第回 フ ラ ー レ ン・ナノ チュー ブ・グ ラ フェン 総 合 シンポ ジウ ム 講 演 要 旨 集

54
44

平成

年３月 日〜 日

30
25

９
11

13
12

F NTG

Research Society

第 54 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 54th Fullerenes-Nanotubes-Graphene General Symposium

講演要旨集
Abstracts2018 年 3 月 9 日（金） ～ 12 日（月）東京大学 伊藤国際学術研究センター
The University of Tokyo, ITO INTERNATIONAL RESEARCH CENTER
主催 フラーレン・ナノチューブ・グラフェン学会
The Fullerenes, Nanotubes and Graphene Research Society
共催 ・ 後援
日本化学会
The Chemical Society of Japan東京大学大学院工学系研究科 School of Engineering, The University of Tokyo
東京大学 CIAiS Consortium for Innovation of Advanced Integrated Science (UTokyo)
東京大学 GMSI Graduate Program for Mechanical Systems Innovation (UTokyo)
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高感度
高ダイナミックレンジ

高 感 度 近 赤 外 線 ２ 次 元 I n G a A s カメラ

高繰り返し

NIRvana :640
TM

低暗電流ノイズ（電子冷却：-80℃、液体窒素：-190℃）
110fps（ビデオレート以上）
標準GigEインターフェースで50ｍまで延長可
空冷ファンと水冷を切替可能
アプリケーション例
・フォトニック結晶PLイメージング及びスペクトル・一重項酸素イメージング及びスペクトル・太陽電池PLイメージング及びスペクトル・天体観測微弱光イメージング
・食品断面イメージング
・In-Vivoイメージング など

仕様
モデル

センサー

NIRvana:640ST

冷却温度

ダークチャージ

読み出しノイズダイナミックレンジ
フレームレート

インターフェース
ソフトウェアNIRvana:640LN

20μm x 20μm

素子サイズ
波長範囲

NIRvana:640
640 x 512 x InGaAs
0.9 〜 1.7 μm
-80℃

-60℃

1500 e-/p/sec<120 e-rms

300 e-/p/sec

16 Bit (>15Bit@1 素子 )110 fps@10MHz

Gig E

-190℃

<8 e-/p/sec
15 e-rms

2.77 fps@250KHz

LightField, SITK-LabVIEW, WinX32

www.pi-j.jp

Abstract of
The 54 Fullerenes-Nanotubes-Graphene General Symposiumth

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

School of Engineering, The University of Tokyo

Consortium for Innovation of Advanced Integrated Science(UTokyo)
Graduate Program for Mechanical Systems Innovation(UTokyo)
Supported by : The Physical Society of JapanThe Japan Society of Applied Physics
The Society of Polymer Science, JapanThe Electrochemical Society of Japan

Date : March 9th (Fri.) – March 12th (Mon.), 2018
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)

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

第 54 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
東京大学大学院工学系研究科
東京大学 CIAiS東京大学 GMSI
協賛 : 日本物理学会、応用物理学会、高分子学会、電気化学会
日時 : 平成 30 年 3 月 9 日(金)～3 月 12 日(月)場所 : 東京大学 伊藤国際学術研究センター〒113-8656 東京都文京区本郷 7-3-1

伊藤謝恩ホール

発表時間 : 特別講演
（発表 25 分 + 質疑応答 5 分）
招待講演
（発表 10 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）
(株）島津製作所(株）シンキー(株）セントラル科学貿易
ナノフォトン（株）
日本シノプシス(同）（株）日本ローパー(株）堀場製作所(株）名城ナノカーボン
DKSHジャパン（株）
WITec (株）広告掲載団体御芳名 (五十音順、 敬称略）
アイクストロン(株)(株) コロナ社(株）セントラル科学貿易
ソーラボジャパン（株）
日本電子（株）(株）日本ローパー（株）堀場製作所

Contents
Time Table ・・・・・・・・・・・・・・・・・・ i
Chairperson ・・・・・・・・・・・・・・・・・iii
ProgramJapanese ・・・・・・・・・・・・ iv
English ・・・・・・・・・・・・ xix
Abstracts
Special Lecture ・・・・・・・・・・ 1
Invited Lecture ・・・・・・・・・ 11
General Lecture ・・・・・・・・・ 13
Poster Preview ・・・・・・・・・・45
Author Index ・・・・・・・・・・・・・・・・161

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
招待講演・・・・・・・・・・・・・11
一般講演・・・・・・・・・・・・・13
ポスター発表・・・・・・・・・・・45
発表索引・・・・・・・・・・・・・・・・・・ 161

プログラム早見表
３月１０日 （土）受付開始 8：30～
講演開始 9：45～
9:00
9:30

３月１１日 （日）３月１２日 （月）受付開始 8：30～
講演開始 9：00～
特別講演 （大島 久純）
9:00-9:30
一般講演 4件受付開始 8：30～
講演開始 9：00～
特別講演 (伊丹 健一郎)
9:00-9:30
一般講演 4件

9:45 特別講演 （Esko I. Kauppinen）
9:45-10:15
10:15
特別講演 （Yan Li）
10:15-10:45
10:45
休憩 10:45-11:00
11:00
一般講演 4件

内包ナノチューブ） 9:30-10:30
10:30
休憩 10:30-10:45
10:45 招待講演（Erik Einarsson）10:45-11:00
11:00
一般講演 4件(ナノチューブの生成と精製 ・ナノチューブの応用）(グラフェンの物性 ・ フラーレン
・ その他 ・ ナノ炭素粒子）

12:00

13:15

11:00-12:00
昼食(幹事会）
12:00-13:15
特別講演 (河野 淳一郎)
13:15-13:45

13:45 招待講演(Qiang Zhang)13:45-14:00
14:00
一般講演 4件

ポスタープレビュー( 1P-1 ～ 1P-38 )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

12:00

11:00-12:00
昼食
12:00-13:15

13:15

授賞式
13:15-14:00

14:00

ポスタープレビュー( 2P-1 ～ 2P-39 )14:00-15:00

15:00

17:45

11:15

9:30-10:30
休憩 10:30-10:45
特別講演 （有江 隆之）
10:45-11:15
一般講演 3件(グラフェンの物性 ・ 原子層）

12:00

11:15-12:00
昼食
12:00-13:15

13:15

ポスタープレビュー( 3P-1 ～ 3P-39 )13:15-14:15

14:15

ポスターセッション（多目的スペース）
14:15-16:00

16:00

特別講演 （柳 和宏）
16:00-16:30
一般講演 4件

ポスターセッション( 多目的スペース )15:00-16:45

特別講演 （齋藤 弥八）
16:45-17:15
特別講演 （町田 友樹）
17:15-17:45
一般講演 5件(グラフェンの物性 ・ ナノチューブの物性 ・ ナノチューブの応用)

16:30-17:30
17:30(グラフェンの応用 ・
原子層 ・ その他）

17:45-19:00
19:00

19:30

懇親会
（多目的スペース）
19:00-20:45
講演会場 伊藤謝恩ホール
特別講演 発表２５分・質疑５分
招待講演 発表１０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

３月９日 （金）第１０回ﾅﾉｶｰﾎﾞﾝ実用化推進研究会（伊藤謝恩ホール）
10:00-16:45

10:30
10:45

16:30
17:15

休憩 17:45-18:00
チュートリアル講師： 松尾 豊
東京大学（伊藤謝恩ホール）
18:00-19:30(フラーレンの化学 ・ 金属内包
フラーレン ・ フラーレンの応用）

評価 ・ ナノチューブの生成と精製 ・

16:45

17:45
18:00

9:30

(ナノチューブの物性 ・ ナノ環境と安全(ナノチューブの応用）
14:00-15:00

15:00

9:00

20:45

i

Time table
March 10 (Sat.)
Registration begins at 8:30
Lectures begin at 9:45

9:45

March 11 (Sun.)
Registration begins at 8:30
Lectures begin at 9:00
9:00
Special Lecture(Hisayoshi Oshima) 9:00-9:30
9:30 General Lectures [4] (Properties ofMarch 12 (Mon.)
Registration begins at 8:30
Lectures begin at 9:00
9:00
Special Lecture(Kenichiro Itami) 9:00-9:30
9:30
General Lectures [4](Chemistry of fullerenes ・Endohedral metallofullerenes ・Applications of fullerenes) 9:30-10:30

Special Lecture

nanotubes ・ Environmental/Safety characterization(Esko I. Kauppinen) 9:45-10:15

of nanomaterials ・ Formation and purification ofSpecial Lecture(Yan Li) 10:15-10:45
Coffee Break 10:45-11:00
General Lectures [4]nanotubes ・ Endohedral nanotubes) 9:30-10:30

10:15
10:45
11:00

10:30 Coffee Break 10:30-10:45
10:45 Invited Lecture (Erik Einarsson)10:45-11:00
11:00
General Lectures [4](Formation and purification of(Properties of graphene ・Fullerenes ・ Other topics ・Carbon nanoparticles) 11:00-12:00

nanotubes ・ Applications of nanotubes)

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

12:00

13:15

Special Lecture

12:00

Lunch
12:00-13:15

13:15

Award Ceremony
13:15-14:00

14:00

Poster Preview( 2P-1 through 2P-39 )14:00-15:00(Junichiro Kono)13:15-13:45

13:45 Invited Lecture(Qiang Zhang)13:45-14:00
14:00
General Lectures [4](Applications of nanotubes)
14:00-15:00
15:00

Poster Preview( 1P-1 through 1P-38 )15:00-16:00

16:00

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

15:00

10:30
10:45

Coffee Break 10:30-10:45
Special Lecture(Takayuki Arie) 10:45-11:15
11:15
General Lectures [3](Properties of graphene ・Atomic Layers) 11:15-12:00
12:00
Lunch
12:00-13:15

13:15

Poster Preview( 3P-1 through 3P-39 )13:15-14:15

14:15

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

Poster Session( Event Space )15:00-16:45
16:00
16:30

16:45

17:45
18:00

Coffee Break 17:45-18:00
Tutorial
Lecturer : Yutaka Matsuo
The University of Tokyo( Ito Hall )18:00-19:30

Special Lecture(Kazuhiro Yanagi) 16:00-16:30

Special Lecture（Yahachi Saito） 16:45-17:15
17:15
Special Lecture（Tomoki Machida）17:15-17:45
17:45
General Lectures [5]General Lectures [4](Properties of graphene ・Properties of nanotubes ・ Applicationsof nanotubes)

16:30-17:30

17:30(Applications of graphene ・Atomic Layers ・ Other topics )17:45-19:00
19:00

19:30

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

March 9 (Fri.)th

The 10 NanoCarbon Application Forum( Ito Hall )10:00-16:45

20:45
Place : Ito Hall
Special Lecture : 25 min (Presentation) + 5 min (Discussion)
Invited Lecture : 10 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10日 (土)セッション
特別講演(Esko I. Kauppinen）

時
間
9:45 ～10:15

座
長
丸山 茂夫

特別講演(Yan Li）

10:15 ～10:45

丸山 茂夫

一般講演

11:00 ～ 12:00
13:15～ 13:45

千足 昇平
齋藤 理一郎

13:45 ～ 14:00
14:00 ～ 15:00

項 榮
項 榮

15:00 ～ 16:00

杉目 恒志
井ノ上 泰輝丸山 茂夫

特別講演(河野 淳一郎）
招待講演(Qiang Zhang）
一般講演
ポスタープレビュー(敬称略）

チュートリアル(松尾 豊）

18:00 ～ 19:30

3月11日 (日)セッション
特別講演(大島 久純）

時
間
9:00 ～ 9:30

一般講演
招待講演(Erik Einarsson ）一般講演
ポスタープレビュー

9:30 ～10:30
10:45 ～11:00
11:00 ～ 12:00
14:00 ～ 15:00

特別講演(町田 友樹）
一般講演

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

3月12日 (月)セッション
特別講演(伊丹 健一郎）

時
間
9:00 ～ 9:30

特別講演(齋藤 弥八）

9:30 ～ 10:30

一般講演
特別講演(有江 隆之）
一般講演
ポスタープレビュー

10:45 ～ 11:15
11:15 ～ 12:00
13:15 ～ 14:15

特別講演(柳 和宏）
一般講演

16:00 ～ 16:30
16:30 ～ 17:30
iii

座
長
野田 優
野田 優
山本 貴博
山本 貴博
大町 遼
蓬田 陽平
篠原 久典
高井 和之
北浦 良

座
長
松尾 豊
村田 靖次郎
長汐 晃輔
長汐 晃輔
廣谷 潤
上野 裕
竹延 大志
加藤 雄一郎３月１０日 （土）特別講演
発表 ２５分 ・ 質疑応答 ５分
招待講演
発表 １０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

Fast characterization of FC-CVD nanotubes using an array of transistors

1

Nan Wei, Patrik Laiho, Saeed Ahmed, Aqeel Hussain, Qiang Zhang, Taher Khan,
Yongping Liao, Ying Tian, Er-Xiong Ding, Yutaka Ohno, * Esko I. Kauppinen

特別講演 ( 10:15-10:45 )1S-2

Manipulating Crystallization and Assembly of Nanomaterials via Fluidic Engineering

2

Yitan Li, Yuguang Chen, Hao Wang, * Yan Li＞＞＞＞＞＞＞ 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 ・ ナノチューブの応用
1-1

Tracing growth processes of individual single-walled carbon nanotubes by digitalisotope coding

13* 大塚 慶吾, 山元 隼, 井ノ上 泰輝, 項 榮, 千足 昇平, 丸山 茂夫
1-2

Effects of Pre-forming the different density layers on ELF method for the separationof metallic and semiconducting SWCNTs

14* 桑原 有紀, 佐々木 扶紗子, 二瓶 史行, 斎藤 毅
1-3

超音波分散によるSWCNTへの欠陥導入に対する溶存酸素の効果

15* 片浦 弘道, 杉田 知子, 久保田 真理子, 田中 丈士
1-4

Determination of association constants in complexation of nanotweezers andnanocalipers with SWNTs

16* Alejandro López-Moreno, Naoki Komatsu＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜特別講演 ( 13:15-13:45 )1S-3

Science and Applications of Wafer-Scale Aligned Carbon Nanotube Films

3

W. Gao, N. Komatsu, F. Katsutani, X. Li, K. Yanagi, * J. Kono

招待講演 ( 13:45-14:00 )1 I-1

Advanced Carbon Based Energy Materials for Lithium-Sulfur Batteries* Qiang Zhang

iv

11

３月１０日 （土）一般講演 ( 14:00-15:00 )ナノチューブの応用
1-5Record-high Efficiency in Carbon Nanotube Electrode-used Perovskite Solar Cells
via employing Formamidinium Lead Iodide (FAPbI3) and Trifluoromethanesulfonic
Acid Vapor Doping17* Il Jeon, Jin-Wook Lee, Anton Anisimov, Esko I. Kauppinen, Yang Yang,
Shigeo Maruyama, Yutaka Matsuo
1-6

Carbon-nanotube differential amplifier on flexible substrate

18

Tomoki Matsuura, Taiga Kashima, Jun Hirotani, Shigeru Kishimoto, * Yutaka Ohno
1-7

Carbon Nanotubes versus Graphene as Flexible Transparent Electrodes in Inverted
Perovskite Solar Cells

19* Jungjin Yoon, Il Jeon, Namyoung Ahn, Mohamed Atwa, Clement Delacou,
Anton Anisimov, Esko Kauppinen, Shigeo Maruyama, Yutaka Matsuo, Mansoo Choi
1-8

高密度カーボンナノチューブフォレストを用いた櫛型電極の開発と電気化学バイオ
センサへの応用20* 杉目 恒志, 牛山 拓也, 西村 圭太, 大野 雄高, 野田 優

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 )フラーレンの化学
1P-1（☆） 若手奨励賞候補

Electronic structures of solid phases of chemically functionalized C60

45* 古谷 匠, 松尾 豊, 岡田 晋

金属内包フラーレン
1P-2

Temperature dependence of anisotropic transient conductivity of
a La@C2v-C82(Ad) crystal

46* 山田 道夫, 佐藤 悟, Wookjin Choi, 関 修平, 阿部 玄之, 鈴木 光明, 前田 優,
永瀬 茂, 赤阪 健
1P-3

Spectroscopic studies of dimetallofullerene anions encapsulating Nd

47* 西本 真也, 菊地 耕一, 阿知波 洋次, 兒玉 健
1P-4

Isolation and Characterization of Tm2@Cn(n=78, 80) anion48* 小林 和博, 古川 貢, 加藤 立久, 菊地 耕一, 阿知波 洋次, 兒玉 健

フラーレン
1P-5

異種原子内包C60のエネルギー論と電子構造

49* 菅谷 優輝, 豊田 雅之, 斎藤 晋, 若林 知成, 金井 保之, 笹尾 登, 吉村 太彦
1P-6

+

2+

N およびN イオンビーム照射によってC60から生成したN@C60

50* 若林 知成, 金井 保之, 笹尾 登, 菅谷 優輝, 豊田 雅之, 斉藤 晋, 吉村 太彦
1P-7

Self-patterning of C60 sheet like crystals by liquid-liquid interfacial precipitation method* 舟守 勇斗, 山本 早織, 権守 宏通, 村田 秀信, 金田 裕子, 谷村 誠, 橘 勝

v51

３月１０日 （土）ナノチューブの物性
1P-8(6,5)単層カーボンナノチューブ薄膜における第三高調波発生過程

52* 横山 嵩弘, 小山 剛史, 岸田 英夫
1P-9

高純度単一(6,5)カイラリティ単層カーボンナノチューブの電気二重層キャリア注入によるゼーベック制御☆

* 一ノ瀬 遥太, 福原 健吾, 枝 淳子, 蓬田 陽平, 柳 和宏

1P-10

Optimizing photothermoelectric effects in semiconducting and metallic carbon nanotubes

53

54* Nugraha Ahmad R. T., Hung Nguyen T., Saito Riichiro
1P-11

カーボンナノチューブ表面の界面活性剤構造に対する鉄イオンの効果55* 平野 篤, 亀田 倫史, 田中 丈士, 片浦 弘道

ナノチューブの応用
1P-12

Near-infrared luminescence thermometric imaging using carbon nanotubes☆

* Kengo Hachiya, Saki Okudaira, Yui Konno, Yutaka Maeda, Kazunari Matsuda,
Yuhei Miyauchi

1P-13

Polymeric p-Type Dopant showing Permanent Doping Durability for Transparent
Carbon Electrodes

56

57* Clement Delacou, Il Jeon, Ahmed Shawky, Rong Xiang, Anton Anisimov,
Esko I. Kauppinen, Yutaka Matsuo, Shigeo Maruyama
1P-14☆

Transparent and flexible triboelectric generator based on carbon nanotube

1P-15
☆

メルトブレンディング法によるMWNT/HDPE複合材料の作製

58* 松永 正広, 廣谷 潤, 岸本 茂, 大野 雄高
59* 小野寺 厚, 関戸 大

ナノチューブの生成と精製
1P-16

その場XANES測定による単層カーボンナノチューブ成長中のCoおよびNi触媒粒子の分析

60* 丸山 隆浩, 熊倉 誠, 才田 隆広, 成塚 重弥
1P-17☆

CoAl2O4およびNiAl2O4触媒のリセットによるCNTの繰り返し合成

1P-18

Controlled Growth of SWNTs Using CoWO4 Nanoparticles as Catalyst Precursor

61* 佐藤 俊裕, 杉目 恒志, ビン リャン, ヨンギュ イー, リチャード レイン, 野田 優
62

* Xu Liu, Feng Yang, Yan Li
1P-19
☆
1P-20

Mechanism of preferential synthesis of (6,4) single-walled carbon nanotube using surface
state control of Co catalyst63* 許 斌, 金子 俊郎, 澁田 靖, 加藤 俊顕
二液相法とラマン／発光分光を利用したCoMoCAT-SWNTの分離

渡瀬 樹, 松岡 朗平, * 鈴木 信三

vi64３月１０日 （土）グラフェン生成1P-21

単層黒鉛/六方晶窒化硼素面内異種複合構造の微視的成長機構解析65* 澤畑 恒来, 山中 綾香, 丸山 実那, 岡田 晋
1P-22
☆
1P-23

Selective Growth of AB-Stacked Bilayer Graphene

66* 寺尾 友里, 河原 憲治, 末永 健志朗, 山本 圭介, 中島 寛, 長汐 晃輔, 日比野 浩樹,
吾郷 浩樹
先進プラズマCVDによる高オンオフ比グラフェンナノリボントランジスタの形成

67* 和藤 勇太, 鈴木 弘朗, 金子 俊郎, 加藤 俊顕

グラフェンの応用
1P-24

グラフェン層間を透過する水分子のエネルギー論

68* 安良岡 健太, 岡田 晋
1P-25☆

数値シミュレーションによるGNRFETの端欠陥効果の解明

1P-26

酸素発生反応用の新規IrRuOx/グラフェン触媒の合成

69* Kengo Takashima, Takahiro Yamamoto70* 原 正則, Badam Rajashekar, Hsin-Hui Huang, 吉村 雅満

グラフェンの物性
1P-27

エチレン架橋構造をもつ二層グラフェンの第一原理計算

71* 横井 裕之
1P-28

水素終端アームチェアエッジを有するNドープグラフェンナノリボンの電子構造72* 安間 愛莉, 丸山 実那, 岡田 晋
1P-29

Tuning of Kagome bands of 2D hydrocarbon networks by the molecular conformations73* 藤井 康丸, 丸山 実那, 岡田 晋
1P-30

Ultrafast photocarrier relaxation in monolayer graphene on SiC substrate due tophonons in the buffer layer

74* 今枝 寛雄, 小山 剛史, 岸田 英夫, 河原 憲治, 吾郷 浩樹, 包 建峰, 寺澤 知潮,
乗松 航, 楠 美智子

原子層
1P-31
☆

Al2O3バッファ層によるMoS2-FETの光応答速度向上機構

1P-32

Direct TEM/STEM imaging of 2D atomic layer crystals on SiO2

75

* 宮本 悠雅, 吉川 大貴, 竹井 邦晴, 有江 隆之, 秋田 成司
76* Rong Xiang, Akihito Kumamoto, Yu Kobayashi, Yasumitsu Miyata, Yuichi Ikuhara,
Shigeo Maruyama
1P-33☆

2段階CVD法を用いた二次元ファンデルワールスp-nヘテロ構造体の合成と輸送特性* 泉本 征憲, アジ アザ スクマ, 吾郷 浩樹

vii

77

３月１０日 （土）1P-34

Investigation on the influence of ball milling conditions to the morphology of exfoliatedhexagonal boron nitride nanosheets78* Naoko Ogino, Gang Liu, Naoki Komatsu
1P-35☆

クラウンエーテル錯塩による単層MoS2の化学ドーピング79* 吉村 真太郎, 小林 佑, 遠藤 尚彦, 真庭 豊, 宮田 耕充

バイオ
1P-36

In vivo behaviors of oxygen-doped carbon nanotube imaging probes after intravenous
administration to mice80

* 飯泉 陽子, 竹内 司, 湯田坂 雅子, 岡崎 俊也
1P-37
☆
1P-38

Experimental System for Testing Dynamics of Carbon Nanomaterials in Lymphatic Vessels

81* Chika Kuroda, Kumiko Ajima, Hisao Haniu, Haruka Ishida, Katsuya Ueda,
Kaoru Aoki, Hiroyuki Kato, Naoto Saito
マウス糞に排出される単層カーボンナノチューブ量の計測法* Mitsuko Takahashi, Yuko Okamatsu-Ogura, Takeshi Tanaka, Hiromichi Kataura,
Masako Yudasaka＞＞＞＞＞＞＞ 休憩 ( 17:45-18:00 ) ＜＜＜＜＜＜＜チュートリアル ( 18:00-19:30 )有機太陽電池の基礎とナノカーボン材料を積極的に活用した太陽電池* 松尾 豊viii

82

３月１１日 （日）特別講演
発表 ２５分 ・ 質疑応答 ５分
招待講演
発表 １０分 ・ 質疑応答 ５分
一般講演
発表 １０分 ・ 質疑応答 ５分
ポスタープレビュー
発表 １分 ・ 質疑応答 なし

特別講演 ( 9:00-9:30 )2S-4

自動車分野でカーボンナノチューブは使われるか？

4* 大島 久純

一般講演 ( 9:30-10:30 )ナノチューブの物性 ・ ナノ環境と安全評価 ・ ナノチューブの生成と精製 ・
内包ナノチューブ
2-1

市販CNT紡糸の構造及び特性に関する研究

21* 渡邉 敬之, 山下 智, 森本 崇宏, 小橋 和文, 岡崎 俊也
2-2

カーボンナノチューブの生分解のサイズ依存性

22* 張 民芳, 鄧 引梅, 楊 梅, 中島 秀朗, 湯田坂 雅子, 飯島 澄男, 岡崎 俊也
2-3

Growth of Horizontally Aligned Chirality-Specific SWNTs using Intermetallic W6Co7
Catalysts

23* Feng Yang, Yan Li
2-4

電子顕微鏡観察による[60]フラーレン二量化反応の速度論および反応機構解析

24* 原野 幸治, 岡田 賢, 小鷲 智理, シュバイグハウザー ルカ, 山内 薫, 中村 栄一＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜

招待講演 ( 10:45-11:00 )2 I-2

Photoexcited states in transition metal dichalcogenide heterostructures

12

Fei Lu, * Erik Einarsson

一般講演 ( 11:00-12:00 )グラフェンの物性 ・ フラーレン ・ その他 ・ ナノ炭素粒子
2-5Energetics and electronic structure of nitrogen-doped graphene with pyridinic structure25* 丸山 実那, 岡田 晋
2-6

Bilayer fullerenes (carbon nano-onions) studied by ion mobility mass spectrometry

26* 中野 元善, 森山 遼一, Wu Jenna, 大下 慶次郎, 美齊津 文典
2-7

トラップ型気相移動度測定システムの開発とナノ物質の測定

27* 菅井 俊樹, 星野 裕大, 森田 博暉, 宮本 莉央奈, 浜野 裕太, 染井 一優, 陣内 涼太
2-8

コロイド溶液における爆轟法ナノダイヤモンドの自己組織性* Toshihiko Tanaka, Yasuhiro F. Miura, Tetsuya Aoyama, Makoto Takahashi,
Takumi Sato, Eiji Osawaix

28

３月１１日 （日）＞＞＞＞＞＞＞ 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 )フラーレンの応用
2P-1（☆） 若手奨励賞候補

Understanding Efficiency Enhancement in Solution-Processed C60/C70 Mixed
Fullerenes Perovskite Solar Cells

83* Haosheng Lin, Il Jeon, Shigeo Maruyama, Yutaka Matsuo
2P-2

Preparation of [C60]fullerene nanowhisker-cadmium sulfide nanoparticle composites
and their photocatalytic activity for degradation of Rhodamine B

84* Jeong Won Ko, Weon Bae Ko

金属内包フラーレン
2P-3

Search for Missing Lu2＠C80(I h )85* 高井 良也, 菊地 耕一, 阿知波 洋次, 兒玉 健
2P-4

Chemical Reduction of Lithium-Ion-Encapsulated Fullerene to Li@C60

86* Hiroshi Okada, Hiroshi Ueno, Yasuhiro Takabayashi, Takeshi Nakagawa,Martina Vrankic, Shinobu Aoyagi, Ken Kokubo, Kimio Akiyama, Ioannis Arvanitidis,
Kosmas Prassides, Yutaka Matsuo

ナノチューブの物性2P-5配列した単層カーボンナノチューブ薄膜の熱電特性

87* 福原 健吾, 一ノ瀬 遥太, 蓬田 陽平,, 河野 淳一郎, 柳 和宏
2P-6

単層カーボンナノチューブにおけるテラヘルツ高調波発生

88* 西留 比呂幸, 永井 恒平, 一ノ瀬 遥太, 福原 健吾, 野崎 純司, 枝 淳子, 蓬田 陽平,
柳 和宏, 田中 耕一郎
2P-7

熱伝導測定と操作に向けた孤立架橋単層カーボンナノチューブの合成

89* 稲葉 工, 島 龍之介, 清水 麻希, 山口 智弘, 石橋 幸治, 本間 芳和

ナノチューブの応用
2P-8

Voltage generation by electrolyte droplet on carbon nanotube thin film: Dependenceof output power on carrier density☆

* 西 涼平, 岸本 茂, 廣谷 潤, 片浦 弘道, 大野 雄高

2P-9

メルトブレンディング法によるSWNT/PE複合材料の作製

90

91* 宇津木 孝一, 大槻 南央, 山田 亮太, 太田 大陸, 小野寺 厚, 関戸 大
2P-10☆

CNT薄膜のモルフォロジーと伝導特性の相関に関する理論研究* 佃 将明, 山本 貴博

x92

３月１１日 （日）ナノチューブの生成と精製
2P-11

高温パルスアーク放電法を用いた２層カーボンナノチューブの生成と評価:放電電極間距離依存性93* 田中 佑弥, 菅井 俊樹
2P-12
☆
2P-13

単層カーボンナノチューブ－多孔質ガラス複合体の加熱処理による精製

94* 松岡 朗平, 林 由樹, 長澤 浩, 鈴木 信三
Growth simulation of chirality-assignable single-walled carbon nanotubes with perfect
cap structure by molecular dynamics

95* 鵜飼 浩行, 吉川 亮, 千足 昇平, 丸山 茂夫

内包ナノチューブ
2P-14

Stability of isomerized forms of photoisomerizable molecules complexed with carbon
nanotubes

96* 濵島 圭佑, 小山 剛史, 斎藤 毅, 岸田 英夫
2P-15

カーボンナノチューブ内包ペリレン分子のエネルギー論

97* 長澤 裕哉, 小山 剛史, 岡田 晋
2P-16

Local structure and properties of polycyclic aromatic hydrocarbon molecule encapsulated
in single-walled carbon nanotubes studied by molecular dynamics simulations(Ⅱ）

98* 永井 涼, 片岡 洋右, 緒方 啓典

グラフェン生成
2P-17
☆
2P-18

Fast Synthesis of Graphene in Three-Dimensional Reaction Field by Chemical Vapor
Deposition

99* 永井 款也, 杉目 恒志, 野田 優
グラファイトの酸素プラズマエッチングによるサイズ制御とその物性評価および液相剥離
への応用

100

* 石黒 康志, 広部 元希, 高井 和之

グラフェンの応用
2P-19

機能化グラフェンナノリボンにおける特異な光伝導特性101* 鈴木 弘朗, 金子 俊郎, 加藤 俊顕
2P-20

First-Principles Calculation of Carrier Injection and Work Function inGraphene/Ferroelectrics Hybrid Material☆

* Hikaru Horii, Satoru Konabe, Takahiro Yamamoto

2P-21

水が凝集したグラフェンの第一原理電子状態計算

102

103

* 木岡 夕星, 前川 侑毅, 笹岡 健二, 山本 貴博

グラフェンの物性
2P-22エピタキシャルグラフェンにおける欠陥導入と水素終端* 小幡 吉徳, 高井 和之

xi

104

３月１１日 （日）

2P-23
☆

Diffusion of Li Atom on Graphene Sheet through V6 Vacancy: First Principles Calculations

2P-24(0001)面上グラフェンナノリボンの作製と電気抵抗測定評価105* 塩田 健斗, 河合 孝純
106* 堀部 真史, 伊藤 誠一郎, 水野 悠也, 王 辰星, 中原 仁, 齋藤 弥八
2P-25

犠牲層を用いたグラフェンへのイオンビーム照射

107* 中村 康輔, 高井 和之, 西村 智朗
2P-26

Near-Field Electron-Photon Matrix Element of Monolayer Graphene108* Fenda Rizky Pratama, M. Shoufie Ukhtary, Riichiro Saito

原子層
2P-27

超高速分光手法を用いた単層WSe2におけるバレー緩和

109* 篠北 啓介, 王 暁凡, 宮内 雄平, 松田 一成
2P-28
☆
2P-29

Layer-by-layer growth of single crystalline transitional metal dichalcogenides thin films
by molecular beam epitaxy

110* Yue Wang, Masaki Nakano, Yuta Kashiwabara, Yoshihiro Iwasa
架橋した単層MoS2の作製と光学的性質

111* 小島 佳奈, Wenjin Zhang, 宮内 雄平, 齊藤 哲輝, 小林 佑, 遠藤 尚彦, 松田 一成,
真庭 豊, 宮田 耕充
2P-30

金属薄膜からのゲルマニウム結晶の表面析出

112* 鈴木 誠也, 稲葉 達郎, 吉村 雅満
2P-31
☆
2P-32

Photoluminescence properties of twisted bilayer transition metal dichalcogenides

113* Masafumi Shimasaki, Wenjin Zhang, Xiaofan Wang, Takashi Taniguchi,
Kenji Watanabe, Kazunari Matsuda, Yuhei Miyauchi
単層WSe2-MoS2面内ヘテロ接合発光ダイオード

114* 蒲 江, Li Ming-Yang, Huang Jing-Kai, 宮内 雄平, 松田 一成, Li Lain-Jong, 竹延 大志
2P-33

Absorption spectra from exciton effect of atomic layer materials

115* 白倉 俊哉, 辰巳 由樹, 齋藤 理一郎

ナノ炭素粒子
2P-34☆

墨作りの原理を活用した炭素微粒子の水への分散II

2P-35

希薄なナノダイヤモンドコロイド溶液へのDLSの適用力116* 石戸 海斗, 中村 一稀, 谷山 功貴, 藤田 健斗, 早川 純平
117* Takumi Sato, Toshihiko Tanaka, Yasuhiro F. Miura, Tetsuya Aoyama, Eiji Osawa

バイオ
2P-36
☆

タンパク質吸着によるカーボンナノチューブの酸化還元反応の抑制* 中山 智仁, 田中 丈士, 白木 賢太郎, 長谷 宗明, 平野 篤

xii

118

３月１１日 （日）2P-37

局所埋入したCNTの体内動態

119* 平田 恵理, 湯田坂 雅子, 前田 由佳利, 田中 丈士, 片浦 弘道, 横山 敦郎

その他
2P-38
☆

Carrier accumulation on functionalized diamond (111) surfaces by an external electric field

2P-39

構造の異なる炭素によるメタン分解における生成炭素の触媒活性評価

120* Yanlin Gao, Susumu Okada
121* 宮本 大, 西井 春樹, 梅田 良人, 濱口 裕昭, 鈴木 正史, 針谷 達, 谷本 壮,
滝川 浩史, 須田 善行

特別講演 ( 16:45-17:15 )2S-5

カーボンナノチューブおよびグラフェンからの電界放出：特徴と関連する現象

5* 齋藤 弥八

特別講演 ( 17:15-17:45 )2S-6

ファンデルワールスヘテロ構造：原子層科学から複合原子層科学へ

6* 町田 友樹

一般講演 ( 17:45-19:00 )グラフェンの応用 ・ 原子層 ・ その他
2-9Graphene-Silicon Schottky Junction for Optoelectronic Devices

29* Xinming Li, Hongwei Zhu, Renzhi Ma, Takayoshi Sasaki
2-10

透明太陽電池に向けたITO/WSe2間のショットキー接合制御

30* 山口 慶樹, 大北 若奈, 李 超, 金子 俊郎, 加藤 俊顕
2-11

ヘリシティに依存したラマン散乱とレイリー散乱の角運動量保存則

31* 辰巳 由樹, 金子 智昭, 齋藤 理一郎
2-12

超高速分光法を用いた3層ReS2におけるキャリアダイナミクス

32* 王 暁凡, 篠北 啓介, 林 宏恩, モハメッド ヌル バイズラ, 宮内 雄平, 松田 一成
2-13

In situ transmission electron microscopy of the formation and annihilation of charge
density waves in 1T -TaSe2* 小林 慶太, 保田 英洋

懇親会 ( 19:00-20:45 )

xiii

33

３月１２日 （月）特別講演
発表 ２５分 ・ 質疑応答 ５分
一般講演
発表 １０分 ・ 質疑応答 ５分
ポスタープレビュー
発表 １分 ・ 質疑応答 なし

特別講演 ( 9:00-9:30 )3S-7

Exploring Molecular Nanocarbon Science7* Kenichiro Itami

一般講演 ( 9:30-10:30 )フラーレンの化学 ・ 金属内包フラーレン ・ フラーレンの応用
3-1

フラーレンカチオン中間体を経るフラーレンの機能化

34* 松尾 豊3-2

内包フラーレンにおける分子内相互作用の検出35* 橋川 祥史, 村田 靖次郎
3-3

Characterization of the spin system in GdM@Cn anion (M=Sc, Y, La; n=78, 80)

36* 三谷 拓示, 古川 貢, 加藤 立久, 菊地 耕一, 阿知波 洋次, 兒玉 健
3-4

Highly Stabilized Perovskite Solar Cells by Li+-Encapsulated [60]Fullerene as
Both Dopant and Anti-Oxidant

37* Hiroshi Ueno, Il Jeon, Seungju Seo, Ryosuke Nishikubo, Hiroshi Okada,
Akinori Saeki, Shigeo Maruyama, Yutaka Matsuo＞＞＞＞＞＞＞ 休憩 ( 10:30-10:45 ) ＜＜＜＜＜＜＜特別講演 ( 10:45-11:15 )3S-8

熱マネジメントに向けたグラフェンのフォノンエンジニアリング

8* 有江 隆之

一般講演 ( 11:15-12:00 )グラフェンの物性 ・ 原子層
3-5グラフェンに適用される分子動力学の過渡分散関係からフォノン群速度の行列の計算方法

38* ゾロツキヒナ タチアナ, 熊木 健太郎, 俵 賢汰
3-6High-yield production of thin layer materials by solid phase ball milling39* Ahmad Tayyebi, Gang Liu, Naoko Ogino, Naoki Komatsu
3-7

ファンデルワールス超格子の自動作製：ロボットによる二次元層状物質の劈開・探索・積層* 増渕 覚, 森本 将崇, 森川 生, 小野寺 桃子, 浅川 裕太, 渡邊 賢司, 谷口 尚,
町田 友樹＞＞＞＞＞＞＞ 昼食 ( 12:00-13:15 ) ＜＜＜＜＜＜＜xiv

40

３月１２日 （月）ポスタープレビュー ( 13:15-14:15 )ポスターセッション ( 14:15-16:00 )金属内包フラーレン
3P-1（☆） 若手奨励賞候補

Chromatographic Separation of FeCl-Fullerene Complexes

122* Yuri Tanuma, Seiji Hosoda, Toru Maekawa, Takashi Uchida
3P-2

Separation and Characterization of Sc-dimetallofullerenes: Sc2Cn(n=76, 78, 80, 82)

123* 吉田 俊, 菊地 耕一, 阿知波 洋次, 兒玉 健
3P-3
☆
3P-4

+

−

124

[Li @C60](TFSI )∙CH2Cl2の結晶構造解析* 三輪 和平, 青柳 忍, 岡田 洋史, 上野 裕, 松尾 豊
Photoreaction of Sc3N@I h -C80 with Disilirane: Formation and Isomerizationof 1,2-, 1,3-, and 1,4-Adducts125* 深澤 新平, 佐藤 雄一, 加固 昌寛, 安井 正憲, 山田 道夫 , 前田 優, 赤阪 健
3P-5

C60に内包された水分子の低温における回転運動

126* 鈴木 晴, 中野 元裕, 橋川 祥史, 村田 靖次郎

ナノチューブの物性
3P-6Electronic structure of carbon nanotube thin films under an external electric field

127* 王 東皓, 岡田 晋
3P-7

局所化学修飾単層カーボンナノチューブにおける置換アリール基の構造異性体に基づく近赤外発光特性変化

128* 白木 智丈, 内村 駿介, 白石 智也, 利光 史行, 中嶋 直敏
3P-8

Response of Localized Carriers to Terahertz Radiation in a Carbon Nanotube Film☆

* Takuya Okamoto, Naoki Fujimura, Xiaowei He, Weilu Gao, Junichiro Kono,
Yukio Kawano

3P-9

Exciton effect of circular dichroism in single-wall carbon nanotubes

129

130

* 岩崎 佑哉, 齋藤 理一郎

ナノチューブの応用
3P-10

Semiconducting Carbon Nanotubes as Charge-transporting Grain Boundary Protectorof Perovskite Solar Cells

131* Seungju Seo, Il Jeon, Zhang Hao, Takeshi Tanaka, Hiromichi Kataura,
Yutaka Matsuo, Shigeo Maruyama
3P-11
☆
3P-12

Fabrication and characterization of self-aligned carbon nanotube thin film transistors132* 鹿嶋 大雅, 松浦 智紀, 廣谷 潤, 岸本 茂, 大野 雄高
CNT Supported Mn-doped ZnO Nanoparticles as Efficient Visible Light- Active
Photocatalyst for Malachite Green Dye Degradation

133* Ahmed Shawky, Reda M. Mohamed, Ibrahim A. Mkhalid
3P-13☆

カーボンナノチューブ分散液中の水溶性ポリマー迅速除去法の開発* 上野 和樹, 大町 遼, 小室 智彦, 廣谷 潤, 大野 雄高, 篠原 久典

xv

134

３月１２日 （月）3P-14

ジアゾニウム塩を修飾したカーボンナノチューブの熱電特性シミュレーション

135* 荒木 那由, 山本 貴博

ナノチューブの生成と精製
3P-15
☆
3P-16

ミストCVDによるAl2O3, Fe及びCNTフォレストの連続堆積

136* 木下 聖也, 苅田 基志, 中野 貴之, 井上 翼, 長岡 宏一
Controlled Growth of Single-walled Carbon Nanotubes Using Graphene
Oxide/CoWO4 Hybrids as Catalyst Precursors

137* Xiyan Liu, Feng Yang, Yan Li
3P-17

Development of Interpenetrating Polymer Network Gel for the Separationof Single-Wall Carbon Nanotubes☆

* Guowei Wang, Takeshi Tanaka, Atsushi Hirano, Hiromichi Kataura

3P-18

Template-directed synthesis of coaxial structure of single-walled carbon nanotubes
and boron nitride nanotubes by chemical vapor deposition

138

139

* Yongjia ZHENG, Ming Liu, Taiki Inoue, Rong Xiang, Shigeo Maruyama

ナノホーン
3P-19

A study of Preparation Conditions of Carbon Nanobrushes: Influence of Target Types140* Ryota Yuge, Fumiyuki Nihey, Kiyohiko Toyama, Masako Yudasaka

ナノワイヤー
3P-20

Energetics and electronic structures of corrugated graphene nanoribbons

141* 米山 和文, 山中 綾香, 岡田 晋

グラフェン生成3P-21

Synthesis of Graphene by Oxidation and Reduction of Copper with Alcohol Chemical
Vapor Deposition142* 尾形 優也, 辻本 茉里奈, 権守 宏通, 倉橋 泰良, 村田 秀信, 橘 勝
3P-22

Sequential CVD growth of h-BN and graphene from ammonia borane and ethanol

143* Kotaro Kashiwa, Naomasa Ueda, Hayato Arai, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Shigeo Maruyama

グラフェンの応用
3P-23
☆
3P-24

12
13
Transverse thermoelectric voltage in C/ C-graphene heterostructures144* 望月 裕太, 竹井 邦晴, 秋田 成司, 有江 隆之
Fabrication of graphene sheets intercalated by carbon spheres for high-performancesupercapacitor electrodes* Zhipeng Wang, Hironori Ogata, Wei Gong, Yanqing Wang, Adavan Kiliyankil Vipin,
Gan Jet Hong Melvin, Josue Ortiz-Medina, Rodolfo Cruz-Silva, Shingo Morimoto,
Yoshio Hashimoto, Bunshi Fugetsu, Ichiro Sakata, Mauricio Terrones, Morinobu Endo

xvi

145

３月１２日 （月）グラフェンの物性
3P-25

白金・ビスマステルル微粒子修飾グラフェンにおけるスピン軌道相互作用

146* Hiroaki Kudo, Masahiro Hatsuda, Taku Nanba, Ryo Tamura, Taketomo Nakamura,
Shingo Katsumoto, Junji Haruyama
3P-26

Energetics and electronic structure of graphene adsorbing COx under an external
electric field

147* 松原 愛帆, 岡田 晋
3P-27

Topology tuning of graphene lattice structure by chemical modification

148* Kentaro Tajima, Kazuyuki Takai

原子層
3P-28

少数層MoS2ナノメッシュのエッジスピン起因磁化149* Akihide Mine, Hiroaki Kudo, Yoshiaki Hashimoto, Gen Kondo, Chika Ohata,
Shingo Katsumoto, Junji Haruyama
3P-29☆

ヒドラジン吸着を行ったMoS2の光学現象における水の存在の影響

3P-30

層状カルコゲナイドを用いた二次元多段ヘテロ構造の連続ヘテロエピタキシー

150* 児玉 尚子, 石黒 康志, 高井 和之
151* 小林 佑, 吉田 昭二, 丸山 実那, 村瀬 康太, 岡田 晋, 真庭 豊, 重川 秀実, 宮田 耕充
3P-31☆

電場誘起による大面積MoS2単層膜の金属-絶縁体転移と量子伝導

3P-32

Second quantization of surface plasmon in graphene and the applications

152* 山田 知之, 蒲 江, Li Lain-Jong, 竹延 大志
153* M. Shoufie Ukhtary, Riichiro Saito
3P-33☆

熱応力が原子層電気機械共振器の共振特性に与える影響

3P-34

CVD成長した単層MoS2を用いたFETの作製と評価

154* 井上 太一, 望月 裕太, 今北 悠貴, 竹井 邦晴, 有江 隆之, 秋田 成司
155* 清水 宏, 小川 峻, 小林 佑, 遠藤 尚彦, 真庭 豊, 宮田 耕充

ナノ炭素粒子3P-35

トラップ型気相移動度測定装置によるグラフェン量子ドットの単粒子観測

156* 星野 裕大, 森田 博暉, 陣内 涼太, 菅井 俊樹
3P-36

Control of photoluminescence and solubility of graphene quantum dots

157

* Hiroki Morita, Kazumasa Somei, Yudai Hoshino, Ryota Jinnouchi, Toshiki Sugai
3P-37

フェニル重合構造体の構造と電子状態

158* 三枝 昌紀, 岡田 晋

その他
3P-38
☆

Plasticity of carbon nanotubes under combined axial and torsional stress* Masafumi Yamanashi, Masayuki Toyoda, Susumu Saito

xvii

159

３月１２日 （月）3P-39

ゾルゲル法により作製した酸化鉄ナノチューブの光学的バンドギャップの凝集状態依存性160

高倉 詩織, * 坂東 俊治

特別講演 ( 16:00-16:30 )3S-9

フェルミレベル制御された単層カーボンナノチューブ薄膜の熱電物性

9* Kazuhiro Yanagi

一般講演 ( 16:30-17:30 )グラフェンの物性 ・ ナノチューブの物性 ・ ナノチューブの応用
3-8

ロックイン発熱解析法による大面積グラフェン局所欠陥の高速・高精度イメージング評価

41* 中島 秀朗, 森本 崇宏, 生田 美植, 沖川 侑揮, 山田 貴壽, 河原 憲治, 吾郷 浩樹,
岡崎 俊也
3-9

Direct Observation of Cross-Polarized Excitons in Aligned and Chirality-Enriched
Single-Wall Carbon Nanotubes

42* Fumiya Katsutani, Weilu Gao, Xinwei Li, Yota Ichinose, Yohei Yomogida,
Kazuhiro Yanagi, Junichiro Kono
3-10

Bilayer Plots for Accurately Determining the Chirality of Single-Walled Carbon
Nanotubes Under Complex Environments

43* Juan Yang, Daqi Zhang, Yuecong Hu, Chenmaya Xia, Sida Sun, Yan Li
3-11

Spectral tuning of optical coupling between air-mode nanobeam cavities andindividual carbon nanotubes* Hidenori Machiya, Takushi Uda, Akihiro Ishii, Yuichiro K. Kato

xviii

44

March 10th, Sat.
Special Lecture: 25min (Presentation) + 5min (Discussion)
Invited Lecture: 10min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)

Special Lecture ( 9:45-10:15 )1S-1
Fast characterization of FC-CVD nanotubes using an array of transistors
Nan Wei, Patrik Laiho, Saeed Ahmed, Aqeel Hussain, Qiang Zhang, Taher Khan,
Yongping Liao, Ying Tian, Er-Xiong Ding, Yutaka Ohno, * Esko I. Kauppinen
Special Lecture ( 10:15-10:45 )1S-2
Manipulating Crystallization and Assembly of Nanomaterials via Fluidic Engineering
Yitan Li, Yuguang Chen, Hao Wang, * Yan Li12＞＞＞＞＞＞＞ Coffee Break ( 10:45-11:00 ) ＜＜＜＜＜＜＜General Lecture ( 11:00-12:00 )Formation and purification of nanotubes ・ Applications of nanotubes
Tracing growth processes of individual single-walled carbon nanotubes by digital
1-1
isotope coding* Keigo Otsuka, Shun Yamamoto, Taiki Inoue, Rong Xiang, Shohei Chiashi,
Shigeo Maruyama
1-2

1-3

1-4

Effects of Pre-forming the different density layers on ELF method for the separationof metallic and semiconducting SWCNTs* Yuki Kuwahara, Fusako Sasaki, Nihey Fumiyuki, Takeshi Saito
Influence of Dissolved Oxygen on Introduction of Defects into SWCNTs during
Ultrasonic Dispersion Process* Hiromichi Kataura, Tomoko Sugita, Mariko Kubota, Takeshi Tanaka
Determination of association constants in complexation of nanotweezers andnanocalipers with SWNTs* Alejandro López-Moreno, Naoki Komatsu

13

14

15

16

＞＞＞＞＞＞＞ Lunch Time ( 12:00-13:15 ) ＜＜＜＜＜＜＜Special Lecture ( 13:15-13:45 )1S-3
Science and Applications of Wafer-Scale Aligned Carbon Nanotube Films
W. Gao, N. Komatsu, F. Katsutani, X. Li, K. Yanagi, * J. Kono
xix

3

March 10th, Sat.

Invited Lecture ( 13:45-14:00 )1 I-1
Advanced Carbon Based Energy Materials for Lithium-Sulfur Batteries* Qiang Zhang

11

General Lecture ( 14:00-15:00 )Applications of nanotubes
Record-high Efficiency in Carbon Nanotube Electrode-used Perovskite Solar Cells
via employing Formamidinium Lead Iodide (FAPbI3) and Trifluoromethanesulfonic
1-5
Acid Vapor Doping* Il Jeon, Jin-Wook Lee, Anton Anisimov, Esko I. Kauppinen, Yang Yang,
Shigeo Maruyama, Yutaka Matsuo

17

1-6

1-7

1-8

Carbon-nanotube differential amplifier on flexible substrate
Tomoki Matsuura, Taiga Kashima, Jun Hirotani, Shigeru Kishimoto, * Yutaka Ohno
Carbon Nanotubes versus Graphene as Flexible Transparent Electrodes in Inverted
Perovskite Solar Cells* Jungjin Yoon, Il Jeon, Namyoung Ahn, Mohamed Atwa, Clement Delacou,
Anton Anisimov, Esko Kauppinen, Shigeo Maruyama, Yutaka Matsuo, Mansoo Choi
Interdigitated electrode with dense carbon nanotube forests for electrochemical
biosensors* Hisashi Sugime, Takuya Ushiyama, Keita Nishimura, Yutaka Ohno, Suguru Noda

Poster Preview ( 15:00-16:00 )Poster Session ( 16:00-17:45 ) （☆）Candidates for the Young Scientist Poster Award
Chemistry of fullerenes
Electronic structures of solid phases of chemically functionalized C60
1P-1* Sho Furutani, Yutaka Matsuo, Susumu Okada
Endohedral metallofullerenes
Temperature dependence of anisotropic transient conductivity of
1P-2
a La@C2v-C82(Ad) crystal* Michio Yamada, Satoru Sato, Wookjin Choi, Shu Seki, Tsuneyuki Abe,
Mitsuaki Suzuki, Yutaka Maeda, Shigeru Nagase, Takeshi Akasaka

18

19

20

45

46

1P-3

Spectroscopic studies of dimetallofullerene anions encapsulating Nd* Shinya Nishimoto, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama

47

1P-4

Isolation and Characterization of Tm2@Cn(n=78, 80) anion* Kazuhiro Kobayashi, Ko Furukawa, Tatsuhisa Kato, Koichi Kikuchi,
Yohji Achiba, Takeshi Kodama

48xxMarch 10th, Sat.

Fullerenes
Energetics and Electronic Structure of Endohedral C60 Fullerenes
1P-5* Yuki Sugaya, Masayuki Toyoda, Susumu Saito, Tomonari Wakabayashi,
Yasuyuki Kanai, Noboru Sasao, Motohiko Yoshimura
1P-6

1P-7

N@C60 produced from C60 by irradiation of N+ and N2+ ion beam
* Tomonari Wakabayashi, Yasuyuki Kanai, Noboru Sasao, Yuki Sugaya,
Masayuki Toyoda, Susumu Saito, Motohiko Yoshimura
Self-patterning of C60 sheet like crystals by liquid-liquid interfacial precipitation
method* Yuto Funamori, Saori Yamamoto, Hiromichi Gonnokami, Hidenobu Murata,
Yuko Kaneda, Makoto Tanimura, Masaru Tachibana

Properties of nanotubes
1P-8
Third-harmonic generation process in a thin film of (6,5) single-wall carbon nanotubes* Takahiro Yokoyama, Takeshi Koyama, Hideo Kishida
1P-9
☆

1P-10

1P-11

Tuning of the Thermoelectric Properties of High-Purity Single-Chirality (6,5)
Single-Walled Carbon Nanotubes by Electrolyte Gating* Yota Ichinose, Kengo Fukuhara, Junko Eda, Yohei Yomogida, Kazuhiro Yanagi
Optimizing photothermoelectric effects in semiconducting and metallic carbon
nanotubes* Ahmad R. T. Nugraha, Nguyen T. Hung, Riichiro Saito
Ferric ions affect surfactant assembly structures on carbon nanotubes* Atsushi Hirano, Tomoshi Kameda, Takeshi Tanaka, Hiromichi Kataura

Applications of nanotubes
Near-infrared luminescence thermometric imaging using carbon nanotubes* Kengo Hachiya, Saki Okudaira, Yui Konno, Yutaka Maeda, Kazunari Matsuda,☆
Yuhei Miyauchi

1P-12

1P-13

Polymeric p-Type Dopant showing Permanent Doping Durability for Transparent
Carbon Electrodes* Clement Delacou, Il Jeon, Ahmed Shawky, Rong Xiang, Anton Anisimov,
Esko I. Kauppinen, Yutaka Matsuo, Shigeo Maruyama

49

50

51

52

53

54

55

56

57

1P-14
☆

Transparent and flexible triboelectric generator based on carbon nanotube* Masahiro Matsunaga, Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno

58

1P-15
☆

Preparation of MWNT/HDPE Composites via Melt Blending* Atsushi Onodera, Masaru Sekido

59

xxi

March 10th, Sat.

Formation and purification of nanotubes
In situ XANES investigation of Co and Ni Catalysts during Single-Walled Carbon
1P-16
Nanotube Growth* Takahiro Maruyama, Makoto Kumakura, Takahiro Saida, Shigeya Naritsuka
1P-17
☆

1P-18

1P-19
☆

1P-20

Repeated CNT synthesis using Resettable CoAl2O4 and NiAl2O4 catalysts* Toshihiro Sato, Hisashi Sugime, Bin Liang, Eongyu Yi, Richard Laine,
Suguru Noda

61

Controlled Growth of SWNTs Using CoWO4 Nanoparticles as Catalyst Precursor* Xu Liu, Feng Yang, Yan Li

62

Mechanism of preferential synthesis of (6,4) single-walled carbon nanotube using
surface state control of Co catalyst* Bin Xu, Toshiro Kaneko, Yasushi Shibuta, Toshiaki Kato
Separation of CoMoCAT-SWNTs by utilizing aqueous two immisible solution
phase (ATP) technique and Raman/fluorescence spectroscopy
Tatsuki Watase, Tokinaru Matsuoka, * Shinzo Suzuki

Graphene synthesis
Atomistic simulations of formation processes of in-plane heterostructures of h-BN
1P-21
and graphene* Hisaki Sawahata, Ayaka Yamanaka, Mina Maruyama, Susumu Okada
1P-22
☆

1P-23

60

Selective Growth of AB-Stacked Bilayer Graphene* Yuri Terao, Kenji Kawahara, Kenshiro Suenaga, Keisuke Yamamoto,
Hiroshi Nakashima, Kosuke Nagashio, Hiroki Hibino, Hiroki Ago
Fabrication of graphene nanoribbon transistors with high on/off ratio using
advanced plasma CVD* Yuta Wato, Hiroo Suzuki, Toshiro Kaneko, Toshiaki Kato

Applications of graphene
1P-24 Energetics of water migration through unstitched grain boundaries of graphene* Kenta Yasuraoka, Susumu Okada

63

64

65

66

67

68

1P-25
☆

Computational Simulation of Edge-Roughness Effects on GNR-based FETs
* Kengo Takashima, Takahiro Yamamoto

69

1P-26

Synthesis of Novel IrRuOx / Graphene Catalyst for Oxygen Evolution Reaction* Masanori Hara, Badam Rajashekar, Hsin-Hui Huang, Masamichi Yoshimura

70

xxii

March 10th, Sat.

Properties of graphene
1P-27 Ab initio study of double-layered graphene with ethylenic linkage structures* Hiroyuki Yokoi
1P-28

1P-29

1P-30

Electronic structures of N-doped graphene nanoribbons with H-terminatedarmchair edges* Airi Yasuma, Mina Maruyama, Susumu Okada
Tuning of Kagome bands of 2D hydrocarbon networks by the molecularconformations* Yasumaru Fujii, Mina Maruyama, Susumu Okada
Ultrafast photocarrier relaxation in monolayer graphene on SiC substrate due tophonons in the buffer layer* Hirotaka Imaeda, Takeshi Koyama, Hideo Kishida, Kenji Kawahara, Hiroki Ago,
Jianfeng Bao, Tomoo Terasawa, Wataru Norimatsu, Michiko Kusunoki

Atomic Layers
Mechanism of photoresponse speed improvement on MoS2-FET by Al2O3
1P-31
buffer layer☆
* Yuga Miyamoto, Daiki Yoshikawa, Kuniharu Takei, Takayuki Arie, Seiji Akita
1P-32

1P-33
☆

1P-34

1P-35
☆

Direct TEM/STEM imaging of 2D atomic layer crystals on SiO2
* Rong Xiang, Akihito Kumamoto, Yu Kobayashi, Yasumitsu Miyata,
Yuichi Ikuhara, Shigeo Maruyama
Two-dimensional van der Walls p-n heterostructures: Two-step CVD growth andtransport properties* Masanori Izumoto, Adha Sukma Aji, Hiroki Ago
Investigation on the influence of ball milling conditions to the morphology of
exfoliated hexagonal boron nitride nanosheets* Naoko Ogino, Gang Liu, Naoki Komatsu
Chemical doping of monolayer MoS2 by crown ether complex salts* Shintaro Yoshimura, Yu Kobayashi, Takahiko Endo, Yutaka Maniwa,
Yasumitsu Miyata

71

72

73

74

75

76

77

78

79

Bio
1P-36

In vivo behaviors of oxygen-doped carbon nanotube imaging probes after
intravenous administration to mice
* Yoko Iizumi, Tsukasa Takeuchi, Masako Yudasaka, Toshiya Okazaki

xxiii

80

March 10th, Sat.

1P-37
☆

1P-38

Experimental System for Testing Dynamics of Carbon Nanomaterials in
Lymphatic Vessels* Chika Kuroda, Kumiko Ajima, Hisao Haniu, Haruka Ishida, Katsuya Ueda,
Kaoru Aoki, Hiroyuki Kato, Naoto Saito
Quantification of Single-Walled Carbon Nanotubes in Mouse Feces: Phantom Experiments* Mitsuko Takahashi, Yuko Okamatsu-Ogura, Takeshi Tanaka,
Hiromichi Kataura, Masako Yudasaka＞＞＞＞＞＞＞ Coffee Break ( 17:45-18:00 ) ＜＜＜＜＜＜＜Tutorial ( 18:00-19:30 )Basics of Organic Solar Cells and Nano-carbon Materials-utilized Solar Cells* Yutaka Matsuo

xxiv

81

82

March 11th, Sun.
Special Lecture: 25min (Presentation) + 5min (Discussion)
Invited Lecture: 10min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)

Special Lecture ( 9:00-9:30 )2S-4
Potential applications of CNT in automotive industries* Hisayoshi Oshima

General Lecture ( 9:30-10:30 )Properties of nanotubes ・ Environmental/Safety characterization of nanomaterials
Formation and purification of nanotubes ・ Endohedral nanotubes
2-1
Systematic studies on structures and properties of commercialized CNT fibers* Takayuki Watanabe, Satoshi Yamashita, Takahiro Morimoto, Kazufumi Kobashi,
Toshiya Okazaki
2-2

2-3

2-4

Biodegradation Rate of Carbon Nanotube Depending on Diameters* Minfang Zhang, Yinmei Deng, Mei Yang, Hideaki Nakajima, Masako Yudasaka,
Sumio Iijima, Toshiya Okazaki
Growth of Horizontally Aligned Chirality-Specific SWNTs using Intermetallic
W6Co7 Catalysts* Feng Yang, Yan Li
Direct Microscopic Analysis of Individual [60]Fullerene Dimerization Events: Kinetics and Mechanisms* Koji Harano, Satoshi Okada, Satori Kowashi, Luca Schweighauser,
Kaoru Yamanouchi, Eiichi Nakamura

4

21

22

23

24

＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Invited Lecture ( 10:45-11:00 )2 I-2
Photoexcited states in transition metal dichalcogenide heterostructures
Fei Lu, * Erik Einarsson

General Lecture ( 11:00-12:00 )Properties of graphene ・ Fullerenes ・ Other topics ・ Carbon nanoparticles
2-5
Energetics and electronic structure of nitrogen-doped graphene with pyridinic structure* Mina Maruyama, Susumu Okada
xxv

12

25

March 11th, Sun.

2-6

2-7

2-8

Bilayer fullerenes (carbon nano-onions) studied by ion mobility mass spectrometry* Motoyoshi Nakano, Ryoichi Moriyama, Jenna Wu, Keijiro Ohshimo,
Fuminori Misaizu
Development of Ion Trap Ion Mobility Measurement System and Observation of
Nanomaterials* Toshiki Sugai, Yudai Hoshino, Hiroki Morita, Reona Miyamoto, Yuta Hamano,
Kazumasa Somei, Ryota Jinnouchi
Self-Assembly of Detonation Nanodiamonds from their Colloidal Solutions* Toshihiko Tanaka, Yasuhiro F. Miura, Tetsuya Aoyama, Makoto Takahashi,
Takumi Sato, Eiji Osawa

26

27

28

＞＞＞＞＞＞＞ 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
Applications of fullerenes
Understanding Efficiency Enhancement in Solution-Processed C60/C70 Mixed
2P-1
Fullerenes Perovskite Solar Cells* Haosheng Lin, Il Jeon, Shigeo Maruyama, Yutaka Matsuo
2P-2

Preparation of [C60]fullerene nanowhisker-cadmium sulfide nanoparticle
composites and their photocatalytic activity for degradation of Rhodamine B* Jeong Won Ko, Weon Bae Ko

Endohedral metallofullerenes
Search for Missing Lu2＠C80(I h )2P-3* Ryoya Takai, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama
2P-4

Chemical Reduction of Lithium-Ion-Encapsulated Fullerene to Li@C60* Hiroshi Okada, Hiroshi Ueno, Yasuhiro Takabayashi, Takeshi Nakagawa,Martina Vrankic, Shinobu Aoyagi, Ken Kokubo, Kimio Akiyama, Ioannis Arvanitidis,
Kosmas Prassides, Yutaka Matsuo

Properties of nanotubes
2P-5
Thermoelectric Properties of Aligned Single-Wall Carbon Nanotube Films* Kengo Fukuhara, Yota Ichinose, Yohei Yomogida, Weilu Gao, Junichiro Kono,
Kazuhiro Yanagi
xxvi

83

84

85

86

87

March 11th, Sun.

2P-6

2P-7

THz high harmonic generation from single wall carbon nanotubes* Hiroyuki Nishidome, Kohei Nagai, Yota Ichinose, Kengo Fukuhara,
Junji Nozaki, Junko Eda, Yohei Yomogida, Kazuhiro Yanagi, Koichiro Tanaka
Growth of Individually-suspended Single-Walled Carbon Nanotubes toward
Thermal Conductivity Measurement and Manipulation* Takumi Inaba, Ryuunosuke Shima, Maki Shimizu, Tomohiro Yamaguchi,
Koji Ishibashi, Yoshikazu Homma

Applications of nanotubes
Voltage generation by electrolyte droplet on carbon nanotube thin film
2P-8
: Dependence of output power on carrier density☆
* Ryohei Nishi, Shigeru Kishimoto, Jun Hirotani, Hiromichi Kataura, Yutaka Ohno
2P-9

2P-10
☆

Preparation of SWNT/PE Composites by Melt Blending* Koichi Utsugi, Nao Otsuki, Ryota Yamada, Riku Ota, Atsushi Onodera,
Masaru Sekido
Computational Study on Optimization of Sheet Conductance of Carbon Nanotube
Transparent Films* Masaaki Tsukuda, Takahiro Yamamoto

Formation and purification of nanotubes
Production and Characterization of Double-wall Carbon Nanotubes by
2P-11 High-temperature Pulsed-arc Discharge: Dependence on Distance between Discharge Electrodes* Yuya Tanaka, Toshiki Sugai
2P-12
☆

2P-13

Purification of SWNT-porous glass (PG) composite by using heat treatment* Tokinaru Matsuoka, Yoshiki Hayashi, Horoshi Nagasawa, Shinzo Suzuki
Growth simulation of chirality-assignable single-walled carbon nanotubes withperfect cap structure by molecular dynamics* Hiroyuki Ukai, Ryo Yoshikawa, Shohei Chiashi, Shigeo Maruyama

Endohedral nanotubes
Stability of isomerized forms of photoisomerizable molecules complexed with
2P-14
carbon nanotubes* Keisuke Hamajima, Takeshi Koyama, Takeshi Saito, Hideo Kishida
2P-15

Energetics of perylene molecules encapsulated in carbon nanotubes* Yuya Nagasawa, Takeshi Koyama, Susumu Okada

xxvii

88

89

90

91

92

93

94

95

96

97

March 11th, Sun.

2P-16

Local structure and properties of polycyclic aromatic hydrocarbon molecule
encapsulated in single-walled carbon nanotubes studied by molecular dynamics
simulations(Ⅱ）* Ryo Nagai, Yosuke Kataoka, Hironori Ogata

Graphene synthesis
Fast Synthesis of Graphene in Three-Dimensional Reaction Field by Chemical
2P-17
Vapor Deposition☆
* Yukuya Nagai, Hisashi Sugime, Suguru Noda
2P-18

Characterization of size controlled graphite by O2 plasma etching and its
application to liquid phase exfoliation* Yasushi Ishiguro, Genki Hirobe, Kazuyuki Takai

Applications of graphene
2P-19 Persistent photo conductivity in functionalized graphene nanoribbons* Hiroo Suzuki, Toshiro Kaneko, Toshiaki Kato
2P-20
☆
2P-21

First-Principles Calculation of Carrier Injection and Work Function inGraphene/Ferroelectrics Hybrid Material* Hikaru Horii, Satoru Konabe, Takahiro Yamamoto
First Principles Calculations of Electrical Structure of Water Absorbed Graphene* Yusei Kioka, Yuki Maekawa, Kenji Sasaoka, Takahiro Yamamoto

Properties of graphene
2P-22 Defect introduction and hydrogen termination in Epitaxial graphene* Yoshinori Obata, Kazuyuki Takai
2P-23
☆

2P-24

Diffusion of Li Atom on Graphene Sheet through V6 Vacancy: First Principles
Calculations* Kento Shiota, Takazumi Kawai
Fabrication and Electrical Resistance Mesurement of Graphene Nanoribbons on
SiC (0001)* Masashi Horibe, Seichiro Ito, Yuya Mizuno, Chenxing Wang, Hitoshi Nakahara,
Yahachi Saito

98

99

100

101

102

103

104

105

106

2P-25

Ion-beam irradiation into Graphene via sacrificial layers* Kosuke Nakamura, Kazuyuki Takai, Tomoaki Nishimura

107

2P-26

Near-Field Electron-Photon Matrix Element of Monolayer Graphene* Fenda Rizky Pratama, M. Shoufie Ukhtary, Riichiro Saito

108

xxviii

March 11th, Sun.

Atomic Layers
2P-27 Valley relaxation in monolayer WSe2 studied by ultrafast spectroscopy* Keisuke Shinokita, Xiaofan Wang, Yuhei Miyauchi, Kazunari Matsuda
2P-28☆

Layer-by-layer growth of single crystalline transitional metal dichalcogenides
thin films by molecular beam epitaxy* Yue Wang, Masaki Nakano, Yuta Kashiwabara, Yoshihiro Iwasa

109

110

2P-29

Preparation and optical properties of suspended monolayer MoS2
* Kana Kojima, Zhang Wenjin, Yuhei Miyauchi, Tetsuki Saito, Yu Kobayashi,
Takahiko Endo, Kazunari Matsuda, Yutaka Maniwa, Yasumitsu Miyata

111

2P-30

Surface segregation of Ge crystal on metal thin films* Seiya Suzuki, Tatsurou Inaba, Masamichi Yoshimura

112

2P-31

Photoluminescence properties of twisted bilayer transition metal dichalcogenides* Masafumi Shimasaki, Wenjin Zhang, Xiaofan Wang, Takashi Taniguchi,
Kenji Watanabe, Kazunari Matsuda, Yuhei Miyauchi

113

2P-32

Monolayer WSe2-MoS2 Lateral Heterojunction Light-Emitting Diodes* Jiang Pu, Ming-Yang Li, Jing-kai Huang, Yuhei Miyauchi, Kazunari Matsuda,
Lain-Jong Li, Taishi Takenobu

114

2P-33

Absorption spectra from exciton effect of atomic layer materials* Toshiya Shirakura, Yuki Tatsumi, Riichiro Saito

115☆

Carbon nanoparticles
2P-34 Aqueous dispersion of carbon materials inspired by Japanese Ink II☆
* Kaito Ishido, Kazuki Nakamura, Koki Taniyama, Kento Fujita, Junpei Hayakawa
2P-35

116

Applicability of DLS to Diluted Nanodiamond Colloidal Solutions* Takumi Sato, Toshihiko Tanaka, Yasuhiro F. Miura, Tetsuya Aoyama, Eiji Osawa

117

Suppression of carbon nanotube redox reaction caused by protein adsorption* Tomohito Nakayama, Takeshi Tanaka, Kentaro Shiraki, Muneaki Hase,
Atsushi Hirano

118

Biodistribution of carbon nanotubes after local implantation of mice
* Eri Hirata, Masako Yudasaka, Yukari Maeda, Takeshi Tanaka,
Hiromichi Kataura, Atusro Yokoyama

119

Bio
2P-36
☆

2P-37

xxix

March 11th, Sun.

Other topics
Carrier accumulation on functionalized diamond (111) surfaces by an external
2P-38
electric field☆
* Yanlin Gao, Susumu Okada
2P-39

Catalytic Activity of Several Carbons with Different Structures and By-Produced
Carbons for Methane Decomposition* Dai Miyamoto, Haruki Nishii, Yoshito Umeda, Hiroaki Hamaguchi,
Masashi Suzuki, Toru Harigai, Tsuyoshi Tanimoto, Hirofumi Takikawa,
Yoshiyuki Suda

120

121

Special Lecture ( 16:45-17:15 )Field Emission from Carbon Nanotube and Graphene: Unique Characteristics and
2S-5
Related Phenomena* Yahachi Saito

5

Special Lecture ( 17:15-17:45 )2S-6
Quantum transport in van der Waals junctions of 2D materials* Tomoki Machida

6

General Lecture ( 17:45-19:00 )Applications of graphene ・ Atomic Layers ・ Other topics
2-9
Graphene-Silicon Schottky Junction for Optoelectronic Devices* Xinming Li, Hongwei Zhu, Renzhi Ma, Takayoshi Sasaki
2-10

Schottky barrier control between indium tin oxide and WSe2 for fabrication oftransition metal dichalcogenide-based transparent solar cell
* Yoshiki Yamaguchi, Wakana Okita, Chao Li, Toshiro Kaneko, Toshiaki Kato

29

30

2-11

Angular momentum conservation in helicity-dependent Raman and Rayleigh scattering* Yuki Tatsumi, Tomoaki Kaneko, Riichiro Saito

31

2-12

Carrier dynamics in 3-layer ReS2 studied by ultrafast spectroscopy* Xiaofan Wang, Keisuke Shinokita, Hong En Lim, Nur Baizura Mohamed,
Yuhei Miyauchi, Kazunari Matsuda

32

2-13

In situ transmission electron microscopy of the formation and annihilation of
charge density waves in 1T -TaSe2* Keita Kobayashi, Hidehiro Yasuda

Banquet ( 19:00-20:45 )xxx

33

March 12th, Mon.
Special Lecture: 25min (Presentation) + 5min (Discussion)
General Lecture: 10min (Presentation) + 5min (Discussion)
Poster Preview: 1min (Presentation)

Special Lecture ( 9:00-9:30 )3S-7
Exploring Molecular Nanocarbon Science* Kenichiro Itami

General Lecture ( 9:30-10:30 )Chemistry of fullerenes ・ Endohedral metallofullerenes ・ Applications of fullerenes
3-1
Functionalization of [60]Fullerene Through Fullerene Cation Intermediates* Yutaka Matsuo
3-2

3-3

3-4

Molecules inside Fullerenes as Magnetic Probes for the Detection of SpecificIntramolecular Interactions* Yoshifumi Hashikawa, Yasujiro Murata
Characterization of the spin system in GdM@Cn anion (M=Sc, Y, La; n=78, 80)* Takuji Mitani, Ko Furukawa, Tatsuhisa Kato, Koichi Kikuchi, Yohji Achiba,
Takeshi Kodama
Highly Stabilized Perovskite Solar Cells by Li+-Encapsulated [60]Fullerene as
Both Dopant and Anti-Oxidant* Hiroshi Ueno, Il Jeon, Seungju Seo, Ryosuke Nishikubo, Hiroshi Okada,
Akinori Saeki, Shigeo Maruyama, Yutaka Matsuo

7

34

35

36

37

＞＞＞＞＞＞＞ Coffee Break ( 10:30-10:45 ) ＜＜＜＜＜＜＜Special Lecture ( 10:45-11:15 )3S-8
Phonon engineering of graphene for thermal management* Takayuki Arie

General Lecture ( 11:15-12:00 )Properties of graphene ・ Atomic Layers
Matrix approach to calculation of phonon group velocities from MD transient
3-5
dispersion relation as applied to graphene* Tatiana Zolotoukhna, Kentaro Kumaki, Kenta Tawara
3-6

High-yield production of thin layer materials by solid phase ball milling* Ahmad Tayyebi, Gang Liu, Naoko Ogino, Naoki Komatsu
xxxi

8

38

39

March 12th, Mon.

3-7

Automated searching and assembly of atomic layers: a robotic building systemof van der Waals superlattices* Satoru Masubuchi, Masataka Morimoto, Sei Morikawa, Momoko Onodera,
Yuta Asakawa, Kenji Watanabe, Takashi Taniguchi, Tomoki Machida40＞＞＞＞＞＞＞ 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
Chromatographic Separation of FeCl-Fullerene Complexes* Yuri Tanuma, Seiji Hosoda, Toru Maekawa, Takashi Uchida

122

3P-2

Separation and Characterization of Sc-dimetallofullerenes: Sc2Cn(n=76, 78, 80, 82)* Shun Yoshida, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama

123

3P-3
☆

Crystal structure analysis of [Li+@C60](TFSI−)∙CH2Cl2* Kazuhira Miwa, Shinobu Aoyagi, Hiroshi Okada, Hiroshi Ueno, Yutaka Matsuo

124

3P-4

3P-5

Photoreaction of Sc3N@I h -C80 with Disilirane: Formation and Isomerizationof 1,2-, 1,3-, and 1,4-Adducts* Shinpei Fukazawa, Yuichi Sato, Masahiro Kako, Masanori Yasui,
Michio Yamada, Yutaka Maeda, Takeshi Akasaka
Rotational dynamics of a H2O molecule encapsulated in a fullerene C60 at low
temperature* Hal Suzuki, Motohiro Nakano, Yoshifumi Hashikawa, Yasujiro Murata

Properties of nanotubes
3P-6
Electronic structure of carbon nanotube thin films under an external electric field* Donghao Wang, Susumu Okada
3P-7

3P-8
☆

Structural Isomer-induced spectral changes in near infrared photoluminescence of
locally-functionalized single-walled carbon nanotubes* Tomohiro Shiraki, Shunsuke Uchimura, Tomonari Shiraishi,
Fumiyuki Toshimitsu, Naotoshi Nakashima
Response of Localized Carriers to Terahertz Radiation in a Carbon Nanotube Film
* Takuya Okamoto, Naoki Fujimura, Xiaowei He, Weilu Gao, Junichiro Kono,
Yukio Kawano

xxxii

125

126

127

128

129

March 12th, Mon.

3P-9

Exciton effect of circular dichroism in single-wall carbon nanotubes* Yuya Iwasaki, Riichiro Saito

Applications of nanotubes
Semiconducting Carbon Nanotubes as Charge-transporting Grain Boundary
3P-10
Protector of Perovskite Solar Cells* Seungju Seo, Il Jeon, Zhang Hao, Takeshi Tanaka, Hiromichi Kataura,
Yutaka Matsuo, Shigeo Maruyama
3P-11
☆

3P-12

3P-13
☆

3P-14

Fabrication and characterization of self-aligned carbon nanotube thin film transistors* Taiga Kashima, Tomoki Matsuura, Jun Hirotani, Shigeru Kishimoto, Yutaka Ohno
CNT Supported Mn-doped ZnO Nanoparticles as Efficient Visible Light- Active
Photocatalyst for Malachite Green Dye Degradation* Ahmed Shawky, Reda M. Mohamed, Ibrahim A. Mkhalid
Rapid and efficient removal of water soluble polymer from carbon nanotube
dispersion* Kazuki Ueno, Haruka Omachi, Tomohiko Komuro, Jun Hirotani, Yutaka Ohno,
Hisanori Shinohara
Computational Design for Thermoelectric Properties of Carbon Nanotubes
Modified by Diazonium Salts* Nayu Araki, Takahiro Yamamoto

Formation and purification of nanotubes
3P-15 Successive deposition of Al2O3, Fe and CNT forest by mist CVD* Toshiya Kinoshita, Motoyuki Karita, Takayuki Nakano, Yoku Inoue,☆
Hirokazu Nagaoka
3P-16

3P-17
☆

3P-18

Controlled Growth of Single-walled Carbon Nanotubes Using Graphene
Oxide/CoWO4 Hybrids as Catalyst Precursors* Xiyan Liu, Feng Yang, Yan Li
Development of Interpenetrating Polymer Network Gel for the Separation ofSingle-Wall Carbon Nanotubes* Guowei Wang, Takeshi Tanaka, Atsushi Hirano, Hiromichi Kataura
Template-directed synthesis of coaxial structure of single-walled carbon nanotubes
and boron nitride nanotubes by chemical vapor deposition* Yongjia ZHENG, Ming Liu, Taiki Inoue, Rong Xiang, Shigeo Maruyama

xxxiii

130

131

132

133

134

135

136

137

138

139

March 12th, Mon.

Nanohorns
3P-19 A study of Preparation Conditions of Carbon Nanobrushes: Influence of Target Types* Ryota Yuge, Fumiyuki Nihey, Kiyohiko Toyama, Masako Yudasaka

140

Nanowires
3P-20 Energetics and electronic structures of corrugated graphene nanoribbons* Kazufumi Yoneyama, Ayaka Yamanaka, Susumu Okada

141

Graphene synthesis
Synthesis of Graphene by Oxidation and Reduction of Copper with Alcohol
3P-21
Chemical Vapor Deposition* Yuya Ogata, Marina Tsujimoto, Hiromichi Gonnokami, Tyler Kurahashi,
Hidenobu Murata, Masaru Tachibana
3P-22

Sequential CVD growth of h-BN and graphene from ammonia borane and ethanol* Kotaro Kashiwa, Naomasa Ueda, Hayato Arai, Taiki Inoue, Rong Xiang,
Shohei Chiashi, Shigeo Maruyama

Applications of graphene
Transverse thermoelectric voltage in 12C/13C-graphene heterostructures* Yuta Mochizuki, Kuniharu Takei, Seiji Akita, Takayuki Arie

3P-23
☆

3P-24

Fabrication of graphene sheets intercalated by carbon spheres for high-performancesupercapacitor electrodes* Zhipeng Wang, Hironori Ogata, Wei Gong, Yanqing Wang,
Adavan Kiliyankil Vipin, Gan Jet Hong Melvin, Josue Ortiz-Medina,
Rodolfo Cruz-Silva, Shingo Morimoto, Yoshio Hashimoto, Bunshi Fugetsu,
Ichiro Sakata, Mauricio Terrones, Morinobu Endo

Properties of graphene
3P-25 Spin-orbit interaction in Pt or Bi2Te3-nanoparticle decorated graphene* Hiroaki Kudo, Masahiro Hatsuda, Taku Nanba, Ryo Tamura,
Taketomo Nakamura, Shingo Katsumoto, Junji Haruyama
3P-26

3P-27

Energetics and electronic structure of graphene adsorbing COx under an external
electric field* Manaho Matsubara, Susumu Okada
Topology tuning of graphene lattice structure by chemical modification* Kentaro Tajima, Kazuyuki Takai

xxxiv

142

143

144

145

146

147

148

March 12th, Mon.

Atomic Layers
3P-28 Magnetism arising from edge spins of few-layer MoS2 nanomeshes* Akihide Mine, Hiroaki Kudo, Yoshiaki Hashimoto, Gen Kondo, Chika Ohata,
Shingo Katsumoto, Junji Haruyama
3P-29
☆

3P-30

3P-31
☆
3P-32

3P-33
☆

3P-34

Effect of the water presence in optical phenomena of hydrazine-adsorbed MoS2
* Naoko Kodama, Yasushi Ishiguro, Kazuyuki Takai
Continuous heteroepitaxy of two-dimensional multi-heterostructures based onlayered chalcogenides* Yu Kobayashi, Shoji Yoshida, Mina Maruyama, Kota Murase, Susumu Okada,
Yutaka Maniwa, Hidemi Shigekawa, Yasumitsu Miyata
Electric-field-induced Metal-Insulator Transition and Quantum Transport inLarge-Area Polycrystalline MoS2 Monolayers* Tomoyuki Yamada, Jiang Pu, Lain-Jong Li, Taishi Takenobu
Second quantization of surface plasmon in graphene and the applications* M. Shoufie Ukhtary, Riichiro Saito
Effect of thermal stress on resonance properties of atomically thin electromechanicalresonators* Taichi Inoue, Yuta Mochizuki, Yuki Imakita, Kuniharu Takei, Takayuki Arie,
Seiji Akita
Fabrication and characterization of field-effect transistors based on CVD-grownmonolayer MoS2
* Hiroshi Shimizu, Shun Ogawa, Yu Kobayashi, Takahiko Endo, Yutaka Maniwa,
Yasumitsu Miyata

149

150

151

152

153

154

155

Carbon nanoparticles
3P-35 Observation of graphene quantum dot using ion trap ion mobility measurement system 156* Yudai Hoshino, Hiroki Morita, Ryota Jinnouchi, Toshiki Sugai
3P-36

Control of photoluminescence and solubility of graphene quantum dots
* Hiroki Morita, Kazumasa Somei, Yudai Hoshino, Ryota Jinnouchi, Toshiki Sugai

157

3P-37

Energetics and electronic structure of All-benzene nanostructures* Masaki Mieda, Susumu Okada

158

Other topics
3P-38 Plasticity of carbon nanotubes under combined axial and torsional stress☆
* Masafumi Yamanashi, Masayuki Toyoda, Susumu Saito
xxxv

159

March 12th, Mon.

3P-39

Dependence of optical band gap on aggregational state of iron oxide nanotube
prepared by sol-gel method
Shiori Takakura, * Shunji Bandow

160

Special Lecture ( 16:00-16:30 )Thermoelectric Properties of Fermi Level Tuned and Aligned Single Wall Carbon
3S-9
Nanotube Thin Films* Kazuhiro Yanagi

9

General Lecture ( 16:30-17:30 )Properties of graphene ・ Properties of nanotubes ・ Applications of nanotubes
Fast and precise imaging of structural defects in large area graphene films via
3-8
lock-in thermography* Hideaki Nakajima, Takahiro Morimoto, Yoshiue Ikuta, Yuki Okigawa,Takatoshi Yamada, Kenji Kawahara, Hiroki Ago, Toshiya Okazaki

41

3-9

3-10

3-11

Direct Observation of Cross-Polarized Excitons in Aligned and Chirality-Enriched
Single-Wall Carbon Nanotubes* Fumiya Katsutani, Weilu Gao, Xinwei Li, Yota Ichinose, Yohei Yomogida,
Kazuhiro Yanagi, Junichiro Kono
Bilayer Plots for Accurately Determining the Chirality of Single-Walled Carbon
Nanotubes Under Complex Environments* Juan Yang, Daqi Zhang, Yuecong Hu, Chenmaya Xia, Sida Sun, Yan Li
Spectral tuning of optical coupling between air-mode nanobeam cavities andindividual carbon nanotubes* Hidenori Machiya, Takushi Uda, Akihiro Ishii, Yuichiro K. Kato

xxxvi

42

43

44

特別講演
Special Lecture

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

1S-1
Fast characterization of FC-CVD nanotubes using an array of transistors○Nan Wei1, Patrik Laiho1, Saeed Ahmed1, Aqeel Hussain1, Qiang Zhang1, Taher Khan1,
Yongping Liao1,Ying Tian1,3, Er-Xiong Ding1, Yutaka Ohno 2, Esko I. Kauppinen1
Department of Applied Physics, Aalto University School of Science, Puumiehenkuja 2,00076 Aalto, Finland
2
Institute of Materials and Systems for Sustainability, Nagoya University, Furo-cho, Chikusaku, Nagoya 464-8603, Japan3
Department of Physics, Dalian Maritime University, Dalian, Liaoning 116026, China
1

Carbon nanotubes (CNTs) grown by thefloating-catalyst chemical vapor deposition(FC-CVD) are known to make fast thin-film
transistors [1,2], however, the electronic
quality of individual FC-CVD SWNTs has
notbeen
directly
investigated. As
the limitations of other types of electronic
grade SWNTs become relatively obvious [35], if this type of SWNTs have indeed
superior performance, it may work aroundthose limitations by a new route of SWNT
Fig.1 Fabrication method and resulting mobility.
processing. We introduce a new method (Fig.
1) for fabricating a statistically significant
number of ultraclean field-effect transistors
using FC-CVD SWNTs, revealing the superior quality of these tubes with a mean field-effectmobility 3.3 times higher than that of high-quality solution-processed SWNTs [6] and on-off
current ratios higher than 107.5. This method enables a fast, reliable and fine-grained inspectionof FC-CVD SWNT population, and provides a strong direct evidence about their electronic
quality. The resulting method can contribute to development of further processing techniques,
and the obtained large number of ultraclean SWNT transistors provide new possibilities to study
the properties of pristine tubes.
[1] D. Sun et al. Nat. Nanotechnol. 6, 156 (2011).
[2] D.-M. Sun et al. Nat. Commun. 4,2302 (2013).
[3] A. E. Islam, J. A. Rogers, and M. A. Alam Adv. Mater. 27, 7908 (2015).
[4] Q. Cao, S. Han, G. S. Tulevski, A. D. Franklin, and W. Haensch ACS Nano 6, 6471 (2012).
[5] E. A. Laird et al. Rev. Mod. Phys. 87, 703 (2015).
[6] P. Stokes and S. I. Khondaker Appl. Phys. Lett.96, 83110 (2010).
Corresponding Author: E. Kauppinen
Tel: +358-40-509-8064, Fax: +358-9-2451-3517,
E-mail: esko.kauppinen@aalto.fi

-1-

1S-2
Manipulating Crystallization and Assembly of Nanomaterials via Fluidic
Engineering
Yitan Li1,2, Yuguang Chen1, Hao Wang3, ○Yan Li1,2
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China
3
College of Engineering, Peking University, Beijing 100871, China
1
2

Solution-based approaches have been intensively employed to prepare, pattern, andassemble nanomaterials. In such processes, the spontaneous fluid flow caused by evaporation,
heating, and composition gradient is inevitable. Actually, such fluid flow can be utilized tomanipulate the mass transfer and the crystallization and assembly of nanomaterials. By
controlling the pattern of the Marangoni flow, which is resulted from the surface tension
variation, we are able to control the morphology of nanocrystals formed and the patterns ofassembled nanomaterials. The examples include the preparation of thin films of carbon
nanotubes or organic semiconductors on water surface, the morphology control of
CH3NH3PbBr3 crystals, the patterning of ordered functional materials (such as perovskite andcarbon nanotubes) on substrates.

Corresponding Author: Yan. Li
Tel & Fax: +86-10-6275-6773
E-mail: yanli@pku.edu.cn

-2-

1S-3
Science and Applications of Wafer-Scale Aligned Carbon Nanotube Films○W. Gao,1 N. Komatsu,1 F. Katsutani,1 X. Li,1 K. Yanagi,2 and J. Kono1
1

Department of Electrical and Computer Engineering, Rice University, Houston, Texas, USA
2
Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo, Japan

We have recently developed a slow vacuum filtration technique (Fig. 1a) to fabricate
wafer-scale films (1 inch [1] and 2 inches [2] in diameter, as shown in Figs. 1b and 1c,
respectively) of aligned and packed SWCNTs; see Figs. 1d-1g. We can further build uniquearchitectures and devices through stacking and doping (Fig. 1c). In this talk, we summarize
some of our recent accomplishments using these unique samples.
We have made the first observation of intersubband plasmons (ISBPs) in gated aligned
films. For parallel polarization (Fig. 1h), the S11, S22, and M11 transitions disappear as carriers
are injected; for perpendicular polarization (Fig. 1i), a new peak due to ISBP appears andgrows as the carrier density increases. We have also made the first direct observation of theE12/E21 peak in the optical absorption of an aligned (6,5) film (Fig. 1j), which allowed us toquantitatively determine the oscillator strength of this transition. We further built an
exciton-polariton architecture by incorporating such films inside a Fabry-Pérot microcavity.
This system displayed a continuous transition from the strong-coupling to the weak-coupling
regime through facile polarization control (Figs. 1k-1m). The obtained dispersion surfaces
revealed the existence of exceptional points and two equienergy arcs (Fig. 1n). Furthermore,
the vacuum Rabi splitting exhibited cooperative enhancement (Fig. 1o).

Fig. 1 (a) Vacuum filtration system to produce (b) 1-inch films, (c) 2-inch films and 3D achitectures of aligned and packed

SWCNTs, as shown in images of (d, e) scanning electron microscopy and (f, g) transmision electron microscopy. (h) Paralleland (i) perpendicular-polarization optical absorption spectra for gated films of aligned SWCNTs. (j) Polarization-dependent
absorption spectra for an aligned (6,5) SWCNT film. Transmittance spectra of an exciton-polariton device with an 8-nm-thickaligned (6,5) SWCNT film for (k) ϕ = 0 and (l) ϕ = 90. (m) Transmittance spectra at zero detuning for varying ϕ. (f)Dispersion surfaces for the device. (g) Vacuum Rabi splitting at ϕ = 0 versus the square root of the film thickness.

[1] He, X., et al., Nat. Nanotech. 11, 633 (2016). [2] Komatsu, N., et al., Adv. Func. Mater. 27, 1606022 (2017).
Corresponding Author: Junichiro Kono, Tel: +1-713-348-2209, Fax: +1-713-348-3091, E-mail: kono@rice.edu

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2S-4
Potential applications of CNT in automotive industries○Hisayoshi Oshima
Advanced Research and Innovation Center, DENSO CORPORATION, Nisshin, Aichi
470-0111, Japan
Role and function of the automotive will be changed drastically in the near future. Key
words are Connected, Autonomous, Shared, and Electric (CASE). Automotive industries think
about they should change their business domains from manufacturing to value creation.
However, I believe that “Those who control materials control technology” pointed by Eiji
Kobayashi, Panasonic.
Carbon nanotube (CNT) have great potential in various fields including automotive
applications, such as, heater, electrical wire, electrode of energy storage devices, reinforced
filler, conductive filler, and so on. However it is very difficult to create killer products at thepresent time.
DESNO has been studying nano-carbon materials synthesis included CNT[1-3] and those
applications[4,5] since 1999. In this symposium, I would like to introduce some of ouractivities related CNTs and discuss important points to achieve practical applications.

[1] H. Oshima et al. Jpn. J. Appl. Phys. 47, 1982 (2008).
[2] H. Oshima et al. J. Phys. Chem C 113, 18523(2009)[3] R. Ohta et al. Chem. Com. 47, 3873(2011)[4] T. Iijima et al. Mat. Exp. 2, 357(2012)[5] H. Oshima et al. The 24th Fullerene Nanotubes General Symposium, 72(2003)
Corresponding Author: H. Oshima
Tel: +81-561-75-1827, Fax: +81-561-75-1185,
E-mail: HISAYOSHI_OOSHIMA@denso.co.jp

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2S-5
Field Emission from Carbon Nanotube and Graphene:
Unique Characteristics and Related Phenomena
Yahachi Saito
Department of Applied Physics, Nagoya University, Nagoya 464-8603, Japan
Carbon nanotube (CNT) possesses various benefits as a field electron emitter, e.g., needle
shape with a sharp tip, high chemical stability, mechanical strength and electrical conductivity.
The sharp tip enables not only low voltage operation but also realization of high brightness
and a small virtual source size which are advantageous for forming a finely focused electron
beam with a simple lens system. Chemical inertness and stability of a CNT surface make anelectron emission stable even under moderate ultrahigh vacuum, which alleviates the need fora massive vacuum pumping system. By employing CNT as an electron source, therefore, afield emission scanning electron microscope (FE-SEM) can be miniaturized whilst keeping
high performance. Recently, a CNT-based FE-SEM hosting a projection type X-ray
microscope (XRM) is developed [1].
Carbon forms a variety of allotropes: e.g., diamond, graphite, fullerene, and CNT.
Besides the established allotropes, carbyne, an infinite carbon chain,
has attracted much interest with significant controversy since the late1960’s.
In 2003 and 2016, linear carbon-chains (LCCs)
encapsulated inside CNTs were discovered in multiwall CNTs
produced by arc discharge [2] and in double-wall CNTs (DWCNTs)
annealed at high-temperature [3], respectively. Recently, we foundunexpectedly LCCs inside SWCNTs, as shown in Fig. 1, after anelectric discharge of the SWCNT films which were used as a cathodeFig. 1 LCC insideof field emission [4]. This method of LCC synthesis is a new route
SWCNT
toward a bulk production of LCCs.
Graphene with a finite size has edges by itself, and electronic states at the edges exhibit
peculiar properties, e.g., spin polarization (ferromagnetic order) at zigzag edges (Fig. 2).
Field emission microscopy (FEM) study on electron emission from graphene edges [5] hasrevealed that FEM patterns from an open graphene edge show a symmetry of π orbitals at agraphene edge. In addition to FEM studies, field ion microcopy(FIM) images exhibiting unoccupied π* orbitals at graphene edges areobserved. Recently, spin-polarization of electrons field-emitted fromgraphene edges was measured using an FE appratus with Mott
detectors, showing the magnitude of spin polarization of about 25 % Fig. 2 Spin polarization at zigzag edges[6].
[1] M. Irita, S. Yamazaki, H. Nakahara, Y. Saito, Presented at ALC’17 (Dec. 3-8, 2017, Kauai, Hawaii).

[2] X. Zhao Y. Ando, Y. Liu, M. Jinno, T. Suzuki, Phys. Rev. Lett. 90 (2003) 187401.
[3] L. Shi et al., Nature Mater. 15 (2016) 634.
[4] S. Toma, K. Asaka, M. Irita Y. Saito, Presented at ALC’17 (Dec. 3-8, 2017, Kauai, Hawaii).
[5] N. Yokoyama, K. Nakakubo, K. Iwata, K. Asaka, H. Nakahara, Y. Saito, Surf. Interface Anal. 48 (2016) 1217.
[6] S. Nagai, H. Ikemizu, K. Kunoh, K. Hata, Y. Watanabe, T. Hoshino, M. Irita, H. Nakahara and Y. Saito, Presented at
ALC’17 (Dec. 3-8, 2017, Kauai, Hawaii).

Tel: +81-52-789-4459, Fax: +81-52-789-3703, E-mail: ysaito@nagoya-u.jp

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2S-6
Quantum transport in van der Waals junctions of 2D materials
Tomoki Machida1,21Institute of Industrial Science, University of Tokyo, Tokyo 153-8505, Japan
2
CREST, Japan Science and Technology Agency, Japan

Recent advances in transfer techniques of atomic layers have enabled one to fabricate vander Waals junctions of various two-dimensional (2D) materials, which include graphene,
hexagonal boron nitride (h-BN), transition-metal dichalcogenides (TMDs), layered
ferromagnetic metal, and layered superconductors. Unique characteristics of the van der
Waals junctions have been opening up new possibilities in fundamental science and device
applications: the stacking of various atomic layers with different material properties without
their lattice matching at the interface, the controllability of twist angle between atomic layers
to modulate the band structure, and the ideal digital-like interfaces without diffusion andsegregation.
Here, we present development of the fabrication techniques and quantum transport
experiments in van der Waals junctions: (i) Dirac fermion reflector in ballistic graphene/h-BN[1], (ii) mechanical exfoliation of magnetic-atom-intercalated transition metal dichalcogenides,
Cr1/3TaS2 and Fe1/4TaS2, and their van der Waals assembly to exhibit tunnel magnetoresistanceeffect [2], (iii) p-type and n-type carrier injection into WSe2 using NbSe2 and graphite,
respectively [3], (iv) suppression of the exciton-exciton annihilation rate in hBN/WS2/hBN
studied by time-resolved photoluminescence spectroscopy [4], (v) inter-subband Landau level
couplings induced by in-plane magnetic fields in trilayer graphene [5], (vi) cyclotron
resonance absorption in monolayer, bilayer, twisted bilayer, and trilayer graphene, (vii) the
influence of the C-doped domains in h-BN on electrical transport and optical properties of 2D
materials above, and (viii) robotic searching and assembly of van der Waals superlattices.
[1] S. Morikawa, Q. Wilmart S. Masubuchi, K. Watanabe, T. Taniguchi, B. Placais, and T. Machida, Semicond.
Sci. and Technol. 32, 045010 (2017).
[2] Y. Yamasaki, R. Moriya, M. Arai, S. Masubuchi, S. Pyon, T. Tamegai, K. Ueno, and T. Machida, 2DMaterials 4, 041007 (2017).
[3] Y. Sata, R. Moriya, S. Masubuchi, K. Watanabe, T. Taniguchi, and T. Machida, Jpn. J. Appl. Phys. 56,
04CK09 (2017).
[4] Y. Hoshi T. Kuroda, M. Okada, R. Moriya, S. Masubuchi, K. Watanabe, T. Taniguchi, R. Kitaura, and T.
Machida, Phys. Rev. B 95, 241403 (2017).
[5] Y. Asakawa, S. Masubuchi, N. Inoue, S. Morikawa, K. Watanabe, T. Taniguchi, and T. Machida, Phys. Rev.
Lett. 119, 186802 (2017).
[6] Y. Ota, R. Moriya, N. Yabuki, M. Arai, M. Kakuda, S. Iwamoto, T. Machida, and Y. Arakawa, Appl. Phys.
Lett. 110, 223105 (2017).
[7] Y. Sata, R. Moriya, N. Yabuki, S. Masubuchi, and T. Machida (submitted).
[8] S. Masubuchi, M. Morimoto, M. Onodera, S. Morikawa, K. Watanabe, T. Taniguchi, and T. Machida(submitted).
Corresponding Author: T. Machida
Tel: +81-3-5452-6742, Fax: +81-3-5452-6743
E-mail: tmachida@iis.u-tokyo.ac.jp

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3S-7
Exploring Molecular Nanocarbon Science
Kenichiro Itami 1,2,3
1

Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa,
Nagoya 464-8602, Japan2
Department of Chemistry, Nagoya University, Chikusa, Nagoya 464-8602, Japan
3
JST-ERATO, Itami Molecular Nanocarbon Project, Chikusa, Nagoya 464-8602, Japan
Toward addressing the grand challenge in nanocarbon science, we are trying to synthesize
structurally uniform nanocarbons and a new form of carbons.[1] To achieve this goal, thedevelopment of new reactions and catalysts has been the key. For example, our powerful
palladium catalyst can promote the regioselective aromatic π-extension (APEX)[2] ofpolycyclic aromatic hydrocarbons (PAHs). This C-H activation methodology can be applied
to various planar and geodesic PAHs to generate graphene nanoribbons[3-5] andthree-dimensional warped nanographenes.[6] In addition to the above-mentioned chemistry ofnanoribbons and saddles, our synthetic campaign toward carbon nanotubes[7] and carbon
nanobelts[8] will also be described.

[1] Y. Segawa et al. Nature Rev. Mater. 1, 15002 (2016).
[2] H. Ito et al. Angew. Chem. Int. Ed. 56, 11144 (2017).
[3] K. Ozaki et al. Nature Commun. 6, 6251 (2015).
[4] Y. Yano et al. In preparation.
[5] Y. Koga et al. Science, in press (2018).
[6] K. Kawasumi et al. Nature Chem. 5, 739 (2013).
[7] H. Omachi et al. Nature Chem. 5, 572 (2013).
[8] G. Povie et al. Science 356, 172 (2017).
Corresponding Author: K. Itami
Tel: +81-52-788-6098, Fax: +81-52-788-6098, E-mail: itami@chem.nagoya-u.ac.jp

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3S-8
Phonon engineering of graphene for thermal management○Takayuki Arie
Department of Physics and Electronics, Osaka Prefecture University, Osaka 599-8531, Japan
Graphene is expected as a candidate fornext-generation electronic devices due to its
extremely high carrier mobility, flexibility, andthermal conductivity. Since the main heat carrier ingraphene is phonon, the structural modification alters
the thermal transport properties in graphene. For
example, isotopically modified graphene shows 50%
reduction in thermal conductivity by introducing
50% 13C into carbon networks [1]. Further reduction
is possible by creating isotopic heterojunctions, bywhich the thermal conductance of graphene isreduced by approximately 90% without changing its
electrical properties [2,3]. These techniques toreduce the thermal conductivity can be applied forenhancing the thermoelectric device performance.
In this talk, the thermal conductivity reduction ofgraphene by another structural modification, defects,
is mainly introduced. The graphene used in this study
was synthesized by chemical vapor deposition with
Cu foils as a catalyst. After transferred onto thesubstrates, controlled amount of defects wasintroduced by O2 plasma. As the defect density
increases, the defect stage changes from sp3-type tovacancy-type, which was identified by Raman
spectroscopy and X-ray photoelectron spectroscopy. Fig.1 (a) Raman spectra and (b) thermal
Consequently, the electrical and thermoelectric conductivity of graphene with various
properties of graphene decrease with the defect defect densities.
development. The thermal conductivity of graphenewith defects, on the other hand, shows tremendous
reduction, one order of magnitude lower than that of pristine graphene. At the vacancy-type
defect stage, the thermoelectric performance of graphene predominantly relies on its thermal
conductivity, resulting in threefold increase in thermoelectric figure of merit of graphenedevices [4].
[1] S. Chen et al., Nat. Mater. 11, 203 (2012).
[2] Y. Anno, K. Takei, S. Akita, and T. Arie, Phys. Status Solidi RRL 8, 692 (2014).
[3] Y. Anno, K. Takei, S. Akita, and T. Arie, Adv. Electron. Mater. 1, 1500175 (2015).
[4] Y. Anno, Y. Imakita, K. Takei, S. Akita, and T. Arie, 2D Mater. 4, 025019 (2017).
Corresponding Author: T. Arie
Tel/Fax: +81-72-254-9265
E-mail: arie@pe.osakafu-u.ac.jp

-8-

3S-9
Thermoelectric Properties of Fermi Level Tuned and Aligned
Single Wall Carbon Nanotube Thin Films
Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Single wall carbon nanotubes (SWCNTs) are one-dimensional materials with sharp van Hove singularities.
Preparation of SWCNTs with a selected electronic structure, fabrication of their aligned thin films,1 andtuning of their Fermi level allow us to reveal unique phenomena, which cannot be observed or correctly
understood in conventional SWCNT random networks. For example, we observed anomalously large opticalabsorption for perpendicular polarization to the tube axis in highly doped aligned SWCNTs, which is related
to intersubband transition plasmon phenomena in SWCNTs.2 This topic may be discussed by Prof. Kono inthis symposium, thus here I discuss thermoelectric properties of Fermi level tuned and aligned SWCNT thinfilms.
In our society, a large amount of heat at relatively low temperature, which is emitted from factories, houses,
human bodies, and so on, is left unused. Development of high-performance flexible thermoelectric devices
is crucial to efficiently convert such unused waste heat into electric
power. Understanding of relationships between electrical conductivity
, Seebeck coefficient S, and thermal conductivity  in thin films offlexible materials and tuning of these parameters is of great importanceto improve the performance. SWCNTs are a model of low dimensional
flexible materials, and will play important roles for realization of highperformance flexible thermoelectric devices. Since the seminal study byHicks and Dresselhaus,3 the thermoelectric properties of low
dimensional materials have been intensively studied, but it still has beenof great importance to experimentally clarify how the low
dimensionality of a material influences and enhances its thermoelectric
properties. For flexible thermoelectric applications, we must evaluate
the thermoelectric properties in a thin film situation of the materials.
Although the thermoelectric properties in a single rope situation of thematerials are well understood, thermoelectric properties in the form ofthin films are still under discussion. For example, in conventional solid
metallic materials, there is a trade off between S and , such as increaseof S leads to decrease of , however, in the case of SWCNTs sometimes
we can observe the breaking of the trade-off (Fig. 1).4 There is auniversal trend in S versus , S∝ -1/4, but we do not have a goodtheoretical model to explain the trend. 5 Moreover, it is not clear whether
the Wiedemann-Franz law is applicable in thin films. Femi level tuned
and aligned SWCNTs allow us to investigate the details of the
background because we can systematically change the electronic
Fig. 1 (a) Relationships between
structure, location of Fermi level, and conditions of contacts between
S, , and  at flexible interfaces as
the tubes. In this talk, I will present recent our results abouta function of carrier density arethermoelectric properties of Fermi-level tuned and aligned SWCNTs
not well understood. For example,
and discuss how electronic structure, location of Fermi level, current,
and thermal flow directions with respect to the tube axis influence on(b) the trade off between S and 
isbroken in metallic SWCNTs
the S,  and  of SWCNT thin films.
References: [1] He et al., Nat. Nanotechnol. 11, 1 (2016), [2] Yanagi, Kono et al., submitted., [3] Hicks &Dresselhaus, PRB 47, 16631 (1993) [4] Yanagi et al., Nano Lett. 14, 6437 (2014) [5] Kang & Snyder, Nature Mater.
16, 252 (2017). Corresponding Author: K. Yanagi, Tel: +81-42-677-2493, E-mail: yanagi-kazuhiro@tmu.ac.jp

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招待講演
Invited Lecture

1I–1
2I–2

1I-1
Advanced Carbon Based Energy Materials for Lithium-Sulfur Batteries
Qiang Zhang 1
1

Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Among various promising candidates with high energy densities, lithium-sulfur (Li-S)
batteries with a high theoretical capacity and energy density are highly attractive;1-2 while thecommercial application of Li-S batteries still faces some persistent obstacles, such as the low
electrical conductivity of sulfur and lithium sulfide and the dissolution of polysulfides. The
introduction of nanocarbon into the field of Li-S batteries sheds a light on the efficientutilization of sulfur by improving the conductivity of the composites and restraining the
shuttle of polysulfides. In this presentation, the concept for the rational design of nanocarbon
for energy storage is explained. The advances in the use of advanced energy materials in thecathode, separator, and anode is explained.3-14 New insights on the relationship between thenanostructure and the electrochemical performance are presented.
References
1)

Peng HJ, Cheng XB, Huang JQ, Zhang Q. Adv Energy Mater 2017, 7, 1700260.

2)

Cheng XB, Zhang R, Zhao CZ, Zhang Q. Chem Rev 2017, 117, 10403

3)

Zhao MQ, Zhang Q, et al. Nature Commun 2014, 5, 3410.

4)

Tang C, Zhang Q, et al. Adv Mater 2014. 26, 6100.

5)Peng HJ, Zhang Q. Angew Chem Int Ed 2015, 54, 11018.

6)

Peng HJ, Zhang G, Chen X, Zhang ZW, Xu WT, Huang JQ, Zhang Q. Angew Chem Int Ed 2016, 55, 12990

7)

Peng HJ, Zhang ZW, Huang JQ, Zhang G, Xie J, Xu WT, Shi JL, Chen X, Cheng XB, Zhang Q. Adv. Mater.
2016, 28, 9551

8)

Cheng XB, Yan C, Chen X, Guan C, Huang JQ, Peng HJ, Zhang R, Yang ST, Zhang Q. Chem 2017, 2, 258.

9)

Zhang XQ, Cheng XB, Chen X, Yan C, Zhang Q. Adv Funct Mater 2017, 27, 1605989.

10) Peng HJ, Huang JQ, Liu XY, Cheng XB, Xu WT, Zhao CZ, Wei F, Zhang Q. J Am Chem Soc 2017, 139,
8458.
11) Hou TZ, Xu WT, Chen X, Peng HJ , Huang JQ, Zhang Q. Angew Chem Int Ed 2017, 56, 8178
12) Zhang R, Chen XR, Chen X, Cheng XB, Zhang XQ, Yan C, Zhang Q. Angew Chem Int Ed 2017, 56, 7764.
13) Zhang XQ, Xu R, Chen X, Cheng XB, Zhang R, Chen XR, Zhang Q. Angew Chem Int Ed 2017, 56, 14207.
14) Sun YZ, Huang JQ, Zhao CZ, Zhang Q. Sci China Chem 2017, 60, 1508.
….
Corresponding Author: T. Tokyo
Tel: +86-10-6278-9041, Fax: +86-10-6277-2051.
E-mail: zhang-qiang@mails.tsinghua.edu.cn- 11 -

2I-2
Photoexcited states in transition metal dichalcogenide heterostructures
Fei Lu1 and ○Erik Einarsson1,2
Department of Electrical Engineering, University at Buffalo, Buffalo, NY USA
Department of Materials Design and Innovation, University at Buffalo, Buffalo, NY USA
1

2

Two-dimensionaltransition
metal
dichalcogenides (TMDCs), such as MoS2 andWS2, have been researched extensively for
their unique electrical and optical properties.
TMDCs are also excellent material systems
for studying the underlying physics ofphotoexcited states, namely excitons andtrions. It is known that the photoluminescence(PL) intensity I and the excitation laser power
L are related by the power law I = Lk.[1] The
value of the exponent k depends on the typeof excited state, with k = 1 for excitons and k= 3/2 for trions.[2] Based on this relation,
many researchers have studied various
exciton states in monolayer (1L) MoS2 and 1L
WS2. Values of k ranging from approximately
0.9 to 1.3 have been reported, and were
attributed to bound excitons, [2–5] but there
are no reports to date of free trions in TMDCs
indicated by k = 1.5.
Here we report power-dependent PL
measurements of CVD-grown TMDC
heterostructures consisting of 1L WS2 atop 1L
MoS2. Our data show power law relations
with k = 1.43 in the WS2 layer and k = 1.51 in
the MoS2 layer, providing the first evidence of
free trions in TMDC heterostructures.

Fig. 1 (Top) Decomposed PL spectrum from
WS2/MoS2 heterostructure and (bottom) MoS2 PL
peak intensity vs. excitation laser power.

[1] T. Schmidt, K. Lischka, W. Zulehner. Phys Rev B 45 (1992) 8989.
[2] D. Kaplan, Y. Gong, K. Mills, V. Swaminathan, P. M. Ajayan, S. Shirodkar, E. Kaxiras. 2D Mater 3 (2016)
015005.
[3] Z. He, W. Xu, Y. Zhou, X. Wang, Y. Sheng, Y. Rong, S. Guo, J. Zhang, J. M. Smith, J. H. Warner. ACS
Nano 10 (2016) 2176.
[4] V. Carozo, Y. Wang, K. Fujisawa, B. R. Carvalho, A. McCreary, S. Feng, Z. Lin, C. Zhou, N. Perea-López,A. L. Elías, B. Kabius, V. H. Crespi, M. Terrones. Sci Adv 3 (2017) e1602813.
[5] J. Shang, X. Shen, C. Cong, N. Peimyoo, B. Cao, M. Eginligil, T. Yu. ACS Nano 9 (2015) 647.
Corresponding Author: E. Einarsson
Tel: +1-716-645-5089,
E-mail: erikeina@buffalo.edu- 12 -

一般講演
General Lecture

1–1 ～ 1–8
2 – 1 ～ 2 – 13
3 – 1 ～ 3 – 11

1-1
Tracing growth processes of individual single-walled carbon nanotubes
by digital isotope coding○Keigo Otsuka1, Shun Yamamoto1, Taiki Inoue1, Rong Xiang1, Shohei Chiashi1,
Shigeo Maruyama1,2
12

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8564, Japan−1

13

SWNT length (µm)

exIntensity (×100 counts/s)

Raman shift (cm )Flow rate(sccm)

Single-walled carbon nanotubes (SWNTs) attract attentions as a perfect alternative ofsilicon for high-performance electronics if those exclusively with semiconducting properties
are prepared in a dense array structure. Despite significant progresses in controlled synthesisof SWNTs [1], the growth process remains a mystery due to their size, variety and systemcomplexity. Although thermodynamic and kinetic control is important for the chirality
controlled-synthesis, it is controversial, for example, whether the growth rate of SWNTs
depends on their chirality [2-4]. Previous in situ and ex situ measurements often missed avariation of SWNTs and the presence of incubation/lifetime of the growth, respectively. Here
we present a method to analyze the growth behavior, e.g. growth rate, incubation and lifetime,of individual SWNTs with length of 10–250 μm by embedding digital isotope labels.
SWNTs were grown from iron nanoparticles
a # 0 0 # 0 1 # 1 0 # 1 1 12C EtOH
patterned in stripes on r-cut quartz substrates [4].
4Binary-like codes were incorporated in SWNTs by
C EtOH2
periodically introducing the pulse of 13C ethanol
00510with three different ratios (Figure 1a), and thenTime (min)b0detected by ex situ Raman mapping. A Raman#
1
11600 110intensity map along an SWNT (Figure 1b) clearlyshows G-band downshifts in three different levels.
1550
5
We found that after various lengths of incubation,
λ = 532 nm
0
SWNTs elongated at constant rates until abrupt
040
80
Position (µm)
ctermination (Figure 1c). This indicates the catalytic
growth termination
150
activity of nanoparticles does not change with time.
In a rare event, the chirality changed along SWNTs,
100
resulting in sudden modulation of the growth rate
50
(Figure 1d). Such junctions could provide unique0
insights on intrinsic chirality-dependences. Similar
0
5
10
CVD time (min)analyses for the growth with a variety of catalystsd8.1 μm/min
10.2 μm/min
and conditions, in combination with other characterization methods, would lead to a quantum leap in thecontrol of chirality, length and density.
[1] S. Zhang et al., Nature 543, 234 (2017).
[2] R. Rao et al., Nat. Mater. 11, 213 (2012).
[3] M. He et al., Carbon 113, 231 (2017).
[4] T. Inoue et al., J. Mater. Chem. A 3, 15119 (2015).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 13 -

λex = 532 nm

Fig.1 (a) Flow rate of 13C (bars) and 12C(shaded) ethanol for 2-bit isotope coding.
(b) G-band spectra along an SWNT. (c)Typical time evolution of SWNT lengths.
(d) Transition of RBM frequency along the
SWNT with an intramolecular junction.

1-2
Effects of Pre-forming the different density layers on ELF method for the
separation of metallic and semiconducting SWCNTs○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, Japan
Single wall carbon nanotubes (SWCNTs) have received much attention as ink materials
having both excellent electronic properties and chemical stability, especially in printed
electronics. In particular, the separation of metallic/semiconducting SWCNTs is very
important for the use of semiconducting properties. Among various separation methods, wehave investigated the electric-field-induced layer formation (ELF) method.1) By applying anelectric field in the longitudinal direction to SWCNT dispersion, separating metallic andsemiconducting SWCNTs into upper and lower layer, respectively. Though the separation
mechanism was unclarified, the difference in specific weight of the solution in the separation
cell has been confirmed in previous work. In this study, we have focused on the density
gradient in the separation cells on the separation of SWCNTs by ELF method and investigatedthe effect of introducing layers with different densities pre-formed in advance on separating
SWCNTs. The analysis showed that the highly pure and concentrated layers of metallic andsemiconducting SWCNT dispersion were formed by the ELF method with pre-formed layers.
It is considered that pre-formed layers play an important role in producing effective density
gradient for the separation of metallic and semiconducting SWCNTs. In this presentation, we
will show the detailed results including the separation behavior of SWCNTs performed undervarious separation conditions.
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: T. Saito,
Tel: +81-29-861-4863, Fax: +81-29-861-4413,
E-mail: takeshi-saito@aist.go.jp- 14 -

1-3
Influence of Dissolved Oxygen on Introduction of Defects into SWCNTs
during Ultrasonic Dispersion Process○Hiromichi Kataura, Tomoko Sugita, Mariko Kubota, Takeshi Tanaka
Nanomaterials Research Institute, AIST, Tsukuba, Ibaraki, 305-8565, Japan
Ultrasonic dispersion is very important process to get individually dispersed single-wallcarbon nanotubes (SWCNTs), which is especially crucial for the metal/semiconductor
separation and electronic device applications. However, it is well known that the ultrasonicdispersion process inevitably induces defects in SWCNT walls. It was suggested that in thedispersion process, dissolved oxygen gives influence to the defects introduction. Since there
have been no systematic research on the effect of dissolved oxygen on the defects
introduction on the SWCNTs, we tried to clarify it in this work.
For the assessment of defect introduction, we used a G/D intensity ratio of Raman
spectrum. SWCNTs produced by electric arc discharge (AP grade, Carbon solutions INC,
USA) was used as starting material. Sodium cholate 0.5 wt% aqueous solution was used assolvent. To avoid the effect of dissolved oxygen, all equipment was installed in a grove box
filled with highly purified N2 gas. As a control, the same experiments were done in air. Afterthe dispersion process, samples were ultracentrifuged for 30 min and upper 80% supernatant
was collected. Then we measured Raman spectra of all samples using 488, 532, 633, and 785
nm lasers. Since mean diameter of AP SWCNT is around 1.4 nm, resonance ofsemiconducting SWCNTs were observed for 488 and 532 excitations. We have analyzed G/Dratios for them. Interestingly, G/D ratio of SWCNTs dispersed in pure N2 was lower than thatin air. Because saturated N2 concentration inwater is smaller than that of air (N2+O2), a
cavitation effect was lower in pure N2 condition.
Therefore, ultrasonic power was applied to
SWCNT more effectively in pure N2 condition,
which causes quicker dispersion but more defects.
To see the true effect of dissolved oxygen,therefore, we have to analyze a relationshipbetween the dispersion efficiency and defectintroduction. Figure 1 shows a relation between
G/D ratio and the dispersion efficiency. In pureN2 condition, G/D ratio was higher for the samedispersion efficiency. This result suggests that theultrasonic dispersion process in pure N2 iseffective to get lower defective SWCNT
dispersion.
This work was supported by JST CREST Figure 1. G/D ratio and dispersion yield
Grant Number JPMJCR16Q2, Japan.
Corresponding Author: H. Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786,
E-mail: h-kataura@aist.go.jp- 15 -

1-4
Determination of association constants in complexation of
nanotweezers and nanocalipers with SWNTs○ Alejandro López-Moreno, Naoki Komatsu
Graduate School of Human and Environmental Studies, Kyoto University, 606-8501 Kyoto
In contrast to soluble host–guest system, the insolubility of SWNTs makes impossible thedetermination of the molar concentration of SWNTs in solution, which limits understanding of
the supramolecular association of SWNTs. However, a new and simple procedure for thequantitative determination of association constants between soluble molecules and insoluble
CNT samples has recently been reported [1]. In this paper, we applied this method to determine
the association constants of pyrene 1, pyrene-based nanotweezers 2, and pyrene-nanocalipers 3
with SWNTs. The structures of the host moelcules 1 - 3 are shown in Figure 1 [2].
The procedure is asfollows: SWNTs (65CoMoCAT)
weresuspended in a solution of
known concentration of
the host, stirred for twohours and filtered. After
thermogravimetricanalysis of the solid, theassociation constant wascalculated by plotting the
Figure 1 Structures of pyrene 1, pyrene-based nanotweezers 2, and pyrenedegree of functionalization
against the concentration based nanocalipers 3.
of the free host. The
association constants (Ka) determined in DMF are shown in Table 1. The nanotweezers 2 andnanocalipers 3 exhibit higher association constants than pyrene 1 by two and three orders ofmagnitude, respectively. This trend is proportional qualitatively to the number of interactions
between the host molecules with SWNT surface to stabilize the complexes. We will also
determine the association constants of porphyrin and porphyrin-based nanotweezers andnanocalipers, and will compare with those of the pyrene analogues.
Table 1 Association constants of 1 – 3 with SWNTs in DMF
Pyrene 1
Nanotweezers 2-1
Association constant Ka (M )12.6 ± 0.6(4 ± 2) x 103

Nanocalipers 3(5 ± 2) x 104[1] A. de Juan, A. López-Moreno, J. Calbo, E. Ortí, E. M. Pérez, Chem. Sci. 6, 7008 (2015); J. Calbo, A.
López-Moreno, A. de Juan, J. Comer, E. Ortí, E. M. Pérez, Chem. Eur. J. 23, 12909 (2017)[2] G. Liu, A. F. M. M. Rahman, S. Chaunchaiyakul, T. Kimura, Y. Kuwahara, N. Komatsu, Chem. Eur.
J. 19, 16221 (2013); G. Liu, F. Wang, S. Chaunchaiyakul, Y. Saito, A. K. Bauri, T. Kimura, Y.
Kuwahara, N. Komatsu, J. Am. Chem. Soc. 135, 4805 (2013); F. Wang, K. Matsuda, A. F. M. M.
Rahman, X. Peng, T. Kimura, N. Komatsu, J. Am. Chem. Soc., 132, 10876 (2010); G. Liu, Y. Miyake,
N. Komatsu, Org. Chem. Front. 4, 911 (2017)
Corresponding Author: A. López-Moreno
Tel: +75-753-7871, E-mail: lopez.alejandro.74a@st.kyoto-u.ac.jp- 16 -

1-5
Record-high Efficiency in Carbon Nanotube Electrode-used Perovskite
Solar Cells via employing Formamidinium Lead Iodide (FAPbI3) and
Trifluoromethanesulfonic Acid Vapor Doping○Il Jeon 1, Jin-Wook Lee 2, Anton Anissimov 3,4, Esko. I. Kauppinen 4, Yang Yang 2, Shigeo
Maruyama 1,5, Yutaka Matsuo 1,61

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Department of Materials Science and Engineering and California Nano Systems Institute,
University of California Los Angeles (UCLA), Los Angeles, CA 90095, USA
3
Canatu Ltd., FI-00390 Helsinki, Finland4
Department of Applied Physics, Aalto University School of Science, Aalto FI-00076, Finland5
Research Institute for Energy Conservation, National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba 305-8565, Japan
6
Hefei National Laboratory for Physical Sciences at Microscale, University of Science andTechnology of China (USTC), Hefei, Anhui 230026, China
2

Perovskite solar cells (PSCs) with their reported power conversion efficiencies (PCEs)
over 20% have emerged as next-generation solar cells. However, stability and high fabrication
cost are limitations to further advancement. Since the first application by Li et al.,[1]researchers around the world have started to incorporate single-walled carbon nanotubes(SWNTs) in PSCs to increase the stability and to bring down the fabrication cost. Snaith andhis colleagues have reported significant improvement in stability by inserting SWNTs undermetal electrode.[2] Aitola et al. reported high thermal and air stability by replacing expensive
metal electrode with SWNTs.[3] In addition, we employed fullerenes and polymer-wrapped
SWNTs at the same time to achieve hysteresis-free and 1000 hour-long stable PSCs.[4]However, the reported top SWNT electrode-based PSCs have exhibited lower PCEs than themetal electrode-based PSCs, due mainly to 1) SWNT-based PSCs not being able to exploit
reflection of sunlight unlike metals and 2) SWNTs possessing lower conductivity than metals.
In metal-electrode PSCs, the long-wavelengths of sunlight, which do not get fully absorbedby the perovskite layer, are reflected by the metal electrode for further absorption. As SWNT
electrode are not reflective, the long-wavelengths of incoming sunlight are wasted in SWNT
top electrode-based PSCs. Therefore, maximising the light absorption by using low-band gap
perovskites, such as FAPbI3, is crucial for the SWNT-used PSCs. Recently, Prof. Yang Yang
of UCLA achieved stable fully FAPbI3 PSCs (submitted). Applying this technology, weachieved a high short-circuit current density (JSC) of 24.2 mA cm-2. To enhance the device
performance even further, we doped the SWNTs with trifluoromethanesulfonic acid (TFMS),
which is extremely effective and durable. We used vapour doping on SWNTs before thelamination, because applying dopant directly onto SWNTs damages underneath layers andthis is why doped SWNT top electrode has not been reported in PSCs, thus far. TFMS
vapour-doped SWNT PSCs resulted in an increased fill factor (FF), producing a record-high
PCE of 17.6% among the reported SWNT PSCs.
[1] Li et al. ACS Nano 8, 6797 (2014). [2] Habisreutinger et al. Nano Lett. 14, 5561 (2014)., Habisreutinger et al.
ACS Energy Lett. 2, 622 (2017). [3] Aitola et al. Energy Environ. Sci. 7, 3690 (2014)., Aitola et al. Adv. Mater.
29, 1606398 (2017). [4] Ahn et al. J. Mater. Chem. A in print.
Corresponding Author: Y. Matsuo
Tel: +81-3-5814-0978
E-mail: matsuo@photon.t.u-tokyo.ac.jp- 17 -

1-6
Carbon-nanotube differential amplifier on flexible substrate
Tomoki Matsuura1, Taiga Kashima1, Jun Hirotani1, Shigeru Kishimoto1, and ○Yutaka Ohno1,2
1

Department of Electronics, Nagoya University, Nagoya 464-8603, Japan
Institute of Material and Systems for Sustainability, Nagoya University, Nagoya 464-8603, Japan2

A differential amplifier is a fundamental analog amplification circuit used for various
sensor devices. For wearable sensors, mechanically-flexible amplifiers are desirable. Carbon
nanotube thin-film transistors (CNT TFTs) are considered as a possible active component offlexible devices because of their high mobility [1] and flexibility. In recent years, high-yieldand reproducible fabrication of CNT TFTs became possible by using purified semiconducting
CNTs, leading extensive study on circuit applications. In this work, we are focusing on theanalog circuit application of CNT TFTs. To design CNT-based analog circuits, circuit
simulations have been performed by using a precise device model which has been built on thebasis of electrical characterizations of CNT TFTs. We have realized differential amplifiers ona flexible and transparent plastic film. CNT-based differential amplifiers were fabricated on apolyethylene naphthalate film as shown in Fig. 1. Bottom-gate CNT TFTs with purified
semiconducting CNTs were used as the active device. A differential output was obtained withrespect to a differential input. Maximum voltage gain of 16.3 (24.3 dB) was achieved for asinusoidal wave input of 100 mVpp at 100 Hz with a power source of -12 V. Figure 2 shows
the gain as a function of frequency, exhibiting -20 dB/ decay. The unity gain frequency was
2.1 kHz.
Acknowledgments: The semiconducting CNTs were provided by TASC. This work waspartially supported by JST/CREST.
[1] D.-M. Sun, et al., Nature Nanotechnol. 6, 156 (2011).
30

measured-20 dB/dec.

25

Gain (dB)

20
15
10
5
0
-5
-10
-15

102

103

104

105

Frequency (Hz)Fig. 1 CNT differential amplifier on plastic Fig. 2 Frequency dependence of voltage gain.
film. (a) Photograph of chip, (b) photographof circuit, (c) SEM image of CNT thin film.
Corresponding Author: Yutaka Ohno, Phone & Fax: +81-52-789-5387, E-mail: yohno@nagoya-u.jp- 18 -

1-7
Carbon Nanotubes versus Graphene as Flexible Transparent Electrodes inInverted Perovskite Solar Cells
Jungjin Yoon 1, Il Jeon 2, Namyoung Ahn 1, Mohamed Atwa 2, Clement Delacou 2, Anton
Anisimov 3, Esko I. Kauppinen 4, Shigeo Maruyama 2, and Yutaka Matsuo 2, and Mansoo
Choi 1
1

Global Frontier Center for Multiscale Energy Systems, Seoul National University, Seoul
08826, South Korea
2
Department of Mechanical Engineering, School of Engineering, The University of Tokyo,
Tokyo 113-8656, Japan
3
Canatu Ltd. Konalankuja 5, FI-00390 Helsinki, Finland4
Department of Applied Physics, Aalto University School of Science, FI-00076 Aalto, Finland
Due to the compatibility of fabrication at low temperature, perovskite solar cells (PSCs)
have attracted much anticipation from scientists and engineers with flexible applications aswell as their high power conversion efficiency (PCE) over 20%. However, thecommonly-used transparent electrode material in flexible solar cells, indium tin oxide (ITO)
hinders a realization of cheap, flexible and highly efficient portable energy devices because of
its cost-issue by limited reserves in nature and inflexibility by its brittleness [1]. This being so,
a cost-effective transparent electrode with high flexibility is needed to realize the flexible
PSCs. Among various candidates as the alternative, carbon-based nanomaterials such asgraphene and carbon nanotubes (CNTs) satisfy both aspect of cost and flexibility and each ofthem was utilized as a transparent electrode of solar cells in previous reports. Still, there has
not been a direct comparison of two carbon-based electrode materials as flexible transparent
electrodes in PSCs.
In this work, we conducted a comparative study of graphene and CNTs as a flexible
transparent electrode in PSCs in terms of reliability and a device performance including PCE
and flexibility [2]. Two commonly used doping method to increase electrical conductance ofthe carbon-based materials were tried and compared. The CNTs- and graphene- based devices
showed PCEs of 12.8% and 14.2%, respectively. The difference of CNTs and graphene in thephotovoltaic performance was due to the difference in surface roughness and opticaltransmittance. Raman spectroscopy and four-probe measurement after stretching samples
showed that graphene is more susceptible to degradation by stretching (bending) than CNTs
due to wrinkles and fissures formed on the graphene during its transfer process. Bending testof the flexible PSCs also showed higher flexural robustness of CNT-based devices comparedwith graphene-based ones, though the difference was marginal. Overall, graphene seems to bea better option than CNTs as flexible transparent electrodes in PSCs because the smootherroughness and transparency, if the transfer process of graphene guarantees the reproducibility
and quality of graphene.
[1] B. J. Kim et al. Energy Environ. Sci., 8, 916 (2015).
[2] I. Jeon et al. J. Phys. Chem. Lett., 8, 21 (2017).
Corresponding Author: Professor Mansoo Choi
Tel: +81-2-887-8626, Fax: +82-2-887-8762,
E-mail: mchoi@snu.ac.kr- 19 -

1-8
Interdigitated electrode with high mass density carbon nanotube forests forelectrochemical biosensors○Hisashi Sugime1, Takuya Ushiyama2, Keita Nishimura2, Yutaka Ohno2, Suguru Noda3
12

Waseda Institute for Advanced Study, Waseda University, Tokyo 169-8050, Japan
Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603,
Japan
3
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan

Electrochemical label-free sensing using redox reactions is one of the powerful andfeasible methods to detect biomolecules with high sensitivity. Among several geometries ofelectrodes, interdigitated electrode (IDE) has an advantage for high sensitivity because thecurrent by redox reactions is amplified by shuttling of analytes if the distance of theelectrodes is smaller than the diffusion length of analytes. As a candidate material for theelectrodes in IDE, carbon materials are widely studied due to their fast electron transfer
kinetics and wide potential windows.1 Among others, carbon nanotubes (CNTs) have several
advantages such as high aspect ratio with large surface area and high electrical conductivity.
Direct growth of CNTs on substrates by chemical vapor deposition is especially a suitable
way to integrate the CNTs into the IDE.
In this report, we applied the dense CNT forests on conductive supports2,3 to the IDE
by combining the UV lithography and the CVD process (Fig. 1a and 1b). By optimizing thegeometry of the electrodes (width and gap) and the morphology of the CNT forests (heightand density), the performance of the IDE was significantly improved. The cyclic voltammetry(CV) measurements of K4[Fe(CN)6] (100 µM) in KCl (100 mM) showed that the redox
current of IDE with CNTs (CNTF-IDE) reachedto the diffusion-limited current much more
rapidly compared to that of conventional
Au-IDE (Fig. 1c and 1d). By the redox cycling,
the redox current was amplified by a factor of~18 with the CNTF-IDE which is ~3 times
higher than that with the Au-IDE. As a modelcase of the biomolecules, dopamine (DA)which is one of the main neurotransmitters wasmeasured under coexistence of L-ascorbic acid(100 µM). The selective detection of DA wasachieved with the linear range of 100 nM – 100µM and the limit of detection (LOD, S/N=3) of~40 nM with the optimized electrode structure.
[1] Niwa et al., Anal. Chem. 66, 285 (1994).

[2] Sugime et al., Appl. Phys. Lett. 103, 073116 (2013).

[3] Sugime et al., ACS Appl. Mater. Interfaces 6, 15440(2014).
Corresponding Author: H. Sugime
Tel: +81-3-5286-2769
E-mail: sugime@aoni.waseda.jp- 20 -

Fig. 1: (a) Oblique-view and (b) side-view SEM
images of the CNT forests on Au electrodes. CV
results of (c) Au-IDE (reference) and (d)CNTF-IDE with the K4[Fe(CN)6] (100 µM) in KCl(100 mM) at the scan rate of 10 mV/s.

2-1
Systematic studies on structures and properties of commercialized CNT
fibers○Takayuki Watanabe1, Satoshi Yamashita2, Takahiro Morimoto1, Kazufumi Kobashi1 andToshiya Okazaki1
1

CNT Application Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, 305-8565, Japan
2
Research Association of High-Throughput Design and Development for Advanced
Functional Materials (ADMAT), Tsukuba, 305-8565, Japan

Fiber structure is one of the commonly used forms when carbon nanotubes (CNTs) areprocessed for application. They have potential abilities as electric wires and high strength
materials because of CNT’s high conductivity and superior mechanical properties. However,in most reports, homemade CNT fibers were used and systematic study of various CNT fibers
have so far been limited. In this presentation, several types of commercially available CNT
fibers are investigated and compared.
Figure 1 shows macro scale structure of CNT fibers studied in this presentation. They are
categorized into 3 types, i.e., A) fiber spun from multi-wall CNT (MWCNT) forest grown by
the CVD method, which is most common type in CNT fiber, B) wet spun fiber and C) others.
Nanocomp Miralon is type C), Meijo eDIPS EC-Y is type B) and other fibers belong to typeA). It is clearly seen that same type CNT fibers show similarities in structural shapes such as
homogeneity and fiber roundness. This result implies that structural quality of A type is highwhile the other types still have room for improvement.
In the presentation, further information of fiber structure (e.g. micro scale structure), basic
property of CNT fiber (conductivity, mechanical strength and so on) and the relationshipbetween them will be reported.
This presentation is based on results obtained from a project (P16010) commissioned by
the New Energy and Industrial Technology Development Organization (NEDO).
Corresponding Author: T. Okazaki
E-mail: toshi.okazaki@aist.go. jpa)b)Fig.1 SEM images of commercially available CNT fibers. a) cross section, and b) side.

- 21 -

2-2
Biodegradation Rate of Carbon Nanotube Depending on Diameters○M. Zhang1, Y. Deng1, M. Yang1, H. Nakajima1, M. Yudasaka1, 2, S. Iijima2, T. Okazaki11
1

National Institute of Advanced Science and Technology (AIST)
2
Faculty of Science & Technology, Meijo University

The widespread applications of carbon nanotubes (CNTs) raise the possibility to get into
the environment. Although studies have shown that most types of CNTs had low toxicity invitro and in vivo, the inhalation exposure of a few types of CNTs induced malignant
mesothelioma in animal studies, suggesting that CNTs may pose hazards similar to asbestos [1].
In order to protect environment and mitigate health problem caused by CNTs, we need to
fully understand the fate of various types of CNTs after entering environment or human body.
The previous studies have shown that CNTs are possible to be degraded by enzymaticoxidation in neutrophil or macrophages [2-3], however, biodegradation characteristics fordifferent types of CNTs are still not clear. Because the biodegradation mechanism of CNTs
was confirmed to be the oxidation of CNTs with hypochlorous acid, which was generated byenzymatic reaction [4], in this study, we have used sodium hypochlorite directly as oxidant totreat CNTs. Our purpose is to clarify the relationships between the structural characteristics
and the degradation capacity of several types of CNTs.
7-types of CNTs including single- and multi-walled CNTs were dispersed homogenously in
BSA aqueous solution by ultrasonic homogenizer for 5 h. The dispersions of CNTs wereadded into 5% sodium hypochlorite solution and kept at 37oC for 24 h. The quantity-changeof CNTs after treatment with sodium hypochlorite solution for 0-24 h was estimated from theabsorbance at 700 nm. The results showed that the degradation of CNTs by sodium
hypochlorite is greatly dependent on their types and diameters. Single-wall CNTs (SWNTs)
and smaller diameter of multi-wall CNTs (MWNTs) were completely degraded by 24 htreatment, but the decrease of larger diameter MWNTs amount was only ~30%. The
degradation rates of CNTs were SWNTs > MWNTs with small diameter > MWNTs withlarger diameter. In addition, we have found that the graphene oxide was an intermediate
product during the degradation of SWNTs, suggesting that the oxidative degradation of CNTs
might proceed via unzipping process. The results obtained in this study will be significant forclarifying the factors that influence the degradation characteristics of CNTs and, therefore, be
helpful to predict the toxicity of CNTs from their physical and chemical properties.
[1] A. Takagi, et al. J. Toxicol. Sci. 33, 105–116 (2008).
[2] V. E. Kagan et al. Nature Nanotech. 5, 354–359 (2010).
[3] M. Zhang et al. Nanoscale, 7, 2834-2840 (2015).
[4] I. I. Vlasova, et al. Russian Journal of Bioorganic Chemistry, 37, 453–463 (2011).
Corresponding Author: M. Zhang
Tel: +81-29-861-6758
E-mail: m-zhang@aist.go.jp- 22 -

2-3
Growth of Horizontally Aligned Chirality-Specific SWNTs using
Intermetallic W6Co7 Catalysts○ Feng Yang, Yan Li*

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
China
High-performance and integrated circuits essentially require SWNT samples
with well-aligned arrays of pure chirality. We have developed a new family ofcatalysts, tungsten-based intermetallic compounds, which have unique crystal
structure and desired atomic arrangements and therefore can act as the structural
templates for chirality specific growth of SWNTs, relying on the high selectivity ingeometry match between catalysts and SWNTs [1-4]. The characterization of catalyst
structure is very important to reveal the growth mechanism of SWNTs. The W6Co7
catalyst structure during and after the CVD process was clearly revealed by X-ray
absorption spectroscopy (XAS) and transmission electron microscopy (TEM). The
size correlation of SWNTs and catalyst seeds including tangential and perpendicularmodes observed from TEM are compared between solid W6Co7 catalysts andlow-melting point metals (e.g., Co and Cu).
Recently, we have developed an approach for the growth of horizontally aligned
chirality-specific SWNT arrays by using uniform and well-dispersed W6Co7
nanocrystals on the sapphire surface. The chiral structure and chirality abundancewere characterized by the comprehensive methods including Raman, polarized opticalabsorption, scalable Rayleigh imaging as well as electron diffraction.
[1] F. Yang, Y. Li et al. Nature 510, 522 (2014).
[2] F. Yang, Y. Li et al. Acc. Chem. Res. 49, 606 (2016).
[3] F. Yang, Y. Li et al. J. Am. Chem. Soc. 137, 8688 (2015).
[4] F. Yang, Y. Li et al. ACS Nano, 11, 186 (2017).
Corresponding Author: Yan Li
Tel: +86-10-6275-6773
E-mail: yanli@pku.edu.cn- 23 -

2-4
Direct Microscopic Analysis of Individual [60]Fullerene Dimerization
Events: Kinetics and Mechanisms○Koji Harano, Satoshi Okada, Satori Kowashi, Luca Schweighauser, Kaoru Yamanouchi,
Eiichi Nakamura
Department of Chemistry, The University of Tokyo, Tokyo, 113-0033, Japan
Observation of the motions and reactions of molecules, being quantum mechanical entities,
has long been an impossible dream. Through advances in transmission electron microscopy(TEM) and methods to anchor molecules on a carbon nanotube (CNT, Fig. 1a), we canvisually study the structural changes of molecules in situ using single-molecule
atomic-resolution real-time TEM (SMART-TEM) imaging [1]. To go one step further to study
reaction kinetics, we need statistical information over time and temperature—information thatis so far inaccessible by many of the single-molecule analytical methods. Here, along-standing interest in this context is to know if the behavior of individual molecules
conforms to the basic assumption of the quantum mechanical theory that isolated molecules
behave as if all their accessible states were occupied in random order.
To address this question, we chose to study [2 + 2] electrocyclic conversion of a van der
Waals (vdW) complex of C60 1 in a CNT to an adduct 2 (step 1, Fig 1b and c)—a well-known
reaction without mechanistic information [2, 3]. Through counting reaction events one by one,we could identify four concurrent reactions. One observed at 393–493 K (step 1H), where the
CNT maintained its structural integrity, involves a singlet excited state [2 + 2] cycloaddition
reaction with an activation energy of 33.5 ± 6.8 kJ/mol. Here the pristine CNT acts as asensitizer of the cycloaddition. Anotherbcelectron beam
pathway found at 103–203 K (step 1L) to aoccur after CNT was heavily damaged by theelectron beam. This reaction takes place withe-beamcycloaddition(120 kV)1
an activation energy of only 1.9 ± 0.7 kJ/mol.
step 1 : 33.5 kJ/mol
1
retro [2 + 2]
step 1 : 1.9 kJ/mol
Here an ionized form of the damaged CNT isconsidered to act as an oxidant to generate areactive radical cation of C60. The third is the
sample2
fusionstage
step 2further conversion of 2 to a fused dimer 3
2(step 2), and the fourth is a purely thermal
retro [2 + 2] reaction frequently occurring
3
above 493 K. Overall we found that the rate3
profile of the [2 + 2] dimerization of the vdW Fig.1 SMART-TEM imaging of the dimerization ofcomplex 1 under the 1D constraints depends C60@CNT. (a) A schematic illustration of the
on
a
using
C60@CNTs
heavily on the reaction temperature, the experiments
temperature-controlled microgrid. (b) TEM images
quality of the CNT, and the competing of intermediates in a 1.4-nm CNT. The scale bar isthermal cycloreversion reaction.
1 nm. (c) Four types of reactions observed using
TEM

H
L

TEM.
[1] E. Nakamura, Acc. Chem. Res. 50, 1281 (2017).
[2] M. Koshino et al. Nat. Chem. 2, 117 (2010).
[3] S. Okada et al. J. Am. Chem. Soc. 139, 18281 (2017)
Corresponding Authors: K. Harano & E. Nakamura
Tel: +81-3-5841-4369, Fax: +81-3-5841-4369
E-mail: harano@chem.s.u-tokyo.ac.jp, nakamura@chem.s.u-tokyo.ac.jp- 24 -

2-5
Energetics and electronic structure of nitrogen-doped graphene withpyridinic structure○Mina Maruyama, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Graphene with structural imperfections, such as atomic vacancies, topological defects, andsubstitutional dopants, has been attracting much attention in terms of their peculiar electronic
structures which are absent in pristine graphene. Substitutional doping of N atoms in graphenecauses versatile electronic structures in the resultant graphene hybrids, depending on thegeometric structure and mutual arrangement of doped N atoms. The π state of pyridinic
nitrogen (two-fold coordinated N atom in hexagonal network) effectively imitate that of C
atom and can terminates π network of graphene without formation of dangling bond states at
the Fermi level. Therefore, we can design the graphitic π electron network by implanting
pyridinic N atoms. In this work, to explore the energetics and electronic structure of graphenewith monovacancies and three pyridinic N atoms in terms of their mutual arrangement anddensities, based on the density functional theory (Fig. 1).
The formation energy of N-doped graphene with monovacancies and pyridinic N atoms isinversely proportional to the defect spacing (Fig. 2). Furthermore, the formation energy also
depends on the mutual arrangement of defect whether or not the graphitic network possesses
Clar structure (full benzenoid structure) as in the case of B3N3-doped graphene [1]. Electronic
structures also depend on the mutual arrangement of defects whether the graphene network
possess Clar structure or not. Owing to the sublattice imbalance in the network, N-doped
graphene with monovacancy possess less dispersive π state near the Fermi level exhibiting
nonbonding state nature throughout the Brillouin zone. Bandwidth of the non-bonding π statealso depend on the graphene network whether they satisfy Clar structure or not.

Fig.1 Optimized structure of N-doped graphene withmonovacancies and pyridinic N atoms.

Fig.2 Formation energy per atom of N-doped
graphene as a function of the inverse of thelattice parameter.

[1] H. Sawahata et al. ChemPhysChem DOI: 10.1002/cphc.201700972.
Corresponding Author: M. Maruyama
Email: mmaruyama@comas.frsc.tsukuba.ac.jp- 25 -

2-6
Bilayer fullerenes (carbon nano-onions)studied by ion mobility mass spectrometry○Motoyoshi Nakano1,2, Ryoichi Moriyama2, Jenna W. J. Wu2,
Keijiro Ohshimo2, Fuminori Misaizu2,3
1

2Institute for Excellence in Higher Education, Tohoku University, Sendai 980-8576, Japan
Department of Chemistry, Grad. School of Sci., Tohoku University, Sendai, 980-8578, Japan3
New Industry Creation Hatchery Center, Tohoku University, Sendai 980-8579, Japan

Carbon cluster ions, Cn, grow and increase in size (n < 100) from linear to two-dimensional
cyclic, and then to cage-like structures. In contrast, nanometer-scale carbon materials form
various structures. After the discovery of carbon nano-onions [1], they were investigatedintensively by electron microscopy and by theoretical calculations, where information about
separated multi-shell fullerenes was obtained. However, only few bilayer structures werereported among the structures, and the actual numbers of constituent carbon atoms are
uncertain with electron microscopic images. Structural isomers of carbon cluster cations in theintermediate size range (Cnz+, n = 100 – 800) have been investigated in this study by ion
mobility mass spectrometry to discuss the growth process of the carbon clusters.
In the experiments, pulsed carbon cluster ions generated by laser vaporization andsupersonic expansion were injected into an ion-drift cell filled with 2.0-Torr He buffer gas.
The ions reached a constant drift velocity with a balance of acceleration with an applied
electrostatic field and deceleration by collisions with He in the ion-drift cell. Thus, the ionsexited the cell with different “arrival times” depending on their charge and collision crosssection (CCS). Finally, the ions were analyzed by the reflectron type time-of-flight mass
spectrometer.
As a result, bilayer fullerene ion series were observed as continuous distributions for n =260-700. Figure shows the experimental CCSs as a function of the number of carbon atoms, n,in the cluster. Both CCSs of monolayer and bilayer fullerenes increase monotonically,
however, the slope of the bilayer series CCSs was smaller than that of the monolayer series.
This difference in slope indicated that the inner layer fullerene does not maintain specificstructure such as C60, instead, it grows as the outer layer grows. The ratio of the slopes,
bilayer/monolayer = 1.4, suggested that as carbon atoms in the outer layer of bilayer
fullerenes increased by 22, the number of atoms in their inner layer increased by 8. According
to this relationship, the inner and outer fullerene layer structure for n = 260 was [C30@C230]+,300 was [C40@C260]+, 600 was[C120@C480]+, and so on. The smallest
nano-onion size at n ≈ 260 was
reasonable from the fact that the inner
layer of C30 was the smallest fullerene
observed in this study and in a previous
one [2].
[1] S. Iijima, J. Cryst. Growth, 50, 675 (1980).
[2] N. G. Gotts et al. Int. J. Mass Spectrom.
149/150, 217 (1995).
Corresponding Author: F. Misaizu
Tel: +81-22-795-6577, Fax: +81-22-795-6580
E-mail: misaizu@m.tohoku.ac.jp

Figure: Plots of collision cross sections of monolayer andbilayer fullerene ions.

- 26 -

2-7
Development of Ion Trap Ion Mobility Measurement System andObservation of Observation of Nanomaterials○Toshiki Sugai , Yudai Hoshino, Hiroki Morita, Reona Miyamoto, Yuta Hamano,
Kazumasa Somei, and Ryota Jinnouchi
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Ion mobility spectrometry (IMS) has been utilized to reveal novel information on
nano materials[1]. However, no long-term successive measurement has been performed with
IMS usually because of the lack of trap functions, which limits the resolution and the varietiesof information. Recently ion trap ion mobility
system has been developed to enhance the
QP
resolution but the trap time is restricted to lessthan 2 seconds and no other measurement such as
optical spectroscopy is combined[2]. Here we
present long-term successive IMS measurementswith optical measurements on nano materials
such as graphene quantum dots (GQD) and metalclusters as single molecules.
Fig. 1 shows TEM images of GQD withaverage diameter around 20 nm. Fig. 2 shows thelong-term time dependence of the observed
velocities of each GQD molecule with various
charges. Single GQD molecules can be observed
and the structures and charge states are conserved
for up to 7 hours. The diameter evaluated to be 20
nm from the velocity and the estimated charge
state, which is in good agreement with that fromthe TEM observation. We have also succeeded toobservenoble
metal
clusters.
Opticalspectroscopy on each molecule are also inprogress by utilizing thus realized long-term trap
functions.

Fig. 1 TEM images of GQD

Fig. 2 Observed velocity of GQD
with various charges[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
[2] F. Fernandez-Lima et al., J. Ion Mobil. Spec. 14, 93 (2011)

TEL: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 27 -

2-8
Self-Assembly of Detonation Nanodiamonds from their Colloidal Solutions○Toshihiko Tanaka1,3, Yasuhiro F. Miura2, Tetsuya Aoyama3, Makoto Takahashi4,
Takumi Sato1, Eiji Osawa4
1

Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, 30 Aza-nagao, Tairakamiarakawa, Iwaki, Fukushima, 970-8034, Japan
2
Hamamatsu University School of Medicine, 1-20-1 Handayama,
Higashi-ku, Hamamatsu city, Shizuoka, 431-3192, Japan
3
Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan
4
Nano Carbon Research Institute Ltd., Asama Research Extension Center,
Shinshu University, 3-15-1 Tokida, Ueda, Nagano, 386-8567 JapanWe demonstrate herein the recent results on the self-assembly of detonation nanodiamonds(DND) from their aqueous colloidal solutions. The self-assembly is significant with respect totheir research and applications because it has suggested the existence of elementary particles
of detonation nanodiamonds (EPDND), which might be the first novel nanocarbon species
containing sp3 carbons. Furthermore, its early stage probably includes a part of the process
where a successful drug delivery1 takes place. Their whiskers were first reported through slow
drying from the solutions by the last author in 20072 and similar ones3 or microsheets4 werealso assembled from acid treated DND solutions. A Langmuir monolayer from arachidic acidalso induced precipitates of ultrathin rectangular nanosheets on the water surface.5
Recent careful observations have revealed that the whiskers has the fine geometry ofrectangular shapes (18×106×＞300 :μm) as well as uniaxial uniform optical anisotropy,
thus showing that they are kinds of colloidal crystals. A laser microscopy image exhibits the
surprisingly fine shape and crossed nicol polarized images demonstrate the uniaxial
birefringence of Δn=0.0013~0.0027[Fig.1a]. A substantial part of the DND must be similarboth in size and shape and otherwise the shape with the optical anisotropy cannot be
explained well. Perhaps such similar species are EPDND or their dimers. The nanosheets[Fig.1b] also have the fine uniformity in thickness of 26 nm shown by AFM. We will discuss
the significance of the self-assembly with respect to the purity of the whiskers or nanosheets.

Fig.1 Microscopic images: a) a
rectangular DND whisker by acrossed nicol polarization withvarious in-plane angular positions;b) a rectangular ultrathin nanosheet(~26 nm thick) precipitated on thewater surface with a Langmuirmonolayer of arachidic acid.

[1] E. K. Chow,X-Q. Zhang, M. Chen, R. Lam, E. Robinson, H. Huang, D. Schaffer, E. Osawa, A. Goga, D. Ho;
Sci. Trans. Med. 3(73ra21), 1-11(2011).
[2] E. Osawa; Diamond & Related Materials. 16, 2018–2022(2007).
[3] H. Huang, L. Dai, D. H. Wang, L-S. Tanc, E. Osawa; J. Mater. Chem., 18, 1347–1352 (2008,).
[4] T. Petit, H. A. Girard, A. Trouve ́, I. Batonneau-Gener, P. Bergonzoa, J.-C. Arnault; Nanoscale, 5(19),8958-62 (2013). [5] T.Tanaka, Y.F. Miura, T. Sato, E. Osawa; Abstract of the 53th FNTG Symposium, 66(2017).
Corresponding Author: Eiji Osawa / Tel: +81--268-75-8381 / E-mail: osawa@nano-carbon.jp- 28 -

2-9Graphene-Silicon Schottky Junction for Optoelectronic Devices○Xinming Li 1,2, Hongwei Zhu 2, Renzhi Ma 1, Takayoshi Sasaki 1
1

International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute forMaterials Science（NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
2
School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

In the last few decades, the advances and breakthroughs in carbon materials andtwo-dimensional (2D) materials have been witnessed both scientific fundamentals andpotential applications.[1] Graphene’s unique electronic and optical properties have made it an
attractive material for developing optoelectronic devices.[1-2]The graphene-silicon Schottky junction solar cell was firstly reported in 2010 by theco-author of the present work (Fig.1(a)).[3-4] This solar cell is considered to be a promisingdemonstration and the power conversion efficiency is raised to 15.6% with electrical andoptical improvement, such as chemical doping, interface engineering, and opticalanti-reflection.[4-8] Furthermore, this graphene-silicon Schottky junction can be utilized forthe development of high-performance photodetectors.[9-10] After employing the verticalbuilt-in field and plasmonic effects, graphene-silicon Schottky junction can be used as theshort-wave infrared (SWIR) photodetectors which can overcome the low optical absorption ofgraphene, as well as the ultrashort lifetime of photoinduced carriers (Fig.1(b)).[11]This device design concept addresses key challenges for high-performancegraphene-silicon Schottky junction optoelectronic devices and is promising for thedevelopment of graphene-based optoelectronic applications.
(a)

(b)

Fig.1 Schematic diagram of the graphene-Si Schottky junction for solar cell (a) and SWIR photodetector (b).
[1] X.M. Li et al. Applied Physics Reviews 4, 021306 (2017).
[2] X.M. Li et al. Physics Today 69(9), 46-51 (2016).
[3] X.M. Li et al. Adv. Mater. 22, 2743-2748 (2010).
[4] X.M. Li et al. Adv. Mater. 27, 6549–6574 (2015).
[5] Y. Song, X.M. Li et.al. Nano Lett. 15, 2104-2110 (2015).
[6] X.M. Li et al. Adv. Energy Mater. 3, 1029-1034 (2013).
[7] X.M. Li et al. Nanoscale 5, 1945-1948 (2013).
[8] Y.X. Lin, X.M. Li(Co-first author) et al. Energy Environ. Sci. 6, 108-115 (2013).
[9] X.M. Li et al. Small 12, 595-601 (2016).
[10] L. Tao, Z.F. Chen, X.M. Li* et al. npj 2D Materials and Applications 1, 19 (2017).
[11] Z.F. Chen, X.M. Li* et al. ACS Nano 11, 430-437 (2017).
Corresponding Author: Xinming Li
E-mail: xmli1015@gmail.com- 29 -

2-10
Schottky barrier control between indium tin oxide and WSe2 for fabricationof transition metal dichalcogenide-based transparent solar cell○Y. Yamaguchi1, W. Okita1, C. Li1, T. Kaneko1, and T. Kato1,2
1

Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
2
JST-PRESTO

Layered transition metal dichalcogenide (TMD) is known as a true 2D material withexcellent semiconducting properties. TMD is one of the most attractive materials for futuretransparent and flexible optoelectrical devices due to their atomically thin structure, band gap
in visible light range, and high optical transparency. Although the solar cell of TMD has been
widely investigated by many groups, those are based on the pn junction type solar cell. Sincecomplicated structures are required to form pn junction structures in TMD such as dual gateelectrodes or position selective doping, the device size of pn junction solar cell with TMD islimited within very small region (few μm). In spite of the outstanding advantages of TMD,
those merits of TMD have not been applied for transparent and flexible solar cell, which is
attracted intense attention as a next-generation energy harvesting technology.
Recently, we have developed a new fabrication process of TMD-based solar cell [1]. In our
process, Schottky type device configuration is utilized, which can be simply formed byasymmetrically contacting electrodes and TMD (Fig.1). The power conversion efficiency
clearly depended on the work function difference between two electrodes (ΔWF), and ahigher efficiency could be obtained with higher ΔWF (Pd-Ni), which is consistent with ourconcept, where Ni and Pd can form large and small Schottky barriers to operate as
power-generation and carrier-collect regions, respectively. Based on the optimizations ofelectrodes and distance, the power conversion efficiency can be reached up to 0.7 %, which is
the highest value for solar cell with similar TMD thickness [1].
In our previous study, we used conventional metals such as Ni and Pd to tune the Schottky
barrier height between electrode and TMD. To improve the transparency of whole device,
however, it is required to use transparent electrodes. In this study, we use indium tin oxide(ITO) as an electrode and form transparent and flexible solar cell. Since controlling ΔWF is a
key to improve the power conversion efficiency in our
device, the surface of ITO was functionalized by various
plasma treatments with hydrogen, nitrogen and oxygen as
reactive species. It is found that the work function of ITO
can be controlled by changing plasma species andtreatment time. After controlling the ΔWF of ITO
electrodes with plasma treatments, clear power generation
can be observed with TMD/ITO based transparent solarcell. Since our simple fabrication process includes highpotential for large scale fabrication, this achievement isvery important for realizing the industrial application of Fig. 1. Optical image of a transparent
and flexible solar cell fabricated with
TMD as a transparent and flexible solar cell.
TMD.
[1] T. Akama, W. Okita, R. Nagai, C. Li, T. Kaneko, and T. Kato, Sci. Reports 7, 11967 (2017).
Corresponding Author: Y. Yamaguchi
Tel: +81-22-795-7046, Fax: +81-22-263-9225, E-mail: yoshiki.yamaguchi.t5@dc.tohoku.ac.jp- 30 -

2-11
Angular momentum conservation in helicity-dependent
Raman and Rayleigh scattering○Yuki Tatsumi, Tomoaki Kaneko, and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Left- (σ+ ) and right-handed (σ− ) circularly-polarized light have angular momentum +ℏ
and −ℏ, respectively [1]. In recent study, many researchers try to use circularly-polarized lightin Raman spectroscopy (helicity-dependent Raman spectroscopy). Chen et al. reported that inplane vibrating modes of transition metal dichalcogenides (IMC modes) change helicity of thelight from σ− ( σ+ ) incident light to σ+ ( σ− ) scattered light in Raman scattering [2].
Furthermore, Drapcho et al. reported that well-known G band in graphene is also the modechanging the helicity of light in Raman scattering [3]. When the helicity of light changes inscattering process, angular momentum of photon exchanges to the material. In such a case, wehave to consider the discrete rotational symmetry of crystal to derive the angular momentum
conservation law. Conservation law of angular momentum in discrete rotational symmetry is
discussed for nonlinear optics from a long time ago [4-7], and also for impulsive stimulated
Raman scattering [8]. However, helicity-dependent Raman spectroscopy is reported in recent
studies and conservation law of angular momentum in scattering phenomena is unclear yet. In
this study, we formulate the angular momentum conservation law of Raman and Rayleighscattering and discuss the dependence of rotational symmetry in a material.
In order to discuss the conservation law of angular momentum in helicity-dependent Raman
and Rayleigh scattering, we combine the conservation law of angular momentum for electronphoton and electron-phonon interaction in discrete rotational symmetry. For Rayleigh scattering,
we found that helicity-changing scattering is observed only in the material with less than 3-foldrotational symmetry. In Fig. 1, we show thecalculated helicity-dependent Rayleigh spectra ofmonolayer (1L) (a) MoS2 and (b) black
phosphorus which have 3- and 2-fold rotational
symmetry, respectively. Weak helicity-changing
peak appears only in 1L black phosphorus. In thepresentation, we also discuss the detail ofsymmetry dependence for Raman scattering.
[1] K.Y. Bliokh et al., Phys. Rep. 592, 1 (2015)[2] S.-Y. Chen et al., Nano Lett. 15, 2526 (2015)[3] S.G. Drapcho et al., Phys. Rev. B 95, 165417 (2017)[4] H.J. Simon et al., Phys. Rev. 171, 1104 (1968)[5] N. Bloembergen, J. Opt. Soc. Am. 70, 1429, (1980)[6] J. Visser et al., Phys. Rev. A 66, 033814 (2002)[7] T. Higuchi et al, Phys. Rev. Lett. 106, 047401 (2011)[8] T. Higuchi et al, Phys. Rev. A 87, 013808 (2013)
Corresponding Author: Yuki Tatsumi
Tel: +81-22-795-6442, Fax: +81-22-795-6447,
E-mail: tatsumi@flex.phys.tohoku.ac.jp- 31 -

Fig. 1 Helicity-dependent Rayleigh spectra for
1L (a) MoS2 and (b) black phosphorus, calculated
by first-principles method. Dotted (Solid) line
indicates the helicity-conserving (changing)
scattering. The 𝐸𝐸L and 𝐸𝐸s are, respectively, theenergy of incident laser and scattered light.

2-12
Carrier dynamics in 3-layer ReS2 studied by ultrafast spectroscopy
Xiaofan Wang, Keisuke Shinokita, Hong En Lim, Nur Baizura Mohamed,○

Yuhei Miyauchi, Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan

R/R

Reflectance contrast

Atomically-thin layered materials including graphene and transition metal dichalcogenides
possess intriguing physical properties originating from the two dimensional honeycomb
structure. ReS2 is a new class of the layered material with reduced symmetry because of the
distorted 1T structure, which imparts highly anisotropic one dimensionarity to optical andelectronic properties [1]. The early study reported that ReS2 remains direct bandgap
semiconductor from bulk to monolayer [2], while the other reported that the band structure
depends on the layer number [3]. The understandings of electronic and optical properties
including the optically excited carrier dynamics are still controversial, and are not fully
understood. Here we described the ultrafast spectroscopy of 3-layer ReS2 using ultrafast
spectroscopy to obtain the insight of band structure and carrier dynamics.
The sample was prepared by mechanically exfoliation onto a quartz substrate using a
polydimethylsiloxane (PDMS). The ReS2 flakes were preferentially broke along b-axis
parallel to Re-Re bonds, and shows the elongated shapes. Figure 1(a) shows the reflectancecontrast of 3-layer ReS2 at 5 K, where the2.5
polarization angles of light with respect to theb-axis are shown. The spectra show
2.0 135
polarization dependence of two exciton
absorption peaks at 1.58 and 1.62 eV, reflecting
1.5
an anisotropic feature of ReS2. Figure 1(b)901.62 eVshows pump-probe differential reflectivity
1.0 45
probed at two-different configuration. The
transient differential reflectivity shows almost
0.5 0
1.58 eVno polarization dependence with decay times ofaround 100 ps. In contrast, time-resolved
0.0
photoluminescence (PL) spectroscopy shows
1.4
1.5
1.6
1.7
Energy (eV)much faster decay signals with less than 10 ps.
The different time scale in the transient
Pump:0 Probe:0 @1.58 eV
1E-03
reflectivity and PL measurement suggests the
Pump:90 Probe:90 @1.62 eVelectron and hole relax to the different
112.5 ps
momentum space in the indirect band structure
1E-04
of 3-layer ReS2. The detail carrier dynamics
and band structure of atomically thin ReS2 will
1E-05
be discussed.
[1] O. B. Aslan et.al., ACS Photonics 3, 96 (2015).
[2] S. Tongay et.al., Nat. Commun. 5, 3252 (2013).
[3] M. Gehlmann et.al., Nano Lett. 17, 5187 (2017).

1E-06

96.7 ps

200 400 600
Delay Time (ps)Fig.1 (a) Polarization-resolved reflectance contrastof 3-layer ReS2 with respect to b-axis. (b)transientdifferential
Polarization-resolved
reflectivity.

Corresponding Author: Kazunari Matsuda
Tel: +81-774-38-3460,
E-mail: matsuda@iae.kyoto-u.ac.jp- 32 -02-13
In situ transmission electron microscopy of the formation and annihilationof charge density waves in 1T-TaSe2○Keita Kobayashi1, Hidehiro Yasuda 1,2
1

Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, 7-1,
Mihogaoka, Ibaraki, Osaka 567-0047, Japan
2
Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka
University, 2-1, Yamadaoka, Suita, Osaka 565-0871, Japan
Some transition metal dichalcogenides (TMDCs)
exhibit charge density waves (CDWs) due to theirunique two-dimensional electron systems [1]. The
CDW phase in TMDCs is generally a stable
low-temperature phase, and the formation or
annihilation of the CDW is dipendent on thespecimen temperature.
In this study, to clarify the dynamics of theformation and annihilation of CDWs in TMDCs, weobserved the behavior of the long-periodic structure(LPS) attributed to the formation of CDWs in
1T-TaSe2 at elevated temperature by in-situ
transmission electron microscopy (TEM).
Figures 1(a) and (b) show the TEM images of
1T-TaSe2 acquired at 298 and 478 K, respectively,
and the corresponding fast Fourier transform (FFT) Fig.1: TEM images and corresponding
FFT patterns of 1T-TaSe2 acquired at (a)patterns. In the TEM image acquired at 298 K, a298
and (b) 478 K.
periodic contrast attributable to the LPS can beclearly observed. The FFT pattern also exhibitsordered reflection due to the LPS. In contrast, although the periodic contrast and orderedreflection attributable to LPS remain in the TEM image acquired at 478 K and thecorresponding FFT pattern, respectively, the TEM image also contains domains lacking theperiodic contrast as indicated by the arrowheads. The area of these domains increases overtime at 478 K. Eventually, the periodic contrast in the TEM image and the ordered reflectionin the corresponding FFT pattern completely disappear. This result indicates that theannihilation of the CDW originates from localized structural fluctuations and progressively
expands throughout the 1T-TaSe2. Furthermore, based on the in situ TEM observations, weconsider that CDW formation also occurs via a similar process.
K. K. thanks Gatan, Inc. for lending the CCD camera and the double-tilt Heating in-situ
holder.
[1] J. A. Wilson, F. J. Di Salvo, S. Mahajan, Adv. Phys. 24, 117 (1975).
Corresponding Author: K. Kobayashi
Tel: +81-6-6879-7941, Fax: +81-6-6879-7942,
E-mail: kobayashi-z@uhvem.osaka-u.ac.jp- 33 -

3-1
Functionalization of [60]Fullerene Through Fullerene Cation Intermediates○Yutaka Matsuo1,21

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, Japan

Fullerene cations, namely, [60]fullerene radical cation (C60¥+) and organo[60]fullerenyl
cation (RC60+), were less investigated as an intermediates in synthetic fullerene chemistry,
because of the intrinsic electro-negativity of C60. However, these two intermediates mediatedreactions provided fullerenes with versatile unexpected derivatives. This presentation mainly
describes the C60¥+ and RC60+ intermediates from generation of these cationic species to theirapplication in fullerene modification reaction, including Friedel–Crafts hydroarylations,
nucleophilic additions, dimerization, intramolecular rearrangement reactions, intramolecularcyclization reactions, as well as organic solar cells application research. Importantly, thispresentation deeply discusses the mechanism for the formation of unique [60]fullerene
derivatives involved with [60]fullerene radical cation and organo[60]fullerenyl cationintermediates containing newly generated lowest unoccupied molecular orbital (LUMO) after
removal of two electrons. These new LUMO are the key for unexpected and important
products useful in photovoltaic research as both organic and perovskite solar cells.
Ar

R

n
X

X = ArX

XRa) rearrangement

LUMO
HOMO

– 2 e–

new LUMOHOMO
X = O, Cb) cyclization

Figure. Concept of the newly LUMO for the further derivatization
References[1] Y. Matsuo et al., J. Mater. Chem. A 2017, 5, 2774.
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-0978, E-mail: matsuo@ustc.edu.cn; matsuo@photon.t.u-tokyo.ac.jp- 34 -

3-2
Molecules inside Fullerenes as Magnetic Probes
for the Detection of Specific Intramolecular Interactions○Yoshifumi Hashikawa and Yasujiro Murata
Institute for Chemical Research, Kyoto University, Uji,(a)Kyoto 611-0011, Japan

(b)

2.5

0.20

Relaxation Time, T1 and T2 (s)Relaxation Time, T1 and T2 (s)T1 / T2 (s)T1 / T2 (s)H
2O@C
59N dimers
thenature + and 0.18
Encapsulation of a small molecule inside fullerene C60 has 2.0an effect Hon
H2O@C59N
chemical reactivity of the outer sphere of C60. Recently, Martín and co-workers reported
that 0.16–
1.5
the entrapped H2O and HF molecules interact with the anionic cage (RC60 ) via an 0.14
intramolecular hydrogen bonding, which resulted in the accelerated
reaction rate relative to 0.12
1.0
1empty one. However, there still remain issues how to elucidate and experimentally detect the 0.10
specific intramolecular interactions in endohedral fullerenes.
0.5
0.08
H2O@ConIn this context, to demonstrate the existence of such interactions, we have focused
60 the0.0magnetic relaxation for nuclear spins of the corresponding molecules
entrapped inside C60. In 0.06 240 260 280
240 260 280 300 320 340 360 380
general, relaxation times are changeable by the influence of the degreeof(K) spin-spin
TemperatureTinteractions as well as the molecular motion. Thus, we expected
that
theentrapped
molecules(d)(c)
with the NMR-active nuclei would act as a probe to (a) 7.0
7.0
evaluate magnetic and electrostatic interactions
6.0
6.0
between the carbon cage and the entrapped molecule.
5.0
5.0
Our recent study showed that the proton relaxation
H2O@C59N+
4.0
4.0
times of entrapped H2O sensitively respond to the
40 K
H2O@C59N
H2@C59N
3.0
3.0
introduction of a heteroatom on the C60 cage,
dimersdimerssuggesting the restricted rotational motion of the water
2.0
2.0
H2O@C60
molecule via electrostatic attraction.2 Such specific1.0
1.0interaction was also observed in H2O@RC59N by
0.0
0.0
replacing a carbon atom in H2O@C60 with the nitrogen240 260 280
240 260 280 300 320 340 360 380
Temperature (K)Tatom even though the intramolecular interaction in(b)
H2O@C60 was concluded to be negligible by themeasurements of longitudinal and transverse relaxation
times, T1 and T2,3 as well as the single moleculejunction study.4 In addition, the electrostatic attraction
was found to be drastically enhanced by the oxidationof H2O@C59N dimers.5 Surprisingly, at the temperatureof 280 K, H2O@C59N+ has much larger value (T1/T2 =6) compared with H2O@C59N dimers (T1/T2 = 2.5) andthe T1/T2 curve is shifted by a factor of +40 K,
Figure 1. (a) Relaxation times and (b)electrostatic potential maps calculated
indicating the strong C59N+•••Oδ–H2 interaction whichat MP2/6-31G(d,p)//M06-2X/6-31G(d,p).
was also supported by the DFT calculations (Figure 1).

[1] (a) Maroto, E. E.; Mateos, J.; Garcia-Borràs, M.; Osuna, S.; Filippone, S.; Herranz, M. Á.; Murata, Y.; Solà,M.; Martín, N. J. Am. Chem. Soc. 2015, 137, 1190–1197. (b) Vidal, S.; Izquierdo, M.; Alom, S.; Garcia-Borràs,M.; Filippone, S.; Osuna, S.; Solà, M.; Whitby, R. J.; Martín, N. Chem. Commun. 2017, 53, 10993–10996.
[2] Hashikawa, Y.; Murata, M.; Wakamiya, A.; Murata, Y. Angew. Chem., Int. Ed. 2016, 55, 13109–13113.
[3] Hashikawa, Y.; Murata, M.; Wakamiya, A.; Murata, Y. J. Am. Chem. Soc. 2016, 138, 4096–4104.
[4] Kaneko, S.; Hashikawa, Y.; Fujii, S.; Murata, Y.; Kiguchi, M. Chem. Phys. Chem. 2017, 18, 1229–1233.
[5] Hashikawa, Y.; Murata, Y. J. Am. Chem. Soc. 2017, 139, 18468–18471.
Corresponding Author: Y. Murata
Tel: +81 774-38-3172, Fax: +81 774-38-3178,
E-mail: yasujiro@scl.kyoto-u.ac.jp- 35 -

3-3
Characterization of the spin system in GdM@Cn anion(M=Sc, Y, La; n=78, 80)○Takuji Mitani1, Ko Furukawa2, Tatsuhisa Kato3, 4, Koichi Kikuchi1, Yohji Achiba1,
Takeshi Kodama1
1

Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Center for Coordination of Research Facilities, Niigata University, Niigata 950-2181, Japan
3
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
4
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

2-

In (Gd2@C80(Ih)) , an excess electron (S=1/2) is located on the internal Gd dimer and two
Gd atoms take the trivalent state (S=7/2). From the ESR study, the ferromagnetic interaction
between three spins was suggested and the resultant spin state of (Gd2@C80(Ih)) is S=15/2[1].
On the other hand, for Gd@C82(C2v), it was reported the antiferromagnetic interaction
between an octet spin of the encapsulated Gd3+ and a doublet spin of an unpaired electron on
the π orbital of the carbon cage[2]. To clarify the magnetic interaction between the spins of
Gd3+ and an excess electron on the internal metal dimer, we synthesized (GdY@C80(Ih)) thathas a nonmagnetic ion Y3+ instead of one Gd3+ of (Gd2@C80(Ih)) [3]. In the previous
symposium, we reported the UV-vis-NIR absorption and the ESR spectra of (GdY@C80(Ih)) ,but we couldn’t analyze the ESR spectrum in detail. In this work, we report the spin system of
new hetero-dimetallofullerenes (GdM@Cn) (M=Sc, La; n=78, 80).
GdM-metallofullerenes (M=Sc, Y, La) were produced and extracted by the method
previously reported[3], and was separated by multi-step HPLC using acetone with an ion-pairreagent, tetrabutylammonium bromide, as an eluent. The UV-vis-NIR absorption spectra of(GdMC78) (M=Sc, Y, La) (Fig.1) and (GdLaC80) are very similar to those of(Gd2@C78(D3h)) and (Gd2@C80(Ih)) , respectively. Then, it was suggested that the cages of
GdMC78 (M=Sc, Y, La) and GdLaC80 are C78(D3h) and C80(Ih), respectively. By the analysisof the W-band ESR spectra (Fig.2), the spin state of (GdM@C78(D3h)) (M=Sc, La) was foundto be S=4, that is, the ferromagnetic interaction between an octet spin of the encapsulated
Gd3+ and a doublet spin of an unpaired electron on the metal-dimer was suggested.

Fig.1 UV-vis-NIR absorption spectra of(GdMC78) (M=Sc, Y, La) and (Gd2@C78(D3h)) .

Fig.2 W-band ESR spectra of (GdM@C78(D3h))(M=Sc, La) observed at 20 K.

[1] T. Mitani, et al. The 50th Fullerenes-Nanotubes-Graphene General Symposium 95 (2016).
[2] K. Furukawa, et al. J. phys. Chem. A 107, 10933-10937 (2003).
[3] T. Mitani, et al. The 52nd Fullerenes-Nanotubes-Graphene General Symposium 92 (2017).
Corresponding Author: Takeshi Kodama
Tel:+81-42-677-2530, Fax:+81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 36 --

3-4
Highly Stabilized Perovskite Solar Cells by Li+-Encapsulated [60]Fullerene
as Both Dopant and Anti-Oxidant○Hiroshi Ueno1, Il Jeon2, Seungju Seo2, Ryosuke Nishikubo3, Hiroshi Okada2,
Akinori Saeki3, Shigeo Maruyama2,4, Yutaka Matsuo1,2
1School of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China
Department of Mechanical Engineering, School of Engineering, The University of Tokyo,
Bunkyo-ku, Tokyo 113-8565, Japan3
Department of Applied Chemistry, Graduate School of Engineering, Osaka University,
Suita, Osaka 565-0871, Japan
4
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8564, Japan
2

With excellent power conversion efficiency (PCE) beyond 20%, lead halide perovskite solar
cells (PSCs) have attracted growing attention as a promising solar energy source in recent years.
Despite the high PCE comparable to silicon solar cell, low stability of PSCs has been the mostserious drawback, which is in dire need of resolution.[1] Previously we reported that Li+encapsulated [60]fullerene salt ([Li+@C60]TFSI−) can be used as an alternative to Li+TFSI− asa dopant for spiro-MeOTAD in MAPbI3-based PSCs. The device exhibited ca. 7 times higher
stability than LiTFSI-used conventional device, however, the PCE dropped significantly from
17.0% to 13.1 %.[2]In this work, formamidinuim and methylammonium mixed (FAPbI3)0.85(MAPbBr3)0.15based PSCs was fabricated using Li+@C60 salt as a dopant for spiro-MeOTAD. A higher PCEof 16.8% was achieved, and such improvement can be attributed to higher VOC and FF, comingfrom much reduced degradation of the perovskite active layer (Figure 1a). The device showed
10 times higher stability than LiTFSI-used device (Figure 1b), which ascribed to thehydrophobic nature and anti-oxidant activity of Li+@C60 and Li@C60.

Figure 1. (a) Optimum J–V curves of MAPbI3- and (FAPbI3)0.85(MAPbBr3)0.15-PSCs using[Li+@C60]TFSI− under 1 sun. (b) Stability data of the (FAPbI3)0.85(MAPbBr3)0.15-PSCs with
[Li+@C60]TFSI− and those with Li+TFSI−, the test condition was that the devices were
unencapsulated in air under constant illumination.
[1] Ahn, N. et al. Nat. Commun. 2016, 7, 13422.
[2] Jeon, I. et al. 53rd FNTG general symposium, 1P-4.
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-0978, E-mail: matsuo@photon.t.u-tokyo.ac.jp- 37 -

3-5
Matrix approach to calculation of phonon group velocities from MDtransient dispersion relation as applied to graphene○Tatiana Zolotoukhina1, Kentaro Kumaki 1, Kenta Tawara 1
1

Department of Mechanical Engineering, University of Toyama, Toyama 930-8555, JapanFor calculation of thermal properties of nanoconfigured materials, knowledge of transportphonon group velocities, and lifetime characteristics is essential. Molecular dynamics (MD)estimation of transient dispersion relation evaluates matrix D(ω,k) distribution. To extractmodes and their velocities through an automated procedure, we propose mode selection on thematrix obtained by differentiation in k-space [1] and spline fitting of modes from the edges ofBrillouin zone along selected ΓΜ path on grid. The spline fitting was tested on the results of
MD calculation of thermally excited graphene nanoribbon. The dispersion relation forgraphene sample shows presence of basic and transient phonon modes in the 1st Brillouinzone [2]. We extract phonon branches from the dispersion matrix by differentiation in k spaceand spline approximation of branches to functional ω(k) form that are easily differentiable byk value to get group velocity of present phonon modes.
x_c_k_Re
x_c_k_Im

6.00E-011
4.00E-011
2.00E-011

x_c_k

0.00E+000-2.00E-011-4.00E-011-6.00E-011-8.00E-011-1.00E-010
0

2000

4000

F_r

Fig.1 The transient dispersion map D(ω,k) in the ΓM direction of the 1st Brillouin zone
(left and center), k-space derivative (right) along one of the k cross-section with the 0values at the place of peak values.

MD estimation of dispersion relation in regions of interest evaluates ω(k) distribution as amatrix. To extract ω(k) for passing modes from the matrix, we use the intensity-dependent
mode cut-off on the transient dispersion matrix and k-space peak selection for approximation
points. The spline fitting of ω(k) functions is attempted by 2-step fitting of the second andthird order by the automatic point selections from the opposite edges of Brillouin zone alongthe ΓΜ path on matrix grid. The spline fitting was applied to the results of MD calculation ofthermally excited graphene nanoribbon with the presence of basic and transient phononmodes along the ΓΜ path in the dispersion relation for graphene sample. We utilized points ofthe second order approximation to build linear approximation of the search area to the pointsof the third order approximation to functional ω(k) form that are required to get groupvelocity of transient phonon modes. The error of such spline approximation can be brought tobe close to 4 - 5% in our estimation.
[1] K. Firouzi, J. Acoust. Soc. Am. 132 , 2012, 1271
[2] T. Zolotoukhina, Proc. of the 15th Int. Tech. Conf. on Packaging and Integration of Electronic and Photonic
Microsystems, 2015, 48297.
Corresponding Author: T. Zolotoukhina
Tel: +81-76-445-6739, Fax: +81-76-445-6739,
E-mail: zolotu@eng.u-toyama.ac.jp- 38 -

3-6
High-yield production of thin layer materials by solid phase ball milling○Ahmad Tayyebi, Gang Liu, Naoko Ogino, Naoki Komatsu
Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Kyoto
606-8501, Japan

Yield, %Two dimensional (2D) materials have attracted much attention due to their potential
applications in energy, environment, optoelectronics, and biomedicine [1]. Several production
methods have been developed in both top-down and bottom-up approaches, in which liquid
phase exfoliation of the bulk layered materials might be the most appropriate in terms ofscalability and simplicity [1]. Recently, our group developed a facile, scalable and high-yieldproduction of 2D nanosheets using solid phaseaexfoliation of ball milling [2,3]. It is importantto find out what controls the morphology andamount of exfoliated 2D materials. For thisreason, we investigate the ball milling
exfoliation of bulk molybdenum disulfide(MoS2) in the presence of sodium cholate (SC)as a surfactant to study the effect of different
operational conditions of ball milling process b b 10
8such as ball size, surfactant/initial MoS2
6
weight ratio (SC/MoS2), and ball milling4
duration and speed.
2First, the effect of surfactant amount in the0ball milling process was studied; the amount
0
0.5
1
1.5
2
of MoS2 was fixed at 0.20 g and the amount of
SC/MoS2
SC was varied from 0.010 to 0.40 g. The
powder obtained after ball milling was Figure 1. (a) Image of MoS2 dispersion withdispersed in deionized water (100 mL) and the different SC amount, and (b) plots of dispersed MoS2
resulting dark-greenish suspension was yield versus initial weight ratio of SC/MoS2.
centrifuged at 3000 rpm (1025g) for 60 min.
The top 75% of the supernatant (Figure 1a) was subjected to UV/vis spectroscopic analysis.
The yield, the mean number of layers, and lengths of the nanosheets were calculated using theextinction and the reported coefficient at 345 nm [4], the wavelength of the exciton peak (lA),and the ratio of the extinction at 605 and 345 nm (Ext605/Ext345), respectively. As shown in
Figure 1a and 1b, the yield of MoS2 increased according to the increase of the weight ratio of
SC/ MoS2. The yield of 9% obtained at the SC/MoS2 weight ratio of 2 is much larger than thatobtained by liquid phase sonication. The morphology of MoS2 nanosheets was determined to
be two layers and 60 - 80 nm in size, from the lA observed at 658 nm and the value of
Ext605/Ext345.
[1] V. Nicolosi, et al. Science, 340, 1420 (2013). [2] G. Liu et al. ChemNanoMat. 35, 9467 (2016). [3]
G. Liu et al. ChemPhysChem 17, 1557 (2016). [4] E. Varrla et al. Chem of Mat. 27, 1129 (2015). [5]
C. Bakes et al. Nat. Commun. 5, 4576 (2014).
Corresponding Author: A. TayyebiTel, Fax: +81-75-753-6833, E-mail: ahmad.tayyebi.28e@st.kyoto-u.ac.jp- 39 -

3-7
Automated searching and assembly of atomic layers: a robotic building
system of van der Waals superlattices○Satoru Masubuchi 1, Masataka Morimoto 1, Momoko Onodera 1, Sei Morikawa 1,
Kenji Watanabe 2, Takashi Taniguchi 2, and Tomoki Machida 1,3
1

2

Institute of Industrial Science, University of Tokyo, Japan,
National Institute for Materials Science, Japan, 3CREST-JST, Japan

Since the advent of van der Waals(vdW) heterostructures, random naturein the shape, thickness, and positions of
exfoliated 2D crystals insist researchers
for repetitive manual tasks of optical
microscopy-based
searchingandsubsequent mechanical transfer. To solve
the long-standing problems, wedeveloped a robotic system, whichenables automated fabrication of vdW
heterostructures.
Thesystemperformance was demonstrated byfinding 1200 monolayer graphene in 4
hours, stacking 30 alternative layers of
atomically thin graphite and hexagonalboron nitride (hBN) in 8 hours, and 7 setsof hBN/graphene/hBN heterostructuresin 3 hours. The system frees up
researchers from the repetitive tasks, andprovides a feasible platform for
prototyping various types of vdW
heterostructures.
Our optical microscopy system
automatically searches atomically thin
two-dimensional crystals on SiO2/Si.
After searching, the catalog of available
2D crystals are developed in a databasesystem. vdW heterostructures aredesigned by selecting 2D crystals fromdatabase. Designated 2D crystals areassembled into vdW heterostructures byautomated stamping machine. The entire
system was developed in glove box
enclosure with inert gas atmosphere,
which enables handling easily-oxidized
2D crystals.
Corresponding Author: S. Masubuchi
Tel: +81-3-5452-6847, Fax: +81-3-5452-6157,
E-mail: msatoru@iis.u-tokyo.ac.jp

Fig. 1. (top panel) Computer assisted design schematics
of automated assembly system. (middle panel)
Schematics for fabrication process. (a) Atomically thin
two-dimensional crystals on SiO2/Si are searched byautomated optical microscope and their information are
stored in database. (b) The combination of 2D crystals
for vdW heterostructures are designed by CAD software.
(c) The designed vdW heterostructures are assembled bystamping machine. (bottom panel) optical microscopy
images of fabricated vdW heterostructures. (i)monolayer graphene encapsulated in h-BN withcrystallographic alignment. (ii) monolayer graphene/3LhBN/bilayer graphene tunnel device. (iii) WS2 contacted
by trilayer graphene. (iv) (graphene/hBN)14 superlattice
structure. Scale bar corresponds to 5 µm.

- 40 -

3-8
Fast and precise imaging of structural defects
in large area graphene films via lock-in thermography○Hideaki Nakajima1, Takahiro Morimoto1, Yoshiue Ikuta1, Yuki Okigawa1,
Takatoshi Yamada1, Kenji Kawahara2, Hiroki Ago2, and Toshiya Okazaki 1
1

National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565,
Japan
2
Global Innovation Center, Kyushu University, Fukuoka 816-8580, Japan

Large area graphene synthesis by chemical vapor deposition (CVD) method has rapidly
progressed for realizing scalable device applications. Nevertheless, the existence of local
defects such as domain boundaries seriously degrade its superior physical properties.
Although several experiments based on scanning tunneling microscopy have shown theinfluence of defects on the electrical transport properties, only the limited area were
investigated in those reports due to long measurement times. Here, we demonstrate the fastand precise electrical characterization of large area CVD graphene sheets by using lock-in
thermography (LIT) technique.
Figure 1 shows the measurement setup. The sample
was the single-layer CVD graphene film epitaxiallygrown on a sapphire substrate. After transferring thegraphene onto a quartz substrate, LIT was carried out by
applying a 25 Hz AC bias between two electrodes. By
using lock-in technique, Joule heat component from thebiased sample was detected separately from backgroundheat storage [1].
Figure 2 (a) shows an optical microscope image of theFig. 1 Schematic diagram of electricalcharacterization with LIT.
sample. Individual graphene domains and boundary lines
can be identified. The LIT image is indicated in Fig. 2 (b).
The heat generation behaviors are clearly exhibited at theboundary locations 1 and 2. Since both locations show
intense D-bands in Raman mapping (not shown), it isfound that the observed thermal features are originatedfrom boundary defects. In contrast, the boundary 3 showsa featureless thermal pattern. There is no D-band
signature in the region, indicating to be a seamlessboundary. These results indicate that the LIT successfully
images the electrical properties of domain boundaries
over a mm-sized graphene film within a reasonable timeframe (10 min.). The detailed analysis of thermal
Fig. 2 (a) Optical microscope and (b)LIT images. The LIT image wasproperties to individual boundary characteristics will beobtained in 10 minutes.
discussed in the symposium.
[1] T. Morimoto et al., The 52nd FNTG general symposium, 2-4 (2017).
Corresponding Author: Toshiya Okazaki
Tel: +81-29-861-4173 / E-mail: toshi.okazaki@aist.go.jp- 41 -

3-9
Direct Observation of Cross-Polarized Excitons in
Aligned and Chirality-Enriched Single-Wall Carbon Nanotubes○ Fumiya Katsutani,1 Weilu Gao,1 Xinwei Li,1 Yota Ichinose,2 Yohei Yomogida,2Kazuhiro Yanagi,2 and Junichiro Kono1
1

Department of Electrical and Computer Engineering, Rice University, Houston, Texas
77005, USA
2
Department of Physics, Faculty of Science and Engineering, Tokyo Metropolitan University,
Hachioji, Tokyo 192-0397, Japan(3.2 𝐴𝐴⊥ -𝐴𝐴∥ )/ 𝐴𝐴∥

AbsorbanceAbsorbanceSingle-wall carbon nanotubes (SWCNTs) show strong absorption peaks due to subbandindex-conserving exciton transitions (Eij, i = j) for light polarized parallel to the nanotube axis.
For light polarized perpendicular to the nanotube axis, absorption peaks are expected at Eij,
where i  j = 1, but they are significantly suppressed by the depolarization effect [1,2]. These“cross-polarized” excitons (especially E12 and E21)(a)
E11
have been previously observed in circular
0.10
E22
dichroism and polarized photoluminescence
0.08
excitation spectroscopy studies on aqueous
suspensions of SWCNTs. However, their direct
E11
0.06
E12/E21phononobservation in optical absorption, combined with
0° = parallel
0.04
quantitative analysis, has been elusive due to the30°
45°
unavailability of suitable samples.
60°
0.02
Here, we report a direct observation of the
90° = perpendicular
0.00
E12/E21 peak in a (6,5)-enriched aligned SWCNT
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
Energy (eV)film. We prepared a pure (6,5) suspension throughE11(b)
pH-controlled gel chromatography [3], and-2
8x10
fabricated an aligned film through slow vacuum
filtration [4]. Figure 1(a) shows polarizationE22
6
dependent absorption spectra. For parallel
polarization, strong E11 and E22 peaks are observed.
𝐴𝐴⊥ ×3.2
4
E11
As the polarization angle increases, these peaks
E12/E21phonon2
gradually decrease in intensity while the E12/E21
𝐴𝐴∥
peak appears and grows at the lower energy side of0
the E22 peak. Figure 1(b) compares the parallel
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
Energy (eV)(𝐴𝐴∥ ) and perpendicular (𝐴𝐴⊥ ) spectra afterE12/E21(c)1.5multiplying 𝐴𝐴⊥ by 3.2, whereas Figure 1(c) shows
the normalized difference between 𝐴𝐴∥ and 3.2𝐴𝐴⊥.
1.0
The E12/E21 peak is observed at 1.88 eV, which is
660 meV higher than E11 and 250 meV lower thanE22. The integrated intensity of the E12/E21 peak in
0.5
𝐴𝐴⊥ is ~10% of that of the E11 peak in 𝐴𝐴∥ .

[1] H. Ajiki et al, Physica B 216, 358 (1996).
[2] S. Uryu et al., Phys. Rev. B. 74, 155411 (2006).
[3] Y. Ichinose et al, J. Phys. Chem. 121 13391 (2017).
[4] X. He et al, Nat. Nanotech. 11, 633 (2016).
Corresponding Author: Junichiro Kono
Tel: +1-713-348-2209, Fax: +1-713-348-3091,
E-mail: kono@rice.edu- 42 -

0.0

1.0

1.2

1.4
1.6
1.8
Energy (eV)

2.0

2.2

Fig. 1 (a) Absorption spectra for an aligned (6,5)
SWCNT film for various angles between the lightpolarization and the nanotube alignment direction. (b),(c) Comparison of absorbance spectra for parallel andperpendicular polarizations.

3-10
Bilayer Plots for Accurately Determining the Chirality of Single-Walled
Carbon Nanotubes Under Complex Environments
Juan Yang*, Daqi Zhang, Yuecong Hu, Chenmaya Xia, Sida Sun, Yan Li
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
The chirality (n,m) determines all the structures and properties of a single-walled carbon
nanotube (SWNT), therefore, accurate and convenient (n,m) assignments are vital in
nanotube-related science and technology [1]. In 1999, H. Kataura et al. [2] first proposed a
calculated Eii–dt plot to explain the absorption and Raman spectra of SWNTs. Later, this plot
was named after him as the Kataura plot, and was widely utilized by the researchers in the
carbon nanotube community. However, the facts that both Eii and the calculated dt from ωRBM
are subject to interactions with the environments make it inconvenient to accurately determine
the (n,m) under complex environments. Here, we propose a series of bilayer plots that take
into account the interactions between the SWNTs and the environments so that the (n,m) of
SWNTs can be accurately determined [3]. These plots are more concise, with less data
overlapping, suitable to be used under complex environments, and can distinguish individualand bundled SWNTs. We strongly encourage the researchers in the carbon nanotube
community to utilize the bilayer plots for all (n,m)-related studies, especially for accurate andconvenient (n,m) determination. We have also launched an (n,m) assignment program on ourgroup website (www.chem.pku.edu.cn/cnt_assign) to assist the researchers in accurately andconveniently determining the (n,m) of various SWNT samples under complex environments
based on the bilayer plots.
SWNT arrays on quartz substrate

QuartzSWNTs on silicon substrate

SiO2/Si“Super-growth” SWNTs
Air-suspended SWNTs
Various SWNT
samples undercomplexenvironments
SDS-dispersed SWNTs

Fig.1

ssDNA-dispersed SWNTs

Bilayer plots for accurately determining the chirality of SWNTs under six different environments[1] D. Zhang, J. Yang, Y. Li, small 9, 1284 (2013).
[2] H. Kataura et al. Synth. Met. 103, 2555 (1999).
[3] J. Yang, D. Zhang, Y. Hu et al. ACS Nano, 11, 10509 (2017).
Corresponding Author: J. Yang
Tel: +86-10-62755357
E-mail: yang_juan@pku.edu.cn- 43 -

3-11
Spectral tuning of optical coupling between air-mode nanobeam cavities
and individual carbon nanotubes○Hidenori Machiya1,2, Takushi Uda1,3, Akihiro Ishii1,4, 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, Japan2

We design high quality factor air-mode nanobeam cavities by finite-differencetime-domain simulations, and utilize the cavities to enhance the emission of air-suspended
carbon nanotubes [1]. The cavities are fabricated from silicon-on-insulator wafers, andnanotubes are synthesized over the cavities by chemical vapor deposition. Photoluminescence
spectroscopy is performed on the devices, where we observe optical coupling when the
nanotube emission energy is close to the cavity resonance. Taking advantage oflaser-heating-induced blueshifts of the nanotube emission, we can reduce the detunings [2].
We derive and numerically calculate the generalized expression for the spectral overlap, andgood correlation to the enhancement factors is obtained.
Work supported by JSPS (KAKEIHI JP16H05962, JP16K13613), and MEXT (Photon
Frontier Network Program, Nanotechnology Platform). H.M. is supported by RIKEN JuniorResearch Associate Program, and T.U. is supported by ALPS and JSPS Research Fellowship.
[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] H. Machiya, T. Uda, A. Ishii, and Y. K. Kato, Appl. Phys. Lett. 112, 021101 (2018).
Corresponding Author: Yuichiro K. Kato
Tel: +81-48-462-1111 (ext. 3432)
E-mail: yuichiro.kato@riken.jp- 44 -

ポスター発表
Poster Preview

1P – 1 ～ 1P – 38
2P – 1 ～ 2P – 39
3P – 1 ～ 3P – 39

1P-1
Electronic structures of solid phases of chemically functionalized C60
Sho Furutani1, Yutaka Matsuo2,3, and Susumu Okada1
1

Graduate School of Pure and Applied Sciences, University of Tsukuba 305-8571,
Japan

2

Hefei National Laboratory for Physical Sciences at Microscale, University of Scienceand Technology of China, Hefei, Anhui 230026, China
3

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

Chemically functionalized fullerenes are known to possess unusual electronic structure,
which is totally different from the pristine fullerene. Therefore, they are commonly used
as electron acceptor in organic photovoltaic devices since the energy level alignment
around the Fermi level can be tunable by functionalization resulting in high open
voltage to electron donor materials. Silylmethyl[60]fullerene (SIMEF) and methano
indene fullerene (MIF) are representative fullerene derivatives which provide theremarkable conversion efficiency. In the photovoltaic devices, chemicallyfunctionalized fullerenes form bulk heterojunction with the donor molecules. Becauseof the asymmetric molecular shape of these functionalized fullerenes, moleculararrangements in their bulk phases crucially affect the carrier mobility that determines
the conversion efficiency. Although the crystalline structures of SIMEF and MIF havebeen experimentally determined, the electronic structures solid phases of SIMEF andMIF are not elucidate yet. Thus, we clarify the electronic structures of crystalline
SIMEF and MIF to give the guiding principle to enhance the electron transport in theirbulk phases, using the density functional theory with the local density approximation.
Fig. 1 shows the electronic band structureof SIMEF and MIF in condensed phase. Our
calculations show that crystalline SIMEF
and MIF exhibit strong anisotropic electronicenergy band in their condensed phases owing
to the various intermolecular spacing andorientation between adjacent molecules. The
calculated effective mass of SIMEF is
ranging from 1.37 to 7.91me depending on
Fig. 1 Electronic band structure of (a)SIMEF andmolecular conformations. Effective electron (b)MIF,
respectively. The LU and HO indicate thelowest branch of the conduction band and themass of MIF is ranging from 0.57 to 4.23me.
highest branch of the valence band, respectively

Corresponding author: S. Furutani (sfurutani@comas.frsc.tsukuba.ac.jp)- 45 -

1P-2
Temperature dependence of anisotropic transient conductivity of a
La@C2v-C82(Ad) crystal○Michio Yamada1, Satoru Sato2, Wookjin Choi3, Shu Seki3, Tsuneyuki Abe2, Mitsuaki
Suzuki1,4 Yutaka Maeda1, Shigeru Nagase5, Takeshi Akasaka1,2,6,7
1

Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki
305-8577, Japan3
Department of Molecular Engineering, Kyoto University, Kyoto 615-8510, Japan
4
Department of Chemistry, Josai University, Saitama 350-0295, Japan
5
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
6
Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
7
State Key Laboratory of Materials Processing and Dye and Mold Technology, School ofMaterials Science and Engineering, Huazhong University of Science and Technology, Wuhan
430074, P. R. China

2Endohedral metallofullerenes (EMFs) and their derivatives have attracted attention due totheir potential for use in organic electronics [1-3]. La@C2v-C82, a typical monometallic EMF,
is a stable neutral radical, in which the spin density is distributed over the carbon sphere. The
open-shell electronic structure is derived from the transfer of three electrons from the encaged
La atom to the C82 cage. As a result, the redox potentials are much smaller than those of C60.
Recently, we found that high electron mobility is achievable by aligning La@C2v-C82
molecules in an orderly fashion [4,5]. The adamantylidene (Ad) adduct of La@C2v-C82(denoted as La@C2v-C82(Ad)), which retains its open-shell electronic structure, forms orderlyaligned nanostructures in crystals where the Ad moiety facilitates crystal growth [6].
Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements of a
La@C2v-C82(Ad) crystal exhibited anisotropic (and extremely high) electron mobility of µ =10 ± 5 cm2 V–1 s–1 along the c-axis at room temperature. In this presentation,
temperature-dependent conductivity measurements of a La@C2v-C82(Ad) crystal is provided
to prove that the electron transport can be described by the electronic band-conduction model
instead of the electron-hopping model [7].
[1] Y. Yasutake et al. Nano Lett. 5, 1057 (2005).
[2] M. Iwamoto et al. J. Phys. Chem. C 114, 14704 (2010).
[3] S. Kaneko et al. Phys. Rev. B 86, 155406 (2012).
[4] S. Sato et al. J. Am. Chem. Soc. 133, 2766 (2011).
[5] S. Sato et al. Angew. Chem. Int. Ed. 51, 1589 (2012).
[6] Y. Maeda et al. J. Am. Chem. Soc. 126, 6858 (2004).
[7] M. Yamada et al. Chem. Lett. 46, 973 (2017).
Corresponding Authors: M. Yamada, S. Seki, T. Akasaka
Tel & Fax: +81-32-329-7493 (M.Y.)
E-mail: myamada@u-gakugei.ac.jp (M.Y.)- 46 -

1P-3
Spectroscopic studies of dimetallofullerene anions encapsulating Nd○Shinya Nishimoto, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama
Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
So far, emission from the encapsulated metal ion in metallofullerenes has been reported
only for Er-metallofullerenes [1] and Tm-metallofullerenes [2]. Around 2006, we searched for
Nd-metallofullerenes, which had the emission around 1 µm from the encapsulated Nd ion, andthe very weak emission for LaNd@C72 at 77 K was reported [3]. In general, the mechanism ofemission from the encapsulated metal ion is supposed that, at first, the fullerene cage is
excited by light, and then the energy transfers from the excited fullerene-cage to the metal ion,and finally the excited ion emits a photon. For Nd3+, emission near 1 µm is due to thetransition of 4F3/2→4IJ(J=15/2, 13/2, 11/2, 9/2), and the shortest wavelength is about 900 nm.
Therefore, to be observed the emission of Nd ion, the onset of the absorption spectrum for
Nd-metallofullerenes should be shorter than 900 nm, which correspond to the lowest cage
excitation energy. Fortunately, the onset for dimetallofullerenes is thought to be shorter thanthat for monometallofullerenes, so that the dimetallofullerenes might be more suitable forobserving emission from encapsulated metals.
Recently, we succeeded in the isolation of(M2@C78(D3h))- and (M2@C80(Ih))- using the method
combining ion-pair chromatography with the extraction by amixed solvent of triethylamine and acetone [4]. In this study,
by using the method, we synthesized and isolated the novel
Nd-dimetallofullerenes that are stable only as an anion form.
Moreover, we investigated the emission properties of theobtained Nd-dimetallofullerenes.
Soot containing Nd-metallofullerenes was produced bydirect-current (60 A) arc discharge of Nd/C composite rods Fig.1 UV-vis-NIR absorptionof (Nd2C78)and(Nd:C=2:98) under a 500 Torr He atmosphere. (Nd2C78)- and spectra(La2@C 78(D3h))-.
(Nd2C80) were extracted and isolated by the previously
reported method [4]. For the obtained Nd-dimetallofullerenes,
the UV-vis-NIR absorption and emission spectra were
measured. As shown in Fig.1 and Fig.2, the UV-vis-NIR
absorption spectra of (Nd2C78)- and (Nd2C80)- were very
similar to those of (La2@C78(D3h))- and (Ce2@C80(Ih))-,respectively. Therefore, (Nd2C78)- and (Nd2C80)- were foundto be (Nd2@C78(D3h))- and (Nd2@C80(Ih))-. The results ofemission measurements will be discussed in the presentation.
Fig.2 UV-vis-NIR absorption
spectraof (Nd2C80)and(Ce2@C80(Ih))-.

[1] X. Ding, et al. Chem. Phys. Lett. 269, 72 (1997).
[2] Z. Wang, et al. ACS Nano 10, 4282 (2016).
[3] N. Murata, et al. The 30th Fullerenes-Nanotubes-Graphene General Symposium 106 (2006).
[4] 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- 47 -

1P-4
Isolation and Characterization of Tm2@Cn(n=78, 80) anion○Kazuhiro Kobayashi1, Ko Furukawa2, Tatsuhisa Kato3, 4, Koichi Kikuchi1, Yohji Achiba1,
Takeshi Kodama1
1

Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Center for Coordination of Research Facilities, Niigata University, Niigata 950-2181, Japan
3
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
4
Institue for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501, Japan

2

Recently, we succeeded in the isolation of the so-called missing metallofullerenes,
Y2@C80(Ih)[1] and Gd2@C80(Ih)[2], as an anion form using the method combining theion-pair chromatography (IPC) with the mixed solvent extraction. Therefore, it was shown apossibility of the production of unknown M2@C80(Ih) containing other metals. At first, we
tried to produce Yb2@C80(Ih) because Yb3+ has the same J value, 7/2, as Gd3+, but thedifferent L and S values (L=3 and S=1/2 for Yb3+; L=0 and S=7/2 for Gd3+). We intended tocompare the spin states of (Yb2@C80(Ih))- and (Gd2@C80(Ih))-, but, unfortunately,
Yb2@C80(Ih) could not be produced. As the reason of the missing production, rather large
ionization potential (IP) of Yb was suspected. So, next, we tried to produce Tm2@C80(Ih)because Tm is an element on the left side of Yb in the periodic table and has rather large IP
like Yb but slightly smaller than that of Yb. So far, Tm-monometallofullerenes, Tm@Cn(n=74,
82, 84, etc.), were isolated and Tm takes the divalent state in the cage. The situation is thesame for Yb. On the other hand, though no dimetallofullerenes were reported for Yb,
Tm-dimetallofullerenes, Tm2@C82 and HoTm@C82, were isolated and Tm takes the trivalentstate in the cage[3]. A Tm3+ ion has two holes on the
4f-shell, so Tm3+ has J value 6 (L=5, S=1) in the groundstate. So, if Tm2@C80(Ih) exists, the spin state of
Tm2@C80(Ih) anion which encapsulates two Tm3+ ionswould be interesting. In addition, Tm2@C78 anion was
also targeted in this work.
We carried out direct-current arc discharge of Tm/C
composite rods under a He atmosphere. The obtained raw Fig.1 LD-TOF-MS spectrum of Tm2C78.
soot was extracted with a mixed solvent of triethylamine
and acetone. The extract was separated by multi-step IPC.
Fig.1 shows LD-TOF-MS spectrum of Tm2C78. From thisspectrum, the isolation of Tm2C78 is confirmed. As
shown in Fig.2, the UV-vis-NIR absorption spectra of(Tm2C78)- and (La2@C78(D3h))- are very similar. Then it
is suggested that the (Tm2C78)- has a C78(D3h) cage, Tmof (Tm2C78)takes a trivalent state, and an excess electron is located Fig.2 UV-vis-NIR spectraand (La2@C78(D3h)) .
on the dimer like (La2@C78(D3h))-.
As for Tm2C80, we will discuss at the symposium.

[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] K. Kikuchi, Endofullerenes, eds. by T. Akasaka and S. Nagase, Kluwer Academic Publishers, 217-230 (2002).
Corresponding Author: Takeshi Kodama
Tel: +81-42-677-2530, Fax: +81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 48 -

1P-5   








 

 C60  

                 C

C60
We
study the energetics and electronic structure of endohedral C(X@C60 
) in
60  fullerenes
theframework of the density-functional theory (DFT) in order to identify the ideal elements X

forproducing the         

        C60  C60         
 C60 C60         C60   C60  C60  C60 
 C60          

 C60      C60      
atom’s position  C60 ’s center         C60     C60 ’s
  
C60 C60 

      

   

 

- 49 -

  
C60 C60
1P-6
N@C60 produced from C60 by irradiation with N+ and N2+ ion beam
○Tomonari Wakabayashi1, Yasuyuki Kanai2, Noboru Sasao,3 Yuki Sugaya,4Masayuki Toyoda4, Susumu Saito4, Motohiko Yoshimura3
1

Department of Chemistry, Kindai University, Higashi-Osaka 577-8502, Japan
Nishina Center for Accelerator-Based Science, RIKEN, Wako 351-0198, Japan
2
Division of Quantum Universe, RIIS, Okayama University, Okayama 700-8530, Japan2
Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551, Japan
2

Nitrogen-doped fullerene C60, namely N@C60, is known for its unique properties of electron
spin systems which can maintain extremely long coherence time [1]. The discovery of N@C60
in 1996 stimulated following researches on the application of the electron spin states to quantum
computation and quantum information processing [2,3]. Methodological modifications havebeen invented for increasing the production yield of N@C60, including ion implantation, plasma
discharge, and ion bombardment. However, quantity of the material accessible in the laboratory
is still limited at most to a few tens of micrograms. For further improvement to obtainmacroscopic amount of N@C60, the formation mechanism is to be clarified under thesystematically controlled experimental conditions. In consideration of the mechanism,
applications to the formation of novel species such as X@C60 where X represents an atom otherthan nitrogen may follow for coherent control of radiation processes [4].
Ion beam of N+ or N2+ was obtained by an electron cyclotron resonance ion source, Capris
ECRIS at Nishina Center in RIKEN. Sediment of C60 on a copper substrate was irradiated by
the ion beam at desired incident energy at 100 eV or 5 keV. After the 2-4 hours of irradiation of
C60 in vacuum with N+ or N2+ ion beam at the current of 17-30 microamperes, the C60 sediment
was collected in the air by dissolving it into a small amount of carbon disulfide. The solution
was filtered to remove undissolved solid particles and subjected to the X-band ESR
spectrometer for the detection of the magnetic species.
Figure 1 shows ESR spectra of the solution
containing ion-beam irradiated C60. The triplet
signal with the hyperfine splitting of 15.8 MHz
indicates the presence of N@C60. The electron
spin of atomic nitrogen at the configuration of
2p3, S = 3/2, couples with the nuclear spin of theisotope of 14N, I = 1, providing the triplet. In
comparison with the result from two types ofexperiment, it turned out that in situ codeposition of C60 was crucial for high yield of
N@C60. The penetration depth of the accelerated
ions into the C60 sediment will be discussed.
[1] T. Almeida-Murphy et al. Phys. Rev. Lett. 77, 1075 (1996).
[2] W. Harneit, Phys. Rev. A 65, 032322 (2002).
[3] J. J. L. Morton et al. Nature Phys. 2, 40 (2006).
[4] A. Fukumi et al. PTEP, 04D002 (2012).
Corresponding Author: T. Wakabayashi
Tel: +81-6-4307-3408, Fax: +81-6-6723-2721,
E-mail: wakaba@chem.kindai.ac.jp- 50 -

Figure 1. ESR spectra of N@C60
produced by irradiation of massselected N+ or N2+ ion beam to predeposited film of C60 (a,b) or to codeposited film of C60 (c,d).

1P-7
Self-patterning of C60 sheet like crystals
by liquid-liquid interfacial precipitation method○Yuto Funamori 1, Saori Yamamoto 1, Hiromichi Gonnokami 1, Hidenobu Murata 1,
Yuko Kaneda 2, Makoto Tanimura 2, Masaru Tachibana 1
1 Department of Materials System Science, Yokohama City University, Kanagawa 236-0027,

Japan

2 Instrumental Analysis Center, Yokohama National University, Kanagawa 240-8501, Japan

C60 nano/micro crystals have attracted much attention due to their unique shapes andproperties [1]. They have been effectively grown by liquid-liquid interfacial precipitation(LLIP) method with good and poor solvents. The shape and structure depend on the solventsused. In the LLIP method, alcohol has been mainly used as poor solvent. Recently weobtained hexagonal sheet like crystals by LLIP method using not alcohol but CCl4 as poor
solvent. Additionally, it was found that the crystals exhibit an interesting change called aself-patterning. In this paper, we report the growth of hexagonal sheet like crystals and theirself-patterning.
C60 nano/micro crystals have attracted much attention due to their unique shapes andproperties [1]. They have been effectively grown by liquid-liquid interfacial precipitation(LLIP) method with good and poor solvents. The shape and structure depend on the solventsused. In the LLIP method, alcohol has been mainly used as poor solvent. Recently weobtained hexagonal sheet like crystals by LLIP method using not alcohol but CCl4 as poor
solvent. Additionally, we found that the crystals exhibit an interesting change called aself-patterning. In this paper, we report the growth of hexagonal sheet like crystals and theirself-patterning.
C60 sheet like crystals were grown by LLIP method(b)(a)
with CCl4 and toluene as poor and good solvents,
respectively. In the procedure, CCl4 was poured in a
glass bottle, and then, C60-saturated toluene wasgently added. The crystals were nucleated from the
10 µm
10 µm
interface of both of the solutions, and was grown for
24 hours in 278 K. Consequently, hexagonal sheet likeFig.1 (a) Crystal placed on the slide
crystals were obtained with several micrometers in glass, and (b) after self-patterning
thickness. The crystals were placed on the slide glass,and were observed in open air using an optical microscope. Interestingly, the partition in eachcrystal appears with the evaporation of solvent while keeping the original hexagonal outline(Fig.1). Each partitioned shape exhibits rod-like one. The long-axis orientations of partitioned
rod-like crystals are arranged along any edges of the original hexagonal shape. We call suchchange a self-patterning. The origin of the self-patterning is discussed in light of thedesolvation of CCl4 with the results of FT-IR, XRD and TEM.
[1] “Fullerene nanowhiskers”, 2nd ed. edited by K. Miyazawa, Y. Ochiai, M. Tachibana, T. Kizuka, S. Nakamura,
Pan Stanford Publishing (2018)
Corresponding Author: Y. Funamori
Tel: +81-45-787-2162, Fax: +81-45-787-2162,
E-mail: author@domain.jp- 51 -

1P-8
Third-harmonic generation process in a thin film of(6,5) single-wall carbon nanotubes○Takahiro Yokoyama, Takeshi Koyama, Hideo Kishida
Department of Applied Physics, Nagoya University, Nagoya 464-8603, Japan
It is expected that single-wall carbon nanotubes (SWCNTs) show large opticalnonlinearities due to their one-dimensional electronic structure [1]. In Ref. [2], the third-ordernonlinear optical susceptibility (𝜒𝜒 (3) ) of SWCNTs was evaluated using the third-harmonic
generation (THG) method. However, resonant processes and excitonic effects on the THG
process in SWCNTs are still open questions. In this study, we measured the |𝜒𝜒 (3) | spectrumfor (6,5) SWCNTs using the THG method.
(6,5) enriched dispersion was made by the method previously reported [3]. After vacuum
filtration of the dispersion, we obtained a thin film and transferred it onto an SiO 2 substrate.

The measured |𝜒𝜒 (3) | spectrum displays a resonance at around 0.64 eV. A comparison with theabsorption spectrum indicates that the resonance at around 0.64 eV is attributed to two-photon
resonance. This result suggests that processes including a transition to a one-photon forbidden
state affect THG in the SWCNTs. By a discrete-level model, we analyzed the THG spectrum
and revealed the dominant THG processes in the observed photon energy region.
[1] V. A. Margulis, T. A. Sizikova, Physica B 245, 173 (1998).
[2] D. T. Morris et al., Phys. Rev. B 87, 161405 (2013).
[3] H. Liu et al., Nat. Commun. 2, 309 (2011).
Corresponding Author: H. Kishida
E-mail: kishida@nagoya-u.jp- 52 -

1P-9
Tuning of the Thermoelectric Properties ofHigh-Purity Single-Chirality (6,5) Single-Walled Carbon Nanotubes
by Electrolyte Gating○Yota Ichinose, Kengo Fukuhara, Junko Eda, Yohei Yomogida, Kazuhiro Yanagi
Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan
One-dimensional materials have potential to exhibit extremely high thermoelectricperformance [1]. One of suggested approaches to achieve the high thermoelectricperformance is to tune the Fermi level of the 1D materials with sharp van Hove singularity(vHS). Single-walled carbon nanotubes (SWCNTs) are a model for 1D system with sharp
vHS, and thus we can investigate how the location of Fermi level influences their
thermoelectric properties. Previously, we have investigated the thermoelectric properties of
SWCNTs as a function of Fermi-level using an electrolyte gating technique [2]. However, theobserved relationships between the Fermi level
and the Seebeck coefficients of semiconducting
SWCNTs were not in agreement with theoreticalpredictions. It is suggested that even a small
amount of impurities (~1%) affects thethermoelectric properties [3]. Recently, weestablished a separating technique, which
controls pH of solutions using CO2 bubbling in
gel-column chromatography, to obtain extremely
high-purity single-chirality SWCNTs (6,5) withpurity of more than 99% [4]. Therefore, in thisstudy, we investigated the relationships between
thermoelectric properties and location of Fermi
levels of high-purity single-chirality SWCNTs.
Fig.1 Optical absorption spectrum of (6,5)
As shown in Figure 2, we found very large
SWCNTsSeebeck coefficient (above 10mV/K), which isabout 102 times larger than previous reported
values. The power factor was also enhanced andabout 10 times lager. We found that the
improvement of semiconducting SWCNTs purity
strongly enhances the film thermoelectric
properties.
[1] Hicks & Dresselhaus, PRB 47, 16631 (1993)[2] K. Yanagi et al. Nano letters, 14(11), 6437 (2014).
[3] D. Hayashi et al. Applied Physics Express, 9(2),025102 (2016)[4] Y. Ichinose et al. J. Phys. Chem. C, 121 (24), 13391(2017)
Corresponding Author: K. Yanagi Tel: +81-42-677-2493,
E-mail: yanagi-kazuhiro@tmu.ac.jp- 53 -

Fig.2 Seebeck coefficient of (6,5) using
electrolyte gating1P-10Optimizing photothermoelectric effects in semiconducting and metallic
carbon nanotubes○ Ahmad R.T. Nugraha, Nguyen T. Hung, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Carbon nanotubes (CNTs) are known to absorb electromagnetic waves in a wide spectral
range, including THz regime [1]. THz detectors are required for many applications inastronomy, sensing, spectroscopy, imaging, defense, and communications. Using CNTs as a
THz detector has been shown by some researchers to be promising due to the intrinsic
polarization sensitivity of the CNTs as the absorbing materials with the THz-light-induced
thermoelectric effect (or photothermoelectric effect), which is assigned as the origin of theTHz signal in the THz detector [1-2]. However, the reported thermoelectric efficiency is quite
low, about a thousand times less efficient than commercial thermoelectric generator.
In this work, we investigate the photothermoelectric effects in CNTs by considering
combinations of semiconducting and metallic CNTs under illumination of THz light. We
propose that the metallic and semiconducting CNTs play independent roles in thephotothermoelectric effect. The metallic CNTs are responsible for absorbing THz light andconvert it into heat, which results in a temperature distribution along the device. On the other
hand, the semiconducting CNTs are responsible for generating voltage difference from thetemperature distribution due to Seebeck’s effect. Since the Seebeck coefficient of CNTs ischirality-dependent [3], we expect that there should be some optimized structures and also
optimized ratios of semiconducting and metallic CNTs to improve the efficiency of thephotothermoelectric effect in the CNT THz detector [4].
[1] L. Ren et al., Nano Lett. 12, 787–790 (2012)[2] X. He et al., Nano Lett. 14, 3953–3958 (2014).
[3] N. T. Hung, A. R. T. Nugraha, et al., Phys. Rev. B 92, 165426 (2015).
[4] A. R. T. Nugraha, N. T. Hung, R. Saito, unpublished.
Corresponding Author: A.R.T. Nugraha
Tel: +81-22-795-6442, Fax: +81-22-795-6447, E-mail: nugraha@flex.phys.tohoku.ac.jp- 54 -

1P-11Ferric ions affect surfactant assembly structures on carbon nanotubes○Atsushi Hirano 1, Tomoshi Kameda 2, Takeshi Tanaka 1, Hiromichi Kataura 1
Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8565, Japan
2
Artificial Intelligence Research Center, National Institute of Advanced Industrial Scienceand Technology (AIST), Tokyo 135-0064, Japan
1

Carbon nanotubes (CNTs) are grown on metal catalyst particles. Ions originating from thecatalyst particles are dissolved into aqueous phases when the CNTs with the catalyst particles
are dispersed into aqueous solutions using surfactants. In this study, we demonstrated that the
ferric ions (Fe3+) from iron catalyst particles modify surfactant assembly structures on the
CNTs, which is determined by adsorption experiments of CNTs onto hydrogel surfaces andmolecular dynamics (MD) simulations. We suggest that the coexisting ferric ions affectcolloidal properties of the CNTs including quality of CNT separation using hydrogels.
We used CNTs produced by the HiPco process in this study. We prepared CNT dispersion
using sodium dodecyl sulfate (SDS). Iron ions from the catalyst particles can thus coexist
with the SDS-dispersed CNTs. Figure 1 shows spectra of the adsorbed CNTs onto thehydrogel (Sephacryl S-200) surfaces at various concentrations of the chelating agent(ethylenediaminetetraacetic acid disodium salt, EDTA-2Na) or NaCl as a control, which werecollected by an eluent (sodium deoxycholate). EDTA-2Na even at 10 M was found toenhance the adsorbability of the CNTs onto the hydrogel surfaces, whereas NaCl was inert in
the same range of sodium concentrations. This result indicates the coexisting iron ions
weaken the CNT adsorbability onto the hydrogel surfaces.
The weakening effect on the CNT
adsorbability onto the hydrogel surfaces
should be attributed by the surfactant density
on the CNT surfaces [1]. To provide a
realistic model of this effect, we performed
MD simulations of SDS molecules around a
CNT in the presence of ferric ions (Fe3+) or
ferrous ions (Fe2+) (Figure 2). Ferric ionsinteracted with the SDS molecules on theFig.1 Absorption spectra of the CNTs adsorbed
CNT, whereas ferrous ions marginallyon the hydrogel surfaces in the presence ofdifferent concentration of EDTA-2Na (A) andinteracted with them. We thus concluded that
NaCl (B).
the coexisting ferric ions increase SDS
density on the CNT surfaces, leading to theattenuation of the CNT adsorbability onto
the hydrogel surfaces. This is the first reportof the effect of ferric ions originating fromthe catalyst particles on the surfactant
assembly structures.
[1] A. Hirano et al. ChemNanoMat 2, 911 (2016).
Corresponding Author: A. Hirano
Tel: +81-29-849-1064, Fax: +81-29-861-2786,
E-mail: hirano-a@aist.go.jp

Fig.2 Conformations of SDS assembly on the
CNT in the presence of Fe3+ ions (A) and Fe2+ ions(B) provided by the MD simulations. Iron ions are
represented by spheres.

- 55 -

1P-12
Near-infrared luminescence thermometric imaging using carbon nanotubes○Kengo Hachiya1, Saki Okudaira1, Yui Konno2, Yutaka Maeda2,
Kazunari Matsuda1, and Yuhei Miyauchi1
12Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan
Department of Chemistry, Tokyo Gakugei University, Koganei, Tokyo 184-8501,
Japan

Single-walled carbon nanotubes (SWNTs) have been considered as nearly ideal luminescentprobes for deep tissue bioimaging because of their photoluminescence in near-infrared range
known as the second optical window of biological tissues [1]. Furthermore, availability ofefficient phonon-assisted up-conversion photoluminescence (UCPL) in SWNTs, for which theexcitation light wavelength can be longer than the emission one, has recently been discovered[2]. With increasing temperature, the UCPL intensity increases while Stokes PL (hereafter, justreferred to as PL) intensity decreases [2]. Thus, the temperature dependent variation of theintensity ratio of the UCPL and PL may potentially be used for optical thermometry applicable
to deep inside of biological tissues. Recently, hyperthermia using nanoparticles has been
considered to be effective for the treatment of tumors [3]. In the hyperthermia treatment, strict
control of the tumor temperature is required. However, the exact temperature control still
remains a challenge because of the difficulty in measuring the temperature of the tumor in deep
tissue. Therefore, development of an effective method for the deep tissue optical thermometry
has been strongly desired.
In this study, we observed UCPL and PL images of SWNTs that were chemicallyfunctionalized in order to enhance both the UCPL from the free excitons and the longer
wavelength PL from the localized excitons [4,5]. The SWNTs were dispersed in water, and it
was sealed in a thin circular cell, and their UCPL and PL were measured by changing the filterswith an InGaAs near-infrared camera. The temperature of the dispersion was directly controlledusing a rubber-heater and a thermostat, and the luminescence image of the UCPL (980 nm) and
the PL (1100 nm) were obtained under epi-illumination using a 1064 nm laser. The PL and
UCPL images were taken under the same temperature, and the ratio of the PL and UCPL
intensities at each spatial position were obtained to construct a ratiometric image. As thetemperature of SWNTs increased, the luminance intensity of UCPL (IUCPL) increased but the PL(IPL) counterpart decreased. Consequently, the value of the ratio (IUCPL/ IPL) increased as shownin Figure 1. Clear increase of the intensity ratio indicates high sensitivity of this method to asmall temperature variation. Performance evaluation for the deep-tissue optical thermometric
imaging will be discussed.
[1] K. Welsher et al., Nat. Nanotechnol. 4, 773 (2009).
[2] N. Akizuki et al., Nat. Commun. 6, 8920 (2015).
[3] Jelena Kolosnjaj-Tabi et al., Pharm. Res. 126, 123(2017).
[4] Y. Maeda, et al., Nanoscale 8, 16916 (2016).
[5] Y. Maeda, et al., Chem. Eur. J. 23, 1789 (2017).
Corresponding Author: Y. Miyauchi
Tel: +81-774-38-3463, Fax: +81-774-38- 3467,
E-mail: miyauchi@iae.kyoto-u.ac.jp

(a)
SWNTs

(b)

(c)

1.7
1.6
1.5
1.4
1.3
1.2

Fig.1: (a) Schematic of a thin circular cell filled withan aqueous dispersion of SWNTs (top view). (b) IUCPL/IPL image at 21.5 ° C and (c) at 35.8 ° C. Color bar
indicates the value of the IUCPL/ IPL in an arbitrary unit.

- 56 -

1P-13Polymeric p-Type Dopant showing Permanent Doping Durability forTransparent Carbon Electrodes○Clement Delacou 1, Il Jeon 2, Ahmed Shawky, Rong Xiang, Anton Anisimov, Esko I.
Kauppinen, Yutaka Matsuo, Shigeo Maruyama 1
1
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan2
Department of Chemistry, The University of Tokyo, Tokyo 113-8656, Japan
Transparent electrodes are vital components for touch panels, displays, and photovoltaic
cells. Widely used indium tin oxide (ITO) transparent electrodes are not suitable for use inflexible electronics because of their brittleness, high cost, and diffusion of impurities within
devices. Carbon nanotube (CNT) has shown considerable promise as replacements for ITObased electrodes, but they fall short in terms of conductivity. To offset this weakness, dopants
are used to increase the conductivity by increasing the concentration of free carriers andreducing the resistance. As reported by Lee and colleagues, trifluoromethanesulfonic acid
(TFMS) displayed nearly ideal durability when used to dope graphene in organic light emitting
diodes.[1] However, TFMS nonetheless does not exhibit permanent durability and has an issue
regarding handling safety when used as a dopant in carbon electrodes.
We investigated the use of high molecular weight polymeric dopant (sulfonatedtetrafluoroethylene-based fluoropolymer-copolymer sulfonic acid i.e., Nafion®) in transparent
conductive CNT films. We expected that entanglement of the CNT network and the long chainsof the polymeric acid would stabilise the donated protons, which in turn would provide an
exceptionally durable doping effect. The polymeric acid doped CNT films satisfied other key
requirements for transparent carbon electrode, including transparency, smooth morphology, andsafety of handling. In this work, various analyses were conducted to compare the polymericacid with the established acid dopants HNO3 and TFMS. This study showed that the polymericacid had similar doping effectiveness but superior durability in comparison with the other
dopants. This excellent durability came from the low volatility and high stability of the acid andits conjugate base, as demonstrated by a number of analytical techniques and comparison of thedoping effects between CNT and graphene. Accordingly, we revealed that the polymeric aciddopant has nearly permanent (1 year) doping durability. Furthermore, organic solar cells (OSCs)
were fabricated using the polymeric acid-doped CNT films and a mixture of PBTZT-stat-BDTT
and PC71BM. The p-type polymeric acid-doped CNT-based OSCs initially produced a PCE of
8.0%, which was retained for more than 60 days, while the ITO-based OSCs had an initial PCE
of 9.1%, which dropped below 8.0%, because ofsuspected degradation of ITO by poly(3,4ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS) and metal diffusion. The devices
using the polymeric acid dopant were the mostdurable when compared with the devices using other
dopants.
[1] T.-H. Han et al. Angew. Chem. Int. Ed. 55, 6197 (2016).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 57 -

Fig.1 Illustration of Nafion-doped CNTbased organic solar cell.

1P-14
Transparent and flexible triboelectric generator based on carbon nanotube○Masahiro Matsunaga1, Jun Hirotani2, Shigeru Kishimoto2, Yutaka Ohno2,3
1

Venture Business Laboratory, Nagoya University, Nagoya 464-8603, Japan2
Department of Electronics, Nagoya University, Nagoya 464-8603, Japan
3
Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603,
Japan

Peak power denssity (mW/m2)

A self-powered device which harvests electrical energy from surrounding environment has
been required for future society. One of the typical energy sources is mechanical vibration.
Several principles such as electromagnetic and piezoelectric effect have been studied forconverting the mechanical vibration into electricity. Recently, the triboelectric generators(TG) have attracted much attention for the energy harvesting device due to many advantages
such as high output voltage, low cost, and simple structure [1,2]. The TG generates electricity
using triboelectrification and electrostatic induction. Here, we report transparent and flexible
TG with carbon nanotube (CNT) thin film and Polydimethylpolysiloxane (PDMS).
Figure 1 shows a schematic TG. The TG was fabricated by sandwiching a CNT thin filmgrown by floating-catalytic chemical vapor deposition with PDMS layers. Cu wire wasconnected by a silver paste for electrical measurement. To enhance the output performance,
the surface of the TG was treated with CF4 plasma for increasing surface charges. The size of
the TG is 5 cm × 5 cm. The fabricated CNT TG is highly transparent and flexible as shown in
Fig. 2. The voltage generation was performed by tapping the surface of TG with fingers with anitrile grove. The output
Nitrile grove
voltage across the external load
Fingerresistance (R = 10 k ~ 1 GΩ)+ + + + +was measured.
PDMS- - - - The peak power density
+ + +
CNT
(P) at various load resistancee Rfrom 10 kΩ to 1GΩ was shownin Fig. 3. The maximum P was~500 mW/m2 at 300 MΩ. The Fig. 1 Schematic CNT TG.
Fig. 2 Photograph of fabricated
CNT TG.
peak voltage and current
density were ~600 V at 1 GΩ600
and ~2.8 mA/m2 at 10 kΩ,~500 mW/m2
500
respectively. These value are
400much higher than the previous
300
transparent and flexible TG
200
which was fabricated using
100
hydrogel [2]. The generated
0
power was sufficient to drive
1k
10k 100k 1M 10M 100M 1G 10G
Load resistance ()30 blue light emitting diodes(LED) as shown in Fig. 4.
Fig. 3 Peak power density versus Fig. 4 Photograph of 30 blue
LEDs drived by CNT TG.
Acknowledgment: This work load resistance.
was supported by JST/CREST(JPMJCR16Q2).

[1] Z. L. Wang, Mater. Today 20, 74 (2017).
[2] S.-H. Shin et al., ACS Nano 9, 4621 (2015)[3] X. Pu et al., Sci. Adv. 3, e1700015 (2017).
Corresponding Author: Y. Ohno
Tel & Fax: +81-52-789-5387, E-mail: yohno@nagoya-u.jp- 58 -

1P-15Preparation of MWNT/HDPE Composites via Melt Blending○Atsushi Onodera 1, Masaru Sekido 2
1

Advanced Course of Production System Engineering ,National Institute of Technology, Sendai College, Natori 981-1239, Japan2
Department of Materials Science and Engineering, National Institute of Technology, Sendai
College, Natori 981-1239, Japan
We have been studying to optimize the conditions to prepare MWNT/Polyethylene(PE) composites by melt blending. Last year we have reported that tensile strength of MWNT/High Density Polyethylene(HDPE), functionalized-MWNT(f-MWNT)/HDPE, MWNT/Low Density
Polyethylene(LDPE) and f-MWNT/LDPE composites prepared by melt-blending was not increased with 1/100(MWNT/PE) weight ratio. In this work, we focused on MWNT/HDPE composites and studied various CNT/PE weight ratio to optimize MWNT/HDPE weight ratio to gethigher tensile strength than HDPE itself. The influence of functionalization of MWNT was alsostudied.
f-MWNT were prepared by using 1,3-dipolar cycloaddition reaction. The mixture of MWNT
(0.5 g), sarcosine (1.5 g) and 3,4-dihydroxybenzaldehyde (1.5 g) in DMF (250 ml) were refluxed. After 3days DMF was removed by rotary evaporator and remaining powder were
washed by water and acetone to obtain f-MWNT (1.9 g). MWNT/HDPE composites were prepared by melt blending at 220 °C, screw speed of 100 rpm and a recycle time of 10 minutes.
Weight ratio of MWNT/HDPE were 1/100, 3/100, 5/100 and 10/100. f-MWNT/HDPE composites were also prepared with 1/100 and 3/100 weight ratio. Tensile strength of MWNT/HDPE
and f-MWNT/HDPE composites were measured by tension tester (Dak System INC.,UTB9052-TT).
The tensile strength of various weight ratio is shown in Fig 1. Tensile strength of 1/100 composites did not increase as expected. While tensile strength of 3/100, 5/100 and 10/100 composites increased about 50%. When using f-MWNT, tensile strength of 1/100 composites did notchange while 3/100 composites were increased about 30% compared with HDPE itself. We will
discuss the reason why f-MWNT did not increase the tensile strength compared with MWNT.

Fig 1. Tensile strength of MWNT/HDPE and f-MWNT/HDPE composites.
Corresponding Author: A. Onodera
Tel: +81-22-381-0329, Fax: +81-22-381-0329
E-mail: a1601008@sendai-nct.jp- 59 -

1P-16
In situ XANES investigation of Co and Ni Catalysts during
Single-Walled Carbon Nanotube Growth○Takahiro Maruyama 1, Makoto Kumakura 2, Takahiro Saida 1, Shigeya Naritsuka 2
Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan
Department of Materials Science and Engineering, Meijo University, Nagoya 468-8502,
Japan
1

2

In general, 3d transition metals, such as Fe, Co and Ni, are widely used as catalysts
for single-walled carbon nanotubes (SWCNTs) growth by chemical vapor deposition (CVD).
However, growth mechanism of SWCNTs from these metal catalysts is still unclear. So far,several groups reported in situ observations for SWCNT growth using transmission electron
microscopy (TEM) [1, 2]. However, TEM can detect only a few catalyst particles, and it isdifficult to characterize chemical states of the overall catalyst particles. In this study, we
carried out in situ X-ray absorption near edge structure (XANES) to investigate the chemicalbonding states of Co and Ni catalyst during SWCNT growth.
Using Co and Ni catalysts, SWCNTs were grown on Al2O3/SiO2/Si substrates byalcohol catalytic CVD. The growth temperature and the ethanol pressure were 650 °C and 50
Pa, respectively. During SWCNT growth, Co and Ni K-edge XANES spectra were measured
every 7-8 min. In addition, just before and after heating the catalysts at 650 °C, XANES
spectra were measured. All XANES measurements were carried out at BL5S1 of Aichi SR(Japan) in the fluorescence mode.
Fig. 1 shows K-edge XANES spectra of Ni catalysts. Before SWCNT growth, Ni
catalysts were partially oxidized, but they were reduced during heating and remained metallic
during SWCNT growth. On the other hand, some portions of Co catalysts became carbide
during SWCNT growth, although they were metallic before the start of growth. Our
observation was consistent with previous density functional tight-binding/MD simulation [3].
The XANES measurement was conductedwith the support of the Aichi Synchrotron
Radiation Center “Project for publishing outcomesfor graduate students 2016.” This study waspartially supported by the Program for the Strategic
Research Foundation at Private Universities
supported by MEXT, Japan and Daiko Foundation.
Part of this study was conducted at the Institute for
Molecular Science (IMS), supported by the“Nanotechnology Platform” of MEXT.
[1] Y. Kohigashi et al. Appl. Phys. Lett. 105, 073108 (2014).
[2] M. Picher et al. Nano Lett. 14, 6104 (2014).
[3] Y. Okamoto et al. J. Comp. Theor. Nanosci. 8, 1755 (2011).
Corresponding Author: T. Maruyama
Tel: +81-52-838-2386, Fax: +81-52-838-1179,
E-mail: takamaru@meijo-u.ac.jp- 60 -

Fig.1 In situ Ni K-edge XANES spectraof Ni catalysts during SWCNT growth.

1P-17
Repeated CNT synthesis by resetting CoAl2O4 and NiAl2O4 catalysts○Toshihiro Sato1, Hisashi Sugime2, Bin Liang3, Eongyu Yi3, Richard M. Laine3, Suguru
Noda1, 4
1

Department of Applied Chemistry, School of Advanced Science and Engineering, Waseda
University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
2
Waseda Institute for Advanced Study, Waseda University, 1-6-1 Nishiwaseda, Shijuku-ku,
Tokyo 169-8050, Japan3
Department of Materials Science and Engineering and the Macromolecular Science andEngineering Center, University of Michigan
4
Waseda Research Institute for Science and Engineering, Waseda University, Tokyo 1698555, Japan.
We achieved repeated synthesis of carbon nanotubes (CNTs) by resetting the catalyst
nanoparticles (NPs). It is well known that the catalyst NPs get coarsened through Ostwald
ripening [1] during chemical vapor deposition (CVD), resulting in CNT growth termination,and no way has been known to reset the coarsened catalyst nanoparticles (NPs). We had Co and
Ni NPs segregating out from their spinel films under reducing environment and dissolving inthe spinel films under oxidizing environment.
CoAl2O4 and NiAl2O4 nanopowders were synthesized by liquid-feed flame spray pyrolysis[2] and sintered in air to yield flexible, dense films (30±10 μm in thickness) without any NPs
on surface. The films were then reduced at 1100 ˚C in H2/Ar, on which NPs were found. Then
CNTs were grown by CVD by flowing C2H2/H2/Ar at 1100 ˚C (① in Figures 1 and 2). The
oxidation treatment of the CNTs/spinel samples O2/N2 at 1100 ˚C yielded the spinel films
without CNTs nor NPs (② in Figures 1 and 2). We repeated the reduction-CVD-oxidation
treatment for three cycles, and confirmed similar CNT growth on the spinel.

Figure 1. Repeated CNT growth on NiAl2O4 film

Figure 2. Repeated CNT growth on CoAl2O4 film
[1] K. Hasegawa, S Noda, Carbon 49, 4497 (2011).
[2] J. Azurdia et al., JACS 89, 2749 (2006).
Corresponding Author: S. Noda, Tel: 03-5286-2769, E-mail: noda@waseda.jp- 61 -

1P-18Controlled Growth of SWNTs Using CoWO4 Nanoparticles as
Catalyst Precursor○ Xu Liu, Feng Yang, Yan Li*

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
China
Single-walled carbon nanotubes (SWNTs) with special structure and excellent
performance are regarded as one of the most promising candidates as building blocks
in the next generation electronics. The Controlled synthesis of the structure andproperties enriched SWNT samples for large-scale integrated carbon nanotube devices
is a great challenge. We have developed a novel tungsten-based intermetallic compound
catalyst by using heteropolyacid containing W and Co as a precursor. The catalyst has
a high melting point and a lower crystal structure symmetry, acting as a structural
template for the growth of carbon nanotubes with specific chirality [1-4]. However, thecomplex preparation process and the pH sensitivity of the specific composition oftungsten heteropolyacid is not conducive to large-scale production in the future.
Therefore, it is important to find a catalyst precursor with simple preparation procedureand good stability.
Recently, we have tried to use uniform CoWO4 nanoparticles, which were preparedin water-in-oil microemulsions, as catalyst precursor. By adjusting the conditions ofchemical vapor deposition, we achieved the diameter, conductivity and chirality
controlled growth of SWNTs on Si / SiO2 substrates.
[1] F. Yang, Y. Li et al. Nature 510, 522 (2014).
[2] F. Yang, Y. Li et al. Acc. Chem. Res. 49, 606 (2016).
[3] F. Yang, Y. Li et al. J. Am. Chem. Soc. 137, 8688 (2015).
[4] F. Yang, Y. Li et al. ACS Nano, 11, 186 (2017).
Corresponding Author: Yan Li
Tel: +86-10-6275-6773
E-mail: yanli@pku.edu.cn- 62 -

1P-19Mechanism of preferential synthesis of (6,4) single-walled carbon nanotube
using surface state control of Co catalyst○ Bin Xu1, Toshiro Kaneko1, Yasushi Shibuta2, Toshiaki Kato1,3
1
2

Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Department of Materials Engineering, University of Tokyo, Tokyo 113-8656, Japan
3
JST-PRESTO

Single-walled carbon nanotubes (SWNTs) are promising candidate for high performance
optoelectrical devices due to the unique 1-dimension structure. Since the physical properties
of SWNTs strongly depend on the chirality, obtaining SWNTs with particular chirality
remains as a critical issue in this scientific community. Based on the previous studies, thecatalyst size [1], component [2], and crystal structure [3] are proven to be contributed todecide SWNTs chirality. However, effect of catalyst surface state on chirality control isseldom being studied.
In this study, we find out that the catalyst surface state can be very sensitive to nucleate
specific type of chirality species and significant change of chirality from (6,5) to (6,4) SWNTs
are observed by controlling the surface state of catalyst [4]. The surface state of catalyst iscontrolled by our newly established catalyst pretreatment process. The annealing of catalyst
nanoparticles under the high vacuum condition with slightly adding small amount of reactive
gas species can control the oxidation degree of catalyst surface.
To elucidate the mechanism of chirality selective nucleation by changing the surface stateof catalyst, systematic investigations have been carried out. The detailed measurements with
X-ray absorption fine structure (XAFS) shows about 50 % of oxidized Co catalyst (CoOx)
were reduced by the pretreatment. The activation energy of SWNTs growth near the lower
threshold of growth temperature increases with the catalyst pretreatment, which is consistent
with the results of first-principle calculations, where the binding energy between cap structureof SWNTs and CoOx catalyst increase by reducing catalyst surface. Theoretical calculation
also reveals that the most preferred chiralangel shift to a smaller chiral angle
through the reduction of Co catalyst. Thisis also in good accordance with theexperimental results. Based on theseresults, it is revealed that the combinationof diameter (to small diameter) and chiralangle (to small angle) shift through thechange of catalyst surface state can cause Fig. 1: Photoluminescence-excitation (PLE) map andthe drastic shift of chirality species from corresponding first principle calculation model of SWNTs
grown from catalyst (a) without and with pretreatment.
(6,5) to (6,4) SWNTs (Fig. 1(a)(b)).
[1] M. Picher, E. Anglaret, R. Arenal and V. Jourdain, ACS Nano 5 (2011) 2118.
[2] W.-H. Chiang and R.M. Sankaran, Nat. Mater. 8 (2009) 882.
[3] F. Yang, et al., Nature 510 (2014) 522.
[4] B. Xu, T. Kaneko, Y. Shibuta, and T. Kato, Sci. Rep. 7 (2017) 11149.
Corresponding Author: B. Xu
Tel: +81-22-795-7046, Fax: +81-22-263-9225
E-mail: xu12@ecei.tohoku.ac.jp- 63 -

1P-20
Separation of CoMoCAT-SWNTs by utilizing aqueous two immisible
solution phase (ATP) technique and Raman/fluorescence spectroscopy
Tatsuki Watase, Tokinaru Matsuoka, ○Shinzo Suzuki,
Department of Physics, Kyoto Sangyo University, Kyoto 603-8555, Japan
In the previous symposium [1], we showed that Raman spectroscopy could have been
applied for evaluating the ratio of metal/semiconductive single-wall carbon nanotubes(SWNTs) in aqueous two immiscible solution phase (ATP) technique, especially for thosemade by using arc-burning technique. This separation technique by using two immiscible
solution phases (e.g., in polyethylene glycol (PEG) and dextran (DX) solution) has been firstreported by C.Y. Khripin et al. [2], where metal/semiconductive SWNTs of large diameter (>1.2 nm) were shown to be successfully separated.
In this presentation, we reported about the separation of CoMoCAT-SWNTs utilizing ATPtechnique combined with Raman spectroscopy, in order to investigate how thinner SWNTs
were separated in ATP solution, since the separation mechanism for those thinner nanotubes in
ATP solution was considered to be different from the case of SWNTs made by arc-burningtechnique [2]. Additionally, by using 785nm laser as an excitation wavelength, it was foundthat some thinner semiconductive nanotubes show fluorescence, indicating that SWNTs arewell mono-dispersed in each solution phase [3]. Further experimental findings will bepresented and discussed.
References:[1] K. Uratani et al., Proc. of the 52nd Fullerene-Nanotube-Graphene General Symposium. 3P-15(2017).
[2] C.Y. Khripin et al., J. Am. Chem. Soc., 135, 6822-6825(2013).
[3] M.S. Strano et al., J. Nanoscience and Nanotechnology, 3, 81-86(2003).
Corresponding Author: Shinzo Suzuki
Tel: +81-75-705-1631, Fax: +81-75-705-1820,
E-mail: suzukish@cc.kyoto-su.ac.jp- 64 -

1P-21
Atomistic simulations of formation processes of in-plane heterostructures ofh-BN and graphene○Hisaki Sawahata1, Ayaka Yamanaka2, Mina Maruyama 1, Susumu Okada 1
1

Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
2
Research Organization for Information Science and Technology (RIST), Shinagawa, Tokyo
140-0001, Japan
In these days, h-BN and graphene have attracted much attention at nanoscience andnanotechnology, because they have unique geometric and electronic properties. Owing to thestructural similarity between graphene and h-BN, they can form in-plane heterostructures witha border between them. An experimental work reported that the zigzag edge of graphene
prefer B atoms with the formation of BC heterobond rather NC heterobond [1]. Our previous
work also corroborated that the BC bond is energetically stable compared with the NC bond.
On the other hand, because of the competition between polarity at the border near the zigzag
shape and the BC bond energy gain, we also demonstrated that the BC dominant border withthe angle of 8 degree is the most stable border structure [2]. However, it is still unclear the
microscopic mechanism of preferential formation of the zigzag border with BC bond at thegraphene edges.
In the present work, to give a theoretical insight into the energetics of the formation
process of the border between graphene and h-BN, we studied the energetics of the graphenewith BN adsorbates and the formation energy of the borders under various conditions, using
the density functional theory combined with the generalized gradient approximation and theeffective screening medium method. Our calculation shows the chemisorption energy of BN
to the zigzag graphene edges indicate that the BC bond is energetically stable compared with
the NC bond, indicating that BN preferentially growth from zigzag edges of graphene have
BC bonds at the border. Furthermore, the preferential formation of BC bond at the border
prevents h-BN growth from the armchair portion of graphene. On the other hand, from theh-BN edges under the high vacuum condition, we found that both zigzag borders with NC andBC bonds are generated in terms of their border formation energy. Our calculations indicatethat the border shape and structure strongly depend on the formation condition of in-plane
heterosheet of graphene and h-BN.

References[1] E. Maeda et al. Appl. Phys. Express. 10, 055102 (2017).
[2] H.Sawahata et al. Abstract of 53rd FNTG general symposium, 3P-24, September (2017).
Corresponding Author: H. Sawahata
E-mail: hsawahata@comas.frsc.tsukuba.ac.jp- 65 -

1P-22
Selective Growth of AB-Stacked Bilayer Graphene○Yuri Terao,1 Kenji Kawahara,2 Kenshiro Suenaga,1 Keisuke Yamamoto,1
Hiroshi Nakashima,1,2 Kosuke Nagashio,3 Hiroki Hibino,4 Hiroki Ago*,1,2
1Interdisciplinary Graduate School of Engineering Sciences, Kyushu University
2
Global Innovation Center (GIC), Kyushu University
3
Department of Materials Engineering, University of Tokyo
4
School of Science and Technology, Kwansei Gakuin University

Bilayer graphene (BLG) with AB stacking shows a tunable band gap by a vertical electricfield, which promises the applications to semiconductor devices [1]. Although the CVD
growth of BLG on Cu catalyst has been reported [2-4], it is still difficult to synthesize largearea BLG due to the self-limiting growth mechanism on Cu surface which generally gives
monolayer graphene. Recently, we reported that a Cu-Ni alloy catalyst deposited on sapphire
substrate can catalyze the uniform growth of BLG [5]. The added Ni metal increases the
carbon solubility in the alloy, increasing the bilayer coverage up to 93% [5]. However, theAB-stacking ratio of the BLG was about 70%, while the remaining 30% was twisted BLG.
The twisted BLG can be useful for intercalation [6], but the semiconductor applications requireAB-stacked BLG.
Here, we present that the AB-stacking ratio can be dramatically improvedby controlling the reaction time, reaching to ~100% AB stacking.
BLG was synthesized by ambient pressure CVD using Cu-Ni alloy (Ni 20%) film depositedon c-plane sapphire. We investigated various growth parameters, such as the Ni concentration,
temperature, and methane/hydrogen concentrations. Interestingly, the growth time was foundto greatly influence the AB/twist ratio. As shown in Figure 1, the AB ratio increased from~70% to 98% by simply extending the growthtime. We speculate that the twisted BLG
grains are less stable than AB-stacked BLG,
thus the former can be etched during the
growth period. As the BLG coverage did notshow substantial change, we think that BLG
grains are regenerated by carbon atoms
supplied from the alloy or vapor.
Ourfinding offers a new strategy to tune thestacking order of BLG for future applications.
Transport properties will be also discussed inFig. 1 Effect of growth time on the AB stacking ratio.
the Symposium.
[1] Y. Zhang et al., Nature, 459, 820 (2009). [2] L. Liu et al., ACS Nano, 6, 8241 (2012).
[3] X Chen et al., Carbon, 107, 852 (2016). [4] Y. Hao et al., Nat. Nanotech., 11, 426 (2016).
[5] Y. Takesaki et al., Chem. Mater., 28, 4583 (2016). [6] H. Kinoshita et al., Adv. Mater., 1702141 (2017).
Corresponding Author: H. Ago (Tel&Fax: +81-92-583-8975, E-mail: h-ago@gic.kyushu-u.ac.jp)- 66 -

1P-23Fabrication of graphene nanoribbon transistors with high on/off ratio using
advanced plasma CVD○Yuta Wato1, Hiroo Suzuki1, Toshiro Kaneko1, and Toshiaki Kato1,2
1

Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
2
JST-PRESTO

Graphene nanoribbons (GNR) combine the unique electronic and spin properties ofgraphene with a transport gap that arises from quantum confinement and edge effects.
Although GNR can be made in a variety of ways, the reliable site and alignment control of
GNR with high on/off current ratios remains a challenge.
Up to now, we have developed a novel method based on the advanced plasma CVD withnanoscale Ni catalyst (Ni nanobar) for directly fabricating suspended GNR devices [1, 2].
Although this method has outstanding advantages in terms of precise site and alignment
controlled growth of suspended GNR, there remain a space to be studied about this method,especially for on/off current ratio. At the current state, GNR grown by Ni nanobar has
relatively low on/off ratio (~5). GNR devices with on/off ratio higher than 103 are useful forthe various semiconductor applications.
In this study, we attempted to improve on/off ratio of field-effect transistor with GNRgrown by advanced plasma CVD. It is known that the band gap of GNR is inversely
proportional to the width of GNR, indicating narrower GNR can obtain higher on/off ratio. To
narrow down the width of GNR, GNR growth was carried out with various kinds of metal
nanobars such as Ni, Cu, Fe, Co, and Ge as catalysts. It was found that there is a clear
correlation between GNR width and melting point (MP) of nanobars. The nanobars withrelatively low MP such as Cu and Ge can grow narrower GNR than that of higher MPmaterials such as Ni. Based on our previous study about the growth model of GNR, it is foundthat the nanobar structure becomes liquid phase during plasma CVD [2]. Although the initialwidth of nanobars was same for all kinds of nanobars, Cu and Ge nanobars may shrink before
GNR nucleation due to the relatively low
MP, resulting in the growth of narrower
width of GNR. The electrical measurement
was also carried out for the GNR grownfrom various kinds of nanobars. The on/off
ratio of GNR grown from Ge nanobar (Fig.
1(b)) shows very high on/off ratio (~104) atroom temperature compared to that of
GNR grown from Ni nanobar (Fig. 1(a)).
This result shows that GNR grown fromGe nanobar includes higher potential for Fig.1 Typical drain-source current (ID) -gate bias
(VG) curves of GNR devices fabricated withthe future application of GNR for various voltage(a) Ni and (b) Ge nanobars.
semiconductor devices.
[1] T. Kato and R. Hatakeyama, Nature Nanotechnology 7, 651 (2012).
[2] H. Suzuki, T. Kaneko, Y. Shibuta, M. Ohno, Y. Maekawa and T. Kato, Nature Communications 7, 11797(2016).
Corresponding Author: Y. Wato
Tel: +81-22-795-7046, E-mail:yuta.wato.s8@dc.tohoku.ac.jp- 67 -

1P-24
Energetics of water migration through unstitched grain boundaries ofgraphene○Kenta Yasuraoka, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571,
Japan
Further miniaturization and integration of electronic devices demand us to design the stable
and reliable Cu interconnect structures against the oxidization. Atomic-layer materials, suchas graphene and boron nitride (h-BN), are possible coating materials for Cu interconnect toprevent their conductivity deterioration by surface oxidization, because of their stiff andflexible covalent network with atom-scale mesh which hinder water migration through thecoating sheet. On the other hand, it has been pointed out that graphene and other atomic-layermaterials usually possesses grain boundary at which the covalent networks possess structuralimperfection, such as topological defects, atomic defects, and unstitched borders. In particular,
unstitched grain boundaries severely affect the water migration through the atomic layermaterials. Thus, in this work, we aim to give theoretical insight into the energetics of water
migration through the unstitched grain boundaries for providing guiding principles fordesigning the high efficient and stable coating layer structures.
All calculations are conducted using the density functional theory with the local density
approximation. To investing the energetics of water migration through the unstitched grainboundary in terms of the overlap length of graphene layers, we consider the structural modelin which the unstitched grain boundary is simulated by the partially stacked graphene ribbons(Fig. 1). Water migrations through the boundaries depend on the area of interlayer overlap:
For the boundaries without interlayer overlap, water can migrate through the boundary
without energy barrier. On the other hand, the barrier for the migration through the boundary
increases with increasing the interlayer overlap up to 0.9 eV. The results indicate thatgraphene with unstitched grain boundaries are not stable and reliable coating materials for Cu
interconnect, because water molecules can migration through the boundaries.

d (A)ΔE (eV)

0
0.0

1.22
-0.5

2.45
0.8

3.66
0.9

Fig. 1 A structural model of unstitched gram boundary of graphene and migration energies (ΔE) as a function ofinterlayer overlap (d).
Corresponding Author: K. Yasuraoka and S. Okada
E-mail: soakda@comas.frsc.tsukuba.ac.jp- 68 -

1P-25Computational Simulation of Edge-Roughness Effects on GNR-based FETs
○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 the formof a nanometer width ribbon, referred as graphene nanoribbons (GNRs). They have beensuccessfully applied to FETs with high on-off ratio. Although the resistance of GNR is known
to increase dramatically with edge disorder[1][2], the effects of edge roughness on the FET
characteristics (e.g., on-off ratio and subthreshold) 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 is modeledby adding or removing pairs of carbon atoms at the edges (Fig. 1). We calculated draincurrent(Id) versus gate voltage(Vg) characters of ED-AGNR-FETs by changing the roughness
concentration P from 0% to 30% and the ribbon-width from 2.21nm (Fig. 2). We confirmedthat average values of device characteristics deteriorated with increasing of P. However, evenfor P = 30%, some GNR-FETs show that sub-threshold slope values are smaller than 60mv/dec
which is the limit value of planer FET as considered here. Furthermore, we investigate optimal
position of edge roughness to improve FET characteristics. Details will be discussed at the
symposium.

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- 69 -

1P-26
Synthesis of Novel IrRuOx / Graphene Catalyst
for Oxygen Evolution Reaction○Masanori Hara, Badam Rajashekar, Hsin-Hui Huang, Masamichi Yoshimura
Toyota Technological Institute, Nagoya 468-8511, Japan
1. Introduction
Recently, environmental issues such as global warming and depletion of fossil fuels havebecome important topic for progress toward sustainable societies. To utilize renewableenergies effectively, conversion of surplus energies to hydrogen via water electrolysis has
attracted attention as energy storage method. However, activity, durability, and cost of
catalysts are insufficient for practical application in water electrolysis systems due to highover-potential and low kinetics of electrode reactions, especially, oxygen evolution reaction(OER) on the anode [1-3]. In the present study, we have synthesized novel alloy nanoparticle
catalysts of iridium oxide (IrO2) and ruthenium oxide (RuO2) on the graphene, both of which
are active catalysts for OER. The IrRuOx / graphene catalyst was characterized and evaluatedin catalytic activity for OER in sulfuric acid solution.
2. Experimental
The IrRuO2 / graphene (or reduced graphene oxide, rGO) catalyst was synthesized byhydrothermal method. Briefly, required amount of metal complexes, H2IrCl6 and RuCl3, andgraphene oxide were dispersed in ethanol/water mixture and the mixture was heated at 80˚Cfor 6 h under constant stirring. Then, the mixture was heated at 150˚C in hydrothermal
autoclave for 4 h. The IrRuOx / rGO catalyst was characterized by TEM, SEM-EDX, XPS,XRD and electrochemical methods (LSV and RDE) in 0.5 M H2SO4 solution.
3. Results and discussion
Figure 1 shows a TEM image of the IrRuOx / rGO
catalyst. The IrRuO2 nanoparticles were dispersed on thesurface of rGO substrate and an average size of thenanoparticles was 1.5 ~ 5 nm. The wide distribution of
the particle size is due to the difference of solubility of
the catalyst metal salts. The characterization by
SEM-EDX and XPS reveals that the ratio of Ir to Ru is
promotional to the ratio of starting materials for the
10 nm
synthesis. The XRD measurement shows the (200) peakFig. 1 TEM image of IrRuO2 / rGO.
of IrRuOx was shifted to small angle and became broader
with increasing Ir ratio of the catalysts. It suggests that nanoparticles of the catalyst form alloyof two metal oxides, RuO2 and IrO2. Thus, we successfully prepared the alloy catalysts ofIrO2 and RuO2 supported on nanocarbon substrate, and can be a promising candidate as anodefor water electrolysis.
[1] M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hydrogen Energy 38 (2013) 4901.
[2] E. Antolini, ACS Catal. 4 (2014) 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- 70 -

1P-27
Ab initio study of double-layered graphenewith ethylenic linkage structures
Hiroyuki Yokoi
Department of Materials Science and Engineering, Faculty of Advanced Science andTechnology, Kumamoto University, Kumamoto 860-8555, Japan
Graphene has no energy gap, which is unfavorable to the application to semiconductor
devices. However, theoretical studies have predicted that modification to the graphene sheet,such as stripping to ribbon or periodic formation of pores could open the energy gap. In
addition, the emergence of magnetism related to the formation of a pore or adsorption of ahydrogen atom has been investigated intensively both theoretically and experimentally. These
preceding studies suggest that we could create novel graphene-based materials throughintroducing a variety of modulating substructures to the honeycomb structure. In this study,
we propose a novel double-layered graphene interconnected with ethylenic chains, andinvestigated the electronic states in the framework of ab initio calculations. We chose ahexagonal supercell with 6x6 hexagonal carbon rings. We designed double-layered graphene
structures with 1-6 bridges per one supercell, where a carbon atom on the bridge connectedwith two carbon atoms at the outer sides of six hexagonal rings surrounding the hexagonalring in the center of the basal plane in the supercell (Fig. 1). Ab initio calculation using the
VASP code has revealed that their electronic states depend on the number of bridges
dominantly. One of the most remarkable results is that the magnetic moment of 2B per one
supercell emerges in the case of the structure with six bridges (Fig. 2). This material might bevery interesting as it could be a magnetic atomic-layer material composed with carbon only.

Fig. 1 Optimized structure of double-layered Fig. 2 Differential spin density distribution in thegraphene with a six-fold ethylenic linkage optimized structure of double-layered graphene
structure.
with a six-fold ethylenic linkage structure.
Corresponding Author: H. Yokoi
Tel: +81-96-342-3727, Fax: +81-96-342-3710,
E-mail: yokoihr@kumamoto-u.ac.jp- 71 -

1P-28
Electronic structures of N-doped graphene nanoribbons with
H-terminated armchair edges○ Airi Yasuma, Mina Maruyama, and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8571, Japan
Electronic structures of graphene nanoribbons (GNRs) are known to be sensitive theirwidth and edge atomic arrangement: GNRs with armchair edges (AGNRs) aresemiconducting of which band gap asymptotically decreases with increasing their width,
while GNRs with zigzag edge (ZGNRs) are magnetic owing to the edge states. In ourprevious work, substitutional doping of N atoms with pyridinic structure in GNRs does
not affect their electronic structure near the Fermi level except the appearance of the
fully occupied dangling bond state of edge N atoms [1]. In the cases, N-doped AGNRs(N-AGNRs) and ZGNRs (N-ZGNRs) also possess semiconducting and magnetic
electronic structures which are quantitatively the same with those of the pristine GNRs.
However, on the other hand, hydrogenation of N atoms was found to modulate theelectronic structure of N-AGNRs and N-ZGNRs. Thus, in this work, we aim to givecomprehensive knowledge of the electronic structure of H-terminated N-AGNRs, byperforming the systematic calculations based on the density functional theory.
Figure 1 shows the electronic
structure of H-terminated NAGNR with the width of N=5 and30. For the wider N-AGNR, wefound degenerated less dispersive
states emerge in the energy gap
between dispersive bonding andantibonding π states. By checking
the squared wave function of thestates at Γ and X points, the states
are extended throughout the ribbon
at Γ point, while they are slightly
localized near the edge atomic siteand extended along the ribbon Fig.1 Electronic structures of H-terminated N-AGNR
direction. We also found that the with the widths of (a) N=5 and (b) N=30. The squaredfunction of the top of valence and the bottom of
bandwidth of these less dispersive wave
conduction bands at X point.
states gradually decreases withincreasing the ribbon width.
[1] A. Yasuma and S. Okada, Abstract of 53rd FNTG general symposium, 2P-27,
September(2017).

Corresponding Author: A. Yasuma (ayasuma@comas.frsc.tsukuba.ac.jp)- 72 -

1P-29Tuning of Kagome bands of 2D hydrocarbon networks by the molecularconformations
Y. Fujii, M. Maruyama, and S. Okada1
Graduate School of Pure and Applied Science, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki305-8571, Japan
2D honeycomb networks consisting of oligoacene and fourfold coordinated hydrocarbon
atoms possess peculiar electronic structures in their valence and conduction states. Becauseof the Kagome network of oligoacene connected through sp3 C atoms, the networks possess
the Kagome bands in their valence and conduction states, which consist of a flat dispersion
band and a Dirac cone, owing to the substantial wave function overlap between the adjacentoligoacene moieties. The band gap and width were found to depend on the oligoacene length,
while the Kagome band near the band edge are robust against the structural modulation. Here,
we studied another possible 2D honeycomb network consisting of polyphenylene which areconnected via sp3 hydrocarbon interconnects, using the density functional theory (Fig. 1).
As the case of the networks consisting of oligoacene, the polypenylene networks are also
semiconductor with the Kagome bands near the band edge. Furthermore, the network also
possesses the Dirac band in the valence states. By rotating the phenyl unit, the Kagome bandin the valence band edge shift downward while the Dirac band shift upward, resulting in thesubstantial electronic structure modulation near the valence band edge (Fig. 2).
30°

Fig.1

2D

honeycomb network

consistingof

polyphenylene and sp3 C atom

45°

60°

Fig.2 Electronic structure of a 2D network ofpolyphenylene connected via sp3 hydrocarbons.

Corresponding author: Y. Fujii and S. Okada (sokada@comas.frsc.tsukuba.ac.jp)- 73 -

1P-30Ultrafast photocarrier relaxation in monolayer graphene on SiC substrate
due to phonons in the buffer layer○Hirotaka Imaeda1, Takeshi Koyama1, Hideo Kishida1, Kenji Kawahara2, Hiroki Ago2,
Jianfeng Bao3, Tomoo Terasawa4, Wataru Norimatsu5, Michiko Kusunoki4
1

Department of Applied Physics, Nagoya University, Japan
2
Global Innovation Center, Kyushu University, Japan
3
College of Physics and Electronics Information, Inner Mongolia University for Nationalities,
China
4
Institute of Materials and Systems for Sustainability, Nagoya University, Japan
5
Department of Materials Chemistry, Nagoya University, Japan
Photoexcited carriers (photocarriers) in graphene are cooled with emission of opticalphonons via carrier-carrier scattering and carrier-optical phonon scattering [1]. When thetemperatures of carriers and optical phonons in graphene become same, carrier cooling slows
down because the cooling rate of carriers is limited by that of phonons (it is called hot phononbottleneck) [2]. Reducing hot phonon bottleneck leads to fast photocarrier relaxation,
resulting in enhancement of the properties for optical switches and saturable absorbers withgraphene [3,4]. It is expected that photocarrier relaxation in epitaxial graphene becomes fasterthan that in transferred graphene because of the shorter distance between graphene and thesubstrate, which will cause faster energy flow to the substrate. In this study, we investigatedthe photocarrier dynamics in epitaxial and transferred monolayer graphene on a SiC substrateby means of femtosecond time-resolved photoluminescence spectroscopy.
The epitaxial monolayer graphene used in this study was grown on a Si face of a
4H-SiC substrate by a thermal decomposition method [5] (hereafter we call this sample
epGr/buffer/SiC). The transferred monolayer graphene used in this study was first synthesizedby chemical vapor deposition method [6] and then transferred onto a buffer layer on the SiC
substrate (hereafter we call this sample trGr/buffer/SiC).
Measured photoluminescence decay in epGr/buffer/SiC at 0.7 eV is faster than that in
trGr/buffer/SiC. In other words, photocarrier relaxation in epGr/buffer/SiC is faster than thatin trGr/buffer/SiC. It is known that out-of-plane acoustic phonons at the M point in the buffer
layer strongly scatter carriers in graphene [7]. The faster relaxation of photocarriers in
epGr/buffer/SiC suggests that the interaction between the carriers in graphene and thephonons in the buffer layer for epGr/buffer/SiC is stronger than that for trGr/buffer/SiC,
which is presumably caused by a short separation between them.
[1] D. Brida et al. Nat. Commun. 4, 1987 (2013).
[2] L. Huang et al. Surf. Sci. 605, 1657-1661 (2011).
[3] T. Husan et al. Adv. Mater. 21, 3874-3899 (2009).
[4] Q. Bao et al. Adv. Funct. Mater. 19, 3077-3083 (2009).
[5] W. Norimatsu and M. Kusunoki, Phys. Chem. Chem. Phys. 16, 3501-3511 (2014).
[6] H. Ago et al. Appl. Phys. Express 6, 075101 (2013).
[7] J. Bao et al. Phys. Rev. Lett. 117, 205501 (2016).
Corresponding Author: T. Koyama
Tel: +81-52-789-4450, Fax: +81-52-789-4450,
E-mail: koyama@nuap.nagoya-u.ac.jp- 74 -

1P-31
Mechanism of photoresponse speed improvement
on MoS2-FET by Al2O3 buffer layer○Yuga Miyamoto, Daiki Yoshikawa, Kuniharu Takei, Takayuki Arie, Seiji Akita
Department of Physics and Electronics, Osaka Prefecture University,
Sakai 599-8531, Japan
It is known that MoS2 field effect transistor (FET) using SiO2 as an insulationg layer shows
persistent photocurrent (PPC) resulting in the limitation of photoresponse speed. Recently, we
have reported that the photoresponse speed of MoS2 FET was greatly improved by inserting 2
nm-thick Al2O3 buffer layer at the MoS2/SiO2 interface.[1] Here, we investigate the mechanismof the improvement of the photoresponse speed.
The Al2O3 buffer layer was deposited by atomic
1.2
layer deposition on n-type Si covered with SiO2 (300Light off
623 nm 860 W/cm
1nm). The MoS2 channel was prepared by the PDMS
w/o Al O
stamp method. The device was annealed at 120 °C in
0.8
: 1700s
vacuum for 12 h to improve the contact resistance.
0.6
Figure 1 shows a comparison of the normalized
0.4transient photoresponses of IDS under the irradiation of
Al O 2nm
0.2
light pulse (623 nm, 860 W/cm2) with or without 2
: 0.50s
0nm-thick Al2O3. The decay characteristic can be
-200
0
200
400
600
Time (s)expressed by exp(-(t/)), which is explained by thereleased electrons from traps formed by local potential Fig. 1 Photoresponses of MoS -FETs with2
fluctuations (RLPF) at the SiO2/MoS2 interface.[2] The or without Al2O3 on SiO2 gate insulator.
decay time constant  drastically decreased from 1700
102
to 0.5 s. Based on the RLPF model, the electrons are
2nd
well bounded around the positively charged traps and101
recombined at lower temperature. On the other hand,the bounded electrons are easily released at higher
100
temperature, which results in PPC. This is consistent
1stwith the experimental results of the temperature
Al2O3: 2 nm
2dependence of  shown in Fig. 2. Figure 3 shows the
10-1 623 nm, 860 W/cm
2.5
2.7
2.9
3.1
3.3
Al2O3 thickness dependence of decay time. The thinner-11000/T (K )Al2O3 enhances the electron trapping and2 Temperature dependence of decay
recombination around the positively charged traps as Fig.
rate.
well as low temperature. The thicker Al2O3 may
103
prevent the bound of the electrons around positively
102
charged trap, which results in the PPC. Thus, the Al2O3
layer controls the extrinsic origin of RLPF and101
enhances the neutralization process of trapped carrier,
1L
100
which results in the higher photoresponse speed.
2L
2

3

I(t)/I(0)23

Acknowledgements This work was partially supported by
KAKENHI Grant Number 16H00920, 16K14259, 16H06504 and
17H01040. Reference [1] Y. Miyamoto et al., submitted, [2] 1 Y.
C. Wu et al., Sci. Rep. 5, 11472 (2015). Corresponding Author:
Y. Miyamoto, Tel: +81-72-254- 9261, E-mail: miyamoto4@pe.osakafu-u.ac.jp- 75 -

Decay rate (s)Decay rate (s)

2

10-1

10-2 0
10

3L
4L

101

Al2O3 thickness (nm)102

Fig. 3 Al2O3 thickness dependence of
decay rate of photocurrent.

1P-32
Direct TEM/STEM imaging of 2D atomic layer crystals on SiO2
○Rong Xiang1, Akihito Kumamoto2, Yu Kobayashi3, Yasumitsu Miyata3, Yuichi Ikuhara2,
Shigeo Maruyama 1, 4
1

Department of Mechanical Engineering,The University of Tokyo, Tokyo 113-8656, Japan
2
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan3
Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
4
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8564, Japan
We recently proposed a method of TEM imaging catalyst and single-walled carbon
nanotubes (SWNTs) directly on a MEMS fabricated Si/SiO2 grid. The strength of this method
is that high temperature chemical vapor deposition (CVD) growth can be performed on thisgrid, and therefore SWNTs can be viewed in their original morphology without any post
treatment or transfer. More importantly, nano-sized catalytic particles, which were previously
difficult to characterize, become visible on SiO2 film with atomic resolution and in astatistical manner. With this method, we demonstrated that Cu can epitaxially anchore Co in
Co-Cu bimetallic system and promote growth of vertically aligned (VA-) SWNT with a
sub-nm diameter.[1] Sputtering prepared Co-W catalyst, which produces (12, 6) SWNTs witha selectivity over 70%,[2] were confirmed to be junctions of metallic W and Co6W6C.[3] We
also employed this method to characterize the zeolite support Fe-Co and on-substrate
momo-metallic Co for ultra-low temperature growth of random and VA-SWNT arrays.[4, 5]
In this study, we further extend this method to a new system: 2D materials. Single crystal,triangle-shaped WS2 flakes are directly synthesized on our Si/SiO2 grid by metal-organic
CVD (MOCVD). This strategy allows a convenient and transfer-free TEM/STEM
investigation of WS2 2D crystals. We confirm that mono- and multi-layer WS2 can be viewed
with an atomic resolution even through the thick SiO2 film (Fig. 1). As the crystals are kept inan “as-grown” form, we can trace their formation mechanism by viewing the edges andsurface of different layers. The atomic structure of the flakes center shows a different stacking
order, and suggests a dislocation-induced formation of rhombohedral multilayers. The edge
evolution and stability at high temperatures will also be discussed.

Figure 1 (a) Schematic of experimental setup; (b) (HR)TEM images of mono- and multi-layer WS2 flakes on
SiO2; STEM image of WS2 (c) mono-layer region and (d) dislocation at the rhombohedral stacking multi-layer
region.
[1] K. Cui et al. Nanoscale, (2016), 8-3, 1608.
[2] H. An et al. Nanoscale, (2016), 8, 14523[3] H. An et al. to be submitted (2018).

[4] B. Hou et al. Carbon, (2017), 119, 502[5] M. Liu et al. Phys. Rev. Appl. (2018)

Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 76 -

1P-33Two-dimensional van der Walls p-n heterostructures: Two-step CVD
growth and transport properties○Masanori Izumoto,1 Adha Sukma Aji,1 Hiroki Ago,1,21Interdisciplinary Graduate School of Engineering Sciences, Kyushu University
2
Global Innovation Center (GIC), Kyushu University

Van der Walls (vdW) heterostructures of semiconducting two-dimensional (2D) materials
have attracted a great interest, because integration of 2D materials with a wide variety ofelectronic structures offers new opportunities to realize unique and excellent physical properties.
In particular, 2D p-n heterojunctions with band alignment of type Ⅱ are useful for electric andphotonic devices, including p-n diodes, photodetectors, and tunneling field-effect transistors(TFETs) due to their staggered band structure [1-3]. Recently, the vdW heterostructures arefabricated by multiple transfer of exfoliated flakes. However, this process lacks scalability, andthe interface can be contaminated with residue introduced during the fabrication processes.
Here, we have synthesized vertically stacked heterostructures of p-type tin sulfide (SnS) andn-type molybdenum disulfide (MoS2) by two-step CVD method. An optical microscope image
shows that square-shaped SnS grains partially overlap with triangular MoS2 grains on SiO2
substrate (Fig. 1a). To evaluate the electrical properties of SnS-MoS2 p-n junctions, wefabricated back-gated FETs with Ni/Au as the electrodes (inset of Fig. 1b). Output curvespresented in Fig. 1b show a clear rectifying behavior, confirming the formation of p-n
heterojunction. The rectification ratio (ratio of forward and reverse bias current) is about 103
without given gate bias (Fig. 3c). We also evaluated the performance of SnS-MoS2 p-n junction
by calculating its ideality factor (n) from Shockley diode equation, I=Is(exp(qVD/nkBT)-1),
where Is is the saturation current, q is the elementary charge, kB is Boltzmann’s constant, T is
the temperature, and VD is the applied voltage. The ideal factor of our SnS-MoS2 device was
2.4. The ideal factors reported for 2D p-n junction devices are generally high (n=2.7 and 6.7)
due to high-density trap states. (a)
(b)
Ni/Au
However, our value is lower thanV = 0 to 60 V
MoS
these values, suggesting cleaner
SnS
interface obtained by CVD thanNi/Auheterostructures
madebyexfoliation method [4-6].
G

2[1] C.-H. Lee et al., Nat. Nanotechnol.,9, 979 (2014). [2] K. Zhang et al., ACS
Nano, 10, 3852 (2016). [3] T. Roy etal., Appl. Phys. Lett., 108, 83111(2016). [4] J-H. Ahn et al., Nano Lett.,
15, 3703 (2015). [5] Y. Deng et al.,ACS Nano, 8, 8292 (2014). [6] A. S.
Aji et al., Phys. Chem. Chem. Phys.,
20, 889 (2018).
Corresponding Author: Hiroki Ago
Tel and Fax: +81-92-583-8852
E-mail: h-ago@gic.kyushu-u.ac.jp

MoS2

SnS

(c)

VG = 0 to 60 V

20 μm

Figure 1. (a) Optical image of SnS-MoS2 heterostructures. Output curvesof SnS-MoS2 at different gate voltages in (b) linear and (c) semi-log scales.
The inset in (b) is an optical image of the SnS-MoS2 heterostructuredevice.

- 77 -

1P-34
Investigation on the influence of ball milling conditions to the morphology
of exfoliated hexagonal boron nitride nanosheets○Naoko Ogino, Gang Liu, Naoki Komatsu
Graduate School of Human and Environmental Studies, Kyoto University,
Sakyo-ku, Kyoto 606-8501, Japan
Hexagonal boron nitride (h-BN) nanosheet is known to have a similar 2D structure to grapheneand have been attracting extensive interest due to its unique physical and chemical properties.
Therefore, the efficient method to produce h-BN nanosheets has been widely investigated.
Recently we reported that bulk molybdenum disulfide (MoS2) and tungsten disulfide (WS2)
was exfoliated in the presence of sodium cholate through ball milling and resulting powder was
readily dispersed in water [1]. Herein, we report the application of this method to the exfoliationof bulk h-BN. In addition, the ball milling conditions were studied thoroughly to control the
thickness and size of the exfoliated h-BN nanosheet.
To prepare h-BN nanosheet and its aqueous dispersion, bulk
h-BN and sodium cholate were ball milled for 6 hours. The
resulting white powder (Fig. 1a) was readily dispersed in waterby shaking by hand for a few seconds and the stabledispersions were obtained by centrifugation at 1000 rpm and3000 rpm (3.78 mg/mL and 1.32 mg/mL, respectively, as
shown in Fig. 1b).
Although h-BN nanosheets were produced through ball
milling, the conditions were not optimized. Therefore, we
studied the relationship between the ball milling conditions
and h-BN nanosheet morphology. In the preliminary
experiments, the influence of ball size and milling duration on
the size and thickness of h-BN nanosheets was investigated; Fig. 1. Photographs of (a) ballthe bulk h-BN and sodium cholate were ball milled at different milled h-BN and (b) aqueous
dispersion after the centrifugation
durations and by using different ball sizes. After centrifugation at 1000 rpm (left) and 3000 rpm
of the aqueous dispersion, the resulting whitish supernatant (right).
was analyzed by AFM. From the result summarized in Fig. 2,
we found that 1) smaller balls grind and exfoliate
h-BN at a slower rate, 2) both size and thickness
are gradually reduced as the ball milling proceeds,
and 3) its size and thickness are maintained, onceh-BN nanosheets becomes thin and small enough.
We are going to make clear the influence of theother ball milling parameters such as speed, theamount of balls, the amount of starting material on
the size and thickness of h-BN nanosheets.
[1] G. Liu and N. Komatsu, ChemNanoMat. 2, 500(2016); ChemPhysChem, 17, 1557 (2016).

Corresponding Author: Naoki Komatsu
Tel, Fax: +81-75-753-6833,
Email: komatsu.naoki.7w@kyoto-u.ac.jp

Fig. 2. Chronological change of the thickness and thesize of h-BN nanosheets during ball milling.

- 78 -

1P-35Chemical doping of monolayer MoS2
by crown ether complex salts○Shintaro Yoshimura1, Yu Kobayashi1, Takahiko Endo1,
Yutaka Maniwa1, Yasumitsu Miyata1
1

Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan

Transition metal dichalcogenide (TMDC) atomic layers have attracted much attention
because of their unique two-dimensional structure and high electrical performance. For
electronics applications, it is essential to develop a sophisticated way to control carrier densityof materials. So far, several reports have used chemical doping through surface charge transfer
for carrier control of TMDCs [1, 2]. For further improvement of doping concentration and air
stability, it is highly desired to find a stable dopant for TMDCs. Recently, Nonoguchi et al.
have reported the electron doping for carbon nanotubes by using crown ether complex salts[3]. In this study, we have applied this technique to MoS2 monolayers (Fig.1a) and haveinvestigated their transport and optical properties.
Monolayer MoS2 single crystals were grown on SiO2/Si substrates by using halide assisted
chemical vapor deposition method [4]. For transport measurements, Au/Ni electrodes were
deposited on the crystals by photolithography (Fig.1b). For the doping, the samples were
immersed into methanol solution with 0.1~1 mol/L 15-Crown-5 and sodium chloride (NaCl).
We found that the doped MoS2 field-effect transistors (FETs) keep n-type behavior and havelower resistance compared with undoped samples (Fig.1c). These results suggest the electron
doping from crown ether complex salts to monolayer MoS2. In the presentation, the details of
optical and transport properties will be discussed.

Fig.1 (a) Schematic illustration of monolayer MoS2 and 15-Crown-5 with Na ion. (b) Optical microscope imageof a monolayer MoS2 FET and (c) Resistance-gate voltage curves of the device before and after the doping.
[1] S. Mouri et al., Nano Lett., 13, 5944 (2013).
[2] D. Kiriya et al., J. Am. Chem. Soc., 139, 7853 (2014).
[3] Y. Nonoguchi et al., Adv. Fanct. Mater., 26, 3021 (2016).
[4] S. Li et al., Appl. Mater. Today, 1, 60 (2015).
Corresponding Author: Yasumitsu Miyata, Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 79 -

1P-36
In vivo behaviors of oxygen-doped carbon nanotube imaging probes after
intravenous administration to mice
○Yoko Iizumi1, Tsukasa Takeuchi1,2, Masako Yudasaka3, Toshiya Okazaki1
1

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

Because of bright fluorescence and low toxicity, single-walled carbon nanotubes(SWCNTs) are promising candidates as in vivo fluorescent imaging probes. Moreover,
SWCNTs show fluorescence in long near-infrared (NIR-II) region, which is ideal forbiological imaging due to the low tissue auto-fluorescence and low absorption coefficient ofwater. For a practical use of the CNT probes, the influence on a living body and the in vivo
kinetics are necessary to be understood.
Recently, we found a very simple and efficient fabrication method of epoxide-type
oxygen-doped single walled carbon nanotubes (ep-SWCNTs), in which the SWCNT thin film
was exposed to ozone generated by a conventional UV ozone cleaner for a few minutes [1]. In
vivo imaging of mice was successfully demonstrated using ep-SWCNTs as NIR fluorescentagents [1]. In this study, time-course of NIR fluorescence images of mice were observed for along period (Figure 1) and the fluorescence intensities of liver and blood were analyzed(Figure 2). Further, the distribution of ep-SWCNT in liver tissue was clarified by Raman
mapping measurements. The influence of ep-SWCNT on metabolomics & lipidomics werealso analyzed. The details of in vivo kinetics of ep-SWCNT in mice body and the performanceof the ep-SWCNT as the imaging probes will be discussed in the presentation.

Figure 1. NIR fluorescence images of
ep-SWCNT administered mouse, changing withtime. Control: No ep-SWCNT injection.

Figure 2. Time-course of the ep-SWCNT
fluorescence intensities in blood and liver inmice.

[1] Y. Iizumi, M. Yudasaka, T. Takeuchi, T. Okazaki, The abstract of the 50th Fullerenes-Nanotubes-Graphene
General Symposium 2016, #1-10, page 22.
Corresponding Author: Toshiya Okazaki, E-mail: toshi.okazaki@aist.go.jp- 80 -

1P-37
Experimental System for Testing Dynamics of Carbon Nanomaterials
in Lymphatic Vessels○Chika Kuroda1, Kumiko Ajima2,3, Hisao Haniu2,4, Haruka Ishida4, Katsuya Ueda4,
Kaoru Aoki5, Hiroyuki Kato1, Naoto Saito2,4
1

Graduate School of Medicine, Shinshu University, Nagano 390-8621, Japan
Institute for Biomedical Sciences, Shinshu University, Nagano 390-8621, Japan
3
The Department of Innovation of Medical and Health Sciences Research, Shinshu University,
Nagano 390-8621
4
Graduate School of Science and Technology, Shinshu University, Nagano 390-8621
5
School of Medicine, Shinshu University, Nagano 390-8621
2

1. Introduction
Numerous questions exist on the evaluation of in vivo dynamics in the development of adrug delivery system (DDS) using carbon nanohorns (CNHs). To investigate the influence of
nanoparticles by means of an experimental system closely related to biological tissue, wehave devised a novel method employing living lymphatic vessels (LVs) as a passageway for
CNHs and other nanoparticles.
2. System
LVs excised from Wistar rats are isolated and then fixed using
glass micropipettes mounted in a chamber (Figure). The LV wall
monitoring system consists of video microscopy as well as an
automatic guiding-type LV diameter measuring device thatchronologically records the amplitude of spontaneous contractions.
Continuous perfusion of Krebs solution is used for the external
environment of the LVs. Inside the vessels, we induce spontaneouscontractions using hydrostatic pressure.

Figure. Isolated lymphatic vessel

3. Procedure
We verified normal functioning of the lymphatic endothelial and smooth muscle cells byadding an acetylcholine and thromboxane A2 receptor agonist to the Krebs solution and were
therefore able to construct a new isolated LV perfusion prototype system that could be used
for assessment based on changes in spontaneous contractions. After perfusion, LVs wereprepared for sectioning, histological evaluation of constituent cells, and evaluation ofadhesion and uptake of nanoparticles by transmission electron microscopy.
4. ExperimentCompared with the perfusion of a dispersant control, it was possible to measure the change
in LV diameter during the flow of CNHs and analyze the lymphatic tissue after particle
perfusion. This experimental system will enable evaluation of the dynamics and safety ofnanoparticles and fine particles considered for use as DDS carriers in LVs and other vessels.
Corresponding Author: N. Saito
Tel: +81-263-37-3547, Fax: +81-263-37-3549, E-mail: saitoko@shinshu-u.ac.jp- 81 -

1P-38Quantification of Single-Walled Carbon Nanotubes in Mouse Feces:
Phantom Experiments○Mitsuko Takahashi1, Yuko Okamatsu-Ogura2, Takeshi Tanaka1, Hiromichi Kataura1,
Masako Yudasaka1, 3
1

Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, 305-8565, Japan2
Department of Biomedical Sciences, Graduate School of Veterinary Medicine, Hokkaido
University, Sapporo 060-0818, Japan
3
Graduate School of Science and Technology, Meijo University, Nagoya 468-8502, Japan
Single-walled carbon nanotubes (CNTs) administered in mice are reportedly shown to be
excreted in feces and urines, where the CNTs in feces and urines are detected by Raman
scattering spectroscopy or transmission electron microscopy. These techniques are not suitable
for the quantification of the CNTs in feces and urines. In this context, the methods for the CNT
quantification in feces and urine should be developed, though it is not easy for the feces as it
contains a vast amount of various undigested foods in addition to the CNTs excreted via biliary
route. We show in this report a method for the extraction of CNTs from the mice feces, enabling
the quantification of CNTs in feces.
Phantom test specimen was prepared by dispersing feces of mice (no CNT administration) inalkaline solution and mixing it with CNTs. From this test specimen, the CNTs were separated
and concentrated by the interface precipitation method. In detail, mice feces were immersed in
an alkaline detergent (non-phosphoric acid type for removal of oil, fat, protein, hydrocarbon)
overnight and bath-sonicated for 3 hours at 25oC. The feces dispersion solutions (1 mL) was
mixed with sodium cholate-CNT aq. dispersion solutions (0.5 mg/mL, 0.01 mL), thus obtained
the phantom specimen. For the separation of CNTs from the phantom specimen, 30% KOH
solution (1 mL) were added and vigorously mixed and centrifuged. As a result, cotton likefloating objects with gray color were obtained at the upper area of the supernatant. The cotton
like objects were sucked (ca. 0.5 mL) and mixed with 30% KOH solution (0.5 mL), after that,
isopropanol (1 mL) was poured and well mixed. After the centrifugation, the dispersion solution
separated in two layers of KOH rich and isopropanol rich ones, and CNTs were precipitated at
the interface of the two layers. Finally, the precipitated CNTs were taken out and its opticalabsorption spectra were measured. The spectra were similar to that of the original one,presenting some peak shifts probably due to the solution pH changes. From the intensity of
CNT absorption peaks, the precipitated CNT quantity was estimated, which reasonably agreed
with the initial CNT quantity.
Corresponding Author: M. Yudasaka, E-mail: m-yudasaka@aist.go.jp- 82 -

2P-1
Understanding Efficiency Enhancement in Solution-Processed C60/C70
Mixed Fullerenes Perovskite Solar Cells○Haosheng Lin 1, Il Jeon 1, Shigeo Maruyama 1, Yutaka Matsuo, 1,2

1 Department of Mechanical Engineering,The University of Tokyo, Tokyo 113-8656, Japan

2 Department of Chemistry, The University of Science and Technology of China, Hefei, Anhui

230026, P. R. China

Organometal halide perovskite solar cells (PSCs) have emerged as next-generation thin-film
solar energy harvesters with high efficiency owing to a long exciton diffusion length, highabsorption coefficient and carrier mobility. Fullerenes, which have been used in organic solar
cells for more than two decades, opened up a new exciting perspective as an electrontransporting layer (ETL) in PSCs. Metal oxides ETLs, such as TiO2 and SnO2, have been used
in PSCs, but they result in large hysteresis originating from charge accumulation and charge
trap. Also, the high temperature process of metal oxide sintering limits flexible applications.
These problems can be avoided by using fullerenes as the ETL in PSCs. Their intrinsic low
chemical capacitance and high electron affinity realize PSCs with no hysteresis. In addition, thefullerenes are reported to act not only as ETLs but also as a passivation layer, reducing thesurface trap density of the perovskite grains. To date, high power conversion efficiency (PCEs)
were reported using fullerenes in which they were thermally deposited or over-coated on metaloxide. However, the thermal deposition is a costly process and the over-coating still relies on
metal oxide which requires high temperature process. Solution deposition of fullerene ispreferred over the thermal evaporation because of its simple and low cost process that allows
large-size application. Fullerene derivatives are widely used in organic solar cells due main to
the solubility issue. However, high concentration of fullerene solution is not necessary for PSCs,
and pristine fullerenes without chemical modification is a better option for the synthesis andpurification of fullerene derivatives are difficult and costly. Also, pristine fullerene films
possess higher mobility and conductivity than fullerene derivatives, for example [6,6]-phenylC61- butyric acid methyl ester (PCBM). Yet, the solution-processed fullerene PSCs do not
produce PCEs as high as the thermal-evaporated fullerene PSCs.
In this work, we investigate the reason behind lower performance of the solution-processed
fullerene PSCs over the thermal-evaporated fullerene PSCs, and provide an answer to obtaininga higher efficiency using the solution-processed fullerene. Crystalline domains and misaligned
packing with remnant solvents are found to be the key difference between those two films.
Based on this finding, we suppress the growth of crystalline domains in the solution-processed
fullerene ETLs by adding a small amount of C70 into a pool of C60, which improved the PSC
performance. The mixture of C60 and C70 (mixed fullerene) film was then dried in vacuum toremove the remaining solvent andenhance the fullerene packing,which further improve the PCE toeven exceed that of the thermalevaporated fullerene PSCs.
Corresponding Author: Y. Matsuo
Tel: + 81-3-5841-0978,
E-mail: matsuo@photon.t.u-tokyo.ac.jp

Figure 1. Illustration of our C60/C70 perovskite solar cell.

- 83 -

2P-2
Preparation of [C60]fullerene nanowhisker-cadmium sulfide nanoparticle
composites and their photocatalytic activity for degradationof Rhodamine B○Jeong Won Ko 1, Weon Bae Ko 1,2
1

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

Cadmium sulfide(CdS) nanoparticles were synthesized by cadmium sulfate(CdSO4),
sodium hydroxide(NaOH), and sodium sulfide(Na2S) dissolved into distilled water, and theresulting solution was refluxed for 5 h. The precipitate was collected by centrifugation andwas dried at 100 ℃ for 12 h to obtain solid state CdS nanoparticles. The CdS nanoparticles
solution was prepared by dissolving powdered CdS nanoparticles in an aqueous solution withsurfactant of polysorbate 20(Tween 20). [C60]Fullerene nanowhisker-CdS nanoparticle
composites were prepared by liquid-liquid interfacial precipitation(LLIP) method using
C60-saturated toluene, the CdS nanoparticles solution and isopropyl alcohol. The product of[C60]fullerene nanowhisker-CdS nanoparticle composites was characterized by X-ray
diffraction, scanning electron microscopy, Raman spectroscopy, and transmission electron
microscopy. Photocatalytic activity of [C60]fullerene nanowhisker-CdS nanoparticle
composites through degradation of Rhodamine B was confirmed by UV-vis spectroscopy.
00 min
30 min (Adsorption )35 min40 min45 min50 min55 min60 min65 min70 min-0.2

ln ( C/ C0 )

-0.4
-0.6
-0.8
-1
-1.2
0

30

35

40

45

50

55

60

65

70

Time(min)Fig.1 Kinetics study for Rhodamine B degradation with [C60]fullerene
nanowhisker- CdS nanoparticle composites at 254 nm.
[1] K. Miyazawa, J. Nanosci. Nanotechnol. 9, 41 (2009).
[2] Q. Y. Liu et al. Bull. Mater. Sci. 40 (7), 1329 (2017).
Corresponding Author: W. B. Ko
Tel: +82-2-3399-1700, Fax:, +82-2-979-5318,
E-mail: kowb@syu.ac.kr- 84 -

2P-3
Search for Missing Lu2@C80(Ih)○Ryoya Takai, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama
Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
In the previous symposium, Nakatori et al. reported the separation of novel Lumetallofullerenes, Lu2C78 and Lu2C80, as an anion form[1]. (Lu2C78)- was isolated, but(Lu2C80)- was obtained as a mixture of (Lu2C78)-. Because the UV-vis-NIR absorption
spectrum of (Lu2C78)- is very similar to those of (M2@C78(D3h))- (M=Y, Ce, etc.), it was
found that (Lu2C78)- is (Lu2@C78(D3h))-. For a mixture of (Lu2C80)-, and (Lu2C78)-, its
UV-vis-NIR absorption spectrum is also very similar to those of (M2@C78(D3h))- (M=Y, Ce,etc.), then it was suggested that the structure of (Lu2C80)- is a carbide type: (Lu2C2@C78(D3h))-,that is, (Lu2@C80(Ih))- was not found. In this work, we reexamined the separation procedureand tried to find (Lu2@C80(Ih))-.
Lu-metallofullerenes were produced and extracted by an almost identical method previously
reported[1]. They were extracted as an anion form, and the separation of obtained anions was
accomplished by the multistage ion-pair chromatography (IPC). The IPC chromatogram at thefirst stage is shown in Fig.1. The fractions A and B contain (Lu2C80)- and (Lu2C78)-,
respectively. By the successive two-stage IPC, (Lu2C80)- was almost isolated. The isolation
was confirmed by LD-TOF-MS. As shown in Fig. 2, the UV-vis-NIR absorption spectrum of(Lu2C80)- is featureless and different from those of (Lu2@C78(D3h))- and (Ce2@C80(Ih))-.
Therefore, the cage structure of (Lu2C80)- could not be determined. Moreover there is apossibility that (Lu2C80)- obtained here differs from previously reported one. In addition, the
ESR spectrum of (Lu2C80)- was measured at low temperature, but only the broad signal was
obtained.

Fig. 1 IPC chromatogram at the first stage.

Fig. 2 UV-vis-NIR absorption spectra of(Lu2@C 78(D3h))-, (Ce2@C80(Ih))- and (Lu 2C80)-.

[1] N. Nakatori, et al. The 52nd Fullerenes-Nanotubes-Graphene General Symposium 27 (2017).
Corresponding Author: Takeshi Kodama
Tell: +81-42-677-2530, Fax: +81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 85 -

2P-4
Chemical Reduction of Lithium-Ion-Encapsulated Fullerene
to Li@C60○Hiroshi Okada,1 Hiroshi Ueno,2 Yasuhiro Takabayashi,3 Takeshi Nakagawa,3Martina Vrankic,3 Shinobu Aoyagi,4 Ken Kokubo,5 Kimio Akiyama,6 Ioannis Arvanitidis,3,7
Kosmas Prassides,3 Yutaka Matsuo1,2,8
1Department of Mechanical Engineering, School of Engineering, The University of Tokyo,
Tokyo 113-8656, Japan. 2Department of Chemistry, Northeast Normal University, Changchun,
Jilin 130024, China. 3Advanced Institute for Materials Research (AIMR), Tohoku University,
Miyagi 980-8577, Japan. 4Dapartment of Information and Basic Science, Nagoya City
University, Nagoya 467-8501, Japan. 5Division of Applied Chemistry, Graduate School ofEngineering, Osaka University, Osaka 565-0871, Japan. 6Institute of Multidisciplinary
Research for Advanced Materials, Tohoku University, Miyagi 980-8577, Japan. 7 Departmentof Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece. 8University of
Science and Technology of China, Hefei, Anhui 230026, China.
Alkaline metal doping of C60 has been attracted much attention for its radical behavior,[1]super conductivity,[2] and chemical reactivities.[3] Neutral Li endohedral fullerene (Li@C60 ≡Li+@C60·–) is, so to speak, ultimate 1 to 1 doping of C60.
We have reported synthesis and isolation of Li@C60 by electrochemical reduction oflithium-ion-encapsulated fullerene Li+@C60 previously.[4] Its productivity was low (0.5–1 mg/ 2–3 days) to investigate further research.
For more productive method to synthesize Li@C60, chemical reduction was undertaken.
The reaction of [Li+@C60]TFSI– and decamethylferrocene FeCp*2 in dichloromethane gavebrown precipitate. A solution of the solid in o-dichlorobenzene showed NIR absorption peakcorresponding to Li@C60. XRD pattern for the solid indicated similarity with azafullerene
dimer (C59N)2,[5] which suggests the formation of (Li@C60)2 dimer in the solid state. In thispresentation, comparison with Li@C60 obtained from electrochemical reduction and ESR data
will be discussed.
TFSI−
Li +

[Li +@C 60]TFSI−+Fe− [FeCp*2]+TFSI−CH2Cl2FeCp*2
decamethylferrocene

Li +Li@C 60

E(Li +@C 60 /Li@C60) = −0.32 V E(FeCp* 2+ /FeCp*2) = −0.59 V
vs. FeCp 2+ /FeCp2
vs. FeCp 2+ /FeCp2

Li +Li@C 60-Li@C 60
dimer

References[1] P. Rapta et al., ChemPhysChem 2002, 3, 351–356.
[2] P. W. Stephens et al., Nature 1991, 351, 632–634.
[3] C. Caron et al., J. Am. Chem. Soc. 1993, 115, 8505–8506.
[4] H. Ueno et al., Chem. Sci. 2016, 7, 5770–5774.
[5] K. Prassides et al., Chem. Mater. 1996, 8, 2405–2408.
Corresponding Author: Y. Matsuo, Tel: +81-3-5841-0978, E-mail: matsuo@photon.t.u-tokyo.ac.jp- 86 -Li +2P-5
Thermoelectric Properties of Aligned Single-Wall Carbon Nanotube Films○Kengo Fukuhara1, Yota Ichinose1, Yohei Yomogida1, Weilu Gao2,
Junichiro Kono2, Kazuhiro Yanagi1
12Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan
Department of Electrical and Computer Engineering, Rice University, Texas 77005, USA

Since the seminal study by Hicks and Dresselhaus [1], it
has been of great importance to experimentally clarify
how the dimensionality of a material influences its
thermoelectric properties and whether reduced
dimensionality can enhance thermoelectric performance.
Single-wallcarbonnanotubes(SWCNTs)are
one-dimensional materials with sharp van Hove
singularities, and their thermoelectric properties have abeen intensively studied. However, we still do notunderstand the relationships between thermoelectricperformance, current, and thermal flow directions withrespect to the tube axis. For example, electricalconductivity along the axis is evidently higher than thatin the perpendicular direction, but it is not clear whether
thermoelectric performance in the parallel direction
should be higher than that in the perpendicular direction.
Since thermoelectric properties are strongly dependent on
the location of the Fermi level [2], it is crucial to evaluate
thermoelectric properties in particular current and thermal
flow directions as a function of Fermi level in order tocorrectly answer the above question.
b
In this study, as a first step, we investigated Seebeckcoefficients and electrical conductivities of aligned
SWCNT films as a function of Fermi level using
electrolyte gating techniques. We fabricated large-areafilms of aligned SWCNTs, a mixture of metallic andsemiconducting types, using the slow filtration method
reported by He et al. [3]. Then we investigated how thethermoelectric properties are influenced by current andthermal flow directions as a function of Fermi level.
We found that, although the electrical conductivity inthe direction parallel to the tube axis is higher than that in
the perpendicular direction, there is no significant Figure 1. Difference of (a) Seebeck
difference in their Seebeck coefficients between the coefficient and (b) electrical current
parallel and perpendicular directions. This fact indicates a between parallel and perpendicular
unique an-isotropy of thermoelectric properties in aligned directions along the tube axis as a
SWCNT films.
function of shift of the gate voltage.
References: [1] Hicks & Dresselhaus, PRB 47, 16631 (1993) [2] Yanagi et al., Nano Lett. 14, 6437 (2014)[3] He et al., Nat. Nanotechnol. 11, 1 (2016)
Corresponding Author: K. Yanagi, Tel: +81-42-677-2493,
E-mail: yanagi-kazuhiro@tmu.ac.jp- 87 -

2P-6
THz high harmonic generation from single wall carbon nanotubes○Hiroyuki Nishidome 1, Kohei Nagai 2, Yota Ichinose 1, Kengo Fukuhara 1, Junji Nozaki 1,
Junko Eda 1, Yohei Yomogida 1, Kazuhiro Yanagi 1, Koichiro Tanaka 2, 3
1

Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397, Japan2
Department of Physics, Kyoto University, Kyoto 606-8502, Japan
3
Institute for Integrated Cell-Material Sciences, Kyoto University, Kyoto 606-8501, Japan
Recent advancement of high power laser source in mid-infrared and terahertz (THz) region
enables us to investigate the extreme nonlinear optics in solids where the ground state of solid
becomes unstable due to strong light-matter interactions [1]. One of the unique phenomena in
the extreme nonlinear optics is high-harmonic generation (HHG). HHG has been intensively
studied in atomic gases, but observation of HHG phenomena in solid has long been difficult
because of unavoidable damage on samples by extremely strong laser light. But sinceobservation of HHG from ZnO [2] using THz light, HHG by intense THz light has been
observed in various kinds of materials such as semiconductor crystals and two dimensional
materials (graphene [3], MoS2 [4], etc.). Physical background of HHG in solid is supposed to
be fundamentally different from that in atomic gases, however, the essential feature of HHG
has still been elusive because of the presence of various physical parameters in solids affecting
nonlinear processes.
To tackle with this problem, we try toinvestigate HHG of single wall carbon
nanotubes (SWCNTs) for the following
reasons. SWCNTs have unique onedimensional structure, and are mechanicallyand chemically very stable for strong THz
light, and we can systematically change
electronic structure of SWCNTs from gapless metallic to semiconductor with different
band-gap. Therefore, we assumed we canclarify how the electronic structure of
SWCNTs influences HHG.
We prepared SWCNT thin films with asystematicallydifferentelectronic
structures, and investigated HHG using 60
THz laser. The type of SWCNTs is metal, Fig.1 HHG spectra from a series of SWCNTs withdifferent electronic structure by using 4800 nm
semiconductor (diameter is 1.4nm),(≈ 60 THz) laser.
semiconductor (diameter is 1.0nm), andsingle-chirality (6,5). The results are shownin Figure 1. We observed HHG from (6,5) and semi. (1.0 nm), and slight 5th HHG from semi.
(1.4 nm), but didn’t find any HHG from metal. These results indicate that electronic structureof samples strongly influences on HHG. In this poster, the physical background of HHG from
SWCNTs will be discussed.
[1] K. Tanaka, Hikaribussei kenkyukai tutorial (2017)[2] S. Ghimire et al., Nature Physics, 7, 138 (2010)[3] N. Yoshikawa et al., Science 356, 736 (2017)[4] H. Liu et al., Nature Physics, 13, 262 (2016)
Corresponding Author: K. Yanagi, Tel: +81-42-677-2494, E-mail: yanagi-kazuhiro@tmu.ac.jp- 88 -

2P-7
Growth of Individually-Suspended Single-Walled Carbon Nanotubes
toward Thermal Conductivity Measurement and Manipulation○Takumi Inaba1, 2, Ryuunosuke Shima1, 2, Maki Shimizu1, 2,
Tomohiro Yamaguchi2, Koji Ishibashi2, Yoshikazu Homma11

Department of Physics, Tokyo University of Science, Tokyo162-8601, Japan
2
Advanced Research Laboratory, RIKEN, Saitama 351-0198, Japan

Thermal management of integrated devices becomes more and more important as the Joule
heating per unit area increases. Single-walled carbon nanotubes (SWCNTs) attracted greatinterest in the field of thermo-mechanics possibly owing to their high thermal-conductivity or
one-dimensional unique structure.
In this presentation, the fabrication procedure of ultra-clean and individually-suspended
SWCNTs with electrode contacts, which is applicable to the thermal-conductivity
measurement of individual SWCNTs,1 will be introduced. Chirality assignment of such
samples can be achieved by photoluminescence measurement for the suspended segment. Leftand right images of Fig. 1 show typical scanning electron and atomic force microscopy(AFM) images of such samples, respectively. Cross sectional drawing is shown in the bottomof the right image. Two SWCNTs grown laterally and suspended on platinum electrodes andthe trench can be clearly observed in both images.
The observation of SWCNTs using AFM were successfully achieved on a trench withthe width below 500 nm. Availability of AFM for those samples enables us to dynamicallycontrol the physical properties of SWCNTs via van der Waals force exerts between suspended
SWCNTs and AFM tip. Some experimental studies have already shown that the electronic
conductivity of suspended carbon nanotubes decrease when the suspended region is pulled
down by AFM tip,2 while the thermal
conductivity of those does not.3
Robust thermal conductivity of
SWCNTs under bending was also
theoretically predicted.4 However, no
studies examined experimentally how
theelectronicandthermalconductivity of an individuallysuspended SWCNT changes when the
SWCNT is touched by AFM.
[1] E. Pop, et al., Nano Lett. 6, 96 (2006)[2] E. D. Minot, et al., Phys. Rev. Lett. 90,
156401 (2003)[3] C. W. Chang, et al., Appl. Phys. Lett. 99,
045901 (2007)[4] F. Nishimura, et al., Appl. Phys. Exp. 2,035003 (2009)
Corresponding Author: T. Inaba
E-mail: takumi.inaba.63@rs.tus.ac.jp

Fig. 1(Left) Scanning electron microscopy image and(Right)atomicforce

microscopy

image

of

two

individually-suspended SWCNTs. Scanned areas of two
images are the same and 5×5 μm. The schematics shown inthe bottom is the cross sectional image of scanned areas.

- 89 -

2P-8
Voltage generation by electrolyte droplet on carbon nanotube thin film:
Dependence of output power on carrier density○

Ryohei Nishi1, Shigeru Kishimoto1, Jun Hirotani1, Hiromichi Kataura2, and Yutaka Ohno1,3
1

Department of Electronics, Nagoya University
National Institute of Advanced Industrial Science and Technology
3
Institute of Materials and Systems for Sustainability, Nagoya University
2

Recently, it has been reported that the voltage generation is caused by the movement of theelectrolyte in contact with graphene or carbon nanotube (CNT) thin film [1-3]. These reports
show that it is possible to harvest electric energy from a small flow in the environment.
Previously, we have reported that the output power was enhanced by increasing the sheet
resistance of the CNT film on the basis of the equivalent circuit analysis. In this work, we havefurther increased the output power by changing the carrier density of the CNT thin film by thefield effect.
We used semiconducting CNTs separated bygelchromatography [5]. Semiconducting CNTs
dispersed in the surfactant solution were collected ona membrane filter by suction filtration, and transferred
on a Si/SiO2 substrate. Ag-paste electrodes wereformed at both ends of a rectangular (30 mm x 5 mm)
CNT thin film. The sheet resistance of the CNT thinfilm was 111.5 kΩ/sq. As shown in Fig. 1, a droplet of
NaCl aqueous solution (0.01 mol/l) was reciprocatedon the CNT film at 10 cm/s. The generated opencircuit voltage and short-circuit current were
measured by a semiconductor device parameter
analyzer (Agilent, B1500A). The carrier density ofFig. 1 Experimental setup.
the CNT thin film was changed by applying a
voltage to the substrate which was used as the
back-gate electrode.
Figure 2 shows the gate voltage dependenceof the output power. As the gate voltage
increased, the output power increased. Thissuggests a possibility of an enhancement of
output power by controlling carrier density.
Acknowledgment: This study was partially
supported by JST/CREST (JPMJCR16Q2).
[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] R. Nishi et. al., The 53rd Fullerenes-NanotubesGraphene General Symposium, 2P-13 (2016).
[5] T. Tanaka et al., Anal. Chem. 87, 9467-9472 (2015).
Corresponding Author: Y. Ohno
Phone & Fax: +81-52-789-5387
E-mail: yohno@nagoya-u.jp- 90 -

Fig. 2 Gate voltage dependence of
output power.

2P-9
Preparation of SWNT/PE Composites by Melt Blending○Koichi Utsugi2, Nao Otsuki2, Ryota Yamada2, Riku Ota2, Atsushi Onodera1, Masaru Sekido2
1

Advanced Course of Production System Engineering ,National Institute of Technology, Sendai College, Natori 981-1239, Japan2
Department of Materials Science and Engineering, National Institute of Technology, Sendai
College, Natori 981-1239, JapanDue to their combination of outstanding mechanical characters, extremely large interfacial
contact area, high aspect ratio, and low mass density CNTs are considered as the ideal reinforcement fillers for the nanocomposite materials. As CNT reinforced nanocomposites we have
prepared MWNT/Polyamide(PA)-6 composites and MWNT/Polyethylene(PE) composites bymelt blending methods. 35% increase of tensile strength has been observed in MWNT/PA-6
nanocomposites while no significant increase has been observed in MWNT/PE nanocomposites.
In this work, we focused on SWNT/PE composites and studied various SWNT/PE weight ratio
to increase tensile strength. SWNT/PE composites were prepared by melt blending at 220 °C,
screw speed of 100 rpm and a recycle time of 10 minutes. Weight ratio of SWNT/PE were1/100, 3/100, 5/100 and 10/100. Tensile strength of SWNT/PE composites were measured bytension tester (Dak System INC., UTB9052-TT).
In another work we have studied with MWNT/PE composites and observed that the tensile
strength of MWNT/HDPE(3/100) composites increased about 50%(Fig.1). We will discuss thedifference of SWNT and MWNT as a reinforcement filler with PE matrix.

Fig 1. Tensile strength of MWNT/HDPE and SWNT/HDPE composites.
Corresponding Author: A. Onodera
Tel: +81-22-381-0329, Fax: +81-22-381-0329
E-mail: a1601008@sendai-nct.jp- 91 -

2P-10Computational Study on Optimization of
Sheet Conductance of Carbon Nanotube Transparent Films○Masaaki Tsukuda1 and Takahiro Yamamoto1
1

Department of Electrical Engineering, Tokyo University of Science,Niijuku 6-3-1, Katsushika-ku, Tokyo 125-8585, Japan

 Carbon nanotube (CNT) thin films are expected as flexible transparent conductive films.
However, the details of electrical transport properties of CNT thin films have not been clarified
yet because network structures in CNT films are extremely complicated. To increase the electric
conductivity of CNT thin films with keeping their transparency, it is essential to understandrelation between the network structure with the nanotube densities, alignment, length anddiameter, and its electrical transport property. In this study, we thus theoretically explored how
nanotube alignment affects electrical transport properties of CNT thin films.
First, we generated two-dimensional random networks in a film with the fixed values of thefilm length of 𝐿𝐿 = 5 μm , the film width 𝑊𝑊 = 5 μm , and the nanotube length 𝑙𝑙CNT =500 nm (Fig1). When nanotubes are distributed, the angle between the axis of nanotube andx axis takes a uniformly random value between −𝜃𝜃max and 𝜃𝜃max . We then calculated the sheet
conductance by solving network equations [1, 2] for the CNT network by changing the valueof alignment angle 𝜃𝜃max for several different nanotube densities N. The obtained results are
summarized as follows.
1.

The more density increases, the more
sheet conductnace increases because
nanotubes can contact each other.

2.

When 𝜃𝜃max exceeds the thresholdvalue, the sheet conductance increases,
depending on the increase of 𝜃𝜃max .

3.
4.

There is a drop of the sheet conductanceat specific alignment angle.
The sheet conductance decreases at thehigh alignment angle region.

References:Fig1. Schematics of a random network
consisting of CNTs

[1] K. Ishizeki, K. Sasaoka, S. Konabe, S. Souma, and T. Yamamoto, Phys. Rev. B, 96, 035428 (2017).
[2] A. Buldum, J. Ping Lu, Phys. Rev. B 63, 161403(2001).
Corresponding Author: T. Yamamoto
Tel: +81-3-5876-1492
E-mail: takahiro@rs.tus.ac.jp- 92 -

2P-11
Production and Characterization of Double-wall Carbon Nanotubes
by High-temperature Pulsed-arc Discharge:
Dependence on Distance between Discharge Electrodes○Yuya Tanaka, Toshiki Sugai
Department of Chemistry, Toho University, Chiba 274-8510, Japan
Double wall carbon nanotubes (DW) can be used to various fields with their uniqueproperties. DW have been produced with highly graphitized homogeneous structures by a hightemperature pulsed-arc discharge (HTPAD)[1]. However the purity of DW realized by HTPAD
has been limited with impurities such as amorphous carbon and single wall carbon nanotubes(SW) even if various production parameters have been optimized[2]. Here we present anenhanced production of DW by controlling the distance between electrodes.
The details of HTPAD system were described elsewhere[1,2]. The pulsed-arc discharges
vaporized the electrodes with catalytic metals and produced nanotubes in Ar at the temperatureand the pressure of 1250 ℃ and 300 Torr, respectively. The distance between discharge
electrodes was controlled from 1 mm to 10 mm. The products were characterized by Raman
with 633 nm laser and TEM.
Fig. 1 shows the dependence on the distance of the ratio between G and D-bands of theRaman spectra of the products. The peak around 8 mm reveals that nanotubes were producedwith less amorphous carbon, which was also confirmed by the TEM observations. This distanceis suitable not only for less amorphous carbon but also for DW. Fig. 2 shows the production
ratio between DW and SW. At 8 mm the ratio was enhanced to 70 %, which is the best
selectivity ever achieved. Those results can be understood with the dependence of thetemperature and the carbon density distribution on the electrode distance recently observed witha steady-arc discharge[3].

Fig.1 G/D ratio at each electrodes distanceFig.2 Diameter distribution[1] T. Sugai et al., Nano Lett. 3, 769 (2003).
[2] Y. Hikichi et al. The 50th FNTG General Symposium. 1P-22.
[3] Feng Liang et al Mater. Res. Bull., 60 158–165 (2014)
Corresponding Author: T. Sugai Tel: 047-472-4406 E-mail: sugai@chem.sci.toho-u.ac.jp- 93 -

2P-12
Purification of SWNT-porous glass (PG) composite by using heat treatment○Tokinaru Matsuoka1, Yoshiki Hayashi1, Hiroshi Nagasawa2, Shinzo Suzuki1,
1

Department of Physics, Kyoto Sangyo University, Kyoto 603-8555, Japan
2
Kankyo Resilience Co. Ltd., Yokohama 240-8501, Japan

ACCVD technique has been widely used in the field of single-wall carbon nanotube(SWNT) growth, partly because that the ambient temperature suitable for the formation of
SWNTs is relatively lower (typically, less than 800°C), and the purity of SWNTs in as-grownmaterial is better than those obtained by other technique, e.g. arc-burning procedure.
In 2005, Aoki et al., reported about the formation of SWNTs in the porous glass (PG)
material by using ACCVD technique [1], where metal particles (e.g. Co particles) were
deposited on the PG material before ethanol was introduced as carbon source for making
SWNTs in the PG material. The advantage of using PG material is that, it is very easy to makeany kind of shape (rod, sheet.., etc.) made of PG, which implies that the as-grown SWNT-PG
complex itself is expected to be used as an optical or other kind of device [2].
In this presentation, the effect of heat treatment aimed for further purification of
SWNT-PG composite, is investigated. A preliminary search for thermal gravimetric (TG)
analysis combined with Raman spectroscopy shows the best condition for heat treatment of
the film made of mono-dispersed SWNT in solution, which indicates SWNT-PG composite
also can also be purified furthermore by similar heat treatment. Further experimental findings
are presented and discussed.
References:[1] Y. Aoki et al., Chem. Lett., 34, 562(2005).
[2] K. Nagao et al., Proceeding of the 46th fullerenes-nanotubes-graphene general symposium, 3P-15(2014).
Corresponding Author: Shinzo Suzuki
Tel: +81-75-705-1631, Fax: +81-75-705-1820,
E-mail: suzukish@cc.kyoto-su.ac.jp- 94 -

2P-13Growth simulation of chirality-assignable single-walled carbon nanotubes
with perfect cap structure by molecular dynamics○Hiroyuki Ukai 1, Ryo Yoshikawa 1, Shohei Chiashi 1, Shigeo Maruyama 1,2
1
2

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Energy NanoEngineering Laboratory, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8564, Japan

Single-walled carbon nanotube (SW-CNT) is an allotrope of carbon, and it is composed ofcap and side wall parts. Ideal CNT has exactly six 5-membered rings and no 7-membered ringin the cap part, and it has only 6-membered rings in the side wall part. If 7-membered rings orextra 5-membered rings exist, they are regarded as defects. Molecular dynamics (MD)simulation is used to simulate CNT growth. Although CNTs with chirality-assignable sidewall part were obtained in our former study [1,2], no ideal CNT has been obtained yet.
In this study, we tried to grow ideal CNTs by MD simulation, focusing the supply ratio ofcarbon atom. Cobalt was used as catalyst and CVD temperature was 1400 K. Carbon supply
ratio was 1.35 atom/ns at the beginning. After the formation of graphitic structure on the
catalyst surface and its lift-off, carbon supply frequency was gradually reduced from 1.35 to
0.0625 atom/ns. The cap part slightly continued to grow up and it became the ideal cap
structure with six 5-membered rings. And then, perfect side wall part, which was composed ofonly 6-membered rings, grew following the ideal cap, and ideal CNT with no defects was
obtained, as shown in Fig. 1.

(a)

(b)

(c)

Fig. 1. (a) Snapshot of MD simulation of ideal CNT growth. The chirality is (13, 5).
Calculation time is 1200 ns. (b) Development of the cap and (c) side wall part.
[1] K. Hisama et al. Proceedings of 46th FNTG general symposium, 2-1 (2014).
[2] R. Yoshikawa et al. Proceedings of 48th FNTG general symposium, 2P-22 (2015).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 95 -

2P-14
Stability of isomerized forms of photoisomerizable molecules complexedwith carbon nanotubes○Keisuke Hamajima1, Takeshi Koyama1, Takeshi Saito2, Hideo Kishida112Department of Applied Physics, Nagoya University, Nagoya 464-8603, Japan
National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8501,
Japan

Photoisomerizable molecules change their conformations (Figure 1) and absorption bands
by light absorption [1,2]. Application of photoisomerizable molecules to optical recording
materials is expected for high-speed data writing and has been studied for decades [3]. For
this application, it is needed that both forms before and after isomerization are stable.
However, there is a problem that the thermal stability of the isomerized form is low. For thisissue, we propose to compound photoisomerizable molecules with π conjugated system andcarbon nanotubes (CNTs). It is expected that both forms of the molecules are stabilized byvan der Waals forces between CNT wall and the molecules [4,5]. In this study, we usedazobenzene and spiopyran as the photoisomerizable molecules.
For preparation of the composites, we used a gas phase reaction [6]. The CNTs weredispersed in water using a surfactant after ring opening treatment. By vacuum filtration of thedispersion, the CNTs were formed into a thin film, and the film was transferred onto a quartz
substrate. Thereafter, the film and powder of the photoisomerizable molecules were sealed in
vacuum in a Pyrex tube and heated in a furnace.
The lifetime of cis form of azobenzene was evaluated by measuring the time dependenceof absorption change. The lifetime in the azobenzene-CNT composite is longer than that inorganic solution. Similarly, the lifetime of merocyanine form of spiropyran is long in thecomposite. In this study, the composites of photoisomerizable molecules and CNTs enhance
the thermal stability of the isomerized forms of the molecules.

Figure 1: Isomerization of a typical photoisomerizable molecule, azobenzene.
[1] G. Zimmerman et al. J. Am. Chem. Soc. 80, 3528 (1957).
[2] E. Fisher et al. J. Chem. Soc. 868, 4522 (1952).
[3] Z. F. Liu et al. Nature 347, 658 (1990).
[4] A. Setaro et al. Phys. Status Solidi B 251, 2356 (2014).
[5] P. Bluemmel et al. J. Phys.: Condens. Matter 24, 394005 (2012).
[6] H. Kataura et al. Synth. Met. 121, 1195 (2001).
Corresponding Author: Takeshi Koyama
Tel: +81-52-789-4450, Fax: +81-52-789-4450,
E-mail: koyama@nuap.nagoya-u.ac.jp- 96 -

2P-15
Energetics of perylene molecules encapsulated in carbon nanotubes○Yuya Nagasawa1, Takeshi Koyama2, and Susumu Okada1
1

Graduate school of Pure and Applied Sciences, University of Tsukuba
Tennodai, Tsukuba 305-8571, Japan2
Department of Applied Physics, Nagoya University, Chikusa, Nagoya 464-8603, Japan
Carbon nanotubes (CNTs) can encapsulate foreign atoms or molecules inside their tubularspacing where encapsulated guest materials form unusual structures. Polycyclic aromatichydrocarbons (PAHs), coronene and perylene, form not only a stacking columnar structure as
their bulk structure but also a lying double-decker structure in which the encapsulated PAHs
are parallelly arranged with respect to the CNT wall. Experiments reported that coronene andperylene can forms these two different molecular conformations inside CNTs depending on
the CNT species and the tiny difference in synthesis conditions [1~3]. However, it is still
unclear that physical and chemical mechanisms of multiple conformations of PAHs in CNTs.
Thus, the purpose of this work is to computationally investigate the detailed energetics ofperylene molecule encapsulated into a metallic (11,11)CNT and a semiconducting (19,0)CNT
for unraveling the physical and chemical mechanism of various metastable conformations of
PAH inside CNT experimentally observed. All calculations are based on the density
functional theory with the generalized gradient approximation in which the van der Waals
correction is taken into account.
Our first-principles total-energy calculations reveal thatcooperation between the encapsulation energy of a perylene
molecule in CNT and the intermolecular interaction renders
the potential energy landscape with double minimum
structures in terms of the molecular orientation to the CNT
wall. The lying molecular conformation energeticallycompetes with the stacking conformation with the tilting
angle of 70 degree with respect to the CNT axis (Fig. 1). A
standing conformation with respect to the CNT wall is theground state conformation for a semiconducting (19,0)CNT,
while a lying conformation is the ground state for a Fig. 1, Formation energy of perylene
metallic (11,11)CNT. In addition to these two chains inside CNTs as a function of
the tilting angle with respect to theconformations, perylene possess the other metastable tube axis. Circle and squares denotemolecular conformation of which energy is higher by 0.1 the energies for (11,11) and (19,0)eV per molecule than that of the lying and stacking CNTs, respectively.
conformations.
References[1] T. Okazaki et al. Angew. Chem. Int. Ed. 50, 4853 (2011).
[2] M. Fujihara et al. J. Phys. Chem. C 116, 15141 (2012).
[3] T. Koyama et al. unpublished.
Corresponding Author: Y. Nagasawa
E-mail: ynagasawa@comas.frsc.tsukuba.ac.jp- 97 -

2P-16
Local structure and properties of polycyclic aromatic hydrocarbon
molecule encapsulated in single-walled carbon nanotubes studied bymolecular dynamics simulations(II)○Ryo Nagai1, Yosuke Kataoka 2 and Hironori Ogata 1,2,3Dept. Chem. Sci. and Technol., Hosei University, Koganei, 184-8584, Japan
2
Graduate School of Sci. and Engin., Hosei University, Koganei, 184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, Koganei, 184-0003, Japan
1

Carbon nanotubes (CNTs) is one of the most promising material because of their superior
electronic, thermal and mechanical properties. One of the applications of Single-Walled
Carbon Nanotube (SWNTs) is their use as a template to synthesize novel nanostructurematerials. Synthesis of graphene nanoribbons (GNRs) encapsulated CNTs was reported byfusion reaction of encapsulated polycyclic aromatic hydrocarbon (PAH) molecules such as
coronene in CNTs as a one-dimensional reactor for fusion [1]. Columnar stacked coronene
molecules encapsulated in a single-walled carbon nanotubes(SWNTs) and their uniqueluminescence properties are reported[3-6]. In this study, molecular dynamics simulation was
performed to clarify the local structure and properties of various kinds of PAH molecules
encapsulated in SWNTs systematically. Figure 1. shows the snapshots of (a)coronene and (b)perylene encapsulated (10,10)SWNT at 298 K. We will report the detailed results ofsimulations several kinds of PAH molecules encapsulated SWNTs.
(a)

(b)

Fig.1: Snapshots of (a)coronene and (b)perylene encapsulated (10,10)SWNT at 298 K.
References:[1] A. V. Talyzin et al., Nano Lett.11(2011)4352-4356.
[2]Miho Fujihara, et al., J. Phys. Chem. C 116(2012)15141−15145.

[3]B. Botka et al., Phys. Status Solidi B 249(2012)2432–2435.
[4]Alexander I. Chernov et al., Phys. Status Solidi B 251(2014)2372–2377.
[5]Ilya V. Anoshkin et al., ChemPhysChem. 15(2014)1660 – 1665.
[6]Y. Sakane, et al., AIP ADVANCES 5 (2015)117113.
[7]Y.Joko, et al., Phys. Chem. Chem. Phys.19(2017)27704-27715.

Corresponding Author: H. Ogata
Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 98 -

2P-17
Fast Synthesis of Graphene in Three-Dimensional Reaction Field byChemical Vapor Deposition○Yukuya Nagai1, 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

Chemical vapor deposition (CVD) using copper (Cu) as catalyst has become themainstream for the synthesis of graphene [1]. Synthesis of 30-inch graphene films wasreported, however with a long process time including 30 min for CVD and 30 min forannealing [2]. Recently, graphene synthesis using “rolled-Cu” foils was reported with careful
pretreatments of electrochemical polishing, oxidation, and reduction of Cu foils and quick
CVD in 5–20 min using typical carbon source of CH4 [3]. The idea of rolled-Cu is excellent
because it can utilize the reactor volume and convert carbon source more efficiently than theconventional layout. However, it is essential to make processes simpler and time shorter forboth pretreatment and CVD toward practical production of graphene.
Here we used a roll of 5×30 cm2-sized Cu foils with simple pretreatment of immersion in
HNO3 aq. for 3 min followed by annealing during heating up the furnace to 975 ºC within 15
min. For the CVD, we used ethylene (C2H4), which is often used for the growth of carbon
nanotubes [4], as a more reactive carbon source than CH4. Within 90 s of CVD, a continuous
graphene film was obtained on the rolled-Cu (Fig. 1a), with a small discontinuous part at thebottom of the roll. Raman spectra of the film showed a sharp G-band peak with a strong
2D-band peak with a negligibly small D-band peak (Fig. 1b). The graphene transferred withthe size of ~1×1 cm2 to quartz glass substrates showed optical transmittances of 94.8−96.7%
and sheet resistances of 0.8−3.6 kΩ/sq without doping. Graphene synthesis using rolled-Cu
was compared with the conventional CVD using flat Cu foils.

Fig.1 Graphene obtained on rolled Cu. (a) SEM images. (b) Raman spectra.
[1] X. Li, et al., Science 324, 1312 (2009).
[2] S. Bae, et al., Nat. Nanotechnol. 5, 574 (2010).
[3] H. Wang, et al., Adv. Mater. 28, 8968 (2016).
[4] G. Eres, et al., J. Phys. Chem. B. 109, 16684 (2005).
Corresponding Author: S. Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 99 -

2P-18Characterization of size controlled graphite by O2 plasma etching and its
application to liquid phase exfoliation○Yasushi Ishiguro1, Genki Hirobe1, Kazuyuki Takai1,212Dept. of Chemical Science and Technology, Hosei University, Tokyo 184-8584, Japan
Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan

Development of a method for producing high-quality graphene in large scale is essential for
actual achievement of graphene applications. In this view point, the liquid-phase exfoliationof graphite have been investigated for graphene production due to its simple and scalable
process. Control of size and form of graphite in the liquid phase exfoliation process isinteresting in view of controlling the structure and properties of graphene, in spite of few
examples reported [1,2]. In this study, the size of highly oriented pyrolytic graphite (HOPG)
was controlled thorough plasma etching treatment using oxygen (O2) gas. The change in
geometry and electronic structure of the etched HOPG was investigated. In addition, theliquid phase exfoliation of graphite by sonication in organic solvent was examined.
The plasma etching treatment was carried out by using RIE-101iPH (ICP 150 W, Bias 50 W)
with cupper grid-shaped mask (Ԃ7.5 µm2). Raman mapping analysis was measured by
LabRAM HR Evolution (532 nm).
According to optical microscope image, the grid-shaped mask pattern is well transcribed on
the etched HOPG. Raman D-band intensity mapping is also agreement with the shape of theetched HOPG (Fig. 1). The Raman G-band position is almost remains even after etching,indicating the Fermi level does not change. Whereas, the D-band / G-band intensity ratio andthe FWHM of the G-band increases after the etching, suggesting the increment in carrier
scattering at defect and edges (Fig. 2).
References:[1] X. Lu et al., Appl. Phys. Lett., 75, 2, 193 (1999). [2] H. Fredriksson et al., Carbon, 47, 1335 (2009).

(a)Fig. 1. Optical microscope image of
HOPG. The inset shows the Raman
D-band intensity mapping.

(b)

(c)

Fig. 2. Raman peaks for graphite with / without etching. (a) G-band
position, (b) D-band / G-band intensity ratio and (c) FWHM of Gband.

- 100 -

2P-19Persistent photo conductivity in functionalized graphene nanoribbons○Hiroo Suzuki1, Toshiro Kaneko1, and Toshiaki Kato1,2
1

Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
2
JST-PRESTO

Graphene nanoribbons (GNRs) combine the unique electronic and spin properties ofgraphene with a transport gap that arises from quantum confinement and edge effects. This
makes them an attractive candidate material for the channels of next-generation transistors.
Up to now, we developed a novel method based on the advanced plasma CVD [1] withnanoscale Ni catalyst (Ni nanobar) for directly fabricating suspended GNRs devices [2].
Through the comparison of molecular dynamics simulation and phase diagram calculation
with the systematically obtained experimental results, the growth dynamics of GNRs in our
method has been also elucidated. By following this growth model, the yield of suspended
GNR growth can be drastically improved (~98%) and wafer-scale synthesis of 1,000,000
suspended GNRs has been realized [3].
Recently, we found that our suspended GNRs include unique optoelectrical features. The
current in GNR can be drastically changed by photo irradiation (Fig. 1a) and the current
change can be maintained for a long time (over 3 days) even after stopping the photo
irradiation, which is known as a persistent photoconductivity (PPC). To further improve the
PPC features such as sustain time and response speed, we attempted to elucidate the detailed
mechanism of PPC in GNR. The PPC was often
observed in samples which were kept in air for long
period (Fig. 1b). Functionalized GNRs by O2 plasma
irradiation were also showed clear PPC features. These
indicate that surface reaction of GNR device (GNR
itself or Ni electrode) with oxygen and related species
should be a key to cause PPC. To identify the surface
structures of GNR device after O2 plasmafunctionalization, detailed measurements were carriedout by X-ray photoelectron spectroscopy (XPS),
atomic force microscopy (AFM) (Fig. 1c-d), andoptical absorption spectroscopy. These measurements
reveal that the Ni electrode is converted to Ni(OH)2, Fig. 1: (a) Schematic image of GNR
and the interface between GNR and Ni(OH)2 can work array-FET under photo irradiation. (b)as a carrier trapping center, causing the PPC. These Comparison of photoresponce of pristine
results indicate the wafer-scale suspended GNRs array and functionalized suspended GNRs array.
(c) Low and (d) high magnification AFM
can be useful as a novel optical-memory device using image of O2 plasma irradiated Ni electrodes.
interface control between metal and suspended GNRs.
Inset in (d) shows height profile along thearrow.
[1] H. Suzuki, T. Kato and T. Kaneko, Plasma and Fusion Res. 9,1206079 (2014).
[2] T. Kato and R. Hatakeyama, Nature Nanotechnology 7, 651 (2012).
[3] H. Suzuki, T. Kaneko, Y. Shibuta, M. Ohno, Y. Maekawa and T. Kato, Nature Communications 7, 11797 (2016).
Corresponding Author: H. Suzuki
Tel: +81-22-795-7046
E-mail: suzuki12@ecei.tohoku.ac.jp- 101 -

2P-20First-Principles Calculation of Carrier Injection and Work Function inGraphene/Ferroelectrics Hybrid Material○Hikaru Horii1, Satoru Konabe1, Takahiro Yamamoto1
1

Faculty of Engineering, Tokyo University of Science, Tokyo 125-8585, Japan

Thermoelectric conversion is a key technology for recovering energy from waste heat. To
obtain high thermoelectric performance, it is required that both the electrical conductivity andthe Seebeck coefficient are high. Currently, graphene has attracted attention as a potential
material for exhibiting such performance. Thermoelectric performance has an optimum value
for a carrier density due to the trade-off relation between the conductivity and the Seebeckcoefficient. Nontheless the chemical doping, on the one hand, is difficult to control the carrier
density and also reduces the mobility of graphene. On the other hand, the electric field doping
uses an external electric source, which is not suitable for energy harvesting.
P
We thus propose a new carrier injection method
using spontaneous polarization of ferroelectricmaterials, which does not need an external electric
source. To validate this new method, we used firstprinciples calculation based on density functional
theory (DFT) and non-equilibrium Green's function
H
F(NEGF) method to theoretically analyze the carrierCC
injection to graphene by the spontaneous polarization
HFof Polyvinylidene Fluoride (PVDF). The calculation
Pmodels are shown in Fig. 1.
P
Our simulation shows that, when graphene contacts(b) negative(a) positive
a surface of positive (negative) polarization of PVDF,
Fig. 1 Two simulation models
electrons (holes) are injected into graphene and thosecarriers penetrate up to the third layer of multilayer graphene from the interface.
It is then necessary to optimize a carrier density to improve thermoelectric performance ofgraphene. The optimum value of the carrier density in monolayer graphene is known asapproximately 1012 cm-2 [1]. On the other hand, a carrier density of 7×1013 cm-2 was injected inour calculation. Therefore, it is possible to optimize thermoelectric performance by adjusting
the spontaneous polarization.
In addition, it is found that such carrier injection is caused by charge transfer from two layersof PVDF interface. Therefore, not only the field effect by the polarization but the difference of
the work function (WF) between PVDF and graphene surfaces must be considered. We thus
calculated WF of graphite and PVDF surfaces by NEGF method. Consequently, we found that
WF of graphite surface was 4.52 eV and that of hydrogen- and fluorine-terminated of PVDF
surface ware 1.68 eV and 8.81 eV, respectively. According to the WF difference, electrons(holes) are transferred from hydrogen (fluorine) of PVDF surface to graphene. These are inexcellent agreement with the results of the carrier injection.
[1] E. H. Hwang et al., Phys. Rev. B 80, 235415 (2009).
Corresponding Author: T. Yamamoto
Tel: +81-3-5876-1492
E-mail: takahiro@rs.tus.ac.jp- 102 -

2P-21First Principles Calculations of Electrical Structure of
Water Absorbed Graphene○Yusei Kioka1, Yuki Maekawa 2, Kenji Sasaoka 3, Takahiro Yamamoto 1,2,3
1

Department of Electrical Engineering, Tokyo University of Science, Tokyo, 125-8585, Japan2
Department of Liberal Arts, Tokyo University of Science, Tokyo, 125-8585, Japan
3
Water Frontier Science & Technology Research Center, RIST, Tokyo University of Science,
Tokyo, 125-8585

It has long been believed that water molecules cannot adsorb on graphene because it is ahydrophobic material. However, the existence of water layers on a graphene surface wastheoretically confirmed by performing classical molecular dynamics (MD) simulations[1,2]. These previous works suggested that water molecules spread out on the graphenesurface. Before these observations and simulations, Homma et al. discovered that similarwater molecular layers can exist around a carbon nanotube (CNT) by both photoluminescencemeasurements and classical MD simulations [3]. Although the structure of surface wateralong the surface normal on a graphene has been systematically and rigorously investigated,the microscopic structure of surface water parallel to a graphene surface has not yet been fully
characterized despite its importance. In addition, the influence of surface water on theelectronic states of a graphene remains to be elucidated yet.
In this study, we thus theoretically investigate the microscopic structure of surface water
on a free-standing graphene using classical MD simulations and the influence of surface wateron the electronic states of a graphene using ab initio calculations based on the density
functional theory. We found that the surface water exhibits a single or double layered
structures on graphene depending on the water vapor pressure. In particular, we clarify thetwo-dimensional hydrogen-bond network is formed on the water layers on graphene surface[4]. In addition, we found that there is no electron transfer between the surface water and thegraphene and that the low-energy electronic state near the Dirac points is unaffected by thesurface water.
[1] T. A. Ho and A. Striolo, J. Chem. Phys. 138, 054117 (2013).
[2] A. Akaishi, T. Yonemaru, and J. Nakamura, ACS Omega 2, 2184 (2017).
[3] Y. Homma, et al., Phys. Rev. Lett. 110, 157402 (2013).
[4] Y. Maekawa, K. Sasaoka, and T. Yamamoto, accepted in Jpn. J. Appl. Phys.
Corresponding Author: Takahiro Yamamoto,Tel&FAX: +81-3-5213-0990,
E-mail: takahiro@rs.tus.ac.jp- 103 -

2P-22
Defect introduction and hydrogen termination in Epitaxial graphene○Yoshinori Obata1, Kazuyuki Takai1, 2
1

Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
2
Research Center of Ion Beam Technology, Hosei University, Tokyo 184-0002, Japan

Although defect introduction is one of the important strategies to tune the properties ofgraphene [1], the number of defects is usually focused, and the chemical structure of defects
has been not well considered. Actually, vacancies in graphene become magnetic depending on
the number and position of termination hydrogen atoms [2]. In this study, atomic vacancies
are introduced into graphene, and its hydrogen termination is investigated in order to clarify
the chemical structure of vacancies in graphene.
Atomic vacancies were introduced into the surface of epitaxial graphene grown on SiC by Ar
ion beam sputtering at 100 eV after pre-annealing, followed by exposing to hydrogenmolecules, or air atmosphere. Raman spectroscopy and XPS were measured by LabRAM HR
Evolution (532 nm) and ESCA 5600, respectively.
The increase of XPS composition ratio of O to C indicates that defects and its termination
atoms gradually increase upon ion beam irradiation (Fig.1). The decrease of oxygen content
by 28% in average for hydrogen adsorption case compared to air adsorption one suggests thatthe termination atoms of defects are controlled by exposure gas after defect introduction into
graphene. Raman intensity ratio of D band to G band increases upon irradiation time for bothof adsorption conditions, but hydrogen adsorption shows a smaller D band as compared to the
air exposure condition (Fig.2). This reveals that the probability of carrier scattering might
depend on the chemical structure of the defect.
This project was supported by JSPS and RFBR under the Japan - Russia Research
Cooperative Program.
[1] Chen, et al., Nat. Phys. 7, 535 (2011). [2] G. Sunnardianto, et al, J. Adv. Sci. Eng. Med. 8, 421-426 (2016).

0.04

0.6
Air exposure

Air exposure

0.02

0.4
H2 adsorption

ID / IG

O/C

0.03

0.01
0

0

10
20
30
Irradiation time (sec)

H2 adsorption
0.2
0

40

Fig. 1 XPS O / C composition ratio

0

10
20
30
40
Irradiation time (sec)Fig. 2 Raman D / G intensities ratio- 104 -

2P-23
Diffusion of Li Atom on Graphene Sheet through V6 Vacancy:
First Principles Calculations○Kento Shiota, Takazumi Kawai
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai
305-8571, Japan
Since nano-carbon materials generally have large pore structures, they have attracted
much attention as a negative electrode material for Li ion batteries with high electrical
capacity. Recent studies show large battery capacities in comparison with theconventional graphite negative electrode. However, the atomic scale understanding of
the Li atom diffusion with some defects is still not clear, where such diffusion throughthe vacancy defect possibly affect the charge/discharge rate and also increase of thebattery capacity. Here, we investigated the adsorption and diffusion of Li atom on thegraphene with V6 defect with various H termination configurations at the defect edge
using first principles electronic state calculations. We calculated Li diffusion paththrough the defect toward backside of the graphene. For V6 terminated with 4 hydrogen,0.70eV is required for Li to diffuse through the defect as shown in Fig.1(a). Although
there is little diffusion barrier for clean edge (Fig.1(b)), Li atom could be trapped at the
deep potential hollow at the defect due to strong interaction between Li atom anddangling bond. We also investigated the Li atom diffusion through V6 defect when the
Li atoms are trapped at the defect site. We found that the trapped Li atoms reduce theattractive potential for a diffusing Li atom and enable the Li atom to diffuse by way of
exchange diffusion.

Reaction Coordinate

Reaction Coordinate

Fig.1 The variation of adsorption energy during diffusion through the V6 defect (a)terminated with 4 hydrogen atoms and(b) without termination.

- 105 -

2P-24Fabrication and Electrical Resistance Mesurement of Graphene
Nanoribbons on SiC (0001)○Masashi Horibe1, Seichiro Ito 1, Yuya Mizuno1, Chenxing Wang1, Hitoshi Nakahara1,
and Yahachi Saito1
1
Department of Quantum Engineering,The University of Nagoya, Nagoya 464-8603, Japan

SiC
(b)

Figure 1: Schematic diagrams of the dfferences
In a graphene nanoribbon structure on a SiC
substrate. (a) With a buffer layer. (b) Without abuffer layer.

30

0.8

78nm with buffer layer

25

0.6

64nm No buffer layer

20
15

0.4

10

0.2

5
0

0

5

Probe distance[μm]100Figure 2: Probe distance vs. resistancecharacteristics of graphene nanoribbons with andwithout buffer layer.

[1] Young-Woo Son et al., Phys. Rev. Lett. 97, 216803 (2006).
[2] Melinda Y. Han et al., Phys. Rev. Lett. 98, 206805 (2007).
[3] Chenxing Wang et al., e-J. Surf. Sci. Nanotech. 15, 13-18 (2017).
Corresponding Author: M. Horibe
Tel: +81-90-6646-7578,
E-mail: h.m030605@gmail.com- 106 -

Resistance(No buffer layer)[kΩ](a)Single layer graphene nanoribbon
Buffer layer

Resistance(With buffer layer)[kΩ]Graphene nanoribbon shows metalic and semiconducting properties depending on the
structure of edges and is expected to be applied to electronic devices[1,2]. Epitaxial graphene
nanoribbons with few defects can be fabricated by growth on a SiC substrate. However, since
the sides of a nanoribbon are connected to a buffer layer [Fig. 1 (a)], the effect of the edge is
not exhibited and it becomes an obstacle to device application. Therefore, we developed atechnology to etch the buffer layer connected to the sides of the nanoribbon selectively byheating the SiC substrate in a low pressure oxygen atmosphere [3] [Fig. 1 (b)]. In this study,
resistance measurement using the 4 probe method was peformed in order to investigate thedifference in electrical conduction characteristics depending on the presence or absence of thebuffer layer. In the resistance mesurement, the distance between the current application probes
was fixed at 15 μm, and the distance between the voltage measurement probes was changed.
Figure 2 shows probe distance vs. resistance characteristics of a nanoribbon with a widthof 78 nm with a buffer layer and a nanoribbon with a width of 64 nm without a buffer layer. In
both cases, the change of the resistance is small when the probe distance for the voltage
measurement is less than 4 μm, and for the larger distance it shows a rapid increase with theincrease of the distance. However, when the resistance values of nanoribbons with andwithout the buffer layer at the probe distance of 5 μm or more are compared with each other,
the nanoribbon with a buffer layer show remarkably small resistance value of 1/10 or less. Asa cause of this, we consider that when the buffer layer is oxygen-etched, defects are generated
in the buffer layer under the single-layer graphene, the current flowing through thenanoribbon may leak to the SiC substrate through the defects.

2P-25
Ion-beam irradiation into Graphene via sacrificial layers○Kosuke Nakamura1, Tomoaki Nishimura2, Kazuyuki Takai 1, 2
1Graduate School of Science and Engineering, Hosei University, Tokyo 184-8584, Japan
2
Research Center of Ion Beam Technology, Hosei University, Tokyo 184-8584, Japan

In view of defect-introduction and chemical modification, irradiation of ion-beam into
graphene is an interesting strategy. Indeed, hole doping to graphene was achieved by Au+ ion
irradiation into SiO2 / Si substrate supporting graphene [1]. In this study, we attempted to inject
Au ion directly to graphene, where the irradiation to bear graphene will cause damage, so asacrificial layer protecting graphene was designed and evaluated to prevent damaging beargraphene by irradiation using Raman spectroscopy (LabRAM HR), Rutherford Backscattering
Spectrometry (RBS), and XPS (ESCA5600).
At first we adopted the resist thin-film as a sacrificial layer, however Au ion irradiation haschanged the structure of the sacrificial layer, which become not removable without introducing
damage to graphene.
Next, ZnO and NaCl thin-film was applied for an alternative sacrificial layer, where it has
been confirmed ZnO can be removed by HCl, and NaCl can be removed by water even after
Au ion irradiation. However, Raman spectroscopy indicates ZnO deposition damages the top
most layer of graphene even before Au ion irradiation, where the degree of damage depends on
the thickness of graphene (Fig.1).
On the other hand, depositing NaCl for sacrificial layer gives little damage to graphene.
Irradiating Au ion to graphene covered with NaCl thin-film had successfully performed at 200
keV at dosage of 1 x 1013 ions / cm2. Raman spectroscopy of Au irradiated graphene with NaCl
thin-film as a sacrificial layer, shows clear G band near 1580 cm-1, indicating honeycomb lattice
structure of graphene remained even after irradiation (Fig.2). A significant Raman D band (1340
cm-1) and D’ band intensity (1620 cm-1) suggests a successful introduction of defects causing
intervalley scattering and intravalley scattering after irradiation, respectively.
This project was supported by JSPS and RFBR under the Japan - Russia Research
Cooperative Program.
[1] K. Nakamura, et al, FNTG symposium (2017)
Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002, E-mail: takai@hosei.ac.jp

3.0

Intensity (arb.unit)

ID / IG

2.0

1.0

0.0

D

G
After

D’

Before1234
Layer number
Fig. 1 Raman ID / IG ratio for Graphene
after ZnO deposition- 107 -

1280

1480
Raman Shift (cm-1)

1680

Fig. 2 Raman spectra of graphene
before / after irradiation

2P-26
Near-Field Electron-Photon Matrix Element of Monolayer Graphene
F.R. Pratama1, M. Shoufie Ukhtary1, R. Saito1
1
Department of Physics, Graduate School of Science, Tohoku University
In the typical experimental set-up of tip-enhanced Raman spectroscopy (TERS), a tip whose
radius around 10 nm is placed near the sample of the characterized material. The presence of tip
enhances the intensity of Raman signal [1] due to the localization of electric field around the tip that iscalled near-field [1, 2]. In this study, we calculate electric near-field enhancement around Au
parabolic tip of radius 10 nm irradiated by light with wavelength of 520 nm. Considering the quasistatic approximation which is valid when the spatial dimension of the object is much smaller than the
wavelegth of the light [3, 4] the calculation is performed by solving the Laplace’s equation
numerically with finite-difference method.
A monolayer graphene is placed 2 nm below the tip. We calculate the electron-photon matrix
element which describes the interaction of electrons with the near-field. The calculated results showthat the magnitude of near-field electron-photon matrix element is significantly higher (by the factor~4) compared to the case of the far-field, thus explaining the origin of the enhanced Raman intensity
in the interband transition between the initial and the final states in graphene TERS [5]. We also
found that while in the case of far-field spectroscopy the optical transition of electron from valence toconduction bands occurs vertically (with no change of electron’s wave vectors) [6], [7] the presenceof the near-field on the graphene plane induces the change of electron’s wave vectors in the opticaltransition.

References:[1] E.C. Le Ru & P.G. Etchegoin, Principles of Surface-Enhanced Raman Spectroscopy, Oxford:
Elsevier (2009).
[2] J. Cui et al., Laser Phys., 23, 076003 (2013).
[3] S.A. Maier, Plasmonics, New York: Springer (2007).
[4] J. Larsson, Am. J. Phys., 75 No. 3 (2007).
[5] M. Ghislandi et al., Appl. Spectrosc. Rev. 47, pp. 371-381 (2012).
[6] A. Grüneis et al., Phys. Rev. B 67, 165402 (2003).
[7] A. Ferreira et al., Phys. Rev. B 84, 235410 (2011).

- 108 -

2P-27
Valley relaxation in monolayer WSe2 studied by ultrafast spectroscopy○Keisuke Shinokita, Xiaofan Wang, Yuhei Miyauchi, Kazunari Matsuda
Institute of Advanced Energy, Kyoto University, Uji 611-0011, Japan[1] X. Xu et al., Nature Physics. 10, 343 (2014).
[2] A. Molina-Sánchez et al., Nano Letters 17, 4549
(2017).
Corresponding Author: K. Shinokita
Tel: +81-774-38-3465, FAX: +81-774-38-4567,
E-mail: shinokita.keisuke.4r@kyoto-u.ac.jp

Δ(δR/R)

Δ(δR/R)

δR/R

Atomically thin transition metal dichalcogenides (TMDs) possess novel physical properties
originating from the extreme low dimensionarity, making monolayer TMDs an ideal platform
to investigate fundamental physics in two-dimensional system. In addition, strong spin-orbit
interaction and no inversion symmetry endow monolayer TMDs with optical band gaps at the
K and K’ valleys with opposite spin configuration. This valley-spin locking results in theability to control valley degrees of freedom using circular polarized light [1]. Realization of
optoelectronic application based on manipulation of the valley-spin polarization of charged
carries, valleytronics, requires the understanding of valley depolarization process to achieve
long-lived valley polarization. Here we report valley relaxation dynamics of electron and holein monolayer TMDs.
We investigated ultrafast valley depolarization dynamics in monolayer WSe2 at 5 K using
circularly polarized pump-probe reflectivity spectroscopy. Figure 1(a) shows reflectancecontrast of monolayer WSe2 with A exciton and B exciton transition, as shown in Figure 1(b).
Figure 1(c) and (d) show time development of pump-probe differential reflectivity probed
around A and B exciton transition, respectively. The circularly polarized pump pulse with aphoton energy of 1.879 eV creates electron-hole pairs in one valley, inducing bleaching ofboth A and B exciton transition because of phase-space filling effect. Figure 1(c) shows A
excition transition has almost no circular polarization dependence of time-resolved reflectivity
change even at 0 ps, which is contrast with(b)(a) 0.1
circularly
polarized
time-integrated
C
0.0
photoluminescence (PL) measurement,
A
B
-0.1
A
V
B
where valley polarization of 40 % was
-0.2
-0.3
observed (not shown). It suggests that A
1.5
2.0
2.5
exciton transition in unexcited valley is
Energy (eV)K’K(d)
suppressed by either electron or hole equally
(c)
17 ps
17 ps
populated in the both valleys after ultrafast
0.06
8.5 psvalley relaxation, and the other carrier is
8.5 ps
0.15
0.05
preferentially populated in the excited valley.
4.3 ps
4.3 psFigure 1(d) also shows no valley dependence
0.04
2.1
ps
0.10
of differential reflectivity of B exciton
2.1 pstransition, identifying the equally populated
0.03
1 ps
carrier is electron. The combinations of
1 ps
0.05
0.02
0.5 pspump-probe and PL results conclude the0.5 psdissimilar intervalley scattering of electron
0 ps
0.01
0.00
and hole: The electron suffers ultrafast
0 ps
intervalley scattering and is populated
0.00
1.72 1.74 1.76 1.78
2.12
2.20
equally in K and K’ valleys, while the hole
Energy (eV)(eV)
Energy (eV)Energyis robust against intervalley scattering [2].
Fig.1: (a) Reflectance contrast of monolayer WSe2 on
Si/SiO2 substrate. (b) Energy level diagram showing A
and B exciton transition. Pump-probe differentialreflectivity for same (solid lines) and opposite (dottedlines) circular polarization of pump and probe pulses
as a function of delay time around A exciton (c) and B
exciton (d) transition.

- 109 -

2P-28Layer-by-layer growth of single crystalline transitional metal
dichalcogenide thin films by molecular beam epitaxy○Y. Wang1, M. Nakano1, Y. Kashiwabara1, Y. Iwasa1,21Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, JapanRIKEN Center for Emergent Matter Science (CEMS), Saitama 351-0198 Japan2

The discovery of graphene has opened research gate on two-dimensional (2D) materials
due to their novel properties from both fundamental and applied viewpoints. To date, main
approach of making 2D materials is “top-down” mechanical exfoliation, with sample typicallyseveral micrometer level, which is not enough for further research development. Therefore“bottom-up” synthesis, which means deposition by both physical and chemical ways on
substrates with millimeter-level size, is getting considerable attention.
We have been developing a growth process by molecular-beam epitaxy (MBE) for highquality transition-metal dichalcogenide (TMDC) thin films, which are composed of various
2D materials with properties ranging from semiconducting to metallic. Recently wesucceeded in establishing a versatile route to layer-by-layer epitaxial growth ofmillimeter-scale TMDC thin films on commercially-available insulating sapphire substrate by
MBE. Especially our semiconducting WSe2 and semi-metallic TiSe2 showed single
crystallinity evaluated by x-ray diffraction measurements both for out-of-plane and in-plane
directions. These films also show high performance in transport properties. The obtained
WSe2 epitaxial thin films exhibited ambipolar transistor operation upon electrolyte gatingwith clear Hall signals for hole-accumulation regime with the maximum mobility of about 3
cm2/Vs at T = 150 K[1], which was in the highest level reported for the first-generation MoS2
thin films grown by chemical-vapor deposition. Obtained 10-monolayer-thick TiSe2 epitaxial
thin films exhibited clear CDW transition at around T = 200 K with the sign change in theHall coefficient, which is consistent to the behavior reported for bulk TiSe2.
[1] M. Nakano, Y. Wang, Y. Kashiwabara, H. Matsuoka, and Y. Iwasa. Nano Letters, 17, 5595-5599 (2017)
Corresponding Author: Y.Wang Tel: 03-5841-6822 E-mail: wangyue@mp.t.u-tokyo.ac.jp

RHEED
e-gun

Heating system(b)

Al2O3 RHEED
monitor2H-WSe23

100

Int (arb.units)(a)Transfer
rod

10
3
10

2H-MoSe2

002

(c)

2H

002

0

10
3
10

2H-TaSe2002

2H-NbSe2

002

0

10
3
10

1T

0

10
3
10

1T-TiSe2

001

0

10

6

8

10 12 14 16 18 20
2(degree)

Figure 1: (a) Schematic image of MBE system in this project. (b) Out-of-plane XRD patterns of various
TMDC thin films with different structure. (c) Schematic image of two main polytypes in TMDC
material. In each column, upper figure shows atomic structure and lower figure shows top view.

- 110 -

2P-29Preparation and optical properties of suspended monolayer MoS2
○Kana Kojima1, Zhang Wenjin2, Yuhei Miyauchi2, Tetsuki Saito1, Yu Kobayashi1,
Takahiko Endo1, Kazunari Matsuda2, Yutaka Maniwa1, Yasumitsu Miyata1
1

Department of Physics, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
Institute of Advanced Energy, Kyoto University, Uji, 611-0011, JapanThe optical properties of transition metal dichalcogenide (TMDC) atomic layers haveattracted much attention because of their unique spin-valley coupling and excitonic opticalresponses. Recently, to probe their intrinsic properties, several groups have used thesuspended atomic layers to suppress the unintentional doping and lattice strain induced by
supporting substrates [1,2]. However, the conventional preparation processes usually require
multistep complex processes and lead to the contamination of polymer for transfer of atomic
layers. To solve these problems, we have developed a facile, clean method to prepare
suspended TMDCs and have investigated their optical properties.
MoS2 monolayers were grown on SiO2/Si substrates by chemical vapor deposition (CVD).
As-grown samples were separated from the substrates by putting a water droplet on thesubstrate, and then the monolayers floating on water were transferred onto another substratewith holes or trenches. We found that the suspended monolayers show brightphotoluminescence (PL) without broadening compared with samples on SiO2 (Fig.1a). The
PL peak also has high-energy shift for suspended samples due to the release of tensile strain
induced by supported substrates. Furthermore, time-resolved PL measurements reveals theincrease of PL lifetime from less than ~10 ps on SiO2 to 50 ps for the suspended samples,indicating the suppression of non-radiative decay process (Fig.1b). In the presentation, thedetails of sample preparation and optical properties of suspended monolayers will be
discussed.

Fig.1 (a) PL spectra and (b) time-resolved PL decay profiles of as-grown monolayer MoS2 on SiO2 andsuspended monolayer MoS2. In (b), Solid and dotted lines correspond to fitting results and instrument response
function (IRF), respectively.
[1] T. Kato, et al. ACS Nano, 10, 9687 (2016).
[2] W. Jin, et al. Phys. Rev. B, 91, 121409 (2015).
Corresponding Author: Y. Miyata, Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 111 -

2P-30Surface segregation of Ge crystal on metal thin films○Seiya Suzuki, Tatsurou Inaba, Masamichi Yoshimura
Graduate School of Engineering, Toyota Technological Institute, Nagoya 468-8511, Japan
Germanene is a single atomic sheet of germanium (Ge). Ge atoms in germanene arearranged in buckled honeycomb structure, which provides massless Dirac fermions andtunable band gap [1]. Although germanene can be epitaxially grown on single crystal surfaceof metals such as gold (Au), aluminum, and platinum in ultra-high vacuum [2], the costly
growth method limits practical electronic applications. Thus, a practical large scale growth ofgermanene is desirable.
To achieve large scale germanene growth, we have studied surface segregation of Ge
crystal on metal thin films. First, we deposited Ge following by Au (or Au/Ag) thin film on
crystalline Si with thin layer oxide through piranha etching. After that, the samples wereannealed under medium vacuum condition (~2 Pa). Then, the sample surface wascharacterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force
microscopy (AFM), and tip-enhanced Raman spectroscopy (TERS).
Figure 1 shows Raman spectra of Au/Ge/Si before~299 cmand after heating at 350 ºC for 1 min. A sharp peak .
u-1
was observed at ~299 cm after heating, indicating .
athat Ge was segregated and crystallized on the sample yt
350 °C, 1 minssurface. Figure 2(a) shows an AFM image of the inesample surface after heating. Aggregated particles tnIRTwith the height of 5 ~ 10 nm are observed. Figure 2(b)shows a TERS map at ~300 cm-1, taken at the same
area in Fig. 2(a). Figure 2(c) shows three()
representative Raman spectra in Fig. 2(b). The results
Fig. 1. Raman spectra of Au/Ge/Si
indicate that crystallization of Ge is occurred aroundbefore and after heating
the aggregated particles. In addition, we measured(b)
3
Au/Ge/Si samples before and after heating by XPS. (a)The XPS results indicate Ge was segregated and Ge
2oxide (GeOx) was formed even at room temperature,
which also potentially prevents the germanene
200 nmformation. To suppress GeOx formation at room1
temperature, we used Au/Ag where Ag has higher
AFM
TERS
solubility of Ge compared to Au. By using Au/Ag(c)instead of Au, the Ge segregation at room temperatureGe.
u
was completely suppressed, which may lead3.
Siagermanene formation by the segregation method.
y
(

)

-1

(

)

0
9
3

0
6
3
1
03m
3c
t
0f
i
0h
3s
0n
7a
2m
a
0R
4
2
0
1
2

t
i
s
n
e
t
n
I

1
2

0
0
8
1
0
0
5
1
01
02m
1c
t
f
0i
0h
9s
n
a
0m
0a
6R

0
0
3

[1] Z. Ni et al., Chem. Nano Lett. 12, 113 (2012).
[2] J. Zhuang et al., ACS Nano 11, 3553 (2017).
Corresponding Author: S. Suzuki
Tel: +81-52-809-1852
E-mail: seiya09417@gmail.com()

Fig. 2. (a) AFM image, (b) TERS map at~300 cm-1 of Au/Ge/Si after heating, and(c) Representative Raman spectra in (b).

- 112 -

2P-31
Photoluminescence properties of twisted bilayertransition metal dichalcogenides○Masafumi Shimasaki1, Wenjin Zhang1, Xiaofan Wang1, Takashi Taniguchi2, Kenji
Watanabe2, Kazunari Matsuda1, and Yuhei Miyauchi1
12Institute of Advanced Energy, Kyoto University, Kyoto 611-0011, Japan
National Institute for Materials Science, Tsukuba, Ibaraki 305-0044, Japan

Atomically-thin transition metal dichalcogenides (TMDCs, MX2, M=Mo, W and X = S,Se, etc.), which are two dimensional semiconductors with a few atom thicknesses, havebeen attracting much attention due to their distinctive electronic and optical properties
promising for future optoelectronic applications. Monolayers of TMDCs are direct gap
semiconductors [1] that exhibit sharp optical absorption and luminescence peaks arisingfrom excitons with binding energy of more than a few hundred meV. Recently, theirheterostructures consisting of various kinds of monolayer TMDCs stacked on each otherhave intensively studied because the stacking leads to completely new optical properties[2,3]. In contrast to the hetero-bilayers, however, the effect of the stacking of the same
TMDC monolayers on their optical and excitonic properties still remains unclear.
In this study, we examined photoluminescence (PL) properties of twisted bilayer
MoSe2, which are artificially structured homo-bilayer materials fabricated by stacking
two MoSe2 monolayers on each other with an arbitral twist angle of the honeycomb
lattice directions between the layers. This stacking retains the direct gap nature of eachmonolayer in the twisted bilayer, and enables to study the effect of the interactions
between the two extremely close-set direct gap semiconductors. Interestingly, thetwisted bilayer sample showed a few to several times higher PL intensity and less PL
nonlinearity than those observed in the monolayer samples. We will discuss the detailed
procedure of these experiments and the possible mechanism for the observed
phenomena.
[1] K. F. Mak, C. Lee, J. Hone, J. Shan, and T. F. Heinz, Phys. Rev. Lett. 105, 136805 (2010).
[2] A. K. Geim, and I. V. Grigorieva, Nature 499, 419 (2013).
[3] S. Mouri, W. Zhang, D. Kozawa, Y. Miyauchi, G. Eda, and K. Matsuda, Nanoscale 9, 6674 (2017).
Corresponding Author: Y. Miyauchi
Tel: 81-774-38-3463, Fax: +81-774-38- 3467,
E-mail: miyauchi@iae.kyoto-u.ac.jp- 113 -

2P-32Monolayer WSe2-MoS2 Lateral Heterojunction Light-Emitting Diodes○Jiang Pu 1, Ming-Yang Li 2, Jing-Kai Huang 2, Yuhei Miyauchi 3, Kazunari Matsuda 3
Lain-Jong Li 2, and Taishi Takenobu 1
1

2

Department of Applied Physics, Nagoya Univ., Nagoya 464-8603, Japan
Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
3
Institute of Advanced Energy, Kyoto Univ., Kyoto 611-0011, Japan

Recent advances of heterostructure fabrications based on transition metal dichalcogenides(TMDCs) yield atomically regulated interfaces due to their intrinsically passivated surfaces,
allowing us to explore unusual electrical and optical phenomena and to make outstanding
improvements to device performance [1]. Although, numerous experimental demonstrationsof vertically stacked heterostructures have been realized using scotch-tape approach, theinvestigation of physical properties of lateral heterojunctions, in which dissimilar TMDCs are
artificially stitched together, has been still limited. In particular, lateral heterojunctions areeasier to tune band offset for designing p-n junction because of their spatial separation.
Moreover, compared with manual transfer of vertical heterostructures, lateral heterojunctions
is ideally adopted for the scalable approach of chemical vapor deposition (CVD) for creating
atomically sharp heterojunctions [2]. Here, we developed a scalable fabrication process for
WSe2-MoS2 lateral heterojunction films and firstly realized its light-emitting device arrays.
WSe2-MoS2 lateral heterojunction films were synthesized by two-step CVD process. As
shown in Fig. 1, W electrodes were firstly patterned for the subsequent location-selective
growth of WSe2 monolayers. And then, epitaxial growth of MoS2 monolayers was performed
to form heterojunctions. Finally, additional Mo pads were deposited, followed by spin-coating
ion gel films for building light-emitting device [3,4]. As applying voltage, holes (electrons)
are injected and accumulated in WSe2 (MoS2) mediatedby electric double layers to form p-n junction (Fig.1).
Figure 2 obviously indicates electroluminescence (EL)image generating along junction interface. Interestingly,
the comparison between photoluminescence (PL) and EL
spectra shown in Fig. 3 revealed inconsistent behavior.
Although both contributions of WSe2 and MoS2 wereobserved in PL, EL only showed MoS2 luminescence.
This suggests band structure evolution at junction
interface; thus we will discuss this physical picture basedon recent scanning tunneling spectroscopy study.
Importantly, we firstly realized lateral heterojunction
light-emitting devices and achieved the improvements of
their external quantum efficiency compared to reported
homojunction devices, providing a new platform forhigh-performance optoelectronic device applications.
[1] K. S. Novoselov et al., Science 353, 461 (2016).
[2] M.-Y. Li et al., Science 349, 524 (2015).
[3] J. Pu, et al. Adv. Mater. 29, 1606918 (2017).
[4] M.-Y. Li, J. Pu, et al. Adv. Func. Mater. under review.
Corresponding Author: J. Pu, T. Takenobu
Tel/Fax: +81-52-789-5165,
E-mail: jiang.pu@ngoya-u.jp, takenobu@nagoya-u.jp- 114 -

2P-33
Absorption spectra from exciton effect of atomic layer materials○ Toshiya Shirakura1, Yuki Tatsumi1, Riichiro Saito1
1

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

In this work, we discuss the absorption of light considering exciton effect with spin orbit coupling inatomic layer materials. We focus on monolayer molybdenum diselenium (MoSe2). MoSe2 is one of thesemiconducting transition metal dichalcogenides (TMD) which have interesting optical properties.
When an electron in the valence band obtain incident light, the electron is excited to the conduction
band. At the same time, exciton is generated by Coulomb interaction from electron in the conduction
band and hole in the valence band. In order to make exciton wave function, the electron and hole wave
functions in the different states are mixed to each other. Then, we can make exciton wave function thatis localized in the real space. Previous works show that the so-called A peak and B peak appear in
TMD from spin orbit coupling around the K and K’ points [1].
Also, peak positions shift from bandgap to low energy region
hBN
MoSe2
which matches to binding energy of exciton. Then, also show
MoS2
MoTe2
how important relative permittivity affect to absorption
spectra, reproducing the previous work [2].
We calculate the absorption spectra by using Wannier function(WF) which is based on tight binding model. Therefore wedevelop a code of optical absorption spectra with exciton andspin orbit coupling effect for WF that is calculated by
Wannier90 and used it for numerical calculation.
In this work, we numerically calculate Coulomb interaction
as a function of relative permittivity. We consider not only
the direct Coulomb interaction between the bottom
conduction band of electron and the top valence band of hole
but also the Coulomb repulsion between the bottom
conduction band of electron and the valence band which is
occupied by all electrons except for the top valence band thatis called self-energy. We also show absorption spectra withexciton and spin orbit coupling effect.
[1] W. G. Gerber, et al., 2D Materials. 2, 4 (2015).
[2] J. Z. Liu, et al., Phys. Rev. Let. 118, 266401 (2017).
[3] W. Zi-Wu, et al., Journal of Physics D: 50.47 (2017): 475306.
Corresponding Author: T. Shirakura,
E-mail: shirakura@flex.phys.tohoku.ac.jp- 115 -

Fig.1 electron-electron interaction whichcomes from self-energy as a function ofrelative permittivity with different
materials. Coulomb interaction seem tochange invers proportional to relative
permittivity [3].

hBN
MoS2

MoSe2
MoTe2

Fig.2 electron-electron interaction whichcomes from the direct exchangeinteraction as a function of relative
permittivity with different materials.
Minus sign means that these materials
have a property as diamagnetism [3].

2P-34
Aqueous dispersion of carbon materials inspired by Japanese Ink II○Kaito Ishido, Kazuki Nakamura, Koki Taniyama, Kento Hujita, Junpei Hayakawa*
Science Team, Nara Prefectural Seiwaseiryo Senior High School, Sango 636-0813, Japan
Japanese ink have been made from susu(soot) andnikawa(glue) unceasingly from Nara Period. It is wellknown that ink is a protective carbon colloid preparedfrom soot and glue.
Solubilization or dispersion of carbon materials suchas, fullerenes, carbon nanotubes and graphene in water
is of great importance because of interesting biologicalFig.1: Aquepus dispersion of carbon
application1~3.
materials utlitizing a glue
On these backgrounds, we studied
aqueous dispersion of carbon
materials, such as [60]fullerene,graphite, graphene and carbon
nanotubes, utilizing a glue4 (Fig. 1).
we considered several kinds ofdispersant to clarify the mechanismof dispersion of carbon materials to Table 1: Examination of dispersant
water (Table 1). First, we examinedan agar which is a gelling agent similar to glue, as a dispersant. In the case of using agar which
is a polysaccharide, not a black colloidal solution but a colorless transparent liquid was obtained(entry 2). On the other hand, in the case of cook gelatin (type-B gelatin), type-A gelatin, andcollagen peptide with molecular weight of about several thousand as a dispersant, black
dispersion was obtained. After centrifugation, we measured the particle size and zeta potentials
indicating colloidal stability. When cook gelatin was used, a result similar to glue was obtained
although the particle diameter was somewhat larger (entry 3). When type-A gelatin was added,
the zeta potential was positively charged and the particle diameter was polydispersed (entry 4).
In the case of using collagen peptide, the zeta potential was low, the particle diameter was
smaller than when glue was used (entry 5). From these results, it can be expected that proteins
with some molecular weight are effective for dispersion of carbon materials in water,
irrespective of whether the dispersed material is charged to positive or negative.
Next, we conducted food analysis and amino acid composition analysis of a glue. The
component of the glue was found to be 84.4% protein, 11.7% moisture, 2.8% saccharide. Aminoacid composition analysis revealed that the glue is a glycine - rich protein that closely resembles
gelatin.
Although details of the mechanism of dispersion with glue have not been elucidated, it was
found that proteins with some molecular weight are effective.

[1] S. Deguchi et al. Sci. Rep, 3, 2094 (2013)[2] M. EstiliS, A. Khademhosseinia et al. Nanoscale, 7, 6436 (2015)[3] N. Nakashima and T. Shiraki. Nippon Gomu Kyoukaishi, 1, 3 (2016).
[4] The 53rd Fullerenes-Nanotubes-Graphene General Symposium, 1-14 (2017)
Corresponding Author: Junpei Hayakawa
Tel: +81- 0745-72-4101, Fax: +81-0745-32-9819
E-mail: hayakawa.j@nps.ed.jp- 116 -

2P-35
Applicability of DLS to Diluted Nanodiamond Colloidal Solutions○Takumi Sato1, Toshihiko Tanaka1,3, Yasuhiro F. Miura2, Tetsuya Aoyama3, Eiji Osawa4
1

Department of Chemistry and Biochemistry, National Institute of Technology, Fukushima
College, 30 Aza-nagao, Tairakamiarakawa, Iwaki, Fukushima, 970-8034, Japan
2
Hamamatsu University School of Medicine, 1-20-1 Handayama,
Higashi-ku, Hamamatsu city, Shizuoka, 431-3192, Japan
3
Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan
4
Nano Carbon Research Institute Ltd., Asama Research Extension Center,
Shinshu University, 3-15-1 Tokida, Ueda, Nagano, 386-8567 Japan
We previously reported that ultrathin rectangular nanosheets were precipitated on thesurface of a 0.005% nanodiamond (ND) colloidal solution carrying a Langmuir monolayer ofa fatty acid.1 The degree of diluting aggregation2 in the solution determines what are theirstarting particles and their thickness should depend on the degree.
However, dynamic light scattering (DLS) measurements have intrinsic difficulties when
they are applied to such diluted ND solutions and we must be cautious there. ND aggregatedparticles are usually 2.6 ~ 100 nm in size for such cases, thus their Rayleigh scattering taking
place there. Rayleigh scattering intensity is proportional to the sixth power of a particle size(the third power of a particle size per volume). Hence, even if a trace of aggregation
contaminates a main component in a single nanometer range, the intensity from contaminants
often exceeds significantly that from the main component. The size resolution from a fitted
autocorrelation function is quite limited in such cases and main component peaks are often
disappeared. For example for a 0.25wt.% ND solution, Fig. 1a shows the average of the 9high resolution data selected from 50 measurements and Fig. 1b shows that of the 50. The
former procedure is able to detect the main peak of ~10 nm, whereas the latter is not: we canestimate that the volume from the main peak is 92%, assuming that a scattering intensity pervolume are proportional to the third power of its peak particle size. In DLS, undesirable
measurements such as ones having accidentally strong scattering are often excluded in
calculating an average from a set of many measurements.
We have further examined with a Malvern zetasizer the dependence of optional
measurement conditions2 (a high speed fitting mode and a statistical discarding process) on
the peak resolution (or main particle sizes) in order to clarify the applicability and limit of theoptions. Then we will discuss the degree of diluting aggregation in the solutions. Probably the
degree2 was overestimated previously.

Fig.1 DLS spectra of scattering intensity for a 0.25wt.% ND solution: a) the average of 9 measurement sets
showing a good peak resolution ; b) that of 50 measurement sets including the 9.
[1] T. Tanaka, Y.F. Miura, T. Sato, E. Osawa; Abstract of the 53th FNTG Symposium, 66(2017)[2] N. O. Mchedlov-Petrossyan, N. N. Kamneva, A. I. Marynin, A. P. Kryshtalc, E. Osawa, Phys. Chem. Chem.
Phys.,17, 16186-16203(2015).
Corresponding Author:Toshihiko Tanaka / Tel: +81-246-46-0810 / E-mail: ttanaka@fukushima-nct.ac.jp- 117 -

2P-36
Suppression of carbon nanotube redox reaction
caused by protein adsorption○Tomohito Nakayama1,2, Takeshi Tanaka2, Kentaro Shiraki1,
Muneaki Hase1, Atsushi Hirano2
1

Division of Applied Physics, Faculty of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8573, Japan
2
Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, Japan

Physicochemical properties of single-wallcarbon nanotubes (CNTs) such as redox
reaction are affected by adsorbed moleculeson the CNT surfaces [1]. In this study, weshow that protein adsorption causes
suppression of CNT redox reaction inaqueous solutions by using bovine serum
albumin (BSA) as a model protein. We
suggest that protein molecules form thicker
layers on the CNT surfaces compared withordinary surfactant molecules such as
sodium dodecyl sulfate (SDS).
We measured absorption and Raman
spectra of HiPco–CNTs at different pHvalues. The inflection point of theabsorbance in the S11 region (e.g. absorbanceat 1275 nm) for BSA adsorbed CNTs (CNT–
BSA) was shifted to a more acidic pH value
compared with that for SDS adsorbed CNTs
(CNT–SDS) (Fig.1), which indicates
suppression of the redox reaction of thesemiconducting CNTs by the adsorbed BSA
molecules. We also investigated redox
reaction of the metallic CNTs by ameasurement of Raman spectra withexcitation at 532 nm. The Raman spectral
intensities of the radial breathing mode for
the CNT–BSA were higher than those for
CNT–SDS (Fig.2), an indication of
suppression of the redox reaction of themetallic CNTs by the BSA molecules. Thesefindings provide a new understanding ofredox chemistry of CNT–protein complex
materials and their behavior in biologicalsystems.
[1] Z. Gao et al. J. Hazard. Mater. 167, 357 (2009).
Corresponding Author: A. Hirano
Tel: +81-29-849-1064, Fax: +81-29-861-2786,
E-mail: hirano-a@aist.go.jp

Fig.1 Absorbance of the CNTs at 1275 nm as afunction of pH value; the CNTs were dispersed
by BSA (circle) and SDS (square). Insets show
the corresponding absorption spectra.

Fig.2 Raman spectra of the CNTs with excitation
at 532 nm, which were dispersed by BSA (upper
panel) and SDS (lower panel).

- 118 -

2P-37
Biodistribution of carbon nanotubes after local implantation of mice
○Eri Hirata1, Masako Yudasaka2, Yukari Maeda1, Takeshi Tanaka2, Hiromichi Kataura2,
Atsuro Yokoyama 1
1

2

Graduate School of Dental Medicine, Hokkaido University, Sapporo 060-8586, Japan
Nanomaterials Research Institute (NMRI), National Institute of Advanced Industrial Scienceand Technology (AIST), Tsukuba Central, Tsukuba 305-8565 Japan.

Carbon nanomaterials (CNMs) are used in the development of various functional materials
and products as well as in the basic research mainly in engineering field. In addition, due to its
high biocompatibility, application to biomaterials is widely expected. We have been studying
the application of CNMs to the biomaterials for bone regeneration [1] [2]. These biomaterials
are implanted in the bone defects, and the local effect is expected. Many researches haveintravenously administered CNMs to examine their kinetics and toxicity. On the other hand,little research on the in vivo kinetics of CNMs implanted locally has been reported.
Therefore, single-walled carbon nanotube (SWNT) [3] were implanted in bone and, in vivo
kinetics was observed by near-infrared (NIR) fluorescence imaging (excitation 730 nm,
emission >1000 nm) as shown in Fig.1. In NIR region, the light is highly transparent in bodyand, auto-fluorescence level is low, therefore NIR fluorescence is suitable for bio-imaging.
SWNTs in the subcutaneous tissue and medullary cavity were visible.
Fluorescence was observed at the implanted part of SWNTs embedded in the bone marrowcavity, and the fluorescence intensity gradually decreased in 24 hours. Similar results wereobtained
when
SWNTs
were
implanted
subcutaneously in the cranial region. Fluorescence
was not observed in any other organs (liver, spleen,lung, etc.) by the whole-body imaging. No
fluorescence was observed in the liver tissue section
by the NIR microscopy. After 56 days, thefluorescence was weakly but clearly observed at the
implanted area. The fluorescence becomes weak withtime perhaps because the SWNTs were bundled oradsorbed certain fluorescence-quenching materials in
Fig.1 Schematic representation of thethe tissue. These results suggested that locallyimaging setup.
implanted SWNTs hardly migrated to other organs andremained in the site of implant.
[1] E. Hirata et al. Chem. Carbon. 49, 3284 (2011).
[2] E. Hirata et al. Nanoscale. 30, 14514 (2016)[3] Y. Yomogida et al. Nat. Commun.,7, 12056 (2016)
Corresponding Author: E Hirata
Tel: +81-11-706-4270
E-mail: erieri@den.hokudai.ac.jp- 119 -

2P-38Carrier accumulation on functionalized diamond (111) surfaces by an
external electric field○Yanlin Gao, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, 305-8571, Japan
Diamond has attracted significant interest due to its promising application to the high-powerand high-frequency electronic devices arising from its excellent electronic and thermal
properties, such as the wide band gap, high thermal conductivity, high breakdown field, andsymmetric carrier mobility. Indeed, it has been demonstrated that the diamond surfaces workas the conducting channels of the field effect transistors. In such devices, the surfaces of the
diamond are chemically functionalized depending on the environmental conditions. Suchsurface functionalization certainly affects the electronic properties of the surfaces undercarrier injection by the gate electrode. However, microscopic mechanism of the carrier
accumulation on the functionalized diamond surface is still unclear. Therefore, in this work,
we aim to elucidate the electronic properties of diamond (111) surfaces under the external
electric field, of which surfaces are functionalized by H, O, COH, and OH functional groups,
based on the density functional theory combined with the effective screening medium method.
Our calculations show that the distribution of accumulated carriers strongly depends onthe functional group and carrier species. For the surfaces functionalized by O and COH
groups, the electron and hole are mainly induced on the attached functional groups, whichcauses the almost constant capacitance for the applied gate voltage. In contrast, for both
surfaces functionalized by H and OH, hole is injected into the functional groups and C atoms
at the vicinity of the surfaces, making
the constant capacitances for the
positive gate voltage, while electron isspilled over the vacuum region outside
the surfaces with the nearly free electron(NFE) nature, since the NFE state shifts
downward and crosses the Fermi levelby the negative gate voltage and thesurface dipole.
Corresponding Author: Y. Gao
TEL: +81-29-853-5921, FAX: +81-29-853-5924
E-mail: ylgao@comas.frsc.tsukuba.ac.jp

Fig. 1 Isosurfaces of induced carriers on diamond (111)
surfaces functionalized by (a) O, (b) COH, (c) H, and (d)OH functional groups under the electric field.

- 120 -

2P-39Catalytic Activity of Several Carbons with Different Structures
and By-Produced Carbons for Methane Decomposition○Dai miyamoto1, Haruki Nishii1, Yoshito Umeda2, Hiroaki Hamaguchi3, Masashi Suzuki3,
Toru Harigai1, Tsuyoshi Tanimoto1, Hirofumi Takikawa1, Yoshiyuki Suda1
1

Department of Electrical and Electronic Information Engineering, Toyohashi University ofTechnology, Toyohashi, Aichi 441-8580, Japan2
Toho Cryogenics Co., Ltd, Nagoya, Aichi 456-0004, Japan
3
Aichi Center for Industry and Science Technology, Toyota, Aichi 470-0356, Japan

Methane conversion ratio (%)

Thermo-catalytic decomposition (TCD) of methane is the attractive hydrogen production
process to mitigate CO2 emissions commonly associated with the conventional processes.
However, the problem of the process is catalyst deactivation by carbon deposition. [1] The
purpose of this study is to investigate the relationship between the catalysts structure and thecatalytic activity of produced carbon during TCD of methane by using four types of carbon
catalysts with different structures. Four types of carbon catalysts were 80 (a)ACtested in the TCD of methane: activated carbon (AC), mesoporous 70
MCCB
carbon (MC), carbon black (CB), and carbon nanofiber (CNF). 60
CNF
50
Experiments were carried out in a fixed-bed reactor using 1.7 g of the 40
catalysts with space velocity of 360 h-1, at a reaction temperature of 30
1173 K. The produced gas was analyzed by a hydrogen detector and 20
gas chromatography. Carbon catalysts before and after the 10
experiments were analyzed by Raman spectroscopic analysis. The 0
0
100
200
300
400
500
600
methane conversion ratio was derived from the following formula
Elapsed time (min)using the hydrogen concentration obtained by gas analysis.
Fig. 1. Temporal change of
𝑀𝑀𝑀𝑀𝑀𝑀ℎ𝑎𝑎𝑎𝑎𝑎𝑎 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐻𝐻2 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐(1)
2 − 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐻𝐻2 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐

methane conversion ratios.

Temporal change of methane conversion ratio of each catalysts is shown in Fig. 1. Methane
conversion ratios of all the tested catalysts eventually reached about 25%. We also investigated
the temporal change of ID/IG that obtained from Raman spectrum of the produced carbon byreaction. ID/IG is the intensity ratio of the G band and the D band in Raman spectrum and, it isused to evaluate the degree of graphitization of the carbonaceous material. [2] After 600 min
elapsed, ID/IG of the produced carbon of all the tested catalysts was about 1.5. Therefore, we
found that the produced carbon by reaction shows the same activity and degree of graphitization
regardless of the structure of catalysts. We also found that Raman spectroscopy is an effective
method for evaluating initial catalytic activity for methane decomposition.
Acknowledgements
A part of this work was supported by “Development project of near-term hydrogen economy forming
technology”for priority of research project of Knowledge Hub Aichi. The authors would like to thank K.
Asato 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, 12-13, 2641-48 (2004)[2] L. Malard et al, Physics Reports., 473, 51 (2009).
Corresponding Author: Y. Suda
Tel: +81-532-44-6726
E-mail: suda@ee.tut.ac.jp- 121 -

3P-1
Chromatographic Separation of FeCl-Fullerene Complexes○Yuri Tanuma1, Seiji Hosoda2 Toru Maekawa1,2,3, Takashi Uchida1,3
1

Graduate School of Interdisciplinary New Science, Toyo University, Kawagoe 350-8585,
Japan
2
Faculty of Science and Engineering, Toyo University, Kawagoe 350-8585, Japan
3
Bio-Nano Electronics Research Centre, Toyo University, Kawagoe 350-8585, Japan

We previously reported the synthesis of iron and chlorine (FeCl)-fullerene complexes,
which are supported to posess interesting magnetic properties and be utilised for drug deliveryor spintronics, by low energy ion irradiation [1]. For a large scale synthesis of the
FeCl-fullerene complexes, we also developed a dc arc discharge setup and confirmed
FeClHC60 in discharged soot by mass spectrometry [2]. In this study, we focused on highperformance liquid chromatography (HPLC) separation of FeClHC60 from other components.
FeCl-fullerene complexes were synthesised by an arc discharge using an
FeCl2-impregnated carbon anode, as described elsewhere [2]. Soxhlet-refluxed soot solution
was investigated by liquid chromatography-mass spectrometry (LC-MS), equipped with aliquid chromatograph (Prominence series, SHIMADZU) and ion trap-type mass spectrograph(amaZon speed -TYU, Bruker Daltonics). We investigated several operational conditions suchas columns, mobile phase, oven temperature, and polarity of detected ions to find the optimal
conditions for separating FeCl-fullerene complexes.
As a result, FeCl-incorporated C60, which is considered to be FeClHC60, eluted earlier
than empty C60 as shown in Fig.1. Furthermore, the isotopic pattern of the detected FeClHC60
showed almost the same feature as the simulated one, as shown in Fig. 2. However, theFeClHC60 eluted with unassigned components, as shown in Fig.3. We observed change in
relative retention time of the FeClHC60 and unassigned components by changing columns andcomposition of mobile phase, i.e., ratio of n-hexane to toluene. We will discuss the separationof the FeClHC60 in more detail.
C60 (m/z: 720.00)
FeClHC60 (m/z: 812.12)
Fig.1 Extracted ion chromatograms of C60 and FeClHC60 using
a buckyprep column and pure toluene mobile phase at 30℃.

(a)

(b)

Fig.2 Isotopic distribution
patterns of (a) detected and(b) simulated FeClHC60.

Fig.3 UV chromatogram of the soxhlet-refluxed soot solution.
l i[1] T. Uchida et al. Rev. Sci. Instrum. 87, 02A720
Corresponding Author: T. Uchida, Y. Tanuma(2016).
Tel: +81-49-239-1940, Fax: +81-49-239-1940,[2] Y. Tanuma et al. The 53rd Fullerene-Nanotube
E-mail:uchida_t@toyo.jp, s3r101700039@toyo.jp-Graphene General Symposium. 2P-6 (2017)- 122 -

3P-2
Separation and Characterization of Sc-dimetallofullerenes: Sc2Cn(n=76, 78, 80, 82)○Shun Yoshida, Koichi Kikuchi, Yohji Achiba, Takeshi Kodama
Department of Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
In the previous symposium, Nakatori et al. reported the production and extraction of Sc2Cn(n=76, 78, 80) as an anion form [1]. (Sc2C76)- and (Sc2C78)- were obtained as a mixture ofthem because (Sc2C76)- and (Sc2C78)- eluted at the almost same retention time in HPLC
separation. Therefore, it was suggested that (Sc2C78)- would not be (Sc2@C78)- but(Sc2C2@C76)-. In addition, (Sc2C80)- was isolated, but its UV-vis-NIR absorption spectrum
was different from those of other (M2@C80(Ih))- (M=Y, Ce, etc.), so its cage structure could
not be determined. Here, we report the partial isolation of (Sc2C76)- and (Sc2C78)-, and finding(Sc2C82)-. Moreover, the ESR spectrum of (Sc2C80)- was measured and analyzed.
Sc-dimetallofullerenes were produced by the direct-current arc discharge (60 A) of Sc/C
composite rods (Sc:C=2:98) under a 500 Torr He atmosphere. The raw soot was extracted for
8 h with a mixed solvent of triethylamine and acetone. The separation of a mixture of(Sc2C76)- and (Sc2C78)- was accomplished by three-stage HPLC using acetone with an ion-pairreagent, tetrabutylammonium bromide (TBABr), as an eluent. On the other hand, the isolationof (Sc2C80)- or (Sc2C82)- was accomplished by one-stage HPLC. For (Sc2Cn)- (n=76, 78, 80,82), the UV-vis-NIR absorption spectra were measured. Furthermore, for (Sc2C80)-, the ESR
spectrum was also measured at the room temperature.
The UV-vis-NIR absorption spectrum of the isolated (Sc2C78)- was different from that of(Sc2C76)-. In addition, the UV-vis-NIR absorption spectra of (Sc2C78)- is different from theseof other (M2@C78(D3h))- (M=Y, Ce etc.), so the cage structures could not be determined. For
the same reason, the cage structure of (Sc2C8)- could not be determined. Fig. 1 shows theUV-vis-NIR absorption spectra of (Sc2C80)- and (Ce2@C80(Ih))-. This indicates that (Sc2C80)is not (Sc2@C80(Ih))- or electronic state of (Sc2@C80(Ih))- is different from that of(Ce2@C80(Ih))-. Fig. 2 showed the ESR spectrum of (Sc2C80)-, which is very complex, and alarge number of peaks over 100 was observed although the nuclear spin of Sc is I=7/2. These
results suggest that (Sc2C80)- was consisted of at least two kind of component, which were
cage structural isomers or metal position isomers.

Fig. 1 UV-vis-NIR absorption spectra of (Sc2C80)and (Ce2@C80(Ih)) .

Fig. 2 X-band ESR spectrum of (Sc2C80)- at 294 K in
TBABr/acetone.

[1] N. Nakatori, et al. The 52nd Fullerenes-Nanotubes-Graphene General Symposium 27 (2017).
Corresponding Author: Takeshi Kodama
Tel:+81-42-677-2530, Fax:+81-42-677-2525
E-mail: kodama-takeshi@tmu.ac.jp- 123 -

3P-3
Crystal structure analysis of [Li+@C60](TFSI−)∙CH2Cl2
Kazuhira Miwa1, Shinobu Aoyagi1, Hiroshi Okada2, Hiroshi Ueno3, Yutaka Matsuo2,3,4
1Dapartment of Information and Basic Science, Nagoya City University, Mizuho-ku, Nagoya

467-8501, Japan
2Dapartment of Mechanical Engineering, School of Engineering, The University of Tokyo,

Bunkyo-ku, Tokyo 113-8656, Japan
Dapartment of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China

3

4Hefei National Laboratory for Physical Sciences at the Microscale, Univarsity of Scienceand Technology of China, Hefei, Anhui 230026, China
Endohedral metallofullerenes with electric and magnetic properties have a potential to be
used for molecular devices such as molecular memories. Lithium ion endohedral
metallofullerene Li+@C60 is commercially available and a promising material for theapplication. Li+@C60 forms salts with anions such as PF 6−, and shows a fast response to analternating electric field by a free rotational motion of the Li + cation inside the C60 cage [1-3].
The motion of Li+ cations in the PF6− salt [Li+@C60](PF6−) is suppressed at low temperature,
and antiferroelectrically ordered below 24 K [3,4]. The antiferroelectric Li+ ordering is caused
by interactions among electric dipole moments formed between the Li + cations inside and thePF6− anions outside the C60 cages. It is expected that the Li+ cations also show a ferroelectricordering in a Li+@C60 salt.
As a candidate for a ferroelectric Li+@C60 salt, we investigate a single crystal of Li+@C60
with bis(trifluoromethanesulfonyl)imide (TFSI−) anion in this study. TFSI− is an asymmetricpolar anion, while PF6− is a symmetric non-polar anion. The polar TFSI− anion is a
prospective counter anion to obtain a polar ferroelectric Li +@C60 crystal. The solubility of the
TFSI− salt is substantially higher than that of the PF 6− salt [5]. The dielectric property andcrystal structure of the TFSI− salt would be also rather different from that of the PF6− salt.
A single crystal of [Li+@C60](TFSI−) was obtained from the dichloromethane (CH 2Cl2)
solution by a vapor diffusion method. The single crystal X-ray diffraction measurement was
performed at SPring-8 to determine the crystal structure. A structural phase transition was
found below 150 K. The crystal structure analysis revealed that the high-temperature phase at
150 K has an orthorhombic polar structure with the space group of Pmc21. The crystal
contains CH2Cl2 solvent molecules with the ratio of [Li +@C60](TFSI−) : CH2Cl2 = 1 : 1. The
determined molecular structure is shown in Fig. 1. A complicated orientation disorder of theC60 cages in the structure is omitted in the figure. Unfortunately, the Li + cations have anantiferroelectric arrangement in the structure despite the polar spacegroup. Further study will reveal the crystal structure in the lowtemperature phase and the dielectric property of [Li +@C60](TFSI−)∙CH2Cl2.
[1] S. Aoyagi et al. Nature Chem. 2, 678-683 (2010).
[2] S. Aoyagi et al. Angew. Chem. Int. Ed. 51, 3377-3381 (2012).
[3] S. Aoyagi et al. J. Phys. Soc. Jpn. 85, 094605 (2016).
[4] H. Suzuki et al. Phys. Chem. Chem. Phys. 18, 31384 (2016).
[5] H. Okada and Y. Matsuo Fuller. Nanotub. Car. N. 22, 262-268 (2014).
Corresponding Author: S. Aoyagi
E-mail: aoyagi@nsc.nagoya-cu.ac.jp
Fig.1 [Li+@C60](TFSI−)∙CH2Cl2- 124 -

3P-4
Photoreaction of Sc3N@Ih-C80 with Disilirane: Formation and
Isomerization of 1,2-, 1,3-, and 1,4-Adducts○Shinpei Fukazawa1, Yuichi Sato1, Masahiro Kako*,1, Masanori Yasui1,
Michio Yamada2, Yutaka Maeda2, Takeshi Akasaka2,3,4
1

Department of Engineering Science, The University of Electro-Communications, Chofu,
Tokyo 182-8585, Japan2
Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
3
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan
4
Foundation for Advancement of International Science, Ibaraki 305-0821, JapanThe functionalization of endohedral metallofullerenes (EMFs) has attracted
considerable attention because of their unique structures encapsulating metal atoms andmetallic clusters. Until now, many researches of exohedral functionalization of EMFs
were conducted to disclose their diverse properties of EMFs, indicating their potential
applications in biochemistry, nanomaterials sciences, and molecular electronics [1]. In
previous studies, we demonstrated that the photoreaction of Sc3N@Ih-C80 with
1,1,2,2-tetramesityl-1,2-disilirane resulted in the formation of 1,2- and 1,4-addition
products [2]. The structural and electronic properties of the 1,4-adduct werecharacterized using spectroscopic, electrochemical, and crystallographic techniques, aswell as theoretical calculations. However, those of the 1,2-adduct have not been fully
characterized because this compound was not isolated [2]. Recently, similar
photoreactions of Lu3N@Ih-C80 with disiliranes were reported to produce thecorresponding 1,4-adducts. Although high-performance liquid chromatography (HPLC)
analysis suggested the formation of less stable intermediates during the photoreactions,further structural analyses of the intermediates were unsuccessful due to their lability[3,4]. These results prompted us to further clarify the addition pattern in the reactions of
Sc3N@Ih-C80 with disiliranes because the properties of EMF derivatives depend on theregiochemistry of exohedral functionalization. We present a detailed report of thephotoreaction of Sc3N@Ih-C80 with 2,6-diethylphenyl(Dep)-substituted disilirane 1,
which include adducts 2, 3, and 4, as the 1,2-, 1,3-, and 1,4-adducts, respectively(Scheme 1). In addition, the isomerization between 2 and 3 was observed at 50 °C in
CDCl3. At 100 °C, both adducts 2 and 3 were quantitatively converted to 4. The detailsof the structural and electronic properties of adducts 2, 3, and 4 will be discussed.
Scheme 1.
Dep

+

Dep
Si

Dep

Sc3N@Ih-C80

Dep

Dep
Dep

1: Dep =

Si

hν

Dep

Dep

Si

Dep

Si

+

Dep

Si

Dep

Si

Dep

+

Dep

Si

Si

Dep
Dep

Dep

2

3

4

Partial structures of 2, 3, and 4 .

[1] L. Dunsch et al. Chem. Rev. 134, 5989–6113 (2013). [2] Y. Iiduka et al. J. Am. Chem. Soc. 128,
9919–9925 (2006). [3] K. Sato et al. Org. Lett. 14, 5908–5911 (2012). [4] M. Kako, et al. Chem. Eur. J.
21, 16411–16420 (2015).
Corresponding Author: Masahiro Kako	  Tel: +81-42-442-5570	
  	  E-mail: kako@e-one.uec.ac.jp- 125 -

3P-5
Rotational dynamics of a H2O molecule encapsulated in a fullerene C60
at low temperature○Hal Suzuki1, Motohiro Nakano1, Yoshifumi Hashikawa2, Yasujiro Murata2
1

2

Graduate School of Science, Osaka University, Osaka 560-0043, Japan
Institute for Chemical Research, Kyoto University, Kyoto 611-0011, Japan

Fullerene C60 has a highly symmetric (almost spherical) vacancy inside with radius of ~3.7
Å, in which atoms or small molecules can be encapsulated. The encapsulated
atoms/molecules are “isolated”, so that their dynamics (especially the rotational dynamics)
resemble those in the gas phase. It is of our interest how these isolated atoms/molecules
behave at low temperature. In our previous works, we have investigated the dynamics of a Li+
ion encapsulated in a fullerene C60 by using terahertz spectroscopy[1] and calorimetry. We
revealed that the Li+ ion is circulating in the C60 cage above 100 K, but is localized into two
positions below 100 K.
10
In this work, we have investigated the dynamics ofa H2O molecule encapsulated in a fullerene C60 and
H O@C
C60O by heat capacity measurements between 0.6 and100 K. Fig. 1 shows the heat capacity obtained for
H2O@C60 in a double logarithmic plot. A broad peak10
is observed at ~ 1 K, which becomes smaller as the
rapidly cooled
sample is annealed at 2.5 K for several tens of hours.
annealed at 2.5 K
Based on the previous spectroscopic works[2], it is
1.5 h
12 h
3h
24 h
concluded that the peak corresponds to the6h
48 h
excitations between the split sublevels of the triplet
10
10
10
10
ground rotational (ortho-) states of the H2O molecule.
T/K
Fig. 1 Heat capacity of H2O@C60
The annealing effect is explained to be due to the
nuclear spin conversion from the triplet (ortho-) tothe singlet rotational (para-) state. Kinetics of theortho-/para- conversion was investigated through the
1.5time variation in heat capacity, and two relaxation
H O@C O
components were found: τ1 ~ 6,000 s and τ2 ~ 47,000 s
1
at 1.8 K (Fig. 2). Heat capacity of H2O@C60O also
showed a broad peak at ~1 K, however the relaxation
phenomenon due to the nuclear spin conversion was
0.5
H O@C
found to be very slow compared with that of
H2O@C60. It was indicated that the dipole moments of0
the epoxide group in the carbon cage significantly
0
20
40
t/h
affect the conversion rate of the H2O molecule.
2

60

–1

Cp / J K mol

–1

2

0

0

1

2

2

60

2

60

–1

Cp / J K mol–1–2[1] H. Suzuki et al. Phys. Chem. Chem. Phys., 18, 31384 (2016).
[2] C. Beduz, et al., Proc. Natl. Acad. Sci. USA, 109, 12894 (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- 126 -

Fig. 2 Time variation in heat capacityof H2O@C60 and H2O@C60O

3P-6
Electronic structure of carbon nanotube thin films under an external
electric field
Donghao Wang and Susumu Okada
Graduate School of Pure & Applied Sciences, University of Tsukuba, Tsukuba
305-8571 Japan
Individual and mat structures of carbon nanotubes (CNTs) can work as conducting channelsof flexible electronic devices. In such devices, CNTs intrinsically feel the external electric field,
which affect their electronic properties. Several theoretical works have elucidated fundamental
properties of individual CNT under the external electric field. On the other hand, it is still
unclear a microscopic insight into the electronic properties of CNT thin films under the external
field, which are essential in the CNT-based electronic devices under the operation. Thus, in thiswork, we aim to elucidate the electronic properties of CNT
thin films with the bilayer structure of (12,0), (13,0), (14,0),(15,0), (16,0), and (17,0) CNTs under the external electricfield, using the density functional theory combined with theeffective screening medium method. In particular, we give
clarify how the electronic properties depend on the CNT
combination.
Our calculations showed that the electrostatic properties
in CNT thin films strongly depend on the electric field andconstituent CNT species. We found the induced electric
filed of which direction is opposite to the applied electricfield for the thin film consisting of (12,0) and (15,0) CNTs
under the electric field of 0.2 V/A (Fig. 1). In contrast,
inversion filed is absent in the thin films comprisingFig.1 Electrostatic potential of

metallic and semiconducting CNTs and semiconducting

the CNT thin film consisting of

CNTs.

(12,0) and (15,0) CNTs underthe external electric field.

Corresponding authors: Donghao Wang and S. Okada
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 127 -

3P-7
Structural Isomer-induced spectral changes in near infrared
photoluminescence of locally-functionalized single-walled carbon nanotubes○Tomohiro Shiraki1,2, Shunsuke Uchimura1, Tomonari Shiraishi1,
Fumiyuki Toshimitsu2, Naotoshi Nakashima2
1

Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan

Defect doping to semiconducting single-walled carbon nanotubes (SWNTs) is a key
approach to produce new near infrared photoluminescence (NIR PL) properties. Therein, thedoping achieves local functionalization of the tubes that provides red-shifted PL withenhanced quantum yields (E11*) in comparison to the PL (E11) of the pristine SWNTs.[1-8] In
the locally functionalized SWNTs (lf-SWNTs), diazonium chemistry allows us to introduce
various chemical structures of the aryl groups on the doped site and, as a result, it is foundthat the chemical structures of the modified molecules play an important role to determine andcontrol the E11* PL wavelengths and their functionalities. For example, we have succeeded ingeneration of remarkably red-shifted PL on the basis of proximal modification usingsynthesized bisdiazonium compounds [5] and development of dynamic wavelength shiftsystems driven by molecular recognition using saccharide binding with introduced
phenylboronic acid groups at the doped
sites [6].
Here, we report a new structural factorof structural isomers that modulate the E11*
PL properties of the aryl functionalized
lf-SWNTs; that is, when positional isomeric
structures of the substituted aryl groups are
introduced for the doped sites of lf-SWNTs(Fig. 1), we observe significantly different Fig. 1 Structure images of the synthesized
diazonium compounds and the prepared isomer
PL of these lf-SWNTs from that of typical modified lf-SWNTs.
para-aryl modified lf-SWNTs.[8] The
meta-aryl modified lf-SWNTs show deviation from the reported liner relationship between the
Hammett substituent constants and E = E11*-E11 of the para-aryl modified lf-SWNTs. For
the ortho-aryl modified lf-SWNTs, two PL peaks are generated by the functionalization andone of them appears in the largely red-shifted region compared to typically observed E11* PL.
The present findings, therefore, are expected to provide new designs for the PL modulationof lf-SWNTs on the basis of the molecular structures of modifiers, which should lead to thedevelopment of novel nanomaterials whose NIR PL properties are applicable to advancephotonic devices and bio/medical diagnostic tools.
[1] R. B. Weisman et al., Science, 330, 1656 (2010); [2] Y. Miyauchi et al., Nat. Photon., 6, 715 (2013); [3] G. C.
Schatz and Y. Wang et al., J. Am. Chem. Soc., 138, 6875 (2016); [4] Y. Maeda et al., Nanoscale, 8, 16916(2016); [5] T. Shiraki and N. Nakashima et al., Sci. Rep., 6, 28393 (2016); [6] T. Shiraki and N. Nakashima et al.,Chem. Commun., 52, 12972 (2016); [7] T. Shiraki and N. Nakashima et al., Nanoscale, 9, 16900 (2017); [8] T.
Shiraki and N. Nakashima et al., Chem. Commun., 53, 12544 (2017)
Corresponding Author: T. Shiraki
Tel: +81-92-802-2841, Fax: +81-92-802-2840
E-mail: shiraki.tomohiro.992@m.kyushu-u.ac.jp- 128 -

3P-8
Response of Localized Carriers to Terahertz Radiation
in a Carbon Nanotube Film
○Takuya Okamoto1, Naoki Fujimura1, Xiaowei He2, Weilu Gao2, Junichiro Kono2,3,4, andYukio Kawano1
1

FIRST, Tokyo Institute of Technology, Tokyo 152-8552, Japan
Department of Electrical & Computer Engineering, Rice University, Houston, Texas, USA
3
Department of Physics & Astronomy, Rice University, Houston, Texas, USA
4
Department of Materials Science & NanoEnginnering, Rice University, Houston, Texas, USA
2

Carbon nanotubes (CNTs) exhibit significant ultrabroadband absorption from themicrowave to the ultraviolet range. They can be used to build a sensitive detector that works atroom temperature in the terahertz (THz, 1012 Hz) band [1]. However, at low temperatures,
carrier localization occurs due to the presence of disorder such as intertube potential barriers,
impurities, and random chiralities. To improve the performance as a THz detector, it is required
to deeply understand the interaction of such localized carrier with THz waves.
In this work, we have investigated electrical transport properties of a highly aligned p-njunction single-wall CNT film under THz irradiation. We first measured the resistance of thissample as a function of temperature, T , in a range between 2.86 K and 295 K. With decreasing
T, the resistance drastically increased at about 10 K, as shown in Fig. 1(a), indicating a transition
from fluctuation-induced tunneling (FIT) to two-dimensional variable range hopping (2DVRH) transport.
To understand how THz irradiation affects this VRH transport, we performed
magnetoresistance (MR) measurements under THz irradiation at 3 K (Fig. 1(b)). The dark MR
showed a negative conductance correction, which is a typical VRH behavior. THz irradiation
then modified this MR curve in a strongly frequency-dependent manner. At high frequencies(2.52 and 3.11 THz), irradiation shifted up the MR curve, whereas low frequencies (1.39 and1.63 THz) irradiation shifted down the MR curve. Through a fitting analysis [2], we estimatedthe localization length to be 8 nm at zero frequency and 12 nm at 1.63 THz, as shown in Fig.
1(c). These results lead us to conclude that the THz waves directly affected the conduction
mechanism of localized carriers, providing a first step toward not only a high-sensitivity THz
detector but also new functional THz devices.
[1] X. He et al., Nano Lett. 14, 3953-3958 (2014).
[2] U. Sivan et al., Phys. Rev. Lett. 60, 1566 (1988).
Corresponding Author: Y. Kawano
Tel & Fax: +81-3-5734-2542
E-mail: kawano@pe.titech.ac.jp

10

8

10

7

10

6

10

5

4

10 2

60

Measure402000100 200 300
Temperature (K)Measure2D-VRH
FIT
3

4 5 6 7102

3

4 5 6 7

Temperature (K)

100

2

3

(c)

20

10

5

No Irradiation
1.39THz
1.63THz
2.52THz
3.11THz

Localized length (nm)(b)

9Normalized Magnetoresistance (%)

Resistance ()10Resistance (M)

(a)

0

-5

-10
0

1

2

3
4
5
Magnetic Field (T)

6

7

8

15

10

5

0

0

1
2
Frequency (THz)3

Fig.1 (a) Temperature dependence of the resistance. Inset: non-logarithmic plot. (b) Magnetoresistancewith/without various-frequency THz irradiation at 3 K. (c) Localization length as a function of frequency.

- 129 -

3P-9
Exciton effect of circular dichroism in single-wall carbon nanotubes○Yuya Iwasaki and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Circular dichroism (CD) is defined by a difference of optical absorption for left- andright-handed circular polarized light. Recently, measurements of the CD spectra for single
chirality of single-wall carbon nanotubes (SWNTs) are reported in separation of anenantiomer for a pair of chiralities by the agarose gel column chromatography method [1] andthe two-phase method with DNA [2]. Sato, et al. [3] shows analytic and numericalcalculations of CD spectra of SWNTs based on electron-photon interaction by the tightbinding method. They explained the structure of CD spectra and chirality dependence formetal and semiconductor SWNTs. However, they cannot discuss CD value quantitatively
because their calculations do not consider exciton effects. Exciton effects in low dimensional
materials are strong due to confinement of electrons and holes in the systems. By the exciton
effect, optical absorption of SWNTs for E11, E22, E12 and so on are enhanced, but theenhancement factors for these peaks may be different one by one [4,5].
In order to discuss the exciton effect of the CD in SWNTs quantitatively, we improve theprogram to calculate the CD spectra of SWNT including exciton effects by the tight binding
method. The optical absorption intensity, which is given by the Fermi golden rule, is
proportional to square of the matrix element. We obtain the exciton-photon matrix elementsfrom the exciton wave function calculated by the Bethe-Salpeter equation (BSE) [4,5]. The
BSE is used to make exciton wave function by a superposition of the electron and hole wave
functions.
In this presentation, we present analytical formula for the CD of SWNTs including exciton
effects and show numerical calculated results. We compare the calculated results withexperiments, and also with previous CD spectra which does not consider the exciton effects.
We also evaluate how much the exciton effect comes out.

[1] X. Wei et al., Nat. Comm. 7,12899 (2016)[2] G. Ao et al., JACS 138, 16677 (2016)[3] N. Sato et al., Phys. Rev. B. 95, 155436 (2017)[4] J. Jiang et al., Phys. Rev. B. 75, 035407 (2007)[5] J. Jiang et al., Phys. Rev. B. 75, 035405 (2007)
Corresponding Author: Yuya Iwasaki
Tel: +81-22-795-6442, Fax: +81-22-795-6447,
E-mail: iwasaki@flex.phys.tohoku.ac.jp- 130 -

3P-10
Semiconducting Carbon Nanotubes as Charge-transporting Grain
Boundary Protector of Perovskite Solar Cells○Seungju Seo1, Il Jeon 1, Zhang Hao1, Takeshi Tanaka2, Hiromichi Kataura2,
Yutaka Matsuo1,3, Shigeo Maruyama 1,4
1 Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2 Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki, 305-0046, Japan
3 Hefei National Laboratory for Physical Sciences at the Microscale, University of Scienceand Technology of China, Hefei, Anhui 230026, China
4 Energy NanoEngineering Lab, National Institute of Advanced Industrial Science andTechnology(AIST), Ibaraki 305-8564, Japan
After the demonstration of prototype liquid-junction perovskite solar cells (PSCs), organo-lead
halide perovskite photovoltaics research has gained momentum with the achievement of thesolid-state PSCs in 2012. High absorption coefficient, long-range diffusion length and high defecttolerance of PSCs enable remarkable certified power conversion efficiencies (PCEs) over 20%.
Although PSCs are proven to be promising next-generation solar devices, further breakthroughs interms of efficiency and stability are necessary to supersede silicon solar cells. With regard to theperformance and stability of PSCs, perovskite grain boundaries play a significant role. Structural
disorders at these boundaries induce shallow trap states and non-radiative recombination of
localised charge carriers which serve as limitations to PSC performance. At the same time, theseareas are also responsible for the perovskite degradation, as the reaction with moisture in air has
been found to initiate from the grain boundaries. Therefore, technologies aiming at large
perovskite grains with protected boundaries are highly desired.
Over the last two decades, carbon nanotubes have generated a lot of excitement among
researchers for their device applicability. Especially, single-walled carbon nanotubes (SWNTs)
show an exceptional charge carrier property with outstanding chemical and mechanical stability,
which is an ideal quality for electronic components. Depending on the chirality of SWNTs, they
can possess either semiconducting or metallic properties. Semiconducting SWNTs (s-SWNTs)
have a wide range of direct bandgap of up to 2 eV, qualifying for a light-harvesting medium withstrong absorption and high carrier mobility. Because carbon nanotubes have high conductivity
along the tube axis, s-SWNTs can function effectively, not only as a light-harvester, but also as acharge-transporter between perovskite grains. While there have been a few reports onphenyl-C61-butyric acid methyl ester (PCBM) as a charge-transporter at the grain boundaries ofperovskite films, fullerenes have inherently low carrier mobility and low stability compared to
SWNTs. It is demonstrated that hydrophobic and air-stable SWNTs can protect the perovskite
layer successfully from the oxygen and moisture.
Here, we fabricated PSCs in which s-SWNTs are located at the perovskite boundaries,functioning as a charge-transporter, light-harvester, and protector from air. By incorporating
aqueous s-SWNTs into the perovskite solution, we produced perovskite films containing large
crystal grains with s-SWNTs in between. By adding a small amount of deionised water to theperovskite solution, 18.0% PCE of the reference PSCs increased to 19.0% due to the increased
perovskite grain size arising from favourable vapour pressure of the solvent. Upon addition ofs-SWNTs, the PCE further increased with improved hysteresis and air/light stability.

Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6421,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 131 -

3P-11Fabrication and characterization of self-aligned
carbon nanotube thin film transistors○Taiga Kashima1, Tomoki Matsuura1, Jun Hirotani1, Shigeru Kishimoto1, and Yutaka Ohno1,2
1

Department of Electronics, 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 promising active component for
flexible electronics because of high carrier mobility and excellent mechanical flexibility. In
recent years, it has become possible to fabricate CNT TFTs with high yield and uniformcharacteristics by using purified semiconductor CNTs. This would lead to the realization offunctional integrated circuits of CNT TFTs. For flexible electronics applicatoins, devices arefabricated on the plastic substrate, which is likey to expand or shrinks in size during the
fabrication process. Then, a large alignment margin in lithography process is necessary. This
results in the degradation of operation speed of the circuits due to the large orverlap
capacitances between the source/drain and the gate electrodes. In this study, we have fabricated
CNT TFTs by self-alignment process, and confirmed
drastic reduction of parasitic capacitance.
Figure 1 shows the structure of the self-aligned CNT
TFT fabricated on the flexible substrate. The device has
a bottom gate structure. The source and drain electrodes
were self-aligned to the gate electrode by exposing UVlight from the backside of the substrate in the lithography
process.
The gate-capacitance verus gate-voltage (C-V)
characteristics of the fabricated CNT TFTs with channel

Fig. 1 Schematic device structure ofself-aligned CNT TFT.

length (L) and channel width (W) of 100 m is shown in
Fig. 2. The capacitance at off state was reduced by afactor of 1/20 by introducing the self-alignment process,compared to the conventional process. In addition, since
the driving current of the self-aligned CNT TFTs werecomparable to that of the conventional devices. These
results show that the operation speed of circuits can be
Fig. 2 C-V characteristics.
improved by introducing the self-alignment process.
Acknowledgments: The semiconducting CNTs were provided by TASC. This work waspartially supported by JST/CREST.
Corresponding Author: Yutaka Ohno, Phone & Fax: +81-52-789-5387,E-mail: yohno@nagoya-u.jp- 132 -

3P-12
CNT Supported Mn-doped ZnO Nanoparticles as Efficient Visible LightActive Photocatalyst for Malachite Green Dye Degradation○Ahmed Shawky1,*,^, Reda M. Mohamed1,2, I. A. Mkhalid2
1

Nanomaterials and Nanotechnology Department, Central Metallurgical R & D Institute,11421 Helwan, P.O. Box, 87 Cairo, Egypt
2
Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80200,
Jeddah 21589, Saudi Arabia

Photocatalysis is photoreaction process occurs in the presence of semiconducting material
resulting an electron-hole pair generation. These carriers are able to generate a free radical(e.g. OH., O.) that can undergo secondary reactions. ZnO is well-known photocatalyst longtime ago. However, the large band gap (~3.2 eV) and low surface area (40~50 m2g-1) aremajor problems for the real industrial applications. Doping of ZnO of transition metal (e.g.
Mn) is one of effective ways to reduce the band gap to be applied in the visible light. On theother hand, Carbon nanotubes (CNT) represents an excellent carbon member in terms of
optoelectronic properties and surface texture in which canintroduce a higher surface area into ZnO. Moreover, CNT canenhance the photocatalytic activity due to the development ofelectron transfer from the surface of ZnO conduction bandand reduce charge recombination.
In this regard, we introduce our recent work on in situ
incorporation of CNT into Mn-doped ZnO nanoparticles that
prepared through simple precipitation. It was found that thedoping as well as the CNT induce a decrease of the band gapof ZnO and improve the charge transfer according toabsorbanceandphotoluminescence
spectroscopy
measurements. The photocatalytic activity was applied forthe degradation of Malachite green (MG) dye as an industrial
model. The degradation efficiency reached up to 94% after
just one hour under the ordinary bulb light. The effect of
doping ZnO and adding CNT on the crystalline structure,surface texture, optical and electronic properties of thephotocatalyst as well as the photocatalytic mechanism (See Fig. 1- Proposed photocatalytic
Fig. 1) and degradation kinetics will be presented in some mechanism for degradation of MG dye.
details.

Corresponding Author: Ahmed Shawky
Current address: Department of Mechanical engineering, The University of Tokyo
7 Chome-3-1 Hongō, Bunkyō-ku, Tōkyō-to 113-0033, Tokyo, Japan
Tel: +81-80-9863-3037, Fax: +81-3-5800-6983,
E-mail: ahmed@photon.t.u-tokyo.ac.jp, phyashawky@gmail.com*^- 133 -

3P-13
Rapid and Efficient Removal of Water Soluble Polymers from
ATP-extracted Semiconducting Single-Wall Carbon Nanotubes○Kazuki Ueno1, Haruka Omachi1,2, Tomohiko Komuro1, Jun Hirotani3, Yutaka Ohno3,4,
Hisanori Shinohara1,5*
1
Graduate School of Science, Nagoya University, Nagoya Nagoya 464-8602, Japan
2
Research Center for Materials Science, Nagoya University, 3 Graduate School ofEngineering, Nagoya University, 4 Institute of Materials and Systems for Sustainability,
and 5Institute for Advanced Research, Nagoya University
Semiconducting single-wall carbon nanotubes (s-SWCNTs) are promising materials forelectronic devices because of its high electronic mobility, mechanical durability, and so on.
Recently, we developed a rapid and single-step aqueous two phase (ATP) extraction ofhighly enriched s-SWCNTs[1]. However, enriched s-SWCNT dispersion contained muchamount of water-soluble polymers which caused the aggregation of s-SWCNTs andnormally-on state of thin film transistor (TFT).
In this work, we accomplished rapid removal of water-soluble polymers froms-SWCNT dispersion. By mixing with halogenated solvent CH2Cl2, polyethylene glycol(PEG) was immediately precipitated out. 1H NMR spectra indicate >99% of PEG polymer
was removed (Fig. 1a). TFT measurements were also carried out and fabricated devices
exhibits a high on/off ratio (>105) with normally-off state (Fig. 1b).

Fig.1 (a) 1H NMR spectra of s-SWCNT dispersion before and after the treatment with CH2Cl2. Imidazole was used asinternal standard (*) and peaks of acetonitrile solvent were observed at 1.92 ppm (#). (b) Transfer characteristics of thinfilm transistors using PEG-removed s-SWCNT dispersion (channel length = 100 µm, Vds = –5 V).

[1] Omachi, H.; Shinohara, H. JP Patent 2017-066945.
Corresponding Author: Hisanori Shinohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442
E-mail: noris@nagoya-u.jp- 134 -

3P-14Computational Design for Thermoelectric Properties of Carbon Nanotubes
Modified by Diazonium Salts○Nayu Araki1 and Takahiro Yamamoto 1
1

Department of Electrical Engineering, Tokyo University of Science, Tokyo 125-8585, Japan

Carbon nanotubes (CNTs) are expected to be high-performance thermoelectric materials
with a large thermoelectric power factor [1]. However, the thermoelectric efficiency of a CNT
is not so high because it has a high thermal conductivity. It is thus essential to develop
experimental techniques to reduce the thermal conductivity of a CNT with maintaining the
Seebeck coefficient and electrical conductivity. Recently, several techniques to reduce thethermal conductivity of a CNT have been theoretically proposed [2,3]. On the other hand, CNTs
modified by a diazonium salt is hopeful for such a purpose since sp3 bonding by a diazonium
salt could lower thermal conductivity. In fact, it is experimentally shown that the thermal
conductivity of CNTs is decreased by chemical modification of diazonium salts and eventuallya figure of merit, ZT, for the thermoelectric efficient is succeeded to increase [4]. However, thedetails of influence of thermoelectric properties of CNTs by chemical modification ofdiazonium salts have not clarified yet. In addition, the optimal density of diazonium-salt
modification has not been known.
In the present study, we thus investigate thermoelectric properties of CNTs modified bydiazonium salts using the NEGF+DFT method [5]. One example of a simulation model isshown in Fig1. We calculated the electrical conductivity and Seebeck coefficient of a (10,0)
CNT by changing the number of benzene rings, i.e., the coverage of absorbed diazonium salts.
Furthermore, we also calculated a thermoelectric power factor. In the presentation, we discuss
the details of thermoelectric properties of CNTs modified by a diazonium salts and present the
optimal coverage of absorbed diazonium salts.

Fig 1: One example of two benzene rings modified a (10,0) CNT[1] Y. Nakai, et al, Appl. Phys. Express 7, 025103 (2014).
[2] T. Yamamoto, K. Sasaoka and S. Watanabe, Phys. Rev. Lett. 106, 215503 (2011).
[3] M. Ohnishi, T. Shiga and J. Shiomi, Phys. Rev. B 95, 155405 (2017).
[4] T. Fujigaya, et al., The 78th JSAP Autumn Meeting 2017 (7a-C22-9).
[5] https://quantumwise.co.jp/
Corresponding Author: T. Yamamoto
Tel: +81-3-5876-1492
E-mail: takahiro@rs.tus.ac.jp- 135 -

3P-15
Successive deposition of Al2O3, Fe and CNT forest by mist CVD○Toshiya Kinoshita1, Motoyuki Karita2, Takayuki Nakano2, Yoku Inoue2, Hirokazu Nagaoka3
1

2

Graduate School of Science and Technology, Shizuoka Univ., Hamamatsu 432-8561
Department of Electronics and Material Science, Shizuoka Univ., Hamamatsu 432-8561
3
JNC Petrochemical Corp., Ichihara, 290-8551

High density carbon nanotube (CNT) forest have been studied for various practicalapplications, such as interconnect, thermal interface material, super capacitor, lithium ion
battery electrode, gas sensor and dry-spinning assembly. In these materials, CNT forest height(CNT length), areal density, diameter, wall number and crystal quality, play important roles. It
is essential to control precisely catalyst formation and catalyst support layer during CNT
chemical vapor deposition (CVD) to control these structural properties. We developed an insitu CNT synthesis method on a substrate by mist CVD, including Al2O3 layer deposition, Fe
catalyst nanoparticle formation and CNT growth. In this study, effects of mist-deposited Al2O3
support layer during in-situ CNT synthesis were investigated to control these CNT properties.
CNTs were grown on oxidized Si wafer by mist CVD method. In the synthesis
procedure, Al2O3 support layer was first formed by flowing Al(III) acetylacetonate(Al(acac)3)/ethanol mist generated by ultrasonic nebulizer. The mist was supplied with a carriergas of Ar onto the substrate. Then, to form Fe catalyst nanoparticles on the support layer, themist was switched to another mist formed from ferrocene/ethanol. After these depositions,acetylene was flown to grow CNT. Effects of the Al2O3 support layer were investigated atvariousthicknesspreparedbyvaryingAl(acac)3/ethanol mist deposition time.
Scanning electron microscopy (SEM) andtransmission electron microscopy (TEM) images ofgrown CNTs on SiO2 with no Al2O3 deposition and on
mist-deposited Al2O3 layer are shown in Fig. 1 (a) and(b), respectively. In the case of no Al2O3 layer,
spaghetti-like multi-walled CNTs (MWCNTs) withmean diameter of 9.5 nm and areal density of 3.6×1010
cm-2, were grown. On the other hand, long and dense
MWCNT forest with mean diameter of 7.0 nm andareal density of 7.0×1010 cm-2 was grown on mistdeposited Al2O3 layer with 6.0 nm in thickness. The
Al2O3 thin layer made catalyst life time 10 times longer.
In addition, as can be seen in TEM images, the CNTs
on the Al2O3 resulted in smaller diameter and fewer
wall number than on the SiO2. These results indicate
possibilities that the mist-deposited Al2O3 layer has
effects on improvement of catalyst life time andsuppression of catalyst nanoparticles agglomeration.
Fig. 1 SEM and TEM images of grown
CNT on (a) SiO2 with no Al2O3 mist
deposition and (b) Al2O3 (6.0 nm inthickness).

Corresponding Author: Toshiya Kinoshita
Tel: +81-53-478-1107, Fax: +81-53-478-1356
E-mail: kinoshita@cnt.eng.shizuoka.ac.jp- 136 -

3P-16
Controlled Growth of Single-walled Carbon Nanotubes Using
Graphene Oxide/CoWO4 Hybrids as Catalyst Precursors○Xiyan Liu, Feng Yang, Yan Li*
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
China

Preparation of the uniform and well-dispersed catalysts is crucially important forthe controlled growth of single-walled carbon nanotubes on substrates [1]. Tungstenbased intermetallic catalyst with high melting points can act as the structural templates
for chirality specific growth of SWNTs [2-4]. Graphene oxide (GO) have been widelyused as dispersants and templates to prepare well-dispersed nanoparticles on surface[5].
Here, we used GO/cobalt tungstate hybrids as the catalyst precursors instead of
the previously used molecular clusters to prepare tungsten-cobalt catalysts. The asprepared catalyst precursors are well dispersed on the GO platforms with uniform size.
The intermetallic W6Co7 structure of the catalysts after the annealing and reduction
process was confirmed by X-ray diffraction (XRD) and high-resolution transmission
electron microscopy (HRTEM). The SWNTs grown on W6Co7/GO platforms possessa uniform diameter. Semiconducting species of high purity were prepared at suitableconditions.

[1] M. Li, Y. Li et al. Top. Curr. Chem. 375, 29 (2017).
[2] F. Yang, Y. Li et al. Nature 510, 522 (2014).
[3] F. Yang, Y. Li et al. Acc. Chem. Res. 49, 606 (2016).
[4] F. Yang, Y. Li et al. ACS Nano, 11, 186 (2017).
[5] H. Wang, H. Dai et al. J. Am. Chem. Soc., 132, 13978 (2010).
Corresponding Author: Yan Li
Tel: +86-10-6275-6773
E-mail: yanli@pku.edu.cn- 137 -

3P-17Development of Interpenetrating Polymer Network Gel for the Separation
of Single-Wall Carbon Nanotubes○Guowei Wang, Takeshi Tanaka, Atsushi Hirano, and Hiromichi Kataura

Nanomaterials Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8565, Japan
Gel

columnchromatography

has

shown

the

potential

for

the

large-scale

metal/semiconductor (M/S) separation and further single-chirality separation of single-wallcarbon nanotubes (SWCNTs) [1]. This method utilizes commercial dextran gel withthree-dimensional structure as the separation medium. A highly reusable gel is desired for thesustainable SWCNT separation. However, the permanent trapping of various carbon species
inside the gel causes the gel fouling. As a result, the separation efficiency of a gel decreases
gradually with increasing number of reuse cycles.
In this study, we aim to synthesize a highly
regenerable

separation

gel

by

introducing

aninterpenetrating polymer network (IPN) structure. This
IPN gel contains two partially interlaced but notcovalently bonded polymer networks: dextran networkand poly (acrylic acid) network. The IPN gel canefficiently separate pristine HiPco SWCNTs to the Mand S-fractions (Fig. 1). This demonstrates that the
dextran network in the IPN gel works as well as the
1. Optical absorption spectra of
dextran network in a commercially available gel does. At Fig.
pristine HiPco SWCNTs and separated

the same time, the poly (acrylic acid) network is highly M- and S-SWCNTs using IPN gel.

pH responsive, enabling the easy controlling of the gel pore size. This function could be used
for eluting all carbon species in the gel and regenerate the gel by increasing the pore size inthe elution step.
This work was supported by KAKENHI No. 25220602.
[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- 138 -

3P-18
Template-directed synthesis of coaxial structure of single-walled carbon
nanotubes and boron nitride nanotubes by chemical vapor deposition○Yongjia Zheng1, Ming Liu1, Taiki Inoue1, Rong Xiang1, Shigeo Maruyama1,2
1

Departure of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Energy Nano Engineering Lab., National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki. 305-8564, Japan

2

Graphene/h-BN interfaces have generated great interests recently due to the possibility of
combining diverse atomic layers to create novel materials and devices [1-2]. In this work, wedemonstrate a coaxial structure with similar interfaces that combines the single-walled carbon
nanotubes (SWCNTs) with boron nitride nanotubes (BNNTs) in the radial direction. Ammonia
borane (BH3NH3) as precursor was directly used to successfully synthesize BNNTs with the aid of
SWCNTs as a template by a facile chemical vapor deposition (CVD) technique (Fig. 1a). Absorption
spectra and Raman spectra confirmed not only the formation of BNNTs from BH3NH3, but also theundamaged condition of SWNTs (Fig. 1b and c). Furthermore, scanning electron microscopy (SEM)
and transmission electron microscopy (TEM) were employed to examine the morphology andquality of the coaxial structure. As shown in Fig. 1e, with 30 min BH3NH3 growth, the number ofwalls increased to 3-5 with the diameter of ~5 nm wide. The heterostructure of coaxial
SWNTs/BNNTs can be promising materials for modern integrated circuitry such as for field effecttransistors (FETs) [3], resonant tunneling diode (RTD) [4], and interconnects. Formation
mechanisms and electronic properties will be discussed.
Fig. 1: (a) Schematic illustrationof a fabrication of SWCNTs/
BNNTs with coaxial heterostructure. In step 1, SWCNTs
were grown using alcohol
catalytic CVD (ACCVD) [5]. In
step 2, BN layers were coatedonto surface of SWCNTs. (b)Absorption spectra and (c)Raman spectra of SWNTs and
SWCNTs/BNNTs on quartz
substrates. (d) SEM images ofcross section of SWCNTs
before and after BN growth. (e)TEM images of SWCNTs/
BNNTs with more than one
layer observed.
[1] M.P. Levendorf et al., Nature, 488, 627 (2012).
[2] Z. Liu et al., Nature Nanotechnology, 8, 119 (2013).
[3] R.Y. Tay et al., Chemistry of Materials, 27, 7156 (2015).
[4] V.H. Nguyen et al., Journal of Physics D: Applied Physics, 45, 325104 (2012).
[5] Y. Murakami et al., Chemical Physics Letter, 385, 298 (2004).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5841-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 139 -

3P-19A study of Preparation Conditions of Carbon Nanobrushes: Influence ofTarget Types○Ryota Yuge1, Fumiyuki Nihey1, Kiyohiko Toyama1, and Masako Yudasaka2, 3
1

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

Fibrous aggregates of single-walled carbon nanohorns, named as carbon nanobrushes(CNBs), were recently discovered [1]. The CNBs are expected as electrode materials of
various devices such as actuators, electric double layer capacitors, and fuel cells since theyshow high dispersibility in solutions, large specific surface areas, and high electricalconductivity. CNBs are easily prepared by CO2 laser ablation of Fe-containing carbon targetat room temperature [1], but their yield is low and the major products are the spherical
single-walled carbon nanohorn aggregates (CNHs). To increase the yield of CNBs, several
preparation conditions such as Fe concentration in carbon targets, target rotation speed, and/or
laser power density have already been investigated [2]. In this study, we tried to prepare
CNBs by using carbon target containing different catalysts other than Fe. We also investigated
the influence of the density of the carbon target itself.
A CO2 laser ablated the catalyst-containing carbon targets at room temperature and ambientpressure. The laser power and target rotation speed were 3.2 kW and 1 rpm, respectively. The
laser ablation was performed for 30 seconds. The gas pressure in the growth chamber was
sustained at 700-800 Torr by controlling the evacuation rate while the buffer gas of nitrogen
was kept at a flow rate of 10 L/min. The carbon target containing Fe (1 at. %, T1: 1.54 g/cm3,
T2: 1.73 g/cm3), CoNi (T3: Co 0.9 at. %, Ni 0.3 at. %, 1.60 g/cm3), or NiY (T4: Ni 4.2 at. %,Y 1.0 at. %, 1.60 g/cm3) was used in our experiments.
The obtained carbon deposits after CO2 laser ablation were 3.6, 1.7, 1.8, and 1.8 mg/s for T1,
T2, T3, and T4, respectively. Fe-containing targets with lower density (1.54 g/cm3) were
evaporated easily during laser ablation and produced more carbonaceous deposits than that ofhigher density (1.73 g/cm3). From scanning electron microscopy (SEM) and scanningtransmission electron microscopy (STEM) observations, CNBs are prepared only for T1 target.
Many amorphous carbons with a little CNHs were obtained for T2, T3, and T4 targets.
Therefore, we found that target density rather than catalyst types such as Fe, Ni and Co is ofimportance for CNB formations. The details will be discussed in the presentation.
[1] R. Yuge et al. Adv. Mater. 28, 7174 (2016).
[2] R. Yuge et al. The 52th FNTG General Symposium, 3P-24 (2017).
Corresponding Author: R. YugeTel: +81-29-850-1566, Fax: +81-29-856-6137, E-mail: r-yuge@bk.jp.nec.com- 140 -

3P-20
Energetics and electronic structures of corrugated graphene
nanoribbons
○Kazufumi Yoneyama1, Ayaka Yamanaka2, and Susumu Okada1
1 Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba

2305-8571, Japan
Research Organization for Information Science and Technology (RIST), Shinagawa,Tokyo 140-0001, JapanThe graphene nanoflakes and nanoribbons are attracting much attention as theconstituent material for the functional devices, owing to their tunable electronic
structure by controlling their sizes and shapes. Even though electronic structure ofgraphene nanoribbons has been elucidated by early theoretical works, a little is known
about the energetics and electronic structure of nanoribbons with structural
perturbations, such as edge roughness and corrugation, those are essentials for practicalapplication of graphene nanostructure. Thus, in this work, we aim to investigate theenergetics and electronic structure of graphene nanoribbons with structural corrugation,using the density functional theory with the generalized gradient approximation andpseudopotential procedure.
Figure 1 shows corrugation energies ofgraphene nanoribbons with armchair,chiral, and zigzag edges as function of
the corrugation angle. The corrugationenergy strongly depends on the edge
shapes. For the zigzag nanoribbon, theenergy keeps constant values up to thecorrugation angle of about 9 deg. In
contrast, for the armchair nanoribbon,
the energy quickly increases with Fig. 1. Corrugation energies of grapheneincreasing the corrugation angle. The nanoribbons with armchair (circles), chiral(squares), and zigzag (triangles) edges aselectronic structure modulation with functions of corrugation angle.
respect to the corrugation also strongly depends on the edge shape of graphene
nanoribbons.

Corresponding Author: K. Yoneyama
E-mail: kyoneyama@comas.frsc.tsukuba.ac.jp- 141 -

3P-21Synthesis of Graphene by Oxidation and Reduction of Copperwith Alcohol Chemical Vapor Deposition○Yuya Ogata1, Marina Tsujimoto1, Hiromichi Gonnokami1, Tyler Kurahashi1, Hidenobu
Murata1, Masaru Tachibana1
1 Department of Materials System Science, Yokohama City University, Kanagawa 236-0027,

Japan

Graphene has attracted enormous attention due to its extraordinary mechanical, thermal,
and electrical properties. Chemical vapor deposition (CVD) is a useful method for the amountsynthesis of graphene. Many studies on CVD synthesis have been reported so far. However,most of reaction time on CVD synthesis has been limited to less than several hours. In thispaper, we report the synthesis of graphene by oxidation and reduction of copper with alcohol
CVD reaction for longer reaction times.
Graphene was synthesized on copper foil by using alcohol CVD where ethanol was used ascarbon source. In the procedure, copper foil was annealed with Ar/H2 gas, and then only
ethanol was flown into the reaction chamber. The reaction times with ethanol flow at 900 ℃
was controlled in the range in 2 to 200 hours. After stopping the ethanol, the chamber was
evacuated to 2 Pa, and then cooled down to room temperature to obtain a sample.
Many hollows are observed on copper surface after CVD process (Fig. 1(a)). Note thatthese hollows are not found in the original copper surface. Interestingly, single-layer
graphenens are formed on only the bottom surface with square-like shape in each hollow (Fig.
1(b)). On the other hand, multi-layer graphenes are observed in all areas except for thehollows. Such hollows can be produced by the oxidation and reduction process beneathcopper surface so that the clean copper surface with square-like shape is appeared at thebottom in each hollow. It is suggested that single-layer graphene is formed on the clean
copper surface by the reprecipitation of dissoluved carbon beneath copper surface. This
technique with the oxidation of copper will lead to the patterning of graphene

Fig. 1 The SEM images of sample with the growth time of 100hours.
(a)Low magnification (b)High magunification
Corresponding Author: Y. Ogata
Tel: +81-45-787-2162, Fax: +81-45-787-2162,
E-mail: n175210a@yokohama-cu.ac.jp- 142 -

3P-22
Sequential CVD growth of h-BN and graphenefrom ammonia borane and ethanol○Kotaro Kashiwa1, Naomasa Ueda1, Hayato Arai1, 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

Hexagonal boron nitride (h-BN) is two-dimensional material with a hexagonal lattice. The
lattice mismatch between h-BN and graphene is only 1.8% [1]. h-BN has a wide band gap of~6 eV and can serve as an ideal supporting layer for graphene devices due to its planer
structure without dangling bonds. Graphene has been a promising material due to its
extraordinarily high mobility. However, graphene does not have band gap and is not easily
applicable to transistors.
Some researchers proposed that by putting graphene on h-BN to form a van der Waals
heterostructure, properties of graphene for device applications such as mobility, can be well
improved compared with those of graphene on SiO2 [2]. In addition, the superlattice potential
induced by lattice mismatch can modify the electronic properties of graphene and lead to gap
opening at Dirac cone. It was also reported that introduction of foreign atoms such as boron or
nitrogen can modify the electronic properties and induce band gap to graphene [3]. Such kindof heterostructures of graphene and h-BN are obtained by CVD process using two kinds ofsource gasses for graphene and h-BN. However, the controllability of such CVD processneeds to be improved.
In this study, we synthesized high-quality pristine h-BN and graphene and also
demonstrated sequential CVD growth of them. We used a coper foil as the catalyst of CVD
for h-BN and graphene. During growth, a CVD furnace was usually kept at 1050 ˚C. For
h-BN and graphene growth, we used ammonia borane and ethanol as the precursors,
respectively. Ammonia borane was kept at 80 ˚C. As shown in Fig. 1(a), single-layer h-BN
was grown and possessed an ideal triangle shape. By supplying two different source gases
sequentially, h-BNC was observed on copper surface (Fig. 1(b)). After transferred on SiO2,
h-BNC was identified by characteristic peaks of Raman spectra, and those spectra suggested
the density of converted atoms were different between inside and outside of the triangle
shape.
(a)
(b)

5 um

20 um
Fig. 1 (a) SEM image of h-BN.

(b) SEM image of h-BNC.

[1] Z. Liu. et al. Nat. Nano. 8, 119 (2013).
[2] C. R. Dean. et al. Nat. Nano. 5, 722 (2010).
[3] W. Eryin. et al. Nat. Phys. 12, 1111 (2016)
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421 E-mail: maruyama@photon.t.u-tokyo.ac.jp- 143 -

3P-23
Transverse thermoelectric voltage in 12C/13C-graphene heterostructures○Yuta Mochizuki, Kuniharu Takei, Seiji Akita, and Takayuki Arie
Department of Physics and Electronics, Osaka Prefecture University, Osaka 599-8531, Japan
Graphene is expected as thermoelectric conversion elements due to its high career mobility
and high power factor. However, the thermal conductivity of graphene is extremely high,resulting in small figure of merit (ZT) values. Therefore, the reduction in thermal conductivityof graphene has been investigated by using isotopes and defects in order to enhance ZT [1-3].
Another root of enhancing the thermoelectric performance of graphene may be transverse
thermoelectric, where materials having different properties arranged alternately show
anisotropic transport behavior, leading to transverse Seebeck and Peltier effects. Since theelectrical and thermal properties of graphene are essentially isotropic, in this study we usedisotopically modified heterostructures that enable devices to present transverse thermoelectriceffect.
Graphene composed of 12C and/or 13C were synthesized by low-pressure chemical vapor
deposition using 12CH4 and/or 13CH4 as carbon sources, respectively. After synthesizing andphotolithographically patterning graphene composed of 13C and 12C (50%/50%), graphenewith only 12C was synthesized on the part of etched region to form isotopic heterostructures.
Transverse thermoelectric voltage appeared in the perpendicular direction to thetemperature difference is expressed as
T l
(1),

V
 S  S  sin 2
2 dwhere ΔT, l/d, θ, S‖ and S⊥ are the temperature difference, aspect ratio of the device, tilt
angle of the isotopic interface, and Seebeck coefficient of graphene heterostructures in theparallel and perpendicular directions to theinterface, respectively (Fig. 1(a)). From our (a)experiments using devices with various tilt
angles, the measured transverse thermoelectric
voltage takes the maximum value ofapproximately 12.0 μV at the tilt angle of 45°(Fig. 1(b)), which corresponds to Eq. 1.
Thermovoltage was found to increase linearlywith increasing the aspect ratio of the device,l/d, which is also consistent with Eq. 1. The
transverse thermoelectric effect, therefore, canbe utilized to improve the thermoelectricperformance of graphene devices.
[1] Y. Anno, K. Takei, S, Akita, T. Arie, Phys. Status
Solidi RRL 8, 692 (2014).
[2] Y. Anno, K. Takei, S. Akita, T. Arie, Adv. Electron.
Mater. 1, 1500175 (2015).
[3] Y. Anno, Y. Imakita, K. Takei, S. Akita, T. Arie, 2DMater. 4, 025019 (2017).
Corresponding Author: T. Arie
Tel/Fax: +81-72-254-9265
E-mail: arie@pe.osakafu-u.ac.jp- 144 -

Fig. 1 Transverse thermoelectric voltage ofgraphene heterostructures as a function of tilt
angle. Bars in (a) represent 10 μm.

3P-24Fabrication of graphene sheets intercalated by carbon spheres forhigh-performance supercapacitor electrodes
1

2,3

1

1

○Zhipeng Wang , Hironori Ogata , Wei Gong , Yanqing Wang , Adavan Kiliyankil

Vipin1, Gan Jet Hong Melvin4, Josue Ortiz-Medina5, Rodolfo Cruz-Silva5, Shingo
Morimoto5, Yoshio Hashimoto5,6, Bunshi Fugetsu7, Ichiro Sakata1,7 Mauricio Terrones5,8,Morinobu Endo5
1

Department of Technology Management for Innovation, School of Engineering, The University of Tokyo,
Bunkyo-ku, Tokyo 113-0032, Japan2
Department of Chemical Science and Technology, Faculty of Bioscience and Applied Chemical and Graduate Schoolof Engineering, Hosei University, 3-7-2, Kajino-cho, Koganei, Tokyo 184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, 3-11-15, Midori-cho, Koganei, Tokyo 184-0003,
Japan
4
Faculty of Engineering, Universiti Malaysia Sabah, Jalan UMS, 88400 Kota Kinabalu, Sabah, Malaysia
5Institute of Carbon Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
6
Department of Electrical and Computer Engineering, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
7
Policy Alternative Research Institute, The University of Tokyo, Bunkyo-ku, Tokyo 113-0032, Japan
8
Department of Physics, Department of Materials Science and Engineering & Materials Research Institute, The
Pennsylvania State University, University Park, Pennsylvania 16802, United States

Due to their excellent physicochemical properties, nanocarbons including activatedcarbon, carbon nanotubes, graphene, and their derivatives have stimulated many
researchers to explore the applications of energy conversion and storage systems [1].
Among them, graphene, a two-dimensional atomic layer of hexagonal carbon atoms, isa dazzling star in the exploration journey of supercapacitor applications. Until now,graphene has been synthesized by three main routes: chemical vapor deposition ofcarbonaceous gases, annealing of silicon carbide, and chemical exfoliation of graphite.
Compared to the other two counterparts, the chemical exfoliation technique has someadvantages such as easy mass production and low cost for graphene synthesis with areduction process of graphite/graphene oxide to graphene [2, 3]. However, thistechnique could achieve only partial reduction of graphite/graphene oxide and encounterthe problems of an agglomeration of graphene sheets during the drying of the solution,
further affect their performances in the practical applications. Thus, it is highly desirable
to develop a new synthetic approach to solve the issues and enhance the performances.
In particular, intercalation of other materials including conductive polymers, metaloxides, and other carbon structures between two graphene sheets to form the composites
is popular in the application of supercapacitors [4-6].
In this work, we employed a hydrothermal technique to fabricate a composite
consisting of graphene sheets and carbon spheres, and heated our samples at hightemperatures. Heat treatment here could further remove the oxygen species of graphenesheets and carbon spheres, increase the conductivity of the composites, and adjust the
microstructures of carbon spheres. The detailed results and discussion will be presented
in the coming conference.
[1] W. Gu, et al. WIREs Energy Environ. 3, 424 (2014). [2] Q. Ke, et al. J. Materiomics 2, 35 (2016). [3]S. Zheng, et al. ACS Nano 11, 4009 (2017). [4] Q. Wu, et al. ACS Nano 4, 1963 (2010). [5] Z-S. Wu, etal. Adv. Funct. Mater. 20, 3595 (2010). [6] J. Li, et al. Chem. Phys. Lett. 693, 60 (2018).
Corresponding Author: Zhipeng Wang.Tel/Fax: +81-3-5841-7461,E-mail: z.wang@ipr-ctr.t.u-tokyo.ac.jp- 145 -

3P-25Spin-orbit interaction in Pt and Bi2Te3-nanoparticle decorated graphene
H. Kudo1, M. Hatsuda1, T. Nanba1, R. Tamura1, T. Nakamura2, S. Katsumoto2, J. Haruyama1,2
1Faculty of Sciences and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
2
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa,
Chiba 277-8581, Japan
The introduction of spin-orbit interactions (SOIs) and the subsequent appearance of a
two-dimensional (2D) quantum phenomena with resolving degenerate degrees of freedom are
crucial for voltage-controlled spintronic devices. In contrast, graphene basically lacks SOIs
due to the small mass of the carbon atom. Recently, SOIs have been experimentally
introduced into graphene [e.g., surface decoration by (1) small-mass adatoms (hydrogen [1] orfluorine) and (2) by heavy nanoparticles (gold, silver), and (3) using heavy substrates (copper,
Bi2Se3, WS2)]. When graphene is sufficiently isolated from the influence of the substrate, longspin relaxation times (s) and large mean free paths of electrons are provided. If SOIs can be
introduced without reducing them, graphene possessing SOIs can yield various quantum
phenomena [e.g., 2D or 1D topological insulating (TI) states (quantum spin Hall effect(SHE)), quantum anomalous SHE, and quantum valley HE] and those practical applications.
Indeed, many theories have predicted SOI and TI states in adatom-decorated graphene [2,3].
Here, we introduce large SOIs into mono-layer graphene by controlling decoration ofheavy-nanoparticles [platinum (Pt) or bismuth telluride (Bi2Te3)], using an innovative
nanoneedle technique [4]. The precise and clean(damageless) decoration leads to theemergence of particle density-dependent non-local resistance (RNL) peaks at room
temperature (Fig.1) and those oscillatory behaviors under in-plane magnetic fields. Theysuggest presence of the SOI energies as large as 30  50 meV and (inverse) SHE. Only
Bi2Te3-particle decorated samples within a low density regime demonstrate quarter integer
fractions of resistance quantum in RNL peaks (Fig.1(b)). The present observation opens doors
to novel physics for topological and quantum phases of graphene, introducible by precise
heavy-nanoparticle decoration. More details are presented in poster.

1m

(a)

2m
4.5m

1m

(b)

2m

Fig. 1 Non-local resistance (RNL) vs. back gate voltage (Vbg) and distances (L) between constant-current
and RNL probes, measured for (a) Pt- or (b) Bi2Te3-nanoparticle decorated graphene.
[1] T. Kato, S. Katsumoto, S. Roche, J. Haruyama et al.,, Royal Soc. Chem. Adv. 6, 67586 (2016).
[2] M.T. Deng et al., Science 354, 1557 (2016). [3] L. Brey, Phys. Rev. B 92, 235444 (2015).
[4] T.Nanba, J. Haruyama et al., Phys. Rev. Lett. submitted
Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 146 -

3P-26
Energetics and electronic structure of graphene adsorbing COx underan external electric field
Manaho Matsubara and Susumu Okada
Graduate School of Pure & Applied Sciences, University of Tsukuba, Tsukuba 305-8571
Japan
Graphene has been attracting much attention in the fields of fundamental and applied sciences
for these decades, because of its unique physical properties. The energetics and electronic
properties of graphene are found to be sensitive to the external environments such as molecularadsorbates and an external electric field. Owing to these characteristics, graphene is regarded as
the key material for the sensing devices. It is expected that tuning of carrier density on graphene
can further improve the sensing and adsorption ability, because the electronic properties ofgraphene is sensitive to the carrier density near the Fermi level. Thus, in the present work, we
aim to give theoretical insight into the energetics and electronic properties of graphene
adsorbing COx molecules in the field effect transistor in terms of the molecular arrangements
and carrier concentration, using the density functional theory
with generalized gradient approximation combined with thevan der Waals correction and the effective screening medium
method.
Our calculations show that the optimum spacing between
COx and graphene strongly depend on the carrier
concentrations (Fig. 1). Both electron and hole injection
decrease the optimum spacing than that under the neutral
condition, indicating that the molecules are tightly bound tographene. The enhancement of the binding energy is ascribedto the Coulomb interaction between polarized COx moleculesand graphene under the carrier injection. These results
indicate that the external electric field plays crucial role todetermine the energetics and electronic properties ofgraphene for the molecular adsorption.

Corresponding author: M. Matsubara
Email: mmatsubara@comas.frsc.tsukuba.ac.jp- 147 -

Fig.1 Optimum spacing between
graphene and COx as a function ofcarrier concentration with various
molecular orientations. Circles andsquares denote horizontal andvertical COx to graphene,
respectively.

3P-27Topology tuning of graphene lattice structure by chemical modification○Kentaro Tajima1, 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

Intensity (arb. unit)

Honeycomb lattice of graphene consists of two A, B sublattices. Braking symmetry of A, B
sublattices by chemical modifications causes change in electronic structure of graphene. In thecase of graphene oxide (GO) having oxygen containing functional groups, the difference intype of functional groups gives difference in the symmetry of the A, B sublattices and causes
the localized electronic states. Indeed, hydroxyl groups bonded to a carbon atom on graphene
plane cause the larger spin magnetism, compared with the epoxy group bonded to two
adjacent carbon atoms [1]. Functionalization of graphene by addition of benzene has been
investigated in recent years, which affects the surface charge of graphene depending on thetype of substituent [2]. The difference in bonding manner between benzene and graphene
gives difference in the topological modification, same as oxygen containing functional groups
in GO. Therefore, it is supposed that the radical addition reaction by bonding benzene to acarbon atom at graphene plane strongly affects the electronic states of graphene comparedwith the cycloaddition reaction by bonding benzene to two adjacent carbon atoms. In thisstudy, we evaluated functionalized graphite synthesized by radical addition and cycloaddition
reaction, in terms of chemical structure andelectronic properties.
Graphite powder were functionalized by
R. T., 80 min
the reactions shown in Scheme 1 and labeled1
as R-graphite (1) and C-graphite (2). Raman
spectroscopy was measured by LabRAM HR
Evolution at 532 nm.
45℃, 24 h
The Raman spectra of graphite and2
Scheme1Functionalizations
by benzene radical
functionalized graphite (1, 2) were shown in
Fig. 1. After functionalization the D band addition (1) and arene cycloaddition (2)increased, because sp3 carbon binding toD’GDbenzene exists as defect in graphene lattice.
In Raman spectrum for 1, the G-band
1
position shifts toward the higher energy sidecompared with graphite and 2, suggestinghole doping caused by nitro substituent
which behaves as electron withdrawing
2
group from benzene. The intensity ratio of D’
to G band (ID’ / IG) of 1 becomes larger ascompared with that of 2. The difference ingraphite
topology tuning in functionalized graphites 1
and 2 might affect carrier scattering ingraphene lattice.
1300 1400 1500 1600 1700
[1] K.Tajima et al, Polyhedron, 136, (2017)
wavenumber (cm-1)[2] F. M. Koehler et al, small, 6, 10, (2010)
Corresponding Author: K. Takai (takai@hosei.ac.jp)

Fig. 1 Raman spectrum of graphite, 1 and 2- 148 -

3P-28Magnetism arising from edge spins of few-layer MoS2 nanomeshes
A. Mine1, H. Kudo1, Y. Hashimoto2, G. Kondo1, C. Ohata1,
S. Katsumoto2, J. Haruyama1,21

Depts. Electrical Eng. and Electro. Aoyama Gakuin University, 5-10-1 Fuchinobe,
Sagamihara, Kanagawa252-5258, Japan
2
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa,
Chiba 277-8581, Japan
Magnetism arising from edge spins is highly interesting, particularly in 2D atomically thinmaterials in which the influence of edges becomes more significant. Among such materials,
molybdenum disulfide (MoS2; one of the transition metal dichalcogenide (TMD) family) is
attracting significant attention. The causes for magnetism observed in the TMD family,
including in MoS2, have been discussed by considering various aspects, such as pure zigzag
atomic-structure edges, grain boundaries, and vacancies. In order to reveal such edge-spinbased magnetisms of 2D atom-thin layers, we formed nanomeshes (NMs; honeycomb-likearray of hexagonal nanopores with low-contamination and low-defect pore edges) using a
specific non-lithographic method (nanoporous alumina template mask) on various atom-thinlayers (e.g., graphene, black phosphorus, and hexagonal boron-nitride (hBN)[1-3]) previously
and reported observation of ferromagnetism (FM) derived from the pore-edge spins, which ishighly sensitive to foreign atoms terminating the pore edges.
Here, we adopt this NM structure to few-layer MoS2 and observe FM [4]. We confirm
robust FM arising from pore edges in oxygen(O)-terminated MoS2-NMs at room temperature,
while it disappears in hydrogen(H)-terminated samples. The observed high-sensitivity of FM
to NM structures and critical annealing temperatures suggests a possibility that the Mo-atom
dangling bond in pore edge is a dominant factor for the FM. The result is analogous to thoseobserved in hBN-NMs. This finding of edge-spin-derived room-temperature FM must enable
the use of atomically thin (or few-layer) MoS2 in unique magnetic and spintronic applicationsin addition to well-established electronic and photonic applications.

Fig.1: (a) Typical magnetization curves of the oxygen(O)-terminated few-layer MoS2-NM. (b)Magnetization curves of the O-terminated few-layer MoS2-NMs annealed at two different temperatures,
including that shown in (a). Inset: Ms values as a function of annealing temperature.
[1]
[2]
[3]
[4]

J. Haruyama, Electronics, 2(4), 368 (2013).
Y. Nakanishi, J. Haruyama et a., Nano Research 10, 718 (2017).
C. Ohata, J. Haruyama et al., Appl. Phys. Lett. 109, 133110 (2016).
G. Kondo, J. Haruyama et al., AIP Advances 7, 125019 (2017).

Corresponding Author: J. Haruyama
Tel: +81-42-759-6256, E-mail: J-haru@ee.aoyama.ac.jp- 149 -

3P-29Effect of the water presence in optical phenomena of
hydrazine-adsorbed MoS2
○Naoko Kodama1, Y. Ishiguro2, K. 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, JapanThe optical properties of 2D materials such as MoS2 strongly depend on the chemical
environments [1]. Indeed, an electron doping by hydrazine monohydrate adsorption makes
Raman A1g mode of MoS2 soften and broaden. However, PL for MoS2 adsorbed with hydrazine
monohydrate measured at 77 K apparently shows irreversible hole-doping behavior [2]. Since
half of hydrazine monohydrate is water, the effect of water might be involved. In this study,
MoS2 single layer adsorbed with water is investigated in order to clarify the effect of moleculardoping on the optical properties of MoS2 in terms of its kinetics.
MoS2 single layer on 90 nm SiO2/Si substrate was prepared by mechanical exfoliation.
Hydrazine monohydrate or water were dropped on MoS2 on the substrate and dried with air
blow, followed by immediate Raman and PL measurement with an excitation wavelength of
532 nm. The same operation was repeated while varying the adsorption time.
As shown in Fig.1, the trion peak contribution A- decreases and exciton peak A increases in
PL as time passes after water adsorption, indicating hole-doping via water adsorption. On theother hand, Raman spectra is not sensitive to hole-doping unlike electron-doping. From theseresults, the apparent irreversible hole-doping observed at 77 K for hydrazine adsorbed MoS2 is
explained by the competition between n-doping by hydrazine and long-term hole doping byatmospheric oxygen assisted by water, similar to that in graphene[3].
This project was supported by JSPS and RFBR under the Japan - Russia Research Cooperative
Program.
[1] S. Mouri et al., Nano Lett., 13, 5944 (2013) [2] N. Kodama et al., FNTG symposium (2017)

A

A-

A

1.5

-

1.8

A

Si

Pristine

Just after
Immersion

A

Intensity (arb.unit)

Intensity (arb.unit)

A-[3] T. Umehara et al.，JPS meeting (2015)

A1g E12g

Pristine
Just after Immersion
Leave 8 days

Leave18 days
370

2.1

420

470

520

Peak position (cm-1)

PL shift (eV)Fig.1 Time evolution of PL at 77 K forwater adsorbed MoS2

Fig.2 Time evolution of Raman forwater adsorbed MoS2

Corresponding Author: Kazuyuki Takai
Tel: +81-42-387-6138, Fax: +81-42-387-7002,
E-mail: takai@hosei.ac.jp- 150 -

3P-30Continuous heteroepitaxy of two-dimensional
multi-heterostructures based on layered chalcogenides○Yu Kobayashi1, Shoji Yoshida2, Mina Maruyama2, Kota Murase2, Susumu Okada2,
Yutaka Maniwa1, Hidemi Shigekawa2, Yasumitsu Miyata1
1

Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
2
Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan
Atomic layers of transition metal dichalcogenides (TMDCs) have attracted significant
attention because of their unique physical and chemical properties. To utilize their fullpotential, it is highly desired to develop a versatile growth process of TMDC-based functional
heterostructures. However, conventional growth processes are usually required multiple
complicated step including interface degradation and/or alloying, and are also difficult tocontrol growth rate precisely [1,2].
Here, we report versatile heteroepitaxial growth of two-dimensional multi-heterostructures
based on TMDCs (Fig. 1a). The use of liquid precursors enables the growth ofhighly-crystalline MoS2, WS2, MoSe2, WSe2 monolayers and their in-plane heterostructures(Fig. 1b). The present process can also realize atomically sharp and zigzag-edge straightjunctions without defect and alloy formations around interface (Fig. 1c). The high-quality
interface allows us to probe intrinsic band diagram, and is found to have larger band offset
along conduction band minimum at MoS2-WS2 heterojunction, which is almost consistent
with the results of first-principles calculations. Furthermore, the present heteroepitaxy also
demonstrate the controlled growth of ribbon-shaped monolayer TMDC with less than 20 nm
width from the straight edges of firstly-grown monolayers. These results open up a novel way
to realize diverse atomically-thin quantum wires and superlattices, and further advanced
applications in electronic and opto-electronics.

Figure 1. (a) Schematic illustration and (b) PL intensity map of in-plane WS2/MoS2/WS2 multiheterostructure. Red and cyan correspond to the intensities of the MoS2 and WS2 PL peaks, respectively. (c)STM image of MoS2/WS2 heterointerface.
[1] Z. Zhang et al., Science, 357, 788 (2017)., [2] M.-Y. Li, et al., Science, 349, 6247 (2015).
Corresponding Author: Y. Miyata, Tel: +81-42-677-2508, E-mail: ymiyata@tmu.ac.jp- 151 -

3P-31
Electric-field-induced Metal-Insulator Transition and Quantum Transportin Large-Area Polycrystalline MoS2 Monolayers○Tomoyuki Yamada1, Jiang Pu1, Lain-Jong Li2, Taishi Takenobu1

Department of Applied Physics, Nagoya Univ., Nagoya 464-8603, Japan
Physical Sciences and Engineering Division, KAUST, Thuwal 23955-6900, Saudi Arabia
1

2

Molybdenum disulfide (MoS2) is attracting increasing interests for future nanoelectronics [1].
The exfoliated single crystalline flakes have realized high mobility, metal-insulator transition,and superconductivity [2]. In addition, quantum transports arising from strong spin-orbit
interaction have also been observed; thus, these superior transport properties offer potentials of
MoS2 for exploring quantum device applications [3]. Although it is necessary to apply largearea films for scalable device integration, the chemically synthesized polycrystalline films
commonly showed poor transports, such as low mobility, due to the effects of grain boundaries
and/or impurities. To overcome this issue, we recently combined electric double layertransistors (EDLTs) with polycrystalline MoS2 films, and achieved high mobility of 30 cm2/Vs[4]. This result suggests that high carrier density accumulations can reduce the adverse effects
of grain boundaries. Here, we apply EDLTs to investigate the temperature- and carrier-densitydependence of resistance and magnetoresistance, resulting in the observation of metallic
conduction and quantum transport in large-area polycrystalline MoS2 monolayers.
Large-area polycrystalline MoS2 monolayers were grown by chemical vapor deposition on
sapphire substrate, and then, we deposited electrodes on it. Finally, ion gel films, mixture ofionic liquids and polymers, were spin-coated on MoS2 and electrode surfaces to perform four
terminal and Hall measurements (Fig. 1). Figure 2 shows the temperature dependence of the
sheet resistance (RS) with different gate voltage (Vg). At low Vg, the RS increases as decreasing
temperature (T), meaning insulating behavior. In contrast, at high Vg, the RS shows metallic
conduction down to T of 1.9 K, which clrealy indicates metal-insulator transition. Hallmeasurement also revealed the carrier density and mobility up to 2.1 × 1014 /cm2 and 27 cm2/Vs,
respectively. Moreover, we observed unique magnetoresistance characteristics of the crossoverfrom weak localization to weak antilocalization, as shown in Fig. 3. These results indicate thathigh carrier density eliminates the effects of grain boundaries, consequently realizing quantum
transports in polycrystalline MoS2 monolayers. We will quantitatively evaluate thesemagnetoresistance behaviors, and discuss the possibility for superconductivity.

Fig. 2
Fig. 1
Fig. 3[1] G. Fiori, et al. Nat.Nanotechnol. 9, 768 (2014), [2] J. T. Ye, et al. Science 338, 1193 (2012)[3] H. Schmidt, et al. Phys. Rev. Lett. 116, 046803 (2016), [4] J. Pu, et al. Adv. Mater. 28, 4111 (2016)
Corresponding Author: T. Takenobu, Tel/Fax: +81-52-789-5165, E-mail: takenobu@nagoya-u.jp- 152 -

3P-32
Second quantization of surface plasmon in graphene and the applications
M. Shoufie Ukhtary, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Surface plasmon (SP) is electromagnetic wave propagating on the surface of a material. SP is
associated with the collective oscillation of charge on the surface of material. The strength ofelectromagnetic field decreases in the perpendicular direction to the surface, making the SP confined.
It is well-known that the excitation of SP by external electromagnetic wave requires the matching
between energy-momentum of external wave and SP. It is also assumed that the energy-momentum
matching will cause an enhancement of electromagnetic wave absorption by the material which isshown by the dip of reflection spectra. However, the explicit physical explanation of the SP excitation
is not understood clearly.
Due to the confinement nature of SP, the quantum treatment of SP is possible, where the SP is
considered as a quasiparticle travelling on the surface. In this work, we study how the SP can bequantized as an oscillator harmonic, similar to the quantization of phonon [1, 2]. In this study, we
use the quantization scheme given by Archambault et al [1], where they quantized the energy ofelectromagnetic wave on the surface by introducing creation-annihilation operator. By quantizing theSP, we can explain why the excitation of SP requires the energy-momentum matching from which
we can obtain the matrix element of photon-plasmon interaction (optical absorption probability).
Quantization of SP
also enables us todetermineba

Why excited?

thepartition function ofSP, which can beused to determine
the thermodynamic
quantities such as(a) Excitation of SP by light. (b) The reflection spectra. The
dip on the spectra is the excitation of SP.

internal energy andenergy spectral the SP.
References:[1] Archambault et al. PRB 82 035411 (2010)[2] Finazzi et al. PRB 86 035428 (2012)- 153 -

3P-33
Effect of thermal stress on resonance properties ofatomically thin electromechanical resonators○Taichi Inoue, Yuta Mochizuki, Yuki Imakita, Kuniharu Takei, Takayuki Arie, Seiji Akita
Department of Physics and Electronics, Osaka Prefecture University,
Sakai 599-8531, Japan

Frequency shift (%)

Frequency shift (%)

Atomically thin mechanical resonators [1] including stacked MoS2/graphene are expected
to be a highly sensitive optical or thermal sensor because of novel opto-mechanicalfunctionalities. However, the thermal effect on resonance properties is still open subject. Here,
we investigate thermal stress on resonance property of the stacked resonator.
Graphene synthesized by chemical vapor deposition (a)was transferred onto a pair of electrodes on a Si/SiO2
substrate and trimmed by O2 plasma. For the stacked
resonator, the mechanically exfoliated MoS2 wastransferred onto the graphene by the gel transfer method.
Lastly, the 300 nm-thick SiO2 layer underneath of thegraphene was etched by buffered HF to obtain thesuspended structure. Fig. 1(a) shows Scanning electron(b)microscope image of drum type stacked MoS2/graphene20
V (V)mechanical resonator with a diameter of ~ 6 m. The
Graphene only
5.0
15
resonance properties were measured by using the
4.5
4.0
3.5
electrical method [2], where the resonator was driven by
10
3.0
2.5
electrostatically by applying the AC source drain voltage
5.0
Vsd. The gate voltage Vg can modulate tension of the0resonator. The temperature dependence of the resonance
-5.0
0
2
4
6
8 10
properties were measured in vacuum at 10-3 Pa.
Temperature change (K)Fig. 1(b) and 1(c) show temperature dependences of(c)resonance frequency shifts of graphene-only or stacked
5.0
V (V)
MoS /graphene
MoS2/graphene mechanical resonators under linear
4.0
5.0
4.5
oscillation regime, respectively. In the case of the
3.0
4.0
3.5
graphene-only resonator, the frequency shift changed
2.0
3.0
2.5
linearly for all Vg with the temperature. This indicates
1.0
that the temperature dependence of the thermal stress0
can be modified by Vg. Note that the slope of frequency
-1.0
0
2
4
6
8 10
shift is changed from positive to negative as increasing
Temperature change (K)Vg. In the case of stacked MoS2/graphene mechanical Fig. 1(a) SEM image of resonator. (b)resonator, the frequency shift was suppressed to ~ 2.5% and (c) are temperature dependence ofcompared with graphene-only resonator for all Vg. The resonance frequency shift of graphene
only or stacked MoS2/graphenecause of this shift is most likely due to the combination mechanical resonator, respectively.
of the positive and negative thermal expansion
coefficients of MoS2 and graphene.
g2g

Acknowledgements This work was partially supported by KAKENHI Grant Number JP15H05869,
JP16K14259, JP16H00920, and JP17H01040. Reference [1] T. inoue et al. ACS Omega, 2017, 2(9),pp 5792-5797 [2] Vera Sazanova et al. Nature 431, 284-287 (2004).
Corresponding Author: T. Inoue, Tel: +81-72-254- 9261, E-mail: t_inoue-4@pe.osakafu-u.ac.jp- 154 -

3P-34Fabrication and characterization of field-effect transistors based on
CVD-grown monolayer MoS2
○Hiroshi Shimizu, Shun Ogawa, Yu Kobayashi, Takahiko Endo,
Yutaka Maniwa, Yasumitsu Miyata*
Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Atomic layers of transition metal dichalcogenide (TMDC) have been intensively studied
because of their unique properties and potential applications in electronics. In early studies,
atomic layers are mainly prepared by mechanical exfoliation of bulk crystals. However,obtained crystals were usually small flakes of around 10 μm in size. In contrast, recently, large
single crystals of TMDC with more than 100 μm can be grown by chemical vapor deposition(CVD). It is, therefore, an important subject to evaluate fundamental crystal quality andelectric transport properties of such samples. For this purpose, we have investigated thetransport properties of large-area monolayer MoS2 single crystals grown by CVD [1]. In thispresentation, we report recent progress of fabrication process and electrical performance of
CVD-grown monolayer MoS2 FETs.
Monolayer MoS2 was grown at 760 ℃ on a silicon substrate using halide-assisted CVD [2].
In this work, molybdenum oxide (MoO2) powder and sulfur flakes were used as precursors.
To fabricate MoS2 FETs, Ni/Au (or Cr/Au) electrodes were deposited on the triangle-shapedmonolayer grains using maskless photolithography (Fig.1a). Typical n-type behaviors can beobserved for MoS2-FETs with Si back gate at room temperature in air (Fig.1b,c). Carrier
mobilities and on/off ratios were evaluated to be 10~40 cm2/Vs and 104~105, respectively, forthe present devices. These results are comparable to the highest values reported for previous
exfoliated and CVD samples [3], and suggest the potential of CVD-grown MoS2 monolayers
for electronics applications.

Fig. 1 (a) Optical image, (b) Id-Vds, and (c) Id-Vgs curves of a monolayer MoS2 FET.
[1] T. Uchida et al., The 53rd FNTG symposium (2017).
[2] S. Li et al., Appl. Mater. Today, 1, 60 (2015).
[3] Z. Yu et al., Adv. Fanct. Mater., 27, 1 (2017).
Corresponding Author: Yasumitsu Miyata
Tel: 042-677-2508, E-mail: ymiyata@tmu.ac.jp- 155 -



3P-35Observation of graphene quantum dot using ion trap ion mobility
measurement system○Yudai Hoshino, Hiroki Morita, Ryota Jinnouchi, and Toshiki Sugai
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Graphene quantum dots (GQD) are nanometer-size graphene fragments, which have highpotential to be applied in a wide range of fields with their unique photoluminescence (PL)properties and low toxicity, etc. However, their structure has not been fully understood letalone the PL mechanism. Here, we present structural evaluation of single GQD particles by
our ion trap ion mobility measurement system with high voltage assisted laser desorption
ionization (HALDI).
Figure 1 shows a schematic view of oursystem with an ionization YAG (266 nm) laser,an observation semiconductor (405 nm) laser, N2
gas inlets, a metal sample rod, multiply stacked
ring ion guide copper electrodes as an ion trap,
and power supplies. The sample GQD producedin our laboratory[1] were placed on the top of
the sample rod where the HALDI voltage andthe YAG laser were introduced to ionize them.
The ionized GQD were held and observed in the Fig.1. Schematic view of ion trap ion mobility
trap under N2 at atmospheric pressure.
measurement system
Figure2showsthevelocity
distribution of GQD under the electricfield of 3.3 kV/m with the HALDI of3 kV. Several peaks appears in every
3.5 mm/sec and the velocity
distributions shift to larger with thelarger HALDI voltage. When weapplied the lowest HALDI voltage of
300 V, the distribution converged to asingle peak. Those results show thatquantized charges were observed withhigh structural uniformity of the GQD andthe single charge state were realized withthe voltage control. The evaluatedstructure from the velocity of the singly
charged GQD [2] is the single layer
graphene disk with the diameter of 20
nm, which are consistent with thoseobtained with TEM[1]. The polarity
Fig.2. Distribution of drift velocity in each HALDI voltage
and the amount of charge can be control
by HALDI voltage. Further measurements on optical spectroscopy are in progress.
[1] H.Morita and T.Sugai, The 53th symposium 2P-23 (2017).
[2] T. Sugai, J. Mass. Spectrom. Soc. Jpn., 58, 2, (2010).
Corresponding Author: T. Sugai, Tel: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 156 -

3P-36
Control of photoluminescence and solubilityof graphene quantum dots
○H. Morita, K. Somei, Y. Hoshino, R. Jinnouchi, T. Sugai
Department of Chemistry, Toho University, Miyama 2-2-1, Funabashi 274-8510, Japan

Graphene quantum dots (GQD) are nanometer-size graphene fragments with unique properties
such as photoluminescence (PL), low toxicity, and photostability. GQD are derived fromvarious carbonaceous bulk materials by top-down approaches with highly oxidized processes
in which hydrophilic carboxylic groups are combined [1]. Thus obtained high water solubility
together with the PL properties is useful for bio-sensors [2]. The high water solubility, however,results in low solubility in organic solvent, which restricts numbers of chemical modification
techniques [3] In addition, the hydrophilic carboxylic groups have been known to be combinedto the PL active site closely [4,5,6]. To control PL property such as modulation of wavelengths
and enhancement of quantum yield, the chemical modification is inevitable. Here we present
chemical modification of GQD soluble in organic solvents and modification of PL properties.
GQD were prepared from CoMoCAT-SWNTs (Sigma-Aldrich) by oxidation in a mixture ofconcentrated H2SO4 and HNO3. The produced water soluble GQD were converted to organosoluble GQD-Hex and GQD-Me by esterification together with 1-hexanol and methanol asbrown oily substances. They were characterized by optical and TEM observation.
GQD-Hex and -Me are both soluble in hexane, toluene and acetone. Fig.1 shows PL emissionexcitation 3D mapping of pristine water-soluble GQD, GQD-Hex and GQD-Me. water-soluble
GQD shows molecular-like excitation-independent sharp emission peaks around 420nm and
520nm (Fig.1a). GQD-Hex and –Me, in contrast, show the broad excitation-dependent peaks at
425nm and 320nm (Fig.1b and c). Those results show that the chemical modification has strong
effect not only to the solubility but also to the PL properties. These methods should contributeto clarify the unknown PL mechanisms of GQD.
[1] Bacon, M., et.al. Part. Part. Syst. Charact. 31, 415 (2014) [2] Ananthanarayanan, A., et.al. Adv. Funct. Mater.
24, 3021(2014) [3] Sekiya, R. et.al. Chem. -A Eur. J. 22, 1–10(2016). [4] Santiago, S. R. M., et.al. Physical
Chemistry Chemical Physics, 18, 2259 (2016). [5] Zhu, S., et.al. Nano Research, 8, 355 (2015). [6] Dong, Y. et.al.;.
Mater. Chem. Phys., 203, 125–132, (2018)
Corresponding Author: T. Sugai. Tel: 047-472-4406,

E-mail: sugai@chem.sci.toho-u.ac.jp

Fig.1 PL mapping of (a) GQD-Me (b) GQD-Hex.

- 157 -

3P-37
Energetics and electronic structure of all-benzene nanostructures
Masaki Mieda and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba
305-8571, Japan
Electronic structure of hydrocarbon molecules is sensitive to the topology of 𝜋𝜋electron distributed throughout their covalent network attributed to 𝜎𝜎 electron. The
electronic structures are ranging from closed-shell to open-shell, depending on themolecular shapes and sizes. It has been well known that the hydrocarbon molecules
sorely consist of hexagonal rings basically possess symmetric electronic structure withrespect to their 𝜋𝜋 and 𝜋𝜋 ∗ states. In contrast, in the molecules with curvature, such as
fullerenes, 𝜋𝜋 − 𝜋𝜋 ∗ symmetric electronic structure is absent near the Fermi level,
making them unique materials for observing unusual physical and chemical phenomena.
In the present work, we theoretically design the all-benzene cage and cyclic structuresby oligomerrization of phenyl group, using the density functional theory with thegeneralized gradient approximation.
Figure 1 shows the geometric structures and total energy of [n]cyclometaphenylene([n]CMP) designed here. The total energy of [n]CMP has the energy minimum at n=7
with the staggered structure to reduce the Coulomb repulsive interaction between H
atoms. By assembling [n]CMP, where n=3, 4, and 5, we also designed all-benzene cagenanostructures which possesses moderate energetic stability and HOMO-LUMO gap
ranging from 1.25 to 2.25 eV.

Fig. 1 Optimized geometries of [5]CMP, [6]CMP, and [7]CMP.

Correspond authors, M. Mieda and S. Okada
E-mail: sokad@comas.frsc.tsukuba.ac.jp- 158 -

3P-38
Plasticity of carbon nanotubes under combined axial and torsional stress○Masafumi Yamanashi1, Masayuki Toyoda1, Susumu Saito1, 2
1

Department of Physics, Tokyo Institute of Technology, 2-12-1 Oh-okayama, Meguro-ku,
Tokyo 152-8551, Japan
2
Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259
Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503, Japan

It is known that electronic properties of carbon nanotubes (CNTs) depend on their chiralindices, ( n, m ). Therefore, it is desirable to selectively obtain CNTs with desired chirality forvarious device applications. As for manipulation of chirality of CNTs, dislocation theory
applied to CNTs under axial tension has shown that plastic elongation of CNTs canaccompany with the change of their chirality from ( n, m ) to ( n, m  1 ) through sequential
Stone-Wales transformations [1]. Here, we study plasticity of CNTs under combined axial andtorsional stress by extending the previous study [1]. It is now revealed that any of six
dislocation directions that change chiral indices from ( n, m ) to ( n  1, m ), ( n  1, m ),( n, m  1 ), ( n, m  1 ), ( n  1, m  1 ) or ( n  1, m  1 ) can become the most energeticallyfavorable direction depending on applied combined stress (Fig.1). We also show our extended
model can explain molecular dynamics (MD) studies reported so far.
Also, to study energetics of the Stone-Wales transformations in CNT under the combined
stress, we have carried out tight-binding MD simulations that well reproduce the energetics of
local density approximation. We confirm that the energetics obtained by MD simulations
show good agreement with our extended model.
From our results, one can optimize the combined stress for any of six transformations tooccur. The present finding therefore opens the way to manipulate the chirality of a CNT andconsequently their electronic properties. Since CNTs have been studied as super-strong wirematerials, this work is also beneficial for comparing yield strength of CNTs having different
chirality against the combined stresses.
[1] B. I. Yakobson, Appl. Phys. Lett. 72, 918 (1998).

Fig.1. Plastic transformation of a (9, 8) CNT to a (8, 8) CNT under combined axial and torsional
stress through sequential Stone-Wales transformations shown as an example.
Corresponding Author: M. Yamanashi
Tel: +81-3-5734-2721
E-mail: yamanashi@stat.phys.titech.ac.jp- 159 -

3P-39Dependence of optical band gap on aggregational state of iron oxide
nanotube prepared by sol-gel method
Shiori Takakura, ○ Shunji Bandow
Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan
Iron oxide nanotubes (Fe-ox-NTs) were synthesized by co-plymerization of iron-nitrate
hydrate on the surface of non-ionic surfactant of a Pluronic F-127 in 1-propanol [1].
As-prepared nanotubes form bundle-like lump in which the individual nanotubes areagglutinated each other as shown in Fig. 1. In order tosegregate these agglutinated nanotubes into individual ones,
we carried out a method based on the collision of highlypressureized oncoming fluids so called Jet Mill (JM) for
the nanotubes dispersed in ethanol (EtOH). Briefly ~10
mg of Fe-ox-NTs were dispersed in 15 ml of EtOH andcrushed by JM at the pressure of 180 MPa for 100 times.
Then the colloidal solution was centrifuged several steps Fig. 1. Bundle-like agglutinatedFe-ox-NTs (TEM of as-preparedby increasing centrifugal acceleration in order to isolate
sample).
nanotubes.
Figue 2 is the NTs observed in the
supernatant at 1000 G.
Upon progressing thecentrifugal stage, size ofthe lump decreased.
X-ray diffraction
patterns of the samples
indicated that Fe-ox-NTs
Fig. 2. TEM of isolated Fe-ox-NTs by centrifuge after JM. Left panel
have Fe3O4 (magnetite)shows the bunble formed by several tens of Fe-ox-NTs. Right panel issingle Fe-ox-NT. Supernatant solution includes both type of NTs, but
structure. Optical bandthe mixing rate of single NT increases as increasing the isolation stage.
gap was evaluated by
the Tauc plot method, which clearly showed the increase of band gap as increasing thecentrifugal isolation stage. Highly aggregated Fe-ox-NTs have the optical band gap between~2.1 and ~2.3 eV (like the sample indicated in Fig. 1), while the isolated ones have muchwider band gap of ~2.7 eV (dominated by the small size of NT-bundle lumps like the left ofFig. 2) and of ~ 2.9 eV (dominated by isolated NTs like the right of Fig. 2). These values did
not depend on the environment of NTs whether dispersed in EtOH or dry powder.
[1] Y. Kosugi, S. Bandow, J. Inorg. Organomet. Polym. 24, 933 (2014).
Corresponding Author: S. Bandow, E-mail: bandow@meijo-u.ac.jp, Tel: +81-52-838-2404- 160 -

発表索引
Author Index

Author Index<A>
Abe, Tsuneyuki
Achiba, Yohji

Arvanitidis, Ioannis
Asakawa, Yuta
Atwa, Mohamed

1P-2
1P-3, 1P-4, 2P-3,
3-3, 3P-2
1P-22, 1P-30, 1P-33,
3-8
1S-1
1-7
1P-33
1P-37
1P-2, 3P-4
1P-31, 3P-23, 3P-33
2P-4
1-5, 1-7, 1P-13
1P-37
2P-4, 3P-3
2-8, 2P-35
3P-22
3P-14
1P-31, 3S-8, 3P-23,
3P-33
2P-4
3-7
1-7

<B>
Bandow, ShunjiBao, Jianfeng

3P-39
1P-30

<C>
Chen, Yuguang
Chiashi, Shohei
Choi, Mansoo
Choi, Wookjin
Cruz-Silva, Rodolfo

1S-2
1-1, 2P-13, 3P-22
1-7
1P-2
3P-24

<D>
Delacou, Clement
Deng, Yinmei
Ding, Er-Xiong

1-7,
2-2
1S-1

<E>
Eda, Junko

1P-9, 2P-6

Ago, Hiroki
Ahmed, Saeed
Ahn, NamyoungAji, Adha Sukma
Ajima, Kumiko
Akasaka, Takeshi
Akita, Seiji
Akiyama, Kimio
Anisimov, Anton
Aoki, Kaoru
Aoyagi, Shinobu
Aoyama, Tetsuya
Arai, Hayato
Araki, Nayu
Arie, Takayuki

1P-13

Einarsson, Erik
Endo, Morinobu
Endo, Takahiko

2 I-2
3P-24
1P-35, 2P-29, 3P-34<F>
Fugetsu, Bunshi
Fujii, Yasumaru
Fujimura, Naoki
Fujita, Kento
Fukazawa, Shinpei
Fukuhara, Kengo
Fumiyuki, Nihey
Funamori, Yuto
Furukawa, Ko
Furutani, Sho

3P-24
1P-29
3P-8
2P-34
3P-4
1P-9, 2P-5, 2P-6
1-2
1P-7
1P-4, 3-3
1P-1

<G>Gao, Weilu
Gao, Yanlin
Gong, Wei
Gonnokami, Hiromichi<H>
Hachiya, Kengo
Hamaguchi, Hiroaki
Hamajima, Keisuke
Hamano, Yuta
Haniu, Hisao
Hao, Zhang
Hara, Masanori
Harano, Koji
Harigai, Toru
Haruyama, JunjiHase, Muneaki
Hashikawa, Yoshifumi
Hashimoto, Yoshiaki
Hashimoto, Yoshio
Hatsuda, Masahiro
Hayakawa, Junpei
Hayashi, Yoshiki
He, Xiaowei
Hibino, Hiroki- 161 -

1S-3, 2P-5, 3-9,
3P-8
2P-38

3P-24
1P-7, 3P-21

1P-12
2P-39
2P-14
2-7
1P-37
3P-10
1P-26
2-4
2P-39
3P-25, 3P-28
2P-36
3-2, 3P-5
3P-28
3P-24
3P-25
2P-34
2P-12
3P-8
1P-22

Hirano, Atsushi
Hirata, Eri
Hirobe, Genki
Hirotani, Jun
Homma, Yoshikazu
Horibe, Masashi
Horii, Hikaru
Hoshino, Yudai
Hosoda, Seiji
Hu, Yuecong
Huang, Hsin-Hui
Huang, Jing-kai
Hung, Nguyen T.
Hussain, Aqeel<I>
Ichinose, Yota
Iijima, Sumio
Iizumi, Yoko
Ikuhara, Yuichi
Ikuta, Yoshiue
Imaeda, Hirotaka
Imakita, Yuki
Inaba, Takumi
Inaba, Tatsurou
Inoue, Taichi
Inoue, Taiki
Inoue, Yoku
Ishibashi, Koji
Ishida, Haruka
Ishido, Kaito
Ishiguro, Yasushi
Ishii, Akihiro
Itami, Kenichiro
Ito, Seichiro
Iwasa, Yoshihiro
Iwasaki, Yuya
Izumoto, Masanori<J>
Jeon, Il
Jinnouchi, Ryota

1P-11, 2P-36, 3P-17
2P-37
2P-18
1-6, 1P-14, 2P-8,
3P-11, 3P-13
2P-7
2P-24
2P-20
2-7, 3P-35, 3P-36
3P-1
3-10
1P-26
2P-32
1P-10
1S-1

1P-9, 2P-5, 2P-6,
3-9
2-2
1P-36
1P-32
3-8
1P-30
3P-33
2P-7
2P-30
3P-33
1-1, 3P-18, 3P-22
3P-15
2P-7
1P-37
2P-34
2P-18, 3P-29
3-11
3S-7
2P-24
2P-28
3P-9
1P-33

1-5, 1-7, 1P-13,
2P-1, 3-4, 3P-10
2-7, 3P-35, 3P-36<K>
Kako, Masahiro
Kameda, Tomoshi
Kanai, Yasuyuki
Kaneda, Yuko
Kaneko, Tomoaki
Kaneko, Toshiro
Karita, Motoyuki
Kashima, Taiga
Kashiwa, Kotaro
Kashiwabara, Yuta
Kataoka, Yosuke
Kataura, Hiromichi

Kato, Hiroyuki
Kato, Tatsuhisa
Kato, Toshiaki
Kato, Yuichiro K.
Katsumoto, Shingo
Katsutani, Fumiya
Kauppinen, Esko I.
Kawahara, Kenji
Kawai, Takazumi
Kawano, Yukio
Khan, Taher
Kikuchi, Koichi
Kinoshita, Toshiya
Kioka, Yusei
Kishida, Hideo
Kishimoto, Shigeru
Ko, Jeong Won
Ko, Weon Bae
Kobashi, Kazufumi
Kobayashi, Kazuhiro
Kobayashi, Keita
Kobayashi, Yu
Kodama, Naoko- 162 -

3P-4
1P-11
1P-5, 1P-6
1P-7
2-11
1P-19, 1P-23, 2-10,
2P-19
3P-15
1-6, 3P-11
3P-22
2P-28
2P-16
1-3, 1P-11, 1P-38,
2P-8, 2P-37, 3P-10,
3P-17
1P-37
1P-4, 3-3
1P-19, 1P-23, 2-10,
2P-19
3-11
3P-25, 3P-28
1S-3, 3-9
1S-1, 1-5, 1-7,
1P-13
1P-22, 1P-30, 3-8
2P-23
3P-8
1S-1
1P-3, 1P-4, 2P-3,
3-3, 3P-2
3P-15
2P-21
1P-8, 1P-30, 2P-14
1-6, 1P-14, 2P-8,
3P-11
2P-2
2P-2
2-1
1P-4
2-13
1P-32, 1P-35, 2P-29,
3P-30, 3P-34
3P-29

Kodama, Takeshi
Kojima, Kana
Kokubo, Ken
Komatsu, N.
Komatsu, Naoki
Komuro, Tomohiko
Konabe, Satoru
Kondo, Gen
Konno, Yui
Kono, Junichiro
Kowashi, Satori
Koyama, Takeshi
Kubota, MarikoKudo, Hiroaki
Kumaki, Kentaro
Kumakura, Makoto
Kumamoto, Akihito
Kurahashi, Tyler
Kuroda, Chika
Kusunoki, Michiko
Kuwahara, Yuki
<L>
Laiho, Patrik
Laine, Richard
Lee, Jin-Wook
Li, Chao
Li, Lain-Jong
Li, Ming-Yang
Li, Xinming
Li, Xinwei
Li, Yan
Li, Yitan
Liang, Bin
Liao, Yongping
Lim, Hong En
Lin, HaoshengLiu, Gang
Liu, Ming
Liu, Xiyan
Liu, Xu

1P-3, 1P-4, 2P-3,
3-3, 3P-2
2P-29
2P-4
1S-3
1-4, 1P-34, 3-6
3P-13
2P-20
3P-28
1P-12
1S-3, 2P-5, 3-9,
3P-8
2-4
1P-8, 1P-30, 2P-14,
2P-15
1-3
3P-25, 3P-28
3-5
1P-16
1P-32
3P-21
1P-37
1P-30
1-2

López-Moreno, Alejandro
Lu, Fei<M>
Ma, Renzhi
Machida, Tomoki
Machiya, Hidenori
Maeda, Yukari
Maeda, Yutaka
Maekawa, Toru
Maekawa, Yuki
Maniwa, Yutaka
Maruyama, Mina
Maruyama, Shigeo

Maruyama, Takahiro
Masubuchi, Satoru
Matsubara, Manaho
Matsuda, Kazunari
Matsunaga, Masahiro
Matsuo, Yutaka

1S-1
1P-17
1-5
2-10
2P-32, 3P-31
2P-32
2-9
1S-3, 3-9
1S-2, 1P-18, 2-3,
3-10, 3P-16
1S-2
1P-17
1S-1
2-12
2P-1
1P-34, 3-6
3P-18
3P-16
1P-18

Matsuoka, Tokinaru
Matsuura, Tomoki
Melvin, Gan Jet Hong
Mieda, Masaki
Mine, Akihide
Misaizu, Fuminori
Mitani, Takuji
Miura, Yasuhiro F.
Miwa, Kazuhira
Miyamoto, Dai
Miyamoto, Reona
Miyamoto, Yuga
Miyata, Yasumitsu
Miyauchi, Yuhei- 163 -

1-4
2 I-2

2-9
2S-6, 3-7
3-11
2P-37
1P-2, 1P-12, 3P-4
3P-1
2P-21
1P-35, 2P-29, 3P-30,
3P-34
1P-21, 1P-28, 1P-29,
2-5, 3P-30
1-1, 1-5, 1-7,
1P-13, 1P-32, 2P-1,
2P-13, 3-4, 3P-10,
3P-18, 3P-22
1P-16
3-7
3P-26
1P-12, 2-12, 2P-27,
2P-29, 2P-31, 2P-32
1P-14
1-5, 1-7, 1P-1,
1P-13, 2P-1, 2P-4,
3-1, 3-4, 3P-3,
3P-10, Tutorial
1P-20, 2P-12
1-6, 3P-11
3P-24
3P-37
3P-28
2-6
3-3
2-8, 2P-35
3P-3
2P-39
2-7
1P-31
1P-32, 1P-35, 2P-29,
3P-30, 3P-34
1P-12, 2P-27, 2P-29,
2-12, 2P-31, 2P-32

Mizuno, Yuya
Mkhalid, Ibrahim A.
Mochizuki, Yuta
Mohamed, Nur Baizura
Mohamed, Reda M.
Morikawa, Sei
Morimoto, Masataka
Morimoto, Shingo
Morimoto, Takahiro
Morita, Hiroki
Moriyama, Ryoichi
Murase, Kota
Murata, Hidenobu
Murata, Yasujiro

2P-24
3P-12
3P-23, 3P-33
2-12
3P-12
3-7
3-7
3P-24
2-1, 3-8
2-7, 3P-35, 3P-36
2-6
3P-30
1P-7, 3P-21
3-2, 3P-5<N>
Nagai, Kohei
Nagai, Ryo
Nagai, Yukuya
Nagaoka, Hirokazu
Nagasawa, Horoshi
Nagasawa, Yuya
Nagase, Shigeru
Nagashio, Kosuke
Nakagawa, Takeshi
Nakahara, Hitoshi
Nakajima, Hideaki
Nakamura, Eiichi
Nakamura, Kazuki
Nakamura, Kosuke
Nakamura, Taketomo
Nakano, Masaki
Nakano, Motohiro
Nakano, Motoyoshi
Nakano, Takayuki
Nakashima, Hiroshi
Nakashima, Naotoshi
Nakayama, Tomohito
Nanba, Taku
Naritsuka, Shigeya
Nihey, Fumiyuki
Nishi, Ryohei
Nishidome, Hiroyuki
Nishii, Haruki
Nishikubo, Ryosuke

2P-6
2P-16
2P-17
3P-15
2P-12
2P-15
1P-2
1P-22
2P-4
2P-24
2-2, 3-8
2-4
2P-34
2P-25
3P-25
2P-28
3P-5
2-6
3P-15
1P-22
3P-7
2P-36
3P-25
1P-16
3P-19
2P-8
2P-6
2P-39
3-4

Nishimoto, Shinya
Nishimura, Keita
Nishimura, Tomoaki
Noda, Suguru
Norimatsu, Wataru
Nozaki, Junji
Nugraha, Ahmad R. T.
<O>Obata, Yoshinori
Ogata, Hironori
Ogata, Yuya
Ogawa, Shun
Ogino, Naoko
Ohata, Chika
Ohno, Yutaka

1P-3
1-8
2P-25
1-8, 1P-17, 2P-17
1P-30
2P-6
1P-10

Okigawa, Yuki
Okita, Wakana
Okudaira, Saki
Omachi, Haruka
Onodera, Atsushi
Onodera, Momoko
Ortiz-Medina, Josue
Osawa, Eiji
Oshima, Hisayoshi
Ota, Riku
Otsuka, Keigo
Otsuki, Nao

2P-22
2P-16, 3P-24
3P-21
3P-34
1P-34, 3-6
3P-28
1S-1, 1-6, 1-8,
1P-14, 2P-8, 3P-11,
3P-13
2-6
2P-4, 3-4, 3P-3
2-4
1P-1, 1P-21, 1P-24,
1P-28, 1P-29, 2-5,
2P-15, 2P-38, 3P-6,
3P-20, 3P-26, 3P-30,
3P-37
1P-38
3P-8
1P-36, 2-1, 2-2,
3-8
3-8
2-10
1P-12
3P-13
1P-15, 2P-9
3-7
3P-24
2-8, 2P-35
2S-4
2P-9
1-1
2P-9

<P>
Prassides, Kosmas

2P-4

Ohshimo, Keijiro
Okada, Hiroshi
Okada, Satoshi
Okada, Susumu

Okamatsu-Ogura, Yuko
Okamoto, Takuya
Okazaki, Toshiya- 164 -

Pratama, Fenda Rizky
Pu, Jiang

2P-26
2P-32, 3P-31<R>
Rajashekar, Badam

Suda, Yoshiyuki
Suenaga, Kenshiro
Sugai, Toshiki

1P-26

Sugaya, Yuki
Sugime, Hisashi
Sugita, Tomoko
Sun, Sida
Suzuki, Hal
Suzuki, Hiroo
Suzuki, Masashi
Suzuki, Mitsuaki
Suzuki, Seiya
Suzuki, Shinzo<S>
Saeki, Akinori
Saida, Takahiro
Saito, Naoto
Saito, Riichiro
Saito, Susumu
Saito, Takeshi
Saito, Tetsuki
Saito, Yahachi
Sakata, Ichiro
Sasaki, Fusako
Sasaki, Takayoshi
Sasao, Noboru
Sasaoka, KenjiSato, Satoru
Sato, Takumi
Sato, Toshihiro
Sato, Yuichi
Sawahata, Hisaki
Schweighauser, LucaSeki, Shu
Sekido, Masaru
Seo, Seungju
Shawky, Ahmed
Shibuta, Yasushi
Shigekawa, Hidemi
Shima, Ryuunosuke
Shimasaki, Masafumi
Shimizu, Hiroshi
Shimizu, Maki
Shinohara, Hisanori
Shinokita, Keisuke
Shiota, Kento
Shiraishi, Tomonari
Shiraki, Kentaro
Shiraki, Tomohiro
Shirakura, Toshiya
Somei, Kazumasa

3-4
1P-16
1P-37
1P-10, 2-11, 2P-26,
2P-33, 3P-9, 3P-32
1P-5, 1P-6, 3P-38
1-2, 2P-14
2P-29
2S-5, 2P-24
3P-24
1-2
2-9
1P-5, 1P-6
2P-21
1P-2
2-8, 2P-35
1P-17
3P-4
1P-21
2-4
1P-2
1P-15, 2P-9
3-4, 3P-10
1P-13, 3P-12
1P-19
3P-30
2P-7
2P-31
3P-34
2P-7
3P-13
2P-27, 2-12
2P-23
3P-7
2P-36
3P-7
2P-33
2-7, 3P-36<T>
Tachibana, Masaru
Tajima, Kentaro
Takabayashi, Yasuhiro
Takahashi, Makoto
Takahashi, Mitsuko
Takai, Kazuyuki
Takai, Ryoya
Takakura, Shiori
Takashima, Kengo
Takei, Kuniharu
Takenobu, Taishi
Takeuchi, Tsukasa
Takikawa, Hirofumi
Tamura, Ryo
Tanaka, Koichiro
Tanaka, Takeshi

Tanaka, Toshihiko
Tanaka, Yuya
Taniguchi, Takashi
Tanimoto, Tsuyoshi
Tanimura, Makoto
Taniyama, Koki
Tanuma, Yuri
Tatsumi, Yuki
Tawara, Kenta
Tayyebi, Ahmad- 165 -

2P-39
1P-22
2-7, 2P-11, 3P-35,
3P-36
1P-5, 1P-6
1-8, 1P-17, 2P-17
1-3
3-10
3P-5
1P-23, 2P-19
2P-39
1P-2
2P-30
1P-20, 2P-12

1P-7, 3P-21
3P-27
2P-4
2-8
1P-38
2P-18, 2P-22, 2P-25,
3P-27, 3P-29
2P-3
3P-39
1P-25
1P-31, 3P-23, 3P-33
2P-32, 3P-31
1P-36
2P-39
3P-25
2P-6
1-3, 1P-11, 1P-38,
2P-36, 2P-37, 3P-10,
3P-17
2-8, 2P-35
2P-11
2P-31, 3-7
2P-39
1P-7
2P-34
3P-1
2-11, 2P-33
3-5
3-6

Terao, Yuri
Terasawa, Tomoo
Terrones, Mauricio
Tian, Ying
Toshimitsu, Fumiyuki
Toyama, Kiyohiko
Toyoda, Masayuki
Tsujimoto, Marina
Tsukuda, Masaaki

1P-22
1P-30
3P-24
1S-1
3P-7
3P-19
1P-5, 1P-6, 3P-38
3P-21
2P-10

<U>
Uchida, Takashi
Uchimura, Shunsuke
Uda, Takushi
Ueda, Katsuya
Ueda, Naomasa
Ueno, Hiroshi
Ueno, Kazuki
Ukai, Hiroyuki
Ukhtary, M. Shoufie
Umeda, Yoshito
Ushiyama, Takuya
Utsugi, Koichi

3P-1
3P-7
3-11
1P-37
3P-22
2P-4, 3-4, 3P-3
3P-13
2P-13
2P-26, 3P-32
2P-39
1-8
2P-9

<X>
Xia, Chenmaya
Xiang, Rong
Xu, Bin<Y>
Yamada, Michio
Yamada, Ryota
Yamada, Takatoshi
Yamada, Tomoyuki
Yamaguchi, Tomohiro
Yamaguchi, Yoshiki
Yamamoto, Keisuke
Yamamoto, Saori
Yamamoto, ShunYamamoto, Takahiro
Yamanaka, Ayaka
Yamanashi, Masafumi
Yamanouchi, Kaoru
Yamashita, Satoshi
Yanagi, Kazuhiro<V>
Vipin, Adavan Kiliyankil
Vrankic, Martina

3P-24
2P-4

<W>
Wakabayashi, Tomonari
Wang, Chenxing
Wang, Donghao
Wang, Guowei
Wang, Hao
Wang, Xiaofan
Wang, Yanqing
Wang, Yue
Wang, Zhipeng
Watanabe, Kenji
Watanabe, Takayuki
Watase, Tatsuki
Wato, Yuta
Wei, Nan
Wenjin, Zhang
Wu, Jenna

1P-5, 1P-6
2P-24
3P-6
3P-17
1S-2
2-12, 2P-27, 2P-31
3P-24
2P-28
3P-24
2P-31, 3-7
2-1
1P-20
1P-23
1S-1
2P-29
2-6

Yang, FengYang, Juan
Yang, Mei
Yang, Yang
Yasuda, Hidehiro
Yasui, Masanori
Yasuma, Airi
Yasuraoka, Kenta
Yi, Eongyu
Yokoi, Hiroyuki
Yokoyama, Atusro
Yokoyama, Takahiro
Yomogida, Yohei
Yoneyama, Kazufumi
Yoon, Jungjin
Yoshida, Shoji
Yoshida, ShunYoshikawa, Daiki
Yoshikawa, Ryo
Yoshimura, Masamichi- 166 -

3-10
1-1, 1P-13, 1P-32,
3P-18, 3P-22
1P-19

1P-2, 3P-4
2P-9
3-8
3P-31
2P-7
2-10
1P-22
1P-7
1-1
1P-25, 2P-10, 2P-20,
2P-21, 3P-14
1P-21, 3P-20
3P-38
2-4
2-1
1S-3, 1P-9, 2P-5,
2P-6, 3S-9, 3-9
1P-18, 2-3, 3P-16
3-10
2-2
1-5
2-13
3P-4
1P-28
1P-24
1P-17
1P-27
2P-37
1P-8
1P-9, 2P-5, 2P-6,
3-9
3P-20
1-7
3P-30
3P-2
1P-31
2P-13
1P-26, 2P-30

Yoshimura, Motohiko
Yoshimura, Shintaro
Yudasaka, Masako
Yuge, Ryota

1P-5, 1P-6
1P-35
1P-36, 1P-38, 2-2,
2P-37, 3P-19
3P-19

<Z>
Zhang, Daqi
Zhang, Minfang
Zhang, Qiang
Zhang, Wenjin
Zheng, Yongjia
Zhu, Hongwei
Zolotoukhna, Tatiana

3-10
2-2
1S-1, 1 I-1
2P-31
3P-18
2-9
3-5

- 167 -

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2018 年 3 月 10 日発行

第 54 回フラーレン・ナノチューブ・グラフェン総合シンポジウム
講演要旨集≪フラーレン・ナノチューブ・グラフェン学会≫〒113-8656 東京都文京区本郷 7-3-1
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極微を観る

私たちJEOLグ ル ープは1949年に電 子 顕 微 鏡 の 開
発・製造会社として設立されました。これからも電子顕微鏡のリーディングカンパニーとして、ナノテクノロ
ジー、バイオテクノロジー、ライフサイエンスなどさま
ざまな分野に最適なソリューションを提供していきます。

原子分解能分析電子顕微鏡

NEOARM JEM-ARM200F
NEOARM は、当社独自の技術で開発されたと冷陰極電界放出形電子銃（Cold-FEG）
高次の収差まで補正可能なを標準搭載し、新型球面収差補正装置（ASCOR）
200 kVの高加速電圧だけでなく
30 kVの低加速電圧においても原子分解能での観察を実現しました。

ショットキー電界放出形走査電子顕微鏡

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超高分解能観察と操作性の両方を実現し、オペレーターのスキルに依存することなく、常に高いパフォーマンスを発揮する
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「理科学・計測機器事業」電子光学機器・分析機器・計測検査機器 「産業機器事業」半導体関連機器・産業機器 「医用機器事業」医用機器