・・・・・・ iv
英文・・・・・・・・・・・・・・ xxi
講演予稿
特別講演・・・・・・・・・・・・・ 1
一般講演・・・・・・・・・・・・・13
ポスター発表・・・・・・・・・・・41
発表索引・・・・・・・・・・・・・・・・・・ 187

プログラム早見表
２月２０日 （土）

２月２１日 （日）２月２２日 （月）受付開始 8：30～
講演開始 9：30～

受付開始 8：30～
講演開始 9：00～
特別講演 （Yan Li）
9:00-9:30
一般講演 3件受付開始 8：30～
講演開始 9：00～
特別講演 (仁科 勇太)
9:00-9:30
一般講演 4件

9:00
9:30 特別講演 （Esko I. Kauppinen）
9:30-10:00
10:00
特別講演 (古月文志)
10:00-10:30
10:30
休憩 10:30-10:45
10:45
一般講演 4件(フラーレン ・ グラフェンの物性）

9:30

13:00
13:30
14:15

10:15
10:30
11:00

休憩 10:15-10:30
特別講演 (福島 孝典)
10:30-11:00
一般講演 3件(グラフェン生成 ・ フラーレン ・
金属内包フラーレン) 11:00-11:45

昼食
(幹事会）
11:45-13:00

11:45

特別講演 (黒部 篤)
13:00-13:30
一般講演 3件(原子層）
13:30-14:15
ポスタープレビュー( 1P-1 ～ 1P-49 )14:15-15:15

13:00
13:30
14:00

15:00
15:15

9:30

(グラフェンの物性 ・ 原子層）

(ナノチューブの生成と精製 ・ナノチューブの物性) 9:30-10:15

10:45-11:45
11:45

9:00

ポスターセッション（多目的スペース）
15:15-17:00

昼食
11:45-13:00

授賞式
13:00-13:30
特別講演 （牧 英之）
13:30-14:00
ポスタープレビュー( 2P-1 ～ 2P-49 )14:00-15:00

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

13:15

ポスタープレビュー( 3P-1 ～ 3P-48 )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 （宮内 雄平）
16:00-16:30
一般講演 4件

ポスターセッション( 多目的スペース )15:00-16:45

16:30
16:45
17:00
17:30
18:15
18:30

特別講演 (橋本 剛)
17:00-17:30
一般講演 3件(ナノチューブの応用）
17:30-18:15
休憩 18:15-18:30
チュートリアル講師： 吾郷 浩樹
九州大学（伊藤謝恩ホール）
18:30-20:00

休憩 10:30-10:45
特別講演 (湯本 潤司)
10:45-11:15
一般講演 3件(ナノチューブの物性）
11:15-12:00
昼食
12:00-13:15

第50回記念 温故知新
パネルディスカッション(フラーレンの応用 ・ ナノ炭素粒子
・ ナノチューブの応用 ・ その他)

16:30-17:30
阿知波洋次, 飯島澄男, 今堀博,
岩佐義宏, 遠藤守信, 大澤映二,
小松紘一, 斎藤晋, 齋藤弥八,
田中一義, 谷垣勝己, 日野照純

18:45

17:30

16:45-18:45
懇親会（多目的スペース）
18:45-20:45

20:00
講演会場 伊藤謝恩ホール
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

２月１９日 （金）
16:30

特別講演
(Mildred S. Dresselhaus)
16:30-17:30

20:45

17:30

i

Time table
February 20 (Sat.)
Registration begins at 8:30
Lectures begin at 9:30
9:30

Special Lecture

February 21 (Sun.)
Registration begins at 8:30
Lectures begin at 9:00
9:00
Special Lecture(Yan Li) 9:00-9:30
9:30
General Lectures [3](Esko I. Kauppinen) 9:30-10:00

Special Lecture(Bunshi Fugetsu) 10:00-10:30
10:30 Coffee Break 10:30-10:45
10:45
General Lectures [4]（Fullerenes ・Properties of graphene）
10:45-11:45
11:45
Lunch
(Administrative meeting)
11:45-13:00(Formation and purification of nanotubes
・ Properties of nanotubes) 9:30-10:15

10:00

13:00

Special Lecture(Atsushi Kurobe) 13:00-13:30
13:30
General Lectures [3](Atomic Layers)
13:30-14:15
14:15
Poster Preview( 1P-1 through 1P-49 )14:15-15:15

10:15
10:30

(Takanori Fukushima) 10:30-11:00

11:00

General Lectures [3](Graphene synthesis ・ Fullerenes ・Endohedral metallofullerenes) 11:00-11:45

11:45

Lunch
11:45-13:00

Award Ceremony
13:00-13:30
13:30
Special Lecture（Hideyuki Maki） 13:30-14:00
14:00
Poster Preview( 2P-1 through 2P-49 )14:00-15:00

Atomic Layers)

9:30-10:30
Coffee Break 10:30-10:45
Special Lecture(Junji Yumoto) 10:45-11:15
11:15
General Lectures [3](Properties of nanotubes)
11:15-12:00
12:00
Lunch
12:00-13:15
10:30
10:45

13:00

15:00
15:15

Coffee Break 10:15-10:30
Special Lecture

February 22 (Mon.)
Registration begins at 8:30
Lectures begin at 9:00
9:00
Special Lecture(Yuta Nishina) 9:00-9:30
9:30
General Lectures [4](Properties of graphene ・Poster Session( Event Space )15:15-17:00

13:15

Poster Preview( 3P-1 through 3P-48 )13:15-14:15

14:15

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

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

Special Lecture(Yuhei Miyauchi) 16:00-16:30
16:30
General Lectures [4]16:45 50th Memorial Panel Discussion
17:00

Special Lecture( Yohji Achiba, Sumio Iijima,
Hiroshi Imahori, Yoshihiro Iwasa,
Morinobu Endo, Eiji Osawa,
Koichi Komatsu, Susumu Saito,
Yahachi Saito, Kazuyoshi Tanaka,
Katsumi Tanigaki, Shojun Hino )(Takeshi Hashimoto) 17:00-17:30

17:30

General Lectures [3](Applications of nanotubes)
17:30-18:15
18:15 Coffee Break 18:15-18:30
18:30
Tutorial
Lecturer : Hiroki Ago
Kyushu University( Ito Hall )18:30-20:00

18:45(Applications of fullerenes ・ Other
topics ・ Applications of nanotubes
・ Carbon nanoparticles)16:30-17:30

17:30

16:45-18:45
Banquet( Event Space )18:45-20:45

20:00
16:30
17:30

February 19 (Fri.)Special Lecture(Mildred S. Dresselhaus)
16:30-17:30

20:45
Place : Ito Holl
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19日（金）

(敬称略）

セッション
時
間
特別講演(Mildred S. Dresselhaus） 16:30 ～17:30

座長
齋藤 理一郎

2月20日（土）セッション
特別講演(Esko I. Kauppinen）
特別講演(古月 文志）
一般講演
特別講演(黒部 篤）
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 ～ 11:45
13:00～ 13:30
13:30 ～ 14:15
14:15 ～ 15:15

特別講演(橋本 剛）
一般講演
チュートリアル(吾郷 浩樹）

17:00 ～17:30
17:30 ～ 18:15
18:30 ～ 20:00

座
長
北浦 良
丸山 茂夫
岡田 晋
山本 貴博
山本 貴博
長谷川 馨
小川 友以
野田 優
野田 優
松尾 豊

2月21日（日）セッション
特別講演(Yan Li）
一般講演
特別講演(福島 孝典）
一般講演
特別講演(牧 英之）
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 ～ 11:45
13:30 ～ 14:00
14:00 ～ 15:00

温故知新
パネルディスカッション

16:45 ～ 18:45

座
長
大野 雄高
大野 雄高
竹延 大志
松尾 豊
長汐 晃輔
桜井 俊介
項 榮
湯田坂 雅子
丸山 茂夫

2月22日（月）セッション
特別講演(仁科 勇太）
一般講演
特別講演(湯本 潤司）
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(宮内 雄平）
一般講演

16:00 ～ 16:30
16:30 ～ 17:30
iii

座
長
長汐 晃輔
長汐 晃輔
丸山 茂夫
千足 昇平
白木 智丈
井ノ上 泰輝小鍋 哲
高井 和之

２月１９日 （金）特別講演

発表 ４０分 ・ 質疑応答 ２０分

特別講演 ( 16:30-17:30 )S-1

What can we learn about low-symmetry materials from spectroscopy?
* Mildred S. Dresselhaus

1

２月２０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

Direct dry printing of SWNT thin films for flexible electronics applications* Esko I. Kauppinen2

特別講演 ( 10:00-10:30 )1S-2酸化グラフェン：量産技術と応用実例* 古月 文志 , Wang Yanqing , 坂田 一郎

3＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜一般講演 ( 10:45-11:45 )フラーレン ・ グラフェンの物性
1-1フラーレン生成過程とC60の選択的成長機構
上野 裕亮 , 陳 智明 , 豊田 雅之 , * 斎藤 晋

13

1-2

Molecular dynamics simulation of the growth of fullerenes from carbon atoms* 陳 智明 , 斎藤 晋

14

1-3

電気化学的手法による単層グラフェンのプロトン透過能評価
中島 浩司 , 熊谷 諒太 , * 保田 諭 , 村越 敬

15

1-4

Magnetic property of two-dimensional networks of high-spin hydrocarbon molecules* 丸山 実那 , 岡田 晋

16＞＞＞＞＞＞＞ 昼食 ( 11:45-13:00 ) ＜＜＜＜＜＜＜特別講演 ( 13:00-13:30 )1S-3『二次元原子分子薄膜』に関するJST/CRESTの紹介－研究総括の方針と応募者への期待－* 黒部 篤iv

4

２月２０日 （土）一般講演 ( 13:30-14:15 )
原子層
1-5

遷移金属ダイカルコゲナイドへの電極接合に対する端の効果* 野内 亮17

1-6

MoS2/WS2半導体ヘテロ接合の一次元界面におけるバンドギャップ変調* 小林 佑 , 吉田 昭二 , 櫻田 龍司 , 斉藤 哲輝 , 渡邊 賢司 , 谷口 尚 , 真庭 豊 ,重川 秀実 , 宮田 耕充

18

1-7

Geometric and electronic properties of thin-layer GeSe and GeSe/MoS 2 heterostructures* Mari Ohfuchi

19

ポスタープレビュー ( 14:15-15:15 )ポスターセッション ( 15:15-17:00 )フラーレンの化学（☆） 若手奨励賞候補

1P-1

C60フラーレンナノウィスカーのラマン分光測定* 今野 俊生 , 平田 千佳 , 若原 孝次 , 宮澤 薫一

41

1P-2

フラーレンと環状炭化水素分子からなる複合構造のエネルギー論と電子状態* 長澤 裕哉 , 岡田 晋

42

金属内包フラーレン
1P-3

Gd, Y金属が２個内包されたフラーレン類のESRスペクトル* 山口 貴久 , 中鳥 なつみ , 三谷 拓示 , 菊地 耕一 , 兒玉 健 , 古川 貢 , 加藤 立久

43

1P-4

Isolation and Characterization of the hidden metallofullerene: Y 2@C78* 中鳥 なつみ , 三谷 拓示 , 山口 貴久 , 古川 貢 , 加藤 立久 , 菊地 耕一 ,阿知波 洋次 , 兒玉 健

44

☆

1P-5

Photoreactions of Trimetallic Nitride Template Endohedral Metallofullerenes with
Digermirane* 宮部 恭輔 , 佐藤 雄一 , 加固 昌寛 , 安井 正憲 , 佐藤 久美子 , 溝呂木 直美 ,Wei-Wei Wang, 永瀬 茂 , 赤阪 健

45

フラーレン
1P-6

Mixed Valence transitions in Rare-earth Fullerides* Takeshi Nakagawa, Yasuhiro Takabayashi, Kosmas Prassides

46

1P-7

μ+SR study of fulleride superconductors across the superconductivity dome
* Melita Menelaou, Yasuhiro Takabayashi, Ruth H. Zadik, Peter J. Baker,
Kosmas Prassides

47

ナノチューブの物性
1P-8

半導体中に埋め込まれたカーボンナノチューブのエネルギー論と電子状態* 古地 健人 , 岡田 晋

48

1P-9
☆

Crossover from Quantum to Classical Transport in Carbon Nanotubes* Keisuke Ishizeki, Kenji Sasaoka, Takahiro Yamamoto49v

２月２０日 （土）

1P-10

1P-11
☆
1P-12

Photoluminescence spectral shift of chemically-modified single-walled carbon nanotubes byexternal stimuli* 鬼塚 悠 , 白木 智丈 , 中嶋 直敏
Morphology Dependence on Thermal Transport Properties of Single-walled Carbon Nanotube
Films* 吉田 周平 , 馮 雅 , 井ノ上 泰輝 , 項 榮 , 千足 昇平 , Kauppinen Esko, 丸山 茂夫
ゼーベック係数が精密制御された単層カーボンナノチューブ薄膜における光熱電変換* 中村 昌稔 , 北村 典雅 , 大島 侑己 , 河合 英輝 , 真庭 豊 , 柳 和宏

50

51

52

ナノチューブの応用
1P-13

Carbon nanotube sheet as a transparent electrode for semi-transparent organic solar cell
* 田中 仙君 , 浦川 直也 , 井上 閑山

53

1P-14

In-situ TEM study on self-oscillations of carbon nanotube during field emission* Tomonori Kato, Hitoshi Nakahara, Koji Asaka, Yahachi Saito

54

1P-15
☆

Transparent, stretchable all-carbon nanotube thin-film transistors for wearable electronics* Takeo Onishi, Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno

55

1P-16

Mechanical and electric properties of continuous polymer-free carbon nanotube fibers* Xueli Wu, Takahiro Morimoto, Ken Mukai, Kinji Asaka, Toshiya Okazaki

56

1P-17

Production and electrical properties of CNT-Cu composite wires* Rajyashree Sundaram, Atsuko Sekiguchi, Takeo Yamada, Kenji Hata

57

ナノチューブの生成と精製
1P-18

1P-19

1P-20
☆

ポリフルオレンの分子鎖長による半導体性単層カーボンナノチューブ選択性発現のメカニズ
ム* 利光 史行 , 中嶋 直敏
Chirality control of in-plane oriented single-walled carbon nanotubes using free electron laser* 川口 大貴 , 小林 弥生 , 春宮 清之介 , 永田 知子 , 岩田 展幸 , 山本 寛
火炎法Co-Al-Oナノパウダーからの10秒スケールでの触媒粒子形成とカーボンナノチューブ
成長* 白江 宏之 , 長谷川 馨 , Eongyu Yi, Richard Laine, 野田 優

58

59

60

1P-21

Chemical reaction analysis of cupper clusters by FT-ICR mass spectroscopy* Ken Mizutani, Yoshinori Sato, Hiroya Minowa, Taiki Inoue, Shohei Chiashi,
Shigeo Maruyama

61

1P-22

高温パルスアーク放電法による二層カーボンナノチューブ生成の流速依存性* 曳地 祐人 , 陣内 涼太 , 菅井 俊樹

62vi

２月２０日 （土）グラフェン生成1P-23

パターン化Wキャップ層を用いた析出法におけるパターン化多層グラフェンの直接成長* 山田 純平 , 上田 悠貴 , 丸山 隆浩 , 成塚 重弥

63

1P-24
☆

水蒸気を用いた異方性エッチングによるグラフェンナノリボンの作製と評価* 小川 峻 , 井上 凌介 , 渡邊 賢司 , 谷口 尚 , 真庭 豊 , 宮田 耕充

64

1P-25

サファイア基板上のグラフェンの無触媒CVDの研究----- 核生成における成長温度の効果 ----* 上田 悠貴 , 山田 純平 , 内堀 樹 , 堀部 真史 , 松田 晋一 , 丸山 隆浩 , 成塚 重弥

65

1P-26
☆

Growth of Large-Grain Graphene and the Role of Oxygen* Dong Ding, Rozan Mohamad Yunus, Pablo Solís Fernández, Hiroki Ago

66

1P-27

黒鉛層間化合物の剥離によって得られた数層グラフェンとその特性* 安武 拓哉 , 衣本 太郎 , 津村 朋樹 , 豊田 昌宏

67

グラフェンの応用
1P-28

二酸化炭素の捕捉における二層酸化グラフェンの活用* 湯村 尚史 , 山崎 愛弓

68

1P-29

グラフェンナノリボンの一軸性圧力下での構造と電子状態* 成田 康平 , 岡田 晋

69

1P-30
☆

Carbon nano-horn peptideを修飾したDpsによるグラフェンへの吸着* 橋間 裕貴 , 石河 泰明 , 上沼 睦典 , 岡本 尚文 , 山下 一郎 , 浦岡 行治

70

1P-31

グラフェン透明電極を有するシリコン薄膜太陽電池* 石川 亮佑 , 大矢 智也 , 野本 隆宏 , 坪井 望

71

1P-32

Substrate dependence of graphene oxide in amidation and esterification reactions* Haruya Okimoto, Yasutaka Yoshii, Masahito Sano72

グラフェンの物性
1P-33

Indirect angle resolved photoemission spectra in graphene* Pourya Ayria, Shin-ichiro Tanaka, Ahmad R. T. Nugraha, Riichiro Saito

73

1P-34

チタンクリーニングされた単層グラフェンのラマン散乱と紙基板への転写* 藤元 章 , 先田 雅史 , 金子 廉 , 中野 良輔 , 佐藤 和郎 , 村上 修一 , 原田 義之 ,前元 利彦 , 矢野 満明

74

単層Mo1-xRexS2における1H-1T’相転移とヘテロ構造形成* 森 勝平 , 佐々木 将悟 , 小林 祐 , 劉 崢 , 吉田 昭二 , 竹内 高広 , 重川 秀実 ,末永 和知 , 真庭 豊 , 宮田 耕充

75

GaTeの光吸収とラマンスペクトルの異方性* 辰巳 由樹 , Shengxi Huang, Xi Ling, Huaihong Guo, Teng Yang,
Mildred S. Dresselhaus, 齋藤 理一郎

76

原子層
1P-35
☆
1P-36

vii

２月２０日 （土）

1P-37
☆

Observation of Biexciton States in high-quality Tungsten Disulfide Atomic Layers from 80 K
to Room Temperature* 岡田 光博 , 宮内 雄平 , 渡邊 賢司 , 谷口 尚 , 松田 一成 , 篠原 久典 , 北浦 良

77

1P-38

走査ゲートによるMoS2トランジスタの視覚化* 樋口 絢香 , 松永 正広 , He Guanchen, Bird Jonathan, 落合 勇一 , 青木 伸之

78

1P-39
☆

Extremely Thin and Flexible Single-Layer WS2 Phototransistors* Aji Adha Sukma, 椎葉 俊明 , 福田 憲二郎 , 吾郷 浩樹

79

1P-40

ダイヤモンド同位体超格子における格子振動* 坂東 優樹 , 斎藤 晋

80

1P-41

Josephson effect in NbSe 2/NbSe2 van der Waals junction* Naoto Yabuki, Rai Moriya, Miho Arai, Yohta Sata, Sei Morikawa, Satoru Masubuchi,
Tomoki Machida

81

☆

ナノホーン
1P-42

1P-43

多次元ガン治療のための機能性カーボンナノホーンの開発* Eijiro Miyako, Svetlana Chechetka, Minfang Zhang, Masako Yudasaka
Characterization and Supercapacitor Properties of Fibrous Aggregates of Single-Walled
Carbon Nanohorns* Ryota Yuge, Fumiyuki Nihey, Kiyohiko Toyama, Masako Yudasaka

82

83

ナノ炭素粒子
1P-44

圧縮下における炭素ナノ材料の粉体電気導電率* 水井 康平 , 大廣 達郎 , 須田 善行 , 針谷 達 , 滝川 浩史 , 植 仁志

84

1P-45

爆轟法ナノダイヤモンドのレーザー脱離イオン化質量スペクトルにおける照射強度依存性* 深谷 真芳 , 大坪 由貴 , 田中 利彦 , 山野井 亮子 , 大澤 映二

85

1P-46

Polymer-derived Nanoporous Carbon Monolith: High Electrochemical Capacitive Behaviors* 王 延青 , 古月 文志 , 坂田 一郎 , 王 志朋 , 龚 伟 , Mauricio Terrones,
Morinobu Endo, Mildred Dresselhaus

86

1P-47

Polyyne formation by laser-induced breakdown in argon-diluted propane gas flow
* 田口 裕貴 , 遠藤 瞳 , 兒玉 健 , 若林 知成 , 阿知波 洋次 , 城丸 春夫

87

1P-48

Polyyne formation by laser ablation of PAH/graphite composite disk in vacuum* 森口 諒一 , 田口 裕貴 , 遠藤 瞳 , 若林 知成 , 兒玉 健 , 阿知波 洋次 , 城丸 春夫

88

1P-49

トラップ型気相移動度測定を用いたナノレベル粒子の電荷状態のサイズ依存性観察* 廣芝 泰祐 , 松林 広延 , 伊藤 拓真 , 陣内 涼太 , 菅井 俊樹

89

その他

viii

２月２０日 （土）特別講演 ( 17:00-17:30 )1S-4

今後のカーボンナノチューブの産業応用について* 橋本 剛5

一般講演 ( 17:30-18:15 )ナノチューブの応用
1-8

1 wt%のカーボンナノチューブによるリチウムイオン電池の結着剤・金属箔なしでの実現* 長谷川 馨 , 野田 優

20

1-9

p-ドープしたカーボンナノチューブ電極を用いた金属電極を用いない透明有機太陽電池* 田 日 , Clement Delacou, Antti Kaskela, Esko I. Kauppinen, 丸山 茂夫 , 松尾 豊

21

1-10

Oxygen-doped carbon nanotubes as near-infrared imaging probes and fluorescent labels* 飯泉 陽子 , 湯田坂 雅子 , 竹内 司 , 岡崎 俊也

22＞＞＞＞＞＞＞ 休憩 ( 18:15-18:30 ) ＜＜＜＜＜＜＜チュートリアル ( 18:30-20:00 )グラフェン ―CVD成長と評価、そして応用―* 吾郷 浩樹

ix

２月２１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-5

Structure-controlled growth of single-walled carbon nanotubes: from catalyst design to growth
conditions* Yan Li

6

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

2-2

2-3

一酸化炭素を用いた900℃を超える高温CNTフォレスト高効率成長* 桜井 俊介 , 山田 真保 , Futaba Don, 畠 賢治
Extended alcohol catalytic chemical vapor deposition for efficient growth of small-diameter
single-walled carbon nanotubes beyond (6,5)* 侯 博 , 項 榮 , 井ノ上 泰輝 , 千足 昇平 , 丸山 茂夫
High resolution EELS on individual carbon nanotubes* 千賀 亮典 , Pichler Thomas, 末永 和知

23

24

25

＞＞＞＞＞＞＞ 休憩 ( 10:15-10:30 ) ＜＜＜＜＜＜＜特別講演 ( 10:30-11:00 )2S-6

超分子足場を用いたC60機能団の精密集積化* 福島 孝典

7

一般講演 ( 11:00-11:45 )グラフェン生成 ・ 金属内包フラーレン ・ フラーレン
2-4

2-5

2-6

アセン型グラフェンナノリボンの表面合成* 中江 隆博 , 宋 少堂 , 小島 崇寛 , 坂口 浩司
Multiple photosynthetic reaction centers of porphyrinic polypeptide/Li +@C60 supramolecularcomplexes* 大久保 敬 , 長谷川 哲也 , Rein Regis, Solladie Nathalie, 福住 俊一
Physical control of insulator-to-metal transition in overexpanded A 3C60
* 高林 康裕 , Zadik Ruth H., 中川 剛志 , Prassides Kosmas＞＞＞＞＞＞＞ 昼食 ( 11:45-13:00 ) ＜＜＜＜＜＜＜

大澤賞・飯島賞・若手奨励賞の授賞式 ( 13:00-13:30 )

x

26

27

28

２月２１日 （日）特別講演 ( 13:30-14:00 )2S-7

集積光・電子デバイスおよび光通信に向けたナノカーボン光源開発* 牧 英之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

8（☆） 若手奨励賞候補

2P-1

アザフレロイドへの位置選択的グリニャール反応* 伊熊 直彦 , 中川 晃二 , 小久保 研 , 大島 巧

90

2P-2

1

91

H NMRによる水酸化炭素材料の固体特性に関する研究* 佐野 喜章 , 緒方 啓典

フラーレンの応用
2P-3

2P-4

フラーレンカチオンを経由した環状骨格を有するフラーレン誘導体の合成と有機薄膜太陽電池への応用* Keisuke Ogumi, Hiroshi Okada, Takafumi Nakagawa, Yutaka Matsuo
Investigation of catalytic activity for reduction of 4-nitrophenol with [C 60]fullerene
nanowhisker-silver nanoparticle composites* Jeong Won Ko, Hwa Jeong Chae, Weon Bae Ko

92

93

金属内包フラーレン
2P-5

各種アミンによる金属内包フラーレンの化学的還元* 佐藤 祐太 , 田中 康介 , 秋山 和彦 , 久富木 志郎

94

2P-6

Isolation and characterization of Gd2@C80 anion whose spin state is S=15/2* 三谷 拓示 , 中鳥 なつみ , 山口 貴久 , 小林 樹来 , 古川 貢 , 加藤 立久 ,菊地 耕一 , 阿知波 洋次 , 兒玉 健

95

☆

2P-7

Reactions of Endohedral Metallofullerenes with Silacyclopropanes: Mono-silylation andCarbosilylation of Lu3N@Ih-C80* 南 和也 , 加固 昌寛 , 佐藤 久美子 , 溝呂木 直美 , 永瀬 茂 , 赤阪 健

96

フラーレン
2P-8

2P-9

外部電界下におけるフラーレン分子の静電相互作用* 反町 純也 , 岡田 晋
Solid-State NMR Studies on the Aggregated Structures of Organic Bulk Heterojunction Solar
Cells with Solvent Additives (III)* Saki Kawano, Hironori Ogata

97

98

ナノチューブの物性
2P-10
☆
2P-11

(n,m )単層カーボンナノチューブの蛍光の濃度依存性* 魏 小均 , 平川 琢也 , 蓬田 陽平 , 平野 篤 , 藤井 俊治郎 , 田中 丈士 , 片浦 弘道
Chirality-Selective Metal Enhanced Fluorescence of DNA-Dispersed Single-Walled Carbon
Nanotubes* Min Lyu, Qinghua Zhao, Juan Yang, Yan Li

xi

99

100

２月２１日 （日）2P-12☆

アルキル化単層カーボンナノチューブの脱離反応における置換基効果について* 武塙 祐哉 , 鈴木 光明 , 山田 道夫 , 前田 優

101

2P-13

電界下におけるカーボンナノチューブの電子物性* 石山 佑 , 岡田 晋

102

ナノチューブの応用
2P-14

光誘起ラジカル生成を利用するポリスチレン側鎖と多層カーボンナノチューブとの化学結合形成* 馬場 拓麻 , 高田 知哉

103

2P-15

放電プラズマ焼結による高充填率CNT-Cuコンポジットの合成* 知久 真一郎 , 野村 雅信 , 西川 博 , 長谷川 隆

104

2P-16
☆

Characterization of carbon nanotube interdigitated electrode for electrochemical biosensors* Takuya Ushiyama, Nguyen Xuan Viet, Shigeru Kishimoto, Yutaka Ohno

105

2P-17

Charging-discharging phenomena of CNT electrical double layer capacitors* Karolina Laszczyk, Atsuko Sekiguchi, Takeo Yamada, Kenji Hata

106

2P-18

ポリマー被覆多層カーボンナノチューブ上へPtクラスターの作製とその燃料電池触媒への利107
用* 濱﨑 祐樹 , 藤ヶ谷 剛彦 , 中嶋 直敏

ナノチューブの生成と精製
2P-192液相法でリモネンを用いた単層カーボンナノチューブの膜作成* 石田 諒 , 大塚 真凜 , 金澤 尚宜 , 長澤 浩 , 小野 晶 , 鈴木 信三

108

2P-20
☆

有機金属蒸気からの浮遊担持触媒の創成とカーボンナノチューブの気相合成* 杉野 裕亮 , 長谷川 馨 , 大沢 利男 , 塚田 高行 , 野田 優

109

2P-21

Growth of Horizontally Aligned Chirality-Specific Single-Walled Carbon Nanotubes* Feng Yang, Yan Li

110

2P-22

Diameter-controlled ACCVD growth of SWNTs using water vapor* Hiroki Takezaki, Shinnosuke Ohyama, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Shigeo Maruyama

111

内包ナノチューブ
2P-23

2P-24
☆
2P-25

Molecular structure of chalcogen encapsulated in single-walled carbon nanotubes studied bymolecular dynamics simulations and First-Principles DFT calculations* 佐藤 豊 , 横倉 瑛太 , 片岡 洋右 , 緒方 啓典
Length-Selective Loading of Gold into the Interior of Carbon Nanotubes* Raman Bekarevich, Masami Toyoda, Shuichi Baba, Toshihiko Nakata, Kaori Hirahara
Local structure and properties of the cesium iodide crystals encapsulated in single-walledcarbon nanotubes studied by molecular dynamics and First-Principles DFT calculations* 横倉 瑛太 , 佐藤 豊 , 片岡 洋右 , 緒方 啓典

xii

112

113

114

２月２１日 （日）グラフェン生成
2P-26

CVDグラフェンの成長基板としてのCu多結晶体の再結晶過程* 小川 友以 , 鈴木 哲 , 小野満 恒二 , 日比野 浩樹 , 山本 秀樹

115

2P-27
☆

Efficient fabrication of graphene/BN heterostructures by metal melting transfer* 井上 凌介 , 渡邊 賢司 , 谷口 尚 , 真庭 豊 , 宮田 耕充

116

2P-28

大気圧CVD法における成長直前の水素オフによるグラフェン核生成抑制* 鈴木 誠也 , 寺田 佳史 , 吉村 雅満

117

グラフェンの応用
2P-29

2P-30

2P-31

2P-32

2P-33

グラフェン誘導体のスピン磁性と化学反応性の評価* 山科 智貴 , 井坂 琢也 , 田嶋 健太郎 , 松尾 吉晃 , 高井 和之
Environmentally Stable Carrier Doping into Graphene Films by Extraordinary Molecular
Lewis Acid
* 宮内 拓也 , 田中 直樹 , 庄子 良晃 , 舟橋 一真 , 金橋 魁利 , 石原 正統 ,長谷川 雅考 , 福島 孝典 , 竹延 大志
水溶媒中での有機反応における酸化グラフェン触媒の評価* 井坂 琢也 , 山科 智貴 , 田嶋 健太郎 , 太田 豊 , 高井 和之
Electrocatalytic properties toward methanol oxidation of Pt-based nanoparticles on surfacemodified carbon nanomaterials* 吉竹 晴彦 , 稲見 栄一 , 王 志朋 , 緒方 啓典
グラフェン／電解質溶液の界面における電気化学相互作用* 鈴木 大輔 , 高井 和之

118

119

120

121

122

グラフェンの物性
2P-34

2層グラフェンを用いた電子の閉じ込め* 井上 裕哉 , 齋藤 理一郎

123

2P-35

グラファイト上単層WS2における電場、電荷変調発光分光* 松木 啓一郎 , Jiang Pu, Daichi Kozawa, Yu Kobayashi, Shogo Sasaki,
Yasumitsu Miyata, Lain-Jong Li, Yutaka Maniwa, Taishi Takenobu

124

2P-36

Behavior of Graphene Oxide in Aqueous Solution* Meng Wang, Yang Niu, Zhenyu Zhang, Yan Li

125

2P-37

ナノグラフェンホストと磁性ゲスト分子間のホスト―ゲスト相互作用* 鈴木 彬 , 高井 和之

126

2P-38

Asymmetric Kohn anomaly in G' band of graphene* ハスデオ エッドウイ , ヌグラハ アフマド , 齋藤 理一郎

127

2P-39

欠陥を有する二層グラフェンの外部電場下における電子構造* 岸本 健 , 岡田 晋

128

☆

xiii

２月２１日 （日）
原子層
2P-40
☆

単層NbドープWS2のハライドアシストCVDと評価* 佐々木 将悟 , 小林 佑 , 劉 崢 , 末永 和知 , 真庭 豊 , 宮田 耕充

129

2P-41

スライド可能な原子層の作製と操作* 小林 佑 , 渡邊 賢司 , 谷口 尚 , 真庭 豊 , 宮田 耕充

130

2P-42
☆

高品質MoS2/WS2積層型ヘテロ構造における層間励起子* 齊藤 哲輝 , 小林 佑 , 渡邊 賢司 , 谷口 尚 , 真庭 豊 , 宮田 耕充

131

2P-43

大面積遷移金属ダイカルコゲナイド単層膜を用いた高性能CMOSインバータ* 蒲 江 , 舟橋 一真 , Chang-Hsiao Chen, Ming-Yang Li, Lain-Jong Li, 竹延 大志

132

2P-44

Photoluminescence Quantum Yield and Exciton Radiative Lifetimes in Monolayer WSe2
* N. Baizura Mohamed, Sandhaya Koirala, Feijiu Wang, Hong En Lim, Shinichiro Mouri,
Yuhei Miyauchi, Kazunari Matsuda

133

引張歪下でのMoS2薄膜の光吸収スペクトル* 福村 武蔵 , 本間 光太郎 , 野崎 純司 , 真庭 豊 , 柳 和宏

134

☆
2P-45

ナノ炭素粒子2P-46

ナノダイヤモンドの磁性と構造へのフッ素化およびアニール効果* 黄金 健太 , 東原 秀和 , 服部 義之 , Vladimir Osipov, Nickolai Romanov, 高井 和之

135

2P-47

カーボンナノバルーンの合成および直接メタノール型燃料電池における触媒活性の評価* 大廣 達郎 , 水井 康平 , 須田 善行 , 針谷 達 , 滝川 浩史 , 植 仁志

136

その他
2P-48
☆
2P-49

Acceleration of separation velocity in electric-field-induced layer formation method byadjusting surfactant concentration* Fusako Sasaki, Fumiyuki Nihey, Yuki Kuwahara, Hiroyuki Endoh, Shinichi Yorozu,
Takeshi Saito
電気化学ドーピング法によるWS2ナノチューブへのキャリア注入* 菅原 光成 , 北村 典雅 , 大島 侑己 , 河合 英輝 , 柳 和宏

第５０回記念 温故知新パネルディスカッション ( 16:45-18:45 )阿知波 洋次 , 飯島 澄男 , 今堀 博 , 岩佐 義宏 , 遠藤 守信 , 大澤 映二 ,小松 紘一 , 斎藤 晋 , 齋藤 弥八 , 田中 一義 , 谷垣 勝己 , 日野 照純

懇親会 ( 18:45-20:45 )

xiv

137

138

２月２２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-8

黒鉛の酸化プロセス解析による酸化グラフェンの自在合成* 仁科 勇太 , 森本 直樹 , 鈴木 秀幸

9

一般講演 ( 9:30-10:30 )グラフェンの物性 ・ 原子層
3-1

単層エピタキシャルグラフェンにおける電子格子相互作用の直接観察* 田中 慎一郎 , 丸山 隆浩 , 田中 清尚 , 出田 真一郎 , 山根 宏之

29

3-2

Anisotropic optical properties of layered monochalcogenide GeSe nanosheets* Dezhi Tan, Yuhei Miyauchi, Shinichiro Mouri, Koirala Sandhaya, Kazunari Matsuda

30

3-3

数層WSe2ショットキー太陽電池における光発電特性* 赤間 俊紀 , 加藤 俊顕 , 金子 俊郎

31

3-4

水素終端によるh-BNナノリボンの極性変調* 山中 綾香 , 岡田 晋

32＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜特別講演 ( 10:45-11:15 )3S-9

Exploring Ultimate Coherent Photon Technology and its Applications* 湯本 潤司

10

一般講演 ( 11:15-12:00 )ナノチューブの物性
3-5Gate-voltage induced trions in suspended carbon nanotubes* Masahiro Yoshida, Alexander Popert, Yuichiro K. Kato

33

3-6

フォトルミネッセンスによる塩基種に依存したDNA-SWNT相互作用の評価* 伊藤 雅浩 , 山洞 絵理 , 梅村 和夫 , 本間 芳和

34

3-7

単層カーボンナノチューブの円偏光２色性* 齋藤 理一郎 , 佐藤 直道 , 辰巳 由樹

35＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜xv

２月２２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
3P-1（☆） 若手奨励賞候補

Degradation of organic dyes under ultraviolet light condition with carbon nanocapsuleencircled by nickel nanoparticle composites* Jeong Won Ko, Hae Soo Park, Jiulong Li, Weon Bae Ko

139

金属内包フラーレン
3P-2

openC60の中に内包された酸素分子のESR測定* 加藤 梓 , 二子石 師 , 村田 靖次郎 , 加藤 立久

140

3P-3

Macroscopic Preparation and Isolation of La@C 60 as a Trifluoromethyl Derivative* 石野 勝真 , 青柳 忍 , 大町 遼 , 王 志永 , 丹羽 宏之 , 中川 綾乃 , 北浦 良 ,

141

☆

3P-4

篠原 久典
Preparation, Structural Determination, and Characterization of Electronic Properties ofCarbosilylated Sc3N@Ih-C80* 杉浦 健 , 深澤 新平 , 宮部 恭輔 , 加固 昌寛 , 安井 正憲 , 山田 道夫 , 鈴木 光明 ,前田 優 , 赤阪 健

142

フラーレン
3P-5
☆
3P-6

Pressure-induced transformations and light irradiation effects on ferrocene-doped C 60
nanosheets* 嘉藤 恭平 , 権守 宏通 , 村田 秀信 , 橘 勝
五重付加体C60の電場下における物性* 古谷 匠 , 岡田 晋

143

144

ナノチューブの物性
3P-7

3P-8
☆
3P-9

3P-10
☆
3P-11

変形したCNTへの電界による電荷蓄積* 長谷川 明子 , 岡田 晋

145

Exact Extraction of Transfer length at Metal/Carbon Nanotube Contacts by Improved
Transmission Line Method* 殿内 規之 , 遠藤 浩幸 , 二瓶 史行 , 横田 知之 , 染谷 隆夫
Experimental investigation of thermal conductivity of single walled carbon nanotube thin filmwith infrared thermal imager* Ya Feng, Makoto Watanabe, Shuhei Yoshida, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Shigeo Maruyama
Emergence of a New Red-Shifted PL from Chemically-Modified Single-Walled Carbon
Nanotubes* 白石 智也 , 白木 智丈 , 中嶋 直敏
Rayleigh Scattering Spectroscopy of Single-Walled Carbon Nanotubes in Various
Surrounding Environments* Toru Osawa, Takeshi Okochi, Yoritaka Furukawa, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Shigeo Maruyama

xvi

146

147

148

149

２月２２日 （月）ナノチューブの応用
3P-12

3P-13
☆

光誘起ラジカル生成を利用するポリ安息香酸ビニル側鎖と多層カーボンナノチューブとの化
150
学結合形成
* 高田 知哉 , 西岡 裕哉 , 馬場 拓麻
Single-Step Extraction of Semiconducting Single-Wall Carbon Nanotubes by Aqueous-Two
Phase (ATP) System* 小室 智彦 , 大町 遼 , 廣谷 潤 , 北浦 良 , 大野 雄高 , 篠原 久典

151

3P-14

単層カーボンナノチューブ表面における架橋高分子層の形成* 藤ヶ谷 剛彦 , 堤 優介 , 中嶋 直敏

152

3P-15

単層カーボンナノチューブによるチオールのジスルフィド結合形成* 平野 篤 , 和田 百代 , 田中 丈士 , 片浦 弘道

153

3P-16
☆

Thermoelectric characterizations of carbon nanotube/curable resin* Wenxin Huang, Tsuyohiko Fujigaya, Naotoshi Nakashima

154

3P-17

Environmentally Stable Carrier Doping into Carbon Nanotube Films by Extraordinary
Molecular Lewis Acid
* 舟橋 一真 , 田中 直樹 , 庄子 良晃 , 中山 航 , 金橋 魁利 , 白江 宏之 , 野田 優 ,福島 孝典 , 竹延 大志

155

ナノチューブの生成と精製
3P-18

3P-19
☆
3P-20

Effect of catalyst support on growth lifetime of carbon nanotube forest* Takashi Tsuji, Shunsuke Sakurai, Maho Yamada, Don Futaba, Kenji Hata
Comparison between Reduced and Intentionally Oxidized Metal Catalysts for Growth ofSingle-Walled Carbon Nanotubes* Yang Qian, Rong Xiang, Hua An, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama
Controlled synthesis of single-walled carbon nanotubes with sputtered W-based catalyst* 安 華 , 項 榮 , 竹崎 大輝 , 大山 真之介 , 銭 洋 , 井ノ上 泰輝 , 千足 昇平 ,

156

157

158

丸山 茂夫
3P-21

Molecular dynamics simulation of single-walled carbon nanotubes grown from binary catalyst 159* Yukai Takagi, Ryo Yoshikawa, Shohei Chiashi, Shigeo Maruyama

3P-22

Quantifying the purity of semiconducting/metallic fractions in ELF separation of SWCNTs* Yuki Kuwahara, Fusako Sasaki, Fumiyuki Nihey, Hiroyuki Endo, Shinichi Yorozu,
Takeshi Saito

160

内包ナノチューブ
3P-23☆

STM/STS studies on Europium nanowires encapsulated in carbon nanotubes* Terunobu Nakanishi, Ryo Kitaura, Shoji Yoshida, Osamu Takeuchi, Hidemi Shigekawa,
Hisanori Shinohara

xvii

161

２月２２日 （月）

3P-24

3P-25

Condensation reaction of 5,5”-dibromo-2,2':5'2”-terthiophene inside single-walled carbon
nanotubes* 佐々木 淳 , 小山 剛史 , 岸田 英夫 , 吉田 幸大 , 齋藤 軍治
High-yield Filling of Hydroxylated Diamantane into Carbon Nanotubes* Yusuke Nakanishi, Haruka Omachi, Natalie A. Fokina, Ryo Kitaura, Peter R. Schreiner,
Jeremy E. P. Dahl, Robert M. K. Carlson, Hisanori Shinohara

162

163

グラフェン生成3P-26☆

熱イオン注入後のダイヤモンド(100)表面上に形成された垂直配向グラファイト層* 稲葉 優文 , 費 文茜 , 平野 優 , 鈴木 和真 , 川原田 洋

164

3P-27

アルコールCVDによる高品質大面積グラフェンの合成条件* 津島 幸平 , 曽田 将来 , 陳 嘯 , 項 榮 , 井ノ上 泰輝 , 千足 昇平 , 丸山 茂夫

165

3P-28

Feインターカレートした2層グラフェンの作製と電気特性の評価* 星野 崚 , 林 佑太郎 , 鈴木 希 , 永田 知子 , 岩田 展幸 , 山本 寛

166

グラフェンの応用
3P-29

2次元物質によるレーザー水分解効果の増大現象* 宮本 良之 , Hong Zhang, Xinlu Cheng, Angel Rubio

167

3P-30

Solvothermal preparation of uranium oxide supported on reduced graphene oxide* Li Ding, Pei Tang, Ding Ma, Yan Li

168

3P-31

酸化グラフェンを正孔輸送層として用いたPlanar型ペロブスカイト太陽電池の作製* 藤井 俊治郎 , 田中 丈士 , 片浦 弘道

169

3P-32

窒化グラフェンの酸素還元触媒効果検証* Takeru Okada, Kumi Inoue, Tomokazu Matsue, Golap Kalita, Masaki Tanemura,
Meyya Meyyappan, Seiji Samukawa

170

グラフェンの物性
3P-33

AFM-ラマン分光法によるグラフェンのナノスケール・キャラクタリゼーション* 中田 靖 , 奥野 義人 , バンタシン サンポン , 田中 嘉人 , ヤン インサン , 尾崎 幸洋 ,

171

中 庸行
3P-34

電界放出及び電界イオン顕微鏡法を用いたグラフェンエミッタの電子放出サイトに関する研究* 横山 昂 , 星野 徹 , 岩田 晃治 , 中原 仁 , 安坂 幸師 , 齋藤 弥八

172

3P-35

グラフェンナノリボンプラズモン共鳴における次元性依存* 森本 崇宏 , 生田 美植 , 岡崎 俊也

173

3P-36

Wavelength dependence of surface roughness in photoreduction of graphene oxide
Maki Ueda, Yoshiki Yamamoto, Yuki Hirano, Kazuto Hatakeyama, Michio Koinuma,
Yasumichi Matsumoto, Masahiro Hara, * Hiroyuki Yokoi

174

xviii

２月２２日 （月）3P-37

グラフェンにおけるラマン強度の磁場依存性* 白倉 俊哉 , 齋藤 理一郎

175

原子層
3P-38
☆

化学気相成長法による大面積かつ高品質な単層六方晶窒化ホウ素の合成と黒リンの表面不活性化への応用* 高林 裕也 , Sinha Sapna, 大町 遼 , 篠原 久典 , 北浦 良

176

3P-39

電気二重層トランジスタを用いた多結晶MoS2薄膜の絶縁体-金属転移* 越阪部 拓也 , 蒲 江 , 枝川 祐介 , Lain-Jong Li, 竹延 大志

177

3P-40
☆

単層単結晶WS2の位置制御合成* 高橋 智之 , 加藤 俊顕 , 金子 俊郎

178

3P-41

単層WSe2/有機分子へテロ構造の光学特性* 木村 祥太 , 小澤 大知 , 松木 啓一郎 , 毛利 真一郎 , 宮内 雄平 , 松田 一成 ,Lain-Jong Li, 竹延 大志

179

3P-42
☆

単層遷移金属ダイカルコゲナイドの偏光分解発光マッピング* 長谷川 勇介 , 王 飛久 , 青田 駿 , 毛利 真一郎 , 松田 一成 , 宮内 雄平

180

3P-43

3P-44

Magnetism arising from pore edges of nanomesh on few-atomic-layerd hexagonal boron
nitride* Kenshin Nagano, Yuichi Tagami, Chika Ohata, Gen Hashimoto, Shingo Katsumoto,
Kyoko Nomura, Junji Haruyama
Geometric and electronic structures of atomic layers of GaN* 高 燕林 , 岡田 晋

181

182

ナノ環境と安全評価
3P-45

マクロファージによるＣＮＴ取り込みにおけるＣＮＴサイズ効果の定量評価* 張 民芳 , 鉄羅 奈央子 , 市楽 佳代 , 藤田 克英 , 飯島 澄男 , 湯田坂 雅子 ,

183

岡崎 俊也

その他
3P-46

分子が規則配列した有機構造体の炭化による窒素ドープカーボンの調製* 白木 智丈 , キム ガヨン , 中嶋 直敏

184

3P-47

多段トラップ型気相移動度測定システムの開発と荷電微粒子の長距離移動制御による分離* 松林 広延 , 廣芝 泰祐 , 陣内 涼太 , 大川 航 , 菅井 俊樹

185

3P-48

トラップ型気相移動度測定法を用いたナノ粒子の測定* 陣内 涼太 , 廣芝 泰祐 , 松林 広延 , 大川 航 , 伊藤 拓真 , 菅井 俊樹

186

xix

２月２２日 （月）特別講演 ( 16:00-16:30 )3S-10

カーボンナノチューブにおける励起子の物理と工学* 宮内 雄平

11

一般講演 ( 16:30-17:30 )フラーレンの応用 ・ その他 ・ ナノチューブの応用 ・ ナノ炭素粒子
3-8

万能性基幹分子応用に向けたC60フラーレン薄膜の半導体‐金属‐半導体特性変化* Nobuyuki Aoki, Wataru Akiyama, Naoto Nakamura, Katsuhiko Miyamoto,Takashige Omatsu, Jonathan P. Bird, Yuichi Ochiai

36

3-9

トラップ型気相移動度測定システムの開発とナノ物質の測定* 菅井 俊樹 , 廣芝 泰祐 , 松林 広延 , 大川 航 , 伊藤 拓真 , 陣内 涼太

37

3-10

加速電圧に依存したカーボンナノホーン上での分子運動の電子顕微鏡観察* Koji Harano, Ricardo M. Gorgoll, Emrah Yücelen, Akihito Kumamoto, Naoya Shibata,
Eiichi Nakamura

38

3-11

ナノダイヤモンド研究開発の最近状況* 大澤 映二 , 佐々木 修一 , 山野井 亮子

39xxFebruary 19th, Fri.
Special Lecture: 40min (Presentation) + 20min (Discussion)Special Lecture ( 16:30-17:30 )S-1

What can we learn about low-symmetry materials from spectroscopy?
* Mildred S. Dresselhaus

1

February 20th, Sat.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)
Special Lecture ( 9:30-10:00 )1S-1

Direct dry printing of SWNT thin films for flexible electronics applications* Esko I. Kauppinen

2Special Lecture ( 10:00-10:30 )1S-2

Graphene oxide: massive production and practical application* Bunshi Fugetsu, Yanqing Wang, Ichiro Sakata

3＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜General Lecture ( 10:45-11:45 )Fullerenes ・ Properties of graphene
1-1

Microscopic Growth Process of Fullerenes and Extreme Abundance of C 60
Yusuke Ueno, Joseph Chan, Masayuki Toyoda, * Susumu Saito

13

1-2

Molecular dynamics simulation of the growth of fullerenes from carbon atoms* Joseph Chan, Susumu Saito

14

1-3

1-4

Electrochemical Evaluation of Proton Permeability of Monolayer Graphene Grown on
Au(111) Electrode
Koji Nakashima, Ryota Kumagai, * Satoshi Yasuda, Kei Murakoshi
Magnetic property of two-dimensional networks of high-spin hydrocarbon molecules* Mina Maruyama, Susumu Okada

1516＞＞＞＞＞＞＞ Lunch Time ( 11:45-13:00 ) ＜＜＜＜＜＜＜Special Lecture ( 13:00-13:30 )1S-3

JST/CREST on “2D Materials”- Research Supervisor’s Policy and the Invitation for Applications * Atsushi Kurobe

xxi

4February 20th, Sat.
General Lecture ( 13:30-14:15 )Atomic Layers
1-5

1-6

1-7

Edge effect on electrode contacts to transition metal dichalcogenides* Ryo Nouchi
Bandgap modulation in one-dimensional interface of MoS2/WS2-based semiconductor
heterojunction* Yu Kobayashi, Shoji Yoshida, Ryuji Sakurada, Tetsuki Saito, Kenji Watanabe,
Takashi Taniguchi, Yutaka Maniwa, Hidemi Shigekawa, Yasumitsu Miyata
Geometric and electronic properties of thin-layer GeSe and GeSe/MoS 2 heterostructures* Mari Ohfuchi

17

18

19

Poster Preview ( 14:15-15:15 )Poster Session ( 15:15-17:00 ) （☆）Candidates for the Young Scientist Poster Award
Chemistry of fullerenes
1P-1

1P-2

Raman spectroscopic measurement of C60 fullerene nanowhiskers* Toshio Konno, Chika Hirata, Takatsugu Wakahara, Kunichi Miyazawa
Energetics and electronic structures of molecular complexes of fullerenes andcyclohydrocarbons* Yuya Nagasawa, Susumu Okada

41

42

Endohedral metallofullerenes
1P-3

ESR spectra of Gd and Y di-metallofullerenes* Takahisa Yamaguchi, Natsumi Nakatori, Takuji Mitani, Koichi Kikuchi, Takeshi Kodama,Ko Furukawa, Tatsuhisa Kato

43

1P-4

Isolation and Characterization of the hidden metallofullerene: Y 2@C78* Natsumi Nakatori, Takuji Mitani, Takahisa Yamaguchi, Ko Furukawa, Tatsuhisa Kato,
Koichi Kikuchi, Yohji Achiba, Takeshi Kodama

44

☆

1P-5

Photoreactions of Trimetallic Nitride Template Endohedral Metallofullerenes with
Digermirane* Kyosuke Miyabe, Yuichi Sato, Masahiro Kako, Masanori Yasui, Kumiko Sato,
Naomi Mizorogi, Wei-Wei Wang, Shigeru Nagase, Takeshi Akasaka

45

Fullerenes
1P-6

Mixed Valence transitions in Rare-earth Fullerides* Takeshi Nakagawa, Yasuhiro Takabayashi, Kosmas Prassides

46

1P-7

μ+SR study of fulleride superconductors across the superconductivity dome
* Melita Menelaou, Yasuhiro Takabayashi, Ruth H. Zadik, Peter J. Baker,
Kosmas Prassides

47

Properties of nanotubes
1P-8

Energetics and electronic structure of CNT embedded in Si* Taketo Kochi, Susumu Okada

xxii

48

February 20th, Sat.
1P-9
☆
1P-10

1P-11
☆

1P-12

Crossover from Quantum to Classical Transport in Carbon Nanotubes* Keisuke Ishizeki, Kenji Sasaoka, Takahiro Yamamoto
Photoluminescence spectral shift of chemically-modified single-walled carbon nanotubes byexternal stimuli* Hisashi Onitsuka, Tomohiro Shiraki, Naotoshi Nakashima
Morphology Dependence on Thermal Transport Properties of Single-walled Carbon Nanotube
Films* Shuhei Yoshida, Ya Feng, Taiki Inoue, Rong Xiang, Shohei Chiashi, Esko Kauppinen,
Shigeo Maruyama
Photothermoelectric Effect in Single Wall Carbon Nanotube Thin Films with Precisely
Controlled Seebeck Coefficients* Masatoshi Nakamura, Yoshimasa Kitamura, Yuki Oshima, Hideki Kawai, Yutaka Maniwa,
Kazuhiro Yanagi

49

50

51

52

Applications of nanotubes
1P-13

Carbon nanotube sheet as a transparent electrode for semi-transparent organic solar cell
* Senku Tanaka, Naoya Urakawa, Kanzan Inoue

53

1P-14

In-situ TEM study on self-oscillations of carbon nanotube during field emission* Tomonori Kato, Hitoshi Nakahara, Koji Asaka, Yahachi Saito

54

1P-15
☆

Transparent, stretchable all-carbon nanotube thin-film transistors for wearable electronics* Takeo Onishi, Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno

55

1P-16

Mechanical and electric properties of continuous polymer-free carbon nanotube fibers* Xueli Wu, Takahiro Morimoto, Ken Mukai, Kinji Asaka, Toshiya Okazaki

56

1P-17

Production and electrical properties of CNT-Cu composite wires* Rajyashree Sundaram, Atsuko Sekiguchi, Takeo Yamada, Kenji Hata

57

Formation and purification of nanotubes
1P-18

1P-19

1P-20
☆

Polymer Length effect on Selective Separation of Semiconducting Single-Walled Carbon
Nanotubes* Fumiyuki Toshimitsu, Naotoshi Nakashima
Chirality control of in-plane oriented single-walled carbon nanotubes using free electron laser* Daiki Kawaguchi, Miu Kobayashi, Shinnosuke Harumiya, Tomoko Nagata,
Nobuyuki Iwata, Hiroshi Yamamoto
Catalyst Nucleation and Carbon Nanotube Growth from Flame-Synthesized Co-Al-O
Nanopowders at 10 Second Time Scale* Hiroyuki Shirae, Kei Hasegawa, Eongyu Yi, Richard Laine, Suguru Noda

xxiii

58

59

60

February 20th, Sat.
1P-21

1P-22

Chemical reaction analysis of cupper clusters by FT-ICR mass spectroscopy* Ken Mizutani, Yoshinori Sato, Hiroya Minowa, Taiki Inoue, Shohei Chiashi,
Shigeo Maruyama
Flow Rate Dependence of Production of Double-wall Carbon Nanotubes by High-temperature
Pulsed-arc Discharge* Yuto Hikichi, Ryota Jinnnouchi, Toshiki Sugai

61

62

Graphene synthesis
1P-23

1P-24
☆

1P-25

1P-26
☆
1P-27

Direct growth of patterned multi-layer graphene by precipitation method using patterned W
capping layer* Jumpei Yamada, Yuki Ueda, Takahiro Maruyama, Shigeya Naritsuka
Fabrication and characterization of graphene nanoribbons by water-assisted anisotropic
etching* Shun Ogawa, Ryosuke Inoue, Kenji Watanabe, Takashi Taniguchi, Yutaka Maniwa,
Yasumitsu Miyata
Study of non-catalytic CVD of graphene on sapphire substrate----- Effect of growth temperature on nucleation ----* Yuki Ueda, Jumpei Yamada, Itsuki Uchibori, Masashi Horibe, Shinichi Matsuda,
Takahiro Maruyama, Shigeya Naritsuka
Growth of Large-Grain Graphene and the Role of Oxygen* Dong Ding, Rozan Mohamad Yunus, Pablo Solís Fernández, Hiroki Ago
Characterization of few-layered graphene obtained by exfoliation of Graphite Intercalation
Compounds* Takuya Yasutake, Taro Kinumoto, Tomoki Tsumura, Masahiro Toyoda

63

64

65

66

67

Applications of graphene
1P-28

The Use of Double-layered Graphene Oxides for Capturing Carbon Dioxides:
A Computational Proposal* Takashi Yumura, Ayumi Yamasaki

68

1P-29

Geometric and electronic structures of graphene nanoribbons under uniaxial pressure* Kohei Narita, Susumu Okada

69

1P-30

Adsorption of Dps onto graphene using carbon nano-horn binding peptide* Yuki Hashima, Yasuaki Ishikawa, Mutsunori Uenuma, Naofumi Okamoto,
Ichiro Yamashita, Yukiharu Uraoka

70

1P-31

Silicon Thin-Film Solar Cells with Graphene Transparent Electrode* Ryousuke Ishikawa, Tomoya Oya, Takahiro Nomoto, Nozomu Tsuboi

71

1P-32

Substrate dependence of graphene oxide in amidation and esterification reactions* Haruya Okimoto, Yasutaka Yoshii, Masahito Sano

72

☆

xxiv

February 20th, Sat.
Properties of graphene
1P-33

Indirect angle resolved photoemission spectra in graphene* Pourya Ayria, Shin-ichiro Tanaka, Ahmad R. T. Nugraha, Riichiro Saito

73

1P-34

Raman Spectroscopy of Ti-Cleaned Single-Layer Graphene and Transfer on Paper Substrate* Akira Fujimoto, Masafumi Sakita, Ren Kaneko, Ryosuke Nakano, Kazuo Satoh,
Shuichi Murakami, Yoshiyuki Harada, Toshihiko Maemoto, Mitsuaki Yano

74

Atomic Layers
1P-35
☆
1P-36

1P-37
☆

1H-1T’ phase transition and heterojunction formation in CVD-grown monolayer Mo1-xRexS2* Shohei Mori, Shogo Sasaki, Yu Kobayashi, Liu Zheng, Shoji Yoshida, Takahiro Takeuchi,
Hidemi Shigekawa, Kazutomo Suenaga, Yutaka Maniwa, Yasumitsu Miyata

75

Anisotropic optical absorption and Raman spectrum in GaTe
* Yuki Tatsumi, Shengxi Huang, Xi Ling, Huaihong Guo, Teng Yang,
Mildred S. Dresselhaus, Riichiro Saito

76

Observation of Biexciton States in high-quality Tungsten Disulfide Atomic Layers from 80 K
to Room Temperature* Mitsuhiro Okada, Yuhei Miyauchi, Kenji Watanabe, Takashi Taniguchi,
Kazunari Matsuda, Hisanori Shinohara, Ryo Kitaura

77

1P-38

Visualization of local transport properties of MoS 2 transistors by scanning gate
* Ayaka Higuchi, Masahiro Matsunaga, Guanchen He, Jonathan Bird, Yuichi Ochiai,
Nobuyuki Aoki

78

1P-39
☆

Extremely Thin and Flexible Single-Layer WS2 Phototransistors* Adha Sukma Aji, Toshiaki Shiiba, Kenjiro Fukuda, Hiroki Ago

79

1P-40

Lattice Vibrations in Isotopic Diamond Superlattice* Yuki Bando, Susumu Saito

80

1P-41

Josephson effect in NbSe 2/NbSe2 van der Waals junction* Naoto Yabuki, Rai Moriya, Miho Arai, Yohta Sata, Sei Morikawa, Satoru Masubuchi,
Tomoki Machida

81☆

Nanohorns
1P-42

1P-43

Functional carbon nanohorns for multi-dimensional cancer elimination* Eijiro Miyako, Svetlana Chechetka, Minfang Zhang, Masako Yudasaka
Characterization and Supercapacitor Properties of Fibrous Aggregates of Single-Walled
Carbon Nanohorns* Ryota Yuge, Fumiyuki Nihey, Kiyohiko Toyama, Masako Yudasaka

82

83

Carbon nanoparticles
1P-44

Electrical conductivity of carbon nanomaterials under compression* Kohei Mizui, Tatsuo Ohiro, Yoshiyuki Suda, Toru Harigai, Hirohumi Takikawa,
Hitoshi Ue

xxv

84

February 20th, Sat.
1P-45

Laser Power Dependence in LDI MS of Detonation Nanodiamonds* Masayoshi Fukaya, Yoshiki Otsubo, Toshihiko Tanaka, Ryoko Yamanoi, Eiji Osawa

85

1P-46

Polymer-derived Nanoporous Carbon Monolith: High Electrochemical Capacitive Behaviors* Yanqing Wang, Bunshi Fugetsu, Ichiro Sakata, Zhipeng Wang, Wei Gong,
Mauricio Terrones, Morinobu Endo, Mildred Dresselhaus

86

Other topics
1P-47

Polyyne formation by laser-induced breakdown in argon-diluted propane gas flow
* Yuuki Taguchi, Hitomi Endo, Takeshi Kodama, Tomonari Wakabayashi, Yohji Achiba,
Haruo Shiromaru

87

1P-48

Polyyne formation by laser ablation of PAH/graphite composite disk in vacuum* Ryouichi Moriguchi, Yuki Taguchi, Hitomi Endo, Tomonari Wakabayashi,
Takeshi Kodama, Yohji Achiba, Haruo Shiromaru

88

1P-49

Observation of Size Dependence of Charge State of Nano-level Particles by Ion Trap Ion
Mobility Measurement* Yasuhiro Hiroshiba, Hironobu Matsubayashi, Takuma Ito, Ryota Jinnouchi,
Toshiki Sugai

89

Special Lecture ( 17:00-17:30 )1S-4

For industrial applications of the future of carbon nanotubes* Takeshi Hashimoto

5

General Lecture ( 17:30-18:15 )Applications of nanotubes
1-8

1-9

1-10

1 wt% carbon nanotubes realized lithium ion batteries without binder nor metal foils* Kei Hasegawa, Suguru Noda
Metal-free Transparent Organic Solar Cell with a P-dopant Enhanced Carbon Nanotube
Electrode* Il Jeon, Clement Delacou, Antti Kaskela, Esko I. Kauppinen, Shigeo Maruyama,
Yutaka Matsuo
Oxygen-doped carbon nanotubes as near-infrared imaging probes and fluorescent labels* Yoko Iizumi, Masako Yudasaka, Tsukasa Takeuchi, Toshiya Okazaki＞＞＞＞＞＞＞ Coffee Break ( 18:15-18:30 ) ＜＜＜＜＜＜＜Tutorial ( 18:30-20:00 )Graphene –CVD growth, characterization, and application–* Hiroki Ago

xxvi

20

21

22

February 21st, Sun.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)
Special Lecture ( 9:00-9:30 )2S-5

Structure-controlled growth of single-walled carbon nanotubes: from catalyst design to growth
conditions* Yan Li

6

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

2-2

2-3

Highly Efficient Synthesis of Vertically-Aligned Carbon Nanotube Array at Temperature
Exceeding 900 ºC Enhanced by Carbon Monoxide* Shunsuke Sakurai, Maho Yamada, Don Futaba, Kenji Hata
Extended alcohol catalytic chemical vapor deposition for efficient growth of small-diameter
single-walled carbon nanotubes beyond (6,5)* Bo Hou, Rong Xiang, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama
High resolution EELS on individual carbon nanotubes* Ryosuke Senga, Thomas Pichler, Kazu Suenaga

23

24

25

＞＞＞＞＞＞＞ Coffee Break ( 10:15-10:30 ) ＜＜＜＜＜＜＜Special Lecture ( 10:30-11:00 )2S-6

Precision Assembly of C60 Functionality Using Supramolecular Scaffolds* Takanori Fukushima

7

General Lecture ( 11:00-11:45 )Graphene synthesis ・ Endohedral metallofullerenes ・ Fullerenes
2-4

Surface Synthesis of Acene-type Graphene Nanoribbon* Takahiro Nakae, Shaotang Song, Takahiro Kojima, Hiroshi Sakaguchi

26

+

2-5

2-6

Multiple photosynthetic reaction centers of porphyrinic polypeptide/Li @C60 supramolecularcomplexes* Kei Ohkubo, Tetsuya Hasegawa, Regis Rein, Nathalie Solladie, Shunichi Fukuzumi
Physical control of insulator-to-metal transition in overexpanded A 3C60
* Yasuhiro Takabayashi, Ruth H. Zadik, Tekeshi Nakagawa, Kosmas Prassides＞＞＞＞＞＞＞ Lunch Time ( 11:45-13:00 ) ＜＜＜＜＜＜＜Awards Ceremony ( 13:00-13:30 )

xxvii

27

28

February 21st, Sun.
Special Lecture ( 13:30-14:00 )2S-7

Nanocarbon-based light sources for integrated optoelectronics and optical communications* Hideyuki Maki

8

Poster Preview ( 14:00-15:00 )Poster Session ( 15:00-16:45 ) （☆）Candidates for the Young Scientist Poster Award
Chemistry of fullerenes
2P-1

Regioselective Addition of Grignard Reagents to Azafulleroids* Naohiko Ikuma, Koji Nakagawa, Ken Kokubo, Takumi Oshima

90

2P-2

Solid properties in hydroxylated carbon materials studied by 1H NMR* Yoshiaki Sano, Hironori Ogata

91

Applications of fullerenes
2P-3

2P-4

Synthesis of Fullerene Derivatives Having Cyclic Structure through Cationic Intermediate for
Organic Solar Cells Application* Keisuke Ogumi, Hiroshi Okada, Takafumi Nakagawa, Yutaka Matsuo
Investigation of catalytic activity for reduction of 4-nitrophenol with [C 60]fullerene
nanowhisker-silver nanoparticle composites* Jeong Won Ko, Hwa Jeong Chae, Weon Bae Ko

92

93

Endohedral metallofullerenes
2P-5

Chemical reduction of Metallofullerene using Various Amine* Yuta Sato, Kosuke Tanaka, Kazuhiko Akiyama, Shiro Kubuki

94

2P-6

Isolation and characterization of Gd2@C80 anion whose spin state is S=15/2* Takuji Mitani, Natsumi Nakatori, Takahisa Yamaguchi, Tatsuki Kobayashi, Ko Furukawa,
Tatsuhisa Kato, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama

95

☆

2P-7

Reactions of Endohedral Metallofullerenes with Silacyclopropanes: Mono-silylation andCarbosilylation of Lu3N@Ih-C80* Kazuya Minami, Masahiro Kako, Kumiko Sato, Naomi Mizorogi, Shigeru Nagase,
Takeshi Akasaka

96

Fullerenes
2P-8

2P-9

Electrostatic Interaction of fullerenes under an external electric field* Jun-ya Sorimachi, Susumu Okada
Solid-State NMR Studies on the Aggregated Structures of Organic Bulk Heterojunction Solar
Cells with Solvent Additives (III)* Saki Kawano, Hironori Ogata

97

98

Properties of nanotubes
2P-10☆

Concentration Dependence of Photoluminescence of (n,m ) Single-Wall Carbon Nanotubes* Xiaojun Wei, Takuya Hirakawa, Yohei Yomogida, Atsushi Hirano, Shunjiro Fujii,
Takeshi Tanaka, Hiromichi Kataura

xxviii99

February 21st, Sun.
2P-11

Chirality-Selective Metal Enhanced Fluorescence of DNA-Dispersed Single-Walled Carbon
Nanotubes* Min Lyu, Qinghua Zhao, Juan Yang, Yan Li

100

2P-12
☆

Substituent effects on defunctionalization of alkylated single-walled carbon nanotubes* Yuya Takehana, Mitsuaki Suzuki, Michio Yamada, Yutaka Maeda

101

2P-13

Electronic structure of CNTs under an external electric field* U Ishiyama, Susumu Okada

102

Applications of nanotubes
2P-14

Chemical Bond Formation between Multi-walled Carbon Nanotube and Polystyrene Side
Chain through Photo-induced Radical Formation* Takuma Baba, Tomoya Takada

103

2P-15

Highly Packed CNT-Cu composite by the Spark Plasma Sintering* Shinichiro Chiku, Masanobu Nomura, Hiroshi Nishikawa, Takashi Hasegawa

104

2P-16
☆

Characterization of carbon nanotube interdigitated electrode for electrochemical biosensors* Takuya Ushiyama, Nguyen Xuan Viet, Shigeru Kishimoto, Yutaka Ohno

105

2P-17

Charging-discharging phenomena of CNT electrical double layer capacitors* Karolina Laszczyk, Atsuko Sekiguchi, Takeo Yamada, Kenji Hata

106

2P-18

Fabrication of Pt nanocluters on polymer warpped multi-walled carbon nanotubes and theiruse as fuel cell catalyst* Yuki Hamasaki, Tsuyohiko Fujigaya, Naotoshi Nakashima

107

Formation and purification of nanotubes
2P-19

2P-20
☆

Film-making of single-wall carbon nanotubes by using limonene in two immiscible aqueous
solution phases* Ryo Ishida, Marin Ohtsuka, Naoki Kanazawa, Hiroshi Nagasawa, Akira Ono,
Shinzo Suzuki
Creation of ”floating supported catalyst” from metalorganic vapors and gas-phase synthesis ofcarbon nanotubes* Sugino Yusuke, Hasegawa Kei, Osawa Toshio, Tsukada Takayuki, Noda Suguru

108

109

2P-21

Growth of Horizontally Aligned Chirality-Specific Single-Walled Carbon Nanotubes* Feng Yang, Yan Li

110

2P-22

Diameter-controlled ACCVD growth of SWNTs using water vapor* Hiroki Takezaki, Shinnosuke Ohyama, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Shigeo Maruyama

111

Endohedral nanotubes
2P-23

Molecular structure of chalcogen encapsulated in single-walled carbon nanotubes studied bymolecular dynamics simulations and First-Principles DFT calculations* Yutaka Sato, Eita Yokokura, Yousuke Kataoka, Hironori Ogata

xxix

112

February 21st, Sun.
2P-24
☆
2P-25

Length-Selective Loading of Gold into the Interior of Carbon Nanotubes* Raman Bekarevich, Masami Toyoda, Shuichi Baba, Toshihiko Nakata, Kaori Hirahara
Local structure and properties of the cesium iodide crystals encapsulated in single-walledcarbon nanotubes studied by molecular dynamics and First-Principles DFT calculations* Eita Yokokura, Yutaka Sato, Yosuke Kataoka, Hironori Ogata

113

114

Graphene synthesis
2P-26

Recrystallization of polycrystalline Cu-foil for CVD-grown graphene* Yui Ogawa, Satoru Suzuki, Koji Onomitsu, Hiroki Hibino, Hideki Yamamoto

115

2P-27
☆

Efficient fabrication of graphene/BN heterostructures by metal melting transfer* Ryosuke Inoue, Kenji Watanabe, Takashi Taniguchi, Yutaka Maniwa, Yasumitsu Miyata

116

2P-28

Suppression of graphene nucleation by turning off hydrogen supply just before atmosphericchemical vapor deposition growth* Seiya Suzuki, Yoshifumi Terada, Masamichi Yoshimura

117

Applications of graphene
2P-29

2P-30

2P-31

2P-32

2P-33

Evaluation of spin magnetism and chemical activity for graphene derivatives* Tomoki Yamashina, Takuya Isaka, Kentaro Tajima, Yoshiaki Matsuo, Kazuyuki Takai
Environmentally Stable Carrier Doping into Graphene Films by Extraordinary Molecular
Lewis Acid
* Takuya Miyauchi, Naoki Tanaka, Yosiaki Shoji, Kazuma Hunahashi, Kaito Kanahashi,
Masatou Ishihara, Masataka Hasegawa, Takanori Hukushima, Taishi Takenobu
Evaluation of Graphene Oxide Catalyst regarding Organic reaction in Aqueous media* Takuya Isaka, Tomoki Yamashina, Kentaro Tajima, Yutaka Ohta, Kazuyuki Takai
Electrocatalytic properties toward methanol oxidation of Pt-based nanoparticles on surfacemodified carbon nanomaterials* Haruhiko Yoshitake, Eiichi Inami, Zhipeng Wang, Hironori Ogata
Electrochemical Interaction at the Interface between Graphene and Electrolyte* Daisuke Suzuki, Kazuyuki Takai

118

119

120

121

122

Properties of graphene
2P-34

Electron confinement in bilayer graphene* Yuya Inoue, Riichiro Saito

123

2P-35

Electric field and charge modulation spectroscopy of monolayer WS2 on graphite* Keiichiro Matsuki, Jiang Pu, Daichi Kozawa, Yu Kobayashi, Shogo Sasaki,
Yasumitsu Miyata, Lain-Jong Li, Yutaka Maniwa, Taishi Takenobu

124

Behavior of Graphene Oxide in Aqueous Solution* Meng Wang, Yang Niu, Zhenyu Zhang, Yan Li

125

☆
2P-36

xxx

February 21st, Sun.
2P-37

Host-Guest interactions between nanographene host and magnetic guest molecule* Akira Suzuki, Kazuyuki Takai

126

2P-38

Asymmetric Kohn anomaly in G' band of graphene* Eddwi Hasdeo, Ahmad Nugraha, Riichiro Saito

127

2P-39

Electronic structure of bilayer graphene with defect under an external electric field* Ken Kishimoto, Susumu Okada

128

Atomic Layers
Halide-assisted CVD and characterization of monolayer Nb-doped WS2* Shogo Sasaki, Yu Kobayashi, Zheng Liu, Kazutomo Suenaga, Yutaka Maniwa,
Yasumitsu Miyata

129

2P-41

Fabrication and manipulation of slidable atomic layers* Yu Kobayashi, Kenji Watanabe, Takashi Taniguchi, Yutaka Maniwa, Yasumitsu Miyata

130

2P-42

Interlayer excitons in high-quality MoS2/WS2 vertical heterostructures* Tetsuki Saito, Yu Kobayashi, Kenji Watanabe, Takashi Taniguchi, Yutaka Maniwa,
Yasumitsu Miyata

131

2P-40
☆

☆

2P-43

2P-44
☆
2P-45

High-Performance Complementary Inverters of Large-Area Transition Metal Dichalcogenide
Monolayers* Jiang Pu, Kazuma Funahashi, Chang-Hsiao Chen, Ming-Yang Li, Lain-Jong Li,
Taishi Takenobu

132

Photoluminescence Quantum Yield and Exciton Radiative Lifetimes in Monolayer WSe2
* N. Baizura Mohamed, Sandhaya Koirala, Feijiu Wang, Hong En Lim, Shinichiro Mouri,
Yuhei Miyauchi, Kazunari Matsuda

133

Optical Absorption Spectra of MoS 2 Monolayer Crystals under Tensile Strain* Musashi Fukumura, Kotaro Homma, Junji Nozaki, Yutaka Maniwa, Kazuhiro Yanagi

134

Carbon nanoparticles
2P-46

2P-47

Fluorination and annealing effects on magnetism and structure of nanodiamond* Kenta Kogane, Hidekazu Touhara, Yoshiyuki Hattori, Vladimir Osipov,
Nickolai Romanov, Kazuyuki Takai
Synthesis of carbon nanoballoon and evaluation of its catalytic activity in direct methanol
fuel cells* Tatsuo Ohiro, Kohei Mizui, Yoshiyuki Suda, Toru Harigai, Hirofumi Takikawa,
Hitoshi Ue

135

136

Other topics
2P-48☆

Acceleration of separation velocity in electric-field-induced layer formation method byadjusting surfactant concentration* Fusako Sasaki, Fumiyuki Nihey, Yuki Kuwahara, Hiroyuki Endoh, Shinichi Yorozu,
Takeshi Saito

xxxi

137

February 21st, Sun.
2P-49

Carrier Injections on WS2 Nanotube Networks by Electrochemical Doping Techniques* Mitsunari Sugahara, Yoshimasa Kitamura, Yuki Oshima, Hideki Kawai,
Kazuhiro Yanagi

50th Memorial Panel Discussion ( 16:45-18:45 )Yohji Achiba, Sumio Iijima, Hiroshi Imahori, Yoshihiro Iwasa, Morinobu Endo,
Eiji Osawa, Koichi Komatsu, Susumu Saito, Yahachi Saito, Kazuyoshi Tanaka,
Katsumi Tanigaki, Shojun Hino

Banquet ( 18:45-20:45 )

xxxii

138

February 22nd, Mon.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)
Special Lecture ( 9:00-9:30 )3S-8

Process study of graphite oxidation toward tailor-made graphene oxide* Yuta Nishina, Naoki Morimoto, Hideyuki Suzuki

9

General Lecture ( 9:30-10:30 )Properties of graphene ・ Atomic Layers
3-1

Direct probing of the electron-phonon scattering in the single-layered epitaxial graphene* Shin-ichiro Tanaka, Takahiro Maruyama, Kiyohisa Tanaka, Shin-ichiro Ideta,
Hiroyuki Yamane

29

3-2

Anisotropic optical properties of layered monochalcogenide GeSe nanosheets* Dezhi Tan, Yuhei Miyauchi, Shinichiro Mouri, Koirala Sandhaya, Kazunari Matsuda

30

3-3

Photovoltaic features of few-layer WSe2 schottky solar cells* Toshiki Akama, Toshiaki Kato, Toshiro Kaneko

31

3-4

Tuning of polarization of h-BN nanoribbons by the edge hydrogenation* Ayaka Yamanaka, Susumu Okada

32＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Special Lecture ( 10:45-11:15 )3S-9

Exploring Ultimate Coherent Photon Technology and its Applications* Junji Yumoto

10

General Lecture ( 11:15-12:00 )Properties of nanotubes
3-5

Gate-voltage induced trions in suspended carbon nanotubes* Masahiro Yoshida, Alexander Popert, Yuichiro K. Kato

33

3-6

Evaluation of DNA-SWNT interaction depending on base type by photoluminescence* Masahiro Ito, Eri Sando, Kazuo Umemura, Yoshikazu Homma

34

3-7

Circular Dichroism of single wall carbon nanotubes* Riichiro Saito, Naomichi Sato, Yuki Tatsumi

35＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜xxxiiiFebruary 22nd, 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

Degradation of organic dyes under ultraviolet light condition with carbon nanocapsuleencircled by nickel nanoparticle composites* Jeong Won Ko, Hae Soo Park, Jiulong Li, Weon Bae Ko

139

Endohedral metallofullerenes
3P-2

ESR measurement of molecular oxygen in openC60* Azusa Kato, Tsukasa Futagoishi, Yasujiro Murata, Tatsuhisa Kato

140

3P-3

Macroscopic Preparation and Isolation of La@C 60 as a Trifluoromethyl Derivative* Katsuma Ishino, Shinobu Aoyagi, Haruka Omachi, Zhiyong Wang, Hiroyuki Niwa,
Ayano Nakagawa, Ryo Kitaura, Hisanori Shinohara

141

☆

3P-4

Preparation, Structural Determination, and Characterization of Electronic Properties ofCarbosilylated Sc3N@Ih-C80* Takeshi Sugiura, Shinpei Fukazawa, Kyosuke Miyabe, Masahiro Kako, Masanori Yasui,
Michio Yamada, Mitsuaki Suzuki, Yutaka Maeda, Takeshi Akasaka

142

Fullerenes
3P-5
☆
3P-6

Pressure-induced transformations and light irradiation effects on ferrocene-doped C 60
nanosheets* Kyohei Kato, Hiromichi Gonnokami, Hidenobu Murata, Masaru Tachibana
Electronic and magnetic properties of pentaorgano[60]fullerenes under an external
electric field* Sho Furutani, Susumu Okada

143

144

Properties of nanotubes
3P-7

3P-8
☆

3P-9

3P-10
☆

Influence of deformations of carbon nanotubes on carrier accumulation under an electric
field* Akiko Hasegawa, Susumu Okada
Exact Extraction of Transfer length at Metal/Carbon Nanotube Contacts by Improved
Transmission Line Method* Noriyuki Tonouchi, Hiroyuki Endoh, Fumiyuki Nihey, Tomoyuki Yokota,
Takao Someya
Experimental investigation of thermal conductivity of single walled carbon nanotube thin filmwith infrared thermal imager* Ya Feng, Makoto Watanabe, Shuhei Yoshida, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Shigeo Maruyama
Emergence of a New Red-Shifted PL from Chemically-Modified Single-Walled Carbon
Nanotubes* Tomonari Shiraishi, Tomohiro Shiraki, Naotoshi Nakashima

xxxiv

145

146

147

148

February 22nd, Mon.

3P-11

Rayleigh Scattering Spectroscopy of Single-Walled Carbon Nanotubes in Various Surrounding
149
Environments* Toru Osawa, Takeshi Okochi, Yoritaka Furukawa, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Shigeo Maruyama

Applications of nanotubes
3P-12

3P-13
☆

Chemical Bond Formation between Multi-walled Carbon Nanotube and Polyvinyl Benzoate
Side Chain through Photo-induced Radical Formation* Tomoya Takada, Yuya Nishioka, Takuma Baba
Single-Step Extraction of Semiconducting Single-Wall Carbon Nanotubes by Aqueous-Two
Phase (ATP) System* Tomohiko Komuro, Haruka Omachi, Jun Hirotani, Ryo Kitaura, Yutaka Ohno,
Hisanori Shinohara

150

151

3P-14

Formation of cross-linked polymer network around single-walled carbon nanotubes* Tsuyohiko Fujigaya, Yusuke Tsutsumi, Naotoshi Nakashima

152

3P-15

Disulfide bond formation of thiols using single-wall carbon nanotubes* Atsushi Hirano, Momoyo Wada, Takeshi Tanaka, Hiromichi Kataura

153

3P-16
☆

Thermoelectric characterizations of carbon nanotube/curable resin* Wenxin Huang, Tsuyohiko Fujigaya, Naotoshi Nakashima

154

3P-17

Environmentally Stable Carrier Doping into Carbon Nanotube Films by Extraordinary
Molecular Lewis Acid
* Kazuma Funahashi, Naoki Tanaka, Yoshiaki Shoji, Ko Nakayama, Kaito Kanahashi,
Hiroyuki Shirae, Suguru Noda, Takanori Fukushima, Taishi Takenobu

155

Formation and purification of nanotubes
3P-18

3P-19
☆
3P-20

3P-21

3P-22

Effect of catalyst support on growth lifetime of carbon nanotube forest* Takashi Tsuji, Shunsuke Sakurai, Maho Yamada, Don Futaba, Kenji Hata
Comparison between Reduced and Intentionally Oxidized Metal Catalysts for Growth ofSingle-Walled Carbon Nanotubes* Yang Qian, Rong Xiang, Hua An, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama
Controlled synthesis of single-walled carbon nanotubes with sputtered W-based catalyst* Hua An, Rong Xiang, Hiroki Takezaki, Shinnosuke Ohyama, Yang Qian, Taiki Inoue,
Shohei Chiashi, Shigeo Maruyama
Molecular dynamics simulation of single-walled carbon nanotubes grown from binary
catalyst* Yukai Takagi, Ryo Yoshikawa, Shohei Chiashi, Shigeo Maruyama
Quantifying the purity of semiconducting/metallic fractions in ELF separation of SWCNTs* Yuki Kuwahara, Fusako Sasaki, Fumiyuki Nihey, Hiroyuki Endo, Shinichi Yorozu,
Takeshi Saito

xxxv

156

157

158

159

160

February 22nd, Mon.
Endohedral nanotubes
3P-23
☆

3P-24

3P-25

STM/STS studies on Europium nanowires encapsulated in carbon nanotubes* Terunobu Nakanishi, Ryo Kitaura, Shoji Yoshida, Osamu Takeuchi, Hidemi Shigekawa,
Hisanori Shinohara
Condensation reaction of 5,5”-dibromo-2,2':5'2”-terthiophene inside single-walled carbon
nanotubes* Makoto Sasaki, Takeshi Koyama, Hideo Kishida, Yukihiro Yoshida, Gunzi Saito
High-yield Filling of Hydroxylated Diamantane into Carbon Nanotubes* Yusuke Nakanishi, Haruka Omachi, Natalie A. Fokina, Ryo Kitaura, Peter R. Schreiner,
Jeremy E. P. Dahl, Robert M. K. Carlson, Hisanori Shinohara

161

162

163

Graphene synthesis
3P-26☆

Vertically oriented Graphite layer formed on hot-implanted diamond (100) surface* Masafumi Inaba, Wenxi Fei, Yu Hirano, Kazuma Suzuki, Hiroshi Kawarada

164

3P-27

Synthesis Conditions of High-Quality and Large-Size Graphene by Alcohol CVD* Kohei Tsushima, Masaki Sota, Xiao Chen, Rong Xiang, Taiki Inoue, Shohei Chiashi,
Shigeo Maruyama

165

3P-28

Synthesis and Electronic Propeｒty of Fe Intercalated Bilayer Graphene* Ryo Hoshino, Yutaro Hayashi, Nozomi Suzuki, Tomoko Nagata, Nobuyuki Iwata,
Hiroshi Yamamoto

166

Applications of graphene
3P-29

3P-30

3P-31

3P-32

Enhancement of laser-induced water decomposition by 2D sheets studied by first-principles
simulations* Yoshiyuki Miyamoto, Hong Zhang, Xinlu Cheng, Angel Rubio
Solvothermal preparation of uranium oxide supported on reduced graphene oxide* Li Ding, Pei Tang, Ding Ma, Yan Li
Fabrication of planar heterojunction perovskite solar cells using graphene oxide as holetransport layer* Shunjiro Fujii, Takeshi Tanaka, Hiromichi Kataura
Investigation of Catalysis of Nitrogen-Doped Graphene for Oxygen Reduction Reaction* Takeru Okada, Kumi Inoue, Tomokazu Matsue, Golap Kalita, Masaki Tanemura,
Meyya Meyyappan, Seiji Samukawa

167

168

169

170

Properties of graphene
3P-33

Nano-scale Characterization of Graphene by AFM-Raman Spectroscopy* Yasushi Nakata, Yoshito Okuno, Sanpon Vantasin, Yoshito Tanaka, In-Sang Yang,
Yukihiro Ozaki, Nobuyuki Naka

xxxvi

171

February 22nd, Mon.

3P-34

Study on field emission sites of graphene emitter by field emission microscopy and field ion
microscopy* Noboru Yokoyama, Toru Hoshino, Kohji Iwata, Hitoshi Nakahara, Koji Asaka,
Yahachi Saito

172

3P-35

Dimensionality Dependence of Plasmon Resonance in Graphene Nanoribbons* Takahiro Morimoto, Yoshiue Ikuta, Toshiya Okazaki

173

3P-36

Wavelength dependence of surface roughness in photoreduction of graphene oxide
Maki Ueda, Yoshiki Yamamoto, Yuki Hirano, Kazuto Hatakeyama, Michio Koinuma,
Yasumichi Matsumoto, Masahiro Hara, * Hiroyuki Yokoi

174

3P-37

Raman intensity magnetic field dependence in graphene* Toshiya Shirakura, Riichiro Saito

175

Atomic Layers
3P-38
☆
3P-39

Chemical vapor deposition growth of high-quality large-area hexagonal boron nitride
monolayers and an application to passivation of black phosphorus* Yuya Takabayashi, Sinha Sapna, Haruka Omachi, Hisanori Shinohara, Ryo Kitaura
Insulator-to-Metal transition in polycrystalline MoS2 films induced by electric double layer
gating* Takuya Osakabe, Jiang Pu, Yusuke Edagawa, Lain-Jong Li, Taishi Takenobu

176

177

3P-40
☆

Position selective synthesis of monolayer and single crystal WS 2
* Tomoyuki Takahashi, Toshiaki Kato, Toshiro Kaneko

178

3P-41

Optical properties of monolayer-WSe2/organic molecule heterostructure* Shota Kimura, Daichi Kozawa, Keiichiro Matsuki, Shinichiro Mouri, Yuhei Miyauchi,
Kazunari Matsuda, Lain-Jong Li, Taishi Takenobu

179

3P-42
☆

3P-43

3P-44

Polarization-resolved photoluminescence mapping in monolayer transition metal
dichalcogenides* Yusuke Hasegawa, Feijiu Wang, Shun Aota, Shinichiro Mouri, Kazunari Matsuda,
Yuhei Miyauchi
Magnetism arising from pore edges of nanomesh on few-atomic-layerd hexagonal boron
nitride* Kenshin Nagano, Yuichi Tagami, Chika Ohata, Gen Hashimoto, Shingo Katsumoto,
Kyoko Nomura, Junji Haruyama
Geometric and electronic structures of atomic layers of GaN* Yanlin Gao, Susumu Okada

xxxvii

180

181

182

February 22nd, Mon.
Environmental/Safety characterization of nanomaterials
3P-45

Quantitative evaluation of size effect on macrophage uptake of carbon nanotubes by opticalabsorption measurement method* Minfang Zhang, Naoko Tetsura, Kayo Ichiraku, Katsuhide Fujita, Sumio Iijima,
Masako Yudasako, Toshiya Okazaki

183

Other topics
3P-46

3P-47

3P-48

Nitrogen-doped carbon preparation from organic frameworks with molecularly-orderedstructures* Tomohiro Shiraki, Gayoung Kim, Naotoshi Nakashima

184

Development of Multi-stage Ion Trap Ion Mobility System for Separation of Charged Particles
185with Long-range Manipulation* Hironobu Matsubayashi, Yasuhiro Hiroshiba, Ryota Jinnouchi, Wataru Ohkawa,Toshiki Sugai
Observation of Nano Particles by Ion Trap Ion Mobility* Ryota Jinnouchi, Yasuhiro Hiroshiba, Hironobu Matsubayashi, Wataru Ohkawa,
Takuma Ito, Toshiki Sugai

186

Special Lecture ( 16:00-16:30 )3S-10

Physics and engineering of excitons in carbon nanotubes* Yuhei Miyauchi

11

General Lecture ( 16:30-17:30 )Applications of fullerenes ・ Other topics ・ Applications of nanotubes
・ Carbon nanoparticles
3-8

3-9

3-10

3-11

Semiconductor-Metal-Semiconductor Transition of C60-Fullerene Thin-films toward
PS-Molecule Application* Nobuyuki Aoki, Wataru Akiyama, Naoto Nakamura, Katsuhiko Miyamoto,Takashige Omatsu, Jonathan P. Bird, Yuichi Ochiai
Development of Ion Trap Ion Mobility Measurement System for Nano Materials* Toshiki Sugai, Yasuhiro Hiroshiba, Hironobu Matsubayashi, Wataru Ohkawa,
Takuma Ito, Ryota Jinnouchi
Electron Microscopic Imaging of Acceleration-Voltage-Dependent Molecular Motion on a
Carbon Nanohorn* Koji Harano, Ricardo M. Gorgoll, Emrah Yücelen, Akihito Kumamoto, Naoya Shibata,
Eiichi Nakamura
Recent progress in nanodiamond research & development* Eiji Osawa, Shuichi Sasaki, Ryoko Yamanoi

xxxviii

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37

38

39

特別講演
Special Lecture

S–1
1S – 1 ～ 1S – 4
2S – 5 ～ 2S – 7
3S – 8 ～ 3S – 10

S-1
The 50th Fullerene-Nanotube-Graphene Society Meeting (Tokyo) 2016.2.19, Univ. Tokyo

What can we learn about low-symmetry materials from spectroscopy?

Mildred S. Dresselhaus

Departments of Physics and Electrical Engineering,
Massachusetts Institute of Technology, Cambridge, MA 02139, USA

In this talk, we overview the spectroscopy of lower-symmetry materials. In optical spectroscopy,
because of the van Hove singularity for electronic density of states, optical spectra show sharp
peaks in resonant optical process such as resonance Raman scattering and resonance Rayleighscattering, which are useful for characterizing the structure of single-wall carbon nanotubes.
However, lower-symmetry layered materials nevertheless yield some specific selection rules for
optical transitions in which group theory still works well, such as for analyzing the spectra oftransition metal dichalcogenides, using graphene as reference material. By showing examples
that we have investigated so far, we will discuss what we can learn about lower-symmetrymaterials from spectroscopy.

Mildred Dresselhaus e-mail: millie@mgm.mit.edu

- 1/1
1-

1S-1

Direct dry printing of SWNT thin films for flexible
electronics applications
Esko I. Kauppinen
Department of Applied Physics, Aalto University School of Science
PO Box 15100, FI-00076 Aalto, FINLAND
e-mail: esko.kauppinen@aalto.fi

We present the industrial scale, ISO 9001:2008 certified direct dry printing (DPP) manufacturing of single
walled carbon nanotube (SWNT) transparent conducting films (TCF) for touch sensors with electrical properties on
par with those of ITO-on-PET, and with optical properties and flexibility better than those of ITO, metal nanowire
and metal mesh [1,2]. We demonstrate SWNT thin film TCF applications as the capacitive touch sensors formobile phones, laptop computers, gaming controls etc. All carbon transparent, flexible and stretchable thin film field
effect transistors (TFT-FET) with properties comparable to those of polycrystalline siliconTFT-FETs as well as
integrated circuits have been made using percolating SWNT network as the semiconductor and SWNT TCF as thesource, drain, gate and interconnect material [3,4]. We discuss the SWNT bundling mechanisms during FC-CVD
synthesis and how the bundling affects both the tube growth rate and the TCF performance [5]. We present theestimate for the ultimate performance of SWNT thin film TCFs to be lower than 30 ohms/sq sheet resistance at
90 % transmission [6].
[1] A. Kaskela et al. NanoLetters 10, 4349 (2010).
[2] A.G. Nasibulin et al. ACS Nano. 5, 3214 (2011).
[3] D.-M. Sun et al. Nature Nanotechnology. 6, 156 (2011).
[4] D.-M. Sun et al. Nature Communications 4, 2302. (2012).
[5] K. Mustonen et al. (2015) Appl. Phys. Lett. 107, 013106.
[6] K. Mustonen et al. (2015) Appl. Phys. Lett. 107, 143113.

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1S-2
Graphene oxide: massive production and practical application(酸化グラフェン：量産技術と応用実例)○ Bunshi Fugetsu1, Yanqing Wang1, 2, Ichiro Sakata1, 2

1

Policy Alternative Research Institute, The University of Tokyo, Tokyo 113-0033, Japan
2
School of Engineering, The University of Tokyo, Tokyo 113-0032, Japan

Graphene oxide was first introduced in 1859 [1] in Britain but has been recalled worldwide inrecent years for a number of reasons. First, GO is a truly sheet-shaped giant-sized molecule. A
single GO molecule can have a length or breadth that is typically larger than micrometers
while its thickness is only one or a few atoms thick. It is possible to cover or overlap a single
and/or a few numbers of certain substances with the atom-thick molecular sheet. Second, GObears many oxygenated functional groups on the basal plane and at the edge; hybrids at
molecular level of combinations which can be further converted into nanoparticles can begenerated simply by linking a suitable chemical species on to GO via the potential
interactions with the oxygenated moieties of GO. Third, GO is highly dispersible and/or
soluble in both aqueous and organic solvents; also, compared with carbon nanotubes (CNTs),
it is much easier to mix GO with other polymers via the solution/solution mixing method withthe polymers and GO being ideally dispersed. Furthermore, GO can be converted to graphene
through a chemical reduction or with a heating treatment. Graphene has many unusual
properties (high in-plane thermal and electrical conductivity and excellent mechanicalstiffness); this enables us to generate a broad new class of high-performance materials byusing GO as the starting element. Moreover, GO is commonly produced by exfoliating
graphite, an abundant material, through simple chemical/physical reactions; thus, GO has theadvantages of low cost and plentiful supply of the starting material. Hummers method [2] haslong been the cornerstone for producing GO; the development of a safer method with higher
yields for producing GO in large quantities still remains a big challenge. We have introduced
a novel approach with expanded graphite as the starting material to massive production of GO.
A foam-like intermediate was firstly produced by intercalating H2SO4 into the expandedgraphite; this has further expanded the graphite. The foam-like graphite was subsequently
oxidized by using KMnO4 as the oxidant; followed by a sonication or a milling treatment, thefully exfoliated GO was obtained. Graphene-dye-printed yarns/fabrics [3], graphene-enhanced
photocatalysts [4], graphene-based high-performance capacitors [5] and graphene/PVA-based
three-dimensional monolith [6] have been stablished by using GO as the key element. The
applications of GO and/or the reduced GO (namely, graphene) is close to unlimited.
[1] B. Brodie, On the atomic weight of graphite, Phil. Trans., 149, 249 (1859).
[2] W. S. Hummers, R. E. Offeman, Preparation of graphite oxide, J. Am. Chem., Soc., 80, 1339 (1958).
[3] B. Fugetsu, E. Sano, H. Yu, K. Mori, T. Tanaka, Graphene oxide as dyestuffs for the creation of electricallyconductive fabrics, Carbon, 48, 3340 (2010).
[4] Y. Wang, L. Sun, B. Fugetsu, Morphology-controlled synthesis of sunlight-driven plasmonic photocatalysts
Ag@AgX(X=Cl, Br) with graphene oxide template, J. Mater. Chem. A, 1, 1256 (2013).
[5] H. Yu, J. He, L. Sun, S. Tanaka, B. Fugetsu, Influence of the electrochemical reduction process on theperformance of graphene-based capacitors, Carbon, 51, 94 (2013).
[6] Y. Wang, B. Fugetsu, I. Sakata, M. Terrones, M. Endo, M. Dresselhaus, Morphology-controlled fabrication ofa three-dimensional mesoporous poly(vinyl alcohol) monolith through the incorporation of graphene oxide,
Carbon, 98, 334 (2016).
Corresponding Author: B. Fugetsu, Tel: +81-3-5841-5815, Fax: +81-3-5841-5815, E-mail:bunshifugetsu@pari.u-tokyo.ac.jp

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1S-3
JST/CREST on “2D Materials”- Research Supervisor’s Policy and the Invitation for Applications ○Atsushi Kurobe1, 2
12

Research Supervisor, JST/CREST, Tokyo 102-0076, Japan
Corporate R&D Center, Toshiba Corporation, Kawasaki 212-8582, Japan

Recently, there has been a growing interest in 2D materials, such as graphene andtransition metal dichalcogenides (TMDs), as they offer intriguing new phenomena whichmight be useful in future applications[1]. In 2014, Japan Science and Technology Agency(JST) launched a new CREST research-area “Development of Atomic or Molecular
Two-Dimensional Functional Films and Creation of Fundamental Technologies for Their
Applications”[2], where the target area is “2D materials” in short.
CREST is a funding program for team-oriented research with the aim of achieving thestrategic goals set forth by the government (“2D materials” in the present case), by promoting
and encouraging the development of break-through technologies. We started to selectproposals from 2014, and this year will be the last (third) year to call for proposals.
We would like this research area to cover an extensive range of disciplines. Fig.1 shows
the overview of the received proposals in 2014 and 2015. Total number of applications was
141 (86 in 2015, 55 in 2016); 75 from Physics, 30 from Chemistry, 27 from Engineering, and9 from Biology. The diversity in the research expertise is evident. Because of financial
difficulties, we could accept only 7 best proposals after intensive discussions with 10
research-area advisors. We welcome additional first-class applications this year as well.
While it is very importantto have envisioned outcomesof the research proposal
including potential
applications, clinging too
stubbornly to any forced
expectations might suppress
fresh ideas and discoveries
that could arise during thecourse of research. We wish
to conduct basic task-oriented
research firmly rooted inscience and aimed atinvestigating principles andestablishing device guidelines,
while being cognizant of
Fig.1 Portfolio of the received proposals in 2015 and 2016
what needs the proposed
technology is targeting.
[1] For example: A. C. Ferrari et al., Nanoscale 7, 4587 (2015); F. Bonaccorso et al., Science 347 1246501(2015); G. Fiori et al., Nature Nanotechnology 9, 768 (2014); M. Xu et al., Chem. Rev. 113, 3766 (2013).
[2] http://www.jst.go.jp/kisoken/crest/research_area/ongoing/bunyah26-4.html
Corresponding Author: A. Kurobe Tel:+81-44-549-2050 E-mail:atsushi.kurobe@toshiba.co.jp

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1S-4
For industrial applications of the future of carbon nanotubes
Takeshi Hashimoto

MEIJO NANO CARBON CO.,LTD.
2271-129 Anagahora, Shimoshidami Moriyama, Nagoya, Aichi 463-0003, Japan
We have already passed more than 20 years from the discovery of carbon nanotubes. And
MEIJO NANO CARBON was passed more than 10 years as a carbon nanotubes venture .

Since foundation, we have been operated as the position of development and manufacturer
company which is specialized to carbon nanotubes.
Now, markets of carbon nanotubes are LIB additive and resin additive. Other ones are amarket for development. LIB and resin are using conductivity of carbon nanotubes. Those are
the use by which conductivity is required for the addition amount less than carbon black. Fora market of carbon nanotubes to become big, we have to find difficult application by carbon
black. We woul d like to think about industrial applications of the future of carbon nanotubes
while considering such thing.

Corresponding Author: T. Hashimoto
Tel: +81-52-736-2322, Fax: +81-52-736-5222,
E-mail: hashimo@meijo-nano.com

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2S-5
Structure-controlled growth of single-walled carbon nanotubes: from
catalyst design to growth conditions○Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Single-walled carbon nanotubes (SWNTs) have shown great potentials in various
applications attribute to their unique structure-dependent properties. Therefore the controlled
preparation of chemically and structurally pristine SWNTs is a crucial issue for their advanced
applications (e.g. nanoelectronics) and has been a great challenge for two decades.The
composition and morphology of the catalyst nanoparticles were widely reported to affect thechirality distribution of SWNTs. Yet chirality-specific SWNT growth had not been realized byalternating catalysts. Inspired by the specificity of enzyme-catalyzed reactions, we realizedthat only catalysts with unique crystal structure and desired atomic arrangements can act as
the structural templates for chirality specific growth of SWNTs, relying on the high selectivity
in geometry match between catalysts and SWNTs. We developed a new family of catalysts,
tungsten-based intermetallic compounds, which have high melting point and very special
crystal structure, to synthesize SWNTs with designed chirality. Using W6Co7 catalysts, (12, 6)
SWNTs was directly grown with the purity higher than 92%. The selective growth of (12, 6)
tubes is due to a good structural match between the carbon atom arrangement around thenanotube circumference and the metal atom arrangement of (0 0 12) planes in the catalyst.
Similarly, (16, 0) SWNT exhibits good structural match to (1 1 6) plane of Co7W6 catalyst. By
manipulating the chemical vapor deposition (CVD) conditions, zigzag (16, 0) SWNTs, which
are generally known as a kinetically unfavorable species in CVD growth, were obtained at the
purity of ~80%. The chirality-specific growth of SWNTs is realized by the cooperation of two
factors: the structural match between SWNTs and the catalysts makes the growth of SWNTs
with specific chirality thermodynamically favorable; and further manipulation of CVD
conditions obtains optimized growth kinetics for SWNTs with this designed chirality. Thisidea has also been proved to be valid for SWNTs with other chiralities and intermetallic
catalysts. We expect that this advanced epitaxial growth strategy will pave a way for theultimate goal of chirality control growth of SWNTs.

[1] F. Yang et al. Nature 510, 522-524 (2014).
[2] F. Yang et al. J. Am. Chem. Soc. 137, 8688-8691 (2015).
[3] 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

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2S-6
Precision Assembly of C60 Functionality Using Supramolecular Scaffolds○Takanori Fukushima1
1

Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama 226-8503, Japan

Molecular self-assembly has been considered to be a useful approach to creating functionalorganic materials with high structural precision. If molecular arrangements and orientations in
self-assembled materials could be perfectly controlled, one may exploit full potential of the
intrinsic properties of constituent molecules for developing high-performance materials thatexhibit, for example, anisotropic charge- and energy-transports, dipolar properties, and evenmechanical responses. However, in reality, it is difficult to predict the structures of molecularassemblies from those of their building blocks. To address this issue, we have designed
supramolecular scaffolds, which direct controlled assembly of a wide variety of functional
molecular units. This presentation will focus on the precision assembly of C60 functionalities
into particular structures using these supramolecular scaffolds. For example, when C60 is
attached to a Gemini-shaped hexa-peri-hexabenzocoronene (HBC) capable of forming ananotubular assembly, a coaxial nanotube results, where the wall consists of hole-transporting
HBC arrays, while the inner and outer surfaces are covered by an electron-transporting
monolayer of C60 [1]. We have also shown that an amphiphilic design of an oligothiopheneC60 dyad provides a rational strategy for tailoring well-defined electron donor and acceptor
arrays [2]. We recently found that a paraffinic tripodal triptycene self-assembles into a 2D
hexagonal structure by nested packing [3]. The interpenetration of the triptycene part may
suppress structural fluctuation, thus enabling the formation of organic films with a remarkably
long-range structural order. Using this tripodal triptycene as a supramolecular scaffold, a C60
functionality can be assembled into a two-dimensional sheet-like structure. The synthesis andproperties of these self-assembled materials containing C60 will be described.
[1] Y. Yamamoto, T. Fukushima, T. Aida et al., Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 21051–21056.
[2] W.-S. Li, T. Fukushima, T. Aida et al., J. Am. Chem. Soc. 2008, 130, 8886–8887.
[3] N. Seiki, Y. Shoji, T. Fukushima et al., Science 2015, 348, 1122–1126.
Corresponding Author: T. Fukushima
Tel: +81-45-924-5220, Fax: +81-45-924-5976
E-mail: fukushima@res.titech.ac.jp

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2S-7
Nanocarbon-based light sources
for integrated optoelectronics and optical communications○Hideyuki Maki1,2
1

Department of Applied Physics and Physico-Informatics, Keio University,
Yokohama 223-8522, Japan
2
JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

NIR light emitters are widely used in the areas of optical communication with opticalfibers and silicon photonics. However, because of their large footprints, the low crystallinityof the compound semiconductors grown directly on Si wafers, these emitters face significant
challenges with respect to their integration with silicon-based platforms. Here we talk about
two topics: (i) single photon generation from an carbon nanotubes (CNTs) [1] and (ii)electrically driven, high-speed light emitters based on nanocarbon materials [2-4].
Photon antibunching from low dimensional materials, such as semiconductor quantum dots,
have been attracted much attention for use as single-photon sources in quantum cryptography.
However, single photon sources at both room temperature and telecommunication wavelength
have not been reported so far. In this study, we demonstrated the photon antibunching in a
SWNT at telecommunication wavelength and room temperature [1].
We also report the electrically driven, high-speed light emitter based on CNTs andgraphene [1-3]. Nanocarbon light emitters, which are based on electron-hole recombination or
blackbody radiation, have advantages for their integration with silicon-based platforms: (i) asmall footprint and simple fabrication processes, (ii) direct integration on a Si wafer.
This work was partially supported by PRESTO and A-STEP from JST, KAKENHI from
MEXT, SCOPE from MIC, Japan.
[1] T. Endo, J. I-Hayase, H. Maki, Appl. Phys. Lett., 106, 113106 (2015).
[2] T. Mori, Y. Yamauchi, S. Honda, H. Maki, Nano Lett. 14, 3277 (2014)..
[3] M. Fujiwara, D. Tsuya, H. Maki, Appl. Phys. Lett., 103, 143122 (2013).
[4] N. Hibino, S. Suzuki, H. Wakahara, Y. Kobayashi, T. Sato, H. Maki, ACS Nano, 5, 1215 (2011).
Corresponding Author: H. Maki
Tel: +81-45-566-1643, Fax: +81-45-566-1587
E-mail: maki@appi.keio.ac.jp

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3S-8
Process study of graphite oxidation toward tailor-made graphene oxide○Yuta Nishina1, 2, Naoki Morimoto3, Hideyuki Suzuki1
1

Research Core for Interdisciplinary Sciences, Okayama University, Okayama 700-8530,
Japan
2
Precursory Research for Embryonic Science and Technology, Japan Science andTechnology Agency, Saitama 332-0012, Japan
3
Graduate School of Medicine, Dentistry, and Pharmaceutical Sciences, Division of
Pharmaceutical Sciences, Okayama University, Okayama 700-8530, Japan.

Oxidation of graphite was reported 175 years ago [1], which was recently improved to the
preparation of graphene oxide [2, 3]. Although there have been reported a lot of modification,
the optimization of the oxidation conditions has depended on try-and-error. The reason would
be because the in situ analysis of the oxidation process is tough to investigate since thereaction is performed in concentrated sulfuric acid or nitric acid with strong oxidant.
Here, we focused on in situ analysis of the oxidation of graphite with potassium
permanganate in concentrated sulfuric acid using synchrotron X-ray absorption fine structure(XAFS) and X-ray diffraction (XRD) analyses, both of which are suitable for the strongly
acidic and oxidative conditions due to the non-contact and non-destructive measurement.

Fig. 1 Time course analysis of graphite oxidation using KMnO4 in H2SO4 by XRD. (a)Graphite dispersion in H2SO4. (b) 1 min, (c) 30 min, (d) 60 min, (e) 90 min, and (f) 120 min
after KMnO4 addition.  = 0.8 Å.
Fig. 1 shows the XRD analysis during theoxidation of graphite. A peak at 13.8° is graphite(002), which is instantly shifted to 11.6° after
KMnO4 addition. As the peak at 11.6° decreased,
new peak appeared at 5.8°. XAFS analysis showedthat most of active Mn species (Mn7+) disappeared
after 120 min. These results suggest that oxidationof graphite can almost complete within 120 min.
[1] C. Schafhaeutl, J. Prakt. Chem. 21, 129-157 (1840).
[2] N. I. Kovtyukhova, et al. Chem. Mater. 11, 771-778 (1999).
[3] D. C. Marcano, et al., ACS Nano, 4, 4806-4814 (2010).
Corresponding Author: Y. Nishina
Tel: +81-86-251-8718, Fax: +81-86-251-8718,
E-mail: nisina-y@cc.okayama-u.ac.jp-9-Fig. 2 Time course analysis of graphiteoxidation using KMnO4 in H2SO4 by
XAFS.

3S-9
Exploring Ultimate Coherent Photon Technology and its Applications
Junji Yumoto
Institute for Photon Science and Technology, Graduate School of Science
The University of Tokyo, Tokyo 113-0033, Japan
More than 55 years have passed since the first laser demonstration in 1960. Over theseseveral decades, laser physics and laser technology have been developed at a rapid pace, andhigh power & ultra-short pulses with a high peak power of several 100 GW, and a pulse
duration in the range of femtoseconds have been achieved. This advanced laser technology
has been creating new fields not only in science but also in industry.
A 10 femtosecond optical pulse at a wavelength of 800nm has a bandwidth of
500nm-1100nm (300 THz) according to the time-bandwidth product limited by uncertain
relations. However, it is very difficult to obtain a Fourier Transform limited pulse because thewide bandwidth of 300 THz deforms the temporal pulse shape due to optical dispersion.
Every media like atom, condensed matter, even biomaterial interacting with strong lightfields demonstrates a lot of phenomena which are beyond our imagination. Interaction
between ultra-short optical pulses and atoms generates higher harmonic optical fields called
High-Harmonic Generation (HHG). Harmonic generation higher than the 100th order, pumpedby 800-nm short laser pulse have been observed and it reached to EUV [1].
A “Coherent Photon Ring (CPR)” is now under development with Laser Technology
Laboratory, RIKEN. CPR is a short pulse ring laser and covers the range from EUV, visible,
IR and THz. It has a feature of simultaneous multi-wavelength operation, which is achievedby placing wavelength conversion elements in the cavity. To achieve multi-wavelength
operation, high peak power & short pulse generation is essential. It is an obstacle, however, togenerate a high peak power of more than 1GW while avoiding optical damage to the opticalcomponents that make up the cavity. To work around this issue, a 100m ring cavity is
employed to reduce the average power in the cavity. That is, a low repetition rate due to thelong cavity length enables high peak power pulses to be generated but with a relatively low
average power. A CPR consisting of a 100m ring cavity has been already demonstrated at arepetition rate of 2.55MHz. It operates at a wavelength of 1030nm with a pulse-width of
710fsec, and the peak power reaches 1.4×1014W/cm2. Argon gas is placed in the cavity andlaser light focused onto the gas is converted to coherent UV light [2].
On the other hand, the development of laser technology also creates a lot of applications,for example, laser material processing. With this type of processing, light-matter interaction is
one of the fundamental mechanisms. We are now working to understand the physics behindthe laser cutting of composite materials (Carbon Fiber Reinforced Plastic) and wide-bandgap
materials (glass and sapphire). Recent laser processing results are also included in the talk.
[1] M. Protopapas, et al., "Atomic physics with super-high intensity lasers", Rep. Prog. Phys.
60, 389 (1997),
K. Ohmori ed., “Attosecond Science”, Kagakudojin (2015) (Japanese)[2] N. Kanda, et al., “Yb:YAG thin disk mode-locked oscillator with high pulse energy for
intra-cavity high harmonic generation”, IEEE Photonics Conference 2014, WG1.3 (Invited).
Corresponding Author: J. Yumoto
Tel: +81-3-5841-4082
E-mail: yumoto@ipst.s.u-tokyo.ac.jp- 10 -

3S-10Physics and engineering of excitons in carbon nanotubes○Yuhei Miyauchi 1,2
12

Institute of Advanced Energy, Kyoto University, Kyoto 611-0011, Japan
Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan

Since the first report of near infrared photoluminescence from individually dispersed
semiconducting single-walled carbon nanotubes (SWNTs) in 2002 [1], their optical properties,
dominated by correlated electron–hole bound states known as excitons [2,3], have been
intensively studied for exploring photophysics in nearly ideal quasi-one-dimensional systems
and their applications in the fields of optoelectronics and bioimaging. Here we discuss someof the interesting photophysics related to excitons in SWNTs clarified over the past decade [4].
These include impacts of the photoluminescence spectroscopy in the researches of SWNT
growth [5,6], effects of exciton–phonon interactions [7], anisotropy in optical absorption andemission [8,9], effects of surrounding materials on the exciton energies [10], radiative
lifetimes of the excitons [11], exciton migration along SWNTs [12], and tunable electronic
correlation effects by carrier doping [13]. On the basis of these knowledge, we will discuss
how the excitonic optical properties in SWNTs can be engineered for their future applications
as near infrared light emitting materials. Especially, we will focus on the impact of localizedstates intentionally embedded in SWNTs on their luminescence properties, such as
brightening of exciton photoluminescence due to dimensionality modification [14,15], andemergence of anomalously efficient upconversion photoluminescence in SWNTs [16].
Potential applications of SWNTs with the engineered localized states and remaining problems
will also be discussed.
[1] M. J. O'Connell et al., Science 297, 593 (2002).
[2] T. Ando, J. Phys. Soc. Jpn. 66, 1066 (1997).
[3] F. Wang, G. Dukovic, L. E. Brus, and T. F. Heinz, Science 308, 838 (2005).
[4] Y. Miyauchi, J. Mater. Chem. C 1, 6499 (2013).
[5] S. Maruyama, R. Kojima, Y. Miyauchi, S. Chiashi, and M. Kohno, Chem. Phys. Lett. 360, 229 (2002).
[6] Y. Miyauchi, S. Chiashi, Y. Murakami, Y. Hayashida, and S. Maruyama, Chem. Phys. Lett. 387, 198 (2004).
[7] Y. Miyauchi, and S. Maruyama, Phys. Rev. B 74, 035415 (2006).
[8] Y. Miyauchi, M. Oba, and S. Maruyama, Phys. Rev. B 74, 205440 (2006).
[9] Y. Miyauchi, H. Ajiki, and S. Maruyama, Phys. Rev. B 81, 121415(R) (2010).
[10] Y. Miyauchi et al., Chem. Phys. Lett. 442, 394 (2007).
[11] Y. Miyauchi, H. Hirori, K. Matsuda, and Y. Kanemitsu, Phys. Rev. B 80, 081410(R) (2009).
[12] Y. Miyauchi et al., J. Phys. Chem. C 114, 12905 (2010).
[13] Y. Miyauchi, et al., Phys. Rev. B 92, 205407 (2015).
[14] Y. Miyauchi, M. Iwamura, S. Mouri, T. Kawazoe, M. Ohtsu, and K. Matsuda, Nat. Photonics 7, 715 (2013).
[15] M. Iwamura, N. Akizuki, Y. Miyauchi et al., ACS Nano 8, 11254 (2014).
[16] N. Akizuki, S. Aota, S. Mouri, K. Matsuda, and Y. Miyauchi, Nat. Commun. 6:8920 (2015).
Corresponding Author: Y. Miyauchi
Tel: +81-774-38-3463, Fax: +81-774-38-3467,
E-mail: miyauchi@iae.kyoto-u.ac.jp- 11 -

一般講演
General Lecture

1 – 1 ～ 1 – 10
2–1 ～ 2–6
3 – 1 ～ 3 – 11

1-1
Microscopic Growth Process of Fullerenes and Extreme Abundance of C60
Yusuke Ueno1, Joseph Chan1, Masayuki Toyoda1, and ○Susumu Saito1-3
1

Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551, Japan
2
International Research Center for Nanoscience and Quantum Physics,
Tokyo Institute of Technology, Tokyo 152-8551, Japan
3
Materials Research Center for Element Strategy, Tokyo Institute of Technology,
Yokohama, Kanagawa 226-8503, JapanThe C60 cluster with truncated-icosahedron geometry was first proposed theoretically by
Osawa in 1970 [1], and the first experimental indication of the abundant production of C60
and other even-number carbon clusters was reported in 1984 although not cage geometries but
linear-chain geometries were considered [2]. One year later, the extreme abundance of C60 in
the carbon cluster beam under specific production condition was observed and the icosahedral
C60 cage geometry was proposed [3]. However, it took five more years for the macroscopic
amount of fullerene-cage C60 clusters to be produced from graphite [4]. Although theicosahedral geometry of the C60 cluster is beautiful, its binding energy per atom is pointed out
to be less than that of the D5h C70 cluster which is usually much less abundant than the C60
cluster [5]. The origin of the extreme abundance of the C60 cluster is, therefore, to be
explained not from the energetics but from the kinetics. However, a quarter century alreadypassed away but the full understanding of the miscroscopic growth process of C60 and otherfullerenes has not been obtained yet. We previously studied the microscopic growth process ofcarbon clusters and fullerenes using the transferable tight-binding model combined with theconstant-temperature molecular-dynamics method, and clarified the importance of the weak
but long-range attractive interaction in the fullerene growth process [6]. The closed fullerene
cage geometry was observed for relatively small clusters, and also the shrinkage of larger
fullerene cages via C2 loss process was observed.
In the present work, we report the statistical analysis of the carbon-cluster
growth/shrinkage process. At certain conditions, the extreme abundance of C60 is found to
emerge (Fig. 1). In our presentation, we discuss the details of this finding.

Fig. 1 Population densities
of carbon clusters[1] E. Osawa, Kagaku (Kyoto) 25, 854 (1970).
[2] E. A. Rohlfing, D. M. Cox, and A. Kaldor, J. Chm. Phys. 81, 3322 (1984).
[3] H.W. Kroto, J. R. Heath, S. C. O'Brien, R. F. Curl, and R. E. Smalley, Nature 318, 162 (1985).
[4] W. Krätschmer, Lowell D. Lamb, K. Fostiropoulos, and D. R. Huffman, Nature 347, 354 (1990).
[5] S. Saito and A. Oshiyama, Phys. Rev. B 44, 11532 (1991).
[6] Y. Ueno and S. Saito, Phys. Rev. B 77, 085403 (2008).
Corresponding Author: Susumu Saito
E-mail: saito@stat.phys.ttiech.ac.jp- 13 -

1-2
Molecular dynamics simulation of the growth of fullerenes from carbon
atoms
Joseph Chan and Susumu Saito
Department of Physics, Tokyo Institute of Technology, Tokyo 152-8550, Japan
In a study by Ueno and Saito [1], the geometries and energetics of small carbon clusters andthe reaction between carbon clusters are studied using the long-range transferable tight-binding
model parametrized by Omata et al. (Omata TB) [2], the local-density approximation (LDA) in
the framework of the density-functional theory, and the constant-temperature molecular
dynamics combined with Omata-TB (Omata TBMD). The study has clarified the microscopic
formation process of C60 and other fullerenes.
In this study we use the same Omata TBMD to revisit in more details the formation of carbon
clusters and reactions among these clusters in the formation process of fullerenes. We first fill
the Molecular Dynamic cell (MD cell) with 300 C atoms with randomized initial positions.
Using constant-temperature molecular dynamics, we carefully monitor and examine theevolution of the system.
In Fig. 1, during an early state of the simulation with 300 C atoms, we observe that shortchains emerge and then larger clusters start to form from these short chains. Rings start to form
too. In Fig. 2, larger clusters emerged. Based on the MD results, we discuss the formation ofcage clusters and fullerenes.

Fig.1 Snapshot of an early state of the MD cell.
Small chains and clusters are formed.
Elapsed time = 1.2 ps
Average energy per atom = -1.65 eV

Fig.2 Snapshot of an evolving state of the MD cell.
Larger chains and clusters are formed.
Elapsed time = 12 ps
Average energy per atom = -8.05 eV[1] Y. Ueno and S. Saito, Phys. Rev. B 77, 085403 (2008).
[2] Y. Omata, Y. Yamagami, K. Tadano, T. Miyake, and S. Saito, Physica E 29, 454–468 (2005).
Corresponding Author: J. Chan
E-mail: joechan@stat.phys.titech.ac.jp- 14 -

1-3
Electrochemical Evaluation of Proton Permeability of Monolayer
Graphene Grown on Au(111) Electrode
Koji Nakashima, Ryota Kumagai, ○Satoshi Yasuda, Kei Murakoshi
Department of Chemistry, Hokkaido University, Sapporo 060-0810, Japan
Graphene has been attracted attention as novel two-dimensional separation
membrane because of high throughput arising from its one-atomic thickness. Current
experimental studies demonstrated that molecules as small as He is impermeable formonolayer graphene while proton is permeable. The proton permeability isfundamentally important as well as industrially useful for hydrogen-based technologies.
However, despite of the significant importance, there have been few experimental
studies on understanding of the intrinsic proton permeability of the monolayer graphene.
In this study, proton permeability of monolayer graphene grown on Au(111) electrodewas evaluated using electrochemical technique. Monolayer graphene with highcrystalline structure was synthesized on Au(111) single crystal by atmospheric CVD.[1]Cyclic voltammetry measurement of the graphene on Au(111) electrode in 0.1M H2SO4
aqueous solution showed inhibition of the(a)oxidation-reduction reactions of the Au, indicatingthat the graphene efficiently blocks water molecule to
3 nm
access the underlying Au surface. On the other hand,cathodic current arising from hydrogen evolution
reaction (HER) could be observed in spite of thegraphene covering. AFM measurement of the(b)graphene on the Au electrode after the HER showedthat several nanometer-size balloon structures were
0 nm
clearly observed at grain boundaries in the graphene(Fig. 1(b)). These results strongly suggest that defect400 nmstructures at the grain boundaries behave as proton
channel, and that the protons selectively penetrates Fig.1
AFM
imagesofgraphene/Au(111)(a)
beforeand(b)underlying Au surface through the defects, resulting
after HER.
in the balloon structure formation.
[1] S. Yasuda et al., J. Phys. Chem. Lett., 6, 3403 (2015).
Corresponding Author: S. Yasuda and K. Murakoshi
TEL & FAX: +81-(0)11-706-4811
E-mail: satoshi-yasuda@sci.hokudai.ac.jp- 15 -

1-4
Magnetic property of two-dimensional networks of high-spin hydrocarbon
molecules○Mina Maruyama, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan

EAP-EP [eV]Hydrocarbon molecules occasionally possess high spin states due to the unpaired πelectrons corresponding to the number difference between two sublattices of their hexagonal
networks. A phenalenyl radical (C13H9 molecule with a triangular shape) is one ofrepresentative example of such high-spin molecules. In the case, due to the sublattice
imbalance, the molecule possesses an unpaired electron leading to the S=1/2 ground state. By
connecting the high-spin molecules via sp2 network, we can easily design the one- or
two-dimensional (2D) sp2 C networks possessing the various magnetic orderings. In this work,
we theoretically design novel 2D magnetic hydrocarbon network consisting of phenalenyl
radicals and benzene molecules which are alternately arranged with the C3 symmetry by using
density functional theory with generalized gradient approximation.
We find that the 2D(b)phenalenyl
network (a)possesses planar atomic
network with various
conformationsofbenzene units connecting
the phenalenyl units.
Furthermore, we findthat the networks possess
two spin states as theirstable states (Fig. 1): The
Fig.1 Isosurfaces of spin density of phenalenyl sheet with (a) antiprallel
polarized radical spin onand (b) parallel spin coupling states.
the phenalenyl unit has
the antiparallel and parallel coupling spin states and
0.0005the antiparallel spin coupling states is more stable0
than parallel spin coupling state by 13.9 meV per-0.0005
unit cell. Furthermore, the relative stability of thespin polarized states depends on the relative-0.001
arrangements of the benzene rings connecting the-0.0015
phenalenyl units. By rotating the benzene ring
-0.002
between phenalenyl units from the flat to-0.0025
perpendicular conformations, the spin interaction-0.003
0
10
20
30
40
50
60
70
80
90
between phenalenyl units monotonically decrease,
Theta [degree]
indicating that the spin states of the sheet is tunable Fig. 2 The spin interaction between
by controlling the orientation of benzene rings (Fig. phenalenyl units as a function of therotational angle of benzene ring.
2).
Corresponding Author: M. Maruyama
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: mmaruyama@comas.frsc.tsukuba.ac.jp- 16 -

1-5
Edge effect on electrode contacts to transition metal dichalcogenides○Ryo Nouchi1
1

Nanoscience and Nanotechnology Research Center, Osaka Prefecture University, Sakai,
Osaka 599-8570, JapanThe operation of semiconductor electronic devices such as field-effect transistors (FETs) islargely governed by metal/semiconductor interfaces where charge carriers (electrons or holes)
are injected from the metallic electrode into the semiconductor channel. A total electric
resistance of a semiconductor device is expressed by a summation of the semiconductor
channel resistance and the parasitic electrode contact resistances. In a short channel device,
the channel resistance is very small, and the contact resistance becomes a dominant
contribution instead. The magnitude of the contact resistance is determined by the height of acharge injection (Schottky) barrier formed at the electrode contact. In the ideal case, thebarrier height can be controlled fully by changing the work function of the electrode.
However, interfacial electronic states formed at the metal contacts generally deteriorate thecontrollability, which is known as the Fermi-level pinning.
This study focuses on metallic electrode contacts to
(a)
Drain
current:
emergent ultrathin two-dimensional (2D) sheets obtained
Cr/Au 1 μm Cr/Au IDS
from exfoliation of semiconducting transition metalA
dichalcogenides (TMDCs). In the case of three-dimensional
300-nm-thick SiO
Highly doped Si(3D) semiconductors, dangling bonds should appear at theGatecrystal surface, leading to significant Fermi-level pinning.
Voltage:
Drain
voltage: VDS
VG
On the other hand, in the case of 2D semiconductors
obtained from layered crystals, small amount of dangling (b) 80
Samplebonds are expected because of the weak inter-layer#160#2
coupling based on van der Waals interactions, which results#340#4
in the higher controllability of the electrode contacts than20
3D counterparts [1,2].
0
However, the previous considerations on electrodecontacts to TMDC sheets have not taken into account their
0
2
4
6
8
10 12
edges. Miniaturization of semiconductor devices requires
W atsourceend (m)
Channelwidth
at sourceend (μm)
the narrowing of the channel in addition to the well-known(c)Energyshortening. In the narrow channel devices, the effect of theECedges should be significantly large. In this presentation, theEFedge-induced effect on the electrode contacts to exfoliatedIDS
flakes of molybdenum disulfide (MoS2), an archetypal
EVy
TMDC, will be discussed. The Schottky barrier height has
0
Edge
In-planebeen found to increase as the channel becomes narrower,
Fig.
1
(a)
Structureof the MoS2
which can be understood by the Fermi-level pinning to the
FET. (b) Channel-width dependentedge states that locate around the mid gap (Fig. 1).
Schottky barrier. (c) Edge-induced
Flat-band
Schottkybarrier (meV)(meV)
Flat-band
barrier height2

band bending.

[1] H. Fang et al., Nano. Lett. 12, 3788 (2012).
[2] W. Liu et al., Nano. Lett. 13, 1983 (2013).
Corresponding Author: R. Nouchi
Tel: +81-72-254-8394, Fax: +81-72-254-8394,
E-mail: r-nouchi@21c.osakafu-u.ac.jp- 17 -

1-6
Bandgap modulation in one-dimensional interface of
MoS2/WS2-based semiconductor heterojunction○Yu Kobayashi1, Shoji Yoshida2, Ryuji Sakurada2, Tetsuki Saitoh1, Kenji Watanabe3,
Takashi Taniguchi3, Yutaka Maniwa1, Hidemi Shigekawa2, Yasumitsu Miyata1,4,*
1

2

Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan
3
National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044, Japan
4
JST-PRESTO, Kawaguchi 332-0012, Japan

Interface of semiconductor heterojunctions has been one of the central topics in modern solidstate physics and applications in electronics and optoelectronics. Recently, atomic layers ofsemiconducting transition metal dichalcogenides (TMDCs) are expected to realize novel onedimensional state at their heterojunction interface [1-5]. However, the realization of conducting
interface state still remains as an unsolved issue. Here, we report the observation of conductivity
enhancement and unique bandgap modulation of the one-dimensional heterojunction interface
based on bilayer TMDCs. The heterojunction is composed of bilayer WS2 and verticallystacked MoS2/WS2 heterostructure (Fig.1a), which canbe grown on graphite by chemical vapor deposition asreported in our previous work [6]. This conductivity
enhancement has never seen for the heterojunctions ofmonolayer MoS2-WS2, and monolayer-bilayer WS2.
Furthermore, STM/STS measurements reveal the upshiftof both valence and conduction band edges and band-gap
narrowing around the heterointerface (Fig.1b). This
bandgap modulation could be explained by stacking
mismatch due to lattice strain around the heterointerface.
The present findings indicate that highly tunable
electronic properties of TMDC systems provide an ideal

bilayer heterojunction. (b) Map of color

system to realize 1D confined electronic system in theheterointerface.

spatially-resolved STS spectra.

Fig.1 (a) Structure model of the present
scale dI/dV curves calculated from the[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)., [4] Y. Kobayashi et al., Nano Res., 8, 3261 (2015).,[5] S. Yoshida, et al. Sci. Rep., 5, 14808 (2015)., [6] Y. Kobayashi et al., ACS Nano, 9, 4056 (2015).
Corresponding Author: Yasumitsu Miyata, Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 18 -

1-7
Geometric and electronic properties of thin-layer GeSeand GeSe/MoS2 heterostructures○Mari Ohfuchi
Fujitsu Laboratories Ltd., Atsugi 243-0197, Japan
Since graphene was discovered, there has been no sign of abandoning the exploration ofnovel two-dimensional materials. Continuous requirements for diversity have been extending
their reach into group IV monochalcogenides, such as GeSe; nevertheless, only a few
theoretical studies have investigated monolayer GeSe [1]. In this study, we perform
first-principles calculations to examine the geometric and electronic properties of thin-layer
GeSe and GeSe/MoS2 heterostructures.
We employed the density functional theory (DFT) code, OpenMX [2]. The lattice
constants of GeSe drastically change as the thickness decreases. Accordingly, the internal
atomic positions also undergo a significant transformation. The Ge atoms lie outside the layer
for the bulk material (Fig. 1(c)), whereas Se atoms lie outside the layer for monolayer (Fig.
1(a)). We found that the direct band gap of bilayer GeSe (Fig.1 (b)) becomes identical to theindirect band gap as does monolayer GeSe [1] because of the quantum confinement of thestate at Γ that spreads over the layers. We also studied the properties of GeSe/MoS2
heterostructures (Fig.2). We found that the lattices of GeSe(4×4) and MoS2(3×5) match towithin 1%. Although the atomic positions in the GeSe layer approach those of bilayer GeSe tosome extent, the Se atoms still lie outside the layer. The distance between the Se layer and the
S layer in MoS2 was obtained to be 0.36 nm, which is slightly greater than the value of 0.31
nm for bilayer GeSe and MoS2. We also found that the discontinuities of the conduction band
minimum (EC) and the valence band maximum (EV) are 0.71 and 1.46 eV respectively. Taking
into consideration that the experimental band gap of the monolayer MoS2 is 1.89 eV [3], theband gap of monolayer GeSe is expected to be 1.14 eV.

Fig.2: Side view of GeSe/MoS2 heterostructure
Fig.1: Side views of atomic geometry and band structures of and schematic band diagram. The dark and light(a) monolayer, (b) bilayer, and (c) bulk GeSe. The dark and gray spheres also represent Mo and S atoms
light gray spheres represent Ge and Se atoms respectively.
respectively.
[1] Y. Hu et al., Appl. Phys. Lett. 107, 122107 (2015). [2] http://www.openmx-square.org/.
[3] K. F. Mak et al., Phys. Rev. Lett. 105, 136805 (2010).
Corresponding Author: M. Ohfuchi
Tel: +81-46-250-8194, Fax: +81-46-250-8274, E-mail: mari.ohfuti@jp.fujitsu.com- 19 -

1-8
1 wt% carbon nanotubes realized lithium ion batteries without binder nor
metal foil
Kei Hasegawa and Suguru Noda

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Carbon nanotubes (CNTs) have been extensively studied as a promising material fornext-generation energy storage devices. Freestanding films of few wall CNTs (FWCNTs) can
capture any material in the conductive matrix without polymer binders and work as current
corrector replacing heavy foils of metal. We have developed scalable synthesis of FWCNTs
with fluidized bed chemical vapor deposition (CVD) [1] and demonstrated the binder-free
CNT/activated carbon freestanding composites for electrochemical capacitor electrodes [2].
To examine the practicality of CNTs for energy storage, we fabricated a graphite/LiCoO2
lithium ion battery with the electrodes only by 1 wt% FWCNTs and 99 wt% active materials
and demonstrated full cells without binder nor metal foil.
Freestanding electrodes of 1-10 wt% FWCNTs with graphite and LiCoO2 wereprepared by co-dispersion in 2-propanol and filtration. Graphite electrodes of 4.5 mg/cm2(corresponding to 20 µm-thick bulk graphite) and LiCoO2 electrode of 11.3 mg/cm2 (22 µm)
were prepared. 2-electrode coin cells were prepared with HiporeTM (12 µm-thick) separator
and electrolyte of 1 M LiClO4 in ethylene carbonate/ diethyl carbonate and galvanostatic
charge/discharge tests were carried out.
Both graphite and LiCoO2 flexible freestanding films were fabricated with FWCNTs of
1 wt% or more. The films showed higher mechanical stability and electric conductivity withlarger amount of CNTs. On the other hand, those with fewer CNTs had higher packing density.
1 wt% CNT networks roughly covered and captured all the 99 wt% active material particles(Fig. 1). Fair cycle durability were shown not only at the half cells but also theGraphite/LiCoO2 full cell (Fig. 2 (left)). The discharge capacity was 267 mAh/ggraphite even ata charge/discharge rate as high as 1C (full charge/discharge in 1 hour). The performance ofthe full cell with line-patterned metal current collectors will also be demonstrated by the 5 cm
× 5 cm laminate cells.

5 µm

5 µm

Fig. 2 Cycle performances of 1 wt% FWCNT cells at 1C
Fig. 1 SEM images of 1 wt% FWCNT electrodes charge/discharge (372 mAh/ggraphite or 160 mA/gLiCoO2) (left).
with graphite (left) and LiCoO2 (right).
Rate performance of the full cell (right).
Acknowledgements: The authors thank Prof. Osaka, Prof. Momma and Mr. Mikuriya in their support in making
cells. This work is supported in part by Grant-in-Aid for Scientific Research (A) #25249111 from MEXT, Japan.
[1] D.Y. Kim, et al., Carbon 49 (2011) 1972. [2] R. Quintero, et al., RSC Adv. 4 (2014) 8230.
Corresponding Author: Suguru Noda, TEL/FAX: +81-3-5286-2769, E-mail: noda@waseda.jp- 20 -

1-9
Metal-free Transparent Organic Solar Cell with a P-dopant Enhanced
Carbon Nanotube Electrode○ Il Jeon1, Clement Delacou2, Antti Kaskela3, Esko I. Kauppinen3, Shigeo Maruyama2,
Yutaka Matsuo1
1

Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan2
Department of Mechanical Engineering, School of Engineering, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan3
Department of Applied Physics, Aalto University School of Science, 15100, FI-00076 Aalto,
Finland
Future organic solar cells are greener technology that possesses multi-functionality such as
wearable devices and surface conforming photovoltaic textiles, and window solar cells.
Prerequisites of these include metal-free, mechanical resilience, and translucency while
retaining high power conversion efficiency. For this to be realized, replacing metal electrodewith flexible and transparent material is the first step towards this achievement. Previously,
many attempts have been made in demonstrating visibly transparent and mechanicallyresilient solar cells. However, transparent conductors often result in low visible lighttransparency and device efficiency with no flexibility because no suitable material as atransparent conductor was deployed in device design and fabrication.
Here we report a carbon nanotube based metal-free OSC and its doping that are mosteffectively structured to date. High-quality dry-deposited carbon nanotube film doped withnitric acid was used as an anode in a transparent organic photovoltaic device. Such concept isunprecedented in the field of organic solar cells and application of CNT doping in thisstructure is the first-time attempt in a transparent photovoltaic device. Our doped andnon-doped SWCNTs employed transparent OSCs showed PCEs of 4.1% and 2.2%, while theleading ITO-based OSC showed a PCE of 7.8%.
Corresponding Author: Y. Matsuo
Tel: +81 3 5841 1476, Fax: +81 3 5841 1476,
E-mail: matsuo@chem.s.u-tokyo.ac.jp

Fig.1 An anatomical illustration of the SWNT-laminatedtransparent solar cell (left) and its real images withdifferent foci (right).

- 21 -

1-10
Oxygen-doped carbon nanotubes as near-infrared imaging probes andfluorescent labels○Yoko Iizumi1, Masako Yudasaka2, Tsukasa Takeuchi1,3 and Toshiya Okazaki1
1

National Institute of Advanced Industrial Science and Technology (AIST), CNT-Application
Research Center, 1-1-1 Higashi Tsukuba 305-8565, Japan
2
National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials
Research Institute, 1-1-1 Higashi Tsukuba 305-8565, Japan
3
Shimadzu Corporation, 1-3 Kanda Nishiki-cho Chiyoda Tokyo 101-8448, Japan

Optical imaging using near-infrared (NIR) fluorescence is a new imaging modality that has
recently emerged in the fields of biology and medicine. Especially, the wavelength range ofabove 1300 nm is ideal for biological imaging because of the low tissue autofluorescence andthe low absorption coefficient of water. Single-walled carbon nanotubes (SWCNTs) show
photoluminescence (PL) in the wavelength region of 1000-1400 nm.
Recently, it was found that the PL efficiency of SWCNTs can be enhanced by substituting
oxygen atoms to the carbon network of the tube wall [1]. The oxygen-doped SWCNTs(o-SWCNTs) have been mostly prepared by the exposure of ozone to the SWCNTs solution
under the UV light. This method can provide only a small amount of o-SWCNTs, which
prevents further applications of the material.
In this conference, we report a very simple method for obtaining o-SWCNTs in bulk
quantities. The produced oxygen-doped (6, 5) SWCNTs show NIR fluorescence at a much
longer wavelength than that of the o-SWCNTs reported previously, which is justadvantageous for NIR imaging (~1280 nm). Immunoassay and fluorescent angiography ofmouse using the o-SWCNTs as the NIR fluorescent labels and imaging agents, respectively,
are demonstrated.
900

(a)

2.000E+04

1.500E+04

800
700

10000

600
5000

500
400

Exitation wavelength (nm)Exitation wavelength (nm)

1000

0.000

900 1000 1100 1200 1300 1400 1500 1600

1000
900

7800

(b)

6240

800

4680

700
3120

600
1560

500
400

Emission wavelength (nm)0.000

900 1000 1100 1200 1300 1400 1500 1600

Emission wavelength (nm)Fig. 1 Photoluminescence contour maps of (a) pristine SWCNTs

Fig. 2 Photoluminescence image ofand (b) oxygen-doped SWCNTs

mouse

with

o-SWCNT

solution

injected from tail vein

[1] S. Ghosh, S. M. Bachilo, R. A. Simonette, K. M. Beckingham, R. B. Weisman, Science, 330, 1656 (2010).
Corresponding Author: Toshiya Okazaki
Tel: +81-29-861-4173, Fax: +81-29-861-6241
E-mail: toshi.okazaki@aist.go.jp- 22 -

2-1
Highly Efficient Synthesis of Vertically-Aligned Carbon Nanotube Array at
Temperature Exceeding 900 ºC Enhanced by Carbon Monoxide○Shunsuke Sakurai, Maho Yamada, Don N. Futaba, Kenji Hata
CNT-Application Center, National Institute of Advanced Industrial Science and Technology(AIST), Tsukuba 305-8565, Japan
Temperature is one of the most critical factors governing the several fundamental aspectsof carbon nanotube (CNT) synthesis, such as efficiency, purity, and the quality of CNTs
including the distributions of diameter, chirality, and crystallinity. However, the effect oftemperature is highly dependent on the growth technique (e.g. arc-discharge method, andchemical vapor deposition (CVD) from catalyst array on a substrate) and is not yet fully
understood, because temperature simultaneously affects multiple aspects of CNT synthesis
process. Specifically, in addition to driving the chemical reaction on catalyst surface,temperature also governs gas phase decomposition of carbon feedstock and the evolution of
metal catalyst particle. The CVD technique using catalyst array on a substrate has been wellestablished to synthesize a vertically aligned CNTs (forests) in a high yield; however, thestandard temperature window typically falls within 700−850 ºC, especially for high yieldsingle-walled CNT (SWNT) synthesis. Although extending to a higher temperature window is
an attractive target to study CNT growth termination, for example, a steep decrease in yieldhas been reported above 850 ºC when using H2O as a growth enhancer [1].
In this study, we used the growth enhancers, such as CO and CO2, in place of H2O, with aC2H2 carbon feedstock and sequentially sputtered catalyst substrate film of Fe (1.8 nm)/AlOx(40 nm) for CNT synthesis at higher temperature. Unsurprisingly, a very poor yield (< 0.1
mg/cm−2) was obtained at a high temperature of 900 ºC when using a H2O; however, incontrast, the use of CO results in a significant increase in yield of SWNT forests (>2 mg/cm−2)
at identical process temperatures, i.e., 900 ºC (Figure 1). The above result, combined withfurther studies including the observation of catalyst evolution at high temperature and theforest growth rate analysis based on
in-situ height measurement, indicate thata growth termination mechanism for CO
at > 900 ºC stems from a rapid Ostwald
ripening of Fe catalyst. The mechanism
for the growth termination at lower
temperature invoked by using H2O, andthe temperature effect on the structure ofsynthesized CNT are also discussed in
the presentation.
[1] H. Kimura, Don N. Futaba, M. Yumura, K.
Hata. J. Am. Chem. Soc. 134, 9219 (2012).
Corresponding Author: S. Sakurai
Tel: +81-29-861-6205, Fax: +81-29-861-4851,
E-mail: shunsuke-sakurai@aist.go.jp

Fig. 1. CNT yield vs temperature for different growthenhancers (white: CO, black: H2O). Inset: SEM imagesof SWNT forests grown on Si substrates.

- 23 -

2-2
Extended alcohol catalytic chemical vapor deposition for efficient growth ofsmall-diameter single-walled carbon nanotubes beyond (6,5)○Bo Hou1, Rong Xiang2, Taiki Inoue2, Shohei Chiashi2, Shigeo Maruyama1,2
1

Energy NanoEngineering Lab., Department of Energy and Environment, AIST, Tsukuba
305-8564, Japan2
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
SWNTs with diameters smaller than (6,5) (~0.8 nm) are known to be very inefficient togrow unless inside of special zeolite pore or inside of an outer nanotube. Hence, super-small
diameter SWNTs were rarely directly grown in reported works. Here we extended the work
window of alcohol catalytic chemical vapor deposition (ACCVD) for efficient growth ofsuper-small diameter SWNTs. The temperature range of growing high-quality SWNTs was
extended lower than 500 oC combining with very low partial pressure of ethanol down to 0.02
Pa. Growth mechanism is clarified through kinetic discussion on the experimental map. The
relationship of temperature and pressure was identified: SWNTs can grow in lower CVD
temperature accompanied with proper lower pressure, and it was found that pressure is
proportional to temperature for growing SWNTs with stable quality.
In particular, the small diameter limit was extended and the ratio of smaller diameter tubes
was significantly increased in the expanded ACCVD. During the decreasing CVD
temperature, super-small diameter SWNTs (0.8 nm > dt > 0.52 nm) were obtained around 500
oC, 5 Pa. Resonant Raman with 5 excitation laser lines, absorption and photoluminescence(PL) are used to characterize the abundance of small diameter nanotubes, and chirality ofsuper-small diameter SWNTs were assigned as (6,4), (5,4), (5,3), (6,1) etc..

Corresponding Author: Shigeo Maruyama
Tel: +81-29-861-2073, Fax: +81-29-851-7523,
E-mail: maruyama.nano@aist.go.jp- 24 -

2-3
High resolution EELS on individual carbon nanotubes○Ryosuke Senga1, Thomas Pichler2 and Kazu Suenaga1
1

2

Nanomaterial research institute, AIST, Tsukuba 305-8565, Japan
Faculty of Physics, University of Vienna, Strudlhofgasse 4, A-1090 Vienna, Austria

Carbon nanotube has been known as an ideal quantum object that can widely alter physicalproperties upon its atomic arrangement. However the direct identification of physicalproperties for individual carbon nanotubes is still difficult. For instance, photoemission and
X-ray absorption spectroscopies which are widely used to measure the optical and electronic
properties do not have the spatial resolution to identify the local changes of the band structure
on an isolated carbon nanotubes. Scanning tunneling spectroscopy is one of the ways tomeasure the local density of states (DOS) of individual carbon nanotubes, though themodification of the DOS by substrates is hardly excluded. Thus, it is necessary to realize both
high-energy resolution spectroscopy and high-spatial resolution imaging simultaneously on
individual freestanding carbon nanotubes.
Herein, we successfully demonstrate highly-localized electronic properties of individualcarbon nanotubes with precise atomic structures by means of transmission electron
microscopy (TEM) consisting of a monochromator (JEOL TripleC#2). The electron energy
loss spectroscopy (EELS) with the monochromated electron source provides well-separated
sharp peaks at the carbon K (1s) absorption edge and in the valence-loss spectra from isolated
single-wall carbon nanotubes (Fig. 1). These peaks unambiguously correspond to the van
Hove singularities and indicate the unique properties of carbon nanotubes with different
characters. Furthermore, we have experimentally investigated the effect on the electronic
structures induced by the nonperiodic structure, such as topological defects or serial junctions.
Such localized measurement of electronic properties for individual carbon nanotubes has
never been realized by any other methods.

Fig. 1 TEM image (left) and EEL spectra of carbon K-edge (right) for two closely aligned single-wall nanotubes.
Corresponding Author: R. Senga
Tel: +81-29-862-6518
E-mail: ryosuke-senga@aist.go.jp- 25 -

2-4
Surface Synthesis of Acene-type Graphene Nanoribbon○Takahiro Nakae, Shaotang Song, Takahiro Kojima, Hiroshi Sakaguchi
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Graphene nanoribbon (GNR), which is a one-dimensional carbon structure, exhibits
semiconductor properties, whereas graphene is a two-dimensional carbon sheet withpseudo-metal, zero band gap characteristics. Bottom-up techniques can produce GNRs with adefined edge-structure and narrow widths, less than 1 nm. The bottom-up approaches reported
to date provide GNRs with a defined edge structure, however suffer from the systematicsynthesis of GNR having different width because of the low solubility of GNRs and the needfor special environments and instruments. Therefore, a simple bottom-up synthetic method forlarge-scale production of GNR is eagerly sought not only for complete characterization of thematerial but also for device applications. Recently, we developed synthetic method of GNR,
2-zone temperature controlled radical-polymerized chemical vapor deposition (2Z
RP-CVD).[1] 2Z RP-CVD method is highly efficient, therefore we can fabricate all 3 families
of armchair-edged GNRs (3p, 3p+1, and 3p+2; p is defined as the number of carbon atoms
along the width) on Au(111) even in extremely low-vacuum conditions.
Here, we synthesized acene-type GNR by using newly designed “Z-bar linkage
precursor”.[2] Using 2Z RP-CVD technique, Z-bar linkage precursor was supplied to Au(111)substrate at 250 °C to achieve surface polymerization. Surprisingly, homochiralpolymerization of monomer, which has surface induced chirality, proceeded and afforded highdensity self-assembled array of polymers. The substrate was subsequently annealed to
produce partially fused polymer,
defective GNR, and acene-type
GNR at 375, 450 and 500 °C,
respectively, observed by STM.
Stepwise dehydrogenation toacene-type
GNR
requiredordered conformation of polymer
andhighdensityofself-assembled
structure.
Therefore, we concluded thatstepwisedehydrogenation
proceeded
newly
found
“conformation-controlled
Figure 1. Category of Graphene nanoribbon cut out from graphenesheet. Acene-type GNR will report in this presentation.
mechanism.”[1] H. Sakaguchi, Y. Kawagoe, Y. Hirano, T. Iruka, M. Yano, T. Nakae, Adv. Mater., 26, 4134 (2014).
[2] Submitted.
Corresponding Author: H. Sakaguchi
Tel: +81-774-38-3505, Fax: +81-774-38-3508,
E-mail: sakaguchi.hiroshi.7z@kyoto-u.ac.jp- 26 -

2-5
Multiple photosynthetic reaction centers of porphyrinic
polypeptide/Li+@C60 supramolecular complexes○Kei Ohkubo1,2, Tetsuya Hasegawa1, Régis Rein3, Nathalie Solladié3, Shunichi Fukuzumi1,2
1

Department of Material and Life Science, Graduate School of Engineering, Osaka
University, ALCA and SENTAN, Japan Science and Technology Agency (JST), Suita, Osaka
565-0871, Japan.
2
Faculty of Science and Technology, Meijo University, ALCA and SENTAN, Japan Scienceand Technology Agency (JST), Nagoya, Aichi 468-8502, Japan
3
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099,
F-31077 Toulouse Cedex 4, France; Université de Toulouse, UPS, INPT, F-31077 Toulouse
Cedex 4, France
Extensive efforts have so far been devoted to mimic light harvesting and charge separation
processes in natural photosynthesis. Light-harvesting and charge-separation units have beencombined by coordination bonds between metalloporphyrins and electron acceptor moieties
bearing Lewis base ligands. Thus, metal centres have been required for construction of
supramolecular complexes between porphyrins acting as light harvesting units and electron
acceptors containing Lewis base ligands for coordination to the metal centers. We reportherein construction of supramolecular complexes of free base porphyrin polypeptides(P(H2P)n: n = 4, 8) with lithium ion-encapsulated C60 (Li+@C60)1.
Nanosecond
laser-induced
transientabsorption spectra of P(H2P)8 with Li+@C60
at the excitation wavelength of 532 nm+
8
showed the transient absorption band at 730
nm due to the triplet excited state ofP(H P)
Li+@C60 (3Li+@C60*) observed together
with the absorption band at 1035 nm due to
Li+@C60¥–. The decay of the absorption at
730 nm coincides with the appearance of
Li+@C60¥–. Thus, electron transfer from
P(H2P)8 to 3Li+@C60* occurs to produce the triplet charge-separate (CS) state ofP(H2P)8¥+ and Li+@C60¥–. The decay of the absorbance at 1035 nm due to Li+@C60¥–
obeyed first-order kinetics with the lifetime of 210 µs. Thus, back electron transferfrom Li+@C60¥– to P(H2P)8¥+ occurs in the supramolecular complex. The lifetime islong because of the spin-forbidden back electron transfer in the triplet CS state.1
O

H
N

O

O

H
N

O

H
N

O

H
N

O

O

H
N

O

H
N

O

H
N

NH

O

O

NH

O

NH

O

NH

O

O

N N

Ar

NH

O

O

N N

Ar
Ar

Ph

O

N N

N N

Ar
Ar

Ph

NH

N N

N N

NH

O

Ar
Ar

Ph

NH

O

O

N N

N N

Ar
Ar

2

O

O

N N

N N

Ph

NH

O

O

O

Ar
Ar

N N

Ar
Ar

N N

Ph

O

N N

Ar
Ar

N N

Ph

Li+

N N

Li+@C60 PF6–

Ar

N N

Ph

Ph

8

O

H
N

O

O

H
N

O

H
N

O

H
N

O

H
N

O

H
N

O

H
N

O

NH

O

O

NH

O

NH

O

O

N N

Ar
Ar

Ph

[1] K. Ohkubo et al. Chem. Commun. 51, 17517 (2015).
Corresponding Author: K. Ohkubo
Tel: +81-6-6879-4734, Fax: +81-6-6879-7370,
E-mail: ookubo@chem.eng.osaka-u.ac.jp- 27 -

NH

O

O

N N

Ar

NH

O

O

N N

N N

Ar
Ar

Ph

NH

O

O

N N

N N

Ar
Ar

Ph

NH

O

O

N N

N N

Ar
Ar

Ph

NH

NH

O

O

O

N N

N N

Ar
Ar

Ph

O

N N

N N

Ar
Ar

Ph

O

N N

N N

Ar
Ar

Ph

N N

Ar

N N

Ph

2-6
Physical control of insulator-to-metal transition in overexpanded A3C60○Yasuhiro Takabayashi 1, Ruth H. Zadik 2, Takeshi Nakagawa 1, Kosmas Prassides 1, 3
1

WPI - Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai
980-8577, Japan2
Department of Chemistry, Durham University, Durham DH1 3LE, UK
3
Japan Science and Technology Agency, ERATO Isobe Degenerate π-Integration Project,
Tohoku University, Sendai 980-8577, Japan

Recently, we found that superconductivity and magnetism in A3C60 (A = alkali metal) canbe sensitively controlled both physically by applying external pressure and chemicallythrough partial substitution of the intercalated alkali ions [1]. We also reported the occurrenceof a temperature-induced isosymmetric phase transformation accompanying the onset of theMott insulator-to-metal transition (MIT) in overexpanded A3C60 under isobaric conditions [1].
This transition is also characterized by a large volume collapse. In this study, thepressure-dependent structural and magnetic properties of the normal state of the Rb0.5Cs2.5C60
superconductor were investigated using synchrotron X-ray powder diffraction (SXRPD) andSQUID magnetometry.
SXRPD of Rb0.5Cs2.5C60 under high pressure atambient temperature showed the occurrence of apressure-induced isosymmetric phase transition at P
≈ 0.5 GPa (V ≈ 765 Å3/C60). At ambient pressure,the temperature dependence of paramagnetic
susceptibility, χ, of Rb0.5Cs2.5C60 showed awell-defined cusp on cooling. The cusp provides
the signature of the MIT. It broadens and shifts tohigher T by increasing P. These results allow us toconstruct an updated global electronic phase
diagram of fullerides encompassing the competing
electronic states - the antiferromagnetic insulator,
the superconductor and the normal metal – as afunction of interfullerene separation both underisothermal and isobaric conditions.
[1] R. H. Zadik et al., Science Advances 1, e1500059 (2015).
Corresponding Author: Yasuhiro Takabayashi
Tel: +81-22-217-5953, Fax: +81-22-217-5995
E-mail: yasuhiro.takabayashi.e4@tohoku.ac.jp- 28 -

Fig.1 Electronic phase diagram for the
A3C60 systems using only data for the
Rb0.5Cs2.5C60

composition.

metal

superconducting

andInsulator-totransition

temperatures and volumes obtained fromSXRPD, magnetic susceptibility and IR
measurement are included.

3-1
Direct probing of the electron-phonon scattering in the single-layered
epitaxial graphene○Shin-ichiro Tanaka1, Takahiro Maruyama 2, Kiyoshisa Tanaka3, Shin-ichiro Ideta3, Hiroyuki
Yamane 3
1 Institute of Scientific and Industrial Research, Osaka University, Ibaraki 567-0047, Japan
2 Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan

3 UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585, JapanThe electron-phonon coupling (EPC) is one of the key issues in the solid/surface
state physics. Recently, we proposed a new experimental method which enables us to probe
the elemental process of the EPC (electron-phonon scattering) in HOPG graphite withresolving the momentum and energy of both the electron and the phonon by using theangle-resolved photoelectron spectroscopy (ARPES)[1]. Here, we demonstrate the validity ofthis method for the EPC in the graphene by applying to the electron-phonon scattering in the
Dirac cone of the epitaxial single layer graphene on SiC.
Experiments were carried out at the beamline 7U of the UVSOR facility of theInstitute for Molecular Science, Japan. Figure 1(a) shows the surface normal photoelectron
spectra taken at several photon energies. In Fig. 1(a), there are steps near 160meV of thebinding energy which are converted into peak shapes as shown in Fig. 1(b) by differentiatingthem with respect to the binding energy. The intensities of the steps are plotted as a functionof the photon energy in Fig. 1(c). According to the reference [1], the steps in the ARPES
spectra can be ascribed to the Fermi edge which is shifted in energy as much as the phonons;
the electron in the Dirac cone near the K-point of the graphene is scattered by the TO- phononwith conserving the total energy and momentum. Fig 1(c) clearly shows the particular final
states of the photoexcitation is necessary to detect this process. Fig. 2 shows theangle-resolved spectra displayed in the differentiated form, and the dispersion of theinteracting TO-phonon is clearly observed. The detail of the scattering process will be
discussed in the presentation.
(c) Step Heighth(eV)
13.0eV
12.0eV
10.8eVMo (x0.1)(b)

10.0eV
8.5eV
10.8eV
13.0eV
10.8eV
8.5eV
10.8eVMo (x0.1)

Step Height (Arb. Units)

Differential(Arb. Units)

Photoelectron Intensity(Arb. Units)(a) Surface Normal EDC( .1)0
6

300 250 200 150 100 50

0

Binding Energy (meV)

-50

8

10

12

14

Photon Energy (eV)[1] S. Tanaka et al. Sci. Rep. 3(2013)3031.
Corresponding Author: S. Tanaka
Tel: +81-6-6879-8491, Fax: +81-6-6879-8494, E-mail: stanaka@sanken.osaka-u.ac.jp- 29 -

3-2
Anisotropic optical properties of layered monochalcogenide
GeSe nanosheets○Dezhi Tan, Yuhei Miyauchi, Shinichiro Mouri, Koirala Sandhaya and Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Two-dimensional (2D) layered materials including graphene and transition metal
dichalcogenides (TMDs) have attracted much interest owing to their unique physicalproperties and potential applications [1,2]. The 2D layered materials offer the fascinating
possibility of novel semiconductors with a single atomic layer thickness, which also be
utilized for the optical and electronic device application using charge, spin and valley degreeof freedom. Among them, the 2D layered materials with anisotropic structure such as black
phosphorus, which are different from other 2D materials with hexagonal in-plane lattice suchas graphene and TMD, have been intensively studied. The DFT calculation predicts that 2D
monochalcogenide, germanium selenide (GeSe) has anisotropic layered structure with anarrow band gap (1.08 eV) p-type semiconducting properties [3]. However, the detailexperimental studies of optical properties and their anisotropy have not been reported in
GeSe.
Here, we studied a new 2D monochalcogenide, germanium selenide (GeSe) withanisotropic layered structure. Figure 1(a) shows the schematic of crystal structure of GeSe,
which exhibits high intrinsic anisotropy with zigzag and armchair directions. We measured
polarized Raman scattering spectra of GeSe nanosheets (thickness of 70 nm) with changing
the direction of incident linear polarized light (2.33 eV). In the Raman spectra (Fig. 1(b)), thethree Raman peaks are clearly observed at 81.4 cm-1 ( A1g mode), 150.7 cm-1 (B3g), and 189.0
cm-1 ( A g2 ). The intensities of Raman peak ( A1g mode) clearly show strong polarization
dependence in Fig. 1(c), which obviously(a) GeSesuggests that the atomic vibrational properties
Geand electronic structures in GeSe have strongSe
anisotropic characteristics. We also conductedcpolarization dependence of differentialreflectivity measurements in GeSe nanosheets.
Our work on the anisotropic properties of
GeSe nanosheets will extend the research fielda (armchair)of 2D layered materials, as well as helping(c)(b)
GeSe to find novel applications.
[1] X. Duan et al. Chem. Soc. Rev. 44, 8859 (2015).
[2] X. Xia et al. Nat. Photonics 8, 899 (2014).
[3] G. Shi et al. Nano Lett. 15, 6926 (2015).
Corresponding Author: Dezhi Tan
Tel: 0774-38-3465, Fax: 0774-38-3460
E-mail: wcdennytun@gmail.com

Fig. 1 (a) Structure of GeSe, (b) Raman
spectrum of GeSe nanosheets (Incident laser
polarization: 0°. (c) Polarization dependent
Raman scattering intensity of- 30 -

A1g mode.

3-3
Photovoltaic features of few-layer WSe2 schottky solar cells○Toshiki Akama, Toshiaki Kato, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai, 980-8579, Japan
Atomic scale 2D sheets attract intense attention due to their superior electrical, mechanical,
and optical features. Layered transition metal dichalcogenide (TMD) is known as a true 2D
material with excellent semiconducting properties [1]. TMD is one of the most attractive
materials for future high performance transparent and flexible solar cells due to their
atomically thin structure, band gap in visible light range, and high optical transparency.
Although the solar cell of TMD has been widely investigated by many groups, those arebased on the pn junction type solar cell. Since complicated structures are required to form pnjunction structures in TMD such as dual gate electrodes or position selective doping, thedevice size of pn junction solar cell with TMD is limited within very small region (few m).
The schottky type solar cell is known as another type of solar cell, and it is possible to scale
up the device up to the practical size because of the simple device structures. However, thedetailed study of schottky type solar cell with TMD has not been reported.
Because the schottky barrier is formed at the contact region between electrode and TMD, it
is important to select appropriate electrode pairs for left and right electrodes. In this study, we
have investigated the combination of left and right electrodes and the distance of eachelectrode to obtain the better performance. Through the adjustment of these factors we havesucceeded in the fabrication of the high performance schottky type solar cells with few-layer
WSe2.
The systematic investigations reveal that energy conversion efficiency increases with work
function difference between left and right electrodes. The highest power conversion efficiency
can be obtained with the combination of Ni and Pd electrodes, which can be explained by thehigh schottky barrier and nearly ohmic contact at Ni-WSe2 and Pd-WSe2 contact region,
respectively. The electrode distance was varied between 0.5 to 14 m, and the highest
efficiency can be given with 2.2 m distance. The photocurrent mapping measurements
revealed that the suitable distance should be decided by the balance of exciton diffusion
length and momentum transfer distance of separated carriers. Based on these optimizations ofelectrodes and distance, the power conversion efficiency
can be reached up to 0.01 %, which is 40 times higher
than that before the optimization (symmetric electrodes
with long distance). This power conversion efficiency iscomparative or slightly higher than that of pn junction
type solar cell with similar TMD thickness. Since ourestablished schottky type solar cell with asymmetricelectrodes can be easily scale up, our findings cancontribute to the practical application of TMD-based
flexible and transparent solar cells.
[1] T. Kato and T. Kaneko, ACS Nano 8, 12777 (2014).
Fig.1: IDS-VDS characteristics of
few-layer WSe2 schottky solar
cells with light illumination.

Corresponding Author: T. Akama
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: akama13@ecei.tohoku.ac.jp- 31 -

3-4
Tuning of polarization of h-BN nanoribbons by the edge hydrogenation○Ayaka Yamanaka, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba
305-8577, Japan
Hexagonal boron nitride (h-BN) is attracting much attention as an insulating version ofgraphene, due to its unique physical properties, such as mechanically strong hexagonal
covalent network, high thermal conductivity, and an insulating electronic structure with wideband gap. Because of these properties, h-BN is regarded as a potential material for the wide
areas in the current and future nanotechnologies. For practical applications of h-BN, it ismandatory to understand their fundamental properties. In this work, we study the electronic
structure of h-BN with various edge structures to give a theoretical insight into the physicalproperties of h-BN with nanostructures. All calculations are performed by using the density
functional theory (DFT) with the generalized gradient approximation. The effective screening
medium (ESM) method is applied to avoid the unintentional dipole interactions with theperiodic images.
In this study, we investigate the electrostatic potential of h-BN nanoribbons withhydrogenated and clean edges of which edge angles are ranging from  = 0° (armchair) to 30°(zigzag). Figure 1 shows the electrostatic potential of h-BN nanoribbons with hydrogenatedand clean edges. The potential difference between the right and left edges of hydrogenatednanoribbons is opposite to that of nanoribbons with clean edges. We found that potential
difference also depends on the edge shapes of h-BN nanoribbons. Nanoribbons do not havepotential difference in both hydrogenated and clean edges for the  = 0°. With increasing ,
the potential difference monotonically increases for then hydrogenated nanoribbons. On theother hand, potential difference exhibits an unusual property with respect to the  for the cleanedges. The facts indicate that the edge shapes and termination can control the polarization ofh-BN nanoribbon.
(a) Hydrogenated(b) CleanFig.1: Electrostatic potential of zigzag h-BN nanoribbons with (a) hydrogenated and (b) clean edges. Smallgray, large white, and black circles denote H, B, and N atoms, respectively.
Corresponding Author: A. Yamanaka
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: ayamanaka@comas.frsc.tsukuba.ac.jp- 32 -

3-5
Gate-voltage induced trions in suspended carbon nanotubes○M. Yoshida, A. Popert, Y. K. Kato*
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
We observe trion emission from suspended carbon nanotubes where carriers are introduced
electrostatically using field-effect transistor structures [1]. The trion peak emerges below theE11 emission energy at gate voltages that coincide with the onset of bright exciton quenching.
By investigating nanotubes with various chiralities, we verify that the energy separation
between the bright exciton peak and the trion peak becomes smaller for larger diameter tubes.
Trion binding energies that are significantly larger compared to surfactant-wrapped carbon
nanotubes are obtained, and the difference is attributed to the reduced dielectric screening insuspended tubes.
Work supported by JSPS (KAKENHI 24340066), the Canon Foundation, the Sasakawa
Scientific Research Grant, and MEXT (Photon Frontier Network Program, Nanotechnology
Platform). M.Y. is supported by ALPS.
[1] M. Yoshida, A. Popert, and Y. K. Kato, Phys. Rev. B 93, 041402(R) (2016).
*Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 33 -

3-6
Evaluation of DNA-SWNT interaction
depending on base type by photoluminescence○Masahiro Ito, Eri Sando, Kazuo Umemura, Yoshikazu Homma
Department of Physics, Tokyo University of Science, Tokyo 152-8601, Japan
Photoluminescence (PL) can be observed from DNA-SWNT ensembles under the dry
condition [1]. PL can be distinguished sensitively the difference of dielectric constant around
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 silica substrate to detect an isolated DNA-SWNT in the laser
spot. We used homo-sequenced ssDNA to evaluate the effect of base type (i.e., U, T, A, C, andG).
PL from isolated DNA-SWNT exhibited different peaks depended on the base type ofDNA, as shown in Fig. 1 for (9,4) SWNT [2]. Clear tendency of the PL peak energy
dependence on the base type, T > A > C > G, can be seen. This tendency was almost the samefor different charilities. We compared the PL peak shift with the adsorption energy of DNA
base. Some theoretical groups [3] and one experimental group [4] have reported adsorptionenergies in the same trend as the PL peak shift. Although adsorption energies calculated bymany groups [5] are C < A < T < G in fact, the interaction of U with SWNT is the smallest in
any theoretical case. Calculated binding energies are listed in Table 1. The polarizability of a
DNA base plays a key role in governing the strength of interaction with the SWNT. It is thus
reasonable to assume that the PL emission peak energy shift represents the actual adsorptionenergies of the DNA bases on the SWNT surface.
In conclusion, we revealed that the PL peak from DNA-SWNT shifted in the order of(dT)30, (dA)30, (dC)30 and (dG)30, which might reflect the adsorption energy of DNA on
SWNT. Based on the result, we will discuss the PL of isolated (dU)30-SWNT.
[1] M. Ito et al. Appl. Phys. Lett. 104, 043102 (2014), [2] M. Ito et al. J. Phys. Chem. C. 119, 21141 (2015)[3] M. K. Shukla et al. Chem. Phys. Lett. 480, 269, (2009), [4] F. Albertorio et al. Nanotechnology 20, 395101,(2009), [5] S. Gowtham et al. Nanotechnology 19, 125701, (2008)
Corresponding Author: M. Ito
Tel: +81-3-3260-4271 ex. 2298, Fax: +81-3-5228-7388,
E-mail: m-ito@rs.tus.ac.jp
Table 1. Calculated binding energy of DNA with SWNT.
Binding energy

Fig 1. PL peaks from various isolated DNA-SWNTs.

- 34 -

Shukla et al. [3]Gowtham et al. [5][kJ/mol]

[eV]

G

32.9

0.49

C

25.1

0.29

A

24.0

0.39

T

23.7

0.34

U

23.0

0.28

3-7
Circular Dichroism of Single Wall Carbon Nanotubes
Riichiro Saito○, Naomichi Sato, Yuki Tatsumi
Department of Physics, Tohoku University, Sendai
Recently, single wall carbon nanotubes (SWNTs) can be separated by various techniques
and we can get physical properties of not only each chirality (n,m) but also handness of
SWNT. Depeneding on the handness of SWNTs, Kataura et al. showed that circulardichroism (CD, The effect of CD is defined by the different optical absorption of amaterial for incident left and right circular light. CD can be observed by chiral (orspiral) molecules) for left and right handed purified SWNT in which the sign of CDvalues changes at each Eii energy and give the opposite values for left and right handed
SWNTs.
In this presentation, we theoretically investigated the symmetry of the wavefunction
and discuss the possible mechanism of CD. Although the complete analysis is notfinished as a function of (n,m), we canbasically explain the formula forobtaining CD values by using so-called dipole

vector approximations thatare discussed in linear polarization of the light in the past. Most mechanism can be
expluded by time-reversal symmetry of the system. It would be nice if we can discuss inthis opportunity for possible mechanism.
This work is partially supported by MEXT grant (Nos. 25286006, 25107005)
Corresponding author: Riichiro Saito
e-mail: rsaito@flex.phys.tohoku.ac.jp
web: http://flex.phys.tohoku.ac.jp/japanesetel: 022-795-7754- 35 -

3-8
Semiconductor-Metal-Semiconductor Transition of C60-Fullerene
Thin-Films toward PS-Molecule Application○Nobuyuki Aoki1,2, Wataru Akiyama1, Naoto Nakamura1, Katsuhiko Miyamoto1,
Takashige Omatsu1,3, Jonathan P. Bird1,4, and Yuichi Ochiai11Graduate School of Advanced Integration Science, Chiba University,
Chiba, 263-8522 Japan
2
JST-PREST, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan
3
JST-CREST, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan
4
Department of Electrical Engineering, University at Buffalo, SUNY, Buffalo, NY
14260-1920, USA
If major components of electronics, such as metal, semiconductor and insulator, can becomprised of one kind molecule and all the materials can be recycled after the use, it would
be an ideal material for a future green electronics. We defined such molecules as “pluripotent
stem (PS) molecules” and found the potentials in C60 fullerene molecules.
Recently, we have succeeded to observe a transition of transport properties of C60 thin film
from semiconducting to metallic by photo-polymerization using optical vortex laser light [1].
Metallic-C60 polymer having rhombohedral structure has been realized by application of highpressure at high temperature condition [2]. However it has not been achieved byphoto-irradiation. Because the inter-molecular distance is shorten and the free rotation of themolecule stops after forming the dimer [3]. Consequently the polymerization no longer
continues by using a usual light source. In this study, we are interested in a use of an opticalvortex laser (OV) for the photo-polymerization of C60 molecules. Since the beam has a helical
wavefront, not only a gradient force in the redial direction but also an optical torque along thetangential direction can be expected toward the C60 molecules. Therefore a successive
polymerization takes a progress by providing the molecules under the beam. It would provide
a unique photo-polymerization mechanism in a C60 thin film which can never achieved byusual light sources. Actually we had reported that we observed formation of additional
two-dimensional films on the surface of the C60 thin film after the irradiation of OV and thefilm shows a metallic transport property (independent to the gate voltage). Recently,
optimizing the irradiation condition, we have succeeded to observe a transition of thetransport properties of a C60 thin-film field effect transistor from semiconducting to metallic
in a same sample by applying excess dose of a green OV laser. Moreover we also confirmedthat the property returned to semiconducting after annealing the sample at high temperature.
Therefore, a reversible transition of electrical property has been achieved in the same sample.
It indicate that the transition is not due to an irreversible destruction of C60 molecules to beamorphous carbon but due to a high level of photo-polymerization of the molecules. These
result is pave a way to realize a reusable electronics composed of PS-molecules.
[1] T. Omatsu et al., Opt. Express 18, 17967 (2010).
[2] Y. Iwasa et al. , Science 264, 1570 (1994).
[3] T. L. Makarova et al., Semiconductors, 35, 243 (2001).
Corresponding Author: N. Aoki
Tel: +81-43-290-3430, Fax: +81-43-290-3427,
E-mail: n-aoki@faculty.chiba-u.jp- 36 -

3-9
Development of Ion Trap Ion Mobility Measurement System for Nano Materials○Toshiki Sugai, Yasuhiro Hiroshiba, Hironobu Matsubayashi, Wataru Ohkawa,
Takuma Ito, and Ryota Jinnouchi
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Ion mobility measurements haverevealed varieties of novel information on nanomaterials. Structures of metallofullerenes show
significant dependence on the number of metal
atoms and the cage size and their novel
structures have been also clarified[1]. Our
newly
developedion
trapmobility
measurement system can hold the ionizedparticles for more than 2 hours realizing
observations on long term transitions. However
those measurements mainly performed on asingle particle and restricted to micro particles.
To apply these measurements to nano systems
and to have statistical information, we havedeveloped new system.
The system consists of a laser
ionization source for polystyrene particles andFig. 1 Detected signal from trappedelectrodes for the trap. The produced ionizedparticles.
particles were trapped and moved in air forseveral minutes. The movement of every
particle was observed by a microscope and position dependent fiber optics to evaluate its
mobility. The detection sensitivity is enhanced by utilizing motion synchronized signal
processing.
Figure 1 shows the Fourier transformed optical signal from the fibers. Peaks arefound at the exact frequency of the motion showing the much enhanced S/N. We are going toapply the methods to various nano materials.
[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
[2] T. Sugai et al., 42nd Fulluerene-nanotue-graphene conference. 3-13

TEL: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 37 -

3-10
Electron Microscopic Imaging of Acceleration-Voltage-Dependent
Molecular Motion on a Carbon Nanohorn○Koji Harano1, Ricardo M. Gorgoll1, Emrah Yücelen2, Akihito Kumamoto3, Naoya Shibata3and Eiichi Nakamura1
1

Department of Chemistry, The University of Tokyo, Tokyo 113-0033, Japan2
FEI Company, Europe Nanoport, 5651 GG Eindhoven, The Netherlands
3
Institute of Engineering Innovation, Graduate School of Engineering, The University ofTokyo, Tokyo 113-8656, Japan
Although σ-bond rotation and the ensuing conformational changes are the fundamental
subject of chemistry, the possibility of visually observing such events at atomic resolution has
long eluded the ability of chemists. We recently tested the utility of transmission electron
microscopy (TEM) and acquired in situ atomic resolution movies of the conformationalchanges of single organic molecules attached to the surface of a carbon nanohorn (CNH, atapered variant of a single-walled carbon nanotube)[1–3]. However visually impressive, themovies themselves are insufficient as a research tool in the absence of a method to change andquantify the magnitude and frequency of the motions. We report here that the frequency of themolecular motions can be increased by (a)
bio =
rigid
lowering the electron accelerating voltage
bio(static)(from 120, 80 to 60 kV) as a consequence of1large scattering cross section, and that thecis-trans isomerization
motionscanbequantified
using
bio
flexibleslow rotation
cross-correlation analysis between the(mobile)very fast rotationneighboring frames of the movie [4]. As a2
platform for this study, we examined biotin (b)derivatives 1 and 2 attached to the surface of a
CNH through two different linkers (Figure a)whose motions were observed as they
happened during several minutes on a TEM
stage at the three different voltages. Molecule
1 is rather static at 80 and 120 kV, but vibrates
frequently at 60 kV. In contrast, the more
flexible molecule 2 is mobile enough at 80 kV
to show us visually the process of stepwise
energy relaxation by sequential rotations of
σ-bonds in vacuum (Figure b)—a piece of
1 nm
information so far unobtainable byexperimental methods but only by theoretical Figure. Biotinylated molecules 1 and 2 on CNH.
(a) Molecular designs. (b) TEM images of rapidly
simulations.
O

H

O

O

H
N

H
N

N
H

O

O

N

CCNH

HN
H

N
N N

O

O

O

NH
H

S

N
H

moving 2 at 80 kV.

[1] E. Nakamura et al. J. Am. Chem. Soc., 130, 7808 (2008).
[2] K. Harano et al. Nat. Mater., 11, 877 (2012). [3] K. Harano et al. J. Am. Chem. Soc., 136, 646 (2014).
[4] R. M. Gorgoll et al. J. Am. Chem. Soc., 137, 3474 (2015).
Corresponding Author: E. Nakamura
Tel: +81-3-5841-1475, Fax: +81-3-5841-1475,
E-mail: harano@chem.s.u-tokyo.ac.jp- 38 -

3-11
Recent progress in nanodiamond research & development○Eiji Osawa, Shuichi Sasaki, Ryoko Yamanoi
NanoCarbon Research Institute, Asama Research Extension Center, Faculty of Textile
Science and Technology, Shinshu University, Ueda, Nagano 386-8567, Japan
Size. The most practical criterion for the quality of primaryparticles of detonation nanodiamond (PPDND) is the size distribution
obtained by DLS under certain conditions. The latest value for our
product is 2.8±0.5nm. Available evidence indicates that this value isclose to the true size. Structure of PPDND (Fig. 1) will be discussed insome detail.
Unique properties. Our PPDND particles differ from otherknown products in the following features: (1) No COOH group is


ⓐ

ⓑ

ⓐ 
ⓑ 


QP

Figure 1-5

present above the detection limit of 1.4·10 eq. This result is supported by
XAS observation [1]. (2) Graphene patches are confirmed to exist on the surface by TEM and
XAS [1]. (3) Zeta potential is about +60 mV [1]. (4) Colloidal stability of aqueous solutionchanges with concentration of PPDND, showing a peculiar trend ‘aggregation by dilution,and dispersion by concentration,’ against chemical common sense. The enigmatic trend isinterpreted in terms of ‘colloid crystal’ or ‘periodic colloid’ [2].
Applications. The unusual properties in PPDND as given above suggest highprospects for major applications. We are currently developing three of them: (i)nano-composites with crystalline solid materials, (ii) nanospacer lubricants, and (iii) drug
carrier in an open DDS for cancer. Application (ii) takes advantage of the quasi-sphericalshape of PPDND and demonstrates a possibility of replacing traditional oil lubrication, which
has been serious environmental hazard since industrial revolution. As shown in Table 1,
dispersion of 2% PPDND to lubrication liquids like water and ethylene glycol reduced
absolute friction coefficients to nearly one tenth in both cases. According to our preliminary
experiments, the sphericity of PPDND particles can be increased by improved self-abrasion.3
Spherical PPDND dispersed in appropriate lubrication liquids will eventually lead to an ideal
lubrication free from friction and contribute to suppress CO2 emission.
Table 1. Effect of ND addition to lubrication liquid on absolute
friction coefficients.1
LL2

H2O

H2O+2%PPDND

EG4

EG+2%PPDND

AFC3

0.65

0.07

0.19

0.03

1

Sapphire ball (Φ1mm /polished SUS304 surface, 20Hz, 120m,
20mN, 40,000 measurements. 2Lubrication liquid, 3Absolute
friction coefficient. 4Ethylene glycol.

- 39 -[1] Petit, T. et al., J. Phys. Chem. Lett.
2015, 6, 2909. [2] Mchedlov-Petrossyan,
N. O. et al., Phys. Chem. Chem. Phys.,2015, 17, 16186. [3] Yamanoi, R. et al.,48th FNTG General Symp., Univ. Tokyo,
Feb. 21-23, 2015, Oral 1P-39.
Corresponding Author: E. Osawa, Tel:+81-0268-75-8381, Fax: +81-0268-758551, E-mail: osawa@nano-carbon.jp

ポスター発表
Poster Preview

1P – 1 ～ 1P – 49
2P – 1 ～ 2P – 49
3P – 1 ～ 3P – 48

1P-1
Raman spectroscopic measurement of C60 fullerene nanowhiskers○Toshio Konno, Chika Hirata, Takatsugu Wakahara, Kun’ichi Miyazawa
Fullerene Engineering Group, Materials Processing Unit, National Institute for Materials
Science (NIMS), 1-1, Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Raman spectroscopy is a powerful tool to investigate the structural and electronic propertiesof C60 molecules. The Ag(2) mode has been often used to characterize C 60 solids, since it is
known that the peak position of Ag(2) mode well reflects the physical state of C60 molecules[1].
C60 nanowhiskers (C60NWs) are the thin needle-like crystals composed of C60 molecules andhave diameters less than 1000 nm, and have many applications such as field-effect transistors,
solar cells, photocatalysts, photosensors, scaffolds for cell growth, superconductors, templates
for chemical synthesis and so forth [2].
In our past researches [3,4], the Raman measurement in air was performed to characterizevarious C60NWs synthesized by the liquid-liquid interfacial precipitation (LLIP) method [5],using the Ag(2) mode as the probe to monitor the vibrational and electronic states of C 60
molecules. However, the measured Ag(2) mode Raman shift of C60NWs is ranging from 1458
cm-1 to 1468 cm-1 in our previous research. Since the down shift of Ag(2) mode Raman shiftreflects the change of the environment where the C60 molecules are located, the current paper
intends to conduct the precise measurement of the Ag(2) mode Raman shift of C60NWs that canbe used as the standard value in air to monitor the physical state of C60 molecules in the solutiongrown C60NWs. The Raman shiftmeasurement of a vacuum-deposited C60
thin film was also conducted and comparedwith the case of C60NWs in order to validate
the measurement method.
The C60NWs dried in vacuum at 120 Cshowed a Raman shift of 1469.95 ± 0.42 cm1with a coverage factor k = 2.0 for a level ofconfidence of 95 % in the air that was very
close to the value of 1469.81 ± 0.38 cm-1 (k= 2.0, level of confidence of 95%) of avacuum-deposited C60 thin film.
The value of 1469.95 ± 0.42 cm-1 can be Fig.1. A Raman spectrum of the C60NWs using laser
used as a standard Ag(2) Raman shift of thebeam power density of 5.7×103 mW / mm2.
C60NWs composed of monomer C60
molecules.
[1] H. Kuzmany et al. Philos. Trans. R. Soc. Lond. A 362, 2375, (2004).
[2] K. Miyazawa Sci. Technol. Adv. Mater. 16, 013502 (2015).
[3] K. Miyazawa et al. J. Nanopart. Res. 13, 5739 (2011).
[4] M. Sathish et al. Molecules 17, 3858 (2012).
[5] K. Miyazawa et al. J. Mater. Res. 17, 83 (2002).
Corresponding Author: K. Miyazawa
Tel: +81-(0)29-860-4528, Fax: +81-(0)29-860-4667,
E-mail: miyazawa.kunichi@nims.go.jp- 41 -

1P-2
Energetics and electronic structures of molecular complexes of fullerenes
and cyclohydrocarbons○Yuya Nagasawa and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba
Tennodai, Tsukuba 305-8571, Japan
Fullerenes and polycyclic aromatic hydrocarbons are known to be constituent units for thevarious molecular complexes and molecular solids in which the constituent units are boundeach other via weak intermolecular interaction. According to the weak interaction, thephysical properties of the molecular complexes basically retain those of each constituent.
However, on the other hand, the small intermolecular hybridization makes the complexes
being unique in their properties which are absent in each unit. Recently, molecular complexes
consisting of C60 and cyclohydrocarbons have experimentally synthesized, such as C60 withcycloparapyhenylene and cyclochrysenylen belts, which are regarded as the shortest armchairand chiral C60-peapods, respectively. By the analogy with large fullerene peapods, similar
inclusion complexes are expected to be synthesized by assembling appropriate large
fullerenes and cyclohydrocarbons, possessing interesting electronic structures. In the present
work, we explore the possibility of novel inclusion complexes of large fullerenes andcyclohydrocarbons using the density functional theory with local density approximation. We
consider the cycloparaphenylene (CPP) and cyclacene (CA) for the belt unit of the complexes,
which incorporate C78(Cv2’) fullerene.
Figure 1 shows the inclusion energy of
C78 in cyclohydrocarbons as a function of
their diameter. The inclusion energy, ΔE,
is evaluated by the reaction: CPP(CA) +C78 → CPP-C78(CA-C78) – ΔE. Our
calculations show that the inclusion of
C78 fullerene in CPP and CA withappropriate diameter is exothermic withthe energy gain of up to 1.2 and 1.5 eV for
CPP and CA, respectively. The factindicates that the inclusion complexes of
C78 and CA/CPP are energetically stable
as the case of C60 inclusion complexes.
Electronic structure of the inclusion
complexes strongly depend on that of thecyclohydrocarbons and the interunit Fig. 1 Inclusion energy of C in CPP and78
spacing.
CA as a function of their diameter

Corresponding Author: Y. Nagasawa
Tel: +81-29-853-5600(ext.; 8233), Fax: +81-29-853-5600,
E-mail: ynagasawa@comas.frsc.tsukuba.ac.jp- 42 -

1P-3
ESR spectra of Gd and Y di-metallofullerenes○Takahisa Yamaguchi1, Natsumi Nakatori3, Takuji Mitani3, Koichi Kikuchi3,
Takeshi Kodama3, Ko Furukawa4, Tatsuhisa Kato1,2
1

Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501,
Japan
2
Institute for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan3
Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
4
Department of Chemistry, Niigata University, Niigata 950-2181, Japan

Endohedral metallofullerenes show their chemical stability in the particular combination of
metal with fullerene cage. In other words the metallofullerenes indicate diversity relied on thenumber and the type of metal and the cage structure. We succeeded to isolate Gadolinium(Gd) and Yttrium (Y) di-metallofullerenes as anion forms, those are (Gd2@C80)－, (Y2@C80)－,(Gd2@C78)－ and (Y2@C78)－, by using an ion-pair chromatography separation method. UVvis-NIR absorption measurements showed that their C80 and C78 cage are Ih and D3hsymmetry. Their characteristic spin states were investigated by ESR spectroscopy. It was
confirmed that their spin states and dynamics depend upon the cage structure.
X-band and Q-band ESR measurements were carried out with Bruker E500 and E680
spectrometer. Cryogenic temperatures were obtained with an Oxford 900 helium cryostat.
Spectral simulations were performed by using EasySpin package with MATLAB program.
Observed electron spin echo field scan (ESEFS) and simulated spectra for (Gd2@C80)－and(Gd2@C78)－are shown in Fig 1. Both spin states werecharacterized by the high spin of S=15/2 and the finestructure with zero-field splitting constants of D andE tabulated in Table 1. It is noticeable that 14
electrons on 4f shells of two Gd ions and an excess
reducing electron are all coupled in ferromagnetic
manner and that (Gd2@C80)－ exhibits much larger E
value than that of (Gd2@C78)－ in spite of the higher
Ih symmetry of cage. On the other hand, the spinstates of both (Y2@C80)－and (Y2@C78)－ wereassigned as the doublet state of S=1/2 with the hyperfine structure (HFS). And tetragonal (axial
symmetric) HFS constants and g tensor were obtained
regardless of cage structure.
Table 1. ESR parameters of (Gd2@C78)－and (Gd2@C80)－
S

g

D /mT

E /mT

Lw /mT-(Gd2@C80)

15/2

1.99

36.5

11

2.5

(Gd2@C78)-

15/2

1.985

53.75

0.25

2.2

Fig 1. Q-band ESEFS spectra (Obs.) of(Gd2@C80)－ and (Gd2@C78)－observed

Corresponding Author: Tatsuhisa Kato
Tel: +81-75-753-6695, Fax: +81-75-753-6695,
E-mail: kato.tatsuhisa.6e@kyoto-u.ac.jp

at 6K. Simulated spectra (Sim.)- 43 -

1P-4
Isolation and Characterization of the hidden metallofullerene: Y2@C78○Natsumi Nakatori1, Takuji Mitani1, Takahisa Yamaguchi2, Ko Furukawa3, Tatsuhisa Kato2, 4,
Koichi Kikuchi1, Yohji Achiba1, Takeshi Kodama1
1
Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan
2
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501,
Japan
3
Department of Chemistry, Niigata University, Niigata 950-2181, Japan
4
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan
Although Y2@C80 has long been notified as a “hidden” or “missing” metallofullerene,
recently, we have succeeded in the isolation and characterization of Y2@C80 using the method
combining the ion-pair chromatography with the mixed solvent extraction [1]. Like Y2@C80,
Y2@C78 has also been the one of the plausible candidates of such a “hidden” metallofullerene,
because La2@C78 has well been known as a stable metallofullerene [2]. In this study, we
isolated Y2@C78 by almost the same method as for Y2@C80, and characterized it.
Y-metallofullerenes were produced and extracted
by the method previously reported [1]. Y2@C78 was
isolated by two-stage HPLC, in which we usedacetone with an ion-pair reagent, tetrabutylammonium bromide, as an eluent. A Buckyprep
column was used in both two stages.
Fig.1 shows the UV-vis-NIR absorption spectrumof the isolated (Y2@C78) and it is very similar to thatof Ce2@C78(D3h). Since the shape of UV-vis-NIR
absorption spectra of the metallofullerenes is mainly
Fig.1 UV-vis-NIR absorption spectra
characterized by the electronic state of the fullereneof (Y2@C78) and Ce2@C78(D3h).
cage, the similarity in the absorption spectra of(Y2@C78)
and Ce2@C78(D3h) indicates that
(Y2@C78) has C78(D3h) cage and an excess electronof (Y2@C78) is located on Y2 dimer. Fig. 2 shows the
ESR spectra of (Y2@C78) and (Y2@C80) . They have	 a very similar pattern: three peaks with intensity ratio
1:2:1, which comes from the nuclear spin of Y (I=1/2).
This pattern and the large hyperfine coupling constant(hfc) indicate that an excess electron exists on Y2
dimer of (Y2@C78) as well as (Y2@C80) . The
Fig.2 X-band ESR spectra of (Y2@C78)
smaller hfc of (Y2@C78) compared to that ofand (Y2@C80) at 4K.
(Y2@C80) suggests (Y2@C78) has the lower electron
spin density on the Y nucleus than (Y2@C80) .

[1] N. Nakatori, et al. The 49th Fullerenes-Nanotubes-Graphene General Symposium 46 (2015).
[2] B. Cao, et al. J. Am. Chem. Soc. 126, 9164-9165 (2004).
Corresponding Author: Takeshi Kodama
E-mail: kodama-takeshi@tmu.ac.jp
Tel:+81-42-677-2530, Fax:+81-42-677-2525- 44 -

1P-5
Photoreactions of Trimetallic Nitride Template Endohedral
Metallofullerenes with Digermirane○Kyosuke Miyabe1, Yuichi Sato1, Masahiro Kako*,1, Masanori Yasui1, Kumiko Sato2,
Naomi Mizorogi2, Wei-Wei Wang3, 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 attracting much interest because of theirfascinating properties regarding electron transfer from the endohedral metal atoms to thecarbon cages. Many studies of the exohedral functionalization of EMFs have been performed
to realize various applications such as organic electronic devices and biological diagnostic
agents [1]. The functionalization of EMFs with electron-donating silyl and germyl groups isuseful for modifying its electronic characteristics. Recently, it was observed that
bis-germylation of Lu3N@Ih-C80 proceeded more efficiently, and that germyl groups shifted
the oxidation potential of Lu3N@Ih-C80 slightly more cathodically than silyl groups [2].
In our continuing study of the functionalization of EMFs, we now report thebis-germylation of Sc3N@Ih-C80 using digermirane 1. The photoreaction of Sc3N@Ih-C80 and
1 was conducted in a mixed solvent of 1,2-dichlorobenzene (ODCB) and toluene using two
500W halogen lamps with an aqueous NaNO2 solution filter (cutoff < 400 nm). Separation of
the reaction mixture afforded the corresponding 1,4-adduct 2 in 66% yield (Scheme 1). The
1,4-adduct 2 was fully characterized by spectroscopic, electrochemical, and theoretical studies,
and was structurally established by single-crystal X-ray crystallography. The difference inreactivity between Sc3N@Ih-C80 and Sc3N@D5h-C80, the latter of which does not react with 1,
is also described.
Scheme 1.
Dep
Dep

+
Sc3N@Ih-C80!

Dep
Dep

Ge Ge
1

Dep
Dep

Ge

Ge

Dep
Dep

Dep =

h!
2

[1] L. Dunsch et al. Chem. Rev. 134, 5989-6113 (2013).
[2] M. Kako, et al. Chem. Eur. J. 21, 16411-16420 (2015).
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 45 -

1P-6
Mixed Valence transitions in Rare-earth Fullerides
Takeshi Nakagawaa, *, Yasuhiro Takabayashia, Kosmas Prassidesa,baWPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University,

Sendai, 980-8577, Japan.

b JST ERATO Isobe Degenerate -Integration Project, Tohoku University, Sendai,

980-8577, Japan.

The family of rare-earth fullerides RE2.75C60 (RE = Sm and Yb) have beenreported to show mixed-valence phenomena associated with the highly
correlated narrow-band behaviour of the 4f electrons. Temperature- andpressure-induced abrupt or continuous valence transitions have been
observed [1-3]. On the contrary, no anomalous behaviour is observed for theisostructural and isoelectronic Ca2.75C60, which lacks an electronically active
4f sublattice. We have now investigated Ca substitution effects in Sm2.75C60
with the synchrotron X-ray diffraction technique in an effort to obtain direct
information on the electronic changes following the dilution of the Sm
sublattice. Here we present the results of the temperature-dependent
crystallographic studies, which probe the evolution of the negative thermal
expansion effects with Ca2+-doping in the (Sm1-xCax)2.75C60 (0 ≤ x ≤ 1) series.

[1] J. Arvanitidis, et al.,Nature 425, 599 (2003)[2] J. Arvanitidis, et al.,Dalton Trans. 3144 (2004).
[3] S. Margadonna, et al., Chem. Mater. 17, 4474 (2005).
Corresponding Author: T. Nakagawa
Tel: +81-22-217-5953, Fax: +81-22-217-5994,
E-mail: takeshi.nakagawa.b5@tohoku.ac.jp- 46 -

1P-7
+SR study of fulleride superconductors across the superconductivity dome
○ Melita Menelaou1,2, Yasuhiro Takabayashi1, Ruth H. Zadik3, Peter J. Baker4,
Kosmas Prassides1,2
1

WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai,
980-8577, Japan.
2
JST ERATO Isobe Degenerate -Integration Project, Tohoku University, Sendai, 980-8577,
Japan.
3
Department of Chemistry, Durham University, Durham DH1 3LE, United Kingdom.
4

The ISIS Facility, Rutherford Appleton Laboratory, Didcot OX11 0QX, United Kingdom.

The electronic phase diagram of fullerides [1,2] exhibits striking similarities to those of many
unconventional superconductors such as the cuprates. Superconductivity emerges from anantiferromagnetic strongly correlated Mott insulating state upon tuning a parameter such aspressure. The Mott insulator-metal transition may be traversed and the entire
superconductivity dome tracked by applying chemical pressure by substituting the smaller
Rb+ cation for Cs+ in the parent insulator, Cs3C60 to generate the RbxCs3xC60 (0 < x  3)
superconductors (Fig. 1) [3]. Here we report the results of transverse-field muon spin rotation(TF-μ+SR) measurements to investigate the superconducting properties of RbxCs3xC60 acrossthe superconductivity dome – from underexpanded (x = 2) through optimally expanded (x = 1)
to overexpanded (x = 0.5) compositions. This allows us to follow the evolution of themagnetic-field penetration depth, , which in turn is related to the superconducting carrier
density, ns and the effective mass, m* across the dome as the importance of correlations
increase and the superconductivity evolves from weakly- to strongly-coupled.

Fig. 1 Global electronic phase diagram of fcc RbxCs3−xC60 [3].
[1] Y. Takabayashi et al., Science 323, 1585 (2009).
[2] A. Y. Ganin et al., Nature 466, 221 (2010).
[3] R. H. Zadik et al., Sci. Adv. 1, e1500059 (2015).
Corresponding Author: M. Menelaou
Tel: +81-70-1140-1980, Fax: +81-22-217-5994,
E-mail: menelaou.melita.b1@tohoku.ac.jp- 47 -

1P-8
Energetics and electronic structure of CNT embedded in Si〇Taketo Kochi and Susumu Okada

University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8571 Japan
Nanoscale vacancies in semiconducting materials can be regarded as negative clusters andmolecules which exhibit interesting electronic properties depending on their sizes and shapes.
Due to the low dimensionality and nanoscale size of vacancies, the vacancies in semiconductors
are applicable for electronic, optical, and optoelectronic devices. Indeed, vacancies in GaAs
filled by C60 have been synthesized experimentally, which acts as quantum dots. However, it isstill uncertain whether the electronic property of the hybrid of vacancies and nanomaterials is
the simple sum of those of constituent units or not. In the present work, we aim to explore thefundamental properties of the one-dimensional nanoscale tunnel in Si, which is filled by acarbon nanotubes (CNTs), as the possible hybrid consisting of negative and positive
nanostructures using density functional theory with local density approximation. In this works,
we construct the tubular vacancies with diameters of 10, 11, 12, and 13 Å along the [130]direction in the Si slabs with H-terminated (001) surfaces, which are filled by (8,0), (9,0), (10,0),and (11,0)CNTs. Figure 1 shows the electrostatic potential of the pristine tunnel and the

CNT-filled tunnels. In the case of the pristine tunnel, inhomogeneous potential profile isobserved, owing to the Si dangling bonds at the wall of the tunnel. Interestingly, although thedangling bond states retain upon CNT doping, we observed the almost flat potential profile
inside the tunnel. We further observe the electronic structure modulation of CNTs within the
tubular vacancies due to the substantial hybridization.

(a)

(b)

(c)

(d)

(e)

Fig. 1 Counter plots of the electrostatic potential of (a) a tubular vacancy with 13Å diameter in Si
and the vacancies filled by (b) (8,0), (c) (9,0), (d) (10,0), and (e) (11,0) CNTs.
Corresponding Author: T. Kochi
Tel: +81-029-853-5600(ext.; 8233) , E-mail: tkochi@comas.frsc.tsukuba.ac.jp- 48 -

1P-9
Crossover from Quantum to Classical Transport in Carbon Nanotubes○Keisuke Ishizeki 1, Kenji Sasaoka 2, Takahiro Yamamoto 1
1
2

Department of Electrical Engineering, Tokyo University of Science
Organization of Advanced Science and Technology, Kobe University

Resistance (kΩ)

Due to their quasi-one-dimensional structures, single-walled carbon nanotubes (SWNTs) are
known to exhibit various remarkable electrical, optical, and thermal properties. In particular,
electronic transport in SWNTs has attracted great attention because it is directly contributed toelectrical device application for next-generation LSI technologies. An SWNT shorter than themean free path (MFP) shows the quantum resistance originating from quantum ballistictransport in one dimension. This can be explained in terms of Landauer’s transport theory. On
the other hand, an SWNT longer than the MFP follows classical Ohm’s law that the electricalresistance is proportional to the system length. This can be understood in terms of Boltzmann’stransport theory.
In this work, we have developed a new quantumBallistic
Diffusivetransport simulation method that can seamlessly210
treat a whole regime from quantum ballistic toclassical ohmic transport regimes. We have applied
the method to armchair SWNTs with various
lengths. Figure 1 shows the nanotube-length
dependence of electrical resistance of a (5,5)1
10
SWNT at 300K. We can clearly find crossover
behavior from the quantized resistance (the broken
Quantum resistanceR=ρLline in Fig. 1) to ohmic resistance (the dotted line in
Fig. 1). The MFP of a (5,5)-SWNT at 300K is given
012
3
as 272 nm from the crossing point between the
10
10
10
10
Nanotubelength(nm)
broken line and the dotted line in Fig. 1.
By performing similar calculations at several Fig. 1. Nanotube-length dependence of electricaltemperatures, we estimated the temperature resistance of a (5,5)-SWNT at 300 K.
dependence of MFP of a (5,5)-SWNT. As seen in(3,3)
Fig. 2, the MFP is inversely proportional to the
T = 300 K
temperature. In addition, we have performed
(5,5)
600
similar calculations for (3,3)-, (8,8)- and (10,10)(8,8)
SWNTs. As shown in the inset of Fig. 2, the(10,10)resistivity of armchair SWNTs is also inversely
Diamiter (nm)400
proportional to the diameter. The diameter
dependence of MFP for thicker SWNTs is inagreement with previous experimental and(5,5)-SWNT
200
theoretical results based on the continuum
100
200
300
400
approximation [1,2].
Temperature (K)[1] H. Suzuura and T. Ando. PRB. 65, 235412 (2002).
[2] M. S. Purewal et al. PRL 98, 186808 (2007).
Corresponding Author: T. Yamamoto
Tel: +81-3-5876-1492 E-mail: takahiro@rs.tus.ac.jp- 49 -

Resistivity (kΩ/nm)

Mean free path (nm)

0.04

0.03

0.02

0.5

1

Fig. 2. Temperature dependence of mean free pathof a (5,5)-SWNT. The inset represents diameter
dependence of the resistivity of armchair SWNTs
at 300 K.

1P-10
Photoluminescence spectral shift of chemically-modified single-walledcarbon nanotubes by external stimuli
Hisashi Onitsuka1, Tomohiro Shiraki1,2, Naotoshi Nakashima1,2
1Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
2 WPI-I2CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan

Semiconducting single-walled carbon nanotubes (SWNTs) have unique opticalproperties exemplified by near-infrared photoluminescence (NIR PL), by which newmaterials for bio-sensing and imaging applications have been developed [1]. Typically,
PL quantum yields of the SWNTs are low; however, a very small amount of chemical
modification on the SWNTs has recently been reported to dramatically enhance theirquantum yield by appearance of a new red-shifted PL (E11*) compared to PL (E11) of thepristine SWNTs [2]. After the finding, several compounds have been examined for thechemical modification of the SWNTs, suggesting suitable molecular design of suchmolecules leads to the preparation of novel functional SWNTs.
In this study, we synthesized a phenyl boronic acid derivative, which has a bindingsite with saccharides through the formation of boronate esters [3]. After the reaction using
the newly-synthesized compound, the new E11* PL was observed around 1150 nm
although absorption spectrum of the resulting SWNTs were hardly changed in comparison
with that of the pristine SWNTs, indicating a limited modification of the SWNTs.
Interestingly, peak shift of the E11* was observed by adding a saccharide solution to the
SWNT solution. The spectral shifting behavior and molecular interactions will be
discussed at the meeting.
[1] M. S. Strano, et al., ChemSusChem. 2011. 4. 848.
[2] Y. Wang et al., Nat. Chem. 2013, 5, 840[3] N. Fujita, S. Shinkai, T. D. James, Chem. Asian J. 2008, 3, 1076.
Corresponding Author: Naotoshi Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 50 -

1P-11Morphology Dependence on Thermal Transport Properties ofSingle-walled Carbon Nanotube Films○Shuhei Yoshida1, Ya Feng1, Taiki Inoue1, Rong Xiang1,
Shohei Chiashi1, Esko Kauppinen2, Shigeo Maruyama1, 3
1. Department of Mechanical Engineering, University of Tokyo, Tokyo 113-8656, Japan
2. Department of Applied Physics, Aalto University School of Science, 15100, FI-00076
Aalto, Finland
3. National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 3058564, Japan

References:[1] J. Hone, et al., Phys. Rev. B, 59, 2514 - 2516 (1999).
[2] J. Hone, et al., Appl. Phys. Lett. 77, 666 - 668 (2000).
[3] A Kaskela, et al., Nano Lett., 10, 4349-4355 (2015).
[4] W. Cai, et al., Nano Lett. 10, 1645 - 1651 (2010).
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 51 -

Normalized Thermal Conductivity [W/K]Single-walled carbon nanotubes (SWNTs) have gotten much attention as a highly
promising material for the use of thermal management such as thermal interface materials
owing to its superior thermal conductivity. According to the previous studies, isolated
individual SWNTs have thermal conductivity as high as 2000 W/mK at room temperature[1]. On the other hand, many studies showed the apparent thermal conductivity of
individual SWNTs inside of vertically aligned SWNT films is not as high as that ofisolated one [2]. The cause of this discrepancy is not fully understood whereas it isdiscussed in many articles.
In this study, we measured the thermal conductivity of high quality random
network SWNT films, whose optical transmittance are 86.4, 80.9, 63.7 and 53.5 %, madeby floating catalyst chemical vapor deposition [3]. Micro Raman spectroscopy was
employed, and thermal conductivities of the films were determined from excitation laser
power dependence of G+ band Raman shift [4]. The results agree with the measurement byusing steady state method with IR camera. In addition, optical absorbance spectra wereused to investigate SWNT bundle network structure of the films. It was observed that thelevel of optical anisotropy is decreased when the thickness of SWNT films is increased,
and the effect of the anisotropy to their thermal transport properties is discussed. Figure 1
shows the positive correlation between film transmittance and normalized thermal
conductivity. This trend suggests that thermal−6[1×10 ]
conductivity of SWNTs can be drastically13
reduced by phonon scattering at tube-tube
interface. It should be noted that no phonon life
12
time reduction around Γ point was confirmed
based on Raman spectra line-width.
11

10
0.6
0.8
Film Transmittance1

Fig. 1: Relationship between filmtransmittance and normalized thermal
conductivity of SWNT films.

1P-12
Photothermoelectric Effect in Single Wall Carbon Nanotube Thin Films
with Precisely Controlled Seebeck Coefficients○Masatoshi Nakamura, Yoshimasa Kitamura, Yuki Oshima, Hideki Kawai, Yutaka Maniwa,
Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Photo-thermoelectric effect is generation of photo-voltage using thermoelectric propertiesof materials through light induced local electron heating. To efficiently generate
photo-induced voltage by photo-thermoelectric effect, it is necessary to use materials withweak electron-phonon interactions and to control spatial distribution of Seebeck coefficientsin a device. Single wall carbon nanotubes (SWCNTs) are known to be a material with very
weak electron-phonon interactions, and photo-voltage through such photo-thermoelectriceffects have been reported in several studies.[1] However, it is very important to precisely
control spatial distribution of Seebeck coefficient in order to efficiently generate voltage.
Recently we developed a technique that enables precise control of the values and the signs (Por N) of Seebeck coefficients of SWCNTs using electric double layer carrier injection
techniques.[2,3] Therefore, in this study, we investigated how efficiently we can generate
photo-voltage through photo-thermoelectric effects in metallicity selected and Seebeck effectcontrolled SWCNT networks.
Figure 1(a) shows a picture of a device. Thin films of Semiconducting or metallic
SWCNTs with diameter of 1.4 nm, which were purified through density-gradientcentrifugation processes, were used as channels. The Seebeck coefficient of the half part ofthe channel was controlled to be negative (N-type) using electric double layer carrier
injections, but the other half was non-controlled and was left to be P-type (Fig. 1(a)). The
device was fabricated on a palylene layer for thermal isolation. Then, we illuminated laser
light with wavelength of 488 nm on a center region
between N and P Seebeck coefficient regions. We
found clear generation of photo-voltage byillumination of laser light in both metallic andsemiconducting SWCNT networks. Even in the caseof metallic SWCNTs, we observed photo-voltage
generation, suggesting voltage generation byphoto-thermoelectriceffect.
The
generatedphoto-voltage in the case of semiconducting
SWCNTs is shown in Fig. 1(b). Photo-voltage was
generated by irradiation of laser light (488 nm). The
generated voltage was 16 mV/W. Although thevalue is lower than the reported efficiency, more
precise tuning will improve the efficiency.
[1] X. He et al, ACS Nano 7, 7271 (2013)[2] K. Yanagi et al., Nano Lett. 14, 6437 (2014)[3] Y. Oshima, Y. Kitamura, Y. Maniwa, K. Yanagi, Appl. Phys.
Lett. 107, 043106 (2015)
Corresponding Author: Kazuhiro Yanagi
Tel: +81-42-677-2494
E-mail: yanagi-kazuhiro@tmu.ac.jp- 52 -

Fig. 1(a) A picture of a device, (b)generatedvoltagesthroughphoto-thermoelectric effects by lightillumination

1P-13
Carbon nanotube sheet as a transparent electrodefor semi-transparent organic solar cell
○Senku Tanaka 1, Naoya Urakawa 1, and Kanzan Inoue 2
1

Graduate School of Science and Engineering, Kinki University, Osaka 577-0818, Japan
2
LINTEC OF AMERICA, Nano-Science & Technology Center, Texas 75081, U.S.A.

Organic electronics devices, such as organic light emitting diodes, organic solar cells(OSC), and organic transistors, have attracted much interest because of its unique potentials oflightweight, flexible and low-cost processing. To use these unique characteristics, it needs
appropriate electrodes for transporting carriers to an external circuit. Carbon nanotube (CNT)
sheet produced from the CNT forest [1] is one of the potential candidates of electrode for theorganic electronics devices. The characteristics of CNT-sheet (light weight, strong, flexible,
transparent, conductive and stable) are suitable for using as the electrode of organic devices.
We have studied the applicability of CNT-sheet as a top electrodes of OSC [2]. The
transparency of CNT-sheet meets a requirement for a semi-transparent OSC. However the
performance of OSC is limited by low conductivity of the CNT-sheet. To improve theconductivity of CNT-sheet, we studied a combination of silver with the CNT-sheet. These
combination satisfied both of high transparency and high conductivity.
A semi-transparent OSC was fabricated on an ITO substrate. As an electron transport layer,
a ZnO layer was deposited on the ITO by using a sol-gel method. As a photoactive layer, weused a bulk-heterojunction of poly (3-hexyl thiophene-2,5-diyl) (P3HT) and 6,6-phenyl C61
butyric acid methyl ester (PCBM). The CNT-sheet (cSilk, Lintec-NSTC) was attached on to
the photoactive layer as the top electrode. In addition, silver and a conductive polymer
solution were used to improve conductivity and adhesiveness. All the fabrication processes
were done under atmospheric pressure. In addition, all the processes were done below 150 C.
The structure of the fabricated device was ITO/ZnO/P3HT:PCBM/modified CNT-sheet (frombottom to top). The device showed an average transmittance of approximately 51% in the
wavelength range of 650–900 nm. (Fig. 1 (a). A photograph of semi-transparent OSC isshown in inset.) A typical photocurrent density-voltage characteristics was shown in fig.1 (b).
The power conversion efficiency of approximately 1.7 % was obtained by the illuminationfrom the ITO side underlight with air mass of 1.5
Detailed(100mW/cm2).
results and properties of the(a)(b)
semi-transparent OSC will
be discussed.
[1] M. Zhang et al., Science, 309
1215 (2005).
[2] S. Tanaka et al. Synthetic
Metals, 159 2326 (2009).
Corresponding Author: S. Tanaka
Tel: +81-6-4307-4327
E-mail: senku@ele.kindai.ac.jp

Fig. 1. (a) Transmittance and (b) Photocurrent density-voltage
characteristics of a semi-transparent organic solar cell. The inset showsa fabricated semi-transparent organic solar cell.

- 53 -

1P-14In-situ TEM study on self-oscillations ofcarbon nanotube during field emission○Tomonori Kato, Hitoshi Nakahara, Koji Asaka and Yahachi Saito
Department of Quantum Engineering, Nagoya University, Furo-cho, Nagoya 464-8603
Oscillations of carbon nanotube (CNT) during field emission (FE) under an applicationof DC voltage have been observed [1], but the origin of the oscillations is not well understood.
In order to clarify the mechanism of the oscillations, we investigated the phenomena undervarious geometrical conditions of CNTs using transmission electron microscopy (TEM).
In previous studies, a mechanism for oscillating has been proposed as follows: a CNT
bends to an anode by the electrostatic force, and then returns to the opposite direction by theelastic restoring force because of the decreased electrostatic force by FE (i.e., discharge) [2].
According to this hypothesis, it is required that the initial
direction of the CNT is inclined from the surface normal of(a)(b)
the anode to a certain extent. It is also required that theelectric resistance of the CNT itself is larger than theresistance in FE [3].
We checked whether these conditions are satisfied or notby experiment using multi-wall carbon nanotube (MWCNT).
FE experiments changing the inclination angle of a MWCNT
showed that oscillations were observed without any
dependence of the angle, even nearly vertical to the anodesurface (Figs. 1(a), (b)). Also we measured current-voltage(I-V) characteristics of a MWCNT measured by two terminal Fig. 1 TEM images of amethod (Fig. 2(a)) and I-V of FE (Fig. 2(b)). From the slope MWCNT emitter and an
anode. (a) Before applyingof the I-V at the current value of 0.1 μA (the current when the voltage, and (b) during FE
oscillation started), we found that the resistance of MWCNT with oscillation.
is smaller than that in FE. From these results on the angle
independence and the relation between the resistances, we(a)consider that the oscillation mechanism of MWCNT during
FE in TEM cannot be explained by the idea previously
reported.
We also investigated the effects of MWCNT length andradius, distance to anode, and found a relationship between
amplitude of oscillation and FE current, but the mechanism
remains unclear. In addition to these observations, the effect(b)of Lorentz force will be discussed.
[1] Y. Saito et al., Diamond & Related Materials 14, 1843-1847 (2005)[2] Jeffrey A. Weldon et al., Nano Lett. 10, 1728-1733 (2010)[3] A. Lazarus et al., Int. J. Mech. Sci. 52, 1396-1406 (2010)
Corresponding Authors: Tomonori Kato, Yahachi Saito
Tel: +81-52-789-3714, Fax: +81-52-789-3703,
E-mail: t-kato@surf.nuqe.nagoya-u.ac.jp, ysaito@nagoya-u.jp- 54 -

Fig. 2 I-V characteristics of(a) a MWCNT and (b) FE.

1P-15
Transparent, stretchable all-carbon nanotube thin-film transistors
for wearable electronics○Takeo Onishi1, Jun Hirotani1, Shigeru Kishimoto1, and Yutaka Ohno1,2
1

2

Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
Institute of Material and Systems for Sustainability, Nagoya University, Nagoya 464-8603,
Japan

Flexible and stretchable electronics offer a wide variety of wearable electronics applications
such as electronic-skins and healthcare/medical devices. Among various conductive materials
for wearable electronics, carbon nanotube (CNT) thin films are advantageous inflexibility/stretchability, conductivity, and transparency. In addition, CNT thin films can be usedboth as a channel material for high-performance transistors [1] and as a metallic conductor forinterconnections [2]; i.e. integrated circuits can be constructed by fully using CNT thin films[3]. A stretchability is one of essential functions for the wearable devices which are able to be
directly attached to body. In this work, we have realized stretchable and transparent all-carbon
devices.
The CNT thin-film transistors (TFTs) were realized on a poly(dimethylsiloxane) (PDMS)
substrate. After the device fabrication was completed on a Si substrate, the devices weretransferred on the PDMS substrate. The transfer process is applicable for a wide variety of
substrates. Purified semiconducting CNTs were used as the channel material. The CNT
electrodes were formed by the dry transfer process [4] and subsequent photolithography process.
The fabricated device is transparent and attachable to human body as can be seen in Fig. 1. The
all-carbon devices provide a new possibility to realize wearable devices without feeling its
presence.
Acknowledgments: The semiconducting CNTs were provided by TASC. This work waspartially supported by Grant-in-Aid by MEXT, JST/SICORP, JST/ALCA, and NEDO.

[1] D.-M. Sun, et al., Nature Nanotechnol. 6, 156 (2011).
[2] N. Fukaya, et al., ACS Nano 8, 3285 (2014).
[3] D.-M. Sun, et al., Nature Commun. 4, 2302 (2013).
[4] A. Kaskela, et al., Nano Lett. 10, 4349 (2010).

Fig. 1 Fabricated device images
Corresponding Author: Yutaka Ohno, Tel & Fax: +81-52-789-5387, E-mail: yohno@nagoya-u.jp- 55 -

1P-16
Mechanical and Electric Properties of Continuous Polymer-Free Carbon
Nanotube Fibers○Xueli Wu1, Takahiro Morimoto2,1, Ken Mukai3,1, Kinji Asaka3,1, Toshiya Okazaki2,1*
1

Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba
305-8565, Japan,
2
Nanotube Application Research Center, National Institute of Advanced Industrial Scienceand Technology (AIST), Tsukuba 305-8565, Japan,
3
Inorganic Functional Materials Research Institute, National Institute of Advanced Industrial
Science and Technology (AIST), Osaka, 563-8577, Japan
Single-walled carbon nanotubes (SWCNTs) have been potentially applied in wide fields
because they have a series of unique properties including electrical and mechanical properties
since their discovery in the early 1993 [1]. One of the major obstacles for their applications is
the poor dispersibility in solvents or polymers. Because strong van der Waals attractions cause
SWCNTs to bundle, dissociation is increasingly difficult for long pristine SWCNTs. For
instance, wet spinning from carbon nanotube (CNT) dispersions has attracted considerable
interest for producing CNT fibers. The most important process of the method is the
preparation of “good” CNT dispersions.
Surfactants have usually been used as supports for the CNTs dispersed in water since
surfactants have adsorbed on the nanotube surface by hydrophobic or π-π interactions. The
surfactant-stabilized CNT aqueous dispersions can be spun to fibers by coagulation. Recently,
polymer-free CNT fibers were produced by a novel wet spinning method without a polymer
coagulating solution or strong acid solvent [2]. CNT dispersions with different dispersing time
were injected into 2-propanol to be coagulated as fibers.
Nevertheless, there are very few reports on the relation between CNT fiber properties andthe character of the CNT dispersions, so far [3]. In this work, we have produced wet-spinning
CNT fibers by using Super-Growth- and eDIPS-SWCNTs with different dispersing conditions.
The prepared SWCNT dispersions were characterized by the far-infrared (FIR) and resonanceRaman spectroscopy. The lengths and qualities of SWCNTs in dispersions were estimatedfrom the FIR peak positions and the G/D values in the Raman spectra [4]. Interestingly, themechanical and electrical properties of these fibers are closely related to the effective
SWCNTs length and the quality of SWCNTs in the dispersions. The present finding suggeststhat it is very important to disperse CNTs without damage for preparing high performance
CNT fibers.
This paper is based on results obtained from a project commissioned by the New Energy andIndustrial Technology Development Organization (NEDO).
[1] S Ijima, T Ichihashi, Nature 363, 603 (1993).
[2] K. Mukai, K. Asaka, T. Murakami, C. Ito, T. Saito, M. Yumura, The 46th Fullerene-Nanotube-Graphene
General Symposium, 3-1, p. 30 (2014).
[3] N Behabtua, M J Greena, M Pasquali, Nano Today 3, 24 (2008).
[4] T. Morimoto, S.-K. Joung, T. Saito, D. N. Futaba, K. Hata, T. Okazaki, ACS Nano, 8, 9897-9904 (2014).
Corresponding Author: Toshiya Okazaki
Tel: +81-29-861-4173, Fax: +81-3-123-4567, E-mail: toshi.okazaki@aist.go.jp- 56 -

1P-17
Production and electrical properties of CNT-Cu composite wires○Rajyashree Sundaram1, Atsuko Sekiguchi 1,2, Takeo Yamada1,2, Kenji Hata1,2
Technology Research Association for Single Wall Carbon Nanotubes (TASC), Central 5,
1-1-1 Higashi, Tsukuba 305-8565, Japan
2
National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1
Higashi, Tsukuba 305-8565, Japan
1

Carbon nanotube-copper (CNT-Cu) composites, which can potentially combine theadvantages of CNTs and Cu, have garnered much attention as promising materials forapplications requiring high electrical and thermal conductivities, high current carrying
capacity, and low coefficient of thermal expansion [1-2]. Here, we report the preparation of
CNT-Cu composite wires by two-stage electrodeposition of dry-spun multiwalled CNT wires.
Our findings indicate that various process parameters, such as plating current, time,environment, solution concentration, etc. affect the Cu filling and distribution, which in turnaffect the electrical properties of the wires. CNT-Cu composite wires prepared under optimum
conditions show uniform Cu distribution along the length and cross section, indicating acontinuous CNT-Cu interface.
This presentation is based on results obtained from a project commissioned by the New
Energy and Industrial Technology Development Organization (NEDO).
[1] C. Subramaniam et al. Nat. Comm. 4, 2202 (2013).
[2] C. Subramaniam et al. Nanoscale 6(5), 2669 (2014).
Corresponding Author: A. Sekiguchi
Tel: +81-29-861-4551, Fax: +81-29-861-4851
E-mail: atsuko-sekiguchi@aist.go.jp- 57 -

1P-18Polymer Length effect on Selective Separation of
Semiconducting Single-Walled Carbon Nanotubes○Fumiyuki Toshimitsu 1 and Naotoshi Nakashima 1,2,3
1

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

Polyfluorene and their derivatives (PFOs) have been intensely investigated as dispersantsfor single-walled carbon nanotubes because they exhibit selectively sorting abilities for thesemiconducting single-walled carbon nanotubes (sem-SWCNTs). The mechanism of selective
extraction of PFOs, however, has not been fully clarified yet, including very fundamental issue
such as effects of main-chain lengths of fluorene-based dispersants The studies investigating
chain-length dependence of fluorene-based dispersants have been very limited [1],[2], because
the conventional preparation methods for PFOs with different main-chain length could not
eliminate the molecular weight distribution problem and not monodisperse.
In this study, we synthesized fluorene oligomers with different
main-chain lengths (FOn, n: the number of fluorene repeating unit,
see Fig. 1) using precise combination of monomers and obtained
monodisperse FOns with n=6, 9, 12, 15, 18, 21, 24, 27 [3]. Sorting
abilities of FOns on SWCNT solubilization showed obvious Figure 1. Chemical structures of FOns.
dependency on main-chain length of FOns (Fig. 2); namely, SWNT
dispersions was observed when the main-chain length was longer
than n = 12 and shorter FOns (n=12 and 15) did not show the semSWCNT selectivity, which was also confirmed from their Raman
spectra. The chiral selectivity was further investigated by theexperimental photoluminescence spectroscopy mapping together
with molecular mechanics simulations, which revealed that themechanism of chiral selectivity and molecular length of FOns. The
present study demonstrated importance of the main-chain length ofthe oligofluorenes on selected sem-SWNT sorting, which is usefulfor designing fluorene-based compounds that sort sem-SWNTs
with a specific chirality.
[1] P. Imin et al., Polym. Chem. 2, 1404 (2011)[2] F. Jakubka et al., ACS Macro Lett. 1, 815 (2012)[3] T. Shiraki et al., Polym. Chem., 6, 5103 (2015)
Figure 2. Raman spectra ofsolubilized SWCNTs witheight different FOns and
SDBS.

Corresponding Author: N. Nakashima
Tel: +81-92-802-2845, Fax: +81-92-802-2845,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 58 -

1P-19Chirality Control of In-Plane Oriented Single-Walled Carbon Nanotubes
Using Free Electron Laser○Daiki Kawaguchi, Miu Kobayashi, Shinnosuke Harumiya,
Tomoko Nagata, Nobuyuki Iwata and Hiroshi Yamamoto
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 highelectric conductivity, high allowable current density and mechanical strength.
Fornano-scale field effect transistor using single-walled carbon nanotubes, metal andsemiconductor separation as well as their chirality are required to be controlled. In addition
growth position / density and in-plane orientation of the SWNTs are also required. In ourprevious study, the growth of all semiconducting SWNTs had been achieved by irradiation of
the free electron laser (FEL) during growing process on SiO 2/Si substrate [1]. The irradiationof the FEL may enhance the growth of SWNTs having specific bandgap, which corresponds
to the photon energy of the FEL. The purpose of this study is selective growth of in-planeoriented SWNTs with specific chirality using FEL irradiation during growth.
Co nano-particles were deposited on ST-cut quartz substrate by evaporation methiod. A
chemical vapor deposition (CVD) was carried out for growth of the SWNTs for 10 min. The
800 nm FEL was irradiated during growth. Surface image revealed the growth of in-planeoriented SWNTs in both cases with FEL and without FEL. Fig.1 shows the Raman spectraof SWNTs grown with 800 nm FEL and without FEL. Without FEL, the RBM peaks wereobserved in 785 nm, 632 nm and 532 nm excitation laser. The calculated diameter was
1.05~1.14 nm (785 nm, ○), 1.55 nm (785 nm, ●), 1.76 nm (632 nm, ○), 1.08 nm (532 nm,●). With FEL irradiation, the RBM peaks were observed only in Raman spectrum using
785 nm excitation laser. The calculated diameter was 1.05~1.14 nm (785 nm, ▽), 1.57 nm(785 nm, ▼). The notation of ▽, ○ and ▼, ● indicates semiconductor and metal
peaks, respectively. These results indicate the FEL irradiation controls the bandgap.

Fig. 1 Raman spectra using excitation lasers of 785, 632, 532 and 441nm. The notation of ▼, ▽ and ●and ○ indicates RBM peaks with FEL and without FEL, respectively. The open (▽, ○) and closed (▼,●) symbols indicate semiconductor and metal. The bottom line of each Raman spectrum is of the substrate.
[1] K. Sakai et al. IEICE Trans. Electron. E94-C, 1861 (2011)
Corresponding Author: Nobuyuki Iwata
Tel: +81-47-469-5457, Fax: +81-47-469-5457, E-mail: iwata.nobuyuki@nihon-u.ac.jp- 59 -

1P-20Catalyst Nucleation and Carbon Nanotube Growth from
Flame-Synthesized Co-Al-O Nanopowders at 10 Second Time Scale○Hiroyuki Shirae1, Kei Hasegawa1, Eongyu Yi2, Richard M. Laine2, Suguru Noda1
Dept. of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Dept. of Material Science and Engineering, University of Michigan, Ann Arbor, 48109, USA
1

2

Carbon nanotubes (CNTs) are an attractive candidate material for electronic devices owing
to their excellent electronic properties, excellent stability in ambient, flexibility, andcompatibility with printing processes. Chemical vapor deposition (CVD) is widely used to
produce CNTs, and improving catalyst technology is still important to establish efficient
production of small diameter CNTs.
In this work, we investigated the use of Co-Al-O nanopowders by liquid-feed flame spraypyrolysis [1] as catalyst for small-diameter CNTs. Quick phase separation of Co from themixed oxide would be the key in producing small Co particles, and thus we coated thenanopowders on SiO2/Si substrate and heated them rapidly at a time scale ~10 s by electric
current (Fig. 1) [2]. The nanopowders were reduced at 800−1200 C with 3−10 vol% H2/
0−14 vol% CO2/Ar at ambient pressure for 0−10 s. Then, CNTs were synthesized by adding
0.5 vol% C2H2 to the gas at the same temperature for 10 s. We examined the effect of Co mole
fraction y in the (CoOx)y-(Al2O3)1−y nanopowder.
The nanopowders with low Co contents (y = 0.05, 0.10, and 0.25) were inert but that with ahigh Co content (y = 0.50) were active to yield single-wall CNTs (SWCNTs) as can be seen in
the scanning electron microscope (SEM) and transmitting electron microscope (TEM) images(Fig. 2). And Raman spectra showed a split G-band peak and RBM peaks with small D-band
peak at high temperatures (1000−1230 C) (Fig. 3). We will show the results for different
synthesis conditions and discuss the mechanisms for catalyst nucleation and CNT growth.

Fig. 1 Schematic of the reactor andtypical temperature profile forelectric current heating.

Fig. 2 Typical SEM image of the
product. Inset shows a typical
TEM image.

Fig. 3 Raman spectra of the CNTs
synthesized by the nanopowder (y =0.50) at various temperatures.

[1] J. Azurdia, et al., J.Am. Ceram. Soc. 89, 2749 (2006).
[2] K. Sekiguchi, et al., Carbon 50, 2110 (2012).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 60 -

1P-21
Chemical reaction analysis of cupper clusters by FT-ICR mass
spectroscopy○Ken Mizutani1, Yoshinori Sato1, Hiroya Minowa1,
Taiki Inoue1, Shohei Chiashi1, Shigeo Maruyama1,2
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
Energy NanoEngineering Lab. National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki. 305-8564, JapanTo synthesize single walled carbon nanotubes (SWCNTs), chemical vapor deposition(CVD) method is one of the most common techniques. During CVD process, hydrocarbon
molecules such as CH4 or ethanol are decomposed on catalytic metal nanoparticles, and
SWCNTs are formed from the carbon atoms at high temperature. As the catalytic metals, Fe,
Ni and Co are often used, and Cu-Co alloy can be used especially for small diameter SWCNT
growth [1]. Cu is also used for graphene growth. Although understanding the reaction
characteristic of Cu clusters is beneficial for improving SWCNTs and graphene growth, it has
not been researched well.
In this study, Cu clusters were investigated by using Fourier transform ion cyclotron
resonance (FT-ICR) mass spectroscopy. Metal clusters are generated by laser vaporization,
injected into FT-ICR cell and trapped. They do cyclotron motion in the magnetic field and theirmasses are calculated by the rotational frequency. Figure 1 (a) shows the mass spectrum of
Cu12+ to Cu15+ clusters. We also detected chemisorption with remaining gas molecules in thechamber. The mass spectra of Co clusters are shown in Figure 1 (b). The comparison of theseresults indicates that Cu clusters have higher reactivity than Co clusters.

Fig.1 Mass spectra of (a) Cu and (b) Co clusters.
[1] K. Cui, et al., Nanoscale (2016) online.
[2] S. Maruyama et al., Rev. Sci. Instrum., 61 (1990), 3686.
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 61 -

1P-22
Flow Rate Dependence of Production of Double-wall Carbon Nanotubes
by High-temperature Pulsed-arc Discharge○Yuto Hikichi, Ryota Jinnouchi, Toshiki Sugai
Department of Chemistry, Toho University, Chiba 274-8510, Japan
A high-temperature pulsed-arc discharge (HTPAD) has been developed to produce
nanocarbon materials. The system utilizes width controlled pulsed arc discharge for thevaporization of electrode in temperature controlled ambient (~760 Torr) Ar. With this width
and temperature control, novel materials have been produced by the system such as
high-quality double wall carbon nanotubes(DWNW) with outer diameter of around 1.8 ±0.2 nm[1]. However the production ratio of DWNT in all produced CNT with by-produced
single-wall carbon nanotube (SWNT) is not high (~10%) and diameter of DWNT cannot be
controlled so far. Recently, however, we have found that the ratio is enhanced up to 30% withlow pressure (~300 Torr) operation[2]. Even in this low pressure condition, the diameter isstill unchanged. To control the diameter and to achieve further enhancement of the ratio, here
we present the effect of flow rate of Ar. The flow rate has been utilized to control thestructures of carbon nanotubes, especially with laser vaporization (LV) method, where thicksingle-wall carbon nanotubes are produced in the low flow rate conditions[3].
The HTPAD system consists of a furnace with a ceramic tube inside, an Ar gas flow andpressure control system, an HV pulse voltage controller, and a water cooling trap. Electrodes
made of graphite containing catalytic metals (Ni/Y 4.2/0.5 at. %:Toyo Tanso Co. Ltd.) werelocated in the ceramic tube. The pulsed arc discharges (0.6 ms, 50 Hz, and 100 A) vaporized
the electrodes and produced nanotubes in the Ar gas at the temperature of 1250 ℃ and at thepressure of 300 Torr. The flow rate was change from 200 ml/min to 400 ml/min. The products
were collected on the trap and were characterized by
TEM observation.
Figure 1 shows the diameter distribution of SWNT
and DWNT. Both of them shift to the larger diameters
as the flow rate is decreased. This flow effects are very
similar to those found in LV experiments[3]. Even
though the diameter enlargement of SWNT is much
more prominent than that of DWNT, the DWNTs
produced in the condition of 200 ml/min with theaverage diameter of 2.3 nm is the thickest DWNT everproduced by HTPAD. Not only the diameter, but also
the production ratio of DWNT is enhanced up to 60%
in the 200 ml/min condition. These flow effects can beinterpreted as that nascent production process of Fig. 1 Diameter dependence on flow rate
DWNT with HTPAD and that of SWNT with LV havesome similarity.
[1] T. Sugai et al., Nano Lett. 3, 769 (2003).
[2] H. Kikuchi et al., 44th Fulluerene-nanotue-graphene conference. 1P-24[3] R. Sen et al., Chem. Phys. Lett. 332, 467 (2000).
Corresponding Author: T. Sugai Tel: 047-472-4406 E-mail: sugai@chem.sci.toho-u.ac.jp- 62 -

1P-23
Direct growth of patterned multi-layer grapheneby precipitation method using patterned W capping layer○Jumpei Yamada1, 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

Graphene is usually grown by CVD method using Cu or Ni catalyst. However, the transfer
process of the graphene is a big problem for the mass production of devices. Not only thetechnical difficulties but also the degradation of their properties during the process are theproblems which should be solved. In recent years, several group reported graphene growth of
directly on a substrate as the alterative for the transfer process.
We also have been studied a direct growth of multi-layer graphene by precipitation method
using W capping layer [1]. As a result, the high quality graphene was successfully grown
directly on a sapphire substrate by precipitation method using W capping layer. In this study,
we report the direct growth of patterned multi-layer graphene by precipitation method using apatterned W capping layer.
Amorphous carbon (a-C) and Nickel (Ni) layers were deposited on a sapphire substrateusing electron-beam deposition. Thereon, patterned tungsten (W) capping layer was deposited.
Patterned W (25 nm)/Ni (300 nm) /a-C (5 nm)/sapphire substrate was annealed at 900 oC for
30min in vacuum. Raman spectroscopy (532 nm) was performed to study the presence of thegraphene on the substrate. Finally, the catalysts were removed by the dipping of the sample inaqua regia.
Figure 1 shows a differential interference micrograph and corresponding Raman spectra of
the sample after the catalyst etching. Raman signal from point (1) shows the presence ofgraphene on the area while the signal from point (2) does the absence of graphene on the area.
The result indicates that the multi-layer graphene successfully formed on the substrate where
the W capping layer existed. On the other hand, graphene was observed on the bare Ni surface
only before the catalyst etching. Therefore, the W capping layer has the function to switch thesides of the precipitation of the graphene. The mechanism will be discussed on the conference
site.

Figure 1. Differential interference microphotograph of substrate after etching,
Raman spectra from point (1) and (2).
[1] J.Yamada et al. The 49th FNTG General Symposium, 3P-22, (2015).
Acknowledgement: This work was supported in part by JSPS KAKENHI Grant Numbers 2660089, 15H03558,
26105002, 25000011.
Corresponding Author: J.Yamada, E-mail: jjjjjjyyyyyy119@gmail.com- 63 -

1P-24Fabrication and characterization of graphene nanoribbons
by water-assisted anisotropic etching

Shun Ogawa1, Ryosuke Inoue1, Kenji Watanabe2, Takasi Taniguchi2,
Yutaka Maniwa1, Yasumitsu Miyata1,3
1Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
2
National Institute for Materials Science, Tsukuba 305-0044, Japan
3
JST, PRESTO, Kawaguchi 332-0012, Japan
Graphene nanoribbons (GNRs) have attracted much attention because of theirunique structure-dependent electrical and magnetic properties. Even though various
fabrication methods have been reported, anisotropic etching provides an effective way
for the preparation of GNRs directly on insulating substrates. In previous reports,hydrogen plasma is used to fabricate zigzag-edge GNRs from graphene flakes [1]. In
contrast, Luo et al. recently demonstrated the selective formation of armchair edges ingraphite by annealing with water vapor [2]. This motivates us to prepare armchair-edge
GNRs using water-assisted anisotropic etching.
Here, we report the fabrication and characterization of GNRs from graphene using
water vapor. Graphene films were prepared by methane CVD on Cu foil, and annealedwith water vapor at 800~900 °C on insulating substrates. As shown in atomic force
microscope image (Fig.1a), the annealing process leads to the formation ofhexagonal-shaped holes in graphene through anisotropic etching, and in some cases, a
GNR was formed between the two holes. Height profile presents that the GNR has awidth of 20 nm and monolayer thickness (Fig.1b). No change in Raman spectra wasobserved for the etched graphene, suggesting that the etching is proceeded preferentiallyat the edge (Fig.1c). These results indicate that the water-assisted etching would be aneffective method to fabricate armchair-edge GNRs on insulating substrates.

Fig. 1(a) AFM image of graphene after the annealing under water vapor. (b) Height profile of the dottedline in (a). (c) Raman spectra of graphene before and after the etching.
[1] R. Yang, et al., Adv. Mater. 22, 4014 (2010) , [2] D. Luo, et al. Small 10, 2809 (2014)
Corresponding Author: Yasumitsu Miyata, Tel: +81-42-677-2508, E-mail: ymiyata@tmu.ac.jp- 64 -

1P-25
Study of non-catalytic CVD of graphene on sapphire substrate----- Effect of growth temperature on nucleation ----○Yuki Ueda1, Jumpei Yamada1, Itsuki Uchibori1, Masashi Horibe1, Shinichi Matsuda1
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
In conventional, chemical vapor deposition (CVD) with a metallic catalyst is used to growhigh-quality, large-area graphene. However, it is necessary to transfer the graphene from thesurface of the catalyst to a certain substrate to fabricate graphene devices. The transfer process
is not only complicated but also harmful for the graphene performances, such as electron
mobility. Therefore, a direct growth of graphene on a substrate has been requested. In thisstudy, non-catalytic CVD of graphene is investigated to directly grow the graphene on therequested substrate. The growth temperature is systematically changed to study its growthmechanism.
A c-plane sapphire was used as a substrate for the graphene growth. Ethanol was supplied
to the growth chamber as a source material with bubbled by N2 at a flow rate of 10 sccm. The
growth temperature was systematically changed between 980-1180 oC while the flow rate ofN2 carrier gas, the growth time, and the pressure of the growth chamber were fixed at 600
sccm, 60 min, and 5x103 Pa, respectively.
Figure 1 shows the Raman spectra of the samples grown at between 980 and 1180 oC,
which indicates that the graphene was successfully grown above 1030 oC because D, G and
G’ peaks were observed. On the other hand, Fig.2 (a) and (b) show the AFM images of thesamples grown at 1080 oC and 1180 oC. The size of the circular islands increased with thegrowth temperature while their density decreased. It is probably because the nucleation of thegraphene was decreased by the thermally-enhanced diffusion of the carbon adatoms.

Fig.1 Raman spectra of samples
grown at between 980-1180 oC.

Fig.2 AFM surface images of graphene grown
at 1080 oC (a) and 1180 oC (b), respectively.

Acknowledgment: This work was supported in parts by JSPS KAKENHI Grant Numbers 2660089, 15H03558,
26105002, 25000011.
Corresponding author: Y. Ueda Tel: +81-52-838-2387, E-mail: 153434003@ccalumni.meijo-u.ac.jp- 65 -

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GLIIHUHQWVWDJHV,QVHWVKRZVPPJUDLQ1P-27
Characterization of few-layered graphene obtained by exfoliation ofGraphite Intercalation Compounds○Takuya Yasutake, Taro Kinumoto,Tomoki Tsumura, Masahiro Toyoda
Department of Applied Chemistry, Faculty of Engineering, Oita University, 700 Dannoharu,
Oita 870-1124, Japan.
INTRODUCTION
Graphene exhibits excellent mechanical, chemical and electrical characteristics such as
conductivity. Graphene has been prepared by numerous methods. In the case of graphene
prepared by the exfoliation of Grapite Intercalation Compounds (GICs) via desalination withalkyl halide solvents, the resulting graphene is expected to exhibit novel characteristics. In
this study, Na-tetrahydrofuran-GICs (Na-THF-GICs) were used as the host material for the
exfoliation through desalination of ternary GICs. Thus, obtained few-layered graphene wasobserved to exhibit no defects and some usual properties.
MATERIALS AND METHODS
Na-THF-GICs were prepared from natural graphite powder with grain size of 100 m in(SN-100, SEC CARBON Ltd.) by a solution method. For exfoliation of the GICs bydesalination was used 2-chloro-2-methylpropane (2CMP, Tokyo Chemical Industry Co., Ltd.)was selected as alkyl halide solvents.
RESULTS AND DISCUSSION
Fig. 1 shows TEM micrograph of few-layered graphene obtained by the exfoliation of the
GICs. Fig. 1(a) shows micrograph of the graphene, whereas Fig. 1(e) shows its 002 lattice,and Fig. 1(f) shows its selected area electron diffraction (SAED) pattern. These results
indicate that the obtained few-layered graphene exhibits a length at a few micrometers inplanar direction and thickness of a few nanometers. Its SAED pattern shows the clear spots,
thereby indicating that the few-layered graphene exhibits orderly stacking and does notcontain defects induced by
the exfoliation process. The
obtained
few-layered
graphene contains special
feature such as holes obtained
thought the reaction between
alkyl halide solvents and Na
in GICs’s interlayers. Further
exaltations of the obtained
few-layered graphene are
currently under way.
Fig. 1 TEM micrographs of (a)-(d) few-layered graphene was

Corresponding Author:
M. Toyoda
Tel: +81-97-554-7094,
Fax: +81-97-554-7094,
E-mail: toyoda22@oita-u.ac.jp

exfoliation by 2CMP, (e) its 002lattice and (f) its SAED pattern of
black cycle in (a).

- 67 -

1P-28The Use of Double-layered Graphene Oxides
for Capturing Carbon Dioxides: A Computational Proposal○Takashi Yumura1, Ayumi Yamasaki 1
1

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

We have investigated whether double-layered graphene oxides (GO) can be utilized to trap
CO2 by using density functional theory (DFT) (PBE functional). Previously, we discussed
migration of CO2 within the interlayer space of anhydrous and hydrous GOs. The study is
relevant to recent experimental reports in Refs. 1 and 2. Our previous DFT studies foundimportant roles of water molecules in trapping CO2 inside the interlayer space of GOs [3]. In
short, migration of CO2 within GOs is prevented by the repulsive interactions with the GO
layers in hydrous forms to trap CO2 inside the interlayer space (Fig. 1a). Such repulsive
interactions cannot be operated within anhydrous GOs, and then CO2 can be released from the
GO interlayer.
For materials candidate for CO2 capture and storage (CCS), aqueous alkanolamine
absorbents and amine-modified solid porous materials have been well studied. In thisdirection, the current study proposes from DFT calculations another strategy for trapping CO2
by GO structures encapsulating ethylenediamine. According to DFT calculations,
ethylenediamine containing GOs have relatively larger interlayer spacings relative to thepristine and hydrous GO cases. Then, interactions between CO2 and GO layers are attractive,
being in contrast to hydrous GOs (Fig. 1a). In addition, CO2 attractively interacts with anitrogen atom of ethylenediamine with lone pair electrons (Fig. 1b). Therefore, CO2 iscaptured by GO with the ethylenediamine guest through attractive CO2-GO layer andCO2-amine interactions. DFT calculations indicated that GO layered materials have different
fashions to capture CO2, depending on guest molecules. Then, GO interlayer spacings are key
to differentiate the fashions for capturing CO2 kinetically from thermodynamically.

Fig. 1 Interactions between CO2 and graphene oxide (GO) layers as a function of GO interlayer spacings.
[1] S. Eigler, C. Dotzer, A. Hirsch, M. Enzelberger, P. Müller, Chem. Mater. 24, 1276 (2012).
[2] D. Kim, D. W. Kim, H.-K. Lim, J. Jeon, H. Kim, H.-T. Jung, H. Lee, J. Phys. Chem. C 118, 11142 (2014).
[3] T. Yumura, A. Yamasaki, Phys. Chem. Chem. Phys. 16, 9656 (2014).
Corresponding Author: Takashi Yumura
Tel: +81-75-724-7571, Fax: +81-75-724-7571, E-mail: yumura@kit.ac.jp- 68 -

1P-29
Geometric and electronic structures of graphene nanoribbons under
uniaxial pressure○Kohei Narita and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba
1-1-1 Tennodai, Tsukuba 305-8571, Japan
Electronic structures of graphene nanoribbons (GNRs) are known to be ranging from a
metal to a semiconductor depending on their edge shape and width due to the discretizedcondition on the two-dimensional metallic energy band of graphene. Recently, the ultra
narrow GNR with edge roughness has been synthesized in nanometer tubular space of carbon
nanotubes (CNTs) by origomerization or polymerization of coronene molecules (C24H12) [1,2].
Inside CNT, it is plausible to apply the uniaxial pressure on the GNRs with the use of theappropriate pressure medium, being expected to induce the structural transition into the novel
one-dimensional structures. In this work, we aim to explore the high-pressure phases of GNRs
with the edge roughness inside CNT and elucidate their electronic structures based on density
functional theory with generalized gradient approximation. In the present work, we consider
the narrow armchair and zigzag GNRs with edge roughness (Fig. 1).
By applying the uniaxial pressure on the GNRs, we find that the GNRs undergo thestructural phase transition into different high-pressure phases shown in Fig. 2: The
high-pressure phase of the armchair GNRs has a double-decker structure of armchair GNRs
which are connected each other via sp C atoms. On the other hand, for the zigzag GNR, thehigh-pressure phase has a diamond nanowire structure sorely consisting of C atoms with thefour-fold coordination. The double-decker armchair GNRs and diamond nanowire are asemiconductor and a metal, respectively.

Fig. 1 Geometric structures of GNRs with (a) armchair

Fig. 2 Top and side views of optimized geometries ofand (b) zigzag edges with edge roughness.

GNRs with (c) armchair and (d) zigzag edges with edge
roughness under the uniaxial pressure.

[1] M. Fujihara, Y. Miyata, R. Kitaura, Y. Nishimura, C. Camacho, S. Irle, Y. Iizumi, T. Okazaki, H. Shinohara,
J. Phys. Chem. C 116, 15141 (2012).
[2] H.E. Lim, Y. Miyata, M. Fujihara, S. Okada, Z. Liu, Arifin, K. Sato, H. Omachi, R. Kitaura, S. Irle, K.
Suenaga, H. Shinohara, ACS Nano, 9, 5034 (2015).
Corresponding Author: K. Narita
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 69 -

1P-30Adsorption of Dps onto graphene using carbon nano-horn binding peptide○Yuki Hashima1, Yasuaki Ishikawa1, Mutsunori Uenuma 1, Naofumi Okamoto1,
Ichiro Yamashita1 and Yukiharu Uraoka1
1, Graduate School of Material Science, Nara Institute of Science and Technology, 8916-5
Takayama, Ikoma, Nara 630-0192, Japan

Graphene exhibits excellent physical and chemical properties for sensing such as highcarrier mobility, ambipolar effect, low noise level, good compatibility, and stability [1].
Graphene sensors that take advantage of those features are becoming a hot spot. We
introduced a Dps, the surface of which was genetically modified with peptides, as sensing key
component in graphene sensors. Dps is a cage-shaped protein. It is possible to encapsulate
inorganic materials in the inner cavity by bio-mineralization. Additionally, N- and C- termini
are protruding outside and two-types of peptides can be genetically added on their outersurface.
In this presentation, we designed and mass-produced Dps displaying carbon nano-hornbinding peptide and Ti binding peptide which was named CDT-1. Carbon nano-horn binding
peptide had been reported to bind to the carbon nanotube [2]. However, adsorption to thegraphene was not yet confirmed. Therefore, we studied adsorption ability of CDT-1 onto
graphene.
Experimentally, CDT-1 solution (0.5 mg/ml Fe-oxide cored CDT-1, 50 mM MES-Tris buffer
pH 6.0) was dropped on CVD graphene on Cu substrate. Then un-binding proteins were
washed away. After the process, samples surface was observed by SEM.
 The SEM image is shown in Fig. 1. The white dots in Fig. 1 are the Fe-oxide core in CDT-1
with 4.5 nm diameter adsorbed onto the graphene surface. The measured adsorption density
for CDT-1 was 7.0×1010 dots/cm2. Based on the SEM images, it was proved that carbon
nano-horn binding peptides anchored Dps onto the graphene surface.
As a result, we successfully demonstrated that the spherical shell protein adsorbed tographene using carbon nano-horn peptide.

Fig 1. A SEM image of CDT-1 adsorbed on graphene.
The white dots is Fe-oxide core in CDT-1.
[1] C. Zheng et al. ACS applied materials & interfaces 7, 16953–16959 (2015).
[2] M. Kobayashi et al. Chem.Commun., 47, 3475-3477 (2011)
Corresponding Author: Yasuaki Ishikawa
Tel: +81- 743-72-6064, Fax: +81- 743-72-6069,
E-mail: yishikawa@ms.naist.jp- 70 -

1P-31
Silicon Thin-Film Solar Cells with Graphene Transparent Electrode○Ryousuke Ishikawa, Tomoya Oya, Takahiro Nomoto, and Nozomu Tsuboi

Faculty of Engineering, Niigata University, Niigata 950-2181, Japan

Transparent electrode is a key component in the multi-junction solar cells, working as window
and intermediate electrodes. It requires high transparency for wide range and suitable electricaljunctions. We focused on graphene, a single atomic layer of sp2 graphitic carbon, as a promisingmaterial for transparent conducting electrode in multi-junction solar cells because of its highelectrical conductivity and optical transparency over a wide range of wavelengths [1]. Here, weinvestigated the potential of graphene electrode in silicon thin-film solar cells.
High quality graphene was fabricated by CVD growth technique using Cu foil as catalyst
substrate. Monolayer of graphene was grown at 1000 oC for 30 min under 22 sccm of CH4 and 44
sccm of H2. After CVD growth, deposited graphene was then transferred by polymethyl
methacrylate (PMMA) assisted process onto glass substrates. By repeating this step on the same
substrate, trilayered graphene films can be prepared that exhibit enhanced electrical and opticalproperties. The p-i-n single-junction solar cells of hydrogenated amorphous silicon carbide (aSiCx:H), hydrogenated amorphous silicon (a-Si:H), and hydrogenated microcrystalline silicon oxide(µc-SiOx:H) were fabricated on the graphene films by plasma enhanced chemical vapor deposition(PECVD) in a multi-chamber system. The schematic image of solar cells structure using graphene
window electrode is shown in Fig. 1. The photovoltaic characteristics of the solar cells with the cellarea of 0.086 cm2 were measured under AM 1.5 G (100 mW/cm2) at 25 oC.
Figure 2 shows the photovoltaic characteristics of the solar cells including the data of thoseusing sputtered ZnO:Al as window electrodes as comparison. As can be seen from the figure, higher
Voc has been obtained with the cell using graphene window electrode. This result is probably due tothe lower Schottky barrier at the graphne/p-layer interface and this can increase the built-in
potential of the cell. Actually, the I-V characteristics of graphene/p-layer exhibited the perfectohmic contact, whereas that of ZnO:Al/p-layer showed the Schottky diode characteristics. Further
investigation is needed to elucidate the origin of the ohmic contact. Higher cell performance would
be expected by further cell optimization.

Fig. 1 The schematic images of fabricated solar cells

Fig. 2 The photovoltaic characteristics of the solar cells.

[1] R. Ishikawa et al. Jpn. J. Appl. Phys., 51 11PF01 (2012).
Corresponding Author: R. Ishikawa, Tel & Fax: +81-25-262-6736, E-mail: ishikawa@eng.niigata-u.ac.jp- 71 -

1P-32
Substrate dependence of graphene oxide in amidation and esterification
reactions○Haruya Okimoto, Yasutaka Yoshii, and Masahito Sano
Department of Polymer Science and Engineering, Yamagata University, Yonezawa, 992-8510,
Japan
Chemical functionalization of graphene oxide (GO) fixed on(a)a solid substrate is a topic of paramount importance, for it
allows fine-tuning of the chemical and physical properties of
GO. In practice, GO film can be easily prepared on various
substrates by wet processes. Therefore it is important tounderstand the influence of a substrate upon GO
functionalization. Especially, amidation and esterification havebeen applied frequently to modify GO, which have significant
amounts of hydroxyl and carboxyl groups. In this study, wedemonstrate that the substrate influences the reactivity of the(b)
top surface of GO using quantitative reactions with fluorescentdyes.
An aqueous dispersion of GO was splay cast on
octadecyltrichlorosilane (OTS) modified SiO2/Si or
3-aminopropyltriethoxysilane (APTES) modified SiO2/Si. A
thin GO film that partially covers the substrate surface and amultilayered thick film that completely covers were made forcomparison.
These
films
were
amidated
with
5-aminofluorecein or esterified with 1-pyrenbutiric acid,
Fig. 1 AFM image of isolated GO
respectively. The amount of reacted dye was quantified by film on (a) APTES/SiO and (b)2hydrolysis of the products.
OTS/SiO2.
Figure 1 shows AFM image of thin GO on each substrate.
Thick GO film
The GO on APTES/SiO2 (hydrophilic surface) spreads flat on
Isolated GO
20
the surface, while the GO on OTS /SiO2 (hydrophobic surface)
appears folded. This indicates that wetting of GO on a solid
substrate has strong influences on the morphology. Figure 2
10shows the reacted amounts for thin and thick GO films for theesterification reaction. It has been reported that the reactivityof graphene is enhanced by strain on graphene films. Since thefolded GO on OTS/SiO2 is strained stronger than the flat GO
0
on APTES/SiO2, the observed reactivity difference can be
APTES/SiO2
OTS/SiO2
explained by the film morphology. For the thick GO films, the Fig 2 Reaction weight ofreactivity does not differ as much as that of the thin film. This
fluorescent agent for GO film onshows that the influence of substrate is limited to the GO that the substrate.
are immediate vicinity of the substrate surface. The amidation
reaction gives a similar result.
In summary, we demonstrate that the reactivity of GO films on the solid substrate is strongly
influenced by the morphology of GO which is determined by wettability.
Reaction weight ( ×10-15g / µm2)

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Corresponding Author: H. Okimoto Tel/FAX: +81-238-26-3074 E-mail: haruya@yz.yamagata-u.ac.jp- 72 -

㻟

1P-33
Indirect angle resolved photoemission spectra in graphene○ Pourya Ayria1, Shin-ichiro Tanaka2 , Ahmad R.T. Nugraha1, and Riichiro Saito1
12

Department of Physics, Tohoku University, Sendai 980-8578, JapanThe Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka
567-0047, Japan

Angle-resolved photoemission spectroscopy (ARPES) can be used to detect the electron-phonon
coupling (EPC) in solids [1]. Most of the previous studies of ARPES in graphene have explored EPC
effects on ARPES spectra by the direct observation of the energy bands near the K point. Recently,
several ARPES experiments observed the indirect transition of ARPES spectra far from the energy
bands around the Γ point and near Fermi energy, where there is no available energy band [2, 3].

In order to explain the evidence of the indirect transition observed in graphene (or graphite) [2, 3], we
theoretically investigate the indirect transition of ARPES spectra as a function of the incident lightpolarizations and the photon energy. The electron-photon and electron-phonon matrix elements arecalculated by the dipole approximation [4] and the rigid-ion approximation [5], respectively, where in
the both of the calculations we utilize first-principles calculation [6]. Our calculation shows that thetransverse optical TO-phonon mode has the strongest EPC for the photo-excited electron at the K point
to the Γ point by the K point phonon mode. This signal is strong for the photon energy ℏ𝜔𝜔 = 11 eV,
which corresponds to the lowest unoccupied electron state near the K and K’ points. We compare thecalculated results of ARPES spectra with the experimental results of graphite.

[1] A. Damascelli et al., Rev. Mod. Phys. 75, 473 (2003).
[2] Y. Liu et al. Phys. Rev. Lett. 105, 136804 (2010)[3] S. Tanaka et al., Sci. Rep. 3, 3031 (2013).
[4] P. Ayria et al., Phys. Rev. B 92, 195148 (2015).
[5] G. Grimvall, Electron-phonon interaction in metals, North-Holland, (1980).
[6] P. Giannozzi et al., J. Phys. Cond. Matt. 21, 395502 (2009).
Corresponding Author: P. Ayria, E-mail: pourya@flex.phys.tohoku.ac.jp- 73 -

1P-34
Raman Spectroscopy of Ti-Cleaned Single-Layer Graphene
and Transfer on Paper Substrate○Akira Fujimoto1,2, Masafumi Sakita3, Ren Kaneko4, Ryosuke Nakano3, Kazuo Satoh5
Shuichi Murakami5, Yoshiyuki Harada1,2, Toshihiko Maemoto2,4, Mitsuaki Yano2,3
1

2

Applied Physics, Faculty of Engineering, Osaka Institute of Technology, Osaka 535-8585, Japan
Nanomaterials Microdevices Research Center, Osaka Institute of Technology, Osaka 535-8585, Japan3
Department of Electronics Information and Communication Engineering, Faculty of Engineering,Osaka Institute of Technology, Osaka 535-8585, Japan
4
Department of Electrical and Electronic Systems Engineering, Faculty of Engineering,Osaka Institute of Technology, Osaka 535-8585, Japan
5
Technology Research Institute of Osaka Prefecture, Izumi, Osaka 594-1157, Japan

Chemical-vapor-deposited (CVD) graphene is good for fabricating devices on a large scale.
However, the charge-neutral point (CNP) appears at a relatively high back-gate voltage (VG)
because of molecular adsorption and impurities on the graphene surface. In this work, weused a Ti-cleaning process for the transferred graphene surface [1] and examined the opticalcharacteristic using Raman spectroscopy. Ti-cleaning process is as follows. 2 nm of Ti was
deposited on the graphene and allowed to oxidize to Ti oxide upon exposure to air. The Ti
oxide was then removed with HF. Owing to Ti cleaning, the CNP shifted to a lower VG, andthe mobility increased [2]. We found that Ti-cleaned graphene showed the same CNP and theelectrical characteristic was maintained for several months. In order to confirm these
phenomena, we examined Raman spectra for Ti-cleaned graphene samples for a few months.
As a result, the peak positions of G and 2D do not shift apparently as time passes. The resultsof Raman spectroscopy by Lee et al.[3] show that the 2D peak position for suspended
graphene are 2676.9±0.7 cm -1 . However, 2D peaks of our samples are larger by about
20 cm-1 than that of Lee’s data, resulting from a compressive strain according to Lee’s
analysis method.
Currently organic electro-luminescence starts to be applied to flexible substrates such aspolyethylene terephthalate (PET), graphene also has a potential to be used on such substrates.
We also tried to transfer CVD-graphene onto paper substrates and evaluated the opticalcharacteristic. Figure 1 shows Raman spectra forgraphene on Si/SiO2 and paper substrates measured atroom temperature. We confirmed that G and 2D
peaks appear for a graphene sample on paper
substrate, which indicates that the graphene transfer
onto paper is carried out well. In the presentationthese details will be discussed together with electriccharacteristics.
[1] C. A. Joiner et al., Appl. Phys. Lett. 104, 223109 (2014).
[2] A. Fujimoto et al., J. Phys. Conf. Series 603, 012021(2015).
[3] J. E. Lee et al., Nature Commun. 3 1024 (2012).
Corresponding Author: A. Fujimoto
Tel: +81-6-6954-4377, Fax: +81-6-6957-2137,
E-mail: akira.fujimoto@oit.ac.jp- 74 -

Fig.1 Raman spectra for graphene on
Si/SiO2 and paper substrates.

1P-35
1 H-1T’ phase transition and heterojunction formationin CVD-grown monolayer Mo1-xRexS2○Shohei Mori1, Shogo Sasaki1, Yu Kobayashi1, Liu Zheng2,3, Shoji Yoshida4, Takahiro
Takeuchi4, Hidemi Shigekawa4, Kazutomo Suenaga3, Yutaka Maniwa1, Yasumitsu Miyata1,51Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
Inorganic Functional Materials Research Institute, AIST, Nagoya, 463-8560, Japan
3
Nanomaterials Research Institute, AIST, Tsukuba, 305-8565, Japan
4
Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan
5
JST, PRESTO, Kawaguchi, 332-0012, Japan
2

Semiconductor heterojunctions based on atomic layers have attracted much attention
because of their potential applications in electronics and optoelectronic. So far, such
heterojunctions have been fabricated by using chemical vapor deposition (CVD) of varioustransition metal dichalcogenides (TMDCs) such as monolayer MoS2, WS2 and Mo1-xWxS2
alloys [1-3]. In contrast, the junctions with different polytypes have been also observed for
exfoliated MoS2 flakes [4], and for the laser- and electron-beam-irradiated samples [5,6].
However, the direct growth of polytype-based heterojunctions still remain as an unsolved
issue. In this study, we report the growth and characterization of heterojunction of 1H and 1T’phase monolayer Mo1-xWxS2 alloys grown by CVD.
 Monolayer Mo1-xRexS2 alloys were formed on graphite and quartz substrate substrates by
CVD of sulfur, molybdenum oxide, and rhenium oxide. Growth of hexagonal-shapedmonolayer grains was confirmed from atomic force microscope (AFM) observation (Fig.1a).
Interestingly, the coexistence of 1H and 1T' phases was found within a single grain throughscanning transmission electron microscope (STEM) image (Fig.1b), Raman spectrum (Fig.1c),and scanning tunneling microscope (STM) observations. In particular, the STEM image
indicates that the 1T’ phase has higher Re concentrations than the 1H phase. In thepresentation, we will report the details of their phase-transition conditions and electronic state.

Fig.1 (a) AFM and (b) STEM images of Mo1-xRexS2. (c) Raman spectra of MoS2, ReS2, and Mo1-xRexS2.
[1] Y. Gong, et al. Nat. Mater., 13, 1135 (2014). [2] Y. Kobayashi et al., Nano Res., 8, 3261 (2015).
[3] S. Yoshida, et al. Sci. Rep., 5, 14808 (2015). [4] Y. Lin, et al. Nat. Nanotechnol., 9, 391 (2014).
[5] S. Cho, et al. Science, 349, 625 (2015). [6] G. Eda, et al. ACS Nano, 6, 7311 (2012).

- 75 -

1P-36
Anisotropic optical absorption and Raman spectrum in GaTe
○Yuki Tatsumi1, Shengxi Huang2, Xi Ling2, Huaihong Guo3, Teng Yang4,
Mildred S. Dresselhaus2, Riichiro Saito1
12

Department of Physics, Tohoku University, Sendai 980-8578, Japan
Department of Electrical Engineering and Computer Science, Massachusetts Institute ofTechnology, Cambridge, Massachusetts 02139 USA
3
College of Science, Liaoning Shihua University, Fushun, 113001, China
4
Institute of Metal Research, CAS, Shenyang 110016, China

Gallium telluride (GaTe) is a newcomer of atomic layer families, whose primitive unit cell
contains 6 Ga and 6 Te atoms [Fig. 1 (a)]. In the bulk form, GaTe is a direct energy gap
semiconductor with the gap energy Egap~1.65eV [1]. We can expect GaTe as an application forphotodetectors since recent experiment [2] reports that GaTe has high photoresponsivity (104A/W) and short response time (6 ms) compared with other atomic layer materials. Opticalproperties of GaTe is still not apparent and in this work, we focus on the anisotropy of opticalabsorption and Raman spectroscopy depending on the polarization of incident photons. In
order to investigate the polarization dependence of electron-photon interaction, we perform
two step calculations: (1) DFT calculation for obtaining the electronic energy bands andeigenfunction, (2) Calculation of matrix elements for electron-photon interaction based on
dipole approximation. We also analyze the polarization of optical transition by group theory
analysis.
Figure 1 (b) shows a polarization
dependence of optical absorption for x andy polarized light. We can find that x
polarized light is absorbed more than ypolarized light. We verify the origin of thisanisotropy by group theory analysis. GaTe
belongs to C2h3 space group and we candiscuss the selection rule of opticaltransition at symmetric point in Brillouinzone [Z and P point in Fig.1 (c)] by thesymmetry of wave function. Figure 1 (c)illustrates the bands symmetry assignment
near the Fermi energy at Z and P point.
Selection rule shows that the transition
near the gap energy is polarized to x
direction and x polarized light is mainly
absorbed. We will present the analysis of
anisotropic Raman spectrum, too.
[1] P. Hu, et al. Nano Res., 7, 694 (2014)[2] F. Liu, et al. ACS Nano, 8, 752 (2014)
Corresponding Author: Yuki Tatsumi
Tel: +81-22-795-6442, Fax: +81-22-795-6447,
E-mail: tatsumi@flex.phys.tohoku.ac.jp

Fig.1: (a) Atomic structure of GaTe. a1, a2, and a3 areprimitive lattice vectors. (b) Polarization dependenceof absorption spectrum in bulk-GaTe on incident
photon energy. P is polarization vector for incident
photon. (c) Bands Symmetry assignment for C2h3
space group at P and Z point of Brillouin zone.
Permitted transition is shown by arrow. Inset ispolarization dependence for matrix element for thesetransitions. 0 (90) degree corresponds to x (y)direction.

- 76 -

1P-37
Observation of Biexciton States in high-quality Tungsten Disulfide Atomic
Layers from 80 K to Room Temperature○Mitsuhiro Okada1, Yuhei Miyauchi2, Kenji Watanabe3, Takashi Taniguchi3, Kazunari
Matsuda2, Hisanori Shinohara1, Ryo Kitaura1
1

Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan
2
Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan
3
National Institute for Materials Science, Tsukuba 305-0044, Japan

Group-VI transition metal dichalcogenides (TMDC) have attracted a great deal of attention
due to their unique physical properties including exciton-dominated photoluminescence (PL),high performance in field effect transistors and valley-contrast properties. To explore these
fascinating properties of TMDC , the preparation of high-quality samples is needed, which are
ideally free from defects, surface roughness and the over extrinsic effects arising fromsubstrates. For this purpose, we have focused on chemical vapor deposition growth of TMDC
directly onto hexagonal boron nitride (hBN). We report here the growth of high quality WS 2
on hBN and detailed PL properties including the observation of biexcitons at 80 K under low
excitation power of 24 W/cm2. This condition is much
milder than that in a previous report (4 K, 50 kW/cm2)[1].
Figure 1 shows a proposed structure model of
WS2/hBN. PL spectra of WS2 grown on hBN show
very strong and sharp PL emission with a FWHM of
21.5 meV, where PL intensity of WS2 on hBN is 300
times as stronger as those grown on sapphire. Figure 2
shows PL spectra observed at 80 K, which shows
additional peaks at the lower energy region. The
excitation power dependence of the PL peak at 2.00
eV shows a linear relation with an alpha of 1.54, and Fig. 1: Schematic view of WS2/hBN.
Hexagonal sheet under WS2 is hBN.
the lifetime measurement of this emission is two times
as shorter as that of excitons. The present results
clearly show that the PL peak can be attributed tobiexcitons, which has been observed with low
excitation power down to 24 W/cm2. PL emission
from biexcitons has been observed even at room
temperature under a high excitation power of 50
kW/cm2. And we think minimal substrate effects andamount of trapping site in WS2/hBN sample are key
factors for the current observation of biexciton states.
[1] G.Plechinger et al., Phys. Status Solidi RRL. 9, 457 (2015).
Corresponding Author: R.Kitaura and H.Shinohara
Tel: +81-52-789-2477, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp and noris@nagoya-u.jp- 77 -

Fig. 2: PL spectra of WS2 on hBN at 80
K.

1P-38Visualization of local transport properties of MoS2 transistors
by scanning gate
○Ayaka Higuchi1, Masahiro Matsunaga1, Guanchen He2, Jonathan P. Bird2, Yuichi Ochiai1
and Nobuyuki Aoki1, 3
1Graduate School of Advanced Integration Science, ChibaUniversity,
Chiba 263-8522, Japan2
Department of Electrical Engineering, University at Buffalo, SUNY,
Buffalo, New York 14260-1920, USA
3
JST-PRESTO, Kawaguchi, Saitama 332-0012, Japan

In recent studies, molybdenum disulfide, MoS2, which has layered structure has been
attracted lots of interests because of its properties. Typically, it exhibits semiconducting
properties having a band gap of 1.8 eV in the monolayer structure. Therefore, it has beenstudied so as to be utilized as field effect transistor (FET). In our study, we use scanning gate
microscopy (SGM) to examine characteristic of MoS2. SGM can visualize local transport
properties in semiconducting materials using a metallic coated cantilever as a mobile top gate.
In our previous report [1], we reported local gate responses within MoS2 FET by SGM.
The results indicated that the SGM response attributed to the transport properties of the MoS2
FET, which is dominated by the properties of ohmic contact at injection side. Combining
electrostatic force microscopy (EFM) observation, we can evaluate the potential discussion
within the channel.
In our study, single layer MoS2 crystals which were directly grown on SiO2/Si substrates
by chemical vapor deposition and provided by the Ajayan group at Rice University [2].
Source and drain electrodes (Cr/Au) were patterned by electron beam lithography.
As results of these measurements, we found SGM responses observed inside the MoS2
channel, away from the electrode in the same sample. In addition, EFM image we obtained
indicated that a huge potential drop was at the same position where the SGM response
observed. Interestingly, some groups reported that a crystalline structure of MoS2 can betransformed from semiconducting (2H-structure) to metallic (1T-structure) by several ways [3,4]. Considering our results of the SGM and the EFM, a Schottky potential barrier could
process. It suggests that a possibility of a partial-structural transition from 2H to 1T might beintroduced by EB lithography.
[1] M. Matsunaga et al, The 49th FNTG General Symposium 3P-36 (2015).
[2] Y. Zhan et al., Small 8, 966-971 (2012).
[3] R. Kappera et al., Nature Mater. 13, 1128 (2014).
[4] Y. C. Lin et al., Nature Nanotech. 9, 391 (2014).
Corresponding Author: N. Aoki
Tel:+81-43-290-3430, Fax:+81-43-290-3427
E-mail:n-aoki@faculty.chiba-u.jp- 78 -

1P-39Extremely Thin and Flexible Single-Layer WS2 Phototransistors○Adha Sukma Aji,1 Toshiaki Shiiba,1 Kenjiro Fukuda,2,3 Hiroki Ago1,3,4,*
1

Interedisciplinary Graduate School of Engineering Sciences, Kyushu University2
Thin-Film Device Laboratory, RIKEN
3PRESTO-JST
4
Institute for Materials Chemistry and Engineering (IMCE), Kyushu University

The discovery of graphene has expanded the research field of two-dimensional (2D)
materials [1]. The 2D materials show unique physical properties, such as high carrier mobility
in graphene and direct band gap in single-layer MoS2 and WS2, which can be developed tonovel electronic and photonic applications. Moreover, their atom-thick structures make devices
very thin, flexible, and transparent.
In the present work, we demonstrate an extremely thin, flexible, and soft phototransistors
using WS2 and graphene as channel and electrodes, respectively. Single-layer WS2 used as achannel was synthesized on sapphire substrates by ambient pressure CVD using WO3 and S
powder. All the source, drain, and gate electrodes weremade by multi-layer graphene which had been grown by
CVD on Cu-Ni foil. We synthesized relatively thickgraphene (~12 nm thick), because it gave much lower
sheet resistance (100 Ω/¨) than that of monolayer
graphene (600 Ω/¨). After patterning WS2 and graphene,
we assembled all these 2D materials on 1 µm-thickparylene substrate, as illustrated in Figure 1a.
The transport property of the all-2D device wasmeasured in vacuum at room temperature. Interestingly,
the device worked by directly contacting probe tips tographene electrodes, without using metals, such as Au and
Ti. Moreover, as shown in inset in Figure 1b, the WS2
channel and graphene electrode showed near Ohmic
behavior, suggesting graphene can form a good contact to
2D materials. Figure 1b presents the transfer curves indark and under illumination of visible light. The on/off
ratio and electron mobility are 2×104 and 2 cm2/Vs,
respectively, in dark. The all-2D device showed a clear
optical response, with photoresponsitivity as high as 70µA/W at Vg=30 V. The internal quantum efficiency (IQE)
were calculated to be 9%. These values indicate good
photon to electron conversion even though the device isnearly transparent. Our result would enrich 2D material
applications for transparent and flexible optoelectronic
Fig 1. (a) Photograph of the all-2D device
devices.
Reference: [1] S. Z. Butler et al., ACS Nano, 7 (2013) 2898.
Corresponding Author: Hiroki Ago (Tel&Fax: +81-92-583-7817,
E-mail: ago@cm.kyushu-u.ac.jp)- 79 -

attached on a human finger. Inset:
Schematic view of the device. (b) Transfer
characteristic of the device.

1P-40Lattice Vibrations in Isotopic Diamond Superlattice○Yuki Bando, Susumu Saito
Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551, Japan
Isotopic Diamond Superlattice Structure where 12C and 13C diamond layers are stacked
alternately was created by Watanabe et al [1]. In this system, the confinement of carriers to
12
C diamond layers was observed by cathodoluminescence experiments. It is expected that
this phenomenon is caused by characteristic electron-phonon interaction in a diamond crystal[2]. However, details of the lattice vibrations and its effects on the electronic structure in
isotopic diamond suprelattice have not been reported theoretically so far.
In our study, we computed lattice vibrations in isotopic diamond suprelattice using density
functional perturbation theory [3] with a special combination of Fourier transformation forisotopic superlattice. As a result, the density of states of lattice vibrations (LV-DOS) of thesuperlattice alternately stacked 36 12C layers and 36 13C layers ((36, 36) superlattice) is foundto be nearly equal to the arithmetic mean of LV-DOS of the 12C diamond and that of the 13C
diamond (Fig. 1). On the other hand, LV-DOS of the (2, 2) superlattice is nearly equal to
LV-DOS of virtual 12.5C diamond (Fig. 2).
(a) Comparison with 12.5C(b) Comparison with arithmetic mean of 12C and 13C

Fig 1. LV-DOS of (36, 36) superlattice stacked toward [001] direction(a) Comparison with 12.5C(b) Comparison with arithmetic mean of 12C and 13C

Fig 2. LV-DOS of (2, 2) superlattice stacked toward [001] direction[1] H. Watanabe, C. E. Nebel, and S. Shikata, Science 324 1425 (2009)[2] F. Giustino, S. G. Louie and M. L. Cohen, Phys. Rev. Lett. 105 265501 (2010)[3] S. Baroni, S. de Gironcoli, and A. D. Corso, Rev. Mod. Phys. 73, 515 (2001)
Corresponding Author: Y. Bando
Tel: +81-03-5734-2387, Fax: +81-03-5734-2739,
E-mail: y-bando@stat.phys.titech.ac.jp- 80 -

1P-41
Josephson effect in NbSe2/NbSe2 van der Waals junction○Naoto Yabuki 1, Rai Moriya 1, Miho Arai 1, Yohta Sata 1, Sei Morikawa 1, Satoru Masubuhi 1,
Tomoki Machida 1,2,3
1

2Institute of Industrial Science, University of Tokyo, Tokyo, Japan
Institute for Nano Quantum Information Electronics, University of Tokyo, Tokyo, Japan
3
CREST, Japan Science and Technology Agency, JapanWe demonstrated the Josephson effect at the van der Waals (vdW) interface. Layered
dichalcogenide superconductor NbSe2 is mechanically exfoliated, and vdW contact between
freshly cleaved surfaces has been built by using dry transfer technique [Fig. 1(a)]. By
optimizing exfoliation and transfer condition, we fabricated highly transparent vdW junction
between NbSe2 crystals with resistance-area product RA=16 Ω-µm2. Cross-sectional TEM
images reveal atomically flat vdW interface without significant oxidation.
Current-voltage characteristics exhibited zero bias current accompanying apparent
hysteresis [Fig. 1(b)]; thus suggesting the Josephson current flow across vdW junction. By
applying magnetic field parallel to the junction, the periodic modulation of the Josephsoncurrent (Fraunhofer pattern) is observed [fig. 1(c)]. The ratio between subgap andnormal-state resistance Rqp/RN = 20 already comparable to that of modern Nb-based
Josephson junction. Furthermore, we demonstrate RNIc product of 1.04 mV; this is close to the
maximum value expected from the Ambegaokar-Baratoff theory. These results indicate thathigh quality vdW Josephson junction has been fabricated in vdW interface [1].
[1] Naoto Yabuki , Rai Moriya et al., Nature Communications, in press.

Fig.1 (a) The schematic illustration of van der Waals Josephson junction fabricated with NbSe2.
(b) Current-voltage characteristics of the junction at 4.5 K. (c) In-plane magnetic field dependence of I-V curves
showing Fraunhofer pattern at 4 K. Dashed line indicates the theoretical calculation.
Corresponding Author: N. Yabuki
Tel: +81-3-5452-6158, Fax: +81-3-5452-6157,
E-mail: yabuki@iis.u-tokyo.ac.jp- 81 -

1P-42Functional carbon nanohorn complexes
for multi-dimensional cancer elimination○Eijiro Miyako1*, Svetlana Chechetka1, Minfang Zhang2, Masako Yudasaka1
Department of Materials and Chemistry, Nanomaterial Research Institute (NMRI), National
Institute of Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba
305-8565, Japan2
Department of Materials and Chemistry, CNT-Application Research Center, AIST, Central 5,
1-1-1 Higashi, Tsukuba 305-8565, Japan1

We have developed multi-componential
nanomaterials that are based on folic acid (FA)andpolyethylenimine(PEI)-functionalized
carbon nanohorn conjugates that encapsulatemagnetite nanoparticles (FA-PEI-MAG-CNHox)(Fig. 1)[1,2]. The nanoconjugates werecharacterized using a variety of experimental
setups, including dynamic light scattering,thermogravimetric analysis, Fourier transform
infrared
spectrometry,andultraviolet–visible–near-infrared (UV–Vis–NIR)
spectroscopy. An NIR laser and a radio
frequency-induction heating system were used toevaluate the heat-generating capability of thenanoconjugates. Aqueous solutions containing
the nanoconjugates exhibited a significant
increase in temperature after laser irradiation
and/or radio frequency induction compared with
controls. The intercellular distribution of thenanoconjugates was quantitatively analyzed
using UV–Vis–NIR spectroscopy with two celllines: human epidermal carcinoma (KB) and
Fig. 1 Chemical structure and water-dispersibility
human embryonic (FHs173We) cells. The of FA-PEI-MAG-CNHox conjugates. (A) A
interaction
betweenthe
FA-modified schematic illustration of the chemical structure ofnanoconjugates and KB cells was enhanced FA-PEI-MAG-CNHox. (B) FA-PEI-MAG-CNHox inthrough overexpression of FA receptors on the an aqueous solution. The FA-PEI-MAG-CNHox was
surface of the KB cells. A stronger interaction dispersed in HEPES buffer (100 mM, pH 7.4) at a
between the nanoconjugates and KB cells was concentration of 300 g/mL.
observed in the presence of a magnet.
Furthermore, laser- and/or radio frequency-induced nanoconjugates in combination withexternal magnetic application reduced the viability of KB cells. Therefore, the present study
will open a new direction for the development of multi-dimensional cancer therapy.
[1] S. Chechetka et al. Carbon 97, 45-53 (2016).
[2] S. Chechetka et al. Chem. Asian J. 10, 160-165 (2015).
*Corresponding Author: E. Miyako
Tel: +81-87-869-3574, Fax: +81-29-861-4413, E-mail: e-miyako@aist.go.jp- 82 -

1P-43Characterization and Supercapacitor Properties of Fibrous Aggregates ofSingle-Walled Carbon Nanohorns○Ryota Yuge1, Fumiyuki Nihey1, Kiyohiko Toyama1, and Masako Yudasaka2, 3
1

Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
National Institute of Advanced Science and Technology (AIST), Tsukuba, 305-8565, Japan
3
Graduate School of Science and Technology, Meijo University, Nagoya 468-8502, Japan
2

Single-walled carbon nanohorns (SWCNHs) [1], a type of nano-carbon materials, areattractive having high dispersibility in solutions and large specific surface area. Recently, we
have succeeded in preparing fibrous aggregates of SWCNHs (fib-CNHs), which also havelarge surface area and, different from SWCNHs, their electrical conductivity is high [2]. As
well known, the large surface area and high electrical conductivity are fundamental properties
for the electrodes materials of supercapacitors, but it is not easy for one substance to havethese two properties. It seems that the fib-CNHs could be an ideal material to make theelectrode of supercapacitor. In this study, the supercapacitors were fabricated by using
fib-CNHs electrodes and the capacitance and quick discharge properties were evaluated.
Fib-CNHs were prepared by CO2 laser ablation of an iron-containing graphite target at room
temperature. The CO2 laser was operated in the continuous-wave mode. The gas pressure in
the growth chamber was sustained at 760 Torr by controlling the evacuation rate while theflow rate of buffer gas of N2 was kept at 10 L/min. The conventional SWCNHs of sphericalstructure (sph-CNHs) were also prepared using an iron-free graphite target, which is used as areference sample. Composite-pellet for the supercapacitor electrode was prepared by
sph-CNHs and/or fib-CNHs with polytetrafluoroethylene binder (PTFE). The supercapacitor
was assembled with 1 M (CH3(CH2)3)4N·BF4/propylene carbonate electrolyte, glass separator,
and the composite-pellet electrodes. Galvanostatic charge/discharge measurements werecarried out in the range of 0 to 2.5 V at 20ºC
The specific surface areas of fib- and sph-CNHs after hole-opening by the oxidation
treatment were 1580 m2/g and 1690 m2/g, respectively. Their capacitances were 20 and 21 F/g,
which mean that the capacitance depends strongly on the specific surface area. The
supercapacitor with hole-opened fib-CNHs indicated the higher capacitance, i.e., lesscapacitance drop at high power operation. The capacitance retention of hole-opened fib-CNHs
at the discharge current at 5 A/g was 40% higher than that of sph-CNHs.
[1] S. Iijima et al. Chem. Phys. Lett. 309, 165 (1999).
[2] R. Yuge et al. The 49th FNTG Symposium, 65 (2015).
Corresponding Author: R. Yuge
Tel: +81-29-850-1566, Fax: +81-29-856-6137,
E-mail: r-yuge@bk.jp.nec.com- 83 -

1P-44
Electrical conductivity of carbon nanomaterials under compression○K. Mizui1, T. Ohiro1, Y. Suda1, T. Harigai1, H. Takikawa1, H. Ue2
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon Co., Ltd., Oyama, Shizuoka 410-1431, Japan

㻌Electrical conductivity / Ω

-1

m

-1

1. Introduction
Carbon black, nanometer-size carbon particles, is commercially used as the catalyst support
in fuel cell owing to its high surface area, porosity, electric conductivity, low density, and low
cost. In the previous work, we have used various carbon nanomaterials as catalyst supports for
direct methanol fuel cell (DMFC) [1]. In this study, we measured the powder conductivity ofcarbon nanomaterials with different geometries and graphitic structures. Under compression it
is shown that the electrical conductivity of carbon black did not only depend on its intrinsic
morphological properties, which determine the degree of packing of the material and hence
the change in density, but also on such extrinsic factors as the applied pressure and theambient humidity.
2. Experimental
The carbon nanomaterials were characterized using scanning electron microscopy (SEM;
S-4500II and SU8000, Hitachi) and compressive conductivity measurements. We used four
samples of carbon nanoballoon (CNB), Vulcan XC-72R (Vulcan), vapor-grown carbon fiber(VGCF-H), ketjen black (KB). The powder conductivity of compressed carbon nanomaterials
is the result of a combination of the number of factors, including the resistivity of theindividual particles, the degree of contact between the particles, and their packing density.
3. Results㻌Fig. 1 shows the variation of the conductivity
1000
CNB
with applied pressure. The effect of the increase
Vulcan800
VGCF
in pressure on conductivity was very strong for all
KB
the samples. Because the contact area between the600
carbon particles increase for the denser carbons.
CNB which was prepared by heat treatment of400
Arc black (AcB) showed comparable powder
200
conductivity to commercial Vulcan and KB.
Moreover, VGCF-H showed the highest
0
0.0
0.2
0.4
0.6
0.8
1.0
conductivity.
Pressure / MPa

Fig. 1. Electrical conductivity versus pressureThis work has been partly supported by the EIRIS Project from Toyohashi University ofTechnology (TUT); JSPS KAKENHI Grant Number 24360108 and 15K13946; and the
Toyota Physical and Chemical Research Institute, “Scholar Project”.
[1] Yoshiyuki Suda, Yoshiaki Shimizu, Masahiro Ozaki, et al. Materials Today Communications, 3 (2015)
96-103
Corresponding Author: Y. Suda
Tel: +81-532-44-6726, Fax: +81-532-44-6757
E-mail: suda@ee.tut.ac.jp- 84 -

1P-45Laser Power Dependence in LDI MS of Detonation Nanodiamonds○Masayoshi Fukaya1, Yoshiki Otsubo1, Toshihiko Tanaka1, Ryoko Yamanoi 2, Eiji Osawa 2
1

Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, 30 Aza-nagao, Tairakamiarakawa, Iwaki, Fukushima, 970-8034, Japan
2
Nano Carbon Research Institute Ltd., Asama Research Extension Centre,
Faculty of Textile Science and Technology, Shinshu University
3-15-1 Tokita, Ueda, Nagano, 386-8567 Japan

Primary particles of detonation nanodiamonds (PPDND) should have strong electric
polarization and it possibly accounts for their enigmatic properties including a successful drugdelivery for cancer therapy.1 The structure of PPDND is therefore essential there and wassimulated by a density functional method.2 Moreover it has been investigated by someexperiments such as TEM, Raman, NMR, and dynamic light scattering (DLS).3-5 Furthrtmore,mass analysis would reveal their sizes as well as their charges with respect to ionization.
We report herein the laser power dependence in laser desorption ionization mass spectra(LDI MS) of the nanodiamonds (NDs) deposited on a stainless plate from the aqueous
solution of highly dispersible PPDND. We reported previously that a positive 12k Da peak(Fig.1) is attributable to the diamond core of PPDND.6 However, abundant oligomeric peaks
under 5k Da suggested that appreciable decomposition takes place through the ionization of
PPDND. Hence, we should take into consideration whether the core becomes thin or fat there
during LDI.
Figure 2 demonstrates that the ion from diamond core became thin through decompositionin the LDI process: peak m/z decreases with the laser power. The other 2 sorts of ion (~39k,~120k) also became thin. Through the ionization, the core therefore should decompose by thelaser exposure and the original size of the core should be larger than 12k Da. Plausible
decomposition reactions as well as possible methods for measuring original core sizes will be
discussed here.
~120k

12

m/z (kDa)

Intensity (a.u)~3k ~12k

~39k

(a)

11
10
9
8

0

20

40

60

Fig.1. LDI MS of NDs.

80

100

120

140

160

180!

m/z !
(kDa)
2

70

80

90

100

110

Laser Power (a.u.)
Fig.2.
Laser power dependence in peak m/z near 12k.
2[1] E. Osawa, D. Ho, H. Huang, M. V. Korobov, N. N. Rozhkova; Dia. Rel. Mat. 18, 904(2009).
[2] A.S.Barnard, E.Osawa; Nanoscale 6, 1188 (2014).
[3] E. Osawa; Dia. Rel. Mat. 16, 2018 (2007).
[4] V. I. Korepanov, H. Witek,H. Okajima, E. Osawa, and H. Hamaguchi; J. Chem. Phys. 140, 41107 (2014).
[5] A. M. Panich, H-M. Vieth, A. I. Shames, N. Froumin, E. Osawa,|A. Yao; J. Phys. Chem. C 114, 774 (2010).
[6] T. Tanaka, R.Yamanoi, E.Osawa; FNTG 48, Proceedings 19(2015).
Corresponding Author:Toshihiko Tanaka / Tel: +81-246-46-0810 / E-mail: ttanaka@fukushima-nct.ac.jp- 85 -

1P-46
Polymer-derived Nanoporous Carbon Monolith: High Electrochemical
Capacitive Behaviors○Yanqing Wang1, Bunshi Fugetsu2, Ichiro Sakata1, 2, Zhipeng Wang3, Wei Gong1, Mauricio
Terrones4, Morinobu Endo3, Mildred Dresselhaus5
1Nano-Agri Laboratory, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-0032, Japan.
2Nano-Agri Laboratory, Policy Alternative Research Institute, The University of Tokyo, Bunkyo-ku, Tokyo 113-0032, Japan.
3Institute of Carbon Science and Technology, Shinshu University; 4-17-1 Wakasato, Nagano 380-8553, Japan.
4Departmentof Physics, Department of Chemistry, Department of Materials Science and Engineering and Center for

2-Dimensional and Layered Materials, The Pennsylvania State University, University Park, PA 16802, USA.
5Research Laboratory of Electronics, Department of Electrical Engineering and Computer Science, Department of Physics,

Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307, USA.

The development of mesoporous carbon materials with well-defined continuous interconnected pore structure
has been growing remarkably in recent years. A monolith, or a single piece of three-dimensional (3D) porous
material was first reported in 1990s and has now become an essential part of polymer chemistry and materials
chemistry. Polyacrylonitrile (PAN) is widely used as fibers in various industries. PAN fibers are also used as
good precursors for carbon fibers. PAN monolith with controlled shape/morphology and pore sizes can be
fabricated through thermal induced phase separation technique and acts as the precursor for activated carbonmonolith (ACM), which has large potential in capacitors and batteries applications. As illustrated in Fig. 1,
mesoporous PAN monoliths with 3D continuous network structure were fabricated successfully. The shape ofmonoliths can be easily tailored in different ways according to the vessels they are used. The conditions such as
DMSO/H2O composition, temperature, holding time, etc. have an important effect on the PAN 3D networks,
including the skeleton structure and pore diameter. Leaf-, ribbon-, skeleton like monolith structures with surface
area ranging from 40 to 200 m2/g and the pore diameters from 8 to 22 nm were created by controlling theparameters. A monolith with an average skeleton size around 18 nm and the average mesopore diameter around11.2 nm was carbonized followed by two steps: pretreatment at 200℃ in air and 600～900℃ heat treatment in
mixture of Ar and CO2. The surface area of the monoliths increased by 2～5 times after carbonization process.
As shown in Fig. 1, PAN monolith with continuous interconnected network structure still keeps in the ACM (Fig.
2). All carbon monoliths showed good rectangular cyclic voltammetry (CV) curves at scan rates 10 mV/s,
indicating effective EDL capacitance as electrode. The capacitance of 26-2, 26-1 and 25-2 was ca. 135 F/g, 21
F/g, 93 F/g, respectively. The galvanostatic charge/discharge curves of carbon monoliths-based electrodes
exhibited symmetric triangular shape, revealing a typical characteristic of EDL capacitor.

Fig. 1. Fabrication process of PAN-based carbon monolith.
\Fig. 2. Electrochemical capacitive behaviors of PAN-based carbon monolith.
Corresponding Author: Y. Q. Wang
Tel: +81-3-5841-7461, E-mail: wang2011@ees.hokudai.ac.jp- 86 -

1P-47
Polyyne formation by laser-induced breakdown
in argon-diluted propane gas flow
○Yuki Taguchi1, Hitomi Endo1, Takeshi Kodama1, Tomonari Wakabayashi2,
Yohji Achiba1, Haruo Shiromaru1
1

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

Polyynes are linear carbon chains composed of alternating single and triple bonds, andare typically terminated by hydrogen atoms. The conventional method of generating polyynes
is laser ablation of graphite powder in organic solvent [1]. Recently, we reported thatpolyynes are produced by laser ablation of graphite in argon/propane mixed gases and theincrease of polyyne yield is observed for higher ratio of propane gas [2]. Both experiments
employ graphite powder as a source of the carbon chain. In the present study, we
gas inexamined polyyne formation without graphite,by laser-induced breakdown in argon/propane
laser
mixed gas flow. The experimental setup isAr
shown Figure 1. The mixed gases (propane gas
70 mm
lens
ratio is 0.1 %~100 %, 50 mL/min) wereintroduced to the glass cell, where the Nd; YAG
PG+
gas out
laser (30 Hz, 532 nm) with the power of 150
hexanemJ/pulse was irradiated for one minute. The-80 ℃ methanol
laser was tightly focused to the center of theglass cell by the lens of focal length 70 mm, to Figure 1 Schematic drawing of theinduce breakdown. The products were carried laser-induced breakdown setup.
by the gas flow, and captured in the hexane at-80 degrees. Liquid propane coexists with the
products at this temperature. After irradiation,liquid propane was evaporated at room
temperature. The soluble products wereanalyzed by UV absorption spectra.
A typical UV spectrum of the sample
solution is shown in Figure 2, where polyynes
C2nH2(n=3~7) and methyl polyyne CH3C16H are
clearly observed. The yields of polyynes show asaturation behavior with respect to the ratios of
the propane gas. The quantitative analysis of the
Figure 2 The UV spectrum of the sample
polyyne yield curves is now under way.

[1] M. Tsuji et al., Chem. Phys. Lett. 355 (2002) 101.
[2] Y. Taguchi et al., CARBON 94 (2015) 124.
Corresponding Author: Yuki Taguchi
Tel: +81-42-677-1111, Fax: +81-42-677-2525
E-mail: taguchi-yuuki@ed.tmu.ac.jp- 87 -

solution obtained from 100 % propane
breakdown. The peaks of polyynes
C2nH2(n=3~7) and methyl polyyne CH3C16H
are indicated by filled circles.

1P-48Polyyne formation by laser ablation of PAH/graphite composite disk in
vacuum○Ryouichi Moriguchi,1Yuki Taguchi,1Hitomi Endo,1Tomonari Wakabayashi,2 Takeshi Kodama,1Yohji Achiba,1and Haruo Shiromaru1
1

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

Polyynes and PAHs play an important role in evolution of interstellar molecules incarbon-rich environment, and long chains up to 8 carbonsterminated with H and those up to
10 carbons terminated with H and CN have been identified in space [1,2]. In contrast to thereactions in space, experimental studies on polyyne formation have been conducted in organic
solvent [3] or in hydrocarbon gas flow of atmospheric pressure [4], initiated by laser ablationof graphite. The laboratory studies indicate that a choice of proper surroundings is importantfor efficient production of polyynes. In the present study, we conducted laser ablation ofmodel compounds of PAHs in vacuum and confirmed that polyynes were efficiently formed
without the aid of surrounding gases/solvents.
The experimental setup is shown in Fig.1. A mixed powder of anthracene and graphite with
wt.-ratios of 1:1 or 1:3 was compressed to prepare a composite disk, which was amodelcompound of PAHs with different degrees of
unsaturation. The disk was set to face its surface to theexit of the ablation cell.The ablation products directedto the exit were captured by hexane solvent in a glass
bottle, which was cooled down to near the freezing
temperature. The ablation cell and solvent bottle were
evacuated by a rotary pump. Loosely focused 2nd
harmonic of pulsed Nd:YAG laser (10 Hz, 0.8 J/cm2)
was irradiated to the disk for three minutes. The soluble
ablation products were analyzed by HPLC and UV
absorption.
Fig. 1 Experimental setup
The absorption spectra of the solutions measured at
known retention times of various lengths of polyynes
are shown in Fig. 2, where characteristic peaks ofpolyynes are clearly seen up to C14H2. The polyynes are
identified both for 1:1 and 1:3 disks, while the yield is
lower for the 1:3 disk. Considering that the ablation
products are rapidly diffused in vacuum, the result
suggests that chain-form carbon clusters are efficiently
terminated by hydrogen formed in a same ablation
event.
[1] M. Guelinet al., A&A309 L27 (1996).[2] M. B. Bellet
al.,ApJ483, L61 (1997). [3] M. Tsujiet al., Chem. Phys.
Lett.355,101 (2002). [4] Taguchi et al., Carbon94, 124(2015).Corresponding Author:H. Shiromaru, Tel:
+81-42-677-1111, Fax: +81-42-677-2525,
E-mail:shiromaru-haruo@tmu.ac.jp- 88 -

Fig. 2UV absorption spectra of the ablation
products from anthracene/graphite 1:1
disk, measured after HPLC analysis.

1P-49Observation of Size Dependence of Charge State ofNano-level Particles by Ion Trap Ion Mobility Measurement○Yasuhiro Hiroshiba, Hironobu Matsubayashi, Takuma Ito,
Ryota Jinnouchi, Toshiki Sugai
Department of Chemistry, Toho University, Chiba 274-8510, Japan
Structural observation techniques have been a key to investigate nano materials. Various
methods, such as TEM and STM, have been developed so far. Those traditional methods are
powerful enough for most of stable nano materials such as carbon nanotubes and metal
particles. To track structural changes of floppy or unstable materials, however, thosetraditional methods may not be mighty. We have been working on the development of ion
mobility spectrometry (IMS) system for the structural observation of nano materials and havefound novel metallofullerene structures by IMS[1]. Furthermore we have succeeded todevelop ion trap ion mobility to trap and observe long-term structural change of m size
particles up to 2 hours[2]. IMS can cover materials with wide-range size but the results
depend not only on their structures but also on their charges[3]. To cover materials withwide-range sizes, here we present the observation of size dependence of charge state ofCharge number

Charge / C

particles with radii from 250 nm to 10 m.
Fluorescent polystyrene particles with precisely
5
10-14
size control (Bay bioscience and Estapor) were10
4
ionized by a Nd:YAG laser (266 nm) ablation. They
10
-15
10
were introduced and trapped in the IMS system. The
3
10trapped particles were repeatedly drove to have
2
4 6 8
2
4 6 8
-6
-5
10
10
Radius of particle
up-down motion in air and their motion were
Fig. 1 Size dependence of charge ofmonitored with an eradiation semiconductor laser
polystyrene particles.
(532 nm) and digital camera. Their mobility andcharge states were calculated with the motion and Stokes’ law[2,3].

Figure 1 shows log-log plot of the size and the amount of charge. We have succeeded toobserve down to nano-level particles with the radius of 250 nm. The charge increases as theparticle size increases. The amount of charge distributes even if the particle size is unchanged.
However, the slope of figure 1 shows that the maximum amount of charge is proportional to
the radius. Those results suggest that the system can be utilized to nano materials and may
reveal their size only by mobility measurement without checking their charge states.
[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
[2] T. Sugai et al., 42nd Fulluerene-nanotue-graphene conference. 3-13
[3] T. Sugai, J. Mass Spectrom. Soc. Jpn. 58, 47, (2010).
Corresponding Author: T. Sugai, Tel: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 89 -

2P-1
Regioselective Addition of Grignard Reagents to Azafulleroids○Naohiko Ikuma, Koji Nakagawa, Ken Kokubo, Takumi Oshima
Division of Applied Chemistry, Graduate School of Engineering,Osaka University, Suita 565-0871, Japan
Multiple functionalization of fullerene C60 is an important technique in the application forthe material chemistry because the introduced groups are able to control their electronic
properties and enhance the solubility for wet-processing. However, C60 has many reaction
sites and would often give a mixture of multiadducts with low selectivity. In order to prepare
the regioselective multifunctionalized fullerenes, we have interested in the intrinsic reactivityof azafulleroids which have one bridged nitrogen atom and two highly twisted bridgehead
double bonds. Previously, we have reported the high regioselectivity of azafulleroids on theacidic arylation [1] and the oxidative deamination with peracids [2]. Here we report theregioselective nucleophilic addition of Grignard reagents to azafulleroids due to thecoordination between bridged nitrogen and magnesium.
For alkyl azafulleroids, Grignard reagents preferably attacked the Cα−carbon following byacidic quench leading to Cβ-hydrogen adduct. This Cβ-hydrogen adduct was furthertransformed to alkyl adduct by alkyliodide under basic condition (KOtBu). On the other hand,for tosyl azafulleroid, Grignard reagents seem to attack the Cβ-carbon to give
1-amino-2-arylfullerenes via the cleavage of C-N bond. The change of reaction site inalkyl/tosyl azafulleroids is well consistent with the transition state calculations.
R1N

R1 = Alkyl

R1

CαadditionN
αβAzafulleroids

R2
H++ R 2 –MgBr
Mg +Br

N

KOtBu
R 3–I

H

R2
R3

R1
N

R1 = Tosyl
Cβaddition

R1

R1

H+

R2

[1] N. Ikuma, Y. Doi, K. Fujioka, T. Mikie, K. Kokubo, T. Oshima, Chem. Asian J. 2014, 9, 3084–3088.
[2] N. Ikuma, K. Fujioka, Y. Misawa, K. Kokubo, T. Oshima, Org. Biomol. Chem. 2015, 13, 5038–5043.
Corresponding Author: N. Ikuma
Tel: +81-6-6879-4592, Fax: +81-6-6879-4593,
E-mail: ikuma@chem.eng.osaka-u.ac.jp- 90 -

NH

R2

2P-2
Solid properties in hydroxylated carbon materials studied by 1H NMR○Yoshiaki Sano1 and Hironori Ogata 1, 2
1Graduate School of Engineering, Hosei University, Koganei, Tokyo 184-8584, Japan
2
Research Center for Micro-Nano Technology, Hosei University, Koganei, Tokyo,
184-0003, Japan

Polyhydroxylated Fullerenes (fullerenol: C60(OH)x) have been thought to havepotential applications in proton conductive materials. It has been reported that
C60(OH)12 solids by Oleum method[1] have proton conductivity in a dry atmosphere.
On the other hands, C60(OH)24 solids by NaOH/TBAH method[2] did not show ionic
conductivity at all [3]. On the other hands, it has not reported on the proton conductivity
in hydroxylated carbon nanotubes(CNT-OH). Detailed proton conduction mechanism ofhydroxylated carbon solids has not been fully elucidated.
We previously reported the synthesis and characterization of hydroxylated
single-walled carbon nanotubes (SWNT-OH)[4]. In this study, we systematicallyinvestigated the proton dynamics in fullerenol (C60(OH)12 and C60(OH)44) and
SWNT-OH by using wide-line 1H-NMR
spectroscopy.
Figure 1 shows the temperaturedependence of the spin-lattice relaxation
time (T1) of 1H-NMR at 400 MHz for
C60(OH)12, C60(OH)44 and SWNT-OH. Solidlines are fitting from high temperature
regions. Detailed results on the properties ofproton motions in these materials will bepresented.

References:

Figure 1 Temperature dependence of thespin-lattice relaxation time (T1) of 1H-NMR at
400 MHz for C60(OH)12, C60(OH)44 and
SWNT-OH[1] L. Y. Chiang et al., Org. Chem. 59, (1994) 3960
[2] J. Li et al., J. Chem. Soc. Chem. Commun. (1993)1784[3] K. Hinokuma et al., Chem. Phys. Lett., 341, (2001) 442.
[4] Y. Sano et al., Proc.of the 49th Fullerene-Nanotubes-Graphene General Symposium (3P-6)
Corresponding Author: H. Ogata
Tel: +81-42-387-6229, Fax: +81-42-387-6229 E-mail: hogata@hosei.ac.jp- 91 -

2P-3
Synthesis of Fullerene Derivatives Having Cyclic Structure
through Cationic Intermediate for Organic Solar Cells Application○Keisuke Ogumi 1, Hiroshi Okada 2, Takafumi Nakagawa 2, Yutaka Matsuo 2
1

Tokyo Metropolitan Industrial Technology Research Institute, 2-4-10, Aomi, Koto-ku, Tokyo
135-0064, Japan2
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan

Introduction
Fullerene cation serves as a versatile platform for functionalization of fullerene [1]. Itsutility attracts attention, however, fullerene cation is difficult to be generated because of theelectronegative nature of fullerene moiety. Previous works indicated utility of fullerene cation
by efficient method of dihydromethanofullerene [2] and regioselective synthesis of
1,2-di(organo)fullerene derivatives [3]. These reactions involve regioselective generation offullerene cation followed by intramolecular annulation. This method established new
synthesis method of fullerene derivatives having cyclic structure adjoins fullerene moiety.
This work
In this work, fullerene derivatives bearing cyclic structure containing oxygen wereobtained from corresponding fullerene dimer precursors. Scheme 1 shows mechanism for
7-membered ring fullerene derivative 1. First fullerene radical was generated from cleavage offullerene dimer by heating. Then I2 oxidized fullerene radical to give fullerene cation. The
annulation reaction was completed by C–O bond cleavage and another C–O bond formation
with demethylation.
Scheme 1. Proposed mechanism for fullerene-cation-mediated cyclization.

This method reaches a 7-membered ring fullerene derivative 1 which is expected as aninteresting organic semiconductor material for its electrochemical property and flexibility due
to conformation of the 7-membered ring. Photovoltaic devices using 1 were fabricated. The
device showed higher VOC value than that of a device using PCBM because of shallow LUMO
level. Device performance depended on annealing temperature. In the case of 80 ºC, PCE wasthe best, 1.74%. This work shows first time a behavior of 7-membered ring fullerene
derivatives as acceptors in organic solar cells and expands fullerene materials in organic
semiconductor field.
[1] (a) Kitagawa, T.; Sakamoto, H.; Takeuchi, K. J. Am. Chem. Soc. 1999, 121, 4298–4299.
(b) Murata, Y.; Cheng, F.; Kitagawa, T.; Komatsu, K. J. Am. Chem. Soc. 2004, 126, 8874–8875.
[2] Zhang, Y.; Matsuo, Y.; Li, C.-Z.; Tanaka, H.; Nakamura, E. J. Am. Chem. Soc. 2011, 133, 8086–8089.
[3] Zhang, Y.; Matsuo, Y.; Nakamura, E. Org. Lett. 2011, 13, 6058–6061.
Corresponding Author: Y. Matsuo
Tel: 03-5841-1476, Fax: 03-5841-1476, E-mail: matsuo@chem.s.u-tokyo.ac.jp- 92 -

2P-4
Investigation of catalytic activity for reduction of 4-nitrophenol
with [C60]fullerene nanowhisker-silver nanoparticle composites○Jeong Won Ko1, Hwa Jeong Chae1, Weon Bae Ko1,2
1

Department of Convergence Science, Graduate School, Sahmyook University, Seoul 139-742,
South Korea, 2 Department of Chemistry, Sahmyook University, Seoul 139-742, South Korea

Silver nanoparticles solution was prepared for adding silver nitrate (AgNO3), trisodium
citrate dihydrate (C6H5Na3O7ㆍ2H2O), sodium borohydride(NaBH4), cetyltrimethyl
ammonium bromide ((C16H33)N(CH3)3Br) and ascorbic acid(C6H8O6) into distilled water andthen, the resulting solution was irradiated for 3 h under ultrasonic irradiation. Silver
nanoparticle-[C60]fullerene nanowhisker composites were prepared using C60-saturated
toluene, silver nanoparticles solution and isopropyl alcohol by liquid-liquid interfacial
precipitation(LLIP) method. The product of silver nanoparticle-[C60]fullerene nanowhisker
composites was confirmed by X-ray diffraction, Raman spectroscopy, scanning electron
microscopy and transmission electron microscopy. Catalytic activity of silver
nanoparticle-[C60]fullerene nanowhisker composites as a catalyst was characterized by the
reduction of 4-nitrophenol by UV-vis spectroscopy.
0ln(C/C0)

-1
-2
-3
-4
-5
0

5

10

15

20

Time (min)Fig.1 Kinetics study for reduction of 4-nitrophenol with the silver nanoparticle-[C60]fullerene nanowhisker
composites[1] S. K. Hong, J. H. Lee, J. M. Kim and W. B. Ko, J. Nanosci. Nanotechnol., 11, 734 (2011).
[2] K. Miyazawa, J. Nanosci. Nanotechnol., 9, 41(2009).
Corresponding Author: W. B. Ko
Tel: +82-2-3399-1700, Fax:, +82-2-979-5318,
E-mail: kowb@syu.ac.kr- 93 -

2P-5
Chemical reduction of Metallofullerene using Various Amine○Yuta Sato, Kosuke Tanaka, Kazuhiko Akiyama, Shiro Kubuki
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
Endohedral metallofullerene(EMF) is well known to have many characteristic properties,
such as encapsulation structure, charge transfer from inside metal atom to cage, and small band
gap energy. These unique characters are expected to apply metallofullerenes to a medicine,an electronic device, and so on. However, in practice, there are very much difficulties for theapplication of metallofullerenes such as small amount of production yield and difficulties in a
separation/purification. Recently, efficient separation methods using smaller electrochemicalband gap character of metallofullerenes than those of empty species were reported. Amongthese separation methods, the separation methods using chemical oxidation and reduction of
metallofullerenes are promising from the view point of total cost
[1,2]. However, the separation mechanisms of these methods,(a)especially for the chemical reduction, have not been made clear
yet. To obtain the knowledge about the chemical reduction of
metallofullerenes by some electron donors, we investigated the
reduction tendency of alkylamine. In this study, we report thechemical reduction of La@C82 in chlorobenzene (CB) byalkylamine measured by UV/vis/NIR absorption spectroscopy.
La@C82 was produced by general arc discharge method.
Purified La@C82 was dissolved into CB solution with theconcentration of 10-5 M. An alkylamine was added to thissolution as the increase of volume falling within a few percent.
(b)
Figure 1 shows vis-NIR spectra of La@C82 in CB with (a)propylamine (PA) and (b) triethylamine (TEA). In both case, it
was found that the absorption peak of La@C82 at 1000nm wasdecreased with increase of alkylamine concentration and also
the absorption peak of [La@C82]- at 932 nm was increased. On
the other hands, the time dependent spectral change was smaller
than those observed in the alkylamine concentration
dependence. These results suggested that the chemical reduction
by alkylamine was a kind of equilibrium reaction such as contact
Fig 1, vis-NIR absorption of
charge transfer.
[1] K. Akiyama, et al., J. Am. Chem. Soc., 2012, 134, 9762
[2] T. Kodama, et al., Chem. Lett. 2005, 34, 464
Corresponding Author: Y. Sato
Tel: +81-42-677-1111, EX, 3587,
E-mail:kakiyama@tmu.ac.jp- 94 -

La@C82 (1000 nm) and[La@C82]- (932 nm) in CB
with (a)Propylamine,
and(b)Ttietylamine/La@C82.

2P-6
Isolation and characterization of Gd2@C80 anion whose spin state is S=15/2○Takuji Mitani1, Natsumi Nakatori1, Takahisa Yamaguchi2, Tatsuki Kobayashi3,
Ko Furukawa4, Tatsuhisa Kato2, 5, Koichi Kikuchi1, Yohji Achiba1, Takeshi Kodama1
12

Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501,
Japan
3
School of Science, Kitasato University, Sagamihara 252-0373, Japan
4
Department of Chemistry, Niigata University, Niigata 950-2181, Japan
5
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

Recently, Nakatori et al. have succeeded in the isolation of Y2@C80[1] which has long
been considered to be one of the hidden metallofullerenes notified by their characteristic
properties such as “those expected to be formed but never isolated”. The key points of thesuccess were due to 1) the extraction of Y2@C80 as an anion form directly from the raw sootwith a mixed solvent of triethylamine (TEA) and acetone, 2) the isolation of Y2@C80 by an
ion-pair chromatography by which Y2@C80 is safely kept as an anion form throughout theprocedures.
In order to confirm such a hidden property of M2@C80 more generally, we chose Gd2@C80
as the next target in the present work. In the anion state of Gd2@C80 if it exists, an excess
electron (S=1/2) is expected to be located on Gd2 dimer and thus, the clarification of theactual spin state of (Gd2@C80)- is definitely of quite interesting. In 2011, Fu et al. isolated
Gd2@C79N, which seems to have similar electronic configuration to that of (Gd2@C80)-, andconcluded that the spin state is S=15/2 by ESR spectroscopy[2]. Here, we report for the firsttime the isolation and characterization of (Gd2@C80)-.
The isolation of Gd2@C80 was accomplished by almost the same method as Y2@C80. Soot
containing Gd-metallofullerenes was produced by adirect-current arc discharge, and the raw soot was
extracted with a mixed solvent of TEA and acetone.
Gd2@C80 was isolated by two-stage HPLC using
acetone with an ion-pair reagent, tetrabutylammonium bromide, as an eluent.
As shown in Fig.1, the UV-vis-NIR absorption
spectrum of the isolated (Gd2@C80)- is very similar to
those of (Y2@C80)- and (Ce2@C80(Ih))-, where thelatter is generated electrochemically. Therefore, it issuggested that the Gd2@C80 also has C80(Ih) cage.
ESR studies revealed that the spin state of(Gd2@C80)- is S=15/2 as expected by Gd2@C79N.
[1] N. Nakatori, et al. The 49th Fullerenes-Nanotubes-Graphene
General Symposium 46 (2015).
[2] W. Fu, et al. J. Am. Chem. Soc. 133, 9741-9750 (2011).
Corresponding Author: Takeshi Kodama
E-mail: kodama-takeshi@tmu.ac.jp
Tel:+81-42-677-2530, Fax:+81-42-677-2525- 95 -

Fig.1 UV-vis-NIR absorption spectraof (Gd2@C80)-, (Y2@C80)- and(Ce2@C80(Ih))-. The inset shows thenegative LD-TOF-MS spectrum for(Gd2@C80)-.

2P-7
Reactions of Endohedral Metallofullerenes with Silacyclopropanes:
Mono-silylation and Carbosilylation of Lu3N@Ih-C80○Kazuya Minami1, Masahiro Kako*,1, Kumiko Sato2, Naomi Mizorogi2,
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
Much attention has been devoted to endohedral metallofullerenes (EMFs) owing totheir unique structures and properties. The exohedral derivatization of EMFs has beendeveloped as an effective method to functionalize EMFs for use in applications such as
molecular electronics, nanomaterials sciences, and biochemistry [1]. Recent studies
have indicated the high efficiency of organic photovoltaic devices based on
Lu3N@Ih-C80, which is a result of the relatively higher lowest unoccupied molecularorbital energy of Lu3N@Ih-C80 compared with that of C60 [2]. Moreover, we reported
that the addition of silylene to Lu3N@Ih-C80 afforded monosilylated adducts thatexhibited remarkable redox properties as potential acceptor materials for organic
photovoltaic devices [3]. This result prompted us to gain more insight into the effects ofmonosilylation and carbosilylation on the properties of Lu3N@Ih-C80.
In this study, we report the reactions of Lu3N@Ih-C80 with silacyclopropanes 1a, 1b,
and 2 as silylating reagents. Upon the heating of Lu3N@Ih-C80 with 1a (or 1b) ino-dichlorobenzene at 150°C in a sealed Pyrex tube, adducts 3a and 3b were obtained by
the addition of silylenes Dmt2Si and Mes2Si, respectively. The structures of 3a and 3b
were determined to be silylene adducts at the [6,6] ring junction of Lu3N@Ih-C80 basedon the nuclear magnetic resonance (NMR) and visible–near-infrared (vis–NIR) spectra.
In contrast, photoirradiation of Lu3N@Ih-C80 with 2 in toluene afforded three adducts
4a–4c as carbosilylated Lu3N@Ih-C80. Both 4a and 4b are structurally assigned to[5,6]-adducts of Lu3N@Ih-C80, while 4c is considered to be the corresponding[6,6]-isomer from spectral data.
Scheme 1.
h"

!

R2Si
3a : R = Dmt
3b : R = Mes

R2Si

Lu3N@Ih-C80

Dmt2SitBp
2

1a : R = Dmt
1b : R = Mes

4a-c

Dmt2
Si

Dmt =

tBp

Mes =
tBp =

[1] M. Yamada, T. Akasaka Bull. Chem. Soc. Jpn. 87, 1289–1314 (2014). [2] (a) R. B. Ross et al. Nat.
Mater. 8, 208–212 (2009). (b) R. B. Ross, et al. Adv. Funct. Mater. 19, 2332–2337 (2009). [3] K. Sato etal. 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- 96 -

2P-8
Electrostatic interaction of fullerenes under an external electric field○Jun-ya Sorimachi, Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
It is known that fullerenes and their derivatives are the constituent materials forphotovoltaic devices and electronic devices. For such applications, the external electric fieldis essential to inject carrier and control the functions of the devices. For the fundamental
aspect, in addition, it is known that electric structures of fullerenes and their derivatives
depend on an external electric field. Therefore, it is important to clarify the physicalproperties of fullerenes under an external electric field. In this work, we investigate theenergetics of fullerenes up to C78, all of which satisfy the isolated pentagon rule (IPR), under
the constant electric field between two parallel planar electrodes using density functional
theory (DFT) with the effective screening medium (ESM) method (Fig. 1).
Figure 2 shows the total energy of C60 and C74 as a function of the electric field. In the caseof C60, the energy is proportional to the square of the electric field, and do not depend on
molecular direction with respect to the field. Thus, the electron system of C60 fullerene can be
regarded as the spherical electron system, since the total energy of dielectric spherical shell is
proportional to the square of the parallel external electric field. In contrast, the total energy of
C74 is substantially stabilized under the non-zero electric field. By further investigation, we
find that C74 cage has polarization with respect to the molecular direction. We further
investigate the total energy of fullerenes up to C78 with various molecular orientations underthe electric field.
C60

Fig. 1; A structural model of fullerenes underthe electric field. Gray slabs represent theparallel electrodes simulated by ESM.

C74Fig. 2; Total energy of C60 and C74 as a function of the electric field.

Corresponding Author: J. Sorimachi
Tel: +81-29-853-5600(ext.; 8233)
E-mail: jsorimachi@comas.frsc.tsukuba.ac.jp- 97 -

2P-9
Solid-State NMR Studies on the Aggregated Structures of Organic Bulk
Heterojunction Solar Cells with Solvent Additives (III)○Saki Kawano1 and Hironori ogata1,2
1Grad. School of Sci. and Engin. , Hosei Univ. , 2Res.Center for Micro-Nano Technol., Hosei Univ.
E-mail: hogata@hosei.ac.jp

Bulk heterojunction (BHJ) organic solar cells are an emerging technology that has the potential toprovide a low cost photovoltaic devices. It is well known that the nanomorphology 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 widely used approach to increase power conversion efficiencies for manyorganic solar cells[1-2]. Solid-state solar NMR spectroscopy offers several techniques for the investigationof the morphological, 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 andmorphology by using solid-state NMR spectroscopy. In this study, we investigated the change in the
crystallinity, morphology, and the properties of molecular motions of P3HT/PCBM BHJ film by adding
another solvent additives(1,8-Octanedithiol(ODT) and 1-Chloronaphthalene(CN)) and also investigated themixing effect of two additives by using 13C and 1H solid-state NMR spectroscopy.
Mixed solution of P3HT/PCBM 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 ofadditive DIO, ODT or CN 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 glass plate and sealed into
4 mm zirconia NMR rotor. Solid-state NMR spectra werewith DIO+CN

collected on Bruker AVANCE300 spectrometer.
Figure 1 shows the

13C-CP/MAS

NMR spectra of(a)P3HT/PCBM BHJ film with DIO+CN additive, (b) with
CN additive and (c)P3HT/PCBM BHJ. The detailed resultsof the change of morphology and the properties of molecularconformations of P3HT/PCBM BHJ films by CN or ODTwith CNw/o additve
200 180 160 140 120 100 80

60

40

20

ppm

addition will be presented.

Fig.1 13C-CP/MAS NMR spectra ofReferences:(a)P3HT/PCBM BHJ film with DIO+CN

1) J. K. Lee et al., J.Am.Chem.Soc.,130(2008)3619.

additive, (b)with CN (c)w/o additive

2) B.R.Aïch et al, Organic Electronics,13 (2012)1736.

- 98 -

0

2P-10Concentration Dependence of Photoluminescence of(n,m) Single-Wall Carbon Nanotubes○Xiaojun Wei, Takuya Hirakawa, Yohei Yomogida, Atsushi Hirano, Shunjiro Fujii,
Takeshi Tanaka and Hiromichi Kataura
Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, Japan

Emission intensity[1] D. A. Tsyboulski et al., Nano Lett. 7, 3080–3085 (2007).
Corresponding Author: H. Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786, E-mail: h-kataura@aist.go.jp- 99 -

Emission wavelength shift (nm)Semiconducting single-wall carbon nanotubes (SWCNTs) show bright photoluminescence(PL) which can be used for estimation of a pair of optical transitions, E11 and E22. In PL
measurement, the emission intensity is also important to know the abundance of specificspecies in a mixture or chirality-sorted sample. For the reliable estimation, however, chirality
dependent quantum efficiency and self-absorption effect should be considered [1]. In order toreveal the PL characteristics of SWCNTs, we investigated the SWCNT concentration
dependence of PL intensity in a fixed surfactant concentration.
In this study, roughly chirality selected semiconducting SWCNTs suspended in 1% sodium
cholate (SC) solution were prepared by gel chromatography. To change the SWCNT
concentration, the sample was diluted by adding 1% SC solution. We confirmed that theabsorbance increased linearly with increasing SWCNT concentration for all chiralities, while
the emission intensity exhibited a nonlinear change. Figure 1 shows the results of theemission intensity and emission wavelength shift for (6,5) and (7,5) as a function of eachabsorbance. In the low absorbance (SWCNT concentration) region, the emission intensity
increased with increasing the absorbance, and the emission wavelength did not change forboth chiralities. In the high absorbance region,
4
3 10
30
however, the emission intensity decreased after
showing a maximum and the E11 emission
20
2.5 104
wavelength red-shifted gradually. This intensity
10change can be explained by a self-absorption4
2 10
effect. The emission wavelength shift is(6,5) 04(7,5) -10
probably due to a change of local electric field.
1.5 10
Importantly, these concentration effects don’t-20
depend on the total SWCNT concentration but
1 104
-30
each chirality concentration. Since the5000
concentrations of (6,5) and (7,5) are different in-40
a solution, each experimental PL efficiency is0-50
different. As a result, PL intensity cannot be
0
0.5
1
1.5
2
2.5
3
Absorbanceused for purity estimation. We will show resultsof more species of SWCNTs to discuss chirality Figure 1. The plots of the emission intensity
dependence of the local environmental effects.
(solid line) and emission wavelength shift (dashedThis work was supported by KAKENHI No. line) as a function of each absorbance for (6,5) and(7,5) SWCNTs.
25220602.

2P-11Chirality-Selective Metal Enhanced Fluorescence of DNA-Dispersed
Single-Walled Carbon Nanotubes○Min Lyu, Qinghua Zhao, Juan Yang, Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
The near-infrared fluorescence of single-walled carbon nanotubes (SWNTs) possesses agreat prospect in biological imaging [1], but its low quantum yield hinders its further
applications. Single-strand DNA (ssDNA) was reported to be able to well disperse SWNTs inaqueous solution [2]. In addition, certain DNA sequence motifs can be used forstructure-specific recognition and seperation of carbon nanotubes [3]. We find that ssDNA
might serve as a superior molecular spacer between gold nanoparticles (AuNPs) and SWNTs
to achieve a good metal-enhanced fluorescence (MEF) effect of the SWNTs.
In this work, we prepare ssDNA-SWNTs-AuNPs hybrids to achieve the chirality-selective
metal-enhanced fluorescence of carbon nanotubes. In addition to the overal fluorescenceenhancement of about 10-fold, a higher enhancement for (7,5) than for other chiralities isobserved when we use the reported (7,5) recognition DNA (ATT)4AT. This method may leadto further in-situ study of metal enhanced fluorescence of SWNTs on substrate.

Figure 1. (a) TEM images of the AuNP-(ATT)4AT-SWNT nano hybrids. (b)PL emission spectra at
excitation of 650 nm of the hybrid with addition of AuNPs from 0 to 34 μL. (c) PL integral area ofall peaks (red dots) and the PL peak area percentage of (8,3), (6,5), (7,5), (10,2), and (7,6) in (a).
PLE maps of the original (ATT)4AT-SWNT solution (d) and with addition of 4 μL (e) and 29 μL
AuNPs (f). The PL intensities for (d)-(f) are in the same color scale.
[1] M. Zheng et al. Nat. Mater. 2, 338 (2003).
[2] Dai et al. Nat. Photon. 8, 723 (2014).
[3] M. Zheng et al. Nature, 460, 250 (2009)
Corresponding Author: Juan Yang
Tel:+86-10-62755357, Fax: +86-10-62755357,
E-mail: yang_juan@pku.edu.cn- 100 -

2P-12
Substituent effects on defunctionalization of alkylated single-walledcarbon nanotubes○Yuya Takehana, Mitsuaki Suzuki, Michio Yamada, Yutaka Maeda
Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
Much attention has been attracted to the introduction of functional groups onto thesingle-walled carbon nanotubes (SWNTs) because it affects not only their dispersibility
but also their optical and electronic properties. However, SWNTs lose their intrinsic
properties by excessive functionalization because of disconnection of the -conjugatedsystem. Thus, control of degree of functionalization of SWNTs is important. Recently,
we studied the substituent effects on two-step reductive alkylation of SWNTs andrevealed that the degree of functionalization can be well controlled by the bulkiness ofalkyl groups of RLi and RBr [1]. In addition, thermal treatment of alkylated SWNTs iseffective to remove the substituent partially [2]. Weisman et al reported the diameterselective thermal defunctionalization of hexylated SWNTs [3]. Herein, we report
substituent effects on thermal defunctionalization of alkylated SWNTs.
Dialkylated SWNTs (nBu-SWNTs-R) were prepared according to the previously
reported method using HiPco SWNT, nBuLi, and RBr (R = nBu, secBu, tBu). Order ofdegree of functionalization for nBu-SWNTs-Bu (nBu-SWNTs-tBu > nBu-SWNTs-nBu >nBu-SWNTs-secBu) was estimated by Raman
spectroscopy and thermogravimetric analysis. After
thermal treatment under a nitrogen flow,
characteristic absorption and Raman peaks assigned
to large diameter SWNTs were recovered
predominantly. Spectral changes of nBu-SWNTs-Bu
before and after the thermal treatment indicate thatdefunctionalization takes place following order:nnBu-SWNTs-tBu<
Bu-SWNTs-nBu<nsec
Bu-SWNTs- Bu.
[1] Y. Maeda et al. J. Am. Chem. Soc. 134, 18101 (2012).
[2] Y. Maeda et al. Chem. Commun. 51, 13462 (2015).
[3] S. Ghosh et al. ACS Nano 9, 6324 (2015).
Corresponding Author: Y. Maeda
Tel: +81-42-329-7512, Fax: +81-42-329-7512
E-mail: ymaeda@u-gakugei.ac.jp- 101 -

Figure . Raman peak changes of nBuSWNTs-Bu after the thermal treatment.

2P-13
Electronic structure of CNTs under an external 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 the FET devices, CNTs form
hybrid structures with foreign materials, other CNTs, and defects, which seriously affect thephysical properties of the FET device. However, it is still unclear whether the defects and
CNT intersections affect the fundamental properties of CNTs under an electric field. In thiswork, we aim to elucidate the electronic properties of various CNT hybrids under the external
electric field. To explore the electronic structures of CNT hybrids under the external electricfield, we used the density functional theory combined with the effective screening medium
method and the local density approximation. An ultrasoft pseudopotential is adopted todescribe the interaction between valence electrons and ions. Here, we consider (10,0), (11,0),and (12,0) CNTs with monovacancies, divacancies, C2 adatoms, and Stone-Wales defects as
for the individual CNT with defects. In addition to the single CNT, we also consider the thinfilms of CNTs consisting of (11,0), (13,0), and (14,0) CNTs forming CNT bilayer structurewith respect to the electrode.
Our calculations show that the local electrostatic potential of CNTs substantially affects thecarrier accumulations by the external electricfield. In the CNTs with defects, we find thatthe gate voltage for accumulating electronsDVand holes strongly depends on the defectspecies and their relative positions in the
CNTs with respect to the electrode (Fig.1).
The gate voltage variation is ascribed to theinternal electric field in the CNTs induced by
the inhomogeneous electron density aroundthe defects. In addition to the inhomogeneityof the charge density, the work function ofeach CNT forming thin films affects thecarrier accumulation in CNT thin films by theelectric field. Gate voltages to inject carriers
depend on CNT arrangement with respect tothe electrode. Further analysis unraveled that Fig. 1: Gate voltages that induce carrier
the unusual electric field is induced between accumulations of 0.1-0.5 electrons and hole in the(11,0) CNT with divacancy (DV). The circles,
CNTs under the low electron concentration
triangles, and squares denote defect arrangementsof θ = 0û, 90û, and 180û, respectively.

Corresponding Author: U Ishiyama
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: yishiyama@comas.frsc.tsukuba.ac.jp- 102 -

2P-14
Chemical Bond Formation between Multi-walled Carbon Nanotube andPolystyrene Side Chain through Photo-induced Radical Formation○Takuma Baba1, Tomoya Takada 2
1

Graduate School of Photonics Science, Chitose Institute of Science and Technology,
Chitose 066-8655, Japan2
Department of Applied Chemistry and Bioscience, Chitose Institute of Science andTechnology, Chitose 066-8655, Japan

Modification of polymers with carbon nanotubes (CNTs) is
important for fabrication of functional materials containing
CNTs. In this work, we prepared polystyrene having
chloromethyl groups on its side chains and attempted to achieve
chemical bond formation of the side chains with multi-walledcarbon nanotubes (MWCNTs) by UV light irradiation.
The polymer was synthesized by radical polymerization ofRaman spectra ofp-(chloromethyl)styrene (p-CMSt). The polymer and MWCNTs Fig.1
polymer-MWCNT
films.
were mixed in 1-methyl-2-pyrrolidone and irradiated with UVlight (250-385nm) from a xenon light source at room
temperature for 24 hours. Polymer films were made by solution
casting, and X-ray photoelectron spectra (XPS) and Raman
spectra of them were recorded. The XPS were recorded using
the equipment installed in the Laboratory of XPS analysis,
Hokkaido University. Similar UV irradiation andcharacterization
using
MWCNTstreatedwithhydroxylammonium chloride to enhance their dispersion insolvent were also carried out in the same manner. To observe Fig.2
Temperature
the temperature change of the samples induced with infrared change induced by IR
light (IR), the samples were irradiated with IR from a xenon irradiation.
light source for 5 min. Their temperature changes during andafter the irradiation were observed by using a thermal imaging camera.
	  From the result of elemental analysis based on XPS, it was found that the content of Cl in
the samples decreased after the UV irradiation. Also, on the basis of the Raman spectra (Fig.
1), surface deformation of MWCNTs was observed after the UV irradiation. The similar
spectral features were also observed also in the case of MWCNTs treated withhydroxylammonium chloride. These results support the radical formation from polymer side
chains and the chemical bond formation between the radicals and MWCNTs. While polymer
film fabricated without MWCNTs did not show obvious temperature change during IR
irradiation, temperature of the film containing MWCNTs rose with IR irradiation (Fig. 2).
This result indicates that the polymer-MWCNT films fabricated in the present way can beused as photothermal conversion materials.
This work was supported by Nanotechnology Platform Program of the MEXT, Japan, and
JSPS KAKENHI.
Corresponding Author: T. Takada
Tel: +81-123-27-6056, Fax: +81-123-27-6056, E-mail: t-takada@photon.chitose.ac.jp- 103 -

2P-15Highly Packed CNT-Cu composite by the Spark Plasma Sintering○Shinichiro Chiku, Masanobu Nomura, Hiroshi Nishikawa and Takashi Hasegawa
Murata Manufacturing Co., Ltd., Nagaokakyo 617-8555, Japan
Carbon nanotube (CNT)-copper composite is reported to exhibit notable properties such as
high current density and low temperature coefficient of the resistivity[1]. But, as they tried, it
is difficult to combine hydrophobic CNTs with metallic copper in liquid phase. We examined
the fabrication process through the synthesis of CNT-Cu powder in solvents and the sintering
the powder under the high temperature and the high pressure.
Multi-walled CNTs (MWCNTs) were dispersed without any dispersing agent in thesolution of copper (II) acetate in N-methyl-2-pyrrolidone (NMP) by the supersonic treatment.
Hydrazine hydrate was added to reduce Cu2+ ions for the growth of copper nanoparticles on
the MWCNTs’ surfaces. Figure 1 shows an FE-SEM micrograph of dried MWCNT-Cu
powder in which we can recognize some copper second particles penetrated by separated
MWCNTs.
MWCNT-Cu powder was sintered by the spark plasma sintering (SPS) method in vacuum
atmosphere. Figure 2 (low magnification) and Figure 3 (high magnification) show FE-SEM
micrographs of a dicer cut face of a sintered composite. In Figure 2, copper forms a
continuous sintered compact and there is no distinct pore nor MWCNT large cohesion. Dark
points are MWCNT small cohesions. In Figure 3, a few MWCNTs appear separately at thecross section generally homogeneous. The carbon content of the composite was analyzed to
be 4wt% (equivalent to 15vol% when CNT density is 2.1g/cm3). The packing fraction was
calculated to be 99%.

20μm

1μm

Fig.1 FE-SEM micrograph of
MWCNT-Cu powder

Fig.2 FE-SEM micrograph of a
MWCNT-Cu compound’s crosssection (low magnification)[1] C. Subramaniam et al. Nature Commu. 4, article number 2202 (2013).
Corresponding Author: S. CHIKU
Tel: +81-77-586-8712, Fax: +81-77-587-6782,
E-mail: tiku@murata.com- 104 -

500nm

Fig.3 FE-SEM micrograph of a
MWCNT-Cu compound’s crosssection (high magnification)

2P-16
Characterization of carbon nanotube interdigitated electrodefor electrochemical biosensors○Takuya Ushiyama1, Nguyen Xuan Viet1, Shigeru Kishimoto1, and Yutaka Ohno1,2
1

Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603, Japan

2

Carbon nanotube (CNT) is promising electrode material for electrochemical biosensors
because of its wide potential window, rapid electron transfer kinetics, [1] and excellent
anti-fouling properties. [2] Previously, we reported the amplified steady-state voltammetry,
utilizing redox cycling process in CNT interdigitated electrode (CNT-IDE). The highamplification factor of ~14 and the anti-fouling property better than gold IDE have beenshown. We also demonstrated the detection of dopamine at LOD of ~50 nM. [3] The
amplification factor of the redox cycling process is mainly determined by relation of thegeometry of IDE and diffusion length of analyte. In this work, we have investigated theeffects of width of a microband electrode and of gap width between the electrodes onelectrochemical characteristics of CNT-IDEs.
We fabricated CNT-IDEs with clean surface on a PEN substrate, using the dry transfer andmicro-fabrication process as our previous work. [3] The electrochemical property of the
CNT-IDEs was evaluated by measuring cyclic
voltammetry of K4[Fe(CN)6]. Figure 1 shows signal
current as functions of (a) gap width between
generator and collector electrodes (Wg) and (b) widthof a microband electrode (We). The signal current
increased with decreasing Wg. This behavior can be
explained by enhancements in concentration gradientof the analyte and collection efficiency of the redox
cycle with decreasing Wg, as reported previously forthe case of metal-based IDEs. [4,5] Although similar
behavior is expected for We dependence, the signal
current decreased in the present device withdecreasing We as shown in Fig. 1(b). This isprobably due to IR drop in CNT microband
electrodes, i.e., the resistance of each CNT
microband electrode increased with decreasing We.

[1] I. Dumitrescu et al., Chem. Commun., 45, 6886 (2009)[2] W. Harreither et al., Anal. Chem., 85, 7447 (2013)[3] T. Ushiyama et al., The 49th FNTG General Symp. 1P-13(2015)
Fig. 1 Signal current versus (a) gap width[4] K. Aoki et al., J. Electroanal. Chem., 256, 269 (1988)
and (b) electrode width.
[5] N. Osamu et al., Anal. Chem., 62, 447 (1990)
Corresponding Author: Y. Ohno, Phone & Fax: +81-52-789-5387, E-mail: yohno@nagoya-u.jp- 105 -

2P-17
Charging-discharging phenomenaof CNT electrical double layer capacitors○Karolina Laszczyk1, Atsuko Sekiguchi 2, Takeo Yamada 2, Kenji Hata2
1

Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba
305-8565, Japan
2
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba
305-8565, JapanThe growing demand for portable (small, light-weight) power sources enabling to achieve
high energy and power have caused the numerous of researchers around the world to work on
principles behind the electrochemical energy storage (EES) mechanism. Its understanding
would lead to low-cost and efficient EES electrodes design, e.g. for supercapacitors. However,since the discovery of the electrical double layer (EDL) mechanism, there are still a lot ofquestions to answer, especially as the model is suitable for anode-electrolyte-cathode systemomitting other phenomena taking place in porous EES electrodes. On the other hand still new
anomalous phenomena have been discovered which analytical solutions have not predicted
before [1,2].
Here, we would like to present the experimental data on dependence of the cell performanceupon various electrodes’ designs and configurations, i.e. the aspect ratio between length andwidth of the cells’ electrodes is changed. The cell were made of porous CNT mesh film usingdeveloped lithography-based process [3]. As result about 100 cells (ave. 25 cells per particular
design) were released, measured and compared about their performance.
The measurements were done using cyclic voltammetry and potentiostatic electrochemical
impedance spectroscopy (PEIS). We found the interesting trend in cells’ performance
expressed in capacitance retention and efficiency to discharge the energy (Fig. 1).
We believe the obtained results will contribute and support the development ofelectro-physical model of EDL systems,
that find use not only in EES domain but insensing, water desalination, power andenergy harvesting and storage, biomedicine,
fluidics, and many others.
This presentation is based on results obtained
from a project commissioned by the New
EnergyandIndustrial
Technology
Development Organization (NEDO).

[1] J. Chmiola et al. Science. 313, 5794 (2006).
[2] N. Miljkovic et al .Nat. Comm. 4, 2517 (2013).
[3] K. Laszczyk et al., Adv. En. Mat. 5, 18 (2015)
Corresponding Author: A. Sekiguchi ,Tel: +81-29-861-4611, Fax: +81-29-861-4851,
E-mail: atsuko-sekiguchi@aist.go.jp

Fig.1 Time relaxation dependence on cell designs
possessing the same volume of CNT electrodes,
where L and w are denoted to the length and widthof an electrode, respectively.

- 106 -

2P-18Fabrication of Pt nanocluters on polymer warpped multi-walled carbon
nanotubes and their use as fuel cell catalyst○Yuki Hamasaki1,2, Tsuyohiko Fujigaya1,2,3, Naotoshi Nakashima1,2
1

Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University, Fukuoka 819-0395, Japan
3
PRESTO, JST, Saitama, 332-0012, Japan

Platinum (Pt) shows excellent catalytic activity for both hydrogen oxidation and oxygen
reduction reaction (ORR) in proton-exchange polymer electrolyte fuel cells (PEFCs). For thewide spread of PEMFCs, reduction of Pt amount is a strong social demand due to its high cost.
One way to solve this issue is the reduction of particle size of Pt in the catalyst. [1-4].
In this study, we fabricate highly dispersed Pt nanoclusters on polybenzoimidazole (PBI)wrapped multi-walled carbon nanotubes (MWNTs) with low damage (Fig. 1). The PBI and
MWNTs work as an anchoring polymer for Pt-coordination and catalyst support, respectively[3,4].

Fig. 1 Schematic illustration of the preparation of the MWNT/PBI/Pt nanocluster

MWNT/PBI composites were prepared according to a previous paper, then dispersed themin water by sonication, to which a Pt precursor solution was added. After stirring, thecomposite solution was washed with water to remove any excess Pt precursor. Then, the solid
product was collected by filtration, which was dried under vacuum. The obtained material wascharacterized by transmission electron microscope (TEM), thermogravimetric analyses (TGA)and X-ray photoelectron spectroscopy (XPS). We examined the ORR activity of the catalyst
in oxygen saturated 0.1 M HClO4, and the result will be reported at the meeting.
[1] J. Chen et al. Energy Environ. Sci. 3, 1286 (2010).
[2] I. N. Leontyev et al. J. Phys. Chem. C 115, 5429 (2011).
[3] N. Nakashima et al. Small 5, 735 (2009).
[4] N. Nakashima et al. Sci. Rep. 4, 6295 (2014).
Corresponding Author: N. Nakashima
Tel & Fax: +81-92-802-2840
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 107 -

2P-19Film-making of single-wall carbon nanotubes by using limonene
in two immiscible aqueous solution phases○Ryo Ishida1, Marin Ohtsuka1, Naoki Kanazawa1, Hiroshi Nagasawa2,
Akira Ono3, Shinzo Suzuki1,
1

Department of Physics, Kyoto Sangyo University, Kyoto 603-8555, Japan
2
Kankyo Resilience Co. Ltd., Yokohama 240-8501, Japan3
Department of Engineering, Kanagawa University, Yokohama 221-8686, Japan
In the previous symposium, we reported about the application of Raman spectroscopy forevaluating the ratio of metal/semiconductive single-wall carbon nanotubes in two immiscible
solution phases by changing excitation photon energy (532 nm and 633 nm) [1, 2]. This
separation technique by using two immiscible solution phases (e.g., in polyethylene glycol(PEG) and dextran (DX) solution) has been first reported by C.Y. Khripin et al. in 2013 [3],where metal/semiconductive SWNTs of large diameter (> 1.2 nm) were shown to be
successfully separated. This technique has been extensively applied for those dispersed in
DNA solution as well, by using slightly modified combination of two immiscible aqueous
solution phases [4, 5].
In this symposium, we reported about the application of Raman spectroscopy in order toshow how metal/semiconductive single-wall carbon nanotubes are separated in these
immisible solution phases. Additionally, in certain experimental condition, where limonene isfurther added to two immiscible solution phases, film of carbon nanotubes could be clealy
seen in the solution. Further experimental findings are presented and discussed.
References:[1] N. Kanazawa et al., Proc. of the 46th Fullerene-Nanotube-Graphene General Symposium. 1P-27(2014).
[2] R. Ishida, et al., Proc. of the 49th Fullerene-Nanotube-Graphene General Symposium. 1P-16(2015).
[3] C.Y. Khripin et al., J. Am. Chem. Soc., 135, 6822-6825(2013).
[4] G. Ao et al., J. Am. Chem. Soc., 136, 10383-10392(2014).
[5] H. Gui et al., Nano Lett., 15, 1642-1645(2015).
Corresponding Author: Shinzo Suzuki
Tel: +81-75-705-1631, Fax: +81-75-705-1820,
E-mail: suzukish@cc.kyoto-su.ac.jp- 108 -

2P-20Creation of "floating supported catalyst" from metalorganic vapors
and gas-phase synthesis of carbon nanotubes○Yusuke Sugino1, Kei Hasegawa1, Toshio Osawa1, Takayuki Tsukada2, Suguru Noda1,*
1

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
2
Hodogaya Chemical, Tokyo 104-0028, Japan

Carbon nanotubes (CNTs) have attracted much interest but further progress is needed forlarge-scale, low-cost production of high quality CNTs to realize their applications. Chemical
vapor deposition (CVD) is most commonly used for their production because of its scalability
and high productivity. CNTs are grown from catalyst nanoparticles either floating in gas [1] or
supported on substrates/powders [2]. Floating catalyst CVD effectively use three-dimensional
reaction space and realized mass-production of carbon fibers and multi-wall CNTs with large
diameters (~100 nm) at ~100 ton/y. It also yields high-quality single-wall CNTs (<10 nm),however, at much smaller production scale due to the small mass of such CNT and the rapid
aggregation of small floating catalysts. Small catalyst particles can be supported densely onflat substrates, however, reaction space is limited to the two dimensional substrate surface.
In this work, we propose "floating supported catalyst" in which each
sub-micrometer-sized oxide particle supports hundreds of catalyst nanoparticles and grows
hundreds of CNTs (Fig. 1). Ferrocene and aluminum isopropoxide were used as precursors forcatalyst (Fe) and support (Al2O3), respectively, and fed as vapors with 4 vol% H2/Ar flow at
300 sccm into a reactor (40 mm in inner diameter and 600 mm in heating zone length) at 800
C. Floating supported catalyst (Fe/Al2O3) were successfully produced and many CNTs grewfrom each particle using carbon in metalorganics (Fig. 2).

Fig. 1 Schematic of the CVD reactor.

Fig. 2 Typical SEM image of the product.

[1] T. Saito, et al., J. Nanosci. Nanotechno. 8, 6153 (2008)[2] K. Hata, et al., Science 306, 1362 (2004).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 109 -

2P-21
Growth of Horizontally Aligned Chirality-Specific Single-Walled Carbon
Nanotubes○Feng Yang, Yan Li
Beijing National Laboratory for Molecular Science, College of Chemistry and MolecularEngineering, Peking University, Beijing 100871, China
High-performance and integrated circuits essentially require SWNT samples withwell-aligned arrays of pure chirality [1]. Recently, employing tungsten-based intermetallic
catalyst with high melting points and consequently are able to maintain their specific crystal
structure during the chemical vapor deposition (CVD) process, which regulates the chiralityof the grown SWNTs [2,3]. We have developed herein an approach for the growth ofhorizontally aligned chirality-specific SWNTs using uniform W6Co7 nanoparticles as catalysts
on the sapphire surface.
Using the uniform W6Co7 nanoparticles as structural templated catalysts, we are able togrow the high abundance of the (13,6) SWNT arrays on the sapphire surface at the optimized
growth condition. Our ﬁndings open up the possibility of the wafer-scale growth of aligned
chirality-specific SWNTs by using uniform intermetallic nanoparticles as catalysts forpractical nanoelectronics applications.
[1] A. D. Franklin. Nature 498, 443 (2013).
[2] F. Yang, Y. Li et al. Nature. 510, 522 (2014).
[3] F. Yang, Y. Li et al. J. Am. Chem. Soc. 137, 8688 (2015).
Corresponding Author: Yan Li
Tel: +86-10-6275-6773, Fax: +86-10-6275-6773,
E-mail: yanli@pku.edu.cn- 110 -

2P-22
Diameter-controlled ACCVD growth of SWNTs
using water vapor○Hiroki Takezaki 1, Shinnosuke Ohyama 1, Taiki Inoue 1, Rong Xiang 1,
Shohei Chiashi 1 and Shigeo Maruyama 2
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
Energy NanoEngineering Lab. National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki. 305-8564, JapanThe method of chirality-controlled synthesis of single-walled carbon nanotubes (SWNTs)
is required to realize the application of SWNTs. It is important to understand the influence ofwater in synthesis of SWNTs such as preferential etching of metallic SWNTs using water
vapor [1] and water-assisted CVD [2]. Here, we studied effects of water vapor both during thecatalyst reduction stage and the growth stage to obtain the knowledge for chirality-controlled
growth of SWNTs.
Co/Mo catalyst was reduced by Ar/H2 gas, and then ethanol vapor was introduced as acarbon source to grow SWNTs at 650  800 C, while water vapor (30  1500 Pa) was addedin the reduction stage and/or the growth stage. SWNTs were characterized by scanningelectron microscope (SEM) and Raman scattering spectroscopy with four different excitation
lasers. Figure 1 shows RBM peaks of SWNTs grown with or without water vapor before andduring growth. By introducing water vapor before CVD growth, smaller diameter SWNTs
were grown. The diameter of SWNTs was further reduced by reducing the temperature of
SWNTs growth. At the same time, we found that the ratio of near-zigzag SWNTs was
drastically decreased as indicated by arrows in Fig. 1.
[1] P. Li, et al., J. Mater. Chem., 21 (2011) 11815.
[2] K. Hata, et al., Science, 306 (2004) 1362.

S<E 44>

2.6

2.4<E 11>

100(9,0)(14,1)

S<E 22>(16,0)

150(8,1)
488 nm(20,0)(12,10)(7,7)(10,1)(b)(c)
S<E 44>(20,0)

2.4

200
250 −1 300
Raman Shift (cm )350(16,0)(7,7)

S<E 22>(10,1)(10,0)

2.3

100

M

<E 11>(21,1)

532 nm(19,0)

150(8,8)(12,0)

200
250
300
−1
Raman Shift (cm )350

λex = 785 nm
0.7

(b)
(c)

2.1 <ES44>

2

S<E 33>

M<E 22>(13,1)(11,1)(15,0)

(7,5)

(8,0)

(7,6)

100

(9,1)

(c)
M

1.6

200
250
300
−1
Raman Shift (cm )

350

100

S

<E 11><E 33>(8,6) <E 22>(18,0)(14,1) (8,7)(11,0)(19,1)(21,0)(9,7)(16,0)(9,8)

785 nm(12,1)(14,0)

1.4

150

150

200
250 −1 300
Raman Shift (cm )Fig. 1 RBM peaks of SWNTs (a) grown at 800 C without water vapor before and during growth,(b) grown at 800 C introducing water vapor before growth and (c) grown at 700 C introducing water
vapor before growth.

- 111 -

0.7

(b)

1.5

(13,0)(16,1)

0.8

(a)

S

1.7

633 nmDiameter (nm)
1 0.9

2

S

<E 11>(20,1)(22,0)

1.8

(6,5)

0.8

(a)

1.9

(17,1)

2.2

(6,5)

S
<E 33>

Diameter (nm)
1 0.9

Intensity (arb.units)

(a)

2.5

M

(18,1)(11,9)

2.5

(6,6)

S
<E 33>

λex = 633 nm
2

0.7

Intensity (arb.units)

(c)

0.8

Intensity (arb.units)(b)

Diameter (nm)
1 0.9

2

Laser Energy (eV)

0.7

(a)

Intensity (arb.units)
Laser Energy (eV)2.7

λex = 532 nm

0.8

Laser Energy (eV)Diameter (nm)
1 0.9

Laser Energy (eV)λex = 488 nm
2Corresponding Author:Shigeo Maruyama
E-mail: maruyama@photon.t.u-tokyo.ac.jp
TEL: +81-3-5841-6421

350

2P-23
Molecular structure of chalcogen encapsulated in single-walled carbon
nanotubes studied by molecular dynamics simulations and First-Principles
DFT calculations○1Yutaka Sato, 1Eita Yokokura, 1Yousuke Kataoka and 1,2,3Hironori Ogata
Graduate School of Science and Engineering, Hosei University, Koganei 184-8584, Japan2
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

1

Single-walled carbon nanotubes(SWNTs) have a hollow space in the nanometer size that canbe encapsulated various functional molecules. Recently, sulfur encapsulated SWNTs andselenium encapsulated DWNTs are synthesized and one-dimensional conductive sulfur chain
structure and double-helices selenium structure were reported[1,2]. However, the tube diameter
dependence of the local structure and properties of the encapsulated chalcogens have not yet
been investigated systematically. In this study, we report the effects of chirality and tube
diameter of CNTs on the local structures and molecular mobility of the chalcogen by using
molecular dynamics(MD) simulations and first-principles DFT calculations.
In our MD simulations using scigressVer2.6.1(Fujitsu). We applied the GEAR method of thefifth order in the numerical integration method and the speed scaling method in thetemperature control method. By placing the CNT and arbitrary number of slufur atoms or
selenium atoms in rectangular cell, and using NTV ensemble. First, we calculated therelaxation structure at 1K. Then, stable structure at 300 K was calculated with the NVT
ensemble after the relaxation calculation at 800 K. In the First-Principles DFT calculation, we
have calculated solid-state 33S NMR parameters(chemical sift and electric field gradient(EFG) tensor). All of the calculations were done using a code package PWscf and GIPAW in
Quantum ESPRESSO. We used the pseudo potential method.
Figure1 shows the structure of sulfur encapsulated in (a) (7,0) and (b) (6,6) carbon nanotubes
at 298K. Sulfur encapsulated in SWNT took one-dimensional linear or zig-zag chain structure.
Detailed results including DFT calculations will be presented.
(a)

(b)

Fig.1 Structure of (a)S@(7,0)SWNT , (b)S@(6,6)SWNT[1] Toshihiko Fujimori et al. Nature Communications4(2013)2162.
[2]Frank H.Stillinger et al. J.Phys.Chem85, 6460 (1986)[3]Frank H.Stillinger et al. J.Phys.Chem.1987, 91 (19), pp4899-4907- 112 -

2P-24
Length-Selective Loading of Gold into the Interior of Carbon Nanotubes○R.V. Bekarevich 1, M. Toyoda 1, S. Baba 2, T. Nakata 2, K. Hirahara 1
1

Department of Mechanical Engineering, Osaka University, Suita 565-0871, Japan
2
Research & Development Group, Hitachi, Ltd., Yokohama 244-0817, Japan

Creation of metal – carbon nanotube (CNT) hybrid structures opens new horizons for suchapplications as optical resonant antennas or pen-tip injectors for additive nanomanufacturing.
Such applications require controlled-loading of metals into the interiors of individual CNTs.
Recent results report the Joule-heat induced filling the inner channel of the CNT bridged
between two metal electrodes. [1-2] In this situation a strong temperature gradient directed
toward the electrode pushes metal melts in the same direction. This may prevent metalloading into the CNT and may lead to its destruction. To eliminate the negative effects, we
proposed to connect the CNT not to electrode directly but to the double-walled CNT(DWCNT) decorated with gold nanoparticles. Such configuration shifts the point of highest
temperature during Joule heating on the supportive DWCNT. This enables us to create atemperature gradient that is always directed toward the open end of the host CNT, ensuringthat thermophoresis promotes rather than hinders the metal loading process. This arrangement
also prevents the Joule heat-induced damage of the host CNT. After establishing a contact
between the host CNT and the supportive DWCNT, voltage was applied and increased until
the gold nanoparticles began to coalesce on the DWCNT and reach diameters roughlymatching the inner diameter of the host CNT. Then we slightly adjusted the positioning of theopen tip of the host CNT so that it was located in front of a gold nanoparticle. The voltage
was then increased until molten gold particles entered inside the host CNT driven by the
impact of thermal gradient. At this step, a gold nanowire with a length of 6–8 nm
encapsulated in CNT was formed. The length of the encapsulated
nanowire can be precisely controlled by the number of serial
contacts with other gold nanoparticles located on the supportive
DWCNT (Fig. 1). The accuracy of the loading strongly depends onthe diameter of loaded nanoparticles and can be vary within 0.5 – 5
nm, what allows the loading of selective portion of gold into theinterior of CNT.
The gold loading process could not be explained by only one
mechanism; instead, the gold loading was attributed to a
combination of multiple mass-transport effects, with the primarymechanisms being thermophoresis and the coalescence of gold
nanoparticles caused by grain boundary diffusion. The effect ofelectromigration was determined to be negligible compared to theabove mechanisms. The results of this study provide a reliable
method for length-selective filling the interiors of CNTs with metal,
which can be applied to the fabrication of novel structures.
[1] R. Zou, et al. Adv. Mater. 25, 2693 (2013).
[2] Z. Fan, et al. Carbon 86, 280 (2015)
Corresponding Author: R. Bekarevich
Tel/Fax: +81-6-6879-7815,
E-mail: bekarevich@ne.mech.eng.osaka-u.ac.jp

Fig.1
Length-selective
growth of the gold
nanowire.

- 113 -

2P-25
Local structure and properties of the cesium iodide crystals encapsulated insingle-walled carbon nanotubes studied by molecular dynamics andFirst-Principles DFT calculations○Eita Yokokura 1, Yutaka Sato1, Yosuke Kataoka 1 and Hironori Ogata1,2
23Graduate School of Engineering, Hosei University, Koganei, 184-8584, Japan
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 molecular assemblies may
exhibit unique low-dimensional structures and solid state properties that can not be realized in
the bulk. Synthesis and structure of several kinds of alkali halide encapsulated SWNTs havebeen reported [1-3]. However, the tube diameter dependence of the local structure of theencapsulated alkali halides have not yet been reported. In this study, we report the effects ofthe diameter and chirality of SWNTs on the local structures of the encapsulated alkali halides
including temperature dependence by using molecular dynamics (MD) and DFT simulations.
In the MD simulation, we used the Born-Mayer-Huggins-Tosi-Fumi intermolecularpotential between the alkali halide ions and the Dreiding potential between carbon atoms in
SWNT. We have investigated on the armchair and zigzag nanotubes with diameters ranging
from 1.1 to 1.6 nm systematically. One SWNT and alkali halide ion pairs (Cs-I) around
SWNT were set in a rectangular cell as initial configuration. Stable structure at 300 K was
calculated with the NVT ensemble after the relaxation calculation at 1000 K. We havedemonstrated that structural phase transition is observed at 410 K in CsI@(9,9)SWNT.
In the First-Principles DFT calculation, we have calculated solid-state 133Cs and 127I NMR
parameters(chemical sift and electric field gradient (EFG) tensor). All of the calculations weredone using a code package PWscf and GIPAW in Quantum ESPRESSO. We used the pseudopotential method. We have demonstrated that 133Cs-NMR spectrum is a useful in which reflect
the differences in the local structure of encapsulated CsI sensitively. The detailed results willbe also presented.

References:[1] J. Sloan, M.C. Novotny, Chem. Phys. Lett., 329 (2000)61.
[2] M. Wilson, P.A. Madden, J. Am. Chem. Soc., 123 (2001)2101.
[3] Ryosuke Senga, Hannu-Pekka Komsa, Zheng Liu, Kaori Hirose-Takai, Arkady V. Krasheninnikov and Kazu
Suenaga, Nature Materials,13(2014)1050.
Corresponding Author: H. Ogata Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 114 -

2P-26
Recrystallization of polycrystalline Cu-foil for CVD-grown graphene○Yui Ogawa1, Satoru Suzuki1, Koji Onomitsu1, Hiroki Hibino2, Hideki Yamamoto1
NTT Basic Research Laboratories, Nippon Telegraph and Telephone Corporation,
Kanagawa 243-0198, Japan
2
School of Science and Technology, Kwansei Gakuin University, Hyogo 669-1337, Japan1

A chemical vapor deposition (CVD) method for graphene using copper (Cu) catalyst andhydro-carbon gases, e.g. methane, has been widely studied as a promising growth techniquefor an inexpensive and large-scale growth[1]. Aligned CVD-grown graphene could beobtained performing epitaxial growth between grapehen and single crystalline Cu[2-4].
Subsequently, the scalable growths of aligned graphene on commercial Cu-foils has beenreported, and the pre-treatments, such as annealing and electropolishing approaches, were
performed to enhance a recrystallization of Cu and to get single crystalline Cu from thepolycrystalline Cu-foils[5,6]. However, various Cu-foils show different trends in therecrystallization process and these mechanisms are not understood well yet.
Here, we report recrystallization (preferentially-appeared orientation and plane, and grain
size of the crystal) of three types of Cu-foil by annealing processes, and CVD growth ofgraphene. Results of secondary ion mass spectrometry (SIMS) and inductively coupledplasma mass spectrometry (ICP-MS) indicate that each Cu-foil has signature of impurities:
aluminum (Al), silver (Ag), and calcium (Ca) in A-foil, B-foil-B, and C-foil, respectively.
A-foil shows lowest impunity concentration. Graphene grown on all type of Cu-foils is
mainly single layer with less defects according to the characterizations of optical microscopy(OM), Raman spectroscopy, and low energy electron microscopy (LEEM). For therecrystallization of the polycrystalline Cu-foil, A-foil and C-foil are sensitive against
hydrogen (H2) concentration during the annealing before CVD growth of graphene. In
contrast, B-foil did not show any dependence on
the annealing condition and could always givelarge Cu grain in centimeter scale. In case of
A-foil, beyond 90 % area was recrystallized with
Cu(111) plane in a centimeter scale, which was
confirmed by OM, electron back scattering
diffraction (EBSD), and X-ray diffraction (XRD)
as shown in Fig. 1, when H2 concentration wasover 5 % in argon (Ar). Also, C-foil provided
Cu(001) and Cu(120) planes.
As results,
impurities contained in Cu-foil and H2 annealing
are considered as important factors to control Fig. 1 XRD patterns of A-foil after (gray)grain size and crystal plane of Cu-foil in theand before (black) H2 annealing.
recrystallization process.
Acknowledgement: A part of Cu-foil is provided by JX Nippon Mining and Metals co.
References:[1] S. Bae et al., Nat. Nanotechnol. 5, 574 (2010). [4] Y. Ogawa et al., J. Phys. Chem. Lett. 3, 219 (2012).
[5] L. Brown et al., Nano Lett. 14, 5706 (2014).
[2] L. Gao et al., Nano Lett. 10, 3512 (2010).
[6] V. L. Nguyen et al., Adv. Mater. 27, 1376 (2015).
[3] B. Hu et al., Carbon, 50, 57 (2012)
Corresponding Author: Yui Ogawa
Tel: +81-46-240-3423, Fax: +81-46-240-4718, E-mail: ogawa.yui@lab.ntt.co.jp- 115 -

2P-27
Efficient fabrication of graphene/BN heterostructuresby metal melting transfer○Ryosuke Inoue1, Kenji Watanabe2, Takashi Taniguchi2,
Yutaka Maniwa1, Yasumitsu Miyata1,3
1Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
National Institute for Materials Science, Tsukuba 305-0044, Japan
3
JST, PRESTO, Kawaguchi, 332-0012, Japan

Chemical vapor deposition (CVD) is widely used for the growth of large-area, uniform
monolayer graphene films. Generally, CVD graphene is grown on metal substrates such as Cu
and Ni foil, and thus graphene films should be transferred from metal substrates to insulating
substrates such as SiO2 and boron nitride (BN) for electronics applications. Conventional
polymer-assisted transfer process, however, includes several unavoidable issues such asremaining polymer and solvent on the graphene surface and at the graphene/substrateinterface. To solve this problem, we have developed a novel transfer method using metal
melting under an inert atmosphere at high temperature [1].
In this study, we have improved the meta-melting transfer process to obtain large-areagraphene/BN heterostructures with high yield. This improvement can be achieved by the useof large-area BN flakes with a size of over 100 m (Fig.1a). For sample preparation, graphene
was grown on Cu foil, and then was fixed on BN substrates. For the transfer, the samples wereannealed at 1150~1200°C to melt Cu foil under Ar/H2 atmosphere. During the Cu melting, thegraphene films can be directly transferred on the BN substrates. The graphene on BN has
highly-clean surface like BN surface and one-atom-thick height profile (Fig.1b,c).
Furthermore, we found that the melting-transfer samples have less frequency variations of G
and 2D bands than the conventional polymer-transfer samples (Fig. 1d). This result indicatesthat the present graphene has less lattice strain and charged impurities [2]. In the presentation,
we will report the details of transfer process and electric transport properties of graphene/BN
heterostructures.

Fig.1 (a) Optical microscope and (b) AFM images, and (c) height profile of the graphene transferred on BN.
(d) Correlation between the frequencies of the G and 2D Raman modes of polymer-transfer andmetal-melting-transfer graphene films.
[1] R. Inoue, et al. 49th FNTG symposium. [2] J. E. Lee et al., Nat. Commun 3, 1024 (2012).
Corresponding Author: Yasumitsu Miyata, Tel: +81-42-677-2508, E-mail: ymiyata@tmu.ac.jp- 116 -

2P-28Suppression of graphene nucleation by turning off hydrogen supply justbefore atmospheric chemical vapor deposition growth○Seiya Suzuki, Yoshifumi Terada, Masamichi Yoshimura
Graduate school of Engineering, Toyota Technological Institute 468-8511, Japan
Chemical vapor deposition (CVD) is a promising method to produce high quality
large-size single-crystal graphene, and further increase in domain size is desirable forelectro/optic applications. Suppression of the nucleation of graphene is a crucial technique toobtain large-size domains of graphene, and several effective methods have been establishedsuch as prolonged annealing [1], wrapping Cu foils [2], and high pressure annealing [3].
However, the long processing time of these methods becomes a significant disadvantage forgraphene fabrication on an industrial scale. Here we report an effective method of suppressing
graphene nucleation in atmospheric CVD of Cu (100 m thickness) by turning off hydrogen
supply just before the growth process. Using this method, we reduced the annealing time
down to 20 minutes and achieved growing isolated graphene domains with ~500 m indiameter.
Figure 1(a) shows a schematic diagram of the CVD growth process. Hydrogen flow was
turned off for 5 minutes just after the annealing process. Figures 1(b) and 1(c) show optical
micrographs of Cu after CVD with and without turning off hydrogen flow, respectively. It was
found that the density of graphene domains was reduced from 95.3 to 51.6 cm-2 by turning offhydrogen.
To reveal the effect of the turning off hydrogen process, we measured the annealed Cu
surfaces (after A and B shown in Fig. 1(a)) by X-ray photoelectron spectroscopy (XPS),
where the amount of oxygen increased ~5% in atomic ratio by the turning off process. This
indicates that the Cu surface was oxidized by residual oxygen in the CVD chamber during theturning off hydrogen. The surface oxidation would be attributed to suppress the graphene
nucleation by passivation of nucleation sites [4].
(a)T (°C)A(b)

Ar (5 min) B

Density: 51.6 cm-2(c)Density: 95.3 cm-2

1035
1000

Ar

RT

H2/Ar

CH4/H2/Ar H2/Ar

1 mm

Time
Annealing GrowthTurning off H2(anneal: 15 min)

1 mm
Without turning off(anneal: 120 min)Fig. 1. (a) Schematic diagram of CVD process. (b,c) Optical micrographs of Cu foils after CVD with andwithout turning off hydrogen, respectively. The Cu foils were heated around 200 ºC to visualize the graphene
domain (shown in white contrast).
[1] H. Wang et al., J. Am. Chem. Soc. 134, 3627 (2012).
[2] S. Chen et al., Adv. Mater. 25, 2062 (2013).
[3] S. Suzuki et al., Jpn. J. Appl. Phys. 53, 095101 (2014).
[4] Y. Hao et al., Science 342, 720 (2013).
Corresponding Author: S. Suzuki
Tel: +81-52-809-1852,
E-mail: seiya09417@gmail.com- 117 -

2P-29Evaluation of spin magnetism and chemical activity
for graphene derivatives○Tomoki Yamashina1, Takuya Isaka1, Kentaro Tajima2,
Yoshiaki Matsuo3, Kazuyuki Takai1,2,
12Graduate 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

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 an edge-riched nanographene assemblymaterial was investigated by XRD, XPS, the magnetic susceptibility, ESR and GC-MS. GO
samples were synthesized by Brodie [2] and Hummers [3] methods (BGO and HGO).
Chemical activities were evaluated by a coupling reaction of aromatic amine using ACFs andGO as catalyst. The spin susceptibilities Nspin estimated by ESR intensities are summarized in
Fig.1 for GO and ACFs samples. Nspin are very close to those obtained from the static magnetic
susceptibility (SQUID). The g-value is lower than 2.0023 for ACFs having electron withshielding effect, while BGO and HGO show g > 2.0023, suggesting sp 3-carbon spin system.

The absence of -electron in GO by oxidation is also

supported by XPS. GC-MS yields for the reaction

from benzylamine to N-benzylidenebenzylamine areshown in Fig.1 for BGO, ACFs and HGO as catalyst.
The spin magnetism is dominant factor for catalytic
activity but other factors such as the presence of-electron influences the results.
[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)
Fig.1 Spin densities and GC yields for

Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002,
E-mail: takai@hosei.ac.jp

BGO, HGO and ACFs

- 118 -

2P-30
Environmentally Stable Carrier Doping into Graphene Films
by Extraordinary Molecular Lewis Acid
○T. Miyauchi1, N. Tanaka2, Y. Shoji2, K. Funahashi3, K. Kanahashi3, M. Ishihara4,
M. Hasegawa4, T. Fukushima2 and T. Takenobu 1,3,5
1

2

Department of applied Physics, Waseda University, Shinjuku 169-8555, Japan
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama 226-8503, Japan3
Department of Advanced Science and Engineering, Waseda University, Shinjuku, Tokyo
169-8555, Japan
4
Carbon-Based Thin Film Materials Group, Nanomaterials Research Institute, National
Institure of Advanced Industrial Science and Technology (AIST), Ibaraki 305-8565, Japan
5
Kagami Memorial Laboratory, Waseda University, Shinjuku, Tokyo 169-0051, Japan

100
80
60
40
20
0
0

Fig. 1 Novel dopant; cation, Mes2B+ andcounter anion, [(C6F5)4B]-

Before doping
After doping

200 400 600
Time [hour]

500
400
300
200
100
0

Rs [/sq]

Normalized Rs [%]Graphene films are one of the most promising materials for the future flexible transparent
electrode due to their high transparency, excellent transport properties, and high flexibility,
which is difficult for commonly-used indium tin oxide (ITO) films. However, sheet resistance(Rs) of graphene films is higher than them of ITO and, therefore, many researchers on charge
charrier doping into Graphene with very diverse dopants (HNO3, AuCl3, etc) have beenreported, resulting in poor air stability [1]. Very recently, we found that the combination of thesuper Lewis acid, diarylborinium ion (Mes2B+; Mes (mesityl) = 2, 4, 6-trimethylphenyl) andcounter anion, tetrakis (pentafluorophenyl) borate ([(C6F5)4B]-) (Fig.1) [2] leads to air-stable
carrier doping in carbon nanotubes. Therefore, we apply this material into graphene films.
We prepared few-layer graphene films by CVD method and transferred on plastic
substrates. These films were films were immersed into the saturated o-dichlorobenzene
solution of dopant, Mes2B+ [(C6F5)4B]-. Before and after the above doping processes, wecharacterized these films by four-probe resistance measurements and confirmed the carrier
doping into graphene films by RS reduction of -26% (Fig.2). Importantly, the doped films
were air-stable for one month.
In conclusion, we succeeded in chemical doping of graphene films by the novel dopants,
Mes2B+ and [(C6F5)4B]-. This researches promotes the use of graphene films as new flexible
electrode.

Fig. 2 Time evolution of Rs increase in graphenefilm doped by novel dopant[1] F. Günes et al., ACS Nano 4, 4595 (2010). [2] Y. Shoji et al., Nature Chemistry 6, 498–503 (2014).
Corresponding Author: T. Takenobu, Tel&Fax: +81-3-5286-2981, E-mail: takenobu@waseda.jp- 119 -

2P-31
Evaluation of Graphene Oxide Catalyst regarding
Organic reaction in Aqueous media○Takuya Isaka1, Tomoki Yamashina1, Kentaro Tajima2, Yutaka Ohta2, Kazuyuki Takai1,2
1Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
Department of Chemical Science and Technology, Hosei University, Tokyo 184-8584, Japan

2

Graphene oxide (GO) having oxygen-containing groups is promising as metal-free andenvironment-compatible catalyst due to its amphiphilic and Brӧnsted acid nature [1], although thedetail mechanism for catalytic activity is not clear yet. In this study, the change in the chemical
structure of graphene oxide as catalytic activity is investigated before / after the synthesis of axanthene derivative in water solvent in order to clarify the mechanism of the catalytic activity.
GO was synthesized from natural graphite flake by Hummers methods. The following reaction
using GO as catalyst was conducted in water medium (Scheme 1). A mixture of benzaldehyde (1)GO
80℃/ 3h1

2

3

Sheme 1 Synthesis for xanthene dericative using GO in water

Inte nsity (arb. units)(2 mmol), dimedone (2) (4 mmol) and GO catalyst (4.9 wt%) dispersed in water was stirred at 80℃
for 3h. After separation of GO catalyst from the reaction media by filtration and washing withcatalyst
Byproductdichloromethane, the water solvent was evaporated. The
3
obtained product was characterized by GC-MS. The
chemical structure of GO before / after the reaction was
2evaluated by XPS.
No catalyst
The GC-MS peak for 3,3,6,6-tetramethyl-9-phenyl3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (3)(m/z = 350) appears in the product of the reaction using GO
catalyst in spite of the absence of the peak on the condition
without GO (Fig. 1), indicating catalytic activity of GO as
Fig. 1 MS spectra for productBrӧnsted acid. The yield and conversion are 22.6% and86.4% respectivity from GC-MS. However, the C/O ratio of
C=O
C-OH/
GO estimated by XPS decreases after the reaction. Taking
C-C spC(O)O
C=C before
the fact that C/O ratio also decreases in the control
C-O-C
experiment without reactants, the C/O decreasing is mainly
after
attributed to the heat-induced reduction during the reaction.
The intensity ratio among C1s peaks for oxygen-containing
controlfunctional groups [2] is almost same for GO after the






reaction and that for control experiment (Fig. 2). Any uniqueBinding energy (eV)contribution of specific functional group in the reaction isFig. 2 The change of XPS C1s peaks
not found.
for GO before / after the reaction[1]Shaabani, A.; Mahyari, M.; Hajishaabanha, F. Res. Chem. Intermed. 2013, 40, 8, 2799-2810[2]Rodriguez-Postor, I.; Ramos-Fernandez, G.; Varela-Rizo, H.; et al. Carbon. 2015, 84, 299-309
Corresponding Author: Kazuyuki Takai,
Tel: +81-42-387-6138, Fax: +81-42-387-7002, E-mail: takai@hosei.ac.jp- 120 -

3

2P-32
Electrocatalytic properties toward methanol oxidation of
Pt-based nanoparticles on surface-modified carbon nanomaterials○1 Haruhiko Yoshitake , 3Eiichi Inami, 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 byelectrodeposition systematically. In this study, we investigated the effects of the radio
frequency(RF) O2 plasma treatment on the dispersion state and electrocatalytic properties of
Pt-based nanoparticles supported on the carbon material (CNSs , SWNTs) byelectrodeposition method. Figure 1 shows the XPS for CNSs before and after RF O2 plasma
treatment and table.1 summarizes their electrochemical characteristics of methanol oxidation.
The detailed results on the shape and dispersion state of Pt-based nanoparticles and theirelectrocatalytic performance for methanol oxidation will be presented.

Pristine CNS

SPt

JF

[cm2]

[mA/cm2]

1.45×103

21.0

If/Ib

VF
[V]

1.21

0.646
(±0.005)

O2 plasma treated

1.70×103

33.3

CNS

Figure 1.

X-ray photoelectron spectra(XPS)for CNSs

References:

Table 1.

0.676(±0.005)

Electrochemical characteristics(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- 121 -

0.76

2P-33
Electrochemical Interaction at the Interface
between Graphene and Electrolyte○Daisuke Suzuki1, Kazuyuki Takai 1, 2
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

In electric storage devices, phenomena at the interface between electrode and electrolyte
play the most important roles. Electric double-layer capacitors depend on physical adsorptionof electrolyte, and battery utilizes an electrochemical reaction at electrodes. Carbon materials
like graphite and its derivatives are widely used in electric storage devices such as negativeelectrode in a battery, where degradation mechanism of electrode and SEI (Solid electrolyte
interphase) formation are crucial in device performance. However phenomena at the interface
between carbon materials and electrolyte in battery devices are still unclear because ofcomplicated structure of conventional carbon electrode materials. In this study, theelectrochemical interaction at the interface between graphene electrode as a model structure ofcarbon electrode materials and electrolyte solution is investigated in order to clarify thephenomena in battery devices.
Gate voltage dependence of the conductivity was measured for graphene FET on SiO2
substrate with the bipolar electrochemical configuration, where the graphene channel and Pt
wire in the electrolyte were applied as working and counter electrodes, respectively. 1 M KClaqueous solution and 1 M LiCl aqueous solution, and 1 M LiBF4 organic solution (EC / DMC)
were used as electrolyte solution. Raman spectroscopy was carried out using excitation
wavelength of 532 nm under an atmospheric condition.
Similar results were obtained in the case of KCl and LiCl aqueous solution. A reversible
behavior of the transfer curve upon the cycle of applying top gate voltage (Pt counter electrode)
was observed for smaller voltage region, where the electrochemical current between top
electrode and graphene channel is negligible. This is attributed to the physisorption ofelectrolyte on the graphene surface. Appling larger gate voltage, irreversible gate-voltage
dependence appears with electrochemical currents due to electrolysis of water at electrodes.
However, no change in Raman spectra after larger voltage applying suggests less structuralchange for graphene. With LiBF4 organic
electrolyte solution (Fig.1), the observed
electrochemical current at more than 2 V
resembles actual battery reactions between
carbon and lithium. On the other hand, thetypical behavior due to formation of SEI that
occurs between 2 - 3 V is absent in thegraphene-based device, suggesting significant
roles of stacking structure and non-ideal
structure of graphene such as edges and defectsof carbon electrode in actual battery devices.
[1] H. Wang et al, ACS. Nano. 4, 7221 (2010)
Corresponding Author: Kazuyuki Takai,
Tel: +81-42-387-6138, Fax: +81-42-387-7002,
E-mail: takai@hosei.ac.jp

Fig.1 Gate voltage dependence of Conductivity
in FET with LiBF4 organic electrolyte solution- 122 -

2P-34
Electron confinement in bilayer graphene○Yuya Inoue1, Riichiro Saito1
1

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

Graphene is a material attracting wide-range of attentions for applications due to its great
physical properties such as high mobility. However, the weakness of graphene is that it can not
be used as field effect transisitor (FET) unless the band gap is made artificially. The reason for
the weakness is well known as the Klein tunneling phenomena that the electron on the monolayer
graphene can not be confined by applying any potential [1].
Some previous works show that FET using bilayer graphene can be realized by applying
electric field perpendicular to the bilayer graphene, which breaks the symmetry between the twolayers and results in opening the energy gap [2,3].
In this work, we also focus on the bilayer
graphene (AB stacking), which has theproperty that complete reflection against thepotential barrier is realized due to the Klein
tunneling effect for bilayer graphene [1]. The
present work shows that changing thepotential height and width in the tunnelingprocesses can be applied to make current
switch. Fig. 1 shows the resonance condition,
where electron in bilayer graphene can go
through the potential barrier with height V0
and width D. If the resonance (T=1) does notoccur, electron can be confined between two
such barriers. We calculate the timedevelopment of wave packet and show thepossibilities of electron confinement andpropose a switching device.

Fig.1: Resonance tunneling condition in bilayer graphene.
T is transmission probability, V0 is the potential height, D
is the potential width, and 𝜙𝜙 is the angle for the incident
electron. The energy of incident electron is ~ 17meV.

[1] M. I. Katsnelson et al. Nature Physics 2, 620 (2006).
[2] Y. Zhang, et al. Nature 459, 820 (2009).
[3] S-L. Li et al. Acs Nano 5, 500 (2011).
Corresponding Author: Y. Inoue
Tel: +81-22-7 95-6442, Fax: +81-22-795-6447,
E-mail: inoue@flex.phys.tohoku.ac.jp- 123 -

2P-35
Electric field and charge modulation spectroscopy ofmonolayer WS2 on graphite○Keiichiro Matsuki 1, Jiang Pu 1, Daichi Kozawa 1,Yu Kobayashi 2, Shogo Sasaki 2,
Yasumitsu Miyata 2, Lain-Jong Li 3, Yutaka Maniwa 2, Taishi Takenobu 1,41

Department of Advanced Science and Engineering, Waseda University, Shinjuku 169-8555
2
Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan3
Physical Sciences and Engineering Division, KAUST, Thuwai 23955-6900, Saudi Arabia
4
Kagami Memorial Laboratory, Waseda University, Shinjuku, Tokyo 169-0051, Japan

Transition metal dichalcogenide (TMDCs) monolayers are known as direct bandgap
semiconductors with ultimately thin thickness (< 1 nm), leading to ideal quantum wells(QWs) and stable charged excitons (trions). Due to their quantum-well structures, electricfield and/or charge modulation of optical properties, such as the quantum confined Stark
effect and many body effect, are expected and it has been already investigated by other groups[1]. However, the solid evidenced of the quantum confined Stark effect and many body effecthave not yet been observed because an additional peak of trions masks the spectral
modulations. To overcome these problems, we focus on the recently reported monolayer WS2
on graphite, in which the effect of trions is negligible [2].
As shown in fig. 1, we fabricated electric double layer capacitors. Monolayer WS2 wassynthesized on exfoliated graphite by chemical vapor deposition methods [2] and Au
electrodes were thermally deposited on graphite as a working electrode and on quartz as agate electrode. For electrolyte, ion gel which is mixture of ionic liquid ([EMIM] [TFSI]) andorganic polymer (PS-PMMA-PS) was spincoated on the sample. We applied gate voltage (VG)
at room temperature. Figure 2 shows PL spectra of monolayer WS2 on graphite at various gate
voltages. We have successfully observed clear VG-dependent spectral change and these spectra
are well explained by single Lorentz fitting analysis, resulting in peak redshift, broadening
and intensity decrease. Importantly, the redshift is proportional to square of VG, strongly
suggesting the quantum confined Stark effect. Moreover, through quantitative analysis basedon the basic theory of quantum confined Stark effect, we found the clear threshold gate
voltage, which separates the simple field modulation and the multiple modulation by bothelectric field charge accumulation, possibly leading to the evidence of many body effect.

Fig. 1

Device structure of EDLC

Fig. 2 Gate voltage dependence ofPL spectra in Monolayer WS2 on graphite[1] A. M. Jones et al. Nature Nanotech., 8, 634 (2013)[2]Y. Kobayashi, S. Sasaki, Y. Miyata et al. ACS NANO, 9, 4056 (2015)
Corresponding Author: Taishi Takenobu,
Tel&Fax: +81-3-5286-2981,- 124 -

E-mail: takenobu@waseda.jp

2P-36
Behavior of Graphene Oxide in Aqueous Solution○Meng Wang, Yang Niu, Zhenyu Zhang, Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China
Graphene oxide (GO), which possesses a range of oxygen-containing functional groups,
such as carboxylic acid groups, hydroxyl and epoxy groups, has very good water solubility
without further functionalization [1]. Considering the structure of GO, it might show similar
properties to the polyelectrolyte in aqueous solution. Here, different sizes of GO sheets wereseparated by a centrifugation-based process, and the size distribution of the obtained GO
solutions were studied by atomic force microscopy (AFM) and static light scattering (SLS).
The aggregation behaviors of GO dispersions in water and under the condition of adding salt
were also studied by SLS. GO solutions were destabilized by adding excess NaCl and MgCl2,
but when adding excess AlCl3, the GO solution remained stable attributed to the inversion of
surface charges of GO sheets.
[1] Dreyer, Daniel R., et al. Chem. Soc. Rev.39, 228-240 (2010).
Corresponding Author: Yan Li
Tel: +86-10-62756773, Fax: +86-10-62751708.
E-mail: yanli@pku.edu.cn- 125 -

2P-37
Host-Guest interactions between nanographene hostand magnetic guest molecule○Akira Suzuki1, Kazuyuki Takai1, 2
12

Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
Department of Chemical Science and Technology, Hosei University, Tokyo 184-8584, Japan

Activated Carbon Fibers (ACFs) consisting of 3D random network of nanographenes isinteresting host material because of its nanopores and localized spins originating inzigzag-edges [1]. In this study, we introduced Ferrocene (FeCp2) having localized d -electron as
guest molecule to ACFs host in order to clarify host-guest magnetic interaction between
nanographene and magnetic molecule.
The guest molecule was introduced by vapor transfer (FeCp2-ACFs). The introduction of theguest molecule is confirmed by Fe2p peaks in XPS. The increment in shake-up peak intensity of
C1s spectrum indicates the increase of conducting electrons (Table 1). The emergence of chargetransfer host-guest interaction is suggested in FeCp2-ACFs, which is also supported by red-shiftof G-band in Raman spectrum. The larger spin concentration of FeCp2-ACFs than that of ACFs
indicates the presence of cationized FeCp2 in which chemical form spin magnetism of 3delectron appears (Fig. 1). Although it has been reported FeCp2-doped ACFs showed
ferromagnetism [2], our sample doesn’t show that. Assuming the simple dipolar interaction
between nanographene’s edge and ferrocenium cation spins, ESR linewidth is expected toincrease 5 times as large as that of ACFs. Actually, the ESR linewidth of FeCp2-ACFs doped at
80°C are much broadened comparing with that of ACFs and the ESR peak disappears.
Table 1 Relative intensities for FeCp2 - ACFs and ACFs in XPS
ACFs

FeCp2-ACFs

C1s (C-C)

1

1

C1s (C-O)

0.26

0.26

C1s (C=O)

0.60

0.50

C1s (shake-up)

0.14

0.18

Fe2p

0

0.03

16
χT (10 -5 emu・K・g -1 )XPS peak[1] T. Enoki and K. Takai Solid State Comm. 149, 1144-1150 (2009)[2] A. Nakayama et al. Synt. Met. 86, 2335-2336 (1997)
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002

12FeCp2 - ACFs
8

ACFs

4
0

0

100

200
300
T (K)
Fig.1 Temperature dependenceof magnetic susceptibility for

E-mail: takai@hosei.ac.jp

FeCp2-ACFs and ACFs

- 126 -

2P-38
Asymmetric Kohn anomaly in G' band of graphene
Eddwi H. Hasdeo, Ahmad R. T. Nugraha, and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, JapanThe existence of the gapless linear energy bands (Dirac cones) in graphene modifies phonon energy,
spectral broadening, and spectral lineshape of the Raman spectra. One of the well-known phenomenais the Kohn anomaly effect, in which the phonon energy (lifetime) becomes lower (shorter) due tosecond-order perturbation by electron-phonon interaction [1]. Peak position (linewidth) of the G band
Raman spectra (~1600 cm -1), the first order Raman scattering, symmetrically increases (decreases) as
a function of absolute value of Fermi energy [2,3]. We shall call these phenomena as symmetric Kohn
anomaly. On the other hand, the Kohn anomaly effect of the G' band (~2700 cm -1), the second order
Raman process, shows two controversial experimental results. Araujo et al. show that G' band gives
symmetric Kohn anomaly effect yet opposite compared to that of the G band, namely peak position(linewidth) symmetrically decreases (increases) as a function of absolute value of Fermi energy [2].
Meanwhile, Das et al. show asymmetric Kohn anomaly of the peak position of G' band, namely peak
position is barely changed on negative Fermi energy but decreases on positive Fermi energy [4]. In
this work, we perform calculation of phonon self energy that responsible to explain the change of bothphonon energy and linewidth as a function of Fermi energy. The calculation results show that at
certain phonon wave vector, asymmetric Kohn anomaly effect is expected. Since the G' band spectra
comes from integration of all possible phonon wavevector depending on laser energy, we will discuss
symmetric or asymmetric Kohn anomaly as a function of laser energy.
[1] M. Lazzeri and F. Mauri, Phys. Rev. Lett. 97, 266407, (2006)[2] D. L. Mafra et al., Phys. Rev. B 86, 195434, (2012)[3] P. T. Araujo et al., Phys. Rev. Lett. 109, 046801, (2012)[4] A. Das et al., Nature Nanotech. 3, 210, (2008)
Corresponding Author: E. H. Hasdeo
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: hasdeo@flex.phys.tohoku.ac.jp- 127 -

2P-39
Electronic structure of bilayer graphene with defect under an external
electric field○Ken Kishimoto and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Electronic structure of graphene is fragile against the formation of the hybrid structure withforeign materials, such as insulating substrate, defect, adsorbent, and other graphene layers.
By adsorbing the graphene with atomic defects on pristine graphene, the resultant bilayer
graphene no longer possesses a pair of linear dispersion bands at Fermi level. The bilayer
graphene one of which layer possesses the defect has a finite energy gap of 0.3 eV in their pielectron states [1]. Thus the bilayer graphene with defects may exhibit different properties tothe pristine graphene under the carrier injection due to the finite energy gap and the defectinduced states. In this work, we aim to reveal the influence of defects on the electronic
structure of bilayer graphene under an external electric field using the density functional
theory combining with the effective screening medium method.
By applying negative and positive gate voltage, injected electrons and holes substantiallymodulate the electronic energy band of the bilayer graphene with the defect (Fig. 1): In theneutral case, the Fermi level crosses the three flat dispersion bands arising from the defect.
For the case of hole doping, the Fermi level located just below the defect states, but therelative position of the defect-induced states is deeper by 0.1 eV than the state without theexcess carrier [Fig. 1(b)]. In contrast, the defect-induced states substantially shift upward by
the electron doping [Fig. 1(c)]. Furthermore, the carrier doping also modulates the bandwidthof the defect-induced
states. The width isnarrower and wider thanthat for the neutral caseby hole and electron
doping, respectively. Thus,
the bilayer graphene withdefect does not exhibit
rigid band nature under
the carrier doping by thecontour electrode. The
Fig. 1, (a) Electronic structures of bilayer graphene one of which layers
physical mechanism ofpossesses monovacancies. Electronic structures of bilayer graphene one
the shift with respect toof which layers possesses monovacancies under (b) hole and (c) electron
the carrier density will be
discussed.
doping. Red horizontal dotted lines denote the Fermi level.

[1] K. Kishimoto and S. Okada, Sur. Sci. 644, 18, (2016).
Corresponding Author: K. Kishimoto
Tel: +81-29-853-5600(ext.; 8233)
E-mail: kkishimoto@comas.frsc.tsukuba.ac.jp- 128 -

2P-40
Halide-assisted CVD and characterization of monolayer Nb-doped WS2○Shogo Sasaki1, Yu Kobayashi1, Zheng Liu2, 3, Kazutomo Suenaga3
Yutaka Maniwa1, Yasumitsu Miyata1, 4
1
2

Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Inorganic Functional Materials Research Institute, AIST, Nagoya, 463-8560, Japan
3
Nanomaterials Research Institute, AIST, Tsukuba, 305-8565, Japan
4
JST, PRESTO, Kawaguchi 332-0012, Japan

Atomic-layer transition metal dichalcogenides (TMDCs) are attractive components for
two-dimensional layered heterostructures because of their tunable electronic properties. To
control their bandgap and carrier densities, there are several approaches such as chemical
doping and alloying. In our previous works, we reported the growth of bandgap-tunableMo1-xWxS2 alloys [1] and highly-conductive Nb1-xWxS2 alloys [2] using thin-film
sulfurization. However, it is difficult to obtain large-area crystals using thin film sulfurization
probably due to the limitation of nucleation densities. To solve this issue, we have developed
a growth method of large-area, monolayer TMDC alloys using chemical vapor deposition(CVD) because of its tunability of supplying rate of precursors.
In this presentation, we report the growth and characterization of monolayer Nb-doped
WS2. Nb-doped WS2 were grown on SiO2/Si substrates by halide-assisted CVD method [3]using WO3, Nb and NaCl powders at 800 ~ 850 °C under argon/sulfur atmosphere. Figure 1ashows an optical image of typical triangle-shaped crystals with a size of 20 m on the SiO2/Si
substrate. Scanning transmission electron microscope (STEM) image indicates that a Nb atom
is substitutional doped at W site (Fig. 1b). The crystals have two characteristic small Ramanpeaks at 380 cm-1 and 400 cm-1 between WS2-E’ and WS2-A1’ peaks (Fig. 1c). These results
suggest that the present approach enables large-area growth of Nb-doped WS2 monolayers,
and could provide an effective way to produce carrier-controlled TMDC-based
heterostructures.

Fig. 1 (a) Optical image of typical monolayer Nb-doped WS2 crystals grown on a SiO2/Si substrate. (b) STEM
image of monolayer Nb-doped WS2. Transmitted electron intensity along the cross direction of blue box in the
STEM image. (c) Raman spectra of undoped and Nb-doped WS2 monolayers.
[1] Y. Kobayashi et al., Nano Res. 8, 3261-3271, (2015).
[2] S. Sasaki et al., The 48th FNTG symposium.
[3] S. Li et al., Applied Materials Today 1, 60-66, (2015).
Corresponding Author: Yasumitsu Miyata, Tel: +81-42-677-2508, E-mail: ymiyata@tmu.ac.jp- 129 -

2P-41Fabrication and manipulation of slidable atomic layers○Yu Kobayashi1, Takashi Taniguchi2, Kenji Watanabe2,
Yutaka Maniwa1, Yasumitsu Miyata1,3,*.
1

Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
2
National Institute for Materials Science, Tsukuba 305-0044, Japan
3
JST-PRESTO, Kawaguchi 332-0012, Japan

Development of novel fabrication and manipulation techniques of atomic-layer
heterostructures is one of the most important challenges to control their emergent
electrical and optical properties. So far, the heterostructures have been prepared mainly
by two major methods including transfer and direct-growth processes of graphene, boron
nitride (BN), and transition metal dichalcogenides (TMDCs). As-preparedheterostructures are usually fixed and are used without any structural modification. If
each layer could be slidable, we can control interlayer coupling by changing stacking
orientation and create various heterostructures such as lateral and vertical junctions.
However, there has been no report of such slidable atomic layers as yet probably due tolarge interlayer frictional force.
Here, we report the preparation and manipulation of slidable atomic layers in clean
heterostructure systems. In this work, TMDC crystals were grown on exfoliated graphite
and BN by chemical vapor deposition as reported in our previous work [1]. We found thatsuch systems have very small interlayer frictional force because of their clean interface
and atomically-flat van der Waals surfaces. For example, a WS2 crystal can be smoothly
moved on graphite by manipulation with a tip (Fig.1). Furthermore, this sliding process
also allows us to suspend and tear atomic layers, and to prepare vertically-stacked andlateral heterostructures by connecting it to another crystal (Fig. 1c). Our findings provide
a novel, effective way to realize a wide variety of atomic-layer heterostructures.

Fig.1 (a-c) SEM images of moving WS2 crystals grown on graphite by prober-tip.
A part of this work was conducted at the AIST Nano-Processing Facility, supported by "Nanotechnology
Platform Program" of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
[1] Y. Kobayashi et al., ACS Nano, 9, 4056 (2015).
Corresponding Author: Yasumitsu Miyata, Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 130 -

2P-42
Interlayer excitons in high-quality MoS2/WS2 vertical heterostructures○Tetsuki Saito1, Yu Kobayashi1, Kenji Watanabe2, Takashi Taniguchi2,
Yutaka Maniwa1, Yasumitsu Miyata1,3
1Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
National Institute for Materials Science, Tsukuba 305-0044, Japan
3
JST, PRESTO, Kawaguchi, 332-0012, Japan

Heterostructures of transition metal dichalcogenides (TMDCs) have attracted attention
because of their emergent optical and electronic properties. As a representative example, thepresence of interlayer excitons has been reported for TMDC-based vertical heterostructures[1,2]. However, in previous studies, an observed photoluminescence (PL) peak relating to theinterlayer excitons has relatively-large linewidth probably due to the presence of
inhomogeneous broadening. To solve this issues, we have developed the CVD process of
TMDCs with highly-uniform optical spectra and their heterostructures [3,4]. Here, we reporton the observation of sharp PL peaks in high-quality MoS2/WS2 vertical heterostructures.
Vertical MoS2/WS2 heterostructures are grown on boron nitride (BN) substrates by
two-step CVD. The presence of a monolayer WS2 grain on a triangle-shaped monolayer MoS2
was confirmed from an atomic force microscope (AFM) image (Fig.1a) and Raman/PL maps.
This heterostructure shows three PL peaks between 1.4~1.7 eV (Fig.1b). These fine structuresof PL have never been observed in the previous CVD-grown MoS2/WS2 heterostructure [2],and can be tentatively assigned to the direct and indirect optical transitions as shown in Fig.1c.
Interestingly, only I3 PL peak has redshift with increase in temperature. Compared to the band
structures considering thermal expansion, I3 peak can be assigned to the interlayer-derived
direct transition at K point. The present results indicate that the high-quality heterostructures
are an ideal system for the precise understanding of interlayer coupling.

Fig.1 (a) AFM image and (b) PL spectrum of the MoS2/WS2 vertical heterostructure on BN. (c) Band structure of
the MoS2/WS2 vertical heterostructure obtained from first-principles calculations.
[1] P. Rivera, et al., Nat. Commun. 6. 6242 (2015), [2] Y. Gong, et al., Nat. Mater. 13, 1135 (2014).
[3] Y. Kobayashi, et al., ACS Nano 9, 4056 (2015). [4] S. Yoshida. et al., Sci. Rep. 8, 14808 (2015).
Corresponding Author: Yasumitsu Miyata, Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 131 -

2P-43High-Performance Complementary Inverters ofLarge-Area Transition Metal Dichalcogenide Monolayers○Jiang Pu 1, Kazuma Funahashi 1, Chang-Hsiao Chen 2, Ming-Yang Li 3,4,Lain-Jong Li 4, and Taishi Takenobu 1,5
1

Department of Advanced Science and Engineering, Waseda Univ., Tokyo 169-8555, Japan
Dept. of Automatic Control Engineering, Feng Chia University, Taichung 40724, Taiwan
3
Research Center for Applied Sciences, Academia Sinica, Taipei 10617, Taiwan
4Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
5
Kagami Memorial Laboratory, Waseda University, Tokyo 169-0051, Japan2

The ultra-thin thickness of transition metal dichalcogenide (TMDC) monolayers ensures anultimately thin transistor active channel, which offers more efficient electrostatic
controllability than bulks and results in a high on/off current ratio of > 106 and a low
subthreshold swing S of 60 mV/dec [1]. Importantly, the large on/off ratio and small S are
crucial for designing high-performance complementary metal-oxide-semiconductor (CMOS)
inverters. Although excellent p-type and n-type transistors have been demonstrated inmechanical-exfoliated TMDC monolayers, it is still difficult to apply these devices for CMOS
inverters. Firstly, a CMOS inverter must combine p-type transistors with n-type transistors
and the method used for reproducible fabrication is crucial for realizing superior device
performance. However, it is almost impossible for exfoliated samples to overcome and theswitching performance of CMOS inverters is still limited, resulting in a low voltage gain
and/or large power consumption [2]. Moreover, although CMOS inverters with low power
consumption is recently reported, the typical film sizes of exfoliated samples are less than 10
μm2, which are not suitable for scalable integration [3]. Considering these obstacles, we focus
on the wafer-scale uniform TMDC monolayers grown by chemical vapor deposition (CVD)methods, and it is mandatory to demonstrate high-performance CMOS inverters.
Here, we demonstrated CMOS inverters using CVD-grown large-area WSe2 and MoS2
monolayers [4,5]. In particular, ion gels, i.e., gelated ionic liquids, are adopted for use as agate electrolyte to tune the material
polarities via efficient switching control
due to high specific capacitance. By
combining p-type WSe2 and n-type MoS2
transistors, we realized CMOS inverters
with the highest voltage gain (> 100)among the 2D materials. Furthermore, inorder to address the practical applications,
we also demonstrated the optimized
inverter characteristics which involved
excellent total noise margin (> 95%), lowpower consumption (~200 pW), andgood switching speed (~1 kHz) withoutcompromising proper gain (Fig. 1).

[1] G. Fiori et al., Nat. Nanotechnol. 9, 768 (2014).
[2] M. Tosun et al., ACS Nano 8, 4948 (2014).
[3] P. J. Jeon et al., ACS Appl. Mater. Interfaces 7, 22333 (2015).
[4] J. K. Huang, J. Pu, et al. ACS. Nano. 8, 923 (2014).
[5] Y. H. Chang, J. Pu, et al. ACS. Nano. 8, 8582 (2014).

- 132 -

Corresponding Author: J. Pu, T. Takenobu
Tel/Fax: +81-3-5286-2981
E-mail: hokoh.apple@fuji.waseda.jp
takenobu@waseda.jp

2P-44
Photoluminescence Quantum Yield and Exciton Radiative Lifetime in
Monolayer WSe2
○N. Baizura Mohamed, Koirala Sandhaya, Feijiu Wang, Hong En Lim, Shinichiro Mouri,
Yuhei Miyauchi and Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, JapanThe discovery of intriguing and unique properties of graphene has opened new research
fields in atomically thin-layered two-dimensional (2D) materials [1]. The atomically thinsemiconducting transition metal dichalcogenides (TMDs), MX2 (M = Mo, W; X = S, Se, Te),with a few nanometer thickness of its monolayer, have attracted great research interest in
recent years due to novel fundamental physics and potential applications of optoelectronic
devices [2,3]. It is essential to obtain the radiative lifetimes of excitons (electron-hole pair)
and its radiative photon emission efficiency, i.e. photoluminescence (PL) quantum yield, bothfrom viewpoint of fundamental research and optical device applications [4].
In this study, we have experimentally evaluated the PL quantum yield and intrinsic excitonradiative lifetimes of semiconducting monolayer WSe2. Figure 1(a) shows the excitation
power dependence of PL spectra of monolayer WSe2 at room temperature. The PL intensity
linearly increases at lower excitation conditions below 60 W/cm2. The PL quantum yield ofWSe2 was estimated using the data of PL intensity at lower excitation condition andabsorbance as about 0.04 %, evaluated by the1500
0.90 kW/cm
relative-method using highly fluorescent dye as a0.80 kW/cm
standard reference [5]. We also conducted the0.60 kW/cm
0.30 kW/cm
time-resolved PL spectroscopy at room temperature,1000
0.10 kW/cm
0.09 kW/cm
as shown in Fig. 1(b). The exciton radiative lifetime of
0.05 kW/cm~ 1.2 s was evaluated from the PL quantum yield and0.04 kW/cm
500
PL decay time of ~ 500 ps. Our experimental result ofconsiderably long exciton radiative lifetime was about(a)three-orders of magnitude larger compared to the
0
1.5
1.6
1.7
1.8
1.9
theoretically predicted values of ns at room
Energy (eV)temperature [6]. The very long exciton radiative
lifetime of monolayer WSe2 can be explained by
IRF
1.0
contribution of the dark states and finite exciton
WSe2
coherence length (coherence area in 2D system).
Fitting2[1] A. K. Geim et al., Nat. Mat. 6, 183 (2007).
[2] A. Splendiani et al., Nano Lett. 10, 1271 (2010).
[3] G. Eda et al., ACS Nano 7, 5660 (2013).
[4] H. Wang et al., arXiv:1409.3996v1 (2014).
[5] A. Wakamiya et al., Angew. Chem. Int. Ed. 46, 4273 (2007).
[6] M. Palummo et al., Nano Lett. 15, 2794 (2015).
Corresponding Author: N. Baizura Mohamed
Tel: +81-774-38-3460
Fax: +81-774-38-3460
E-mail: nur.mohamed.26v@st.kyoto-u.ac.jp- 133 -

Photon count (a. u.)

PL Intensity (a. u.)

2
2
2
2
2
2
2

PL ~ 500 ps

0.5

(b)
0.0

0

1

2

3

4

Decay time (ns)Figure 1: (a) Excitation power dependenceof PL spectra for WSe2, (b) PL decay profile
at 2.25 eV excitation photon energy.

2P-45
Optical Absorption Spectra of MoS2 Monolayer Crystals
under Tensile Strain○Musashi Fukumura, Kotaro Homma, Junji Nozaki, Yutaka Maniwa, Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Monolayer transition metal dichalcogenides (TMDCs) are atomically thin materials, andthey have attracted a lot of interest because of their remarkable physical and electronic
properties such as direct gap optical characteristics, electroluminescence, high carrier mobility,and valley spin polarization. Especially, remarkable piezoelectricity has been reported.[1]When strain is applied in the arm chair direction, charges of opposite polarity are induced at
the zig-zag edges of a monolayer MoS2 flake, and then piezoelectric voltage and current out
put were observed with increasing strain.[1] Strains
significantly influence on the electronic structuresof MoS2, thus in this study we investigated how
their optical absorption spectra are influenced bystrain.
MoS2 monolayer thin films are synthesized usingchemical vapor deposition (CVD) methods. In thisstudy, we used Ar + H2 gas flow for reduction of
MoO3 powders and N2 gas for growth. Thus
prepared MoS2 monolayer crystals were transferredusing a PMMA polymer to a silicone rubber sheetwith very high optical transparency. Then we
investigated their optical absorption spectra understrain.
Figure 1 (a) and (b) show photoluminescence(PL) images of MoS2 on non-stretched and 5%
stretched silicone rubber with conventional optical
microscope using 532 nm laser excitation. As
shown here, slight decrease of PL intensities wasobserved. Then we investigated their opticalabsorption spectra using a super-continuum lightsource. Figure 1 (c) indicates the optical absorption
spectra of MoS2 on non-stretched and 5% stretchedsilicone rubber. When we stretched the rubber, wefound clear shift of the A peak optical absorption
peak and slight decrease of its absorbance,suggesting significant influences of tensile strainson their electronic properties.
[1] W. Wu et al., Nature 514, 470 (2014).

Figure 1. PL mapping images of
MoS2 on (a) non-stretched and (b)5% stretched silicone rubber. (c)Optical absorption spectra

Corresponding Author: Kazuhiro Yanagi
Tel: +81-42-677-2494
E-mail: yanagi-kazuhiro@tmu.ac.jp- 134 -

2P-46
Fluorination and annealing effects onmagnetism and structure of nanodiamond○Kenta Kogane1・Hidekazu Touhara2・Yoshiyuki Hattori2・

Vladimir Osipov3・Nickolai Romanov4・Kazuyuki Takai1, 5

1Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
Faculty of Textile Science and Technology, Shinshu University, Nagano 386-8567, Japan
3
Ioffe Physical-Technical Institute, St.Petersburg 194021, Russia
4Peter the Great St.Petersburg Polytechnic University, St.Petersburg 195251, Russia
5
Faculty of Bioscience and Applied Chemistry, Hosei University, Tokyo 184-8584, Japan2[1] Eiji Osawa, Journal of the surface science society ofjapan, 30, 258-266 (2009).
[2] Hidekazu Touhara, Akiko Yonemoto, Nanocarbon
Handbook, part3, chapter 4 (2007).
[3] J.W. Park, Current Applied Physics, 6, 188–193 (2006).
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002
E-mail: takai@hosei.ac.jp

ΔHPP / mT

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 states and the surface structure by fluorinationby using X-ray diffraction (;XRD, Mo K), X-ray photoemission spectra (;XPS, Al K),
infrared (;IR) absorption spectroscopy 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 several days. Hereafter, eachsample is labeled as FND623K, FND733K, and FND873K according to the maximum
temperature during synthesis, while Non-fluorinated one is referred to as ND. XRD profile
reveals that well crystalline diamond core structure with a diameter of 3 – 4 nm in all samples
and the fluorination only at the surface part in FNDs. According to XPS, the fluorine content
increases up to F/C = 0.2 for FND873K with increasing fluorination temperature withformation of C-F bonding, supported by IR. For both of NDs and FNDs, ESR linewidth
decreases and becomes a minimum upon annealing (fluorination) temperature, and eventually
increasing with the further raising of the temperature (Fig. 1). This is mainly attributed to thestructural relaxation by heat-treatment [3]. Subtracting the contribution of the heat-treatment
effect, FNDs shows increasing in the linewidth of
0.05 – 0.1 mT. The hybridization of the spin state
1.22
NDwith the fluorine orbitals having the larger
FND
hyperfine coupling is responsible for the
1.18
increment in the linewidth in FNDs.
1.14
1.1

1.06
1.02

200

500

800

Temperature / K

Fig. 1 Annealing temperature dependenceof ESR linewidth- 135 -

2P-47
Synthesis of carbon nanoballoon and evaluation of
its catalytic activity in direct methanol fuel cells○T. Ohiro1, K. Mizui1, Y. Suda1 T. Harigai1, H. Takikawa1, H. Ue2
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon Co., Ltd., Oyama, Shizuoka 410-1431, Japan

1. Introduction
Carbon black, nanometer-size carbon particles, is commercially used as the catalyst
support in fuel cell owing to its high surface area, porosity, electric conductivity, low density,and low cost. In the previous work, we have used various carbon nanomaterials as catalyst
supports for direct methanol fuel cells (DMFC) [1]. In this study, we used carbon nanoballoon(CNB) as a catalyst support and measured the catalytic activity of CNB-supported PtRu
catalyst.
2. Experimental
The twin-torch arc discharge apparatus was used for AcB synthesis. CNB was prepared bya heat treatment in Ar gas at 2600°C [2]. The particle shape of CNB is hollow. CNB isgraphitic and has high conductivity. We prepared PtRu catalysts for the DMFC anode. The
PtRu catalysts were loaded onto CNB by the reduction method using sodium boron hydrate(NaBH4), and a counterpart employing the commercial Vulcan-supported PtRu catalyst wasalso prepared.
3. Results
Table 1 shows the electrical conductivity, the electrochemically active surface area
(ECSA) and the peak current density during methanol oxidation reaction (MOR) of the PtRu
catalysts. The catalyst activity of catalyst-supported CNB was better than that of
catalyst-supported of Vulcan. This is mainly due to the higher electrical conductivity in theanode catalyst layers benefiting from the structure of CNB.
Table 1. Electrochemical properties of PtRu catalyst particles loaded on carbon nanoballoon and Vulcan

Electrical conductivity

ECSA/m2 g-1/Ω-1 m-1

Peak current
density/mA cm -2

PtRu/CNB

43.4

53.8

2.07

PtRu/Vulcan

17.5

16.8

0.39

This work has been partly supported by the EIIRIS Project from Toyohashi University ofTechnology (TUT); JSPS KAKENHI Grant Number 24360108 and 15K13946; and the
Toyota Physical and Chemical Research Institute, "Scholar Project".
[1] Y. Suda et al. Materials Today Communications. Vol 3, pp. 96-103 (2015).
[2] T. Ikeda et al. Japanese Journal of Applied Physics Vol 50, 01AF13 (2011).
Corresponding Author: Y. Suda
Tel: +81 532 44 6726, Fax: +81 532 44 6757
E-mail: suda@ee.tut.ac.jp- 136 -

2P-48Acceleration of separation velocity in electric-field-induced layer formation
method by adjusting surfactant concentration○Fusako Sasaki1, Fumiyuki Nihey2, Yuki Kuwahara1,3, Hiroyuki Endoh2, Shinichi Yorozu2,
Takeshi Saito1,3*
1Technology Research Association for Single Wall Carbon Nanotubes, Tsukuba 305-8565,
Japan
2
Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
3
National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565, JapanThe electric-field-induced layer formation (ELF) method had been recently proposed as anionic-contamination-free method for separating metallic and semiconducting single-wallcarbon nanotubes (m- and sc-SWCNTs) [1]. However, probably due to the low
responsiveness of nonionic surfactant to electric field, the separation velocity in ELF method
was relatively slow, which was still remained as an important issue. In this presentation, we
report the effect of adjusting the surfactant concentration in ELF on the separation velocity.
In this work, SWCNTs synthesized by eDIPS [2] were dispersed in aqueous solutions ofpolyoxyethylene (100) stearyl ether (Brij S100) with the concentrations of 0.25 and 1 wt% bysonication and ultracentrifugation for ELF separation experiments. The typical opticalabsorption spectra of separated fractions (0.25 wt%) shown in Fig. 1 support the effectiveenrichment of m- and sc-SWCNTs. Figure 2 plots the condensing velocity of sc-SWCNTs
layer that suggests the acceleration of separation process by reducing the Brij concentration.
The other results will be reported in the presentation.

1.2
1
0.8

Lower layer(sc-SWCNT rich)

0.6
Upper layer(m-SWCNT rich)

0.4
0.2
0

0.25 wt%㻌

100
Position (mm)Absorbance (arb. unit)

1.4● 1 wt%㻌

Pristine
400

800

50

0

1200

Initial2day㻌□ 0.25 wt%㻌

0

1
2
3
4
5
Separation Time (days)

Wavelength (nm)Fig. 1 Typical optical absorption spectra of separated

Fig. 2 The position (top face) of condensing

m- and sc-SWCNTs.

sc-SWCNTs layer in the case of 0.25 wt% and 1 wt%.

Acknowledgment: This presentation is based on results obtained from a project subsidized by the New Energy
and Industrial Technology Development Organization (NEDO).
References: [1] K. Ihara et al., J. Phys. Chem. C 115, 22827 (2011).
[2] T. Saito et al., J. Nanosci. Nanotechnol. 8, 6153 (2008).
*Corresponding Author: Tel: +81-29-861-4683, Fax: +81-29-861-4413, E-mail: takeshi-saito@aist.go.jp- 137 -

2P-49Carrier Injections on WS2 Nanotube Networks
by Electrochemical Doping Techniques○Mitsunari Sugahara, Yoshimasa Kitamura, Yuki Oshima, Hideki Kawai, Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Thermoelectrics are one of very important technologies to efficiently convert waste heat toelectric power. Hicks and Dresselhaus have proposed that the performance can besignificantly enhanced using low-dimensional materials, and one-dimensional materials are
the most promising for thermoelectric devices with highest performance.[1] Single wall
carbon nanotubes are a model for one-dimensional materials, and we have investigated the
Fermi level dependence of their thermoelectric properties. We found significant enhancementof their power factor,[2,3] however, the large thermal conductance in a single rope of SWCNT
has been a week point for their thermoelectric applications. Therefore, it is also important toinvestigate other one-dimensional materials to realize the highest thermoelectric performanceof one-dimensional materials. There are a plenty of one-dimensional materials, however, wehave to use materials whose Fermi level will be well controlled because the thermoelectricperformance strongly depend on the position of the Fermi level.[2,3] In this study, weinvestigated WS2 multi-layered nanotubes because they have less dangling bonds on theirsurfaces, which will enable us to shift the Fermi level by electrochemical doping approaches.
Previously, field effect transport characteristics of a single rope of WS2 nanotube werereported,[4] suggesting capability of control of electrical properties by carrier injection.
First we dispersed WS2 nanotubes (NanoMaterials Co.) to toluene solutions and deposited
on gold electrodes and investigated Raman intensities with carrier injections using ionic liquid
gating. Here carriers were injected to WS2 nanotubes through formation of electric double
layers on their surfaces by side-gating. Figure 1 shows the Raman spectra of WS2 nanotube
networks as a function of gate voltages. As shown in Fig. 1, the Raman peak originating from
WS2 nanotubes was significantly changed by the positive shift of the reference voltage. The
results suggested that the electron injections on the WS2 nanotube networks were possible.
Then we fabricated their thin films andclarified their transport properties. The
results suggested that optical andelectrical properties of WS2 nanotube
network films were controllable byelectro-chemical doping approaches.
[1] Hicks & Dresselhaus, Phys. Rev. B 47, 16631(1993).
[2] K. Yanagi et al., Nano Lett. 14, 6437 (2014)[3] Y. Oshima, Y. Kitamura, Y. Maniwa, K.
Yanagi, Appl. Phys. Lett. 107, 043106 (2015)[4] R. Levi et al., Nano Lett. 13, 3736 (2013)
Corresponding Author: Kazuhiro Yanagi
Tel: +81-42-677-2494
E-mail: yanagi-kazuhiro@tmu.ac.jp

Figure 1. Raman spectra of WS2 nanotube
networks as a function of gate voltages.
WS2NT and IO indicate peaks originating from
WS2 nanotubes and ionic liquid we used.

- 138 -

3P-1
Degradation of organic dyes under ultraviolet light condition with carbon
nanocapsule encircled by nickel nanoparticle composites○Jeong Won Ko1, Hae Soo Park1, Jiulong Li1, Weon Bae Ko1,2
1

Department of Convergence Science, Graduate School, Sahmyook University, Seoul 139-742,
South Korea, 2 Department of Chemistry, Sahmyook University, Seoul 139-742, South Korea

In this work, we got a novel product of carbon nanocapsule encircled by nickel
nanoparticle composites by the reaction of [C70]fullerene and nickel hydroxide at 700 ℃
for 2 h. The carbon nanocapsule encircled by nickel nanoparticle composites werecharacterized by X-ray diffraction, scanning electron microscopy, transmission electron
microscopy. It may be confirmed the structure of [C70]fullerene changed into capsule like typeof carbon nanomaterials and nickel nanoparticles were surrounded by carbon nanocapsules
using TEM. The carbon nanocapsule encircled by nickel nanoparticle composites were
evaluated as a photocatalyst in the degradation of organic dyes under ultraviolet light at 254
nm.
0
y = -0.0638x

ln (C/C0)

-1
-2

BG

-3

y = -0.2442x

MG
y = -0.285x-4y = -0.3405x

-5

MO
RhB

-6
0

5

10

15

Time (min)Fig.1 Photocatalytic activity for organic dyes degradation under ultraviolet light using carbon nanocapsuleencircled by nickel nanoparticle composites[1] S. K. Hong, J. H. Lee and W. B. Ko, J. Nanosci. Nanotechnol., 11, 6049 (2011).
[2] H. S. Park and W. B. Ko, J. Nanosci. Nanotechnol., 15, 8215 (2015).
Corresponding Author: W. B. Ko
Tel: +82-2-3399-1700, Fax:, +82-2-979-5318,
E-mail: kowb@syu.ac.kr- 139 -

3P-2
ESR measurement of molecular oxygen in openC60○Azusa Kato1, Tsukasa Futagoishi 2, Yasujiro Murata2, Tatsuhisa Kato 1,3
1

Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501,
Japan
2
Institute for Chemical Research, Kyoto University, Kyoto 611-0011, Japan
3
Institute for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

Molecular oxygen (O2) is a fundamental bi-radical molecule. The electron spin resonance(ESR) absorption of O2 in the electronic ground state, 3Σg-, has been studied in the gas phase,and the detailed analysis was well documented. However few observations have been
described for O2 in condensed phase because of the difficulty in stable trapping of themolecule. Some ESR measurements reported the spectrum of O2 trapped in a few matrices at
the temperature below 10K, and the line broadening mechanism led to the absence of the ESR
signal above 10K. [1] We performed the molecular surgery synthesis of the endohedral
fullerene of O2@openC60, in which O2 is trapped in the inside of openC60 cage, and succeededin obtaining clear ESR spectra of O2 in frozen solution and powder forms at various
temperatures.
X-band and W-band ESR measurements at cryogenic temperatures were carried out with
Bruker E500 and E680 spectrometers equipped by Oxford 900 and CF935 helium cryostats
respectively. Simulations of ESR spectra were carried out by using EasySpin package with
MATLAB program.
X-band ESR spectra of O2@openC60 powder were observed at temperatures from 4K to 64K,
as shown in Fig. 1. The W-band ESR spectrum in toluene solution was also obtained at 10K.
All spectra were recorded at the position of resonance field expected from the energy levels of
the spin system with S=1, and wellsimulated by using ESR parameters in
Table.1. The temperature dependence of
signal intensity correctly obeyed the
Boltzmann statistics in the energy levels
without any unexpected broadening
effect.
Table.1 ESR parameters of O2@openC60g

D / cm-1

E / cm-1

ΔH / mT

2.0023

3.73

0.015

20

[1] Hideo Kon, J. Am. Chem. Soc. 95, 1045-1049(1973).
Corresponding Author: Tatsuhisa Kato
Tel: +81-75-753-6695, Fax: +81-75-753-6695,
E-mail: kato.tatsuhisa.6e@kyoto-u.ac.jp

Fig.1 X-band ESR spectra of O2@openC60 powder
observed at 4K, 8K, 16K, and 20K (Obs.). And
simulated spectra (Sim.).

- 140 -

3P-3
Macroscopic Preparation and Isolation of La@C60
as a Trifluoromethyl Derivative○Katsuma Ishino1, Shinobu Aoyagi2, Haruka Omachi1, Zhiyong Wang1, Hiroyuki Niwa1,
Ayano Nakagawa1, Ryo Kitaura1, and Hisanori Shinohara1
1

2

Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan.
Department of Information & Biological Science, Nagoya City University, Nagoya
467-8501, Japan.

The macroscopic preparation and isolation of M@C60-type
metallofullerenes has been a long-standing challenge in fullerene
science, since M@C60 is one of the most interesting fullerenes due
to its theoretically predicted fascinating properties likesuperconductivity. Although the first production of La@C60 canbe traced back to a week after the discovery of C60 in 1985 [1], its
complete separation/purification has not yet been achieved.
Highly reactive La@C60 has led to readily form insoluble

Fig. 1 A schematic view of

La@C60polymers in arc-processed soot. This has precluded so far theisolation of La@C60 from other fullerenes by liquid chromatographic techniques.
Here we demonstrate the first isolation of the missing metallofullerene La@C60 as atrifluoromethyl derivative, which was prepared by using the in situ exohedral trifluoromethyl

functionalization method we developed[2]. Solubilization of La@C60 by trifluoromethyl groups
can lead to chromatographic separation. In laser desorption mass spectroscopy of the isolated
derivative, an intense peak of La@C60(CF3)4 was observed with their fragments (Fig. 2). Opticalabsorption analyses indicate that the HOMO- LUMO gap of La@C60(CF3)4 is ca.1.7 eV,suggesting that this derivative is almost as stable as C60.
(a)

(b)

Fig. 2 MALDI-TOF mass spectrum (a) and optical absorption spectrum (b) of La@C 60 derivative.
[1] J. R. Heath et al., J. Am. Chem. Soc., 107, 7779 (1985). [2] (a) Z. Wang et al., Angew. Chem. Int. Ed., 52,
11770 (2013). (b) Z. Wang et al., Angew. Chem. Int. Ed., early view.
Corresponding Author: Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442, E-mail: noris@nagoya-u.jp- 141 -

3P-4
Preparation, Structural Determination, and Characterization ofElectronic Properties of Carbosilylated Sc3N@Ih-C80○Takeshi Sugiura1, Shinpei Fukazawa1, Kyosuke Miyabe1, Masahiro Kako*,1, Masanori
Yasui1, Michio Yamada2, Mitsuaki Suzuki2, Yutaka Maeda2, Takeshi Akasaka2,3,4
1

Department of Engineering Science, The University of Electro-Communications, Chofu,
Tokyo 182-8585, Japan2
Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
3
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan
4
Foundation for Advancement of International Science, Ibaraki 305-0821, JapanThe chemical functionalization of endohedral metallofullerenes (EMFs) has been
extensively exploited from the synthetic viewpoints of various applications [1]. For
example, the introduction of a silicon-based functionality into fullerene cages induces
remarkable changes in the electronic characteristics of fullerenes. The photoreaction ofdisilirane with Sc3N@Ih-C80, which is the most abundant and well-studied trimetallic

nitride template (TNT) EMF, has been reported to afford the corresponding bis-silylated
adduct with significant electronic properties [1]. Conversely, the reaction of
Sc3N@Ih-C80 with silylene, which is a monosilylating reagent, provided trace amountsof silylated products, whereas the addition of silylene to Lu3N@Ih-C80 affordedmonosilylated adducts in moderate yields [2]. These results prompted us to study
complementary bis-silylation and monosilylation reactions for the utilization of TNT
EMFs as functional materials. Very recently, we reported the preliminary result thatphotoreaction of Sc3N@Ih-C80 with silirane 1a afforded two [5,6]-carbosilylated adducts
2a and 3a, and one [6,6]-adduct 4a [3]. However, the characterization of 4a wasunsuccessful owing to its low product yield. Herein, we describe the details of thesynthesis, characterization, and electronic properties of the carbosilylated Sc3N@Ih-C80
obtained by photoreaction with 1b.
Scheme 1.
+

Si

h!

Si
R

Sc3N@Ih-C80

R

R

R

tBp

1a : R = Dmt
1b : R = Dep

R
R

tBp

Dmt =

R

tBp
2a-4a: R = Dmt
2b-4b: R = Dep

tBp

Si
R
2a, 2b: R = Dmt
3a, 3b: R = Dep

Si

Dep =

tBp =
4a: R = Dmt
4b: R = Dep[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).
[3] M. Kako et al. Phosphorus, Sulfur, and Silicon and the Related Elements. in press.
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 142 -

3P-5
Pressure-induced transformations and light irradiation effects on
ferrocene-doped C60 nanosheets○Kyohei Kato1, Hiromichi Gonnokami1, Hidenobu Murata1, Masaru Tachibana1
1

Department of Nanosystem Science, Yokohama City University, 22-2 Seto, Kanazawa-ku,
Yokohama 236-0027, Japan

Micro- and nano-crystals of fullerene C60 have attracted much interest due to theirunique morphologies, structures and properties depending on solvents or dopants containedin C60 lattices. Recently, it was reported that ferrocene-doped C60 (C60(Fc)2) nanosheetswith layer structure alternating C60 and ferrocene layers exhibited unique pressure-induced
transformations, e.g. reversible polymerization of C60 at room temperature [1,2]. These are
due to the charge transfer from ferrocene to C60 and the limited polymerization in 2D layerof C60 under pressure. We found that higher pressure gives rise to new polymeric phase of
C60. In addition, light irradiation led to not only the promotion of the pressure-induced
transformations but also their modification. In this paper, we report the pressure-induced
transformations of ferrocene-doped C60 nanosheets up to 12.5 GPa and their lightirradiation effect.
C60(Fc)2 nanosheets were prepared by liquid-liquid interfacial precipitation method, inwhich an interface was formed between isopropyl alcohol and toluene [3]. For the highpressure studies, a diamond anvil cell of CLOCK type generated pressrue and rubyluminescence method was used for pressure determination. Samples and ruby ball were
loaded into a 300 µm diameter hole in a stainless-steel gasket. Silicone oil was used aspressure medium. The pressure-induced transformation of C60(Fc)2 were observed in insitu Raman measurements at room temperature with a 532 nm Nd:YVO4 as excitation. The
excitation laser also served as the light irradiation.
The pressure dependence of the Raman spectra exhibits two main changes at 1.0 and 2.8
GPa, respectively. The former is the discontinuous change of the slope of the pressure
dependence of the peak position of main Raman bands in C60 and ferrocene. The latter isthe appearance of the shoulder, i.e. new peak, at the lower frequency than original Ag(2)one of C60 by 10 cm-1. These changes are associated with the orientation disorder-ordertransition and polymerization of C60, respectively. It should be noted that higher
compression at 12.5 GPa gives rise to new peaks at lower frequencies. These peakfrequencies are much lower than original Ag(2) one by 18 and 25 cm-1, which are in good
agreement with those of L-shape and 2D tetragonal polymeric phases, respectively,
reported previously [4]. These polymeric phases are reversible with the pressure, which are
different from those by light irradiation and high pressure and temperature reported
previously [5]. These features of the pressure-induced polymers in C60(Fc)2 will be
discussed comparing with the results by light irradiation.
[1] W. Cui et al., J. Phys. Chem. B 116, 2643 (2012), [2] K. Kato et al., Trans. Mat. Res. Soc. Japan (inpress), [3] T. Wakahara et al., J. Am. Chem. Soc. 131, 9940 (2009), [4] D. Porezag et al., Phys. Rev. B 52,
14963 (1995), [5] A. M. Rao et al., Science 259, 955 (1993).
Corresponding Author: M. Tachibana
Tel & Fax: +81-45-787-2307
E-mail: tachiban@yokohama-cu.ac.jp- 143 -

3P-6
Electronic and magnetic properties of pentaorgano[60]fullerenes under anexternal electric field○Sho Furutani and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba
Tennodai, Tsukuba 305-8571, JapanDue to the moderate chemical reactivity of fullerene molecules, fullerenes can form thevarious derivatives by attaching the functional groups onto the covalent network, which areconstituent materials of photovoltaic and organic semiconductor devices. On the other hand,chemically functionalized fullerenes possess unusual electronic and magnetic properties dueto the segmentation of their spherical π electron systems. Indeed, pentaorgano and decaorgano
C60 molecules exhibit various spin polarized states as the ground states depending on thearrangement of functional groups attached to the cage. In the present work, we investigate theelectronic and magnetic properties of pentamethyl C60 (C60(Me)5) and pentaphenyl C60(C60(Ph)5) under an external electric field by using the density functional theory combinedwith the effective screening medium method.
Before examining the magnetic properties of C60(Me)5 and C60(Ph)5 under the electric field,
we investigate the electrostatic properties of these pentaorgano C60. Due to the asymmetric πelectron network and the attached functional groups, the molecule has large potential
difference between head and tail of 0.62 V arising form the dipole moment of the molecule.
Five functional groups are attached to the C atoms surrounding one of twelve pentagons,leading to the spin polarization on the segmented pentagonal ring. Our calculation shows thatthe polarized electron spin on the pentagonal ring is robust against the carrier injection by theexternal electric field. Figure 1 shows the number of polarized electron spin, Δρ = ρup−ρdn, asa function of the number of injected carrier. Injection of 1 hole into molecule leads to thetriplet spin states with S=1 due to the doubly degenerated singly occupied states. On the other
hand, the electron injection leads to the nonmagnetic ground states as the case of
cyclopentadienyl anion. Furthermore, the number of polarized spin gradually decreases withincreasing the electrons.

Fig.1: The number of polarized
electron spin as a function of
injected carriers.

Corresponding author: S. Furutani
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: sfurutani@comas.frsc.tsukuba.ac.jp- 144 -

3P-7
	  Influence of deformations of carbon nanotubes on carrier accumulation
under an electric field
Akiko Hasegawa and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba 305-8571, Japan

It has been demonstrated that semiconducting carbon nanotubes (CNTs) can work as the conducting
channel of field-effect transistors (FETs). In FET, it is plausible that the CNTs are deformed by theinteraction with the substrates and other CNTs. However, it is still unclear how the carrier
accumulation in CNT by the gate electrode depends on the structural deformation of CNTs in the FET
structure. Thus, in the present work, we aim to investigate the influence of CNT deformation on
carrier accumulation under the electric field by the gate electrode. All calculations are performed in
the framework of the density functional theory (DFT) with local density approximation combining
with the effective screening medium method to apply the external field on CNTs. In this work, we
consider the structural model in which the deformed CNT is located above the planar gate electrode tosimulate the CNT-FET device structure. As for the deformed CNTs, we consider (20,0) CNT withcircular, squashed, and ellipsoidal cross sections.
Figure 1 shows the contour plot of the accumulated electrons by the external electric field. The
injected electrons are mainly distributed at the electrode side of the CNTs. In addition to the electrodeside of the CNT, we find the electron depletion and accumulation throughout the CNT, depending on
their cross sections. For the circular CNT, charge oscillation occurs along their circumference [Fig.
1(a)]. In contrast, for the squashed and ellipsoidal CNTs, the electron density oscillates along thenormal to the CNT walls [Figs. 1(b) and 1(c)]. In accordance with the carrier accumulation depending
on CNT shapes, capacitance also depends on the cross section of CNTs.
Figure 2 shows the contour plot of the electrostatic potential and vector plot of the electric field of
CNTs with the 0.2 electrons. We can find that the field concentration occurs around protruded areas
with large curvature of circular and squashed CNTs [Fig. 2(a) and 2(b)]. On the other hand, the field
does not concentrate for the CNT with the ellipsoidal shape [Fig.2 (c)].
Fig.1: The contour plot of thecharge redistribution of CNTs with(a) circular, (b) squashed, and (c)ellipsoidal cross section under the
positive gate voltage injecting 0.2
electrons.
Fig.2: The contour and vector plotsof electrostatic potential and electricfield, respectively, of CNTs with (a)circular, (b) squashed, and (c)ellipsoidal cross sections under the
positive gate voltage injecting 0.2
electrons.
Corresponding Author: A. Hasegawa
Tel: +81-29-853-5921, FAX: +81-29-853-5924
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 145 -

3P-8
Exact Extraction of Transfer Length at Metal/Carbon Nanotube Contacts
by Improved Transmission Line Method
1,3

1,3

1

○Noriyuki Tonouchi , Hiroyuki Endoh , Fumiyuki Nihey ,2

2,3

Tomoyuki Yokota , and Takao Someya

1

Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
Phone: +81-29-850-1157 E-mail: n-tonouchi@ab.jp.nec.com
2
Department of Electrical Engineering, School of Engineering,
The University of Tokyo, Tokyo 113-8656, Japan
3
Institute for Nano Quantum Information Electronics, Tokyo 153-8505, JapanTo achieve high-frequency operation of carbon-nanotube thin-film transistors (CNT-TFTs), it isessential to reduce parasitic capacitances between device constituents such as a gate and a drain.
Previously, we have reported high-frequency back-gated CNT-TFTs with narrow source/drainelectrodes whose parasitic capacitances are greatly reduced. From a device design viewpoint, theelectrode width (Wel ) should be sufficiently larger than a transfer length (lt ) that scales a region

required for electric carriers to be transferred from an electrode to an overwrapping CNT film at theelectrode edge. In general, transmission line method (TLM) is used to obtain lt by assuming that the

sheet resistance of semiconductor channels that overwrap with electrodes (rsh2) is the same as that in

between the electrodes (rsh1 ) as shown in Fig. 1. For CNT-TFTs, however, rsh2 should differ fromrsh1 because of their very thin channels. Thus, it is necessary to evaluate rsh2 to obtain correct lt . In

this study, we propose improved transmission line method to extract the exact values of rsh2 and lt .

We measured the voltage drop V(Wel) between the CNT film and the metal electrode at the opposite

end of electrode. Figure 2 shows that V(Wel) depends exponentially on Wel, supporting the validity of

our analytical method. Using the values of V(Wel) and contact resistance obtained by conventional
TLM, we successfully extracted the exact values of rsh2 and lt . They are different from thoseobtained by the conventional TLM by an order of magnitude. We revealed that it is necessary to deal

rsh2 and rsh1 separately for the exact extraction of lt and confirmed the effectiveness of our
improved method.

Not detectable
due to the limit

Fig. 1 Equivalent circuit around electrodeFig. 2 Dependence of V(Wel) on Wel- 146 -

3P-9
Experimental investigation of thermal conductivity of single walled carbon
nanotube thin film with infrared thermal imager
Ya FENG1, Makoto WATANABE1, Shuhei YOSHIDA1, Taiki INOUE1, Rong XIANG1,
Shohei CHIASHI1, Shigeo MARUYAMA1,2
1. Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2. Energy NanoEngineering Lab., National Institute of Advanced Industrial Science andTechnology, Tsukuba 305-8564, Japan
In theory, single walled carbon nanotubes (SWNT) have been proven to be withextraordinarily high axial thermal conductivity owing to its unique quasi-one-dimensional
structure1, thus having been expected to mitigate the severe heat dissipation problem in thecontinuously shrinking electronic devices. In its bulk counterpart form, the ballistic phonontransfer is seriously impeded by the tube-tube interface scattering, but the remarkable thermal
conductivity of single SWNT still boost the application of SWNT thin film as a thermalinterface material2. Therefore, researches are extensively conducted, trying to precisely
measure the thermal conductivity of carbon nanotube films grown in laboratory, which still
remains quite a difficulty.
In the present work, we proposed a new method to directly measure the thermal
conductivity of SWNT thin film. Two cantileveredsilicon thin plates (thickness of 100μm) were joinedwith the SWNT thin film in between them, while theother ends were respectively bathed in different
temperatures to form a steady state heat flow along.
With the infrared thermal imager recording thetemperature distribution along the targeted structure,
the silicon plates with known thermal conductivity
can work as a reference to calculate the heat flux
transporting through the SWNT thin film. Repeating
the experiment without the SWNT thin film, the effectof thermal radiation can be neatly deducted.
Thereupon, the thermal conductivity of the SWNT
thin film with 90% transparency is obtained throughFig. 1 The experimental setup andFourier’s law, which is around 22W/m K.
temperature profile.
[1] MS Dresselhaus et al. Adv. Phys. 49 (6), 705-814 (2000).
[2] Tong Tao et al. IEEE T Compon. Pack. T 30 (1), 92-100 (2007).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 147 -

3P-10Emergence of a New Red-Shifted PL from
Chemically-Modified Single-Walled Carbon Nanotubes
Tomonari Shiraishi1, Tomohiro Shiraki1,2, Naotoshi Nakashima1,2
1Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
2 WPI-I2CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan

Single-walled carbon nanotubes (SWNTs) show photoluminescence (PL) in the NIR region
based on the first sub-band transition in chirality-dependent electronic structures and arepromising for a wide variety of applications such as optoelectronic, sensing, and imaging
devices. Therefore, new techniques for controlling emission wavelength would expand SWNT
research fields in not only fundamentals but also applications over the chirality-dependentfeatures. Recently, a very limited amount of chemical modification with aryl functional groups
on SWNT (Ar-SWNT) has been reported to create a new red-shifted PL labeled as E11*, whichshows superior PL properties to those of pristine (non-modified) SWNT in terms of quantum
yields and longer wavelength emission [1]. The E11* PL could be considered due to the band
splitting of the degenerated electronic states of the SWNTs by the structural symmetry-breaking
through the partial chemical modification [2]. Therefore, one can think that chemical
modification would be a key factor to change PL properties with dependence on the chemical
structures of the modified compounds.
In this study, the chemical modification using newly-synthesized compounds having two
reactive groups (2Ar) was examined, resulting in appearance of a new red-shifted PL peak
(E112*) at the longer wavelength region compared to the emission of Ar-SWNT (E11*).
Importantly, the observed E112* at 1255 nm has not been observed for pristine SWNT and ArSWNT. Based on the position of E11 in the pristine SWNT, the shifted value of E112* was 270
nm (271 meV) in 2Ar-SWNT, which was much larger than 150 nm (165 meV) of E11* in ArSWNT. From the absorption spectra of the 2Ar-SWNT, there was little change before and after
the chemical modification indicating that small amount of the chemical modification using 2Ar
induces the new E112* emission. The detailed results and mechanism will be reported at themeeting.
[1] Y. Wang et al., Nat. Chem. 5, 840 (2013).
[2] N. Nakashima et al., J. Phys. Chem. C, in press (2015).
Corresponding Author: Naotoshi Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 148 -

3P-11
Rayleigh Scattering Spectroscopy of Single-Walled Carbon Nanotubes in
Various Surrounding Environments○Toru Osawa1, Takeshi Okochi1, Yoritaka Furukawa1, Taiki Inoue1,
Rong Xiang1, Shohei Chiashi1, Shigeo Maruyama1, 2
1

2

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki, 305-8564, Japan

Single-walled carbon nanotube (SWNT) is one of the most promising materials forelectronic devices such as a field effect transistor because of their high mobility andnanostructure. However, it is known that electronic structures of SWNTs depend not only on
their chiralities, but also on their surrounding environment. Therefore, accurate and in-situ
evaluation of their electronic structures is critical for high performance and reliability ofelectronic devices. Recently, Rayleigh scattering spectroscopy has attracted much attention as
an efficient method to investigate the 1D electronic structure of SWNTs [1, 2].
In this study, we constructed the measurement system and observed Rayleigh scattering
spectra and images of various SWNT samples. The attenuated continuum laser (the range of
wavelength is 400 - 2500 nm) was focused on SWNTs. Scattered light was measured with CCD
array and InGaAs detectors for spectroscopy and with 2D CCD camera for image. We measured
Rayleigh scattering of dispersed SWNTs in the surfactant solutions [3], dry-deposited SWNT
films [4], suspended SWNTs in a slit and horizontally aligned SWNTs on substrates [5]. As one
example, Fig. 1 and 2 show Rayleigh scattering image and a spectrum of a suspended SWNT,
respectively. From these experimental results, we compared characteristic features of SWNT
electronic structures depending on surrounding environments.

Slit

Slit

50 mm

3.1
Intensity [arb. units][1] M. Y. Sfeir et al., Science 306, 1540 (2004).
[2] K. Liu et al., Nat. Nonotechnol. 8, 917 (2013).
[3] H. Liu et al., Nat. Commun. 2, 309 (2011).
[4] A. Kaskela et al., Nano Lett. 10, 4349 (2010).
[5] T. Inoue et al., J. Phys. Chem. C 117, 11804 (2013).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421,
E-mail: maruyama@photon.t.u-tokyo.ac.jp

Energy [eV]2.2
1.3

(19,17)400

600
800 1000
Wavelength [nm]Fig. 1: Rayleigh scattering image of a suspended

Fig. 2: Rayleigh scattering spectrum of a

SWNT.

suspended SWNT.

- 149 -

3P-12
Chemical Bond Formation between Multi-walled Carbon Nanotube andPolyvinyl Benzoate Side Chain through Photo-induced Radical Formation○Tomoya Takada1, Yuya Nishioka 1, Takuma Baba 2
1

Department of Applied Chemistry and Bioscience, Chitose Institute of Science andTechnology, Chitose 066-8655, Japan
2
Graduate School of Photonics Science, Chitose Institute of Science and Technology,
Chitose 066-8655, Japan
Chemical hybridization of polymers and carbon nanotubes (CNTs) is an important
technique for fabrication of functional materials containing CNTs. In this work, we preparedpolysvinyl benzoate derivative having chloromethyl groups on its side chains and attemptedto achieve chemical bond formation of the side chains with multi-walled carbon nanotubes(MWCNTs) by UV light irradiation.
The polymer was synthesized by esterification of polyvinyl alcohol withp-(chloromethyl)benzoyl chloride. Degree of the esterification was estimated by means ofultraviolet absorption spectroscopy. The polymer and MWCNTs were mixed in
1-methyl-2-pyrrolidone and irradiated with UV light (250-385nm) from a xenon light sourceat room temperature for 24 hours. Polymer films were made by solution casting, and X-ray
photoelectron spectra (XPS) and Raman spectra of them were recorded. The XPS wererecorded using the equipment installed in the Laboratory of XPS analysis, Hokkaido
University. Similar UV irradiation and characterization using MWCNTs treated withhydroxylammonium chloride to enhance their dispersion in solvent were also carried out inthe same manner. To observe the temperature change of the samples induced with infrared
light (IR), the samples were irradiated with IR from a xenon light source for 5 min. Theirtemperature changes during and after the irradiation were observed by using a thermal
imaging camera.
	  From the result of elemental analysis based on XPS, it was found that the content of Cl in
the samples decreased after the UV irradiation. Also, on the basis of the Raman spectra,
surface deformation of MWCNTs was observed after theUV irradiation. The similar spectral features were also
observed also in the case of MWCNTs treated withhydroxylammonium chloride. These results support theradical formation from polymer side chains and thechemical bond formation between the radicals and
MWCNTs. While polymer film fabricated without
MWCNTs showed only small temperature change during
IR irradiation, temperature of the film containing
MWCNTs significantly rose with IR irradiation (Fig. 1). Fig.1 Temperature change inducedThis result indicates that the polymer-MWCNT films by IR irradiation.
fabricated in the present way can be used as photothermal
conversion materials.
This work was supported by Nanotechnology Platform Program of the MEXT, Japan, and
JSPS KAKENHI.
Corresponding Author: T. Takada
Tel: +81-123-27-6056, Fax: +81-123-27-6056, E-mail: t-takada@photon.chitose.ac.jp- 150 -

3P-13Single-Step Extraction of Semiconducting Single-Wall Carbon Nanotubes
by Aqueous-Two Phase (ATP) System○Tomohiko Komuro,1 Haruka Omachi,1 Jun Hirotani,2 Ryo Kitaura,1 Yutaka Ohno,2,3and Hisanori Shinohara1*
1

Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya

464-8602, Japan. 2 Graduate School of Engineering, Nagoya University, Nagoya, 464-8603,
Japan, 3 Institute of Materials and Systems for sustainability, Nagoya University, Nagoya,464-8603, Japan
Semiconducting single-wall carbon nanotubes (s-SWCNTs) are promising materials forelectronic devices [1]. However, because the conventional as-grown carbon nanotubes containca. 30 % metallic (m-) SWCNTs, separation is required to obtain high purity s-SWCNTs. In
2013, Zheng and co-workers first demonstrated spontaneous partition of s- and m-SWCNTs
by using aqueous two-phase (ATP) system [2]. The method, however, requires a multi-step
extraction to attain high purity s-SWCNTs. In addition, there has been no study reported onthin film transistor (TFT) fabrication using ATP-extracted s-SWCNTs.
In this work, a rapid and single-step ATP extraction of highly enriched s-SWCNTs isdemonstrated. The extraction with the combination of polyethylene glycol and polysaccharide
yielded >95% purity of s-SWCNTs from arc-discharge samples (Figure 1). After extensive
screenings, we were able to fabricate the s-SWCNTs thin films so-extracted. Figure 2 shows
the AFM image of such s-SWCNTs film, which exhibits a uniform and thin film composed ofisolated CNTs. The electronic measurement of so-fabricated TFT will also be reported in thepresentation.
5 nm

before extraction
after extraction

Absorbance / a.u.

10.00 nm

2.0µm
400

600

800

1000

Wavelength / nm

0 nm

1200

Figure 1. Optical absorption
spectra of SWCNT dispersions[1] D. Park et al., Appl. Phys. Lett., 82, 2145 (2003)

Figure 2. AFM image of extracted
s-SWCNT film
[2] M. Zheng et al., J. Am. Chem. Soc., 135, 6822 (2013)

Corresponding Author: Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442, E-mail: noris@nagoya-u.jp- 151 -

3P-14
Formation of cross-linked polymer network around single-walled carbon
nanotubes
Yusuke Tsutsumi1, ○Tsuyohiko Fujigaya1,2,3, and Naotoshi Nakashima1,2
1 Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,

744 Motooka, Fukuoka 819-0395, Japan

2 WPI-I2CNER, Kyushu University 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
3PRESTO, JST, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

Synthesis of a cross-linked polymer on single-walled carbon nanotubes (SWNTs) is apromising method for functionalization of the SWNTs due to their high coating stability
together with their intactness to the SWNTs. We here reveal a requirement for vinyl
monomers to form such cross-linked polymers on the SWNTs, which is highly important togeneralize this method as well as to develop many polymer-SWNT hybrids with a uniquestructure and functions.
Poly(ethylene glycol) methacrylate (PEG-MA) (average molecular weight (Mn) = 526), N,
N-dimethylacrylamide (DMAAm), methyl methacrylate (MMA), vinyl acetate (VA), methyl
acrylate (MA), acrylamide (AAm) and 2-hydroxyethyl methacrylate (HEMA) were chosen as
the vinyl monomers. N, N’-methylenebisacrylamide (BIS) was used as a cross-linker
monomer. The SWNTs were individually solubilized in a 0.2 wt% sodium dodecyl sulfate(SDS) aqueous solution, to which a specific monomer and ammonium persulfate (APS) as an
initiator were added, then heated at 70 ºC. After heating for 7 h, the obtained solution wasthen filtered (1st filtration) using a membrane filter (molecular weight cut-off = 10,000) toremove any excess amounts of SDS and unreacted monomers, then the precipitate generated
after the redispersion in water was removed by a 2nd filtration using cotton as a filter toprovide an aqueous solution of the polymer-SWNT hybrids[1, 2].
Fig. 1 shows the absorption spectra (b-g) and photographs (i-o) of the aqueous dispersionsof the polymer-SWNT hybrids. As shown in
Figs. 1i-1n, the SWNT/poly(PEG-MA)(SWNT/PPEG),
SWNT/poly(DMAAm)(SWNT/PDMAAm),
SWNT/poly(MMA)(SWNT/PMMA),SWNT/poly(VA)(SWNT/PVA)
andSWNT/poly(MA)(SWNT/PMA)
providedtransparent
black-colored solutions, while a light black
color
was
observed
forthe
SWNT/Poly(AAm) (SWNT/PAAm). In
contrast, an aggregate was formed during the
preparation of the SWNT/Poly(HEMA)(SWNT/PHEMA) (Fig. 1o). The origin ofsuch differences will be discussed [3].
[1] T. Fujigaya et al. RSC Adv., 2014, 4, 6318.
[2] T. Fujigaya et al. Nanoscale 2015, 7, 19534.
[3] T. Fujigaya et al. Chem. Lett., in press.
Corresponding Author: Tsuyohiko Fujigaya
E-mail: fujigaya-tcm@mail.cstm.kyushu-u.ac.jp
Tel & Fax: +81-92-802-2842

Fig.1 (a) Absorption spectrum and (h) photograph of
SWNTs solubilized in SDS aqueous solution. (b-g)
Absorption spectra and (i-n) photographs of thepolymer-SWNT hybrids in an aqueous solution.
Yields of the polymer-SWNT hybrids are also shownin parenthesis. (o) Photograph of SWNT/PHEMA in
an aqueous solution before the 2nd filtration.

- 152 -

3P-15Disulfide bond formation of thiols using single-wall carbon nanotubes○Atsushi Hirano 1, Momoyo Wada 1, Takeshi Tanaka 1, Hiromichi Kataura 1
1

Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8565, Japan

Carbon nanotubes are known to be oxidized by O2/H2O redox couple in aqueous solutions.
Such oxidation reaction is reversible and can be reduced by reductants. Recently, thiols, e.g.
cysteine and dithiothreitol (Fig.1), are reported to have ability to reduce the oxidized carbon
nanotubes [1,2]. However, the mechanism of the reduction remains unclear. In this study, wedemonstrated that two thiol groups form a disulfide bond through the reduction reaction. The
disulfide bond formation was also found to occur on the matrices immobilizing carbon
nanotubes in a liquid chromatography system.
Suspension of carbon nanotubes, whichO
were synthesized by the HiPco process,OH
containing cysteine was subjected toSHOHHSultrasonication. Supernatant of the suspension HS
NH2OH
was collected after ultracentrifugation. Fig.2A
shows absorption spectra of cysteine in the
Cysteine
Dithiothreitol
supernatants in presence and absence of the
carbon nanotubes. A spectral shoulder was
Fig.1 Chemical structure of cysteine andobserved around 250 nm in the presence of thedithiothreitol
carbon nanotubes, which is correspond to
disulfide bond. Similar results were also
obtained for other thiols such as dithiothreitol(data not shown). Fig.2B shows absorption
spectra of carbon nanotubes dispersed in 1%
SDS at different concentrations of cysteine.
The spectral intensities in S11 bands were foundto be restored by the addition of cysteine. It
was thus concluded that thiols reduce thecarbon nanotubes and then form disulfide
Fig.2 (A) Absorption spectra of cysteine
bonds. The reaction was also available on
subjected to ultrasonication in the presence andabsence of the carbon nanotubes. (B)matrices immobilizing the carbon nanotube in a
Absorption spectra of the carbon nanotubes atliquid chromatography system (data not shown).
different cysteine concentrations.
This system is reusable and will be useful as achemical reactor for thiols.
[1] N. V. Kurnosov; V. S. Leontiev; A. S. Linnik; V. A. Karachevtsev. Chem. Phys. Lett. 623, 51 (2015).
[2] S. Sen; F. Sen; A. A. Boghossian; J. Q. Zhang; M. S. Strano. J. Phys. Chem. C 117, 593 (2013).
Corresponding Author: A. Hirano
Tel: +81-29-849-1064, Fax: +81-29-861-2786
E-mail: hirano-a@aist.go.jp- 153 -

3P-16
Thermoelectric characterizations of carbon nanotube/curable resin○Wenxin Huang1, Tsuyohiko Fujigaya1,2,3, and Naotoshi Nakashima1,2
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
744 Motooka, Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
3
PRESTO, JST, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

Polymer composites containing carbon nanotubes (CNT/polymer) are a promisingthermoelectric (TE) material, due to their high electrical conductivity of the CNTs together
with the low thermal conductivity of the polymers. Previously, we reported that thesingle-walled carbon nanotubes (SWNTs) can be homogeneously embedded in thephoto-curable resin matrix (R712, Kayarad, Nihon Kayaku) and the thermal conductivity of
SWNTs has severely suppressed [1], which suggests that the composite (SWNT/R712) is apotential TE material. In this work, we first optimized the preparation condition such as
mixing technique to improve the electrical conductivity. Then we fabricated the composite
films (CNT/R712) with different CNT loading amount using three types of CNTs andevaluated their TE properties.
SWNTs (HiPco, Unidym) were added to R712 and mixed by tube homogenizer (Tube drive
VT-1, BioLabs), bead mill homogenizer (Tube drive VT-1, BioLabs) and tip homogenizer(Polytron, KINEMATICA), respectively, for 30 min (4000 rpm). The obtained pastes were
further mixed after adding 1 wt % of photo-initiator (IRGACURE819) and then degassed for
10 min by conditioning mixer (THINKY) at 2200 rpm. The pastes poured into the molds (50µm in depth) were exposed to UV light (high pressure Hg lamp, SEN, LIGHTS CORP.) for 4
min to initiate the curing reaction to afford HiPco/R712 films. SWNTs (eDIPS, Meijo) andmulti-walled carbon nanotubes (MWNTs, Nikkiso) were used as CNTs in the same fashion toprepare eDIPS/R712 and MWNT/R712 films by tube homogenizer.
Figure 1 shows HiPco/R712 films fabricated by 3 different homogenizers and we foundthat the film prepared by the tube homogenizerabc(Figure 1a.) demonstrates the best dispersibility, as
clearly indicated by its color. Indeed, surface
resistivity measurements revealed this film showed alower resistance value (4.46×104 Ω/sq.) than the
Figure 1. Photos of films prepared by tube
homogenizer (a), bead mill homogenizer
films prepared by bead mill homogenizer (Figure 1b.
(b) and tip homogenizer (c), contained 0.1>107 Ω/sq.) and tip homogenizer (Figure 1c. >107
wt% of HiPco SWNTs.
Ω/sq.). Tube homogenizer dispersion was applied toprepare HiPco/R712, eDIPS/R712 and MWNT/R712 films and their TE properties (Table 1.)
were measured. We found eDIPS/R712 film illustrates the highest ZT value due to the highelectrical conductivity and Seebeck coefficient. Since CNT/R712 was viscous solution
before curing reaction, we can expect the printable fabrication of integrated TE device withthis material.
Table 1. The TE properties of CNT/R712 films (0.5 wt%) prepared by the tube homogenizer
HiPco/R712
eDIPS/R712
MWNT/R712-1Electrical conductivity (S m )
2.459
4.902
1.683
Seebeck coefficient (µV K-1)
30.10
52.57
25.90
Thermal conductivity (W m-1 K-1, through plane)
0.247
0.300
0.277
-6
-6
ZT
2.699 × 10
13.64 × 10
1.236 × 10-6
[1] T. Fujigaya, T. Fukumaru, and N. Nakashima, Synth. Met., 2009, 159, 827-830. Tel & Fax: +81-92-802-2842
Corresponding Author: Tsuyohiko Fujigaya E-mail: fujigaya-tcm@mail.cstm.kyushu-u.ac.jp- 154 -

3P-17
Environmentally Stable Carrier Doping into Carbon Nanotube Films
by Extraordinary Molecular Lewis Acid
○Kazuma Funahashi1, Naoki Tanaka2, Yoshiaki Shoji2, Ko Nakayama3, Kaito Kanahashi1,
Hiroyuki Shirae1, Suguru Noda4, Takanori Fukushima2 and Taishi Takenobu1,3,5
1Department of Advanced Science and Engineering, 3Department of Applied Physics,
4
Department of Applied Chemistry, Waseda University, Shinjuku, Tokyo 169-8555, Japan
2
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama 226-8503, Japan
5
Kagami Memorial Laboratory, Waseda University, Shinjuku, Tokyo 169-0051, Japan
Carbon nanotube thin films (CNT-TFs) are one of the most promising materials as analternative for commonly-used indium tin oxide (ITO) transparent electrodes because they aremuch flexible than ITO and high performance (sheet resistance (RS) of 50-100Ω/sq at 85-90%transmittance) is realized by the chemical doping. However, in most previous reports, doped
CNTs are not stable to air, including the hole doping by nitric acid, which is the mostcommon doping method. In the nitric acid doping, it is reported that the 240-hours storing of
doped samples in air results in 30% increase of RS [1] and, thus, air-stable carrier dopants arestrongly required for practical application. Therefore, in this work, we focus on the
combination of the super Lewis acid, diarylborinium ion (Mes2B+; Mes (mesityl) = 2, 4,
6-trimethylphenyl) and thermally-stable counter anion, tetrakis (pentafluorophenyl) borate([(C6F5)4B]-) (Fig.1) [2] as the novel air-stable dopants.
We used CNTs grown by enhanced direct injection pyrolytic synthesis method(eDIPS-CNT). These CNT thin films were immersed into the saturated o-dichlorobenzene
solution of dopant, Mes2B+ [(C6F5)4B]-. As a reference, the nitric acid doping was also
conducted. Before and after the above doping processes, we characterized these films by
Vis-NIR absorption spectroscopy and four-probe resistance measurement. As a result, we
confirmed the carrier doping into CNT films by both absorption and conductivity
measurements, resulting in RS reduction of -35% and one-month stability (Fig.2). Importantly,
this RS reduction is comparable to that of nitric acid and the stability is much superior.
In summary, we succeeded in air-stable carrier doping to CNT-TFs by the novel dopants,
Mes2B+ and [(C6F5)4B]-, which promotes the use of CNT-TFs as future transparent electrodes.

Fig. 1 Novel dopant; cation, Mes2B+ andcounter anion, [(C6F5)4B]-

Fig. 2 Time evolution of Rs increase in CNTs
doped by nitric acid and novel dopant[1] R. Jackson et al., Adv. Funct. Mater. 18, 2548–54, 2008 [2] Y. Shoji et al., Nat. Chem. 6, 498-503, 2014
Corresponding Author: T. Takenobu Tel & Fax: +81-3-5286-2981, Email: takenobu@waseda.jp- 155 -

3P-18
Effect of catalyst support on growth lifetime of carbon nanotube forest○Takashi Tsuji, Shunsuke Sakurai, Maho Yamada, Don N. Futaba, Kenji Hata
CNT-Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, 305-8565, Japan
Chemical vapor deposition (CVD) of vertically aligned carbon nanotube forest is one of
the most powerful methods for a mass production of single-walled carbon nanotubes(SWNTs). To achieve a high efficiency in the above method, aluminum oxide (Al2O3) isfrequently used as a key material for catalyst support. The important role of Al2O3 has beenreported as the immobilization of iron particles to maintain small and homogeneously-sizedcatalyst particles during the CVD process. Magnesium oxide (MgO) is also known as thecatalyst support for the growth of SWNT forest [1], though a SWNT forest higher than 100
μm has not been obtained yet. Amama et al. showed that subsurface diffusion of Fe catalyst
on MgO support is much higher than that on Al2O3 support, and predicted a short lifetime of
the catalyst on MgO support than catalyst on Al2O3 support [2].
In this study, we analyzed the growth curves (temporal changes in height) of CNT forest
synthesized on Fe/MgO and Fe/Al2O3 catalyst systems. In our experimental conditions, thetermination of CNT forest growth was always observed within 2 min on MgO support, thougha long catalyst lifetime (>10 min) was confirmed on Al2O3 support. As a result, the height of
CNT forest on MgO support was not higher than 200 m. AFM observation shows thedisappearance of Fe catalyst particles from the surface of MgO support within 5 minutes ofannealing in the growth ambient without carbon feedstock, while the size and number densityof Fe catalyst on Al2O3 support remain even after 10 minutes. These results indicate that ashort growth lifetime of CNT forest on MgO is due to strong subsurface diffusion of Fe
particles into support layer.
[1] C. Pint et al. J. Nanosci. Nanotech. 8, 6158 (2008).
[2] P. B. Amama et al. Carbon 50, 2396 (2012).
Corresponding Author: S. Sakurai
Tel: +81-29-861-4654, Fax: +81-29-861-4851,
E-mail: shunsuke-sakurai@aist.go.jp- 156 -

3P-19Comparison between Reduced and Intentionally Oxidized Metal Catalysts
for Growth of Single-Walled Carbon Nanotubes○Yang Qian1, Rong Xiang1, Hua An1, Taiki Inoue1, Shohei Chiashi1, Shigeo Maruyama1, 2
1
2

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8564, Japan

Many efforts and progresses have been made in the past decades towards controlled
production of single-walled carbon nanotubes (SWNTs). However, as the pearl of the crown,
direct growth of SWNTs with defined structures and properties has been the bottleneck for
decades [1]. This is strongly associated with the insufficient understanding of the catalytic
formation process of SWNTs and thereby absents control over the product.
One important ingredient for efficient growth of SWNTs is the oxygen atmosphere. Besides
the ethanol in alcohol catalytic chemical vapor deposition (ACCVD) [2], the water or oxygengas in the super-growth also shows the important role of oxygen in the synthesis of SWNTs [3,4]. However, the detailed mechanism how oxygen affects the catalysts or carbon deposition isstill not yet fully clarified. In addition, some un-disclosed factors like chamber impurities androom moisture are often related with nanotube growth [5]. Therefore, a careful investigation on
the catalytic behavior of oxide particles may also help to understand the effects of un-intentional
catalyst oxidation that possibly exists sometimes, and hopefully the robustness of CVD process
could be improved hereafter.
In this presentation, we perform a detailed comparative study on the catalytic behavior of
metallic and oxidized particles in CVD synthesis of SWNTs. Intentionally oxidized Co particles
are found also capable of growing SWNTs but the yield is significantly decreased. Meanwhile
the SWNTs grown from oxidized particles show a smaller and narrower diameter distribution.
X-ray photoelectron spectroscopy and in-plane transmission electron microscopy studies revealthat Co particles, though in CoO form before growth, are quickly reduced into metallic form by
ethanol through an in-situ reduction process. However, this reduction process is strongly sizedependent and smaller particles are
preferably reduced to grow SWNTs,
resulting in the absence of larger-diameter
SWNTs in the product. Accordingly,
nucleation density decreases significantly
and SWNT morphology changes fromvertically aligned arrays to thin random
networks. Our strategy has been further
applied to Ni and the results are similar. Ourfindings are insightful for controlling thediameter and morphology of the produced Fig.1 (a) Experimental flow of pre-reduction and
SWNTs, as well as for improving the oxidation CVD processes. (b) SEM images of the asreproducibility and robustness of CVD grown SWNTs from two CVD processes. (c) Raman
spectra of the as-grown SWNTs from two CVD processes.
process.
[1] T. Ebbesen et al. Nature 382, 54 (1996). [2] S. Maruyama et al. Chem. Phys. Lett. 360, 229 (2002). [3] K. Hata
et al. Science, 306, 1362 (2004). [4] G. Zhang et al. Proc. Natl. Acad. Sci. U. S. A. 102, 16141 (2005). [5] C.
Oliver et al. ACS Nano, 7, 3565 (2013). Corresponding Author: S. Maruyama, Tel: +81-3-5841-6421, Fax: +813-5800-6983, E-mail: maruyama@photon.t.u-tokyo.ac.jp- 157 -

3P-20Controlled synthesis of single-walled carbon nanotubes
with sputtered W-based catalyst
Hua An1, Rong Xiang1, Hiroki Takezaki1, Shinnosuke Ohyama1, Yang Qian1,
Taiki Inoue1, Shohei Chiashi1, Shigeo Maruyama1,2
1. Department of Mechanical Engineering, the University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo,113-8656, Japan
2. Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), 1-2-1 Namiki, Tsukuba, 305-8564, JapanThe application of single-walled carbon nanotubes (SWNTs) in nanodevices is limited by the
impurities and mixed chiralities of SWNTs assemblies. Great efforts have been made in the
purification and separation of SWNT mixtures. However, direct synthesis of SWNTs with single
chirality is more challenging but attracts considerable attention among researchers. CoW clusters
were recently reported to grow a single chirality, (12, 6) with over 90% abundance via hightemperature (1030ºC) reduction and growth [1]. By further control of the catalyst structure andgrowth conditions, a zigzag SWNT (16, 0), with near 80%, was obtained [2].
In this report, we show that a sputtered CoW catalyst can selectively grow (12, 6) SWNTs by
low pressure chemical vapor deposition at low temperature [3]. Statistical Raman mapping
analysis and optical absorption spectrum of the as-grown SWNTs reveal that the abundance of(12, 6) is over 50%. Parametric study of this CoW bimetallic catalyst system demonstrates thatthe reduction temperature before growth is critical for the intermediate catalyst structure and theselectivity. Moreover, the morphology and structure of catalyst is investigated by electron
diffraction, which discloses the complicated structure changes before and after growth. Further
study is needed to optimize conditions to obtain better chirality control of SWNTs.
[1] F. Yang et al., Nature. 510, 522(2014).
[2] F. Yang et al., J. Am. Chem. Soc. 137, 8688 (2015).
[3] S. Maruyama et al., Chem. Phys. Lett. 360, 229 (2002).
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 158 -

3P-21
Molecular dynamics simulation of single-walled carbon nanotubes
grown from binary catalyst○Yukai Takagi1, Ryo Yoshikawa1, Shohei Chiashi1 and Shigeo Maruyama1,2
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8564,
Japan
1

2

Atomic scale simulation is important for analyzing the growth mechanism of
single-walled carbon nanotubes (SWNTs). In molecular dynamics (MD) simulations, it has
been observed that high quality SWNTs are grown from monometallic catalysts such as Co
and Fe [1]. Some experiments have indicated the possibility that, by using binary (W-Co)
catalysts, chirality of SWNTs can be controlled to a certain extent [2]. Therefore, simulationsof SWNT growth from binary catalyst are desired for analyzing the function of binary alloy
catalysts.
For expressing the interaction between W, Co and C, we newly made Tersoff-type
potentials based on density functional theory calculation and genetic algorithm [3]. Then, we
performed classical MD simulations by preparing a metal cluster with 60-104 atoms in aperiodic cell (10×10×10 nm3 , 1350-1500K) and supplying carbon atoms to the cell withkeeping maximum 3 carbons in the cell. The catalyst contained 50-55 % Co and 45-50% W.
We set up two types of initial position that W and Co atoms were alternately arranged and that
W and Co were placed separately in two segments.
In simulations, the W-Co catalysts were solid and the structure of catalysts depended on
the initial condition to some extent. It was observed that C atoms which bonded to W atoms
did not connect another C atoms, and C atoms which formed cap structure were bonded to not
W but Co. The Cap formation occurred fairly faster and SWNTs were grown more rapidly on
W-Co catalyst than on monometallic catalysts [1]. It is suggested that Co has a main functionof growing SWNTs and that W stabilizes the structure of catalysts and accelerates the lift-off
of cap structure.
(a)

W atom(b) Cap formation

(c)
SWNT

Co atom

Fig. 1 Snap shots of SWNT growth in MD simulations. (a) W-Co catalyst (W42Co36)
after anneal process, (b) Cap formation and (c) SWNT growth.
[1] K. Hisama et al., to be submitted.
[2] F. Yang et al. Nature, 510 (2014) 522.
[3] T. Kumagai et al. Modelling Simul. Mater. Sci. Eng. 14 (2006) S29.
Corresponding Author: Shigeo Maruyama Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 159 -

3P-22
Quantifying the purity of semiconducting/metallic fractions
in ELF separation of SWCNTs○Yuki Kuwahara1,3, Fusako Sasaki1, Fumiyuki Nihey2, Hiroyuki Endoh2, Shinichi Yorozu2,
Takeshi Saito1,3*
1Technology Research Association for Single Wall Carbon Nanotubes,
Tsukuba 305-8565, Japan
2
Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
3
National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565, Japan
The purity characterization of semiconducting/metallic single-wall carbon nanotubes(SWCNTs) is important not only for the development of separation processes, but also for theinvestigation of semiconductor devices. Because it is well known that the purification ofsemiconducting SWCNTs considerably improves the performance of their semiconductor
devices, further highly purified semiconducting SWCNTs are demanded for their integrations
and practical uses [1]. Spectroscopic characterization methods such as optical absorption andresonance Raman are commonly used for their purity evaluation. However, when the purity
becomes high, it is difficult to quantify it precisely. In this work, we report an evaluation
method for the purity of the metallic/semiconducting SWCNTs separated by theelectric-field-induced layer formation (ELF) method [2] based on the analysis results of
optical absorption spectra.
In ELF separation, we can fractionate the pristine SWCNTs with the semiconductor purityof ca. 66% into semiconductor- and metal-enriched fractions without any apparent changes inthe diameter distribution. In this situation, when we subtract the normalized spectrum of
metal-enriched fraction from that of the pristine appropriately, only the contribution of thesemiconducting SWCNTs in the pristine should be obtained. Figure 1 shows a typical analysis
result of absorption spectra of separated SWCNTs. Here, the spectrum shape of calculated
semiconducting SWCNTs was surely obtained from the normalized spectra of pristine andmetal-enriched fraction. By using the calculated spectra of metallic and semiconducting
SWCNTs, we quantified the metallic/semiconducting ratio/purity of separated SWCNTs.
Detailed analysis method will be shown in thepresentation.
㻜㻚㻡

Corresponding Author: T. Saito
Tel: +81-29-861-4683, Fax: +81-29-861-4413, E-mail:takeshi-saito@aist.go.jp- 160 -

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㻜㻚㻟㻡
㻜㻚㻟

㻭㼎㼟㻚

References[1] A. D. Franklin, Nature 498, 443 (2013).
[2] K. Ihara et al., J. Phys. Chem. C 115, 22827 (2011).

㼜㼞㼕㼟㼠㼕㼚㼑㻌㻔㻱㼤㻕㻜㻚㻠㻡

Acknowledgment
This presentation is based on results obtained from a
project subsidized by the New Energy and Industrial
Technology Development Organization (NEDO).

㻜㻚㻞㻡

㻜㻚㻞
㻜㻚㻝㻡
㻜㻚㻝

㻜㻚㻜㻡
㻜
㻜㻚㻡

㻝㻚㻡

㻞㻚㻡

㻟㻚㻡

㻱㼚㼑㼞㼓㼥㻌㼇㼑㼂㼉

Fig. 1 Absorption spectra of pristine (blackline), metal-enriched fraction (gray line) andcalculated semiconducting SWCNTs (dash line).

3P-23
STM/STS studies on Europium nanowires
encapsulated in carbon nanotubes○Terunobu Nakanishi1, Ryo Kitaura1, Shoji Yoshida2,
Osamu Takeuchi2, Hidemi Shigekawa2 , Hisanori Shinohara1
1

Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya,464-8602, Japan
2
Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, 305-8573, JapanThe discovery of carbon nanotubes (CNTs) and their fascinating properties have ignitedintense research interests on one-dimensional nanosystems. Although ultrathin atomic wires
are one of the ideal one-dimensional systems, preparation of the ultrathin wires withdiameters of 1~several nanometers has been difficult. Previously, we have reported thesynthesis and characterization of ultrathin metal nanowires encapsulated in CNTs.[1][2] Here,
we present the preparation and investigation of spatially-resolved electronic structure of Eu
nanowires
encapsulatedin
CNT(EuNW@CNT)
byscanning
tunneling

Figure 1 shows a STS spectrum of EuNW@CNT,
where a new peak due to a localized density ofstates (DOS) of the encapsulated Eu nanowire canbe seen. Figure 2 shows a dI/dV mapping
observed at a bias voltage of -0.4 V, which

䢶dI/dV /a.u.

microscopy/spectroscopy (STM/STS).
EuNW@CNT was synthesized by the direct
nano-filling method[1] and deposited on Au(111)
surface by the pulsed-jet deposition technique.[3]

䢵
䢴
䢳

䢲
䢯䢳䢰䢲

䢯䢲䢰䢷

䢲䢰䢲

䢲䢰䢷

䢳䢰䢲

Sample voltage/V

Fig.1 STS spectra of EuNW@CNT. Black
curve is taken at Eu encapsulated point andgray curve is taken at empty area on the same
CNT.

corresponds to the voltage where the new DOS
peak was observed. The bright region in the dI/dV map corresponds to the position where theencapsulated Eu nanowire locates. Spatially-resolved STS spectra reveal the position of Eu
atoms in EuNW@CNT directly, which leads to a precise assignment of the STS peak and theinteraction between Eu nanowires and CNTs.

[1] R.Kitaura et al. Angew.Chem.Int.Ed. 48, 8298, (2009).
[2] R.Nakanisihi et al. Phys. Rev. B, 86 , 115445, (2012).
[3] N. Fukui et al. J. Nanosci. Nanotechnol. 7, 4267 (2007).
Corresponding Author: H. Shinohara
Tel: +81-52-789-2477, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp and noris@nagoya-u.jp- 161 -

high

2.0nm

low

Fig.2 dI/dV mapping at -0.4 V. A bright spot
on the left side of image is high localized
density of state point where europium
nanowire is encapsulated.

3P-24
Condensation reaction of 5,5"-dibromo-2,2':5'2"-terthiophene
inside single-walled carbon nanotubes○Makoto Sasaki1, Takeshi Koyama1, Hideo Kishida1,
Yukihiro Yoshida2, Gunzi Saito2,3
1

Department of Applied Physics, Nagoya University, Nagoya 464-8603, Japan
2
Faculty of Agriculture, Meijo University, Nagoya 468-8502, Japan3
Toyota Physical and Chemical Research Institute, Nagakute 480-1192, Japan
Single-walled carbon nanotubes (SWNTs) have a one-dimensional (1D) hollow cavity.
Because of the confined space, SWNTs can be utilized as 1D chemical reactors, and various
new 1D materials have been synthesized inside SWNTs [1, 2]. Recently, polymerization ofoligothiophenes and electrochemical doping of the obtained polythiophenes inside SWNTs
have been presented [3]. In the present study, we explore a new and facile synthetic route to
doped conjugated polymers from single-species molecules by thermal polymerization under
low temperatures.
5,5"-Dibromo-2,2':5'2"-terthiophene (Br2-3T) was used as a precursor. Br2-3T molecules
were encapsulated in SWNTs by vapor phase reaction (10-5 torr at 160 °C for 24 h), and themolecules adsorbed outside SWNTs were removed by washing with toluene. The obtained
composite materials are referred to as Br2-3T/SWNT samples. Several pieces ofBr2-3T/SWNT samples were then thermally treated at 265 °C for 24 h for condensation
reaction of the encapsulated molecules. These samples are referred to as Br2-3T/SWNT(T)samples. We also prepared reference samples with terthiophene (3T) molecules as a precursor
using a similar procedure.
The Raman spectrum for the Br2-3T/SWNT sample is shown as a gray line in Figure 1.
Two peaks are observed at 1455 and 1527 cm-1, which are assigned to C=C symmetric andantisymmetric stretching modes of thiophene ring, respectively [4]. The peak positions areclose to those of 3T [4], although slight shifts caused by interactions with SWNTs and/or
bromine-termination are seen. It is suggested that the encapsulated molecules exist as Br2-3T
molecules. A black line in Figure 1 is the Raman spectrum for the Br2-3T/SWNT(T) sample.
The peaks of C=C symmetric and antisymmetric stretching modes show upshift to 1461 cm-1
and downshift to 1506 cm-1, respectively. This result suggests that the number of thiophenerings increased to six [4]; namely, sexithiophene molecules were synthesized in SWNTs.
Optical absorption measurements support the condensation reaction of Br2-3T. Comparisonof the absorption spectra between the Br2-3T/SWNT(T) and reference samples and energy
dispersive x-ray spectroscopy suggest the Br-doping of
the sexithiophenes.
[1] A. V. Talyzin et al. Nano Lett. 11, 4352 (2011).
[2] Y. Nakanishi et al. Angew. Chem. Int. Ed. 54, 10802 (2015).
[3] K. Miyaura et al. The 45th FNTG General Symposium, 1-12,(2013).
[4] Y. Furukawa et al. Synth. Met. 18, 151 (1987).
Corresponding Author: T. Koyama
Tel: +81-52-789-4450, Fax: +81-52-789-4450
E-mail: koyama@nuap.nagoya-u.ac.jp- 162 -

Fig. 1 Raman spectra for Br2-3T/SWNT(gray line) and Br2-3T/SWNT(T) (blackline) samples.

3P-25High-yield Filling of Hydroxylated Diamantane into Carbon Nanotubes○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.
2

Carbon nanotubes (CNTs) are ideal molds for the synthesis of one-dimensional (1D)nanostructures. [1] As a part of our exploration for obtaining novel 1D nanomaterials by the
CNT-templated annealing, we have worked on the syntheses of 1D nanodiamonds fromdiamantane, i.e., the molecule that can be superimposed on bulk diamond. [2] Although theirfabrication has been achieved by the present research group, the yields were relatively low.
One of the reasons lies on the severe inclusion of diamantane. In contrast to π-conjugatedfullerenes, hydrogen-terminated diamantane is not easily taken up by CNTs. Preparation ofhighly filled CNTs must be accomplished to achieve high-yield production of 1D
nanodiamonds, which allows for exploring for their potential applications.
Here we report new findings with regard to
the selective introduction of diamantane skeleton
into CNTs. 1,6-bis(hydroxymethyl)diamantane isinserted into CNTs with high yields under an
optimized condition that inhibits the absorption of
non-substituted diamantane (Fig. 1). Transmission
electron microscopy revealed that the diol
derivative forms a self-assembled structure within
CNTs via a weak interaction. The presence ofhydrogen bonding was inferred from infrared
spectroscopy. This finding should be useful for Fig. 1 Image of 1,6-bis(hydroxymethyl)the design and synthesis of the precursors for 1D diamantane.
nanodiamonds. Detailed discussion will bepresented in the conference.
[1] (a) R. Kitaura et al. Nano Lett., 8, 693 (2008); (b) Z. Wang et al. J. Am. Chem. Soc., 132, 13840 (2010); (c)H. E. Lim et al. ACS Nano, 9, 5034 (2015). [2] (a) J. Zhang et al. Angew. Chem. Int. Ed., 52, 3805 (2013); (b)Y. Nakanishi et al. Angew. Chem. Int. Ed., 54, 10802 (2015).
Corresponding Author: H. Shinohara
Tel: +81-52-789-2482／Fax: +81-52-747-6442／E-mail: noris@nagoya-u.ac.jp- 163 -

3P-26
Vertically oriented Graphite layer formed on hot-implanted diamond (100)surface○Masafumi Inaba1, Wenxi Fei1, Yu Hirano1, Kazuma Suzuki1, Hiroshi Kawarada1
1

Graduate School of Advanced Science and Engineering, Waseda University, Tokyo 1698555, Japan

Carbon nanomaterials, such as graphene and carbon nanotubes (CNTs), are formed on
silicon carbide (SiC) by high temperature thermal annealing without any surface cap layer. Si
atoms combine with oxygen from chamber residual and sublimate as silicon mono-oxide(SiO).[1] The remaining carbon atoms reform the nanocarbon materials. Also, for diamondsurface, graphene layers parallel to the diamond (111) surface is formed by high temperatureannealing.[2] In this study, we investigated the behavior of intercalated carbon atoms caused by
implantation during the high temperature annealing on SiC and diamond using transmission
electron microscopy (TEM).
Aluminum ions were implanted to both 4H-SiC (000-1) face (C-face) and the diamondsubstrate with (100) surface with the density of 1018 cm-3 for 1 μm thickness at the temperatureof 500 ºC. The direction of the implantation was tilted by approximately 7 degrees to avoid
channeling effect. The implantation condition was adjusted to form box profile of aluminum
impurity. The implanted samples were annealed at the temperature of 1700 ºC in vacuum for 2
hours. The sample was observed by high resolution TEM.
Fig. 1 shows a TEM image of the surface graphite layers on SiC from the direction of [1120]. Multilayered graphene sheets were lain on SiC. Fig. 2 shows a TEM image of the surface
graphite layers from the direction of [110]. Vertically oriented carbon layer-like structure wasobserved with the thickness of ~10 nm. This corresponds to the graphite structure, and theinterlayer distance was approximately 0.34 nm (graphite interlayer distance).
The formation mechanism of the vertically oriented graphite (VOG) we suspect is as follows.
A part of the intercalating atoms caused by implantation moved to the surface and forms sp2
layers. Generally, the diffusivity of atoms in diamond is extremely low, but it is possible forvacancies to enhance the diffusivity of atoms. The detail information will be reported on site.

Fig. 1 Cross-sectional TEM imageof graphene layers on SiC (000-1).

Fig. 2 Cross-sectional TEM image of vertically oriented graphite layers
on diamond (100).

[1] M. Kusunoki, T. Suzuki, T. Hirayama, N. Shibata, and K. Kaneko, Appl. Phys. Lett. 77, 4 (2000).
[2] N. Tokuda, M. Fukui, T. Makino, D. Takeuchi, S. Yamsaki, and T. Inokuma, Jpn. J. Appl. Phys. 52, 11R (2013).
Corresponding Author: M. Inaba
Tel&Fax: +81-3-5286-3391 E-mail: inaba-ma@ruri.waseda.jp- 164 -

3P-27
Synthesis Conditions of High-Quality and Large-Size Grapheneby Alcohol CVD○Kohei Tsushima1, Masaki Sota1, Xiao Chen1, Rong Xiang1, Taiki Inoue1, Shohei Chiashi1,
Shigeo Maruyama1, 2
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
Energy NanoEngineering Lab., National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8564, Japan

Graphene has superior mechanical and electrical properties and is expected for applicationof innovative devices. Toward graphene industrialization, it is essential to obtain high-quality
and large-size graphene. The chemical vapor deposition (CVD) is one of the most promising
methods for producing such graphene. CVD growth of graphene on copper foils has beenreported [1] and methane is often used as the carbon source. On the other hand, CVD growthof graphene using alcohol is recently reported [2]. In this study, we investigated synthesis
conditions of graphene by alcohol CVD, and revealed the dependence of synthesis parameterson graphene growth rate.
A typical CVD procedure is as follows: 80-μm-thick copper foils were oxidized at 220 °C
for 60 minutes in air. The pocket structure was formed by folding the copper foil [3]. The
copper foil was put in CVD equipment, heated to 1075 °C with Ar buffer gas, and annealed at1075 °C with Ar/H2 buffer gas for 1 h. CVD was conducted by changing synthesis parameterswith constant growth time of 2 h. The parameters include gas velocity, H2 to ethanol partialpressure ratio, and ethanol partial pressure.
An optical image of the copper foil surface after CVD is shown in Fig. 1. It was oxidized
in air for direct observation of graphene. Several isolated graphene which is considered as
single-crystal is observed. The result shows the maximum growth rate is 1 mm/h, while it was~0.2 mm/h in our previous study [2]. Figure 2 shows the dependence of ethanol partialpressure on growth rate at a constant gas velocity and partial pressure ratio. We found apositive correlation between ethanol partial pressure and growth rate. The effect of otherparameters was also revealed. In conclusion, we succeeded in increasing graphene growth rateby adjusting synthesis conditions.
1.4
1.2

Growth rate (mm/h)[1] X. Li, et al., Science 324, 1312 (2009).
[2] X. Chen, et al., Carbon 94, 810 (2015).
[3] X. Li, et al., J. Am. Chem. Soc. 133, 2816 (2011).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6408, Fax: +81-3-5841-6408,
E-mail: maruyama@photon.t.u-tokyo.ac.jp

1
0.8
0.6
0.4
0.2

0

5 mm

0.2

0.4

0.6

0.8

1

1.2

Ethanol partial pressure (Pa)Fig. 1 Optical image of graphene on thecopper foil.

1.4

Fig. 2 The dependence of ethanol partial pressure
on growth rate.

- 165 -

3P-28Synthesis and Electronic Property of Fe Intercalated bilayer graphene○Ryo Hoshino, Yutaro Hayashi, Nozomi Suzuki,
Tomoko Nagata, Nobuyuki Iwata, Hiroshi Yamamoto
College of Science &Technology, Nihon University, 7-24-1 Narashinodai, Funabashi-shi,
Chiba 274-8501 japan
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 synthesis of Fe intercalated bilayer graphene
and its electric property.
The single-layered graphene sheet was grown on Cu foil by chemical vapor deposition(CVD) method, using CH4, H2 and Ar as process gases. After etching of Cu foil byFe(NO3)3 aqueous solution, the single-layered graphene 㻌was transferred on SiO2/Si substrate. On the single-layered(1)(2) Cu Etchinggraphene, additional single-layered graphene wastransferred again to be bilayer graphene as shown in Fig. 1.
Figure1 shows the Fe intercalation method. The Fe ions in
Fe(NO3)3 aqueous solution during the Cu etching process
was remained between bilayer graphene. From the resultsof SEM-EDX of Fe intercalated bilayer graphene, atomic %of the Fe was 12.40%. This result suggests that bilayer
graphene was intercalated Fe by this intercalation method.
Figure-1. Fe intercalation method㻌

[1] Akimitsu, Parity. MARUZEN. 05, 6-12 (2008).
Corresponding Author: Nobuyuki Iwata
Tel: +81-47-469-5457
E-mail: iwata.nobuyuki@nihon-u.ac.jp- 166 -

3P-29Enhancement of laser-induced water decomposition by 2D sheets studied byfirst-principles simulations○Yoshiyuki Miyamoto1, Hong Zhang2, Xinlu Cheng3, Angel Rubio4
1

Research Center for Computational Design of Advanced Functional Materials, AIST,
Central 2, 1-1-1, Umezono, Tsukuba, 305-8568, Japan
2
College of Physical Science and Technology, Sichuan University, Chengdu 610065, China
3
Key Laboratory of High Energy Density Physics and Technology of Ministry of Education;
Sichuan University, Chengdu, 610064, China
4
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany
Photo-induced water decomposition with aid of photo-catalysis has become a hot topic
since 1979 [1]. Photo-carrier generation and subsequent hole-transfer to water oxidation leveland electron-transfer to reduction level protons are believed to play a main role [2]. Recently
graphitic carbon nitride (gC3N4) sheets are found to assist water decomposition with UV andvisible light [3,4] and usage of graphitic materials as photo-catalysis for water decomposition
seems to be promising.
We here propose application of femtosecond laser, which has higher photon-flux thanordinary light thus can decompose water with higher yield. In this study, we have performed
first-principles molecular dynamics for studying water decomposition under strong laser fieldwith full-width of half maximum 10 fs and basic wavelength of 800 nm. In performing thesimulation, we applied real-time propagation time-dependent density functional theory
combined with Ehrenfest type molecular dynamics under presence of the laser field by using acode FPSEID [5] including optical field [6].
The threshold of laser-field intensity fordecomposing an isolated water molecule wascomputed as 9 V/Å by using local density
approximation and by using the generalized
gradient approximation. On the other hand,
this value is reduced less than 7 V/Å whenwater molecule is located above graphitic
Fig.1 Snapshots of first-principles molecular
dynamics of water decomposition above a
sheets, i. e. graphene, hexagonal boron nitride,graphene sheet
and gC3N4. Fig. 1 shows snapshots of theresults of water decomposition above agraphene sheet. We will discuss possible mechanisms of reducing threshold intensity andfurther applications.
[1] T. Inoue, A. Fujishima, S. Konishi, and K. Honda, Nature, 277, 637 (1979).
[2] J. Wirth, R. Neumann, M.Antoniettib and P. Saalfrank, Phys. Chem. Chem. Phys. 16, 15917 (2014).
[3] X. Wang et al, Nature Mat. 8, 76 (2009).
[4] J. Liu et al, Science 347,970 (2015).
[5] O. Sugino and Y. Miyamoto, Phys. Rev. B59, 2579 (1999).
[6] Y. Miyamoto and H. Zhang, Phys. Rev. B77, 165123 (2008).
Corresponding Author: Y. Miyamoto
Tel: +81-29-849-1498, Fax: +81-29-851-5426,
E-mail: yoshi-miyamoto@aist.go.jp- 167 -

3P-30
Solvothermal preparation of uranium oxide supported on reduced
graphene oxide○Li Ding, Pei Tang, Ding Ma, Yan Li
Key Laboratory for the Physics and Chemistry of Nanodevices, Beijing National Laboratory
for Molecular Science, College of Chemistry and Molecular Engineering, State Key
Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing
100871, China
Uranium oxides have been used as good catalysts for different kinds of reactions owning totheir special structural features and chemical properties [1]. The oxidation state of uranium isa crucial factor influencing its catalytic performance. Thus, the synthesis of pure phaseuranium oxides with different oxidation states is very important for studying their catalytic
properties [2]. Previously, uranium oxide at the nano size were synthesized in a mixture ofoleic acid (OA) and, oleylamine (OAm) which surrounded the surface of particle and further
hindered the application in catalysis [3][4]. In the present work, the uranium oxides loaded on
the reduced graphene oxide (rGO) sheets were synthesized by solvothermal route as shown in
Scheme 1. We found that the composition of the solvent is a key issue for controlling thephase of the products.The water present in the solvent was benefical for the formation of
U3O8.And UO2 was obtained favorablely in the solvent with ethylene glycol.

Schem 1. The formation of uranium oxide/rGO ina two step synthesis process. AUOH is ammonia
uranium oxide hydrate.
[1] Taylor, S. H. et al., Nature 1996, 384 (6607), 341-343.
[2] Idriss, H. et al., Journal of Catalysis 2004, 224 (2), 358-369.
[3] Meyer, D. et al., Nano Research 2013, 7 (1), 119-131[4] Cao, Y. C. et al., Journal of the American Chemical Society 2006, 128 (51), 16522-16523
Corresponding Author: Yan Li, Ding Ma
Tel: +86-10-62756773, Fax: +86-10-62751708; Tel：010-62758603, Fax：010-62758603;
E-mail:yanli@pku.edu.cn; dma@pku.edu.cn- 168 -

3P-31Fabrication of planar heterojunction perovskite solar cells usinggraphene oxide as hole transport layer○Shunjiro Fujii1, Takeshi Tanaka1, and Hiromichi Kataura1

1

Nanomaterials Research Institute, National Institute of Advanced Industrial Scienceand Technology (AIST), Ibaraki 305-8565, Japan
Organometal halide perovskite solar cells are of special interest owing tosolution-processable fabrications and their high power conversion efficiency (PCE).
There are two main structures for the perovskite solar cells. One is a mesoporous
structure [1] commonly using titanium dioxide as the electron transport scaffold layer.
The other device structure is an inverted planar heterojunction (PHJ) [2], in which
PEDOT:PSS is widely used as a hole transport material (HTM). Recently, carbon
nanotube/graphene oxide (GO) layer has been demonstrated as efficient HTM ofperovskite solar cells with mesoporous structure [3]. However, inverted PHJ perovskite
solar cells using GO as HTM have not been investigated.
In this work, we fabricated inverted PHJ solar cells utilizing GO as HTM. The GO
used in this study exhibited few-layered sheets with a typical thickness of below 2 nm
(Figure 1). The device structure was Glass/ITO/GO/perovskite (CH3NH3PbI3−xClx)/Ag(Figure 2). Figure 3 shows the current density-voltage (J-V) curves for solar cells using
PEDOT:PSS or GO as HTM. The PCEs extracted from the J-V curves were 5.1% and4.0%, respectively. The detailed device characteristics will be discussed. This work was
supported by KAKENHI Nos. 26790021, 25220602.

2

Current Density (mA/cm )

-5

1 m
Figure 1 AFM image of GO
spin-coated on SiO2/Si.
Ag
PC71BM
CH3NH3PbI3−xClx
GO
ITO/GlassFigure 2 Schematic illustrationof perovskite solar cell.

0

5

10

15

△without HTM●GO○PEDOT:PSS

0

0.2

0.4
0.6
Voltage (V)0.8

1Figure 3 J-V characteristics under AM 1.5G (100 mW/cm2).
[1] A. Kojima et al., J. Am. Chem. Soc. 131 (2009) 6050
[2] I. Jeon et al., Nano Lett. 15 (2015) 6665
[3] F. Wang et al., The 49th FNTG General symposium 2015, 3-8
Corresponding Author: Hiromichi Kataura
E-mail: h-kataura@aist.go.jp- 169 -

3P-32
Investigation of Catalysis of Nitrogen-Doped Graphene for Oxygen
Reduction Reaction○Takeru Okada1, Kumi. Y. Inoue2, Tomokazu Matsue2,3, Golap Kalita4, Masaki Tanemura4,
Meyya Meyyappan5, and Seiji Samukawa1,3
1Institute of Fluid Science, Tohoku University, Sendai 980-8577, Japan
2
Graduate School of Environmental Studies, Tohoku University
3
WPI-AIMR, Tohoku University
4
Department of Frontier Materials, Nagoya Institute of Technology
5NASA Ames Research Center

Nitrogen-doped (N-doped) graphene promises to improve the application potential current
graphene based devices. To this end, the bonding states between carbon and nitrogen atoms
can be manipulated to tailor the properties of the doped graphene. For example, graphitic
nitrogen is known to promote desired catalytic activities (oxygen reduction reaction, ORR) in
graphene fuel-cell systems. While some studies have demonstrated the catalytic enhancementof N-doped graphene, they have also indicated that factors such as the location and thebonding state of the N-dopants may be determinants in graphene property design. According
to previous report [1], graphitic N-dopants are better at enhancing graphene’s catalytic
activities, compared to their pyrrolic and pyridinic counterparts— illustrating the importanceof the N-dopant bonding state. However, established nitrogen-doping methods lack selectivity
in dopant chemical identity and in dopant location; both are key factors in graphene property
design because the properties depend on the chemical identity and location of the dopant.
Recently we have reported a post-treatment method that selectively controls the location
and bonding state for synthesizing N-doped graphene [2]. Our approach uses a charge neutral
nitrogen beam with tunable beam energy to insert N-dopants into graphene. We utilize thebeam energy to determine both the N-dopant locations and bonding state. We found bonding
state of nitrogen depends on beam energy of neutral beam. The location and bonding state canbe controlled in terms of the nitrogen doping of graphene. A low energy is suitable for thedoping only at the edge. A CN single bond is dominantly formed under a moderate beamenergy condition (7 eV), and a high energy NB forms a high doping concentration with defectformation.
Here we report investigation of electrochemical activity of graphitic nitrogen rich graphene.
CVD grown graphene was transferred onto a rotating disk electrode. Then it was treated byneutral nitrogen beam under 7 eV condition. Electrochemical measurement was carried out inoxygen saturated 0.1 M KOH solution and N-doped graphene was used as the working
electrode. ORR was considered to be detected around -0.2 V. Although quantitative analysis is
still ongoing, the current density seems to be higher than that for pristine graphene. Thisimplies catalytic effect and that the conductivity of graphene is enhanced by the insertion of
nitrogen atom to hexagons in graphene. Detail will be discussed in the presentation.
[1] H. Wang et al. ACS Catalysis 2 781–94 (2012)[2] T. Okada et al. Nanotechnology 26, 485602 (2015)
S.Samukawa and T. Okada
Tel: +81-22-217-5240/5318,
E-mail: samukawa@ifs.tohoku.ac.jp/okada@sammy.ifs.tohoku.ac.jp- 170 -

3P-33Nano-scale Characterization of Graphene by AFM-Raman Spectroscopy〇Yasushi Nakata1, Yoshito Okuno1, Sanpon Vantasin2, Yoshito Tanaka4, In-Sang Yang3,
Yukihiro Ozaki2, and Nobuyuki Naka1
1

Scientific and Semiconducting instruments R&D department Optical Analysis Team,HORIBA Ltd.
2School of Science and Technology, Kwansei Gakuin University, 3 Ewha Womans University,
4
The University of Tokyo
Graphene has attracted much attention for its promising variety of applications on
nano-electronic device [1]. To evaluate the performance of the graphene devices, aninvestigation of their properties with nanometer spatial resolution is strongly demanded.
We have newly developed AFM-Raman system for side-illuminated Tip-Enhanced Raman
Spectroscopy (TERS) as a powerful tool for nano-scale characterization. Fig.1 shows AFM
and TERS image of special graphene, to which high current density of 3.0×108 A/cm2 wasapplied, on silicon substrate. TERS image was constructed by plotting the peak intensity of
Raman band appearing at 1530cm-1, and it exactly corresponded to AFM image taken at same
region. The spatial resolution in this image was estimated as 25 nm. Through detailed TERS
image analysis, edge phonons [2], which are characteristic of graphene nanoribbons, wereobserved. We had peaks appearing at 1530 cm-1 and 1450 cm-1, which are considered to be
derived from armchair and zigzag structure. From the results, we assumed the high current
density caused C-O bonding on the surface, which resulted in periodic defects or distortion of
atomic arrangement. To best of our knowledge, this was the first time nano-spectroscopic
studies of the graphene showing the characteristic of nanoribbons.
[nm]

60

(b)

(a)

[a.u.]
High

(c)

40
20

0

200 nmTERS area

Intensity [a.u.]

Low

(d)

@Edge

(e) nm
500@Off Edge

500

100 nm

1500
2500
Raman shift [cm-1]

References[1] K. S. Novoselov et. al., Science, 306, 666 (2004)[2] W. Ren et. al., Phys. Rev. B, 81, 035412 (2010)
Corresponding Author: Y. Nakata
Tel: +81-75-325-5038, Fax: +81-75-315-9525,
E-mail: yasushi.nakata@horiba.com- 171 -

3500

Fig.1 (a) AFM image of Graphene.
(b) AFM image and (c) TERS imageof Graphene in targeted area in (a).
TERS spectra of (d) edge ofgraphene and (e) off graphene.

3P-34
Study on field emission sites of graphene emitterby field emission microscopy and field ion microscopy○Noboru Yokoyama, Toru Hoshino, Kohji Iwata, Hitoshi Nakahara, Koji Asakaand Yahachi Saito
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
A time sequential series of field emission microscopy (FEM) patterns from a graphene
emitter and the corresponding time trace of emission current under a constant voltage areshown in Fig. 1. The FEM patterns show a striped pattern (or “lip pattern”) consisting of anarray of streaked spots; the direction of striation is perpendicular to the graphene sheet, andeach stripe is divided into two wings by a central dark band running parallel to the graphenesheet.
With the elapse of time, the size of the lip pattern is extended with the increase of
the number of striated spots, the emission current being concurrently increased even under theconstant voltage.
Figs. 2 (a) and (b) show FEM patterns
from a clean graphene emitter andAl-deposited one, respectively. Mean
thickness of deposited Al was 5.9 nm.
By the deposition of Al, a spotty pattern
exhibiting 4-fold and 6-fold symmetries
appeared. The contrast of the spotty
pattern is reminiscent of the structure of
an atomic cluster with a shape of
cubo-octahedron (Fig. 2 (c)), which is a
crystal form characteristic of face-centeredcubic metals.
The distance between
Fig.1 Change of FEM patterns and theneighboring atoms along the surface of Al
corresponding time trace of emission current
is 0.286 nm when the lattice constant inunder constant voltage.
the cluster is kept the same as that of bulk
Al. Using this interatomic distance as a0.14 nm㻌
measure of the magnification of these FEM
images, the spacing between adjacent streaked
0.23 nm㻌
spots for clean graphene emitters is estimated to0.286 nm㻌
be in a range between 0.14 and 0.23 nm. The
derived distances of 0.14 and 0.23 nm in the lip
(a)㻌
(ｂ)㻌
pattern are very close to the C-C bond length(ｃ)㻌
(0.144 nm) and the distance between theoutermost carbon atoms at the zigzag edge
(0.249 nm), respectively. In order to clarify the0.286nm㻌edge structure in atomic resolution, field ion
microscopy of the graphene will be discussed.
Fig.2 FEM pattern from (a) a clean

graphene emitter, and (b) Al-deposited
one. (c) Structure model of the Al cluster
Corresponding Authors: N. Yokoyama, Y. Saito
with the cubo-octahedral shape.
Tel: +81-52-789-3714, Fax: +81-52-789-3703
E-mail: yokoyama@surf.nuqe.nagoya-u.ac.jp, ysaito@nagoya-u.jp- 172 -

3P-35
Dimensionality Dependence of Plasmon Resonance in Graphene
Nanoribbons○

Takahiro Morimoto, Yoshiue Ikuta and Toshiya Okazaki
CNT-Application Research Center, National Institute of Advanced Industrial Science andTechnology, Tsukuba 305-8565, Japan

We will discuss the details of the measurement andthe analysis method. The comparison between
measurement results and theoretical predictions are also
shown in this presentation.
[1]T. Nakanishi and T. Ando. JPSJ, 78, 114708, (2009). [2]S. Das
Sarrma and E. H. Hwang. PRL, 102, 206412, (2009).
[3]T.Morimoto et al., ACS Nano 8, 9897 (2014). [4]T.Morimoto
and T.Okazaki, APEX, 8, 055101 (2015).
Corresponding Author: Takahiro. Morimoto
Tel: +81-29-861-3804, Fax: +81-29-861-6241,
E-mail: t-morimoto@aist.go.jp- 173 -

㻼㼑㼍㼗㻌㻼㼛㼟㼕㼠㼕㼛㼚㼟㻌㻔㼏㼙㻙㻝㻕The localized plasmon resonances are of particular interested because the observed
phenomena drastically depend on various properties including geometry of nano-structuresand excitation energy dispersions of carbon materials. Especially, the carbon nanotubes(CNTs) and graphene have been expected unique carrier density dependence originated fromtheir linear energy dispersion and strongly confined structures [1,2]. Recently, we reported
the plasmon resonance of clean CNT channels both single-walled [3] and multi-walled [4]CNTs. In these CNTs, the conventional carrier density dependence (ns1/2) never been
observed by chemical doping measurements. In the case of graphene, the carrier density
dependence of plasmon resonances is theoretically expected from ns1/4 (2D) to ns0 (1D) by
decreasing confinement dimensions. Therefore, in this study, we will report thedimensionality dependence of plasmon resonance in graphene nano-ribbons fabricated froma single layer graphene.
Figure.1 shows the AFM image of the measured sample fabricated on the opticaltransparent SiO2/Si substrate. The graphene nanoribbons were pattered as same length (750nm) and different width (150 to 1000 nm) by the EB lithography. The optical and transport
properties were measured with same sample on the same substrate. The carrier density of eachnanoribbon was controlled by the gate voltage with conventional back gate configurations.
The carrier density in each gate voltage was estimated from the Drude absorptions observed
lower frequency regions. The Far-infrared (FIR)
resonance signals were measured with polarized
conditions as shown in Fig.1.
Figure.2 shows typical results of carrier density
dependence of FIR resonance peak positions withdifferent width samples. The wider width sample (2D)shows clear ns1/4 dependence as expected theoreticalmodels. By decreasing width, however, the carrier
density dependence is strongly suppressed as shown in
Fig.2. In the narrow width sample, the carrier density
dependence is lost and peak positions are almost
Fig.1 The AFM image of graphene
constant.
nano-ribbons.
㻞㻜㻜●990 nm▲673 nm■490 nm▼186 nm

㻝㻤㻜

㻝㻢㻜

㻝㻜㻜㻜

㻝㻞㻜㻜

㻝㻠㻜㻜

㻝㻢㻜㻜

㻝㻤㻜㻜

㼚㻝㻛㻠㻌㻔㼏㼙㻙㻝㻛㻞㻕Fig.2 The carrier density dependence of
FIR peak positions.

3P-36
Wavelength dependence of surface roughness
in photoreduction of graphene oxide
Maki Ueda1, Yoshiki Yamamoto2, Yuki Hirano2, Kazuto Hatakeyama3, Michio Koinuma3,
Yasumichi Matsumoto3, Masahiro Hara2, ○Hiroyuki Yokoi4
Department of Materials Science and Engineering, Faculty of Engineering, Kumamoto
University, Kumamoto, 860-8555, Japan2
Department of Physics, Graduate School of Science and Technology, Kumamoto University,
Kumamoto, 860-8555, Japan3
Department of Applied Chemistry and Biochemistry, Graduate School of Science andTechnology, Kumamoto University, Kumamoto, 860-8555, Japan
4
Department of Materials Science and Engineering, Graduate School of Science andTechnology, Kumamoto University, Kumamoto, 860-8555, Japan
1

Graphene oxide (GO) is graphene-like material which can be produced through oxidationof graphite. Carbon atoms in the basal plane or on the edges of GO are partially modified withfunctional groups containing oxygen. Several reduction processes have been investigated torestore its graphitic structure. However, it has been found very difficult to achieve it. For
example, additional defects were induced and pores were formed eventually in GO sheets in aphotoreduction process using ultra-high pressure mercury lamp[1].
In this study, we have conducted photoreduction of GO using monochromatic lights of 350,
450, 550 nm in wavelength. We analyzed the surface roughness of photoreduced GO sheetswith an atomic force microscope (SPM-9700, Shimadzu Corp.). It has been found that thesurface roughness becomes worse in 350 nm and does not change in 550 nm, but improves in
450 nm. There results might suggest that the functional group can be removed from GO
selectively without destroying the graphitic network of GO by visible light with a shorter
wavelength.
[1] M. Koinuma et al. J. Phys. Chem. C 116, 19822 (2012).
Corresponding Author: H. Yokoi
Tel: +81-96-342-3727, Fax: +81-96-342-3710,
E-mail: yokoihr@kumamoto-u.ac.jp- 174 -

3P-37
Raman intensity magnetic field dependence in graphene○ Toshiya Shirakura1, Riichiro Saito1
1

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

In this work, we calculate magnetic field-dependence of Raman intensity of graphene in which the opticalphonon and the inter Landau-level (LL) electronic transitions are coupled together. The physics ofgraphene in the presence of the magnetic field has been studied by the magneto Raman spectroscopy [1,2, 3], in which the high quality of graphene samples are reflected by the long lifetime of the Diracfermions and then the narrow spectral widths of the LL [4]. For evaluating the in-plane crystal size, thedefects and the LL spectral width can be compared by using Raman spectroscopy in magnetic field [4,5].
A previous theoretical work has calculated the Raman spectra of graphene under the magnetic field byusing fitting parameter which corresponds to G-peaks from experiment of Raman spectra in their formula[6]. However, they did not consider the microscopic picture of interference of the peaks.
In this work, we directly calculate the G-band Raman spectra by considering electron-photon andelectron-phonon interaction. In order to get the result, we consider time-dependent perturbation theory,
and we adopt dipole approximation for electron-photon matrix element. Dipole approximation meansthat wave length of laser is sufficiently long compared with atomic bond length of graphene. In the caseof electron-phonon interaction, only two phonon modes (iLO and iTO) contribute to the Raman intensity.
By calculating Raman spectra in the LL quantized graphene, we will discuss the G-band magnetic fielddependence.

[1] M. O. Goerbig, et al., Phys. Rev. Lett. 103, 087402 (2009).
[2] T. Ando, et al., J. Phys. Soc. Jpn. 76, 024712 (2007).
[3] C. Faugeras, et al., Phys. Rev. Lett. 103, 186803 (2009).
[4] J. Yan, et al., Phys. Rev. Lett. 105, 227401 (2010).
[5] C. Faugeras, et al., Phys. Rev. Lett. 107, 036807 (2011).
[6] C. Qiu, et al., Phys. Rev. B. 88, 165407 (2013).
Corresponding Author: T. Shirakura,
E-mail: shirakura@flex.phys.tohoku.ac.jp- 175 -

3P-38Chemical vapor deposition growth of high-quality large-area
hexagonal boron nitride monolayers and an application to passivation of
black phosphorus○Yuya Takabayashi, Sinha Sapna, Haruka Omachi, Hisanori Shinohara and Ryo Kitaura
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
Hexagonal boron nitride (hBN) has attracted a great deal of attention not only as a substrate
for high-quality atomic-layer devices but also as an ultrathin insulator for passivation andprotection of reactive atomic layers. hBN possesses large bandgap (6 eV), high mechanicalstrength, high thermal stability and chemical inertness[1], and its monolayer form can be madeand easily transferred onto desired substrates. These fascinating properties of hBN provide great
potential in applications for ultrathin dielectric layers, tunneling barriers, and protective layers.
Monolayer hBN with uniform thickness, large grain size and high crystallinity is critical forthese applications, and it is still a great challenge to prepare such hBN. Mechanical exfoliation
provide high crystallinity hBN flakes, but in this case preparation of large-area monolayer hBN
is extremely difficult. In contrast, the chemical vapor deposition (CVD), is a promising method
to realize high-quality large-area hBN. We report here the CVD growth of hBN using aelectropolished Cu foil as a substrate and application of the so-grown hBN to passivation of
black phosphorus (BP).
Figure 1 shows a typical optical microscope image of monolayer hBN grains synthesized;
the weak contrast region corresponds to hBN, whose lateral size is ~20 m in edge length(Figure 1). Figure 2 shows a Raman spectrum that shows sharp Raman band assigned to the E2g
vibration mode. The full width at half-maximum (FWHM) value of the hBN peak is only 15
cm-1 and this sharpness of the FWHM suggests high crystalline hBN.
Furthermore, we have fabricated hBN/BP heterostructure by a dry transfer method wedeveloped. Although BP rapidly degrades upon exposure to air [2], the hBN/BP heterostructure
does not show any signs of degradation even after a week, which was confirmed by AFM
observations (Figure 3). This result suggests that the present CVD-grown hBN is in a highquality and good protection layers that easily applies to other 2D materials.

Fig.1 Optical images of hBN
domains grown on Cu foil

Fig.2 Raman spectra of the hBNtransferred onto a SiO2/Si substrate

Fig.3 AFM image of hBN/BP
heterostructure after a week

[1] L. Wang et al. adv. Mater. 26, 1559(2013). [2] J. D. Wood et al. Nano Lett. 14, 6964(2014).
Corresponding Author: R. Kitaura and H. Shinohara
E-mail: r.kitaura@nagoya-u.jp and noris@nagoya-u.jp- 176 -

3P-39Insulator-to-Metal transition in polycrystalline MoS2 films
induced by electric double layer gating○Takuya Osakabe1, Jiang Pu2, Yusuke Edagawa1, Lain-Jong Li3, Taishi Takenobu 1,2,4
12

Department of Applied Physics, Waseda University, Shinjuku 169-8555, Japan
Department of Advanced Science and Engineering, Waseda Univ.,Shinjuku 169-8555, Japan3
Physical Science and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
4
Kagami Memorial Laboratory, Waseda University, Shinjuku 169-8555, Japan
Recently, transition metal dichalcogenide (TMDC) thin films have attracted attentions dueto their unique optical and electrical properties. In particularly, electric double layertransistors (EDLTs) of single-crystal molybdenum dichalcogenide films (MoX2, X = S, Se,Te) are very interesting because of the strong electric field and high density carrier
accumulation, resulting in the electric field induced superconductivity and the peculiar roleof strong spin orbit interactions [1,2]. However, until now, the electric field induced
insulator-to-metal transition (IMT) in MoX2 has only been observed in extremely tiny
single-crystalline samples and, for future applications, it is very important to apply thistechnique into CVD-grown large-area samples. Although we observed the metallic behavior
above 220 K in EDLTs of CVD-grown MoS2 films previously [3], the metallicity at low
temperature, which is the first important step for the electric field induced superconductivity,
have not yet been clarified. Therefore, in this research, we tried to measure field effectinduced transition in polycrystalline MoS2 monolayer films at 2 K.
Figure 1 shows the device structure of EDLTs. As the gate dielectric, we selected the iongel, which is mixture of ionic liquid (DEME-TFSI) and organic polymer (P(VDF-HFP)).
Figure 2 shows the Temperature dependence of sheet resistance at various gate voltages anddashed line is the quantum resistance, which is the text-book border between insulator andmetal. We successfully observed n-type transistor behavior and sheet resistance was less than
the quantum resistance at gate voltage of 3.5V. Finally, by cooling the sample, we observed
the solid evidence of IMT in polycrystalline films. Particularly, it remained metallic state at
2 K, which is the first mille stone for large-area electric field induced superconductors.   

Fig.1. Device structure of large-area MoS2 EDLTs

    Fig.2. Temperature dependence of
sheet resistance at various gate voltages[1] J. T. Ye et al., Science 338, 1193 (2012). [2] Y. Saito et al., Nature Phys DOI: 10.1038/NPHYS3580 (2015).
[3] J. Pu, T. Takenobu et al., Nano Lett. 12, 4013 (2012).
Corresponding Author: Taishi Takenobu Tel&Fax:+81-3-5286-2981 E-mail: takenobu@waseda.jp- 177 -

3P-40
Position selective synthesis of monolayer and single crystal WS2○Tomoyuki Takahashi, Toshiaki Kato, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Atomic scale two dimensional sheets attract intense attention due to their superior electrical,
mechanical, and optical features [1, 2]. Layered transition metal dichalcogenide (TMD) is
known as a true two-dimensional (2D) material with excellent semiconducting properties [3].
In spite of its potential, there are still remained lots of issues for the practical applications of
TMD-based optoelectrical devices. In particular, the large area growth, defect free growth,and position selective growth are regarded as crucial issues in their production stage.
In this study, we have developed a novel synthesis method to realize the integrated
synthesis of monolayer and single crystal tungsten disulfide (WS2) array using Au dots as anucleation promoter. Au dot arrays were fabricated with a conventional electron-beamlithography, vacuum evaporation, and lift-off process. WS2 growth was carried out byatmospheric pressure thermal CVD with WO3 as a source material.
Based on the systematic investigations, it is found that the nucleation of WS2 with Au dotsstrongly relies on Au dots diameter and growth temperature. The crystallinity (single crystal
or poly-crystal) of monolayer WS2 is also found to be sensitive to the diameter of Au dots.
The size distribution of WS2 growing with Au dots was uniformed compared to that ofwithout Au dots and the average size of monolayer WS2 can be controlled by the growthtemperature and Au dot distance. Through the adjustment of these growth conditions, we havesucceeded in the synthesis ofsingle crystal and monolayer
WS2 arrays in large scale withnarrow size distributions (Fig. 1).
This large-scaled and integrated
synthesis of monolayer WS2
array can contribute to thedevelopment of TMD-based highperformance optoelectricalFig. 1: (a) Scanning electron microscope image and (b)devices.
Photoluminescence intensity mapping image of large scale
synthesis of monolayer and single crystal WS2 array.
[1] T. Kato and R. Hatakeyama, ACS Nano 6, (2012) 8508.
[2] T. Kato and R. Hatakeyama, Nature Nanotechnology 7, (2012) 651.
[3] T. Kato and T. Kaneko, ACS Nano 8, (2014) 12777.
Corresponding Author: T. Takahashi
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: takahashi13@ecei.tohoku.ac.jp- 178 -

3P-41
Optical properties of monolayer-WSe2/organic molecule heterostructure○Shota Kimura1, Daichi Kozawa1, Keiichiro Matsuki2, Shinichiro Mouri3, Yuhei Miyauchi3,

Kazunari Matsuda3, Lain-Jong Li4 and Taishi Takenobu1,2
Department of Applied Physics, 2Department of Advanced Science and Engineering,
Waseda University, Shinjuku Tokyo 169-8555, Japan
3
Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan4
Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
1

Monolayers of transition metal dichalcogenides (TMDCs) are realized by the mechanicalexfoliation method and, recently, unique interlayer phenomenon has been observed in theirartificial hetero-bilayer, which is the combination of different types of TMDC monolayers [1,2]. Although these new materials are interesting, clean and uniform interfaces between
mechanically exfoliated monolayers are still difficult. To overcome these problems, we focusedon organic molecules as a partner of TMDCs due to their no dangling bond and well-defined
HOMO-LUMO gap, resulting in energetically-designed interface between organic crystal and
TMDC monolayer. Here, we chose rubrene (5,6,11,12-tetraphenyltetracene, C42H28, Fig. 1) asorganic molecules and fabricated rubrene/monolayer-WSe2 heterostrucrure.
We prepared CVD-grown single crystals of WSe2. Then, as shown in Fig. 2, we fabricatedrubrene/monolayer-WSe2 heterostrucrure by lamination of thin rubrene single crystals or
vacuum vapor deposition of polycrystalline rubrene thin films. Very importantly, from theenergy diagram of Fig. 1, we can expect the energetical coupling between rubrene and WSe2
and, to confirm it, we measured PL spectra of rubrene. Finally, we observed the strong PL
quenching on WSe2 monolayers, indicating energy transfer from rubrene to WSe2. Our results
expand the possibility of new stacking combination, organic-inorganic hybrid heterostructure.

Fig.1 Energy diagram.

Fig.2 Schematic picture and PL of rubrene/1L-WSe2 heterostructure.

[1] D. Kozawa et al., arXiv: 1509.01875[2] T. F. Heinz et al., Nano Lett. 2015, 15(8):5033

Corresponding Author: Taishi Takenobu,  Tel&Fax: +81-3-5286-2981,  E-mail: takenobu@waseda.jp- 179 -

3P-42
Polarization-resolved photoluminescence mapping in monolayertransition metal dichalcogenides○Yusuke Hasegawa1, Feijiu Wang1, Shun Aota1, Shinichiro Mouri1, Kazunari Matsuda1
and Yuhei Miyauchi1, 2
12

Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama
332-0012, Japan

Recently, ‘valleytronics’, which is expected as future optoelectronic technology relying onvalley degree of freedom of electrons, has attracted much attention from the viewpoint ofdeveloping low energy consumption and high speed signal processing devices. One of thepossible candidate materials is monolayer of transition metal dichalcogenides (1L-TMDs)
such as MoS2 and WSe2 [1-3]. The intrinsic structural inversion asymmetry in these 1L-TMDs
gives rise to coupling of electron (hole) spin and valley degrees of freedom. This
characteristic enables valley-selective optical excitation in these materials using
circular-polarized incident photons [1,2]. The 1L-TMDs have thus been intensively studied aspromising materials for valleytronics [1,2]. However, correlations between observed valley
polarization and local conditions in the 1L-TMDs such as local doping, strain, defects andedges have been unclear.
Here we study the spatial dependence of the polarized
photoluminescence (PL) spectra in 1L-TMDs. We observed
position- and polarization-resolved PL spectra of 1L-TMDs tovisualize the position-dependent valley polarization degree as afunction of in-plane coordinates.
Figure 1 shows the polarization-resolved PL intensity maps of
1L-MoS2 at room temperature. Circular-polarized incident
photons (1.96 eV) were set to be   helicity, and   and  
1µm
components of the PL signals were separately detected at thesame time for each position on the sample. The PL intensity of the  emission ( I+ ) (averaged in the range of 1.82-1.88 eV,corresponding to exciton and trion PL) is higher than the  emission (I- ), suggesting finite valley polarization in 1L-MoS2 atroom temperature [1,2] whereas low valley polarization on themulti-layer (ML) part. We will show the results for various
1L-TMDs and the spatial dependence of the observed valley
polarization under variable temperature conditions. The
correlations between the local conditions indicated by the PL
spectra and the morphologies observed by optical and atomic
force microscope will be also discussed.
[1] K. F. Mak et al., Nat. Nanotechnol. 7, 494 (2012).
[2] H. Zeng et al., Nat. Nanotechnol. 7, 490 (2012).
[3] S. Mouri, Y. Miyauchi, K. Matsuda, Nano Lett. 13, 5944 (2013).
Corresponding Author: Y. Miyauchi
Tel/Fax: +81-774-38-3465/+81-774-38-4567
E-mail: miyauchi@iae.kyoto-u.ac.jp- 180 -

Fig.1 Polarization-resolved
PL intensity maps of 1LMoS2 at room temperature
for I+ (top panel) and I(bottom panel) components.
ML indicates the multi-layerpart.

3P-43Magnetism arising from pore edges of nanomesh on few-atomic layered
hexagonal boron nitride○K. Nagano, Y. Tagami, C. Ohata, G. Hashimoto1, S. Katsumoto1, K. Nomura, J. Haruyama
Faculty of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
1Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
Physics and applications of two-dimensional mono(few) atomic layers of various materials
are attracting considerable attention (e.g., graphene, black phosphorene (BP), MoS2 andh-BN). Among those, mono(few)-atomic layer of h-BN has been actively used for sufficientisolation between graphene and SiO2/Si substrate. On the other hand, we have investigatedmagnetism arising from edges of graphene and BP.
In the case of graphene, flat band ferromagnetism arising from edges state of zigzag
atomic-structure edges were theoretically well known. We experimentally observed it inhydrogen(H)-terminated graphene nanomesh (GNM), which has honeycomb like array ofhexagonal nanopores with zigzag pore edges fabricated by non-lithographic method [1]. In
contrast, the ferromagnetism disappeared in oxygen(O)-terminated GNM. For O-terminatedfew-layer BP nanomesh (BPNM) fabricated following the same method as that for GNM, weobserved ferromagnetism approximately 10 – 100 times greater than those in H-terminated
GNM, while it disappeared in H-terminated BPNM [2].
Here, we have fabricated few-layer h-BNNM using the same non-lithographic method
applied to mechanically exfoliated h-BN. We find ferromagnetism in O-terminated BNNM.
However, it is highly sensitive to annealing temperature after formation of nanomesh and also
kinds of the foreign atoms for the pore edge termination. It is theoretically known thatappearance of edge magnetism strongly depends on kinds of atoms at edge dangling bond (i.e.,
B or N) and its termination [3]. Various dependence (e.g., on annealing temperature,termination atoms) and theoretical discussion will be presented at poster.
Fig. 1: Magnetization curve of oxidized

few-layer h-BN nanomesh annealed at
500 ℃ under high vacuum right after theformation. It does not appear at annealing
temperature (Ta) above 600 ℃ and themagnitude of saturation magnetization
value decreases in the samples with Ta <500℃.

[1] T. Hashimoto, J. Haruyama, S. Roche et al., Appl. Phys. Lett. 104, 252410 and 105, 183111 (2014)[2] Y. Nakanishi, J. Haruyama, S. Roche et al., Phys. Rev. Lett. In press[3] A. Du et al., J. Am. Chem. Soc. 131, 17354 (2009)
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 181 -

3P-44
Geometric and electronic structures of atomic layers of GaN○Yanlin Gao, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, 305-8571, Japan
Two-dimensional (2D) materials with an atom thickness exhibit peculiar properties arisingfrom the constituent elements and network topologies that allow them for being promisingmaterials in the wide areas of the future nanotechnology. Following the discovery of graphene,
h-BN and silicene have been synthesized by using various experimental techniques. GaN is awide band gap semiconductor with excellent optical and electrical properties, which areapplicable of optical and high frequency electronic devices because of their high carrier
mobility and wide direct band gap. In the present work, we aim to explore the possibility of the2D atomic network of GaN by analogy with h-BN as the other candidate of the III-V atomic
layer materials, based on the density functional theory by combining with the effective
screening medium method.
Our calculations show that GaN thin films with four or less atomic layers and (0001)/(0001) surfaces prefer the layered structures consisting of planar GaN sheets rather than a Wurtzite
crystal structure. For the monolayer of GaN, the GaN possesses hexagonal network with the
optimum lattice constant of 3.2 Å (Fig. 1). The sheet is a semiconductor with indirect energy
gap of 2.28 eV between K and G points for the valence band top and the conduction band
bottom, respectively. By applying the compressive pressure along the lateral direction, theplanar sheet undergoes a structural transition at a lattice constant of 2.8 Å, at which the GaN
has a buckled structure as in the case of free standing silicene [Fig. 2(a)]. According to thebuckled structure, GaN sheet is a metal with polarization normal to the atomic sheet. We further
investigate the geometric and electronic structures of GaN sheet with structural buckling of
which surfaces are fully hydrogenated. The calculations show that the fully hydrogenated GaN
monolayer is a semiconductor with a direct band gap of 3.68 eV, and is endowed with a buckled
structure with a height of 1.31 Å at the optimum lattice constant of 3.2 Å [Fig. 2(b)].
Interestingly, the out-of-plane polarization of hydrogenated GaN is opposite to that of the clean
GaN under the compression. The fact indicates that the polarization tuning is possible bycontrolling the H coverage of the surfaces of GaN atomic layer.

Fig. 1. The top and side views ofplanar 2D GaN sheet.

Fig. 2. Side views of (a) compressed and(b) hydrogenated 2D GaN layers.

Corresponding Author: Y. Gao
TEL: +81-29-853-5921, FAX: +81-29-853-5924
E-mail: ylgao@comas.frsc.tsukuba.ac.jp- 182 -

3P-45
Quantitative evaluation of size effect on macrophage uptake of carbon
nanotubes by optical absorption measurement methodO

Minfang Zhang1*, Naoko Tetsura1, Kayo Ichiraku1, Katsuhide Fujita1, Sumio Iijima1, 2,
Masako Yudasaka1, 2, Toshiya Okazaki1
1

National Institute of Advanced Science and Technology (AIST),
2
Faculty of Science & Technology, Meijo University

The safety assessment and toxicity evaluation of carbon nanotubes (CNTs) havebeen performed by using different types of CNTs with various surface properties, shapes,
and sizes in vivo and in vitro. Although the results have shown that the long and short
CNTs have different biodistribution and toxicity after intravenous or tracheal
administration into mice, the size-effect of CNTs on cellular uptake and toxicity is stillongoing problem and the data reported previously often conflict. This is mainly due tothe lack of a unified and standard approach to quantify CNTs within cells, which would
be highly desirable. In this study, we have developed a method to quantify the amountof CNTs inside the cells by using the characteristics of CNT of optical absorption innear infrared region. Our purpose is to clarify the influence of CNTs sizes to the cellular
uptake quantity and cytotoxicity in vitro.
For investigation of the size-effect, 7-types of CNTs (single- or multi-walled CNTs)
with similar surface properties but different dynamic sizes measured by dynamic lightscattering methods were exposed to macrophage of RAW 264.7. All types of CNTs weredispersed homogenously in 10 mg/mL of BSA aqueous solution by ultrasonichomogenizer for 5 h. The quantity of CNTs in cell lysate after incubation for 4-48 h wasestimated from the absorbance of cell lysate at 750 nm. The results showed that theuptake of CNTs by macrophage is greatly dependent on the dynamic sizes of
CNT-particles in dispersions, doses and incubation time. Especially, the cellular uptake
quantities increased with the increase of sizes of CNTs. More CNTs taken up by cells,
more cytotoxicity was found from the investigation of cell viability and ROS generation.
The method proposed in this study is significantly important for the safety assessmentand nanomedicine application of CNTs.

Corresponding Author: M. Zhang
E-mail: m-zhang@aist.go.jp- 183 -

3P-46
Nitrogen-doped carbon preparation from organic frameworks withmolecularly-ordered structures
Tomohiro Shiraki1,2, Gayoung Kim1, Naotoshi Nakashima1,2
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan

Hetero atom doping in carbon materials is a promising method to create new functions for
future applications. In particular, nitrogen-doped carbons are attracting great attentions due toemergence of electrocatalytic activities on an oxygen reduction reaction (ORR), which isimportant to develop higher performance and low cost fuel cells without using rare metals
such as platinum.[1]In this study, we have newly fabricated nitrogen-doped carbons through carbonization
using organic materials with molecularly-ordered structures, which are covalent organic
frameworks (COFs)[2] constructed by crystalline molecular networks composed ofcovalently-linked organic molecules (Fig. 1). One of interesting features of COFs is facile
geometrical design based on the molecular structures and combination of the building blocks,
which allows a wide variety of architectural constructions, such as pore shapes and moleculararrangement. Recently, we have succeeded in room temperature synthesis of COF1 (Fig. 1),
resulting in the formation of a highly crystalline structure compared to reported one.[3]Carbonization of COF1 at 700 C under a nitrogen atmosphere provided a nitrogen-doped
graphitic structure, which was confirmed by Raman and X-ray photoelectron spectroscopies.
N
N

N
O

H

N

H

N

O
O

N

N

H

(i)

N

(ii)

N

N
N

N

Nitrogen-dopedcarbon

N
H2N

NH2

N

N
N

N

N

COF1

Fig.1 Schematic route for nitogen-doped carbon synthesis through carbonization of COF1:(i) room temperature synthesis, (ii) carbonization.
[1] L. Dai, Y. Xue, L. Qu, H.-J. Choi, J.-B. Baek, Chem. Rev. 115, 4823 (2015)[2] J. W. Colson, W. R. Dichtel, Nat. Chem. 5, 453 (2013)[3] T. Shiraki, G. Kim, N. Nakashima, Chem. Lett. 44, 1488 (2015)
Corresponding Author: T. Shiraki
Tel: +81-92-802-2841, Fax: +81-92-802-2840,
E-mail: shiraki.tomohiro.992@m.kyushu-u.ac.jp- 184 -

3P-47Development of Multi-stage Ion Trap Ion Mobility System for Separation of Charged
Particles with Long-range Manipulation.
○Hironobu Matsubayashi, Yasuhiro Hiroshiba, Ryota Jinnouchi,
Wataru Ohkawa, and Toshiki Sugai,
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Ion mobility spectrometry (IMS) have revealed
varieties of novel information on nano materials.
Novel Structures of metallofullerenes have been
revealed by IMS[1]. Furthermore our newly
developed ion trap ion mobility measurement
system can hold the charged particles for morethan 2 hours realizing observations on long term
structuralchanges[2].
Howeverthosemeasurements mainly performed on a single
particle and the structural resolution is limited
because the system utilizes only two trap units
and the transfer length is restricted to 3 mm. To
break these limits to introduce new functions
such as separation, here we present theFig. 1 Schematic View of Multi-stage Ion
Trap Ion Mobility System.

development of multi-stage system.
Figure 1 shows the schematic view of thesystem, which consists of an electrosprayionization source for salt solution, and 10
separated quadrupole ion trap units. To eachunits, radio frequency field and DC bias wereapplied to confine and manipulate the particles.
The movements of the particles were observed

Fig. 2 Particle Separationby the semiconductor laser eradiation.
Figure 2 shows the observed separation of two particles. The high charge particle (r=280 nm
and q=+40e) stayed in one unit while the low charge particle (r=350 nm and q=+10e) passed
through. Both of them were transferred from the injection point to the trap point achieving the
movement of 80 mm, which is 30 times longer than that realized in the previous system.

[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
[2] T. Sugai et al., 42nd Fullerene-nanotube-graphene conference. 3-13

TEL: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 185 -

3P-48Observation of Nano Particles by Ion Trap Ion Mobility.
○Ryota Jinnouchi, Yasuhiro Hiroshiba, Hironobu Matsubayashi,
Wataru Ohkawa, Takuma Ito, and Toshiki Sugai,
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Ion mobility spectrometry (IMS) haverevealed varieties of novel information on
nano materials. For example, novel structuresof metallofullerenes have been revealed by
IMS[1]. Furthermore our ion trap ion mobility
measurement system can hold the charged
particles for more than 2 hours realizing
observations on long term structuralchanges[2]. However the detected particles
have been limited to m sized ones becauseof the trap efficiency and detection sensitivity.
Here we present the observation of particles
with a radii of 50 nm by the newly developed
ion trap ion mobility system.
Figure 1 shows the trapped and detected

Fig. 1 Observed charged particles witha radius of 50 nm and a charge of +4000e.

nano polystyrene particle with a radius of
50±5 nm and a charge of +4000e. Since theup and down continuous motion was applied
to the particle to measure its mobility, its
image was observed to be a trace and theamplitude of the trace is proportional to its
mobility. Figure 2 shows the amplitudedependence on the particle size. Apparently,

Fig. 2 Amplitude Dependence on Particle Radii

the amplitude rapidly increases as the size decreases up to nm level. The amplitude has been
observed to be quite steady for m level particles [3] so that the results show that the collision
processes of nano particles with nitrogen and oxygen molecules in air are quite different thoseof micro particles. We are going to study various nano materials with this system.
[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
[2] T. Sugai et al., 42nd Fulluerene-nanotue-graphene conference. 3-13
[3] Y. Hiroshiba et al., 50th Fulluerene-nanotue-graphene conference.

TEL: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 186 -

発表索引
Author Index

Author Index<A>
Achiba, Yohji
Ago, Hiroki
Aji, Adha Sukma
Akama, Toshiki
Akasaka, Takeshi
Akiyama, Kazuhiko
Akiyama, Wataru
An, Hua
Aoki, Nobuyuki
Aota, Shun
Aoyagi, Shinobu
Arai, Miho
Asaka, Kinji
Asaka, Koji
Ayria, Pourya

1P-4, 1P-47, 1P-48,
2P-6
1P-26, 1P-39
1P-39
3-3
1P-5, 2P-7, 3P-4
2P-5
3-8
3P-19, 3P-20
1P-38, 3-8
3P-42
3P-3
1P-41
1P-16
1P-14, 3P-34
1P-33

<B>
Baba, Shuichi
Baba, Takuma
Baker, Peter J.
Bando, Yuki
Bekarevich, Raman
Bird, Jonathan

2P-24
2P-14, 3P-12
1P-7
1P-40
2P-24
1P-38, 3-8<C>Carlson, Robert M. K.
Chae, Hwa Jeong
Chan, Joseph
Chechetka, Svetlana
Chen, Chang-Hsiao
Chen, Xiao
Cheng, Xinlu
Chiashi, Shohei

Chiku, Shinichiro

3P-25
2P-4
1-1, 1-2
1P-42
2P-43
3P-27
3P-29
1P-11, 1P-21, 2-2,
2P-22, 3P-9, 3P-11,
3P-19, 3P-20, 3P-21,
3P-27
2P-15

<D>
Dahl, Jeremy E. P.
Delacou, Clement

3P-25
1-9

Ding, Dong
Ding, Li
Dresselhaus, Mildred S.

1P-26
3P-30
S-1, 1P-36, 1P-46<E>
Edagawa, Yusuke
Endo, Hiroyuki
Endo, Hitomi
Endo, Morinobu
Endoh, Hiroyuki

3P-39
3P-22
1P-47, 1P-48
1P-46
2P-48, 3P-8

<F>
Fei, Wenxi
Feng, Ya
Fernández, Pablo Solís
Fokina, Natalie A.
Fugetsu, Bunshi
Fujigaya, Tsuyohiko
Fujii, Shunjiro
Fujimoto, Akira
Fujita, Katsuhide
Fukaya, Masayoshi
Fukazawa, Shinpei
Fukuda, Kenjiro
Fukumura, Musashi
Fukushima, Takanori
Fukuzumi, Shunichi
Funahashi, Kazuma
Furukawa, Ko
Furukawa, Yoritaka
Furutani, Sho
Futaba, Don
Futagoishi, Tsukasa

3P-26
1P-11, 3P-9
1P-26
3P-25
1S-2, 1P-46
2P-18, 3P-14, 3P-16
2P-10, 3P-31
1P-34
3P-45
1P-45
3P-4
1P-39
2P-45
2S-6, 3P-17
2-5
2P-43, 3P-17
1P-3, 1P-4, 2P-6
3P-11
3P-6
2-1, 3P-18
3P-2

<G>
Gao, Yanlin
Gong, Wei
Gonnokami, Hiromichi
Gorgoll, Ricardo M.
Guo, Huaihong

3P-44
1P-46
3P-5
3-10
1P-36

<H>
Hamasaki, Yuki

2P-18

- 187 -

Hara, Masahiro
Harada, Yoshiyuki
Harano, Koji
Harigai, Toru
Harumiya, Shinnosuke
Haruyama, Junji
Hasdeo, Eddwi
Hasegawa, Akiko
Hasegawa, Kei
Hasegawa, Masataka
Hasegawa, Takashi
Hasegawa, Tetsuya
Hasegawa, Yusuke
Hashima, Yuki
Hashimoto, Gen
Hashimoto, Takeshi
Hata, Kenji
Hatakeyama, Kazuto
Hattori, Yoshiyuki
Hayashi, Yutaro
He, Guanchen
Hibino, Hiroki
Higuchi, Ayaka
Hikichi, Yuto
Hirahara, KaoriHirakawa, Takuya
Hirano, Atsushi
Hirano, Yu
Hirano, Yuki
Hirata, Chika
Hiroshiba, Yasuhiro
Hirotani, Jun
Homma, Kotaro
Homma, Yoshikazu
Horibe, Masashi
Hoshino, Ryo
Hoshino, Toru
Hou, Bo
Huang, Shengxi
Huang, Wenxin
Hukushima, Takanori
Hunahashi, Kazuma

3P-36
1P-34
3-10
1P-44, 2P-47
1P-19
3P-43
2P-38
3P-7
1-8, 1P-20, 2P-20
2P-30
2P-15
2-5
3P-42
1P-30
3P-43
1S-4
1P-17, 2-1, 2P-17,
3P-18
3P-36
2P-46
3P-28
1P-38
2P-26
1P-38
1P-22
2P-24
2P-10
2P-10, 3P-15
3P-26
3P-36
1P-1
1P-49, 3-9, 3P-47,
3P-48
1P-15, 3P-13
2P-45
3-6
1P-25
3P-28
3P-34
2-2
1P-36
3P-16
2P-30
2P-30

<I>
Ichiraku, Kayo
Ideta, Shin-ichiro
Iijima, Sumio
Iizumi, Yoko
Ikuma, Naohiko
Ikuta, Yoshiue
Inaba, Masafumi
Inami, Eiichi
Inoue, Kanzan
Inoue, Kumi
Inoue, Ryosuke
Inoue, Taiki

Inoue, Yuya
Isaka, Takuya
Ishida, Ryo
Ishihara, Masatou
Ishikawa, Ryousuke
Ishikawa, Yasuaki
Ishino, Katsuma
Ishiyama, U
Ishizeki, Keisuke
Ito, MasahiroIto, Takuma
Iwata, Kohji
Iwata, Nobuyuki<J>Jeon, Il
Jinnouchi, Ryota<K>
Kako, Masahiro
Kalita, Golap
Kanahashi, Kaito
Kanazawa, Naoki
Kaneko, Ren
Kaneko, Toshiro
Kaskela, Antti
Kataoka, Yosuke
Kataoka, Yousuke
Kataura, Hiromichi- 188 -

3P-45
3-1
3P-45
1-10
2P-1
3P-35
3P-26
2P-32
1P-13
3P-32
1P-24, 2P-27
1P-11, 1P-21, 2-2,
2P-22, 3P-9, 3P-11,
3P-19, 3P-20, 3P-27
2P-34
2P-29, 2P-31
2P-19
2P-30
1P-31
1P-30
3P-3
2P-13
1P-9
3-6
1P-49, 3-9, 3P-48
3P-34
1P-19, 3P-28

1-9
1P-22, 1P-49, 3-9,
3P-47, 3P-48

1P-5, 2P-7, 3P-4
3P-32
2P-30, 3P-17
2P-19
1P-34
3-3, 3P-40
1-9
2P-25
2P-23
2P-10, 3P-15, 3P-31

Kato, Azusa
Kato, Kyohei
Kato, Tatsuhisa
Kato, Tomonori
Kato, Toshiaki
Kato, Yuichiro K.
Katsumoto, Shingo
Kauppinen, Esko I.
Kawaguchi, Daiki
Kawai, Hideki
Kawano, Saki
Kawarada, Hiroshi
Kikuchi, Koichi
Kim, Gayoung
Kimura, Shota
Kinumoto, Taro
Kishida, Hideo
Kishimoto, Ken
Kishimoto, Shigeru
Kitamura, Yoshimasa
Kitaura, Ryo
Ko, Jeong Won
Ko, Weon Bae
Kobayashi, Miu
Kobayashi, Tatsuki
Kobayashi, Yu
Kochi, Taketo
Kodama, Takeshi
Kogane, Kenta
Koinuma, Michio
Kojima, Takahiro
Kokubo, Ken
Komuro, Tomohiko
Konno, Toshio
Koyama, Takeshi
Kozawa, Daichi
Kubuki, Shiro
Kumagai, Ryota
Kumamoto, Akihito
Kurobe, Atsushi
Kuwahara, Yuki

3P-2
3P-5
1P-3, 1P-4, 2P-6,
3P-2
1P-14
3-3, 3P-40
3-5
3P-43
1S-1, 1-9, 1P-11
1P-19
1P-12, 2P-49
2P-9
3P-26
1P-3, 1P-4, 2P-6
3P-46
3P-41
1P-27
3P-24
2P-39
1P-15, 2P-16
1P-12, 2P-49
1P-37, 3P-3, 3P-13,
3P-23, 3P-25, 3P-38
2P-4, 3P-1
2P-4, 3P-1
1P-19
2P-6
1-6, 1P-35, 2P-35,
2P-40, 2P-41, 2P-42
1P-8
1P-3, 1P-4, 1P-47,
1P-48, 2P-6
2P-46
3P-36
2-4
2P-1
3P-13
1P-1
3P-24
2P-35, 3P-41
2P-5
1-3
3-10
1S-3
2P-48, 3P-22<L>
Laine, Richard
Laszczyk, Karolina
Li, Jiulong
Li, Lain-Jong
Li, Ming-Yang
Li, YanLim, Hong En
Ling, Xi
Liu, Zheng
Lyu, Min<M>
Ma, Ding
Machida, Tomoki
Maeda, Yutaka
Maemoto, ToshihikoMaki, Hideyuki
Maniwa, Yutaka

Maruyama, Mina
Maruyama, Shigeo

Maruyama, Takahiro
Masubuchi, Satoru
Matsubayashi, Hironobu
Matsuda, Kazunari
Matsuda, Shinichi
Matsue, Tomokazu
Matsuki, Keiichiro
Matsumoto, Yasumichi
Matsunaga, Masahiro
Matsuo, Yoshiaki
Matsuo, Yutaka
Menelaou, Melita
Meyyappan, Meyya
Minami, Kazuya- 189 -

1P-20
2P-17
3P-1
2P-35, 2P-43, 3P-39,
3P-41
2P-43
2S-5, 2P-11, 2P-21,
2P-36, 3P-30
2P-44
1P-36
2P-40
2P-11

3P-30
1P-41
2P-12, 3P-4
1P-34
2S-7
1-6, 1P-12, 1P-24,
1P-35, 2P-27, 2P-35,
2P-40, 2P-41, 2P-42,
2P-45
1-4
1-9, 1P-11, 1P-21,
2-2, 2P-22, 3P-9,
3P-11, 3P-19, 3P-20,
3P-21, 3P-27
1P-23, 1P-25, 3-1
1P-41
1P-49, 3-9, 3P-47,
3P-48
1P-37, 2P-44, 3-2,
3P-41, 3P-42
1P-25
3P-32
2P-35, 3P-41
3P-36
1P-38
2P-29
1-9, 2P-3
1P-7
3P-32
2P-7

Minowa, Hiroya
Mitani, Takuji
Miyabe, Kyosuke
Miyako, Eijiro
Miyamoto, KatsuhikoMiyamoto, Yoshiyuki
Miyata, Yasumitsu

Miyauchi, Takuya
Miyauchi, Yuhei
Miyazawa, Kunichi
Mizorogi, Naomi
Mizui, Kohei
Mizutani, Ken
Mohamed, N. Baizura
Mori, Shohei
Moriguchi, Ryouichi
Morikawa, Sei
Morimoto, Naoki
Morimoto, Takahiro
Moriya, Rai
Mouri, Shinichiro
Mukai, Ken
Murakami, Shuichi
Murakoshi, Kei
Murata, Hidenobu
Murata, Yasujiro<N>
Nagano, Kenshin
Nagasawa, Hiroshi
Nagasawa, Yuya
Nagase, Shigeru
Nagata, Tomoko
Naka, Nobuyuki
Nakae, Takahiro
Nakagawa, Ayano
Nakagawa, Koji
Nakagawa, Takafumi
Nakagawa, Takeshi
Nakahara, Hitoshi
Nakamura, Eiichi

1P-21
1P-3, 1P-4, 2P-6
1P-5, 3P-4
1P-42
3-8
3P-29
1-6, 1P-24, 1P-35,
2P-27, 2P-35, 2P-40,
2P-41, 2P-42
2P-30
1P-37, 2P-44, 3S-10,
3-2, 3P-41, 3P-42
1P-1
1P-5, 2P-7
1P-44, 2P-47
1P-21
2P-44
1P-35
1P-48
1P-41
3S-8
1P-16, 3P-35
1P-41
2P-44, 3-2, 3P-41,
3P-42
1P-16
1P-34
1-3
3P-5
3P-2

3P-43
2P-19
1P-2
1P-5, 2P-7
1P-19, 3P-28
3P-33
2-4
3P-3
2P-1
2P-3
1P-6, 2-6
1P-14, 3P-34
3-10

Nakamura, Masatoshi
Nakamura, Naoto
Nakanishi, Terunobu
Nakanishi, Yusuke
Nakano, Ryosuke
Nakashima, Koji
Nakashima, Naotoshi

Nakata, Toshihiko
Nakata, Yasushi
Nakatori, Natsumi
Nakayama, Ko
Narita, Kohei
Naritsuka, Shigeya
Nihey, Fumiyuki
Nishikawa, Hiroshi
Nishina, Yuta
Nishioka, Yuya
Niu, Yang
Niwa, Hiroyuki
Noda, Suguru
Nomoto, Takahiro
Nomura, Kyoko
Nomura, Masanobu
Nouchi, Ryo
Nozaki, Junji
Nugraha, Ahmad<O>
Ochiai, Yuichi
Ogata, Hironori
Ogawa, ShunOgawa, Yui
Ogumi, Keisuke
Ohata, Chika
Ohfuchi, Mari
Ohiro, Tatsuo
Ohkawa, Wataru
Ohkubo, Kei
Ohno, Yutaka
Ohta, Yutaka- 190 -

1P-12
3-8
3P-23
3P-25
1P-34
1-3
1P-10, 1P-18, 2P-18,
3P-10, 3P-14, 3P-16,
3P-46
2P-24
3P-33
1P-3, 1P-4, 2P-6
3P-17
1P-29
1P-23, 1P-25
1P-43, 2P-48, 3P-8,
3P-22
2P-15
3S-8
3P-12
2P-36
3P-3
1-8, 1P-20, 2P-20,
3P-17
1P-31
3P-43
2P-15
1-5
2P-45
1P-33, 2P-38

1P-38, 3-8
2P-2, 2P-9, 2P-23,
2P-25, 2P-32
1P-24
2P-26
2P-3
3P-43
1-7
1P-44, 2P-47
3-9, 3P-47, 3P-48
2-5
1P-15, 2P-16, 3P-13
2P-31

Omatsu, Takashige
Onishi, Takeo
Onitsuka, Hisashi
Ono, Akira
Onomitsu, Koji
Osakabe, Takuya
Osawa, Eiji
Osawa, Toru
Osawa, Toshio
Oshima, Takumi
Oshima, Yuki
Osipov, VladimirOtsubo, Yoshiki
Oya, Tomoya
Ozaki, Yukihiro

2P-19
2P-22, 3P-20
2P-3
1P-37
1-4, 1P-2, 1P-8,
1P-29, 2P-8, 2P-13,
2P-39, 3-4, 3P-6,
3P-7, 3P-44
3P-32
1P-30
1-10, 1P-16, 3P-35,
3P-45
1P-32
3P-11
3P-33
3P-3, 3P-13, 3P-25,
3P-38
3-8
1P-15
1P-10
2P-19
2P-26
3P-39
1P-45, 3-11
3P-11
2P-20
2P-1
1P-12, 2P-49
2P-46
1P-45
1P-31
3P-33

<P>
Park, Hae Soo
Pichler, Thomas
Popert, Alexander
Prassides, Kosmas
Pu, Jiang

3P-1
2-3
3-5
1P-6, 1P-7, 2-6
2P-35, 2P-43, 3P-39<Q>
Qian, Yang

3P-19, 3P-20

Ohtsuka, Marin
Ohyama, Shinnosuke
Okada, Hiroshi
Okada, Mitsuhiro
Okada, Susumu

Okada, Takeru
Okamoto, Naofumi
Okazaki, Toshiya
Okimoto, Haruya
Okochi, Takeshi
Okuno, Yoshito
Omachi, Haruka<R>Rein, Regis
Romanov, Nickolai
Rubio, Angel<S>
Saito, Gunzi
Saito, Riichiro
Saito, Susumu
Saito, Takeshi
Saito, Tetsuki
Saito, Yahachi
Sakaguchi, Hiroshi
Sakata, Ichiro
Sakita, Masafumi
Sakurada, Ryuji
Sakurai, Shunsuke
Samukawa, Seiji
Sandhaya, Koirala
Sando, Eri
Sano, Masahito
Sano, Yoshiaki
Sapna, Sinha
Sasaki, Fusako
Sasaki, Makoto
Sasaki, Shogo
Sasaki, Shuichi
Sasaoka, KenjiSata, Yohta
Sato, KumikoSato, Naomichi
Sato, Yoshinori
Sato, Yuichi
Sato, Yuta
Sato, Yutaka
Satoh, Kazuo
Schreiner, Peter R.
Sekiguchi, Atsuko
Senga, Ryosuke
Shibata, Naoya
Shigekawa, Hidemi
Shiiba, Toshiaki
Shinohara, Hisanori- 191 -

2-5
2P-46
3P-29

3P-24
1P-33, 1P-36, 2P-34,
2P-38, 3-7, 3P-37
1-1, 1-2, 1P-40
2P-48, 3P-22
1-6, 2P-42
1P-14, 3P-34
2-4
1S-2, 1P-46
1P-34
1-6
2-1, 3P-18
3P-32
3-2, 2P-44
3-6
1P-32
2P-2
3P-38
2P-48, 3P-22
3P-24
1P-35, 2P-35, 2P-40
3-11
1P-9
1P-41
1P-5, 2P-7
3-7
1P-21
1P-5
2P-5
2P-23, 2P-25
1P-34
3P-25
1P-17, 2P-17
2-3
3-10
1-6, 1P-35, 3P-23
1P-39
1P-37, 3P-3, 3P-13,
3P-23, 3P-25, 3P-38

Shirae, Hiroyuki
Shiraishi, Tomonari
Shiraki, Tomohiro
Shirakura, Toshiya
Shiromaru, Haruo
Shoji, Yoshiaki
Solladie, Nathalie
Someya, Takao
Song, Shaotang
Sorimachi, Jun-ya
Sota, Masaki
Suda, Yoshiyuki
Suenaga, Kazu
Suenaga, Kazutomo
Sugahara, Mitsunari
Sugai, Toshiki
Sugino, Yusuke
Sugiura, Takeshi
Sundaram, Rajyashree
Suzuki, Akira
Suzuki, Daisuke
Suzuki, Hideyuki
Suzuki, Kazuma
Suzuki, Mitsuaki
Suzuki, Nozomi
Suzuki, Satoru
Suzuki, Seiya
Suzuki, Shinzo<T>Tachibana, Masaru
Tagami, Yuichi
Taguchi, Yuki
Tajima, Kentaro
Takabayashi, Yasuhiro
Takabayashi, Yuya
Takada, Tomoya
Takagi, Yukai
Takahashi, Tomoyuki
Takai, Kazuyuki
Takehana, Yuya
Takenobu, Taishi

1P-20, 3P-17
3P-10
1P-10, 3P-10, 3P-46
3P-37
1P-47, 1P-48
2P-30, 3P-17
2-5
3P-8
2-4
2P-8
3P-27
1P-44, 2P-47
2-3
1P-35, 2P-40
2P-49
1P-22, 1P-49, 3-9,
3P-47, 3P-48
2P-20
3P-4
1P-17
2P-37
2P-33
3S-8
3P-26
2P-12, 3P-4
3P-28
2P-26
2P-28
2P-19

3P-5
3P-43
1P-47, 1P-48
2P-29, 2P-31
1P-6, 1P-7, 2-6
3P-38
2P-14, 3P-12
3P-21
3P-40
2P-29, 2P-31, 2P-33,
2P-37, 2P-46
2P-12
2P-30, 2P-35, 2P-43,
3P-17, 3P-39, 3P-41

Tatsumi, Yuki
Terada, Yoshifumi
Terrones, Mauricio
Tetsura, Naoko
Tonouchi, Noriyuki
Toshimitsu, Fumiyuki
Touhara, Hidekazu
Toyama, Kiyohiko
Toyoda, Masahiro
Toyoda, Masami
Toyoda, Masayuki
Tsuboi, Nozomu
Tsuji, Takashi
Tsukada, Takayuki
Tsumura, Tomoki
Tsushima, Kohei
Tsutsumi, Yusuke

3P-23
1P-35
1-10
2P-22, 3P-20
1P-44, 2P-47
3-2
3-1
2P-5
2P-30, 3P-17
1P-13
1P-33, 3-1
2P-10, 3P-15, 3P-31
1P-45
3P-33
3P-32
3P-30
1-6, 1P-24, 1P-37,
2P-27, 2P-41, 2P-42
1P-36, 3-7
2P-28
1P-46
3P-45
3P-8
1P-18
2P-46
1P-43
1P-27
2P-24
1-1
1P-31
3P-18
2P-20
1P-27
3P-27
3P-14

<U>
Uchibori, Itsuki
Ue, Hitoshi
Ueda, Maki
Ueda, Yuki
Ueno, Yusuke
Uenuma, Mutsunori
Umemura, Kazuo
Urakawa, Naoya

1P-25
1P-44, 2P-47
3P-36
1P-23, 1P-25
1-1
1P-30
3-6
1P-13

Takeuchi, Osamu
Takeuchi, Takahiro
Takeuchi, Tsukasa
Takezaki, Hiroki
Takikawa, Hirofumi
Tan, Dezhi
Tanaka, Kiyohisa
Tanaka, Kosuke
Tanaka, Naoki
Tanaka, Senku
Tanaka, Shin-ichiro
Tanaka, Takeshi
Tanaka, Toshihiko
Tanaka, Yoshito
Tanemura, MasakiTang, Pei
Taniguchi, Takashi- 192 -

Uraoka, Yukiharu
Ushiyama, Takuya

1P-30
2P-16

<V>
Vantasin, Sanpon
Viet, Nguyen Xuan

3P-33
2P-16

<W>
Wada, Momoyo
Wakabayashi, Tomonari
Wakahara, Takatsugu
Wang, Feijiu
Wang, Meng
Wang, Wei-Wei
Wang, Yanqing
Wang, Zhipeng
Wang, Zhiyong
Watanabe, Kenji
Watanabe, Makoto
Wei, Xiaojun
Wu, Xueli<X>
Xiang, Rong<Y>
Yabuki, Naoto
Yamada, Jumpei
Yamada, Maho
Yamada, Michio
Yamada, Takeo
Yamaguchi, Takahisa
Yamamoto, Hideki
Yamamoto, Hiroshi
Yamamoto, Takahiro
Yamamoto, Yoshiki
Yamanaka, Ayaka
Yamane, Hiroyuki
Yamanoi, Ryoko
Yamasaki, Ayumi
Yamashina, Tomoki
Yamashita, Ichiro

3P-15
1P-47, 1P-48
1P-1
2P-44, 3P-42
2P-36
1P-5
1S-2, 1P-46
1P-46, 2P-32
3P-3
1-6, 1P-24, 1P-37,
2P-27, 2P-41, 2P-42
3P-9
2P-10
1P-16

1P-11, 2-2, 2P-22,
3P-9, 3P-11, 3P-19,
3P-20, 3P-27

1P-41
1P-23, 1P-25
2-1, 3P-18
2P-12, 3P-4
1P-17, 2P-17
1P-3, 1P-4, 2P-6
2P-26
1P-19, 3P-28
1P-9
3P-36
3-4
3-1
1P-45, 3-11
1P-28
2P-29, 2P-31
1P-30

Yuge, Ryota
Yumoto, Junji
Yumura, Takashi
Yunus, Rozan Mohamad

1P-12, 2P-45, 2P-49
2P-21
3P-33
2P-11
1P-36
1P-34
1-3
1P-5, 3P-4
1P-27
1P-20
3P-36
2P-23, 2P-25
3P-8
3P-34
2P-10
2P-48, 3P-22
3-5
1-6, 1P-35, 3P-23
1P-11, 3P-9
3P-24
1P-32
3P-21
2P-28
2P-32
3-10
1-10, 1P-42, 1P-43,
3P-45
1P-43
3S-9
1P-28
1P-26

<Z>
Zadik, Ruth H.
Zhang, Hong
Zhang, Minfang
Zhang, Zhenyu
Zhao, Qinghua
Zheng, Liu

1P-7, 2-6
3P-29
1P-42, 3P-45
2P-36
2P-11
1P-35

Yanagi, Kazuhiro
Yang, FengYang, In-Sang
Yang, Juan
Yang, Teng
Yano, Mitsuaki
Yasuda, Satoshi
Yasui, Masanori
Yasutake, Takuya
Yi, Eongyu
Yokoi, Hiroyuki
Yokokura, Eita
Yokota, Tomoyuki
Yokoyama, Noboru
Yomogida, Yohei
Yorozu, Shinichi
Yoshida, Masahiro
Yoshida, Shoji
Yoshida, Shuhei
Yoshida, Yukihiro
Yoshii, Yasutaka
Yoshikawa, Ryo
Yoshimura, Masamichi
Yoshitake, HaruhikoYücelen, Emrah
Yudasaka, Masako- 193 -

複写をご希望の方へ
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2016 年 2 月 19 日発行

第 50 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

JEM-ARM300F
JEM-ARM300Fは、JEM-ARM200Fで培った高安定化技術を基に開発された装置です。
冷陰極電界放出電子銃を標準搭載し、STEMおよびTEMに球面収差補正装置が搭載可能な最高加速電圧300 kVの世界最高峰の超高分解能電子顕微鏡です。
300 kV STEM Imaging（GaN[211]）
暗視野像

63 pm

Ga-Ga 原子カラム

63 pm

1 nm

80 kV TEM Imaging（グラフェン）

1 nm

本社・昭島製作所

営業企画室

東京都昭島市武蔵野3-1-2

東京都千代田区大手町2-1-1

http://www.jeol.co.jp/

TEL
（042）
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TEL（03）
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京 電子光学機器営業グループ TEL（03）6262-3581 │ 分析機器営業グループ TEL（03）6262-3582 │ 産業機器営業部
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TEL
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TEL
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TEL（052）
581-1406

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

書籍のご案内■◇定価は本体価格＋税です。

カーボンナノチューブ・
グラフェンハンドブック

カーボンナノチューブの基礎

フラーレン・ナノチューブ・
グラフェン学会 編
B5判／368頁
本体10,000円

齋藤弥八・坂東俊治
共著
A5判／220頁
本体2,800円

本ハンドブックでは，カーボンナノチューブの基本的事項を解説しながら，エレクトロニクスへの応用，近赤外発光と吸収によるナノチューブの評
価と光通信への応用の可能性を概観。最近嘱目のグラフェンやナノリスクについても触れた。

カーボンナノチューブはC 60フラーレンに次ぐ新しい炭素材料であり，エレクトロニクスやエネル
ギー分野への応用が注目されている。本書は，ナノチューブとその関連物質の作製法，構造，物性および応用を平易に述べた入門書である。

カーボンナノチューブの材料科学入門関連書籍のご案内

齋藤弥八 編著
坂東俊治・中山喜萬・
春山純志・久保佳実
共著
A5判／250頁
本体3,400円

詳説 半導体物性David K. Ferry 著／落合勇一・関根智幸・青木伸之 共訳／
A5判／2016年2月刊

小さなものをつくるための
ナノ/サブミクロン評価法― μmからnm寸法のものをつくるための
材料,物性,形状,機能の評価法―
肥後矢吉 編著／A5判／208頁／本体3,000円（エコトピア科学シリーズ 2）

環境調和型社会のための材料科学に新分野を創出し，エレクトロニクスからエネルギー分野まで広範囲な応用が期待される
ナノテクノロジー材料の典型物質「カーボンナノチューブ」について，その製法から物性，実用の可能性までを解説した。

ナノ材料科学

名古屋大学エコトピア科学研究所 編／A5判／186頁／本体2,600円

ワイドギャップ半導体パワーデバイス
山本秀和 著／A5判／230頁／本体3,500円

科学技術と共に歩む

株式
会社

コロナ社

〒１
１２-０
０
１
１ 東京都文京区千石４-４
６１- ０ 振替０
０
１
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０-８１
-４８
４
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TEL（０
３）
３
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１-３
１
３
１
（代）
，-３
１
３２，-３
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（営業部直通）http://www.coronasha.co.jp
FAX（０
３）
３
９４
１-３
１
３
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E-mail eigyo@coronasha.co.jp

溶液中の物質のナノレベル微細化・分散

昨今のナノ・テクノロジーの発展及び粉体関連技術の発展により、より微細な粒子に対する分散処理の要望が増えてまいりました。
超音波ホモジナイザーを使用し、均質な乳化分散処理を行い、安定させることにより製品の機能は向上します。一次粒子の凝集力にも拠りますが概ね 100nm 程度までの分散力があります。
ブランソン社の超音波ホモジナイザーは、コンバーター部での超音波振動変換効率が 98%以上ある為、ホーン先端部の振幅の安定性が高く、強力なキャビテーションが得られ、高効率で、再現性の高い破砕・分散処理が可能です。
ブランソン社では卓上型実験用 20kHz 機・40kHz 機、及び 1,100W～
3,300W の高出力機で大量処理も可能なシステムも用意しております。

超音波ホモジナイザー (20kHz)
BRANSON SONIFIER シリーズ

微量用・超音波ホモジナイザー
BRANSON

SLPe(40kHz)

大量処理システム

主なアプリケーション
分散
カーボンナノチューブ 有機・無機顔料 感光体 記録材料 磁性粉 シリカ アルミナ セラミック
ポリマー ラテックス 製紙 ファンデーション 光触媒 触媒 半導体 電子基盤 液晶 セメントワクチン 体外診断薬 歯磨き粉 貴金属 金属 宝石 タイヤ 発酵菌類 その他
乳化
エマルジョン製剤 農薬 トナー ラテックス 界面活性剤 クリーム 乳液 クリーム 等------------------------------------------------------

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
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E-mail: kagaku@marubun.co.jp

Tel: 03-5781-0931 Fax: 03-5781-0940

Tel: 03-3639-1336 Fax: 03-3662-1349

Sincere Spirit

フラーレン・ナノチューブ・グラフェンの㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 評価装置を紹介致します！
・複雑なパラメーターを入力しなくても測定出来るSCAN ASSIST HR搭載

高分解能小型試料用AFM
Mutimode 8 AFM

最適な分散手段を御提案致します！
・A4サイズの小型タイプ
㻌 㻌 ・グローブボックスに入る大きさ！
㻌 㻌 ・本体寸法：W22cm×D30cm×H25cm
㻌 㻌 ・本体重量：7kg

A4サイズコンパクトFT-IR
ALPHA

・震動に強い光学計㻌 㻌 ・Bruker Optics独自のRockSolid干渉計搭載
㻌 㻌 ・強固な干渉計に震動に強い堅牢構造なので、㻌 㻌 㻌 持ち運んでも光軸がブレにくい
・様々なモジュール（透過測定・ダイヤモンドATR等）
㻌 が特別な工具なく簡単に交換出来ます㻌㻌

最適な分散状態を簡易的に測定致します

パルスNMR方式粒子界面評価装置

Acorn Area

株式会社三ツワフロンテック
首都圏営業課㻌 〒103-0004㻌 東京都中央区東日本橋2-8-5㻌㻌㻌㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 東日本橋グリーンビルアネックス8Ｆ㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 TEL ：03-5823-2323 㻌 FAX：03-3863-5188
本㻌 㻌 㻌 㻌 㻌 㻌 社㻌 〒530-0041㻌 大阪市北区天神橋3-6-24
㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 㻌 TEL.06（6351）9631㻌 FAX.06（6351）9632

宇部支店㻌 〒755-0053 山口県宇部市西中町4-28
千葉営業所㻌 〒260-0834㻌 千葉市中央区今井1-19-12 （MKビル）
神奈川営業所㻌 〒252-0804㻌 神奈川県藤沢市湘南台1-7-4（綴ビル）
つくば営業所㻌 〒305-0817㻌 茨城県つくば市研究学園5-12-10
滋賀営業所㻌 〒520-3032 㻌 滋賀県栗東市苅原278（メゾンドケイズ）
岡山営業所㻌 〒710-0826 岡山県倉敷市老松町3-8-7(ビバリーガーデン老松)
広島営業所㻌 〒733-0821 広島市西区庚午北2-17-4（船本ビル）
周南営業所㻌 〒744-0002 山口県下松市東海岸通り1-11

フロンティアカーボンのフラーレン製品
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

フラーレン C70

SU

98/昇華精製品

0.5

nanom mix

ST

C60,C70,その他高次フラーレンの混合物

50

銘

分子構造

柄
ST
TL
SU
SUH
SC

nanom purple
フラーレン C60

nanom orange

混合フラーレン

nanom spectra[60]PCBM(phenyl C61-butyric acid methyl
ester)

E100

O

99

1

99.5

1

99.9

0.5

99/異性体トータル

0.5

O

E102
E110

(phenyl C71-butyric acid methyl
ester)

E112[70]PCBM※微粒化品（ ST-F）もあります

E100H

nanom spectraOO※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

nanom spectra Q100
nanom spectra Q40 0

2[60]インデン２付加体

0.599/異性体トータル1※位置異性体の混合物

HO

nanom spectra D100

HO

C60OHn n=10を主成分とする混合物(n = ca.10)

1

H

nanom spectra A100

H

水素化フラーレン

n/2

0.5

99

[60]インデン付加体

水酸化フラーレン

1

n/2

C60Hn n=30を主成分とする混合物(n = ca. 30)※銘柄、取扱数量等は予告無く変更する場合がございます。 ※試験研究用途向けです。

当社製品は、下記から購入いただけます。直接お問い合わせください。
・関東化学株式会社 試薬事業本部〒103-0022 東京都中央区日本橋室町2-2-1 TEL:03-6214-1090 FAX:03-3241-1047
http://www.kanto.co.jp E-mail:reag-info@gms.kanto.co.jp
・中山商事株式会社 筑波営業所 （担当 落合敬宝）〒300-2651茨城県つくば市鬼ケ窪1139-1 TEL:029-847-7355 FAX:029-847-1923
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