F NTG

Research Society

第 52 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 52nd Fullerenes-Nanotubes-Graphene General Symposium

講演要旨集
Abstracts2017 年 2 月 28 日（火） ～ 3 日（金）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 ・ 後援
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
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)
東京大学大学院工学系研究科 School of Engineering, The University of Tokyo
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 52 Fullerenes-Nanotubes-Graphene General Symposiumnd

Sponsored by : The Fullerenes, Nanotubes and Graphene Research Society
Co-Sponsored by : The Chemical Society of Japan

IRENA Project by JST-EC DG RTD, SICORP

Consortium for Innovation of Advanced Integrated Science(UTokyo)
Graduate Program for Mechanical Systems Innovation(UTokyo)

School of Engineering, The University of Tokyo

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

Date : February 28th(Tue.) – March 3rd(Fri.), 2017
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 52 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･後援 : 日本化学会
JST 戦略的国際共同研究プロジェクト IRENA東京大学 CIAiS東京大学 GMSI東京大学大学院工学系研究科
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 29 年 2 月 28 日(火)～3 月 3 日(金)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）
埼玉県庁 産業労働部 先端産業課（株）島津製作所（株）シンキー（株）セントラル科学貿易
東京ダイレック (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）
ブルカー・エイエックスエス（株）(株）堀場製作所（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
埼玉県庁 産業労働部 先端産業課
シグマ アルドリッチ ジャパン（同）（株）セントラル科学貿易
ソーラボジャパン（株）

Contents
Time Table ・・・・・・・・・・・・・・・・・・ i
Chairperson ・・・・・・・・・・・・・・・・・iii
ProgramJapanese ・・・・・・・・・・・・ iv
English ・・・・・・・・・・・・ xix
Abstracts
Special Lecture ・・・・・・・・・・ 1
General Lecture ・・・・・・・・・ 11
Poster Preview ・・・・・・・・・・43
Author Index ・・・・・・・・・・・・・・・・171

目次
早見表 ・・・・・・・・・・・・・・・・・・・ i
座長一覧・・・・・・・・・・・・・・・・・・・iii
プログラム 和文・・・・・・・・・・・・・・・ iv
英文・・・・・・・・・・・・・・ xix
講演予稿
特別講演・・・・・・・・・・・・・ 1
一般講演・・・・・・・・・・・・・11
ポスター発表・・・・・・・・・・・43
発表索引・・・・・・・・・・・・・・・・・・ 171

プログラム早見表
３月１日 （水）３月２日 （木）

受付開始 8：30～
講演開始 9：45～
9:00
9:30
9:45

特別講演 （篠原 久典）
9:45-10:15

10:15 特別講演 （Esko I. Kauppinen）
10:15-10:45
10:45
休憩 10:45-11:00
11:00
一般講演 4件(ナノチューブの生成と精製 ・ナノチューブの物性 ・ グラフェンの
物性）
11:00-12:00

12:00

昼食
(幹事会）
12:00-13:15

13:15 特別講演 （Christophe Bichara）
13:15-13:45
13:45
特別講演 (松本 和彦)
13:45-14:15
14:15
一般講演 3件
ポスタープレビュー( 1P-1 ～ 1P-42 )15:00-16:00

16:00

ポスターセッション（多目的スペース）
16:00-17:45

9:30-10:30
10:30
休憩 10:30-10:45
10:45 特別講演（Shyamal Kumar Saha）
10:45-11:15
11:15
一般講演 3件(原子層）
11:15-12:00
12:00
昼食
12:00-13:15

13:15

授賞式
13:15-14:00

14:00

ポスタープレビュー( 2P-1 ～ 2P-43 )14:00-15:00

15:00

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

休憩 17:45-18:00
チュートリアル講師： 篠原久典
名古屋大学（伊藤謝恩ホール）
18:00-19:30

３月３日 （金）
9:00
9:30(ナノチューブの生成と精製 ・ナノチューブの物性)(グラフェンの物性 ・ グラ
フェンの応用） 14:15-15:00

15:00

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 4件

10:30
10:45
11:15

受付開始 8：30～
講演開始 9：00～
特別講演 (河野 淳一郎)
9:00-9:30
一般講演 4件(ナノチューブの物性）
9:30-10:30
休憩 10:30-10:45
特別講演 （Kaihui Liu）
10:45-11:15
一般講演 3件(ナノチューブの物性 ・ ナノ
チューブの応用) 11:15-12:00

12:00

昼食
12:00-13:15

13:15

ポスタープレビュー( 3P-1 ～ 3P-42 )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

ポスターセッション( 多目的スペース )15:00-16:45

特別講演 （野田 優）
16:45-17:15
一般講演 7件(フラーレンの応用 ・ 金属
内包フラーレン ・ フラーレン
・ ナノ炭素粒子 ・ その他）

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

17:15-19:00
19:00

19:30

懇親会
（多目的スペース）
19:00-20:45

２月２８日 （火）第８回ﾅﾉｶｰﾎﾞﾝ実用化推進研究会（伊藤謝恩ホール）
第６回ﾅﾉｶｰﾎﾞﾝﾊﾞｲｵｼﾝﾎﾟｼﾞｳﾑ
（３階中教室）

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

20:45

i

Time table
March 1 (Wed.)
Registration begins at 8:30
Lectures begin at 9:45

9:45
10:15

Special Lecture(Formation and purification of nanotubes(Hisanori Shinohara) 9:45-10:15

・ Properties of nanotubes)

Special Lecture

9:30-10:30
Coffee Break 10:30-10:45
Special Lecture(Esko I. Kauppinen) 10:15-10:45

10:45
11:00

March 2 (Thu.)
Registration begins at 8:30
Lectures begin at 9:00
9:00
Special Lecture(Yan Li) 9:00-9:30
9:30
General Lectures [4]Coffee Break 10:45-11:00
General Lectures [4](Formation and purification of nanotubes

10:30
10:45

11:00-12:00
Lunch(Administrative meeting)
12:00-13:15

of graphene）

13:15

Special Lecture

12:00

Award Ceremony
13:15-14:00

14:00

Poster Preview( 2P-1 through 2P-43 )14:00-15:00

11:15

General Lectures [3](Properties of graphene ・ Applications

14:15-15:00
Poster Preview( 1P-1 through 1P-42 )15:00-16:00

16:00

15:00

13:15

Poster Preview( 3P-1 through 3P-42 )13:15-14:15

14:15

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

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

Poster Session( Event Space )16:00-17:45

16:00

Special Lecture(Erik Einarsson) 16:00-16:30
16:30
General Lectures [4]16:45

Special Lecture（Suguru Noda） 16:45-17:15
17:15
General Lectures [7]

17:45
18:00

Coffee Break 17:45-18:00
Tutorial
Lecturer : Hisanori Shinohara
Nagoya University( Ito Hall )18:00-19:30

11:15-12:00
Lunch
12:00-13:15

of nanotubes)

12:00

of graphene)

15:00

Coffee Break 10:30-10:45
Special Lecture(Kaihui Liu) 10:45-11:15
General Lectures [3](Properties of nanotubes ・ Applications

Special Lecture(Kazuhiko Matsumoto)13:45-14:15

14:15

General Lectures [3](Atomic Layers)
11:15-12:00
Lunch
12:00-13:15

13:15(Christophe Bichara) 13:15-13:45

13:45

10:30
10:45

(Shyamal K Saha) 10:45-11:15

11:15

・ Properties of nanotubes ・ Properties

12:00

March 3 (Fri.)
Registration begins at 8:30
Lectures begin at 9:00
9:00
Special Lecture(Junichiro Kono) 9:00-9:30
9:30
General Lectures [4](Properties of nanotubes)
9:30-10:30(Applications of fullerenes ・Endohedral metallofullerenes ・Fullerenes ・ Carbon nanoparticles
・ Other topics )(Graphene synthesis ・Applications of graphene)

16:30-17:30
17:30

17:15-19:00
19:00

19:30

Banquet( Event Space )19:00-20:45

February 28 (Tue.)The 8th NanoCarbon Application Forum( Ito Hall )February 28 (Tue.)The 6th NanoCarbon-Bio Symposium( 3F Seminar Room )20:45
Place : Ito Hall
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)
3月1日 (水)セッション
特別講演 (篠原 久典）
特別講演 (Esko I. Kauppinen）
一般講演
特別講演 (Christophe Bichara）
特別講演 (松本 和彦）
一般講演
ポスタープレビュー時
間
9:45 ～10:15
10:15 ～10:45
11:00 ～ 12:00
13:15～ 13:45
13:45 ～ 14:15
14:15 ～ 15:00
15:00 ～ 16:00

チュートリアル (篠原 久典）

18:00 ～ 19:30

3月2日 (木)セッション
特別講演 (Yan Li）
一般講演
特別講演 (Shyamal Kumar Saha）
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
14:00 ～ 15:00

特別講演 (野田 優）
一般講演

(敬称略）

16:45 ～ 17:15
17:15 ～ 17:30
17:30 ～ 19:00

3月3日 (金)セッション
特別講演 (河野 淳一郎）
一般講演
特別講演 (Kaihui Liu）
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 (Erik Einarsson）
一般講演

16:00 ～ 16:30
16:30 ～ 17:30

iii

座
長
丸山 茂夫
篠原 久典
北浦 良
丸山 茂夫
長汐 晃輔
長汐 晃輔
杉目 恒志
大町 遼
丸山 茂夫

座
長
野田 優
野田 優
斎藤 晋
高井 和之
桜井 俊介
長谷川 馨
吾郷 浩樹
吾郷 浩樹
松尾 豊
座
長
加藤 雄一郎
松田 一成
Yan Li
宮内 雄平
蓬田 陽平
井ノ上 泰輝千足 昇平
大野 雄高

３月１日 （水）特別講演
発表 ２５分 ・ 質疑応答 ５分
一般講演
発表 １０分 ・ 質疑応答 ５分
ポスタープレビュー
発表 １分 ・ 質疑応答 なし
特別講演 ( 9:45-10:15 )1S-1

3

Putting sp -diamondoids into carbon nanotubes* 篠原 久典

1

特別講演 ( 10:15-10:45 )1S-2

Direct dry deposition of SWNTs by thermophoresis* Esko I. Kauppinen, Patrik Laiho, Kimmo Mustonen, Shigeo Maruyama, Yutaka Ohno2＞＞＞＞＞＞＞ 休憩 ( 10:45-11:00 ) ＜＜＜＜＜＜＜一般講演 ( 11:00-12:00 )ナノチューブの生成と精製 ・ ナノチューブの物性 ・ グラフェンの物性
1-1Fabrication of multiple transistors from semiconducting single-walled carbon nanotube
arrays after water-assisted burning of metallic tubes* 大塚 慶吾 , 井ノ上 泰輝 , 千足 昇平 , 丸山 茂夫

11

1-2

2層カーボンナノチューブにおける非対称な電荷蓄積* 古地 健人 , 岡田 晋

12

1-3

Enhancement of Raman scattering from monolayer graphene by photonic crystal nanocavities* Issei Kimura, Masahiro Yoshida, Masaki Sota, Hidenori Machiya, Taiki Inoue,
Shohei Chiashi, Shigeo Maruyama, Yuichiro K. Kato

13

1-4

二次元炭化水素ネットワークの磁性* 反町 純也 , 岡田 晋

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

Growth modes and chiral selectivity of Single Wall Carbon Nanotubes* Christophe Bichara

3

特別講演 ( 13:45-14:15 )1S-4糖鎖修飾グラフェンを用いた高感度ウイルス検出* 松本 和彦4

一般講演 ( 14:15-15:00 )グラフェンの物性 ・ グラフェンの応用
1-5

Opening a Gap in Graphene Field Effect Devices with Periodic Uniaxial Strain* 友利 ひかり , 平出 璃音可 , 大塚 洋一 , 渡辺 賢司 , 谷口 尚 , 神田 晶申iv

15

３月１日 （水）1-6

Gas Adsorption Effects on Stabilities and Electronic Properties of Graphene Bilayers* Yoshitaka Fujimoto, Susumu Saito

16

1-7

Edge Roughness Analysis for Developing GNR-based FET* Kengo Takashima, Takahiro Yamamoto

17

ポスタープレビュー ( 15:00-16:00 )ポスターセッション ( 16:00-17:45 )金属内包フラーレン
1P-1

1P-2

（☆） 若手奨励賞候補

Photochemical Addtion of Siliranes to Sc 3N@Ih-C80: Interconversion of the [6,6]and [5,6]-Adducts* 杉浦 健 , 宮部 恭輔 , 加固 昌寛 , 安井 正憲 , 山田 道夫 , 前田 優 , Jingdong Guo,
永瀬 茂 , 赤阪 健
Conclusive Characterization of Li@C60 by X-ray Structure Analysis* Hiroshi Ueno, Shinobu Aoyagi, Naohiko Ikuma, Hiroshi Okada, Kei Ohkubo,
Tatsuhisa Kato, Shunichi Fukuzumi, Yutaka Matsuo, Ken Kokubo

43

44

ナノチューブの物性
1P-3

1P-4
☆
1P-5

1P-6

Diameter and defect density dependence of intermediate frequency Raman mode of
single-walled carbon nanotubes* 稲葉 工 , 小鍋 哲 , 本間 芳和
Spectral tuning of optical coupling between air-mode nanobeam cavities and individualcarbon nanotubes* Hidenori Machiya, Takushi Uda, Akihiro Ishii, Yuichiro K. Kato
Tuning of Photo-thermoelectric effect of Metallic and Semiconducting Single wall carbon
nanotube thin films by electrolyte gating* 中村 昌稔 , 一ノ瀬 遥太 , 河合 英輝 , 蓬田 陽平 , 柳 和宏
単層カーボンナノチューブの蛍光特性：フォトン再吸収効果* 魏 小均 , 都築 真由美 , 蓬田 陽平 , 王 国偉 , 平野 篤 , 藤井 俊治郎 , 田中 丈士 ,

45

46

47

48

片浦 弘道
1P-7

カーボンナノポットの表面状態－KFM観察－* 横井 裕之 , 池田 晃三 , 畠山 一翔 , 鯉沼 陸央

49

1P-8

界面活性剤溶液中でのSWCNTの分散安定性に対するアニオンの効果* 平野 篤 , Gao Weilu, He Xiaowei, 河野 淳一郎

50

ナノチューブの応用
1P-9

Paper-based carbon nanotube field effect transistor by photolithography* Jong Mok Shin, Do Hyun Kim, InYeob Na, Ho-Kyun Jnag, Jun Hee Choi, Se Jeong Park,
Gyu-Tae Kim

51

1P-10
☆

Doping effect of electrolyte droplet on carbon nanotube thin film
* Tomohiro Yasunishi, Shigeru Kishimoto, Yutaka Ohno

52v

３月１日 （水）
1P-11

1P-12
☆

1P-13

メルトブレンディングによるCNT/Polyethylene複合材料の開発* 小野寺 厚 , Sami Ristimäki, 関戸 大
Defluorination-Assisted Synthesis of Nitrogen-Doped Single-Walled Carbon Nanotubes andTheir Catalytic Activity of Oxygen Reduction Reaction for Polymer Electrolyte Fuel Cells* Koji Yokoyama, Shun Yokoyama, Yoshinori Sato, Masashi Yamamoto, Tetsuo Nishida,
Kenichi Motomiya, Hiromichi Ohta, Hideyuki Takahashi, Kazuyuki Tohji, Yoshinori Sato
Film fabrication of Semiconducting Single-Wall Carbon Nanotubes by Aqueous-Two Phase
System and Thin Film Transistor Applications* Haruka Omachi, Tomohiko Komuro, Jun Hirotani, Yutaka Ohno, HIsanori Shinohara

53

54

55

ナノチューブの生成と精製
1P-14

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

56

1P-15
☆

高濃度エチレン原料からのサブミリメータ長カーボンナノチューブの高収率流動層合成* 蜂谷 宗一郎 , 陳 忠明 , 川端 孝祐 , 長谷川 馨 , 大沢 利男 , 野田 優

57

1P-16

電界誘起層形成法を用いた大量連続金属型・半導体型CNT分離* 二瓶 史行 , 佐々木 芙紗子 , 桑原 有紀 , 斎藤 毅 , 遠藤 浩幸

58

1P-17
☆

Development of gels for high-efficiency metal/ semiconductor separation of SWCNTs* Guowei Wang, Xiaojun Wei, Atsushi Hirano, Takeshi Tanaka, Hiromichi Kataura

59

1P-18

Purity Analysis and Purification of Double-walled Carbon Nanotubes* Kenshi Miyaura, Hidekazu Nishino, Shirou Honda

60

内包ナノチューブ
1P-19
☆

1P-20

An experimental and theoretical study on the scanning spectroscopy of europium nanowires
encapsulated in carbon nanotubes* Terunobu Nakanishi, Ryo Kitaura, Takazumi Kawai, Susumu Okada, Shoji Yoshida,
Osamu Takeuchi, Hidemi Shigekawa, Hisanori Shinohara
単層カーボンナノチューブに内包されたヨウ化セシウムの電子状態および固体NMR
パラメーターのDFT計算* 横倉 瑛太 , 片岡 洋右 , 緒方 啓典

6162

グラフェン生成
1P-21

Au-Ni触媒CVDによる高い均一性を有する多層グラフェン成長に関する研究* 上田 悠貴 , 山田 純平 , 藤原 亨介 , 山本 大地 , 丸山 隆浩 , 成塚 重弥

63

1P-22
☆

一酸化炭素からのグラフェンの熱力学的制御合成* 永井 款也 , 長谷川 馨 , 野田 優

64

グラフェンの応用
1P-23

Fe及びCaを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* 倉金 夏己 , 星野 崚 , 櫻井 亮太 , 山岸 多門 , 永田 知子 , 岩田 展幸 , 山本 寛

vi65

３月１日 （水）1P-24

Functional group dependence of Spin magnetism of Graphene oxide* 田嶋 健太郎 , 井坂 琢也 , 山科 智貴 , 松尾 吉晃 , 高井 和之

66

1P-25

Highly efficient, mechanically durable perovskite solar cells with graphene electrodes* Jungjin Yoon, Namyoung Ahn, Mansoo Choi

67

1P-26

溶液分散した酸化グラフェン単一片の還元反応のトワイライト蛍光顕微鏡による追跡* 佐藤 光 , 佐野 正人

68

1P-27

Production and characterization of graphene quantum dots derived from SWNTs and graphite* 森田 博暉 , 菅井 俊樹

69

グラフェンの物性
1P-28

1P-29
☆

BNドープグラフェンのエネルギー論と電子状態* 澤畑 恒来 , 丸山 実那 , 岡田 晋
Charge transfer dynamics at graphene/SiC interface studied by time-resolved soft X-ray
photoemission spectroscopy* 染谷 隆史 , 吹留 博一 , 山本 達 , 遠藤 則史 , 松田 巌

70

71

1P-30

顕微ラマン分光を使ったグラフェンのひずみ方位の簡単な決定法* 中村 和史 , 友利 ひかり , 神田 晶申

72

1P-31

グラフェンナノリボンの力学特性* 米山 和文 , 山中 綾香 , 岡田 晋

73

1P-32

Introduction of spin-orbit interaction into graphene by various methods* T. Nanba, T. Tamura, Y. Katagiri, C. Ohata, Pierre Seneor, J. Haruyama

74

1P-33

Influences of Graphene Structure on Electrochemical Interactions in LiBF 4 Organic
Electrolyte Solution* 鈴木 大輔 , 高井 和之

75

原子層
1P-34

1P-35
☆
1P-36

1P-37
☆

Detection of photo current arising from atom-thin MoS2 Schottky junction fabricated byelectron beam irradiation* Yuto Katagiri, C. Ohata, Y. Inoue, S. Maruyama, T. Nakamura, S. Katumoto, A. Ishi,
M. Hasegawa, G. Fioli, S. Roche, J. Haruyama
マイルド酸素プラズマ処理による架橋型2層WSe2デバイスのコンタクト抵抗改善機構* 永井 黎人 , 金子 俊郎 , 加藤 俊顕
Optical spectroscopy on monolayer transition metal dichalcogenides immersed in an aqueous
solution* Wenjin Zhang, Yusuke Hasegawa, Kazunari Matsuda, Yuhei Miyauchi
グラフェンと遷移金属ダイカルコゲナイドにおけるヘリシティ選択的な１次共鳴ラマン
スペクトル* 辰巳 由樹 , 齋藤 理一郎

vii

76

77

78

79

３月１日 （水）C60が吸着したグラフェンのエネルギー論と電子状態* ソーシアー アレキサンダー大和 , 丸山 実那 , 岡田 晋

80

カーボンナノチューブのマウス組織中アップコンバージョン発光スペクトル* 奥平 早紀 , 飯泉 陽子 , 湯田坂 雅子 , 岡崎 俊也 , 松田 一成 , 宮内 雄平

81

1P-40

Electrical properties of defective hexagonal boron nitride nanosheet* Ho-Kyun Jang, Jun Hee Choi, Kook Jin Lee, Do-Hyun Kim, Gyu Tae Kim

82

1P-41

Modification of Electrical Properties in MoS 2 by Using Catalytic Oxidation* Jun Hee Choi, Ho-Kyun Jang, Jun Eon Jin, Jong Mok Shin, Do-Hyun Kim, Gyu-Tae Kim

83

1P-42

Hidden symmetries in one-dimensional photonic crystals* M. Shoufie Ukhtary, Haihao Liu, Riichiro Saito

84

1P-38

バイオ
1P-39

その他

＞＞＞＞＞＞＞ 休憩 ( 17:45-18:00 ) ＜＜＜＜＜＜＜チュートリアル ( 18:00-19:30 )ナノカーボンが創るナノ空間の創製と探索* 篠原 久典

viii

３月２日 （木）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

Catalyst design for controlled growth of single-walled carbon nanotubes* Yan Li

5

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

酸化マグネシウム触媒下地層のアニール処理による単層カーボンナノチューブフォレスト
合成効率の大幅な向上* 辻 享志 , 畠 賢治 , フタバ ドン , 桜井 俊介

18

2-2

交流インピーダンス法によるCNTスラリーの分散状態評価* 渡邉 敬之 , 小橋 和文 , 森本 崇宏 , 岡崎 俊也

19

2-3

垂直配向CNT成長用の鉄触媒粒子形成における貴金属元素添加効果* 桜井 俊介 , 畠 賢治 , フタバ ドン

20

2-4

ロックインサーモグラフィーを用いたCNTネットワーク構造の可視化* 森本 崇宏 , 阿多 誠介 , 山田 健郎 , 岡崎 俊也

21＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜特別講演 ( 10:45-11:15 )2S-6

Functionalized 2D materials for sensing applications* Shyamal K Saha, Diptiman Dinda

6

一般講演 ( 11:15-12:00 )
原子層
2-5

2-6

2-7

Scanning Electrochemical Cell Microscopy for Visualization of Local Electrochemical
Activities on Graphene/Graphite* 熊谷 明哉 , 三浦 千穂 , 岡田 健 , 寒川 誠二 , 珠玖 仁 , 高橋 康史 , 末永 智一
Out-of-Plane Strain Generation of Monolayer MoS2 and MoSe2 Formed a Moiré
Superstructure on the Au(111) Surface
Ryosuke Takahashi, Ryo Osaka, Yasumitsu Miyata, Susumu Okada, Yuhei Hayamizu,* Satoshi Yasuda, Kei Murakoshi
Magnetic tunnel junction built from intercalated transition metal dichalcogenide ferromagnets
with different magnetic anisotropy* 山崎 雄司 , 守谷 頼 , 荒井 美穂 , 増渕 覚 , 卞 舜生 , 為ヶ井 強 , 上野 啓司 ,

町田 友樹

ix

22

23

24

３月２日 （木）＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜
大澤賞・飯島賞・若手奨励賞の授賞式 ( 13:15-14:00 )ポスタープレビュー ( 14:00-15:00 )ポスターセッション ( 15:00-16:45 )フラーレンの化学（☆） 若手奨励賞候補

2P-1

計算化学的手法による活性化フラーレンの電子特性と反応性の評価* 伊熊 直彦 , 小久保 研 , 大島 巧

85

2P-2
☆

Pd触媒を用いたフラーレンの位置選択的変換反応と構造* 橋川 祥史 , 村田 理尚 , 若宮 淳志 , 村田 靖次郎

86

2P-3

リチウムイオン内包フルオレノ[60]フラーレンの合成* 松尾 豊 , 岡田 洋史 , 上野 裕

87

フラーレンの応用
2P-4

フラーレン二重膜をテンプレートとしたポリマー集合体のナノスケール形態制御* 原野 幸治 , ゴルゴル リカルドミゾグチ , 中村 栄一

88

2P-5

電子線照射によるフラーレン薄膜の金属的重合化* 上野山 寛人 , 田中 悠 , 山之内 真悟 , 落合 勇一 , 青木 伸之

89

2P-6

2P-7

Synthesis of CdS-Mn-[C60]Fullerene Nanocomposites and Their Photocatalytic Activities for
Degradation of Organic Dyes
* Jeong Won Ko, Jiulong Li, Weon Bae Ko
Studies on the Aggregated Structures and Crystallinities of Bulk Heterojunction Films
Constituting Organic Solar Cells* 河野 紗希 , 緒方 啓典

9091

金属内包フラーレン
2P-8

Production and Characterization of Hetero-dimetallofullerene: GdY@C 80(Ih)* 三谷 拓示 , 中鳥 なつみ , 山口 貴久 , 古川 貢 , 加藤 立久 , 菊地 耕一 ,阿知波 洋次 , 兒玉 健

92

2P-9
☆

La@C60(CF3)5 の単離と構造解析* 西野 眞希子 , 青柳 忍 , 大町 遼 ,, 中川 綾乃 , 北浦 良 , 篠原 久典

93

2P-10

Photoreactions of Cyclic Organosilanes with Trimetallic Nitride Template Endohedral
Metallofullerenes* 深澤 新平 , 杉浦 健 , 宮部 恭輔 , 加固 昌寛 , 赤阪 健

94

フラーレン
2P-11

1次元SIMEF鎖のエネルギー論と電子状態* 古谷 匠 , 岡田 晋95x

３月２日 （木）

2P-12

2P-13

Absolute yield of fullerene formed by graphite laser ablation at medium-high ambient
temperatures* Haruka Suzuki, Yuki Taguchi, Takeshi Kodama, Yohji Achiba, Haruo Shiromaru
Energetics and electronic properties of fullerenes consisting of fused pentagonal rings* 岡田 晋96

97

ナノチューブの物性
2P-14Macroscopic aligned single-walled carbon nanotubes achieved with vacuum filtration* 張 浩 , 項 榮 , 井ノ上 泰輝 , 千足 昇平 , 丸山 茂夫

98

2P-15
☆

Selective phonon mode generations in single wall carbon nanotubes and graphene nanoribbons* Ahmad R. T. Nugraha, Eddwi H. Hasdeo, Riichiro Saito

99

2P-16

Electrically conductive multi-walled boron nitride nanotubes by catalytic etching* Do-Hyun Kim, Ho-Kyun Jang, Min-Seok Kim, Sung-Dae Kim, Dong-Jin Lee, Gyu Tae Kim

100

ナノチューブの応用
2P-17
☆
2P-18

2P-19
☆

Artificial muscle using single wall carbon nanotube bundles* グエン タン フン , アフマド リドワン トレスナ ヌグラハ , 齋藤 理一郎
Electrochemical Properties of Nitrogen-Doped Vertically Aligned Multi-Walled Carbon
Nanotubes Prepared by Defluorination* Rei Nonomura, Takashi Itoh, Yoshinori Sato, Masashi Yamamoto, Tetsuo Nishida,
Kenichi Motomiya, Kazuyuki Tohji, Yoshinori Sato
基板上CNT合成と集合形態制御、電子エミッタ応用* 北川 紗映 , 杉目 恒志 , 野田 優

101

102

103

ナノチューブの生成と精製
2P-20

2P-21
☆

2P-22

2P-23
☆
2P-24

Analysis of Pt catalyst for SWNT growth by In-situ XANES* 熊倉 誠 , 桐林 星光 , 才田 隆広 , 成塚 重弥 , 丸山 隆浩

104Time-dependent selective synthesis and growth mechanism of single-walled carbon nanotubes
105
from sputtered W-Co catalyst* Hua An, Rong Xiamg, Akihito Kumamoto, Taiki Inoue, Shohei Chiashi, Yuichi Ikuhara,
Shigeo Maruyama
Extraction of High-Purity Single-Chirality Single-Wall Carbon Nanotubes by Precise Tuningof pH using CO2 Bubbling* 一ノ瀬 遥太 , 枝 淳子 , 真庭 豊 , 蓬田 陽平 , 柳 和宏
単層カーボンナノチューブ成長過程に対する磁場効果とその機構の検討* 高嶋 泰正 , 浜崎 亜富 , 内村 仁 , 尾関 寿美男
Chemical reaction analysis of Fe-Co and Co-Cu clusters with ethanol by FT-ICR mass
spectrometer* 水谷 健 , 佐藤 仁紀 , 箕輪 紘弥 , 山田 涼平 , 井ノ上 泰輝 , 千足 昇平 ,

丸山 茂夫

xi

106

107

108

３月２日 （木）グラフェンの物性
2P-25端の水酸基化によるグラフェンリボンへの自由電子注入* 平 麗実 , 山中 綾香 , 岡田 晋

109

2P-26

電場によるNドープグラフェンの電子構造制御* 松原 愛帆 , 岡田 晋

110

2P-27

Electronic structures of graphene exposed to electrolyte solution* Mari Ohfuchi

111

2P-28

エッジ状態スピンとフェロセニウムイオンスピン間の磁気的相互作用* Akira Suzuki, Kazuyuki Takai

112

2P-29

過熱還元された酸化グラフェンの電気伝導特性* 石田 拓也 , 仁科 勇太 , 青木 伸之

113

2P-30

グラフェンへの分子吸着による電荷移動における水分子の影響梅原 隆 , * 高井 和之

114

2P-31
☆

二次元積層系のための均一な多層h-BNの大面積成長* 仲村渠 翔 , 河原 憲治 , 内田 勇気 , 山崎 重人 , 光原 昌寿 , 吾郷 浩樹

115

2P-32

2次元材料によるレーザー水分解の高効率化II* 宮本 良之 , Hong Zhang, Xinlu Cheng, Angel Rubio

116

原子層

2P-33
☆
2P-34

2P-35
☆

Photoluminescence and photocurrent properties of monolayer WSe 2 FETs fabricated by
dry-transfer process* 王 暁凡 , 張 文金 , モハメッド ヌル バイズラ , 譚 徳志 , リム ホンエン , 宮内 雄平 ,

117

松田 一成
Piezoelectric properties of 3R bulk transition metal dichalcogenides* 小鍋 哲 , 山本 貴博
Molecular beam epitaxy growth of molybdenum diselenide atomic layers on hexagonal boron
nitride substrates* Takuto Tokuda, Takato Hotta, Kenji Watanabe, Takashi Taniguchi, Hisanori Shinohara,
Ryo Kitaura

118

119

ナノ炭素粒子
2P-36

隕石ナノダイヤと爆轟法ナノダイヤは同一物質* 大澤 映二 , バーナード アマンダ , 田中 利彦 , 深谷 正義

120

2P-37

窒素ドープカーボンナノバルーンの合成* 高橋 良太 , 針谷 達 , 滝川 浩史 , 須田 善行

121

その他
2P-38

界面活性剤を用いたゾルゲル法で作製した試料からの酸化鉄ナノチューブの分離とキャラクタリゼ―ション
田中 佑佳 , * 坂東 俊治

xii

122

３月２日 （木）2P-39

多段トラップ気相移動度測定装置の開発とナノ物質の分離* 菅井 俊樹 , 椎野 恭平 , 星野 裕大 , 寺田 夏樹 , 浜野 裕太 , 森田 博暉 ,

123

陣内 涼太
2P-40

トリプチセン誘導体の力学特性* 秋葉 実樹 , 岡田 晋

124

2P-41

メタン熱触媒分解による炭素触媒の活性低下メカニズムの調査* 西井 春樹 , 梅田 良人 , 濱口 裕昭 , 鈴木 正史 , 針谷 達 , 滝川 浩史 , 須田 善行

125

2P-42

直接メタノール型燃料電池用触媒の触媒活性に対するPtRu合金化率の効果* 川崎 航平 , 大廣 達郎 , 針谷 達 , 滝川 浩史 , 植 仁志 , 須田 善行

126

2P-43

集束イオンビーム加工装置を用いたカーボンナノコイルの微細加工* 高橋 宗浩 , 針谷 達 , 滝川 浩文 , 植 仁志 , 須田 善行

127

特別講演 ( 16:45-17:15 )2S-7

カーボンナノチューブの合成・機能化とエネルギーデバイス応用* 野田 優7

一般講演 ( 17:15-19:00 )フラーレンの応用 ・ 金属内包フラーレン ・ フラーレン ・ ナノ炭素粒子 ・ その他
2-8

メタノインデンフラーレンを用いたペロブスカイト太陽電池における開放電圧の向上* 松尾 豊25

2-9Electronic Structures and Stability of Metal Encapsulated C 80 fullerenes: Ab initio DFT study* Archana Velloth, Yutaka Imamura, Takeshi Kodama, Masahiko Hada

26

2-10

Searching for the unprecedented endohedral metallofullerenes by applying the separation
method for those stable only in an anion form
* 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
+

27

2-11

C60フラーレンに内包されたLi イオンの運動* 鈴木 晴 , 石田 美咲 , 山下 将嗣 , 大谷 知行 , 河地 和彦 , 笠間 泰彦 , 權 垠相

28

2-12

Geometric and electronic structures of polymerized C40 fullerene* Mina Maruyama, Susumu Okada

29

2-13

炭化水素ガス流中のレーザー誘起ブレークダウンによるポリイン生成
田口 裕貴 , 遠藤 瞳 , 兒玉 健 , 若林 知成 , 阿知波 洋次 , * 城丸 春夫 , Wales Benji,
Sanderson Joseph

30

2-14

爆轟法ナノダイヤモンドにおける基本粒子の内核* 田中 利彦 , 深谷 真芳 , バーナード アマンダ , 大澤 映二

31

懇親会 ( 19:00-20:45 )xiii

３月３日 （金）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-8Strong Light-Matter Coupling in (6,5) Carbon Nanotubes* Junichiro Kono, Weilu Gao, Kankan Cong, Xinwei Li, G. Timothy Noe II, Huaping Liu,
Takeshi Tanaka, Hiromichi Kataura

8

一般講演 ( 9:30-10:30 )ナノチューブの物性
3-1

3-2

Optical bistability in carbon nanotubes* Takushi Uda, Akihiro Ishii, Yuichiro K. KatoSingle photon generation through exciton-exciton annihilation in air-suspended carbon
nanotubes* Akihiro Ishii, Takushi Uda, Yuichiro K. Kato

32

33

3-3

Raman Spectroscopy of Individual Single-Walled Carbon Nanotubes* Juan Yang, Daqi Zhang, Yan Li

34

3-4

酸化単層カーボンナノチューブの修飾率に依存する競争的な脱離と分解反応* 前田 優 , 曽根 絵理香 , 西野 朱音 , 天谷 優里 , Wang Wei-Wei, 山田 道夫 ,鈴木 光明 , 松井 淳 , 三ツ石 方也 , 岡崎 俊也 , 永瀬 茂

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

Optical Spectroscopy of Individual Carbon Nanotubes with Defined Atomic Structure* Kaihui Liu

9

一般講演 ( 11:15-12:00 )ナノチューブの物性 ・ ナノチューブの応用
3-5

多層カーボンナノチューブ電子源を搭載したナノ分解能FE-SEMとX線顕微鏡の開発* 入田 賢 , 山崎 慎太郎 , 勝山 翔太 , 中原 仁 , 安坂 幸師 , 齋藤 弥八 , 村田 英一 ,

36

大野 輝昭
3-6

3-7

Cold exciton electroluminescence from air-suspended carbon nanotube split-gate devices
Noriyuki Higashide, * Masahiro Yoshida, Takushi Uda, Akihiro Ishii, Yuichiro K. Kato
ペロブスカイト太陽電池におけるコストおよび安定性の問題解決へ向けたオールカーボンアプローチ* 田 日 , Namyoung Ahn, Jungjin Yoon, Esko Kauppinen, Mansoo Choi, 松尾 豊 ,

丸山 茂夫

xiv

37

38

３月３日 （金）＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜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 )金属内包フラーレン（☆） 若手奨励賞候補

3P-1

Attempt to produce dimetallofullerenes containing Yb* 小林 和博 , 三谷 拓示 , 中鳥 なつみ , 菊地 耕一 , 阿知波 洋次 , 兒玉 健

3P-2

Spectroscopic studies of La 2@C78 anion* 西本 真也 , 小林 和博 , 平山 貴晟 , 三谷 拓示 , 中鳥 なつみ , 山口 貴久 ,古川 貢 , 加藤 立久 , 菊地 耕一 , 阿知波 洋次 , 兒玉 健

128

129

ナノチューブの物性
3P-3

ディスク式遠心沈降法によるナノ材料の分散状態の評価* Naoko Tajima, Takahiro Morimoto, Yuichi Kato, Kazufumi Kobashi, Takeo Yamada,Toshiya Okazaki

130

3P-4
☆

Unified analysis of quantum and classical transport properties on metallic carbon nanotubes* Keisuke Ishizeki, Kenji Sasaoka, Satoru Konabe, Satofumi Souma, Takahiro Yamamoto

131

3P-5

High Temperature Surface Enhanced Raman Scattering of Single-Walled Carbon Nanotubes* Ming Liu, Keigo Otsuka, Rong Xiang, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama

132

3P-6

Fabrication and photoluminescence characterization of carbon nanotube dual-gate devices* Akihiro Sasabe, Takushi Uda, Masahiro Yoshida, Akihiro Ishii, Yuichiro K. Kato

133

3P-7

Optical Measurement of Single-Walled Carbon Nanotubes Using Rayleigh Scattering
Spectroscopy* 大河内 健史 , 大沢 徹 , 古川 頼誉 , 大鋸本 達郎 , 鎌倉 駿 , 井ノ上 泰輝 ,千足 昇平 , 丸山 茂夫

134

ナノチューブの応用
3P-8

熱界面材料に向けた銅箔上のカーボンナノチューブの垂直配向成長と構造制御* 小林 峻司 , 長谷川 馨 , 杉目 恒志 , 大堀 真直 , 塩見 淳一郎 , 周 暁松 ,二瓶 瑞久 , 野田 優

3P-9

Selective detection of neurotransmitters by adsorption voltammetry with carbon nanotube film 136* Takuya Ushiyama, Shigeru Kishimoto, Yutaka Ohno

3P-10

3P-11
☆

Time-dependent change of the semiconducting-CNT ink evaluated from the performance of
CNT-TFTs* 桑原 有紀 , 佐々木 扶紗子 , 二瓶 史行 , 斎藤 毅

135

137

Lamination of Vertically Aligned Single-Walled Carbon Nanotube Forests on Perovskite Solar
138
Cells via Membrane Filter Transfer Method* Seungju Seo, IL Jeon, Takahiro Sakaguchi, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Yutaka Matsuo, Shigeo Maruyama

xv

３月３日 （金）3P-12Yields of carbon nanotube integrated circuits on flexible plastic film
* Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno

139

3P-13
☆

Modeling of carbon nanotube thin-film transistor on flexible plastic film
* 鹿嶋 大雅 , 松浦 智紀 , 廣谷 潤 , 岸本 茂 , 大野 雄高

140

3P-14

Improved Efficiency and Stability of Perovskite Solar Cells with Single-Walled Carbon
Nanotube Electrodes* Takahiro Sakaguchi, Jeon Il, Hiroki Suko, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Esko I. Kauppinen, Nam-Gyu Park, Yutaka Matsuo, Shigeo Maruyama

141

ナノチューブの生成と精製
3P-15２液相法とラマン分光を利用した金属／半導体単層カーボンナノチューブの比の評価
裏谷 研人 , 金澤 尚宜 , * 鈴木 信三

142

3P-16
☆

ハロゲンガスによる多様なカーボンナノチューブからの触媒金属の除去* 浜田 航綺 , 杉目 恒志 , 野田 優

143

3P-17

Controllable growth of single-walled carbon nanotubes in quality and uniformity by extended
alcohol catalytic chemical vapor deposition* Bo Hou, Cheng Wu, Yuko Iizumi, Takahiro Morimoto, Toshiya Okazaki, Taiki Inoue,
Shohei Chiashi, Rong Xiang, Shigeo Maruyama

144

3P-18

W-Co触媒を用いた構造制御合成* Shinnosuke Ohyama, Shun Yamamoto, Hua An, Feng Yang, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Yan Li, Shigeo Maruyama

145

3P-19

Growth of Semiconducting (14,4) Carbon Nanotubes using W-Co Salts as Catalyst Precursor* Xiulan Zhao, Feng Yang, Yan Li

146

3P-20

Single-Walled Carbon Nanotube Growth from Bimetallic Catalyst by Molecular Dynamics
Simulations* 吉川 亮 , 鵜飼 浩行 , 高木 勇海 , 千足 昇平 , 丸山 茂夫

147

内包ナノチューブ
3P-21☆

Template Synthesis of π-Conjugated Nanomaterials using Inner Space of Carbon Nanotubes* Yasuhiro Kinno, Haruka Omachi, Ryo Kitaura, Hisanori Shinohara

148

3P-22

第一原理計算によるカーボンナノチューブに内包されたカルコゲンの電子状態評価* 佐藤 豊 , 横倉 瑛太 , 片岡 洋右 , 緒方 啓典

149

ナノホーン
3P-23

リポポリサッカライド処理をしたマクロファージに対するカーボンナノホーンの影響* 中村 真紀 , 黒岩 輝代子 , 飯島 澄男 , 湯田坂 雅子

150

3P-24

A study of Preparation Conditions of Carbon Nanobrush* Ryota Yuge, Fumiyuki Nihey, Kiyohiko Toyama, Masako Yudasaka

151

xvi

３月３日 （金）グラフェン生成
3P-25
☆
3P-26

Analysis of Initial Formation Process of Graphene on SiC(0001) Surfaces Based on the FirstPrinciples Molecular Dynamics* Fumihiro Imoto, Jun-Ichi Iwata, Mauro Boero, Atsushi Oshiyama
Growth of Single-Crystal Single-Layer and Bi-Layer Graphene Using Alcohol Catalytic CVD* Masaki Sota, Kotaro Kashiwa, Naomasa Ueda, Keigo Otsuka, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Shigeo Maruyama

152

153

グラフェンの応用
3P-27

太陽電池応用に向けたグラフェン電極上の高配向CuInS2薄膜* 石川 亮佑 , 大矢 智也 , 山田 図南 , 野本 隆宏 , 坪井 望

154

3P-28

Controlled fabrication of graphene liquid cells* Yoshimasa Michiya, Tomohiro Yasunishi, Yutaka Ohno, Hisanori Shinohara, Ryo Kitaura

155

3P-29

酸化アミンカップリング反応における酸化グラフェンの反応性の要因* 井坂 琢也 , 田嶋 健太郎 , 山科 智貴 , 高井 和之

156

3P-30

CVD成長した大面積二層グラフェンへのMoCl5のインターカレーションと透明導電膜応用* 木下 博貴 , 河原 憲治 , 寺尾 友里 , Il Jeon, 丸山 実那 , 松本 里香 , 岡田 晋 ,松尾 豊 , 吾郷 浩樹

157

グラフェンの物性
3P-31

3P-32
☆

グラフェン端への酸素吸着のエネルギー論* 安間 愛莉 , 山中 綾香 , 岡田 晋
Band unfolding study on Fermi-level-velocity reduction induced by Dirac cone interaction in
twisted bilayer graphene* 西 紘史 , 松下 雄一郎 , 押山 淳

158

159

3P-33

グラフェン端形成過程のエネルギー論* 山中 綾香 , 岡田 晋

160

3P-34

Electronic structure of edge functionalized graphene under an external electric field* Yanlin Gao, Susumu Okada

161

3P-35

Brillouin zone topology and band structure of four-dimensional diamond
Yuichi Kato, * Masanori Yamanaka

162

3P-36

単原子空孔を有する二層グラフェンの電導特性* 岸本 健 , 岡田 晋

163

原子層
3P-37
☆

Tuning of local optical properties of MoS 2 monolayer and its structural control using
electric-field-effect scanning near-field optical microscopy techniques* 野崎 純司 , 福村 武蔵 , 青木 孝晶 , 真庭 豊 , 蓬田 陽平 , 柳 和宏

xvii

164

３月３日 （金）3P-38

Optical properties of superacid-treated MoS 2* 林 宏恩 , モハメッド ヌル バイズラ , 宮内 雄平 , 松田 一成

165

3P-39

原子層物質ヘテロ積層構造における層間エキシトンの緩和過程* 岡田 光博 , 暮石 宥介 , 長谷川 勇介 , Kutana Alex, 渡邊 賢司 , 谷口 尚 ,
宮内 雄平 , 松田 一成 , 篠原 久典 , 北浦 良

166

Transition of crystal structure and electrical property of MoTe 2 crystal by laser irradiation* Kota Kamiya, Tomoki Yamanaka, Masahiro Matsunaga, Ayaka Higuchi, Yuichi Ochiai,
Michio Kida, Jonathan P. Bird, Nobuyuki Aoki

167

☆
3P-40

ナノ炭素粒子3P-41

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* 深谷 真芳 , 田中 利彦 , バーナード アマンダ , 大澤 映二

168

3P-42

窒素ガス中衝突反応によるナノ粒子上でのアミノ酸合成* 三重野 晢 , 大河内 一輝 , 関口 俊介 , 長谷川 直

169

特別講演 ( 16:00-16:30 )3S-10

Localized growth of transition metal dichalcogenides on patterned graphene* Erik Einarsson, Fei Lu, Arka Karmakar, Simran Shahi

10

一般講演 ( 16:30-17:30 )グラフェン生成 ・ グラフェンの応用
3-8Fabrication and characterization of IrO 2 / nano-carbon catalysts* 原 正則 , Badam Rajashekar, Kanishka De Silva, Hsin-Hui Huang, 吉村 雅満

39

3-9

Bottom-up approach for edge-functionalized graphene nanoribbons* Hideyuki Jippo, Junichi Yamaguchi, Shintaro Sato, Hironobu Hayashi, Hiroko Yamada,Mari Ohfuchi

40

41
3-10

CoCu触媒を用いた単層グラフェンの低温成長* 杉目 恒志 , Lorenzo D’Arsié, Robert Weatherup, Santiago Esconjauregui,Guofang Zhong, Xingyi Wu, John Robertson

3-11

2層グラフェンを用いた熱的に安定なSERS基板の作製* 鈴木 誠也 , 吉村 雅満

xviii

42

March 1st, Wed.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)

Special Lecture ( 9:45-10:15 )1S-1
Putting sp3-diamondoids into carbon nanotubes* Hisanori ShinoharaSpecial Lecture ( 10:15-10:45 )1S-2
Direct dry deposition of SWNTs by thermophoresis* Esko I. Kauppinen, Patrik Laiho, Kimmo Mustonen, Shigeo Maruyama,
Yutaka Ohno

12＞＞＞＞＞＞＞ Coffee Break ( 10:45-11:00 ) ＜＜＜＜＜＜＜General Lecture ( 11:00-12:00 )Formation and purification of nanotubes ・ Properties of nanotubes
・ Properties of graphene
Fabrication of multiple transistors from semiconducting single-walled carbon
1-1
nanotube arrays after water-assisted burning of metallic tubes* Keigo Otsuka, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama
1-2

1-3

1-4

Asymmetric carrier accumulation in double-walled carbon nanotube under
an electric field* Taketo Kochi, Susumu Okada
Enhancement of Raman scattering from monolayer graphene by photonic crystal
nanocavities* Issei Kimura, Masahiro Yoshida, Masaki Sota, Hidenori Machiya, Taiki Inoue,
Shohei Chiashi, Shigeo Maruyama, Yuichiro K. Kato
Magnetic properties of two-dimensional hydrocarbon networks* Jun-ya Sorimachi, Susumu Okada

11

12

13

14

＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜Special Lecture ( 13:15-13:45 )1S-3
Growth modes and chiral selectivity of Single Wall Carbon Nanotubes* Christophe Bicharaxix

3March 1st, Wed.
Special Lecture ( 13:45-14:15 )1S-4
Sugar Chain Modified Graphene FET for Detection of Virus* Kazuhiko Matsumoto

4

General Lecture ( 14:15-15:00 )Properties of graphene ･ Applications of graphene
1-5Opening a Gap in Graphene Field Effect Devices with Periodic Uniaxial Strain* Hikari Tomori, Rineka Hiraide, Youiti Ootuka, Kenji Watanabe,
Takashi Taniguchi, Akinobu Kanda

15

1-6

Gas Adsorption Effects on Stabilities and Electronic Properties of Graphene Bilayers* Yoshitaka Fujimoto, Susumu Saito

16

1-7

Edge Roughness Analysis for Developing GNR-based FET* Kengo Takashima, Takahiro Yamamoto

17

Poster Preview ( 15:00-16:00 )Poster Session ( 16:00-17:45 ) （☆）Candidates for the Young Scientist Poster Award
Endohedral metallofullerenes
Photochemical Addtion of Siliranes to Sc3N@Ih-C80: Interconversion of the [6,6]1P-1
and [5,6]-Adducts* Takeshi Sugiura, Kyosuke Miyabe, Masahiro Kako, Masanori Yasui,
Michio Yamada, Yutaka Maeda, Jingdong Guo, Shigeru Nagase, Takeshi Akasaka
1P-2

Conclusive Characterization of Li@C60 by X-ray Structure Analysis* Hiroshi Ueno, Shinobu Aoyagi, Naohiko Ikuma, Hiroshi Okada, Kei Ohkubo,
Tatsuhisa Kato, Shunichi Fukuzumi, Yutaka Matsuo, Ken Kokubo

Properties of nanotubes
Diameter and defect density dependence of intermediate frequency Raman mode of
1P-3
single-walled carbon nanotubes* Takumi Inaba, Satoru Konabe, Yoshikazu Homma
1P-4
☆

1P-5

Spectral tuning of optical coupling between air-mode nanobeam cavities andindividual carbon nanotubes* Hidenori Machiya, Takushi Uda, Akihiro Ishii, Yuichiro K. Kato
Tuning of Photo-thermoelectric effect of Metallic and Semiconducting Single wall
carbon nanotube thin films by electrolyte gating* Masatoshi Nakamura, Yota Ichinose, Hideki Kawai, Yohei Yomogida,
Kazuhiro Yanagi

xx

43

44

45

46

47

March 1st, Wed.
1P-6

Photoluminescence Characteristic of Single-Wall Carbon Nanotubes:
Photon Reabsorption Effect* Xiaojun Wei, Mayumi Tsuzuki, Yohei Yomogida, Guowei Wang, Atsushi Hirano,
Shunjiro Fujii, Takeshi Tanaka, Hiromichi Kataura

48

1P-7

Surface state of carbon nanopot -KFM study* Hiroyuki Yokoi, Kozo Ikeda, Kazuto Hatakeyama, Michio Koinuma

49

1P-8

Anion effects on colloidal stability of surfactant-dispersed SWCNTs* Atsushi Hirano, Weilu Gao, Xiaowei He, Junichiro Kono

50

Applications of nanotubes
1P-9
Paper-based carbon nanotube field effect transistor by photolithography* Jong Mok Shin, Do Hyun Kim, InYeob Na, Ho-Kyun Jnag, Jun Hee Choi,
Se Jeong Park, Gyu-Tae Kim

51

1P-10
☆

Doping effect of electrolyte droplet on carbon nanotube thin film
* Tomohiro Yasunishi, Shigeru Kishimoto, Yutaka Ohno

52

1P-11

Development of CNT/Polyethylene Composites via Melt Blending* Atsushi Onodera, Sami Ristimäki, Masaru Sekido

53

1P-12

☆

1P-13

Defluorination-Assisted Synthesis of Nitrogen-Doped Single-Walled Carbon
Nanotubes and Their Catalytic Activity of Oxygen Reduction Reaction for Polymer
Electrolyte Fuel Cells* Koji Yokoyama, Shun Yokoyama, Yoshinori Sato, Masashi Yamamoto,Tetsuo Nishida, Kenichi Motomiya, Hiromichi Ohta, Hideyuki Takahashi,
Kazuyuki Tohji, Yoshinori Sato
Film fabrication of Semiconducting Single-Wall Carbon Nanotubes by Aqueous-Two
Phase System and Thin Film Transistor Applications* Haruka Omachi, Tomohiko Komuro, Jun Hirotani, Yutaka Ohno,
Hisanori Shinohara

Formation and purification of nanotubes
1P-14 Growth of Horizontally Aligned Chirality-Specific Single-Walled Carbon Nanotubes* Feng Yang, Yan Li
1P-15☆

Fluidized-bed synthesis of sub-millimeter-long carbon nanotubes at high yield fromconcentrated ethylene source* Soichiro Hachiya, Zhongming Chen, Kosuke Kawabata, Kei Hasegawa,Toshio Osawa, Suguru Noda

xxi

54

55

56

57

March 1st, Wed.
1P-16

Large-scale continuous separation of metallic / semiconducting carbon nanotubes byelectric-field-induced layer formation method* Fumiyuki Nihey, Fusako Sasaki, Yuki Kuwahara, Takeshi Saito, Hiroyuki Endoh

58

1P-17
☆

Development of gels for high-efficiency metal/ semiconductor separation of SWCNTs* Guowei Wang, Xiaojun Wei, Atsushi Hirano, Takeshi Tanaka, Hiromichi Kataura

59

1P-18

Purity Analysis and Purification of Double-walled Carbon Nanotubes* Kenshi Miyaura, Hidekazu Nishino, Shirou Honda

60

Endohedral nanotubes
An experimental and theoretical study on the scanning spectroscopy of europium
1P-19
nanowires encapsulated in carbon nanotubes* Terunobu Nakanishi, Ryo Kitaura, Takazumi Kawai, Susumu Okada,☆
Shoji Yoshida, Osamu Takeuchi, Hidemi Shigekawa, Hisanori Shinohara
1P-20

DFT calculations of electronic states and solid state NMR parameters in Cesium
Iodide encapsulated single-walled carbon nanotubes* Eita Yokokura, Yosuke Kataoka, Hironori Ogata

Graphene synthesis
1P-21 Study of Au-Ni catalytic CVD of uniform multilayer graphene* Yuki Ueda, Jumpei Yamada, Kyosuke Fujiwara, Daichi Yamamoto,
Takahiro Maruyama, Shigeya Naritsuka
1P-22☆

Thermodynamically Controlled Synthesis of Graphene from Carbon Monoxide* Yukuya Nagai, Kei Hasegawa, Suguru Noda

Applications of graphene
1P-23 Fabrication and Electric Properties of Fe and Ca intercalated Bilayer Graphenes* Natsuki Kuragane, Ryo Hoshino, Ryota Sakurai, Tamon Yamagishi,
Tomoko Nagata, Nobuyuki Iwata, Hiroshi Yamamoto

61

62

63

64

65

1P-24

Functional group dependence of Spin magnetism of Graphene oxide* Kentaro Tajima, Takuya Isaka, Tomoki Yamashina, Yoshiaki Matsuo,
Kazuyuki Takai

66

1P-25

Highly efficient, mechanically durable perovskite solar cells with graphene electrodes* Jungjin Yoon, Namyoung Ahn, Mansoo Choi

67

1P-26

Reduction reaction of a single graphene oxide sheet in solution as probed by twilightfluorescence microscopy* Hikaru Sato, Masahito Sano

xxii

68

March 1st, Wed.
1P-27

Production and characterization of graphene quantum dots derived from SWNTs andgraphite* Hiroki Morita, Toshiki Sugai

Properties of graphene
1P-28 Energetics and electronic structure of B3N3-doped graphene* Hisaki Sawahata, Mina Maruyama, Susumu Okada
1P-29
☆

1P-30

Charge transfer dynamics at graphene/SiC interface studied by time-resolved
soft X-ray photoemission spectroscopy* Takashi Someya, Hirokazu Fukidome, Susumu Yamamoto, Norifumi Endo,
Iwao Matsuda
Simplified estimation of crystallographic orientation of strained graphene bymicro-Raman spectroscopy* Kazushi Nakamura, Hikari Tomori, Akinobu Kanda

69

70

71

72

1P-31

Mechanical properties of graphene nanoribbons* Kazufumi Yoneyama, Ayaka Yamanaka, Susumu Okada

73

1P-32

Introduction of spin-orbit interaction into graphene by various methods* T. Nanba, T. Tamura, Y. Katagiri, C. Ohata, Pierre Seneor, J. Haruyama

74

1P-33

Influences of Graphene Structure on Electrochemical Interactions in LiBF4 Organic
Electrolyte Solution* Daisuke Suzuki, Kazuyuki Takai

Atomic Layers
Detection of photo current arising from atom-thin MoS2 Schottky junction fabricated
1P-34
by electron beam irradiation* Yuto Katagiri, C. Ohata, Y. Inoue, S. Maruyama, T. Nakamura, S. Katumoto,
A. Ishi, M. Hasegawa, G. Fioli, S. Roche, J. Haruyama
1P-35
☆

1P-36

Mechanism of contact-resistance improvement in suspended device of bi-layer WSe2
by mild oxygen plasma treatment* Reito Nagai, Toshiro Kaneko, Toshiaki Kato
Optical spectroscopy on monolayer transition metal dichalcogenides immersed in an
aqueous solution* Wenjin Zhang, Yusuke Hasegawa, Kazunari Matsuda, Yuhei Miyauchi

xxiii

75

76

77

78

March 1st, Wed.
1P-37
☆
1P-38

Helicity-resolved first order resonant Raman spectra of graphene and transition metal
dichalcogenides* Yuki Tatsumi, Riichiro Saito

79

Energetics and electronic properties of C60 adsorbed on graphene* Yamato Alexander Saucier, Mina Maruyama, Susumu Okada

80

Upconversion photoluminescense spectra of carbon nanotubes in mice tissues* Saki Okudaira, Yoko Iizumi, Masako Yudasaka, Toshiya Okazaki,
Kazunari Matuda, Yuhei Miyauchi

81

Bio
1P-39

Other topics
1P-40 Electrical properties of defective hexagonal boron nitride nanosheet* Ho-Kyun Jang, Jun Hee Choi, Kook Jin Lee, Do-Hyun Kim, Gyu Tae Kim

82

1P-41

Modification of Electrical Properties in MoS2 by Using Catalytic Oxidation* Jun Hee Choi, Ho-Kyun Jang, Jun Eon Jin, Jong Mok Shin, Do-Hyun Kim,
Gyu-Tae Kim

83

1P-42

Hidden symmetries in one-dimensional photonic crystals* M. Shoufie Ukhtary, Haihao Liu, Riichiro Saito84＞＞＞＞＞＞＞ Coffee Break ( 17:45-18:00 ) ＜＜＜＜＜＜＜Tutorial ( 18:00-19:30 )Exploring the Nano-space Made in Nanocarbon* Hisanori ShinoharaxxivMarch 2nd, Thu.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)

Special Lecture ( 9:00-9:30 )2S-5
Catalyst design for controlled growth of single-walled carbon nanotubes* Yan Li

General Lecture ( 9:30-10:30 )Formation and purification of nanotubes ・ Properties of nanotubes
Drastically improved efficiency of single wall carbon nanotube forest synthesis
2-1
on a MgO catalyst underlayer by a simple annealing process* Takashi Tsuji, Kenji Hata, Don Futaba, Shunsuke Sakurai
2-2

2-3

2-4

A study of dispersion states of CNTs in slurry by AC impedance method* Takayuki Watanabe, Kazufumi Kobashi, Takahiro Morimoto, Toshiya Okazaki
The effect of noble metals on the formation of iron catalyst nanoparticle for thesynthesis of vertically-aligned carbon nanotubes* Shunsuke Sakurai, Kenji Hata, Don Futaba
Lock-in thermography technique for visualization of CNT network structures* Takahiro Morimoto, Seisuke Ata, Takeo Yamada, Toshiya Okazaki

5

18

19

20

21

＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Special Lecture ( 10:45-11:15 )2S-6
Functionalized 2D materials for sensing applications* Shyamal K Saha, Diptiman Dinda

6

General Lecture ( 11:15-12:00 )Atomic Layers
Scanning Electrochemical Cell Microscopy for Visualization of Local
2-5Electrochemical Activities on Graphene/Graphite* Akichika Kumatani, Chiho Miura, Takeru Okada, Seiji Samukawa, Hitoshi Shiku,
Yasufumi Takahashi, Tomokazu Matsue

22

xxv

March 2nd, Thu.
2-6

2-7

Out-of-Plane Strain Generation of Monolayer MoS2 and MoSe2 Formed a Moiré
Superstructure on the Au(111) Surface
Ryosuke Takahashi, Ryo Osaka, Yasumitsu Miyata, Susumu Okada,Yuhei Hayamizu, * Satoshi Yasuda, Kei Murakoshi
Magnetic tunnel junction built from intercalated transition metal dichalcogenide
ferromagnets with different magnetic anisotropy* Yuji Yamasaki, Rai Moriya, Miho Arai, Satoru Masubuchi, Sunseng Pyon,
Tsuyoshi Tamegai, Keiji Ueno, Tomoki Machida2324＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜Awards Ceremony ( 13:15-14:00 )Poster Preview ( 14:00-15:00 )Poster Session ( 15:00-16:45 ) （☆）Candidates for the Young Scientist Poster Award
Chemistry of fullerenes
2P-1
Theoretical estimation for the electronic property and reactivity of activated fullerenes* Naohiko Ikuma, Ken Kokubo, Takumi Oshima
2P-2
☆
2P-3

Palladium-Catalyzed Functionalization of C60 Derivatives: Regioselectivity and
Structures* Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, Murata Yasujiro
Synthesis of Lithium-ion-encapsulated Fluoreno[60]fullerenes* Yutaka Matsuo, Hiroshi Okada, Hiroshi Ueno

Applications of fullerenes
2P-4
Nanoscale Control of Polymer Assembly on Fullerene Bilayer Membranes* Koji Harano, Ricardo M. Gorgoll, Eiichi Nakamura
2P-5

2P-6

Metallic Polymerization of C60 Thin Film by Electron-Beam Irradiation* Hiroto Uenoyama, Yu Tanaka, Shingo Yamanouchi, Yuichi Ochiai, Nobuyuki Aoki
Synthesis of CdS-Mn-[C60]Fullerene Nanocomposites and Their Photocatalytic
Activities for Degradation of Organic Dyes
* Jeong Won Ko, Jiulong Li, Weon Bae Ko

xxvi

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2P-7

Studies on the Aggregated Structures and Crystallinities of Bulk Heterojunction
Films Constituting Organic Solar Cells* Saki Kawano, Hironori Ogata

Endohedral metallofullerenes
Production and Characterization of Hetero-dimetallofullerene: GdY@C80(Ih)
2P-8

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92

* Takuji Mitani, Natsumi Nakatori, Takahisa Yamaguchi, Ko Furukawa,
Tatsuhisa Kato, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama
2P-9

Isolation and structural analysis of La@C60(CF3)5☆

* Makiko Nishino, Shinobu Aoyagi, Haruka Omachi, Zhiyong Wang,
Ayano Nakagawa, Ryo Kitaura, Hisanori Shinohara

2P-10

Photoreactions of Cyclic Organosilanes with Trimetallic Nitride Template
Endohedral Metallofullerenes* Shinpei Fukazawa, Takeshi Sugiura, Kyosuke Miyabe, Masahiro Kako,
Takeshi Akasaka

Fullerenes
2P-11 Energetics and electronic structure of SIMEF chains* Sho Furutani, Susumu Okada
2P-12

2P-13

Absolute yield of fullerene formed by graphite laser ablation at medium-highambient temperatures* Haruka Suzuki, Yuki Taguchi, Takeshi Kodama, Yohji Achiba, Haruo Shiromaru
Energetics and electronic properties of fullerenes consisting of fused pentagonal rings* Susumu Okada

Properties of nanotubes
2P-14 Macroscopic aligned single-walled carbon nanotubes achieved with vacuum filtration* Zhang Hao, Rong Xiang, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama
2P-15
☆
2P-16

Selective phonon mode generations in single wall carbon nanotubes and graphene
nanoribbons* Ahmad R. T. Nugraha, Eddwi H. Hasdeo, Riichiro Saito
Electrically conductive multi-walled boron nitride nanotubes by catalytic etching* Do-Hyun Kim, Ho-Kyun Jang, Min-Seok Kim, Sung-Dae Kim, Dong-Jin Lee,Gyu Tae Kim

xxvii

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Applications of nanotubes
2P-17 Artificial muscle using single wall carbon nanotube bundles☆
* Nguyen Tuan Hung, Ahmad Ridwan Tresna Nugraha, Riichiro Saito
2P-18

2P-19
☆

Electrochemical Properties of Nitrogen-Doped Vertically Aligned Multi-Walled
Carbon Nanotubes Prepared by Defluorination* Rei Nonomura, Takashi Itoh, Yoshinori Sato, Masashi Yamamoto, Tetsuo Nishida,
Kenichi Motomiya, Kazuyuki Tohji, Yoshinori Sato
Synthesis and morphology control of carbon nanotubes on substrate for electron
emitter application* Sae Kitagawa, Hisashi Sugime, Suguru Noda

Formation and purification of nanotubes
2P-20 Analysis of Pt catalyst for SWNT growth by In-situ XANES* Makoto Kumakura, Hoshimitsu Kiribayashi, Takahiro Saida, Shigeya Naritsuka,
Takahiro Maruyama
2P-21
☆

2P-22

2P-23
☆

2P-24

Time-dependent selective synthesis and growth mechanism of single-walled carbon
nanotubes from sputtered W-Co catalyst* Hua An, Rong Xiamg, Akihito Kumamoto, Taiki Inoue, Shohei Chiashi,
Yuichi Ikuhara, Shigeo Maruyama
Extraction of High-Purity Single-Chirality Single-Wall Carbon Nanotubes
by Precise Tuning of pH using CO2 Bubbling* Yota Ichinose, Junko Eda, Yutaka Maniwa, Yohei Yomogida, Kazuhiro Yanagi
Magnetic field effects on the growth process of SWCNTs and examination of its
mechanism* Yasumasa Takashima, Atom Hamasaki, Jin Uchimura, Sumio Ozeki
Chemical reaction analysis of Fe-Co and Co-Cu clusters with ethanol by FT-ICR
mass spectrometer* Ken Mizutani, Yoshinori Sato, Hiroya Minowa, Ryohei Yamada, Taiki Inoue,
Shohei Chiashi, Shigeo Maruyama

Properties of graphene
Carrier injection in nearly free electron states of graphene nanoribbons by edge
2P-25hydroxylation* Remi Taira, Ayaka Yamanaka, Susumu Okada
2P-26

Fermi level tuning of N-doped graphene by an external electric field* Manaho Matsubara, Susumu Okada
xxviii

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105

106

107

108

109

110

March 2nd, Thu.
2P-27

Electronic structures of graphene exposed to electrolyte solution* Mari Ohfuchi

111

2P-28

Magnetic interactions between Edge-state spins and Ferrocenium ion spins* Akira Suzuki, Kazuyuki Takai

112

2P-29

Electrical properties of reduced graphene oxide by thermal annealing* Takuya Ishida, Yuta Nishina, Nobuyuki Aoki

113

2P-30

Influence of Water Molecules on Molecular Adsorption induced Charge Transfer
in Graphene
Takashi Umehara, * Kazuyuki Takai

Atomic Layers
Growth of large-area and uniform multilayer hexagonal boron nitride as an ideal
2P-31
2D insulator* Sho Nakandakari, Kenji Kawahara, Yuki Uchida, Shigeto Yamasaki,☆
Masatoshi Mitsuhara, Hiroki Ago
2P-32

2P-33
☆

2P-34

2P-35
☆

Enhancement of laser-induced water decomposition by 2D sheets studied
by first-principles simulations II* Yoshiyuki Miyamoto, Hong Zhang, Xinlu Cheng, Angel Rubio
Photoluminescence and photocurrent properties of monolayer WSe2 FETs fabricatedby dry-transfer process* Xiaofan Wang, Wenjin Zhang, Nur Baizura Mohamed, Dezhi Tan, Hong En Lim,
Yuhei Miyauchi, Kazunari Matsuda
Piezoelectric properties of 3R bulk transition metal dichalcogenides* Satoru Konabe, Takahiro Yamamoto
Molecular beam epitaxy growth of molybdenum diselenide atomic layers
on hexagonal boron nitride substrates* Takuto Tokuda, Takato Hotta, Kenji Watanabe, Takashi Taniguchi,
Hisanori Shinohara, Ryo Kitaura

Carbon nanoparticles
2P-36 Meteorite- and detonation-nanodiamonds are the same substances* Eiji Osawa, Amanda Barnard, Toshihiko Tanaka, Masayoshi Fukaya
2P-37

Synthesis of N-doped carbon nanoballoons with nitrogen plasma* Ryota Takahashi, Toru Harigai, Hirofumi Takikawa, Yoshiyuki Suda

xxix

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119

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March 2nd, Thu.
Other topics
Separation of iron oxide nanotubes from the products prepared by surfactant
2P-38
assisted sol-gel method and characterization
Yuka Tanaka, * Shunji Bandow
2P-39

2P-40

2P-41

Development of Multi-stage Ion Trap Ion Mobility Measurement System andSeparation of Nano Materials* Toshiki Sugai, Kyohei Shiino, Yuudai Hoshino, Natsuki Terada, Yuuta Hamano,
Hiroki Morita, Ryota Jinnouchi
Mechanical properties of nano-rotors: Energetics of triptycene derivatives* Miki Akiba, Susumu Okada
Study of deactivation mechanism of carbon catalyst by thermo-catalytic
decomposition of methane* Haruki Nishii, Yoshito Umeda, Hiroaki Hamaguchi, Masashi Suzuki,
Toru Harigai, Hirofumi Takikawa, Yoshiyuki Suda

122

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124

125

2P-42

Effect of PtRu alloying on catalytic activity of catalysts for direct methanol fuel cells* Kohei Kawasaki, Tatsuo Ohiro, Toru Harigai, Hirofumi Takikawa, Hitoshi Ue,
Yoshiyuki Suda

126

2P-43

Microfabrication of carbon nanocoil using Focused Ion Beam
* Munehito Takahashi, Toru Harigai, Hirofumi Takikawa, Hitoshi Ue,
Yoshiyuki Suda

127

Special Lecture ( 16:45-17:15 )2S-7
Production and functionalization of carbon nanotubes for energy devices* Suguru Noda

General Lecture ( 17:15-19:00 )Applications of fullerenes ・ Endohedral metallofullerenes ・ Fullerenes
・ Carbon nanoparticles ・ Other topics
Improvement of Open-circuit Voltage in Perovskite Solar Cells by Using
2-8
Methano-Indene-Fullerene (MIF)* Yutaka Matsuo
2-9Electronic Structures and Stability of Metal Encapsulated C80 fullerenes:
Ab initio DFT study* Archana Velloth, Yutaka Imamura, Takeshi Kodama, Masahiko Hada

xxx

7

25

26

March 2nd, Thu.
2-10

Searching for the unprecedented endohedral metallofullerenes by applying
the separation method for those stable only in an anion form
* Natsumi Nakatori, Takuji Mitani, Takahisa Yamaguchi, Ko Furukawa,
Tatsuhisa Kato, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama

27

2-11

Dynamics of Li+ ions encapsulated in C60 fullerene at low temperature* Hal Suzuki, Misaki Ishida, Masatsugu Yamashita, Chiko Otani,
Kazuhiko Kawachi, Yasuhiko Kasama, Eunsang Kwon

28

2-12

Geometric and electronic structures of polymerized C40 fullerene* Mina Maruyama, Susumu Okada

29

2-13

Polyyne formation by laser induced breakdown in hydrocarbon gas flow
Yuki Taguchi, Hitomi Endo, Takeshi Kodama, Tomonari Wakabayashi,
Yohji Achiba, * Haruo Shiromaru, Benji Wales, Joseph Sanderson

30

2-14

Inner Core in the Elementary Particles of Detonation Nanodiamond* Toshihiko Tanaka, Masayoshi Fukaya, Amanda Barnard, Eiji Osawa

31

Banquet ( 19:00-20:45 )xxxi

March 3rd, Fri.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)

Special Lecture ( 9:00-9:30 )3S-8Strong Light-Matter Coupling in (6,5) Carbon Nanotubes* Junichiro Kono, Weilu Gao, Kankan Cong, Xinwei Li, G. Timothy Noe II,
Huaping Liu, Takeshi Tanaka, Hiromichi Kataura

General Lecture ( 9:30-10:30 )Properties of nanotubes
3-1
Optical bistability in carbon nanotubes* Takushi Uda, Akihiro Ishii, Yuichiro K. Kato
3-2

3-3

3-4

Single photon generation through exciton-exciton annihilation in air-suspended
carbon nanotubes* Akihiro Ishii, Takushi Uda, Yuichiro K. Kato
Raman Spectroscopy of Individual Single-Walled Carbon Nanotubes* Juan Yang, Daqi Zhang, Yan Li
Competitive elimination and decomposition reaction of oxidized single-walledcarbon nanotubes depending on the degree of functionalization* Yutaka Maeda, Erika Sone, Akane Nishino, Yuri Amagai, Wei-Wei Wang,
Michio Yamada, Mitsuaki Suzuki, Jun Matsui, Masaya Mitsuichi, Toshiya Okazaki,
Shigeru Nagase

8

32

33

34

35

＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Special Lecture ( 10:45-11:15 )3S-9
Optical Spectroscopy of Individual Carbon Nanotubes with Defined Atomic Structure* Kaihui Liu

9General Lecture ( 11:15-12:00 )Properties of nanotubes ・ Applications of nanotubes
Development of Nano-Resolution Desktop FE-SEM and X-ray microscope with
3-5
Multi-Walled Carbon Nanotube Electron Source* Masaru Irita, Shintarou Yamazaki, Shota Katsuyama, Hitoshi Nakahara,
Koji Asaka, Yahachi Saito, Hidekazu Murata, Teruaki Ohno

36

xxxii

March 3rd, Fri.
3-6

3-7

Cold exciton electroluminescence from air-suspended carbon nanotube split-gatedevices
Noriyuki Higashide, * Masahiro Yoshida, Takushi Uda, Akihiro Ishii,
Yuichiro K. KatoThe Solution to Stability and Cost in Perovskite Solar Cells by All-Carbon Approach* Il Jeon, Namyoung Ahn, Jungjin Yoon, Esko Kauppinen, Mansoo Choi,
Yutaka Matsuo, Shigeo Maruyama

3738＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜Poster Preview ( 13:15-14:15 )Poster Session ( 14:15-16:00 ) （☆）Candidates for the Young Scientist Poster Award
Endohedral metallofullerenes
3P-1
Attempt to produce dimetallofullerenes containing Yb* Kazuhiro Kobayashi, Takuji Mitani, Natsumi Nakatori, Koichi Kikuchi,
Yohji Achiba, Takeshi Kodama
3P-2

Spectroscopic studies of La2@C78 anion* Shinya Nishimoto, Kazuhiro Kobayashi, Takaaki Hirayama, Takuji Mitani,
Natsumi Nakatori, Takahisa Yamaguchi, Ko Furukawa, Tatsuhisa Kato,
Koichi Kikuchi, Yohji Achiba, Takeshi Kodama

Properties of nanotubes
Evaluation of dispersion states of nanomaterials by disc centrifuge sedimentation
3P-3
technique* Naoko Tajima, Takahiro Morimoto, Yuichi Kato, Kazufumi Kobashi,
Takeo Yamada, Toshiya Okazaki
3P-4
☆

3P-5

Unified analysis of quantum and classical transport properties on metallic carbon
nanotubes* Keisuke Ishizeki, Kenji Sasaoka, Satoru Konabe, Satofumi Souma,
Takahiro Yamamoto
High Temperature Surface Enhanced Raman Scattering of Single-Walled Carbon
Nanotubes* Ming Liu, Keigo Otsuka, Rong Xiang, Taiki Inoue, Shohei Chiashi,
Shigeo Maruyama

xxxiii

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129

130

131

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March 3rd, Fri.
3P-6

3P-7

Fabrication and photoluminescence characterization of carbon nanotube dual-gatedevices* Akihiro Sasabe, Takushi Uda, Masahiro Yoshida, Akihiro Ishii, Yuichiro K. Kato
Optical Measurement of Single-Walled Carbon Nanotubes Using Rayleigh Scattering
Spectroscopy* Takeshi Okochi, Toru Osawa, Yoritaka Furukawa, Tatsuro Ogamoto,Shun Kamakura, Taiki Inoue, Shohei Chiashi, Shigeo Maruyama

Applications of nanotubes
Synthesis and structure control of vertically-aligned carbon nanotubes on Cu foils
3P-8
for thermal interface materials* Shunji Kobayashi, Kei Hasegawa, Hisashi Sugime, Masanao Obori,
Junichiro Shiomi, Xiaosong Zhou, Mizuhisa Nihei, Suguru Noda
3P-9

3P-10

3P-11
☆

Selective detection of neurotransmitters by adsorption voltammetry with carbon
nanotube film
* Takuya Ushiyama, Shigeru Kishimoto, Yutaka Ohno
Time-dependent change of the semiconducting-CNT ink evaluated from theperformance of CNT-TFTs* Yuki Kuwahara, Fusako Sasaki, Fumiyuki Nihey, Takeshi Saito
Lamination of Vertically Aligned Single-Walled Carbon Nanotube Forests
on Perovskite Solar Cells via Membrane Filter Transfer Method* Seungju Seo, IL Jeon, Takahiro Sakaguchi, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Yutaka Matsuo, Shigeo Maruyama

133

134

135

136

137

138

3P-12

Yields of carbon nanotube integrated circuits on flexible plastic film
* Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno

139

3P-13
☆

Modeling of carbon nanotube thin-film transistor on flexible plastic film
* Taiga Kashima, Tomoki Matsuura, Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno

140

3P-14

Improved Efficiency and Stability of Perovskite Solar Cells with Single-Walled
Carbon Nanotube Electrodes* Takahiro Sakaguchi, Jeon Il, Hiroki Suko, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Esko I. Kauppinen, Nam-Gyu Park, Yutaka Matsuo,
Shigeo Maruyama

xxxiv

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March 3rd, Fri.
Formation and purification of nanotubes
Evaluation of the ratio of metal/semiconductive SWNTs by utilizing ATP technique
3P-15
and Raman spectroscopy
Kento Uratani, Naoki Kanazawa, * Shinzo Suzuki
3P-16
☆

3P-17

3P-18

3P-19

3P-20

Removing catalyst metals from various carbon nanotubes by halogen gas* Koki Hamada, Hisashi Sugime, Suguru Noda
Controllable growth of single-walled carbon nanotubes in quality and uniformity
by extended alcohol catalytic chemical vapor deposition* Bo Hou, Cheng Wu, Yuko Iizumi, Takahiro Morimoto, Toshiya Okazaki,
Taiki Inoue, Shohei Chiashi, Rong Xiang, Shigeo Maruyama
Synthesis and Characterization of SWNTs Using W-Co Catalyst* Shinnosuke Ohyama, Shun Yamamoto, Hua An, Feng Yang, Taiki Inoue,
Rong Xiang, Shohei Chiashi, Yan Li, Shigeo Maruyama
Growth of Semiconducting (14,4) Carbon Nanotubes using W-Co Salts as Catalyst
Precursor* Xiulan Zhao, Feng Yang, Yan Li
Single-Walled Carbon Nanotube Growth from Bimetallic Catalyst by Molecular
Dynamics Simulations* Ryo Yoshikawa, Hiroyuki Ukai, Yukai Takagi, Shohei Chiashi, Shigeo Maruyama

Endohedral nanotubes
Template Synthesis of π-Conjugated Nanomaterials using Inner Space of Carbon
3P-21
Nanotubes☆
* Yasuhiro Kinno, Haruka Omachi, Ryo Kitaura, Hisanori Shinohara
3P-22

Electronic states of chalcogen encapsulated in single-walled carbon nanotubes
studied by First-principles DFT calculations(Ⅱ)* Yutaka Sato, Eita Yokokura, Yousuke Kataoka, Hironori Ogata

Nanohorns
Effect of carbon nanohorns on lipopolysaccharide-induced RAW264.7 macrophage
3P-23
cells
* Maki Nakamura, Kiyoko Kuroiwa, Sumio Iijima, Masako Yudasaka
3P-24

A study of Preparation Conditions of Carbon Nanobrush* Ryota Yuge, Fumiyuki Nihey, Kiyohiko Toyama, Masako Yudasaka

xxxv

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144

145

146

147

148

149

150

151

March 3rd, Fri.
Graphene synthesis
Analysis of Initial Formation Process of Graphene on SiC(0001) Surfaces Based3P-25
on the First-Principles Molecular Dynamics☆
* Fumihiro Imoto, Jun-Ichi Iwata, Mauro Boero, Atsushi Oshiyama
3P-26

Growth of Single-Crystal Single-Layer and Bi-Layer Graphene Using Alcohol
Catalytic CVD* Masaki Sota, Kotaro Kashiwa, Naomasa Ueda, Keigo Otsuka, Taiki Inoue,
Rong Xiang, Shohei Chiashi, Shigeo Maruyama

Applications of graphene
Highly Oriented CuInS2 Thin-Films on Graphene Electrodes for Solar Cells
3P-27
Applications* Ryousuke Ishikawa, Tomoya Oya, Tonan Yamada, Takahito Nomoto,
Nozomu Tsuboi

152

153

154

3P-28

Controlled fabrication of graphene liquid cells* Yoshimasa Michiya, Tomohiro Yasunishi, Yutaka Ohno, Hisanori Shinohara,
Ryo Kitaura

155

3P-29

Factors for reactivity of GO regarding oxidative amine coupling reaction* Takuya Isaka, Kentaro Tajima, Tomoki Yamashina, Kazuyuki Takai

156

3P-30

Highly conductive and transparent large-area bilayer graphene realized by
MoCl 5 intercalation* Hiroki Kinoshita, Kenji Kawahara, Yuri Terao, Il Jeon, Mina Maruyama,
Rika Matsumoto, Susumu Okada, Yutaka Matsuo, Hiroki Ago

Properties of graphene
3P-31 Energetics of edge oxidization of graphene nanoribbons with clean edges* Airi Yasuma, Ayaka Yamanaka, Susumu Okada
3P-32☆

Band unfolding study on Fermi-level-velocity reduction induced by Dirac coneinteraction in twisted bilayer graphene* Hirofumi Nishi, Yu-ichiro Matsushita, Atsushi Oshiyama

157

158

159

3P-33

Energetics of Edge Formation Processes of Graphene* Ayaka Yamanaka, Susumu Okada

160

3P-34

Electronic structure of edge functionalized graphene under an external electric field* Yanlin Gao, Susumu Okada

161

xxxvi

March 3rd, Fri.
3P-35

Brillouin zone topology and band structure of four-dimensional diamond
Yuichi Kato, * Masanori Yamanaka

162

3P-36

Transport property of bilayer graphene with monovacancy* Ken Kishimoto, Susumu Okada

163

Atomic Layers
Tuning of local optical properties of MoS2 monolayer and its structural control using
3P-37
electric-field-effect scanning near-field optical microscopy techniques* Junji Nozaki, Musashi Fukumura, Takaaki Aoki, Yutaka Maniwa,☆
Yohei Yomogida, Kazuhiro Yanagi

164

3P-38

Optical properties of superacid-treated MoS2
* Hong En Lim, Nur Baizura Mohamed, Yuhei Miyauchi, Kazunari Matsuda

165

3P-39

Relaxation Mechanism of Interlayer Excitons in 2D van der Waals Heterostuctures* Mitsuhiro Okada, Yusuke Kureishi, Yusuke Hasegawa, Alex Kutana,
Kenji Watanabe, Takashi Taniguchi, Yuhei Miyauchi, Kazunari Matsuda,
Hisanori Shinohara, Ryo Kitaura

166

☆

3P-40

Transition of crystal structure and electrical property of MoTe2 crystal
by laser irradiation* Kota Kamiya, Tomoki Yamanaka, Masahiro Matsunaga, Ayaka Higuchi,
Yuichi Ochiai, Michio Kida, Jonathan P. Bird, Nobuyuki Aoki

Carbon nanoparticles
3P-41 The LDI spectra of Detonation Nanodiamonds* Masayoshi Fukaya, Toshihiko Tanaka, Amanda Barnard, Eiji Osawa
3P-42

Impact synthesis of amino acids on carbon nano-particles in nitrogen gas* Tetsu Mieno, Kazuki Okochi, Syunsuke Sekiguchi, Sunao Hasegawa

167

168

169

Special Lecture ( 16:00-16:30 )3S-10 Localized growth of transition metal dichalcogenides on patterned graphene* Erik Einarsson, Fei Lu, Arka Karmakar, Simran Shahi

10

General Lecture ( 16:30-17:30 )Graphene synthesis ・ Applications of graphene
Fabrication and characterization of IrO2 / nano-carbon catalysts
3-8* Masanori Hara, Badam Rajashekar, Kanishka De Silva, Hsin-Hui Huang,
Masamichi Yoshimura

39

xxxvii

March 3rd, Fri.
3-9

Bottom-up approach for edge-functionalized graphene nanoribbons* Hideyuki Jippo, Junichi Yamaguchi, Shintaro Sato, Hironobu Hayashi,
Hiroko Yamada, Mari Ohfuchi

40

3-10

Low temperature growth of fully covered single layer graphene using CoCu catalyst* Hisashi Sugime, Lorenzo D’Arsié, Robert Weatherup, Santiago Esconjauregui,Guofang Zhong, Xingyi Wu, John Robertson

41

3-11

Fabrication of a thermally stable SERS substrate using bilayer graphene* Seiya Suzuki, Masamichi Yoshimura

42

xxxviii

特別講演
Special Lecture

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

1S-1
Putting sp3-Diamondoids into Carbon Nanotubes
Hisanori Shinohara
Department of Chemistry & Institute for Advanced Research,
Nagoya University,
Nagoya 464-8602, Japan
By putting atoms, molecules, and, even, nanowires of various kind into carbon nanotubes(CNT), one can easily and drastically alter the electronic structures, electron transport andmagnetic properties of CNTs, in which charge transfers between encapsulates and CNTs may
oftentimes play crucial roles [1]. In some cases, novel one-dimensional (1D) nanowires canbe fabricated within carbon nanotubes which are not possible to produce in the conventionalbulk conditions [2-5].
A similar thing can be achieved when bilayer graphene is used for “sandwiching” atoms
and molecules to fabricate unique nano-materials as well as to observe novel phenomena, but
in two dimensional (2D) fashion [6,7].
In this talk, I will discuss some unique and novel properties of 1D and 2D nano-space andits application to syntheses of new materials prepared by nanotubes and bilayer graphene,
respectively.
References:[1] L.H.G.Tizei et al. Phys.Rev.Lett. 114, 197602 (2015).
[2] H.E.Lim et al. ACS Nano, 9, 5034 (2015).
[3] H.E.Lim et al. Nature Commun. 4，2548 (2013).
[4] R.Nakanishi et al. Sci.Rep.3, 1385 (2013).
[5] Y.Nakanishi et al. Angew.Chem.Int.Ed. 54, 10802 (2015).
[6] Y.Sasaki et al. Appl.Phys.Express, 5. 065103 (2012).
[7] Y.Sasaki et al. Chem.Phys.Lett. 650, 107 (2016).
Corresponding Author: H.Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442
E-mail: noris@nagoya-u.jp

-1-

1S-2
Direct dry deposition of SWNTs by thermophoresis
Patrik Laihoa, Kimmo Mustonena,b, Shigeo Maruyamac, Yutaka Ohnod and Esko I. Kauppinena
Department of Applied Physics, Aalto University School of Science,
P.O. Box 15100, FI-00076 Aalto, FinlandbPhysics of Nanostructured Materials, Faculty of Physics, University of Vienna,
Boltzmanngasse 5, A-1090 Vienna, Austriac
Department of Mechanical Engineering, The University of Tokyo,
Bunkyo-ku, Tokyo 113-8656, Japand
EcoTopia Science Institute, Nagoya University , Furo-cho, Chikusa-ku,
Nagoya 464-8603, Japana

We have developed the dry and continuous thermophoretic deposition of pristine,
individual single-walled carbon nanotubes grown using a floating-catalyst CVD process.
Based on aerosol loss measurements, the thermophoretic terminal velocity of SWCNTs ismuch lower i.e. approximately only one third of the usual free molecular regime prediction
and shows a weak dependence on the nanotube diameter. Scanning electron microscopy andatomic force microscopy of the deposited samples indicate that pristine, as-synthesized
SWCNTs with controllable densities, ranging from individual, separated nanotubes tomultilayer thin films, can be deposited on practically any flat substrate with high efficiencies
close to unity. Depending on the lateral flow inside the precipitator, the angular distribution of
the deposited SWCNTs can be changed from uniform to non-uniform. As a demonstration of
the applicability of our technique, we have used thermophoretic deposition to fabricate carbon
nanotube thin film transistors with uniform electrical properties and a high, over 99,5% yieldand high field effect electrical mobility exceeding 400 cm2/Vs while simultaneously having a
ION/IOFF in excess of 106.
e-mail: esko.kauppinen@aalto.fi

-2-

1S-3
Growth modes and chiral selectivity of SWNTs
Christophe Bichara

CINaM, Aix‐Marseille University and CNRS
bichara@cinam.univ‐mrs.fr

Significant progress has been made recently in the synthesis of single wall carbon nanotube (SWNT)
by catalytic chemical vapor deposition (CCVD), along with a rise of commercially viable applications. A property
selective synthesis seems still elusive, though, because of specific issues. High synthesis temperatures,nanometric sizes and a large number of correlated growth parameters make the experimental investigation of
the growth mechanisms specially challenging. Theoretical approaches are not easier, but I will show here that
dedicated computer simulations, including tight binding models [1], as well as DFT based calculations canprovide a useful insight. Different aspects have been investigated.
It starts with the complex stability pattern of atomic carbon dissolved in subsurface layers of
crystalline Ni, that depends on the presence of a graphene layer on top of it [2]. For catalyst nanoparticles
below 3 nm, relevant for the CCVD growth, the presence of carbon dissolved in the surface layers induces a
gradual melting at temperatures well below the melting temperature of pure nanoparticles of the same size.
Calculated size dependent phase diagrams for Ni‐C nanoparticles [3] indicate that facetted crystalline
nanoparticles are unlikely to be observed in this size range under growth conditions.
This raises the question of the role of the carbon dissolved in the catalyst during growth that is shownto have a strong influence on the wetting properties of the metal‐SWNT interface [4]. Through careful
Transmission Electron Microscopy observations [5], so called tangential and perpendicular growth modes wereidentified. Computer simulations were used to analyze these growth modes at the atomic scale, demonstratingthat tangential mode corresponds to a weak carbon supply and slow growth, while perpendicular one isobserved when the carbon fraction in the nanoparticle is larger [6]. Growth experiments designed to tune thecarbon fraction in the nanoparticle by changing the carbon feedstock (CO and CH4) confirm this analysis.
Finally the role of different contributions to the stability and dynamics of the nanotube/nanoparticle interface
on the possibility of a chiral selectivity will be discussed.
References[1] Amara, H. et al. Phys. Rev. B 79, 014109 (2009).
[2] Weatherup, R. S. et al. J. Am. Chem. Soc., 136, 13698–13708 (2014).
[3] Magnin, Y. et al. Phys. Rev. Lett., 205502, 1–5 (2015).
[4] Diarra, M. et al. Phys. Rev. Lett., 109, 185501 (2012).
[5] Fiawoo, M.‐F. C. et al. Phys. Rev. Lett., 108, 195503 (2012).
[6] He, M. et al. Carbon, 113, 231‐6 (2017).

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1S-4
	
 

Sugar Chain Modified Graphene FET for Detection of Virus
Kazuhiko Matsumoto

Institute of Scientific & Industrial Research, Osaka University, Osaka 567-0047, Japan
We formed a bio-platform by modified the surface of graphene FET with the sugar chain,
which emulates a biological surface of human cell, and have succeeded in detecting
electrically the human & bird influenza virus selectively, and also the dissociation process ofvirus from the sugar chain.
In order to selectively detect the influenza virus, two types of the graphene FET, one ismodified by the human type sugar chain, the other is modified by the birds sugar chain, areprepared as shown in Fig.1. For the purpose of the safety, the pseud influenza virus, such as
Lectin was used.
Figure 2 shows the selective detection of the pseud human influenza virus. SSA is theLectin for the pseud human influenza virus, the MAM for the pseud bird influenza virus, and
BSA is completely non target protein. In Fig.2, the pseud human influenza virus can beselectively caught by the human-type sugar chain and modified the current of the graphene
FET, that means the selective detection of the pseud human influenza virus.

Fig.1, Schematics of SG(Sugar
Chain)- functionalized graphene
FET for the selective detection of
Influenza Virus.

Fig.2, Selective detection ofpseud Human flu virus (Lectin)
by Human sugar chain modified
graphene FET.

Fig. 3, Time course of theneuraminidase
reactionmonitored by the graphene
FET.

When virus released from the cell to another cell and continues the infection, neuraminidaseof the virus tip dissolves the sialic acid of the sugar chain where the hemagglutinin is attached.
There was no approach to the physical measurement of the status of this dissociation processuntil now.
We introduced the neuraminidase to the system of sugar chain modified graphene FET. The
neuraminidase dissolves sialic acid, and the negative charge of the carboxyl group of thesialic acid is removed. Then, the induced positive charge in the graphene channel by thisnegative charge is decreased, and we have first succeeded in observing the decrease of thedrain current by this reaction as shown in Fg.3. This is the first time result that captures thedissociation process of virus by the neuraminidase from sugar chain by electrical method.
Corresponding Author: K. Matsumoto
Tel: +81-6-6879-8410, Fax: +81-6-6879-8414,
E-mail: k-matsumoto@sanken.osaka-u.ac.jp

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2S-5
Catalyst design for controlled growth of single-walled carbon nanotubes○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 in more than two decades.
The composition and morphology of the catalyst nanoparticles and the property of the catalyst
supports were widely reported to affect the structure of SWNTs produced. In this talk, I will
discuss the strategy in catalyst design for the structural controlled growth of SWNTs.

[1] F. Yang et al. Acc. Chem. Res. 49, 606-615 (2016).
[2] F. Yang et al. Nature 510, 522-524 (2014).
[3] F. Yang et al. J. Am. Chem. Soc. 137, 8688-8691 (2015).
[4] X. Qin et al. Nano Lett. 14, 512-517 (2014).
[5] 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
Functionalized 2D materials for sensing applications
Diptiman Dinda and Shyamal K Saha
Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur,
Kolkata 700032, India

It is needless to mention that graphene is an excellent electronic material, however, it’s opticalproperty is very poor due to zero band gap. In this presentation, I would like to focus how opticalproperty could be generated in graphene using functionalization technique. Graphene oxide isfunctionalized by organic moieties to develop superior optical property with intense
photoluminescence behavior. Exploiting large surface area of graphene, hazardous heavy metals
viz. Cr, Hg, As etc. are adsorbed on the surface of functionalized graphene oxide, which has
potential application in water purification. This attachment of heavy metal ions on functionalizedgraphene oxide surface will be supported by photoluminescence quenching technique. Finally,using photoluminescence quenching technique, selective detection of nitroexplossives will also
be discussed.

Ref:
1.

Emerging Photoluminescence in azo-pyridine intercalated graphene oxide layers.
Abhisek Gupta and Shyamal K. Saha; Nanoscale, 2012, 4, 6562

2.

Removal of toxic Cr(VI) by UV-active functionalized graphene oxide for water purification,
DiptimanDinda, Abhisek Gupta and Shyamal K. Saha
J. Mater. Chem. A, 2013, 1, 11221

3.

Highly Selective Detection of Trinitrophenol by Luminescent Functionalized Reduced Graphene Oxide
through FRET Mechanism. Diptiman Dinda, Abhisek Gupta, Bikash Kumar Shaw, Suparna Sadhu, and S.
K. Saha; ACS Appl. Mater. Interfaces, 2014, 6 (13), 10722.

4.

Thymine Functionalized Graphene Oxide for Fluorescence “Turn-off-on” Sensing of
Hg2+ and I–in Aqueous Medium. Diptiman Dinda, Bikash Kumar Shaw, and Shyamal Kumar Saha.
ACS applied materials & interfaces. 2015,27, 14743-14749

Corresponding Author:
Shyamal K Saha; Email: cnssks@iacs.res.in

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2S-7
Production and functionalization of carbon nanotubes for energy devices○Suguru Noda
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, JapanTo efficiently use renewable energy at larger scale and support society, energy devices
should be produced at lower cost using abundant chemical elements. Carbon nanotubes(CNTs), which are composed of carbon, are attractive due to their properties including highspecific surface area, fairly high electric conductivity, lightness, flexibility, thermal/chemical
stability, and good compatibility with solution processing. We focus on their use as passive
electrode materials in combination with various active materials in energy devices.
Transparent conductive films (TCFs) are an attractive target, which need 5−10 mg CNTs
per 1 m2 and thus are cost effective. But such small amount of CNTs need to carry sufficientcurrent. We proposed repetitive dispersion-centrifugation process to overcome the qualityquantity trade-off and realized >90% conversion of CNTs into TCFs of 80% transmittanceand 50 Ω/sq resistance with HNO3 doping [1]. We used such solution-processed CNT-TCFs tofabricate CNT-Si heterojunction solar cells and realized ~10% photoconversion efficiency
with flat n-Si wafer with HNO3 doping and with textured n-Si wafer without doping (Fig. 1)[2]. This technology will be combined with our large-grain Si films fabricated rapidly in 1
min by vapor deposition [3] toward low-cost, stable, and flexible CNT-Si solar cells.
Battery/capacitor electrodes are also an attractive target in which carbon black and carbon
nanofibers have been used as conductive fillers. Small-diameter CNTs show uniqueself-supporting nature, and we are trying to replace heavy 2D metal foils with light-weight 3D
CNT sponges for current collectors. We use long CNTs by fluidized bed [4] for CNT sponges.
Electrodes of activated carbon particles captured in 10 wt% few-wall CNTs realized capacity
3 of pure single-wall CNTs [5], and worked with metal contact on only their edge [6].
Electrodeposition of MnO2 nanoparticles in CNT papers realized practically thickpseudocapacitive electrodes [7]. 1 wt% CNTs realized self-supporting LiCoO2 cathodes andgraphite anodes, which minimized the use of metal foils in lithium ion batteries (Fig. 2) [8].
CNT-sponge based S cathodes and Si anodes will also be presented.

Fig. 1. CNT-Si solar cells [2].

Fig. 2. CNT-sponge-based lithium ion battery [8].

[1] H. Shirae, et al., Carbon 91, 20 (2015).
[2] E. Muramoto, et al., RSC Adv. 6, 93575 (2016).
[3] Y. Yamasaki, et al., CrystEngComm 18, 3404 (2016).
[4] Z. Chen, et al., Carbon 80, 339 (2014).
[5] R. Quintero, et al., RSC Adv. 5, 16101 (2015).
[6] R. Quintero, et al., RSC Adv. 4, 8230 (2014).
[7] M. Narubayashi, et al., RSC Adv. 6, 41496 (2016).
[8] K. Hasegawa and S. Noda, J. Power Sources 321, 155 (2016).
Corresponding Author: S. Noda

Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp

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3S-8
Strong Light-Matter Coupling in (6,5) Carbon Nanotubes
Weilu Gao,1 Kankan Cong,1 Xinwei Li,1 G. Timothy Noe II,1 Huaping Liu,2 Takeshi Tanaka,2Hiromichi Kataura,2 and Junichiro Kono1
1

Department of Electrical and Computer Engineering, Rice University, Houston, TX, U.S.A.
2
Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology, Tsukuba, Ibaraki, Japan

Strong resonant coupling between light and interband transitions in semiconductors leads
to the formation of hybridized excitations, i.e., exciton-polaritons, which exhibit a rich varietyof coherent many-body phenomena. In single-wall carbon nanotubes (SWCNTs), the large
oscillator strength of excitons is expected to lead to extremely large light-matter couplingstrengths. Moreover, the one-dimensional nature of excitons in SWCNTs provides a versatile
platform for tunable light-matter coupling via polarization control.
Recent progress on large-scale separation of high-purity SWCNTs [1] and macroscopicallyaligned chirality-enriched SWCNT films [2] paves the way for such research. First, westudied a high-purity (6,5) SWCNT suspension, prepared through gel chromatography,
utilizing pump-probe spectroscopy in free space. Upon resonant optical pumping with the E11
excitonic transition, within the laser pulse duration the E11 absorption peak splits into Rabi
doublets; see Figs. 1(a)-1(c). Furthermore, a macroscopically aligned (6,5) film, preparedthrough vacuum filtration, was sandwiched between a pair of metals forming a Fabry-Perot
microcavity. By adjusting the angle between the incident light polarization and the nanotube
alignment direction, the Rabi splitting can be widely and continuously tuned from ~ 170 meV(parallel, Fig. 1(d)) to zero (perpendicular, Fig. 1(e)), as shown in Fig. 1(f).

Fig.1 Strong light-matter coupling in (6,5) suspension (a)-(c) and macroscopically aligned film (d)-(f).
1. H. Liu, D. Nishide, T. Tanaka, and H. Kataura, Nat. Comm. 2, 309 (2011)
2. X. He et al., Nat. Nanotechnol. 11, 633 (2016)
Corresponding Author: J. Kono
Tel: +1-713-348-2209, Fax: +1-713-348-3091
E-mail: kono@rice.edu

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3S-9
Optical Spectroscopy of Individual Carbon Nanotubes
with Defined Atomic Structure
Kaihui Liu
School of Physics, Peking Univerisity, Beijing 100871, China
When the characteristic length of a material shrink to 1 nm scale, many distinct physicalphenomena, such as quantum confinement, enhanced many-body interactions, strong van der
Waals inter-material couplings and ultrafast charge separation, will appear. To investigate therelated fascinating low-dimensional physics, we need a tool to quantitatively link the atomic
structures to the physical properties of these very small nano-materials. In this talk, I will
introduce our recently developed in-situ TEM + high-sensitive ultrafast nanooptics technique[1,2], which combines capability of structural characterization in TEM and property
characterization in nanooptics on the same individual nano-materials. Several examples ofusing this technique to study the 1D carbon nanotube system will be demonstrated [3,4].
[1] Kaihui Liu, Xuedong Bai*, Enge Wang*, and et al, “Chirality-Dependent Transport Properties ofDouble-Walled Nanotubes Measured in Situ on Their Field-Effect Transistors”, J. Am. Chem.
Soc. 2009, 131, 62.
[2] Kaihui Liu, Feng Wang* and et al., “High-throughput Optical Imaging and Spectroscopy ofIndividual Carbon Nanotubes in Devices”, Nature Nanotechnology 2013, 8, 917-922.
[3] Kaihui Liu, Steven G. Louie, Enge Wang*, Feng Wang* and et al. “An atlas of carbon nanotube
optical transitions”, Nature Nanotechnology 2012, 7, 325-329.
[4] Kaihui Liu, Enge Wang, Feng Wang* and et al., “Van der Waals-Coupled Electronic States in
Incommensurate Double-walled Carbon Nanotubes”, Nature Physics 2014, 10, 737-742.
Corresponding Author: Kaihui Liu
Tel: +86-10-6276-6013,
E-mail: khliu@pku.edu.cn-9-3S-10Localized growth of transition metal dichalcogenides onpatterned graphene
Fei Lu1, Arka Karmakar1, Simran Shahi1, ○Erik Einarsson1,2
1

2

Department of Electrical Engineering, University at Buffalo, Buffalo, NY USA
Department of Materials Design and Innovation, University at Buffalo, Buffalo, NY USA

As we deepen our understanding of two-dimensional (2D) materials, there is an increasing
shift in focus from individual materials to 2D heterostructures. The vastly different properties
and atomically sharp interfaces give rise to unique properties [1]. The result depends on the
combination of materials chosen, with graphene, hexagonal boron nitride, and transition metal
dichalcogenides being the most common. Although various heterostructures have beenstudied and several devices demonstrated, they are almost always fabricated by picking andplacing exfoliated materials. The ability to grow these materials in place is expected toconsiderably facilitate and accelerate this area of research.
Here we report the localized growth of transition metal dichalcogenides on patternedgraphene using chemical vapor deposition (CVD). We initially grew graphene on copper foilusing methane as a precursor.
After growth, we transferred
the graphene onto a SiO2/Si
wafer using a commerciallyavailable
copolymerinadditiontopoly(methyl
methacrylate) (PMMA) [2],and then patterned thegraphene using conventional
photolithography and oxygen
plasma. We found that if weused the SiO2/Si wafer andpatterned graphene as a
substrate, MoS2 growth islimited to the graphene areas.
This was confirmed using
Raman spectroscopy, withmapped areas shown in Fig. 1.
When growing WS2 instead ofFig. 1 (a) Optical micrograph of MoS2 grown on patterned
MoS2, the crystallinity isgraphene. (b) Overlaid Raman map of MoS2 peaks, integrating
improved but the coverage issignal from 370 cm-1 to 420 cm-1. (c) Overlaid Raman map ofless, presumably due to poorly
graphene G-peak and (d) 2D peak intensity. Scale bars are 20 µm.
optimized growth conditions.
[1] A.C. Ferrari, F. Bonaccorso, V. Fal’ko, K.S. Novoseov et al., Nanoscale 7 (2015) 4598.
[2] A. Karmakar, M.A. Philip, E. Einarsson, Carbon (under review).
Corresponding Author: E. Einarsson
Tel: +1-716-645-5089,
E-mail: erikeina@buffalo.edu- 10 -

一般講演
General Lecture

1–1 ～ 1–7
2 – 1 ～ 2 – 14
3 – 1 ～ 3 – 11

1-1
Fabrication of multiple transistors from semiconducting single-walledcarbon nanotube arrays after water-assisted burning of metallic tubes○Keigo Otsuka1, 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), 305-8564, Japan

Single-walled carbon nanotubes (SWNTs) have attracted attention as a material for highperformance field-effect transistor (FET) channels. Densely-packed arrays of aligned
semiconducting (s-) SWNTs are an ideal structure for the application. Selective removal of
metallic (m-) SWNTs after lattice-oriented growth on single-crystal substrates has been studied
intensively to obtain this structure. We have been working on an extended method of electricalbreakdown [1], by which m-SWNTs are selectively removed in much longer length with theassistance of polymer coating and water vapor [2]. However, one-way burning from initial
breakdown position hindered full-length removal of m-SWNTs and thus reproducible
fabrication of multiple FETs with high on/off ratio. Here, we report that reproducible full-length
removal of m-SWNTs was achieved by re-burning from site-controlled nanogaps. In addition,
multiple FETs was fabricated on the resultant long s-SWNT arrays, which showed advantagesof this method over conventional electrical breakdown in fabrication of both short-channel
FETs and scaled-up integrated devices at the same time.
Horizontally aligned SWNTs were grown on r-cut quartz substrates by the alcohol chemical
vapor deposition method, and then were transferred on Si substrates with oxide layer (100 nm).
Long-channel (~10 μm) FET structures were fabricated by patterning Au electrodes. As shownin Fig. 1a, nanogaps in m-SWNTs were created near the lower side of electrodes (white arrows)
by the electrical breakdown method [1](a)(b)
using temporally placed intermediate
5 μm
5 μm
electrodes. Broken m-SWNTs on theupper side were re-burned almost in fulllength by further voltage application
with polymer coating and water vapor
exposure [2,3] (Fig. 1b). Multiple FETs
nanogap
fabricated from the resultant s-SWNT
metallicarrays showed high on/off ratio (Fig.
(d)
V = −1 V(c)101c,d), which indicates the possibility of
5 μm
m− & s−arrays−arrayhighly integrated FET fabrication by
10
this strategy.
[1] P. G. Collins et al., Science 292, 706 (2001).
[2] K. Otsuka et al., The 49th FNTG general
symposium, 3P-16 (2015)[3] K. Otsuka et al., Nanoscale 8, 16363 (2016).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp

ON/OFF ratio

3

DS

2

10

1

10

0

0

500
Channel length (nm)1000

Fig.1 Fabrication procedures of multiple FETs after mSWNT removal. Identical SWNT array (a) after gap
formation, (b) after full-length removal of m-SWNTs, and (c)after the patterning of source and drain electrodes with small
separation. (d) On/off ratio of FETs versus channel length.

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1-2
Asymmetric carrier accumulation in double-walled carbon nanotube
under an electric field○Taketo Kochi and Susumu Okada

University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8571 Japan
Carbon nanotubes (CNTs) are attracting much attention because of their uniquegeometric and electronic structure. Due to such unique properties, CNTs act as aconductive channel of the ﬁeld effect transistor (FET). In the FET, CNTs intrinsicallyform the hybrid structures with other CNT and foreign materials, which affect thecarrier accumulation by the gate electric field. Indeed, our previous calculation showedthat the distribution of the accumulated carrier in the CNT thin films strongly depends
on the CNT and carrier species, leading to
the unusual induced electric field between
CNTs [1]. In this work, we aim to elucidate
the carrier accumulation in double-walled
CNT (DWCNTs) in FET structure by theexternal electric field, using the density
functional theory combined with theeffective screening medium method. In thiswork, we consider the (7,0)@(16,0) and(8,0)@(17,0)
astherepresentative
DWCNTs. As shown in Fig. 1, thedistribution of accumulated carrier issensitive to the carrier species. For the hole
doping, injected hole is primary distributedon the outer CNT, while the carriers areabsent on the inner CNT. In contrast, forFig. 1. Isosurfaces of the accumulated carriersin (a) (7,0)@(16,0) and (b) (8,0)@(17,0)
nanotubes. In each panel, hole and electron
denote the injection of holes and electrons,
respectively. Yellow and blue isosurfaces
indicate regions where electrons and holes

the electron doping, the accumulated
increase, respectively, under the electric field.
electron is distributed both on outer andinner CNTs, owing to their complex electronic structure around the energy gap.
[1]T. Kochi and S.Okada, Appl. Phys. Express 9, 085103(2016).
Corresponding Author: T. Kochi
Tel: +81-29-853-5600(ext.; 8233) , E-mail: tkochi@comas.frsc.tsukuba.ac.jp- 12 -

1-3
Enhancement of Raman scattering from monolayer graphene by photonic
crystal nanocavities○I. Kimura1,2, M. Yoshida1,3, M. Sota 4, H. Machiya1,2, T. Inoue4, S. Chiashi4, S. Maruyama4,
Y. K. Kato1,3
1

Nanoscale Quantum Photonics Laboratory, RIKEN, Saitama 351-0198, Japan
Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
3
Quantum Optoelectronics Research Team, RIKEN Center for Advanced Photonics, Saitama
351-0198, Japan
4
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2

Monolayer graphene is an atomically thin two-dimensional material that shows strong
Raman scattering, while photonic crystal nanocavities with small mode volumes allow for
efficient optical coupling at the nanoscale [1]. Here we demonstrate resonant enhancement ofgraphene Raman G’ band by coupling to photonic crystal cavity modes. Hexagonal-latticephotonic crystal L3 cavities are fabricated from silicon-on-insulator substrates [2, 3], andmonolayer graphene sheets grown by chemical vapor deposition are transferred onto thenanocavities. Excitation wavelength dependence of Raman spectra show that the Raman
intensity is enhanced when the G’ peak is in resonance with the cavity mode. By performing
imaging measurements, we confirm that such an enhancement is only observed at the cavity
position.
Work supported by JSPS KAKENHI Grant Numbers JP16K13613, JP25107002 andMEXT (Photon Frontier Network Program, Nanotechnology Platform).
[1] X. Gan, K. F. Mak, Y. Gao, Y. You, F. Hatami, J. Hone, T. F. Heinz, and D. Englund, Nano Lett. 12, 5626
(2012).
[2] R. Watahiki, T. Shimada, P. Zhao, S. Chiashi, S. Iwamoto, Y. Arakawa, S. Maruyama, and Y. K. Kato, Appl.
Phys. Lett. 101, 141124 (2012).
[3] X. Liu, T. Shimada, R. Miura, S. Iwamoto, Y. Arakawa, and Y. K. Kato, Phys. Rev. Applied 3, 014006(2015).
Corresponding Author: Y. K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 13 -

1-4
Magnetic properties of two-dimensional hydrocarbon networks○Jun-ya Sorimachi, Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba
305-8571, Japan
Electronic and magnetic properties of hydrocarbon materials are sensitive to their πelectron network. By assembling the appropriate hydrocarbon molecules as constituent
units for two-dimensional covalent networks, we can tailor the electronic structure of
the resultant network from a semiconductor to metal. For instance, the hexagonal
network consisting of phenalenyl and phenyl, which are alternately arranged inhexagonal manner, has both Dirac cones and Kagome bands at and near the Fermi level,
respectively, leading to the magnetic ordering which depends on the carrier
concentration [1]. Although sp3 C atoms intrinsically terminate the π electron networkof hydrocarbon materials, they allow us to design further variation of hydrocarbon
covalent networks, of which electronic properties are absent in all sp2 C network
materials. In the present work, we theoretically design the novel hydrocarbon covalent
network comprising sp2 and sp3 C atoms as possible candidates for magnetichydrocarbon materials with Kagome flat bands, using the density functional theory withgeneralized gradient approximation. As for the constituent blocks of the network, we
consider the propellane and iptycene molecules consisting of sp2 and sp3 C atoms (Fig.
1). Because both molecules have C3 symmetry with respect to their molecular axis, they
can form honeycomb networks containing sp2 and sp3 C atoms.
Our calculations show that these two-dimensional hydrocarbon network possess
Kagome band at or near the Fermi level of which energy and width are sensitive to the
network topology of sp2 C networks (polyacene structure) bridging sp3 atoms. The
networks with propelanes exhibit spin polarization with various long-range ordering as
their metastable spin configurations, owing to the partially filled Kagome flat band.
(a)

(b)

Fig. 1: Geometric structures of (a) propellane and (b) iptycene derived networks.

Reference[1] M. Maruyama, N. T. Cuong, S. Okada, Carbon 109, 755 (2016).
Corresponding Author: J. Sorimachi
Tel: +81-29-853-5921,
E-mail: jsorimachi@comas.frsc.tsukuba.ac.jp- 14 -

1-5
Opening a Gap in Graphene Field Effect Devices
with Periodic Uniaxial Strain○Hikari Tomori1,2, Rineka Hiraide1, Youiti Ootuka1, Kenji Watanabe3, Takashi Taniguchi3,
Akinobu Kanda11Division of Physics and TIMS, University of Tsukuba, Tsukuba, 305-0006, Japan
2
PRESTO-JST, Kawaguchi, 332-0012 Japan
3
National Institute for Materials Science (NIMS), Tsukuba, 305-0047, JapanDue to high mobility, graphene is a promising candidate for electronic materials. However,for successful application of graphene to switching devices, gap formation is indispensable. In
this study, we explore the gap formation in graphene based on strain engineering [1, 2].
For the periodic uniaxial strain, a band gap has been observed only in scanning tunnel
spectroscopy, while it has not been confirmed in actual field effect devices [3]. This missing
gap is presumably due to the relaxation of strain in device fabrication processes. Here, wedevelop a novel device fabrication method which makes graphene largely strained even after
the formation of electrical contacts. In this method, a graphene film is placed on a periodic
array of resist HSQ bars. The introduction of strain was confirmed with micro-Raman
spectroscopy. The back gate voltage dependence of the conductance in the strained graphene
exhibited remarkable difference from the conventional V-shaped curve observed in graphene
placed on SiO2. The minimum conductance showed thermal activation behavior at hightemperatures (> 100 K). From the Arrhenius plot, the band gap was estimated to be 2.4 meV(Fig. 1). Besides, the current-voltage characteristics became nonlinear around the origin. The
high resistance region extended within +/- 2 meV at the gate voltage corresponding to theminimum conductance. This value agreed well with the band gap estimated from thetemperaturedependence.
These
observations confirm the formation of
the band gap in our strained graphene.
We expect that optimization of thedevice structure extends the gap andimproves device performance.
[1] F. Guinea et al, Nat. Phys. 6, 30 (2010)[2] V.M. Pereira and A. H. Neto, Phys. Rev. Lett.
103, 046801 (2009).
[3] J. K. Lee et al., Nano Lett. 13, 3494 (2013).
Corresponding Author: H. Tomori
Tel: +81-29-853-4345,
Fax: +81-29-853-4345,
E-mail: tomori@lt.px.tsukuba.ac.jp

Fig.1 Arrhenius plot of minimum conductance. (insert)
Gate voltage dependence of conductance at 250 K, 77
K and 4K.

- 15 -

1-6
Gas Adsorption Effects on Stabilities and Electronic Properties of Graphene
Bilayers○Yoshitaka Fujimoto1 and Susumu Saito1,2,3
1

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

Ever since the successful exfoliation of graphene from multilayer graphite, graphene hasreceived much interest from the viewpoints of fundamental physics and relevant applicationsin nanoelectronics because it shows various unique properties. Specifically, due to its
extremely high carrier mobility, graphene still is a potential device material fornext-generation nanoelectronics.
One of the effective ways to control the electronic properties of graphene is to dopewith heteroatoms. Furthermore, substitutionally doped graphene can often enhance its
chemical reactivity. Thus, doped graphene is also a good candidate for promising sensor
applications because of the high carrier mobility as well as the high sensitivity.
In this talk, we report polluting or toxic gas adsorption effects on the stabilities and theelectronic properties of graphene bilayers doped with boron and nitrogen atoms based on our
first principles density functional study [1, 2]. We show that NO and NO 2 molecules can bindon B-doped bilayer graphene with chemical bonds. Furthermore, we also show that theadsorptions of NO and NO 2 molecules on the B-doped bilayer graphene can lead to chargetransfers between gas molecules and graphene layers (Fig. 1). We also discuss the possibilities
for these doped graphene layers to be applied to gas sensors.
[1] Y. Fujimoto and S. Saito, Surf. Sci. 634 (2015) 57.
[2] Y. Fujimoto and S. Saito, Chem. Phys. 478 (2016) 55.

Fig. 1 Side views of charge transfers between B-doped bilayer graphene and gas
molecules: (a) NO and (b) NO2 molecules (Ref. [2]).
Corresponding Author: Yoshitaka Fujimoto
TEL: +81-3-5734-2368, FAX: +81-3-5734-2368, E-mail: fujimoto@stat.phys.titech.ac.jp- 16 -

1-7
Edge Roughness Analysis for Developing GNR-based FET○Kengo Takashima1, Takahiro Yamamoto1, 2
12

Department of Engineering, Tokyo University of Science, Tokyo 125-8585, Japan
Department of Liberal Arts, Tokyo University of Science, Tokyo 125-8585, Japan

Graphene is expected to be a channel material of field effect transistors (FETs) because of its
high carrier mobility. However, no band gap of the graphene is a serious problem for its FET
application. One possible way to overcome the gap-opening problem is to process it in theform of a nanometer width ribbon, referred as graphene nanoribbons (GNRs). They have beensuccessfully applied to FETs with high on-off ratio. We recently reported that resistance of
GNR increase dramatically with edge disorder[1][2]. However, the edge roughness effect on
the GNR-FET properties have not been clarified yet.
In this study, we have investigated the coherent electronic transport in edge-disorderedarmchair GNR FETs (ED-AGNR-FETs) using the nonequilibrium Green’s function method
combined with a tight-binding model[3]. In our simulation model, the edge vacancy ismodeled by adding or removing pairs of carbon atoms at the edges (Fig. 1). We calculated
drain current(Id) versus gate voltage(Vg) characters of ED-AGNR-FETs by changing theroughness concentration P from 0% to 30% and the ribbon-width from 2.21nm (Fig. 2). We
confirmed that a variance of on current(ΔIon) is independent of Ion and ΔIon is constant(universal conductance fluctuation), where P is under 10 %. On the other hand, when P
exceed 10 %, ΔIon and variance of subthreshold become large drastically. This result provides
a guideline for developing GNR-based FETs.

Fig. 1 Edge-disordered AGNR-FET

Fig. 2 Id-Vg curves of edge-disordered AGNR-FETs

References:[1] K. Takashima and T. Yamamoto, APL., 104, 093105 (2014).
[2] K. Takashima, S. Konabe and T. Yamamoto, JAP., 119, 024301 (2016).
[3] P. Koskinen and V. Mäkinen, Computational Materials Science, 47, 237 (2009)
Corresponding Author: T. Yamamoto
E-mail: takahiro@rs.tus.ac.jp- 17 -

2-1
Drastically improved efficiency of single wall carbon nanotube forest
synthesis on a MgO catalyst underlayer by a simple annealing process○Takashi Tsuji, Kenji Hata, Don N. Futaba, Shunsuke Sakurai
CNT-Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, JapanOne of the important factors to synthesize single wall carbon nanotube (SWCNT) forest is
the catalyst underlayer to support catalyst nanoparticle array. Up to date, alumina is the only
choice to grow millimeter-scale SWCNT forest and reports on the use of other catalyst
underlayer such as silica (SiO2), magnesia (MgO) and zirconia (ZrO2) have shown difficultyin achieving high efficiency (e.g. > 100 m). This difficulty comes from the instability of iron(Fe) catalyst on these catalyst underlayers. For example, as we reported in the 50th FNTG
conference [1], growth lifetime of CNTs from Fe catalyst supported on a sputtered MgO layer
was much shorter than sputtered Al2O3 layer, which was due to strong subsurface diffusion of
Fe catalyst into the underlayer.
We recently demonstrated the drastic increase in the efficiency of SWCNT forest synthesis
on a sputtered MgO catalyst underlayer by a simple pretreatment process. By annealing theas-sputtered MgO layer in the air (750oC, 20 min) before the deposition of Fe catalyst layer,
the height of CNT forest synthesized by water assisted chemical vapor deposition (10 min)increased about 5000% from 0.02 mm to 1.2 mm [2]. High percentage of SWCNTs in theforest (95%) was verified by transmission electron microscopy (TEM) observation.
Furthermore, the growth lifetime of the SWCNT forest characterized by the in-situ heightmeasurement was on par with those grown on Al2O3. Such high growth efficiency can be
explained by the improved nanoparticle stability. Analyses by X-ray diffraction, X-ray
photoelectron spectroscopy, and atomic force microscopy suggest that the underlayer
treatment increased crystallinity of the MgO underlayer, that suppressed Fe subsurface
diffusion into underlayer and retained the Fe metallic state. In this presentation, the effect of
the annealing treatment temperature on the yield and structures (diameter, wall number) of
CNT forest is also discussed. This presentation is based on results obtained from a projectcommissioned by the New Energy and Industrial Technology Development Organization(NEDO).
[1] T. Tsuji et al. Abstracts of the 50th Fullerene-Nanotubes-Graphene General Symposium (2015).
[2] T. Tsuji et al. J. Am. Chem. Soc. 138, 16608 (2016).
Corresponding Author: S. Sakurai
Tel: +81-29-861-4654, Fax: +81-29-861-4851,
E-mail: shunsuke-sakurai@aist.go.jp- 18 -

2-2
A study of dispersion states of CNTs in slurry by AC impedance method○Takayuki Watanabe1, Kazufumi Kobashi1,2, Takahiro Morimoto1,2, Toshiya Okazaki1,2
1Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba,
305-8565, Japan
2
CNT Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, 305-8565, Japan
We report CNT-type and density dependences of the electrical properties of thesurfactant-free CNT-dispersed organic solvents. CNT slurry/paste without surfactant is one of
the measure forms in industrial application because it’s easy to handle compared to thepowder form. However, only few studies have been reported about the states of CNTs in the
produced slurries despite of its industrial importance. To develop the effective evaluation
method, AC impedance behaviors of several CNT slurries are systematically investigated.
Figure 1(a) shows CNT weight density dependence of conductivity of the CNT slurries
measured by conventional impedance measurement setup (Fig. 1(b)). The CNT types we usedhere are super-growth-, e-DIPS- and VGCF-CNTs. They showed significant conductivity
increases above threshold values of CNT weight density, which is well known as percolation
behavior. All three slurries showed different threshold values and slope magnitude. These
values seem to be affected by each type of CNTs, but they don’t simply depend on individual
CNT property, for example, the length. This is probably because property of CNT slurrystrongly depends not only on isolated CNT properties, but also on degree of aggregation,
distribution of particle sizes and so on. The relationship between the dispersion states of CNTs
in each slurry and the AC impedance behaviors will be discussed in detail.
This study is based on results obtained from a project commissioned by the New Energy
and Industrial Technology Development Organization (NEDO)a)b)

Impedance analyzer

Inset

Fig.1 a) CNT weight density dependence of CNT slurry conductivity. b) Schematic image of measurement
setup. An expected equivalent circuit model of CNT slurry is shown in the inset.
Corresponding Author: Toshiya Okazaki
E-mail: toshi.okazaki@aist.go.jp- 19 -

2-3
The effect of noble metals on the formation of iron catalyst nanoparticle forthe synthesis of vertically-aligned carbon nanotubes○Shunsuke Sakurai, Kenji Hata, Don N. Futaba
CNT-Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, Japan
A highly dense assembly of metal iron nanoparticle formed on the substrate is frequently
utilized as the catalyst for the synthesis of carbon nanotubes (CNTs) forest (i.e. verticallyaligned CNTs) using chemical vapor deposition (CVD) method [1]. Commonly, such an
assembly of catalyst nanoparticle is prepared by annealing the thin film of iron compounds inthe reductive ambient (e.g. hydrogen) [2]. The importance of annealing in hydrogen is also
demonstrated by the wide range modulation of single-walled CNT diameter in the forest by
the parametric change in the annealing conditions [3].
Although the importance of reductive gases are widely recognized, we further investigatedthe preparation method of catalyst nanoparticle assembly, since most of the reductive gases
are explosive and/or toxic. Here, we demonstrated that even without any reductive gases, thesynthesis of CNT forest can be enabled by adding noble metals (such as iridium andruthenium) into the iron catalyst film. First, aqueous solutions including iron chloride, citrateacid, polymer agents, and chloride of noble metals are coated on the alumina layer sputteredon silicon wafer to prepare catalyst substrates. Next, obtained substrates are annealed inhelium ambient (750 ºC, 6 min), and then
15 nm
acetylene is introduced in the furnace withaddition of water vapor for 10 min. Although theheight of CNT forest is shorter than 10 μm when
only iron chloride is used, forests taller than 300
μm were successfully synthesized by adding-15 nm
iridium and ruthenium chlorides. The formation of
catalyst nanoparticle by annealing in helium issuggested by the atomic force microscopy (AFM)
images (Figure 1). The mechanism for theformation of catalyst nanoparticle without Figure 1. AFM image of catalyst particle
obtained after annealing iron/iridium film
reductive gases triggered by noble metals are also in helium ambient (500 nm × 500 nm).
discussed in the presentation.
[1] K. Hata, D. N. Futaba, K. Mizuno, T. Namai, M. Yumura, S. Iijima Science 306, 1362 (2004).
[2] S. Sakurai, H. Nishino, D. N. Futaba, S. Yasuda, T. Yamada, A. Maigne, Y. Matsuo, E. Nakamura, M.
Yumura, and K. Hata J. Am. Chem. Soc. 134, 2148 (2012).
[3] S. Sakurai, M. Inaguma, D. N. Futaba, M. Yumura, K. Hata Small 9(21), 3584 (2013).
Corresponding Author: S. Sakurai
Tel: +81-29-861-6205, Fax: +81-29-861-4851,
E-mail: shunsuke-sakurai@aist.go.jp- 20 -

2-4○

Lock-in thermography technique for visualizationof CNT network structures

Takahiro Morimoto1,2, Seisuke Ata1,2, Takeo Yamada1,2 and Toshiya Okazaki1,2
1
CNT-Application Research Center, National Institute of Advanced Industrial Science andTechnology, Tsukuba 305-8565, Japan
2
Technology Research Association for Single Wall Carbon Nanotubes (TASC), JapanThe randomly networked carbon nanotubes are important structures for various functional
materials and devices. The bulk properties of these materials are understood by formalizationof the percolation theory. In this theory, however, it is difficult to accurate expectation thebulk properties depending on various experimental conditions. For more efficient material
and device developments, the analysis method for the inside structures is strongly demanded
as real space and short time measurement method.
In this time, we will present the new analysis method for these randomly networked
systems. In many case, the CNTs added to base materials are connected each other insidematerials. These network structures contribute to improve the electrical, thermal andphysical properties of bulk properties. In the case of CNTs, these randomly network structure
have conductivity after percolation threshold concentrations.
Figure.1 shows the schematic images of suggested method. The ac bias voltages (< 100Hz) are applied to the materials contained CNTs. In that time, the infrared is radiated fromthe sample surface including both Joule heating and background heat storage. For the
separation of these components, the lock-in
technique is applied for thermal images.
Figure.2 shows the effect of the lock-in process
at same sample and same conditions. In theconventional method (integrated thermal image),the detail structures are completely smeared out by
the background heat storage of the base materials
as shown in Fig.2 (a). In the case of lock-in
thermal image, on the other hand, the current paths
Fig.1 The schematic image of lock-in
on the conductive network structures are clearly
thermography.
visualized depending on the local resistance andcurrent distributions as shown in Fig. 2 (b). In the(a)presentation, we will show the results on various
materials and processes. We will also discuss themechanism of heating structures related to bulk
properties.
(b)
This paper is based on results obtained from a
project commissioned by NEDO.

[1] T. Morimoto et al., in preparation.
Corresponding Author: Takahiro Morimoto
Tel: +81-29-861-3804, Fax: +81-29-861-6241,
E-mail: t-morimoto@aist.go.jp

Fig.2 (a) non-lock-in image. (b) lock-in
image.

- 21 -

2-5
Scanning Electrochemical Cell Microscopy for Visualization of
Local Electrochemical Activities on Graphene/Graphite○Akichika Kumatani 1, Chiho Miura 1, Takeru Okada 2, Seiji Samukawa 2,3, Hitoshi Shiku 1,
Yasufumi Takahashi 4,5 Tomokazu Matsue 1,3
1

Tohoku University, Sendai 980-8579, Japan
Institute of Fluid Science, Tohoku University, Sendai 980-8577, Japan
3
Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
4
Kanazawa University, Kanazawa 920-1192, Japan
5
JST PRESTO, Saitama 332-0012, Japan2

Towards the establishment of low-carbon emission society, one urgent issue is to
standardize a highly efficient electrochemical device to store unused energy for secondary
batteries or to generate hydrogen evolution for energy source of fuel cells. Two-dimensional
layered materials such as graphene have shown great performance for those applications. It isalready known that a careful control of their edge structures, defects or functionalization on
the surface are a key to enhance their performance. In general, their unique properties areevaluated by indirect methods such as electrochemical analysis in bulk or probing techniques
for electronic conductivities. It is therefore necessary to develop an electrochemical analyticaltechnique in nanometer for classification of the factors at the desired location.
In this study, we introduce a scanning electrochemical cell microscopy with a single-barrel
nanopipette filled with electrolyte and a reference electrode (nanoSECCM) in Fig. 1 (a) for
direct visualization of local electrochemical activities under sub-micrometer scale [1]. 5 mM
hexaammineruthenium chloride and 25 mM KCl in phosphate buffer or deionized water was
prepared for an electrolyte. Then, the electrolyte was filled in nano-pipettes (100 nm or 1 µm
in a diameter) with Ag/AgCl reference electrode for inducing redox reaction of ruthenium ionon the sample surface. The nanoSECCM was applied to graphite or cleaved graphene on
silicon substrates. Once the pipette was in proximity of the sample surface, a meniscus wascreated as an electrochemical cell. Through the cell, local electrochemical activities wasanalyzed at a confined area. Also, by scanning the pipette on the sample surface, bothelectrochemical activities and topography simultaneously were obtained as shown in Fig 1 (b).
Consequently, high activities at the edges of graphene/graphite were visualized.

Fig.1 (a) a schematic of nanoSECCM, (b) nanoSECCM images of graphite/graphene surface on thesubstrate: Left electrochemical activities and topography.
[1] Y. Takahashi, A. Kumatani et al. Nat. Comm. 5:6450 (2014).
Corresponding Author: Akichika Kumatani, Tomokazu Matsue
Tel: +81-22-795-7281, Fax: +81-22-795-6167,
E-mail: kumatani@bioinfo.che.tohoku.ac.jp, matsue@bioinfo.che.tohoku.ac.jp- 22 -

2-6Out-of-Plane Strain Generation of Monolayer MoS2 and MoSe2
Formed a Moiré Superstructure on the Au(111) Surface
R. Takahashi1, R. Osaka1, Y. Miyata2, S. Okada3, Y. Hayamizu4,○S.Yasuda1, K. Murakoshi1
12Department of Chemistry, Hokkaido University, Sapporo, 060-0810, Japan
Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
3
Graduate School of Pure and Applied Science, University of Tsukuba, Tsukuba,
Ibaraki 305-8571, Japan
4
Department of Organic and Polymeric Materials, Tokyo Institute of Technology,
Ookayama, 152-8552, Japan

Contact of transition metal dichalcogenides (TMDCs) with a metal surface isessential for fabricating and designing electronic devices. It generates strain in the
TMDCs and consequently may affect phonons and electrons in the TMDCs. Therefore
detailed understanding of the mechanism of the strain generation is important for fullycomprehend the phonon and electronic modulation effects. In this study, we grow MoS2
and MoSe2 monolayers on Au surface by chemical vapor deposition and investigated
the influence of the metal contact upon the structure and electronic properties. Raman
spectroccopy revealed that the contact with a crystalline Au(111) surface gives rise to
only out-of-plane strain in both MoS2 and MoSe2 layers, whereas no strain generation isobserved on polycrystalline Au or SiO2/Si surfaces. STM analysis provided information
regarding consequent specific adsorption sites between lower S (Se) atoms in the
S-Mo-S (Se-Mo-Se) structure and Au atoms via unique moiré superstructure formation
for MoS2 and MoSe2 layers on Au(111) (Fig. 1). This observation indicates that theadsorption sites of the Au(111) surface
strongly interact with lower S (Se) atoms
in MoS2 or MoSe2 layers, giving rise to
local out-of-plane strain in the layers. The
finding would serve as complementary
information for profound understanding of
the modulation effect of phonons andelectronic structure by TMDC-metal
contact.

Fig. 1 STM images of (a) MoS2/Au(111) (Vs =+0.2 V and It = 1nA) and (b) MoSe2/Au(111)(Vs = +0.3 V and It = 1nA).

Corresponding Author: S. Yasuda
TEL & FAX: +81-(0)11-706-4811
E-mail: satoshi-yasuda@sci.hokudai.ac.jp- 23 -

2-7
Magnetic tunnel junction built from intercalated transition metal
dichalcogenide ferromagnets with different magnetic anisotropy○Yuji Yamasaki1, Rai Moriya 1, Miho Arai 1, Satoru Masubuchi 1, Sunseng Pyon 2,
Tsuyoshi Tamegai 2, Keiji Ueno 3, and Tomoki Machida 1,4
1

2

Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, Japan
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Chemistry, Saitama University, Saitama 338-8570, Japan
4
CREST-JST, Saitama 332-0012, Japan

Ferromagnetic two-dimensional (2D) materials have received considerable attention for
constructing spintronic devices with all-2D-material heterostructures. Previously, we revealed
mechanical exfoliation of the Fe-intercalated 2H-TaS2, Fe1/4TaS2, and construction of magnetic
tunnel junction from two different flakes of Fe1/4TaS2 [1]. So far FexTaS2 is the only material
that is experimentally verified as an exfoliatable metallic ferromagnet. Demonstration of otherexfoliatable ferromagnets is in demand. Here, we investigate mechanical exfoliation of otherintercalated transition metal dichalcogenide Cr1/3TaS2. Anisotropic magnetoresistancemeasurement reveals that exfoliated Cr 1/3TaS2 exhibits ferromagnetic ordering below ~110 K
and its easy axis is along in-plane direction, in contrast to Fe1/4TaS2 whose easy axis is along
out-of-plane.
Further, we constructed heterojunction between Cr1/3TaS2 and Fe1/4TaS2 by using exfoliationand dry transfer method (Figs. 1 and 2). Due to the native oxidation of intercalated materials,
Ta2O5 tunnel barrier is formed at the heterojunction; thus device exhibits
Fe1/4TaS2/Ta2O5/Cr1/3TaS2 structure. The fabricated junction showed clear signature of tunnel
magnetoresistance (TMR) effect (Fig. 3) [2]. We obtained maximum TMR ratio of 13% in
Fe1/4TaS2/Ta2O5/Cr1/3TaS2 junction and this value was significantly higher than the previous
report on Fe1/4TaS2/Ta2O5/Fe1/4TaS2 [1]; revealing larger tunnel spin polarization by using
Cr1/3TaS2. These findings demonstrate possibilities to use magnetic atom intercalated transition
metal dichalcogenaide materials in the field of 2D material spintronics.
[1] M. Arai et al. Appl. Phys. Lett. 107, 103107 (2015).

Fig.1
An
illustrationof
Fe1/4TaS2/Cr1/3TaS2
junction.
Magnetization
easy
axis
directions are indicated byarrows.

[2] Y. Yamasaki et al. (submitted).

Fig.2 A micrograph ofthe device.

Fig.3 Magnetoresistance data obtained
from Fe1/4TaS2/Cr1/3TaS2 junction at 8 K.

Corresponding Author: Y. Yamasaki
Tel: +81-3-5452-6158, Fax: +81-3-5452-6157, E-mail:yu-yama@iis.u-tokyo.ac.jp- 24 -

2-8
Improvement of Open-circuit Voltage in Perovskite Solar Cells by Using
Methano-Indene-Fullerene (MIF)○Yutaka Matsuo1,2,3
1

Hefei National Laboratory for Physical Sciences at the Microscale, University of Scienceand Technology of China, Hefei, Anhui 230026, China
2
Department of Mechanical Engineering, School of Engineering, The University of Tokyo,
Bunkyo-ku, Tokyo 113-8656, Japan3
Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China
Methano-indene-fullerene (MIF, C60(CH2)Ind) has been used in polymer/fullerene organic
solar cells[1] and small-molecule organic solar cells[2] to have high open-circuit voltage (VOC).
Methano and indeno addends reduces the π-conjugation of fullerene for a higher lying LUMO
level, giving high VOC values >1.0 V without any significant loss in short-circuit current
density (JSC) and fill factor (FF) due to the small volume of the indeno group that can provide
short fullerene–fullerene contact distance for high electron mobility.
In this presentation, we will discuss the use of MIF in the inverted planar
NiO-diethanolamine/CH3NH3PbI3/fullerene p–i–n solar cells.[3] Compared the using PCBM,
VOC increased to 1.13 V because of the energy loss at the interface between perovskite andfullerene layers.

Figure. Device structure, energy diagram, and device performance of pervskite solar cells using
methano-indene-fullerene.
References[1] Y. Matsuo, J. Kawai, H. Inada, T. Nakagawa, H. Ota, S. Otsubo, E. Nakamura, Adv. Mater. 2013, 25,6266–6269.
[2] J. W. Ryan, Y. Matsuo, Sci. Rep. 2015, 5, 8319.
[1] Q. Xue, Y. Bai, M. Liu, R. Xia, Z. Hu, Z. Chen, X.-F. Jiang, F. Huang, S. Yang, Y. Matsuo, H.-L. Yip, Y. Cao,Adv. Energy Mater. 2017, 1602333
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-0978, E-mail: matsuo@ustc.edu.cn; matsuo@photon.t.u-tokyo.ac.jp- 25 -

2-9
Electronic Structures and Stability of Metal Encapsulated C80 fullerenes:
Ab initio DFT study○Archana Velloth1, Yutaka Imamura 1, Takeshi Kodama1, Masahiko Hada 1
1

Department of Chemistry, Tokyo Metropolitan University, Hachioji-shi 192-0397, Japan

Endohedral metallofullerenes are novel derivatives of fullerenes which find potential
applications ranging from nanomemory devices to biomedical field.[1] Here, an extensive
study of the structural and electronic properties on a series of neutral and anionic species ofendohedral dimetallofullerenes[2] (di-EMFs) based on DFT and ab-initio computational
calculations has been performed. Initially, we considered different configurations of M2@C80(M= Sc, Y, La, Gd and Lu) followed by examining the ground state of these di-EMFs. In thestudied di-EMFs, except La2@C80, all other di-EMFs prefer to exist in the higher spin state asa ground state. The di-EMFs with a higher spin ground state were found to be kineticallyunstable due to the unpaired spin distribution over the C80 cage. Recently, the isolation ofanion species of Y2@C80[3] and Gd2@C80[4] were reported. In order to find more stable species,
further we analysed the anions of these di-EMFs. Then, we were able to find that theconfinement of the unpaired electron inside the carbon cage enhanced the stability of anions
of di-EMFs. Additionally, to gain more insight to the excited state, we have also investigatedabsorption spectra for the [M2@C80]- using time-dependent density functional theory(TDDFT) method. Finally, we have also examined a series of M1M2@C80 hetero-di-EMFs
incorporating different lanthanides like LaLn@C80 (Ln= Ce to Gd) and yielded interesting
results where Gd based analogues exhibits a higher stability.

Fig 1. Optimized structure of M2@C80[1] a) S. Yannoni et al. Nature, 366, 123 (1993). b) H. Shinohara et al. J. Am. Chem. Soc., 125, 4391 (2003).
[2] a) A.A. Popov et al. Chem. Rev., 113, 5989 (2013). b) H. Shinohara, Rep. Prog. Phys., 63, 843 (2000).
[3] N. Nakatori, et al. The 49th Fullerenes-Nanotubes-Graphene General Symposium 46 (2015).
[4] T. Mitani, et al. The 50th Fullerenes-Nanotubes-Graphene General Symposium 95 (2016).
Corresponding Author: M. Hada
Tel: + 81-42-677-2554, Fax: + 81-42-677-2525
E-mail: hada@tmu.ac.jp- 26 -

2-10
Searching for the unprecedented endohedral metallofullerenes by applying
the separation method for those stable only in an anion form
◯Natsumi Nakatori1, Takuji Mitani1, Takahisa Yamaguchi2, Ko Furukawa3,
Tatsuhisa Kato2,4, 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
Center for Instrumental Analysis, Niigata University, Niigata 950-2181, Japan
4
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

In dimetallofullerenes, it has been well known only La, Ce, and Pr are encapsulated in the
C80(Ih) cage, and Y, Sc, Lu, and other metals are encapsulated in other cages such as C82 andC84. So, until very recently, M2@C80(Ih) (M≠La, Ce, Pr) has been thought to be one of the“hidden” metallofullerenes. However, for M=Y, we have succeeded in the isolation andcharacterization of Y2@C80(Ih) using the method combining the ion-pair chromatography(IPC) with the extraction by a mixed solvent of triethylamine and acetone [1]. This newtechnique opened the door for investigating more generally the “hidden” metallofullerenes
those are unstable in a neutral form but stable in an anion form. In this study, we apply themethod to explore the unprecedented metallofullerenes encapsulating Sc or Lu.
Sc or Lu-metallofullerenes were produced and extracted by the almost identical method
previously reported [1]. Separation was accomplished by the multi-stage IPC. The first-stage
IPC chromatograms of Y, Sc, and Lu-metallofullerenes are shown in Fig.1, and the portionsof the dimetallofullerenes are indicated. The elution behaviors are rather different depending
on metals. For Sc-metallofullerenes, Sc2C76 and Sc2C78
eluted in the same time. Therefore, Sc2C78 would be not
Sc2@C78 but Sc2C2@C76. Moreover, Sc2C80 was isolated,
but its absorption spectrum was a little bit different fromother M2@C80(Ih), then, we couldn’t assign Sc2C80 is
Sc2@C80(Ih). For Lu-metallofullerenes, Lu2C78 andLu2C80 showed the same elution behavior. Then, like
Sc2C78, Lu2C80 should be not Lu2@C80 but Lu2C2@C78.
Lu2@C80(Ih) was not obtained in our experiment.
[1] N. Nakatori, et al. The 49th Fullerenes-Nanotubes-Graphene
General Symposium 46 (2015).
Corresponding Author: Takeshi Kodama
Tel:+81-42-677-2530, Fax:+81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 27 -

Fig.1 IPC chromatograms of Y, Sc,
Lu-metallofullerenes.

2-11
Dynamics of Li+ ions encapsulated in C60 fullerene at low temperature○Hal Suzuki1, Misaki Ishida2, Masatsugu Yamashita2, Chiko Otani2,
Kazuhiko Kawachi3, Yasuhiko Kasama3, Eunsang Kwon4
1 Graduate School of Science, Osaka University, Toyonaka, Japan
2 RIKEN, Center for Advanced Photonics, Sendai, Japan
3 Idea International Inc., Sendai, Japan
4 Graduate School of Science, Tohoku University, Sendai, Japan
Endohedral fullerenes show potentially useful properties such as a single molecular switch
or as a qubit in a quantum computer. These compounds are unique in that the encapsulated
atoms and C60 are not chemically bonded with each other, so that the atoms can move freely
in the cage. The dynamics of encapsulated atoms is, therefore, expected to show quantum
features at low temperature. In this work, we have investigated the dynamics of Li+ ionsencapsulated in C60 cage in [Li+@C60](PF6–) crystal by terahertz absorption spectroscopy (0.5
– 9.0 THz) between 10 K and 300 K.[1]The THz spectrum at 300 K shows two peaks; a broad peak at ~1.2 THz and a sharp one at
2.3 THz. The former one was assigned to the rotational band of Li+ ion in the carbon cage,
and the latter one was assigned to the lattice vibration of [Li+@C60](PF6–) crystal. The
features of the rotational band were successfully explained by a free rotation model of Li+ ion
with radius of ~1.5 Å. This interpretation is consistent with the preceding crystallographic
study, where the Li+ ion was found to delocalized on a spherical shell with radius of ~1.5 Å in
the C60 cage.[2] It is interesting that the dynamics of the Li+ ion was explained not by thelibrational and hopping model but by the free rotation model, indicating that the height of therotational potential barriers are comparable to the zero point energy of Li+ ions.
The spectrum dramatically changes at low temperature: As the temperature is loweredfrom 300 K to 120 K, the rotational band of Li+ ion shifts to lower frequency, and it starts
disappearing below 120 K. In addition, a new peak appears at 2.2 THz below 120 K. It is
indicated that Li+ ion does not rotate at low temperature, but librates with frequency at 2.2
THz.
Combining these results with the preceding
crystallographic results, which revealed that the
Li+ ion localizes into two positions below 100
K, we have proposed an energy scheme of therotational dynamics for the Li+ ions (Fig. 1). In
this scheme, a librational level lies beneath freerotational levels by 2.2 THz. The temperaturedependences of the spectral peak intensities at~1.2 THz and 2.2 THz were successfully Fig. 1 A schematic energy diagram proposed to
explain the spectral results.
explained by this model.
[1] H. Suzuki et al. Phys. Chem. Chem. Phys., 18, 31384 (2016).
[2] S. Aoyagi, et al. Angew. Chem., Int. Ed., 51, 3377 (2012).
Corresponding Author: H. Suzuki
Tel: +81-6-6850-5526, Fax: +81-6-6850-5526,
E-mail: h_suzuki@chem.sci.osaka-u.ac.jp- 28 -

2-12
Geometric and electronic structures of polymerized C40 fullerene○Mina Maruyama, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8577,
Japan
Moderate chemical reactivity of fullerenes arising from their hollow-cage structure allows
them atom-like constituent units of nanocarbon network materials by forming intermolecularcovalent bonds. For instance, C60 can form various polymeric forms, in which C60 isconnected to its neighboring molecules via [2+2] cycloaddition or other covalent bonding,resulting in their electronic structures from a metal to a semiconductor depending on the local
atomic structures. Small fullerenes are expected to inherently possess polymerized structures
because of their higher chemical reactivity than that of the conventional fullerenes larger thanC60. Among such small fullerene, C40 with Td symmetry and an acorn shape is an interesting
fullerene in its polymeric phase, because it contains four acepentalene (three pentagonal rings
sharing their edges) being expected to result in remarkable chemical reactivity and spinpolarization. In this work, we aim to investigate geometric and electronic structures of C40
polymers in which C40 is covalently connected in two-dimensional honeycomb network, using
the density functional theory with generalized gradient approximation.
Figure 1 shows optimized structures of C40 polymers with parallel and antiparallelintermolecular arrangements under the optimum lattice constant of 13.5 nm. In polymeric
structures, C40 is connected to its three adjacent molecules via cycloaddition covalent bonds.
Total energies of C40 polymers withparallel and antiparallel arrangements(a)(b)
are 0.596 and 0.597 eV/atom withrespect to that of graphene. Although
C40 polymers with antiparallel andparallelarrangementsaresemiconductors with direct band gap of
0.08 and 0.05 eV at M point,respectively, C40 polymers possess spinpolarization around the apex of acorn
owing to the narrow bandwidth andsmall band gap. Furthermore, C40
polymer sheet possesses dipole moment
normal to the polymeric layer owing totheir asymmetric molecular shape. Thus,
the network is an all carbon Figure 1: Optimized structures of C polymer with (a)40
two-dimensional material exhibiting
antiparallel and (b) parallel intermolecular arrangements.
both magnetic and electric polarities.

Corresponding Author: M. Maruyama
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: mmaruyama@comas.frsc.tsukuba.ac.jp- 29 -

2-13
Polyyne formation by laser induced breakdown
in hydrocarbon gas flow
Yuki Taguchi1, Hitomi Endo1, Takeshi Kodama1, Tomonari Wakabayashi2, Yohji Achiba1,○Haruo Shiromaru1, Benji Wales3, Joseph H. Sanderson3
1

Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan2
Department of Chemistry, Kindai University, Osaka, 577-8502, Japan3
Department of Physics and Astronomy, University of Waterloo, Canada

Nowadays polyynes have been easily synthesized by laser ablation of graphite in an
organic solvent, or its vapor, in which hydrogen termination of chain-form carbon clusters is
considered to be the main pathway [1-3]. At the 50th FNTG symposium, we reported thatpolyynes were efficiently produced also by laser-induced breakdown (LIB) in argon-diluted
propane gas flow, in which bottom-up formation process, namely chain growth fromcarbon-rich fragments, is most likely the main pathway [4]. In the present study we employedvarious hydrocarbon molecules as starting materials and found that the efficiency of thepolyyne-forming reactions are highly target-dependent [5].
Flowing gases of hydrocarbon molecules seeded in Ar were irradiated by tightly focused ns
and fs laser, and the products were captured in hexane solution. In the case of ns laser
irradiation, short polyynes up to C10H2 were produced efficiently
from all the hydrocarbons (propane, hexane, octane, benzene,
toluene). The yields vary significantly among the products fromdifferent target molecules, extending beyond the effects ofdifference in the vapor pressures. Among them, LIB in benzene
gives polyynes most efficiently. As shown in Fig.1, polyynes up
to C12H2 is clearly identified, while the longest polyyne
identified for other starting materials is C10H2. The visible
emission spectrum of the focused spot is shown in Fig. 2, whereemission of C2 fragment is observed, indicating deep
fragmentation takes place. In the case of fs laser irradiation ofhexane, polyynes were produced efficiently much more than the
ns-laser case, whereas for the toluene target, polyynes were not Fig.1 UV absorption spectra
produced. Such a variation in the polyyne yield suggests there of the solution prepared bywould be more suitable molecules for formation of polyynes, or ns-LIB in benzene, separatedby HPLC.
any other carbon-rich materials, by gas-phase laser irradiation
method.
H[1] M. Tsuji et al., Chem. Phys. Lett. 355, 101 (2002).
[2] Y. Taguchi et al, Carbon 94, 124 (2015).
[3] T. Wakabayashi et al., Carbon 50, 47 (2012).
[4] Y. Taguchi et al., 50th FNTG, 87 (2016).
[5] Y. Taguchi et al, Carbon, in press.
Corresponding Author: H. Shiromaru,
Tel: +81-46-677-1111, Fax: +81-42-677-2533,
E-mail: shiromaru-haruo@tmu.ac.jp

C2
C2
Ar

Fig.2 Emission spectrum of thens(1064 nm)-LIB in benzene.

- 30 -

2-14
Inner Core in the Elementary Particles of Detonation Nanodiamond○Toshihiko Tanaka1 , Masayoshi Fukaya1 , Amanda S. Barnard2 and Eiji Ōsawa3
1

Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, 30 Aza-nagao, Tairakamiarakawa, Iwaki, Fukushima, 970-8034, Japan
2
CSIRO Materials Science and Engineering, 343 Royal Parade,
Parkville, Victoria 3052, Australia
3
NanoCarbon Research Institute Ltd., Asama Research Extension Centre,
Faculty of Textile Science and Technology, Shinshu University 3-15-1 Tokita,Ueda, Nagano, 386-8567 Japan

Elementary particles of detonation nanodiamond (PPDND) could be the 4th novel
nanocarbon following fullerenes, nanotubes, and graphenes. PPDND is known to be strongly
polarized due to the core-shell structure [1]. Details of the internal structure have been
revealed by density functional theory (DFT) calculations, consisting of a shell of sp2 carbons
and doubly layered core of sp2+x and sp3 carbons [2]. However, its experimental confirmation
has been delayed due to technical difficulties in isolating analytical samples. Elaborate
attrition milling of the agglutinates of detonation nanodiamonds recently produced aqueous
solution of single-nano sized PPDNDs in high purity [1].
We report herein that the inner core of PPDND is a cubic diamond containing nearly 1000
sp3 carbon atoms based on laser desorption ionization mass spectra (LDI MS). Korepanov et.
al confirmed the size by 3D-phonon confinement analysis of Raman spectra [3]. The positive
ion mass peak of ~12k Da (~C1000) was first reported two years ago [4]. Little change of thepeak from a linear to a reflector mode shows the significant stability of the peak [Fig.1], thus
convincing us that it is the inner core of~C1000. We think that the peak isgenerated from the PPDND crystals thatcan be precipitated at drying only fromthe well-dispersed solution of PPDNDs.
We need a higher laser power togenerate the inner core peak from thecrystal, showing that it should besignificantly decomposed into an
emerged inner core, thermally andphotochemically.
Suchastablefragment furthermore should be the
cubic diamond ion that corresponds to
be one of the energy-minimized model
structures simulated by a DFT Fig.1 LDI MS of the detonation nanodiamonds deposited
calculation.
from the aqueous solution of dispersible PPDNDs.

[1] E. Osawa, D. Ho, H. Huang, M. V. Korobov,
N. N. Rozhkova; Diam. Rel. Mat. 18, 904 (2009).
[2] A. S. Barnard, E. Osawa; Nanoscale 6, 1188 (2014).
[3] V. I. Korepanov, H. Witek,H. Okajima, E. Osawa, and H. Hamaguchi; J. Chem. Phys. 140, 41107 (2014). 	
 [4] T. Tanaka, R. Yamanoi, E.Osawa; 48th FNTG, Abstract Book, No. 19 (2015).
Corresponding Author:Toshihiko Tanaka/Tel: +81-246-46-0810/E-mail: ttanaka@fukushima-nct.ac.jp- 31 -

3-1
Optical bistability in carbon nanotubes○T. Uda1,2, A. Ishii1,3, Y. K. Kato1,4
1

Nanoscale Quantum Photonics Laboratory, RIKEN, Saitama 351-0198, Japan
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
4
Quantum Optoelectronics Research Team, RIKEN center for Advanced Photonics, Saitama
351-0198, Japan
2

Optical bistability refers to situations with two stable optical outputs for the same optical
input, and it has been studied for applications involving all-optical switching and opticalmemories. Here we report on the observation of optical bistability in individual carbon
nanotubes (Fig. 1). Excitation power dependence of photoluminescence (PL) spectra takenwith various energy detunings reveals that the bistability occurs due to simultaneous shifts ofabsorption and emission resonances. We also demonstrate reversible and reproducible opticalswitching (Fig. 2), and perform time resolved measurements to obtain time scales of theoperation. Our results open up new pathways for utilizing carbon nanotubes as an
all-optical-switching medium at the nanoscale.

Fig.1 Excitation power dependenceof PL energy and linewidthFig. 2 All-optical switching of PL

Work supported by JSPS (KAKENHI JP26610080, JP16H05962), Canon Foundation, andMEXT (Photon Frontier Network Program, Nanotechnology Platform). T.U. is supported by
ALPS, and A.I. is supported by MERIT and JSPS Research Fellowship.
Corresponding Author: Yuichiro K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 32 -

3-2
Single photon generation through exciton-exciton annihilation in
air-suspended carbon nanotubes○Akihiro Ishii1,2, Takushi Uda1,3, Yuichiro K. Kato1,4
1

Nanoscale Quantum Photonics Laboratory, RIKEN, Saitama 351-0198, Japan
Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
4
Quantum Optoelectronics Research Team, RIKEN center for Advanced Photonics, Saitama
351-0198, Japan
2

Counts / hour

Carbon nanotubes have great potential for single photon sources as they have stable
exciton states even at room temperature and their emission wavelengths cover thetelecommunication bands. In recent years, single photon emission from carbon nanotubes has
been achieved by creating localized states of excitons. In contrast to such an approach, here
we utilize mobile excitons and show that single photons can be generated in air-suspended
carbon nanotubes, where exciton diffusion length is as long as several hundred nanometersand exciton-exciton annihilation is efficient [1]. We perform photoluminescence microscopy
on as-grown air-suspended carbon nanotubes in order
2.0
to determine their chirality and suspended length.
Room temperature
Photon correlation measurements are performed ong(2)(0) = 0.43
1.5
nanotube emission at room temperature using a
Hanbury-Brown-Twiss setup with InGaAs/InP single
1.0
photon detectors. We observe antibunching with aclear excitation power dependence, where we obtain
0.5g(2)(0) value less than 0.5 at low excitation powers(Fig. 1), indicating single photon generation. We
0.0-39 -26 -13
0
13
26
39
show such g(2)(0) data with different chiralities andTime delay (ns)suspended lengths, and the effects of exciton
Fig.1 Photon correlation of an individual
diffusion on single photon generation processes are (9,7) carbon nanotube measured at room
discussed.
temperature.
Work supported by KAKENHI (JP26610080, JP16H05962), The Canon Foundation, andMEXT (Photon Frontier Network Program, Nanotechnology Platform). A.I. is supported by
MERIT and JSPS Research Fellowship, and T.U. is supported by ALPS.
[1] A. Ishii, M. Yoshida, Y. K. Kato, Phys. Rev. B 91, 125427 (2015).
Corresponding Author: Yuichiro K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 33 -

3-3
Raman Spectroscopy of Individual Single-Walled Carbon Nanotubes○Juan Yang, Daqi Zhang, Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Single-walled carbon nanotubes (SWNTs) have been one of the most intensively studiedmaterials since the discovery in 1993 [1]. Among all the characterization methods of SWNTs,
Raman spectroscopy is widely recognized as a versatile tool that can achieve the mostinformation with the maximum simplicity. To explicitly explore the intrinsic structures andproperties of SWNTs, we study Raman spectra of individual SWNTs at the single-tube levelto minimize the ambiguities caused by the assortment of different tube species.
1. Single chirality enriched individual SWNTs on standard silicon substrates have beenrealized recently [2] and are a promising candidate for the next generation of electronic andphotoelectronic devices. We provide a convenient and nondestructive method based on
Raman spectroscopy to make (n,m) assignments and quantification for such samples. We
establish a relation of ωRBM = 235.9/dt + 5.5. We develop a counting-based quantification
method calibrated by the tube density and laser resonance window [3].
2. We observe multiple electronic Raman scattering (ERS) features in individual metallic
SWNTs (M-SWNTs) [4]. These features provide direct measurements on the excitonic
transition energies (Mii+ and Mii‒) using a commercialized Raman spectrometer with several
laser lines. Mii’s can be determined with an extremely small uncertainty of ±1 meV for asingle measurement, and of ±10 meV when environmental effects are taken into account. We
study the environmental effects including bundling, substrate, and laser heating on the Raman
features. We observe a constant Mii splitting value that is insensitive to environmental changes,
and thus use this value as a universal criteria for assignments in various environments [5].
3. We decorate gold nanoparticles (AuNPs) onto individual SWNTs to enhance the weak
Raman signals via the surface enhanced Raman scattering (SERS) effect. Enormous Raman
enhancements, up to 33000 times of the original Raman intensity, is achieved. Such enormous
enhancement are attributed to the polyhedral shape of the AuNPs and the narrow spacing
between the AuNPs, and more importantly, to the fact that SWNTs are located exactly at the“hot spots” produced by AuNPs.
RBM

G
ERS+

2D
ERS-

G+2D 2n+m=33(16,1)(15,3)(14,5)(13,7)(12,9)

1000

2000 3000 4000
-1
Raman
shift
(cm(cm
) -1)
Raman
shift

5000

Fig. 1 ERS spectra of the 2n+m=33 family.

Fig. 2

TEM image and Raman enhancement of SWNT-AuNPs.

[1] S. Iijima and T. Ichihashi, Nature 363, 603 (1993).
[2] F. Yang, X. Wang, D. Zhang, et al. Nature 510, 522 (2014).
[3] D. Zhang, J. Yang*, F. Yang, et al. Nanoscale 7, 10719 (2015).
[4] D. Zhang, J. Yang*, E. H. Hasdeo, et al. Phys. Rev. B 93, 245428 (2016).
[5] D. Zhang, J. Yang*, M. Li, et al. ACS Nano. 10, 10789 (2016)
Corresponding Author: J. Yang
Tel: +86-10-62755357
E-mail: yang_juan@pku.edu.cn- 34 -

3-4
Competitive elimination and decomposition reaction of oxidized
single-walled carbon nanotubes depending on the degree offunctionalization○Yutaka Maeda1, Erika Sone1, Akane Nishino1, Yuri Amagai1, Wei-Wei Wang2, Michio
Yamada1, Mitsuaki Suzuki1, Jun Matsui3, Masaya Mitsuishi4, Toshiya Okazaki5, Shigeru
Nagase21

Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan3
Department of Material and Biological Chemistry, Yamagata University, Yamagata
990-8560, Japan
4
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku
University, Sendai 980-8577, Japan
5
CNT-Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565, Japan
2

Epoxide is a useful functional group owing to its high reactivity. At this point, Barron et alreported reversible epoxidation of SWNTs.[1] Furthermore, chemical reactions of theepoxidized SWNTs with nucleophiles were also studied by Fusco et al.[2] In 2010, Weisman
et al. reported that photoreaction of SWNTs with ozone resulted in new, bright, and red
shifted photoluminescence (PL).[3] It is worthwhile to increase NIR PL efficiency for practicalapplications of SWNTs such as bioprobe, biosensor, and so on. It is important to control
functionalization degree of SWNTs because it is strongly influenced on their electronic andoptical properties including the efficiency of the newly generated NIR PL. Therefore, we
focus our attention on the control of functionalization degree of alkylated SWNTs and theirNIR PL efficiency by thermal elimination reaction.[4,5] In this context, we here present thethermal elimination and decomposition reaction of the oxidized SWNTs depending on theirfunctionalization degrees.[6]Oxidized SWNTs (SWNTs-O) were prepared by photoreaction of SWNTs in the presenceof disulfide and oxygen.[7] The fuctionalization degrees of SWNTs-O were controlled by thephoto irradiation time. Decrease of the characteristic absorption peaks and that of the RBM
and G bands with increase of the D bands upon photo-irradiation indicated the progress of the
sidewall oxidation. The characteristic peaks recovered by the thermal treatment under thenitrogen flow when the degree of functionalization was low. In contrast, the characteristic
peaks did not recover except for the D bands by the thermal treatment when the degree offunctionalization was high. Considering the results of XPS analysis, it is suggested thatelimination reaction proceeded predominantly when the degree of oxidation was low, but
decomposition reaction competed as the degree of oxidation increased. We also studied apossible pathway for the decomposition of oxidized SWNTs using density functional
calculations.

[1] D. Ogrin et al. J. Am. Chem. Soc. 128, 11322 (2006). [2] C. Annese et al. Eur. J. Org. Chem. 1666 (2014).
[3] S. Ghosh et al. Science 330, 1656 (2010). [4] Y. Maeda et al. J. Am. Chem. Soc. 134, 18101 (2012). [5] Y.
Maeda et al. Chem. Commun. 51, 13462 (2015). [6] Y. Maeda et al. Chem. Eur. J. 22, 15373 (2016). [7] Y.
Maeda et al. J. Am. Chem. Soc. 135, 6356 (2013).
Corresponding Author: Y. Maeda
Tel: +81-42-329-7512, Fax: +81-42-329-7512,
E-mail: ymaeda@u-gakugei.ac.jp- 35 -

3-5
Development of Nano-Resolution Desktop FE-SEM and X-ray microscopewith Multi-Walled Carbon Nanotube Electron Source○Masaru Irita1,2, Shintarou Yamazaki1, Shota Katsuyama1, Hitoshi Nakahara1, Koji Asaka1,
Yahachi Saito1, Hidekazu Murata3, Teruaki Ohno4
1

Department of Quantum Engineering, Nagoya Univ., Nagoya 464-8603, Japan
2
Venture Business Laboratory, Nagoya Univ., Nagoya 464-8603, Japan3
Department of Electric and Electronic Engineering, Meijo Univ., Nagoya 468-8502, Japan
4
Technex Lab Co., Tokyo 194-0044, Japan
Field emission (FE) from carbon nanotube (CNT) have been studied over 25 years [1].
Multi-walled CNT (MWNT) have exhibited high brightness 109 ~ 1010 A/(cm2¥sr) as anelectron source for FE - scanning electron microscope (SEM) [2]. Furthermore, the FE current
is stable even under a poor vacuum condition 10-6 ~ 10-7 Pa without ion pump [3]. In thescene of an archaeological site excavation, the mobile microscope is necessary to investigate.
In this work, we developed a desktop FE-SEM and X-ray microscope (XRM) with a single
isolated MWNT electron source, and its spacial-resolution was investigated.
MWNT electron source
and Butler electrostatic lens
were installed in a gunchamber with an ICF-114
flange, and the chamber was
evacuated with a turbo pumpdown to 10-7 Pa. The SEM
image was acquired using
focused beam current 61.1 pA
at Butler voltage Vbut = 1.5 kV
and accelerating voltage Vacc
~ 15 kV as shown in Fig. 1 (a).
The observed sample is Au-Pd
coated Polystyrene latex
sphere (PLS) with 200 or 500
nm in diameter. Fig. 1 (c)shows the line profile between Fig. 1 (a) SEM image of Au-Pd coated PLS. (b) XRM image of Au
substrate and PLS. The spatial mesh. (c), (d) Line profiles of the SEM (a) and XRM (b) images
resolution,
which
was obtained at lines indicated in respective images.
estimated from the width at 80-20% of a fitting profile across the SEM image, was 9 nm,
suggesting that the beam diameter was approximately 9 nm. A projection-type XRM based on
the CNT-FE-SEM also was constructed with an Au target for the X-ray source. The XRM
image was acquired by 30-min exposure at Vbut = 1.5 kV and Vacc ~ 17 kV as shown in Fig. 1(b). The observed sample is 400-mesh Au. Fig. 1 (d) shows the line profile between hole andbar. The spatial resolution was 200 nm. These results demonstrate nano-resolution desktop
microscope with the MWNT electron source.
[1] Y. Saito et al., Nature, 389, 554–555, (1997).
[2] H. Nakahara et al., Appl. Surf. Sci. 256, 1214–1217, (2009).
[3] H. Nakahara et al., e-J. Surf. Sci. Nanotech. 9, 400-403, (2011).
E-mail: masaru.irita@surf.nuqe.nagoya-u.ac.jp- 36 -

3-6
Cold exciton electroluminescence fromair-suspended carbon nanotube split-gate devices
Noriyuki Higashide1, ○Masahiro Yoshida2,3, Takushi Uda2,4, Akihiro Ishii1,2,
Yuichiro K. Kato2,3
1

Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
Nanoscale Quantum Photonics Laboratory, RIKEN, Saitama 351-0198, Japan
3
Quantum Optoelectronics Research Team, RIKEN center for Advanced Photonics, Saitama
351-0198, Japan
4
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
Electroluminescence from individual carbon nanotubes within split-gate devices areinvestigated. The devices are fabricated from silicon-on-insulator substrates [1], and the top
silicon layer is used as gates for electrostatic carrier doping [2]. By characterizing the
nanotubes with photoluminescence spectroscopy, chirality is identified andelectroluminescence peaks are assigned. We observe electroluminescence linewidthcomparable to photoluminescence, indicating negligible heating and state-mixing effects.
Split-gate and bias voltage dependences are consistent with emission from an electrostaticallyformed pn-junction.

[1] M. Jiang, Y. Kumamoto, A. Ishii, M. Yoshida, T. Shimada, Y.
K. Kato, Nature Commun. 6, 6335 (2015).
[2] S. Yasukochi, T. Murai, S. Moritsubo, T. Shimada, S.
Chiashi, S. Maruyama, Y. K. Kato, Phys. Rev. B 84, 121409(R)(2011).
Corresponding Author: Yuichiro K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 37 -

80 (a)
60
40
20
0

EL

600 (b)PL

Intensity (counts/s)

Worksupportedby
JSPS(KAKENHI
JP16H05962, JP26610080), MEXT (Photon Frontier
Network Program, Nanotechnology Platform), CanonFoundation, and Asahi Glass Foundation. A.I. is
supported by MERIT and JSPS Research Fellowship,
and T.U. is supported by ALPS.

400
200
0
1100

1200 1300 1400
Wavelength (nm)Fig. 1(a-b) EL and PL spectra, respectively.
An individual (10,5) nanotube is measuredin N2 atmosphere at room temperature.

3-7
The Solution to Stability and Cost in Perovskite Solar Cells by All-Carbon
Approach○ Il Jeon1, Namyoung Ahn2, Jungjin Yoon2, Esko I. Kauppinen3, Mansoo Choi1 Yutaka
Matsuo1,4, Shigeo Maruyama1,5
1
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan2
Department of Mechanical and Aerospace Engineering, Seoul National University, Seoul
08826, South Korea
3
Department of Applied Physics, Aalto University School of Science, FI-00076 Aalto, Finland
4
Hefei National Laboratory for Physical Sciences at Microscale, University of Science andTechnology of China, Anhui 230026, China
5
National Institute of Advanced Industrial Science and Technology,, Ibaraki 305-8564, Japan
Since Miyasaka and colleagues adopted perovskite semiconductors into photovoltaic
devices, and Park and colleagues realized solidified lead halide perovskite, perovskite solar
cells (PSCs) have received much attention on account of high power conversion efficiency(PCE) and other advantages of organic solar cells. Their reported PCEs have soared rapidly inthe last five years, and now some certified efficiencies exceed 20%. However, there remains
several shortcomings, prominently high-cost and stability that need to be addressed.
Here, we report PSCs in which the lead halide perovskite layer is sandwiched by C60
and single-walled carbon nanotubes (SWCNTs) as the solution to both stability and cost (Fig.
1). Such all-carbon approach enabled low-cost fabrication by removing metal electrodes. The
new device structure not only allowed room temperature process, but also long-term stability
by preventing vapor penetration and charge trapping. Air-processed PSCs with a configurationof ITO/C60/CH3NH3PbI3/SWCNT were tested in the stability and cost perspectives by adding
three mainstream hole-transporting materials (HTMs), namely, 2,2’,7,7’-tetrakis(N,N-di-pmethoxyphenylamino)-9,9’-spirobifluorene, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine],and poly(3-hexylthiophene-2,5-diyl) (P3HT) (Fig. 2).

Fig.1

Device Schematics

Fig.2 Stability data under constant one sun illumination inambience

Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 38 -

3-8
Fabrication and characterization of IrO2 / nano-carbon catalysts○Masanori Hara, Badam Rajashekar, Kanishka De Silva, Hsin-Hui Huang,
Masamichi Yoshimura
Toyota Technological Institute, Nagoya 468-8511, Japan
1. Introduction
In recent years, environmental issues, such as global warming and depletion of fossil fuels,
have become important topic for progress toward sustainable societies. In terms of energy
storage, conversion of renewable energies to hydrogen via water electrolysis has attracted
attention. However, in water electrolysis systems, activity, durability, and cost of catalysts are
insufficient for practical application due to high over-potential and low kinetics of electrodereactions, especially, oxygen evolution reaction (OER) on the anode [1-3]. In this study, we
have prepared novel nanoparticle catalysts of iridium oxide (IrO2), which is one of the mostactive catalysts for OER, supported on nano-carbon materials, graphene and carbon nanotube(CNT), with high stability and conductivity. Electrochemical properties of the IrO2-grapheneand IrO2-CNT catalysts were examined in sulfuric acid solution.
2. Experimental
The IrO2-graphene (or reduced graphene oxide, rGO) and IrO2-CNT catalysts weresynthesized by hydrothermal method. In brief, required amount of H2IrCl6 complex and GO
or oxidized CNT (CNT-COOH) were dispersed in ethanol/water mixture and the mixture washeated at 80 ˚C for 6 h and then heated at 150 ˚C in hydrothermal autoclave for 4 h. The
IrO2-rGO and IrO2-CNT catalysts were characterized by XRD, TEM, EDX, XPS andelectrochemical methods, LSV and RDE.
3. Results and discussion(a)(b)
Figs. 1 show TEM images of
the IrO2-rGO and IrO2-CNT
catalysts. The IrO2 nanoparticles
were dispersed on the substrates
surface and an average particle
size of IrO2 on both the substrates
10 nm
10 nm
was ca. 1.5 nm. Electrochemicalmeasurement of the IrO2-rGO and
Fig. 1 TEM images of (a) IrO2-rGO and (b) IrO2-CNT.
IrO2-CNT catalysts reveals highactivity of both the catalysts for OER; onset potential is ca. 1.43 V vs. RHE and mass activity
at 1.60 V is ca. 380 A g-1. In addition, both the catalysts showed very high durability for 1000
potential cycling between 1.2 – 1.65 V with 20% and 9% reduction in the current density,
respectively. The overvoltage of the IrO2 / nano-carbon catalysts is 70 mV lower than that ofconventional catalysts. The present results suggest that the IrO2 / nano-carbon catalysts withhigh activity and durability is promising anode for polymer electrolyte water electrolyzer.
[1] M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hydrogen Energy 38 (2013) 4901.
[2] E. Antolini, ACS Catal. 4 (2014), 4, 1426.
[3] J. Cheng, H. Zhang, H. Ma, H. Zhong, Y. Zou, Electrochim. Acta 55 (2010) 1855.
Corresponding Author: M. Hara
Tel: +81-52-809-1850, Fax: +81-52-809-1851,
E-mail: haram@toyota-ti.ac.jp- 39 -

3-9
Bottom-up approach for edge-functionalized graphene nanoribbons○Hideyuki Jippo1, Junichi Yamaguchi1, Shintaro Sato1, Hironobu Hayashi2, Hiroko Yamada2,
Mari Ohfuchi1
1Advanced System Research & Development Unit, Fujitsu Limited, 10-1
Morinosato-Wakamiya, Atsugi, Kanagawa 243-0197, Japan
2
Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST),
8916-5, Takayama-cho, Ikoma, Nara 630-0192, JapanTo realize graphene-based electronics, it is important to modulate the electronic propertiesof graphene nanoribbons (GNRs), which can be realized by, for instance, chemical
modification of the edges. A bottom-up synthesis [1] is one of the promising approaches for
obtaining edge-functionalized GNRs. In this study, we have attempted edge-fluorination of
GNRs using the bottom-up approach.
Figure 1 shows an expected reaction scheme from precursor molecules of HFH-DBTA to
HFH-7AGNRs. However, our scanning tunneling microscopy and X-ray photoelectron
spectroscopy measurements indicate that the GNRs fabricated on Au(111) surface have no
fluorinated edges and that the defluorination occurred during the cyclodehydrogenation
process from the polyanthrylenes to the GNRs.
We calculated activation energies using the nudged elastic band method based on density
functional theory to reveal the mechanism of the dissociation of the strong C-F bond. We havefound that the activation energy of the direct F desorption from the polyanthrylenes or the
GNRs to the metal surface is over 200 kJ/mol; however the activation energies areapproximately 80 kJ/mol and 40 kJ/mol for the reactions of I0→I1 and I1→I2 (Fig. 2),
respectively. The dissociation of the C-F bond can proceed along the reaction from I0 to I2 via
I1 states during the cyclodehydrogenation process.
These results suggest that it is important to design precursors considering the structuraltransformation during the reaction process for synthesizing edge-functionalized GNRs.

Fig. 1: Reaction scheme from precursorsof HFH-DBTA to HFH-7AGNR.

Fig. 2: Optimized geometries of the intermediate states of I0,
I1, and I2 along the C-F dissociation path.

This work was partly supported by JST, CREST.
[1] J. Cai et al., Nature 466, 470 (2010).
Corresponding Author: H. Jippo, Tel: +81-46-250-8843, E-mail: jippo.hideyuki@jp.fujitsu.com- 40 -

3-10
Low temperature growth of fully covered single layer graphene using CoCu
catalyst○Hisashi Sugime1,2, Lorenzo D’Arsié2, Robert S. Weatherup2, Santiago Esconjauregui2,
Guofang Zhong2, Xingyi Wu2, John Robertson2
1

Waseda Institute for Advanced Study, Waseda University, Tokyo 169-8050, Japan
Department of Engineering, University of Cambridge, Cambridge CB3 0FA, UK

2

Chemical vapour deposition (CVD) has emerged as the most scalable technique togrow large area graphene for industrial applications, and improving the growth method forhigh quality single layer graphene (SLG) is required. Lowering the growth temperature is a
key requirement especially when the graphene is grown directly on devices. Cu is the mostcommonly used catalyst to grow SLG [1], able to produce complete coverage SLG with theaverage grain size in the millimetre-scale [2]. Although its low carbon solubility plays animportant role for the growth of uniform SLG, the low catalytic activity makes it necessary touse high growth temperature, typically ~1000°C. On the other hand, Ni or Co are well known
catalysts for the low temperature growth of carbon nanotubes due to their high catalytic
activity [3]. They are supposed to be applied for the low temperature graphene growth,
however the higher carbon solubility of Ni or Co compared to Cu promotes multilayer
graphene growth [4].
Here we investigate the growth of SLG on bimetallic CoCu alloy catalyst films. The
growth outcome is found to vary significantly as the Cu concentration is changed. At 700 750°C, the addition of ~1 at% Cu to Co leads to uniform SLG growth and suppresses themultilayer formation, typically observed using pure Co. X-ray photoemission spectroscopy(XPS) shows Co and Cu form an alloy at high temperatures, which has a drastically lower
carbon solubility, as determined by the calculated Co-Cu-C ternary phase diagram. By Raman
characterisation, we observe CoCu-catalysed graphene presents high quality and spatial
uniformity across large catalyst surface. The fully covered single layer graphene shows holemobilities as high as ~1,100 cm2 V−1 s−1 in ambient conditions, suggesting bimetallic catalysts
may pave the way to produce graphene with tailored properties [5].
[1] X.S. Li, et al., Science 324, 1312
(2009).
[2] X.Y. Wu, et al., Sci. Rep. 6,21152 (2016).
[3] J. Robertson, et al., Jpn. J. Appl.
Phys. 51, 01AH01 (2012).
[4] Q. Yu, et al., Appl. Phys. Lett.
93, 113103 (2008).
[5] H. Sugime et al., in preparation.
Corresponding Author: H. Sugime
Tel: +81-3-5286-2769
E-mail: sugime@aoni.waseda.jp

Fig. 1: SEM and OM images of fully covered graphene grown on (a)CoCu (Cu: 6 nm on Co: 500 nm) and (b) Co (500 nm) catalyst. (c)Representative Raman spectra of the samples shown in (a) and (b). The
scale bars in OM images (a, b) are common for SEM images.

- 41 -

3-11
Fabrication of a thermally stable SERS substrate using bilayer graphene○Seiya Suzuki, Masamichi Yoshimura
Graduate School of Engineering, Toyota Technological Institute, Nagoya 468-8511, Japan

1181

612
773

(

)

Surface enhanced Raman scattering (SERS) technique is a novel method to highly sense
molecular and lattice vibrations. Although nanostructured silver (Ag) surface provides themost intense SER signals [1], Ag is not chemically stable compared to gold which is anotherrepresentative element for SERS. Graphene has very high chemical and thermal stability. We
previously demonstrated that a graphene coated Ag nanoparticles show SERS with tolerance
for strong acids (hydrogen chloride) [2]. Here, we report that bilayer graphene (BLG) canserve high thermal stability to nanostructured Ag surface for SERS.
A 10 nm thick Ag thin film was deposited on a quartz substrate by vacuum evaporation.
Graphene, which consists of mainly single layer and partially bilayer, was grown byatmospheric pressure chemical vapor deposition on a Cu foil [3], and was transferred onto theAg/quartz substrate with a polymethyl methacrylate (PMMA) supporting layer. The PMMA
was removed by immersing in an organic mixture (acetone, methyl isobutyl ketone, andisopropyl alcohol) and heating in air at 350 ºC. To examine thermal durability of the graphenecoated Ag on quartz (graphene/Ag/quartz), the sample was heated at 800 ºC in vacuum (<2Pa). Subsequently, rhodamine 6G (R6G) was loaded by dropping and drying of 20 µL solution(50 nM). Raman spectra were obtained using a 532 nm laser after each step of sample
preparation (removal of PMMA, heating at 800 ºC, and R6G deposition).
Figure 1(a) shows an optical microscope image of the (a)SLGgraphene/Ag/quartz after heating at 800 ºC in vacuum.
The hexagonal BLG domain showed bright contrast.
Enhancements of Raman peaks of graphene (D, G, and G’
20 µm
peaks) were only observed in the BLG domain but not in
BLG domain
single layer (SLG) region, and D peak was appeared in the(b)entire graphene after the heating. These indicate that thegraphene BLG region
Ag underneath BLG was remained, while the other Ag
Heat
Ag
was evaporated by the heating through defects in the top
Evaporation of Ag
layer (Fig. 1(b)).
Figure 1(c) shows Raman spectra from different sample. (c)G’
The BLG/Ag/quartz shows very large Raman peaks of .
ugraphene and the observed enhancement factor of G’ peak .
ais ~ 43. The R6G/BLG/Ag shows strong Raman peaks of yti
R6G (indicated by arrows in Fig. 1(c)) implying that the s
R6G/BLG/Ag/quartz
n
e
D G
n
BLG/Ag/quartz has SERS ability after high temperature tI
BLG/Ag/quartz
heating (800 ºC) in vacuum.
0
0
7
2
0
0
4
2
1
-

(

m
c

- 42 -ih[1] K. Kneipp et al., “Surface-Enhanced Raman Scattering”,
Springer (2006).
[2] S. Suzuki and M. Yoshimura, “Graphene coated silver
substrate for SERS with acid tolerance”, FNTG51 (2016).
[3] S. Suzuki et al., e-J. Surf. Sci. Nanotech. 13, 404 (2015).
Corresponding Author: Seiya Suzuki
Tel: +81-52-809-1852, E-mail: seiya09417@gmail.com

0
0
5
1
t
f

m

0s
0n
2
1
a

0a
0
9R

0
0
6

BLG/quartz)

Fig. 1. (a) Optical microscope
image of the graphene/Ag/quartz
after the heating. (b) Schematic
model of evaporation of Ag byheating. (c) Raman spectra of
BLG/quartz, BLG/Ag/quartz, andR6G/BLG/Ag/quartz.

ポスター発表
Poster Preview

1P – 1 ～ 1P – 42
2P – 1 ～ 2P – 43
3P – 1 ～ 3P – 42

1P-1
Photochemical Addtion of Siliranes to Sc3N@Ih-C80: Interconversion of
the [6,6]- and [5,6]-Adducts○Takeshi Sugiura1, Kyosuke Miyabe1, Masahiro Kako*,1, Masanori Yasui1,
Michio Yamada2, Yutaka Maeda2, Jingdong Guo3,
Shigeru Nagase3, Takeshi Akasaka2,4,5
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
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
4
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan
5
Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
Functionalization of endohedral metallofullerenes (EMFs) has been exploredextensively to broaden their range of potential applications in biochemistry,
nanomaterial science, and molecular electronics. Among the many functionalizing
reactions, 1,3-dipolar cycloaddition of azomethine ylides has been frequently employed
as a versatile method to afford the corresponding pyrrolidino derivatives [1]. For
example, the addition of azomethine ylides to Sc3N@Ih-C80 affords the corresponding[5,6]- and [6,6]-adducts. Several mechanistic studies indicated that the reactions ofazomethine ylides initially produce the [6,6]-adducts, which subsequently isomerize tothe thermodynamically stable [5,6]-adducts. As these reactions are generally conductedin heated or refluxed solutions, the substantial [6,6] to [5,6] isomerization of adducts
should occur during the addition of azomethine ylides. To the best of our knowledge,
the example of the isolation of [6,6]-pyrrolidino-Sc3N@Ih-C80 has been limited to thesynthesis using N-tritylazomethine ylide [2]. Meanwhile, we reported the preliminary
results of the photochemical carbosilylation of Sc3N@Ih-C80 [3]. We now report thedetails of the photoreaction of Sc3N@Ih-C80 with silirane 1, which afforded thecorresponding [5,6]-adducts 2, 3, and the [6,6]-adduct 4. Furthermore, theinterconversion of 2, 3, and 4 took place at 100 °C. The relative stabilities of theseadducts are consistent with the result obtained by the density functional theory
calculations.
Scheme 1.
Dep

Dep
+

Si
Dep

Sc3N@Ih-C80

h!

1

tBp

Dep

R1

R2

Dep
Dep

Si

tBp

Si

H

Dep =

tBp =
2: R1 = tBp, R2 = H

3: R1 = H, R2 = tBp

4

Partial structures of 2, 3, and 4 .

[1] M. Prato et al. J. Am. Chem. Soc. 115, 9798−9799 (1993).
[2] H. C. Dorn et al. J. Am. Chem. Soc. 128, 6486−6492 (2006).
[3] M. Kako et al. Phosphorus, Sulfur, and Silicon and the Related Elements. 191, 201–206 (2016).
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 43 -

1P-2
Conclusive Characterization of Li@C60 by X-ray Structure Analysis○Hiroshi Ueno1, Shinobu Aoyagi2, Naohiko Ikuma3, Hiroshi Okada4, Kei Ohkubo5,
Tatsuhisa Kato6, Shunichi Fukuzumi7,8, Yutaka Matsuo1,4,9, Ken Kokubo3
1

Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China
Department of Information and Basic Science, Nagoya City University, Mizuho-ku, Nagoya
467-8501, Japan
3
Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita,
Osaka 565-0871, Japan
4
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
5
Division of Innovative Research for Drug Design Institute of Academic Initiatives, Osaka
University, Suita, Osaka 565-0871, Japan
6
Department of Interdisciplinary Environment, Graduate School of Human and Environment
Studies, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
7
Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 120750, Korea
8
Faculty of Science and Engineering, Meijo University, and SENTAN, Japan Science andTechnology (JST), Nagoya, Aichi 468-0073, Japan
9
Hefei National Laboratory for Physical Sciences at Microscale, University of Science andTechnology of China, Hefei, Anhui 230026, China
2Endohedral metallofullerenes (EMFs) are one of the best studied materials for the past
30 years. Among all EMFs, C60-based EMFs are attracted special attention owing to its highly
symmetrical structure and expected unique electronic properties. Due to the difficulty of theirisolation and the lack of the structural evidences especially by the X-ray structure analysis,
however, the studies on metallo[60]fullerenes are much stagnant. Although previously wehave succeeded the isolation of Li@C60,[1] the X-ray structure analysis has been neverachieved yet.
The Li@C60 was synthesized by theelectrochemical reduction of cationic
Li+@C60.[2-4] The appropriate single crystal
for X-ray structure analysis was obtained by
the electrochemical reaction in the presenceof NiOEP. As shown in Fig. 1, dimerized
structure which could be formed by the
coupling of spin centers of Li@C60s were
determined. This is the first report of
Fig. 1. Crystal structure of Li@C60C60-based EMF characterized by X-ray
NiOEP co-crystal measured at 100 K.
structure analysis. The details will be
discussed on the presentation.
[1] H. Ueno et al., The 46th FNTG general symposium (2014) 3P-3.
[2] S. Aoyagi et al., Nature Chem. 2010, 2, 678.
[3] H. Ueno et al., Chem. Commun. 2013, 49, 7376.
[4] H. Ueno et al., Chem. Sci. 2016, 7, 5770.
Corresponding Author: H. Ueno and Y. Matsuo
Tel: +81-3-5841-0978, E-mail:ueno@photon.t.u-tokyo.ac.jp; matsuo@photon.t.u-tokyo.ac.jp- 44 -

1P-3
Diameter and defect density dependence of intermediate frequency Raman
mode of single-walled carbon nanotubes○Takumi Inaba1, Satoru Konabe2, and Yoshikazu Homma 1,2
Department of Physics, Tokyo University of Science, Kagurazaka 1-3, Shinjuku Tokyo
162-8601, Japan
2
Research Institute of Science and Technology, Tokyo University of Science, Niijuku 6-3-1,
Katsushika Tokyo125-8585, Japan
1

Raman spectroscopy provides fruitful information of lattice structures. For the Raman
spectroscopy of SWCNTs, not only graphene originated Raman modes but also nanotube
exclusive modes such as the radial breathing mode and G- mode can be observed. Besides
those peaks including the D mode that originates from finite momentum phonon, Raman
emission peaks exist in the range of intermediate frequency (IFM, 300-1000 cm-1), whichwere not fully analyzed with single molecule spectroscopy level. Here, the results of Raman
spectroscopy for singly suspended SWCNTs are shown in order to discuss Raman emission in
the IFM range.
In our experiments, individual SWCNTs suspended between micropillars were used.
After the synthesizing suspended SWCNTs, Photoluminescence (PL) excitation map was
acquired so that bundled effects were excluded. SWCNTs with relatively intense PL emission
showed detailed Raman emission in IFM range (Fig.1). The Raman emission peak energy inthe range of 1.50-1.55 eV showed chirality dependence indicating the signature of nanotube
exclusive phonon mode. Furthermore, the intensity of this Raman emission increased as anincrease in optical defect density.
Corresponding Author: T. Inaba
Tel: +81-3-5228-8244
E-mail: takumi.inaba.63@rs.tus.ac.jp

Figure 1. Photoluminescence (Left) and Raman (Right) simultaneous spectroscopy for a (11,3) nanotube
with relatively intense PL emission.

- 45 -

1P-4
Spectral tuning of optical coupling between air-mode nanobeam cavities
and individual carbon nanotubes○Hidenori Machiya1,2, Takushi Uda1,3, Akihiro Ishii1,2, Yuichiro K. Kato1,4
1

Nanoscale Quantum Photonics Laboratory, RIKEN, Saitama 351-0198, Japan
Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
4
Quantum Optoelectronics Research Team, RIKEN center for Advanced Photonics, Saitama
351-0198, Japan
2

Air-mode nanobeam cavities allow for high efficiency coupling to air-suspended
carbon nanotubes due to their unique mode profile that has large electric fields
in air [1]. Here we utilize heating-induced energy shift of carbon nanotube
emission [2] to investigate the cavity quantum electrodynamics effects. In
particular, we use laser-induced heating which causes a large blue-shift of thenanotube photoluminescence as the excitation power is increased. Combinedwith a slight red-shift of the cavity mode at high powers, detuning of nanotube
emission from the cavity can be controlled. We estimate the spontaneousemission coupling factor β at different spectral overlaps and find an increase of βfactor at small detunings, which is consistent with Purcell enhancement of
nanotube emission.
Work supported by JSPS (KAKENHI JP26610080, JP16K13613), Asahi GlassFoundation, Canon Foundation, and MEXT (Photon Frontier Network Program,
Nanotechnology Platform).
[1] R. Miura, S. Imamura, R. Ohta, A. Ishii, X. Liu, T. Shimada, S. Iwamoto, Y. Arakawa, and Y. K. Kato,
Nature Commun. 5, 5580 (2014).
[2] P. Finnie, Y. Homma, and J. Lefebvre, Phys. Rev. Lett. 94, 247401 (2005).
Corresponding Author: Yuichiro K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 46 -

1P-5
Tuning of Photo-thermoelectric effect of Metallic and Semiconducting
Single wall carbon nanotube thin films by electrolyte gating○Masatoshi Nakamura1, Yota Ichinose1, Hideki Kawai1, Yohei Yomogida1, Kazuhiro Yanagi1
1Department of Tokyo Metropolitan University, Tokyo 192-0397, Japan

Photo-thermoelectric (PTE) process is a process that can generate photo-voltage throughthermoelectric properties of materials. In this processes, increase of electron temperaturecaused by absorption of light can be converted to the electricity through thermoelectric
properties of materials. In the field of nano-carbon materials, because of their small heat
capacity, this process has often been observed, for example photo-voltage generations fromPTE effects have been reported in carbon nanotubes, graphene, transition-metal
di-chalcogenides and so on. Especially, in the case of carbon nanotubes, they can absorb THz
light energy because of the presence of their longitudinal surface plasmon modes, thus, PTE
process attracts a lot of interest for applications toward THz light detection devices. The PTE
processes strongly depend on the thermoelectric performance of SWCNTs, and previously wehave succeeded to tune the thermoelectric properties of SWCNT using electrolyte gating
techniques.[1] Here we tuned the PTE performance of SWCNTs using electrolyte gating
techniques. Figure 1 indicates the generated PTE
voltages of metallic and semiconducting SWCNTs
with diameter of 1.4 nm as a function of shift ofreference voltage (Vr). As show here, the PTE
voltages of metallic SWCNTs increased as theincrease of the amount of injected carriers in bothelectron and hole regions. It has been considered thatthe metallic SWCNTs are useless for PTE devices
because of their small Seebeck coefficient. However,
the observation indicates the PTE voltage can beenhanced by carrier injections. We found thathigh-carrier injections induced large Seebeckcoefficient and then large PTE voltages. The factsuggests the breaking of the thermoelectric trade-off,in which increase of conductivity induces decrease ofSeebeck coefficient.
References: [1] Yanagi et al, Nano Lett. 14, 6437-6442(2014), Oshima et al, APL 107, 043106 (2015)
Corresponding Author: K. Yanagi
Tel: +81-42-677-2493, E-mail: yanagi-kazuhiro@tmu.ac.jp- 47 -

Fig1.
Relationships
betweenphotovoltage and reference voltage
of Metal, Semi

1P-6
Photoluminescence Characteristic of Single-Wall Carbon Nanotubes:
Photon Reabsorption Effect○Xiaojun Wei1, Mayumi Tsuzuki1, Yohei Yomogida2, Guowei Wang1, Atsushi Hirano1,
Shunjiro Fujii1, Takeshi Tanaka1, and Hiromichi Kataura1
1

Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, Japan2
Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan

Semiconducting single-wall carbon nanotubes (SWCNTs) exhibit (n,m)-specificnear-infrared E11 photoluminescence (PL) via E22 excitation. By assigning this pair of E 11 andE22 wavelengths, we can identify individual (n,m) species contained in the examined samples.
In PL measurement, the PL intensity is also important to deduce the abundance of specific(n,m) species in the as-grown mixture or (n,m)-sorted sample. It is important to note that theexperimentally measured PL intensity does not correspond to the true intensity due to photon
reabsorption effect [1]. The detailed analysis of the PL characteristic induced by photon
reabsorption is very significant for quantitatively evaluating the abundance of specific (n,m)
species.
In this study, (n,m)-sorted semiconducting SWCNTs suspended in 0.5% sodium cholate(SC) solution were prepared by gel chromatography. To modulate photon reabsorption, the
SWCNT concentration of each (n,m) sample was gradually increased. We confirmed that theE11 absorbance increased linearly with increasing SWCNT concentration for all (n,m)
SWCNTs, while the PL intensity exhibited a nonlinear change. Figure 1 shows the results of
the PL intensity normalized by E22 absorbancefor near-armchair (7,6) and zigzag (10,0)
SWCNTs with the same 2n+m value, as afunction of each E11 absorbance (SWCNT
concentration). After magnifying the intensitiesof (10,0) samples 5 times, the trend of thenonlinear change of (10,0) samples is consistent
with that of (7,6). It suggests that (7,6) SWCNTs
is 5 times the PL efficiency of (10,0). For both
(7,6) and (10,0) SWCNTs, photon reabsorption
probability was gradually increased withincreasing SWCNT concentration, leading tothis nonlinear intensity change. We also
investigated the photon reabsorption induced PL
Figure 1. The plots of the PL intensity normalized
characteristics of other (n,m) species and foundby E22 absorbance for (7,6) (solid dots) and (10,0)that individual (n,m) SWCNTs have the same
(open dots) as a function of each E11 absorbance.
photon reabsorption characteristic, but their PL
All PL intensities of (10,0) were magnified 5
efficiencies are depending on (n,m) structures.
times for comparing that of (7,6).
This work was supported by KAKENHI No.
25220602.
[1] T. S. Ahn et al., Rev. Sci. Instrum. 78, 086105 (2007).
Corresponding Author: H. Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786, E-mail: h-kataura@aist.go.jp- 48 -

1P-7
Surface state of carbon nanopot –KFM study○Hiroyuki Yokoi1, Kozo Ikeda2, Kazuto Hatakeyama1, Michio Koinuma1
1Faculty of Advanced Science and Technology, Kumamoto University, Kumamoto 860-8555,
Japan
2
Faculty of Engineering, y, Kumamoto University, Kumamoto 860-8555, Japan

Carbon nanopot, a novel material developed recently[1], is a pot-shaped material
composed with multi-layered graphene sheets, and is produced in series to form fibers(nanopot fibers). The typical size of carbon nanopot is 20-40 in diameter and 100-200 nm inlength. Its narrow and deep mesopore is closed on one end, which suggests that this material
could be applied as nano-container.
It has been revealed through high-resolution TEM studies that carbon nanopot consists ofseveral parts including a multi-wall CNT like part and a tapered part where graphene edges
are exposed and distributed densely. Furthermore, an XPS study has suggested that thosegraphene edges may be terminated by hydroxyl groups. We expect that the surface states in
the MWCNT-like part and those in the tapered part could be different. In this study, we
employed a Kelvin force microscope (KFM) to investigate local surface states of carbon
nanopot. We have obtained a result that the surface potential varies by about 7 mV between
the ends of nanopot and the middle of the tapered part. We tentatively attribute this variationof the local potential to the difference of surface morphology, i.e. graphene wall-like surface
or surface with densely exposed and OH-terminated graphene edges.
[1] H. Yokoi et al. J. Mater. Res., 31, 117-126 (2016).
Corresponding Author: H. Yokoi
Tel: +81-96-342-3727, Fax: +81-96-342-3710,
E-mail: yokoihr@kumamoto-u.ac.jp- 49 -

1P-8
Anion effects on colloidal stability of surfactant-dispersed SWCNTs○Atsushi Hirano 1, Weilu Gao 2, Xiaowei He 2, Junichiro Kono 2,3,4
1

Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8562, Japan2
Department of Electrical and Computer Engineering, Rice University, Houston, Texas 77005,
USA
3
Department of Physics and Astronomy, Rice University, Houston, Texas 77005, USA
4
Department of Materials Science and NanoEngineering, Rice University, Houston, Texas
77005, USA
The colloidal stability of surfactant-dispersed single-wall carbon nanotubes (SWCNTs) isreflected in microscopic physicochemical processes, such as SWCNT association, partitioning
into a biphasic system, and adsorption propensities onto hydrogels. These processes can becontrolled by the addition of salts due to the alteration of the colloidal stability. Previous
studies clarified the effects of cations on the colloidal stability of the SWCNTs [1], whereas
the effects of anions remain unclear. Here, we show the anion effects on the SWCNTs
dispersed by sodium dodecyl sulfate (SDS) using sodium salts, such as NaCl and NaSCN.
We observed that Raman spectral intensity in the radial breathing mode of the SWCNTs
tended to decrease with increasing salt concentration (Fig.1), even at concentrations less than
25 mM, which is consistent with the reported results concerning SWCNT association [2,3].
Importantly, the effect was stronger with NaSCN than with NaCl, which means NaSCN more
readily causes the SWCNT association. We attribute this association to thermodynamic
destabilization of SDS assemblies on the SWCNTs by the salts (Fig.2) [4], which was further
confirmed through SWCNT separation experiments using a biphasic system and gel
chromatography. These findings provide a basis for understanding the colloidal behavior of
surfactant-dispersed SWCNTs and for developing the separation technology of SWCNTs.

Fig.1
Raman spectra of the SDS-dispersed
Fig.2 Schematic diagrams of the free energy of
SWCNTs excited at 785 nm in 25 mM salt
the SDS-dispersed SWCNTs in the salt solutions
solutions.
[1] S. Niyogi et al. J. Am. Chem. Soc. 131, 1144 (2009).
[2] M.S. Strano et al. J. Nanosci. Nanotechnol. 3, 81 (2003).
[3] D.A. Heller et al. J. Phys. Chem. B 108, 6905 (2004).
[4] S. Ikeda et al. J. Phys. Chem. 85, 106 (1981).
Corresponding Author: A. Hirano
Tel: +81-29-849-1064, Fax: +81-29-861-2786,
E-mail: hirano-a@aist.go.jp- 50 -

1P-9
Paper-based carbon nanotube field effect transistor by photolithography○Jong Mok Shin, Do Hyun Kim, InYeob Na, Ho-Kyun Jang, Jun Hee Choi, So Jeong Park,
Gyu-Tae Kim
School of Electrical Engineering, Korea University, Seoul 02841, South Korea
Paper electronic devices are emerging as a newresearch topic in accordance with the increasing needs
for eco-friendly materials.[1] Generally, the shadow
mask[2] or ink-jet printing[3] method is used topattern the metal contacts of the channel devices on apaper substrate, but it has a limit in reducing thepattern size. On the other hand, the photolithographymethod frequently used in the conventional substrates
can be utilized for realizing the design beyond thebounds of the shadow mask process. In this work, theFig.1 Conventional paper cup
carbon nanotube field effect transistor was fabricatedon the paper substrate through the photolithography process. To avoid wetting paper, thepaper cups designed to contain water were used as the base substrates without any additional
water-repellent treatment. However, it was difficult to deposit the liquid material including
photoresist by spin coating method since the paper was hydrophobic. Thus, the argon plasma
treatment was carried out on the paper to change thesubstrate from hydrophobic to hydrophilic. In thepresentation, the device characteristics of carbon
nanotube field effect-transistors on paper substrates
will be shown.
Beyond photolithography techniques, electron
beam lithography techniques can also be applied topaper substrates. This will enable the fabrication of
nano-sized electronic devices smaller thanFig.2 Paper based field effect transistor
micro-sized devices on paper substrates. With thesepatterned by photolithography.
methods, the device will could be freely
manufactured as it is processed on silicon substrates.
[1] D. Tobjork et al. Adv. Mater. 23, 1935 (2011)[2] Y. Li et al. Organic Electronics 13, 815 (2012)[3] X. Li et al. Collids and Surfaces B: Biointerfaces 76, 564 (2010)
Corresponding Author: Jong Mok Shin
Tel: +82-10-2951-4530, Fax: +82-2-953-3780,
E-mail: jmshin89@korea.ac.kr- 51 -

1P-10
Doping effect of electrolyte droplet on carbon nanotube thin film
○Tomohiro Yasunishi1, Shigeru Kishimoto1, and Yutaka Ohno1,2
1

2

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

Energy harvesting from environment energy sources is emerging technology for driving
sensor devices for IoT. Recently, the voltage generation of a few millivolts from the
movement of electrolyte solution have been demonstrated by using graphene [1, 2] andcarbon nanotubes (CNTs) [3]. Previously, we fabricated the generator using the single-walled
CNT thin film on flexible substrate and proposed the simple model of voltage generation
mechanism on the basis of their characteristics such as the dependences on concentration ofelectrolyte solution. In this work, we have investigated the doping effect of electrolyte
solution on the CNT film by using Raman scattering spectroscopy.
Highly-conductive CNT thin films were formed on a quartz substrate by the dry transfer
process based on the floating-catalyst chemical vapor deposition [4]. NaCl aqueous solutionof 0.01 mol/l was used as the electrolyte. The Pt electrode was used as the counter electrode toapply the potential difference between the CNT film and electrolyte droplet (Fig. 1(a)). We
measured Raman scattering spectroscopy through the quartz substrate at various potential
differences. The line mapping measurement was
carried out across the edge of electrolyte droplet.
When the counter electrode potential
increased from 0V to 0.9 V, the G-peak shifted tosmaller wave number in the region covered by
the electrolyte solution as shown in Fig. 1(b). It
is known that G-peak frequency depends on
carrier density in the CNT film [5]. Even when
the Pt electrode was electrically open, G-peakfrequency shifted as much as the case undervoltage of ~0.2 V. This result shows the contact
to the electrolyte solution has an doping effect on
the CNT film.
[1] P. Dhiman et. al., Nano Lett. 11, 3123, (2011).
[2] J. Yin et. al., Nat. Nanotechnol. 9, 378, (2014).
[3] S. Ghosh et. al., Science 299, 1042 (2003).
[4] A. Kaskela et. al., Nano Lett. 10, 4349 (2010).
[5] J. C. Tsang et. al., Nature Nanotechnol. 2, 725 (2007).
Corresponding Author: Y. Ohno
Phone & Fax: +81-52-789-5387,
E-mail: yohno@nagoya-u.jp

Fig. 1 (a) Schematic of measured device. (b)G-peak positon versus position at various
potential differences.

- 52 -

1P-11Development of CNT/Polyethylene Composites via Melt Blending○Atsushi Onodera 1, Sami Ristimäki 2, Masaru Sekido 3

1

Advanced Course of Production System Engineering ,National Institute of Technology, Sendai College, Natori 981-1239, Japan
2
Machine Automation, Metropolia University of Applied Sciences, Finland3
Department of Materials Science and Engineering, National Institute of Technology, Sendai
College, Natori 981-1239, Japan
Resin composites are used as structural materials in airplanes, helicopters and so on. Adding
CNTs to resin nanocomposites may increase various properties of resin composites, such as
high tensile strength, high thermal conduction, and high electric conduction. Previously wehave reported that tensile strength of MWNT/Nylon 6 (PA-6) prepared by simple
melt-blending was increased [1]. In this work we have prepared CNT/Polyethylene (PE) andfunctionalized-CNT (f-CNT) /PE composite and studied the effect on tensile strength.
f-CNTs were prepared by using 1,3-dipolar cycloaddition reaction. The mixture of SWNT
(0.5 g), sarcosine (1.5 g), and 3,4-dihydroxybenzaldehyde (1.5 g) in DMF were refluxed. After 3 days DMF was removed by rotary evaporator and remaining powder were washed bywater and acetone to obtain f-SWNT (2.0 g). CNT/PE composites were prepared by melt
blending at 220 °C for 10 minutes. Tensile strength of CNT/ PE composites were measured bytension tester (Dak System Inc., UTB9052-TT).
The result of tensile strength is shown in table 1. Tensile strength of SWNT/PE (entry 2 and7), f-SWNT/PE (entry 3 and 8), MWNT/PE (entry 4 and 9), and f-MWNT/PE (entry 5 and
10) were compared with HDPE (entry 1) and LDPE (entry 6) and did not show the improvement as expected. However, f-SWNT/LDPE composite showed a slight improvement of tensile strength.
Table 1. The result of tensile strength.

entry

CNT

PE

6
7

Non

SWNT

HD
HD

tensile strength(MPa)27.2659±1.2556
25.6690±1.3491

SWNT

LD
LD

tensile strength(MPa)
13.6884±2.0841
10.2684±0.3321

3

f-SWNTHD

25.4298±0.6568

8

f-SWNTLD

14.8636±0.8021

4

MWNT

HD

25.6728±1.4943

9

MWNT

LD

10.4611±0.3560

5f-MWNTHD

26.0849±1.1807

10f-MWNTLD

10.6018±0.1663

entry

CNT

PE

1
2

Non

[1] Yoshimi Muraoka et al. The 46th Fullerenes-Nanotubes-Graphene General Symposium, 3P-17(2014)

Corresponding Author: A. Onodera
Tel: +81-22-381-0329, Fax: +81-22-381-0329
E-mail: a1601008@sendai-nct.jp- 53 -

1P-12
Defluorination-Assisted Synthesis of Nitrogen-Doped Single-Walled
Carbon Nanotubes and Their Catalytic Activity of Oxygen Reduction
Reaction for Polymer Electrolyte Fuel Cells○Koji Yokoyama1, Shun Yokoyama1, Yoshinori Sato2, Masashi Yamamoto2, Tetsuo Nishida2,
Kenichi Motomiya1, Hiromichi Ohta3, Hideyuki Takahashi1, Kazuyuki Tohji1, Yoshinori
Sato1,4,*
1

Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan
Stella Chemifa Corporation, Osaka 595-0075, Japan
3
Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan
4
Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research,
Shinshu University, Matsumoto 390-8621, Japan
2

Nitrogen-doped single-walled carbon nanotubes (N-SWCNTs) are now focused on as
excellent catalysts for oxygen reduction reaction (ORR) which can alternate for platinum-based
catalysts[1]. In N-SWCNT catalysts, controlling structural factors such as nitrogen doping levels
and the chemical states of doped nitrogen atoms (e.g. pyridinic-, pyrrolic-, and graphitic-types)
is key to improving their ORR catalytic activities. However, in the existing methods forsynthesizing N-CNTs based on “direct doping”, it is hard to control the above structural factors.
Here, we report a new synthesis process for N-SWCNTs using defluorination-assisted “postdoping” approach[2]. Also, we evaluate the ORR catalytic activity of the prepared N-SWCNTs.
Highly crystalline SWCNTs (hc-SWCNTs) synthesized by an arc discharge method were
fluorinated using a gas mixture of F2 (20%) and N2 (80%) at
250 °C for 4 h. The fluorinated SWCNTs were reacted with agas mixture of NH3 (1%) and N2 (99%) at temperatures of 300600 °C for 30 min. The nitrogen doping levels and chemical
states of doped nitrogen atoms were characterized using X-ray
photoelectron spectroscopy (XPS). Linear sweep voltammetry
was performed to evaluate the ORR catalytic activity, using
the RDE technique in 0.5 M H2SO4.
From the results of XPS analysis, their levels of nitrogen
doping were estimated to be 1.38-3.04 at%, with enriched Fig. 1 Nitrogen contents andpyridinic- and pyrrolic-nitrogen species (Fig. 1). The onset composition of the N-SWCNTs.
potential value (Eonset) and number of electrons transferred per
oxygen molecule (n) in ORR of the N-SWCNTs were +0.51 V
and 3.31, while those of hc-SWCNTs were +0.16 V and 2.32,
respectively (Fig. 2)[3]. These results clearly show that our
defluorination-assisted post-nitrogen doping is more effective
for introducing nitrogen atoms at high concentrations, and the
prepared N-SWCNTs exhibit excellent ORR catalytic activity.
[1] D. Yu et al., J. Am. Chem. Soc. 2010, 132, 15127.
[2] K. Yokoyama et al., Carbon 2015, 94, 1052.
[3] K. Yokoyama et al., J. Mater. Chem. A 2016, 4, 9184.
Corresponding Author: Y. Sato
Tel & Fax: +81-22-795-3215, E-mail: yoshinori.sato.b5@tohoku.ac.jp*- 54 -

Fig. 2 Eonset and n of hc-SWCNTs,
N-SWCNTs, and Pt-C[3].

1P-13
Film fabrication of Semiconducting Single-Wall Carbon Nanotubes by
Aqueous-Two Phase System and Thin Film Transistor Applications○Haruka Omachi,1 Tomohiko Komuro,1 Jun Hirotani,2 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.
Reacently, a rapid and single-step aqueous two-phase (ATP) extraction [2] of highly enricheds-SWCNTs is demonstrated. The extraction with the combination of polyethylene glycol andpolysaccharide yielded >95% purity of s-SWCNTs from arc-discharge samples.
In this work, we report the s-SWCNTs thin films fabrication and thin film transistor (TFT)
applications. With high-purity s-SWCNTs currently separated, we succeeded to fabricate theuniform films (Figure 1). An extra addition of dispersants prevented a self-aggregation of
extracted s-SWCNTs. The performance of the fabricated devices was improved by the dry
etching process (Figure 2).
5 nm
10.00 nm

2.0µm

0 nm
Figure 1. AFM image ofextracted s-SWCNT film

Figure 2. TFT device performances
before and after the dry etching process[1] D. Park et al., Appl. Phys. Lett., 82, 2145 (2003)[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- 55 -

1P-14Growth 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 (18,7) 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. Acc. Chem. Res. 49, 606 (2016).
Corresponding Author: Yan Li
Tel: +86-10-6275-6773, Fax: +86-10-6275-6773,
E-mail: yanli@pku.edu.cn- 56 -

1P-15
Fluidized-bed synthesis of sub-millimeter-long carbon nanotubes at high yieldfrom concentrated ethylene source
Soichio Hachiya, Zhongming Chen, Kosuke Kawabata,
Kei Hasegawa, Toshio Osawa and Suguru Noda*
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Fluidized-bed chemical vapor deposition (FBCVD) has realized mass production of carbon
nanotubes (CNTs) [1] owing to the catalysts supported on powders which are filled in 3D in the reactor.
Such CNTs, however, are entangled with catalyst powders. We previously reported submillimeter-long
CNTs by FBCVD using 0.5-mm-sized alumina beads with flat surfaces, which enabled easy separationof CNTs (99 wt%) from the beads [2–4]. Highly reactive C2H2 was fed with H2O at low concentrations
and high flow rates. The process realized efficient conversion of C2H2 at a carbon yield of 70% andresidence time of ~0.3 s, however, wasted a larger amount of the carrier gas than the carbon source gas.
We here report FBCVD synthesis of CNTs using less reactive C2H4 and CO2 at higher concentration
instead of C2H2 and H2O vapor to reduce the production cost by using cheaper carbon source and lesscarrier gas. We used smaller alumina beads (0.3 mm) for support to reduce the gas flow rate and increase
the bead surface area so as to achieve high conversion of C2H4. Fe (1– 5 nm)/Al (15 nm)/Fe (0.6 nm)/Al(15 nm) catalysts are deposited on the beads by sputtering. The catalyst is annealed by flowing 10 vol%H2/N2 and then CNTs are synthesized by flowing 20 vol% C2H4/10 vol% H2/1 vol% CO2/N2 both byfluidized bed at 675–850 ºC. The nominally 1 nm-thick Fe catalyst yielded single-wall CNTs at 204
mg/910 mg and 6.3 at%/28 at% using 10 g/30 g beads in 1 batch of 10 min at 850 C (Fig. 1a,d).
Whereas the nominally 5 nm-thick Fe thickness were deactivated 850 ºC due to the tar formation. The
catalyst worked efficiently at lower temperatures for longer period, yielding multi-wall CNTs at 244
mg/1025 mg and 2.5 at%/11 at% using 10 g/50 g beads in one batch of 30 min at 725 C (Fig. 1a,b,c,e).

Fig. 1 Submillimeter-long CNTs by FBCVD. Yield vs (a) CVD temperature, (b) CVD time, and (c) beads amount.
TEM and SEM images of (d) SWCNTs by the 1-nm-Fe catalyst and (e) MWCNTs by the 5-nm-Fe catalyst.
[1] Q. Zhang, et al., ChemSusChem 4, 864 (2011). [2] D.Y. Kim, et al., Carbon 49, 1972 (2011).
[3] D.Y. Kim, et al., Carbon 50, 1538 (2012). [4] Z. Chen, et al., Carbon 80, 1972 (2014).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 57 -

1P-16Large-scale continuous separation of metallic / semiconducting carbon
nanotubes by electric-field-induced layer formation method○Fumiyuki Nihey1,*, Fusako Sasaki2, Yuki Kuwahara2,3, Takeshi Saito2,3, Hiroyuki Endoh1
1

2

IoT Devices Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
Technology Research Association for Single Wall Carbon Nanotubes, Tsukuba 305-8565
3
National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565

The electric-field-induced layer formation (ELF) method [1] is an electrophoretic method
for separating metallic and semiconducting carbon nanotubes (CNTs) without the use of
supporting media (such as gel). Electrophoresis is commonly conducted by batch processing;
introducing the dispersion, applying electric-field, and then collecting separated fractions. In
this case, the separation yield is limited by the separation-cell volume and the separation time
(typically 0.1 L and 24 hours, respectively, in or ELF). Therefore, in order to obtain higher
yield in the ELF separation, the enlargement of cell volume and the development ofcontinuous processing are required. In this presentation, we report a large-scale andcontinuous process for separating metallic and semiconducting CNTs by free-flow
electrophoresis based on the ELF method.
CNTs synthesized by eDIPS method [2] were dispersed in the aqueous solution ofpolyoxyethylene (100) stearyl ether (Brij S 100) for the free-flow electrophoresis experiments.
We have designed and fabricated a narrow rectangular 5-litter-volume container with theseveral pairs of anodes and cathodes as a separation cell for free-flow electrophoresis. Here,on a side of the cell, multiple inlets are located to inject CNT dispersion and carrier solution
during the application of electric-field. On the opposite side of the cell, multiple outlets arelocated to collect separated CNTs. By controlling the contents of CNT dispersion / carrier
solution and the injection speed, it has been confirmed that the metallic and semiconducting
CNTs has been successfully separated. The details will be discussed in the presentation.
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: +81-29-856-1168, E-mail: nihey@cd.jp.nec.com- 58 -

1P-17Development of gels for high-efficiency metal/ semiconductor
separation of SWCNTs
G. Wang, X. Wei, A. Hirano, T. Tanaka, and H. Kataura＊
Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, Japan
Gel

columnchromatographymethod

has

shown

a

substantial

potentialforscalable

metal/semiconductor (M/S) separation and further single-chirality separation of single-wall carbon
nanotubes (SWCNTs) [1]. However, the role of the gel is not well known. Towards higher separation
efficiency, more efforts should be made to clarify the role and to develop novel gels. Commerciallyavailable Sephacryl gel (GE Healthcare) has been often used for gel column chromatography. However,Sephacryl was not designed for SWCNT separation but was designed for size exclusion chromatography.
There could be room for development of better performance for SWCNT separation.
In this study, as the first step of gel development, we have synthesized dextran-based gels containing
different concentrations of allyl dextran as analogues of Sephacryl. Our research showed that more
semiconducting (s-) SWCNTs adsorbed in the gels as the ratio of allyl dextran increased, indicating theincrease of the adsorption site for s-SWCNTs. Surprisingly, our best gel adsorbed 15 times more s-HiPco
SWCNTs (diameter, 1.00.3 nm) than Sephacryl S-200 did. This means the new gel can separate 15 times
more s-SWCNTs without changing column size. This enhancement in the separation efficiency can
reduce the cost of industrial scale M/S separation of SWCNTs. Furthermore, all the synthesized gelsshowed chirality selectivity for the overloading of SWCNT, demonstrating a potential for the
single-chirality separation.
[1] H. Liu et al. Nat. Commun 2, 309 (2011).
Corresponding Author: H. Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786,
E-mail: h-kataura@aist.go.jp- 59 -

1P-18Purity Analysis and Purification of
Double-walled Carbon Nanotubes○Kenshi Miyaura, Hidekazu Nishino, Shirou Honda
Chemicals Research Laboratories, Toray Industries, Inc., Nagoya 455-8502, Japan
We have started development of the applied product for double-walled carbon natnotubes(DWCNTs) since 2001. The applied products of DWCNTs have been developed astransparent conductive film (TCF). The DWCNTs-TCF has very high conductivity, highstretching and durable bending. We are trying to apply for devices on which these features
can be utilized. The DWCNT-TCFs have been commercialized as upper electrode of e-paper.
The high electric conductivity DWCNTs have been synthesized by chemical vapor
deposition (CVD). DWCNTs have both merit of SWCNTs which have small diameter andhigh conductivity and MWCNTs which have high durability and productivity. In particular,
DWCNTs can be purified in severe condition than SWCNTs. We have synthesized DWCNTs
and studied many reaction parameters. Finally, we have succeeded development of high purity
DWCNTs. The features of our DWCNTs are very small diameter (<2 nm), high DWCNT
ratio (>90%) and high crystallinity (Raman G/D ratio is more than 80). In this presentation,
we report the purity analysis techniques required when DWCNTs are purified.
This work is partially supported by the New Energy and Industrial Technology
Development Organization (NEDO).
Corresponding Author: H. Nishino
Tel: +81-52-613-5276, Fax: +81-52-613-5283
E-mail: Hidekazu_Nishino@nts.toray.co.jp- 60 -

1P-19An experimental and theoretical study on the scanning tunnelingspectroscopy of europium nanowires encapsulated in carbon nanotubes○Terunobu Nakanishi1, Ryo Kitaura1, Takazumi Kawai2, Susumu Okada3, Shoji Yoshida4,
Osamu Takeuchi4, Hidemi Shigekawa4, and Hisanori Shinohara1
1

Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya,464-8602, Japan
2
Smart Energy Research Laboratories, NEC Corporation, Tsukuba, 305-8501, Japan
3
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, 305-8571,
Japan
4
Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, 305-8573, JapanPDOS / (states/eV)

Metal nanowires, whose diameter is typically one to several atoms, are one of the mostideal one-dimensional nanosystems, the preparation and characterization of these have beendifficult because of their high reactivity towards air. Previously, we have found that ultrathin
europium (Eu) nanowires can be synthesized in the interior space of carbon nanotubes(CNTs).[1-2] Here, the spatially-resolved electronic structure of a CNT encapsulating the Eu
nanowire (EuNW@CNT) investigated with scanning tunneling spectroscopy (STS) revealthat an electronic state, which is absent in thecorresponding pristine CNT, appears just below the (a)first van-Hove singularity of the CNT. To identify
the origin of this electronic state, we have calculated
the electronic states of EuNW@CNTs by density
functional theory using the generalized gradientapproximation + U method.
Figure 1(a) presents a geometrically optimized
structure of EuNW@CNT which is shown
schematically along the tube axis. As shown in theCEufigure, two rows of Eu atoms align at the middle of (b)the interior space of the CNT. Atom- and0.6
Eu sspin-resolved density of states (DOS) shown in Fig.
Eu d
C p
0.3
1(b) clearly demonstrate that a peak arising from
Eu-6s state exists at the gap region of CNT. The
0.0
C-2p state also has a finite DOS at the energy where
the Eu-6s state exists. This suggests that the Eu-0.3
encapsulation can generate an additional peak in the-0.6
STS spectra, which is consistent with the current
-1.5
-1.0
-0.5
0.0
observation.
Energy / eV
[1] R.Kitaura et al. Angew.Chem.Int.Ed. 48, 8298, (2009).
[2] R.Nakanisihi et al. Phys. Rev. B 86, 115445, (2012).
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- 61 -

Fig. 1(a) Structure model of EuNW@CNTs.
(b)Partial DOS. +y axis shows spin up statesand –y spin down states.

1P-20DFT calculations of electronic states and solid state NMR parameters
in Cesium Iodide encapsulated single-walled carbon nanotubes○Eita Yokokura 1, Yosuke Kataoka 1 and Hironori Ogata1,2
12Graduate 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 alkali halide encapsulated SWNTs have been reported[1-4]. In our previous studies, the systematic studies of tube diameter dependence, chirality
dependence and temperature dependence on the local structures and electronic properties ofalkali halides encapsulated in SWNTs were systematically investigated [5].
In this study, we calculated solid 133Cs- or 127I-NMR parameters (NMR chemical sifttensors and electric field gradient (EFG) tensors). All of the calculations were done by using aOpen-Source computer code package PWscf and GIPAW in Quantum ESPRESSO. We used
the pseudo potential methods.
Table 1. shows the chiral vector dependence of 133Cs-NMR chemical shift tensors in
CsI@SWNT. Figure 1 also shows the predicted 133Cs-NMR spectrum in CsI@(10, 10)SWNT
Detailed results including another will be presented.
Table 1 .NMR chemical sift and Electric field gradient (EFG) tensor in CsI@SWNT

Materials

δiso ⊿δanis=3/2(δ33-δiso)
(ppm)
(ppm)

bulkCsI0
CsI@(6, 6)SWNT 187.68
CsI@(8, 8)SWNT 50.41
CsI@(9, 9)SWNT +90±5
CsI@(10, 10)SWNT 9.12

0786.75591.75119±5236.75

Fig.1133Cs -NMR spectrum of CsI@(10,10)SWNT.

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] ChiYung Yam, ChiChiu Ma, XiuJun Wang and GuanHua Chen . Appl. Phys. Lett. 85, 4484 (2004)[4] Ryosuke Senga, Hannu-Pekka Komsa, Zheng Liu, Kaori Hirose-Takai, Arkady V. Krasheninnikov
and Kazu Suenaga, Nature Materials,13(2014)1050.
[5] Abstract of the 50rd Fullerenes-Nanotubes-Graphene General Symposium 2P25.
Corresponding Author: H. Ogata Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail:hogata@hosei.ac.jp- 62 -

1P-21
Study of Au-Ni catalytic CVD of uniform multilayer graphene○Yuki Ueda1, Jumpei Yamada1, Daichi Yamamoto1, Kyosuke Fujiwara1
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
Chemical vapor deposition (CVD) is conventionally used to grow a high-quality,
single-layer graphene using a cupper foil. However, a multilayer graphene is difficult to growby the method because the growth is terminated by the covering of the catalyst by the grownlayer. Though Ni is sometimes used as a catalyst to grow multilayer graphene, the uniformityof the grown layers is very bad. In this study, Au-Ni catalysis is used to grow high-quality
multilayer graphene, whose alloy was reported to be useful to grow uniform few-layer
graphene at very low temperature of 450oC [1].
Au and Ni layers were deposited on a c-plane sapphire substrate. The ally composition of
the catalyst can be controlled by the thickness ratio of these layers. Ethanol was supplied to
the low-pressured CVD chamber as a source material with bubbled by H2 carrier gas. The
growth temperature and alloy compositions were systematically changed to optimize thegrowth conditions so as to obtain both uniform and high-quality multilayer graphene.
Figure 1 shows a surface optical microscope image of the sample grown on Au-Ni catalyst
at 1150 oC. It shows a very uniform growth was performed though the grain boundaries of thecatalyst is recognized in the figure. The Raman signal in Fig.2a shows the high-quality of thelayer, and the transmittance spectra in Fig.2b demonstrates its thickness of about 9monolayers. The addition of Au in the catalyst is thought to functionally decrease both thecarbon solubility and the interaction between the catalyst and the grown layer [2], which helps
the uniform growth of high-quality multilayer graphene.

(a)Fig.1 Surface image of sample
grown using Au-Ni catalyst.

(b)

Fig.2 Raman signal (a) and its transmittance spectra (b) of multilayer
graphene after transferred on sapphire substrate.

Acknowledgment: This work was supported in parts by JSPS KAKENHI Grant Numbers 2660089, 15H03558, 26105002,
25000011.
[1] R. S. Weatherup, B. C. Bayer, R. Blume, C. Ducati, C. Baehtz, R. Schlogl, and S. Hofmann, NANO Lett., 11 (2011) 4154.
[2] M. H. Kang, S. C. Jung, and J. W. Park, Physic. Rev., 82 (2010) 085409.
Corresponding author: Y. Ueda Tel: +81-52-838-2387,

E-mail: 153434003@ccalumni.meijo-u.ac.jp- 63 -

1P-22
Thermodynamically Controlled Synthesis of Graphene from Carbon
Monoxide○Yukuya Nagai1, Kei Hasegawa1, Suguru Noda1,*
1

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan

Chemical vapor deposition (CVD) has become the mainstream for the synthesis ofgraphene in which copper (Cu) having low carbon solubility is widely used as catalyst [1].
High temperatures closed to the melting point of Cu (1085 C) are often applied to achieve
better crystallinity and larger grains, and to prevent multilayer formation, CH4 is widely used
due to its less reactive nature.
Here we notice that carbon monoxide (CO) can also be a less reactive carbon source, which
has been used for the synthesis of carbon nanotubes (CNTs) [2]. CO yields C through thedisproportionation reaction (2CO⇌C+CO2). This reaction is thermodynamically favored at
low temperatures, oppositely to the decomposition of CH4 (Fig. 1). Thus CO needs be highlypressurized to mass-produce CNTs in the HiPco process [2]. However, low-pressure CO may
be enough for the synthesis of graphene of 1–2 atomic layers on Cu.
We conduct H2-free ambient-pressure CVD for the synthesis of graphene from CO on Cu
foils. We change partial pressure of CO (0.09 and 10 vol%), CVD temperature (600–1000 ºC),
and CVD time (30 and 60 min). We analyze obtained graphene on Cu foils by scanningelectron microscope (SEM) and Raman scattering spectroscope. As Fig. 2 shows, single-layer
graphene (SLG) and bilayer graphene (BLG) with tens-micrometer grains are obtained at 800ºC. Graphene formation is thermodynamically favored but kinetically suppressed at low
temperatures, resulting in graphene at high coverage and small grain size. Graphene formation
process will be discussed in terms of both thermodynamics and kinetics.
(b)

CH4→C+2H2

Intensity / -ΔrGo / kJ mol-1 K-1

100

0

-100

-200
0

Fig. 1. Gibbs free energy ofreaction: C from CH4 vs CO.

D

G

SLG

BLG

2CO→C+CO2
500
1000
Tempearture / K

2D

1000

1500

2000
3000
Raman shift / cm-1

Fig. 2. Graphene formed from CO on Cu (10 vol%, 800 C, 60 min).
(a) SEM, (b) Raman.

[1] X. Li, et al., Science 324, 1312 (2009).
[2] P. Nikolaev et al., Chem. Phys. Lett. 313, 91 (1999).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 64 -

1P-23Fabrication and Electric Properties of Fe and Ca intercalated Bilayer Graphenes○N. Kuragane, R. Hoshino, R. Sakurai, T. Yamagishi, T. Ngata, N. Iwata, H. 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 metalintercalated bilayer graphene, in which the electron-exciton coupling is expected to generatehigh temperature superconductivity [1]. In this study, we fabricated metal intercalated
bilayer graphene with different metal and different concentration. The electric properties ofiron- and calcium-intercalated bilayer graphenes are discussed.
The single-layered graphene sheet was synthesized on Cu foil by chemical vapor
deposition (CVD) method. Graphene/Cu foil was dipped in Fe(NO)3 and CaCl2 solution toetch the Cu foil and leave the Fe and Ca atoms on the graphene. Metal intercalated bilayer
graphene was fabricated by transferring another graphene on the etched graphene/SiO2/Si.
Fig. 1 shows the temperature dependence of a sheet resistance of the bilayer graphene
detected by traditional four wire resistance measurement. Bilayer graphene of Fig.1(a) was
fabricated using 0.06mol/L of Fe(NO)3 solution. Sheet resistance of Fig.1(a) at room
temperature is 30 kΩ/sq. The bilayer graphene showed semiconducting property. Bilayer
graphene of Fig.1(b) was fabricated by 0.12mol/L of Fe(NO)3 solution. Sheet resistance of
Fig.1(b) at room temperature was 1300 Ω/sq. The bilayer graphene showed metallic
property by increasing the amount of intercalated metal.
(b)

5x109

Sheet resistance [sq.]

Sheet resistance [sq.]

(a)

4x109
3x109
2x109
1x109
0

0

50

100 150 200 250
Temperature [  ]

300

1500

1000

500

0

0

50

100

150

200

Temprature [  ]Fig. 1 Temperature dependence of the sheet resistance of the bilayer graphene Bilayer graphene

250

300

The electrical properties of the Ca intercalation of metal intercalated bilayer graphene will
be discussed.
References :[1] Jun Akimitsu, Parity. MARUZEN. 05, 6-12 (2008).
[2] Yan-Feng, Appl. Phys. Lett. 102, 231906(2013).
Corresponding Author: N. Kuragane
Tel: : +81-47-469-5457 , E-mail: csna13035@g.nihon-u.ac.jp- 65 -

1P-24
Functional group dependence of Spin magnetism of Graphene oxide○Kentaro Tajima1, Takuya Isaka1, Tomoki Yamashina1, Yoshiaki Matsuo2, Kazuyuki Takai1,3
1Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584 Japan
2
Graduate School of Engineering, University of Hyogo, Hyogo 671-2201 Japan3
Department of Chemical Science and Technology, Hosei University, Tokyo 184-8584 Japan
Graphene oxide (GO) has different hydration / solvation properties according to thesynthesis method [1]. However, there is little research on chemical structure and electronic
properties of GO synthesized by different methods. In this study, we evaluated GOs
synthesized by Brodie [2] (BGO) method and Hummers [3] (HGO) method in terms ofchemical structure and spin magnetism.
FT-IR spectra were recorded by the FT/IR6600 (JASCO co.). XPS spectra were obtainedusing ESCA5600. The magnetic susceptibility was measured using a squid magnetometer(Quantum Design, MPMS-XL).
The FT-IR spectra of GO and graphite were shown in Fig. 1, where peaks for hydroxyl,carboxyl, epoxy and carbonyl groups [4] appear for GO in spite of absence of any peak forgraphite. Interestingly, the peak around 1224 cm-1 attributed to C-OH stretching for HGO islarger than that for BGO, while the peak around 1050 cm-1 for C-O-C stretching is larger for
BGO. Hydroxyl and epoxy groups are more likely to be introduced by Hummers and Brodie
method, respectively. This is also supported by the C1s region of XPS spectra for BGO which
exhibits the larger component for epoxy groups at 286.6 eV than that for HGO, being
consistent with the FTIR results. The magnetic susceptibility shows an order of magnitudelarger localized spin concentration of HGO (Ns = 2×1019) than that of BGO (Ns = 2×1018)(Fig. 2). The difference in functional groups between HGO and BGO explains the larger spin
magnetism for HGO. In the case of introduction of epoxy group, oxygen atom bonds toadjacent carbon atoms, remaining symmetry of A, B sub-lattice of graphene lattice. On theother hand, attaching hydroxyl group occurs randomly on carbon atoms of graphene andbreaks symmetry of A, B-sublattice, resulting in the emergence of the localized states and thespin magnetism.

Fig.2 Temperature dependence of themagnetic susceptibility for HGO and BGO

Fig.1 FT-IR spectrum of HGO and BGO[1] A. V. Talyzin et al, Nanoscale, 6, 272, (2014) [2] T. Nakajima, Y. Matsuo, Carbon, 32, 469-475 (1994) [3] D.
C. Marcano et al, ACS Nano, 4, 8, 4806–4814 (2010) [4] J. Guerrero-Contreras, F. Caballero-Briones, Mater.
Chem. Phys., 153, 209 (2015).
Corresponding Author: K. Takai (takai@hosei.ac.jp)- 66 -

1P-25Highly efficient, mechanically durable perovskite solar cells with graphene
electrodes
Jungjin Yoon1,2, Namyoung Ahn1,2, and Mansoo Choi1,21Department of Mechanical Engineering, Seoul National University, Seoul 08826, Republicof Korea
2
Global Frontier Center for Multiscale Energy Systems, Seoul National University, Seoul
08826, Republic of Korea

Organic-inorganic hybrid perovskites have unique properties such as high absorption
coefficient, tunable bandgap, and ambipolar charge transport. Since Miyasaka's groupreported their use as a photoactive material of solar cells in 2009 [1], the perovskite solar cells(PSCs) have been intensively researched by many research groups and their power conversion
efficiency (PCE) reached even over 20% [2]. Usually, metal oxides such as TiO2 and Al2O3
have been adopted to general device architecture of PSCs, which require high processtemperature over 450 ∘C and are not compatible with the low-cost manufacturing. As analternative to the metal oxides, organic materials were exploited in PSCs, which enable lowtemperature and solution processes leading to low-cost production.
Taking advantages of these features, the PSCs have been demonstrated on flexible
substrates, where indium tin oxide (ITO) on plastic substrates has been mostly used [3].
However, it was found that ITO generated cracks and induced fracture under bending
condition due to its mechanical brittleness. Furthermore, the limited supplement of indium
accelerates the development of alternative transparent electrodes. Considering theirapplications as flexible and portable devices, the transparent electrode material should coverfollowing conditions: high optical transparency, mechanical robustness against bending,electrical conductibility, abundance of raw material, and lightweight. In this regard, graphenemust be a promising candidate as an alternative transparent electrode in PSCs.
Here, we demonstrated highly efficient and mechanically durable perovskite solar cellswith graphene electrodes. A few nanometers doping of MoO3 layer on graphene lowered sheet
resistance and work function of graphene. Besides, the MoO3 layer made the graphene surfacehydrophilic so that the reproducibility of device performance could be guaranteed.
Furthermore, to verify the mechanical robustness of graphene electrode, we fabricated the
PSCs with same architecture on plastic substrate and carried out bending cycle test. Under abending radius of 4 mm, PCEs of ITO-based flexible PSCs were shown to < 30% of theirinitial values, which was attributed to cracks generated on the ITO surface. Whereas, thegraphene-based PSCs maintained their PCEs by 85% even after 5000 bending cycles.
Additionally, the graphene device maintained a PCE of
85% of its initial after 5000 cycles under bending radiusof 2 mm.
[1] A. Kojima et al. J. Am. Chem. Soc., 131, 6050-6051 (2009).
[2] W. S. Yang et al. Science, 348, 1234-1237 (2015).
[3] B. J. Kim et al. Energy Environ. Sci., 8, 916 (2015).
Corresponding Author: Jungjin Yoon
Tel: +82-2-887-8626, Fax: +82-2-887-8762
E-mail: jyoon27@snu.ac.kr- 67 -

Figure 1. Schematic of perovskite solar
cell with graphene electrode1P-26
Reduction reaction of a single graphene oxide sheet in solution
as probed by twilight fluorescence microscopy○Hikaru Sato1, Masahito Sano 2
1

Department of Polymer Science and Engineering, Yamagata University, 992-8510, Japan2
Department of Organic Materials Science, Yamagata University, 992-8510, Japan

Graphene oxide (GO) is used widely in various applications because of excellent
dispersibility, large surface areas, high catalytic activities, and photoluminescence properties.
For electrical and mechanical applications, it is preferable to reduce GO so that graphene-like
properties can be recovered. Presently, the reduction efficiency stays about 80% at best. Oneof the reasons for incomplete reduction is that the reaction is conducted using a mixture of
GO sheets with various sizes, layers and degrees of oxidation. A small piece has a larger
contribution from reactive edges. A layer that is hidden inside a multilayer sheet has lesschance of collisions with reactant molecules. It is difficult to improve and optimize thereaction when the only available sample is a mixture of GO sheets with various parameters.
Recently, we have developed Twilight Fluorescence (TwiF) Microscopy that is capable ofimaging each GO sheet dispersed in solution. A GO solution is mixed with a highly
concentrated fluorescent dye. A small fluorescence change caused by GO-dye interactions
gives enough contrast to image individual sheet floating in solution. Using TwiF microscopy,
it may become possible to evaluate a reaction process at a single sheet level. In this study, we
have examined whether a reaction can be followed as a change of image contrasts in real time.
The first requirement is to find a reducing agent
that has no significant effect on dye yet reduces
GO efficiently. A screening test using various
compounds indicated that L-ascorbic acid satisfies
the condition using rhodamine as a dye. NMP waschosen as a solvent, since we had observed
previously that GO gives a bright image whereas
an independently prepared reduced GO appears
dark. NMP also dispersed reduced GO well. An
extent of reaction was followed by quantifying thecontrasts of several GO sheets with varying sizes
appearing within a single imaging window.

D 

E 

F 

G 

Fig.1. TwiF images of a GO sheet in thereacting solution, (a) 0, (b) 300, (c) 600, and(d) 2700 sec after initiation.

Corresponding Author: M. Sano
Tel: +81-238-26-3072,
E-mail: mass@yz.yamagata-u.ac.jp- 68 -

1P-27
Production and characterization of graphene quantum dots derived from
SWNTs and graphite.
○H. Morita and T. sugai
Department of Chemistry, Toho University, Miyama 2-2-1, Funabashi 274-8510, Japan

Graphene quantum dots (GQD) are nanometer-size graphene fragments derived from various
carbonaceous materials. They are promising materials because of their unique fluorescent
properties which should be independent of excitation like fluorescent molecules for theapplications such as biomarkers. However, the emission wavelength of GQD depends on
excitation wavelength.[1] Here we present production of GQD with molecule-likefluorescence by chemical oxidation from various carbon materials.
GQD was prepared from CoMoCAT-SWNTs (Sigma-Aldrich) and graphite powder (nacalaitesque) by oxidation in a mixture of concentrated H2SO4 and HNO3. The solution was mildly
treated by a bath sonicator for tens of hours. The oxidized mixture was diluted with deionizedwater followed by centrifugation at 10000 rpm for 30 min to separate GQD. Collectedsupernatant containing GQD was neutralized with NaOH and re-crystallized to eliminate
by-produced salt. The produced GQD was characterized by TEM, absorption, andfluorescence observation.
Fig.1 shows emission spectra of the GQD
prepared from (a)SWNTs and (b)graphite. GQD
from SWNTs shows the emissions at 410 and
520 nm independent of the excitation
wavelength. Those molecular like emission may
come from the mild preparation conditions
utilized here compared to the conventional
reflux in concentrated H2SO4 and HNO3 athigh-temperature.[2] On the other hand, GQD
from graphite shows emissions similar to thosederived from graphite reported previously[3]but much weaker than those derived from
SWNTs. Those salient differences should comefrom the differences in the production processes.

Fig.1 Emission spectra of GQD derived from(a)SWNTs and (b)graphite.

[1] D. Pan, J. Zhang, Z. Li, M. Wu, Adv. Mater., 22, 734-738 (2010)[2] R. Sekiya, Y. Uemura, H. Naito, K. Naka, & T. Haino, Chem. Eur. J., 22, 1-10 (2016).
[3] L. Lu, Y Zhu, C. Shi, Y. T. Pei, Carbon 109, 373-383 (2016).
Corresponding Author: T. Sugai. Tel: 047-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 69 -

1P-28Energetics and electronic structure of 𝐁𝐁𝟑𝟑 𝐍𝐍𝟑𝟑 -doped graphene○Hisaki Sawahata, Mina Maruyama, and Susumu Okada

Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba
305-8571, Japan
Electronic structures of porous sp2 carbon networks strongly depend on their network
topology and an arrangement of the pores, making them a semiconductor or metal. In addition
to pores, interfaces with other two-dimensional materials also modulate the electronic structureof graphene depending on the interface shape and constituents. These facts open a question
whether the energetics and electronic structure of porous graphene is further tunable by filling
pores with nanoflakes of other two-dimensional materials. Among various two-dimensional
materials, BN is an appropriate counterpart of the fillers. Thus, in this work, we aim toinvestigate the energetics and electronic structure of
BN-doped graphene in which B3N3 (borazine unit) is
triangularly embedded, using the density functional
theory with the generalized gradient approximation.
Figure 1 shows the total energy of B3N3-doped
graphene as a function of the spacing between adjacent
B3N3. The total energy is found to be inversely
proportional the B3N3 spacing. Furthermore, the energy
also depends on the network topology of the graphene
domain. The heterosheet with full-benzenoid graphene
domain is more stable than the other sheets. Network
Fig. 1, Total energy of BNC
topology of the graphene domain also affects theheterosheets as a function of theelectronic structures of B3N3-doped graphene. Figure 2
lattice parameter.
shows the band gap energy of the heterosheet as afunction of the spacing between B3N3, indicating that the
all sheets are semiconductors with finite energy gap
irrespective to the arrangements of B3N3 in graphene.
The gap also monotonically decreases with increasing
the B3N3 spacing. The heterosheet with full-benzenoid
graphene domain has a direct gap at theΓpoint, while
the other heterosheets have direct gap at K point.
Calculated band gap in full-benzenoid sheets is narrower
than that in non-benzenoid sheets with the almost thesame B3N3 spacing.
Corresponding author: H. Sawahata
TEL: +81-29-853-5921, FAX: +81-29-853-5924
E-mail: hsawahata@comas.frsc.tsukuba.ac.jp- 70 -

Fig. 2, Band gap of BNC
heterosheets as a function of thelattice parameter.

1P-29Charge transfer dynamics at graphene/SiC interface
studied by time-resolved soft X-ray photoemission spectroscopy○T. Someya1, H. Fukidome 2, S. Yamamoto 1, N. Endo 2, I. Matsuda 1
1

2

Institute for Solid State Physics, The University of Tokyo, Kashiwa 277-8581, Japan
Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577, Japan

Graphene, a two-dimensional carbon crystal with a gas of massless Dirac fermions, haspromise as a material that is useful in photonic and electronic devices. For these applications,
epitaxial growth of graphene by thermal decomposition of a silicon carbide (SiC) is one of thesuited fabrication methods as it can directly produce graphene sheet on a semiconducting
substrate. However it has been known that graphene/SiC interface have negative effects onelectrical properties of graphene, such as carrier mobility, and therefore unrevealing thecharge transfer at the interface is essential for the device applications.
In this study, we observed surface photovoltage (SPV) effect at the graphene/SiC interface
by using time-resolved X-ray photoemission spectroscopy and succeeded in uncovering therole of interface state to the charge transfer dynamics at the interface.
Figure 1 shows the relaxation dynamics of the SPV observed as the transient shifts of theC1s core level spectra. For comparison, we prepared two types of graphene samples whichhave different interface
properties; graphene on SiC(0001) Si-terminated surface and_graphene on SiC(0001) C-terminated surface. On the C-terminated face, carriers survived
until 100 ns while on the Si-terminated face, carrier relaxed within 10 ns. These relaxation
processes are successfully understood by phenomenological thermionic emission model of the
Schottky diode.
In the poster session, we will discuss the origin of the carrier lifetime on different
graphene/SiC interfaces.
Figure 1. (a, b)
Time-resolved C1s corelevel spectra of grapheneon SiC(0001)
and_
SiC(0001).
(c, d) Relaxation of
surface photovoltage on
C-face and Si-facegraphene, respectively.
Probe light : 740 eV
Pump light : 3.0 eV(350 µJ/cm2)
Temperature : 300 K.

Corresponding Author: I. Matsuda

Tel: +81-4-7136-3402, Fax: +81-4-7136-3402,
E-mail: imatsuda@issp.u-tokyo.ac.jp- 71 -

1P-30
Simplified estimation of crystallographic orientation of strained grapheneby micro-Raman spectroscopy○Kazushi Nakamura1, Hikari Tomori1,2, Akinobu Kanda112Division of Physics and TIMS, University of Tsukuba, Tsukuba 305-8571, Japan
PRESTO, Japan Science and Technology Agency, Kawaguchi 332-0012, Japan

Strain engineering is a promising but unexplored method of modulating electron transport
in graphene. Graphene has a peculiar property that lattice strain produces a vector potential
exerted only on conduction electrons[1]. The resulting spatially varying pseudo magnetic field
can be used, for example, to induce a transport gap in graphene.[2] Here, it is noted that themagnitude of the pseudo magnetic field strongly depends on the crystallographic orientationof strain. Thus, for the further understanding of the strain related phenomena, determinationof the crystallographic orientation of strain is indispensable.
So far, the crystallographic orientation of strain has been estimated by using the polarized
Raman spectroscopy.[3] Under uniaxial strain, the Raman G band splits into two subbands(G+ and G-), which have different polarization dependence. The polarization dependence of
the G+ (G-) amplitude together with the orientation of the polarizer gives the crystallographic
orientation of strain. However, when a commercial micro-Raman spectroscopy system is used,
it is not easy to accurately determine the orientation of the polarizer inserted in the system, theerror of which is directly connected to the error of the strain orientation. Here, we propose a
simple method by which one can determine the strain orientation regardless of the accuracy ofthe polarizer orientation.
Our method of estimating the strain orientation is based on a recent theory telling that byuniaxial strain the Raman 2D band splits into three subbands with different polarization
dependence[4]. From the comparison of the polarization dependence of G and 2D bands, one
can derive the strain orientation and the polarizer
orientation simultaneously. An example is shown in
Fig. 1. Here, we induced uniaxial strain in exfoliatedgraphene by placing parallel resist bars between
graphene and the substrate. Due to small strain,
neither G nor 2D band splits, but the peak frequencyof each band exhibits periodic modulation as afunction of the rotation angle of the sample, r, fromwhich we estimated the strain orientation withrespect to the zigzag direction to be 50.3 degree. The
details will be explained in the presentation.
[1] H. Suzuura and T. Ando, Phys. Rev. B 65, 235412 (2002).
[2] V.M. Pereira and A.H.C. Neto, Phys. Rev. Lett. 103,
046801 (2009).
[3] M. Huang et al., Proc. Natl. Acad. Sci. 106, 7304 (2009).
[4] V.N. Popov and P. Lambin, Carbon 54, 86 (2013).
Corresponding Author: A. Kanda
Tel: +81-29-853-5081, Fax: +81-29-853-4345,
E-mail: kanda@lt.px.tsukuba.ac.jp

Fig. 1: Peak positions of (a) G and (b) 2D
bands as a function of the the rotation
angle of the sample.

- 72 -

1P-31
Mechanical properties of graphene nanoribbons
Kazufumi Yoneyama, Ayaka Yamanaka, and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba
305-8571, Japan
Grapehene exhibits remarkable mechanical strength of which Young’s modulus is up toTPa, allowing it a promising material for designing novel mechanical andelectromechanical devices. For the practical application of graphene in these devices, it
is mandatory to precisely control their size and geometry. Nanoscale graphene flakes
and ribbons are attracting much attention because of their potential application for thenanoscale mechanical devices. Experimental and theoretical works have elucidated
electronic structure and energetics of graphene nanoribbons. However, a little is known
for microscopic mechanical aspects of graphene nanoribbons. Thus, in this work, we
aim to elucidate mechanical properties of graphene nanoribbons in terms of their edge
atomic arrangements, using the density functional theory with the generalized gradientapproximation and pseudopotential procedure.
Figure 1 shows the geometric structure ofgraphene nanoribbon with hydrogenated edges
studied here. In this work, we focus on thegraphene nanoribbons, of which edge angles are
0 (armchair), 16, and 30 (zigzag) degrees, toelucidate whether the edge shape affects the Fig. 1, Geometric structures ofmechanical properties of these graphene graphene nanoribbons with edge
angles of 0, 16, and 30 degree.
nanoribbons. Calculated Young’s modulus is124, 114, and 131 GPa for the ribbons with armchair (0 deg.), chiral (16 deg.), andzigzag (30 deg.) shapes, respectively, indicating that the mechanical properties are
sensitive to their edge shapes. We apply the uniaxial tensile strain on these ribbons to
elucidate an initial process of the mechanical fracture in these ribbons. In the ribbon
with the edge angle of 16 degree, the fracture is started at the boundary between zigzag
and armchair edges, where the charge density on the chemical bond is slightly lower
than the other edges.
Corresponding Author: K. Yoneyama
TEL/FAX: +81-29-853-5921/+81-29-853-5924
E-mail: kyoneyama@comas.frsc.tsukuba.ac.jp- 73 -

1P-32Introduction of spin-orbit interaction into graphene by various methods
T. Nanba, T. Tamura, Y. Katagiri, C. Ohata, Pierre Seneor1, J. Haruyama
Faculty of Sciences and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
1
CRNS/Thales
Introduction of spin-orbit interaction into graphene is highly important and interesting fortwo-dimensional topological insulator with small mass and voltage-controlled spintronic
devices. Nevertheless, experimental reports are few, although there are many theories.
Basically, the following two different methods exist for it; (1) Rashba-type SOI introduced bydestructing out-of-plane symmetry by attaching extremely small amount of hydrogen (H) or
fuluoro atoms to graphene surface and (2) Proximity SOI realized by large-mass particles(e.g., Au, Ag, Cu) placed on graphene. Previously, we carried out (1) following [1] andreported possibility that internal magnetic field unique to graphene SOI tends to suppressdephasing of electro spin waves in weak interaction[2,3]. However, precise control of H atom
amount and its estimation was difficult. Here, we demonstrate (2) in the present poster.
Graphene has been fabricated on SiO2/Si substrate following mechanical exfoliation
method of HOPG by scotch tape. In order to effectively detect SOI, spin Hall Effect (SHE),
and its distance dependence, Hall pattern shown in Fig.1 has been designed. Au and Ag
particles are placed on this pattern SHE has been investigated as non-local resistance (RNL)
peaks for back-gate voltage (Vbg) change. Figure 2 shows the result. Indeed, large RNL peaks
are observed for them. Because they cannot be observed in graphene without metal particles
and also Larmor spin precession has been detected for the RNL peaks, they are attributed to
SOI and SHE. More details are presented in poster.

RNL ()200

100

Au T=1.5K
B=0

Fig.1: Graphene Hall pattern forAg

Fig. 2: Non-local resistance observed

detection of SOI and AHE

in Fig.1-pattern with Au and Ag
particles

F
図１
20m
Fig. 10-30

0Vbg (V)30

Fig. 2[1] J. Balakrishnan, et al., Nature Commun. DOI: 10.1038 /ncomm5748 (2014).
[2] T. Kato, T. Nakamura, S. Katsumoto, J. Haruyama et al.,J. Royal Society of Chemistry Advances 6, 67586 (2016).
[3] T. Nakamura, J. Haruyama, S. Katsumoto, J. Phys. Soc. Japan 85, 105002 (2016)
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 74 -

1P-33
Influences of Graphene Structure on Electrochemical Interactionsin LiBF4 Organic Electrolyte Solution○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

Phenomena at the interface between carbon electrode and electrolyte are crucial for the
performance of energy storage devices; such as ion storage, degradation mechanism, and Solid
Electrolyte Interphase (SEI) formation. However these are still unclear in the case of actual
carbon electrode materials due to its complex structure. In this study, the influence of thestructure of graphene as a model material for carbon electrodes was investigated in terms ofelectrochemical interaction at the interface between graphene and organic electrolyte.
Electrochemical potential dependence of conductivity was measured for mechanicallyexfoliated graphene and epitaxial graphene (EG), where the graphene channel and Pt wire in
the electrolyte (1 M LiBF4 in EC: DMC (1:1 v/v %)) were applied as working and counterelectrodes, respectively. Raman spectra and XPS were measured by LabRAM HR and
ESCA5600, respectively.
Increment of electrochemical current below – 2 V becomes suppressed after cycles ofelectrochemical gate sweeping (Fig.1), attributed to SEI formation by the reaction between
graphene and EC/DMC [1] [2]. In the case of EG, the intensity ratio of Raman G’ to G bands
increases after cycles of sweeping. This indicates an increment of the number of layers ofgraphene by Li intercalation between buffer layer of graphene and SiC substrate. This is
supported by XPS, where the larger take-off angle is, the larger intensity of Li spectrum is(Fig.2). In addition, both peaks for graphene and SiC shifted to the higher energy side after
applying electrochemical potential, indicating an oxidation reaction at the interface between
graphene and SiC substrate. The presence of the substrate significantly affects phenomena at
the interface between electlyte and graphene.
Cycle5

-5
-10
-15
-20

Cycle1

-25
-30

-3

-2

15°

Intensity (arb. units)

Conductivity σ (mS)

0

-1

0

45°

75°

70

65

60

55

50

Binding Energy (eV)VGraphene - Topgate (V)Fig.2 Li 1s spectra of EG after electrochemical
cycles with various take-off angle

Fig.1 Gate voltage dependence of Conductivity
in FET with LiBF4 organic electrolyte solution[1] Elad Pollak et al, Nano.lett. 10, 3386 (2010)[2] Jingshu Hui et al, ACS.Nano. 10, 4248 (2016)
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002, E-mail: takai@hosei.ac.jp- 75 -

1P-34
Detection of photo current arising from atom-thin MoS2 Schottky junction
fabricated by electron beam irradiation
Y. Katagiri, C. Ohata, Y. Inoue1, S.Maruyama1, T. Nakamura2, S. Katumoto2, A. Ishi3,
M. Hasegawa3, G. Fioli4, S. Roche5, J. Haruyama
Depts. Electrical Eng. and Electro. 3Chemi. and Bio., Aoyama Gakuin University, 5-10-1
Fuchinobe, Sagamihara, Kanagawa252-5258, Japan
1Department of Mechanical Eng., The University of Tokyo, Tokyo 113-8656, Japan
2Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa,
Chiba 277-8581, Japan
4University of Pisa, 5Barcelona Institute of Sci. and Tech
Research of post-graphene atom-thin two-dimensional layers are highly active and its
advancement as van der Waals engineering is significant. Among them, molybdenum
disulfide (MoS2) is attracting considerable attention as atom-thin semiconductor with directenergy band gap [1]. Our group reported creation of atom-thin MoS2 lateral Schottky junction
with barrier height of 0.18 eV, fabricated only by irradiating electron beam (EB) and causing
4 2
semiconductor(2H)/metal(1T)transition. We revealed weak Fermi-level pinning as uniqueproperty of this atom-thin Schottky
1 junction [2]. Here, we report on photo current properties
arising from this junction.
3
Few-layer MoS2 has been fabricated on SiO2/Si substrate following mechanical exfoliation
method of bulk material using scotch tape. EB has been irradiated to this MoS 2 with dose in
160Me for 1.5m2 at room temperature. Two electrode-pairs, in which one locates on
d 1T-metal region (i.e., EB irradiated region) while the other on 2H, have been fabricated bothsides of this junction with different distance from the junction. Figure 1 shows PL property ofElectron Beam
Irradiated Region
the MoS2 including 1T metal region as a basic feature. Laser beam has been irradiated withD of 488 nm under applied no bias voltage in inset. The number (#1-5) noted onwave lengtheach spectrum corresponds to position of PL mapping shown in inset. Two PL peaks unique to
direct exciton transition in 2H semiconductor phase are observed at position #1-3, while nopeak is detected at position #4, which corresponds to 1T metal region. These suggest presenceof expected 2H/1T regions. In contrast, clear 2H/1Tinterface cannot be observed in the inset
with 0.25 m space resolution. This may be due to carbon contamination existing around thejunction, because of the large EB dose. Figure 2 shows photo current (Isd) as a function ofphoto intensity observed in forward and reverse voltage bias (Vsd) regions in the Schottoky
junction. Large increase in Isd in reverse voltage region suggests concentration of high electricfieldEnergy
on the Schottky
junction. These promise high-efficient photo sensor using this structure.
Binding
(eV)

a b

d

5

216
J2

4

J3
328

250

-1

300

shift (cm )

G
f

3

Vsd=4

2

Vsd=2.5

Vsd=-51350

0shift (cm ) -1

図１
Fig.1 Wavelength (nm)[1] M. Acerce, M.
Chhowalla et al., Nature
Nanotechnology 10, 313(2015).
[2] Y. Katagiri, T.
Nakamura, S. Katsumoto,
S. Roche, J. Haruyama etal., Nano Lett.. 16, 3788
(2016).

Vbg=0

 ISD  (A)m

Vsd=-2.5

0

1

2

3

4

5

Fig.2 Photo intensity (mW)Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 76 -

1P-35
Mechanism of contact-resistance improvement in suspended device ofbi-layer WSe2 by mild oxygen plasma treatment○Reito Nagai, Toshiro Kaneko, Toshiaki Kato
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Mono or few-layer transition metal dichalcogenide (TMD) is known as an atomically-thin
two-dimensional (2D) material with excellent optical and electrical properties. For the
fabrication of high performance optoelectrical devices, it is required to reduce the contact
resistance between TMD and metals used for electrodes. Suppressing the impurity scatteringfrom the substrate is also another critical issue for their high performance applications. The
suspended-device structure of 2D materials is one of the ideal structures, which can reduce
impurity scattering from the substrate obtaining better optoelectrical-device performance suchas ballistic carrier transport and bright photoluminessence (PL) of graphene and carbon
nanotubes. However, the contact between TMD and electrodes in the suspended device isusually very poor due to the van der Waals gap caused by atomically-flat TMD surface.
Therefore, developing the post process, which can reduce the contact resistance ofsuspended-TMD device with maintaining the original high optical properties becomes as animportant issue for realizing high performance optoelectrical device with TMD.
Here, we developed a simple method to obtain the low contact resistance of suspended
TMD device. The short time (a few tens of seconds) mild oxygen plasma treatment [1,2] can
improve the contact resistance of bi-layer WSe2 field effect transistor (FET), resulting in highon current density of 2.8 µA and relatively low ～106 Ωµm contact resistance with suspended
configuration, which is about 105 times higher and 107 times lower than that of before plasma
treatment, respectively. The bright PL can be obtained even after the mild-plasma treatment.
Through the systematic investigations, we found that mild O2 plasma treatment can
introduce local defects such as vacancies of W atom or partial oxidation (WOx) in bi-layer
WSe2. These local defects may introduce the formation of covalent bonds between WSe2 andmetal electrode, suppressing the original van der Waals gap.
We also measured photoresponse of suspended bi-layer WSe2. Our plasma-treated device
showed the relatively fast response time of ～20 ms and high photoresponsivity of ～12000
A/W at a wavelength of 400 nm, indicating the mild plasma treatment is very useful for the
fabrication of TMD-based high performance optoelectrical devices.
[1] T. Kato, L. Jiao, X. Wang, H. Wang, X. Li, L. Zhang, R. Hatakeyama, and H. Dai, Small 7, 574 (2011).
[2] T. Kato and R. Hatakeyama, Nat. Nanotechnol. 7, 651 (2012).
Corresponding Author: R. Nagai
Tel: +81-22-795-7046
E-mail: nagai14@ecei.tohoku.ac.jp- 77 -

1P-36
Optical spectroscopy on monolayer transition metal dichalcogenides
immersed in an aqueous solution
Wenjin Zhang, Yusuke Hasegawa, Kazunari Matsuda, and Yuhei Miyauchi
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan

Norm. Intensity

Intensity (arb. units)

Monolayer (1L) transition-metal dichalcogenides (TMDCs) MX2, where M and X
are a transition metal (typically Mo, W) and a chalcogen (typically S, Se, or Te),
respectively, have recently emerged as two-dimensional (2D) direct gap
semiconductors [1,2] promising for future electronics and optoelectronics
applications. To date, various intriguing optical properties of atomically thin TMDCs
in vacuum or ambient air conditions have been intensively studied using optical
spectroscopy techniques [1-4]. However, knowledge on the optical spectra of thesematerials in liquids has still been quite limited, although variety of phenomena
occurring at the interfaces of liquid and atomically thin TMDCs may considerably
modify their physical properties and affect their usefulness in applications.
Here we demonstrate a simple procedure for optical spectroscopic studies onmechanically exfoliated TMDCs immersed in a liquid, which will provide an
excellent platform for examining impacts of various physical chemistry phenomena at
the liquid/TMDC interface on their physical properties. 1L-TMDCs were preparedusing standard mechanical exfoliation method, and transferred on transparent glass
substrates. The substrate with the transferred 1L-TMDC was then tightly bonded witha glass tube to compose a liquid reservoir in which an enough amount of liquid can be
kept over the sample during the measurements. The optical measurements were
performed through the glass substrate using oil immersion objective lens and ahome-made confocal optical measurement system.
Figure 1 shows PL spectra of 1L-MoS2 in
1.0
water and air conditions, respectively.
Considerable modifications in the PL
intensity and spectral line shape (inset) wereobserved for the 1L-MoS2 just by
immersion in water. Dependence of the PL
0
0.5
1.6 1.7 1.8 1.9
spectra on the solution pH and theEnergy (eV)mechanism of the spectral modulation will
In water (pH 7)
be discussed.
In air[1] K. F. Mak, et al., Phys. Rev. Lett. 105, 136805(2010).
[2] A. Splendiani, et al., Nano Lett. 10, 1271 (2010).
[3] K. Matsuda, J. Phys. Soc. Jpn. 84, 121009(2015).
[4] S. Mouri, Y. Miyauchi, and K. Matsuda, Nano
Lett. 3, 5944 (2013).
Corresponding Author: Y. Miyauchi
Tel/Fax: +81-774-38-3463/+81-774-38-4567
E-mail: miyauchi@iae.kyoto-u.ac.jp- 78 -

0
1.6

1.7
1.8
Photon Energy (eV)

1.9

Fig. 1. PL spectra of 1L-MoS2 in water ofpH 7 (solid curve) and air conditions(dashed curve). Inset compares the PL
spectra normalized by their intensities atthe peak maxima.

1P-37
Helicity-resolved first order resonant Raman spectra of graphene andtransition metal dichalcogenides○Yuki Tatsumi and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Raman spectroscopy is one of the conventional method to verify the crystal and electronic
structure of materials. Recently, helicity-resolved and angle-resolved Raman spectroscopies
of atomic layer materials attract many interests due to their unique properties depending on
the crystal structure, phonon modes, and the polarization direction of incident light. Recent
experimental study by S.-Y. Chen et al. [1] shows that the
Raman mode switches themodehelicity of photon [right-handed circular polarized ( ) light is scattered], but thedoes not switch the helicity [left-handed circular polarized ( ) light is scattered] in Raman
incident light. This fact implies that the
scattering of monolayer MoS2 when we apply thephonon transfers the angular momentum to the photo-excited electron in the process ofRaman scattering. L. Zhang, et al. [2] discusses the chirality of the phonon which switches thehelicity of photon at high-symmetry points in monolayer hexagonal lattices. However, there isno actual calculation result to show the Raman intensity of the helicity-resolved Raman
spectra up to now.
In order to know the property of helicity-resolved Raman spectra, we develop the program
to calculate the first order resonant Raman spectra based on the first-principles calculation.
Raman intensity is proportional to the product of two electron-photon matrix elements and anelectron-phonon matrix element. We obtain the electron-photon matrix element with dipole
approximation given from the wave function calculated by Quantum Espresso package [3]and electron-phonon matrix element by EPW package [4].
In Fig. 1, we show the resonant Raman spectrum of G band in graphene calculated by ourprogram. As Fig. 1 shows, scattered light of G band changes the helicity of photon. This result
is in good agreement with previous theoretical study [2] and implies that the phonon transfers
the angular momentum to the photo-excited electron in the process of Raman scattering. In
this presentation, we discuss the helicity-resolved
selection rule of first order Raman scattering ingraphene and monolayer MoS2 by considering thesymmetry of electron-phonon matrix elements.
[1] S.-Y. Chen, et al., Nano Lett. 15, 2526 (2015)[2] L. Zhang, et al., Phys. Rev. Lett. 115, 115502 (2015)[3] P. Giannozzi, et al., J. Phys.: Condens. Matter 21, 395502(2009)[4] J. Noffsinger, et al., Compt. Phys. Commun. 181, 2140
(2010)
Corresponding Author: Yuki Tatsumi
Tel: +81-22-795-6442, Fax: +81-22-795-6447,
E-mail: tatsumi@flex.phys.tohoku.ac.jp

Fig1. Calculated resonant Raman spectrum of
G band in graphene. Solid (Dashed) line is
the helicity-resolved Raman intensity with
(without)
switchingofhelicityofphoto-excited electron. Incident laser energy
is 0.5 eV.

- 79 -

1P-38Energetics and electronic properties of C60 adsorbed on graphene○Yamato A. Saucier, Mina Maruyama, and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba
305-8571, Japan
Graphite intercalation compounds (GICs) are the representative van der Waals
heterostructures consisting of graphene and intercalant layers which are characterized by thestaging structure corresponding to the number of graphene layers sandwiching intercalant layers.
An early theoretical work has predicted a GIC consisting of graphene and C60 sheets, which arealternately stacked each other [1]. Following the theoretical prediction, an experimental work
demonstrated that the possibility of the C60-GIC and C60 molecular layer on graphene [2].
Motivated by these early works, we are now aiming to investigate the physical properties of the
all carbon thin film consisting of monolayer
graphene and C60 molecular sheet as the thinnest
version

of

the

all

carbon

van

der

(a)

(b)

Waals

heterostructure with mixed dimensionality, using thedensity functional theory combined with theeffective screening medium method. Owing to thework function difference between C60 and graphene,
the sheet exhibits dipole moment normal to the sheetwith the potential difference of 0.15 V [Fig. 1(a)].
We also demonstrated that the biaxial compressive
strain causes the electron transfer from graphene to
C60, because of the different compressibility between

Fig. 1, Contour plots of (a) electrostatic
potential and (b) charge redistribution of
C60 adsorbed on graphene.

graphene and C60 layers [Fig. 1(b)].
References:[1] S. Saito and A. Oshiyama, Phys. Rev. B 49, 17413 (1994).
[2] E. V. Rut’kov, A. Ya. Tontegode, and M. M. Usufov, Phys. Rev. Lett. 74 758 (1995).
Corresponding Authors: Y. A. Saucier and S. Okada

E-mail: sokada@comas.frsc.tsukuba.ac.jp- 80 -

1P-39Upconversion photoluminescense spectra of carbon nanotubes
in mice tissues○Saki Okudaira1, Yoko Iizumi2, Masako Yudasaka2, Toshiya Okazaki2, Kazunari Matsuda1,
and Yuhei Miyauchi1
12Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki
305-8562, JapanUCPL intensity [a.u.]Single-walled carbon nanotubes (SWNTs) have been considered as promising luminescentprobes for deep-tissue bioimaging because of their intrinsic photoluminescence (PL) in thenear infrared wavelength range of ~1000-1300 nm called NIR-II [1,2]. The near infrared lightreadily penetrates into highly scattering media such as biological tissues; this enables PL
imaging of deep inside of them. However, it is necessary to use Stokes PL at longer
wavelengths than ~1100 nm to avoid autofluorescence from the biological tissues, andstandard Si-based detectors cannot be used in this wavelength range. Recently, efficient
upconversion PL (UCPL) of SWNTs has been discovered [3]. The UCPL phenomena enable
SWNTs excited at wavelengths longer than ~1050-1200 nm(a)to emit PL shorter than 1000 nm in which standard Si-based
detectors have finite sensitivity. The availability of the
UCPL thus drastically enhances the usefulness of SWNTs as)luminescent probes in their bioimaging applications.
In this study, we examine UCPL spectra of SWNTs in
biological tissues of mice using a Si-based CCD and an
InGaAs photodiode array detector. We measured both PL
and UCPL spectra of sectioned liver tissues of mice into
which SWNTs were intravenously injected. Figure 1(a) and1(b) show a UCPL image and a UCPL spectrum of SWNTs(b)in the sectioned liver tissue excited at 1064 nm, respectively.
20
A circle in Fig. 1(a) indicates the position at which the
UCPL spectrum shown in Fig. 1(b) was measured. The)
UCPL showed a major peak at about 1010 nm; similar
UCPL peak was also observed for the SWNTs before the10
injection. Relatively broad UCPL feature implies bundlingof SWNTs [4]. Results for the UCPL imaging andspectroscopy in other conditions will also be discussed.
0900[1] K. Welsher et al., Nat. Nanotechnol. 4, 773 (2009).
[2] Y. Iizumi, et al., ACS Appl. Mater. Interfaces 5, 7665 (2013).
[3] N. Akizuki et al., Nat. Commun. 6, 8920 (2015).
[4] S. Aota, et al., Appl. Phys. Express 9, 045103 (2016).
Corresponding Author: Y. Miyauchi
Tel: 81-774-38-3463, Fax: +81-774-38-4567
E-mail: miyauchi@iae.kyoto-u.ac.jp- 81 -

950
1000
Wavelength [nm]Fig. 1. (a) UCPL image of SWNTs in asectioned tissue of a mouse liver excited
at 1064 nm. (b) UCPL spectrum taken at
the position indicated by a circle in (a).

1P-40Electrical properties of defective hexagonal boron nitride nanosheet○ Ho-Kyun Jang, Jun Hee Choi, Kook Jin Lee, Do-Hyun Kim, Gyu Tae Kim
School of Electrical Engineering, Korea University, Seoul 02841, Korea
Boron nitride (BN) has a good thermal conductivity [1] but, it has no electricalconductivity due to its large bandgap. Theoretical calculations predicted that hexagonal BN
nanosheet (BNNS) with some defects can have an electrical conductivity because of newenergy states of these defects between conduction and valence band [2]. In this study, we
created vacancy defects on BNNS by the method of forming multi-vacancies on BN
nanotubes [3]. As a result, we observed a change in the electrical properties of the BNNS.
BNNS was transferred on SiO2/Si substrate using mechanical exfoliation method. The
source and drain electrodes for BNNS were patterned by E-beam lithography and gold was
deposited by chemical vapor deposition to form theelectrodes. Then, the BNNS was impregnated withCo precursor and heated at about 200 oC under air
atmosphere to form defective structures in BNNS by
catalytic oxidation. In the electrical measurements,
the pristine BNNS did not show any electricalproperties. However, BNNS with defects exhibited
an electrically metallic behavior. To investigate thisphenomenon, the electronic structures of BNNS withmono- and di-vacancy defects were calculated basedon density functional theory. Calculation results andFig.1 Schematic image of defective
actual experimental results were compared andBNNSdeviceanalyzed.
[1] J. H. Lan et al. Phys. Rev. B. 79(11), 115401 (2009)[2] P. Tang et al. RSC Adv. 2, 6192-6199 (2012)[3] D.-H. Kim et al. Phys. Chem. Chem. Phys. 19, 976-985 (2017)
Corresponding Author: Ho-Kyun Jang
Tel: +82-2-3290-3801, Fax: +82-2-953-3780,
E-mail: pleastandup@korea.ac.kr- 82 -

1P-41
Modification of Electrical Properties in MoS2 by Using Catalytic Oxidation○ Jun Hee Choi, Ho-Kyun Jang, Jun Eon Jin, Jong Mok Shin, Do-Hyun Kim
Gyu-Tae Kim
School of Electrical Engineering, Korea University, Seoul 136-701, South Korea
Modulation of electrical properties in MoS2 attracts much attention in terms ofcomplementary circuit design based on monolayer two-dimensional material [1-3]. In thiswork, we demonstrate an effective method to change electronic transport characteristics of
MoS2 by using catalytic oxidation (MoS2 + O2 → MoOx + SOx). Ambipolar behavior in
MoS2 field effect transistors (FETs) can be easily obtained by heating MoS2 flakes under air
atmosphere in the presence of cobalt oxide catalyst.
From the microscopic observation by SEM and AFM,
the catalytic oxidation of MoS2 flakes between
source-drain electrodes resulted in lots ofnanoparticles (NPs) on MoS2 flakes with thickness
reduction. The oxidation state of the NPs was
confirmed by XPS analysis to be MoOx, meaningthat catalytic oxidation happened on the top layer of
MoS2 flakes. N-type behavior of MoS2 FETs was
Fig.1 Schematic diagram of achieving
converted to ambipolar transport characteristics byambipolar behavior in FETs by partially
MoOx NPs which inject hole carriers to MoS2 flakes
modifying MoS2 flakes via catalyticoxidation using CoO NPs.
[4]. Theoretical calculations were performed toinvestigate the change in the electronic structure of
MoS2 by MoOx NPs.
[1] K. Dolui et al. S. Phys. Rev. B, 88, 075420 (2013).
[2] M. R. Laskar et al. S. Appl. Phys. Lett. 104, 092104 (2014).
[3] J. Suh et al. Nano Lett. 14, 6976 (2014).
[4] S. Chuang et al. A. Nano Lett. 14, 1337 (2014).
Corresponding Author: Jun Hee Choi
Tel: +82-2-3290-3801, Fax: +82-2-953-3780,
E-mail: cjuny426@gmail.com- 83 -

1P-42
Hidden symmetries in one-dimensional photonic crystals
M. Shoufie Ukhtary, Haihao Liu, and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Nowadays, transferring information across a long distance efficiently has been the main subject incommunication field of science. Light is used mainly for this purpose due to its velocity and its versatile
properties which is sensitive to the medium it passes. Photonics is a branch of science that studies how thelight propagates through the material and how to modify its propagation, such as how to prevent the
propagation or to localize the light [1]. One-dimensional photonic crystal (PC), which is a system
containing N layers of varying dielectric media, is usually used to achieve this purpose. By manipulating
the sequence of dielectric media within the PC, we can control the light propagation through it [2].
Previous studies have shown that by controlling the sequence of PC, the light propagation can becontrolled. This allows the development of optical devices such as optical filter and optical switches.
However, the studies focus only on some specific sequences of PC, such as Fibonacci and Cantor
sequences [3,4]. A study for optical properties of arbitrary sequences is not yet done as far as we know. In
this work, we study theoretically the light propagation within arbitrary sequences. We use onedimensional PC containing N layers made of two kinds of dielectric media. In contrast to previous studies,
we study all the possible sequences of the PC, which is in total of 2N sequences [5]. We will show thatthe number of light transmission probability (T) values for the N layers is not arbitrary, instead there are
either (N/2 + 1) or (N + 1) discrete values of T for even or odd number N, respectively. This highdegeneracy implies the existence of hidden
symmetries within the PC, which we will explainin this work. One of symmetries found in thiswork is shown in figure 1. Studying thesymmetries within the PC can be useful for
designing a sequence of PC with desirable

Figure 1: The mirror symmetry: Mirrored sequenceof dielectric media will give the same transmission
probability (T).

properties, such as a PC with specific T.
[1] J.D. Joanopolous et al.Photonics crystal : molding the flow of light. (2011)[2] B.E Saleh et al. Fundamentals of photonics. (1991).
[3] R. Endo and R. Saito. JOSA B 28, 2537. (2011)[4] P. Xu et al. JOSA B27, 640. (2010)[5] H. Liu et al. in preparation. (2017)
Corresponding Author: M. Shoufie Ukhtary
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: shoufie@flex.phys.tohoku.ac.jp- 84 -

2P-1
Theoretical estimation for the electronic property and reactivityof activated fullerenes○Naohiko Ikuma, Ken Kokubo and Takumi Oshima 1
1

Division of Applied Chemistry, Graduate School of Engineering, Osaka University,
Suita 565-0871, JapanOne of the advantages of nanocarbon materials is the modification of properties andsolubility by various organic reactions; therefore, control of the reactivity and regioselectivity
is an important issue for obtaining new materials effectively. To enhance the reactivity andregioselectivity of fullerene, we have investigated on the activated fullerenes with increasing
cage strain or introducing an electrophilic cation. In this presentation, we will show
theoretical evaluation for the reactivity and regioselectivity on these reactions.
Activation by cage modification: Carbon- or nitrogen-bridged fullerenes, named as
fulleroids or azafulleroids respectively, showed high reactivity and regioselectivity on
Diels–Alder reaction, mCPBA oxidation, acidic arylation [1] and Grignard reaction, because
of increased strain on the adjacent bridgehead olefins. These reactivities and regioselectivities
were well explained by DFT transition state (TS) calculations.
Activation by an internal cation: Li-encapsulated fullerene Li+@C60 has higher
electrophilicity due to the internal "naked" lithium cation. Electrochemical reduction gave thestable ion pair of a radical anionic cage and the internal Li-cation. [2] Moreover, the internal
cation promoted Diels–Alder reaction (2400-fold vs. C60) due to its Lewis acidity estimatedby both kinetic measurements and DFT calculations. [3]RX

Enhancementof strain by a carbon
or nitrogen bridge

Enhancementof electrophilicity byan internal cation

Li +strained
olefins

Diels-AlderreactionR

C60

Fulleroid (X = CH)
Azafulleroid (X = N)

electrochemical
reduction

Acidicarylation (X = N)

X

Ar

Ar
HH
Li +

H

Li +

Ar

Ar
regioselective
addition

Li +@C60
Diels-AlderreactionAr

cation surroundedradical anionic cage

selective multiaddition~2400-fold faster
addition (vs. C60)

[1] N. Ikuma, Y. Doi, K. Fujioka, T. Mikie, K. Kokubo, T. Oshima., Chem. Asian J. 9, 3084 (2014).
[2] (a) H. Ueno, K. Kokubo, Y. Nakamura, K. Ohkubo, N. Ikuma, H. Moriyama, S. Fukuzumi, T. Oshima, Chem.
Commun. 49, 7376 (2013); (b) H. Ueno, S. Aoyagi, Y. Yamazaki, K. Ohkubo, N. Ikuma, H. Okada, T. Kato, Y.
Matsuo, S. Fukuzumi, K. Kokubo, Chem. Sci. 7, 5770 (2016).
[3] H. Ueno, H. Kawakami, K. Nakagawa, H. Okada, N. Ikuma, S. Aoyagi, K. Kokubo, Y. Matsuo, T. Oshima, J.
Am. Chem. Soc. 136, 11162 (2014).
Corresponding Author: N. Ikuma
Tel: +81-6-6879-4592, Fax: +81-6-6879-4593 ;E-mail: ikuma@chem.eng.osaka-u.ac.jp- 85 -

2P-2
Palladium-Catalyzed Functionalization of C60 Derivatives:
Regioselectivity and Structures○Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, Yasujiro Murata
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, JapanThe multi-functionalized fullerene C60 derivatives have been studied for the elucidation of
their nature and for application in electronic devices.1 Though a number of methods for
multi-functionalization of C60 have been reported, in some cases, reactions are unctrollable
and/or isolation of a desired compound from a reaction mixture is not facile.
We developed a method for thesynthesis of arene-fused C60 derivatives byutilizing a catalytic amount of palladium.
Firstly, we optimized conditions using
different palladium sources for thereaction of C60 and 1-halogenatednaphthalene (1-XNp). Under the optimized
conditions, compound 1 was found to beobtained in 52% yield (Scheme 1). To
investigate the reaction scope, we applied
the same conditions to 1,4-di-n-butyl C60(2), which resulted in the regioselective
formation of 3 in 35% yield. This reaction
can be applied to open-cage C60 derivative
4 to give 5, albeit in 17% yield. The
relatively low yield of 5 arises from theside reaction, thermal dehydrogenationfrom the opening of 4. However, when
1-BrNp was used as an arene-source
instead of 1-ClNp, compound 5 was
obtained in 53% yield since thetemperature required for this reaction decreased to 180 °C from 220 °C, which prevented thethermal dehydrogenation of 4. It is noteworthy that the compounds 2 and 4 have the samestructural motif of acenaphtylene where the palladium-catalyzed reaction takes place. The
DFT calculations suggested that the HOMO is predominantly localized on this moiety.
To get further insights into the reaction mechanism, we performed the DFT calculations on
the reaction of C60 and 1-BrNp along with two plausible reaction pathways, Heck-type andconcerted metalation-deprotonation mechanisms.2 The optimized conditions, DFT
calculations, and the single crystal X-analysis will be presented in detail.
[1] Hirsch, A. Fullerenes: Chemistry and Reactions; Wiley-VCH: Weinheim, 2005.
[2] (a) Lapointe, D.; Fagnou, K. Chem. Lett. 2010, 39, 1118–1126. (b) Tang, S.-Y.; Guo, Q.-X.; Fu, Y.
Chem.–Eur. J. 2011, 17, 13866–13876. (c) Tan, Y.; Hartwig, J. F. J. Am. Chem. Soc. 2011, 133, 3308–3311.
Corresponding Author: Y. Murata
Tel: +81 774-38-3172, Fax: +81 774-38-3178,
E-mail: yasujiro@scl.kyoto-u.ac.jp- 86 -

2P-3
Synthesis of Lithium-ion-encapsulated Fluoreno[60]fullerenes○Yutaka Matsuo1,2,3, Hiroshi Okada2, Hiroshi Ueno3
1

Hefei National Laboratory for Physical Sciences at the Microscale, University of Scienceand Technology of China, Hefei, Anhui 230026, China
2
Department of Mechanical Engineering, School of Engineering, The University of Tokyo,
Bunkyo-ku, Tokyo 113-8656, Japan3
Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China
Lithium-ion-containing [60]fullerene, Li+@C60, is a highly electron accepting material,
which have been utilized in electron transfer chemistry, supramolecular chemistry,
photovoltaics, singlet oxygen generation, and so on. Considering what chemical modificationof fullerene has played in, that for Li+@C60 would be a significant step for further
functionalization of this compound.[1-7]
In this presentation, we will report the modification of Li+@C60 by using the fluorenogroup. The reaction of Li+@C60 and diazofluorene gave the desired product smoothly.
Difference in the reactivity in the synthesis of diphenylmethano-modified Li+@C60 andfluoreno-modified one will be discussed.

Figure. Structures of Lithium-ion-encapsulated fluoreno- and diphenylmethano[60]fullerenes.
References[1] Y. Matsuo et al., Org. Lett. 2012, 14, 3784–3787.
[2] H. Okada et al., RSC Adv. 2012, 2, 10624–10631.
[3] Y. Noguchi et al., J. Phys. Chem. C 2013, 117, 15362–15368.
[4] H. Kawakami et al., Org. Lett. 2013, 15, 4466–4469.
[5] Y. Kawashima et al., ChemPhysChem 2014, 15, 3782–3790.
[6] H. Ueno et al., J. Am. Chem. Soc. 2014, 136, 11162–11167.
[7] H. Ueno et al., Chem. Sci. 2016, 7, 5770-5774.
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-0978, E-mail: matsuo@ustc.edu.cn; matsuo@photon.t.u-tokyo.ac.jp- 87 -

2P-4
Nanoscale Control of Polymer Assembly on Fullerene Bilayer Membranes○Koji Harano, Ricardo M. Gorgoll, Eiichi Nakamura
Department of Chemistry, The University of Tokyo, Tokyo 113-0033, Japan
Preparation of nanostructured polymer materials templated by self-assembled scaffolds haslong been inspired by biosynthetic machinery on cell membranes, but has still remained to bea challenging subject of research in laboratories. Noticing that one of the fundamental
problems in this challenge is the excessive fluidity of a lipid or lipid-mimetic membrane, we
conjectured on the use of a self-assembled bilayer made of an anionic fullerene amphiphile
1–3 (Figure), from which an aqueous solution of a vesicle of a uniform size (typically 30 nm
in diameter) is formed spontaneously upon dissolution in water (V1–V3, respectively). The
fullerene bilayer keeps the hydrophilic fullerene anion inside and exposes the hydrophobicgroups on an aqueous environment to create three regions: surface, interior and fullerene-richcore. Herein we report a catalyst–membrane system where catalyst 6 doped on the vesicle forring-opening metathesis polymerization (ROMP) controls the assembly of polymer products
from a norbornene diethyl ester (4a) in three different ways by the choice of the fluorousvesicle V1, the octyl vesicle V2 and the eicosanyl vesicle V3, depending on the miscibility of
the growing polymer to the interior of the bilayer. Thus, the polymerization of 4a on the
fluorous vesicle V1 occurred heterogeneously on the vesicle surface to afford 6-nm sized
spherical particles composed mostly of a single polymer chain. In contrast, polymerization of
4a on the octyl vesicle V2 occurred homogeneously near the fullerene core of the bilayer toafford a hollow polymer capsule of 35-nm size composed of tightly entangled 20–30 polymer
chains. Polymerization on V3 occurred in the eicosanyl alkyl environment to afford a soft andsticky capsule.
=

R

R

K+ R
R
R
–

H 2O

1: R = nC8F17; 2: R = nC8H17
3: R = nC20H 41
vesicle4
nm

V2

Fullerene bilayer
vesicle V1–V3
ca. 30 nm

polymer conjugate

catalyst–membrane

V1

polymerparticle–V1
ROMP

ca. 6 nm

–V2

4
nm

capsuleca. 35 nm

V38nm

SEM images
5a on V1: Nodules

–V3

soft
capsule=Mes N N Mes
Cl
Ru
Cl
iPrO
SiR 3

5a on V2: Smooth

6: R = CH2CH2nC8F17
R1

=

4

R2

=

n

R1

5

R2

4a: R1,R 2 = CO2Et;
4b: R1 = dansyl, R 2 = H;
4c: R1,R 2 = CO2(CH 2)2Br;

10 nm

Fig. Controlled polymer growth and assembly in a synthetic catalyst–bilayer system made of fullerene
amphiphiles 1-3.
[1] R. M. Gorgoll, K. Harano, E. Nakamura, J. Am. Chem. Soc., 138, 9675 (2016).
Corresponding Author: E. Nakamura
Tel: +81-3-5841-4369, Fax: +81-3-5841-4369,
E-mail: harano@chem.s.u-tokyo.ac.jp- 88 -

2P-5
Metallic Polymerization of C60 Thin Film by Electron-Beam Irradiation
Hiroto Uenoyama1, Yu Tanaka1, Shingo Yamanouchi1, Yuichi Ochiai1, and Nobuyuki Aoki1,2
1 Chiba University, Chiba, Japan, 2 JST-PRESTO
Although C60 molecules form fcc (3d) structure in the vander Waals crystal, various kinds of crystalline structures
have been found in the polymers by using different
triggers for the polymerization. For example,

2.5
2
DrainI(nA)

1.5
orthorhombic (1d) structure by visible or ultraviolet light1
irradiation, tetragonal and rhombohedral (2d) structure by
0.5
high pressure application at high temperature, and peanut0shape (1d) polymer by electron beam (EB) irradiation [1]
-0.5
-50
0
50
GateV(V)have been reported. Different structure leads to different
Fig. 1. Gate voltage dependence of drain
physical properties such as electrical properties. Here, we current of C60 thin film before (lower) andare interested in EB irradiation using electron beam after (upper) EB irradiation.
lithography system, because we can expose EB toward theselected area to form metallic patterns in electrical circuits within a semiconducting C60 thinfilm.
We prepared the sample of C60 thin film FET on SiO2/p++-Si substrate by vacuum
evaporation. The sample was extracted to the atmosphere and settled into a vacuum chamberof a scanning electron microscope (SEM). Before EB irradiation, the sample was heated to453 K for 19 hours in the SEM chamber to remove oxygen absorbed on the sample surface.
And then, the sample was irradiated by EB with an acceleration voltage of 2 kV. We measured
the FET property of the sample before and after irradiation for 2 hours. As shown in Fig. 1,
n-type semiconductor property changed to a metallic one which exhibits conductive but nodependence of current in the gate voltage sweep. The resistivity is an order of 10 Ω·m or less.
The change must be due to the polymerization of C60 molecules during the EB exposure.
Moreover, we confirmed the metallic properties are still kept after exposure to air. We will
discuss the characteristics including the surface morphology using atomic-force microscopeobservation and the results of micro Raman scattering spectroscopy.
[1] J. Onoe et al, Fullerenes, Nanotubes, and Carbon Nanostructures. 20, 1 (2012)
Corresponding Author: N.Aoki
Tel: +81-43-290-3430, Fax: +81-43-290-3427,
E-mail: n-aoki@faculty.chiba-u.jp- 89 -

2P-6
Synthesis of CdS-Mn-[C60]Fullerene Nanocomposites and Their
Photocatalytic Activities for Degradation of Organic Dyes
○ Jeon Won Ko1, Jiulong Li1 and Weon Bae Ko1,2
12

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

Manganese doped CdS nanocomposites were prepared by using manganese (II) sulfate
monohydrate (MnSO4 •H2O), cadmium sulfate 8/3 hydrate (3CdSO4 •8H2O) and sodium
sulfide (Na2S) as source reagent in basic aqueous solution. Manganese (II) sulfate
monohydrate (MnSO4•H2O) and cadmium sulfate 8/3 hydrate (3CdSO4•8H2O) were addedwith a mole ratio of 1:10. CdS-Mn-[C60]Fullerene nanocomposites were synthesized throughheating CdS-Mn nanocomposites and [C60]Fullerene at a mass ratio of 2:1 in the electric
furnace at 700 ℃ for 2 h. The synthesized nanocomposites were characterized by X-ray
diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) andtransmission electron microscopy (TEM).
As a photocatalyst, CdS-Mn-[C60]Fullerene nanocomposites were used in the degradation oforganic dyes like BG, MB, MO and RhB under 254 nm ultraviolet light. The photocatalytic
activities and kinetics study of CdS-Mn nanocomposites and CdS-Mn-[C60]Fullerenenanocompo
sites were evaluated by UV-vis spectrophotometer.
0y = -0.0003x - 0.0907

-0.5

-1

ln (C/C0)

y = -0.0026x - 0.3931

BG

-1.5

y = -0.0039x - 0.4843

MB
MO
RhB

-2

-2.5
y = -0.0088x - 0.3651
-3
0

50

100

150

200

250

300

Time (min)Fig.1 Kinetics study of various organic dyes with CdS-Mn-[C60]Fullerene nanocomposites at 254 nm.

[1] M.Grandcolas, J.Ye and K. Miyazawa, Ceram. Int. 40, 1297 (2014).
[2] Z. Lian, P. Xu, W. Wang, D. Zhang, S. Xiao and G. Li, Appl. Mater. Interfaces 7, 4533 (2015).
[3] H.S.Park and W.B.Ko, J. Nanosci. Nanotechnol. 15, 8125(2015).
Corresponding Author: W. B. Ko
Tel: +82-2-3399-1700, Fax: +82-2-979-5318,
E-mail: kowb@syu.ac.kr- 90 -

2P-7
Studies on the Aggregated Structures
and Crystallinities of Bulk Heterojunction Films Constituting Organic
Solar Cells○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 to provide
a low cost photovoltaic devices. It is well known that the nanomorphology of the polymer:fullerene BHJ isa 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, 1,8-Octanedithiol(ODT) and 1-Chloronaphthalene(CN) addition of
P3HT/1-(3-methoxy- carbonyl)propyl-1-phenyl-(6, 6)(C61-PCBM) BHJ films on the local crystallinity andmorphology by using solid-state NMR spectroscopy. In this study, we have investigated the change in the
crystallinity, morphology, and the properties of molecular motions of P3HT/C71-PCBM BHJ film bychanging material by using 13C and 1H solid-state NMR spectroscopy.
Mixed solution of P3HT/C71-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. Additives
were 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/C-71PCBM BHJ films were prepared bydropping the solution in a glass plate and dried in a glove box under argon atmosphere using different
drying rates. Dried film were removed from the glass plate and sealed into 4 mm zirconia NMR rotor.
Solid-state NMR spectra were collected on Bruker AVANCE300 spectrometer.
Detailed results of their crystallinities, morphologies, and the properties of P3HT/C71-PCBM BHJ film
the will be presented.
References:
1) J. K. Lee et al., J.Am.Chem.Soc.,130(2008)3619.
2) B.R.Aïch et al, Organic Electronics,13 (2012)1736.
3) Ryan C. Nieuwendaal et al., ACS Macro Lett. 3(2014)130−135.

- 91 -

2P-8
Production and Characterization of Hetero-dimetallofullerene:
GdY@C80(Ih)○Takuji Mitani1, Natsumi Nakatori1, Takahisa Yamaguchi2, Ko Furukawa3, Tatsuhisa Kato2, 4,
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
Department of Chemistry, Niigata University, Niigata 950-2181, Japan
4
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

In the previous symposium, we reported the isolation and characterization of Gd2@C80(Ih)anion, which are not stable as a neutral form but stable as an anion form[1]. In (Gd2@C80(Ih)) ,an excess electron is located on the internal Gd dimer and Gd takes the trivalent state. Then,the spin system of (Gd2@C80(Ih)) consists of one doublet spin and two octet spins. From the
ESR study, the spin state of (Gd2@C80(Ih)) was found to be S=15/2, that is, the ferromagnetic
interaction between three spins was suggested. On the other hand, the antiferromagnetic
interaction was reported in mono-metallofullerene encapsulating a Gd atom: Gd@C82, whose
spin system consists of one octet spin of the encapsulated Gd3+ and one doublet spin of an
unpaired electron on the π orbital of the carbon cage[2]. Here, we report the production andcharacterization of (GdY@C80(Ih)) . To clarify more simply the magnetic interaction between
the spins of Gd3+ and an excess electron on the internal metal dimer, we exchange one Gd3+ of
Gd2@C80(Ih) for Y3+ that is a nonmagnetic ion.
Soot containing Gd,Y-metallofullerenes wasproduced by a direct-current arc discharge, and the raw
soot was extracted with a mixed solvent oftriethylamine and acetone. MM’C80 mixture (M,M’=Gd, Y) was separated by two-stage HPLC using
acetone with an ion-pair reagent, tetrabutylammonium
bromide, as an eluent. The presence of GdYC80 was
confirmed by LD-TOF-MS (Fig.1). Furthermore, since Fig.1 LD-TOF-MS spectrum (negative
the UV-vis-NIR absorption spectrum of MM’C80 ion mode) for MM’C80 mixture (M,mixture was found to be very similar to those of M’=Gd, Y).
(Gd2@C80(Ih)) and (Y2@C80(Ih)) as shown in Fig.2, itis suggested that the GdYC80 would be GdY@C80(Ih).
The results of ESR measurements on (GdY@C80(Ih))
will also be discussed in the presentation.
[1] T. Mitani, et al. The 50th Fullerenes-Nanotubes-Graphene
General Symposium 95 (2016).
[2] K. Furukawa, et al. J. phys. Chem. 107, 10933-10937 (2003).
Corresponding Author: Takeshi Kodama
Tel:+81-42-677-2530, Fax:+81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 92 -

Fig.2 UV-vis-NIR absorption spectraof (MM’C80) mixture (M, M’=Gd, Y),(Gd2@C80(Ih)) and (Y2@C80(Ih)) .

2P-9Isolation and structural analysis of La@C60(CF3)5○Makiko Nishino1, Shinobu Aoyagi2, Haruka Omachi1, Zhiyong Wang1,
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.

La@C60 is historical fullerene, which is first metallofullerene found on earth[1] and istheoretically predicted to have properties like superconductivity. Despite such a big prospect,
M@C60 have not been easily isolated since 1985 because of severe instability. Accordingly,
there were some opinions even claiming that La atom is not encapsulated inside fullerene. To
solve this issue, the stabilization technique of metallofullerenes by introducing CF3
substituents has been developed in our group[2].
We finally isolated La@C60(CF3)3, La@C60(CF3)5(isomer I) and La@C60(CF3)5(isomer II)
by multi-step HPLC purification with two types of buckyprep columns alternately (Fig.1 (a)).
Furthermore, first X-ray crystallographic structure of La@C60(CF3)5(I) was revealed. The
ORTEP drawing was shown in Fig1 (b). La atom was definitely incorporated within thefullerene cage. One of C–CF3 bonds was formed at a point distant from other four CF3 groups.
Although single crystal of M@C60 has not been found so far because of high degree of
freedom, this crystal was neither co-crystal nor including solvent. This miracle is supposed tohave happened by existence of solely distant CF3 substituent.
(b)

(a)

Fig.1 (a) Negative MALDI-MS of isolated CF3-functionalized La@C60 derivatives. (b) X-ray structure of
La@C60(CF3)5(I). Thermal ellipsoids are shown at 50% probability.
[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.,55,199 (2016)
Corresponding Author: Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442, E-mail: noris@nagoya-u.jp- 93 -

2P-10
Photoreactions of Cyclic Organosilanes with Trimetallic Nitride Template
Endohedral Metallofullerenes○Shinpei Fukazawa1, Takeshi Sugiura1, Kyosuke Miyabe1,
Masahiro Kako*,1, Takeshi Akasaka2,3,4
1

Department of Engineering Science, The University of Electro-Communications, Chofu,
Tokyo 182-8585, Japan
2
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan3
Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
4
Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
Endohedral metallofullerenes (EMFs) have acquired a lot of interest from researchers
because of their fascinating structural and electronic properties. Exohedral functionalization isa crucial method that enables the utilization of EMFs for various applications in molecularelectronics and biomedicine. As a part of our continuing study of functional EMF derivatives,
we have been developing reactions of disiliranes and siliranes with EMFs to afford thecorresponding silylated derivatives, which exhibit remarkable electronic properties comparedwith their parent EMFs [1]. Previously, it was reported that the photoreaction of disilirane 1
with C60 in benzonitrile produced 3 and 4 as the adducts of 1 and benzonitrile instead of the
adduct of 1 and C60 [2]. These results prompted us to examine the solvent effect on thephotoreactions of disilirane 1 and silirane 2 with M3N@Ih-C80 (M = Sc, Lu).
When Sc3N@Ih-C80 and 1 was irradiated in a mixed solvent of toluene and benzonitrile bytwo 500 W halogen lamps under an argon atmosphere, two benzonitrile adducts 3 and 4 wereobtained in 42% and 14% yields, respectively. In the case of Lu3N@Ih-C80, a similar reaction
took place to produce 3 and 4 in 44% and 23% yields, respectively. In contrast, thephotoreaction of Sc3N@Ih-C80 (or Lu3N@Ih-C80) and 2 under the same conditions afforded thecorresponding oxygenated product 5, and no benzonitrile adduct of 2 was obtained. The
formation of 5 may result from oxygenation by the residual oxygen in the solvent during thephotolysis. The mechanistic pathway of photochemical conversions of 1 and 2 in the presenceof M3N@Ih-C80 (M = Sc, Lu) will be discussed.
Scheme 1.
Mes

Mes
Si

Si

Mes
M3N@Ih-C80(M = Sc, Lu)

Mes
1

Dep

Mes

Mes
Si

Si
Mes

Dep

Si

N

Ph

tBp
2

Mes

3

Mes
Mes

Mes =

Mes

Si

Si

N

N

Ph

Ph
4

Mes

Dep

tBp
Si

Dep

O

O

5

[1] M. Yamada and T. Akasaka, Bull. Chem. Soc. Jpn. 87, 1289–1314 (2014).
[2] T. Akasaka, et al. Org. Lett. 1, 1509–1512 (1999).
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 94 -

Dep =

tBp =

2P-11
Energetics and electronic structure of SIMEF chains
Sho Furutani and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8571, Japan
Fullerene and fullerene derivatives are widely used for electron acceptor in organic photovoltaic
devices because of their deep lowest unoccupied state resulting in the high open voltage to theelectron donor materials. Silylmethyl[60]fullerene (SIMEF) is one of representative fullerene
derivatives which has high electron mobility due to their crystal packing structure in device
structures. Although experiments are advancing the efficiency of the devices, a little is known
the detailed electronic properties of SIMEF in packed structure. In particular, because of thecomplicated crystalline structure, the effective mass of SIMEF is not sufficiently address to date.
Therefore, in this work, we aim to investigate the energetics and electronic structures of SIMEF
chains with various intermolecular arrangements to give theoretical insight into the preferable
geometries and physical origin of the highelectron mobility in terms of their electronicenergy band. All calculations are conductedusing the density functional theory with local
density

approximation

andultrasoft

pseudopotentials. To unravel the physicalorigin of the high carrier mobility, we evaluate
the electron effective mass along SIMEF
chainswithvariousintermolecularFig. 1 The structural model of SIMEF chains withmolecular angles of (a) 0, (b) 30, (c) 60, and (d) 90°.

arrangements under the optimum spacing (Fig. 1).
Our calculations show that the chain chains possess the effective masses of 3.0me, 15.2me,
10.1me, and 871.0me for the intermolecular angles of 0, 30, 60, and 90°, respectively. Thus, thechain with molecular angle of 0° give the smallest electron effective mass among these chains.
On the other hand, the biding energy of the chain with 60° is the most favorable intermoleculararrangement.
Corresponding author: S. Furutani
Tel: +81-29-853-5600 (ext.8233), Fax: +81-29-853-5924,
E-mail: sfurutani@comas.frsc.tsukuba.ac.jp- 95 -

2P-12Absolute yield of fullerene formed by graphite laser ablation
at medium-high ambient temperatures○Haruka Suzuki, Yuki Taguchi, Takeshi Kodama, Yohji Achiba, and Haruo Shiromaru
Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
In our previous paper, we have shown that a macroscopic amount of C60 is produced bylaser ablation of graphite in a room temperature gas flow and the yield is considerably higher
than that expected from the extrapolation of the yields by high-temperature laser ablation,
above 500 C [1-3]. In the present study, we produced C60 in a similar way while theirradiation cell was gently heated up to 200 C. The experimental setup is the same with that
employed in Ref. [1] except for an external heating device, a kanthal electric heating wirearound a glass, as schematically shown in Fig. 1. Flowing Ar gas (100 mL/min), Nd: YAG
laser (10 Hz, 532 nm) with the power of 300 mJ/pulse was irradiated for 30 minutes. The gas
temperature was measured with a thermocouple placed 5 mm downstream of the ablation area,
in an independent measurement with the same flow rate of Ar. It should be noted that the gas
temperatures rise about 85 degrees under laser ablation at room temperature.
The ablation products carried by Ar gas flow were
captured in 5 mL toluene. Soluble products attached to
the glass cell were extracted by sonication for about 20
minutes in excessive amounts of toluene. The solution
was then concentrated to a volume of 5 mL. The
amount of vaporized graphite was measured as thedifference in the weight before and after irradiation.
The products, which were carried by Ar gas flow
and attached to the cell, were analyzed by HPLC
(column: Buckyprep, eluent: toluene). The yields areshown in Fig. 2 together with the reference data. At
23 °C, the total amount of C60, the average of six Fig. 1 Schematic drawing of the
independent runs, was 1.0×10-3 mg and the yield of experimental setup.
C60 was 0.034 wt%. At 100 °C and 200 °C, the yields
of C60 show a nearly flat behavior with respect to thegas temperature, suggesting a need of reconsiderationof the formation mechanism of C60.
[1] H. Endo et al., Chem. Phys. Lett. 642, 35 (2015).
[2] T. Wakabayashi et al., Structure and Dynamics of Clusters,p. 535 (1996).
[3] D. Kasuya et al., Eur. Phys. J. D, 9 355 (1999).
Corresponding Author: H. Suzuki,
Tel: +81-42-677-1111, Fax: +81-42-677-2525,
E-mail: suzuki-haruka4@ed.tmu.ac.jp- 96 -

Fig. 2 C60 yield vs. temperature graph.
△: “Laser-furnace” at 500 Torr [2],○: “Laser-furnace” at 200 Torr [3] ,■: present study.

2P-13
Energetics and electronic properties of fullerenes consisting of fused
pentagonal rings
Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba
305-8571, Japan
A fused pentagon trimer, an acepentalene structure, can be a constituent unit of a
two-dimensional covalent network of sp2 C atoms, by assembling them in hexagonalmanner, which exhibits ferromagnetic spin ordering throughout the sheet owing to theflat dispersion band at the Fermi level [1,2]. In the case, the network contains
dodecagonal ring as the pore in the network. By substituting the other polygons smaller
than dodecagon, we can get hollow cage structures of fused pentagonal rings as the zero
dimensional version of graphitic network of fused pentagons. In this work, wetheoretically studied the energetics and electronic structures of the hollow-cagepentagonal network, C28, C56, and C140 fullerenes, using the density functional theory
with generalized gradient approximation. Our calculation showed that the total energiesof these fullerenes are almost the same as that of the planar sheet of fused pentagons,
while those are higher by about 0.2 eV than that of C60. According to the small gap
between the highest occupied and the lowest unoccupied states, C140 exhibits spinpolarization in which the polarized electron spins are extended throughout their cage.
Reference[1] M. Maruyama and S. Okada, Appl. Phys. Express 6, 095101 (2013).
[2] M. Maruyama and S. Okada, Jpn. J. Appl. Phys. 53, 06JD02 (2014).

Corresponding Author: S. Okada
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 97 -

2P-14
Macroscopic aligned single-walled carbon nanotubes achieved withvacuum filtration○ Hao Zhang1, Rong Xiang1, Taiki Inoue1, Shohei Chiashi1, Shigeo Maruyama1,2
12

Department of Mechanical Engineering, the University of Tokyo, Tokyo 113-8656, Japan

National Institute of Advanced Industrial Science and Technology (AIST), Ibaraki 305-8564,
Japan

Excellent electronic, thermal and optical properties found in individual single-walledcarbon nanotubes has made this one-dimensional material one of the best candidates formany new-generation applications such as nanoprobes, molecular reinforcements incomposites, displays, sensors, energy-storage media and molecular electronic devices [1].
Recently, a novel vacuum filtration method (Fig. 1) was proposed by Xiaowei He et al.
[2] for fabricating well aligned SWNT films at macro scale. However, the aligned films
made from different SWNTs vary markedly in quality and the detailed mechanism is still
unclear. Here, we are trying to build a connection between starting materials and thedegree of the alignment.
By far, with the recipe from this pioneering paper, horizontally aligned SWNT arrays
at centimeter scale have been successfully reproduced as confirmed by SEM. (Fig. 2)
Further, the characterization of the films with Resonance Raman spectroscope, UV-visNIR spectrometer, TEM and etc. will be presented.

Alignment direction

Fig. 1. A schematic of the vacuum filtration setup.

[1]. R. H. Baughman et al., Science 297, 787-792 (2002)[2]. X. He et al., Nature Nanotech, 10.1038 (2016)
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-7434, Fax: +81-3-5841-7437
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 98 -

Fig. 2. SEM image of aligned SWNT film
produced with vacuum filtration method and
SEM image of higher magnification (Inset).

2P-15
Selective phonon mode generations in single wall carbon nanotubes andgraphene nanoribbons○ Ahmad R.T. Nugraha, Eddwi H. Hasdeo, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Ultrashort laser pulses given to a single wall carbon nanotube (SWNT) sample with duration
less than a phonon period in the SWNT may generate lattice oscillations coherently, known as
coherent phonons. By using sub-10-fs laser pulses, many coherent phonon modes withfrequency around 100-3000 cm-1 could be observed in an enriched SWNT sample [1]. This
opened up a possibility to utilize particular coherent phonon modes of the SWNT as ananoresonator with a wide frequency range. Besides SWNTs, graphene nanoribbons (GNRs)
also have several modes available in the THz regime [2]. However, in order to take advantage
of each coherent phonon mode as a basis of phononic devices [3], we have to select a single
coherent phonon mode among many phonon modes that have been excited.
In this work, we theoretically investigate theultrafast pulse-train technique in pump-probe
spectroscopy to keep a single coherent phononmode while suppressing the other phonon modes in
SWNTs and GNRs. In particular, we focus on theselectivity of the radial breathing mode (RBM) and

Figure 1 Ratio of coherent G band and RBM
intensities for a (11,0) SWNT.

the G band for a given SWNT [4]. By adjusting thelaser pulse width and pulse train repetition period, we find that if the repetition period
matches with integer multiple of the RBM phonon period, the RBM phonon could be kept
while the other modes are suppressed. As for the G band, which has a higher frequency(shorter period) than the RBM, the number of pulses in the pulse train also affects theselectivity through the ratio of the G band and RBM’s periods so that some special values ofthe pulse number could give a good selectivity (Figure 1). By understanding the selectivity ofeach phonon mode, we expect that it could be possible to develop SWNT and GNR’s
phononic devices in the near future.
[1] Y.-S. Lim et al., Nano Lett. 14, 1426-1432 (2014).
[2] G. D. Sanders et al., Phys. Rev. B 85, 205401 (2012).
[3] R. Ruskov and C. Tahan, J. Phys.: Conf. Ser. 398, 012011 (2012).
[4] A. R. T. Nugraha et al., J. Phys. Condens. Matter 29, 055302 (2017).
Corresponding Author: A.R.T. Nugraha
Tel: +81-22-795-6442, Fax: +81-22-795-6447, E-mail: nugraha@flex.phys.tohoku.ac.jp- 99 -

2P-16
Electrically conductive multi-walled boron nitride nanotubes by catalytic
etching○Do-Hyun Kim1, Ho-Kyun Jang1, Min-Seok Kim2, Sung-Dae Kim2, Dong-Jin Lee3, Gyu Tae
Kim1
1

School of Electrical Engineering, Korea University, 5-Ga, Anam-dong, Seongbuk-Gu,
Republic of Korea
2
Metallic Materials Division, and Advanced Characterization and Analysis Group, Korea
Institute of Materials Science, 797 Changwondaero, Changwon, Republic of Korea
3
New Functional Components Research Team, Korea Institute of Footware & Leather
Technology, 152 Danggamseo-ro, Busanjin-gu, Busan 614-100, Republic of Korea
Boron nitride nanotubes (BNNTs) are hardly oxidized below 1000 °C due to their superior
thermal stability and electrically almost insulators with a band gap of 5 eV in the electronic
structure. Hence, oxidizing BNNTs at low temperature and converting their electricalproperties to a conductive behavior are challenging tasks.
In this work, we report that BNNTs can be etched at low temperature in the air by catalyticoxidation. To realize this, multi-walled BNNTs (MWBNNTs) were impregnated with Co
precursor (Co(NO3)2·6H2O) and simply heated at 350 °C under air atmosphere. Consequently,
various shapes of etched structures like pits and thinned walls were formed on the surface of
MWBNNTs. Furthermore, the original crystallinity and the tubular structure of MWBNNTs
were kept in the etched MWBNNTs in spite of oxidation. Interestingly, insulating MWBNNTs
showed a conductive behavior in the electrical measurement after etching by catalyticoxidation. It was revealed by theoretical calculations that a new energy state in the gap and a
Fermi level shift contributed to MWBNNTs being conductive.

Fig.1 Etched multi-walled boron nitride nanotubes by catalytic oxidation

Corresponding Author: Do-Hyun Kim, Gyu Tae Kim
Tel: +82-2-3290-4791
E-mail: nanotube@korea.ac.kr, gtkim@korea.ac.kr- 100 -

2P-17
Artificial muscle using single wall carbon nanotube bundles○ Nguyen T. Hung, Ahmad R. T. Nugraha, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, JapanAn artificial muscle is a novel actuator based on a variety of polymers or composites thatchange their shape when excited electrically. A composite of single wall carbon nanotubes(SWNTs) is known to be one of the strongest and stiffest materials [1, 2], and it can reversibly
contract and expand in volume under an applied voltage, similar to the natural muscle. Almost
two decades ago, Baughman et al. [3] built an ultra-strong artificial muscle from bundles of
SWNTs with electrochemical charging, in which the artificial muscle could be about 100
times stronger than the natural muscle in terms of force generated per unit area. Their work
indicated importance of understanding the effects of doping on the structural deformation of
the bundles of SWNTs. However, while both structural deformation and electronic structureof the individual SWNTs under electromechanical charging have been extensively
investigated by theory [4, 5], a detailed first-principles study for the SWNT bundles isnecessary to discuss since most of the actuators are made of the bundles. Now since SWNTs
are commercially available, the application for artificial is now getting promising.
In this work, we perform a first-principles simulation to
discuss the effects of electron and hole doping on the
structural deformation and on the electronic structure of
SWNT bundles. We use a (6, 6) SWNT bundle as a model[Fig. 1] and we predict a mechanical deformation in the (6,6) SWNT bundle as a function of gate voltage, which
provides the basis for electromechanical actuators. The (6, 6)
SWNT bundle exhibits a broken symmetry and pseudogaps
around the charge neutral condition with a band gap ofFigure 1 (6, 6) SWNT bundle model.
about 0.41 eV. We find that the magnitude of the actuation
response of hole-doped (6, 6) SWNT bundle is larger than that of electron-doped (6, 6)
SWNT bundle, suggesting the hole-doped SWNT bundle for a building block of artificial
muscles.
[1] M. F. Yu et al., Science 28, 637 (2000).
[2] N. T. Hung et al. Comput. Mater. Sci. 114, 167 (2016).
[3] R. H. Baughman et al., Science 284, 1340 (1999).
[4] L. C. Yin et al., Carbon 49, 4774 (2011).
[5] Y. N. Gartstein et al., Phys. Rev. Lett. 89, 045503 (2002).
Corresponding Author: Nguyen Tuan Hung
Tel: +81-22-795-6442, Fax: +81-22-795-6447, E-mail: nguyen@flex.phys.tohoku.ac.jp- 101 -

2P-18
Electrochemical Properties of Nitrogen-Doped Vertically Aligned
Multi-Walled Carbon Nanotubes Prepared by Defluorination○Rei Nonomura1, Takashi Itoh2, Yoshinori Sato3, Masashi Yamamoto3, Tetsuo Nishida3,
Kenichi Motomiya1, Kazuyuki Tohji1, Yoshinori Sato1,4,*
1

Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan
Frontier Research Institute for Interdisciplinary Sciences, Tohoku University, Sendai
980-8579, Japan
3
Stella Chemifa Co., Osaka 595-0075, Japan
4
Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research,
Shinshu University, Matsumoto 390-8621, Japan
2

Vertically aligned carbon nanotubes (VACNTs) have been utilized as electrodes of electric
double-layer supercapacitors (EDLSCs) because of their excellent electrical properties bywhich the EDLSCs exhibit high power densities with keeping specific capacitances, incompared with activated carbon electrodes. In chemically functionalized CNTs, the specificcapacitances are larger than those of unfunctionalized CNTs. Therefore, functionalized
VACNTs are great candidates as electrodes for high-performance EDLSCs. Here, we report
the synthesis of nitrogen-doped vertically aligned multi-walled carbon nanotubes(VAMWCNTs) via defluorination[1,2] and their electrochemical properties.
As-grown VAMWCNTs synthesized by a chemical vapor deposition method were
fluorinated using a mixture of F2 (20%) and N2 (80%) at 250 °C for 30 min. The
fluorinated-VAMWCNTs (F-VAMWCNTs) placed at the center into a quartz tube werereacted with flowing a mixture of NH3 (1%) and N2 (99%) at the temperature of 573-873 K
for 30 min (N-VAMWCNTs). The samples were characterized using scanning electron
microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray
photoelectron spectroscopy (XPS), and Raman scattering spectroscopy. Electrochemical
properties were evaluated by cyclic voltammetry and AC impedance spectroscopy using a twoor three electrode coin-type cell in propylene carbonate (PC) electrolyte containing
trietylmethylammonium tetrafluoroborate (TEMABF4)[3]. We will report the detailed data inthis presentation.
[1] K. Yokoyama et al. Carbon 94, 1052 (2015).
[2] K. Yokoyama et al. J. Mater. Chem. A 4, 9184 (2016).
[3] Y. Honda et al. J. Power Sources 185, 1580 (2008).
*Corresponding Author: Yoshinori Sato
Tel: +81-22-795-3215, Fax: +81-22-795-3215,
E-mail: yoshinori.sato.b5@tohoku.ac.jp- 102 -

2P-19Synthesis and morphology control of carbon nanotubes on substrates
for electron emitter application○Sae Kitagawa1, Hisashi Sugime2, Suguru Noda1,*
1
2

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Waseda Institute for Advanced Study, Waseda University, Tokyo 169-8050, Japan

Electron emitters are used for display, X-ray tube and so on. In conventional electron
emitters, thermionic emission is widely used, in which electrons are emitted from heatedfilament. But this method has some problems, such as large power consumption and shortlifespan. Field emission (FE), in which electrons are emitted by high electric field, is analternative method, which can solve these problems [1]. Carbon nanotubes (CNTs) are asuitable material for electron emitters due to their high aspect ratio, electric conductivity,
thermostability and mechanical strength. In order to enhance electric field and increase
current and lifespan, adequate density of CNT tips is necessary. Lithography is often used toform microstructure of CNTs and previously our laboratory reported that morphology
controlled CNTs by e-beam lithography showed good FE performance [2,3].
In this work, we fabricate CNT-FEs with controlled morphology via quick self-organization
processes without using lithography. Textured Si wafers and stainless steel mesh (SUS 304)
are used as growth substrates for CNTs. Si wafers are treated with HF to remove surface SiO2
and then etched in 2 wt% NaOH solution to form surface texture (Fig. 1). Fe/TiN and
Fe/Al/Ti are sputtered on the textured Si substrate and SUS mesh, respectively. These
substrates are set in a CVD reactor (inner diameter of 34 mm, heating zone length of 300 mm)
and annealed for 3 min at 700 C under H2 flow. Subsequently, C2H2 as carbon source isintroduced to grow CNTs under 1.0 vol% C2H2/10 vol% H2/Ar for 1–5 min. Obtained CNTs
are evaluated in a diode configuration at <4×10–5 Pa. CNTs/substrate is used as cathode,which opposes to anode of ITO glass with a 500 µm gap using glass spacer. Emitter array size
is approximately 0.80.8 cm2. Sweep voltage (0–600V) is applied for 100 times and FE
properties and lifespan are evaluated.
Fig. 2 shows a SEM image of CNTs synthesized for 5 min on a SUS mesh. The Ti/Al
under layer enables CNTs growth on the SUS mesh, which results in morphologicallycontrolled CNTs. Fig. 3 shows FE currents extracted from the CNTs on SUS mesh. Electrons
are efficiently emitted by external field with 2 mA at 600 V.

Fig. 1. Textured Si substrate

Fig. 2. CNTs on mesh (5 min)Fig. 3. I-V curves[1] Yuan Cheng et al, C. R. Physique 4 (2003).
[2] Y. Shiratori et al, Nanotechnology 20 (2009).
[3] K. Sekiguchi et al, Carbon 50 (2012).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 103 -

2P-20Analysis of Pt catalyst for SWNT growth by In-situ XANES○Makoto Kumakura1, Hoshimitsu Kiribayashi1, Takahiro Saida2, Shigeya Naritsuka 1,
Takahiro Maruyama2
1

Department of Material Science and Enginnering,Meijo Univ, 1-501 Shiogamaguchi,
Tempaku, Nagoya 468-8502, Japan2
Department of Applied Chemistry, Meijo Univ, 1-501 Shiogamaguchi, Tempaku, Nagoya
468-8502, Japan
Single-walled carbon nanotubes (SWNTs) have been anticipated for applications toelectronic devices because SWNTs have superior electrical characteristics. The smaller an
SWNT diameter, the wider its bandgap, so it is important to grow small-diameter SWNTs. So
far, using Pt catalyst, we have succeeded in obtaining SWNTs with small diameters below 1.0
nm [1]. However, growth mechanism of SWNTs from Pt catalysts has been unclear. In thisstudy, we investigated chemical states of Pt catalysts during SWNT growth by in-situ X-ray
absorption near edge structure (XANES).
Using Pt catalysts, SWNTs were grown on SiO2/Si substrates by CVD method in in-situ
CVD chamber. The growth temperature and the ethanol pressure were 700 °C and 20 Pa,
respectively. The growth time was 60 min. In addition, Pt catalysts just before and after
heating at 700 °C were analyzed. XANES were carried out at BL5S1 of Aichi SR.
Fig. 1 shows Pt L3-edge XANES spectra of Pt catalysts at each process. After deposition,
the white line intensity was larger than that of Pt foil, but became smaller after heating.
During SWNT growth, XANES spectra did not change. This indicates that Pt catalysts werereduced after heating and that Pt catalysts were metallic during SWNT growth [2]. Thismeans that carbon atoms did not solved into Pt catalysts and diffused on the catalyst surface
during SWNT growth. Our results indicate that SWNTs grew from Pt catalysts based on thevapor-solid-solid (VSS) model.

Fig.1 In-situ Pt L3-edge XANES spectra of Pt catalysts for the samples (a)as deposition and during heating at
700 °C and (b) after SWNTs growth for 6 and 58 min.
[1] T. Maruyama et al. Mater. Express 1 (2011) 267.
[2] T. Shishido et al., Catal. Lett. 131 (2009) 413.
Corresponding Author: Takahiro Maruyama
Tel: 052-838-2386
E-mail: takamaru@meijo-u.ac.jp- 104 -

2P-21Time-dependent selective synthesis and growth mechanism of
single-walled carbon nanotubes from sputtered W-Co catalyst
1

1

2

1

1

○ Hua An , Rong Xiang , Akihito Kumamoto , Taiki Inoue , Shohei Chiashi , Yuichi

Ikuhara2, Shigeo Maruyama1, 3

1 Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656,
Japan
2 Institute of Engineering Innovation, The University of Tokyo, Yayoi 2-11-16,
Bunkyo-ku, Tokyo 113-8656, Japan
3 Energy NanoEngineering Laboratory, National Institute of Advanced Industrial
Science and Technology (AIST), 1-2-1 Namiki, Tsukuba, 305-8564, Japan
The potential industrial applications are impeded by the mixed chiralities of
as-grown SWNT assemblies. Direct synthesis of SWNTs with single chirality ischallenging but always attracts considerable attention among researchers. Catalyst
plays an important role in the chirality definition of SWNTs during growth process.
Bimetallic catalysts have been explored for the selective growth of SWNTs because of
their inhibition for the aggregation of catalyst particles at growth temperature. The
Co7W6 clusters were reported to successfully grow a single chirality SWNT (12, 6),with over 90% abundance and a zigzag SWNT (16, 0), with near 80%, by controllingthe catalyst structure and growth conditions with a high-temperature reduction andgrowth [1, 2]. We have proposed a simple sputtering method to prepare W-Co catalyst
to selectively grow (12, 6) SWNTs with the enrichment of 50%-70% where theselectivity is strongly associated with the intermediate structure of Co6W6C [3]. A 5
min-growth with alcohol catalytic chemical vapor deposition (ACCVD) [4] will give
only Co particles indicating a complicated evolution of catalyst structure. Here wewill present a detailed time-dependent study on the selectivity and the structural
evolution within 5 min-growth with ethanol. The complicated structure evolution will
be illustrated by electron diffraction and energy-dispersive X-ray spectroscopy (EDS)
mapping. The as-reduced catalyst particles are confirmed to be W and W6Co6C. Upon
the introduction of ethanol, additional W will be removed gradually through a gas
phase reaction and the ratio of W decreases. The further loss of W will result in the
precipitation of Co from the carbide particles. A possible mechanism will be discussed
in detail.
[1] F. Yang et al., Nature. 510, 522(2014).
[2] F. Yang et al., J. Am. Chem. Soc. 137, 8688 (2015).
[3] H. An, et al., Nanoscale, 8 (2016) 14523.
[4] 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- 105 -

2P-22Extraction of High-Purity Single-Chirality Single-Wall Carbon Nanotubes
by Precise Tuning of pH using CO2 Bubbling○Yota Ichinose, Junko Eda, Yutaka Maniwa, Yohei Yomogida, Kazuhiro Yanagi
Tokyo Metropolitan University, Tokyo 192-0397, Japan
Gel-column chromatography is known as a powerful tool to extract a specific chirality ofsingle-chirality single-wall carbon nanotubes (SWCNTs) in high-purity from a solution with amixture of different chiralities of SWCNTs [1]. In this purification processes, we sometimes
find that extraction results vary how long eluent solutions are left in ambient air. It is reported
that pH of eluent solutions influences on the extraction results [2]. Thus we thought that theCO2 in the air would induce the pH changes
and then influence the result. To clarify thishypothesis, we adjusted the the pH of theeluent solutions using CO2 bubbling, andthen investigated how slight difference of pH
influences on extraction results.
In this study, we investigated the influenceof pH on the basis of a reported technique toextract the single-chirality SWCNTs without
pH adjustment [1]. We found that metallic
SWCNTs were residual (original, Fig.1) after(6,5) chirality extraction. However, tosystematically and precisely adjust the pH
value of the eluent solutions, from 8.2 to 7.7
in 0.1 steps by CO2 bubbling, we found that
Fig. 1. Removal of metallic SWCNTs using
systematically different pH solutions
the residual metallic SWCNTs could becompletely removed at a proper condition (atthe pH of ~8.0). As a result, we could obtainhigh-purity single-chirality (6,5) SWCNTs(Fig. 2). The purity of the sample was
evaluated to be more than 99% from opticalabsorption spectra, and preparation of such
purity sample was crucial for correct
evaluation of thermo-electric performance of
SWCNTs.
Reference:[1] Yomogida et al., Nature Commun 7, 12056 (2016)[2] Hirano et al., ACS Nano 7, 10285 (2013)
Corresponding Author: K. Yanagi
Tel: +81-42-677-2493,
E-mail: yanagi-kazuhiro@tmu.ac.jp- 106 -

Fig. 2. Optical absorption spectrum of (6,5)
SWCNTs2P-23Magnetic field effects on the growth process of SWCNTs andexamination of its mechanism○Yasumasa Takashima, Atom Hamasaki, Jin Uchimura, Sumio Ozeki
Graduate School of Science and Technology, Shinshu University,
Matsumoto, Nagano 390-8621, Japan
Magnetic fields have possibility controlling carbon structure, which leads to various
functions. We reported magnetic field effects (MFEs) on a few carbon materials [1-2].
Number of crystallite of graphite precursor was increased by magnetic fields during
heat-treatment of coal tar pitch and multi-walled carbon nanotubes aligned to the direction ofa magnetic field. These structural changes were explained by magnetic orientation of carbon
hexagonal layer. In this study, MFEs on single-walled carbon nanotubes (SWCNTs) was
found, although the magnetic orientation was not observed in its growth process.
Carbon materials including SWCNTs grew on carbon paper substrate by thermal
decomposition of alcohols dissolving cobalt (II) acetate tetrahydrate.
The liquid
decomposition method was carried out at 1053 K by resistance-heating of a solution undermagnetic field of up to 10 T using a superconducting magnet.
Metallic SWCNTs of just 1.0 nm diameter grew preferentially under magnetic fields(Fig. 1). Sub-peak of C 1s in X-ray photoelectron spectra at 288.5 eV decreased withincreasing magnetic field, which corresponds to a change in carbon-oxygen bond (Fig. 2).
Structural changes in SWCNTs were possibly brought about by an anomalous growthenvironment due to magnetic fields.

Fig. 1. Raman spectra excited with 532 nm of carbon
materials prepared under various magnetic fields.

Fig. 2. C 1s spectra of carbon materials
prepared under 0 and 10 T.

[1] A. Sakaguchi, A. Hamasaki, T. Sadatou, Y. Nishihara, S. Yamamoto, Y. Sekinuma, S. Ozeki, Chem. Lett.,
2012, 41, 1576.
[2] A. Sakaguchi, A. Hamasaki, S. Ozeki, Chem. Lett., 2013, 42, 304.
Corresponding Author: Atom Hamasaki
Tel: +81-263-37-2466, Fax: +81-263-37-2559, E-mail: atom@shinshu-u.ac.jp- 107 -

2P-24
Chemical reaction analysis of Fe-Co and Co-Cu clusters with ethanol
by FT-ICR mass spectrometer○Ken Mizutani1, Yoshinori Sato1, Hiroya Minowa1, Ryohei Yamada1,
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, JapanThe alcohol catalytic chemical vapor deposition (ACCVD) is an efficient method tosynthesize single walled-carbon nanotubes (SWCNTs). In ACCVD method, alcohol is used as
the carbon source and metal nanoparticles, such as Fe, Co, Cu, or binary alloy of these metals
are used as the catalyst. The alcohol molecules are decomposed on the catalyst and supply
carbon atoms. The choice of catalysts affects the quality and quantity of SWCNTs. For instance,
Fe-Co gives highly crystalline SWCNTs with high yield [1], while Co-Cu gives small-diameter
SWCNTs compared to other catalysts [2]. However, the chemical reactions between these metal
catalysts and alcohol molecules are unclear and understanding the reactions contributes to thedevelopment of the synthesis method.
In this study, the chemical reactivity of Fe-Co and Co-Cu clusters was investigated by
Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. These clusters
generated by laser vaporization are trapped in a strong magnetic field and reacted with ethanol.
The reaction processes can be observed as the change of the mass spectra depending on thereaction time. Figure 1 (a) shows that an ethanol molecule is simply chemisorbed to Fe-Co
clusters. On the other hand, Fig. 1 (b) shows that an ethanol molecule is not simply chemisorbed
to Co-Cu clusters, and Con-1Cu cluster is more stable than other compositions.

Fig. 1 Mass spectra of (a) FenCo7-n and (b) ConCu7-n clusters reacted with ethanol.
[1] E. Flahaut et al., Chem. Phys. Letters 300, 236 (1999).
[2] K. Cui et al., Nanoscale 8, 1608 (2016).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421, E-mail: maruyama@photon.t.u-tokyo.ac.jp- 108 -

2P-25Carrier injection in nearly free electron states of graphene
nanoribbons by edge hydroxylation
Remi Taira, Ayaka Yamanaka, and Susumu Okada
University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8571 JapanWork function of the graphene edges is sensitive to the edge shapes and edge functional groups.
It has been demonstrated that the work function of edges of graphene ribbons is tunable byattaching appropriate chemical functional group; a work function of zigzag edges functionalizedby hydroxyl group is smaller than those by carboxyl, ketone, and carbonyl groups [1]. The fact
implies that the free electron carriers are induced by the asymmetrical edge functionalization ofgraphene nanoribbon, one of which edges is functionalized by hydroxyl group. Thus, in thiswork, we aim to investigate the electronic properties of asymmetrically edge functionalizedgraphene nanoribbons containing hydroxyl group, using the density functional theory with thelocal density approximation. To investigate their electronic structures, we consider the graphene
nanoribbon with width of 1.5 nm and zigzag edges of which edges are terminated byfunctionalized groups, -H, -O, -OH, -COH, and -COOH. Figure 1 shows the electronic structureof the asymmetrically terminated graphene ribbons containing hydroxyl group. For the edges
with hydroxyl group, we found that the nearly free electron (NFE) state substantially shifts
downward and crosses the Fermi level, indicating the free electron carriers are generated
alongside the hydroxylated edge of graphene ribbons.

H-OH

O-OH

OH-COH

OH-COOH

Fig. 1: Electronic structure and the wave function of the branch of conduction band of asymmetrically edge
functionalized graphene ribbons containing hydroxyl group.

[1] R. Taira, A. Yamanaka, and S. Okada, Appl. Phys. Express 9, 115102, (2016).
Corresponding author: R. Taira (resoccermi222@gmail.com)- 109 -

2P-26

Fermi level tuning of N-doped graphene by an external electric field
Manaho Matsubara and Susumu Okada
Graduate School of Pure & Applied Sciences, University of Tsukuba, Tsukuba 305-8571
Japan
Graphene has been keeping a premier position not only in the field of nanoscale sciences but also
in the field of nanotechnology due to its unique structural and electronic properties. For applicationin nanotechnology, owing to the tunable electronic structure by the external condition and the highcarrier mobility, graphene could be a constituent material for electronic, optical, optoelectronic, andcatalytic devices, being expected to exhibit remarkable efficiency. For the applications, the Fermi
level tuning is the one of important issues for controlling their functionality and operation. In
addition to pristine graphene, graphene can form hybrid structure with foreign materials, resulting
in further variation in their electronic properties that allow them emerging materials for future
devices. N-doped graphene is one of representative hybrids exhibiting unusual electronic properties
being applicable for electronic and catalytic devices. In such devices, to tailor the device properties,
it is mandatory to precisely tune the Fermi level by the external electric field. Thus, in this work, weare interested in the effect of external electric field on band structures and carrier accumulation, and aim to
give theoretical insight into the electronic properties of N-doped graphene under the external electric field,
using the density functional theory combined with effective screening medium method. Here, we consider
four possible N-doped graphene; graphitic, pyridinic, and pyrrolic structures (Fig. 1).

Our calculations show that N-doped graphene does not possess the Dirac cone but a finite energy
gap in their π electron state irrespective to the defect species. On the other hand, the electronic
structures near the Fermi level are sensitive to the defect species. Under the external electric field,
the electronic states near the Fermi level exhibit unusual modulation that depends on the
distribution of wave function of these states: The electronic state associated with the dangling bonds
substantially shifts under the external electric field while the π states are insensitive to the electricfield. According to the asymmetric shift of the electronic states, the electronic structure of N-doped
graphene under the electric filed does not exhibit ridged band nature.

Fig.1：Geometric structures of N-doped graphene.

Corresponding author: M. Matsubara
Email: mmatsubara@comas.frsc.tsukuba.ac.jp- 110 -

2P-27
Electronic structures of graphene exposed to electrolyte solution○Mari Ohfuchi1,2
1

2

Fujitsu Laboratories Ltd., Atsugi 243-0197, Japan
Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603,
Japan

Power generation from the flow of electrolyte solution is an emerging technology forenvironmental energy harvesting. A voltage of a few millivolts has been generated by usinggraphene [1] or carbon nanotube thin films [2]. However, the underlying physics is poorly
understood. In this work, we study the graphene exposed to electrolyte solution using density
functional theory, considering the oxygen molecules (O2) that can be dissolved in the solution.
When the solution has only electrolyte ions, as shown in Fig. 1(a), the graphene has no net
charge (see the band diagram). The sodium ion (Na+) near the graphene produces a negative
charge distribution in the graphene; however, the same amount of the opposite charge is
induced around it, The chlorine ion (Cl−) near the graphene gives the same results. On theother hand, when O2 lies on the graphene (Fig. 1(b)), the band diagram and the charge
distribution show that electronic charge is transferred from the graphene to O2. Whenelectrolyte ions and O2 coexist, as shown in Fig. 1(c), Cl− near the graphene makes more
electronic charge transfer from the graphene to O2. The O2 molecules seem to be able to act asa charge source or sink. This may be related to the voltage generation from the electrolyte
solution flow using nanocarbon materials. This work was supported by CREST, JST.

Fig.1: Optimized atomic structures, band diagrams, and induced charge distribution for electrolyte solution ongraphene. The solution has (a) only Na + and Cl−, (b) only O2, and (c) both of electrolyte ions and O2. The gray(black and white) sticks represent graphene (water). The black, dark gray, and light gray spheres indicate O, Na,
and Cl atoms. The solid line and the two dotted curves in the band diagrams show the chemical potential and the
majority and minority spins. The dark and light gray colors indicate negative and positive charges, respectively.
[1] J. Yin et al., Nat. Nanotechnol. 9, 378 (2014). [2] T. Yasunishi et al., The 51th FNTG Symp., 3P-10 (2016).
Corresponding Author: M. Ohfuchi, E-mail: mari.ohfuti@jp.fujitsu.com- 111 -

2P-28Magnetic interactions between Edge-state spinsand Ferrocenium ion spins○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

Absorbance (arb. unit)

Activated Carbon Fibers (ACFs) is promising as nanographene-based host material having
localized spins originating in zigzag edges of graphene. We have successfully developed amagnetic host-guest system between ACFs and Ferrocene (FeCp2) based on - stack design[1]. The spin magnetism of guest FeCp2+ was induced by charge-transfer host-guest
interaction between nanographene host and FeCp2, resulting in the 5 times larger spin
concentration of FeCp2-ACFs synthesized with FeCp2 vapor of 5.6×103 Pa than that of ACFs.
In this study, we investigated the magnetic interactions between induced ferrocenium ion spinand nanographene spin by using ESR and FT-IR.
No X-band ESR signal was observable even for the sample prepared at 100 Pa due toextremely broad linewidth. ESR linewidth Hpp for the sample prepared at 15 Pa (1/300 lower
pressure than that in the previous study) shows the 7 times larger than that for ACFs (Fig. 1),
where FeCp2 doping of at the lower pressure was confirmed by FT-IR (Fig. 2). Taking only
dipole interaction into consideration, Hpp should be only 5 times larger than that for ACFs
even for FeCp2-ACFs synthesized at 5.6×103 Pa. The observed “excess” broadening suggests
the presence of the exchange interaction between non-identical spins (nanographene spin and
FeCp2+ spin).

2400

Fig. 1 RT ESR spectra for ACFs and
FeCp2-ACFs synthesized at 55 °C
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002
E-mail: takai@hosei.ac.jp- 112 -FeCp2
(FeCp2-ACFs) - ACFs

700

1000

1300

Wavenumber (cm-1)

Fig. 2 The infrared spectrum of FeCp2 anddifferential absorbance spectrum between
FeCp2-ACFs synthesized at 55 °C and ACFs

2P-29
Electrical properties of reduced graphene oxide by thermal annealing○Takuya Ishida1, Yuta Nishina2, and Nobuyuki Aoki1
1

Graduate School of Advanced Integration Science, Chiba University,
Chiba 263-8522, Japan
2
Research Core for Interdisciplinary Sciences, Okayama University, Okayama 700-8530,
Japan
Graphene oxide (GO) is one of the well-known materials studied since 1850’s. It can besynthesized easily from carbon black. The electrical properties are almost insulating however
it becomes conductive after the reduction process by thermal annealing, UV irradiation in
vacuum, chemical treatment using hydrazine, and so on. Since large scale sheets of graphene
oxide can be provided easily due to recent development of the method, reduced graphene
oxide (r-GO) is expected for the use in electrical devices. Since the hydroxyl groups andoxygen atoms removed from the GO sheet during the annealing process, holy structures are
introduced in the carbon skeleton structure. Such a GO sheet having voids is called as “holygraphene oxide (hGO)”. And then, such a holy structure can be expected as a network ofgraphene-nano-ribbon. However the transport properties of r-hGO sheets have been studied
mainly in the macroscopic scale so far. In this study, we confirmed a transition of transport
properties of r-GO (r-hGO) sheet from macroscopic to mesoscopic transport regime.
The GO material was synthesized from Kish Graphite oxidized by KMnO4 in H2SO4
solution [1]. The GO freaks are dispersed on a SiO2/Si substrate by a spin-coating andreduced by thermal annealing at 473 K in vacuum condition for 20 hours to obtain r-GO films.
Electric contacts were fabricated by electron beam
1 10
lithography to form square-shape channels. The
sizes of each channel are 100 nm, 300 nm, 1 μm, 38 10
μm and 10 μm, respectively. These contacts wereprepared on the same monolayer r-GO sheet to
6 10
confirm the size dependence of the resistance.
4 10
Figure 1 shows channel size dependence of theresistance. The resistance drastically increases when2 10
it is reduced to submicron scale. In a0
two-dimensional square sample, the sheet resistance1010
10Channel size (m)should be independent on the size (scale). The
experimental results suggest that the transport Fig.1. Channel size dependence of r-GO
regime of the r-GO sample changes when it is sample. The broken line is guide for
eyes.
reduced in the submicron scale.
11

Resistance ()

10

10

10

10

-7

[1] N. Morimoto et al., Sci. Rep., 6, 21715, (2016).
Corresponding Author: N. Aoki
Tel:+81-43-290-3430, Fax:+81-43-290-3427
E-mail:n-aoki@faculty.chiba-u.jp- 113 -

-6-5

2P-30Influence of Water Molecules on
Molecular Adsorption induced Charge Transfer in Graphene○Takai Umehara1, 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

Electronic and Structural properties of Graphene as an actual carbon material rather than an
ideal model for two dimensional systems with novel Dirac Fermion is significantly influenced
by the presence of edges, defects and impurities [1], and so on. Especially, surrounding guest
chemical species play an important role for two dimensional host materials like graphene,
where the host-guest interactions though the surface and the interface between supporting
substrate is classified into three types according to the energy scale of interactions; chemical
modification by covalent bonding, charge transfer by electrostatic interaction, and mechanicalstrain by physisorption [3]. In this talk, I would like to focus mainly on the charge transfer
interactions caused by guest chemical species facing with graphene. Indeed, surface
modification of supporting substrate by self-assemble monolayer of molecules having various
electric dipole and eigen frequency of molecular vibration enables tuning of the Fermi energy
EF of graphene [5]. Interestingly, such molecular proximity effects for adsorbed molecules on
the surface of graphene show significant dependence on EF experimentally tuned by gate
voltage, where hole and electron doping by oxygen [4] and hydrazine molecules, respectively,
exhibit opposite dependence on EF. In addition, the kinetic for the charge transfer induced bymolecular adsorption is quite slower in comparison with usual time scale for the electron
system. Moreover, the absolute value of the characteristic times of the charge transfer by
hydrazine (1.25 min) is much faster than that for oxygen (18 min), in the former of whichlarge amount of water molecules coexist as hydration water in contrast to oxygen as dry gas.
This is explained by a mechanism by electrochemical process involving co-existing watermolecule for charge transfer phenomena by molecular adsorption on graphene. Indeed, the isa graphene FET characteristic measurement under precise controlling of atmosphere in UHVchamber reveals that the oxygen induced charge transfer process is much accelerated
accompanied with increasing in partial pressure of water in oxygen gas.
1.8
1.76

F (10-1 eV)[1] T. Enoki, S. Fujii, and K. Takai, Carbon, 50,
3141-3145 (2012).
[2] Y. Kudo, K. Takai, and T. Enoki, J. Mater. Res., 8,1097-1104 (2013).
[3] K. Takai, H. Kumagai, H. Sato, T. Enoki, Phys.
Rev. B, 73, 035435 (2006).
[4] Y. Yokota, K. Takai, and T. Enoki, Nano Lett., 11,3669-3675 (2011).
[5] Y. Sato, K. Takai, and T. Enoki, Nano Lett., 11,3468-3475 (2011).

1.72
1.68
1.64

Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002
E-mail: takai@hosei.ac.jp- 114 -

O₂ + H₂O
O₂

0

10
20
O2 exposure time (min)30

2P-31
Growth of large-area and uniform multilayer hexagonal boron nitride
as an ideal 2D insulator○Sho Nakandakari1, Kenji Kawahara2, Yuki Uchida1, Shigeto Yamasaki,1Masatoshi Mitsuhara,1 Hiroki Ago1,2,3,*
1

Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, Fukuoka 816-8580, Japan
2
Global Innovation Center (GIC), Kyushu University, Fukuoka 816-8580, Japan
3
PRESTO, Japan Science and Technology Agency, Saitama 332-0012, Japan

Recently, hexagonal boron nitride (h-BN, Fig. 1a) has become an important 2D insulator
which significantly improves electrical and optical properties of various 2D materials,
including graphene and TMDCs [1-3]. When these 2D materials are stacked on multilayerh-BN, influences from the SiO2 substrate surface, such as charge impurity, surface roughness,and optical phonons, are screened by the h-BN, realizing the intrinsic properties of the 2D
materials. However, most of the h-BN films employed in previous works are obtained bymechanical exfoliation from bulk h-BN crystal [1-3], which limits further development of 2D
device applications. Although CVD has been applied to the growth of h-BN, monolayerh-BN is widely obtained by CVD [4,5] which is not thick enough to screen the influence froma SiO2, while there exists a problem in uniformity of CVD-grown multilayer h-BN [6,7].
In this study, we demonstrate the synthesis of highly uniform multilayer h-BN by catalytic
CVD. Growth of multilayer h-BN requires the controlled segregation of B and N atoms
from a metal catalyst. We found that there are three essential factors that determine thecrystallinity and uniformity of multilayer h-BN; (i) precursor feedstock, (ii) [B]/[N] balance,and (iii) catalyst composition. Throughout a systematic study, we succeeded in growing thelarge-area, highly uniform multilayer h-BN by using borazine (B3N3H6) feedstock andepitaxial metal alloy thin film catalysts. Figure 1b shows the optical image of a transferredmultilayer h-BN film, indicating the uniformity of the film. The Raman spectra confirmed
the growth of h-BN (Fig. 1b inset). To assess the quality of the CVD-grown multilayerh-BN, monolayer WS2 grains were grown on the h-BN and SiO2 substrates (Fig. 1c). Much
more intense and narrower PL spectrum was observed for the WS2 grains grown on the h-BNthan those grown on SiO2. This suggests that our multilayer h-BN film is almost comparable
to exfoliated h-BN flakes [3]. Our achievement of the synthesis of uniform multi-layerh-BN is expected to stimulate industrial applications of 2D materials.

Fig. 1 (a) Atomic model of multilayer h-BN. (b) Optical micrograph and Raman spectra of uniform
multilayer h-BN transferred on SiO2. (c) PL spectra of WS2 grown on h-BN/SiO2 and SiO2 substrates.
References: [1] C. R. Dean, Nat. Nanotechnol., 5, 722 (2010). [2] X. Cui, Nat. Nanotechnol, 10, 534 (2015). [3]M. Okada, ACS Nano, 8, 8273 (2014). [4] K. K. Kim, Nano Lett., 12, 161 (2012). [5] Y. Stehle, Chem. Mater.,
27, 8041 (2015). [6] S. K. Jang, Sci. Rep., 6, 30449 (2016). [7] S. M Kim, Nat. Commun., 6, 8662 (2015).
Correspondence: H. Ago (Tel&Fax: +81-92-583-8815, E-mail: h-ago@gic.kyushu-u.ac.jp)- 115 -

2P-32
Enhancement of laser-induced water decomposition by 2D sheets studied byfirst-principles simulations II○Yoshiyuki Miyamoto1, Hong Zhang2, Xinlu Cheng3 Angel Rubio4
1

Research Center for Computational Design of Advanced Functional Materials, AIST,
Umezono, 1-1-1 Central 2, Tsukuba 305-0685, 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 and Center for
Free-Electron Laser Science, Luruper Chaussee 149, 22761 Hamburg, Germany
This work was motivated by recent report of metal-free photocatalysis consisting ofgraphitic carbon nitride (gC3N4) [1,2] and we have proposed usage of high-intensity pulse
laser as an alternative to ordinary light-source for achieving higher yield of H2O
decomposition. Continuing to our presentation in the last meeting, we are still investigating
property of 2D material in enhancement of laser-induced H2O decomposition by means of thefirst-principles simulation. Here we present updated results; 1) We have compared thresholdlaser intensity of H2O decomposition for an isolated molecule and for molecules above
2D-sheets, and we will present dependence of pulse-width of the laser. 2) We have proposed
an idea to combine electrical hole-doping in graphene and pulse-laser H2O decomposition forhigher yield of H and OH generation.
We have obtained significantly lower threshold laser-intensity of H2O decomposition when
H2O is above 2D sheets. [3] The cause of the threshold lowering is attributed as a fieldenhancement effect by the 2D sheets studied by this work. The threshold is further decreased
when we extended the full-width-of-half-maximum (FWHM) from 10 fs to 20fs, yet theestimated laser fluence for the H2O becomes larger with wider FWHM. The details of thecomputational method, results,
and potential application forgenerating hydrogen fuel will
be discussed. The figure shows
snapshot of the H2O dynamics
which was strongly bind tographeneunderelectricalhole-doping condition. (At the Snapshots of H2O dynamics upon pulse-laser illumination
beginning, the O-side of water (FWHM=10fs, 800nm) with laser field intensity 7V/Å.
is closer to graphene due to polar nature of the H2O molecule.)
This work is supported by the fund from JSPS KAKENHI, Project No.JP16H00925.
[1] X. Wang et al, Nature Mat. 8, 76 (2009).
[2] J. Liu et al, Science 347,970 (2015).
[3] Paper in preparation.
Corresponding Author: Y. Miyamoto
Tel: +81-29-849-1498, Fax: +81-29-851-5428,
E-mail: yoshi-miyamoto@aist.go.jp- 116 -

2P-33
Photoluminescence and photocurrent properties of monolayer WSe2 FETs
fabricated by dry-transfer process○Xiaofan Wang, Wenjin Zhang, Nur Baizura Mohamed, Dezhi Tan, Hong En Lim,
Yuhei Miyauchi, Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Recently, transition metal dichalcogenides (TMDs) have attracted much attention as novel
two-dimensional semiconductors, which opens the new research fields [1,2]. Thesematerials are also promising candidates for the future optical and electronic devices such as
light emitting diodes and field effect transistors (FETs) [3]. The standard TMD FETs
reported to date have been fabricated using conventional electron-beam orphoto-lithography technique followed by multiple wet processes, in which the process using
the polymer may affect the device performance and optical properties [4]. As an alternative
method, the multilayer MoS2 FET fabricated by dry-transfer process has been reported [5].
In this work, we investigated the device performance and optical properties of monolayer(1L) WSe2 FET fabricated by the dry-transfer process with Pt electrode. Figure 1(a) shows
the transfer characteristics of 1L WSe2 device. The sharp and large on/off current ratio of~104 are observed. We extract the high field-effect hole mobility of 86.3 cm2/V∙s, which is ahigh value to compare with the devices fabricated by standard method. This suggests thatthe quality of 1L WSe2 FET device fabricated by(a) -5[1] Q. H. Wang et.al., Nat. Nanotechnol. 7, 699 (2012).
[2] S. Mouri et.al., Nano Lett. 14, 5944 (2013).
[3] B. Radisavljevic et.al., Nat. Nanotechnol. 6, 147(2011).
[4] A. G. F. Garcia et.al., Nano Lett. 12, 4449 (2012).
[5] Yang et.al., J. Vac. Sci. Tech. B 32, 061203 (2014).
Corresponding Author: Kazunari Matsuda
Tel/Fax: +81-774-38-3460
E-mail: matsuda@iae.kyoto-u.ac.jp

10

VD=2 V

10-6

ID (A)

10-7
10-8

10-9
-80

(b)
PL Intensity (a .u.)

the dry-transfer method shows high quality.
Figure 1(b) shows the photoluminescence (PL)spectra of 1L WSe2 with varying thebias-voltages (VG) at room temperature. The
spectral change of PL spectra depending on the
VG is observed. We will discuss the detail of PL
and photocurrent properties in high quality 1L
WSe2 fabricated by the dry-transfer process.

1.5

-40

0
VG (V)

40

80
-70 V
-40 V
0V
+40 V
+70 V

1.6
1.7
Photon Energy (eV)1.8

Figure 1 (a) Transfer characteristics (opticalimage) of 1L WSe2 device (inset: bar is 10m). (b) PL spectra under different VG.

- 117 -

2P-34
Piezoelectric properties of 3R bulk transition metal dichalcogenides○Satoru Konabe1,2 and Takahiro Yamamoto1,2,3
1

RIST, Tokyo University of Science, Tokyo, Japan
Department of Electrical Engineering, Faculty of Engineering,Tokyo University of Science, Tokyo, Japan3
Department of Liberal Arts (Physics), Faculty of Engineering,Tokyo University of Science, Tokyo, Japan.

2

The bulk transition metal dichalcogenides (TMDCs) mainly exhibit two different typesof crystal structures, i.e., 2H and 3R. While TMDCs with 2H structure have thecentrosymmetry, TMDCs with 3R structure lose their centrosymmetry, resulting in the valley
related physics such as valley selectivity by a circular polarized light [1]. The noncentrosymmetry structure of 3R bulk TMDCs could lead to the other important property likepiezoelectricity, where strain gives rise to electrical polarization. Besides the bulk TMDCs, it
has been shown that the monolayer TMDCs, which also have the non-centrosymmetry
structure, exhibit a large piezoelectric response. The first principles calculation predicted thelarge piezoelectric coefficients in monolayer TMDCs such as MoS2, MoSe2, WS2, and WSe2[2]. After the theoretical calculation, the piezoelectricity of monolayer TMDCs is confirmed
experimentally and the measured values are consistent with the theoretical calculations [3-6].
Similarly to the TMDC monolayers, we expect piezoelectricity in the bulk 3R-TMDCs. If bothmonolayer and bulk structures exhibit the piezoelectricity, it opens a variety of applications
from the usual piezoelectric devices to flexible energy harvesting devices.
In the present work, we perform a systematic investigation of piezoelectric propertiesof the bulk 3R-TMDCs (MoS2, MoSe2, WS2, and WSe2) using the first principles calculations
based on the density functional theory. We calculate the elastic constant Cij, the piezoelectric
constant eij, and the piezoelectric constant dij from Cij and eij. We find that the piezoelectric
constants are sufficiently large or comparable compared with the conventional bulk
piezoelectric materials such as a -quartz, wurtzite GaN, and wurtzite AlN. Our simulation
demonstrates that the bulk 3R-TMDCs are potential materials for piezoelectric applications aswell as the monolayer counterparts.
References:[1] R. Suzuki, et al, Nature Nanotechnology 9, 611 (2014).
[2] K.-A. N. Duerloo, et al, The Journal of Physical Chemistry Letters 3, 2871 (2012).
[3] W. Wu, et al, Nature 514, 470 (2014).
[4] H. Zhu, et al, Nature Nanotechnology 10, 151 (2014).
[5] T. Wu, et al, Angewandte 54, 4432 (2015).
[6] J. Qi, et al, Nature Communications 6, 1 (2015).
Corresponding Author: Satoru Konabe
E-mail: konabe@rs.tus.ac.jp
Tel: +81-3-5876-1494 (ext. 2713)- 118 -

2P-35
Molecular beam epitaxy growth of molybdenum diselenide atomic layers on
hexagonal boron nitride substrates○Takuto Tokuda1, Takato Hotta1, Kenji Watanabe2 , Takashi Taniguchi2, Hisanori Shinohara1
and Ryo Kitaura1
1

Department of Chemistry, & Institute for Advanced Research Nagoya University, Nagoya
464-8602, Japan, 2 National Institute for Materials Science, Tsukuba 305-0044, Japan

The progress on graphene research has yielded the discovery of its fascinating properties
including the extremely high carrier mobility (~ 500,000 cm2/Vs), the room temperature
quantum hall effect and the fractional quantum hall effect, etc [1]. The fascination withgraphene research has led to searching for other two-dimensional systems, and hexagonalboron nitrides (hBN) and transition metal dichalcogenides (TMDs) have been isolated in its
monolayer form. In particular, TMD provides a family of two-dimensional systems, including
semiconductors, metals and superconductors, and they provide an excellent and widespread
platform to explore novel chemistry and physics in two-dimensions. To further explore thefundamental properties and possibility in future device applications of TMDs, development ofcontrolled growth of high-quality sample is indispensable. As a controlled growth method of
TMDs, chemical vapor deposition has been intensively studied, whereas anotherrepresentative thinfilm growth technique, molecular beam epitaxy (MBE), has not been
explored very well [2]. In this study, we have focused on application of MBE method to growa TMD, MoSe2. Figure 1 shows AFM image of grown MoSe2 at 885 K on hBN substrate; Mo
and Se are supplied with e-beam heating and low temperature K-cell, respectively. As clearly
seen, MoSe2 are grown as a hexagonal flake, which is consistent with the hexagonal crystal
system of MoSe2. The PL spectrum shown in Figure 2 exhibits the single peak at 1.57 eV,
which is assigned to the emission from free excitons. Temperature dependence of the PL
spectrum have shown that PL from trions is very weak, which indicates minimal amount of
unintentionally doping. In the presentation, further details of MBE growth and discussion of
optical properties will be given.
[1] A. S. Mayorov, et al., Nano Lett., 11, 2396 (2011). [2] K. Kang et al., Nature, 520, 656 (2015).
Corresponding Author: Hisanori Shinohara and Ryo Kitaura
Tel: +81-52-789-2477, Fax: +81-52-747-6442, E-mail: noris@nagoya-u.jp and r.kitaura@nagoya-u.jp

Fig.1 AFM image of grown MoSe2

Fig.2 PL spectra of grown MoSe2- 119 -

2P-36
Meteorite- and detonation-nanodiamonds are the same substances
Eiji Ōsawa1, Amanda S. Barnard2, Toshihiko Tanaka3 and Masayoshi Fukaya3
1

NanoCarbon Research Institute, Asama Research Extension Center, Faculty of Textile
Science and Technology, Shinshu University, Ueda, Nagano 386-8567, Japan
2
CSIRO Material Science and Engineering, Parkville, Victoria 3052, Australia
3
Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, Iwaki, Fukushima 970-8034, Japan
Nanodiamond was first isolated from the well-known presolar ‘Allende/Marchison
meteorite’ as fine-grained tan-colored carbon by R. S. Lewis and his coworkers, who initially
expected that the meteorite carbon could be C60 buckminsterfullerene[1]. This lucky incidence
took place in 1987, two years after the discovery of C60[2]. Later, Danilenko disclosed thatthey had synthesized nanodiamond by using detonation method earlier in 1963[3]. Although
this discovery was a brilliant achievement, he isolated only micron-sized agglutinates.
Single-crystalline, elementary particles of detonation nanodiamond (EPDND) have long
defied isolation. However, once isolated in dispersed state and characterized[4], EPDND
proved identical with Lewis’ meteorite nanodiamond despite vastly different origins!
The first indication of identity came from comparison of particle sizes. Disintegration of
crude agglutinates of detonation nanodiamond by attrition milling initially produced complex
mixture of oligomers like dimers and trimers in addition to the monodisperse elementary
particles, and used to give average diameters exceeding 3nm. Careful optimization of milling
conditions finally led to a minimum and constant diameter of 2.63±0.4 nm, which we believe
to represent the true EPDND[4]. As shown in Table 1, the diameter of EPDND perfectly
agrees with those from meteorites [5-7].
Table 1. Reported average sizes of meteorite nanodiamond in nm

MethodMeteorite
Murchison
AllendeTEM pointcountin [5,6]
2.6, 2.579
2.841

MALDI-TOF-MS [7]mode averagemean average
2.4
2.4
2.6
2.7

The second evidence was obtained by comparing LDI-TOF-MS of EPDND[8-9] with thoseof meteorite nanodiamond [7]. Convergence of the single-nano diamonds grown in different
environments into the same size and internal structure [8-9] suggests that similar
circumstances for diamond growth were created by shock waves generated from thedetonation of military explosives in closed vessel or from the grandiose explosion of asupernova considered responsible for the eventual formation of our solar system billions ofyears ago.

[1] R. S. Lewis et al., Nature 326, 160-162 (1987). [2] H. Kroto et al., Nature 318, 162-163 (1985). [3] V. V.
Danilenko, Phys. Solid State, 46, 595-599 (2004). [4] E. Ōsawa et al., manuscript in preparation. [5] R. S. Lewis
et al., Nature 339, 117-121 (1989). [6] T. L. Daulton et al., Geochim. Cosmochim. Acta, 60, 4853-4872 (1996).
[7] I. C. Lyon, Meteorit. Planet. Sci. 40, 981-200 (2005). [8] M. Fukaya et al., FNTG 52th General Symposium,
2017, Tokyo. [9] T. Tanaka et al., FNTG 52th General Symposium, 2017, Tokyo.
Corresponding Author: E. Ōsawa, Tel: +81-(0)268-75-8381, E-mail: osawa@nano-carbon.jp- 120 -

2P-37
Synthesis of N-doped carbon nanoballoons with nitrogen plasma○Ryota Takahashi 1, Toru Harigai1, Hirofumi Takikawa 1, Yoshiyuki Suda 1
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan

Doping a carbon nanomaterial with other atomic species (like nitrogen) provides a meansof altering its electronic and transport properties. Carbon nanoballoons (CNBs) have apentagonal ring in a part of a graphite layer with hexagonal rings. CNBs are a hollow andspherical structure, and has high conductivity. To control the electronic properties of CNBs,
we performed a substitutional doping of nitrogen atoms by using N2 plasma.
CNBs were synthesized by heat treatment of arc black at 2600C in Ar gas [1]. CNBs
mixed with polyvinylidene difluoride (PVDF) in a mass ratio of 9:1 was applied to a silicon
substrate and dried. N2 radio frequency (RF) magnetron plasma was applied to CNBs fixed ona substrate. X-ray photoelectron spectroscopy (XPS) was used to determine the chemicalbonding of CNBs.
Fig. 1 shows the C 1s and N 1s XPS spectra of(a)
CNBs treated with N2 plasma. In Fig. 1(a), there isa possibility that the asymmetric C 1s spectra is
influenced by C-N bonding [2]. The main C 1s
peak (284.4 eV) shows a shift to higher binding
energy. This shift is in agreement with increasing
structural disorder due to the disruptions in the sp2
carbon framework by the incorporation of nitrogen[3]. In Fig. 1(b), the two peaks at 398.5 eV and
400.1 eV can be assigned to pyridinelike N andpyrrolelike N, respectively. The small peak at
401.7 eV can be considered to graphitelike N, i.e.,
threefold coordinated sp2 N in the hexagonal rings (b)of CNBs [4].
This work has been partly supported by the
JSPS KAKENHI Grant Number 15K13946.
[1] Y. Okabe et al. Electrochim. Acta. 131, 207 (2014).
[2] C. Morant et al. Phys. Status. Solidi A. 203, 1069 (2006).
[3] S. Maldonado et al. J. Phys. Chem. B. 109, 4707 (2005).
[4] Y. C. Lin et al. Appl. Phys. Lett. 96, 133110 (2010).
Corresponding Author: Y. Suda
Tel: +81 532 44 6726, Fax: +81 532 44 6757
E-mail: suda@ee.tut.ac.jp- 121 -

Fig. 1 XPS spectra of (a)C 1(b)N 1s of
CNBs treated with N2 plasma.

2P-38
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Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan&RSRO\PHUL]DWLRQRILURQQLWUDWHK\GUDWHRQWKHVXUIDFHRIQRQLRQLFVXUIDFWDQWRID3OXURQLF
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2P-39

多段トラップ気相移動度測定装置の開発とナノ物質の分離（東邦大理）○菅井 俊樹・陣内 涼太・星野 裕大・寺田 夏樹・椎野 恭平・浜野 裕太・森田 博暉
Development of Multi-stage Ion Trap Ion Mobility Measurement System and Separation of
Nano Materials (Department of Chemistry, Toho University) ○Toshiki Sugai, Ryota Jinnouchi,
Yuudai Hoshino, Natsuki Terada, Kyohei Shiino, Yuuta Hamano, Hiroki Morita
Ion mobility together with mass spectrometry has been utilized to reveal novel structures ofnano materials1). However, almost no long-term successive structural measurements have been
performed. We have been developing ion trap ion mobility measurement system with opticalobservation on particles with the sizes from several tens of m to 50 nm by enhancing thesensitivity. Here we present newly developed system that realize separation based on mobility.
Figure 1 shows a schematic view of the system with multiply stacked ring ion guide (SRIG)
electrodes, which operate as many connected ion traps. The potential of the electrodes arecontrolled by newly developed power supplies which control both of ion trap radio frequency
high-voltage (RF) and low frequency low-voltage (LF) simultaneously. With this system wehave succeeded to observe and separate charged NaCl water solution particles and fluorescentnano materials. We are now improving the separation resolution.
Keywords：Ion Mobility; Ion Trap; Multi-stage

気相移動度測定は質量分析と組み合わせることでナノ物質の新規構造解明などに有用である 1)。しかし、長時間の構造変化の追跡観測はこれまでなされていなかった。
我々はこれまで、複数個のイオントラップとトラップ電位の制御により、移動度測定を行いながら、数時間にわたる継続観察を蛍光や散乱光を用いて行ってきた。さらに光検出感度を向上させることにより、測定対象を直径数 10 mの微粒子から直径 50 nm のナノ物質まで縮小させてきた。今回我々は、これらの技術を発展させ、新たに移動度に基づいた空間分離を試みた。図 1にシステムを示す。このシステムは多数の多段積
層リング型電極(SRIG)で構成された、複数連結イ
オントラップとこれらのトラップ用高周波電場と移動度用低周波電場を制御する、多チャンネル
電源で構成される。このシステムを用いて NaCl Fig. 1 Schemetic View of Multiple
水溶液荷電微粒子と蛍光ナノ物質の観測と移動 SRIG type Ion Mobility Ion Trap
度分離保持を実現した。現在分離分解能向上を図 Measurement System with control
power supplies.
っている。
1) T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).

- 123 -

2P-40Mechanical properties of nano-rotors: Energetics of triptycene derivatives
Miki Akiba and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Following the experimental demonstration of nanoscale machines, much effort has been
devoted to design further variations of nanoscale machines and to elucidate theirmechanical properties. Hydrocarbon molecules are one of representative constituent
units for such nanoscale machines due to their ridged covalent network within themolecules and flexible intermolecular covalent bonds. Although, the experiments
reported various nanoscale mechanical machines, fundamental mechanics of thenano-machines is still unclear. In the present work, we
aim to elucidate the nanomeachnics for the rotationalmotion of nano-rotors consisting of triptycene andotherhydrocarbon

molecules,

using

the

densityfunctional theory with the generalized gradientapproximation. In this work, we focus on triptycene
derivatives

in

which

hydrocarbon

molecules,

naphthalene, anthracene, and triptycene, are attachedto the triptycene via linear C2 unit (Fig. 1). Our
calculations show that the energy barrier for the

Fig. 1, Geometric structureof triptycene derivatives
where R is naphthalene,
anthracene, and triptycene

rotational motion strongly depends on the attachedhydrocarbon species: Triptycene gives the largest
barrier while the symmetrically attached anthracene
gives the smallest barriers (Fig. 2). We further studied
the angular velocity and torque for the rotationalmotion of these hydrocarbon molecules.
Corresponding Authors: M. Akiba and S. Okada
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 124 -

Fig 2. Total energy of
triptycene derivatives as afunction of the rotational angle.

2P-41
Study of deactivation mechanism of carbon catalyst by thermo-catalytic
decomposition of methane○Haruki Nishii1, Yoshito Umeda2, Hiroaki Hamaguchi 3, Masashi Suzuki3, Toru Harigai1,
Hirofumi Takikawa1, Yoshiyuki Suda1
1

2

Toyohashi Univ. of Technol., Japan
Chubu Region Institute for Sorcial and Economic Reserach, Japan
3
Aichi Science & Technology Foundation, Japan

Temporal change of methane conversion at 920℃ is shown in Fig. 1.
Although the methane conversion of initial reaction (at 20 min) reached60%, after 40 min, the methane conversion dropped to 33% rapidly.
Subsequently, it decreased gradually, and after 330 min, reached 23%.
Fig. 2 shows SEM micrographs of as-prepared catalyst and used ones
for methane conversion after 20 to 330 min. From Fig. 2 (a), it isconfirmed that AC had a lot of pores on the surface. However, in Fig. 2(b), pores diameter of 5 nm disappeared. From Figs. 2 (c) and (d), it isconfirmed that carbon grown spherically, and completely covered theMethane conversion ratio / %Thermo-catalytic decomposition (TCD) of methane is the attractive hydrogen production
process to mitigate CO2 emissions commonly associated with the conventional processes(such as steam methane reforming). However, the problem of process is catalyst deactivation.
[1]
The purpose of this study is to investigate deactivation mechanism of carbon catalyst by
analyzing carbon deposited over carbon catalysts.
Activated carbon sample was used as the catalyst for the TCD of methane. Experiments
were carried out in a fixed-bed reactor. After heating to 920℃ under nitrogen, methane wasflowed for different time periods. [2]After experiments, methane conversion ratio was
calculated by the following equation. The obtained carbon was analyzed by X-ray diffraction
65(XRD) and scanning electron microscopy (SEM).
60
55
50
45
40
35
30
25
20

0

40

80 120 160 200 240 280 320

Elapsed time / minFig. 1 Temporal change of
Methane conversion ratio(b)(a)
100 nm

500 nmcatalyst, respectively.
(c)(d)
From these results and study of N. Muradov et al.[3], initial drop of
)))
1μm
2μm
reaction and subsequent gradual decrease are considered to be attributed)
to block micro-pores, meso-pores and macro-pores by carbon deposition.
Fig. 2 SEM micrograph of (a)Acknowledgements

A part of this work was supported by “Development project of near-term AC (as prepared), (b) after 20hydrogen economy forming technology“ for priority of research project of min, (c) after 40 min, and (d)after 330 min.
Knowledge Hub Aichi. The authors would like to thank K. Azato for emeritus prof.
of Gifu Univ. and H. Yamashita for emeritus prof. of Nagoya Univ. with discussion about correlation
between produced carbon and methane conversion.

[1] Lee, Eun Kyoung, et al. Carbon 42, no. 12–13 (2004): 2641-48.
[2] Abánades, et al. International Journal of Hydrogen Energy, 36, no. 20 (2011): 12877-86.
[3] N.Muradov, et al. Catalysis Communications 2, no. 3–4 (2001): 89-94.
Corresponding Author: Y. Suda
Tel: +81-3-0532-44-6726
E-mail: suda@ee.tut.ac.jp- 125 -

2P-42
Effect of PtRu alloying degree on catalytic activity of catalysts
for direct methanol fuel cells○K. Kawasaki1, T. Ohiro1, T. Harigai1, H. Takikawa1, H. Ue2, Y. Suda1
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

Carbon black, nanometer-size carbon particles, is commercially used as a catalyst support
in fuel cells owing to its high surface area, porosity, electric conductivity, low density, andlow cost. In the previous work, we have used various carbon nanomaterials as a catalyst
support for direct methanol fuel cells (DMFC) [1]. In this study, we used carbon nanocoils(CNCs) as a catalyst support and measured the catalytic activity and PtRu alloying degree of
CNC-supported PtRu catalyst.
An automatic chemical vapor deposition (CVD) system was used for CNC synthesis.
CNC was prepared by using Fe/Sn catalytic solution [1]. CNCs are helical-shaped carbon
nanofibers (CNFs). CNCs are graphitic. We supported PtRu catalysts for the DMFC anode.
Sodium boron hydrate (NaBH4) was used as a reducing agent in the reduction method [2].
Deionized water was used as solvent in the reduction method. We mixed CNCs-dispersed
solution, PtRu precursor solution, and reducing agent solution. We changed the concentrationof mixed solution by adjusting the amount of solvent and prepared PtRu catalysts.
Table 1 shows the electrochemically active surface area (ECSA), onset potential ofmethanol oxidation reaction (MOR) of the PtRu catalysts, and PtRu alloying degrees. The
PtRu alloying degree was evaluated from the X-ray diffraction spectra of the PtRu catalysts.
The alloying degrees decreased with reducing of concentration. Low alloying degree caused
to low MOR onset potential. This is mainly due to increase of unalloyed Ru in PtRu catalyst[3].
Table 1. Electrochemical properties and alloying degrees of CNC-supported PtRu catalyst

ConcentrationECSA

MOR onset potential

Alloyed Ru/L gCNC/m gPt

/V

/%

-1

2

-1

2.5

100.6

0.214

4

5.0

96.7

0.263

12

10.0

109.9

0.264

13

This work has been partly supported by JSPS KAKENHI Grant Number 15K13946.
[1] Y. Suda et al. Materials Today Communications. Vol. 3, pp. 96-103 (2015).
[2] T.C. Deivaraj et al. Journal of Power sources. Vol. 142, pp. 43-49 (2005)[3] J. Guo et al. Journal of Power sources. Vol. 168, pp. 299-306 (2007).
Corresponding Author: Y. Suda
Tel: +81 532 44 6726, Fax: +81 532 44 6757
E-mail: suda@ee.tut.ac.jp- 126 -

2P-43
Microfabrication of carbon nanocoil using Focused Ion Beam
○Munehiro Takahashi1, Toru Harigai 1, Hirohumi Takikawa1, Hitoshi Ue2, Yoshiyuki Suda 1
1

Toyohashi Univ. of Technol., 2Tokai Carbon Co., Ttd.

Carbon nanocoils (CNCs), which are synthesized by chemical vapor deposition (CVD)method, have a coil diameter of 500-1500 nm [1]. CNCs are expected such as electromagnetic
wave shielding and counter electrode of solar cells [2,3]. CNCs are expected to be used as ananoinductor. However the effect of nanoinductor on CNCs are low due to high resistivity [4].
In addition, we do not know magnetic property of single CNCs, and CNCs are obtained as anaggregate when synthesized. In this study, we have made the CNC substrate for measuring
magnetic property
CNCs are obtained by chemical vapor deposition method. Fig. 1 shows processing of themeasurement substrate. Au film having a thickness of 150 nm was formed on SiO2 substrateusing an ion coater. A single CNC is extracted by using focused ion beam (FIB). Au on SiO2
substrate was etched to draw a line by using FIB. The single CNC was bridged there. Then Pt
gas deposited at both ends of the bridged single CNCs to fix it, and the measurement substrate
was prepared. A plural of measurement substrates were prepared.

Fig. 1 Processing of the measurement substrate

Table 1 shows the geometry of the bridged single CNCs. The number of turns and fiber
length tend to increase when the pitch angle is decreased. From these results, we can expect tomeasure the magnetic properties by using the measurement substrate.
Table 1. Configuration of CNCs.

Sample

Coil

Fiber

Pitch

NumberFibernumberdiameterdiameterangle

of turns

length

[nm]

[nm]

[deg]

1

765

385

35.1

7.91

23.3

2

582

130

14.8

21.5

40.8

3

551

124

14.4

17.2

30.8

[1] G. Xu, et. al, Jpn. J. Appl. Phys, 44, 1569 (2005)[2] G. Kang, et. al, Applied Surface Science, 380, 114 (2016)[3] G. Wang, et. al, Materials Letters, 174, 14 (2016)[4] Y. Nakamura, et. al, Appl. phys. Lett, 108, 153108 (2016)- 127 -

[µm]

3P-1
Attempt to produce dimetallofullerenes containing Yb○Kazuhiro Kobayashi, Takuji Mitani, Natsumi Nakatori, Koichi Kikuchi, Yohji Achiba,
Takeshi Kodama
Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan
So far, M2@C80(Ih) (M=La, Ce, Pr) have been isolated and characterized, but M2@C80(Ih)containing other metals like Y, Gd, etc. have never been obtained, then called as a ‘‘hidden’’or ‘‘missing’’ metallofullerenes. Quite recently, however, we succeeded in the isolation of
Y2@C80(Ih) [1] and Gd2@C80(Ih) [2] as an anion form using the method combining theion-pair chromatography with the mixed solvent extraction. In other words, Y2@C80(Ih) andGd2@C80(Ih) are unstable and unable to be extracted as a neutral form but are produced in the
raw soot.
For Yb-metallofullerenes, the isolations of monometallofullerenes, Yb@Cn (n=74, 76, 78,
80, 82, 84), have been reported [3], but there is no report on the Yb-dimetallofullerenes,
Yb2@Cn. Because there is a possibility of the production of Yb2@Cn in the raw soot like thatfor Y2@C80(Ih) and Gd2@C80(Ih), we tried to extract and separate Yb2@Cn as an anion form.
First, we carried out direct-current(DC) arc discharge (60 ~ 65 A) of Yb/C composite rods
(Yb:C=2:98) or Yb/Ni/C composite rods (Yb:Ni:C=2:1:97) under a 500 Torr He atmosphere.
In the latter, Ni was used as a catalyst. Unfortunately, in the both experiments, the obtainedsoot was little and no evidence of Yb-metallofullerenes
in the extract was presented. Then, we next executed
DC arc discharge (60 A) of Yb/Y/C composite rods
(Yb:Y:C=1:1:98) under a 500 Torr He atmosphere, andthe sufficient soot was obtained. The raw soot was
extracted for 8 h with a mixed solvent of triethylamine
and acetone. The extract was separated by HPLC usinga Buckyprep column and acetone with an ion-pairreagent, tetrabutylammonium bromide, as an eluent.
Figures 1 and 2 show HPLC chromatogram and Fig. 1 HPLC chromatogram of the extract.
LD-TOF mass spectra of the fraction A and B,
respectively. In the fraction A, the peak of Y2C78,
which should be Y2@C78(D3h), was observed but nopeak of YYbC78 and Yb2C78. Similarly, in the fraction
B, the peak of Y2C80, which should be Y2@C80(Ih),
was observed but no peak of YYbC80 and Yb2C80.
Therefore, it was suggested that dimetallofullerenes
containing Yb, not only Yb2@Cn but also YYb@Cn, Fig. 2 LD-TOF-MS spectra of the fraction
were not produced or not extracted as an anion form if
A and B.
existed in the raw soot.

[1] N. Nakatori, et al. The 49th Fullerenes-Nanotubes-Graphene General Symposium 46 (2015).
[2] T. Mitani, et al. The 50th Fullerenes-Nanotubes-Graphene General Symposium 95 (2016).
[3] J. Xu, et al. Chem. Mater. 16, 2959-2964 (2004).
Corresponding Author: Takeshi Kodama
Tel: +81-42-677-2530, Fax: +81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 128 -

3P-2
Spectroscopic studies of La2@C78 anion○Shinya Nishimoto1, Kazuhiro Kobayashi 1, Takaaki Hirayama 1, Takuji Mitani1,
Natsumi Nakatori1, Takahisa Yamaguchi2, Ko Furukawa3, Tatsuhisa Kato2, 4,
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
Department of Chemistry, Niigata University, Niigata 950-2181, Japan
4
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

In 2004, Cao et al. reported that La2@C78 has C78(D3h) cage and exhibits the absorption
spectrum with several characteristic features in the visible region [1]. Recently, we succeededin the isolation of M2@C78(M=Y, Gd) anion and measured their UV-vis-NIR absorption
spectra [2,3]. The obtained spectra are very similar to that of La2@C78(D3h) neutral. In order
to interpret such a similarity between anion and neutral forms of metallofullerenes, it was
speculated that M2@C78(M=Y, Gd) anion has C78(D3h) cage and an excess electron is locatedon M2. To confirm this speculation, it has been desired to measure the absorption spectrum of
La2@C78(D3h) in anion form and compare it with that of its neutral form. In this study, we
isolated La2@C78 anion and measured its absorption spectrum. Moreover, its ESR spectrum
was also measured to check whether an excess electron of La2@C78 anion is located on La2.
Soot containing La-metallofullerenes was produced bydirect-current (60 A) arc discharge of La/C composite rods
(La:C=2:98) under a 500 Torr He atmosphere. The raw sootwas extracted for 8 h with a mixed solvent of triethylamine
and acetone. The isolation of La2@C78 anion was
accomplished by two-stage HPLC. Acetone with an ion-pairreagent, tetrabutylammonium bromide (TBABr), was used as
an eluent in all the stages. For the isolated La2@C78 anion,
the UV-vis-NIR absorption and ESR spectra were measured. Fig.1 UV-vis-NIR absorption
After the solvent was replaced to neutralize La2@C78 anion spectra of each solution of
from acetone to CS2, or toluene, the UV-vis-NIR absorption La2@C78.
spectra were measured for each solution.
Figure 1 shows the UV-vis-NIR absorption spectra of eachsolution of La2@C78. All the spectra are almost the same,
though their positions of a characteristic peak near 650 nm
are slightly different from each other (TBABr/acetone: 648
nm, CS2: 662 nm, toluene: 652 nm). Figure 2 shows the ESR
spectrum of La2@C78 anion, showing the presence of thevery large hyperfine constant. These results indicate theFig.2 X-band ESR spectrum ofassumed speculation for M2@C78(M=Y, Gd) anion is valid.
anion at 4 K in
La @C
2

78

TBABr/acetone.

[1] B. Cao, et al. J. Am. Chem. Soc. 126, 9164-9165 (2004).
[2] N. Nakatori, et al. The 50th Fullerenes-Nanotubes-Graphene General Symposium 44 (2016).
[3] T. Mitani, et al. The 10th Annual Meeting of Japan Socity for Molecular Science 3P077(2016).
Corresponding Author: Takeshi Kodama
Tel: +81-42-677-2530, Fax: +81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 129 -

3P-3
Evaluation of dispersion states of nanomaterials by disc centrifuge sedimentation
technique○Naoko Tajima1, Takahiro Morimoto1,2, Yuichi Kato1,2, Kazufumi Kobashi1,2, Takeo
Yamada1,2, Toshiya Okazaki1,2
1Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba,
305-8565, Japan
2
CNT Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, 305-8565, JapanTo evaluate the dispersion state of nanomaterials such as carbon nanotubes (CNTs) is very
important for the application of the material. As one of the evaluation methods, we havemeasured the particle size (Stokes diameter) distribution of the dispersion using disk
centrifuge (DC24000, CPS Instruments Inc.), which is based on differential sedimentationaccording to Stokes’ law.
Figure 1 shows the particle size distribution of multi-walled CNT (MWCNT) in the water
dispersion (CNT-Aqua, Microphase Co., Ltd.). The distribution is bimodal, the smaller size
fraction is associated with individual CNTs and the larger size fraction with aggregated CNTs.
For rod-like substance, Henn [1] suggested its Stokes diameter (D) is calculated from
relational equation with the substance diameter (d) and length (L) concerning thesedimentation process of the substance.
㻌㻌㻌㻌
By using the dimensions of the MWCNT (d：～0.01μm, L：30-600 μm) specified by the
manufacturers used for CNT-Aqua in this equation, D is calculated 0.029 to 0.034 μm, which
is close to the obtained peak value (0.025 μm) of the smaller size fraction in Fig. 1.
Similarly, for the other MWCNTs, the diameters measured by DC24000 were comparedwith the calculated values with this equation. Here, d and L of each CNT were obtained from
SEM and/or AFM observation. As a result, they agreed with each other within a certain range,
and it was found that the equation is effective also for individual CNT. The dispersion statesof graphene oxide and cellulose nanofiber will also be discussed in detail.
This study is based on results
obtained from a project commissionedby the New Energy and Industrial
Technology Development Organization(NEDO).

[1] A. R. Henn. Part. Part. Syst. Charact. 13,
249 (1996).
Corresponding Author: Toshiya Okazaki
E-mail: toshi.okazaki@aist.go.jp
Fig.1 Particle size distribution of MWCNT
in the water dispersion- 130 -

3P-4
Unified analysis of quantum and classical transport properties
on metallic carbon nanotubes○Keisuke Ishizeki1, Kenji Sasaoka2,3, Satoru Konabe1,4, Satofumi Souma3,
Takahiro Yamamoto1,4,5
1

2

Department of Engineering, Tokyo University of Science, Tokyo 125-8585, Japan
Organization of Advanced Science and Technology, Kobe University, Kobe 657-8501, Japan3
Department of Engineering, Kobe University, Kobe 657-8501, Japan
4
RIST, Tokyo University of Science, Tokyo 125-8585, Japan
5
Department of Liberal Arts (Physics), Tokyo University of Science, Tokyo 125-8585, Japan
Metallic carbon nanotubes (CNTs) are expected to be wiring materials of next-generation
LSIs because of their high carrier mobility. It is known that a CNT shows different electronictransport properties depending on the system size. While the transport property shows
diffusive transport when the system size is much longer than a mean free path, it showsballistic transport when the system size is much shorter than a mean free path [1]. On theother hand, a phase coherence length is a characteristic length to divide coherent andincoherent transport. Conventionally, each transport property has been studied by different
transport theories. However, a transport theory that can treat the two transport retimes
including the crossover has not been established in spite of the importance for designing
LSIs.
In this study, we developed a new quantum transport simulation method that can treat anopen system of millions of atoms with atomic vibration at finite temperature. Using the new
simulation method, we investigated the electronic transport properties of metallic CNTs atroom temperature. As a result, we succeeded to calculate electrical resistance from ballistic
to diffusive transport regime in a unified manner, and estimate a mean free path at room
temperature (Fig. 1. (a)). Moreover, we also succeeded to extract the coherent component ofelectronic current which goes through a system with preserving an initial energy, andestimate a phase coherence length (Fig. 1. (b)).

Fig. 1. System length dependence of (a) electrical resistance and (b) the coherent component

References:[1] S. Datta, Electronic transport in Mesoscopic Systems (Cambridge University Press, Cambridge, 1995)
Corresponding Author: T. Yamamoto
E-mail: takahiro@rs.tus.ac.jp- 131 -

3P-5
High Temperature Surface Enhanced Raman Scattering of Single-Walled
Carbon Nanotubes
Ming Liu1, Keigo Otsuka1, Rong Xiang1, Taiki Inoue1, Shohei Chiashi1, Shigeo Maruyama1, 2
1
2

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
National Institute of Advanced Industrial Science and Technology (AIST), Ibaraki 305-8564,
Japan

In situ Raman scattering is a significant technique to characterize the growth process of
single-walled carbon nanotubes (SWNTs), which can provide both formation dynamics andpopulation evolution of the obtained SWNTs. [1] However, Raman intensity obtained at hightemperature is too weak to explicitly identify the structure-related fingerprints, e.g. position andshape of G- peak. [2] In our previous work,
the poor stability of metal nanoparticles athigh temperature was the main restriction toachieve surface-enhanced Raman scattering(SERS) of SWNTs during growth process.
[3] In this study, Ag@SiO2 core shellparticle was investigated to be the stable
SERS particle to enhance Raman scatteringof SWNTs at high temperature. By detectionof Rhodamine B at room temperature, this
Ag@SiO2 structure (Fig. 1(a)) was
confirmed to be an effective SERS substrate,
which could be a promising application for
detecting other organic pollutants. The
stability of Ag@SiO2 particle at hightemperature was verified by a series ofheating experiments and characterization.
Additionally SERS enhancement ofhorizontally aligned SWNTs (HA-SWNTs)
at different temperatures was confirmed to
be stable and temperature insensitive in our Fig. 1 (a) Schematic illustration of Ag@SiO2 SERS
experiment (Fig. 1(b)). Besides, the substrate. (b) Non-SERS spectra of HA-SWNTs on
spectra of the same HAannealing process of nanodiamond at high silicon substrate and SERSSWNTs on Ag@SiO2 10nm substrate at different
temperature was also monitored in real time temperatures; (c) Temperature dependent Raman spectraon this SERS substrate (Fig. 1(c)). This of nanodiamond on Ag@SiO2 10nm substrate during
study paves a way to achieve in situ annealing process;. Excitation laser 488 nm for (b) and (c).
characterizing of growth process of SWNTs
at high temperature by Raman scattering.
[1]. Li-Pook-Than A. et al. J. Phys. Chem. C 114, 11018 (2010).
[2]. Huong, P. V. et al. Phys. Rev. B 51, 10048 (1995).
[3]. Liu, M. et al. Carbon 80, 311 (2014).
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-7437, Fax: +81-3-5841-7437,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 132 -

3P-6
Fabrication and photoluminescence characterization of carbon nanotube
dual-gate devices○Akihiro Sasabe1,2, Takushi Uda1,2, Masahiro Yoshida1,3, Akihiro Ishii1,4, Yuichiro K. Kato1,3
1

Nanoscale Quantum Photonics Laboratory, RIKEN, Saitama 351-0198, Japan
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
3
Quantum Optoelectronics Research Team, RIKEN center for Advanced Photonics, Saitama
351-0198, Japan
4
Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656, Japan2

Photoluminescence from carbon nanotubes subjected to a DC gate voltage is quenched due
to induced carrier accumulation [1], whereas applying a square-wave gate voltage to nanotubes
causes luminescence recovery as a result of carriers being swept into contact electrodes [2].
Here we characterize photoluminescence of carbon nanotubes in dual-gate devices which allow
for simultaneous and independent application of a DC gate voltage and a square-wave gate
voltage. The devices are fabricated from silicon-on-insulator substrates, where trenches isolate
two regions of the top silicon layer for use as the dual gates. We then perform thermal oxidation
to form a gate dielectric, and air-suspended carbon nanotubes are grown over the trench between
the dual gates. Photoluminescence measurements are used to identify the chirality of the asgrown individual nanotubes, and we examine the response of the nanotube emission to various
combinations of the dual-gate voltages.
Work supported by KAKENHI (JP16H05962), Asahi Glass Foundation, and MEXT (Photon
Frontier Network Program, Nanotechnology Platform). T.U. is supported by ALPS and A.I. is
supported by MERIT and JSPS Research Fellowship.
[1] S. Yasukochi, T. Murai, S. Moritsubo, T. Shimada, S. Chiashi, S. Maruyama, Y. K. Kato, Phys. Rev. B 84,
121409(R) (2011).
[2] M. Jiang, Y. Kumamoto, A. Ishii, M. Yoshida, T. Shimada, Y. K. Kato, Nature Commun. 6, 6335 (2015).
Corresponding Author: Yuichiro K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 133 -

3P-7

Optical Measurement of Single-walled Carbon Nanotubes Using
Rayleigh Scattering Spectroscopy○Takeshi Okochi1, Toru Osawa1, Yoritaka Furukawa1, Tatsuro Ogamoto1, Shun
Kamakura1, Taiki Inoue1, Shohei Chiashi1, Shigeo Maruyama1,2
1
Department of Mechanical Engineering, The University of Tokyo, Hongo 7-3-1,
Bunkyo-ku, Tokyo, Japan
2
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba
Because SWNTs are nano-materials and have large specific surface, the interaction
between SWNTs and the environments sometimes changes the electronic property. Thischange needs to be studied because it may influence the performance and reliability of
SWNT devices. In this study, we measured Rayleigh scattering spectra [1] to investigate
the electronic structure of various SWNT samples. We constructed the optical system formeasuring Rayleigh scattering spectra and Rayleigh scattering images. The continuum
laser (the range of wavelength was 400 – 2500 nm) was used as the excitation light. To
improve the S/N ratio of measurement, we utilized
cross polarization technique [2]. We measured
Rayleigh scattering spectra of suspended SWNTs,
SWNTs on Si substrates, dispersed SWNTs in thesurfactant solutions [3] and dry-deposited SWNT
films [4]. For example, we obtained Rayleigh spectraof a suspended SWNT as shown in fig. 1, and weestimated its chirality. We will discuss the influenceof the environmental conditions on the electronic
structures of SWNTs led to by environmental
conditions on the basis of on experimental results.
[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).
Corresponding author: S. Maruyama
Tel: +81-3-5841-6421
Email: okochi@photon.t.u-tokyo.ac.jp- 134 -

Fig.

1:

Rayleighscattering

spectrum of a suspended SWNT.

3P-8
Synthesis and structure control of vertically aligned carbon nanotubes
on Cu foils for thermal interface materials○Shunji Kobayashi1, Kei Hasegawa1, Hisashi Sugime2, Masanao Obori3,
Junichiro Shiomi3, Xiaosong Zhou4, Mizuhisa Nihei4, Suguru Noda1
1

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Waseda Institute for Advanced Study, Waseda University, Tokyo 169-8050, Japan3
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
4
Huawei Technologies Japan K. K., Kanagawa 221-0056, Japan
2

In order to release heat from electronic device chip to heat sink, thermal interface materials(TIMs) are used. To fill the air gap between the chips and heat sinks, composites of polymer
and metal particles are widely used as TIMs. Many researchers have studied TIMs withcarbon nanotubes (CNTs), which have high thermal conductivity and high flexibility. We havepreviously reported ~50 µm-tall, 0.2-0.3 g/cm3-dence vertically-aligned (VA) CNTs grownboth faces of Cu foils, which showed TIM performance comparable to the typical indium
sheet [1]. This time we propose Cu-CNT composite, in which Cu particles are held bythermally conductive VA-CNTs instead of thermally less conductive polymer matrix.
VA-CNTs were synthesized following the previous method [1]. Fe (2 nm)/TiN (15 nm)/Ta(10 nm) was sputter-deposited on both sides of Cu foil, and VA-CNTs were synthesized by
CVD using C2H2 (0.2 Torr)/H2 (2 Torr)/Ar (12.8 Torr) at 700 oC for 30 min. Then the
VA-CNTs were coated with carbon using C2H2 (21.3 Torr)/Ar (78.7 Torr) at 800 oC for 30 min
to prevent them from shrinking during the electrodeposition process. Then Cu waselectrodeposited on VA-CNTs using Cu(NO3)2 aq under condition shown in Table 1.
As grown VA-CNTs shrank after dipping-drying with water, but the carbon-coated
VA-CNTs stayed stable. Cu particles were electrodeposited on the carbon-coated VA-CNTs by
applying electric pulses; high overpotential promotes nucleation of Cu particles while interval
enables sufficient diffusion of Cu2+ from outside to inside of the VA-CNTs. Fabricated
Cu/VA-CNT is shown in Fig.1. Cu was deposited fairly uniformly with volume fractions of
7.73 vol%, 7.61 vol% and 10.55 vol% at the top, middle and bottom of the VA-CNTs.
The thermal resistance of VA-CNT will be measured and reduced by optimizing
electrodepositing condition.
Target Cu
fraction
30 vol%Table 1. Condition for Cu electrodeposition on VA-CNTs.
Total
Pulse
Pulse
NumberPulse
chargecurrent
widthof pulses
interval
81.6 C
0.4 A
1.5 s
136
100 s
(b)

(a)

50 µm

(c)

500 nmTotal time
1.37104 s(d)

500 nm

500 nmFig. 1. Cross-sectional SEM images of Cu/VA-CNTs. (a) Overall view (b) top (c) middle (d) bottom.
Acknowledgement: This work is supported by Huawei Innovation Research Program.
[1] N. Na et al., Jpn. J. Appl. Phys. 54, 095102 (2015).
Corresponding Author: S. Noda, Tel&Fax: +81-03-5286-2769, E-mail: noda@waseda.jp- 135 -

3P-9
Selective detection of neurotransmitters by adsorption voltammetry
with carbon nanotube film
○Takuya Ushiyama1, 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, Japan2[1] K. O. Schwab et al., Eur. J. Clin. Chem. Clin. Biochem., 30,
541 (1992)[2] T. Okumura et al., J. Chromatogr. B, 694, 305 (1997)[3] C. B. Jacobs et al., Analyst, 136, 3557 (2011)[4] T. Ushiyama et al., The 51st FNTG General Symp., 2P-14 (2016)[5] A. S. Kumar et al., J. Electroanal. Chem., 641, 131 (2010)
Corresponding Author: Y. Ohno
Phone & Fax: +81-52-789-5387, E-mail: yohno@nagoya-u.jp- 136 -

Current (nA)

Neurotransmitters are emitted by nerve cells to convey information in brain. They are also
known as one of stress markers in saliva. The concentrations of neurotransmitters are 10-1000
nM in cerebrospinal fluid and ~100 pM in saliva [1, 2]. Carbon nanotube (CNT) is promising
electrode material for electrochemical sensors to detect neurotransmitters [3]. We had proposed
adsorption voltammetry using a CNT film, and demonstrated ultra-high sensitivity detection ofneurotransmitters of 100 pM [4]. This method consists of pre-concentration and detection
processes; neurotransmitters are concentrated by adsorption onto electrode surface andsubsequently detected by cyclic voltammetry. In practical biological samples, many impurity
substances are contained as well as small amount of objective molecule. Therefore,
electrochemical sensors are required to have selectivity in addition to sensitivity. In this work,
we investigated the selectivity in detection of neurotransmitters by the adsorption voltammetry.
We fabricated electrochemical sensors with clean single-walled CNTs on a plastic substrate,using the dry transfer and micro-fabrication process as our previous work [4]. Adsorption
voltammetry was performed for PBS solutions containing dopamine (DA), serotonin (5-HT) or
their mixture. First, we applied fixed potential to CNT electrode for 600 s in sample solution in
the pre-concentration process. Then, we scanned potential in the detection process to measureoxidation current similar to cyclic voltammetry.
Figure 1 shows the voltammogram for 10-M 5-HT (dashed curve) and a mixture of 10-M
5-HT and 1-M DA (solid curve). We observed a sharp oxidation peak at ~0.1 V for the mixture
sample (5-HT+DA) although broad peak at ~0.35 V appeared for both 5-HT and 5-HT+DA.
According to our previous work, the peak originating from adsorbed DA is presumed to appear
at the potential of ~0.1 V [4]. The potential of75
oxidation peak for adsorbed species is lower than that
5-HT
50of peak observed in conventional cyclic voltammetry[5]. The result shows DA can be detected selectively
DA25
in presence of 5-HT by the adsorption voltammetry.
5-HT + DA

0
-25
-0.2

Scan rate: 50 mV/s

0.0

0.2

0.4

0.6

Potential (V)0.8

Fig. 1 Voltammograms for 5-HT (dashedcurve) and a mixture of 5-HT and DA (solid
curve) obtained by adsorption voltammetry3P-10Time-dependent change of the semiconducting-CNT ink evaluated from theperformance of CNT-TFTs○Yuki Kuwahara1,3, Fusako Sasaki3, Fumiyuki Nihey2, Takeshi Saito1,3
1

National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565, Japan
2
IoT Devices Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
3
Technology Research Association for Single Wall Carbon Nanotubes, Tsukuba 305-8565, JapanThe network of carbon nanotubes (CNTs) has been used as a channel of thin filmtransistors (TFTs) which enables us fabricating flexible, large-area, and low-cost electronic
devices by a printed-electronics technique. Usually, CNT dispersion is used as ink that can bedeposited on various substrates. The uniformity of CNT network, as well as the purity ofsemiconducting CNTs, is one of the important factors to produce high performance
CNT-TFTs for their practical use. Recently, we have investigated the electric-field-induced
layer formation (ELF) method [1] in order to separate metallic and semiconducting CNTs. By
using the CNT ink extracted by ELF, high device performance with low variability have been
demonstrated [2]. Although the condition of CNT-ink deposition was investigated for
improving the device performance, the temporal stability of CNT ink was still remained as anopen question. In this study, we have investigated the time-dependent change of thesemiconducting-CNT ink by the evaluation on the basis of the CNT-TFTs’ performances.
CNTs synthesized by eDIPS method [3] were dispersed in the aqueous solution ofpolyoxyethylene (100) stearyl ether (Brij S 100). Then the semiconducting-CNT ink was
extracted from the CNT dispersion by ELF, in which the semiconductor purity of >95% was
obtained by the optical-absorption-spectroscopy characterization. We have stored the CNT ink
in the refrigerator for up to ca. 2 months to check the temporal stability. The CNT network
films were prepared moment to moment by depositing the ink on silicon substrates, and thenrinsing with isopropyl alcohol (IPA) after several minutes. On the CNT network film, Au
electrodes were deposited through ametal mask to fabricate CNT-TFTs.
Figure 1 plotting the performance of
CNT-TFTs fabricated at different ink
ages shows that the deterioration of the
CNT ink is negligible from theviewpoint of the TFT performance. In
presentation, we will also discuss the Fig. 1 Performance of CNT-TFTs prepared in 1day (left),morphological changes of CNT 18days later (center) and 51days later (right).
networks by AFM observation.
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] S. Ohmori et al., RSC Adv., 2, 12408 (2012).
[3] T. Saito et al., J. Nanosci. Nanotechnol. 8, 6153 (2008).
Corresponding Author: T. saito, Tel: +81-29-861-4863, Fax: +81-29-861-4413, E-mail: takeshi-saito@aist.go.jp- 137 -

3P-11Lamination of Vertically Aligned Single-Walled Carbon Nanotube Forests
on Perovskite Solar Cells via Membrane Filter Transfer Method○Seungju Seo1, Il Jeon1, Takahiro Sakaguchi1, Taiki Inoue1, Rong Xiang1, Shohei Chiashi1,
Yutaka Matsuo1,2, Shigeo Maruyama1,3
12

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Hefei National Laboratory for Physical Sciences at the Microscale, University of Scienceand Technology of China, Hefei, Anhui 230026, China
3
Energy NanoEngineering Lab, National Institute of Advanced Industrial Science andTechnology(AIST), Ibaraki 305-8564, Japan

Single-walled carbon nanotubes (SWNTs) are well-known as an outstanding electricalconductor with their excellent mobility, about 100,000 cm2/Vs at room temperature. Also, thefact that they have an alignment orientation makes SWNTs stand out among other carbon
conductors such as graphite, graphene. Arrays of vertically-aligned single-walled carbon
nanotubes (VA-SWNTs) [1] so called SWNTs forests, offer remarkable vertical conductivity,
which is not observed with disordered SWNTs. VA-SWNTs can be viewed as a new type offunctional bulk material that is useful for numerous applications. Their potential can be
maximized if their unique features are met with the device’s properties, and a successfultransfer is accomplished.
Over the past five years, the rapid emergence of perovskite solar cells (PSCs) are attracting
increased attention on account of their high power conversion efficiency (PCE) and simple
processes in addition to low material costs. Along with the optimization of perovskite crystal
formation, the approach from the diversity of device concepts and new material, the PCE has
risen from 3% to over 20%, which is close to that of conventional solar cell families such as
Si, CIGS, and CdTe [2].
Thus far, VA-SWNTs application in perovskite solar cells has not been reported. This isbecause VA-SWNTs are non-transparent and their conventional transfer method involves
water, which prompts perovskite degradation. Other alternative dry transfer methods, such as
PDMS infiltration also take too much time and difficult to accomplish [3].
In our work, we demonstrate an application of VA-SWNTs in perovskite solar cells using a
new transfer method using membrane filter, which offers a facile and reproducible way tolaminate VA-SWNTs film (Fig.1) without moisture contact to the perovskite layer. PSCs witha structural configuration of glass/fluorine-doped tinoxide (FTO)/C60/CH3NH3PbI3/VA-SWNTs/Au were
fabricated. The inclusion of VA-SWNTs enhanced both
power conversion efficiency (PCE) and stability of thedevices. Improved PCE was due to the increase inopen-circuit voltage originated from energy level
matching between perovskite layer and gold. Improved
stability is attributed to hydrophobic and densely packed
nature of the VA-SWNTs.

[1] Y. Murakami et al., Chem. Phys. Lett., 385 (2004) 298.
Fig.1 SEM image of VA-SWNTs film
[2] http://www.nrel.gov/ncpv/images/efficiency_chart.jp[3] D. H. Lee et al., Adv. Mat 22.11 (2010): 1247.
on Si/SiO2 Substrate
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421, E-mail: maruyama@photon.t.u-tokyo.ac.jp- 138 -

3P-12
Yields of carbon nanotube integrated circuits on flexible plastic film
○Jun Hirotani1, Shigeru Kishimoto1, and Yutaka Ohno1,2
1

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

2

Carbon nanotube thin-film transistors (CNT TFTs) are attracted much attention in flexible
electronics because of their high carrier mobility [1] and excellent mechanical flexibility. To
realize integrated circuits in large scale, an improvement of yield of devices is essential. We
have reported wafer-scale and high-yield fabrication of CNT TFTs with small characteristic
variation by using purified semiconducting CNTs [2]. In this work, we have investigated theyields of integrated circuits such as inverters and ring oscillators which consist of TFTs withpurified semiconductor CNTs.
The integrated circuits were fabricated on a poly(ethylene naphthalate) (PEN) substrate.
Purified semiconducting CNTs were used as the channel. The gate oxide of a 40-nm-thick Al2O3
layer was deposited by atomic layer deposition. The channel width and length were 100 m.
The inverters were constructed in E/D configuration. The load TFT was slightly doped with
F4TCNQ (tetrafluoro-tetracyano quinodimethane) to shift the threshold voltage to be depletion
mode. Ring oscillators of 3, 11, and 24 stages with an output buffer were fabricated.
Figure 1 shows input-output characteristics of 24 inverters. All of the inverters worked
successfully. The voltage gain was as high as ~30 in average. Although their large logic
threshold voltages dispersed from -3.5 to -2.2 V, logic signal transfer to the subsequent stage
would be possible even under an existence of hysteresis. The yields of ring oscillators degradedwith an increase in integration scale, i.e., 3stage (100%), 11-stage (75 %), and 21-stage(50%). The yield of TFTs were 96.2 %,which should be improved further for highyield fabrication of integrated circuits.
Acknowledgments: The semiconducting CNTs
were provided by TASC. This work waspartially supported by Grant-in-Aid by MEXT,
JST/SICORP, and JST/CREST.
[1] D.-M. Sun, et al., Nature Nanotechnol. 6,156 (2011).
[2] J. Hirotani et al., The 48th FNTG
symposium, 3P-12
Corresponding Author: Yutaka Ohno, Phone &Fax:+81-52-789-5387,
E-mail:yohno@nagoya-u.jp

Fig. 1 Input-output characteristics of 24 inverters.

- 139 -

3P-13Modeling of carbon nanotube thin-film transistor on flexible plastic film
○Taiga Kashima1, Tomoki Matsuura2, Jun Hirotani2, Shigeru Kishimoto2, and Yutaka Ohno2,3
1

School of Engineering, Nagoya University, Nagoya 464-8603, Japan
Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
3
Institute of Material and Systems for Sustainability, Nagoya University, Nagoya 464-8603, Japan
2

Carbon nanotube thin-film transistors (CNT TFTs) are promising active devices for flexible
electronics because of their high carrier mobility [1] and excellent mechanical flexibility. In
recent years, high-yield fabrications of CNT TFTs with small characteristic variation havebecome possible with purified semiconductor CNT materials. This leads to progressive
researches on large-scale integration and analog circuit applications of CNT TFTs. To design
functional integrated circuits, the modeling of transistors for circuit simulations areindispensable. In this work, we have built a model of CNT TFTs on the basis of the electricalcharacterizations.
The device structure of the CNT TFTs is shown in the inset of Fig. 1(b). The device wasfabricated on poly(ethylene naphthalate) (PEN) substrate. Purified semiconducting CNTs wereused as the channel. The gate oxide of a 40-nm-thick Al2O3 layer was deposited by atomic layer
deposition. The channel width was 100 m, and the channel length was from 5 to 100 m.
We constructed a device model based on Shichman and Hodges's MOSFET model [2]. Somemodifications were applied to express subthreshold current and off current. Figure 1 shows
measured characteristics and the fitted model. The developed model can well express the both
output and transfer characteristics. The model was also applicable to n-type CNT TFTs.
Acknowledgments: The semiconducting CNTs were provided by TASC. This work waspartially supported by Grant-in-Aid by MEXT, JST/SICORP, and JST/CREST.
[1] D.-M. Sun, et al., Nature Nanotechnol. 6, 156 (2011).
[2] H. Shichman and D. A. Hodges, J. Solid-State Cir. 3, 285 (1968).

Fig. 1 Measured characteristics and fitted model. (a) Output and (b) transfer characteristic.
Corresponding Author: Yutaka Ohno, Phone & Fax: +81-52-789-5387,E-mail: yohno@nagoya-u.jp- 140 -

3P-14
Improved Efficiency and Stability of Perovskite Solar Cells with
Single-Walled Carbon Nanotube Electrodes○Takahiro Sakaguchi1, Jeon Il1, Hiroki Suko1, Taiki Inoue1, Rong Xiang1, Shohei Chiashi1,
Esko I. Kauppinen2, Nam-Gyu Park3, Yutaka Matsuo1,4, Shigeo Maruyama1,5
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Department of Applied Physics, Aalto University School of Science, Espoo 15100, Finland
3
School of Chemical Engineering and Department of Energy Science, Sungkyunkwan
University, Suwon 440-746, Korea
4
Hefei National Laboratory for Physical Sciences at Microscale, University of Science andTechnology of China, Hefei, Anhui 230026, China
5
Energy NanoEngineering Lab, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8564, Japan

2

Perovskite solar cells [1] are attracting a lot of attention due to their high power
conversion efficiency (PCE) with low-cost materials. The PCE was 3.8 % in 2009 [1]and has drastically increased to 22.1 % [2]. As anodes, gold electrodes and SpiroMeOTAD are used in conventional perovskite solar cells. Both gold and SpiroMeOTAD are expensive, and the latter is unstable in ambient. Single-walled carbon
nanotubes (SWNTs) have been reported to act as anodes in perovskite solar cells by
substituting gold and Spiro-MeOTAD [3]. However, PCEs of perovskite solar cells with
SWNT anodes have not yet attained those with conventional anodes.
In this study, we improved stability and efficiency of perovskite solar cells using SWNTs
as anodes by adding polymethyl methacrylate (PMMA) onto SWNTs. Dry-deposited SWNT
films [4] were employed, and solar cell structures were fabricated by deposition of TiO2 layers,
perovskite crystals, and SWNT films on FTO/glass substrates. Figure 1 shows the J-V
characteristics of cells with PMMA and without PMMA. While the PCE of 10 % was obtainedin the case of cell without PMMA, we achieved the PCE of 11.8 % by adding PMMA on SWNT
films. Figure 2 shows the time change of the PCEs of both cells. The cell with PMMA wasfound to have higher stability than the cell without PMMA. These indicate that the PMMA
densifies and mildly dopes SWNT films, and protects cells from moisture.

10
PCE (%)[1] A. Kojima et al., J. Am. Chem.
Soc.,131, 6050 (2009).
[2] http://www.nrel.gov/ncpv/
images/efficiency_chart.jpg[3] Z. Li et al., ACS Nano, 8, 6797
(2014).
[4] A. Kaskela et al., Nano Lett.,
10, 4349 (2010).
Corresponding
Author:S.
Maruyama
Tel: +81-3-5841-6421,
Fax: +81-3-5841-6421,

500with PMMA
without PMMA
1

Weeks

2

3

Fig. 1 J-V characteristics of cells

Fig. 2 Stability plots of perovskite

with PMMA and without PMMA.

solar cells with and without
PMMA.

E-mail: maruyama@photon.t.u-tokyo.ac.jp- 141 -

3P-15
Evaluation of the ratio of metal/semiconductive SWNTs
by utilizing ATP technique and Raman spectroscopy
Kento Uratani1, Naoki Kanazawa1, ○Shinzo Suzuki1
1

Department of Physics, Kyoto Sangyo University, Kyoto 603-8555, Japan

In this presentation, ATP technique and Raman spectroscopy were applied in order toevaluate the ratio of metal/semiconductive SWNTs by changing excitation wavelength (532
nm and 633 nm). Briefly, mono-dispersed sodium cholate (SC) solution (2 wt%) of SWNTs
produced by arc-burning of Ni/Y-carbon composite rod in helium atmosphere was utilized for
two immiscible aqueous solution phases (ATP), i.e., PEG and DX solution phases, following
the recipe by C.Y. Khripin et al. [1]. After[SWNT(PEG)]/[SWNT(DX)]recognizing that each solution phase shows100
different color because of the difference in theratio of metal/semi-conductive SWNTs, Raman
10
spectra were obtained by different excitation
1
photon energy (532 nm and 633 nm) for eachsolution phase, and the ratio of metal /0.1
semiconductive SWNTs was evaluated byanalyzing those spectra [2].
0.01
case1(s-SWNT)
case2(s-SWNT)
Figure 1 shows the reproducibility of the ratio
case3(s-SWNT)
0.001
of metal/semiconductive SWNTs obtained by thiscase1(m-SWNT)
case2(m-SWNT)
technique, in case that the concentration of SC in 0.0001
case3(m-SWNT)
ATP was slightly varied. It was confirmed that the-5
10
reproducibility of the ratio was reasonable,
0
2
4
6
8
10
12
indicating that this technique can be useful for
SC / µL
in-situ evaluation of the ratio of metal/semiconductive SWNTs in ATP separation
Fig. 1.
procedure.

[1] C.Y. Khripin et al., J. Am. Chem. Soc., 135, 6822-6825(2013).
[2] N. Kanazawa et al., The 46th fullerenes-nanotubes-graphene general symposium, 1P-27.
Corresponding Author: S. Suzuki
Tel: +81-75-705-1631, Fax: +81-75-705-1640,
E-mail: suzukish@cc.kyoto-su.ac.jp- 142 -

3P-16
Removing catalyst metals from various carbon nanotubes by halogen gas○Koki Hamada1, Hisashi Sugime 2, Suguru Noda 1
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Waseda Institute for Advanced Study, Waseda University, Tokyo 169-8050, Japan

1
2

Extensive efforts have been made to remove catalyst metals from as-produced carbon
nanotubes (CNTs). Two-step purification is popular; first the carbon shells (C-shells) covering
catalyst particles are removed by gas-phase or liquid-phase oxidation and then the catalyst
metals are dissolved by acids [1]. But the oxidation step causes damage to CNTs and thesolution process causes aggregation of CNTs upon drying and yields liquid wastes. Somegroups recently reported dry purification process in which catalyst metals such as Ni [2] or Fe[3] are etched away by the reaction with Cl2 gas at elevated temperatures of ~1000 C.
However, this method is not widely used and reaction mechanism remains unclear.
In this research, we applied this method for various CNTs including single-wall CNTs
(SWCNTs) by arc discharge (from Meijo Nano Carbon), multi-wall CNTs (MWCNTs) bychemical vapor deposition (CVD) (from Meijo Nano Carbon), and Tuball SWCNTs (fromOCSiAl). We examined the process parameters (temperature, Cl2 and Br2 pressures, andreaction time) and discuss the rate determining step and reaction mechanism.
Fig. 1 shows transmission electron microscope (TEM) images of the CNTs before and after
purification with 10 vol% Cl2/Ar. Both Ni (a) and Fe (b,c) catalysts are efficiently removed(d–f), leaving hollow carbon spheres. Mercier, et al. reported such structure and proposed amechanism that Cl2 diffuses through the C-shells, metal expands upon chlorination, causing
cracks in the shells, promoting Cl2 diffusion and metal chloride vaporization [4]. Following
this mechanism, metal in crack-free shells cannot be removed. We propose another model thatmetal diffuses through the shells at a small probability and metal on the shells immediately beetched away by Cl2. To identify diffusion species (halogen or metal), we examined Br2 as
etchant and found that it can also remove metal efficiently (Fig. 2). We are now studying therate process at milder condition to identify the diffusion species and rate determining step.

Fe content (wt%)

301000 oC, 60 min

20
10
0

Fig. 1. CNTs before and after purification.

Before Cl2
Br2
Br2
1 Torr 1 Torr 3 Torr

Fig. 2. Fe contents in Tuball.

[1] J. Vejpravova, et al., Analyst 141, 2639 (2016). [2] A. Desforges, et al., Carbon 76, 275 (2014).
[3] E. Remy, et al., Carbon 93, 933 (2015). [4] G. Mercier, et al., New J. Chem. 37, 790 (2013).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 143 -

3P-17
Controllable growth of single-walled carbon nanotubes in quality anduniformity by extended alcohol catalytic chemical vapor deposition○Bo Hou1, Cheng Wu2,, Yoko Iizumi3, Takahiro Morimoto3, Toshiya Okazaki3, Taiki Inoue2,
Shohei Chiashi2, Rong Xiang2, and Shigeo Maruyama1,2
1

Energy NanoEngineering Lab., Department of Energy and Environment, AIST, Tsukuba 3058564, Japan2
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
3
Nanotube Research Center, AIST, Tsukuba 305-8564, Japan

In the extended conventional alcohol catalytic chemical vapor deposition (ACCVD), CVD
temperature was varied from 350 oC to 1050 oC combined with the pressures range over 6
magnitudes. In this work, we will report the high-quality SWNTs which are nearly none defectwere obtained within a specific work window of extended ACCVD using zeolite-supported FeCo system. Furthermore, several other catalysts (zeolite-supported Rh-Co, Cu-Co and Rh) werealso studied in the extended ACCVD. By using Rh-Co as the catalyst, the efficient growth of
uniform diameter SWNTs was achieved in extended ACCVD. Scanning Raman with manylaser lines, absorption, and photoluminescence (PL) were used to characterize the chirality andabundance of SWNTs. TEM was employed to examine the quality of SWNTs and explore thecondition of catalysts near the growth boundary. The success of the direct growth of highquality SWNTs and the realization of diameter uniformity SWNTs in extended ACCVD
suggest the promising future for application and fundamental understanding of growth of
SWNTs.

G/D ratio
No SWNTs
3−10
10−15
15−20
20−25
7
70
25−50
70 0
50−

51.8

10

2

10

1

? 70.470.4

100Good SWNTs

10

−1

10

3

10

2

10

1

10

0

10

−2

10

−1

Too Low 10
Pressure

−3

10

−2

10
300 400 500 600 700 800 900 10001100
Temperature (°C)

−4Too Low
Temperature

(b)

(c)
20−25

Pressure (mbar)

Pressure (Pa)(a) 104

Fig (a). Extended ACCVD map. (b). 3D mapping of G/D ratio. (c) TEM image of high-quality
SWNTs.
Corresponding Author: Shigeo Maruyama
Tel: +81-29-861-2073, Fax: +81-29-851-7523,
E-mail: maruyama.nano@aist.go.jp- 144 -

3P-18Synthesis and Characterization of SWNTs Using W-Co Catalyst○Shinnosuke Ohyama1, Shun Yamamoto1, Hua An1, Feng Yang2, Taiki Inoue1, Rong Xiang1,
Shohei Chiashi1, Yan Li2, Shigeo Maruyama1,3
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Beijing National Laboratory for Molecular Science, Key Laboratory for the Physics andChemistry of Nanodevices, State Key Laboratory of Rare Earth Materials Chemistry andApplications, College of Chemistry and Molecular Engineering, Peking University, Beijing
100871, China.
3
Energy NanoEngineering Lab, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8564, Japan
2

Chirality controlled growth of SWNTs is highly expected toward the applications of SWNTs.
Recently, it was reported that W6Co7 alloy catalyst realized the growth of single-chirality
SWNTs with purity over 90% through pretreatment and growth at high temperature using
molecular cluster as a catalyst precursor [1, 2]. Furthermore, in our group, (12, 6) SWNTs
were selectively grown at lower temperature by using a sputtered bimetallic W-Co in thealcohol catalytic chemical vapor deposition [3, 4]. The structure of the sputtered catalyst
identified by TEM analysis was W6Co6C, which is different from that from the molecularcluster.
In this report, we deposited W-Co catalyst by dip-coating of solution of WCl6 andCo(CH3COO)2, and compared the grown SWNTs with those from sputtering and themolecular cluster. We succeeded in producing SWNTs with high yield and chirality selectivity
to some extent by relatively lower temperature growth. We changed ratio of W/Co andinvestigated the effects of W by using Raman spectra (Fig. 1). From the spectra, we found thatsample (c) exhibited the highest selectivity of (12, 6). We will also discuss the effects of water
vapor treatment during the reduction process.

Fig. 1 Raman spectra of SWNTs from W-Co catalyst deposited by dip-coat method (a) Co: 1.68 mM,(b) W: 5.0 mM, Co: 1.0 mM, (c) W: 5.0 mM, Co: 3.0 mM and (d) W: 5.0 mM, Co: 5.0 mM.
[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). [4] H. An et al., Nanoscale 8, 14523 (2016).
Corresponding Author: S.Maruyama
Tel: +81-3-5841-6408, Fax: +81-3-5841-6408,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 145 -

3P-19Growth of Semiconducting (14,4) Carbon Nanotubes Using W-Co
Salts as Catalyst Precursor○Xiulan Zhao, Feng Yang, Yan Li
Beijing National Laboratory for Molecular Science, College of Chemistry andMolecular Engineering, Peking University, Beijing 100871, China
Tungsten-based intermetallic catalyst with high melting points can maintain their
specific crystal structure during the chemical vapor deposition (CVD) process andregulate the chirality of the grown SWNTs [1-2]. Instead of the previously usedmolecular clusters, here, we simply used salts containing W and Co, respectively, as
precursors to prepare intermetallic W6Co7 catalysts. (NH4)6W7O24·6H2O and
Co(CH3COO)2·4H2O with rational molecular ratio were mixed, annealed and reduced
at suitable conditions to prepare W6Co7 intermetallic compounds. Using the resultant
W6Co7 nanoparticles as catalysts, we realized the synthesis of semiconducting
SWNTs with the purity of ∼97%, in which (14,4) tubes are at the abundance of ~ 62%
under the optimized growth condition. It seems that this is a flexible pathway to growsemiconducting SWNTs with one enriched chirality.
[1] F. Yang, Y. Li et al. Nature. 510, 522 (2014).
[2] F. Yang, Y. Li et al. ACS Nano. 10.1021/acsnano.6b06890 (2014)
Corresponding Author: Yan Li
Tel: +86-10-6275-6773, Fax: +86-10-6275-6773,
E-mail: yanli@pku.edu.cn- 146 -

3P-20Single-Walled Carbon Nanotube Growth from Bimetallic Catalyst
by Molecular Dynamics Simulations○Ryo Yoshikawa1, 2, Hiroyuki Ukai1, Yukai Takagi1, Shohei Chiashi1, Shigeo Maruyama1, 2
1 Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2 National Institute of Advanced Industrial Science and Technology, Ibaraki 305-8564, Japan

It is reported that some of bimetallic catalyst can control the chirality of single-walledcarbon nanotubes (SWCNTs) during growth and it is suggested that a specific chirality of
SWCNTs fit the structure of the catalyst alloy [1].
In this study, we conducted molecular dynamics (MD) simulations to investigate SWCNT
growth from two types of bimetallic catalyst, Cu-Co and W-Co. We constructed Tersoff-type
potential for the triatomic system including two metal elements of the catalyst and carbon.
Brenner-Tersoff potential was applied among carbon atoms forming covalent bonds andLennerd-Jones potential was applied between non-bonded carbon atoms. The catalyst metal
nanoparticle was put at the center of 10 × 10 × 10 nm3 cell with periodic boundary condition
along the three axes. The temperature of the catalyst metal nanoparticle was controlled with
Nosé-Hoover thermostat. Carbon atoms were supplied into the cell so that the number ofgas-phase carbon atoms (n) was constant.
Figure 1 shows SWCNT caps formed on W-Co catalyst and Co monometallic catalyst. On
W-Co catalyst, SWCNT caps were formed at high temperature (1500-2000 K), compared to
Co monometallic catalyst (1350-1550 K). Since few W atoms were bonded to sp2 carbon
atoms, W atoms were considered to support Co atoms rather than to catalyze the cap
formation. The size of the caps was almost the same as that on Co monometallic catalysts.
Figure 2 shows a Cu-Co particle after reaction with carbon atoms. The Cu-Co catalyst was
divided into Cu-rich and Co-rich parts, and amorphous carbon formed between two parts.
Over 700 K, the catalysts were completely separated into the two parts.
(a)

(b)

Fig. 2. A Cu30Co30 particle withcarbon atoms, 700 K, n=1.

Fig. 1. (a) Cap formed on a W30Co30 particle. 2000 K, The blue atoms are Co, then=1. The blue atoms are Co, the yellow atoms are W, and yellow atoms are Cu, and thethe others are C. (b) Cap on a Co60 particle. 1400 K, n=3. others are C.
[1] F. Yang, et al., Nature, 510 (2014) 522.
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-21
Template Synthesis of π-Conjugated Nanomaterials using
Inner Space of Carbon Nanotubes○Yasuhiro Kinno 1, Haruka Omachi1,2, Ryo Kitaura1, and Hisanori Shinohara1,3
1

Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan.
2

Research Center for Materials Science, Nagoya University
3
Institute for Advanced Research, Nagoya University

It is possible to stably contain substances such as fullerene in the internal space of theCNTs, and it is expected to develop new physical properties [1,2]. Reacently, we havedemonstrated the synthesis of 1D diamondoid polymer by using the internal space of CNTs asa reaction platform [3]. Utilizing the selective cleavage of carbon–halogen bonds, biradical
diamantine species reacted each other inside of the nanotubes. However, this synthetic
methodology has been applicable to only sp3 carbon nanomaterials.
In this study, we developed the template synthesis of 1D π-conjugated nanomaterials
into the CNTs under milder reaction conditions. Vapor-phase reaction of oligothiophenes
substituted with bromine atoms at α positions furnished the linear polythiophenes into CNTs
(Figure 1a). Using experimental techniques, we revealed that the oligothiophenes moieties
were linked each other inside CNTs. Our new synthetic method might provide various 1D
aromatic polymer utilizing a huge number of dihalogenated aromatic compounds.
In the TEM observation, a 1D substance could be confirmed inside the CNTs (Figure1b), and the peaks of polythiophene could be detected by the Raman spectra measurement(Figure 1c). These results suggest that 1D polythiophene was synthesized successfully.

Fig.1 (a) Structural model of a polythiophene@CNTs ;(b) TEM image of 1D polythiophene@CNT;(c) Raman spectra of 1D polythiophene@CNT[1] J. Lee, et al., Nature, 415, 683 (2002).
[2] T. Takenobu, et al., Nat. Mater., 2, 683 (2003).
[3] Y. Nakanishi, et al., Angew. Chem., Int. Ed., 54, 10802 (2015).
Corresponding Author: Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442,
E-mail: noris@nagoya-u.jp- 148 -

3P-22
Electronic states of chalcogen encapsulated in single-walled carbon
nanotubes studied by First-Principles DFT calculations(II)○1Yutaka Sato, 2Yousuke Kataoka, 1Eita Yokokura and 1,2,3 and Hironori Ogata
1

Graduate School of Science and Engineering, Hosei University, Koganei 184-8584, Japan
Department of Faculty of Bioscience and Applied Chemistry, Hosei University, Koganei,
184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, Koganei 184-0003, Japan
2

Single-walled carbon nanotubes(SWNTs) have a hollow space in the nanometer size that canbe encapsulated various functional molecules. The conﬁned molecular assemblies is expected
to exhibit unique low-dimensional structures and solid state properties that can not be realized
in the bulk states. Recently, syntheses of sulfur encapsulated SWNTs or selenium
encapsulated DWNTs and unique one-dimensional conductive sulfur chain structure or
double-helices selenium structure were reported. In this study, we report the effects ofchirality and diameter of CNTs on the electronic states of the chalcogens encapsulated by
SWNTs by using First-Principles DFT calculations.
In the First-Principles DFT calculations, we used a code package PWscf and GIPAW in
Quantum ESPRESSO. We have calculated the electronic states of encapsulated chalcogenassemblies and their solid-state NMR parameters(chemical sift and electric field gradient(EFG) tensor) with several kinds of SWNTs. Fig.1. show the predicted static 33S-NMR
spectrum in S@(5,5)SWNT or S@(7,0)SWNT at 21.1 tesla. The detailed results will bepresented.

Fig.1. Predicted

S-NMR spectrum in S@(5,5)SWNT and S@(7,0)SWNT

33

References[1] Toshihiko Fujimori et al. Nature Communications4(2013)2162.
[2] Toshihiko Fujimori et al. ACS Nano vol.7 No.6(2013)5067-5613.
[3]T.A wagler et al. Journal of Magnetic resonance 161 (2003) 191-197.
[4]L.A. O’Dell, I.L. Moudrakovski. Journal of Magnetic Resonance 207 (2010) 345-347.
[5] P. Giannozzi et al., J.Phys.:Condens.Matter, 21(2009)395502.
Corresponding Author: H. Ogata Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 149 -

3P-23
Effect of carbon nanohorns on lipopolysaccharide-induced RAW264.7
macrophage cells○Maki Nakamura 1, Kiyoko Kuroiwa 1, Sumio Iijima 2, Masako Yudasaka 1,2
1

National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi,
Tsukuba 305-8565, Japan
2
Meijo University, 1-501 Shiogamaguchi, Nagoya 468-8502, Japan

Carbon nanohorns (CNHs, Fig. 1) have great potential fordelivery carriers of drug delivery systems. For the treatment ofinflammatory diseases, drug delivery of anti-inflammatorysteroid drugs to the diseased site is expected to minimize thesystemic side effects. Determination of interleukin-6 (IL-6)
produced from lipopolysaccharide (LPS)-induced RAW264.7
macrophage cells can be one of the effective way to evaluate
an anti-inflammatory effect of steroid drug-loaded CNHs invitro. In this report, we investigated the effect of CNHs on the
production of IL-6 from LPS-induced RAW264.7 macrophagecells, and discussed the suitability of this evaluation method.

50 nm

Fig. 1 A transmission electron
microscopy image of CNHs

The oxidized CNHs (oxCNHs) were prepared bysimultaneous light irradiation and heating of as-grown CNHs in an aqueous hydrogen
peroxide solution [1]. The resultant oxCNHs were dispersed in ultrapure water and sterilized.
This oxCNH solution was added to the RAW264.7 macrophage cells that were cultured at
37 °C in a 5% CO2 atmosphere (final concentration of oxCNH: 0, 1.46, 7.3, 36.5 μg/mL).
After incubation for 3 h, LPS was added to each well in order to induce inflammation (final
concentration of LPS: 0, 0.1 μg/mL). After incubation for 44 h, culture medium was collected
and centrifuged at 18,000 g for 50 min to remove oxCNHs. The amounts of IL-6 in the
supernatants were quantified by enzyme-linked immunosorbent assay.
The amounts of IL-6 produced from the LPS (0.1 μg/mL)-induced RAW264.7 macrophagecells incubated with oxCNHs (1.46, 7.3, 36.5 μg/mL) were larger than those without oxCNHs(0 μg/mL). With increasing concentration on oxCNHs, the amounts of IL-6 increased. In
contrast, without LPS treatment (0 μg/mL), IL-6 was seldom produced even in the presence of
oxCNHs. These results indicated that LPS induced inflammation more strongly in thepresence of oxCNHs. It was considered that LPS adsorbed on oxCNHs in culture medium andwas incorporated into the cells with oxCNHs, resulting in the large quantity of LPS inside thecells. Therefore, the LPS, a commomly-used reagent to induce inflammatory response, is notsuitable to be employed for the evaluation of an anti-inflammatory effect of steroid
drug-loaded CNHs in vitro.
[1] M. Zhang, M. Yudasaka, K. Ajima, J. Miyawaki, S. Iijima, ACS Nano, 1, 265 (2007).
Corresponding Authors: M. Nakamura
Tel: +81-29-861-4604, Fax: +81-29-861-3005,
E-mail: ma-ki-nakamura@aist.go.jp (M.N.)- 150 -

3P-24
A study of Preparation Conditions of Carbon Nanobrush○Ryota Yuge1, Fumiyuki Nihey1, Kiyohiko Toyama1, and Masako Yudasaka2, 3
1

IoT Devices 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) are generally in spherical aggregates [1], andthey are attractive due to high dispersibility in solutions and large specific surface area.
However, when used for energy devices such as electrical capacitors and fuel cells, highelectrical conductivity has been also required. Recently, we have succeeded in preparing theradially-assembled and fibrously connecting SWCNHs, named as carbon nanobrushes [2].
They have high dispersibility in solutions, large specific surface areas, and high electricalconductivity [2]. Therefore, the carbon nanobrush is an excellent candidate for the electrodematerials of various energy devices. Although the carbon nanobrushes are prepared by CO2
laser ablation of iron-containing carbon target at room temperature, the yield is quite small
and the major products are the spherical SWCNHs. In this study, we have changed the laser
power and the rotation speed of target to increase the yield.
In the laser ablation, the CO2 laser was operated at 2.5-4.5 kW in the continuous-wave mode.
The iron-containing carbon target with cylindrical form (diameter 3 cm, length 10 cm) wasused. The iron content in the target was 1 at. %. The target was rotated at 0.5-4 rpm for 30 sec
during the laser ablation. The gas pressure in the growth chamber was sustained at 700-800
Torr by controlling the evacuation rate while the buffer gas of N2 was kept at the flow rate of
10 Lmin-1.
SEM and STEM observations showed that the samples obtained at 2.5-4.5 kW of the laser
power and 2 rpm of target rotation speed were mainly spherical SWCNHs. The preparation ofcarbon nanobrushes did not strongly depend on the laser power. When the rotation speed oftarget was changed, a variety of carbon materials was obtained. At low rotation speed, thegraphitic particles and/or carbon nanotubes were dominantly formed. On the other hand, athigh rotation speed, spherical SWCNHs were formed. Thus, we found that carbon
nanobrushes were obtained at the intermediate rotation speed of the target. The details will be
discussed in the presentation.
[1] S. Iijima et al. Chem. Phys. Lett. 309, 165 (1999).
[2] R. Yuge et al. Ad. Mater. 28, 7174 (2016).
Corresponding Author: R. Yuge
Tel: +81-29-850-1566, Fax: +81-29-856-6137
E-mail: r-yuge@bk.jp.nec.com- 151 -

3P-25
Analysis of Initial Formation Process of Graphene on SiC(0001) Surfaces
Based on the First-Principles Molecular Dynamics○Fumihiro Imoto 1, Jun-Ichi Iwata 1, Mauro Boero 2, Atsushi Oshiyama1
1

2

Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504, and University ofStrasbourg and CNRS, F-67034 Strasbourg, France

Thermal decomposition of SiC (0001) surfaces is a promising way to form graphene
because it provides large-area graphene supported on regular SiC substrates. It is
experimentally known that Si atoms are desorbed selectively from the SiC, leading to thegrowth of graphene layers on a carbon-rich 6 3×6 3 buffer layer[1]. Before the thermal
decomposition, hydrogen etching of the SiC is performed and ordered nanofacets appear on
the surface[2]. Several experiments[1,3] have revealed that graphene layers grow from such
nanofacets toward terraces. This nanofacet is theoretically identified as a bunched structure of
single bilayer atomic steps[4].
The aim of our work is to unravel the microscopic mechanisms of graphene formationfrom the step edge, which constitutes the nanofacet. In our previous calculations based on thedensity functional theory, we found that the energy barrier for the desorption of an Si atom at
the step edge is lower than that of a C atom by 0.75 eV, which indicates the selective
desorption of Si atoms[5]. However, this result does not provide sufficient information on freeenergy barriers, which should be overcome at finite temperature (~1500 K) during theheating.
In this talk, we report Car-Parrinello molecular dynamics calculations that clarify
atom-scale mechanisms of the initial formation process of graphene from 4H-SiC (0001)[1120] step edge. Free energy profiles have been calculated by metadynamics, in which Si
desorption is forced to occur by filling up the free energy surface. The stacking of Si-C
bilayers along the [0001] direction in 4H-SiC is ⋯ ABCB ⋯, which results in two possible
step edge configurations, the cubic upper terrace (A as the upper terrace and B as the lower
terrace) and the hexagonal upper terrace (B as the upper terrace and C as the lower terrace).
Our calculation has been performed for these two possible step edges. We find that an Si isdesorbed toward the lower terrace with the rate-determining barrier of 1.50 eV for the cubic
upper terrace and 1.10 eV for the hexagonal upper terrace. The obtained reaction pathways
are in good agreement with our previous results and we further study subsequent Si
desorption to clarify carbon bond formation process near the step edge.
0.0

Corresponding Author: F. Imoto
Tel: +81-80-3157-8122
E-mail: fimoto@comas.t.u-tokyo.ac.jp

cubic upper terrace
hexagonal upper terrace−0.5Free energy (eV)[1] J. B. Hannon et al. Phys. Rev. B 77, 241404(R) (2008).
[2] T. Kimoto et al. Appl. Phys. Lett. 66, 3645 (1995).
[3] W. Norimatsu et al. Physica E 42, 691 (2010).
[4] K. Sawada et al. Appl. Phys. Lett. 104, 051605 (2014).
[5] F. Imoto et al. [arXiv:1611.04404] (2016).

−1.0
−1.5
−2.0
−2.5
−3.0
−3.5
1.0

1.5

2.0

2.5

3.0

CV [Å]

3.5

4.0

4.5

Fig.1: Free energy profiles of Si desorption- 152 -

3P-26Growth of Single-Crystal Single-Layer and Bi-Layer Graphene
Using Alcohol Catalytic CVD○Masaki Sota1, Kotaro Kashiwa1, Naomasa Ueda1, Keigo Otsuka1,
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 (AIST), Ibaraki 305-8564, Japan

Graphene, an sp2-bonded single-layer honeycomb lattices, is a promising material due toits extraordinary mechanical, thermal, and electrical properties. However, single-layer
graphene (SLG) is conductor and inapplicable to semiconductor applications. Several groups
reported that a bandgap up to 250 meV can be induced by an external electric field in
AB-stacked bi-layer graphene (BLG) [1]. Therefore, the synthesis of BLG is essential forelectronic applications of graphene. Chemical vapor deposition (CVD) is an effective method
for the synthesis of large-scale graphene. Since grain boundaries in poly-crystal graphenedegrade its superior properties, many efforts have been focused on enlarging the size of
single-crystal graphene. As a result, single-crystal SLG of large size has been synthesizedusing CVD, but there is a problem that the size of the single-crystal BLG is still not large.
In this research, we synthesized single-crystal SLG and BLG using the alcohol catalytic
CVD (ACCVD) [2]. We used a copper foil as the catalyst and oxidized and folded it into a
pocket before synthesis. CVD was performed at 1065 ˚C with various pressures of Ar/H2 andethanol. We found that single-crystal BLG can be grown by low pressure of the CVD
condition. Figure 1 is a dark field (DF) optical image of graphene on copper foil, which shows
the crystal orientation of single-crystal BLG matches that of SLG. Figure 2 shows large-size
flakes of single-crystal BLG and many of them have the same orientation. This indicates BLG
are epitaxially grown on SLG in the ACCVD.

Fig. 1 DF optical image of SLG and BLG.

Fig. 2 DF optical image of large flakes ofsingle-crystal BLG.

[1] Y. Zhang et al. Nature, 459, 820 (2009).
[2] X. Chen et al. Carbon, 107, 852 (2016).
Corresponding Author: S. Maruyama
Tel: +81-03-5841-6421, Fax: +81-03-5841-6421,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 153 -

3P-27Highly Oriented CuInS2 Thin-Films on Graphene Electrodes for Solar Cells
Applications○Ryousuke Ishikawa, Tomoya Oya, Tonan Yamada, Takahiro Nomoto, and Nozomu Tsuboi

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

Thin-film solar cells based on multinary compound semiconductors represented byCu(In,Ga)Se2 (CIGS) have demonstrated a high conversion efficiency over 20%. Other multinary
compound semiconductors such as CuInS2 (CIS), Cu2SnS3 (CTS), and Cu2ZnSn(S,Se) have been
also considered to be potential photovoltaic materials for next-generation solar cells with highefficiency. Graphene, a single atomic layer of sp2 graphitic carbon, is a promising material fortransparent electrodes due to its high electrical conductivity and optical transparency over a wide
range of wavelength [1]. We attempted using the high-crystalline graphene layers on several typesof substrates to grow highly oriented CuInS2 films.
High quality graphene was fabricated by chemical vapor deposition (CVD) growth techniqueusing Cu foil for monolayer (1L-graphene) or Ni thin film for multilayer graphene (ML-graphene)
as catalyst substrates. After CVD growth, deposited graphene was then transferred by polymethyl
methacrylate (PMMA) assisted process onto glass substrates. The CuInS2 films were deposited byreactive-sputtering with facing targets system on obtained graphene or Mo.
The peak intensity and intensity ratio of (112) in CuInS2 films on graphene were greater thanthat on Mo as shown in Fig. 1. Especially, the SLG/1-L graphene sample indicated a highlyorientation. Because the CuInS2 (112) plane has hexagonal symmetry, CuInS2 thin-film might cause
quasi-superlattice matching with highly-oriented graphene which consists of perfect honeycomb
structure. The cross-sectional images revealed that larger and columnar grains were grown in the
CuInS2 films on graphene as shown in Fig. 2 (a) compared to the films on Mo as shown in Fig. 2 (b).
The top-surface view of the CuInS2 films on graphene exhibited the dense microstructure as shownin Fig. 2 (c). On the other hand, the CuInS2 films on Mo had many boundaries and voids as shownin Fig. 2 (d). Moreover, the electrical junction of graphene/CIS interface exhibited perfect ohmic
characteristics comparable to Mo/CIS interface.
Here we demonstrated the potential of graphene as transparent electrode in the compound
semiconductors based thin-film solar cells toward to multi-junctions solar cells with ultra-highefficiency.

10

(224)

(112)

SLG/1L-graphene/CIS

20(204)/(220)30

40

SLG/Mo/CIS
*

(312)
(224)

*
(204)/(220)

(c)

(312)
(224)

SLG/5L-graphene/CIS(112)(004)/(200)

(b)

(112)
(004)/(200)

X-ray Intensity (arb.unit)

(a)

50 60
2θ (deg.)70

Fig. 1 The XRD patterns of CuInS2 films

*Mo

80

90

Fig. 2 The cross-sectional and top-surface SEM images of CuInS2 films[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- 154 -

3P-28Controlled fabrication of graphene liquid cells○Yoshimasa Michiya,1 Tomohiro Yasunishi,2 Yutaka Ohno,2,Hisanori Shinohara,1and Ryo Kitaura1
1
2

Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan.

Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan

Transmission electron microscopy (TEM) is a very
powerful tool to visualize structure of materials at thenanoscale. If TEM can be applied to observations ofliquid, there is a possibility that a wide range ofphenomena including dissolution, precipitation andvarious liquid phase reactions can be directly visualized at
the nanoscale. In conventional TEM observations ofliquid, liquid is encapsulated in a liquid cell with thickFigure.1
Schematic view of amembranes (typically, 50 nm SiN) to prevent the liquid
graphene liquid cell.
form vaporization under the high vacuum. In this case,scattering of electrons arising from the membranes greatly limits resolution and contrast of
TEM images. In order to solve this problem, we have been focusing on graphene liquid cells(Figure.1), where graphene completely prevents liquid from vaporization with minimal
degradation of resolution and contrast. In this work, in order to develop controllable fabrication
method of the graphene cells, we have applied a semiconductor microfabrication technique
including electron beam lithography (EBL).
Figure.2 shows a schematic cross-sectional view of thegraphene liquid cell; in this liquid cell, graphite is used asbottom and side walls of the cell. To make the graphite
vessel structure, graphite with thickness of about 100 nm
was etched with reactive ion etching on a hole penetrating
Figure.2 Cross-sectional view of adesigned graphene liquid cell. It is
possible to control the part indicated by
the black arrow.

through a Si substrate. The width, depth and shape can be
microly controlled with accuracy of about 10 to 100 nm.
After putting Liquid (water) in the vessel, graphene istransferred on the structure. In the presentation, in
addition to details of sample fabrication, TEM
observations of the graphene liquid cells will be shown.

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- 155 -

3P-29
Factors for reactivity of GO regarding oxidative amine coupling reaction○Takuya Isaka1, Kentaro Tajima1, Tomoki Yamashina1, 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

Investigating Graphene Oxide (GO) properties before / after the catalytic reaction is apromising strategy for clarification of the mechanism for GO catalytic activity. Additionally, it
is known that removing oxidative debris on GO by base-treatment is important factor to get
the higher yield for the following catalytic reaction [1]. We have reported that base-treated
GO (baGO) used as catalyst once gives the higher yield than that in the 1st cycle reaction inoxidative amine coupling reaction [2]. In this study, the principle for reactivity is investigatedby conducting the oxidative amine coupling reaction of benzylamine (1) toN-benzylidenebenzylamine (2) using baGO and thermally reduced one (rbaGO) (Scheme 1).
baGO / rbaGO(1)

60˚C / 24h(2)

Scheme 1 Oxidative amine coupling reaction of benzylamine to N-benzylidenebenzylamine

Intensity (arb. units)

Table 1 Yield for (2) using each baGO
baGO-Pristine was obtained by washing GO,
Catalyst sample
Yield (%)
synthesized by Hummers method, with NaOH.
rbaGO was prepared by reducing baGO at 450˚C.
baGO-Pristine
13
talystsampleYield
After Scheme 1, the reaction media filtered for
baGO-1st cycle 13
39
baGO-Pristine
removing the catalyst was characterized by
rbaGO
6baGO-1st cycle
39
GC-MS. After the 1st cycle reaction, therbaGO-1st cycle 5.6
6
rbaGO-Pristine
recovered catalyst was used as that for the 2nd
rbaGO-1st cycle 6
cycle (baGO-1st cycle, rbaGO-1st cycle). The
Table O/C
1 yield
for using baGOeach
N/C
Pristinechemical structure of each catalyst after thebaGO0.44  0
baGObaGO
Pristine sample
1st cycle
reaction was evaluated by XPS (Al K), where itbaGO0.09 0.05
rbaGO
was washed with ethanol after the reaction.
1st cycle
rbaGO
0.11  0
The GC-MS yields of (2) for each catalyst is
rbaGOrbaGO
0.10 0.02
1st cycle
summarized in Table 1. The atomic ratio O/C of-1st cycle
catalyst much decreases after the reduction or 1st
cycle reaction and rbaGO shows poor yield,
suggesting roles of baGO / rbaGO not as catalyst





Binding energy (eV)but as oxidant (Fig.1). However, baGO-1st cycle
Fig.1 XPS C1s peak for each baGO after
exhibits the highest yield in spite of C1s spectrum
the reaction
and O/C similar to that of rbaGO and rbaGO-1st
cycle, which also indicates no more reduction for rbaGO in the 1st cycle reaction. Taking
these results and appearance of nitrogen content after the 1st cycle reaction into consideration,a different mechanism in the 2nd cycle reaction is suggested, where nitrogen incorporated into
rbaGO / baGO in the 1st cycle reaction plays an important role for the reactivity.
[1]C. Su, M. Acik, K. Takai et al. Nat. Commun., 3, 1298 (2012) [2]T. Isaka et al. FNTG51 conference (2016)
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002, E-mail: takai@hosei.ac.jp- 156 -

3P-30Highly conductive and transparent large-area bilayer graphene
realized by MoCl5 intercalation○Hiroki Kinoshita,1 Kenji Kawahara,2 Yuri Terao,1 Il Jeon,3 Mina Maruyama,4Rika Matsumoto,5 Susumu Okada,4 Yutaka Matsuo,3 Hiroki Ago1,2,6,*
1

Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, Fukuoka 816-8580, Japan
2
Global Innovation Center (GIC), Kyushu University, Fukuoka 816-8580, Japan3
School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
4
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8577, Japan
5
Faculty of Engineering, Tokyo Polytechnic University, Kanagawa 243-0297, Japan
6
PRESTO, Japan Science and Technology Agency, Saitama 332-0012, Japan

Being different from monolayer graphene, bilayer graphene (BLG) possesses a unique
two-dimensional (2D) nanospace sandwiched by the two graphene sheets. Intercalation ofmolecules/ions into this 2D nanospace provides a new avenue for realizing novel
functionalities without deteriorating the graphene -network. P-type doping of few-layer
graphene was demonstrated by intercalating FeCl3, reducing the sheet resistance [1,2].
However, the intercalation has been mostly applied to small, exfoliated graphene flakes, thus
limiting its practical applications. Also, most of the previous literature employed FeCl3 as
an intercalant [1-3]. Here, we demonstrate the intercalation of a new metal chloride, MoCl5,
into large-area, uniform BLG sheets which are grown by CVD.
A uniform BLG sheet grown by CVD on a Cu-Ni alloy catalyst [4] was sealed with MoCl5
powder in a glass tube, followed by heating in vacuum. The Raman G-band of the BLG
upshifted from 1585 cm-1 to 1616 cm-1 after the intercalation, indicating significant p-type
doping of the BLG. We found that the MoCl5 intercalation proceeds at lower temperatureand more uniformly, as compared with FeCl3. Interestingly, the intercalation of MoCl5 was
found to strongly depend on the stacking order of the BLG, as shown in Fig. 1a,b. Figure 1ashows a Raman mapping image (I2D/IG ratio) of the as-grown BLG, indicating the coexistenceof AB- and twist-stacked areas. After the exposure to MoCl5, the twisted area showed afully intercalated state, while the AB area showed only surface doping without intercalation(Fig. 1b). Figure 1c compares the sheet resistance of BLG sheets. Here, AB- and twist-rich
BLG sheets were selectively synthesized by controlling the CVD condition. The twist-rich
BLG showed much lower sheet resistance, 80 Ω/□ (~95% transmittance), which is thelowest value reported so far for BLG. Moreover, the intercalated state was stable in air for
more than 30 days. Our work offers a new route to functionalize graphene which can beapplied to transparent electrodes in various flexible devices.
Fig. 1 Raman
mapping of
I2D/IG ratio ofpristine BLG (a)and G-band
position after
intercalation (b).
(c) Sheet
resistance ofdifferent BLG
samples (in air).
[1] I. Khrapach et al., Adv. Mater., 24, 2844 (2012). [2] D. Zhan et al., Small, 11, 1177 (2015). [3] N. Kim et al.,Nano Lett., 11, 860 (2012). [4] Y. Takesaki et al., Chem. Mater., 28, 4583 (2016).
Corresponding Author: H. Ago (Tel&Fax: +81-92-583-8852, E-mail: h-ago@gic.kyushu-u.ac.jp)- 157 -

3P-31
Energetics of edge oxidization of graphene nanoribbons with cleanedges○ Airi Yasuma, Ayaka Yamanaka, and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8571, Japan
Graphene has been keeping premier position in nanoscale science and technology in thisdecade, because of their unique geometric and electronic structure, allowing them an emerging
material for future functional devices in the near future. To utilize graphene for devices, it ismandatory to control their geometries and elucidate their stability against the formation of
hybrid structures with foreign materials. Edgestability against chemical attachment is one ofimportantfactorstodeterminethegraphenegeometries. In this work, we aim to elucidate theenergetics of GNRs by the edge oxidization in termsof their detailed edge geometries, using the density
functional

theorywithgeneralized

gradient

approximation. As for the structural model, we
consider the GNR with clean edges and five edge
angles from armchair (0°) to zigzag (30°) (Fig.1).

Figure 2 shows the adsorption energy of O atoms

to the edges of GNRs with edge angles from0°  to  30°. The adsorption energy strongly depends

Fig.1 Optimized structures of GNRs withclean edges.

not only on the edge angle but also on the edge

atomic site in each edge shape. Our calculations
demonstrate that the edges with zigzag shape are

preferentially oxidized compared with the edge witharmchair portion. Furthermore, O atoms attached tothe step edge lead to the substantial structuraldeformation around the edges.

Corresponding Author: A. Yasuma

Tel: +81-29-853-5921, Fax: +81-29-853-5924
E-mail: ayasuma@comas.frsc.tsukuba.ac.jp- 158 -

Fig.2 Adsorption energy of oxygen to GNRs

3P-32
Band unfolding study on Fermi-level-velocity reduction induced
by Dirac cone interaction in twisted bilayer graphene○Hirofumi Nishi, Yu-ichiro Matsushita, Atsushi Oshiyama
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
Graphene shows the linear dispersion (Dirac cone) which causes great notable properties
such as high mobility, Klein tunneling, and the anomalous quantum Hall effect. It is reported
that when two sheets of graphene are stacked, Dirac cones are modified depending on the wayof the stacking. In particular, in twisted bilayer graphene (tBLG), the Fermi velocity
drastically reduces in tiny twisted angles. The origin of this mysterious modification of the
Fermi velocity in tBLG has been discussed: The continuum theory shows that the interactions
between Dirac cones located at different K points causes this reduction [1]. However, why
this long-range modulation of atomistic structure in real space causes the cone-coneinteractions in reciprocal space is unclear yet.
In this study, we have adopted the band-unfolding method with the tight-binding model, by
which we can unfold the electronic band structure calculated in the supercell Brillouin zone
(BZ) of tBLG to that in primitive cell BZ of monolayer. Using this technique, we can easily
visualize how the Dirac cones of the monolayer graphene are modulated in tBLG, and clarify
the relation between atomistic structure modulation in real space and Dirac-cone modulationin reciprocal space. As a result, we find the band-gap opening at particular points in thereciprocal space, that elucidates the drastic reduction of the Fermi-level velocity with the tiny
twisted angles in tBLGs. Moreover, it is found that the band-gap openings correspond to low
energy van Hove singularity in thedensity of states as shown in FIG. We
find that moiré pattern caused by thetwist of the two graphene layers
generates interactions among Diraccones, otherwise absent, and theresultantcone-coneinteractions
peculiar to each point in thereciprocal space causes the energy
gap and thus reduced the Fermi-levelvelocity [2].
[1] R. Bistrizer and A. H. MacDonald, Proc.
Natl. Acad. Sci. USA 108, 12233 (2011).
[2] H. Nishi, Y. Matsushita, and A. Oshiyama
arXiv:1609.05297 (2016).
Corresponding Author: H. Nishi
Tel: +81-3-5841-6812,
E-mail: nishi@comas.t.u-tokyo.ac.jp

FIG. Contour plots of the unfolded bands andtotal density of states of tBLGs near the Fermi
energy with twisted angle θ=5.09°.

- 159 -

3P-33
Energetics of Edge Formation Processes of Graphene○Ayaka Yamanaka, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba
305-8577, Japan
Ever since the synthesis of graphene by mechanical exfoliation technique, graphene has
attracted a great deal of attention in both pure and applied sciences due to its unique structuraland electronic properties. For the application of graphene, it is very important to precisely
control their geometric and electronic structure. Theoretical works demonstrated thatnear-zigzag edges are less stable than near-armchair edges because of the large number ofstates at the Fermi level in nanoribbons with near-zigzag edges. However, on the other hand,graphene with zigzag edges have been occasionally observed in TEM and STM experiments.
The fact implies that the edge shape of graphene flakes strongly depends on their formation
process. In this study, we aim to investigate (a) A-1(d) Z-1
the energetics of graphene edges with atomic
desorption to clarify the formation process ofgraphene edges by using the density
functional theory.
We consider the several edge structure of (b) rebonded A-1(e) Z-2graphene generated by atomic desorption
from the pristine armchair and zigzag edges
as shown in Fig. 1. Figure 2 shows thestability of graphene edges with atomic(f) rebonded Z-2
desorption of C atoms from pristine graphene (c) A-2
edges. We consider the methane and ethane
as the references of the desorbed C atoms. As
shown in Fig. 2, the A-2 structure isremarkably stable than the perfect armchair Fig.1 Optimized structures of nanoribbons with atomic
edges. This defective edge possesses zigzag
desorption. Black and pink disks denote theportions in accordance to the diatomic
carbon and hydrogen atoms, respectively.
desorption. This result indicates (a)(b)
that the zigzag edges are
preferentially generated under
the certain condition.
Corresponding Author: A. Yamanaka
Tel: +81-29-853-5600 (ext. 8233),
Fax: +81-29-853-5924,
E-mail:ayamanaka@comas.frsc.tsukuba.ac.jp
Fig.2 Desorption energies for (a) armchair and (b) zigzag edges.
Energies are measured from the total energy of the pristinearmchair and zigzag edges. Red and blue lines denote theenergies calculated by using the chemical potentials of methaneand ethane, respectively.

- 160 -

3P-34
Electronic structure of edge functionalized graphene under an external
electric field○Yanlin Gao, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, 305-8571, Japan
Graphene has attracted a great deal of attention in the fields of nanoscience andnanotechnology due to its peculiar physical property and extensive application prospects.
Graphene has atom thickness, high electrical conductivity, and remarkable chemical stability,
which allow it to be a possible candidate for a field emission source in field emission devices.
In the ambient condition, edges of graphene are usually terminated by functional groups,
depending on the environment. In this work, we aim to elucidate the correlation between thework function and critical electric field of the field emission from the zigzag edges of graphene,
which is terminated by functional groups (ketone, aldehyde, hydrogen or carboxyl group), using
the density functional theory combined with the effective screening medium method.
Figure 1(a) shows the structure model for simulating the field emission from the edges ofgraphene terminated by functional groups. The edge is simulated by the graphene nanoribbon
with zigzag edges which are terminated by H and functional groups. The ribbons are located in
front of the planar electrode with 6 Å vacuum spacing. Our calculations show that functionalgroups affect the critical electric field resulting in the field emission at which the electrostatic
potential at the electrode crosses the
Fermi level [Fig. 1(b)]. For the edges
functionalized by H, ketone, aldehyde,
and carboxyl groups, the critical electricfield leading to the electron emission is
proportional to their work function. In
contrast, the edge terminated by thehydroxyl group has a larger criticalelectric field in spite of its small work
function. The large critical electric field
for the hydroxylated edge is ascribed tothe spilled electron outside the edges
arising from the nearly free electron Fig.1(a) A structural model and (b) schematicstates: The electron distribution outside diagram of the electrostatic potential forthe edge causes the potential barriers at functionalized graphene nanoribbon under
this region preventing the electron
the electric field.
emission from the edge.
Corresponding Author: Y. Gao
TEL: +81-29-853-5921, FAX: +81-29-853-5924
E-mail: ylgao@comas.frsc.tsukuba.ac.jp- 161 -

3P-35Brillouin zone topology and band structure of four-dimensional diamond
Yuichi Kato, ○Masanori Yamanaka
Department of Physics, College of Science and Technology, Nihon University, Tokyo
101-8308, Japan
We study the diamond lattice in 4d [1] which a descendant of the 3d diamond lattice, or 2d
hexagonal lattice. We determine the first Brillouin zone explicitly as a 4d polytope and draw
the band structure of the tight-binding model on a normal piece of 2d paper. By the polyhedral
decomposition, we find the zone boundary of the first Brillouin zone in 4d to be theomnitruncated 5-cell, otherwise known as the great prismatodecachoron, which comprises 10
truncated octahedra glued to 20 hexagonal prisms. The irreducible zone is determined to be a
4d polytope with the heptahedron as the base polyhedron and the origin in the momentum
space as the apex. We found the 2d isotropic Dirac cone at the W-point and the 2d anisotropic
Dirac cone on the line node to the D-point where the coefficients of two components differ.
Gapless line nodes are characterized by a linear dispersion relation and we have a total of 60
line nodes inside the hexagonal prisms in the first Brillouin zone.

Fig.1 Irreducible zone and the $k$-points defined on the zone boundary. We obtained these polyhedra by
projecting the 4d zone boundary polyhedra onto the perpendicular bisecting 3d space. The axes ($k_x$,$k_y$, $k_z$) are the local coordinate systems on the projected 3d spaces. The $¥Gamma$-point is theorigin of the 4d momentum space and is outside of the projected 3d spaces. The dotted lines between the$¥Gamma$-point and the $k$-points on these polyhedra stretch to the 4th axes and are also outside of theseprojected 3d spaces. Then, the irreducible zone is a 4d polytope with the heptahedron as the basepolyhedron and the $¥Gamma$-point as the apex. There is a Dirac line node on the plane $¥gamma_2 U_2
W_1 L_2$ from point $W_1$ to $W_1'$ and $D$ where $D$ is a point that internally divides points$U_2$ and $¥gamma_2$ in a ratio of 1:5.

[1] Y. Kato and M. Yamanaka, accepted for publication in J. Phys. Soc. Japan.
Corresponding Author: M. Yamanaka, Tel: +81-3-3259-0921, Fax: +81-3-3259-0921,
E-mail: yamanaka@phys.cst.nihon-u.ac.jp- 162 -

3P-36
Transport property of bilayer graphene with monovacancy○Ken Kishimoto and Susumu Okada
Graduate school of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Graphene has unique geometric and electronic structures, allowing it an emerging material
for various functional devices in the near future. On the other hand, its electronic structure isfragile against the formation of hybrid structures with foreign materials, such as molecules,
insulating substrate, metal electrode, and other atomic layer materials. Furthermore, atomic andtopological defects also modulate the electronic structure of graphene near the Fermi level. In
the hybrid structure, interaction between constituents cooperatively and competitively affects
the electronic structures of resultant hybrids. Indeed, the bilayer graphene, in which one of twolayers possesses defects, possesses finite energy gap in  states instead of a pair of linear
dispersion bands [1] owing to the defect and interlayer interaction. The result indicates that thetransport properties of graphene hybrids may also exhibit unusual features, which are not thesimple sum of that of each constituent. In
this work, we aim to investigate thetransport property of the bilayer
graphene, one of which layers possesses
monovacancies
using
the
non
equilibrium Green’s function method
within the framework of the density
functional theory.
Our calculations show that the I-V
characteristics of bilayer graphene withmonovacancy (MV) exhibit unusual
feature. Although the bilayer graphene
contains pristine graphene layer, thecurrent density is smaller than that for thepristine monolayer graphene (Fig. 1).
Thus, the transport properties ofgraphene hybrids are sensitive to theirgeometries which cooperatively affectFig. 1. I-V characteristics of pristine monolayer
their electronic structures.
graphene (MLG) and bilayer graphene (BLG) withmonovacancy (MV).

Reference[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- 163 -

3P-37
Tuning of local optical properties of MoS2 monolayer
and its structural control using electric-field-effect scanning near-field
optical microscopy techniques○Junji Nozaki, Musashi Fukumura , Takaaki Aoki, Yutaka Maniwa , Yohei Yomogida, andKazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
Transition metal dichalcogenides (TMDCs) attract a lot of interests because of theirremarkable physical characteristics. Especially, unique optical properties, such as single
photon emission and non-linear optical processes, have been reported at peculiar sites on amonolayer TMDC, such as defects, grain boundaries, and hetero interfaces.1,2 How to tune
such optical characteristics is of great importance for their optoelectronic applications. It is
known that optical properties of TMDCs can be modulated by application of electric field.3
Thus here, as shown in Fig. 1(a), we developed scanning near-field optical microscopy(SNOM)4 measurement techniques under electric fields in order to reveal relationships
between local optical properties and applied biased voltages on monolayer TMDCs.
A schematic illustration of our experimental setup
is shown in Fig. 1(a). We applied a bias voltage to amonolayer sample from a cantilever of our SNOM
system and then optical properties of a site underelectric field were measured. As shown in Fig. 1(b),photoluminescence (PL) on a site of MoS2
monolayer was reversibly modulated in the spatial
resolution of about 100 nm by this method,
indicating that electron injection control andevaluation of its optical properties on the site wereachieved at the same time by this method. In addition,
in hole injection regime, we found the structure ofmonolayer MoS2 was unstable and sometimes
decomposed. On the basis of this observation, wedeveloped a method to etch MoS2 crystal usingnear-field light in combination with negatively biased
voltages. Furthermore, using this technique, wefabricated a MoS2 nanoribbon with a width ofapproximately 500 nm from a triangle MoS2
monolayer crystal. This technique enables us to tune
local optical properties of atomic monolayer samples
and to freely design their structural forms.
References: [1] Y. He et al. Nat Nanotechnol. 10, 497 (2015).
[2] X. Yin et al. Science. 344, 488 (2014). [3] K. F. Mak et al.
Nat Mater. 12, 207 (2012). [4] J. Nozaki et al. JJAP 55, 038003,
06GB01 (2016).
Corresponding Author: K. Yanagi, Tel: +81-42-677-2494,
E-mail: yanagi-kazuhiro@tmu.ac.jp- 164 -

Fig.1 PL modulation in a site of amonolayer MoS2 by local carrier injection
control using our electric-field-effectscanning near-field optical microscopy
system. (a) Schematic illustration of ourexperimental setup. (b) Modulation of
local PL spectra on MoS2 monolayer at asite in the spatial resolution of about 100nm.

3P-38
Optical properties of superacid-treated MoS2
○Hong En Lim, Nur Baizura Mohamed, Yuhei Miyauchi, Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Research on 2D materials, such as transition metal dichalcogenides (TMDCs), has
generated profound interests for their application in optoelectronics, valleytronics, andspintronics [1]. Nevertheless, because of the defects and surface contamination, monolayersof TMDCs have been suffering from low photoluminescence (PL) quantum yields (QY).
Molybdenum disulfide, MoS2 for instance, has a maximum reported QY of <1 % with anextremely short PL life time of less than hundreds picoseconds. This prevents the thoroughunderstanding on details of their excitation dynamics, as well as valley polarization/coherence
physics, and therefore limiting their immediate use in nano-optical devices. Recently, a
breakthrough was achieved by Amani et al. [2,3], where the QY of MoS2 had beensignificantly improved to >95 % by using an organic superacid, bis(trifluoro-methane)
sulfonamide (TFSI). However, detailed understanding on the optical properties ofsuperacid-treated MoS2 has not been fully understood.
Here we examined the optical properties of such chemically treated MoS2 monolayer.
Under the excitation of 2.33 eV, a substantial increase (~100 times) in the PL intensity of thetreated sample is observed (Fig. 1(a)) at 298 K. The value is comparable to those reported
ones, implying the effectiveness of this method towards PL enhancement. Besides, thetreatment has resulted in a decrease in the full width half maximum (FWHM) of the peakregistered from 87 to 59 meV. We decomposed the PL spectra of the as-exfoliated and
TFSI-treated MoS2 into exciton and charged peaks [4] as shown in Fig. 1(b) and (c),respectively. These results reveal a distinct change in each component, with a noticeable
increase in the exciton population after the reaction. Further details on the results obtained at
low temperature (5 K) will be discussed.

Normalized intensity / a. u.

Intensity x 103 / counts(b)As-exfoliated

8

TSFI-treated
6

4

X 118
2

As-exfoliatedExcitonTrion(c)Normalized intensity / a. u.

(a)TSFI-treatedFitting
Experimental

Exciton

Trion

0
1.4

1.6

1.8

2.0

Photon energy / eV

2.2 1.6

1.8

2.0

Photon energy / eV

2.2 1.6

1.8

2.0

2.2

Photon energy / eV

Fig.1 (a) PL spectra for the as-exfoliated and TFSI-treated MoS2 monolayer with exciton and trion features fittedusing Voigt function in (b) and (c).
[1] F. Xia et al. Nat. Photonics 8, 12 (2014). [2] M. Amani et al. Science 350, 6264 (2015).
[3] M. Amani et al. Nano Lett. 16, 4 (2016). [4] S. Mouri, Y. Miyauchi, and K. Matsuda, Nano Lett. 13, 5944
(2016).
Corresponding Author: H. E. Lim

Tel: +81-774-38-3460, Fax: +81-774-38-3460,
E-mail: limhongen@gmail.com- 165 -

3P-39Relaxation Mechanism of Interlayer Excitons in 2D van der Waals
Heterostuctures○Mitsuhiro Okada1, Yusuke Kureishi1, Yusuke Hasegawa2, Alex Kutana3, Kenji Watanabe4,
Takashi Taniguchi4, Yuhei Miyauchi2, Kazunari Matsuda2, Hisanori Shinohara1, Ryo Kitaura1
1

Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan
2
Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan3
Department of Materials Science and Nanoengineering, Rice University, Houston, TX 77005,
USA
4
National Institute for Materials Science, Tsukuba 305-0044, Japan

Intensity / countTwo-dimensional (2D) semiconductors, including MoS2, WS2, MoSe2, etc., have provided
a fascinating opportunity to explore optical properties in 2 dimensions. In particular, van der
Waals (vdW) heterostructures composed of these 2D semiconductors, such as WS2/MoS2,
offer a novel platform for optical physics, where strong inter-layer interaction drasticallyalters optical transitions. To explore the intrinsic PL properties of TMDC vdW
heterostructures, we have focused on fabricating high-quality samples achieved by fully-hBN
encapsulated WS2/MoS2 heterostructures (Fig.1). In this work, we report drastic excitationenergy dependence in PL spectra, where relaxation pathway of photoexcited careers plays animportant role.
We synthesized monolayer MoS2 and WS2 by chemical vapor deposition method andprepared thin hBN flakes by mechanical exfoliation method. hBN-encapusulated
heterostuructures (hBN/WS2/MoS2/hBN) were prepared with the polymer-assisted
dry-transfer method. Fabricated heterostructure shows PL emission from interlayer excitons
around 1.4 to 1.7 eV in addition to A-excitons from WS2 and MoS2 at RT (Fig. 2). Theinterlayer excitons in WS2/MoS2 vdW heterostructures
were observed in previous papers, giving a single broad
peak at around 1.4 eV. [1] In contrast, the observed
interlayer PL peak gives more detailed spectral features,
which might originate from high-quality (clean interface
and surface flatness) of our sample. At 15 K, the PL
spectra show strong excitation energy dependence atinterlayer exciton region. At low excitation energy(under 2.38 eV), PL spectra show single and sharp Fig. 1 A structure model of thefabricated heterostructure.
interlayer exciton peak at 1.77 eV, whereas broadinterlayer exciton emission at 1.4-1.77 eV is observed
1200
with 2.54 eV excitation. We think this is caused by a1000
characteristic relaxation pathway at “band nesting”
800
region, which is consistent to DFT calculation.
600[1] Y.Gong et al. Nature Mater. 13, 1135 (2014).

Observed
WS2-A exciton
MoS2-A exciton
Interlayer exciton 1
Interlayer exciton 2Interlayer exciton 3

400
200
0

Corresponding Author: H. Shinohara and R. Kitaura
Tel: +81-52-789-2477, Fax: +81-52-747-6442,
E-mail: noris@nagoya-u.jp, r.kitaura@nagoya-u.jp

1.4

1.6

1.8

2.0

2.2

Photon energy / eV

Fig.2 PL spectrum of hBN-encapsulated
WS2/MoS2 vdW heterostructure
measured at RT.

- 166 -

3P-40Transition of crystal structure and electrical property of MoTe2 crystal bylaser irradiation○Kota Kamiya1, Tomoki Yamanaka1, Masahiro Matsunaga1, Ayaka Higuchi1, Yuichi Ochiai1,
Michio Kida1, Jonathan P. Bird2 and Nobuyuki Aoki1
1

Graduate School of Advanced Integration Science, Chiba University,
Chiba 263-8522, Japan2
Department of Electrical Engineering, University at Buffalo, SUNY,
Buffalo, New York 14260-1920, USA

Transition metal dichalcogenides (TMDCs) have attracted a lot of interests due to its
various properties[1]. One of its unique properties is that the transport property can bechanged from semiconducting (2H) to metallic (1T’) depending on the structure. It is known
that such a structural change occurs relatively easily in MoTe2 [2]. Recently, S. Cho et al.,achieved the phase transition from 2H to 1T’ in MoTe2 by laser patterning [3]. In this study,
we fabricated 1T’ structure in a MoTe2 crystal by optical laser irradiation and confirmed theelectronic properties.
In our study, we used multilayer MoTe2 crystals exfoliated onto Si/SiO2 substrates. The
green laser (λ = 532 nm) was irradiated by a single line scan at various laser powers throughan objective lens under atmospheric condition. After the exposure, the phase transition was
confirmed from the Raman scattering spectra. Fabricating several FET structures with orwithout 1T’ phase region, we confirmed the difference of the electrical properties. Figure 1
shows a Raman spectra of MoTe2 crystal after a laser scanning. The Raman peak shifts from~230 cm-1 to 125 cm-1 after the irradiation, which is consistent with the peak positions of 2H
and 1T’ structures. It indicated that the phase transition occurred within the irradiated region
with decreasing the thickness of the crystal by a local heating. Figure 2 shows transfer curves
obtained in 1T’ and 2H phase devices. No gate voltage dependence was observed at 1T’channel device while the usual 2H device showed ambipolar characteristic.
In conclusion, we observed the phase transition from 2H to 1T’ structure in MoTe2 crystals
by optical laser thinning. In addition, we confirmed that the 1T’ phase shows metallic
behavior.

Figure 1. Raman map and spectra of the laser patterned Figure 2. Transfer curves obtained (a) 1T’ channeland (b) 2H channel device.
MoTe2 crystal.
[1] Q. H. Wang et al. Nature Nanotech, 7, 699 (2012).
[2] K.-A. Alexander et al., Nature Comm. 5, 4214 (2014).
[3] S. Cho et al. Science, 349, 625 (2015).
Corresponding Author: N. Aoki
Tel: +81-43-290-3430, Fax: +81-43-290-3427
E-mail: n-aoki@faculty.chiba-u.jp- 167 -

3P-41
The LDI spectra of Detonation Nanodiamonds○Masayoshi Fukaya1, Toshihiko Tanaka1, Amanda S. Barnard2, Eiji Osawa3
1

Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, 30 Aza-nagao, Tairakamiarakawa, Iwaki, Fukushima, 970-8034, Japan
2
CSIRO Materials Science and Engineering, 343 Royal Parade,
Parkville, Victoria 3052, Australia
3
Nano Carbon Research Institute Ltd., Asama Research Extension Center,
Faculty of Textile Science and Technology, Shinshu University
3-15-1 Tokida, Ueda, Nagano, 386-8567 Japan

We reported previously the laser desorption ionization mass spectra (LDI MS) of thedetonation nanodiamonds deposited on a stainless plate from the aqueous solution of welldispersed primary particles of detonation nanodiamonds (PPDNDs).1-3 Among fivepositive-peaks (<0.5kDa, 1~5kDa, ~12kD, ~40kDa broad, ~120kDa broad) observed, thethird peak was assigned to the remnant of PPDNDs after losing all the shell and about
one-third of the core. Abundant peaks under 5kDa represent the fragments from the shell andouter core. Although the solution was dried before LDI measurements, they were observed
from it and not from raw detonation materials, thus the third peak having not been explained
well. The purpose of this poster is to substantiate the unusual assignment.
Recent LDI MS results herein show that a 12kDa ion should be attributable to the inner sp3
core of PPDND. We think that the inner core ions can be generated from the colloidal crystalsof PPDNDs [Fig.1]. Whiskers5 prepared from the aqueous solution also shows similar innercore peaks whereas a freeze-dried solution does not surprisingly. Slow drying from dispersed
PPDNDs probably forms the
crystals that cannot desorb
themselves because of their hugemass. The shell and outer core
decomposes harder, thus emerging
the stable inner core ions. The
12kDa peak is observed by both alinear and reflector modes, whereas
two larger peaks (~40kDa,~120kDa) are lost in the reflector
mode, thereby demonstrating thestability of the 12kDa peak during
the flight in the analyzer to a
detector. The inner core size wasalso estimated to be ~12kDa by aconfined mode of Raman
Fig.1 generation of the core peak in the LDI from the precipitation
spectra.4 Such a stable ion isfrom the solution of highly dispersible PPDNDs.
therefore the inner core.
[1] E. Osawa, D. Ho, H. Huang, M. V. Korobov, N. N. Rozhkova; Dia. Rel. Mat. 18, 904(2009). [2] M.Fukaya,
Y,Otsubo, T. Tanaka, R.Yamanoi, E.Osawa; FNTG 50 Proceedings 85(2016). [3] T. Tanaka, R.Yamanoi,
E.Osawa; FNTG 48 Proceedings 19(2015). [4] V. I. Korepanov, H. Witek,H. Okajima, E. Osawa, and H.
Hamaguchi; J. Chem. Phys. 140, 41107 (2014). [5] E. Osawa, Diamond & Related Materials 16, 2018–2022(2007). Corresponding Author:Toshihiko Tanaka / Tel: +81-246-46-0810 / E-mail: ttanaka@fukushima-nct.ac.jp- 168 -

3P-42
Impact synthesis of amino acids on carbon nano-particles in nitrogen gas○Tetsu Mieno1, 2, Kazuki Okochi2, Syunsuke Sekiguchi2, Sunao Hasegawa3
1

Graduate School of Science & Technology, Shizuoka University, Shizuoka 422-8529, Japan2
Department of Physics, Shizuoka University, Shizuoka 422-8529, Japan
3
Institute of Space & Astronautical Science, JAXA, Sagamihara, 252-5210, JapanWe are interested in synthesis of carbon clusters and carbon molecules in space. Carbon
materials have been produced by impacts of asteroids onto surfaces of planets/satellites like
Titan. We have done impact experiment using a light-gas gun simulating the space-impacts,and found synthesis of many kinds of carbon clusters (fullerenes, nanotubes, metalencapsulated carbon capsules, balloon-like carbons). [1] Here, we analyzed smaller
carbonaceous molecules, which can not be observed by TEM. A poly-carbonate bullet isaccelerated by a gas-gun (6.5 km/s) and injected onto an iron target (an ice + iron target, ahexane + ice + iron target) under 1 atm of nitrogen gas. Figure 1 shows scheme of thepressurized chamber in which the impact takes place. After the impact, a hog-gas plume
generates for about 50 µs, and strong emission from CN and C2 molecules (Trot~ 5000 K) is
observed. Then, the gas-plume cools down and many carbon nanoparticles deposit on the
inner surface. The carbon sample is carefully collected to avoid contamination, refluxedusing pure water, filtered and condensed. The sample is dabsyllized and analyzed using a
HPLC. As a result, strong peaks of amino acids (glycine and alanine) are obtained. [2]Figure 2 shows the HPLC chart. In 1 mg of soot, 2 nmol of glycine and 0.9 nmol of alanine
are included. We conjecture that during the cooling process of carbon particles, carbon
radicals and CN radicals react on the particle’s surface, and amino acids are synthesized.
[1] T. Mieno et al., ,Jpn. J. Appl. Phys. 50 (2011) 125102.

[2] K. Okochi, T. Mieno et al., Org. Life Evol.

Biosp. 45 (2015) 195.

Fig.1 Scheme of the pressurized chamber.

Fig.2 HPLC chart detecting glycine & alanine.

- 169 -

発表索引
Author Index

Author Index<A>
Achiba, Yohji
Ago, Hiroki
Ahn, Namyoung
Akasaka, Takeshi
Akiba, Miki
Amagai, Yuri
An, Hua
Aoki, Nobuyuki
Aoki, Takaaki
Aoyagi, Shinobu
Arai, Miho
Asaka, Koji
Ata, Seisuke

2-10, 2-13, 2P-8,
2P-12, 3P-1, 3P-2
2P-31, 3P-30
1P-25, 3-7
1P-1, 2P-10
2P-40
3-4
2P-21, 3P-18
2P-5, 2P-29, 3P-40
3P-37
1P-2, 2P-9
2-7
3-5
2-4

<B>
Bandow, Shunji
Barnard, Amanda
Bichara, Christophe
Bird, Jonathan P.
Boero, Mauro

2P-38
2-14, 2P-36, 3P-41
1S-3
3P-40
3P-25

<C>
Chen, Zhongming
Cheng, Xinlu
Chiashi, Shohei

Choi, Jun Hee
Choi, Mansoo
Cong, Kankan

1P-15
2P-32
1-1, 1-3, 2P-14,
2P-21, 2P-24, 3P-5,
3P-7, 3P-11, 3P-14,
3P-17, 3P-18, 3P-20,
3P-26
1P-9, 1P-40, 1P-41
1P-25, 3-7
3S-8

<D>
D’Arsié, Lorenzo
De Silva, Kanishka
Dinda, Diptiman

3-10
3-8
2S-6

<E>
Eda, Junko
Einarsson, Erik

2P-22
3S-10

Endo, Hitomi
Endo, Norifumi
Endoh, Hiroyuki
Esconjauregui, Santiago

2-13
1P-29
1P-16
3-10

<F>
Fioli, G.
Fujii, Shunjiro
Fujimoto, Yoshitaka
Fujiwara, Kyosuke
Fukaya, Masayoshi
Fukazawa, Shinpei
Fukidome, Hirokazu
Fukumura, Musashi
Fukuzumi, Shunichi
Furukawa, Ko
Furukawa, Yoritaka
Furutani, Sho
Futaba, Don

1P-34
1P-6
1-6
1P-21
2-14, 2P-36, 3P-41
2P-10
1P-29
3P-37
1P-2
2-10, 2P-8, 3P-2
3P-7
2P-11
2-1, 2-3<G>Gao, Weilu
Gao, Yanlin
Gorgoll, Ricardo M.
Guo, Jingdong

1P-8, 3S-8
3P-34
2P-4
1P-1

<H>
Hachiya, SoichiroHada, MasahikoHamada, Koki
Hamaguchi, Hiroaki
Hamano, Yuuta
Hamasaki, Atom
Hao, Zhang
Hara, Masanori
Harano, Koji
Harigai, Toru
Haruyama, J.
Hasdeo, Eddwi H.
Hasegawa, Kei
Hasegawa, M.
Hasegawa, Sunao- 171 -

1P-15
2-9
3P-16
2P-41
2P-39
2P-23
2P-14
3-8
2P-4
2P-37, 2P-41, 2P-42,
2P-43
1P-32, 1P-34
2P-15
1P-15, 1P-22, 3P-8
1P-34
3P-42

Hasegawa, Yusuke
Hashikawa, Yoshifumi
Hata, Kenji
Hatakeyama, Kazuto
Hayamizu, Yuhei
Hayashi, Hironobu
He, Xiaowei
Higashide, Noriyuki
Higuchi, Ayaka
Hiraide, Rineka
Hirano, Atsushi
Hirayama, Takaaki
Hirotani, Jun
Homma, Yoshikazu
Honda, Shirou
Hoshino, Ryo
Hoshino, Yuudai
Hotta, Takato
Hou, Bo
Huang, Hsin-Hui
Hung, Nguyen T.
<I>
Ichinose, Yota
Iijima, Sumio
Iizumi, Yoko
Ikeda, Kozo
Ikuhara, Yuichi
Ikuma, Naohiko
Imamura, Yutaka
Imoto, Fumihiro
Inaba, Takumi
Inoue, Taiki

Inoue, Y.
Irita, Masaru
Isaka, Takuya
Ishi, A.
Ishida, Misaki
Ishida, Takuya
Ishii, Akihiro
Ishikawa, Ryousuke

1P-36, 3P-39
2P-2
2-1, 2-3
1P-7
2-6
3-9
1P-8
3-6
3P-40
1-5
1P-6, 1P-8, 1P-17
3P-2
1P-13, 3P-12, 3P-13
1P-3
1P-18
1P-23
2P-39
2P-35
3P-17
3-8
2P-17

1P-5, 2P-22
3P-23
1P-39, 3P-17
1P-7
2P-21
1P-2, 2P-1
2-9
3P-25
1P-3
1-1, 1-3, 2P-14,
2P-21, 2P-24, 3P-5,
3P-7, 3P-11, 3P-14,
3P-17, 3P-18, 3P-26
1P-34
3-5
1P-24, 3P-29
1P-34
2-11
2P-29
1P-4, 3-1, 3-2,
3-6, 3P-6
3P-27

Ishizeki, Keisuke
Itoh, Takashi
Iwata, Jun-Ichi
Iwata, Nobuyuki<J>Jang, Ho-Kyun
Jeon, Il
Jin, Jun Eon
Jinnouchi, Ryota
Jippo, Hideyuki
Jnag, Ho-Kyun<K>
Kako, Masahiro
Kamakura, Shun
Kamiya, Kota
Kanazawa, Naoki
Kanda, Akinobu
Kaneko, Toshiro
Karmakar, Arka
Kasama, Yasuhiko
Kashima, Taiga
Kashiwa, Kotaro
Katagiri, Y.
Kataoka, Yosuke
Kataoka, Yousuke
Kataura, Hiromichi
Kato, Tatsuhisa
Kato, Toshiaki
Kato, Yuichi
Kato, Yuichiro K.
Katsuyama, Shota
Katumoto, S.
Kauppinen, Esko I.
Kawabata, Kosuke
Kawachi, Kazuhiko
Kawahara, Kenji
Kawai, Hideki
Kawai, Takazumi
Kawano, Saki
Kawasaki, Kohei- 172 -

3P-4
2P-18
3P-25
1P-23

1P-40, 1P-41, 2P-16
3-7, 3P-11, 3P-14,
3P-30
1P-41
2P-39
3-9
1P-9

1P-1, 2P-10
3P-7
3P-40
3P-15
1-5, 1P-30
1P-35
3S-10
2-11
3P-13
3P-26
1P-32, 1P-34
1P-20
3P-22
1P-6, 1P-17, 3S-8
1P-2, 2P-8, 2-10,
3P-2
1P-35
3P-3, 3P-35
1-3, 1P-4, 3-1,
3-2, 3-6, 3P-6
3-5
1P-34
1S-2, 3-7, 3P-14
1P-15
2-11
2P-31, 3P-30
1P-5
1P-19
2P-7
2P-42

Kida, Michio
Kikuchi, Koichi

Koinuma, Michio
Kokubo, Ken
Komuro, Tomohiko
Konabe, Satoru
Kono, Junichiro
Kumakura, Makoto
Kumamoto, Akihito
Kumatani, Akichika
Kuragane, Natsuki
Kureishi, Yusuke
Kuroiwa, Kiyoko
Kutana, Alex
Kuwahara, Yuki
Kwon, Eunsang

3P-40
2-10, 2P-8, 3P-1,
3P-2
1P-9, 1P-40, 1P-41,
2P-16
1P-9, 1P-40, 1P-41,
2P-16
2P-16
2P-16
1-3
3P-21
3P-30
2P-20
3P-36
1P-10, 3P-9, 3P-12,
3P-13
2P-19
1P-19, 2P-9, 2P-35,
3P-21, 3P-28, 3P-39
2P-6
2P-6
2-2, 3P-3
3P-1, 3P-2
3P-8
1-2
2-9, 2-10, 2-13,
2P-8, 2P-12, 3P-1,
3P-2
1P-7
1P-2, 2P-1
1P-13
1P-3, 2P-34, 3P-4
1P-8, 3S-8
2P-20
2P-21
2-5
1P-23
3P-39
3P-23
3P-39
1P-16, 3P-10
2-11

<L>
Laiho, Patrik

1S-2

Kim, Do Hyun
Kim, Gyu-Tae
Kim, Min-Seok
Kim, Sung-Dae
Kimura, Issei
Kinno, Yasuhiro
Kinoshita, Hiroki
Kiribayashi, Hoshimitsu
Kishimoto, Ken
Kishimoto, Shigeru
Kitagawa, Sae
Kitaura, Ryo
Ko, Jeong Won
Ko, Weon Bae
Kobashi, Kazufumi
Kobayashi, Kazuhiro
Kobayashi, Shunji
Kochi, Taketo
Kodama, Takeshi

Lee, Dong-Jin
Lee, Kook Jin
Li, Jiulong
Li, Xinwei
Li, YanLim, Hong En
Liu, Haihao
Liu, Huaping
Liu, Kaihui
Liu, Ming
Lu, Fei<M>
Machida, Tomoki
Machiya, Hidenori
Maeda, Yutaka
Maniwa, Yutaka
Maruyama, Mina
Maruyama, S.
Maruyama, Shigeo

Maruyama, Takahiro
Masubuchi, Satoru
Matsubara, Manaho
Matsuda, Iwao
Matsuda, Kazunari
Matsue, Tomokazu
Matsui, Jun
Matsumoto, KazuhikoMatsumoto, Rika
Matsunaga, Masahiro
Matsuo, Yoshiaki
Matsuo, Yutaka

Matsushita, Yu-ichiro
Matsuura, Tomoki
Matuda, Kazunari- 173 -

2P-16
1P-40
2P-6
3S-8
1P-14, 2S-5, 3-3,
3P-18, 3P-19
2P-33, 3P-38
1P-42
3S-8
3S-9
3P-5
3S-10

2-7
1-3, 1P-4
1P-1, 3-4
2P-22, 3P-37
1P-28, 1P-38, 2-12,
3P-30
1P-34
1-1, 1-3, 1S-2,
2P-14, 2P-21, 2P-24,
3-7, 3P-5, 3P-7,
3P-11, 3P-14, 3P-17,
3P-18, 3P-20, 3P-26
1P-21, 2P-20
2-7
2P-26
1P-29
1P-36, 2P-33, 3P-38,
3P-39
2-5
3-4
1S-4
3P-30
3P-40
1P-24
1P-2, 2-8, 2P-3,
3-7, 3P-11, 3P-14,
3P-30
3P-32
3P-13
1P-39

Michiya, Yoshimasa
Mieno, Tetsu
Minowa, Hiroya
Mitani, Takuji
Mitsuhara, Masatoshi
Mitsuichi, Masaya
Miura, Chiho
Miyabe, Kyosuke
Miyamoto, Yoshiyuki
Miyata, Yasumitsu
Miyauchi, Yuhei
Miyaura, Kenshi
Mizutani, Ken
Mohamed, Nur Baizura
Morimoto, Takahiro
Morita, Hiroki
Moriya, Rai
Motomiya, Kenichi
Murakoshi, Kei
Murata, Hidekazu
Murata, Michihisa
Mustonen, Kimmo<N>
Na, InYeob
Nagai, Reito
Nagai, Yukuya
Nagase, Shigeru
Nagata, Tomoko
Nakagawa, Ayano
Nakahara, Hitoshi
Nakamura, Eiichi
Nakamura, Kazushi
Nakamura, Maki
Nakamura, Masatoshi
Nakamura, T.
Nakandakari, Sho
Nakanishi, Terunobu
Nakatori, Natsumi
Nanba, T.
Naritsuka, Shigeya

3P-28
3P-42
2P-24
2-10, 2P-8, 3P-1,
3P-2
2P-31
3-4
2-5
1P-1, 2P-10
2P-32
2-6
1P-36, 1P-39, 2P-33,
3P-38, 3P-39
1P-18
2P-24
2P-33, 3P-38
2-2, 2-4, 3P-3,
3P-17
1P-27, 2P-39
2-7
1P-12, 2P-18
2-6
3-5
2P-2
1S-2

1P-9
1P-35
1P-22
1P-1, 3-4
1P-23
2P-9
3-5
2P-4
1P-30
3P-23
1P-5
1P-34
2P-31
1P-19
2-10, 2P-8, 3P-1,
3P-2
1P-32
1P-21, 2P-20

Nihei, Mizuhisa
Nihey, Fumiyuki
Nishi, Hirofumi
Nishida, Tetsuo
Nishii, Haruki
Nishimoto, Shinya
Nishina, Yuta
Nishino, Akane
Nishino, Hidekazu
Nishino, Makiko
Noda, Suguru
Noe, II G.Timothy
Nomoto, Takahito
Nonomura, Rei
Nozaki, Junji
Nugraha, Ahmad R. T.
<O>Obori, Masanao
Ochiai, Yuichi
Ogamoto, Tatsuro
Ogata, Hironori
Ohata, C.
Ohfuchi, Mari
Ohiro, Tatsuo
Ohkubo, Kei
Ohno, Teruaki
Ohno, Yutaka

Ohta, Hiromichi
Ohyama, Shinnosuke
Okada, Susumu
Okada, Hiroshi
Okada, Mitsuhiro
Okada, Susumu

Okada, Takeru
Okazaki, Toshiya- 174 -

3P-8
1P-16, 3P-10, 3P-24
3P-32
1P-12, 2P-18
2P-41
3P-2
2P-29
3-4
1P-18
2P-9
1P-15, 1P-22, 2S-7,
2P-19, 3P-8, 3P-16
3S-8
3P-27
2P-18
3P-37
2P-15, 2P-17

3P-8
2P-5, 3P-40
3P-7
1P-20, 2P-7, 3P-22
1P-32, 1P-34
2P-27, 3-9
2P-42
1P-2
3-5
1S-2, 1P-10, 1P-13,
3P-9, 3P-12, 3P-13,
3P-28
1P-12
3P-18
1P-38
1P-2, 2P-3
3P-39
1-2, 1-4, 1P-19,
1P-28, 1P-31, 2-6,
2-12, 2P-11, 2P-13,
2P-25, 2P-26, 2P-40,
3P-30, 3P-31, 3P-33,
3P-34, 3P-36
2-5
1P-39, 2-2, 2-4,
3-4, 3P-3, 3P-17

Okochi, Kazuki
Okochi, Takeshi
Okudaira, Saki
Omachi, Haruka
Onodera, Atsushi
Ootuka, Youiti
Osaka, Ryo
Osawa, Eiji
Osawa, Toru
Osawa, Toshio
Oshima, Takumi
Oshiyama, Atsushi
Otani, Chiko
Otsuka, Keigo
Oya, Tomoya
Ozeki, Sumio

3P-42
3P-7
1P-39
1P-13, 2P-9, 3P-21
1P-11
1-5
2-6
2-14, 2P-36, 3P-41
3P-7
1P-15
2P-1
3P-25, 3P-32
2-11
1-1, 3P-5, 3P-26
3P-27
2P-23

<P>
Park, Nam-Gyu
Park, Se Jeong
Pyon, Sunseng

3P-14
1P-9
2-7

<R>
Rajashekar, Badam
Ristimäki, Sami
Robertson, John
Roche, S.
Rubio, Angel

3-8
1P-11
3-10
1P-34
2P-32

<S>
Saha, Shyamal K
Saida, Takahiro
Saito, Riichiro
Saito, Susumu
Saito, Takeshi
Saito, Yahachi
Sakaguchi, Takahiro
Sakurai, Ryota
Sakurai, Shunsuke
Samukawa, Seiji
Sanderson, Joseph
Sano, Masahito
Sasabe, Akihiro
Sasaki, Fusako

3P-4
Sasaoka, Kenji
1P-26
Sato, Hikaru
3-9Sato, Shintaro
1P-12, 2P-18, 2P-24
Sato, Yoshinori
Sato, Yoshinori (Stella Chemifa Co.) 1P-12, 2P-18
3P-22
Sato, Yutaka
Saucier Yamato, Alexander 1P-38
1P-28
Sawahata, Hisaki
1P-11
Sekido, Masaru
3P-42
Sekiguchi, Syunsuke
1P-32
Seneor, Pierre
3P-11
Seo, Seungju
3S-10
Shahi, Simran
1P-19
Shigekawa, Hidemi
2P-39
Shiino, Kyohei
2-5
Shiku, Hitoshi
1P-9, 1P-41
Shin, Jong Mok
1S-1, 1P-13, 1P-19,
Shinohara, Hisanori

Sugiura, Takeshi
Suko, Hiroki
Suzuki, Akira
Suzuki, Daisuke
Suzuki, Hal
Suzuki, Haruka
Suzuki, Masashi
Suzuki, Mitsuaki
Suzuki, Seiya
Suzuki, Shinzo

2P-9, 2P-35, 3P-21,
3P-28, 3P-39, Tutorial
3P-8
2-13, 2P-12
1P-29
3-4
1-4
1-3, 3P-26
3P-4
2P-37, 2P-41, 2P-42,
2P-43
1P-27, 2P-39
2P-19, 3-10, 3P-8,
3P-16
1P-1, 2P-10
3P-14
2P-28
1P-33
2-11
2P-12
2P-41
3-4
3-11
3P-15

<T>
Taguchi, Yuki

2-13, 2P-12

Shiomi, Junichiro
Shiromaru, Haruo
Someya, Takashi
Sone, Erika
Sorimachi, Jun-ya
Sota, Masaki
Souma, Satofumi
Suda, Yoshiyuki

2S-6
2P-20
1P-37, 1P-42, 2P-15,
2P-17
1-6
1P-16, 3P-10
3-5
3P-11, 3P-14
1P-23
2-1, 2-3
2-5
2-13
1P-26
3P-6
1P-16, 3P-10

Sugai, Toshiki
Sugime, Hisashi- 175 -

Taira, Remi
Tajima, Kentaro
Tajima, Naoko
Takagi, Yukai
Takahashi, Hideyuki
Takahashi, Munehito
Takahashi, Ryosuke
Takahashi, Ryota
Takahashi, Yasufumi
Takai, Kazuyuki
Takashima, Kengo
Takashima, Yasumasa
Takeuchi, Osamu
Takikawa, Hirofumi
Tamegai, Tsuyoshi
Tamura, T.
Tan, Dezhi
Tanaka, Takeshi
Tanaka, Toshihiko
Tanaka, Yu
Tanaka, Yuka
Taniguchi, Takashi
Tatsumi, Yuki
Terada, Natsuki
Terao, Yuri
Tohji, Kazuyuki
Tokuda, Takuto
Tomori, Hikari
Toyama, Kiyohiko
Tsuboi, Nozomu
Tsuji, Takashi
Tsuzuki, Mayumi<U>
Uchida, Yuki
Uchimura, Jin
Uda, Takushi
Ue, Hitoshi
Ueda, Naomasa
Ueda, Yuki
Ueno, Hiroshi
Ueno, Keiji

2P-25
1P-24, 3P-29
3P-3
3P-20
1P-12
2P-43
2-6
2P-37
2-5
1P-24, 1P-33, 2P-28,
2P-30, 3P-29
1-7
2P-23
1P-19
2P-37, 2P-41, 2P-42,
2P-43
2-7
1P-32
2P-33
1P-6, 1P-17, 3S-8
2-14, 2P-36, 3P-41
2P-5
2P-38
1-5, 2P-35, 3P-39
1P-37
2P-39
3P-30
1P-12, 2P-18
2P-35
1-5, 1P-30
3P-24
3P-27
2-1
1P-6

2P-31
2P-23
1P-4, 3-1, 3-2,
3-6, 3P-6
2P-42, 2P-43
3P-26
1P-21
1P-2, 2P-3
2-7

Uenoyama, Hiroto
Ukai, Hiroyuki
Ukhtary, M. Shoufie
Umeda, Yoshito
Umehara, Takashi
Uratani, Kento
Ushiyama, Takuya

2P-5
3P-20
1P-42
2P-41
2P-30
3P-15
3P-9

<V>
Velloth, Archana

2-9

<W>
Wakabayashi, Tomonari
Wakamiya, Atsushi
Wales, Benji
Wang, Guowei
Wang, Wei-Wei
Wang, Xiaofan
Wang, Zhiyong
Watanabe, Kenji
Watanabe, Takayuki
Weatherup, RobertWei, Xiaojun
Wu, ChengWu, Xingyi

2-13
2P-2
2-13
1P-6, 1P-17
3-4
2P-33
2P-9
1-5, 2P-35, 3P-39
2-2
3-10
1P-6, 1P-17
3P-17
3-10

<X>
Xiang, Rong<Y>
Yamada, Hiroko
Yamada, Jumpei
Yamada, Michio
Yamada, Ryohei
Yamada, Takeo
Yamada, Tonan
Yamagishi, Tamon
Yamaguchi, Junichi
Yamaguchi, Takahisa
Yamamoto, Daichi
Yamamoto, Hiroshi
Yamamoto, Masashi
Yamamoto, Shun

- 176 -

2P-14, 2P-21, 3P-5,
3P-11, 3P-14, 3P-17,
3P-18, 3P-26

3-9
1P-21
1P-1, 3-4
2P-24
2-4, 3P-3
3P-27
1P-23
3-9
2-10, 2P-8, 3P-2
1P-21
1P-23
1P-12, 2P-18
3P-18

Yamamoto, Susumu
Yamamoto, Takahiro
Yamanaka, Ayaka

Yoneyama, Kazufumi
Yoon, Jungjin
Yoshida, Masahiro
Yoshida, Shoji
Yoshikawa, Ryo
Yoshimura, Masamichi
Yudasaka, Masako
Yuge, Ryota

1P-29
1-7, 2P-34, 3P-4
1P-31, 2P-25, 3P-31,
3P-33
3P-35
3P-40
2P-5
2P-31
2-7
1P-24, 3P-29
2-11
3-5
1P-5, 2P-22, 3P-37
1P-14, 3P-18, 3P-19
3-3
2-6
1P-1
2P-2
3P-31
1P-10, 3P-28
1P-7
1P-20, 3P-22
1P-12
1P-12
1P-5, 1P-6, 2P-22,
3P-37
1P-31
1P-25, 3-7
1-3, 3-6, 3P-6
1P-19
3P-20
3-8, 3-11
1P-39, 3P-23, 3P-24
3P-24

<Z>
Zhang, Daqi
Zhang, Hong
Zhang, Wenjin
Zhao, Xiulan
Zhong, GuofangZhou, Xiaosong

3-3
2P-32
1P-36, 2P-33
3P-19
3-10
3P-8

Yamanaka, Masanori
Yamanaka, Tomoki
Yamanouchi, Shingo
Yamasaki, Shigeto
Yamasaki, Yuji
Yamashina, Tomoki
Yamashita, Masatsugu
Yamazaki, Shintarou
Yanagi, Kazuhiro
Yang, FengYang, Juan
Yasuda, Satoshi
Yasui, Masanori
Yasujiro, Murata
Yasuma, Airi
Yasunishi, Tomohiro
Yokoi, Hiroyuki
Yokokura, Eita
Yokoyama, Koji
Yokoyama, Shun
Yomogida, Yohei- 177 -

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◆要件 企業の一つ以上が県内企業であること、若しくは      埼玉県先端先端創造プロジェクトにおける各分野の研究会やネットワーク等に参加し、      かつ開発の成果が県内中小企業の振興に寄与すること◆事例 %06配合フッ素樹脂製品の開発、フラーレン分散接着剤の開発、フラーレン配合化粧品の開発

企業様向け補助金② 上限１００万円（補助率）
◆対象 日本国内に本申請に係る主たる技術開発のための拠点を有する企業
◆要件 県内企業でない場合は、開発の成果が県内中小企業の振興に寄与すること◆要件 %06発熱ヒーターの開発、グラフェン太陽電池の開発、%06配合ゴムの開発大学・研究機関様向け補助金 上限５０万円（補助率）






◆対象 大学若しくは公的研究機関又は公的産業支援機関
◆要件 ①県の先端産業の育成に資する研究開発を行う共同開発体であること②共同開発体に大学若しくは公的研究機関を含めること ③共同開発体に県内中小企業を含むこと◆要件 %06樹脂コンポジットの開発、%06線材の開発、グラフェン鉛電池の開発                    詳細情報については*2でご確認ください                            JVVRYYYUCKVCOCNGCFKPIGFIGRTQLGEVLR

研究開発パートナーを探します

ネットワークを広げます

埼玉県産業振興公社ではナノカーボン事業に取り組む
企業に対して、専門家による技術相談やマッチング相談等、様々な相談支援メニューで支援しています。

ナノカーボンに関する情報・人材・技術を埼玉に
カーボンに関する情報・人材・技術をを埼玉を埼玉結集するため、定期的に先端技術交流会を開催しています。ナノカーボンを活用した新たな技術開発に挑戦する大手企業や中小企業の取組などを紹介するとともに、懇親会の開催などを通じて、新
たなネットワークづくりにつなげます。

企業
マッチング支援
研究開発課題

企業、大学
研究機関

研究開発課題

講演

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問い合わせ先産業振興公社

問い合わせ先公益財団法人 埼玉県産業振興公社
先端産業支援センター埼玉
6'.：
/CKN：UGPVCP"UCKVCOCLQTLR

埼玉県産業労働部先端産業課 推進担当
 6'.
又は /#+.C"RTGHUCKVCOCNILR

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シャワーヘッド方式
ガス供給

Yes

Yes

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プラズマ

Yes

Yes

No

ハンドラー/インライン
インテグレーション

No

Yes

Yes

両面コーティング

No

No

Yes

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インテル®

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第 2 世代のインテル® Xeon Phi™ プロセッサーを含む、最新のインテル® プロセッサー向けに最適化された、高速かつ信頼性の高い C/C++、Fortran、Python*

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ハードウェア・パフォーマンスにとって重要な 3 つのメトリックを素早くプロファイル
システム構成 : ハードウェア : インテル® Xeon® プロセッサー E3-1245 v5 @ 3.50GHz、ハイパースレッディング有効、ターボブースト有効、32GB RAM。ソフトウェア : インテル ® Fortran コンパイラー 17.0、Absoft*15.0.1、PGI*
Fortran 15.10 (Windows®)/16.4 (Linux*)、Open64 4.5.2、GFortran 6.1.0。Linux* OS: Red Hat* Enterprise Linux*
Server 7.2、カーネル 3.10.0-327.4.5.el7.x86_64。Windows® OS: Windows® 10 Pro (10.0.10240 N/A Build 10240)。
Polyhedron* Fortran ベンチマーク (www.fortran.uk)。
Windows® コンパイラー・オプション : Absoft*: -m64 -O5 -speed_math=10 -fast_math -march=core -xINTEGER-stack:0x80000000。インテル ® Fortran コンパイラー : /fast /Qparallel /QxCORE-AVX2 /nostandard-realloc-lhs /link /stack:64000000。PGI* Fortran: -fastsse -Munroll=n:4 -Mipa=fast,inline -Mconcur=numa。
Linux* コンパイラー・オプション : Absoft*: -m64 -mavx -O5 -speed_math=10 -march=core -xINTEGER。GFortran:-Ofast -mfpmath=sse -flto -march=native -funroll-loops -ftree-parallelize-loops=4。インテル® Fortran
コンパイラー : -fast -parallel -xCORE-AVX2 -nostandard-realloc-lhs。PGI* Fortran: -fast -Mipa=fast,inline-Msmartalloc -Mfprelaxed -Mstack_arrays -Mconcur=bind。Open64: -march=auto -Ofast -mso –apo。
性能に関するテストに使用されるソフトウェアとワークロードは、性能がインテル ® マイクロプロセッサー用に最適化されていることがあります。SYSmark* や MobileMark* などの性能テストは、特定のコンピューター・
システム、コンポーネント、ソフトウェア、操作、機能に基づいて行ったものです。結果はこれらの要因によって異なります。製品の購入を検討される場合は、他の製品と組み合わせた場合の本製品の性能など、ほかの情報や性能テストも参考にして、パフォーマンスを総合的に評価することをお勧めします。 * その他の社名、製品名などは、一般に各社の表示、商標または登録商標です。
ベンチマークの出典 : インテル コーポレーション

最適化に関する注意事項 : インテル® コンパイラーでは、インテル® マイクロプロセッサーに限定されない最適化に関して、他社製マイクロプロセッサー用に同等の最適化を行えないことがあります。これには、インテル® スト
リーミング SIMD 拡張命令 2、インテル® ストリーミング SIMD 拡張命令 3、インテル® ストリーミング SIMD 拡張
命令 3 補足命令などの最適化が該当します。インテルは、他社製マイクロプロセッサーに関して、いかなる最適化の利用、機能、または効果も保証いたしません。本製品のマイクロプロセッサー依存の最適化は、インテル®
マイクロプロセッサーでの使用を前提としています。インテル® マイクロアーキテクチャーに限定されない最適化のなかにも、インテル® マイクロプロセッサー用のものがあります。この注意事項で言及した命令セットの詳細については、該当する製品のユーザー・リファレンス・ガイドを参照してください。注意事項の改訂 #20110804

製品詳細、無料評価版はこちらから

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