第44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 44th Fullerenes-Nanotubes-Graphene General Symposium

Research Society

講演要旨集
Abstracts

2013年3月11日（月）〜13日（水）
東京大学 伊藤国際学術研究センター 伊藤謝恩ホール
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

日本化学会
The Chemical Society of Japan
東京大学GMSI The University of Tokyo Global COE Program“Global Center of Excellence for Mechanical Systems Innovation”

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

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Abstract

The 44th Fullerenes-Nanotubes-Graphene General Symposium➨ 44 ᅇࣇ࣮ࣛࣞࣥ㺃ࢼࣀࢳ࣮ࣗࣈ㺃ࢢࣛࣇ࢙ࣥ⥲ྜࢩ࣏ࣥࢪ࣒࢘
ㅮ₇せ᪨㞟
The Fullerenes, Nanotubes and Graphene Research Society
The Chemical Society of JapanThe Japan Society of Applied Physics
The Physical Society of JapanThe Electrochemical Society of JapanThe Society of Polymer Science, JapanThe University of Tokyo Global COE Program

Global center of Excellence for Mechanical Systems Innovation୺ദ㸸ࣇ࣮ࣛࣞࣥ㺃ࢼࣀࢳ࣮ࣗࣈ㺃ࢢࣛࣇ࢙ࣥᏛ఍
ඹദ㸸᪥ᮏ໬Ꮫ఍
ᮾி኱Ꮫࢢ࣮ࣟࣂࣝ COE ࣉࣟࢢ࣒ࣛ          ᶵᲔࢩࢫࢸ࣒㺃࢖ࣀ࣮࣋ࢩࣙࣥᅜ㝿ᣐⅬ
༠㈶㸸᪥ᮏ≀⌮Ꮫ఍࣭ᛂ⏝≀⌮Ꮫ఍࣭㟁Ẽ໬Ꮫ఍࣭㧗ศᏊᏛ఍   
Date: 

March 11th(Mon)㸫13th(Wed), 2013

Place:The University of Tokyo, ITO INTERNATIONAL RESEARCH CENTER
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656

Presentation: Plenary Lecture (40 min presentation, 5min discussion)Special Lecture (25 min presentation, 5min discussion)
General Lecture (10 min presentation, 5min discussion)
Poster Preview (1 min presentation, no discussion)᪥᫬㸸ᖹᡂ 25 ᖺ 3 ᭶ 11 ᪥ ᭶ 㹼13 ᪥ Ỉሙᡤ㸸ᮾி኱Ꮫ ఀ⸨ᅜ㝿Ꮫ⾡◊✲ࢭࣥࢱ࣮ ఀ⸨ㅰᜠ࣮࣍ࣝ   ࠛ113-8656 ᮾி㒔ᩥி༊ᮏ㒓 7-3-1Ⓨ⾲᫬㛫㸸ᇶㄪㅮ₇
㸦Ⓨ⾲ 40 ศ࣭㉁␲ᛂ⟅ 5 ศ㸧≉ูㅮ₇     㸦Ⓨ⾲ 25 ศ࣭㉁␲ᛂ⟅ 5 ศ㸧୍⯡ㅮ₇㸦Ⓨ⾲ 10 ศ࣭㉁␲ᛂ⟅ 5 ศ㸧࣏ࢫࢱ࣮ࣉࣞࣅ࣮ࣗ㸦Ⓨ⾲ 1 ศ࣭㉁␲ᛂ⟅ ࡞ࡋ㸧䚷䚷䚷䚷䚷䚷䚷䚷ᒎ♧ᅋయᚚⰾྡ䚷㻔஬༑㡢㡰䚸䚷ᩗ⛠␎䠅䜰䜲䜽䝇䝖䝻䞁䠄ᰴ䠅䠄ᰴ䠅㻭㼀㻾
㻽㼡㼍㼚㼠㼡㼙㼃㼕㼟㼑㻌㻶㼍㼜㼍㼚䠄ᰴ䠅䝁䝇䝰䞉䝞䜲䜸䠄ᰴ䠅䝃䞊䝰䝣䜱䝑䝅䝱䞊䝃䜲䜶䞁䝔䜱䝣䜱䝑䜽䠄ᰴ䠅䠄ᰴ䠅ᓥὠ〇సᡤ㻔ᰴ䠅䝇䜼䝜䝬䝅䞁㻔ᰴ䠅䝉䞁䝖䝷䝹⛉Ꮫ㈠᫆
䝘䜹䝷䜲䝔䝇䜽䠄ᰴ䠅䝘䝜䝣䜷䝖䞁䠄ᰴ䠅᪥ᮏ㟁Ꮚ䠄ᰴ䠅䠄ᰴ䠅䝙䝳䞊䝯䝍䝹䝇䜶䞁䝗䜿䝭䜹䝹䝇䝁䞊䝫䝺䞊䝅䝵䞁᪥❧ᕤᶵ䠄ᰴ䠅㻔ᰴ䠅ᇼሙ〇సᡤ㻔ᰴ䠅ྡᇛ䝘䝜䜹䞊䝪䞁䚷䚷䚷䚷䚷䚷䚷䚷ᗈ࿌ᥖ㍕ᅋయᚚⰾྡ䚷㻔஬༑㡢㡰䚸䚷ᩗ⛠␎䠅䜰䜲䜽䝇䝖䝻䞁㻔ᰴ㻕䜲䝕䜰䞉䜲䞁䝍䞊䝘䝅䝵䝘䝹㻔ᰴ䠅䝁䝇䝰䞉䝞䜲䜸䠄ᰴ㻕䠄ᰴ䠅䝁䝻䝘
䝃䞊䝰䝣䜱䝑䝅䝱䞊䝃䜲䜶䞁䝔䜱䝣䜱䝑䜽䠄ᰴ䠅䝅䜾䝬䜰䝹䝗䝸䝑䝏䝆䝱䝟䞁㻔ᰴ䠅㻔ᰴ䠅䝉䞁䝖䝷䝹⛉Ꮫ㈠᫆
䝘䜹䝷䜲䝔䝇䜽䠄ᰴ䠅䝘䝜䝣䜷䝖䞁䠄ᰴ䠅᪥ᮏ㟁Ẽ䠄ᰴ䠅᪥ᮏศᯒᕤᴗ䠄ᰴ䠅䝣䝻䞁䝔䜱䜰䜹䞊䝪䞁䠄ᰴ䠅࿴ග⣧⸆ᕤᴗ䠄ᰴ䠅

Contents
Time Table ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ i
Chairperson ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭iii
Program   Japanese ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ iv
English ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ xvii
Abstracts
Plenary Lecture, Special Lecture ࣭࣭࣭ 1
General Lecture ࣭࣭࣭࣭࣭࣭࣭࣭࣭ 11
Poster Preview ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭45
Author Index ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭185┠ḟ
᪩ぢ⾲ ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ iᗙ㛗୍ぴ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭iii
ࣉࣟࢢ࣒ࣛ ࿴ᩥ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ iv
ⱥᩥ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ xvii
ㅮ₇ண✏  ᇶㄪㅮ₇࣭≉ูㅮ₇࣭࣭࣭࣭࣭࣭࣭࣭ 1୍⯡ㅮ₇࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭11
࣏ࢫࢱ࣮Ⓨ⾲࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭45Ⓨ⾲⣴ᘬ࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭࣭ 185䚷䝥䝻䜾䝷䝮᪩ぢ⾲䠏᭶䠍䠍᪥䚷䠄᭶䠅䠏᭶䠍䠎᪥䚷䠄ⅆ䠅䠏᭶䠍䠏᪥䚷䠄Ỉ䠅ཷ௜㛤ጞ䚷䠔䠖䠏䠌䡚ཷ௜㛤ጞ䚷䠔䠖䠏䠌䡚ㅮ₇㛤ጞ䚷䠕䠖䠌䠌䡚ཷ௜㛤ጞ䚷䠔䠖䠏䠌䡚ㅮ₇㛤ጞ䚷䠕䠖䠌䠌䡚ㅮ₇㛤ጞ䚷䠕䠖䠏䠌䡚
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ͳʹǣ͵Ͳ

ͻǣ͵ͲǦͳͲǣͲͲ
䚷ȋͳǦͳͳǦͶ͹ȌͳͲǣͲͲǦͳͲǣͶͷ
ȋ ȌͳͲǣͶͷǦͳʹǣ͵Ͳ ȋȌͳʹǣ͵ͲǦͳ͵ǣͶͷͳ͵ǣͶͷ   ȋǤȌͳ͵ǣͶͷǦͳͶǣͳͷͳͶǣͳͷ ȏ͸Ȑȋ 䞉  䞉ȌͳͶǣͳͷǦͳͷǣͶͷ
ͳͷǣͶͷ
ͳ͸ǣͲͲ

ͳ͸ǣ͵Ͳ

ͳ͹ǣ͵Ͳ

ͳͺǣͲͲ

ʹͲǣͲͲ

ͳͳǣͲͲ

ͳʹǣ͵Ͳ

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ȋ  ȌͳͳǣͲͲǦͳʹǣ͵ͲͻǣͲͲ  ȋȌͻǣͲͲǦͻǣͶͷͻǣͶͷ ȏ͵Ȑȋ䞉 
ȌͻǣͶͷǦͳͲǣ͵ͲͳͲǣ͵Ͳ ͳͲǣ͵ͲǦͳͲǣͶͷͳͲǣͶͷ   ȋǤȌͳͲǣͶͷǦͳͳǣͳͷͳͳǣͳͷ ȏͶȐȋ䞉 
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ͳ͵ǣ͵ͲǦͳͶǣͳͷͳͶǣͳͷ   ȋǤȌͳͶǣͳͷǦͳͶǣͶͷͳͶǣͶͷ
䚷ȋʹǦͳʹǦͶ͸ȌͳͶǣͶͷǦͳͷǣ͵Ͳͳͷǣ͵Ͳ
ȋ Ȍͳͷǣ͵ͲǦͳ͹ǣͲͲ
ͳ͹ǣͲͲ
ͳ͹ǣͳͷ
ͳͺǣͳͷ
ͳͺǣ͵Ͳ

ʹͲǣ͵Ͳ

ͳ͹ǣͲͲǦͳ͹ǣͳͷ ȏͶȐȋ 䞉 Ȍͳ͹ǣͳͷǦͳͺǣͳͷ
ȋ Ȍͳͺǣ͵ͲǦʹͲǣ͵Ͳ ͳ͵ȋǤȌͺǣ͵Ͳ ͻǣͲͲͻǣͲͲ   ȋǤȌͻǣͲͲǦͻǣ͵Ͳ ȏͶȐͻǣ͵Ͳȋ䞉 Ȍ

ͳͲǣ͵Ͳ
ͳͲǣͶͷ

ͳʹǣͲͲ

ͻǣ͵ͲǦͳͲǣ͵ͲͳͲǣ͵ͲǦͳͲǣͶͷ ȏͷȐȋȌͳͲǣͶͷǦͳʹǣͲͲ ͳʹǣͲͲǦͳ͵ǣͳͷͳ͵ǣͳͷ   ȋǤ Ȍͳ͵ǣͳͷǦͳ͵ǣͶͷͳ͵ǣͶͷ
䚷ȋ͵Ǧͳ͵ǦͶ͸Ȍͳ͵ǣͶͷǦͳͶǣ͵ͲͳͶǣ͵Ͳ
ȋ ȌͳͶǣ͵ͲǦͳ͸ǣͲͲ
ͳ͸ǣͲͲ
ͳ͸ǣͳͷ

ͳ͸ǣͶͷ

ͳ͹ǣͶͷ

ͳ͸ǣͲͲǦͳ͸ǣͳͷ  ȋǤȌͳ͸ǣͳͷǦͳ͸ǣͶͷ ȏͶȐȋ
Ȍͳ͸ǣͶͷǦͳ͹ǣͶͷ ǣͶͲȋȌΪͷȋ Ȍ  ǣʹͷȋȌΪͷȋ Ȍ ǣͳͲȋȌΪͷȋ ȌǣͳȋȌ

ii

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㻟᭶㻝㻝᪥㻔᭶䠅

㻔ᩗ⛠␎䠅
᫬䚷䚷䚷㛫

ᗙ䚷䚷䚷㛗

≉ูㅮ₇䠄㉥㜰䚷೺䠅㻌㻥䠖㻟㻜㻌䡚㻌㻝㻜䠖㻜㻜୸ᒣ䚷ⱱኵ䝫䝇䝍䞊䝥䝺䝡䝳䞊㻝㻜䠖㻜㻜㻌䡚㻌㻝㻜䠖㻠㻡㧗஭䚷࿴அ䝫䝇䝍䞊䝉䝑䝅䝵䞁㻝㻜䠖㻠㻡㻌䡚㻌㻝㻞䠖㻟㻜

༓㊊䚷᪼ᖹ≉ูㅮ₇䠄ᑠᯇ䚷⣫୍䠅㻝㻟䠖㻠㻡㻌䡚㻌㻝㻠䠖㻝㻡

⠛ཎ䚷ஂ඾

୍⯡ㅮ₇

㻝㻠䠖㻝㻡㻌䡚㻌㻝㻡䠖㻠㻡ᐑ⏣䚷⪔඘≉ูㅮ₇䠄Ụ⏣䚷๛㍤䠅

㻝㻢䠖㻜㻜㻌䡚㻌㻝㻢䠖㻟㻜

࿃㒓䚷ᾈᶞ

୍⯡ㅮ₇

㻝㻢䠖㻟㻜㻌䡚㻌㻝㻣䠖㻟㻜ᮏ㛫䚷ⰾ࿴≉ู䝟䝛䝹䝉䝑䝅䝵䞁㻝㻤䠖㻜㻜㻌䡚㻌㻞㻜䠖㻜㻜Ỉ㇂䚷Ꮥ㻘䚷୸ᒣ䚷ⱱኵ

᫬䚷䚷䚷㛫

ᗙ䚷䚷䚷㛗

ᇶㄪㅮ₇㻔㻹㼕㼚㼓㻌㼆㼔㼑㼚㼓䠅㻥䠖㻜㻜㻌䡚㻌㻥䠖㻠㻡

୰ᔱ䚷┤ᩄ

୍⯡ㅮ₇

㻌㻥䠖㻠㻡㻌䡚㻌㻝㻜䠖㻟㻜ຍ⸨䚷㞝୍㑻

≉ูㅮ₇㻔୰ᔱ䚷┤ᩄ䠅㻝㻜䠖㻠㻡㻌䡚㻌㻝㻝䠖㻝㻡

∦ᾆ䚷ᘯ㐨

୍⯡ㅮ₇

㻝㻝䠖㻝㻡㻌䡚㻌㻝㻞䠖㻝㻡ᒸ⏣䚷᫴≉ูㅮ₇㻔ሯ㉺䚷୍ோ䠅㻝㻠䠖㻝㻡㻌䡚㻌㻝㻠䠖㻠㻡㛗ộ䚷᫭㍜䝫䝇䝍䞊䝥䝺䝡䝳䞊㻝㻠䠖㻠㻡㻌䡚㻌㻝㻡䠖㻟㻜ᐑෆ䚷㞝ᖹ䝫䝇䝍䞊䝉䝑䝅䝵䞁㻝㻡䠖㻟㻜㻌䡚㻌㻝㻣䠖㻜㻜

ᑠ㘠䚷ဴ

୍⯡ㅮ₇

㻝㻣䠖㻝㻡㻌䡚㻌㻝㻤䠖㻝㻡

ሯ㉺䚷୍ோ

᫬䚷䚷䚷㛫

ᗙ䚷䚷䚷㛗

≉ูㅮ₇㻔➉ᘏ䚷኱ᚿ䠅㻥䠖㻜㻜㻌䡚㻌㻥䠖㻟㻜㰻⸨䚷⌮୍㑻

୍⯡ㅮ₇㻌㻥䠖㻟㻜㻌䡚㻌㻝㻜䠖㻟㻜

ᯇ⏣䚷୍ᡂ

୍⯡ㅮ₇

㻝㻜䠖㻠㻡㻌䡚㻌㻝㻞䠖㻜㻜➉ᘏ䚷኱ᚿ≉ูㅮ₇㻔⏫⏣䚷཭ᶞ䠅㻝㻟䠖㻝㻡㻌䡚㻌㻝㻟䠖㻠㻡ᒣᮏ䚷㈗༤

䝫䝇䝍䞊䝥䝺䝡䝳䞊㻝㻟䠖㻠㻡㻌䡚㻌㻝㻠䠖㻟㻜Ἀᮏ䚷἞ဢ䝫䝇䝍䞊䝉䝑䝅䝵䞁㻝㻠䠖㻟㻜㻌䡚㻌㻝㻢䠖㻜㻜ຍ⸨䚷ಇ㢧≉ูㅮ₇㻔ᯇᑿ䚷㇏䠅㻝㻢䠖㻝㻡㻌䡚㻌㻝㻢䠖㻠㻡

㔝⏣䚷ඃ

୍⯡ㅮ₇

㻝㻢䠖㻠㻡㻌䡚㻌㻝㻣䠖㻠㻡໭ᾆ䚷Ⰻ㻟᭶㻝㻞᪥䠄ⅆ䠅㻟᭶㻝㻟᪥䠄Ỉ䠅

iii

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠍᪥㻌䠄᭶䠅㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌≉ูㅮ₇䚷䚷䚷Ⓨ⾲䠎䠑ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌୍⯡ㅮ₇䚷䚷䚷Ⓨ⾲䠍䠌ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䝫䝇䝍䞊䝥䝺䝡䝳䞊䚷䚷䚷Ⓨ⾲䠍ศ䚷䞉䚷㉁␲ᛂ⟅䛺䛧≉ูㅮ₇㻌㻌㻔㻥㻦㻟㻜㻙㻝㻜㻦㻜㻜㻕㻝㻿㻙㻝㔠ᒓෆໟ䝣䝷䞊䝺䞁䜢㘽≀㉁䛸䛩䜛㧗ḟ䃟✵㛫䛾๰Ⓨ㉥㜰㻌೺㻝䝫䝇䝍䞊䝥䝺䝡䝳䞊㻌㻌㻔㻝㻜㻦㻜㻜㻙㻝㻜㻦㻠㻡㻕䝫䝇䝍䞊䝉䝑䝅䝵䞁㻌㻌㻔㻝㻜㻦㻠㻡㻙㻝㻞㻦㻟㻜㻕䚷䚷䚷䚷䠄䖪䠅䚷ⱝᡭዡບ㈹ೃ⿵
䝘䝜䝏䝳䞊䝤䛾≀ᛶ㻌
Optical coupling of air-suspended carbon nanotubes to silicon microdisk resonators* Saneyuki Imamura, Ryosuke Watahiki, Ryohei Miura, Yuichiro K. Kato

㻠㻡

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X-ray diffraction profile of highly purified (6,5) SWCNTs* Tadera Shin, Haruka Kyakuno, Yusuke Nakai, Kazuhiro Yanagi, Yasumitsu Miyata,
Hiromichi Kataura, Yutaka Maniwa

㻠㻢

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Observation of circular dichroism in individual air-suspended single-walled carbon nanotubes* A. Yokoyama, A. Ishii, M. Yoshida, Y. K. Kato

㻠㻣

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㻯㻺㼀ศᩓ⁐ᾮ୰䛾ศᩓ๣䠄㻮㼞㼕㼖㻣㻤䠅䛾ᐃ㔞㻖㻌ኴ⏣㻌୍ᚨ㻘㻌᪩ᕝ㻌⏤ኵ㻘㻌ᑠ㔝㻌Ὀⶶ㻘㻌ᒣ⬥㻌ᾈ㻘㻌ᒣᮏ㻌࿴ᘯ㻘㻌ᮏ⏣㻌୍໷

㻠㻤

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Effect of Impurity Scattering on AC Transport in Carbon Nanotubes* Daisuke Hirai, Takahiro Yamamoto, Satoshi Watanabe

㻠㻥

㻝㻼㻙㻢

ᾮ┦ἲ䛻䜘䜛䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䝽䜲䝲䞊㻌㻖㻌㧗ᮌ㻌ຬᶞ㻘㻌኱ᓥ㻌ຬ࿃㻘㻌ᰗ㻌࿴ᏹ㻘㻌➉ᘏ㻌኱ᚿ

㻡㻜

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䖪

䝷䝬䞁ศග㟁Ẽ໬Ꮫ ᐃἲ䛻䜘䜛㻿㼃㻯㻺㼀㼟䛾㓟໬㛤ጞ㟁఩䛾ゎᯒ㻌㻖㻌ᆏᮏ㻌ఙᝅ㻘㻌෠Ọ㻌ᫀே

㻡㻝

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㓟⣲䝗䞊䝥䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛻䛚䛡䜛ᙉ䛔Ⓨග㣬࿴㻌ᒾᮧ㻌᐀༓௦㻘㻌㻖㻌ᐑෆ㻌㞝ᖹ㻘㻌⛅᭶㻌┤ே㻘㻌ẟ฼㻌┿୍㑻㻘㻌ᯇ⏣㻌୍ᡂ

㻡㻞

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䖪

㉮ᰝ䝀䞊䝖㢧ᚤἲ䛻䜘䜛㻿㼃㻺㼀䝛䝑䝖䝽䞊䜽㻲㻱㼀୰䛷ほ 䛥䜜䜛㔞Ꮚఏᑟ⌧㇟䛾᳨ウ㻌㻖㻌㨯㻌ᑠᆒ㻘㻌ᯇỌ㻌ṇᗈ㻘㻌๓⏣㻌㈼἞㻘㻌▮ⴗ㻌㐩ᮁ㻘㻌㟷ᮌ㻌ఙஅ㻘㻌䠦㻚䠬㻚㻌䝞䞊䝗㻘㻌▼ᶫ㻌ᖾ἞㻘㻌ⴠྜ㻌ຬ୍

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㻝㻼㻙㻝
䖪

䖪

䖪

䝘䝜䝏䝳䞊䝤䛾ᛂ⏝㻝㻼㻙㻝㻜㻼㻱㻰㻻㼀㻦㻼㻿㻿㻛༢ᒙ䚸ከᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤」ྜ⭷䜢ṇᏍ㍺㏦ᒙ䛻⏝䛔䛯᭷ᶵⷧ⭷ኴ㝧㟁ụ㻌㻖㻌ᓊ㻌┤ᕼ㻘㻌ᯘ㻌⣧㍤㻘㻌ᩪ⸨㻌Ẏ㻘㻌᭮ᡃ㻌ဴኵ㻘㻌⚄ಖ㻌Ꮥᚿ

㻡㻠

㻝㻼㻙㻝㻝

High efficiency carbon nanotube/silicon heterojunction solar cells fabricated using highquality carbon nanotube network film㻡㻡䖪㻌㻖㻌⋤㻌㣕ஂ㻘㻌ᑠ⃝㻌኱▱㻘㻌ᐑෆ㻌㞝ᖹ㻘㻌ẟ฼㻌┿୍㑻㻘㻌኱㔝㻌㞝㧗㻘㻌ᯇ⏣㻌୍ᡂ㻝㻼㻙㻝㻞䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤㟁Ẽ஧㔜ᒙ䝖䝷䞁䝆䝇䝍䛻䛚䛡䜛㼜㻙㼚᥋ྜ䛾ᙧᡂ㻡㻢* Ryo Shimizu, Yijin Zhang, Kazuhiro Yanagi, Yoshihiro Iwasa, Taishi Takenobu
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䖪
㻝㻼㻙㻝㻠

High-mobility, filexible, n-type carbon nanotube thin-film transistors* Tomohiro Yasunishi, Yutaka Ohno, Shigeru Kishimoto, Takashi Mizutani㻡㻣ච␿ ᐃᛂ⏝䜢┠ᣦ䛧䛯䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾ᢠయ䛻䜘䜛ಟ㣭㻌㻖㻌㣤Ἠ㻌㝧Ꮚ㻘㻌ᒸᓮ㻌ಇஓ㻘㻌ụཎ㻌ㆡ㻘㻌ᑠ಴㻌╬㑻㻘㻌‫⏣‮‬ᆏ㻌㞞Ꮚ㻡㻤

iv㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠍᪥㻌䠄᭶䠅䝘䝜䝏䝳䞊䝤䛾⏕ᡂ䛸⢭〇㻝㻼㻙㻝㻡䜺䝇 ᗘไᚚ䜰䞊䜽ᨺ㟁䛻䜘䜛䝘䝜䝏䝳䞊䝤ྜᡂ㻌㻖㻌୕㔜㔝㻌ဴ㻘㻌㕥ᮌ㻌ᓫ

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㻝㻼㻙㻝㻢

㔜Ỉ䞉㍍Ỉΰྜᾮ䜢⏝䛔䛯㟁⏺ㄏ㉳ᒙᙧᡂἲ䛻䜘䜛㔠ᒓᆺ㻛༙ᑟయᆺ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ศ㞳㻌㻖㻌బ䚻ᮌ㻌ᢇ⣪Ꮚ㻘㻌἟⏣㻌⚽᫛㻘㻌ᩪ⸨㻌Ẏ㻘㻌஧⎼㻌ྐ⾜

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㻝㻼㻙㻝㻣

㧗ရ㉁䛺༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ᡂ㛗䛻䛚䛡䜛䝁䞊䝹䝗䜴䜷䞊䝹໬ᏛẼ┦ᡂ㛗⿦⨨䛾䝠䞊䝍䞊㒊ᨵⰋ
㻌㻖㻌ὠ⏣㻌ᝆస㻘㻌ᅵ⫧㻌ᬛྐ㻘㻌▼஭㻌ᏹ἞㻘㻌ᒾ⏣㻌ᒎᖾ㻘㻌▮ᓥ㻌༤ྐ㻘㻌ᒣᮏ㻌ᐶ

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㻝㻼㻙㻝㻤

Nitrogen-doped single-walled carbon nanotubes and their growth mechanism* Theerapol Thurakitseree, Christian Kramberger, Akihito Kumamoto, Shohei Chiashi,
Erik Einarsson, Shigeo Maruyama

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㻝㻼㻙㻝㻥
䖪

䝟䝹䝇䝥䝷䝈䝬㻯㼂㻰ἲ䛻䜘䜛䠄㻢㻘㻌㻡䠅༢ᒙ䜹䞊䝪䞁䞁䝘䝜䝏䝳䞊䝤䛾㑅ᢥⓗከ㔞ྜᡂ㻌㻖㻌ᮧ㉺㻌ᖾྐ㻘㻌ຍ⸨㻌ಇ㢧㻘㻌␊ᒣ㻌ຊ୕㻘㻌㔠Ꮚ㻌ಇ㑻

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㻝㻼㻙㻞㻜

䜰䝹䝁䞊䝹㻯㼂㻰ἲ䛻䜘䜛䝣䝷䞊䝺䞁䜢⏝䛔䛯༢ᒙ㻯㻺㼀䛾ྜᡂ㻌㻖㻌୰ᮧ㻌ㅬኴ㻘㻌ᾏ㔝㻌㈗ᚨ㻘㻌༓㊊㻌᪼ᖹ㻘㻌୸ᒣ㻌ⱱኵ

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㻝㻼㻙㻞㻝

㉮ᰝᆺ㢧ᚤ㙾䛻䜘䜛Ỉᬗᇶᯈୖ䛾Ỉᖹ㓄ྥ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾ศᯒ㻌㻖㻌㛗㇂ᕝ㻌኱♸㻘㻌஭䝜ୖ㻌Ὀ㍤㻘㻌኱ሯ㻌៞࿃㻘㻌䝞䝎䝹㻌䝃䜲䝣䝑䝷䞊㻘㻌༓㊊㻌᪼ᖹ㻘㻌୸ᒣ㻌ⱱኵ

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㻝㻼㻙㻞㻞

String-like Aggregates of Aligned (6, 5) Single Wall Carbon Nanotubes㻢㻢䖪㻌㻖㻌Ἑྜ㻌ⱥ㍤㻘㻌㛗㇂ᕝ㻌ถ㻘㻌୰ὠ㻌஽㻘㻌ෆ⸨㻌Ὀஂ㻘㻌㧗ᮌ㻌ຬᶞ㻘㻌➉ᘏ㻌኱ᚿ㻘㻌ᰗ㻌࿴ᏹ㻝㻼㻙㻞㻟䝇䞊䝟䞊䜾䝻䞊䝇䠖㻌㧗⃰ᗘపάᛶⅣ⣲※䜢⏝䛔䛯㧗཰㔞㻯㻺㼀ྜᡂἲ㻌㻖㻌ᮌᮧ㻌ᐶᜨ㻘㻌ᚋ⸨㻌₶኱㻘㻌ಖ⏣㻌ㅍ㻘㻌ᱜ஭㻌ಇ௓㻘㻌‫‮‬ᮧ㻌Ᏺ㞝㻘㻌஧ⴥ㻌䝗䞁㻘㻌␊㻌㈼἞

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㻝㻼㻙㻞㻠

㧗 䝟䝹䝇䜰䞊䜽ᨺ㟁䛾ᅽຊ౫Ꮡᛶ
㻌㻖㻌⳥ụ㻌㞙ே㻘㻌຾ⱥ㻌ᑎ⏣㻘㻌Ⳣ஭㻌ಇᶞ㻢㻤䖪ෆໟ䝘䝜䝏䝳䞊䝤
㻝㻼㻙㻞㻡⁐ᾮ୰䛷㼇㻝㻜㼉㻯㼥㼏㼘㼛㼜㼍㼞㼍㼜㼔㼑㼚㼥㼘㼑㼚㼑䛸ඹᏑ䛩䜛㻺㻬㻯㻢㻜䛾㻱㻿㻾 ᐃ㻌㻖㻌ᒸᮏ㻌ගᘯ㻘㻌ᒾᮏ㻌㈗ᐶ㻘㻌ᒣᏊ㻌ⱱ㻘㻌ຍ⸨㻌❧ஂ

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㻝㻼㻙㻞㻢
䖪

㧗ᛶ⬟䝷䝬䞁䜲䝯䞊䝆䞁䜾䝬䞊䜹䞊䛸䛧䛶䛾䝫䝸䝏䜸䝣䜵䞁䜢ෆໟ䛧䛯䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤㻌㻖㻌ᐑᾆ㻌೺ᚿ㻘㻌ᐑ⏣㻌⪔඘㻘㻌ⱝ᳃㻌⫱ஓ㻘㻌䝪䜰䝛䝹䝀䝇㻌䝔䞁䝕䜱㻘㻌໭ᾆ㻌Ⰻ㻘㻌⠛ཎ㻌ஂ඾㻣㻜䝘䝜䝩䞊䞁㻌
㻝㻼㻙㻞㻣䜹䞊䝪䞁䝘䝜䝩䞊䞁䛾⏕≀ศゎ㻌㻖㻌ᙇ㻌Ẹⰾ㻘㻌ᥭ㻌ᱵ㻘㻌䝤䝉䜲㻌䝅䝸䝹㻘㻌䜰䝸䞊䝪䝉䝍㻌䝦䜲䝛䞁㻘㻌㣤ᓥ㻌⃈⏨㻘㻌䝁䝇䝍䜲䝷䝇㻌䝁䝇䝍䝇㻘‫⏣‮‬ᆏ㻌㞞Ꮚ

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㻝㻼㻙㻞㻤

Carbon nanohorns induced RAW264.7 apoptosis: Lysosomal membrane destabilization
caused reactive oxygen* Mei Yang, Minfang Zhang, Yoshio Tahara, Sumio Iijima, Masako Yudasaka

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㻝㻼㻙㻞㻥

㓟⣲㑏ඖゐ፹⬟䜢᭷䛩䜛❅⣲䝗䞊䝥䜹䞊䝪䞁䝘䝜䝩䞊䞁㞟ྜయ㻌㻖㻌ᘪ๐㻌ுኴ㻘㻌┾Ꮚ㻌㝯ᚿ㻘㻌ᆏᮾ㻌ಇ἞㻘㻌‫⏣‮‬ᆏ㻌㞞Ꮚ㻘㻌␜ᒣ㻌Ύᙪ㻘㻌ᒣཱྀ㻌㈗ྖ㻘㻌㣤ᓥ㻌⃈⏨㻘୰㔝㻌჆୍㑻

㻣㻟䜾䝷䝣䜵䞁⏕ᡂ㻝㻼㻙㻟㻜䖪䝦䝔䝻䜶䝢䝍䜻䝅䝱䝹㻯㼡㻔㻝㻝㻝㻕ୖ䛷䛾㻮㼑㼞㼚㼍㼘✚ᒙ䛧䛯஧ᒙ䜾䝷䝣䜵䞁䛾㻯㼂㻰ᡂ㛗㻌㻖㻌⏣ୖ㻌⩧ኴ㻘㻌Ἑཎ㻌᠇෬㻘㻌㎷㻌ṇ἞㻘㻌࿃㒓㻌ᾈᶞ㻣㻠㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠍᪥㻌䠄᭶䠅㻝㻼㻙㻟㻝

Scalable processing of crystallographic etching for graphite powder using supercritical fluid㻣㻡㻌㻖㻌➚ᒃ㻌㧗᫂㻘㻌⏣ᮧ㻌┤㈗㻘㻌ᮏ㛫㻌᱁㻝㻼㻙㻟㻞䖪໬ᏛẼ┦ᡂ㛗ἲ䛻䜘䜛䜾䝷䝣䜵䞁ᡂ㛗㐣⛬䛾཯ᑕ㧗㏿㟁Ꮚᅇᢡ䛭䛾ሙほᐹ㻌㻖㻌‖㻌ᣅ㑻㻘㻌୰ཎ㻌ோ㻘㻌Ᏻᆏ㻌ᖾᖌ㻘㻌㰻⸨㻌ᘺඵ

㻣㻢

㻝㻼㻙㻟㻟

Influence of applied potentials for electrochemical exfoliation of graphite* Haruya Okimoto, Syun Takabayashi, Yuhei Sobe, Masahito Sano㻣㻣䜾䝷䝣䜵䞁䛾ᛂ⏝㻝㻼㻙㻟㻠䖪ᙧ≧ไᚚ䛥䜜䛯䜾䝷䝣䜵䞁䞉❅໬䝩䜴⣲」ྜ䝅䞊䝖䛾㻯㼂㻰ྜᡂ㻌㻖㻌๓⏣㻌ᯞ㔛Ꮚ㻘㻌ᐑ⏣㻌⪔඘㻘㻌໭ᾆ㻌Ⰻ㻘㻌⠛ཎ㻌ஂ඾

㻣㻤

㻝㻼㻙㻟㻡

㻯㼂㻰䜾䝷䝣䜵䞁ୖ䛷䛾᪉ྥไᚚ䛥䜜䛯㻺㼎㻿㻞䝘䝜䝅䞊䝖䛾ྜᡂ㻌㼃㼍㼚㼥㼕㼚㻌㻳㼑㻘㻌Ἑཎ㻌᠇἞㻘㻌㎷㻌ṇ἞㻘㻌㻖㻌࿃㒓㻌ᾈᶞ

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㻝㻼㻙㻟㻢
䖪

䜾䝷䝣䜵䞁ಟ㣭⾲㠃䛻䛚䛡䜛᭷ᶵ༙ᑟయศᏊ䛾䝘䝜ᰕ≧⤖ᬗᡂ㛗㻌㻖㻌ᒸ⏣㻌㈼㻘㻌ྂᕝ㻌ಇ㍜㻘㻌⏣୰㻌⚽ᖾ㻘㻌ཎ㔝㻌ᖾ἞㻘㻌୰ᮧ㻌ᰤ୍㻤㻜䜾䝷䝣䜵䞁䛾≀ᛶ㻝㻼㻙㻟㻣㻴㼑䜲䜸䞁㢧ᚤ㙾䛷䜾䝷䝣䜵䞁䛾᱁Ꮚീ䛜䜏䛘䜛䛛䠛㻌䠖㻌➨୍ཎ⌮ィ⟬䛻䜘䜛ண㻌㻖㻌ᐑᮏ㻌Ⰻஅ

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㻝㻼㻙㻟㻤
䖪

Ḟᦆ䛾䛒䜛䜾䝷䝣䜵䞁䝘䝜䝸䝪䞁䛻䛚䛡䜛䜰䞁䝎䞊䝋䞁ᒁᅾ㻌㻖㻌㧗ᓥ㻌೺ᝅ㻘㻌㧗⏣㻌ᖾᏹ㻘㻌ᒣᮏ㻌㈗༤

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㻝㻼㻙㻟㻥

Gapped and gapless graphene and graphene-nanoribbon/nanotube complex* Shota Kizukuri, Takashi Koretsune, Susumu Saito

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㻝㻼㻙㻠㻜

SGM investigation of graphene nano structure㻤㻠㻌㻖㻌ྂᒇ㻌᝷ᖹ㻘㻌㧗஭㻌࿴அ㻘㻌బ⸨㻌៞᫂㻘㻌ᴮ㻌ᩄ᫂
㻝㻼㻙㻠㻝
䖪
㻝㻼㻙㻠㻞

Raman spectroscopy of mechanically strained chemically functionalized graphene* Mark Bissett, Masaharu Tsuji, Hiroki Ago㻤㻡䝘䝜䜾䝷䝣䜯䜲䝖䞊㓟⣲ศᏊ㛫䛾☢Ẽⓗ┦஫స⏝㻌㻖㻌㧗஭㻌࿴அ㻘㻌㻭㼘㼑㼤㼍㼚㼐㼑㼞㻚㻌㻵㻌㻿㼔㼍㼙㼑㼟㻘㻌㼂㼘㼍㼐㼕㼙㼕㼞㻌㼅㼡㻌㻻㼟㼕㼜㼛㼢㻘㻌㻭㼘㼑㼤㼍㼚㼐㼑㼞㻌㼅㼍㻌㼂㼡㼘㻓㻘㻌㙴ᮌ㻌⿱㻘ᯘ㻌༟ஓ㻘㻌ᴮ㻌ᩄ᫂㻤㻢䝘䝜Ⅳ⣲⢏Ꮚ
㻝㻼㻙㻠㻟⇿㎘ἲ䝘䝜䝎䜲䝲䝰䞁䝗䛾᪂ᒎ㛤㻌㻖㻌బ䚻ᮌ㻌ಟ୍㻘㻌ᒣ㔝஭㻌ுᏊ㻘㻌኱⃝㻌ᫎ஧

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㻝㻼㻙㻠㻠

䝞䜲䜸䝭䝯䝔䜱䝑䜽䞉䜰䝥䝻䞊䝏䛻䜘䜛㧗ᙉᗘ䝘䝜䝎䜲䝲䝰䞁䝗」ྜᮦᩱ䛾ྜᡂ㻌㻖㻌⸨ཎ㻌ᆂử㻘㻌ఀ⚄㻌ಇ㍤㻘㻌ఀ⸨㻌ṇ㞞㻘㻌ᑠ⃝㻌⌮ᶞ

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㻝㻼㻙㻠㻡

ගㄏ㉳཯ᛂ䛻䜘䜛䝫䝸䜲䞁䇷䝶䜴⣲㘒య䛾⏕ᡂ䛻䛚䛡䜛㏿ᗘㄽⓗ⪃ᐹ㻌㻖㻌࿴⏣㻌㈨Ꮚ㻘㻌ⱝᯘ㻌▱ᡂ

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㻝㻼㻙㻠㻢

䜹䞊䝪䞁䝘䝜䝁䜲䝹ῧຍ䛻䜘䜛䝞䝑䜻䞊䝨䞊䝟䞊䛾ᶵᲔⓗ≉ᛶ䛾ྥୖ㻌㻖㻌୸ᒣ㻌ⓡྖ㻘㻌㡲⏣㻌ၿ⾜㻘㻌⁪ᕝ㻌ᾈྐ㻘㻌⏣ୖ㻌ⱥே㻘㻌᳜㻌ோᚿ㻘㻌ΎỈ㻌୍ᶞ㻘㻌ᱵ⏣㻌Ⰻே

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㻝㻼㻙㻠㻣

Measurement of electric resistance of a single carbon nanocoil

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䛭䛾௚

㻌㻖㻌ᅧᮏ㻌㝯ྖ㻘㻌⡿ᮧ㻌Ὀ୍㑻㻘㻌㡲⏣㻌ၿ⾜㻘㻌⏣ୖ㻌ⱥே㻘㻌⁪ᕝ㻌ᾈྐ㻘㻌᳜㻌ோᚿ㻘㻌ΎỈ㻌୍ᶞ㻘㻌ᱵ⏣㻌Ⰻே㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌᫨㣗㻌㻌㻔㻝㻞㻦㻟㻜㻙㻝㻟㻦㻠㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘vi㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠍᪥㻌䠄᭶䠅≉ูㅮ₇㻌㻌㻔㻝㻟㻦㻠㻡㻙㻝㻠㻦㻝㻡㻕㻝㻿㻙㻞䝣䝷䞊䝺䞁䛾ᅛయ཯ᛂ㻌㻙㻙
ᑠᯇ㻌⣫୍

ᨾ▱᪂㻙㻙

㻞

୍⯡ㅮ₇㻌㻌㻔㻝㻠㻦㻝㻡㻙㻝㻡㻦㻠㻡㻕䝣䝷䞊䝺䞁䛾໬Ꮫ䚷䞉㻌㻌䝣䝷䞊䝺䞁䛾ᛂ⏝䚷䞉㻌㻌䝣䝷䞊䝺䞁㻝㻙㻝䝦䝸䜴䝮ෆໟ䝣䝷䞊䝺䞁䛾᭷ᶵྜᡂ䛺䜙䜃䛻㻌䠎䛴䛾␗✀ཎᏊ䜢ෆໟ䛧䛯䝣䝷䞊䝺䞁䛾Ⓨ⏕㻖㻌᳃୰㻌⿱ኴ㻘㻌బ⸨㻌ᝅ㻘㻌ⱝᐑ㻌῟ᚿ㻘㻌஧ᕝ㻌⚽ྐ㻘㻌⁁࿅ᮌ㻌┤⨾㻘㻌⏣㑔㻌ྐ⾜㻘㻌ᮧ⏣㻌⌮ᑦ㻘ᑠᯇ㻌⣫୍㻘㻌ྂᕝ㻌㈉㻘㻌ຍ⸨㻌❧ஂ㻘㻌Ọ℩㻌ⱱ㻘㻌㉥㜰㻌೺㻘㻌ᮧ⏣㻌㟹ḟ㑻

㻝㻝

㻝㻙㻞

Fullerene bis-carboxylic acid derivatives by Prato reaction㻝㻞㻌䜰䝻䜴䜰㻌䝃䝣䝽䞁㻘㻌㻖㻌ᒣ㉺㻌ⴥᏊ㻝㻙㻟᭷㝈㛗䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛸䝣䝷䞊䝺䞁䛛䜙䛺䜛ศᏊ䝧䜰䝸䞁䜾䛾ᵓ⠏䛸ᅇ㌿ᣲື㻌㻖㻌୍ᮡ㻌ಇᖹ㻘㻌ᒣ㷂㻌Ꮥྐ㻘㻌㣤ሯ㻌ு௓㻘㻌☾㒊㻌ᐶஅ

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㻝㻙㻠

䜰䝹䝁䜻䝅䝣䝷䞊䝺䞁㻯㻢㻜㻔㻻㻾㻕㻡㻮㼞䛾㑅ᢥⓗྜᡂ䠖䜰䝹䝁䞊䝹䛻䜘䜛㻯㻢㻜㻮㼞㻢䛾⨨᥮཯ᛂ㻌㻖㻌ෆᒣ㻌ᖾஓ㻘㻌᳃ᒣ㻌ᗈᛮ㻘㻌୚ᗙ㻌೺἞

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Ỉ㓟໬䝣䝷䞊䝺䞁ᅛయ䛾㻝㻴㻙㻺㻹㻾䛻䜘䜛䝥䝻䝖䞁䝎䜲䝘䝭䜽䝇㻌㻖㻌㤿ሙ㻌ၨ㍜㻘㻌⥴᪉㻌ၨ඾㻝㻡

Kinetic Stability Governs Relative Fullerene Isomer Abundance

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㻌㻖㻌䜲䝺㻌䝇䝔䝣䜯䞁㻘㻌すᮧ㻌ዲྐ㻘㻌㻭㼘㼑㼤㼍㼚㼐㼑㼞㻌㻲㼑㼐㼛㼞㼛㼢㻘㻌㻴㼑㼚㼞㼥㼗㻌㼃㼕㼠㼑㼗㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌ఇ᠁㻌㻌㻔㻝㻡㻦㻠㻡㻙㻝㻢㻦㻜㻜㻕㻌䠘䠘䠘䠘䠘䠘䠘≉ูㅮ₇㻌㻌㻔㻝㻢㻦㻜㻜㻙㻝㻢㻦㻟㻜㻕㻝㻿㻙㻟䜾䝷䝣䜵䞁䛚䜘䜃䛭䛾௚䛾㻞ḟඖᮦᩱ䛾⺯ග≉ᛶ
Ụ⏣䚷๛㍤

㻟

୍⯡ㅮ₇㻌㻌㻔㻝㻢㻦㻟㻜㻙㻝㻣㻦㻟㻜㻕䜾䝷䝣䜵䞁䛾≀ᛶ㻝㻙㻣㧗㏿ᾮయ䜽䝻䝬䝖䜾䝷䝣䜱䞊䛻䜘䜚ศ㞳䛧䛯䜾䝷䝣䜵䞁㔞Ꮚ䝗䝑䝖䛾ගᏛ≉ᛶ㻌㻖㻌෤㔝㻌┤ே㻘㻌ᑠ⃝㻌኱▱㻘㻌ᐑෆ㻌㞝ᖹ㻘㻌ẟ฼㻌┿୍㑻㻘㻌໭ᾆ㻌Ⰻ㻘㻌⠛ཎ㻌ஂ඾㻘㻌ಖ⏣㻌ᚨ㻘㻌ᑠᯇ㻌┤ᶞ㻘
ᯇ⏣㻌୍ᡂ

㻝㻣

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໬Ꮫ䝗䞊䝢䞁䜾䛻䜘䜛༢ཎᏊᒙ㻹㼛㻿㻞䛾ගᏛ䝇䝨䜽䝖䝹䛾ኚㄪ㻌㻖㻌ẟ฼㻌┿୍㑻㻘㻌ᐑෆ㻌㞝ᖹ㻘㻌ᯇ⏣㻌୍ᡂ

㻝㻤

㻝㻙㻥

㻞ᒙ䜾䝷䝣䜵䞁䛻䛚䛡䜛䜽䞊䝻䞁䝗䝷䝑䜾䛸ບ㉳Ꮚ⤯⦕య㻌㻖㻌ᑠ㘠㻌ဴ㻘㻌ᒸ⏣㻌᫴

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㻝㻙㻝㻜

Resonance and interference effect of Raman spectroscopy of graphene in the magnetic field* Riichiro Saito, Qiu Caiyu, Yu Ting㻞㻜㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌ఇ᠁㻌㻌㻔㻝㻣㻦㻟㻜㻙㻝㻤㻦㻜㻜㻕㻌䠘䠘䠘䠘䠘䠘䠘≉ู䝟䝛䝹䝉䝑䝅䝵䞁㻌㻌㻔㻝㻤㻦㻜㻜㻙㻞㻜㻦㻜㻜㻕䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾䜹䜲䝷䝸䝔䜱ไᚚྜᡂ䛻ྥ䛡䛶䚷Ỉ㇂㻌Ꮥ㻘㻌㻌㜿▱Ἴ㻌ὒḟ㻘㻌㻌ᩪ⸨㻌᫴㻘㻌㻌␊ᒣ㻌ຊ୕㻘㻌㻌ᮏ㛫㻌ⰾ࿴㻘㻌㻌⠛ཎ㻌ஂ඾㻘㻌㻌㔝⏣㻌ඃ㻘㻌㻌୸ᒣ㻌ⱱኵ

vii㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠎᪥㻌䠄ⅆ䠅㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌ᇶㄪㅮ₇䚷䚷䚷Ⓨ⾲䠐䠌ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌≉ูㅮ₇䚷䚷䚷Ⓨ⾲䠎䠑ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌୍⯡ㅮ₇䚷䚷䚷Ⓨ⾲䠍䠌ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䝫䝇䝍䞊䝥䝺䝡䝳䞊䚷䚷䚷Ⓨ⾲䠍ศ䚷䞉䚷㉁␲ᛂ⟅䛺䛧
ᇶㄪㅮ₇㻌㻌㻔㻥㻦㻜㻜㻙㻥㻦㻠㻡㻕㻞㻿㻙㻠Combining separation and synthesis to achieve structure control of carbon nanotubes
Ming䚷Zheng㻠୍⯡ㅮ₇㻌㻌㻔㻥㻦㻠㻡㻙㻝㻜㻦㻟㻜㻕䝘䝜䝏䝳䞊䝤䛾≀ᛶ䚷䞉㻌䝘䝜䝏䝳䞊䝤䛾⏕ᡂ䛸⢭〇㻞㻙㻝༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾㟁Ꮚ‽఩䛾⤒㦂ⓗண㻌㻖㻌ᖹම㻌ᗣᙪ㻘㻌ᐑෆ㻌㞝ᖹ㻘㻌ẟ฼㻌┿୍㑻㻘㻌ᯇ⏣㻌୍ᡂ㻘㻌୰ᔱ㻌┤ᩄ

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Ỉ⵨Ẽ㞺ᅖẼୗ䛷䛾㻿㼃㻺㼀䛾㻾㻮㻹䛻㛵䛩䜛ศᏊືຊᏛィ⟬㻌㻖㻌ᮏ㛫㻌┤ᶞ㻘㻌బ⸨㻌ៅኴ㑻㻘㻌༓㊊㻌᪼ᖹ㻘㻌ᮏ㛫㻌ⰾ࿴㻘㻌ᒣᮏ㻌㈗༤

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㻞㻙㻟

䝣䝹䜸䝺䞁⣔䝫䝸䝬䞊䛻ໟ䜎䜜䛯༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛻䛚䛡䜛Ⓨග䝢䞊䜽䛾䜶䝛䝹䜼䞊䝅䝣䝖㻌㻖㻌୹ୗ㻌ᑗඞ㻘㻌ᒸᓮ㻌ಇஓ㻘㻌㣤ᓥ㻌⃈⏨㻞㻟㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌ఇ᠁㻌㻌㻔㻝㻜㻦㻟㻜㻙㻝㻜㻦㻠㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘≉ูㅮ₇㻌㻌㻔㻝㻜㻦㻠㻡㻙㻝㻝㻦㻝㻡㻕㻞㻿㻙㻡

Fundamental and Advanced Materials Design of Soluble Carbon Nanotubes

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୰ᔱ㻌┤ᩄ

୍⯡ㅮ₇㻌㻌㻔㻝㻝㻦㻝㻡㻙㻝㻞㻦㻝㻡㻕䝘䝜䝏䝳䞊䝤䛾≀ᛶ䚷䞉㻌䝘䝜䝏䝳䞊䝤䛾⏕ᡂ䛸⢭〇䚷䞉㻌䝘䝜Ⅳ⣲⢏Ꮚ㻞㻙㻠

Simultaneous Discrimination of Diameter, Handedness, and Metallicity of SingleWalled Carbon Nanotubes with Chiral Diporphyrin Nanocalipers㻞㻠㻌㻖㻌๽㻌๛㻘㻌ứ㻌鼲㻘㻌㻯㼔㼍㼡㼚㼏㼔㼍㼕㼥㼍㼗㼡㼘㻌㻿㼛㼚㼓㼜㼛㼘㻘㻌ᮌᮧ㻌㝯ⱥ㻘㻌᱓ཎ㻌⿱ྖ㻘㻌ᑠᯇ㻌┤ᶞ㻞㻙㻡䝁䞊䝹㓟䝘䝖䝸䜴䝮䛸ᵝ䚻䛺㙐㛗䛾䜸䝸䝂㻰㻺㻭䛾༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤⾲㠃䛷䛾⨨᥮཯ᛂ㻌㻖㻌஭ୖ㻌ᙬⰼ㻘㻌ຍ⸨㻌㞝୍㻘㻌᪂␃㻌ᗣ㑻㻘㻌୰ᔱ㻌┤ᩄ

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⣸እ㏱㐣㢧ᚤ㙾䜢⏝䛔䛯䝫䝸䜲䞁ศᩓᅛయ䛾ගᏛ≉ᛶ䛾◊✲㻌㻖㻌ⱝᯘ㻌▱ᡂ㻘㻌≻㻌࿴ᡂ㻘㻌ᰘ⏣㻌ᐂᘏ㻘㻌࿴⏣㻌㈨Ꮚ

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⢓ᾮ≧䝘䝜䝎䜲䝲䝰䞁䝗䝣䜯䜲䝞䞊䛾ᙧᡂ㻌຾㔝㻌ಇస㻘㻌㻖㻌ఀ⸨㻌ṇ㞞㻘㻌ᑠ⃝㻌⌮ᶞ㻞㻣㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌᫨㣗㻌㻌㻔㻝㻞㻦㻝㻡㻙㻝㻟㻦㻟㻜㻕㻌䠘䠘䠘䠘䠘䠘䠘኱⃝㈹䞉㣤ᓥ㈹䞉ⱝᡭዡບ㈹䛾ᤵ㈹ᘧ㻌㻌㻔㻝㻟㻦㻟㻜㻙㻝㻠㻦㻝㻡㻕≉ูㅮ₇㻌㻌㻔㻝㻠㻦㻝㻡㻙㻝㻠㻦㻠㻡㻕㻞㻿㻙㻢Band engineering in bilayer graphene for future electron-devices* K.Tsukagoshi, H.Miyazaki, S.-L.Li, A.A.Ferreira, M.Y.Chan, K. Komatsu, S.Nakaharai㻢䝫䝇䝍䞊䝥䝺䝡䝳䞊㻌㻌㻔㻝㻠㻦㻠㻡㻙㻝㻡㻦㻟㻜㻕䝫䝇䝍䞊䝉䝑䝅䝵䞁㻌㻌㻔㻝㻡㻦㻟㻜㻙㻝㻣㻦㻜㻜㻕䚷䚷䚷䚷䠄䖪䠅䚷ⱝᡭዡບ㈹ೃ⿵
䝣䝷䞊䝺䞁䛾໬Ꮫ㻞㻼㻙㻝㼇㼚㼉㻯㼥㼏㼘㼛㼜㼍㼞㼍㼜㼔㼑㼚㼥㼘㼑㼚㼑㻌䜹䝏䜸䞁䝷䝆䜹䝹䛾㻱㻿㻾 ᐃ㻌㻖㻌㤶ᒣ㻌㈗ᙪ㻘㻌ⱴཎ㻌ᰤ୍㻘㻌ᒣᏊ㻌ⱱ㻘㻌ຍ⸨㻌❧ஂ

viii

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㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠎᪥㻌䠄ⅆ䠅㻞㻼㻙㻞䖪䝸䝏䜴䝮䜲䜸䞁ෆໟ䝣䝷䞊䝺䞁䛾䝅䜽䝻䝨䞁䝍䝆䜶䞁௜ຍయ䛾༢㞳䛸≀ᛶ㻌㻖㻌ᕝୖ㻌⿱㈗㻘㻌ᒸ⏣㻌ὒྐ㻘㻌ᯇᑿ㻌㇏

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㻞㻼㻙㻟

㻲㼑㻯㼘㻟䜢౑䛳䛯⁐ᾮ┦୰䛷䛾㻯㻝㻞㻜䝎䞁䝧䝹ᆺ䝎䜲䝬䞊ྜᡂ㻥㻠㻌ᶫཱྀ㻌ᫀᙪ㻘㻌㻖㻌✄⏣㻌ᐶ㻘㻌ᯇᑿ㻌㇏䝣䝷䞊䝺䞁䛾ᛂ⏝㻞㻼㻙㻠

Growth and Electric Properties of C60 Whiskers Directly Grown between Electrodes
by Surface Treatment㻥㻡㻌㻖㻌⢥⏣㻌ඞ▮㻘㻌ᒾ⏣㻌ᒎᖾ㻘㻌ᒣᮏ㻌ᐶ㔠ᒓෆໟ䝣䝷䞊䝺䞁㻞㻼㻙㻡㻸㼍㻞㻬㻯㻤㻜䛾⎔໬௜ຍ཯ᛂ䛸᣺㟁┦஫స⏝ᐦᗘゎᯒ㻥㻢㻌㻖㻌᫓⏣㻌┤Ẏ㻘㻌బ⸨㻌ᚭ㻘㻌⏣୰㻌୍⩏㻞㻼㻙㻢᪂つ㼚㼛㼚㻙㻵㻼㻾㔠ᒓෆໟ䝣䝷䞊䝺䞁㻦㻌㻸㼍㻞㻬㻯㼟㻔㻝㻣㻠㻥㻜㻕㻙㻯㻣㻢䖪㻌㻖㻌㕥ᮌ㻌ග᫂㻘㻌⁁࿅ᮌ㻌┤⨾㻘㻌䝇䝷䝙䝘㻌䝈䝕䝛䜽㻘㻌䝻䜴㻌䝅䞁㻘㻌Ọ℩㻌ⱱ㻘㻌㉥㜰㻌೺㻞㻼㻙㻣Ỉ⁐ᾮ୰䛾㻳㼐㻬㻯㻤㻞㻙㻼㻱㻳㻙㼎㻙㻼㻭㻹㻭㘒య䝟䞊䝔䜱䜽䝹䛜♧䛩☢ᛶ㻥㻣㻥㻤㻌㻖㻌┦⃝㻌ಇ༤㻘㻌ᇼཱྀ㻌ㅍྜྷ㻘㻌㛗ᓮ㻌ᖾኵ㻘㻌⠛ཎ㻌ஂ඾㻘㻌ຍ⸨㻌❧ஂ

䝣䝷䞊䝺䞁
㻞㻼㻙㻤

ᾮ䇷ᾮ⏺㠃ᯒฟἲ䛻䜘䜛㻯㻣㻜䝘䝜䝅䞊䝖䛾ྜᡂ㻥㻥㻌㻖㻌ᑠⷵỤ㻌ె⳯㻘㻌㮵㔝㻌ு♸㻘㻌ᶲ㻌຾㻞㻼㻙㻥ྵ◲㯤㛤ཱྀ㒊䜢䜒䛴㻯㻢㻜ㄏᑟయ䛾ྜᡂ䛸❅⣲ศᏊෆໟయ䛾㼄⥺ᵓ㐀䖪㻌㻖㻌஧Ꮚ▼㻌ᖌ㻘㻌ᮧ⏣㻌⌮ᑦ㻘㻌ᮧ⏣㻌㟹ḟ㑻㻞㻼㻙㻝㻜

Polymerization in C60 thin films deposited under in situ UV light irradiation

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㻝㻜㻝

* Daijiro Arai, Hisanori Tanimoto, Manabu Ohtomo, Shiro Entani,
Yoshihiro Matsumoto, Seiji Sakai䝘䝜䝏䝳䞊䝤䛾≀ᛶ
㻞㻼㻙㻝㻝
䖪
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Chirality dependence of exciton diffusion in air-suspended single-walled carbon nanotubes* A. Ishii, A. Yokoyama, M. Yoshida, T. Shimada, Y. K. Kato㻝㻜㻞Electric Double Layer Transistors using Thick Films in Single Chiral States of (6,5)
and (11,10) Single-Wall Carbon Nanotubes㻝㻜㻟㻌㻖㻌ᕤ⸨㻌ග㻘㻌Ἑྜ㻌ᑗ฼㻘㻌⯪㏕㻌཭அ㻘㻌㔝ᡣ㻌ຬᕼ㻘㻌➉ᘏ㻌኱ᚿ㻘㻌ᰗ㻌࿴ᏹ㻞㻼㻙㻝㻟䝁䞊䝹㓟䝘䝖䝸䜴䝮䛸㻰㻺㻭஺᥮཯ᛂ䛛䜙ぢ䜙䜜䜛༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ୖ䛾䝁䞊䝹㓟䝘䝖䝸䜴䝮䛾␗䛺䜛ᖹ⾮≧ែ㻌㻖㻌ຍ⸨㻌㞝୍㻘㻌᪂␃㻌ᗣ㑻㻘㻌୰ᔱ㻌┤ᩄ

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㟁Ẽ஧㔜ᒙ䜢⏝䛔䛯䜻䝱䝸䜰ὀධ䛻䜘䜛༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾ග྾཰ไᚚ
㻌㻖㻌஬༑ᔒ㻌㏱㻘㻌㛗㇂ᕝ㻌ถ㻘㻌⯪㏕㻌཭அ㻘㻌ᑠ㔝㻌᪂ᖹ㻘㻌ᰗ㻌࿴ᏹ

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䝁䞊䝹㓟䝘䝖䝸䜴䝮䛸㻞ᮏ㙐㻰㻺㻭䛾䝘䝜䝏䝳䞊䝤⾲㠃䛷䛾⨨᥮཯ᛂ䛻䛚䛡䜛⇕ຊᏛ㻌㻖㻌⧰㻌᫂Ꮚ㻘㻌஭ୖ㻌ᙬⰼ㻘㻌ຍ⸨㻌㞝୍㻘㻌᪂␃㻌ᗣ㑻㻘㻌୰ᔱ㻌┤ᩄ

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ᚋᕤ⛬ฎ⌮䛻䜘䜛㻯㻺㼀䛾≉ᛶྥୖ㻌㻖㻌ᯇᮏ㻌ᑦஅ㻘㻌኱ᓥ㻌䛒䛪䛥㻘㻌‫‮‬ᮧ㻌Ᏺ㞝㻘㻌஧ⴥ㻌䝗䞁㻘㻌␊㻌㈼἞

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䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤⧄⥔䜢ᵓᡂ䛧䛶䛔䜛䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤༢య䛾ᘬᙇᙉᗘ㻌㻖㻌㕥ᮌ㻌ⱥᙲ㻘㻌బ⸨㻌⩏೔㻘㻌ᒣᮏ㻌๛㻘㻌ᮏᐑ㻌᠇୍㻘㻌ᶫ⏣㻌ಇஅ㻘㻌⏣㊰㻌࿴ᖾ

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ix

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠎᪥㻌䠄ⅆ䠅䝘䝜䝏䝳䞊䝤䛾ᛂ⏝㻞㻼㻙㻝㻤

Bending Properties of Single-Walled Carbon Nanotube Film Transistors* Hiroki Hamahata, Yuki Nobusa, Yohei Yomogida, Kazuhiro Yanagi,
Yoshihiro Iwasa, Taishi Takenobu

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High-performance, flexible carbon nanotube transparent conductive films of double
layered structure* Norihiro Fukaya, Yusuke Kataoka, Dong Young Kim, Shigeru Kishimoto,Takashi Mizutani, Suguru Noda, Yutaka Ohno

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ᑟ㟁ᛶ㻭㻲㻹䜢⏝䛔䛯㻯㻺㼀㻛㻿㼕㻯⏺㠃䛾᥋ゐ᢬ᢠホ౯㻌㻖㻌῰㇂㻌ᜨ㻘㻌✄ⴥ㻌ඃᩥ㻘㻌኱ཎ㻌୍៞㻘㻌ⴠྜ㻌ᣅᾏ㻘㻌ቑ⏣㻌ె✑㻘㻌ᖹᒾ㻌⠜㻘㻌ᴋ㻌⨾ᬛᏊ㻘㻌ᕝཎ⏣㻌ὒ

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High-mobility carbon nanotube thin-film transistors fabricated on transparent plastic
film by flexographic printing technique* Kentaro Higuchi, Yuta Nakajima, Takuya Tomura, Masafumi Takesue,
Shigeru Kishimoto, Takashi Mizutani, Katsuhiko Hata, Yutaka Ohno㻝㻝㻞䜺䝇㞺ᅖẼ䛜༙ᑟయ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤㻛㻿㼕䝦䝔䝻᥋ྜᆺග㟁ኚ᥮䝕䝞䜲䝇≉ᛶ䛻୚䛘䜛ᙳ㡪䛻䛴䛔䛶㻌㻖㻌ᗉྖ㻌┿㞝㻘㻌୰㔝㻌╬㻘㻌⥴᪉㻌ၨ඾

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䖪

䖪

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䝘䝜䝏䝳䞊䝤䛾⏕ᡂ䛸⢭〇㻞㻼㻙㻞㻟༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䚸䝭䝸䝯䞊䝍䞊䝇䜿䞊䝹ᡂ㛗䛻䛚䛡䜛㓟໬䜰䝹䝭䝙䜴䝮ୗᆅ䛾ᙳ㡪㻌㻖㻌㛗㇂ᕝ㻌㤾㻘㻌㔝⏣㻌ඃ

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Ⅳ⣲ཬ䜃䝙䝑䜿䝹䛾䝎䝤䝹䝍䞊䝀䝑䝖䜢⏝䛔䛯䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾ྜᡂ㻌㻖㻌▼஭㻌ᏹ἞㻘㻌ᒾ⏣㻌ᒎᖾ㻘㻌ᒣᮏ㻌ᐶ㻘㻌▮ᓥ㻌༤ᩥ

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䝣䝷䝡䞁ㄏᑟయ䜢⏝䛔䛯༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾䜹䜲䝷䝸䝔䜱㑅ᢥⓗྍ⁐໬㻌㻖㻌ຍ⸨㻌㞝୍㻘㻌᪂␃㻌ᗣ㑻㻘㻌୰ᔱ㻌┤ᩄ

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㧗┿✵䜰䝹䝁䞊䝹䜺䝇䝋䞊䝇ἲ䛻䜘䜛㻭㼘㻞㻻㼤ᒙୖ㻼㼠ゐ፹䛛䜙䛾༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ᡂ㛗㻌㻖㻌⚟ᒸ㻌┤ஓ㻘㻌㏆⸨㻌ᘯᇶ㻘㻌⃝ᮌ㻌♸ဢ㻘㻌㻾㼍㼚㼍㼖㼕㼠㻌㻳㼔㼛㼟㼔㻘㻌ᡂሯ㻌㔜ᘺ㻘㻌୸ᒣ㻌㝯ᾈ

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ᑟ㟁ᛶୗᆅୖ䛷䛾䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤⛻ᐦ㓄ิ䛾ప㻌㻖㻌⨶㻌䝚䝸㻘㻌⫝̸㻌ⱥ⣖㻘㻌ᗄཎ㻌㞝୍㻘㻌㔝⏣㻌ඃ

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ศᏊ䜺䝷䝇䛾⇕䝸䝋䜾䝷䝣䜱䜢⏝䛔䛯㔠ᒓᛶ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾㑅ᢥⓗ㝖ཤ㻌㻖㻌኱ሯ㻌៞࿃㻘㻌஭䝜ୖ㻌Ὀ㍤㻘㻌㛗㇂ᕝ㻌኱♸㻘㻌༓㊊㻌᪼ᖹ㻘㻌୸ᒣ㻌ⱱኵ

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Effects of discharge current direction and magnetic field for the production of singlewalled carbon nanotubes in the arc discharge method* Mohammad Jellur Rahman, Tetsu Mieno

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䝀䝹䜹䝷䝮䜽䝻䝬䝖䜾䝷䝣䜱䞊䛻䜘䜛㔠ᒓᆺ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾䜹䜲䝷䝸䝔䜱ศ㞳㻌㻖㻌⏣୰㻌୔ኈ㻘㻌༦㒊㻌ὈᏊ㻘㻌∦ᾆ㻌ᘯ㐨

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ᡂ㛗

ෆໟ䝘䝜䝏䝳䞊䝤
㻞㻼㻙㻟㻝㗪ᆺἲ䛻䜘䜛㉸ఏᑟ㔠ᒓⅣ໬≀䛾䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ෆ㒊䜈䛾ෆໟ㻌㻖㻌ᑠᯘ㻌៞ኴ㻘㻌ᩪ⸨㻌Ẏ㻘㻌Ύᐑ㻌⥔᫓㻘㻌ಖ⏣㻌ⱥὒ

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▷䛔㻯㻺㼀䛻ෆໟ䛥䜜䛯㻯㻢㻜䛾䜶䝛䝹䜼䞊ㄽ䛸㟁Ꮚᵓ㐀㻌㻖㻌ᮌᬽ㻌⪷ኴ㻘㻌ᒸ⏣㻌᫴㻝㻞㻟䜾䝷䝣䜵䞁⏕ᡂ㻞㻼㻙㻟㻟

Effect of inert gas on the growth of epitaxial graphene on Si-terminated SiC (0001)* Akkawat Ruammaitree, Hitoshi Nakahara, Yahachi Saito㻝㻞㻠㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠎᪥㻌䠄ⅆ䠅㻞㻼㻙㻟㻠䖪

ᬯど㔝㏱㐣ᆺ㟁Ꮚ㢧ᚤ㙾䜢⏝䛔䛯䜾䝷䝣䜵䞁➃䛾ᵓ㐀ホ౯㻌㻖㻌⸨ཎ㻌⨾ᕹ㻘㻌ᐑ⏣㻌⪔඘㻘㻌໭ᾆ㻌Ⰻ㻘㻌๓⏣㻌ᯞ㔛Ꮚ㻘㻌⠛ཎ㻌ஂ඾

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❅⣲⨨᥮ᵓ㐀䛜ไᚚ䛥䜜䛯䜹䞊䝪䞁ᮦᩱ䛾ྜᡂ㻌㻖㻌ಖ⏣㻌ㅍ㻘㻌వ㻌ຊ㻘㻌ᮧ㉺㻌ᩗ

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ゐ፹䜹䝑䝔䜱䞁䜾䜢⏝䛔䛯㧗ᐦᗘ䜾䝷䝣䜵䞁䝘䝜䝸䝪䞁䛾స〇㻌㻖㻌჆㝧㻌Ᏻ⌮㻘㻌䝋䝸䝇䚷䝣䜵䝹䝘䞁䝕䝇㻌䝟䝤䝻㻘㻌ྜྷ⏣㻌࿴┿㻘㻌㎷㻌ṇ἞㻘㻌࿃㒓㻌ᾈᶞ㻝㻞㻣䜾䝷䝣䜵䞁䛾ᛂ⏝㻞㻼㻙㻟㻣⾪ᧁᅽ⦰ἲ䛻䜘䛳䛶䜹䞊䝪䞁䝘䝜䜴䜷䞊䝹䛛䜙⏕ᡂ䛥䜜䛯㏱᫂䜾䝷䝣䜯䜲䝖䝍䜲䝹㻌㻖㻌୰ᮧ㻌࿴㈗㻘㻌㜿⸨㻌ᩄ⾜㻘㻌ᗞ℩㻌ᩗྑ㻘㻌୰ᮧ㻌୍㝯㻘㻌ᶲ㻌຾

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䝫䝸䜾䝸䝉䝻䞊䝹ಟ㣭䛻䜘䜛䜾䝷䝣䜵䞁䛾Ỉ⁐໬㻌㻖㻌ಖ⏣㻌ᚨ㻘㻌㉿㻌฼㻘㻌๽㻌๛㻘㻌㟷἟㻌⚽ඣ㻘㻌ᮌᮧ㻌㝯ⱥ㻘㻌ᑠᯇ㻌┤ᶞ

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䝬䜲䜽䝻Ἴ䝥䝷䝈䝬㻯㼂㻰ἲ䛻䜘䜛䜹䞊䝪䞁䝘䝜䝅䞊䝖ⷧ⭷䛾ᙧែ䠈㟁Ꮚ≀ᛶ䛸㟁⏺ᨺฟ≉ᛶ䛾㛵ಀ㻌㻖㻌᪩℩㻌຾ᖹ㻘㻌⋤㻌ᚿ᭸㻘㻌⥴᪉㻌ၨ඾㻝㻟㻜䜾䝷䝣䜵䞁䛾≀ᛶ㻞㻼㻙㻠㻜䝬䜲䜽䝻Ἴ䝥䝷䝈䝬㻯㼂㻰ἲ䛻䜘䜚ሁ✚䛥䛫䛯䜾䝷䝣䜵䞁⭷䛾㟁Ẽఏᑟ≉ᛶホ౯㻌㻖㻌Ἀᕝ㻌ౡ᥹㻘㻌ὠᕝ㻌࿴ኵ㻘㻌ᒣ⏣㻌㈗ኖ㻘㻌▼ཎ㻌ṇ⤫㻘㻌㛗㇂ᕝ㻌㞞⪃

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䝘䝜䜾䝷䝣䜵䞁䛸䜺䝇ศᏊ䛾䝩䝇䝖䞊䝀䝇䝖┦஫స⏝㻌㻖㻌㧗ᇛ㻌㡰୍㻘㻌㧗஭㻌࿴அ㻘㻌ᮌཱྀ㻌Ꮫ㻘㻌ᴮ㻌ᩄ᫂㻘㻌ᒣ⏣㻌೺㑻㻘㻌␊㻌㈼἞㻘㻌▼஭㻌Ꮥᩥ㻘㻌ி㇂㻌㝯

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㒊ศⓗ䛻Ỉ⣲⤊➃䛥䜜䛯䝎䜲䝲䝰䞁䝗ᵓ㐀㻔㻝㻝㻝㻕㠃䛻䛚䛡䜛⥺ᙧศᩓ䝞䞁䝗㻌㻖㻌᭮᰿㻌‽ᇶ㻘㻌ᒸ⏣㻌᫴

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䜾䝷䝣䜵䞁䛾ᶵᲔⓗኚᙧ䛜⇕≀ᛶ䛻୚䛘䜛ᙳ㡪㻌㻖㻌⯪㇂㻌ᐅႹ㻘㻌ᒣᮏ㻌㈗༤㻘㻌ᑠᕝ㻌┿ே㻘㻌┦㤿㻌⪽ᩥ

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䜶䝑䝆ಟ㣭䛥䜜䛯䜰䞊䝮䝏䜵䜰ᆺ䜾䝷䝣䜵䞁䝘䝜䝸䝪䞁䛾➨୍ཎ⌮ィ⟬㻌㻖㻌ᐿᐆ㻌⚽ᖾ㻘㻌኱ῡ㻌┿⌮

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㓟໬㕲䝘䝜䝏䝳䞊䝤䞉Ỉ㓟໬䝣䝷䞊䝺䞁」ྜయ䛻䛚䛡䜛ගㄏ㉳㟁ὶ䛾ቑ኱㻌ⓑᮌ㻌ຬ႐㻘㻌㻖㻌୕ရ㻌㞝ᇶ㻘㻌ᆏᮾ㻌ಇ἞

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ከẁ䝖䝷䝑䝥Ẽ┦⛣ືᗘ㻌㻖㻌Ⳣ஭㻌ಇᶞ㻝㻟㻣䛭䛾௚ᐃ䝅䝇䝔䝮䛾㛤Ⓨ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌ఇ᠁㻌㻌㻔㻝㻣㻦㻜㻜㻙㻝㻣㻦㻝㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘୍⯡ㅮ₇㻌㻌㻔㻝㻣㻦㻝㻡㻙㻝㻤㻦㻝㻡㻕䜾䝷䝣䜵䞁⏕ᡂ䚷䞉㻌䜾䝷䝣䜵䞁䛾≀ᛶ㻞㻙㻤䜾䝷䝣䜵䞁䠉㔠ᒓ㟁ᴟ䝁䞁䝍䜽䝖≉ᛶ䛻ᑐ䛩䜛㓟⣲྾╔ຠᯝ㻌㻖㻌బ⸨㻌៞᫂㻘㻌㧗஭㻌࿴அ㻘㻌ᴮ㻌ᩄ᫂

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Atomic structure determination of the graphee/sapphire interface by normal incident
X-ray standing wave spectroscopy* Shiro Entani, Pavel Sorokin, Pavel Avramov, Manabu Ohtomo, Yoshihiro
Matsumoto, Liubov Antipina, Ayumi Narita, Norie Hirao, Iwao Shimoyama,
Tetsuhiro Sekiguchi, Hiroshi Naramoto, Yuji Baba, Seiji Sakai

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㧗ᛶ⬟䜾䝷䝣䜵䞁䝘䝜䝸䝪䞁䝖䝷䞁䝆䝇䝍䛾㞟✚໬㻌㻖㻌ຍ⸨㻌ಇ㢧㻘㻌␊ᒣ㻌ຊ୕㻘㻌㔠Ꮚ㻌ಇ㑻

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㻯㼂㻰䜾䝷䝣䜵䞁䛻䛚䛡䜛䝗䝯䜲䞁㛫䛾䜻䝱䝸䜰㍺㏦≉ᛶ㻌㻖㻌ᑠᕝ㻌཭௨㻘㻌Ἑཎ㻌᠇἞㻘㻌ᐑୗ㻌㞞኱㻘㻌㎷㻌ṇ἞㻘㻌ᑠᯇ㻌ඞఀ㻘㻌ሯ㉺㻌୍ோ㻘㻌࿃㒓㻌ᾈᶞ㻟㻝xi㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠏᪥㻌䠄Ỉ䠅㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌≉ูㅮ₇䚷䚷䚷Ⓨ⾲䠎䠑ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌୍⯡ㅮ₇䚷䚷䚷Ⓨ⾲䠍䠌ศ䚷䞉䚷㉁␲ᛂ⟅䠑ศ㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䝫䝇䝍䞊䝥䝺䝡䝳䞊䚷䚷䚷Ⓨ⾲䠍ศ䚷䞉䚷㉁␲ᛂ⟅䛺䛧≉ูㅮ₇㻌㻌㻔㻥㻦㻜㻜㻙㻥㻦㻟㻜㻕㻟㻿㻙㻣᪂䛧䛔ᶵ⬟ᛶ䝘䝜䝏䝳䞊䝤䝖䝷䞁䝆䝇䝍
➉ᘏ㻌኱ᚿ

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୍⯡ㅮ₇㻌㻌㻔㻥㻦㻟㻜㻙㻝㻜㻦㻟㻜㻕䝘䝜䝏䝳䞊䝤䛾≀ᛶ䚷䞉㻌䝘䝜䝏䝳䞊䝤䛾ᛂ⏝㻟㻙㻝㼚ᆺ䛚䜘䜃㼜ᆺ䝗䞊䝟䞁䝖ศᏊ䜢ෆໟ䛧䛯༙ᑟయᆺ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䜢⏝䛔䛯㻯㻹㻻㻿䜲䞁䝞䞊䝍䛾స〇㻌㻖㻌ఀ⸨㻌㟹ᾈ㻘㻌⸨஭㻌ಇ἞㑻㻘㻌ΎỈ㻌㯞ᕼ㻘㻌⏣୰㻌୔ኈ㻘㻌∦ᾆ㻌ᘯ㐨

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Micro-Honeycomb Network Structure of Single-Walled Carbon Nanotube Film for
Solar Cells

㻟㻟㻌㻖㻌ᓲ㻌ྍ⯟㻘㻌༓ⴥ㻌Ꮥ᫛㻘㻌ᮌୗ㻌ⱥ඾㻘㻌㉿㻌䝨䜲㻘㼀㼔㼑㼑㼞㼍㼜㼛㼘㻌㼀㼔㼡㼞㼍㼗㼕㼠㼟㼑㼞㼑㼑㻘㻌஭ୖ㻌Ὀ㍤㻘
㻱㼞㼕㼗㻌㻱㼕㼚㼍㼞㼟㼟㼛㼚㻘㻌༓㊊㻌᪼ᖹ㻘㻌୸ᒣ㻌ⱱኵ㻟㻙㻟ᆶ┤㓄ྥ㻯㻺㼀䛾⇞ᩱ㟁ụ㟁ᴟ䜈䛾ᛂ⏝㻌㻖㻌ᮧ⏣㻌ᡂு㻘㻌௒す㻌㞞ᘯ㻘㻌㛗㇂ᕝ㻌ⱱᶞ㻘㻌㞴Ἴ㻌Ⰻ୍

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Electromigration suppression in copper by carbon nanotubes : A mechanistic insight* Chandramouli Subramaniam, Takeo Yamada, Don N. Futaba, Kenji Hata, Motoo Yumura㻟㻡㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌ఇ᠁㻌㻌㻔㻝㻜㻦㻟㻜㻙㻝㻜㻦㻠㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘୍⯡ㅮ₇㻌㻌㻔㻝㻜㻦㻠㻡㻙㻝㻞㻦㻜㻜㻕䝘䝜䝏䝳䞊䝤䛾≀ᛶ䚷㻟㻙㻡㻿㼃㻺㼀ⷧ⭷䛾⇕㉳㟁ຊ䛾➨୍ཎ⌮䝅䝭䝳䝺䞊䝅䝵䞁㻌㻖㻌ຍ⸨㻌ဴᖹ㻘㻌⮻஭㻌ಙᚿ㻘㻌ᒣᮏ㻌㈗༤

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Influence of Carbon nano-inclusion dimensionality in the thermal conductivity
enhancement of aqueous and non-aqueous fluids* Sivasankaran Harish, Kei Ishikawa, Erik Einarsson, Shohei Chiashi, Junichiro Shiomi,
Shigeo Maruyama

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First Principles-Based Estimate of the Critical SWCNT Length for Raman D
and G Band Intensity Inversion㻟㻤㻌㻖㻌すᮧ㻌ዲྐ㻘㻌㻴㼑㼚㼞㼥㼗㻌㼃㼕㼠㼑㼗㻘㻌㻿㼠㼑㼜㼔㼍㼚㻌㻵㼞㼘㼑㻟㻙㻤

Exciton effects on coherent phonon spectroscopy of carbon nanotubes㻟㻥㻌㻖㻌䜰䝣䝬䝗㻌䝚䜾䝷䝝㻘㻌䝝䝇䝕䜸㻌䜶䝑䝗䜴䜱㻘㻌㰻⸨㻌⌮୍㑻㻟㻙㻥High-temperature in-situ TEM Observation of Zipper-like Wall-to-Wall Coalescenceof Double-Wall Carbon Nanotubes㻠㻜㻌㻖㻌㉿㻌ᛮ℟㻘㻌໭ᾆ㻌Ⰻ㻘㻌ᐑ⏣㻌⪔඘㻘㻌⠛ཎ㻌ஂ඾㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌᫨㣗㻌㻌㻔㻝㻞㻦㻜㻜㻙㻝㻟㻦㻝㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘≉ูㅮ₇㻌㻌㻔㻝㻟㻦㻝㻡㻙㻝㻟㻦㻠㻡㻕㻟㻿㻙㻤

Ballistic transport in graphene/h-BN* Tomoki Machida, Satoru Masubuchi, Masahiro Onuki, Sei Morikawa,Kazuyuki Iguchi, Takehiro Yamaguchi, Miho Arai, Kenji Watanabe, Takashi Taniguchixii㻤㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠏᪥㻌䠄Ỉ䠅䝫䝇䝍䞊䝥䝺䝡䝳䞊㻌㻌㻔㻝㻟㻦㻠㻡㻙㻝㻠㻦㻟㻜㻕䝫䝇䝍䞊䝉䝑䝅䝵䞁㻌㻌㻔㻝㻠㻦㻟㻜㻙㻝㻢㻦㻜㻜㻕䚷䚷䚷䚷䠄䖪䠅䚷ⱝᡭዡບ㈹ೃ⿵
䝣䝷䞊䝺䞁䛾໬Ꮫ㻟㻼㻙㻝㻯㻢㻜䛸䝅䝷䝅䜽䝻䝥䝻䝟䞁䛾⇕཯ᛂ䠖䜹䝹䝪䝅䝸䝹໬䝣䝷䞊䝺䞁䛾⏕ᡂ㻝㻟㻤㻌㻖㻌㣤⏣㻌ு௓㻘㻌㧗ᮌ㻌㈼ኴ㑻㻘㻌ຍᅛ㻌ᫀᐶ㻘㻌㛗㇂ᕝ㻌ṇ㻘㻌๓⏣㻌ඃ㻘㻌ᒣ⏣㻌㐨ኵ㻘㻌㉥㜰㻌೺㻟㻼㻙㻞䝣䝷䞊䝺䞁㻯㻣㻜䛻䛚䛡䜛㛤ཱྀ㒊ᵓ⠏䛸ỈศᏊ䛾ෆໟ䖪㻌㻖㻌ᙇ㻌㗦㻘㻌ᮧ⏣㻌⌮ᑦ㻘㻌ᮧ⏣㻌㟹ḟ㑻㻟㻼㻙㻟ⰾ㤶᪘䝆䜶䝘䝭䞁䛸㻯㻢㻜䛾⇕㼇㻞㻗㻞㼉⎔໬௜ຍ཯ᛂ

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㻌㻖㻌ఀ⇃㻌┤ᙪ㻘㻌ᒣᮏ㻌ᾈஅ㻘㻌୕ᮌỤ㻌⩼㻘㻌ᑠஂಖ㻌◊㻘㻌኱ᓥ㻌ᕦ䝣䝷䞊䝺䞁䛾ᛂ⏝㻟㻼㻙㻠ග↷ᑕ䛻䜘䛳䛶స〇䛧䛯㻯㻢㻜ග㔜ྜయ䛾ఏᑟ≉ᛶホ౯㻝㻠㻝* Naoto Toriumi, Tatsuya Doi, Daiki Momiyama, Wataru Akiyama,
Katsuhiko Miyamoto, Takashige Omatsu, Jonathan Bird, Yuichi Ochiai, Nobuyuki Aoki㻟㻼㻙㻡㻼㻯㻮㻹䛸ΰྜ䝗䝘䞊䜢⏝䛔䛯᭷ᶵⷧ⭷ኴ㝧㟁ụ䛾స〇㻌㻖㻌⸨஭㻌ಇ἞㑻㻘㻌ẁ㻌᐀⠊㻘㻌ዟᕝ㻌Ꮥ⣖㻘㻌ᰗ㻌㞝୍㑻㻘㻌ྜྷ⏣㻌ဴ㻘㻌⏣୰㻌୔ኈ㻘㻌すᒸ㻌Ὀᇛ㻘㻌∦ᾆ㻌ᘯ㐨㻝㻠㻞㔠ᒓෆໟ䝣䝷䞊䝺䞁㻟㻼㻙㻢

Trimetallic Nitride Template-Endohedral Metallofullerenes(TNT-EMFs)䛸䜰䝆䝸䝆䞁䛾཯ᛂ䖪㻌㻖㻌ᮌᮧ㻌ோኈ㻘㻌ୖ⏣㻌䛱䜂䜝㻘㻌ᒣ⏣㻌㐨ኵ㻘㻌๓⏣㻌ඃ㻘㻌㛗㇂ᕝ㻌ṇ㻘㻌㉥㜰㻌೺㻟㻼㻙㻣䝖䝸䜶䝏䝹䜰䝭䞁㻙䜰䝉䝖䞁ΰྜ⁐፹䜢⏝䛔䛯୙Ᏻᐃ」᰾㔠ᒓෆໟ䝣䝷䞊䝺䞁䛾ᢳฟ㻌㻖㻌෠ᶔ㻌ឡ⨾㻘㻌ඤ⋢㻌೺㻘㻌⸨⏣㻌΅㻘㻌⳥ᆅ㻌⪔୍㻘㻌㜿▱Ἴ㻌ὒḟ

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䝣䝷䞊䝺䞁
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䝷䝆䜹䝹䜢᭷䛩䜛䝣䝷䞊䝺䞁䛾䝇䝢䞁≧ែ㻌㻖㻌ᒸ⏣㻌᫴㻘㻌ᒣᮏ㻌㈗༤

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㻟㻼㻙㻥
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༑㔜௜ຍయ䝣䝷䞊䝺䞁䛾☢ᛶ≧ែ㻌㻖㻌᪂䝍㻌ᬕዉ㻘㻌ᒸ⏣㻌᫴

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㻟㻼㻙㻝㻜

㧗ᙉᗘ䝣䜵䝮䝖⛊䝺䞊䝄䞊䜢⏝䛔䛯⁐ᾮෆ཯ᛂ䛻䜘䜛㻯㻢㻜䛛䜙䛾㼚㼛㼚㻙㻵㻼㻾䝣䝷䞊䝺䞁䛾ྜᡂ㻝㻠㻣㻌㻖㻌ඤ⋢㻌೺㻘㻌⸨㔝㻌❳ஓ㻘㻌ᇛ୸㻌᫓ኵ㻘㻌㜿▱Ἴ㻌ὒḟ䝘䝜⎔ቃ䛸Ᏻ඲ホ౯㻟㻼㻙㻝㻝䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛸䝩䝰䝫䝸䝨䝥䝏䝗䛾┦஫స⏝㻌㻖㻌ᖹ㔝㻌⠜㻘㻌ட⏣㻌೔ྐ㻘㻌⏣୰㻌୔ኈ㻘㻌∦ᾆ㻌ᘯ㐨㻝㻠㻤䝘䝜䝏䝳䞊䝤䛾≀ᛶ㻟㻼㻙㻝㻞䖪༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䝞䞁䝗䝹⏺㠃䛻䛚䛡䜛ศᏊㄆ㆑㻌㻖㻌ᰗ㻌㙂Ὀ㻘㻌⸨䞄㇂㻌๛ᙪ㻘㻌୰ᔱ㻌┤ᩄ

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Enhancement of photoluminescence from single-walled carbon nanotubes
by photonic crystal nanocavities
Ryosuke Watahiki, * Takashi Shimada, Pei Zhao, Shohei Chiashi, Satoshi Iwamoto,
Yasuhiko Arakawa, Shigeo Maruyama, Yuichiro K. Kato

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༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾㟁Ẽ໬Ꮫ䝞䞁䝗䜼䝱䝑䝥䜈䛾⁐፹ຠᯝ䛾᳨ウ㻌㻖㻌ᐑᓮ㻌኱ᝅ㻘㻌ᖹම㻌ᗣᙪ㻘㻌᪂␃㻌ᗣ㑻㻘㻌୰ᔱ㻌┤ᩄ

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༢ᒙ䞉஧ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾ᵓ㐀≉ᛶ䛻ᑐ䛩䜛㻻㻼㻻䝺䞊䝄䞊↷ᑕ䛾ᙳ㡪㻌㻖㻌኱⸨㻌ဴဢ㻘㻌⇃ἑ㻌㝧㻘㻌㛗ᒇ㻌♸㤶㻘㻌ᅵᒇ㻌ዲྖ㻘㻌▼஭㻌ᛅᾈ㻘㻌▮ᓥ㻌༤ᩥ

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xiii

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠏᪥㻌䠄Ỉ䠅㻟㻼㻙㻝㻢䖪

Vernier spectrum in finite-length armchair carbon nanotubes㻝㻡㻟㻌㻖㻌㎮ᕭ㻌⏤ᶞ㻘㻌Ἠ⏣㻌΅㻘㻌㰻⸨㻌⌮୍㑻㻟㻼㻙㻝㻣⣽䛔䝘䝜䝏䝳䞊䝤䛻䛚䛡䜛㻾㻮㻹䛾➨୍ཎ⌮ィ⟬㻌㻖㻌᫝ᖖ㻌㝯㻘㻌ᩪ⸨㻌᫴

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ᖹ⾜㟁⏺䛻䜘䛳䛶㟁Ⲵ䛜⵳✚䛥䜜䛯䜻䝱䝑䝥௜䛝䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾㟁Ꮚ≀ᛶ㻌㻖㻌ᒣ୰㻌⥤㤶㻘㻌ᒸ⏣㻌᫴

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Electronic Raman scattering and origin of the Fano resonance in metallic carbon nanotubes* Eddwi Hasdeo, Ahmad Nugraha, Kentaro Sato, Riichiro Saito㻝㻡㻢䝘䝜䝏䝳䞊䝤䛾ᛂ⏝㻟㻼㻙㻞㻜

Selective Dispersion of Single-Walled Carbon Nanotubes into Nano-Cage of HelicalConformation of Poly(m-phenylene-ethynylene) Derivatives
Fumito Kobayashi, Yuki Moriyama, * Masahiro Takahashi, Masayoshi Tange,
Toshiya Okazaki, Keiki Kishikawa, Shigeo Kohmoto

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༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾䝫䝸䜾䝸䝉䝻䞊䝹ಟ㣭䛻䜘䜛ྍ⁐໬䛸ᾮయ䜽䝻䝬䝖䜾䝷䝣䜱䛻䜘䜛䝃䜲䝈ศ㞳㻌㻖㻌୰ᮧ㻌ᆂ♸㻘㻌㉿㻌฼㻘㻌㟷἟㻌⚽ඣ㻘㻌ᮌᮧ㻌㝯ⱥ㻘㻌ᑠᯇ㻌┤ᶞ

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Electric double layer transistors of aligned carbon nanotube thin film
* Yoshifumi Wada, Jiang Pu, Yuki Takagi, Kazuhiro Yanagi, Taishi Takenobu

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༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤⭷䛾ග⇕㉳㟁ຊ≉ᛶ㻌㻖㻌ᴬཎ㻌⏠㻘㻌బ⸨㻌⩏೔㻘㻌ఀ㔝㻌ᾈ௓㻘㻌ఀ⸨㻌ᬡᙪ㻘㻌ᮎỌ㻌ᬛ୍㻘㻌ᚋ⸨㻌Ꮥ㻘㻌ᮏᐑ㻌᠇୍㻘㻌⏣㊰㻌࿴ᖾ

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Specific biosensor based on biotin-labeled double-walled carbon nanotube FET* Akihiro Kuno, Yuka Nagaya, Koji Tsuchiya, Akira Hida, Koji Ishibashi, Hirofumi Yajima䖪䝘䝜䝏䝳䞊䝤䛾⏕ᡂ䛸⢭〇㻟㻼㻙㻞㻡㘒య䝫䝸䝬䞊䛻䜘䜛༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾㑅ᢥⓗྍ⁐໬㻌㻖㻌฼ග㻌ྐ⾜㻘㻌⸨䞄㇂㻌๛ᙪ㻘㻌୰ᔱ㻌┤ᩄ

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ศᏊືຊᏛ䝅䝭䝳䝺䞊䝅䝵䞁䛻䛚䛡䜛༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ᡂ㛗䛾䜹䜲䝷䝸䝔䜱ゎᯒ㻌㻖㻌ᕝ㕥ᮌ㻌ᬛဢ㻘㻌ஂ㛫㻌㤾㻘㻌㧗ᮌ㻌ຬ㍤㻘㻌༓㊊㻌᪼ᖹ㻘㻌୸ᒣ㻌ⱱኵ

㻝㻢㻟

㻟㻼㻙㻞㻣

Methane-assisted CVD yielding millimeter-tall single-wall carbon nanotubes of smaller
diameters㻝㻢㻠䖪㻌㻖㻌㝞㻌ᛅ᫂㻘㻌㔠㻌ᮾᴿ㻘㻌㛗㇂ᕝ㻌㤾㻘㻌㔝⏣㻌㻌ඃ㻟㻼㻙㻞㻤䝢䝺䞁ศᏊ䝜䜼䝇䛻䜘䜛㔠ᒓ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾㑅ᢥⓗᢳฟ㻌๽㻌๛㻘㻌㻖㻌ᑠᯇ㻌┤ᶞ㻘㻌ᮌᮧ㻌㝯ⱥ

㻝㻢㻡

㻟㻼㻙㻞㻥

In situ Raman monitoring formation of SWNTs: process optimization and low
temperature synthesis* Ming Liu, Yuquan Su, Rong Xiang, Zikang Tang

㻝㻢㻢

㻟㻼㻙㻟㻜

One-Step Catalyst-Free Mist Flow CVD Growth of Single-Wall Carbon Nanotubes
using C60 Fullerenes

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䖪
㻟㻼㻙㻟㻝

* Yun Sun, Ryo Kitaura, Jinying Zhang, Yasumitsu Miyata, Hisanori Shinohara༢ᒙ㻯㻺㼀䝣䜷䝺䝇䝖ᡂ㛗ไᚚ䛻ྥ䛡䛯ゐ፹ᚤ⢏Ꮚ䜰䝺䜲ᙧᡂ㐣⛬䛾䝰䝕䝹ศᯒ㻌㻖㻌ᱜ஭㻌ಇ௓㻘㻌䝣䝍䝞㻌䝗䞁㻘㻌‫‮‬ᮧ㻌Ᏺ㞝㻘㻌␊㻌㈼἞

xiv

㻝㻢㻤

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠏᪥㻌䠄Ỉ䠅㻟㻼㻙㻟㻞䝁䞊䝹䝗䜴䜷䞊䝹໬ᏛẼ┦ᡂ㛗ἲ䛻䜘䜛༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䛾఩⨨䚸䜹䜲䝷䝸䝔䜱䚸㠃ෆ㓄ྥ䛾ྠ᫬ไᚚ
㻌㻖㻌┦Ⰻ㻌ᣅᐇ㻘㻌ᅵ⫧㻌ᬛྐ㻘㻌▼஭㻌ᏹ἞㻘㻌ᒾ⏣㻌ᒎᖾ㻘㻌▮ᓥ㻌༤ᩥ㻘㻌ᒣᮏ㻌ᐶ㻝㻢㻥ෆໟ䝘䝜䝏䝳䞊䝤
㻟㻼㻙㻟㻟

Diameter Dependent Interaction between Single-Walled Carbon Nanotubes andEncapsulated Ferrocenes㻝㻣㻜㻌㻖㻌㕥ᮌ㻌ᾈ⣖㻘㻌㣤Ἠ㻌㝧Ꮚ㻘㻌ᒸᓮ㻌ಇஓ㻟㻼㻙㻟㻠䖪༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤ෆ㒊䛻సᡂ䛧䛯༢ᒙ❅໬䝩䜴⣲䝘䝜䝏䝳䞊䝤䛾ศගศᯒ㻌㻖㻌୰す㻌ு㻘㻌໭ᾆ㻌Ⰻ㻘㻌ᒣᮏ㻌ᝆኴ㻘㻌Ⲩ஭㻌㔜ຬ㻘㻌㼃㼍㼞㼚㼑㼞㻌㻶㼍㼙㼕㼑㻘㻌ᐑ⏣㻌⪔඘㻘㻌⠛ཎ㻌ஂ඾㻝㻣㻝䜾䝷䝣䜵䞁⏕ᡂ㻟㻼㻙㻟㻡ゐ፹㻯㼂㻰ἲ䛻䛚䛡䜛ከᒙ䜾䝷䝣䜵䞁⏕ᡂ䛾ศᏊືຊᏛ䝅䝭䝳䝺䞊䝅䝵䞁㻌㻖㻌㧗ᮌ㻌ຬ㍤㻘㻌ஂ㛫㻌㤾㻘㻌ᕝ㕥ᮌ㻌ᬛဢ㻘㻌༓㊊㻌᪼ᖹ㻘㻌୸ᒣ㻌ⱱኵ

㻝㻣㻞

㻟㻼㻙㻟㻢
䖪

䝷䞊䝆䜾䝺䜲䞁༢ᒙ㻮㻺䝗䞊䝥䜾䝷䝣䜵䞁䛾ྜᡂ䛸ホ౯㻌㻖㻌ᑠᯘ㻌భ㻘㻌ᐑ⏣㻌⪔඘㻘㻌๓⏣㻌ᯞ㔛Ꮚ㻘㻌໭ᾆ㻌Ⰻ㻘㻌⠛ཎ㻌ஂ඾

㻝㻣㻟

㻟㻼㻙㻟㻣

ᐊ ㉸ఏᑟ䜢ᐇ⌧䛩䜛䜾䝷䝣䜯䜲䝖㻛䜾䝷䝣䜵䞁ᒙ㛫໬ྜ≀䛾⏕ᡂ䛸≉ᛶホ౯㻌㻖㻌బ⸨㻌⚈࿃㻘㻌ᕷᕝ㻌༤ு㻘㻌ᒾ⏣㻌ᒎᖾ㻘㻌ᒣᮏ㻌ᐶ

㻝㻣㻠

㻟㻼㻙㻟㻤
䖪

ᇶᯈᑐྥ㻯㼂㻰ἲ䛻䜘䜛㻯㼡ୖ䛷䛾䜾䝷䝣䜵䞁䛾ᣦྥᛶᡂ㛗㻌㻖㻌ቑ⏣㻌❳ஓ㻘㻌Ἑཎ㻌᠇෬㻘㻌࿃㒓㻌ᾈᶞ㻘㻌㔝⏣㻌ඃ㻝㻣㻡䜾䝷䝣䜵䞁䛾ᛂ⏝㻟㻼㻙㻟㻥Monte Carlo Particle Simulations of Local Heating Properties in Graphene-channel
nano-FETs

㻝㻣㻢㻌㻖㻌኱ᮌ㻌⚽♸㻘㻌୕⃝㻌ኴ୍㻘㻌⢖㔝㻌♸஧㻟㻼㻙㻠㻜䖪䜾䝷䝣䜵䞁䜢⏝䛔䛯㉸㧗㏿㯮యᨺᑕⓎග⣲Ꮚ㻌㻖㻌ᶓ஭㻌ᬛဢ㻘㻌㧗ᒣ㻌㞝௓㻘㻌᳃㻌㐩ஓ㻘㻌ὠ㇂㻌኱ᶞ㻘㻌∾㻌ⱥஅ

㻝㻣㻣

㻟㻼㻙㻠㻝

Few-layer Graphene/silicon Heterojunction Photovoltaic Cells by Microwave PlasmaEnhanced Chemical Vapor Deposition* Z. Wang, S. Hayase, M Shoji, H Hironori㻝㻣㻤䜾䝷䝣䜵䞁䛾≀ᛶ㻟㻼㻙㻠㻞㐲ᚰศ㞳䛧䛯㓟໬䜾䝷䝣䜵䞁䛾㓟໬ᗘ㻌㻖㻌ᶓ஭㻌⿱அ㻘㻌㩾἟㻌㝣ኸ㻘㻌␊ᒣ㻌୍⩧㻘㻌㇂ཱྀ㻌㈗❶㻘㻌ᯇᮏ㻌Ὀ㐨

㻝㻣㻥

㻟㻼㻙㻠㻟

Spin polarization of hexagonal boron nitride/Ni(111) interface studied by spin-polarized
metastable de-excitation spectroscopy.

㻝㻤㻜㻌㻖㻌኱క㻌┿ྡṌ㻘㻌ᒣෆ㻌Ὀ㻘㻘㻌ᅭ㇂㻌ᚿ㑻㻘㻌ᯇᮏ㻌ྜྷᘯ㻘㻌ᴍᮏ㻌ὒ㻘㻌ቃ㻌ㄔྖ㻟㻼㻙㻠㻠䖪㻞ḟඖ㔠ᒓⅣ⣲ྠ⣲య䛾≀ᛶ㻌㻖㻌୸ᒣ㻌ᐇ㑣㻘㻌ᒸ⏣㻌᫴

㻝㻤㻝

㻟㻼㻙㻠㻡

䜾䝷䝣䜯䜲䝖䛾䝺䞊䝄䞊䜰䝤䝺䞊䝅䝵䞁䛻䜘䜚⏕ᡂ䛧䛯䜾䝷䝣䜵䞁䝘䝜≀㉁㻌㻖㻌୰ᮧ㻌┿⣖㻘㻌Ἑྜ㻌Ꮥ⣧㻘㻌ධỤ㻌㊰Ꮚ㻘㻌ᘪ๐㻌ுኴ㻘㻌㣤ᓥ㻌⃈⏨㻘㻌ᆏᮾ㻌ಇ἞㻘㻌‫⏣‮‬ᆏ㻌㞞Ꮚ

㻝㻤㻞

㻟㻼㻙㻠㻢

䜶䝑䝏䞁䜾ᾮ䛸ྜᡂ ᗘ䛜❅⣲䝗䞊䝥䛧䛯䜾䝷䝣䜵䞁⭷䛾⾲㠃᢬ᢠ⋡䛻ཬ䜌䛩ຠᯝ㻌Ỉ㔝㻌㈗⿱㻘㻌㻖㻌ᆏᮾ㻌ಇ἞㻝㻤㻟㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌ఇ᠁㻌㻌㻔㻝㻢㻦㻜㻜㻙㻝㻢㻦㻝㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘xv

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠏᭶䠍䠏᪥㻌䠄Ỉ䠅≉ูㅮ₇㻌㻌㻔㻝㻢㻦㻝㻡㻙㻝㻢㻦㻠㻡㻕㻟㻿㻙㻥᭷ᶵⷧ⭷ኴ㝧㟁ụ䛻⏝䛔䜛䝣䝷䞊䝺䞁ㄏᑟయ䛾タィ䛸ྜᡂ䛚䜘䜃≀ᛶᯇᑿ㻌㇏㻥୍⯡ㅮ₇㻌㻌㻔㻝㻢㻦㻠㻡㻙㻝㻣㻦㻠㻡㻕㔠ᒓෆໟ䝣䝷䞊䝺䞁㻟㻙㻝㻜㔠ᒓෆໟ䝣䝷䞊䝺䞁䛾ᡂ㛗ᶵᵓ㻌㻖㻌㜿▱Ἴ㻌ὒḟ㻘㻌ඤ⋢䚷㻌೺㻘㻌ᶫᮏ㻌೺ᮁ㻘㻌ᇛ୸㻌᫓ኵ

㻠㻝

㻟㻙㻝㻝

༢⤖ᬗ㼄⥺ᅇᢡ䛻䜘䜛పᑐ⛠ᛶ䝣䝷䞊䝺䞁䛻ෆໟ䛥䜜䛯䝒䝸䜴䝮ཎᏊ䛚䜘䜃Ⅳ⣲䜽䝷䝇䝍䞊䛾ᵓ㐀ゎᯒ㻌㻖㻌బ㐨㻌♸㈗㻘㻌㟷ᰗ㻌ᚸ㻘㻌Ἠ㻌஀㔛Ꮚ㻘㻌໭ᾆ㻌Ⰻ㻘㻌㼀㼕㼙㻌㻷㼛㼣㼍㼘㼏㼦㼥㼗㻘㻌㻶㼕㼍㼚㻌㼃㼍㼚㼓㻘㻌㻿㼠㼑㼜㼔㼍㼚㻌㻵㼞㼘㼑㻘すᇼ㻌ⱥ἞㻘㻌ᮡᮏ㻌㑥ஂ㻘㻌⠛ཎ㻌ஂ඾

㻠㻞

㻟㻙㻝㻞

䝸䝏䜴䝮ෆໟ䝣䝷䞊䝺䞁䛸䜽䝻䝸䞁ㄏᑟయ䛾㉸ศᏊෆග㟁Ꮚ⛣ື཯ᛂ㻌㻖㻌኱ஂಖ㻌ᩗ㻘㻌ᕝᓥ㻌㞝ᶞ㻘㻌㛫℩㻌ㅬኴᮁ㻘㻌⚟ఫ㻌ಇ୍

㻠㻟

㻟㻙㻝㻟

㻳㼐㻟㻺㻬㻯㻤㻜䛸㻱㼞㻟㻺㻬㻯㻤㻜䛾⣸እග㟁Ꮚ䝇䝨䜽䝖䝹㻠㻠㻌㻖㻌ᐑᓮ㻌㝯ᩥ㻘㻌୰す㻌ຬ௓㻘㻌బ䚻ᮌ㻌♸⏕㻘㻌୹⩚㻌ᏹஅ㻘㻌㔝⏣㻌⚈Ꮚ㻘㻌す㻌㱟ᙪ㻘㻌ኴ⏣㻌▱㑣㻘⠛ཎ㻌ஂ඾㻘㻌᪥㔝㻌↷⣧xvi㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻝㼠㼔㻘㻌㻹㼛㼚㻚㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻦㻌㻞㻡㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻌㻗㻌㻡㼙㼕㼚㻌㻔㻰㼕㼟㼏㼡㼟㼟㼕㼛㼚㻕㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻦㻌㻝㻜㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻌㻗㻌㻡㼙㼕㼚㻌㻔㻰㼕㼟㼏㼡㼟㼟㼕㼛㼚㻕㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻼㼛㼟㼠㼑㼞㻌㻼㼞㼑㼢㼕㼑㼣㻦㻌㻝㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻥㻦㻟㻜㻙㻝㻜㻦㻜㻜㻕㻝㻿㻙㻝

New Vistas in Chemistry of Endohedral Metallofullerenes
Takeshi Akasaka㻝㻼㼛㼟㼠㼑㼞㻌㻼㼞㼑㼢㼕㼑㼣㻌㻌㻔㻝㻜㻦㻜㻜㻙㻝㻜㻦㻠㻡㻕㻼㼛㼟㼠㼑㼞㻌㻿㼑㼟㼟㼕㼛㼚㻌㻌㻔㻝㻜㻦㻠㻡㻙㻝㻞㻦㻟㻜㻕䚷䠄䖪䠅㻯㼍㼚㼐㼕㼐㼍㼠㼑㼟㻌㼒㼛㼞㻌㼠㼔㼑㻌㼅㼛㼡㼚㼓㻌㻿㼏㼕㼑㼚㼠㼕㼟㼠㻌㻼㼛㼟㼠㼑㼞㻌㻭㼣㼍㼞㼐㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻝㻼㻙㻝䖪

Optical coupling of air-suspended carbon nanotubes to silicon microdisk resonators* Saneyuki Imamura, Ryosuke Watahiki, Ryohei Miura, Yuichiro K. Kato

㻠㻡

㻝㻼㻙㻞

X-ray diffraction profile of highly purified (6,5) SWCNTs* Shin Tadera, Haruka Kyakuno, Yusuke Nakai, Kazuhiro Yanagi, Yasumitsu Miyata,
Hiromichi Kataura, Yutaka Maniwa

㻠㻢

㻝㻼㻙㻟
䖪

Observation of circular dichroism in individual air-suspended single-walled carbon nanotubes* A. Yokoyama, A. Ishii, M. Yoshida, Y. K. Kato

㻠㻣

㻝㻼㻙㻠

Determination of surfactant (Brij 78) in aquatic CNT dispersion* Kazutoku Ohta, Yoshio Hayakawa, Taizo Ono, Hiroshi Yamawaki, Kazuhiro Yamamoto,Kazumasa Honda

㻠㻤

㻝㻼㻙㻡
䖪

Effect of Impurity Scattering on AC Transport in Carbon Nanotubes* Daisuke Hirai, Takahiro Yamamoto, Satoshi Watanabe

㻠㻥

㻝㻼㻙㻢

Solution growth of carbon-nanotube wires* Yuki Takagi, Yugo Oshima, Kazuhiro Yanagi, Taishi Takenobu

㻡㻜

㻝㻼㻙㻣

In-situ Raman spectroelectrochemical investigation on diameter-dependent onset potentialof oxygenation reaction of SWCNTs* Shingo Sakamoto, Masato Tominaga

㻡㻝

㻝㻼㻙㻤

Strong saturation of photoluminescence from local quantum states in oxygen-doped carbon nanotubes
Munechiyo Iwamura, * Yuhei Miyauchi, Naoto Akizuki, Shinichiro Mouri, Kazunari Matsuda

㻡㻞

㻝㻼㻙㻥
䖪

Quantum Mechanical Transport in SWNTs Network FETs Studied via Scanning Gate Microscopy* Xiaojun Wei, Masahiro Matsunaga, Kenji Maeda, Tatsurou Yahagi, Nobuyuki Aoki,
Jonathan P. Bird, Koji Ishibashi, Yuichi Ochiai㻡㻟䖪㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻝㻼㻙㻝㻜

Polymer Solar Cells with PEDOT:PSS / SWCNTs and MWCNTs Composite as Hole Transport Layer* Naoki Kishi, Junki Hayashi, Takeshi Saito, Tetsuo Soga, Takashi Jimbo

㻡㻠

㻝㻼㻙㻝㻝

High efficiency carbon nanotube/silicon heterojunction solar cells fabricated using high quality
carbon nanotube network film
* Feijiu Wang, Daichi Kozawa, Yuhei Miyauchi, Shinichiro Mouri, Yutaka Ohno, Kazunari Matsuda

㻡㻡

㻝㻼㻙㻝㻞

P-N junction in Carbon Nanotube Electric Double Layer Transistor* Ryo Shimizu, Yijin Zhang, Kazuhiro Yanagi, Yoshihiro Iwasa, Taishi Takenobu

㻡㻢

㻝㻼㻙㻝㻟
䖪

High-mobility, filexible, n-type carbon nanotube thin-film transistors* Tomohiro Yasunishi, Yutaka Ohno, Shigeru Kishimoto, Takashi Mizutani

㻡㻣

㻝㻼㻙㻝㻠

Functionalization of Carbon Nanotubes with Antibody for Immunoassay* Yoko Iizumi, Toshiya Okazaki , Yuzuru Ikehara, Mutuo Ogura, Masako Yudasaka

㻡㻤

䖪

xvii

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Arc Production of SWNTS under Controlled He Gas Temperature* Tetsu Mieno, Takashi Suzuki

㻡㻥

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Electric-field-induced layer formation of metallic and semiconducting single-wall carbon
nanotubes in D2O – H2O mixtures* Fusako Sasaki, Hideaki Numata, Takeshi Saito, Fumiyuki Nihey

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Development of Substrate Heater System of Cold-Wall Chemical Vapor Deposition Equipment
for Improvement of Single-Walled Carbon Nanotubes Quality* Yusaku Tsuda, Satoshi Doi, Koji Ishii, Nobuyuki Iwata, Hirihumi Yajima, Hiroshi Yamamoto

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Nitrogen-doped single-walled carbon nanotubes and their growth mechanism* Theerapol Thurakitseree, Christian Kramberger, Akihito Kumamoto, Shohei Chiashi,
Erik Einarsson, Shigeo Maruyama

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㻝㻼㻙㻝㻥
䖪

Selective synthesis of large amount of (6, 5) single-walled carbon nanotubes using pulse plasma CVD* Koshi Murakoshi, Toshiaki Kato, Rikizo Hatakeyama, Toshiro Kaneko

㻢㻟

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Alcohol Catalytic CVD Synthesis of Single-Walled Carbon Nanotubes Using C 60 as the Catalysts* Kenta Nakamura, Takanori Umino, Shohei Chiashi, Shigeo Maruyama

㻢㻠

㻝㻼㻙㻞㻝

Characterization of Horizontally Aligned Single-Walled Carbon Nanotubes Grown on Crystal Quartz
by Using Scanning Microscopy* Daisuke Hasegawa, Taiki Inoue, Keigo Otsuka, Saifullah Badar, Shohei Chiashi, Shigeo Maruyama

㻢㻡

㻝㻼㻙㻞㻞
䖪

String-like Aggregates of Aligned (6, 5) Single Wall Carbon Nanotubes* Hideki Kawai, Kai Hasegawa, Touru Nakatsu, Yasuhisa Naitou, Yuuki Takagi,
Taishi Takenobu, Kazuhiro Yanagi

㻢㻢

㻝㻼㻙㻞㻟

Super Growth: Unexpectedly High Yield Carbon Nanotube Synthesis from Low Activity Carbon
Feedstocks at High Concentrations* Hiroe Kimura, Jundai Goto, Satoshi Yasuda, Shunsuke Sakurai, Motoo Yumura,
Don Futaba, Kenji Hata

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㻝㻼㻙㻞㻠

Pressure dependence of High-temperature Pulsed-arc Discharge* Hayato Kikuchi, Katsuhide Terada, Toshiki Sugai㻢㻤䖪㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻝㻼㻙㻞㻡

ESR Measurements of N@C60 with [10]Cycloparaphenylene in Solution* Mitsuhiro Okamoto, Takahiro Iwamoto, Shigeru Yamago, Tatsuhisa Kato

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㻝㻼㻙㻞㻢
䖪

Polythiophene encapsulated in carbon nanotubes as a high-throughput Raman imaging marker* Kenshi Miyaura, Yasumitsu Miyata, Ikuya Wakamori, Boanerges Thendie, Ryo Kitaura,
Hisanori Shinohara㻣㻜㻺㼍㼚㼛㼔㼛㼞㼚㼟㻝㻼㻙㻞㻣

Biodegradation of Single-Wall Carbon Nanohorns* Minfang Zhang, Mei Yang, Cyrill Bussy, Hanene Ali-Boucetta, Sumio Iijima,
Kostas Kostarelos, Masako Yudasaka

㻣㻝

㻝㻼㻙㻞㻤

Carbon nanohorns induced RAW264.7 apoptosis: Lysosomal membrane destabilization caused
reactive oxygen species generation, leading cell apoptosis* Mei Yang, Minfang Zhang, Yoshio Tahara, Sumio Iijima, Masako Yudasaka

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㻝㻼㻙㻞㻥

Nitrogen-doped carbon nanohorn aggregates with electrocatalytic activity for oxygen reduction* Ryota Yuge, Takashi Manako, Shunji Bandow, Masako Yudasaka, Kiyohiko Toyama,
Takashi Yamaguchi, Sumio Iijima, Kaichiro Nakano

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xviii

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻝㼠㼔㻘㻌㻹㼛㼚㻚㻳㼞㼍㼜㼔㼑㼚㼑㻌㼟㼥㼚㼠㼔㼑㼟㼕㼟㻝㻼㻙㻟㻜䖪

CVD Growth of Bernal Stacked Bilayer Graphene on Heteroepitaxial Cu(111) Film
* Shota Tanoue, Kenji Kawahara, Masaharu Tsuji, Hiroki Ago

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㻝㻼㻙㻟㻝

Scalable processing of crystallographic etching for graphite powder using supercritical fluid* Takaaki Tomai, Naoki Tamura, Itaru Honma

㻣㻡

㻝㻼㻙㻟㻞
䖪

In situ RHEED Study on Growth Process of Graphene by Chemical Vapor Deposition* Takuro Minato, Hitoshi Nakahara, Koji Asaka, Yahachi Saito

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㻝㻼㻙㻟㻟

Influence of applied potentials for electrochemical exfoliation of graphite* Haruya Okimoto, Syun Takabayashi, Yuhei Sobe, Masahito Sano㻣㻣㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻝㻼㻙㻟㻠䖪

CVD synthesis of shape-controlled graphene and boron nitride heterostructures* Eriko Maeda, Yasumitsu Miyata, Ryo Kitaura, Hisanori Shinohara

㻣㻤

㻝㻼㻙㻟㻡

Orientation Controlled Growth of NbS 2 Nanosheets on CVD Graphene
Wanyin Ge, Kenji Kawahara, Masaharu Tsuji, * Hiroki Ago

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㻝㻼㻙㻟㻢
䖪

Nanocolumnar Crystal Growth of Organic Semiconductor Molecules on a Graphene-Modified Surface* Satoshi Okada, Shunsuke Furukawa, Hideyuki Tanaka, Koji Harano, Eiichi Nakamura㻤㻜㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻝㻼㻙㻟㻣

Imaging graphene lattice by the helium ion microscope: A prediction by ab initio simulations* Yoshiyuki Miyamoto

㻤㻝

㻝㻼㻙㻟㻤
䖪

Anderson Localization of Edge-Disordered Graphene Nanoribbons* Kengo Takashima, Yukihiro Takada, Takahiro Yamamoto

㻤㻞

㻝㻼㻙㻟㻥

Gapped and gapless graphene and graphene-nanoribbon/nanotube complex* Shota Kizukuri, Takashi Koretsune, Susumu Saito

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SGM investigation of graphene nano structure* Souhei Furuya, Kazuyuki Takai, Yoshiaki Sato, Toshiaki Enoki

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㻝㻼㻙㻠㻝
䖪

Raman spectroscopy of mechanically strained chemically functionalized graphene* Mark Bissett, Masaharu Tsuji, Hiroki Ago

㻤㻡

㻝㻼㻙㻠㻞

Magnetic Interactions between Nanographite and Oxygen Molecule* Kazuyuki Takai, Alexander. I Shames, Vladimir Yu Osipov, Alexander Ya Vul',
Yutaka Kaburagi, Takuya Hayashi, Toshiaki Enoki㻤㻢㻯㼍㼞㼎㼛㼚㻌㼚㼍㼚㼛㼜㼍㼞㼠㼕㼏㼘㼑㼟㻝㻼㻙㻠㻟A New Stage in Detonation Nanodiamond Research* Shuichi Sasaki, Ryoko Yamanoi, Eiji Osawa

㻤㻣

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Biomimetic approach toward tough nanodiamond materials* Keita Fujiwara, Toshiki Ikami, Tadamasa Ito, Masaki Ozawa

㻤㻤

㻝㻼㻙㻠㻡

Kinetic consideration on the formation of polyyne-iodine complex by photoinduced reaction* Yoriko Wada, Tomonari Wakabayashi㻤㻥㻻㼠㼔㼑㼞㻌㼠㼛㼜㼕㼏㼟㻝㻼㻙㻠㻢Improved Mechanical Property of Bucky Paper by Adding Carbon Nanocil* Koji Maruyama, Yosiyuki Suda, Hirohumi Takikawa, Hideto Tanoue, Hitosi Ue,
Kazuki Simizu, Yosito Umeda

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㻝㻼㻙㻠㻣

Measurement of electric resistance of a single carbon nanocoil* Ryuji Kunimoto, Taiichiro Yonemura, Yoshiyuki Suda, Hideto Tanoue, Hirofumi Takikawa,
Hitoshi Ue, Kazuki Shimizu, Yoshito Umeda

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xix

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻝㼠㼔㻘㻌㻹㼛㼚㻚㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻸㼡㼚㼏㼔㻌㼀㼕㼙㼑㻌㻌㻔㻝㻞㻦㻟㻜㻙㻝㻟㻦㻠㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻟㻦㻠㻡㻙㻝㻠㻦㻝㻡㻕㻝㻿㻙㻞

Solid-State Chemistry of Fullerenes --Learning the New, through Visiting the Old-Koichi Komatsu㻞㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻠㻦㻝㻡㻙㻝㻡㻦㻠㻡㻕㻯㼔㼑㼙㼕㼟㼠㼞㼥㻌㼛㼒㻌㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟䚷䞉㻌㻌㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟䚷䞉㻌㻌㻲㼡㼘㼘㼑㼞㼑㼚㼑㼟㻝㻙㻝

Organic Synthesis of Helium-Containing Fullerenes and Generation of Endohedral Fullerenes
Encapsulating Two Different Atoms* Yuta Morinaka, Satoru Sato, Atsushi Wakamiya, Hidefumi Nikawa, Naomi Mizorogi,
Fumiyuki Tanabe, Michihisa Murata, Koichi Komatsu, Ko Furukawa, Tatsuhisa Kato,
Shigeru Nagase, Takeshi Akasaka, Yasujiro Murata

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Fullerene bis-carboxylic acid derivatives by Prato reaction
Safwan Aroua, * Yoko Yamakoshi

㻝㻞

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Molecular Bearing of Finite Carbon Nanotube and Fullerene in Ensemble Rolling Motion* Shunpei Hitosugi, Takashi Yamasaki, Ryosuke Iizuka, Hiroyuki Isobe

㻝㻟

㻝㻙㻠

Selective synthesis of alkoxyfullerenes C60(OR)5Br: Substitution reaction of C60Br6 with alcohol㻝㻠* Kouya Uchiyama, Hiroshi Moriyama, Kenji Yoza
㻝㻙㻡

Proton dynamics in Fullerenol solids studied by 1H-NMR* Keisuke Baba, Hironori Ogata

㻝㻡

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Kinetic Stability Governs Relative Fullerene Isomer Abundance* Stephan Irle, Yoshifumi Nishimura, Alexander Fedorov, Henryk Witek㻝㻢㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻯㼛㼒㼒㼑㼑㻌㻮㼞㼑㼍㼗㻌㻌㻔㻝㻡㻦㻠㻡㻙㻝㻢㻦㻜㻜㻕㻌䠘䠘䠘䠘䠘䠘䠘㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻢㻦㻜㻜㻙㻝㻢㻦㻟㻜㻕㻝㻿㻙㻟

Photoluminescence properties of some graphene-based and inorganic two-dimensional materials
Goki Eda㻟㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻢㻦㻟㻜㻙㻝㻣㻦㻟㻜㻕㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻝㻙㻣

Optical properties of graphene quantum dots separated by high performance liquid chromatography* Naoto Fuyuno, Daichi Kozawa, Yuhei Miyauchi, Shinichiro Mouri, Ryo Kitaura,
Hisanori Shinohara, Toku Yasuda, Naoki Komatsu, Kazunari Matsuda

㻝㻣

㻝㻙㻤

Modulation of Optical Spectra of Monolayer MoS2 by Chemical Doping㻝㻤* Shinichiro Mouri, Yuhei Miyauchi, Kazunari Matsuda
㻝㻙㻥Coulomb drag and excitonic insulator in double-layer graphene* Satoru Konabe, Susumu Okada

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㻝㻙㻝㻜

Resonance and interference effect of Raman spectroscopy of graphene in the magnetic field* Riichiro Saito, Qiu Caiyu, Yu Ting㻞㻜㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻯㼛㼒㼒㼑㼑㻌㻮㼞㼑㼍㼗㻌㻌㻔㻝㻣㻦㻟㻜㻙㻝㻤㻦㻜㻜㻕㻌䠘䠘䠘䠘䠘䠘䠘㻿㼜㼑㼏㼕㼍㼘㻌㻼㼍㼚㼑㼘㻌㻿㼑㼟㼟㼕㼛㼚㻌㻌㻔㻝㻤㻦㻜㻜㻙㻞㻜㻦㻜㻜㻕䚷
Toward the chirality controlled growth of carbon nanotubes
Takashi Mizutani, Yohji Achiba, Susumu Saito, Rikizo Hatakeyama, Yoshikazu Homma,
Hisanori Shinohara, Suguru Noda, Shigeo Maruyamaxx㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻞㼠㼔㻘㻌㼀㼡㼑㻚㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻼㼘㼑㼚㼍㼞㼥㻌㻸㼑㼏㼠㼡㼞㼑㻦㻌㻠㻜㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻌㻗㻌㻡㼙㼕㼚㻌㻔㻰㼕㼟㼏㼡㼟㼟㼕㼛㼚㻕㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻦㻌㻞㻡㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻌㻗㻌㻡㼙㼕㼚㻌㻔㻰㼕㼟㼏㼡㼟㼟㼕㼛㼚㻕㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻦㻌㻝㻜㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻌㻗㻌㻡㼙㼕㼚㻌㻔㻰㼕㼟㼏㼡㼟㼟㼕㼛㼚㻕㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻼㼛㼟㼠㼑㼞㻌㻼㼞㼑㼢㼕㼑㼣㻦㻌㻝㼙㼕㼚㻌㻔㻼㼞㼑㼟㼑㼚㼠㼍㼠㼕㼛㼚㻕㻼㼘㼑㼚㼍㼞㼥㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻥㻦㻜㻜㻙㻥㻦㻠㻡㻕㻞㻿㻙㻠Combining separation and synthesis to achieve structure control of carbon nanotubes
Ming Zheng㻠㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻥㻦㻠㻡㻙㻝㻜㻦㻟㻜㻕㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟䚷䞉䚷㻲㼛㼞㼙㼍㼠㼕㼛㼚㻌㼍㼚㼐㻌㼜㼡㼞㼕㼒㼕㼏㼍㼠㼕㼛㼚㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻞㻙㻝Empirical Prediction of Electronic Potentials of Single-Walled Carbon Nanotubes* Yasuhiko Hirana, Yuhei Miyauchi, Shinichirou Mouri, Kazunari Matsuda, Naotoshi Nakashima

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Molecular Dynamics Simulation on RBM of Single-Walled Carbon Nanotubes in Water Vapor* Naoki Homma, Shintaroh Sato, Shohei Chiashi, Yoshikazu Homma, Takahiro Yamamoto

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㻞㻙㻟

Energy shift of photoluminescence peaks of SWCNTs wrapped by fluorene-based polymers* Masayoshi Tange, Toshiya Okazaki, Sumio Iijima㻞㻟㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻯㼛㼒㼒㼑㼑㻌㻮㼞㼑㼍㼗㻌㻌㻔㻝㻜㻦㻟㻜㻙㻝㻜㻦㻠㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻜㻦㻠㻡㻙㻝㻝㻦㻝㻡㻕㻞㻿㻙㻡

Fundamental and Advanced Materials Design of Soluble Carbon Nanotubes
Naotoshi Nakashima㻡㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻝㻦㻝㻡㻙㻝㻞㻦㻝㻡㻕㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻌䞉㻌㻲㼛㼞㼙㼍㼠㼕㼛㼚㻌㼍㼚㼐㻌㼜㼡㼞㼕㼒㼕㼏㼍㼠㼕㼛㼚㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻌䞉㻌㻯㼍㼞㼎㼛㼚㻌㼚㼍㼚㼛㼜㼍㼞㼠㼕㼏㼘㼑㼟㻞㻙㻠㻞㻠
Simultaneous Discrimination of Diameter, Handedness, and Metallicity of Single-Walled
Carbon Nanotubes with Chiral Diporphyrin Nanocalipers* Gang Liu, Feng Wang, Songpol Chaunchaiyakul, Takahide Kimura, Yuji Kuwahara, Naoki Komatsu㻞㻙㻡Exchanges of sodium cholate and oligo-DNAs with different chain length on single-walled carbon
nanotubes* Ayaka Inoue, Yuichi Kato, Yasuro Niidome, Naotoshi Nakashima

㻞㻡

㻞㻙㻢

Optical Properties of Polyyne Molecules Dispersed in Solids as Studied by An UV Transmission
Microscope* Tomonari Wakabayashi, Kazunari Koma, Okinaga Shibata, Yoriko Wada

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Slimy fibers of nanodiamonds assembled in polyacrylamide aqueous solutions
Shunsaku Katsuno, * Tadamasa Ito, Masaki Ozawa㻞㻣㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻸㼡㼚㼏㼔㻌㼀㼕㼙㼑㻌㻌㻔㻝㻞㻦㻝㻡㻙㻝㻟㻦㻟㻜㻕㻌䠘䠘䠘䠘䠘䠘䠘㻭㼣㼍㼞㼐㼟㻌㻯㼑㼞㼑㼙㼛㼚㼥㻌㻌㻔㻝㻟㻦㻟㻜㻙㻝㻠㻦㻝㻡㻕㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻠㻦㻝㻡㻙㻝㻠㻦㻠㻡㻕㻞㻿㻙㻢Band engineering in bilayer graphene for future electron-devices* K.Tsukagoshi, H.Miyazaki, S.-L.Li, A.A.Ferreira, M.Y.Chan, K. Komatsu, S.Nakaharaixxi㻢㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻞㼠㼔㻘㻌㼀㼡㼑㻚㻼㼛㼟㼠㼑㼞㻌㻼㼞㼑㼢㼕㼑㼣㻌㻌㻔㻝㻠㻦㻠㻡㻙㻝㻡㻦㻟㻜㻕㻼㼛㼟㼠㼑㼞㻌㻿㼑㼟㼟㼕㼛㼚㻌㻌㻔㻝㻡㻦㻟㻜㻙㻝㻣㻦㻜㻜㻕䚷䠄䖪䠅㻯㼍㼚㼐㼕㼐㼍㼠㼑㼟㻌㼒㼛㼞㻌㼠㼔㼑㻌㼅㼛㼡㼚㼓㻌㻿㼏㼕㼑㼚㼠㼕㼟㼠㻌㻼㼛㼟㼠㼑㼞㻌㻭㼣㼍㼞㼐㻯㼔㼑㼙㼕㼟㼠㼞㼥㻌㼛㼒㻌㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟㻞㻼㻙㻝

ESR Measurements of Series of [n]Cycloparaphenylene Cation Radicals in Solution㻥㻞* Takahiko Kouyama, Eiichi Kayahara, Shigeru Yamago, Tatsuhisa Kato㻞㻼㻙㻞

Isolation and Properties of a Cyclopentadiene Adduct of Lithium-ion Encapsulated [60] Fullerene䖪* Hiroki Kawakami, Hiroshi Okada, Yutaka Matsuo㻞㻼㻙㻟Solution-phase Synthesis of Dumbbell-Shaped Dimer C120 by the Use of FeCl3㻥㻟㻥㻠

Masahiko Hashiguchi, * Hiroshi Inada, Yutaka Matsuo㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟㻞㻼㻙㻠

Growth and Electric Properties of C60 Whiskers Directly Grown between Electrodes
by Surface Treatment* Katsuya Uruchida, Nobuyuki Iwata, Hiroshi Yamamoto㻥㻡㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌㼙㼑㼠㼍㼘㼘㼛㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟
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Cycloadditions to La2@C80 and vibronic coupling density analysis

㻥㻢* Naoki Haruta, Tohru Sato, Kazuyoshi Tanaka㻞㻼㻙㻢

A Novel Non-IPR Endohedral Metallofullerene: La2@Cs(17490)-C76

䖪* Mitsuaki Suzuki, Naomi Mizorogi, Zdenek Slanina, Xing Lu, Shigeru Nagase, Takeshi Akasaka㻞㻼㻙㻣Magnetic Properties of Gd@C82-PEG-b-PAMA-complexed Nanoparticle㻥㻣㻥㻤* Toshihiro Aizawa, Yukichi Horiguchi, Yukio Nagasaki, Hisanori Shinohara, Tatsuhisa Kato㻲㼡㼘㼘㼑㼞㼑㼚㼑㼟㻞㻼㻙㻤Synthesis of C70 Nanosheets by Liquid-Liquid Interfacial Precipitation Method㻥㻥* Kana Osonoe, Ryosuke Kano, Masaru Tachibana
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䖪
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Synthesis of C60 Derivatives Having a Sulfur-containing Opening and X-ray Structure of N 2
Encapsulated Molecule* Tsukasa Futagoishi, Michihisa Murata, Yasujiro Murata

㻝㻜㻜

Polymerization in C60 thin films deposited under in situ UV light irradiation㻝㻜㻝* Daijiro Arai, Hisanori Tanimoto, Manabu Ohtomo, Shiro Entani, Yoshihiro Matsumoto, Seiji Sakai㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻞㻼㻙㻝㻝䖪

Chirality dependence of exciton diffusion in air-suspended single-walled carbon nanotubes* A. Ishii, A. Yokoyama, M. Yoshida, T. Shimada, Y. K. Kato

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Electric Double Layer Transistors using Thick Films in Single Chiral States of (6,5) and (11,10)Single-Wall Carbon Nanotubes* Hikaru Kudo, Masatoshi Kawai, Tomoyuki Hunabasama, Yuki Nobusa, Taishi Takenobu,
Kazuhiro Yanagi

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Existence of two distinct equilibrium states in the exchange reaction of sodium cholate and oligo
DNA on single-walled carbon nanotubes* Yuichi Kato, Yasuro Niidome, Naotoshi Nakashima㻝㻜㻠Control of UV Optical Absorption of Single-Wall Carbon Nanotubes Using Electro-chemical
Doping Techniques* Toru Igarashi, Kai Hasegawa, Tomoyuki Funabasama, Shimpei Ono, Kazuhiro Yanagi

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䖪
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xxii

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Thermodynamics for the exchange reaction of sodium cholate and double-stranded DNA
on single-walled carbon nanotubes* Akiko Tsuzuki, Ayaka Inoue, Yuichi Kato, Yasuro Niidome, Naotoshi Nakashima

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Improvement of CNT Properties through a Post Synthetic Treatment* Naoyuki Matsumoto, Azusa Oshima, Motoo Yumura, Don Futaba, Kenji Hata

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Tensile strength of individual multi-walled carbon nanotube constituting MWCNT fiber* Hideaki Suzuki, Yoshinori Sato, Go Yamamoto, Kenichi Motomiya, Toshiyuki Hashida,
Kazuyuki Tohji

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䖪

㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻞㻼㻙㻝㻤

Bending Properties of Single-Walled Carbon Nanotube Film Transistors* Hiroki Hamahata, Yuki Nobusa, Yohei Yomogida, Kazuhiro Yanagi, Yoshihiro Iwasa,
Taishi Takenobu

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㻞㻼㻙㻝㻥
䖪

High-performance, flexible carbon nanotube transparent conductive films of double layered structure* Norihiro Fukaya, Yusuke Kataoka, Dong Young Kim, Shigeru Kishimoto, Takashi Mizutani,
Suguru Noda, Yutaka Ohno

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㻞㻼㻙㻞㻜

Evaluation of the contact resistivitiy at CNT/SiC interface using conductive AFM* Megumi Shibuya, Masafumi Inaba, Kazuyoshi Oohara, Takumi Ochiai, Yoshiho Masuda,
Atsushi Hiraiwa, Michiko Kusunoki, Hiroshi Kawarada

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㻞㻼㻙㻞㻝

High-mobility carbon nanotube thin-film transistors fabricated on transparent plastic filmby flexographic printing technique* Kentaro Higuchi, Yuta Nakajima, Takuya Tomura, Masafumi Takesue, Shigeru Kishimoto,Takashi Mizutani, Katsuhiko Hata, Yutaka Ohno㻝㻝㻞

Effect of gas atmosphere on the photovoltaic characteristics of semiconducting single-walledcarbon nanotubes/Si heterojunction photovoltaic cells* Mao Shoji, Atsushi Nakano, Hironori Ogata

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䖪
㻞㻼㻙㻞㻞

㻲㼛㼞㼙㼍㼠㼕㼛㼚㻌㼍㼚㼐㻌㼜㼡㼞㼕㼒㼕㼏㼍㼠㼕㼛㼚㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻞㻼㻙㻞㻟

Effect of oxidized Al support property for millimeter-scale SWCNT growth* Kei Hasegawa, Suguru Noda

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CNT Synthesis by Laser Ablation Method Using Carbon and Nickel Double Target* Koji Ishii, Nobuyuki Iwata, Hiroshi Yamamoto, Hirofumi Yajima

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Solubilization of single-walled carbon nanotubes using a flavin derivative in organic solvents* Yuichi Kato, Yasuro Niidome, Naotoshi Nakashima

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㻞㻼㻙㻞㻢

SWNT growth from Pt catalysts on Al2Ox buffer layer by Alcohol Gas Source Method in High Vacuum 㻝㻝㻣* Naoya Fukuoka, Hiroki Kondo, Yuya Sawaki, Ranajit Ghosh, Shigeya Naritsuka,
Takahiro Maruyama

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Low temperature growth of dense carbon nanotube arrays on conductive underlayers* Nuri Na, Yeong-Gi So, Yuichi Ikuhara, Suguru Noda

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Selective Removal of Metallic Single-Walled Carbon Nanotubes Utilizing Thermal Lithographyof Molecular Glass Thin Films* Keigo Otsuka, Taiki Inoue, Daisuke Hasegawa, Shohei Chiashi, Shigeo Maruyama

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Effects of discharge current direction and magnetic field for the production of single-walledcarbon nanotubes in the arc discharge method* Mohammad Jellur Rahman, Tetsu Mieno

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xxiii

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Chirality separation of metallic single-wall carbon nanotubes by gel column chromatography* Takeshi Tanaka, Yasuko Urabe, Hiromichi Kataura㻝㻞㻝㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻞㻼㻙㻟㻝

Encapsulation of superconductive metal carbide in the inner space of carbon nanotubes
by template method* Keita Kobayashi, Takeshi Saito, Masaharu Kiyomiya, Hidehiro Yasuda

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Energetics and Electronic Structures of C60 Rolled in the Shortest Zigzag Carbon Nanotubes* Shota Kigure, Susumu Okada㻝㻞㻟㻳㼞㼍㼜㼔㼑㼚㼑㻌㼟㼥㼚㼠㼔㼑㼟㼕㼟㻞㻼㻙㻟㻟

Effect of inert gas on the growth of epitaxial graphene on Si-terminated SiC (0001)* Akkawat Ruammaitree, Hitoshi Nakahara, Yahachi Saito

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Structural characterization of graphene edges using dark-field TEM* Miho Fujihara, Yasumitsu Miyata, Ryo Kitaura, Eriko Maeda, Hisanori Shinohara

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Synthesis of Nitrogen-doped Carbon Materials Controlled Nitrogen Bonding Configuration* Satoshi Yasuda, Li Yu, Kei Murakoshi

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Preparation of High-Density Graphene Nanoribbons by Anisotropic Catalyst Cutting* Yasumichi Kayo, Pablo Solís-Fernández, Kazuma Yoshida, Masaharu Tsuji, Hiroki Ago㻝㻞㻣㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻞㻼㻙㻟㻣Transparent graphitic tiles synthesized from carbon nanowalls by shock compression* Kazutaka Nakamura, Toshiyuki Atou, Keisuke Niwase, Kazutaka Nakamura, Masaru Tachibana

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㻞㻼㻙㻟㻤
䖪

Water-Soluble Graphene through Polyglycerol Grafting* Toku Yasuda, Li Zhao, Gang Liu, Shuji Aonuma, Takahide Kimura, Naoki Komatsu

㻝㻞㻥

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Relationship between morphology, electric properties and field emission characteristics
of carbon nanosheets films by microwave plasma-enhanced chemical vapor deposition* Shohei Hayase, Zhipeng Wang, Hironori Ogata㻝㻟㻜㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻞㻼㻙㻠㻜Characterization of Elecrical Properties for Graphene Film Deposited by Microwave Plasma CVD* Yuki Okigawa, Kazuo Tsugawa, Takatoshi Yamada, Masatou Ishihara, Masataka Hasegawa

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Host-guest Interactions between Nanographene and Gas molecules* Junichi Takashiro, Kazuyuki Takai, Manabu Kiguchi, Toshiaki Enoki, Takeo Yamada,
Kenji Hata, Takafumi Ishii, Takashi Kyotani

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Linear Dispersion Bands on Partially H-Terminated (111) Surface of Diamond Structure* Junki Sone, Susumu Okada

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Influence of mechanical deformation on thermal properties of graphene* Takashi Funatani, Takahiro Yamamoto, Matsuto Ogawa, Satofumi Souma

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First-principles study of edge-modified armchair graphene nanoribbons* Hideyuki Jippo, Mari Ohfuchi㻝㻟㻡㻻㼠㼔㼑㼞㻌㼠㼛㼜㼕㼏㼟㻞㻼㻙㻠㻡Enhancement of photo-induced current in the complex of iron oxide nanotubes and fullerenols
Yuki Shiraki, * Yuki Mishina, Shunji Bandow

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Development of Multi-stage Ion Trap Mobility System* Toshiki Sugai

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xxiv

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Oxygen Adsorption Effect on Graphene–Metal Contact Characteristics* Yoshiaki Sato, Kazuyuki Takai, Toshiaki Enoki

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Atomic structure determination of the graphee/sapphire interface by normal incident X-ray
standing wave spectroscopy* Shiro Entani, Pavel Sorokin, Pavel Avramov, Manabu Ohtomo, Yoshihiro Matsumoto,Liubov Antipina, Ayumi Narita, Norie Hirao, Iwao Shimoyama, Tetsuhiro Sekiguchi,
Hiroshi Naramoto, Yuji Baba, Seiji Sakai

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Integration of high performance graphene nanoribbon field effect transistors* Toshiaki Kato, Rikizo Hatakeyama, Toshiro Kaneko

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Transport Property of CVD Graphene across Domain Boundary* Yui Ogawa, Kenji Kawahara, Masahiro Miyashita, Masaharu Tsuji, Katsuyoshi Komatsu,
Kazahito Tsukagoshi, Hiroki Ago

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Taishi Takenobu㻣㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻥㻦㻟㻜㻙㻝㻜㻦㻟㻜㻕㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟䚷䞉䚷㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻟㻙㻝

Fabrication of CMOS inverters using semiconducting SWCNTs encapsulating n- and p-type
dopant molecules* Yasuhiro Ito, Shunjiro Fujii, Maki Shimizu, Takeshi Tanaka, Hiromichi Kataura

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Micro-Honeycomb Network Structure of Single-Walled Carbon Nanotube Film for Solar Cells* Kehang Cui, Takaaki Chiba, Hidenori Kinoshita, Pei Zhao, Theerapol Thurakitseree,
Taiki Inoue, Erik Einarsson, Shohei Chiashi, Shigeo Maruyama

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Application of Vertically Aligned CNTs for Electrodes of PEMFC* Shigeaki Murata, Masahiro Imanishi, Shigeki Hasegawa, Ryoichi Namba

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Electromigration suppression in copper by carbon nanotubes : A mechanistic insight* Chandramouli Subramaniam, Takeo Yamada, Don N. Futaba, Kenji Hata, Motoo Yumura㻟㻡㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻯㼛㼒㼒㼑㼑㻌㻮㼞㼑㼍㼗㻌㻌㻔㻝㻜㻦㻟㻜㻙㻝㻜㻦㻠㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻜㻦㻠㻡㻙㻝㻞㻦㻜㻜㻕㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻟㻙㻡

First-Principles Simulation on Thermoelectric Power of SWNT Buckypapers* Teppei Kato, Shinji Usui, Takahiro Yamamoto

㻟㻢

㻟㻙㻢

Influence of Carbon nano-inclusion dimensionality in the thermal conductivity enhancementof aqueous and non-aqueous fluids* Sivasankaran Harish, Kei Ishikawa, Erik Einarsson, Shohei Chiashi, Junichiro Shiomi,
Shigeo Maruyama

㻟㻣

㻟㻙㻣

First Principles-Based Estimate of the Critical SWCNT Length for Raman D and G Band
Intensity Inversion* Yoshifumi Nishimura, Henryk Witek, Stephan Irle

㻟㻤

㻟㻙㻤

Exciton effects on coherent phonon spectroscopy of carbon nanotubes* Ahmad Nugraha, Eddwi Hasdeo, Riichiro Saito

㻟㻥

㻟㻙㻥

High-temperature in-situ TEM Observation of Zipper-like Wall-to-Wall Coalescenceof Double-Wall Carbon Nanotubes* Sihan Zhao, Ryo Kitaura, Yasumitsu Miyata, Hisanori Shinohara㻠㻜㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻸㼡㼚㼏㼔㻌㼀㼕㼙㼑㻌㻌㻔㻝㻞㻦㻜㻜㻙㻝㻟㻦㻝㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻟㻦㻝㻡㻙㻝㻟㻦㻠㻡㻕㻟㻿㻙㻤

Ballistic transport in graphene/h-BN* Tomoki Machida, Satoru Masubuchi, Masahiro Onuki, Sei Morikawa, Kazuyuki Iguchi,
Takehiro Yamaguchi, Miho Arai, Kenji Watanabe, Takashi Taniguchi

xxvi

㻤

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻟㼠㼔㻘㻌㼃㼑㼐㻚㻼㼛㼟㼠㼑㼞㻌㻼㼞㼑㼢㼕㼑㼣㻌㻌㻔㻝㻟㻦㻠㻡㻙㻝㻠㻦㻟㻜㻕㻼㼛㼟㼠㼑㼞㻌㻿㼑㼟㼟㼕㼛㼚㻌㻌㻔㻝㻠㻦㻟㻜㻙㻝㻢㻦㻜㻜㻕䚷䠄䖪䠅㻯㼍㼚㼐㼕㼐㼍㼠㼑㼟㻌㼒㼛㼞㻌㼠㼔㼑㻌㼅㼛㼡㼚㼓㻌㻿㼏㼕㼑㼚㼠㼕㼟㼠㻌㻼㼛㼟㼠㼑㼞㻌㻭㼣㼍㼞㼐㻯㼔㼑㼙㼕㼟㼠㼞㼥㻌㼛㼒㻌㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟㻟㻼㻙㻝

Thermal Reactions of C60 with Siliranes: Formation of Carbosilylated Fullerenes

㻝㻟㻤* Ryosuke Iida, Kentaro Takagi, Masahiro Kako, Tadashi Hasegawa, Yutaka Maeda,
Michio Yamada, Takeshi Akasaka㻟㻼㻙㻞䖪Construction of an Opening on Fullerene C 70 and Encapsulation of a Water Molecule* Rui Zhang, Michihisa Murata, Yasujiro Murata

㻝㻟㻥

㻟㻼㻙㻟

Thermal [2+2] cycloaddition of C60 with aryl dienamines㻝㻠㻜* Naohiko Ikuma, Hiroyuki Yamamoto, Tsubasa Mikie, Ken Kokubo, Takumi Oshima㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟㻟㻼㻙㻠Transport Characteristics of C60 Photo-Polymers Fabricated by Focused Optical Vortex Irradiation㻝㻠㻝* Naoto Toriumi, Tatsuya Doi, Daiki Momiyama, Wataru Akiyama, Katsuhiko Miyamoto,Takashige Omatsu, Jonathan Bird, Yuichi Ochiai, Nobuyuki Aoki
㻟㻼㻙㻡Fabrication of bulk-heterojunction organic solar cells using PCBM and mixed donorsof P3HT and phenylene–thiophene oligomer* Shunjiro Fujii, Zongfan Duan, Takanori Okukawa, Yuichiro Yanagi, Akira Yoshida,
Takeshi Tanaka, Yasushiro Nishioka, Hiromichi Kataura㻝㻠㻞㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌㼙㼑㼠㼍㼘㼘㼛㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟
㻟㻼㻙㻢
䖪

㻝㻠㻟
Reaction of Trimetallic Nitride Template-Endohedral Metallofullerenes(TNT-EMFs) with Aziridine* Masato Kimura, Chihiro Ueda, Michio Yamada, Yutaka Maeda, Tadashi Hasegawa, Takeshi Akasaka㻟㻼㻙㻣Extraction of unstable di-metallofullerenes using a mixed solvent of triethylamine and acetone* Aimi Togashi, Takeshi Kodama, Wataru Fujita, Koichi Kikuchi, Yohji Achiba㻝㻠㻠㻲㼡㼘㼘㼑㼞㼑㼚㼑㼟㻟㻼㻙㻤

Spin Configurations of Three Radicals on Fullerenes* Susumu Okada, Takahiro Yamamoto

㻝㻠㻡

㻟㻼㻙㻥
䖪

Magnetic Properties of Deca-Methyl Fullerenes* Haruna Nitta, Susumu Okada

㻝㻠㻢

㻟㻼㻙㻝㻜

Synthesis of non-IPR fullerenes from C60 in liquid phase by irradiation of intense femtosecond
laser pulses* Takeshi Kodama, Tatsuya Fujino, Haruo Shiromaru, Yohji Achiba㻝㻠㻣㻱㼚㼢㼕㼞㼛㼚㼙㼑㼚㼠㼍㼘㻛㻿㼍㼒㼑㼠㼥㻌㼏㼔㼍㼞㼍㼏㼠㼑㼞㼕㼦㼍㼠㼕㼛㼚㻌㼛㼒㻌㼚㼍㼚㼛㼙㼍㼠㼑㼞㼕㼍㼘㼟㻟㻼㻙㻝㻝Interaction of carbon nanotubes with homopolypeptides* Atsushi Hirano, Tomoshi Kameda, Takeshi Tanaka, Hiromichi Kataura㻝㻠㻤㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻟㻼㻙㻝㻞䖪

Molecular recognition of external grooves on bundled surfaces of single-walled carbon nanotubes* JongTae Yoo, Tsuyohiko Fujigaya, Naotoshi Nakashima

㻝㻠㻥

㻟㻼㻙㻝㻟

Enhancement of photoluminescence from single-walled carbon nanotubes by photonic crystal
nanocavities
Ryosuke Watahiki, * Takashi Shimada, Pei Zhao, Shohei Chiashi, Satoshi Iwamoto,
Yasuhiko Arakawa, Shigeo Maruyama, Yuichiro K. Kato

㻝㻡㻜

㻟㻼㻙㻝㻠
䖪

Effect of Solvents on Electrochemical Band Gaps of Single-Walled Carbon Nanotubes* Daigo Miyazaki, Yasuhiko Hirana, Yasuro Niidome, Naotoshi Nakashima

㻝㻡㻝

xxvii

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻟㼠㼔㻘㻌㼃㼑㼐㻚㻟㻼㻙㻝㻡

Effects of OPO Laser Irradiation on the Structural Characteristics of Single- and Double-Walled
Carbon Nanotubes* Tetsuya Oto, Akira Kumazawa, Yuka Nagaya, Koji Tsuchiya, Tadahiro Ishii, Hirofumi Yajima

㻝㻡㻞

㻟㻼㻙㻝㻢
䖪

Vernier spectrum in finite-length armchair carbon nanotubes* Yuki Tatsumi, Wataru Izumida, Riichiro Saito

㻝㻡㻟

㻟㻼㻙㻝㻣

First-principles study of radial breathing modes in small-diameter carbon nanotubes* Takashi Koretsune, Susumu Saito

㻝㻡㻠

㻟㻼㻙㻝㻤

Electronic Properties of Capped Carbon Nanotubes with Accumulated Electrons
by a Parallel Electric Field* Ayaka Yamanaka, Susumu Okada

㻝㻡㻡Electronic Raman scattering and origin of the Fano resonance in metallic carbon nanotubes* Eddwi Hasdeo, Ahmad Nugraha, Kentaro Sato, Riichiro Saito

㻝㻡㻢

䖪
㻟㻼㻙㻝㻥

㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻟㻼㻙㻞㻜

Selective Dispersion of Single-Walled Carbon Nanotubes into Nano-Cage of HelicalConformation of Poly(m-phenylene-ethynylene) Derivatives
Fumito Kobayashi, Yuki Moriyama, * Masahiro Takahashi, Masayoshi Tange, Toshiya Okazaki,
Keiki Kishikawa, Shigeo Kohmoto

㻝㻡㻣

㻟㻼㻙㻞㻝
䖪

Chromatographic Separation of Highly Soluble SWNTs Prepared by Polyglycerol Grafting* Keisuke Nakamura, Li Zhao, Shuji Aonuma, Takahide Kimura, Naoki Komatsu

㻝㻡㻤

㻟㻼㻙㻞㻞

Electric double layer transistors of aligned carbon nanotube thin film
* Yoshifumi Wada, Jiang Pu, Yuki Takagi, Kazuhiro Yanagi, Taishi Takenobu

㻝㻡㻥

㻟㻼㻙㻞㻟
䖪

Photo-thermoelectric power of single-walled carbon nanotube films* Hajime Sakakibara, Yoshinori Sato, Kosuke Ino, Akihiko Ito, Tomokazu Matsue,
Takashi Goto, Kenichi Motomiya, Kazuyuki Tohji

㻝㻢㻜

㻟㻼㻙㻞㻠

Specific biosensor based on biotin-labeled double-walled carbon nanotube FET* Akihiro Kuno, Yuka Nagaya, Koji Tsuchiya, Akira Hida, Koji Ishibashi, Hirofumi Yajima㻝㻢㻝㻲㼛㼞㼙㼍㼠㼕㼛㼚㻌㼍㼚㼐㻌㼜㼡㼞㼕㼒㼕㼏㼍㼠㼕㼛㼚㻌㼛㼒㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻟㻼㻙㻞㻡

Selective Solubilization of Semiconducting-Carbon Nanotubes by Using Weak-Bond Connecting
Fluorene-Based Polymers* Toshimitsu Fumiyuki, Tsuyohiko Fujigaya, Naotoshi Nakashima

㻝㻢㻞

㻟㻼㻙㻞㻢

Chirality Analysis of Single-walled Carbon Nanotubes Growth in Molecular Dynamics Simulation* Tomoya Kawasuzuki, Kaoru Hisama, Yuki Takaki, Shohei Chiashi, Shigeo Maruyama

㻝㻢㻟

㻟㻼㻙㻞㻣
䖪

Methane-assisted CVD yielding millimeter-tall single-wall carbon nanotubes of smaller diameters* Zhongming Chen, Dong Young Kim, Kei Hasegawa, Suguru Noda

㻝㻢㻠

㻟㻼㻙㻞㻤

Pyrene-based nanocalipaers for selective extraction of metallic SWNTs
Gang Liu, * Naoki Komatsu, Takahide Kimura

㻝㻢㻡

㻟㻼㻙㻞㻥

In situ Raman monitoring formation of SWNTs: process optimization and low temperature synthesis* Ming Liu, Yuquan Su, Rong Xiang, Zikang Tang

㻝㻢㻢

㻟㻼㻙㻟㻜

One-Step Catalyst-Free Mist Flow CVD Growth of Single-Wall Carbon Nanotubes using C 60
Fullerenes* Yun Sun, Ryo Kitaura, Jinying Zhang, Yasumitsu Miyata, Hisanori Shinohara㻝㻢㻣Modeling the catalyst formation process to achieve diameter and density control of single-wallcarbon nanotube forests* Shunsuke Sakurai, Don Futaba, Motoo Yumura, Kenji Hata

㻝㻢㻤

䖪
㻟㻼㻙㻟㻝

xxviii㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻟㼠㼔㻘㻌㼃㼑㼐㻚㻟㻼㻙㻟㻞

Simultaneous Growth Control of Position, Chirality, and in-plane Orientation of Single-Walled
Carbon Nanotubes by Cold-Wall Chemical Vapor Deposition Method* Takumi Sagara, Satoshi Doi, Koji Ishii, Nobuyuki Iwata, Hirofumi Yajima, Hiroshi Yamamoto㻝㻢㻥㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌㼚㼍㼚㼛㼠㼡㼎㼑㼟㻟㻼㻙㻟㻟

Diameter Dependent Interaction between Single-Walled Carbon Nanotubes and Encapsulated
Ferrocenes* Hironori Suzuki , Yoko Iizumi, Toshiya Okazaki

㻝㻣㻜

㻟㻼㻙㻟㻠

Spectroscopic studies of single-wall boron nitride nanotubes synthesized in single-wallcarbon nanotubes* Ryo Nakanishi, Ryo Kitaura, Yuta Yamamoto, Shigeo Arai, Jamie Warner, Yasumitsu Miyata,
Hisanori Shinohara㻝㻣㻝䖪㻳㼞㼍㼜㼔㼑㼚㼑㻌㼟㼥㼚㼠㼔㼑㼟㼕㼟㻟㻼㻙㻟㻡

Molecular Dynamics Simulation of Multi-layer Graphene Growth by Catalytic CVD Method* Yuki Takaki, Kaoru Hisama, Tomoya Kawasuzuki, Shohei Chiashi, Shigeo Maruyama

㻝㻣㻞

㻟㻼㻙㻟㻢
䖪

Synthesis and characterization of large sized-grain, single-layer BN-doped graphene* Yu Kobayashi, Yasumitsu Miyata, Eriko Maeda, Ryo Kitaura, Hisanori Shinohara

㻝㻣㻟

㻟㻼㻙㻟㻣

Synthesis and Characterization of Intercalated Graphite and Graphene for Room Temperature
Superconductivity* Shogo Sato, Hiroaki Ichikawa, Nobuyuki Iwata, Hiroshi Yamamoto

㻝㻣㻠

㻟㻼㻙㻟㻤
䖪

Directional growth of graphene over Cu catalyst by face-to-face configuration CVD* Tatsuya Masuda, Kenji Kawahara, Hiroki Ago, Noda Suguru㻝㻣㻡㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻟㻼㻙㻟㻥Monte Carlo Particle Simulations of Local Heating Properties in Graphene-channel nano-FETs* Shusuke Oki, Taichi Misawa, Yuji Awano

㻝㻣㻢

㻟㻼㻙㻠㻜
䖪

Electrically driven ultra-high-speed black body emitters based on graphene* Tomoya Yokoi, Yusuke Takayama, Tatsuya Mori, Daiju Tsuya, Hideyuki Maki

㻝㻣㻣

㻟㻼㻙㻠㻝

Few-layer Graphene/silicon Heterojunction Photovoltaic Cells by Microwave Plasma-Enhanced
Chemical Vapor Deposition* Z. Wang, S. Hayase, M Shoji, H Ogata㻝㻣㻤㻼㼞㼛㼜㼑㼞㼠㼕㼑㼟㻌㼛㼒㻌㼓㼞㼍㼜㼔㼑㼚㼑㻟㻼㻙㻠㻞

Degree of oxidation of centrifuged graphene oxide* Hiroyuki Yokoi, Michio Koinuma, Kazuto Hatakeyama, Takaaki Taniguchi, Yasumichi Matsumoto

㻝㻣㻥

㻟㻼㻙㻠㻟

Spin polarization of hexagonal boron nitride/Ni(111) interface studied by spin-polarized
metastable de-excitation spectroscopy* Manabu Ohtomo, Yasushi Yamauchi, Pavel Avramov, Shiro Entani, Yoshihiro Matsumoto,
Hiroshi Naramoto, Seiji Sakai

㻝㻤㻜

㻟㻼㻙㻠㻠

Tetragonal C4 Polymer: A Two-dimensional Metallic sp2 Carbon Allotrope* Mina Maruyama, Susumu Okada

㻝㻤㻝

㻟㻼㻙㻠㻡

Graphene-based nanomaterials prepared by laser ablation of graphite* Maki Nakamura, Takazumi Kawai, Michiko Irie, Ryota Yuge, Sumio Iijima, Shunji Bandow,
Masako Yudasaka

㻝㻤㻞

㻟㻼㻙㻠㻢

Effects of etchant and synthesis temperature on the sheet-resistivity of nitrogen doped graphene film
Takahiro Mizuno, * Shunji Bandow

㻝㻤㻟

䖪

xxix

㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻹㼍㼞㼏㼔㻌㻝㻟㼠㼔㻘㻌㼃㼑㼐㻚㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌䠚䠚䠚䠚䠚䠚䠚㻌㻯㼛㼒㼒㼑㼑㻌㻮㼞㼑㼍㼗㻌㻌㻔㻝㻢㻦㻜㻜㻙㻝㻢㻦㻝㻡㻕㻌䠘䠘䠘䠘䠘䠘䠘㻿㼜㼑㼏㼕㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻢㻦㻝㻡㻙㻝㻢㻦㻠㻡㻕㻟㻿㻙㻥Design, Synthesis, and Properties of Fullerene Derivatives for Organic Thin Film Solar Cells
Yutaka Matsuo㻥㻳㼑㼚㼑㼞㼍㼘㻌㻸㼑㼏㼠㼡㼞㼑㻌㻌㻔㻝㻢㻦㻠㻡㻙㻝㻣㻦㻠㻡㻕㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌㼙㼑㼠㼍㼘㼘㼛㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟㻟㻙㻝㻜A hypothetical intermediate structure in growth of metallofullerenes* Yohji Achiba, Takeshi Kodama, Kenro Hashimoto, Haruo Shiromaru

㻠㻝

㻟㻙㻝㻝

Structure of Thulium and Carbon Cluster Encapsulated in Low-Symmetry C82(Cs(6)) Fullerene
Cage by Single Crystal X-ray Diffraction* Yuki Sado, Shinobu Aoyagi, Noriko Izumi, Ryo Kitaura, Tim Kowalczyk, Jian Wang,
Stephan Irle, Eiji Nishibori, Kunihisa Sugimoto, Hisanori Shinohara

㻠㻞

㻟㻙㻝㻞

Photoinduced electron transfer in supramolecules between Li+@C60 and chlorin derivatives* Kei Ohkubo, Yuki Kawashima, Kentaro Mase, Shunichi Fukuzumi

㻠㻟

㻟㻙㻝㻟

Ultraviolet Photoelectron Spectra of Gd3N@C80 and Er3N@C80

㻠㻠* Takafumi Miyazaki, Yusuke Nakanishi, Yuki Sasaki, Hiroyuki Niwa, Shoko Noda,
Tatsuhiko Nishi, Tomona Ohta, Hisanori Shinohara, Shojun Hino

xxx

ᇶㄪㅮ₇
Plenary Lecture≉ูㅮ₇Special Lecture

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

1S-1
New Vistas in Chemistry of Endohedral Metallofullerenes
Takeshi Akasaka
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba 305-8577, Japan
The paper will present a description of recent advances in fundamental aspects of thechemistry of endohedral metallofullerenes for future applications as organic carbon
nanomaterials.1-3 Synthesis and characterization of endohedral metallofullerenes and theirderivatives are particularly addressed. Throughout this presentation, guidelines forunderstanding structural, electronic and chemical properties of endohedral metallofullerenes
will be provided.

[1] Chemistry of Nanocarbons; T. Akasaka, F. Wudl. S. Nagase, Eds.; Wiley-Blackwell: London, 2010;
Endofullerenes: A New Family of Carbon Cluster; T. Akasaka, S. Nagase, Eds.; Kluwer Academic Publisher:
Dordrecht, 2002.
[2] See recent book chapters: "Handbook of Carbon Nano Materials" F. D'Souza and K. M. Kadish, Eds.; World
Scientific, 2011; Vol. 1, pp. 145-184; "Chemistry of Nanocarbons" , T. Akasaka, F. Wudl, and S. Nagase Eds.;
John Wiley & Sons, Chichester, 2010; pp 261-286; "Carbon Nanotubes and Related Structures" , D. Guldi and
N. Martin Eds.; Wiley-VCH, Verlag GmbH & Co. KGaA, Weinheim, 2010; pp 455-490; "Rare EarthCoordination Chemistry - Fundamentals and Applications" , C. H. Huang Ed.; John Wiley & Sons, Singapore,
2010; pp 269-304.
[3] See recent reviews: Chem. Soc. Rev. 41, 7723-7760 (2012) (Critical Review); Chem. Rec. 12, 256-259(2012); Polyhedron, in press. [DOI: 10.1016/j.poly.2012.06.072]; Chem. Eur. J. (Concept article) 18, 5136-5148(2012); Chem. Commun. 47, 5942-5957 (2011) (Feature Article); Nanoscale, 3, 2421 (2011); Acc. Chem. Res.,43, 92-102 (2010).
Corresponding Author: T. Akasaka
Tel: +81-29-853-6409, Fax: +81-29-853-6409,
E-mail: akasaka@tara.tsukuba.ac.jp, takasaka04@yahoo.co.jp

-1-

1S-
Solid-State Chemistry of Fullerenes–– Learning the New, through Visiting the Old ––Koichi Komatsu
Professor Emeritus, Kyoto University, Uji 611-0011, Kyoto, Japan
It is now well recognized that fullerene C60
undergoesvarioustypes

ofliquid-phaseaffording a whole variety of its derivatives.

reactions,aYet, there arebstill some reactions, which can take place only under thesolid-state reaction conditions.

The typical example is1[2+2] dimerization, giving dumbbell-shaped C120 (1). [1]
The X-ray crystallography on 1 indicates that the two kinds of single bonds a and b in thecentral four-membered ring are of comparable length suggesting that the energies for bondcleavage of a and b are nearly the same.

Here, if the intra-cage bond b could be selectively

cleaved, the shape of C120 would be transformed into a peanuts-type such as 2 after
rearrangements.

However,

simplyupon

heating,

dumbbell-shaped C120 1 only dissociates into the starting
C60 quantitatively. [1]Then, is the formation of peanuts type dimer 2
impossible?

2

Previously, Onoe and coworkers inferred the formation of such a dimer by

irradiation of electron beam on a thin layer of C60, based on IR studies.[2]The clearer

evidence of the formation of peanuts-shaped C120 is the direct TEM-observation of
coalescence of two molecules of C60 inside of a single-walled carbon nanotube (SWNT) upon
the electron-beam irradiation.[3]This clearly indicates that the inside of the SWNT provides

a highly activated space for reactions to afford molecules of novel structures.
[1] G-W. Wang, K. Komatsu, Y. Murata, M. Shiro, Nature 387, 583 (1997).
[2] A. Takashima, J. Onoe, T. Nishii, J. Appl. Phys. 108, 033514 (2010).
[3] M. Koshino, Y. Niimi, E. Nakamura, H. Kataura, T. Okazaki, K. Suenaga, S. Iijima, Nature Chemistry 2, 117(2010).
Corresponding Author: K. Komatsu
Tel: +81-75-761-8039, Fax: +81-75-761-8089
E-mail: komatsu@scl.kyoto-u.ac.jp

--

1S-3
Photoluminescence properties of some graphene-based and inorganic
two-dimensional materials○Goki Eda1,2,3
1

Department of Physics, National University of Singapore, Singapore 117542
Department of Chemistry, National University of Singapore, Singapore 117543
3
Graphene Research Centre, National University of Singapore, Singapore 117546
2

Two-dimensional (2D) crystals derived from layered structures exhibit a unique set ofproperties as strikingly demonstrated for graphene. Semiconducting 2D structures are
attractive building blocks for novel electronic and optoelectronic devices. In this talk, we willreport photoluminescence properties of two distinct classes of 2D semiconductors, graphene
oxide and transition metal dichalcogenides, and discuss how their spectral features provide
insight into the evolution of chemical, structural, and electronic properties of these materials.
Graphene oxide (GO) is a localized insulator consisting of sp2 carbon clusters embedded
inside a sp3 carbon matrix. Due to chemical inhomogeneity and spatial confinement of πelectrons, GO exhibits heterogeneous electronic structure with locally varying energy gaps.
We demonstrate that GO exhibits tunable photoluminescence over the visible spectrum duringcontrolled reduction [1,2]. We show that blue photoluminescence can be attributed toelectron-hole recombination within small sp2 clusters.
A single layer molybdenum disulfide (MoS2) is a direct gap semiconductor in striking
contrast to its indirect gap bulk counterpart [3]. We report differential reflectance andphotoluminescence spectra of mono- to few-layer
WS2 and WSe2 that indicate that the band structureofthesematerials
undergoessimilarindirect-to-direct gap transition when thinned to asingle monolayer (Fig. 1) [4]. The transition isevidenced by distinctly enhanced PL peak centeredat 630 and 750 nm in monolayer WS2 and WSe2,
respectively. We demonstrate that indirect gap
emission and direct gap hot electron emission is
pronounced in few-layer WSe2 due to small energy
difference between the two transitions. Temperaturedependence of their photoluminescence spectra
Fig.1 Photoluminescence spectra of 1
indicate crossover of these band edges similar to theto 5 layer WS2 and WSe2.
case of MoSe2 [5].
[1] Eda et al. Adv. Mater. 22, 505 (2010) .
[2] Chien et al. Angew Chem. Int. Ed. 51, 6662 (2012).
[3] K. F. Mak et al. Phys. Rev. Lett. 105, 136805 (2010).
[4] Zhao et al. ACS nano. DOI: 10.1021/nn305275h[5] Tongay et al. Nano Lett. 12, 5576 (2012).
Corresponding Author: G. Eda
Tel: +65- 6516-2970, Fax: +65- 6777 - 6126,
E-mail: g.eda@nus.edu.sg

--

2S-4
Combining separation and synthesis to achieve structure controlof carbon nanotubesżMing Zheng
Materials Science and Engineering Division, National Institute of Standards and Technology
Gaithersburg, Maryland 20899, United States
Carbon nanotubes (CNTs) possess a unique set of physical properties that may enable
many technologies ranging from ultrahigh capacity, ultralow dissipation power transmission
lines to CNT-based digital electronics as the replacement of the current CMOS technology.
Making CNTs of defined structure has been a fundamental challenge hampering the scienceand technology of CNTs for many years. Recent works coming from my lab and that of ourcollaborators are aimed at providing a route to solve the CNT structure control problem:
1.
2.

We have developed [1] a DNA-based method to purify single-chirality CNTs fromsynthetic mixtures.
Using DNA-purified single-chirality CNTs as seeds, we have shown [2] that new
CNTs of identical chirality can be grown without the aid of metal catalyst.

In this presentation, I will discuss these results and report our latest findings in achievingchirality control via combined separation and synthesis approach.
[1] Tu et al., Nature 460, 250(2009)[2] Liu et al., Nature Communications 3, 1199 (2012)
Corresponding Author: Ming Zheng
Tel: 301-975-8995, Fax: 301-975-4924
E-mail: ming.zheng@nist.gov

--

2S-5
Fundamental and Advanced Materials Design of Soluble Carbon
Nanotubes○Naotoshi Nakashima1,2,3
1

Department of Applied Chemistry,Kyushu University, Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University, Fukuoka 819-0395, Japan
3
JST-CREST

One of the key issues in the utilization of carbon nanotubes (CNTs) for basic researches together with theirpotential applications in many areas is to develop a methodology to solubilize/disperse them in solvents.[1]After brief introduction about the strategy to solubilize CNTs in solution, we report our recent study on thefollowing five topics.
i) Determination of precise electronic states of individually dissolved (n,m)single-walled carbon nanotubes(SWNTs), and SWNT trions [2-5]ii) SWNT chirality recognition/extraction by polymers and its application[6-10]iii) High conductive transparent SWNT ultrathin films[11]iv) CNTs/polymer gel-near IR responsive materials [12-14]v) Electrocatalyst for fuel cell using soluble CNTs[15-19]
Topic (i): Electronic structures of SWNTs, one of the fundamental features of nanotubes, strongly depend on thechirality of the nanotubes. We have discovered that we can determine the precise electronic states of isolated
SWNTs having their own chirality indices by in situ near-IR photoluminescence spectroelectrochemistry at the
fabricated modified ITO electrode.
Topic (ii): The facile separation of a mixture of SWNTs into specific chirality components has recently attracted
great attention. We report that certain chiral polyfluorene copolymers can well recognize SWNTs with certain
chirality preferentially, leading to solubilization of specific chiral SWNTs. This is the first example showing therational design and synthesis of novel fluorene-based copolymers toward the recognition/extraction of targeted(n,m)-chirality of the SWNTs.
Topic (v): We report new electrocatalysts composed of CNTs, polybenzimidazole (PBI) and platinum
nanoparticles that act as in which CNTs are efficient catalysts for fuel cells. The design and synthesis of anitrogen-containing calcined PBI/CNT hybrid that acts as an oxygen reduction catalyst will be also reported.

References (authors: N. Nakashima et al.)[1](Review) J. Nanoscience Nanotechnol., 2012, 12, 1739-1747. [2] Angew. Chem. Int. Ed. 2009, 48,7655-7659. [3] J. Am. Chem. Soc. 2010, 132, 13072Ð13077. [4] Bull. Chem. Soc. Jpn., 2012, 85,
1262-1267. [5] J. Am. Chem. Soc. 2012, 134, 14461-14466. [6] Angew. Chem. Int. Ed., 2009, 48,
5435-5438. [7] J. Am. Chem. Soc. 2011, 133, 2651Ð2657. [8] Chem. Eur. J. 2011, 17, 13438-13444.
[9] J. Am. Chem. Soc. 2011, 133, 14771Ð14777. [10] J. Am. Chem. Soc. 2012, 134, 12700-12707. [11]Scientific Reports, 2012, 2, doi:10.1038/srep00733. [12] J. Am. Chem. Soc., 2010, 132, 16581Ð16586.
[13] Soft Matter, 2011, 7, 2647-2652. [14] ACS Nano, 2011, 5, 4414-4421. [15] Small, 2009, 5,
735-740. [16] Adv. Functional Mater., 2011, 21, 1089Ð1094. [17] J. Mater. Chem., 2011, 21,1187-1190. [18] Chem. Commun. 2011, 47, 6843-6845. [19] Adv. Mater., in press.
Corresponding Author: N. Nakashima; Tel/FAX: +81-92-802-2840
E-mail: e-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp

--

2S-6
Band engineering in bilayer graphene for future electron-devices○K.Tsukagoshi1, H.Miyazaki1, S.-L.Li1, A.A.Ferreira1, M.Y.Chan1, K. Komatsu1,
S.Nakaharai2,
1
WPI-MANA, NIMS, Tsukuba, 305-0047, Japan
2
GNC, AIST, Tsukuba, 305-8569, Japan
We present a review of our experiments on graphene transistors in its potential use as
atomic film switching devices.
We found that large transport energy gaps (>100 meV) can be fulfilled in dualgated bilayer
graphene underneath a simple alumina passivation top gate stack, which directly contacts thegraphene channels without an inserted buffer layer. With the presence of energy gaps, theelectrical properties of the graphene transistors are significantly enhanced, as manifested byenhanced on/off current ratio, subthreshold slope, and current saturation. For the first time,complementary-like semiconducting logic graphene inverters are demonstrated that show alarge improvement over their metallic counterparts.
We also demonstrated a tunneling (Fig.1) and rectification behavior in bilayer graphenewith bandgap. A stepped dielectric top gate creates a spatiallymodulated electric field, which opened the band gap in thegraphene and produced an insulating region at the p–ninterface. Furthermore, series of tunneling junctions enabled
unipolar graphene transistors.
This result may open the way for logic applications of
gap-engineered graphene.
Acknowledgments: This work was supported in part by a
FIRST Program from the Japan Society for the Promotion of
Science.

Fig.1
Optical-microscope
image of gate-tunable bilayer
graphene transistor.

References
1. H.Miyazaki, K.Tsukagoshi, A.Kanda, M.Otani, S.Okada, Nano Letters
10, 3888 (2010)
2. S.-L.Li, H.Miyazaki, A.Kumatani, A.Kanda, K.Tsukagoshi, Nano Letters 10 (7) 2357-2362 (2010).
3. H.Miyazaki, S.-L.Li, H.Hiura, K.Tsukagoshi, A.Kanda, Journal of Physical Society of Japan 81, 014708(2012).
4. A.A.Ferreira, H.Miyazaki, S.-L.Li, K.Komatsu, S.Nakaharai, K.Tsukagoshi, Nanoscale 4 (24) 7842 (2012).
Corresponding Author: K.Tsukagoshi
TEL:+81-29-860-4894, FAX:+81-29-860-4706
E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp

--

3S-7
Novel Functional Carbon-Nanotube Transistors
Taishi Takenobu
Department of Applied Physics, Waseda University, Shinjuku 169-8555, Japan
Flexible, printed, and stretchable electronics are attracting considerable attention as thenext-generation functional electronics because it is believed that in future many electronic
assemblies on rigid substrates will be replaced by mechanically flexible or even stretchable
alternatives. This is a consequence of the ambient intelligence vision where the citizen carries
along more and more electronics systems, near the body, on or even inside the body. Thesesystems must be light weighted, must preferably take the shape of the object in which they areintegrated, and must even follow all complex movements of these objects, explaining the needfor stretchability. Although organic materials have been playing the main role in theseresearch fields, in this study, we would like to show you the considerable potential in
single-walled carbon-nanotube (SWCNT) films.
High-performance SWCNT transistors: As the first step for carbon-nanotube flexible,
printed, and stretchable electronics, we found the simple method to fabricate
high-performance SWCNT film transistors using the enriched semiconductor SWCNT [1,2]and one of the solid electrolyte dielectric materials, ion gel [3,4]. These semiconducting
SWCNT transistors hold carrier mobility of more than 100 cm2/Vs and on/off ratio of 104-105.
Flexible SWCNT transistors: Based on this method, we fabricated SWCNT transistors on
flexible plastic substrates. The flexible SWCNT transistors also show high performance withcarrier mobility of more than 100 cm2/Vs and on/off ratio of 104. Moreover, we have tested
bending durability of devices on flexible substrates down to curvature radius of 300 ȝm.
During the bending test, both on- and off-current of SWCNT transistor was almost constant,and transistor kept high performance without degradation. To the best of our knowledge, thiscurvature radius of less than 300 ȝm is minimum champion record among SWCNT flexible
transistors [5].
Printed SWCNT transistors: Because we have already performed the ink-jet printing of
SWCNT transistors [6,7], the fully ink-jet printed all-carbon SWCNT transistors were
fabricated on flexible plastic films. We ink-jet printed the enriched metallic SWCNT, enrichedsemiconducting SWCNT, and ion gel as electrodes, active layer, and dielectric layer,
respectively. These printed SWCNT transistors also revealed high performance and excellent
flexibility.
Stretchable SWCNT transistors: We applied our SWCNT films into a stretchablepoly(dimethylsiloxane) (PDMS) substrates and successfully fabricated stretchable SWCNT
transistors. We have preliminary tested expanding durability of devices on PDMS substrates
up to strain of 10% and, during expanding test, both carrier mobility and on/off ratio wereapproximately constant, which is better stretchability than the recent graphene transistors [8].

Picture of SWCNT transistor[1] K.Yanagi, T.T et al., ACS NANO 4 (2010) 4027.
[2] K.Yanagi, T.T et al., Adv. Mater. 23 (2011) 2811.
[3] Y. Yomogida, T.T et al., Adv. Mater. 24 (2012) 4392.
[4] J. Pu, T.T et al., Nano Lett. 12 (2012) 4013.
[5] S. Aikawa, et al., Appl. Phys. Lett. 100 (2012) 063502.
[6] H. Okimoto, T.T et al., Adv. Mater. 22 (2010) 3981.
[7] D. Fu, T.T, et al., Adv. Mater. 22 (2010) 4867.
[8] S. K. Lee, et al., Nano Lett. 11 (2011) 4642.
Tel/Fax: +81-3-5286-2981, E-mail: takenobu@waseda.jp

--

3S-8
Ballistic transport in graphene/h-BNżTomoki Machida1,2,3, Satoru Masubuchi1,2, Masahiro Onuki 1, Sei Morikawa 1, Kazuyuki
Iguchi 1, Takehiro Yamaguchi 1, Miho Arai 1, Kenji Watanabe 4, Takashi Taniguchi 4
1

Institute of Industrial Science, University of Tokyo, Tokyo 153-8505, Japan
2
INQIE, University of Tokyo, Tokyo 153-8505, Japan
3
PRESTO, Japan Science and Technology Agency, Saitama 332-0012, Japan
4
National Institute for Materials Science, Tsukuba, 305-0044, Japan
The presence of unique relativistic charge carriers, masless Dirac fermions, in monolayer
graphene has lead to the emergence of novel transport phenomena. When the mean free pathof the Dirac fermions exceeds the size of conductor, the charge carriers in a ballistic transport
regime exhibit more intriguing transport phenomena.
In this work, we study magnetotransport in ballistic graphene mesoscopic wires onhexagonal boron nitride (h-BN). We observed anomalous magnetoresistance curves withcharacteristic peak structures where the peak field scales with the ratio of cyclotron radius RC
and wire width W [1]. The obtained commensurability ratio D { W / RC 0.95 r 0.1
contrasts with D 0.55 in semiconductor two-dimensional electron gas systems.
The graphene mesoscopic wire/h-BN was fabricatedusing the mechanical exfoliation and transfer technique.
A monolayer graphene deposited on a spin-coated
PMMA was transferred on the h-BN crystal using analignment technique under an optical microscope. A
wire-shaped geometry was defined using the standard
electron-beam lithography and subsequent oxygen
plasma etching technique. The carrier mobility is
70,000 cm2/Vs at 4 K, and the carrier mean free pathexceeds 1 Pm at high carrier density of 3 u 1012 cm-2.
Two-terminal resistance shows an anomalous peakstructure indicating that the carriers are transmitted
ballistically in an inner region of the conduction
channel and scattered diffusively at the boundary. The
resistance peak occurs at a magnetic field which scaleswith the ratio of RC and W as W / RC 0.95 r 0.1
independently from W. The result suggests thecharacteristic commensurability ratio and uniqueboundary scattering in graphene.
The carrier focusing effect in a ballistic transport
regime and the photovoltaic effect due to the cyclotron Fig.1 Two-terminal resistance R as afunction of magnetic field B at T = 4 K for
resonance in graphene/h-BN will also be presented.
[1] S. Masubuchi et al. Phys. Rev. Lett. 109, 036601 (2012).
Corresponding Author: Tomoki Machida
Tel: +81-3-5452-6742, Fax: +81-3-5452-6743,
E-mail: tmachida@iis.u-tokyo.ac.jp--the device with L = 2.3 Pm and W = 1.0
Pm withback-gate voltaqge VBG = -50,
-48,…, -28 V (bottom to top). Each curve
was offset vertically. The dotted line andcolored area indicate the expected peak

3S-9
Design, Synthesis, and Properties of Fullerene Derivatives
for Organic Thin Film Solar Cells○Yutaka Matsuo
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan
Development of organic thin-film photovoltaic cells have become important subjects
because those devices are expected to provide renewable energy technology. Fullerenes arecommonly used as photoelectrochemically active materials in organic photovoltaics due totheir high electron affinity that enables efficient photoinduced electron transfer and charge
separation. To achieve efficient and mechanistically well-defined photo-energy conversion,
rational design of fullerene derivatives and construction of their ordered supramolecular
structures in solid states as well as on surface are of importance. Herein we report design of
new fullerene derivatives and their application to organic photovoltaic devices.
Photoelectronic functions of fullerene derivatives mainly depend on the size and shape of
their π-electron conjugated systems, which can be modified by the change of number andposition of organic addends on the fullerene core. In this presentation, we focus ondevelopment of new fullerene derivatives that have suitable LUMO levels for highopen-circuit voltage, high electron mobility, and self-assembling ability to achieve
high-performance organic photovoltaic cells.

[1] Y. Matsuo et al. J. Am. Chem. Soc. 2009, 131, 16048.
[2] Y. Zhang et al. J. Am. Chem. Soc. 2011, 133, 6890.
[3] Y. Matsuo et al. Appl. Phys. Lett. 2012, 100, 063303.
[4] Y. Matsuo et al. Chem. Commun. 2012, 48, 3878.
[5] Y. Matsuo et al. Org. Lett. 2012, 14, 3784.
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-1476, Fax: +81-3-5841-1476
E-mail: matsuo@chem.s.u-tokyo.ac.jp--୍⯡ㅮ₇
General Lecture

1 – 1 䡚 1 – 10
2 – 1 䡚 2 – 11
3 – 1 䡚 3 – 13

1-1
Organic Synthesis of Helium-Containing Fullerenes andGeneration of Endohedral Fullerenes Encapsulating Two Different AtomsżYuta Morinaka1, Satoru Sato2, Atsushi Wakamiya1, Hidefumi Nikawa2, Naomi Mizorogi2,
Fumiyuki Tanabe1, Michihisa Murata1, Koichi Komatsu1, Ko Furukawa3, Tatsuhisa Kato4,
Shigeru Nagase5, Takeshi Akasaka2, Yasujiro Murata1,61Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan
3
Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan
4
Institute for the Promotion of Excellence in Higher Education, Kyoto University,
Kyoto 606-8501, Japan
5
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
6
JST, PRESTO
2Previously, we have synthesized open-cage fullerenes and introduced hydrogenmolecule(s) into the fullerene cages through the opening [1]. Under the similar conditions, ahelium atom was incorporated inside the open-cage C60 derivative 1 followed by theirradiation with a high-pressure mercury lamp to give He@2 at occupation level of 30%(Scheme 1) [2]. After the restoration of the openings, synthesis of the He@C60 was achieved at
occupation level of 30%. He@C70 was also synthesized by applying this synthetic technique.
The encapsulated helium atom inside C60 was confirmed by the single crystal X-ray analysis
of He@C60 as the first report on X-ray diffraction data containing helium [3].
Scheme 1
Py
O

Ph
N
Ph
O

S
O

Py
O

1) He (1230 atm)

Phr.t., 1.5 h(Py = 2-pyridyl)

PyPh

115 °C, 1 h

N

Ph
Ph

TiCl4, Zn2) h (vis.), benzene
1

N
O

He

28%

400 °CODCB/THF (25/3)
85 °C, 1 h

He@2/2 (3/7)

He

61%

He

vacuum, 2 h76%

He@3/3 (3/7)

He@C60/C60 (3/7)

It is well known that a nitrogen atom can be encapsulated into C60 and C70 under nitrogenradio-frequency (RF) plasma conditions. In this study, we tried insertion of a nitrogen atom
into He@C60 and He@C70 under plasma conditions [3]. The ESR analyses of the products
demonstrated that novel endohedral fullerenes encapsulating both helium and nitrogen atoms
were generated (Scheme 2). This is the first achievement for the production of endohedral
fullerenes by combining two individual insertion techniques.
[1] M. Murata, Y. Murata, K. Komatsu, Chem. Commun. 6083 (2008).
[2] Y. Morinaka, F. Tanabe, M. Murata, Y. Murata, K. Komatsu,
Chem. Commun. 46, 4532 (2010).
[3] Y. Morinaka, S. Sato, A. Wakamiya, F. Nikawa, N. Mizorogi,
F. Tanabe, M. Murata, K. Komatsu, K. Furukawa, T. Kato, S. Nagase,
T. Akasaka, Y. Murata, submitted.
Corresponding Author: Yasujiro Murata
Tel: +81-774-38-3172, Fax: +81-774-38-3178
E-mail: yasujiro@scl.kyoto-u.ac.jp- 11 -

1-2
Fullerene bis-carboxylic acid derivatives by Prato reaction○Safwan Aroua and Yoko Yamakoshi
1

Laboratorium fŸr Organische Chemie, ETH-ZŸrich, Wolfgang-Pauli-Strasse 10 CH8093
ZŸrich, Switzerland

In order to prepare water-soluble fullerene materials, bis-carboxylic acid derivatives of C60
and M3N@C80 (M = Sc, Y, Lu, Gd) were synthesized by Prato reaction with a glycine
derivative 1 and formaldehyde. The subsequent addition of PEG chains by amide formation
successfully leads to water-soluble fullerene materials.
The glycine derivative 1 was prepared from di-tert-butyl 3-oxopentanedioate and subjectedto the reaction with fullerenes in the presence of formaldehyde (Figure 1). In the reaction of
C60, mono [6,6]-adduct was observed as a major product (Figure 2). In the reactions of
M3N@C80, the initial adducts were [6,6]-adducts, which were converted to [5,6]-adducts byheating (Figure 3). The reaction rate of the isomerization step was dependent on the metalcluster size inside of the C80 cage, with smaller sizes leading to slower rates. Interestingly, inthe case of larger metal cluster (Y and Gd), the isomerization occurred in equilibrium (Figure4). By addition of PEG moieties via amide formation using HPTU as a coupling reagent,water-soluble materials of C60 and Gd3N@C80 were successfully prepared. These materials
appear to form micelle-like small particles in aqueous solution.
O

O
+

O
O

HN

O

O

OH

C60

O
O

O

N

H

H

HO

O

OH
O

N

O

TFA
CHCl3
rt, 18 h
94%

Toluenereß., 24 h
38%

1

2

3

Figure 1. Prato reaction of C60.

Figure 2. Perspective
view of 2.
O

O
O

O

O

O
O

HN

O

O

OH

1

O
H

O

O
O

N

O

5a, 5b: [5,6]-adduct
M = Sc, Lu

HO

o-DCB, 120¡COO

M3N@C80

NN

O

4: [6,6]-adduct
4a: M = Sc
4b: M = Lu
4c: M = Y
4d: M = Gd

5c, 5d: [5,6]-adduct
M = Y, Gd

Figure 3. Prato reaction of M3N@C80.

Figure 4. Thermal conversion of Gd3N@C80[6,6]-adduct to [5,6]-adduct (upper) and [5,6]-adduct to[6,6]-adduct (lower) upon heating (HPLC: Buckyprep,
toluene, 1 mL/min, 390 nm).

[1] A. Safwan et al. J. Am. Chem. Soc. 134, 20242 (2012).
Corresponding Author: Y. Yamakoshi
Tel: +41-44-633-6420, Fax: +41-44-633-1235,
E-mail: yamakoshi@org.chem.ethz.ch, website: http://www.yamakoshi.ethz.ch/- 12 -

1-3
Molecular Bearing of Finite Carbon Nanotube and Fullerene
in Ensemble Rolling Motion○Shunpei Hitosugi, Yamasaki Takashi, Ryosuke Iizuka, Hiroyuki Isobe
Department of Chemistry, Tohoku University, Sendai, 980-8578, JapanThe combination of convex and concave surfaces of carbonaceous entities provides aninteresting element of nanoscale machines because of its ultralow friction originates from thesmoothness and the non-directional van der Waals nature of the attractive forces at thecomplementary interface. Although the multi-wall carbon nanotube based prototype
machine has attracted an immediate interest, the advancement in the chemical production ofsuch carbonaceous machinery is much slower than expected. The major obstacle toadvancement is the lack of discrete carbon nanotubes that can be handled as a molecular
entity: Inhomogeneous molecular structures of available carbon nanotubes allow for handling
only as a mixture of various structures and hamper the rational molecular design of themachinery. We report a minimal carbonaceous bearing composed of finite single-wallcarbon nanotube (SWNT) and fullerene molecules.
The finite SWNT bearing in our study is [4]cyclochrysenylene ([4]CC), a belt-persistentvariant of tubular cycloarylene molecules from bottom-up synthesis.[1] We determined theassociation constant between (P)-(12,8)-[4]CC and C60 by using the fluorescence quenching
titration to obtain the value, log Ka = 12.3 in benzene, which surpassed that of the previously
tightest complex with C60 (Fig. 1a). The introduction of a "shaft" moiety into the C60 journal
allowed us to realize the anisotropic ensemble rolling motion in the peapod bearing. The
functionalized journal is a protonated form of N-methyl fulleropyrrolidine 1 that possesses afive-membered ring as the shaft on the spherical journal. The results of VT-NMR analysis
demonstrate that the journal in the bore rolls rapidly on the NMR timescale and acts as a"symmetry top" from 25 ¡C to Ð60 ¡C (Fig. 1b).[2]Fig. 1 (a) A molecular model of (P)-(12,8)-[4]CCC60. Hexyl groups of [4]CC are represented as balls forclarity. (b) A molecular model of a protonated form of N-methyl fulleropyrrolidine 1 encapsulated in(P)-(12,8)-[4]CC and the aromatic resonances in 1H NMR spectra in CD2Cl2.
[1] Hitosugi, S.; Nakanishi, W.; Yamasaki, T.; Isobe, H. Nat. Commun. 2, doi: 10.1038/ncomms1505 (2011).
Hitosugi, S.; Yamasaki, T.; Isobe, H. J. Am. Chem. Soc. 134, 12442 (2012).
[2] Isobe, H.; Hitosugi, S.; Yamasaki, T.; Iizuka, R. Chem. Sci. published online (doi: 10.1039/C3SC22181D).
Corresponding Author: H. Isobe
Tel: +81-22-795-6585, Fax: +81-22-795-6586,
E-mail: isobe@m.tohoku.ac.jp- 13 -

1-
Selective synthesis of alkoxyfullerenes C60(OR)5Br:
Substitution reaction of C60Br6 with alcoholżKouya Uchiyama 1, Hiroshi Moriyama *1, Kenji Yoza 2
1

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

Halofullerenes, C60Xn, such as chlorofullerene and bromofullerene, are recognized as
suitable starting materials for further synthesis of fullerene derivatives, because they haverelatively weak C–X bonds; therefore, substitution reactions with various nucleophiles caneasily occur to give multifunctionalized fullerene derivatives regioselectively. However,compared with chlorofullerenes, bromofullerenes have not so far been studied intensively
because of their low solubility in organic solvents.
We have reported a selective substitution reaction of octabromofullerene C60Br8 [1] withmethanol and ethanol in the presence of a silver salt, which facilitates the substitution reactionof all bromine atoms to give novel alkoxyfullerenes C60(OR)8 (R = CH3, C2H5) [2], as theresult of total substitution of the bromines of C60Br8. We characterized the products by 1H and
13
C NMR spectroscopy, and single-crystal X-ray crystal structure analysis. The molecular
structure of these alkoxyfullerenes, C2v, was found to be retained, which is completely
consistent with the addition pattern.
Here we report another type ofreaction,hexabromofullerene
C60Br6 [1] with alcohols, in whichnovel pentakisalkoxyl- fullerenes
C60(OR)5Br (R = Me, Et, nPr,
nBu, iBu, nPn, 2-MeEt) were
newly obtained and characterizedby 1H and 13C NMR spectroscopy.
The substitution reaction proceeds
efficiently in the presence of Ag2O,
which
facilitatesbromineelimination.
SchemeThepentakisalkoxylfullerenes
C60(OR)5Cl (R = Me, Et) have been reported [3]; however, no pentakisalkoxylfullerenes
with a longer alkyl chain such as Pr, Bu, Pn, have been reported in the case of C60(OR)5Cl.
The substitution of bromine seems rather easier than is the case for chlorine. However, it was
found that the unique bromine atom at the center of the fullerene molecule was not substituted
under these reaction conditions, as was observed for C60(OR)5Cl. A new oxygen-bridged
tetrakisalkoxylfullerne compound, C60(OR)4O, was also obtained, depending on the bulkinessof the alkyl group. These alkoxyfullerene derivatives, C60(OR)5Br, seem to have potential use
as unique starting compounds for the synthesis of other fullerene derivatives.
[1] P. R. Birkett, P. B. Hitchcock, H. W. Kroto, R. Taylor, D. R. M. Walton, Nature, 357, 479–481 (1992).
[2] K. Uchiyama, H. Moriyama, K. Yoza, The 43rd FNTG Symposium Abstract, 1P-14 (2012); JP2012–194209.
[3] A. G. Avent, P. R. Birkett, A. D. Darwish, S. Houlton, R. Taylor, K. S. T. Thomson, X.-W. Wei, J. Chem. Soc., Perkin
Trans. 2, 5, 782–786 (2001).

Corresponding Author: Hiroshi Moriyama
TEL: +81-47-472-1211, FAX: +81-47-476-9449, E-mail: moriyama@chem.sci.toho-u.ac.jp- 1 -

1-
Proton dynamics in Fullerenol solids studied by 1H-NMR○Keisuke Baba1 and Hironori Ogata 1,2
1

Department of Chemical Science and Technology, Hosei University, Koganei 184-8584,
Japan
2
Research Center for Micro-Nano Technology, Hosei University, Koganei 184-0003, Japan
Fullerenols (Polyhydroxylated Fullerene: C60(OH)x) have been a subject of intense
research in many fields with the claim of possible applications in a variety of areas, including
optoelectronics, medical therapeutics, biotechnology, chemical mechanical polishing, and fuelcells, owing to their high solubility in a large variety of solvents (depending on the number ofhydroxyl groups, x). It is reported that C60(OH)n (n~12) show proton conductivity and theirapplications for the proton conducting membrane of a polymer electrolyte fuel cell (PEFC)
is proposed. However, their proton conduction mechanism has not been thoroughly studied
yet. We previously reported the fabrication of both nanosheets and nanocrystals consist of thetwo types of fullerenols(C60(OH)13.5 and C60(OH)38.7(O)1.6) by the liquid phase growth method
using both good and poor solvents.
We have studied proton dynamics in both C60(OH)13.5 and C60(OH)38.7(O)1.6 solids bymeans of 1H-solid-state NMR. Figure 1 shows the temperature dependence of 1H-NMR
spectra in (a)C60(OH)13.5 and (b)C60(OH)38.7(O)1.6. The detailed results about their proton
dynamics will be reported.
(a)C60(OH)13.5

100

50

(b)C60(OH)38.7(O)1.6

230 K
210 K
190 K
170 K

0

-50

-100 100

50

0

230 K
210 K
190 K
170 K

-50

-100

Chemical Shift (ppm)

Chemical Shift (ppm)

Fig.1.Temperature dependence of 1H-NMR line shapes in (a) C60(OH)13.5 and (b) C60(OH)38.7(O)1.6.
[1] K. Hinokuma et al., Chem. Phys. Lett., 341, 442 (2001)[2] Chiang et al. J. Org. Chem., 59, 3960 (1994)[3] K. Kokubo, et al., ACS Nano, 2, 327 (2008)[4] K. Baba, et al., The 43rd Fullerenes-Nanotubes-Graphene General Symposium, 1P-24 (2012)
Corresponding Author: Hironori Ogata
Tel: +81-42-387-6229, Fax: +81-42-387-6229,
E-mail: hogata@hosei.ac.jp- 1 -

1-
Kinetic Stability Governs Relative Fullerene Isomer Abundance○ Stephan Irle1, Yoshifumi Nishimura1, Alexander S. Fedorov2, Henryk A. Witek3
1

Department of Chemistry and WPI-Institute of Transformative Bio-Molecules, Nagoya
University, Nagoya 464-8602, Japan
2
Kirensky Institute of Physics, Akademgorodok 50, Krasnoyarsk, 660036, Russia
3
Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung
University, Hsinchu 30010, Taiwan
A methodology to evaluate the kinetic stability of molecular nanostructures is presented
based on the assumption of the independent and random nature of thermal vibrations,calculated at the density functional theory (DFT) level of theory using the harmonic
approximation [1]. The kinetic stability (KS) is directly correlated to the cleavage
probability for the weakest bond of a given molecular geometry. The application of thepresented method to a selection of fullerenes (see Fig. 1) and carbon nanotubes yields clear
correlation to their experimentally observed relative isomer abundances.
Moreover, we present good
agreement of harmonic vibrational
eigenmodes between DFT and thecomputationally more efficientdensity-functionaltight-binding(DFTB) method [2-4].
Thus,
DFTB-based KS calculations
allow the estimation of kinetic
stability for more than 100,000
isomers of the fullerenes C20-C100.
We found that the experimentallyobserved isomer abundances, as
recorded for instance by mass
spectroscopic investigations, arereasonably well reproduced by the
Boltzmann-weighted
kinetic
stabilities of the cage isomers.
Fig.1 Calculated relative kinetic stability (upper part) andThis result suggests a mechanism
cohesion energy (bottom part) for different fullerenes.
of fullerene formation involving
cage destruction, such as recently
predicted by quantum chemical molecular dynamics (QM/MD) simulations [5-6].
[1] A. S. Fedorov et al., Phys. Rev. Lett., 107, 175506 (2011).
[2] H. A. Witek et al., J. Chem. Phys., 121, 5163 (2004).
[3] E. Małolepsza et al., Chem. Phys. Lett., 412, 237 (2005).
[4] H. A. Witek et al., J. Chem. Phys., 125, 214706 (2006).
[5] S. Irle et al., J. Phys. Chem. B, 110, 14531 (2006).
[6] B. Saha et al., J. Phys. Chem. A, 115, 22707 (2011).
Corresponding Author: S. Irle
Tel: +81-52-747-6397, Fax: +81-52-747-6397
E-mail: sirle@chem.nagoya-u.ac.jp- 1 -

1-
Optical properties of graphene quantum dots separated byhigh performance liquid chromatography
11, Shinichiro Mouri1, Ryo Kitaura3,
Hisanori Shinohara , Toku Yasuda , Naoki Komatsu4, and Kazunari Matsuda1○Naoto Fuyuno , Daichi Kozawa , Yuhei Miyauchi
3

1, 2

4

1

Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama
332-0012, Japan3
Department of Chemistry and Institute for Advanced Research, Nagoya University,
Nagoya 464-8602, Japan
4
Department of Chemistry, Shiga University of Medical Science, Otsu 520-2192, Japan
2

Graphene quantum dots (GQDs), which are nanometer-size graphene pieces, haveattracted a great deal of interest from the viewpoints of fundamental physics andoptoelectronics. Although the optical properties of GQDs could be controlled bychanging size due to the quantum confinement effect, accurate control of their size has
not been achieved and thus their luminescence mechanism is not well understood.
Therefore, achievement of size separation of GQDs, which would lead to narrower
emission peaks, is important for both understanding their size-dependent opticalproperties and future optical applications.
In the present study, we conducted optical measurements on the GQDs separated byhigh performance liquid chromatography (HPLC) to explore the possibility of size
separation and clarify their size-dependent optical properties. The GQDs were
fabricated by the acid treatment of pitch-based carbon fibers [1] and then collected
separately by HPLC (HPLC-GQDs). Figure 1 shows the photoluminescence excitation
spectroscopy (PLE) maps of the HPLC-GQDs where the numbers in the maps indicate
the fractions of the collection (larger
numbers correspond to the longer
retention times). Several luminescencefeatures indicated by white ellipses (A,B, C and D) are observed in the PLE
maps. These features could originate
from different species since theirpatterns vary depending on the fractions.
These results suggest that GQDs withvarious optical characteristics could be
separated by HPLC, probably caused by
the size variation of GQDs.
[1] J. Peng et al., Nano lett. 12, 844 (2012).
Corresponding Author: N. Fuyuno
Tel: +81-774-38-3465, Fax: +81-774-38-3467
E-mail: fuyuno.naoto.67n@st.kyoto-u.ac.jp

Fig. 1 PLE maps of the GQDs after the separation
by HPLC. The numbers shown in the maps
correspond to the fractions of the collection.

- 1 -

1-
Modulation of Optical Spectra of Monolayer MoS2 by Chemical DopingżShinichiro Mouri1, Yuhei Miyauchi1,2, Kazunari Matsuda1
12Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan

Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama
332-0012, Japan

Monolayer molybdenum disulfide (MoS2) has attracted much attention as a novel
two-dimensional direct band gap semiconductor [1], and also is a promising candidate torealize the ‘valleytronic’ devices since the valley selective optical excitation is possible [2].
The control of fundamental optical properties including excitonic effects is necessary to open
up such applications. Charge-carrier doping is one of the effective methods to modify the
excitonic behavior of ultrathin nanostructures, such as carbon nanotubes [3]. Recently, tightly
bound trion, a quasi-particle composed of two electrons and a hole, has been observed in amonolayer MoS2 FET device using the electro-static doping [4]. In this study, we investigatedthe chemical doping effects on the photoluminescence (PL) spectra of monolayer MoS2.
Monolayer MoS2 was prepared by the mechanical exfoliation and deposited on SiO2/Si
substrate. Excitation light source for the PL experiments was the cw solid-state laser (2.33 eV:
20 PW). We drop-casted a typical p-type dopant (F4TCNQ) dissolved in toluene solution (1Pg/ml) on the surface of the monolayer MoS2. Figure 1 shows the normalized PL spectra of
as-prepared and hole-doped monolayer MoS2 at room temperature. The PL peak around 1.8–
1.9 eV can be decomposed into two components corresponding to the exciton (Peak A) andtrion (Peak A-) PL [4]. In the as-prepared monolayer MoS2, the trion PL (A-, ~1.85 eV) is
dominant, because excitons can be easily bound by spontaneously doped negative
charge-carriers (electrons) [4]. On the other hand, we found that exciton PL (A, ~1.89 eV)
becomes dominant in the hole-dopedmonolayer MoS2 presumably because thedoped-holes compensate the Fermi energy
shift induced by spontaneously doped
negative charges. These results suggest thatthe optical properties of monolayer MoS2 canbe controlled by the chemical doping method.
[1] A. Splendiani et.al. Nano Lett. 10, 1271 (2010).
[2] T. Cao et.al. Nature Commu. 3, 1882 (2012).
[3] S. Mouri et.al., Phys. Rev. B 87, 045408 (2013).
[4] K. Fai. Mak et.al.Nature. Material. 7, 494 (2012).
Corresponding Author: Shinichiro Mouri
Tel: +81-774-38-3463,
Fax: +81-774-38-3467,
E-mail: iguchan@iae.kyoto-u.ac.jp

Figure 1 PL spectra of as-prepared (above) and
F4TCNQ doped (below) monolayer MoS2.

- 1 -

1-
Coulomb drag and excitonic insulator in double-layer graphene○Satoru Konabe1,2 and Susumu Okada1,2
1Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki

305-8571, Japan

2Japan Science and Technology Agency, CREST, 5 Sanbancho, Chiyoda, Tokyo 102-0075,Japan

The Coulomb interaction among Dirac electrons leads to peculiar phenomena ingraphene related systems [1]. For example, it has been theoretically proposed that an
excitonic insulator phase could appear in two-monolayer graphene (double-layer graphene)[2]. The excitonic insulator is a phase where excitons are spontaneously generated atthermodynamic equilibrium even in the absence of an optical excitation. Such phase arises by
the instability of the normal ground state of semiconductor or semimetal against the
spontaneous formation and its condensation of bound electron-hole pairs. In the graphene
double-layer system, electrons are distributed in one of two layers and holes are in the otherlayer, those of which form bound pairs through the interlayer Coulomb interaction. However,
it is still unclear whether such state exist or not [3]. It is thus crucial to identify physicalquantities that directly measure the excitonic insulator phase. To meet such demand, theCoulomb drag resistivity is the most favorable, which measures the ratio of a current passed
through one of the layer and the induced voltage drop of the other layer [4].
In this work, we theoretically investigate transport properties of double-layer
graphene, focusing on interlayer Coulomb interaction. For this purpose, we develop a theoryof Coulomb drag in this system, which covers from the strongly fluctuated normal phase to
the excitonic insulator phase. Using the theory, we calculate the drag resistivity that evaluate
how the drag resistivity captures the phase transition to the excitonic insulator phase.
References:[1] V. N. Kotov et al. Rev. Mod. Phys. 84, 1067 (2012).
[2] H. Min et al. Phys. Rev. B 78, 121401(R) (2008).
[3] M. Y. Kharitonov et al. Phys. Rev. B 78, 241401 (2008), Y. E. Lozovik et al. JETP Lett. 87, 61 (2008), R. B.
Bistritzer et al. Phys. Rev. Lett. 101, 256406 (2008), D. K. Efimkin et al. JETP Lett. 93, 238 (2011), M. P. Mink
et al. Phys. Rev. B 84, 155409 (2011), I. Sodemann et al. Phys. Rev. B 85, 195136 (2012).
[4] A.Kamenev et al. Phys. Rev. B 52, 7516 (1995).
Corresponding Author: Satoru Konabe
E-mail: konabe@comas.frsc.tsukuba.ac.jp
Tel: +81-2-9853-5600 ext.8233- 1 -

1-10
Resonance and interference effect of Raman spectroscopyof graphene in the magnetic field○Riichiro Saito1, Qiu Caiyu2, Yu Ting2
1

2

Department of Physics, Tohoku University, Sendai, 980-8578, Japan
Division of Physics and Applied Physics, School of Physical and Mathematical Sciences,
Nanyang Technological University, 637371, Singapore

In the Raman spectroscopy of graphene, some recent experiments show the resonance andinterference effects on the Raman intensity and on the spectra shape. When the excitationenergies of two elementary excitations such as (1) phonon, (2) optical absorption or (3)phonon of other molecule on graphene etc. are the same to each other, the resonanceenhancement of Raman intensity may occur. Further if the initial and the final states of the
optical processes for Raman spectra is the same, the scattering amplitudes of light can beinterfered to each other which make can change the spectral shape [1]. Here we discuss theseeffects by recent measurement of Raman spectra of graphene in the presence of the magnetic
field.
In the magnetic field, the electronic structure ofgraphene forms the Landau levels (LLs). The
optical dipole transition energies between two
LLs are observed as a function of the magnetic
fields [2,3]. When the transition energy is close to
the G band phonon energy, we expect aninterference effect which is reported by several
groups. In this case, G and and LLs transition arecoupled together and split into two peaks denotedG
by G+ and G-. Further if we use graphite as thesubstrate for graphene sample, the G band ofgraphite (Gi) can be resonance to the opticaltransition between LLs. In this case, we can see
three peaks G-, Gi and G+ from a lower energy
for a magnetic field (4.65T) of the crossing the Fig. 1. Raman spectra of graphenearound G band for different magnetic
LLs transition energy and G band phonon energy.
fields. We can see three peaks G-, Gi
Here we discuss how to explain the experi- and G+ from lower energies for eachmental results by a model of graphene and what magnetic field. The magnetic field for
optical transition energy which is thekind of physics are there in this system.
same as G band energy is around
4.65T.
References:[1] A. Jorio et al. “Raman Spectroscopy of graphene related systems” Wiley (2011).
[2] Q. Caiyu et al. unpublished.
[3] J. Yang et al., Phys. Rev. Lett., 105, 22 (2010).
Corresponding Author: R. Saito
Tel: +81-22-795-7754, Fax: +81-22-795-6447,
E-mail: rsaito@flex.phys.tohoku.ac.jp- 20 -

2-1
Empirical Prediction of Electronic Potentials ofSingle-Walled Carbon Nanotubes○Yasuhiko Hirana,1 Yuhei Miyauchi,2,3 Shinichirou Mouri,2 Kazunari Matsuda,2Naotoshi Nakashima1,4,5
1Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
Motooka 744, Fukuoka 819-0395, Japan
2

3

Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho Kawaguchi, Saitama
332-0012, Japan
4
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu
University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan
5

CREST, Japan Science and Technology Agency (JST), 5 Sanbancho, Chiyoda-ku, Tokyo,
102-0075, JapanThe redox properties (i.e. electronic densities, the Fermi levels, redox potentials) of
single-walled carbon nanotubes (SWNTs) are related to the structures of SWNTs that have a
specified diameter and chiral angle uniquely related to a pair of integers (n,m); the so-calledchiral index. We have previously reported a PL spectroelectrochemical method that
determines the redox potentials of individual (n,m)SWNTs (d = 0.75-1.10 nm).1,2,3 For a
deeper understanding of the electronic properties, the determination of the redox potentials of
SWNTs with a wide range of diameters is very important.
At the meeting, we will provide empirical equations that predict the reduction andoxidation potentials of (n,m)SWNTs for a wide range of diameters and chiral angles. The
study also revealed that the reduction and oxidation potentials of (n,m)SWNTs show
somewhat different nanotube diameter dependence.
[1] Y. Tanaka, Y. Hirana, Y. Niidome, K. Kato, S. Saito, N. Nakashima, Angew. Chem. Int. Ed. 2009, 48, 7655.
[2] Y. Hirana, Y. Tanaka, Y. Niidome, N. Nakashima, J. Am. Chem. Soc. 2010, 132, 13072.
[3] Y. Hirana, Y. Tanaka, Y. Niidome, N. Nakashima, Bull. Chem. Soc. Jpn. 2012, 85, 1262.
Corresponding Author: Naotoshi Nakashima
Tel: +81-92-802-2842, Fax: +81-92-802-2842
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 21 -

2-2
Molecular Dynamics Simulation on RBM of Single-Walled Carbon
Nanotubes in Water Vapor○Naoki Homma1, Shintaroh Sato1, Shohei Chiashi2, Yoshikazu Homma1, and Takahiro Yamamoto3
1

Dept. of Physics, Tokyo University of Science, Shinjuku, Tokyo 162-8601, Japan
Dept. of Mechanical Engineering, The University of Tokyo, Bunkyo, Tokyo 113-8656, Japan
3
Dept. of Liberal Arts, Tokyo University of Science, Chiyoda, Tokyo 102-0073, Japan

2

Radial breathing mode (RBM) is one of the most important vibrational modes of SWNTs,
because the measurement of RBM frequency ωRBM enables us to uniquely assign the chiralityof an individual SWNT by combining it with the theory of resonant transitions. The diameter
dependence of ωRBM can be phenomenologically written as ωRBM = A/dt +B, where dt is a tube
diameter, and A and B are constant parameters with dt. In particular, B gives the frequency
shift by environmental effects.
Figure 1 shows our experimental results on dt dependence of ωRBM in vacuum (4.0Pa) andin saturated water vapor (630Pa). The experimental data well fit the form ωRBM = A/dt +B,
where B ≈ 0 in vacuum or B =7.5±2.5cm-1 in vapor. It is noted that the value of B in air(≈1atm) is similar to that in vapor (630Pa).
To reveal underlying physics of this experiment, we theoretically investigatedconfiguration of water molecules around an SWNT and effects of water vapor on ωRBM using
the classical molecular-dynamics simulation in the NVT ensemble. As shown in Fig. 2, oursimulation results on dt dependence of ωRBM are in excellent agreement with the experimental
results in Fig. 1. Water molecules are condensed around an SWNT surface due to the Van der
Waals interactions between water molecules and an SWNT (left inset in Fig. 2). The
condensed water molecules formed the hydrogen-bond network parallel to the SWNT surface
and eventually they construct a few-layer structure. The first layer is physically bound to the
SWNT, whereas the other layers are weakly bound. In consequence, only the first layer gives
a significant contribution to the frequency shift B, and the value is almost independent of thenumber of water layers. This is a reason that experimental values of B in both air and vapor
cases are similar each other.

Fig.1 RBM frequency（experiment）
Corresponding Author: Takahiro Yamamoto,Tel&FAX: +81-3-5213-0990,
E-mail: takahiro@rs.tus.ac.jp- 22 -

Fig.2 RBM frequency（calculation）

2-3
Energy shift of photoluminescence peaks of SWCNTs wrapped byfluorene-based polymers○Masayoshi Tange, Toshiya Okazaki, and Sumio Iijima
Nanotube Research Center, AIST, Tsukuba, 305-8565, JapanThe structures, i.e., tube diameter and chiral angle identified by chiral indices (n,m), of
semiconducting single-walled carbon nanotubes (SWCNTs) can be investigated withphotoluminescence excitation (PLE) spectroscopy because the optical transitions of SWCNTs
are dependent on the tube structures. In general, photoluminescence (PL) peak positions
predicted from empirical functions by Weisman and Bachilo[1] are used for the assignment ofeach PL peak in the PLE map to different (n,m). However, when organic solvents are used for
SWCNT solutions, a noticeable discrepancy between observed and predicted PL peaks willappear because the predicted peaks are proper for SWCNT aqueous solutions with surfactants
such as sodium dodecyl sulfate (SDS). In particular, when only specific (n,m) species ofsemiconducting SWCNTs are selectively extracted via polymer wrapping sensitive to tube
structures, the discrepancy disturbs the assignment of the PL peaks to (n,m). To avoid thenoticeable discrepancy due to different solvents, we can use the PL peak positions ofpoly(9,9-di-n-dodecylfluorene) (PFD)-extracted SWCNTs, which show the geometricalpatterns for SWCNT family “2n+m” because PFD disperses various semiconducting
SWCNTs in organic solvents, regardless of the structures of semiconducting SWCNTs.[2]Moreover, the comparison between PFD and selective polymers will reveal the influence of
wrapping polymers on the optical transitions of SWCNTs in organic solvents.
Recently, we reported poly(9,9-dioctylfluorene-alt-pridine) (PFOPy) to selectively extract
specific semiconducting SWCNTs showing 1500 nm emissions in toluene.[3] For the study,
SWCNTs synthesized by pulsed-laser vaporization (PLV) were used as initial materials. In
this work, to investigate the influence of PFOPy wrapping on the optical transitions, we havecompared PL peak positions of PFOPy-wrapped SWCNTs with those of PFD-wrapped
semiconducting SWCNTs, which were extracted from the same PLV-SWCNTs to exclude an
influence due to differences in the product processes of SWCNTs. As a result, emissions of afew (n,m) species in PFOPy-wrapped SWCNTs are found to be blue-shifted relative to thoseof PFD-wrapped SWCNTs as shown in Figure 1. On the other hand, the excitation
wavelengths for the PL peaks were inversely shifted, i.e., red-shifted. On the basis of theenergy shift of optical transitions due to a strain effect,[4] we can interpret the energy shifts of
optical transitions to be partially governed by strains of SWCNTs due to the PFOPy wrapping.
In addition, when p-xylene, which has a similar dielectric constant to toluene, was used as theorganic solvent for the PFOPy-wrapped SWCNT solution,, remarkable changechanges in emission
energies of PFOPy-wrapped SWCNTs occurred in(14,3) and (15,4) tubes, being consistent with theinterpretation that wrapping PFOPy imposes stress on
the specific SWCNTs in toluene.
[1] R.B. Weisman and S.M. Bachilo, Nano Lett. 3, 1235 (2003).
[2] M. Tange et al., J. Am. Chem. Soc. 133, 11908 (2011).
[3] M. Tange et al., ACS Appl. Mater. Interfaces 4, 6458 (2012).
[4] L. Yang and J. Han, Phys. Rev. Lett. 85, 154 (2000).
Corresponding Author: T. Okazaki and M. Tange
E-mail: toshi.okazaki@aist.go.jp and masa-tange@aist.go.jp Fig. 1. Emission energy shift of PFOPy-wrapped
SWCNTs relative to PFD-wrapped ones.

- 23 -

2-4
Simultaneous Discrimination of Diameter, Handedness, and Metallicity ofSingle-Walled Carbon Nanotubes with Chiral Diporphyrin Nanocalipers○Gang Liu1, Feng Wang1, Songpol Chaunchaiyakul2, Takahide Kimura1, Yuji Kuwahara2,
Naoki Komatsu1
1

2

Department of Chemistry, Shiga University of Medical Science, Otsu 520-2192, Japan.
Department of Precision Science and Technology, Osaka University, Osaka 565-0871, Japan

We have been developing the methodology to discriminate the handedness and diameter of
SWNTs through molecular recognition using chiral diporphyrin nanotweezers such as 1 and 2
shown in Fig. 1a and 1b, respectively [1-4]. Although relatively small diameters of SWNTs (lessthan 1.0 nm) were recognized well [4], nanotweezers were not able to form stable complexes
with the SWNTs with the diameters larger than 1.0 nm. In this context, we designed chiraldiporphyrin 3 with much larger cavity; namely “nanocalipers” (Fig. 1c) [5]. The feature of the
newly designed host molecule is 1) long spacer with more than 1.4 nm consisting of threearomatic moieties, 2) nearly parallel orientation of the two porphyrins, 3) restricted conformation
by biaryl linkages, 4) strong interaction of two porphyrins and anthracene with the surface of a
SWNT through π-π stacking, and 5) stereogenic centers at the periphery of porphyrins
discriminating helicity of SWNTs.
As expected, we obtained optically active
SWNTs with more than 1.0 nm in diameter(Fig. 2) and, unexpectedly, enriched metallic
SWNTs over semiconducting ones. The
optically active metallic SWNTs are identified
for the first time, in addition to the optically
active semiconducting SWNTs with suchlarge diameters (Fig. 2). The nanocalipers are Fig. 1 Complex structures of (6,5)-, (9,4)-, and (9,7)found to recognize the diameter, handedness, SWNTs with chiral diporphyrin nanotweezers 1 (a) and 2(b), and nanocalipers 3 (c), respectively.
and metallicity of SWNTs simultaneously [5].
References[1] G. Liu, N. Komatsu, in Handbook of carbon
nano materials, World Scientific, 2012; Vol. 3, p203; [2] X. Peng, N. Komatsu, Chem. Lett. 2010,
39, 1022. [3] G. Liu, N. Komatsu, Org. Biomol.
Chem. 2012, 10, 5830; [4] F. Wang, K. Matsuda,
N. Komatsu, J. Am. Chem. Soc. 2010, 132, 10876.
[5] G. Liu, F. Wang, S. Chaunchaiyakul, Y. Saito,
A. K. Bauri, T. Kimura, Y. Kuwahara, N.
Komatsu, submitted.
Corresponding Author: Gang Liu
Tel: +81-77-548-2102, Fax: +81-77-548-2405,
E-mail: gliu@belle.shiga-med.ac.jp

Fig. 2 CD spectra of SWNTs extracted with (R)- and (S)3, and absorption spectra of SWNTs extracted with (S)-3.

- 24 -

2-5
Exchanges of sodium cholate and oligo-DNAs with different chain length
on single-walled carbon nanotubes○Ayaka Inoue1, Yuichi Kato1, Yasuro Niidome 1, 2, Naotoshi Nakashima 1, 2, 3
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
Fukuoka 819-0395, Japan2
WPI I2CNER, Fukuoka 819-0395, Japan
3
JST-CREST, Tokyo 102-0075, Japan

Single-walled carbon nanotubes (SWNTs) are rolled-up graphene sheets with rigid
one-dimensional structures. The diameter and optical band gap of SWNTs are uniquely
related to their chiral indices (n,m), which represent how the graphene sheets are rolled up.
Evaluation of the interactions between solubilizing molecules and SWNTs has attracted muchresearch. Fluorescence and Raman spectroscopies provide important information about themolecules on the SWNTs. However, such studies are not very powerful to understand theinteraction between solubilizing molecules and SWNTs quantitatively.
In this work, we quantitatively evaluated exchanges of solubilizers (here sodium cholate(SC) and DNA) on SWNTs. In this method, sonication procedure is not contained, thus,
denaturation of the DNA does not need to consider. The exchanges were monitored withnear-IR absorption spectral changes of the solubilized SWNTs that were caused from thechange in microscopic environments around the SWNTs.
We examined the exchange of SC on SWNTs using oligo-DNAs (dCn (n = 4, 5, 6, 7, 8, 10,15, and 20)). The fractions of the DNA-solubilized SWNTs were quantitatively evaluatedfrom the analysis of absorption spectral change of the SWNTs [1, 2]. The spectral changes of
the SWNTs were fitted with Hill equation, from which K, H and S of the exchange
reactions were evaluated. It was found that the exchanges of SC for dCn (n = 8-20) wereendothermic, while for dCn (n = 4, 5), they were exothermic. For dC6 and dC7, the exchanges
were switched from endothermic to exothermic depending on the chiralities. Notably, thethermodynamic parameters have indicated that theexchanges depend on the chiralities of the SWNTs
as well as the chain length of the DNAs.
[1] Y. Kato, Y. Niidome, N. Nakashima, Chem. Lett. 40, 730(2011).
[2] Y. Kato, A. Inoue, Y. Niidome, N. Nakashima, Scientific
Reports 2, 733 (2012).
Corresponding Author: N. Nakashima
Tel: +81-3-802-2841, Fax: +81-3-802-2841,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp
Fig. 1. Thermodynamic parameters of enthalpy
changes (H) for the exchanges of SC withdCn on SWNTs with different chiral indices.

- 25 -

2-6
Optical Properties of Polyyne Molecules Dispersed in Solids as
Studied by An Ultraviolet Transmission Microscope○Tomonari Wakabayashi, Kazunari Koma, Okinaga Shibata, Yoriko Wada
Department of Chemistry, Kinki University, Higashi-Osaka 577-8502, Japan
Linear carbon chain molecules, Cn (n=3-15), are highly reactive even under the cryogenic
condition [1]. As they are terminated at each end by a hydrogen or a cyanide group,
cyanopolyynes H(C≡C)nC≡N (n=3-6), known as interstellar molecules (n=3-5), are stableenough to be isolated in organic solvents under the laboratory condition [2]. For a stable solidmaterial, hydrogen-end-capped polyynes, H(C≡C)nH (n=4-6), are readily encapsulated inside
SWNT [3], as extended to H(C≡C)nH@SWNT at n=8 [4].
Polyynes are characteristic in their optical properties related to molecular symmetry.
Besides the conspicuous absorption bands in the UV, there are some weak absorption featuresin the near UV to visible wavelength regions [5]. The mechanism for the weak transition issuggested to be activation of an electric dipole by symmetry lowering due to nuclear
displacements along a specific normal coordinate of the molecular vibration. According to thedifference in the mechanisms between the allowed and forbidden transitions, directions in thetransition dipole can be different [6]. The difference should be reflected on the optical spectra.
In this work, polyyne molecules are dispersed in solid materials, e.g., a transparent filmwith PVA (poly-vinyl alcohols), and their absorption spectra were measured in the UV-vis
region. For the study on the direction of transition dipoles for polyyne molecules dispersed in
the solid material, we have developed a new transmission microscope using an UV lightsource. The principle of the microscope, the aim of our research concerning the mechanism in
optical transitions in the polyyne molecule, and some preliminary results will be introduced.
[1] T. Wakabayashi and W. KrŠtschmer, ÒCarbon Chain Molecules in
Cryogenic MatricesÓ, Chapter 1 in Polyynes: Synthesis, Properties,
and Applications, F. Cataldo ed., Taylor&Francis-CRC, pp.1-13(2006).
[2] T. Wakabayashi, M. Saikawa, Y. Wada, T. Minematsu, Carbon 50,
47 (2012).
[3] D. Nishide, T. Wakabayashi, T. Sugai, R. Kitaura, H. Kataura, Y.
Achiba, H. Shinohara, J. Phys. Chem. C 111, 5178 (2007).
[4] T. Wakabayashi, T. Murakami, H. Nagayama, D. Nishide, H.
Hataura, Y. Achiba, H. Tabata, S. Hayashi, H. Shinohara, Eur.
Phys. J. D 52, 79 (2009).
[5] T. Wakabayashi, H. Nagayama, K. Daigoku, Y. Kiyooka, K.
Hashimoto, Chem. Phys. Lett. 446, 65 (2007).
[6] T. Wakabayashi, Y. Wada, N. Iwahara, T. Sato, J. Phys. Conf. Ser.
(2013) in press.
Corresponding Author: T. Wakabayashi
Tel: +81-6-6721-2332, Fax: +81-6-6723-2728,
E-mail: wakaba@chem.kindai.ac.jp- 26 -

1 mm
Fig. 1. UV-microscope images ofcrystalline α-cyclodextrin/hexane
inclusion compounds containing an
impurity amount of polyyne C10H2.

2-7
Slimy fibers of nanodiamonds assembled in polyacrylamide aqueous
solutionsShunsaku Katsuno, ○Tadamasa Ito, Masaki Ozawa
Department of Materials Science and Engineering,Meijo University, Aichi 468-8502, Japan
Nanodiamond is a material of chemical interest. Functionalization of diamond surfaces
causes no fundamental modification on the interior diamond lattices, unlike sp2-basedmaterials. The outstanding chemical resistivity and hardness also facilitate chemical surface
decorations. Only the problem is that such nanoparticles often form aggregates spontaneously
upon addition of reactants or pH variations [1]. We had disclosed a facile method to break up
those aggregates mechanically by sonication in the presence of hard ceramic beads, which inaddition, can be readily incorporated in conventional glass systems for organic chemistry [2].
By using this technique, functionalization of primary nanodiamond particles can be performed
even under an aggregating condition. Nanodiamonds thus functionalized are found assembled
into slimy fibers, when a colloid is added into polyacrylamide aqueous solution. In this study,
the assembling conditions, properties of the products, and the mechanisms were investigated.
Surface graphitized detonation nanodiamonds at 900 °C were allowed to react withdiazonium salts of aryl derivatives having carboxyl or sulfo groups in aqueous media [3].
Slight amount of the resultant nanodiamond derivatives dispersed in water as well as
non-functionalized nanodiamond colloids were then gave into polyacrylamide aqueous
solutions. When mixed in solutions by tweezers, the dark brownish diamond colloids turned
to look as sticky aggregates of finefibers. Fig. 1(a) shows a colloid viscous(b)(a)
enough to be pulled out from thesolutions. It stretched like algae on
chopsticks, but didn’t shrink like elastic
cords. Formation of fibrous aggregates
was observed also by an optical
microscope as demonstrated in Fig. 1(b).
The viscosity highly depended on thesurface groups of nanodiamonds as wellas on the polymerization degrees ofpolyacrylamides. The trends indicatedFig.1 Slimy nanodiamond fibers assembled withhydrogen bonds between amino groups
polyacrylamides. (a) The sticky aggregates ofof polyacrylamides and diamond
nanodiamonds in a polyacrylamide aqueous solution
surfaces playing a crucial role in thecan be pulled out from the solution. (b) Optical
microscopy demonstrates formation of fibers.
formation of those fibrous aggregates.
[1] M. Ozawa et al. Adv. Mater. 19, 1201 (2007).
[2] Y. Liang et al.ACS Nano 3, 2288 (2009).
[3] Y. Liang et al. J. Colloid Interface Sci. 354, 23 (2011).
Corresponding Author: T. Ito
Tel: +81-52-838-2410, Fax: +81-52-831-1170,
E-mail: 123434005@ccalumni.meijo-u.ac.jp- 27 -

2-8
Oxygen Adsorption Effect on Graphene–Metal Contact Characteristics○Yoshiaki Sato, Kazuyuki Takai, Toshiaki Enoki
Department of Chemistry, Tokyo Institute of Technology, Tokyo 152-8551, Japan
Understanding the electron transport properties through the graphene–metal contact is
crucial to realize high-performance graphene-based electronic devices. Recent studies haverevealed that the long-range band bending [1] and the resistive carrier injection [2] at thecontact region result in modification of carrier transport properties in graphene device, which
are attributed to the small density of state of graphene and the charge transfer interactions atgraphene–metal interface. Though these contact properties are inevitably affected by ambient
through the various interactions with gas species, details still remain unclear. In the present
study, we investigate the oxygen adsorption effect on the graphene–metal contact junction
properties comparing various kinds of metals for contact materials.
Graphene flakes were obtained by “sticky-tape” method on SiO2 (90 nm)/n++-Si substrate.
Attaching Cr (3 nm)/Au (30 nm) or Pd (25 nm) contacts to graphene, typical back-gatedfield-effect transistor (FET) structure was fabricated by means of photolithography. To
enhance the electron transport characteristics in the vicinity of the contact region, we usedshort-channel devices with graphene channel length of ≾ 1 μm. Conductivity measurements
were performed under high vacuum ( 10 Pa) at room temperature after fully eliminating
surface contamination by vacuum annealing of graphene device (200 °C, over 10 h).
The top panels of Fig. 1 show resistance () of graphene FETs as a function of gate-bias
voltage ( ). Irrespective of contact materials, the gate-bias voltage giving resistance peak(,) gradually shifts towards   0 direction from its original position (, ~0 V)
with increasing time of O2 gas exposure, which indicates that the adsorbed oxygen species
bring hole doping on graphene channel [3]. In contrast, asymmetric components in  vs 
curves,   Δ   Δ  with Δ    , , strongly depends on contact
materials (the bottom panels of Fig. 1). The positive (negative)  in Δ  0 region wasobserved for devices with Pd (Cr/Au) contacts before exposure to O2 gas, which is explainedby p-type (n-type) feature ofpristine Pd (Cr/Au) contacts.
However, the exposure to O2 gas
drastically changes all the metal
contacts to p-type, at much shortertime scale (< 1 min) than progressof hole doping to the graphene
channel. These results suggest theextreme sensitivity of graphene–
metal contact to oxygen adsorption.
[1] R. Nouchi & K. Tanigaki Jpn. J. Appl.
Phys. 50, 070109 (2011) [2] F. Xia et al.,Nat. Nanotechnol. 6, 179 (2011) [3] Y.
Sato, K. Takai & T. Enoki Nano Lett.11,
3468 (2011)
Corresponding Author: T. Enoki
Tel: +81-3-5734-2242
E-mail: enoki.t.aa@m.titech.ac.jp

Fig.1 The  vs  characteristics (top panels) and their odd
parts (bottom panels) for pristine and for O2-exposed ( 0.5, 1,
2, 4, 8, 16 min) devices attached with Pd or Cr/Au contacts.

- 28 -

2-9
Atomic structure determination of the graphene/sapphire interface
by normal incident X-ray standing wave spectroscopy○Shiro Entani1, Pavel B. Sorokin2, Pavel V. Avramov1, Manabu Ohtomo1, Yoshihiro Matsumoto1,
Liubov Yu. Antipina2, Ayumi Narita3, Norie Hirao3, Iwao Shimoyama3, Tetsuhiro Sekiguchi3,
Hiroshi Naramoto1, Yuji Baba3, and Seiji Sakai1
1Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, 319-1195, Japan
2
Technological Institute for Superhard and Novel Carbon Materials, Moscow, 142190,
Russian Federation
3
Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai, 319-1195, Japan
Direct growth of graphene films on insulating substrates is one of the most important
subjects for graphene-based nanoelectronics and spintronics. Despite such interest, the atomic
structure and interactions at the graphene/insulator interface have not been studied extensively.
Normal incident X-ray standing wave (NIXSW) spectroscopy is a powerful tool forinvestigating heterointerfaces, because the vertical arrangement of atoms on the single-crystal
surface can be determined precisely and element-specifically [1]. The vertical atomic
arrangement at the interface could be also a criterion for the interface interactions. In thisstudy, the interface between c-plane sapphire (-Al2O3(0001)) and single-layer graphene(SLG) directly grown on the surface has been studied by NIXSW spectroscopy.
The graphene growth on -Al2O3(0001) was performed in a vacuum quarts tube furnacewith a base pressure of 2  10-6 Pa. The SLG film was grown by exposing the -Al2O3(0001)
surface to methanol vapor in a pressure of 1000 Pa at the substrate temperature of 1273 K.
The NIXSW measurements were conducted at the BL-27A station (the details of themeasurement method are described in Ref. 2). The
NIXSW profiles were obtained by recording theintensities of the Al 1s, O 1s and C 1s photoelectrons as
a function of the photon energy, respectively.
Figure 1 shows the C 1s NIXSW profile for the C
atoms in SLG/-Al2O3(0001) and the vertical atomic
arrangement at the interface obtained by the NIXSW
measurements. The vertical location of the SLG layer isestimated to be 2.6 Å from the top of the -Al2O3(0001)
surface. This value lies between the interlayer distancein graphite (3.35 Å) and the distance between SLG and
the Ni(111) surface (2.12 Å) [3], suggesting rather
strong interaction at the SLG/-Al2O3(0001) interface.
The details and origins of the strong interface
interaction will be discussed with results of ab initio
calculations.
[1] D.P. Woodfuff et al. Phys. Rev. Lett. 58, 1460 (1987).
[2] S. Baba et al. e-J. Surf. Sci. Nanotech. 10, 69 (2012)[3] Y. Gamo et al. Surf. Sci. 374, 61 (1997)
Corresponding Author: S. Entani
Tel: +81-29-284-3802, Fax: +81-29-282-5939,
E-mail: entani.shiro@jaea.go.jp- 29 -

Fig. 1 C 1s NIXSW profile. The solidline represents the best-fit result(top),
and the schematic representation of
the atomic structure at SLG/-Al2O3(0001) interface (bottom).

2-10Integration of high performance graphene nanoribbon
field effect transistors○Toshiaki Kato, Rikizo Hatakeyama, and Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai 980-8579, Japan
Graphene nanoribbons combine the unique electronic and spin properties of graphene with atransport gap that arises from quantum confinement and edge effects. This makes them anattractive candidate material for the channels of next-generation transistors. Although nanoribbons
can be made in a variety of ways, the reliable site and alignment control of nanoribbons with highon/off current ratios remains a challenge. Plasma chemical vapor deposition (CVD) is known as
fruitful method for the structural-controlled growth and damage-free functionalization of nanocarbon materials such as carbon nanotubes (CNTs) [1-3] and graphene [4,5]. We have developed anew, simple, scalable method based on the advanced plasma CVD method for directly fabricating
narrow (~23 nm) graphene nanoribbon devices with a clear transport gap (58.5 meV) and a highon/off ratio (>104) (Fig.1). Since the establishment of our novel graphene nanoribbon fabrication
method, direct conversion of a Ni nanobar to a graphene nanoribbon is now possible. Indeed,graphene nanoribbons can be grown at any desired position on an insulating substrate without any
post-growthtreatment,
andRapid Heatinglarge-scale,
twoandthree
dimensional integration of graphene
nanoribbon devices should be
realizable [6].

Plasma CVD

Graphene nanoribbon

Graphenenanoribbon

23nm

Hydro carbon
Ni nanobar[1] T. Kato and R. Hatakeyama, J.
Am. Chem. Soc. 130, 8101 (2008).

Fig. 1: Schematic illustration of graphene nanoribbon growth process.

[2] T. Kato and R. Hatakeyama, ACS Nano 4, 7395 (2010).
[3] Z. Ghorannevis, T. Kato, T. Kaneko, and R. Hatakeyama, J. Am. Chem. Soc. 132, 9570 (2010).
[4] T. Kato, L. Jiao, X. Wang, H. Wang, X. Li, L. Zhang, R. Hatakeyama, and H. Dai,
Small 7, 574 (2011).
[5] T. Kato and R. Hatakeyama, ACS Nano 6, 8508 (2012).
[6] T. Kato and R. Hatakeyama, Nature Nanotechnology 7, 651 (2012).
Corresponding Author: T. Kato
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: kato12@ ecei.tohoku.ac.jp- 30 -

2-11
Transport Property of CVD Graphene across Domain Boundary◦Yui Ogawa,1 Kenji Kawahara,2 Masahiro Miyashita,1 Masaharu Tsuji1,2
Katsuyoshi Komastu,3 Kazuhito Tsukagoshi,3,* and Hiroki Ago1,2,*
1

Graduate School of Engineering Sciences, Kyushu University, Fukuoka 816-8580, Japan
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8580, Japan
3
International Center for Materials Nanoarchitectonics (WPI-MANA),
National Institute for Materials Science (NIMS) Ibaraki 305-0044, Japan

2

Chemical vapor deposition (CVD) growth of graphene on Cu catalyst has attracted aninterest for large area and low cost synthesis. The CVD graphene has multi domain structurewith a number of domain boundaries [1] which limit the physical properties [2,3]. Therefore,
it is important to investigate and control the domain structure of CVD graphene [4,5]. We
previously reported the orientation-controlled graphene produced by epitaxial CVD growthusing single-crystalline Cu and Co films [5-7]. And, we found that two neighboringgraphene domains merged with a different angle always give the Raman D-band at its domainboundary. On the other hand, two merged domains with the identical angle sometimes gaveno D-band at the domain boundary [8].
In this study, we investigated the transport properties of two merged domains in terms of
the effect of the domain boundary by fabricating graphene field effect transistor (FET).
Large hexagonal graphene domains with three main relative orientations, 0, 30, and -10
degrees were synthesized by CVD at 1075 °C on the hetero-epitaxial Cu(100) film. We
measured the carrier transport within a hexagonal domain (intra-domain) and over two
merged domains (inter-domain) for two types of merged domains; merged with the identicalangle and different angles. The inter-domain region showed higher resistivity than theintra-domain region irrespective of merged angle. This phenomenon was observed not only
for the domains with different angles but also for those with the identical angle. Our results
suggest that defects formed at the domain boundary cause electron scattering and reduce
carrier mobility. We will also discuss a relationship between Raman D-band and thetransport property.
References:[1] P. Y. Huang et al., Nature 469, 389 (2011). [2] H. S. Song et al., Sci. Rep. 2, 1 (2012). [3] C. M. Orofeo etal., Carbon 50, 2189 (2012). [4] Q. Yu et al., Nat. Mater. 10, 443 (2011). [5] Y. Ogawa et al., J. Phys. Chem.
Lett. 3, 2 (2012). [6] H. Ago et al., ACS Nano 4, 1414 (2010). [7] B. Hu et al., Carbon 50, 57 (2012). [8] Y.
Ogawa et al., The 43rd Fullerenes-Nanotubes-Graphene General Symposium, 3P-8
Corresponding Authors (H. Ago : ago@cm.kyushu-u.ac.jp, K. Tsukagoshi : TSUKAGOSHI.Kazuhito@nims.go.jp)- 31 -

3-1
Fabrication of CMOS inverters using semiconducting
SWCNTs encapsulating n- and p-type dopant molecules○Yasuhiro Ito1,2, Shunjiro Fujii1,2, Maki Shimizu1,2, Takeshi Tanaka1, Hiromichi Kataura1,2
1

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki, 305-8562, Japan
2
Japan Science and Technology Agency, CREST, Kawaguchi, Saitama, 330-0012, Japan
A thin film transistor (TFT) using semiconducting single-wall carbon nanotube(s-SWCNTs) is promising for low-cost and high-performance printed electronics applications.
For the practical applications to logic circuits such as a complementary metal-oxide
semiconductor (CMOS) type operation, n- and p-type s-SWCNTs are both necessary. It is
known that a chemical doping can fabricate n- and p-type s-SWCNT TFTs. However, theexternal doping requires additional patterning process that is not suitable to the printed
electronics. In this work, we tried carrier control of TFT channel by an internal chemical
doping using molecular encapsulation into s-SWCNTs.
Semiconducting APJ-type SWCNTs (φ = ~1.4 nm) were purified by a gel column
chromatography method [1]. N- and p-type s-SWCNT inks using aqueous sodium
deoxycholate suspensions were prepared by inserting cobaltocene and F4TCNQ(2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) molecules into the s-SWCNTs,
respectively. Then n- and p-type TFTs were successfully prepared on SiO2/Si substrates with
Ti/Au electrode [2]. Figure 1a and b show the transfer characteristics of cobaltocene and
F4TCNQ encapsulated s-SWCNT-TFTs measured under vacuum, respectively. These TFTs
showed almost n- and p-type transfer characteristics. These results suggest that electron andhole carrier densities in s-SWCNTs can be controlled by molecular encapsulation.
Furthermore, the CMOS inverter operation was confirmed (figure 2). Typical voltage gain
was 10. To our knowledge, this result is the world-first demonstration of CMOS inverter
operation fabricated simply using molecular encapsulating s-SWCNTs.
-5

-6

10

Ids / Ab)

Cobaltocene

F4TCNQ

-8

10

-9

10

12
10

9
6

5

Voltage gain

-7

10

a)

Vout / V

10

3

-10

10

0

-11

10

-40

-20

0

Vg / V

20

40

-40

-20

0

Vg / V20

40

Fig.1 Transfer characteristics of the (a) cobaltoceneand (b) F4TCNQ encapsulated s-SWCNT-TFTs
under vacuum (7.4×10-6 Torr). The channel length
and width are 100 and 200 μm, respectively. The
drain-source voltage is -1 V.

-25

0
-20

V /V

-15

-10

in

Fig.2 Output characteristics of the CMOS inverter
constructed with molecular encapsulated s-SWCNTTFTs. The power supply voltage (Vdd) was 12 V.
Voltage gain of the devices was around 10.

[1] Y. Miyata et al., Nano Res., 4, 963 (2011). [2] S. Fujii et al., Phys. Stat. Sol. B 248, 2692 (2011).
Corresponding Author: Hiromichi Kataura
E-mail: h-kataura@aist.go.jp Tel: +81-29-861-2551, Fax: +81-29-861-2786- 32 -

3-2
Micro-Honeycomb Network Structure of Single-Walled Carbon Nanotube
Film for Solar Cells
żKehang Cui 1, Takaaki Chiba 1, Hidenori Kinoshita 1, Pei Zhao 1, Theerapol Thurakitseree 1,
Taiki Inoue 1, Erik Einarsson 2, Shohei Chiashi 1, Shigeo Maruyama 1
1
2

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Global Center of Excellence for Mechanical Systems Innovation, The University of Tokyo,
Tokyo 113-8656, Japan

2

J (mA/cm )To bridge the superior nanoscale electrical, optical, thermal and mechanical properties ofsingle-walled carbon nanotubes (SWNTs) with corresponding device-level performance, themicro/macroscale morphologies of SWNTs are of great importance. We propose here aself-organized micro-honeycomb network structure of single-walled carbon nanotubes(SWNTs) obtained by water vapor treatment of as-synthesized vertically aligned SWNTs(VA-SWNTs) [1] for a SWNT/n-Si heterojunction solar cell [2-6]. Dependence ofphotovoltaic conversion efficiency (PCE) on the nanotube network structure was examined.
The VA-SWNTs were synthesized by the standard alcohol-catalytic CVD method with
Co/Mo dip-coated on Si/SiO2 substrate [1]. The micro-honeycomb structured film was
obtained by exposing the VA-SWNT film to water vapor. Changing the exposure conditons
resulted in different morphologies (Fig. 1).
Figure 2 shows current density and voltage (J-V)
characteristics of the SWNT-Si heterojunction solar
cells. The optimal photovoltaic conversion efficiency(PCE) under AM1.5 is 5.04%, with a fill factor of
59.2%. The open-circuit voltage and short-circuitcurrent are 0.53V and 16.06 mA/cm2, respectively.
This showed a substantial improvement comparedwith previously reported results [3-6]. We attribute theimprovement to the self-organizing micro-honeycomb
network, in which the random SWNTs in good contact Figure 1 (a, b, c) SEM morphologies ofwith the Si serve as the charge carrier separation self-organizing
micro-honeycomb
networks
of
SWNTs;(d)enlarged image
interface, and the artery-like condensed SWNTs serveofcondensed
SWNTs
bundlesfrom c.
as hole collector and transport highway.
20
Part of this work was financially supported byrandomGrant-in-Aid for Scientific Research (22226006,
honeycomb
quasi- honeycomb
19054003), JSPS Core-to-Core Program, and Global
COE Program 'Global Center for Excellence for0
Mechanical Systems Innovation'.
[1] Y. Murakami et al., Chem. Phys. Lett., 385 (2004) 298.
[2] Y. Jia et al., Adv. Mat., 20 (2008) 4594.
[3] P. Wadhwa et al., Nano Lett., 10 (2010) 5001.
[4] D. Kozawa et al., Appl. Phys. Express, 5 (2012) 042304.
[5] P. Ong et al., Nanotechnology, 21 (2010) 105203.
[6] Y. Jia et al., Mater. Res. Bull., 45 (2010) 1401.
Corresponding Author: S. Maruyama
Tel: +81-3- 5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 33 -- 20

0Bias (V)

0.4

Figure 2 J-V characteristics of SWNT
devices with random, honeycomb andquasi-honeycob morphologies underdark and AM1.5

3-3
Application of Vertically Aligned CNTs for Electrodes of PEMFCżShigeaki Murata, Masahiro Imanishi, Shigeki Hasegawa, Ryoichi Namba
Fuel Cell System Development Division, Toyota Motor Corporation, Susono 410-1193, JapanThe fabrication process of the conventional fuel cell electrode is basically not changed
from the beginning of 1990s [1]. It is ink-based process and the structure of the electrodes,
such as thickness, porosity or pore size, is fixed through the process condition. An alternative
structure and process is desired in which the structure can be designed and controlled. We
successfully developed an electrode of polymer electrolyte membrane fuel cells making highcurrent density operation possible using vertically aligned carbon nanotubes (CNTs) as thecatalyst support, and also prepared membrane electrodes assemblies (MEAs) applicable sizefor vehicle use. Fig. 1 shows the concept of the electrodes. The structure of the electrodes
improved the mass transport of the reactance in electrodes and made it possible to perform
2.6A/cm2 @0.6V with 0.1mgPt/cm2 @Cathode. The mechanism to improve the masstransport was concluded that the continuity of the pore, no agglomeration of catalyst supports
by SEM observation (Fig.2) and better contact between catalyst layer and micro porous layer
by evaluation tests of the elasticity of the CNTs.
CNTs were grown on stainless steel substrate by CVD method developed by Hitachi Zosen
Corporation [2]. The specification of the CNTs is listed in Table 1. Platinum was deposited on
the CNTs by conventional impregnation/H2-reduction method. The solution of the Pt salt wasconverted from water base acid to ethanol. After the platinum deposition, the Pt/CNTs wascoated with ionomer by applying an ethanol-diluted ionomer solution and drying it. The watercontent of the ionomer solution should be decreased lower than 2%. MEAs were fabricated by
hot-pressing the ionomer coated Pt/CNTs electrodes to electrolyte membrane at 140 deg.C
and peeling off the substrate. It was the key point to apply the wavy CNTs having resistanceagainst agglomeration and to change the solutions to lower surface tension ones. The CNTs
compressed in the cells were no more vertically aligned (Fig.2). It was concluded that theproperty vertically aligned served an important function in MEA fabrication process but was
not critical for the cell performance.
Table 1. Specification of CNTs.

Fig. 1. Concept of VACNT Electrodes.

Fig. 2. Cross Section of Electrodes.
Left: Conventional, Right: CNTs.

Length40-60ȝm

Tortuosity

2

Diameter

20nm

Number Density

3×109/cm2

Average Distance

200nm

Weight0.3mg/cm2

SSA
200m2/g[1] M. S. Wilson
and S. Gottesfeld, J. Appl. Electrochem., 22 (1992) 1-7.
[2] H. Shioyama, Y. Yamada, Y. Sairyo: TANSO, 209(2003), 171-173 (in Japanese).
Corresponding Author: S. Murata
Tel: +81-55-997-7987, Fax: +81-55-997-7120,
E-mail: shigeaki@murata.tec.toyota.co.jp- 34 -

3-4
Electromigration suppression in copper by carbon nanotubes : A
mechanistic insight○Chandramouli Subramaniam1, Takeo Yamada1,2, Don N. Futaba1,2, Kenji Hata1,2 and Motoo
Yumura1,2
1Technology Research Association for Single Wall Carbon Nanotubes (TASC), Central 5,
1-1-1 Higashi, Tsukuba 305-0046, Japan.
2
National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1
Higashi, Tsukuba 305-0046, Japan.
Recently, we reported a 100 times enhancement in the current-carrying-capacity of copperby using super-growth carbon nanotubes (CNT). Such high current-carrying-capacity offers
diverse areas of applications ranging from miniaturized electronics components to heavy dutytransmission cables. Here, we present mechanistic insights to explain the higher
current-carrying-capacity of CNT-Cu composite compared to any metal.
First, we experimentally estimate the activation energy for Cu diffusion in CNT-Cu
composite, from Black’s theory of electromigration. The value estimated thus for CNT-Cu
composite (2.1 eV) corresponds with the activation energy of Cu lattice/bulk diffusion in pureCu (2.0 – 2.3 eV). This is also higher than Cu diffusion value at surface (~1.0 eV) andgrain-boundaries (~1.2 eV) in pure Cu. Thus, we interpret that the CNT present in CNT-Cu
composite suppresses the diffusion of Cu at surface and grain boundaries (easiest failure
pathways). Cu bulk diffusion being the most difficult pathway (requiring the highest
activation energy) provides the CNT-Cu composite with higher stability againstelectromigration and consequently higher current-carrying-capacity.
Second, from the activation energy analysis, we estimate the diffusion coefficient, D*
which is related to the ease of electromigration.
  Ea 
D*  D0 exp kT 
where, D0 is the diffusion coefficient at infinity (~10-8 cm2/s), Ea is the activation energy, k theBoltzmann constant and T the temperature. The estimated D* of Cu in the CNT-Cu composite(3.7 x 10-31 cm2/s) by bulk diffusion was 104 times lower than that of copper (2.2 x 10-27 cm2/s),
which should significantly contribute to the observed high current-carrying-capacity.
Finally, we numerically estimate the maximum-allowable current through the CNT-Cu
composite before material-failure from Joule-heating. The current-carrying-capacity estimatedthus (1200 MA/cm2) is in good agreement with the experimentally observed value (600
MA/cm2), validating our understanding.
In conclusion, we understand that the CNT in CNT-Cu composite plays a significant role in
suppressing Cu diffusion and providing it with superior electrical properties than metals. Thiseffect is analogous to the well-known practice alloying steel with carbon for strengthening.
Corresponding Author: Kenji Hata
Tel: +81-298614654, Fax: +81-298614851,
E-mail: kenji-hata@aist.go.jp- 35 -

3-5
First-Principles Simulation on Thermoelectric Power of SWNT Buckypapers○Teppei Kato1, Shinji Usui2, Takahiro Yamamoto1,3
1

Dept. of Electrical Engineering, Tokyo Univ. of Science, Chiyoda-ku, Tokyo 102-0073, Japan

2

QuantumWise Japan KK, Shinjuku-ku, Tokyo 160-0023, Japan

3

Dept. of Liberal Arts, Tokyo Univ. of Science, Chiyoda-ku, Tokyo 102-0073, Japan

An SWNT buckypaper is expected to be a ubiquitous thermoelectric material with large
thermoelectric power factor. Recent experiments reported that the temperature dependence anddoping dependence of Seebeck coefficient (thermoelectric power) of SWNT buckypapers are
essentially different from those of an individual SWNT [1,2]. However, such unusual behaviors ofSeebeck coefficient of SWNT buckypapers have not been understood yet. In this study, we clarify
the Seebeck coefficient of SWNT buckypapers by performing the first-principles simulation basedon density-functional theory and the none-equilibrium Green’s function method [3]. We consider thatthe above unusual behaviors originate from the contacts between SWNTs, and we set a simulation
model consisting of the laterally-contacted SWNTs as shown in Fig.(a). The obtained results are as
follows.
(1) Seebeck coefficients exhibit larger value of the orderof 100μV/K at the room temperature.

(a)(2) The sign of Seebeck coefficient can change at the
low temperature.
(b)(3) The temperature dependence of Seebeck coefficientis sensitive to small changes of the chemical
potential.
These simulation results are in good agreements withexperimental results and can be understood in terms ofMott’s formula.
References[1] Hone et al., Phys. Rev. Lett. 80, 1042 (1998).
[2] Bradley et al., Phys. Rev. Lett. 85, 4361 (2000).
[2] http://quantumwise.co.jp/
Corresponding Authors: Takahiro Yamamoto
TEL&FAX: +81-3-5213-0990
E-mail: takahiro@rs.tus.ac.jp- 36 -

Fig.: (a) (8,0)/(8,0)SWNT contact,(b) T-dependence of Seebeck coefficient.

3-6Influence of Carbon nano-inclusion dimensionality in the thermal
conductivity enhancement of aqueous and non-aqueous fluidsӑ Sivasankaran Harish1, Kei Ishikawa1, Erik Einarsson1, 2, Shohei Chiashi1,

Junichiro Shiomi1, Shigeo Maruyama1

1

Department of Mechanical Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
Tokyo 113-8656, Japan.

2

Global Center of Excellence for Mechanical Systems Innovation, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.

In the present work we systematically investigate the thermal conductivity enhancement of water,
ethylene glycol and phase change alkane n-Octadecane in the presence of spherical, onedimensional and two-dimensional carbon nano inclusions. Single-walled carbon nanohorns,
single-walled carbon nanotubes and exfoliated graphite nanoplatelets were used as the nanoinclusions. Thermal conductivity measurements were carried out using a transient hot-wire
technique for different temperature and loadings of nano inclusions. It was found that twodimensional inclusions lead to higher thermal conductivity improvement followed by onedimensional and spherical inclusions. Solidification of n-Octadecane resulted in higher thermal
conductivity enhancement in the solid state compared to the liquid state irrespective of thedimensionality of the nano inclusion. In the solidified state carbon nanotubes outperformedgraphite nanoplatelets and carbon nanohorns due to their ability to form percolating networks at
low loading. Viscosity measurements show that the viscosity of suspensions increases linearlywith increasing nano-inclusion loading. The potential mechanism behind the thermal
conductivity enhancement and the critical yet detrimental role of thermal boundary resistance inlimiting the heat conduction is discussed, and the experimental results are compared withclassical heat conduction models and other results in the literature.

[1] S. Harish et al. Int. J. Heat Mass Transfer, 55, 3885 (2012)[2] S. Harish et al. Int. Mater. Express, 2, 213 (2012)

Corresponding Author: Prof. Shigeo Maruyama
Tel: +81-3-5874-6421
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 37 -

3-7
First Principles-Based Estimate of the Critical SWCNT Length for Raman
D and G Band Intensity Inversion○Yoshifumi Nishimura1, Henryk A. Witek2, Stephan Irle1
1

Department of Chemistry and Institute of Transformative Bio-Molecules, Nagoya University,
Nagoya 464-8602, Japan2
Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung
University, Hsinchu 30010, Taiwan

We present theoretical prediction of physical and spectroscopic properties ofhydrogen-terminated single-walled carbon nanotube (SWCNTs) model systems containing up
to ~1000 atoms on the basis of the self-consistent-charge density-functional tight-binding(SCC-DFTB) [1] method. Employing our implementation of analytical second-ordergeometrical derivatives [2] and specifically developed parameter sets [3], this approximate
density functional theory (DFT) method has already demonstrated the accurate calculations ofvibrational frequencies and infrared (IR) and Raman intensities for fullerenes [4] andnanodiamonds [5] in excellent agreement with standard DFT for the smaller model systems.
Here, evolution of SWCNT molecular models withrespect to elongation of tube length and different
diameter size is focused on.
For example, simulations of Raman spectra forarmchair (n, n) SWCNTs with n = 3 to 7 at a fixed
length of 8 nm (largest model: C924H28) confirm thepreviously found quantitative inverse relationshipbetween tube diameter and radial breathing mode(RBM) frequency [6] (See Fig. 1). Fig. 2 shows thelength dependence of Raman intensities forhydrogen-terminated (5,4) SWCNTs with lengths
ranging from 1 to 10 nm, i.e. C80H18 to C740H18,
Fig.1 Correlation between SCC-DFTB
harmonic
frequency
andinverseindicating the critical SWCNT length for Raman D
relationshipofdiameter
[6]
for
RBM
to G band intensity inversion is already observed
mode.
around 1 nm.
In our presentation, other properties – IR spectra,
electronic and vibrational density of states, andHOMO-LUMO gaps of the various SWCNT finite
systems will be discussed together with thecomparison of corresponding bulk quantities.
[1] M. Elstner et al., Phys. Rev. B, 58, 7260 (1998).
[2] H. A. Witek et al., J. Chem. Phys., 121, 5163, (2004).
[3] E. Małolepsza et al., Chem. Phys. Lett., 412, 237, (2005).
[4] H. A. Witek et al., J. Chem. Phys., 125, 214706, (2006).
[5] W. Li et al., ACS Nano, 4, 447, (2010).
[6] A. Jorio et al., Phys. Rev. Lett., 86, 1118, (2001).
Corresponding Author: S. Irle
Tel: +81-52-747-6397, Fax: +81-52-747-6397
E-mail: sirle@chem.nagoya-u.ac.jp- 38 -

Fig.2 SCC-DFTB simulated Raman
spectra of hydrogen-terminated (5,4)
SWCNTs with increasing tube lengthfrom 1 to 10 nm.

3-8
Exciton effects on coherent phonon spectroscopy of carbon nanotubes○ Ahmad R.T. Nugraha, Eddwi H. Hasdeo, Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
In this work, we consider ultrafast carrier dynamics and coherent phonons in carbon nanotubes bytaking into account exciton effects. In an ultrafast pump-probe spectroscopy, femtosecond laser pumppulses applied to a SWNT sample induce photo-excited electron-hole pairs bound by the Coulombinteraction, called as excitons [1]. Shortly after the exciton relaxations to the lowest exciton states(~10 fs), the coherent lattice vibrations are generated by the exciton-phonon interactions. The coherent
phonon motions can be observed as oscillations of either the differential transmittance or reflectivityof the probed light as a function of delay time between pump and probe pulses. By taking a Fouriertransformation of the oscillations in the light transmission or reflection with respect to time, we obtaincoherent phonon spectra as a function of phonon frequencies.The most easily observed coherent
phonon modes in SWNTs are the so-called radial breathing mode, in which the tube diameter caninitially expand or contract depending on the family classification and excitation energies [2].
Previously, we developed a microscopic theory for the generation and detection of coherent phonons
in SWNTs within an extended tight binding model and effective mass theory [3]. We found that such
expansion and contraction simply originate from k-dependent electron-phonon interaction in SWNTs.
However, we neglected the presence of excitons in SWNTs which have a strong binding energy evenat room temperature [1]. Exciton effects should give the Gaussian-like driving force in the real spaceinstead of the constant driving force considered previously. Therefore, we modify the coherent phonon
equation motion by including the spatial dependence based on a periodic Gaussian structure. The
equation of motion for the coherent phonons is modeled phenomenologically in terms of theKlein-Gordon equation, from which we can solve for the oscillations amplitudes as a function of space
and time. By taking an average of the calculated amplitudes per nanotube length, we obtaintime-dependent coherent phonon amplitudes that resemble homogeneous oscillations observed in thepump-probe experiments. This leads to a hypothesis that the pump-probe measurements are only able
to see a spatial average of coherent phonon oscillations over the wavelength of light in carbon
nanotubes. We then calculate the time-dependent absorption spectra as a result of macroscopic atomic
displacements induced by the coherent phonon oscillations and thus reproduce the oscillation featureof the transmission or reflectance in the pump-probe spectroscopy experiments.
[1] J. Jiang et al., Phys. Rev. B 75, 035405 (2007).
[2] J.-H. Kim et al., PRL 102, 037402 (2009); Y.-S. Lim et al., ACS Nano 4, 3222-3226 (2010).
[3] G. D. Sanders et al., PRB 79, 205434 (2009); A. R. T. Nugraha et al., PRB 84, 174302 (2011).
Corresponding Author: A. R. T. Nugraha
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: nugraha@flex.phys.tohoku.ac.jp- 39 -

3-9

High-temperature in-situ TEM Observation of Zipper-like Wall-to-Wall
Coalescence of Double-Wall Carbon Nanotubes○ Sihan Zhao, Ryo Kitaura, Yasumitsu Miyata and Hisanori Shinohara
Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan
We report, for the first time, the detailed in-situ TEM observation of wall to wallcoalescence[1,2] of double-wall carbon nanotubes (DWCNTs) at very high temperature(>2000˚C). The present observation is achieved by developing a high-temperature compatible
TEM sample heating holder equipped with a micro-sizedcarbon nanotubes (CNTs) network heater (Figure 1). This
micro-sized CNT network can heat a sample up to extremely
high temperature (up to 3000˚C) while minimizing spatial driftof the nanotube samples induced by the heating.
Figure 2 shows a time sequence on TEM images of abundle of DWCNTs observed at 2,000 ˚C. A single
larger-diameter DWCNT is formed at the final stage
through a zipper-like mechanism of

Figure 1. working principle of newly
developed technique for in-situ
heating TEM observationwall-to-wall coalescence between two
individual outer shells and two individual
inner shells. The time sequential TEM
images obtained throughout the reaction
suggests the presence of the Stone-Wales
type transformation, which provides
insight on thermal reconstruction processof the nanocarbon materials.
[1] M. Terrones et al. Science 2000, 288, (5469),
1226-1229[2] M. Endo et al. Nano Letters 2004, 4, (8),1451-1454.
Corresponding Author: R. Kitaura
Tel: +81-52-789-2477
E-mail: r.kitaura@nagoya-u.jp&
H. Shinohara
Tel: +81-52-789-2482
E-mail: noris@cc.nagoya-u.ac.jp

Figure 2. selective time sequential TEM images (withstructural models) showing the main reaction stages ofwall to wall coalescence of DWNTs- 40 -

3-10
A hypothetical intermediate structure in growth of metallofullerenes○Yohji Achiba, Takeshi Kodama, Kenro Hashimoto and Haruo Shiromaru
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
The isolation and characterization of metallofullerenes has been one of the biggest issues
in the fullerene science and technology soon after the discovery of C60 in 1985. Actually, after
the first isolation and purification work of La@C82 with a bulk quantity in 19931), a lot of
isolation works on metallofullerenes have been appeared in the literatures. Some of their cage
structures have been well characterized by 13C NMR in solution. Furthermore, during the last
10 years, a single crystal X-ray diffraction method has been successfully introduced to carryout the crystallographic identification of a particular isomer with a particular size ofmetallofulerenes, and so far, over 36 different cage structures have been examined andidentified2). On the basis of these experimental progresses in determining cage structures, inthe present work, we are intended to clarify Òwhat causes the selection of a particular cage
structure in the metallofullerene growth processÓ.
In order to construct a growth model for such a selective formation of a particular isomerstructure, first, we have to consider the reason why a particular isomer structure isexperimentally isolated and stabilized. There might be at least four key-factors by which someof metallofullerene isomers formed in the soot are actually experimentally isolated andidentified: 1) Energetics (stability of Òa particular charged stateÓ of thecage network with aparticular size), 2) chemical stability of the particular charged state (large HOMO-LUMO gap
is better, preventing from polymerization or other reactions), 3) 5/6 network structure
superiority (closely related to network growth rate andstability), and 4) cage size (non IPR cage structure
becomes to be much more important in the smaller size
range). These four factors are definitely more or lessrelated with each other even on the way of network
forming process, but in the present work we willemphasize the important role of specific network
structures of the intermediate precursors for the ÒreallyÓ
isolated fullerenes.
Figure 1 shows one of the typical 5/6 network
consisting of 4 pentagons and 15 hexagons with 48
carbons. An interesting aspect of this particular 5/6
Fig.1 A hypothetical intermediate structure
network should be described by the fact that among 18
structurally determined M@C2n, 12 kinds of M@C2n, metallofullerenes with different sizes
and structures commonly possess this patch in their 5/6 networks. Furthermore, our recent
semi-empirical calculations (AM1) on over ten different kinds of C48 molecules suggest thatthe structure shown in Fig.1 is one of the most energetically stable species as a di-anion
among them. We will discuss in more detail on the plausible intermediate structures for theÒrealÓ growth of metallofullerenes in terms of both theoretical and experimental points.
[1] K. Kikuchi et al., Chem. Phys. Lett., 216, 67 (1993).
[2] see recent published literatures by Prof. T. Akasaka and Prof. A. Balch research group.
Corresponding Author: Y. Achiba
Tel: +81-42-677-2534, Fax: +81-42-677-2525,
E-mail: achiba-yohji@tmu.ac.jp- 41 -

3-11
Structure of Thulium and Carbon Cluster Encapsulated in Low-Symmetry
C82(Cs(6)) Fullerene Cage by Single Crystal X-ray Diffraction○Yuki Sado1, Shinobu Aoyagi2, Noriko Izumi1, Ryo Kitaura1, Tim Kowalczyk1, Jian Wang1,
Stephan Irle1, Eiji Nishibori3, Kunihisa Sugimoto4, and Hisanori Shinohara1
1

Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya
464-8602, Japan2
Department of Information and Biological Science, Nagoya City University, 467-8501,
Japan
3
RIKEN RSC-RIGAKU Collaboration Center, RIKEN SPring-8 Center, RIKEN 1-1-1 Kouto,
Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan
4
Spring-8/JASRI, Kouto, Sayo, Hyogo 679-5198, Japan
Endohedral metallofullerenes are among the most attractive molecules because of theirunique structural and electronic properties1. These properties have been found to depend
strongly on the encapsulated species and carbon cage structure. Detailed structural analyses ofendohedral metal atoms and clusters are essential to understand the properties of endohedral
metallofullerenes.
For a deep understanding of the endohedral structure of metal atom(s) encapsulated,systematic structural studies with the same cage structure but with different number ofendohedral atoms provide crucial knowledge. C82 based endohedral fullerenes, Mx@C82 (M:metal), are the most feasible metallofullerenes for this purpose since many C82 based
metallofullerenes, including mono-, di-, tri-metal and the corresponding metal-carbide
endohedral fullerenes, have been synthesized and structurally characterized during the past acouple of decades. Recently, a structure of divalent mono-metallofullerene Sm@C82(Cs(6))
has been synthesized and structurally characterized2. The cage structure of Sm@C82(Cs(6)) is
the same as that of Er2@C82(Cs(6)) reported by Olmstead et al3. Therefore, the systematic
production and structural characterizations of a series of C82 based metallofullerenes with thesame fullerene cage is a promising route toward a deep understanding of the structural
stability of endohedral metallofullerenes.
Here, we report single-crystal synchrotron X-ray structure analyses of Tm2 @C82(I) andTm2C2 @C82(I), both of which have a low-symmetry C82(Cs(6)) cage. The single-crystal X-ray
diffraction (XRD) experiments utilizing the third-generation synchrotron radiation with highcounting statistics were performed at BL02B1 in SPring-8 (Hyogo, Japan). The structure
analysis involving disorder of carbon cage orientation reveals that the Tm atoms and C2 unit
statically occupy specific positions inside the low-symmetry C82(Cs(6)) cage. The resultant
molecular structure is also energetically stable according to quantum chemical calculations.
The determined structure can also be compared to that of the mono-metallofullerene,
Tm@C82(Cs(6)).
1.
H. Shinohara, Rep. Prog. Phys., 2000, 63, 843-892.
2.
H. Yang, H. Jin, X. Wang, Z. Liu, M. Yu, F. Zhao, B. Q. Mercado, M. M. Olmstead3.

and A. L. Balch, J. Am. Chem. Soc., 2012, 134, 14127-14136.
M. M. Olmstead, A. de Bettencourt-Dias, S. Stevenson, H. C. Dorn and A. L. Balch, J.
Am. Chem. Soc., 2002, 124, 4172-4173.

- 42 -

3-12
Photoinduced electron transfer in supramolecules
between Li+@C60 and chlorin derivatives○Kei Ohkubo, Yuki Kawashima, Kentaro Mase, Shunichi Fukuzumi
Department of Material and Life Science, Graduate School of Engineering, Osaka University,
ALCA, Japan Science and Technology Agency, Suita, Osaka 565-0871, Japan
Fullerenes and porphyrinoids that have highly delocalized π systems are suitable for efficientelectron transfer because the uptake or release of electrons results in minimal structural andsolvation changes upon electron transfer.[1] Thus, they are suitable electron donor andacceptor for formation of the long-lived charge separated states. Therefore, there have been
many reports of photoinduced charge separation in porphyrin-fullrene linked- andsupramolecular systems. In natural systems, however, reduced porphyrins, namely chlorins
are the electron donor pigments of the electron transfer processes. It is of great interest to
examine the use of chlorophyll-like molecules such as chlorins. We report herein constructionof chlorin/fullerene supramolecular system and photoinduced charge separation in a polarbenzonitrile (PhCN) solution.
UV-vis absorption spectrum of anK!
anionic zinc chlorin (ZnCh– Bu4N+) in(1)!
+!
PhCN was changed upon addition of acationic lithium encapsulated C60(Li+@C60 PF6–). The formation constant
Li+@C60 !
ZnCh–/Li+@C60 !
ZnCh– !
(K) was determined from the titration to
be 1.9 × 104 M–1. This result exhibits that strong supramolecular binding between ZnCh– andLi+@C60 occurs by ionic interaction in PhCN (eq 1). The transient absorption spectra ofZnCh–/Li+@C60 supramolecular complex were measured by nanosecond laser flash photolysis.
The absorption band of the excited state of ZnCh– (3[ZnCh–]*) decays with increasing theabsorbances at 790 and 1035 nm, which can be assigned to [ZnCh–]•+ and Li+@C60•–,
respectively.[2-4] It clearly indicating the formation of the CS state by photoinduced electrontransfer from 3[ZnCh–]* to Li+@C60. The lifetimes of the triplet CS state in the supramolecularcomplex is determined to be 170 µs at 298 K. The quantum yield of the CS state isdetermined to be 0.62.
[1] S. Fukuzumi and K. Ohkubo et al. Chem. Eur. J. 9, 1585 (2003).
[2] S. Fukuzumi and K. Ohkubo et al. J. Am. Chem. Soc. 133, 15938 (2011).
[3] K. Ohkubo, Y. Kawashima, S. Fukuzumi Chem. Commun. 48, 4314 (2012).
[4] Y. Kawashima, K. Ohkubo, S. Fukuzumi J. Phys. Chem. A 116, 5942 (2012).
Corresponding Author: K. Ohkubo
Tel: +81-6-6879-7369, Fax: +81-6-6879-7370,
E-mail: ookubo@chem.eng.osaka-u.ac.jp- 43 -

3-13
Ultraviolet Photoelectron Spectra of Gd3N@C80 and Er3N@C80
żTakafumi Miyazaki1, Yusuke Nakanishi3, Yuki Sasaki3, Hiroyuki Niwa3, Shoko Noda3,
Tatsuhiko Nishi2, Tomona Ohta1, Hisanori Shinohara3 and Shojun Hino1
1
Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan
2
Institute for Molecular Science, Okazaki, 444-8585, Japan
3
Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
We have been measuring ultraviolet photoelectron spectra (UPS) of endohedral
fullerenes to elucidate their electronic structure. Here, we present the UPS of Gd3N@C80 and
Er3N@C80 and compare them with those of M3N@C80 (M=Sc, Tm, Dy) [1-3].
The UPS of Gd3N@C80 and Er3N@C80 are shown in Figure 1. These spectra were
measured using a synchrotron radiation light source. The UPS of Sc3N@C80, Tm3N@C80 and
UPS onset energy of Er3N@C80 is 1.2 eV,
which is the smallest among them. The UPSof deeper valence band region (BE>5eV) of
these endohedral fullerenes shows fairly goodcorrespondence. The upper valence band
UPS (BE<5eV) of Er3N@C80, Gd3N@C80 and
Dy3N@C80 resemble each other, but they are

Photoelectron counts

Dy3N@C80 were also shown in the figure. The[1]

Sc3N@C80

E

slightly different from those of Tm3N@C80
and Sc3N@C80 particularly in their peakD

positions and relative intensity. Comparison

C

B

A

of the UPS with DFT calculated simulation[2]

Tm3N@C80[3]spectra indicates that the structure of

Dy3N@C80

E

entrapped Sc3N and Tm3N is flat as wasDreported [1, 2] and that of Dy3N@C80 isC

Gd3N@C80
B

A

triangular [3]. From the analogy of the UPS
Er3N@C80

features the structure of the entrapped Gd3N
and Er3N cluster might be triangular.

6

4

2

0

[1] L. Alvarez et al., Phys. Rev. B, 66,

Binding Energy / eV

035107 (2002). [2] X. Liu. et al., ibid. 72,

Figure 1. The UPS of M3N@C80(M=Er,
Gd, Dy, Tm, Sc) endohedral fullerenes.

085407 (2005), [3] H. Shiozawa et al., ibid. 72,
195409 (2005),

Corresponding Authors: T. Miyazaki, E-mail: miyazaki@eng.ehime-u.ac.jp, phone: 089-9279930; S. Hino, E-mail: hino@eng.ehime-u.ac.jp, phone: 089-927-9924.

- 44 -

࣏ࢫࢱ࣮Ⓨ⾲
Poster Preview

1P – 1 㹼 1P – 47
2P – 1 㹼 2P – 46
3P – 1 㹼 3P – 46

1P-1
Optical coupling of air-suspended carbon nanotubes to silicon microdisk○Saneyuki Imamura, Ryosuke Watahiki, Ryohei Miura, Yuichiro K. Kato
Institute of Engineering Innovation,The University of Tokyo, Tokyo 113-8656, Japan
Optical coupling of individual air-suspended single-walled carbon nanotubes towhispering-gallery modes in silicon microdisk resonators is studied. We fabricate silicon
microdisks with diameters of ~3 µm on SiO2 supporting posts from silicon-on-insulator
substrates, and synthesize carbon nanotubes from patterned catalysts by alcohol chemical
vapor deposition to suspend them onto the microdisks. Interactions between carbon nanotubes
and evanescent fields of microdisk modes are investigated by microspectroscopy at room
temperature. We observe microdisk modes with quality factors of ~3000 at wavelengths
longer than those of silicon emission, even at positions that are a few micrometers from thesuspended carbon nanotubes. In addition, as microdisk modes also exist at excitation laser
wavelengths, the photoluminescence intensity can be resonantly enhanced by tuning the laser
wavelength to those modes.
This work is supported by SCOPE, KAKENHI, The Asahi Glass Foundation, andPhoton Frontier Network Programs of MEXT, Japan. The devices were fabricated at theCenter for Nano Lithography & Analysis at The University of Tokyo.
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 45 -

1P-2
X-ray diffraction profile of highly purified (6, 5) SWCNTs
żShin Tadera1, Haruka Kyakuno1, Yusuke Nakai1, Kazuhiro Yanagi1, Yasumitsu Miyata2,
Hiromichi Kataura2,3, Yutaka Maniwa1,3
1

Department of Physics, Faculty of Science, Tokyo Metropolitan University, 1-1
Minami-Osawa Hachioji, Tokyo 192-0397, Japan
2
Nanosystem Research Institute (NRI), National Institute of Advanced Industrial Science andTechnology (AIST), Cental 4, Higashi 1-1-1, Tsukuba, Ibaraki 305-8562, Japan
3
JST, CREST, Kawaguchi, 332-0012, Japan
Single-walled carbon nanotubes (SWCNTs) have a cylindrical structure that consists of arolled graphene sheet. Physical properties of SWCNT are highly dependent on its diameterand chiral index. A diameter of SWCNT is geometrically determined by its chiral index andC-C bond length. The C-C bond length of SWCNT is usually considered to be equal to that ingraphene sheet, 1.42Έ which was experimentally determined in bulk graphite. However, no
one reports a precise experimental value of the C-C bond length of SWCNTs.
We prepared highly purified (6,5) SWCNTs sample (see Fig. 1) with gel column separation
method [2] and density gradient ultracentrifugation. We performed powder X-ray diffraction(XRD) measurements at KEK-PF, BL-8B, and found well-defined peaks near Q =5 Έ-1,
whose structures were not observed in low purity samples. We determined the C-C bondlength by comparing with simulation patterns. Besides it was found that the XRD profiles canbe used for fingerprinting of the chiral index of SWCNTs.
RJQVQPGPGTI[=G8?


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

(KI

(KI
+PVGPUKV[ CW#DUQTDCPEG CW











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
YCXGNGPIVJ=PO?

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Fig. 1 Optical absorbance spectra of the SWCNT sample studied.
Fig. 2 Observed X-ray diffraction profile.
[1] Gmelin Handbuch Der Anorganischen Chemie, eighth ed., Handbuch der Anorganischen Chemie, vol. 14B/2
Verlag Chemie, Weinheim, 1968, p. 143.
[2] H. Liu, et al., Nature Commun. 2 (2011) 309.
Corresponding Author: Yutaka Maniwa

Tel: +81-42-677-2490, E-mail: maniwa@phys.se.tmu.ac.jp- 46 -

1P-3
Observation of circular dichroism in individual air-suspended singlewalled carbon nanotubes
ӑA.Yokoyama, A. Ishii, M. Yoshida, Y. K. Kato

Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
We have performed circular dichroism measurements on individual air-suspended
single-walled carbon nanotubes, using photoluminescence intensity for detection.
Inspection of photoluminescence spectra for right and left circularly polarized excitation
reveals modulation of nanotube photoluminescence, while emission from silicon substrateshows negligible changes. Comparison of photoluminescence and polarization images
shows that circular dichroism signal is spatially localized on nanotubes. The spectral andspatial localization of the signal supports the interpretation that circular dichroism
originates from nanotubes. In addition, utilizing automated rotation and translation stages,
we have performed measurements as a function of angle between optical axis and thenanotube. We find that the signal has large angle dependence and even changes its sign.
This work is supported by SCOPE, KAKENHI and the Photon Frontier Network
Program of MEXT, Japan. Samples were fabricated at the Center for Nano Lithography &Analysis at The University of Tokyo.
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 47 -

1P-4
Determination of surfactant (Brij 78) in aqueous CNT dispersion○Kazutoku Ohta1, Yoshio Hayakawa1, Taizo Ono1, Hiroshi Yamawaki2,
Kazuhiro Yamamoto2, Kazumasa Honda3
1

Research Institute of Instrumentation Frontier, Nagoya 463-8560, Japan
Research Institute of Instrumentation Frontier, Tsukuba 305-8565, Japan
3
Research Institute of Science for Safety and Sustainability, Tsukuba 305-8565, Japan
2

Introduction Aqueous carbon nanotube (CNT) dispersion is commonly prepared byultrasonication of aqueous surfactant solution including CNT. Following ultrasonication,
ultracentrifugation is utilized for the removal of aggregated CNT in order to enhance thestability of the dispersion. The ultracentrifugation causes the difficulty for the accurate
determination of CNT in the dispersion due to the uncertainty on the amount of the removed
CNT. Therefore, it is much more difficult to determine free and adsorbed surfactant.
In this presentation, we propose a simple and useful way for the determination of CNT
and surfactant (polyoxyethylene(20)stearyl ether, Brij 78) in high concentrated CNT
dispersion.
CNT dispersion A 20-ml of aqueous 1-% (W/V) Brij 78 solution including 40-mg
single-walled CNT (DIPS) was ultrasonicated using Branson S-450D with 1/2” tapped horn
(amplitude 35%) at 20 ˚C for 1-6 h. After the ultrasonication, the solution was
ultracentrifuged using Hitachi CS-100GXL with S52ST swing rotor (20,000 rpm) for 1 h.
Weighing of CNT A 45-ml tetrahydrofuran (THF) was added to 5-ml of CNT dispersion toremove Brij 78 adsorbed on CNT. A 50-ml water was added to the solution to agglutinate
CNT. The solution was filtrated with 0.5-µm PTFE filter. The resultant CNT was washedthoroughly with THF and weighed after drying at 140 ˚C for 2 h.
Determination of Brij 78 Determination of Brij 78 was carried out by reversed-phase
HPLC. In-line filter equipment (filter pore size: 0.45-µm) was inserted between injector andseparation column. Total Brij 78 was determined using CNT dispersion itself as a sample.
Free Brij 78 was determined using the filtrate obtained by removing CNT with 0.20-µm PTFE
filter. The amount of adsorbed Brij 78 was calculated by subtracting the amount of free Brij
78 from that of total Brij 78.
Result Table 1 shows analytical results of CNT and Brij 78 in dispersions. The weight ofdispersing CNT increased with increasing time of sonication. The amount reached 1.0 mg(per 1-ml dispersion) at 6 h sonication. In contrast, the amount of adsorbed Brij 78 (per1-mg CNT) was almost the same and the values were ca. 5 (mg/1-mg-CNT) under thedispersion conditions.
Table 1. Analytical results of CNT and Brij 78 in CNT dispersions.
Sonication time(h)CNT
(mg/ml)Free Brij 78(mg/ml)Adsorbed Brij 78(mg/mg-CNT)

1
2
4
6

0.64
0.77
0.93
1.0

5.0
4.1
4.0
3.2

4.8
5.4
5.4
5.2

Corresponding Author: K. Ohta,
Tel: +81-52-736-7363, Fax: +81-52-736-7224,
E-mail: kazu.ohta@aist.go.jp- 48 -

1P-5
Effect of Impurity Scattering on AC Transport in Carbon Nanotubes○Daisuke Hirai1, Takahiro Yamamoto2, Satoshi Watanabe1
12Department of Materials Engineering, The University of Tokyo
Department of Electrical Engineering and Liberal Arts, Tokyo University of Science

Due to peculiar structures of carbon nanotubes (CNTs), the electronic transport propertiesof metallic CNTs are sensitive to the range of impurity potential, d: in the case where thepotential range is larger than the lattice constant, a, electron back-scatterings are suppressed;in the case of a short-range potential (d < a), the electron back-scatterings occur, which leadto the decrease of the DC conductance [1]. The back-scatterings must also affect the ACtransport properties, but this issue has not been clarified yet.
In this study, we simulated the AC response of metallic CNTs with randomly distributed
impurities to clarify the effect of impurity scatterings on the AC response. For calculating
admittance, we used nonequilibrium GreenÕs function method within the nearest-neighbor
π-orbital tight-binding approximation and wide-band limit approximation [2-4]. We foundthat the behavior of the phase difference between the current and bias voltage drasticallychanges with the impurity-potential range: In the case of the short-range potential, the phasedifference is smaller than that of pristine metallic CNTs and becomes smaller with an increaseof the potential amplitude (Fig. 1(a)), while it is larger than that of the pristine ones and therelation between the phase difference and potential amplitude is opposite in the case of thelong-range potential (Fig. 1(b)). This can be understood from the competition between thecapacitive response due to electron back-scatterings [3,4] and inductive response due to thekinetic inductance [2]. As mentioned previously, the back-scatterings occur in the case of theshort-range potential while they are suppressed in the case of the long-range potential. On theother hand, even if the electron back-scatterings are suppressed, the dwell time of theelectrons increases, which increases the kinetic inductance [2] as well as the cases having theback-scatterings. Therefore, the difference in the back-scatterings between the short-range andlong-range potentials causes the different AC response behaviors.

E/G0 (eV 1 )

1700

(a)

1735

1600

1730

1500

1725

1400

1720

1300

1715

1200

1710

(b)

Fig. 1. Phase difference between the current andbias voltage (emittance: E) of a 1µm-long (10,10)
CNT with impurity potentials of (a) d = 0.1a and (b)d = 1.5a, for several potential amplitudes:  is theemittance of the pristine CNT and □, ◯, and  arethose of CNTs with impurity potentials of theamplitudes of 0.25, 0.5, and 0.75 eV, respectively.

[1] T. Ando et al., J. Phys. Soc. Jpn. 67, 1704 (1998).
[2] T. Yamamoto et al., Phys. Rev. B 81, 115448 (2010).
[3] D. Hirai et al., Appl. Phys. Express, 4, 075103 (2011).
[4] D. Hirai et al., Jpn. J. Appl. Phys., 51, 04DN01 (2012).
Corresponding Author: Daisuke Hirai
Tel: +81-3-5841-7136, Fax: +81-3-5841-1286,
E-mail: daisuke.hirai@cello.t.u-tokyo.ac.jp- 49 -

1P-6
Solution growth of carbon-nanotube wires○Yuki Takagi 1, Yugo Oshima 2, Kazuhiro Yanagi 3, Taishi Takenobu 1
1

Department of Applied Physics, Waseda University, Shinjuku 169-8555, Japan
2
RIKEN, Wako 351-0198, Japan3
Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Carbon nanotube (CNT) is known as excellent material which has nano-scale one
dimensional structure and great transport properties. In particular, macro-scale thin-film
devices consisting of networks of CNTs are of interest due to their applicability to flexible
and printed electronics. In networks of CNTs, junctions between CNTs prevent the efficientcharge transport and their reduction by making aligned CNT films or wires is crucially
important for macro-scale CNT applications. Therefore, it is strongly required to establish
fabrication method of such wire-like CNT thin films. Very recently, solution based
crystallization method for one of nano-carbon materials, C60, has been developed [1]. Here,we applied this method to another nano-carbon material, CNT, and tried to grow thehigh-density CNT aggregations.
Figure 1 shows a schematic illustration of fabrication process. CNTs were dispersed in
N-methylpyrrolidone and the dispersion was dropped on substrate. Small hydrophilic
substrate was put on large hydrophobic substrate to pin the droplet. Then, as shown in Fig. 1,
CNT wires were self-assembly fabricated. We used small piece of Si substrate as hydrophilicpining center and Si substrate modified with self-assembled monolayers (SAMs) as
hydrophobic substrate. Because substrate surface energy and drying rate are important for
growth of CNT wire, we optimized condition of fabrication process by preparing some typesof SAMs and changing the drying condition. As a result, we achieved fabricating macro-scale
wire-like CNT thin films (Figure 2).
In summary, we performed fabrication of wire-like CNT thin films via solution based
growing method. This result enables us to fabricate separated and purified CNT wire which is
expected to be used for physical properties research and high performance thin film device.

Fig. 2 (a); Atomic Force Microscope (AFM) image of
fabricated semiconducting CNT thin film

Fig. 1 The schematic of fabrication process(b); 3D image of dashed square region in (a)[1] H. Y. Li et al. J. Am. Chem. Soc. 134, 2760 (2012).
Corresponding Author: Taishi Takenobu, Tel and Fax: +03-5286-2981, E-mail: takenobu@waseda.jp- 50 -

1P-7In-situ Raman spectroelectrochemical investigation on diameter-dependent
onset potential of oxygenation reaction of SWCNTs○Shingo Sakamoto1, Masato Tominaga1,2
1Graduate School of Science and Technology, Kumamoto University, Kumamoto 860-8555,
Japan
2
Kumamoto Institute for Photo-Electro Organics (Phoenics), Higashimachi, Kumamoto
862-0901, JapanThe oxygenation reaction of single-walled carbon nanotubes (SWCNTs) is an important
issue because chemical and physical properties, such as chemical reactivity, electronic
conductance and optical characteristics, would be changed [1-4]. In this study, the onset
oxygenation potential of SWCNTs in neutral aqueous solution was investigated by using
in-situ Raman spectroelectrochemical measurements.
Fig. 1 shows the in-situ Raman spectra of SWCNTs/Au in the RBM band region. The peakintensity of the RBM at 0.4 V using 2.41 eV decreased in comparison with the initial peakintensity. However, the peak intensity returned to its initial value when the potential wasapplied at -0.2 V. This reversible intensity change between these potentials was likely due tothe fact that electron depletion from the valence band of the SWCNTs would occur duringpotential application at 0.4 V, and electrons re-filling to the band would occur during -0.2 V.
This intensity reversibility wasobserved at potentials up to 0.5
V. On the other hand, after the
potential was applied up to 0.6
V, the peak intensity did not
return to its initial intensity,
even if a potential of -0.2 V
was applied. This irreversible
change was caused by theoxygenation of the SWCNTs.
A similar tendency was also
observed at 1.58 eV using an
exciting
laser.
FurtherFig. 1. In-situ Raman spectra of SWCNTs at various potentials
discussion
ondiameter
excited by two laser energies of 2.41 (a) and 1.58 eV (b).
dependence of oxygenation
reaction will be presented.
[1] P. G. Collins, K. Bradley, M. Ishigami and A. Zettl, Science, 2000, 287, 1801-1804.
[2] S. Ghosh, S. M. Bachilo, R. A. Simonette, K. M. Beckingham and R. B. Weisman, Science, 2010, 330,
1656-1659.
[3] M. Pumera, T. Sasaki and H. Iwai, Chem. Asian J., 2008, 3, 2046-2055.
[4] M. Tominaga, S. Sakamoto and H. Yamaguchi, J. Phys. Chem. C, 2012, 116, 9498-9506.
Corresponding Author: M. Tominaga
Tel/ Fax: +81-96-342-3655, E-mail: masato@gpo.kumamoto-u.ac.jp- 51 -

1P-8
Strong saturation of photoluminescence from local quantum states inoxygen-doped carbon nanotubes
Munechiyo Iwamura1, ○Yuhei Miyauchi1, 2, Naoto Akizuki1,
Shinichiro Mouri1 and Kazunari Matsuda1
12Institute of Advanced Energy, Kyoto University, Uji, Kyoto, 611-0011, Japan
PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama, 332-0012, Japan

Acknowledgements: The authors thank Prof. B. Lounis, Dr. L. Cognet and
Dr. J. Shaver (UniversitŽ de Bordeaux) for helpful discussions.
[1] R. Matsunaga et al., Phys. Rev. Lett. 101, 147404 (2008).
[2] Y. Miyauchi et al., Phys. Rev. B 80, 081410(R) (2009).
[3] K. Iakoubovskii et al., Appl. Phys. Lett. 89, 173108 (2006).
[4] S. Ghosh et al., Science 330, 1656 (2010).
[5] Y. Murakami and J. Kono, Phys. Rev. Lett. 102, 037401 (2009).
Corresponding Author: Y. Miyauchi
Tel: +81-774-38-3463, E-mail: miyauchi@iae.kyoto-u.ac.jp- 52 -

Normalized PL Intensity

Optically excited electrons and holes in single-walled carbon nanotubes (SWNTs) form
two-particle bound states called as excitons. In contrast to intensive studies over the past
decade on the intrinsic one-dimensional (1D) exciton photophysics in SWNTs [1,2], there
have been only limited number of reports [3,4] on the impact of local quantum states on
excitonic properties of SWNTs. If a well-organized 0D-like local luminescent state is
generated in an intrinsic 1D SWNT, such a complex nanostructure can be viewed as anunprecedented, nearly ideal 1D-0D hybrid low dimensional system where novel exciton
photophysics may emerge. Moreover, the modifications originating from the additional local
states may exert changes on the intrinsic optical properties of SWNTs that are favorable for
their optoelectronics applications.
In this study, we explore novel exciton photophysics in 1D-0D hybrid nanostructures
through the observations of excitation power dependence of photoluminescence (PL) from
0D-like local luminescent states generated by atomic oxygen doping [4] in 1D SWNTs. We
observed extraordinary rapid saturation behavior of PL intensity from the local states at E11*
with increasing continuous-wave (cw) excitation power density as shown in Fig. 1. Based on
the Monte Carlo simulation of the exciton dynamics where diffusion, trapping, andrecombination of excitons at the local states are taken into account, the strong saturation
behavior is attributed to the state filling in the local states that originates from the efficientaccumulation of the excitons photogenerated in the intrinsic 1D segments into the small
number of the local states. Our findings indicate that the excited state population of the local
states can exceed the ground state population even under
Excitation Photon Energy: 1.48 eV
relatively low power cw optical excitation regime, namely,
E11 (6,5)
population inversion necessary for lasing, which has been
E11*120
hampered by the rapid exciton-exciton annihilation processes inkW/cm
intrinsic SWNTs [5], is readily achievable for the local states in
SWNTs.
38
2

9.2

0.39

0

1.0

1.1

1.2

1.3

Photon Energy (eV)Fig.1. PL spectra of pristine andoxygen doped SWNTs measured
at various excitation power
density.
Eachspectrumisnormalized by the corresponding
excitation power density.

1P-9
Quantum Mechanical Transport in SWNTs Network FETs
Studied via Scanning Gate Microscopy○Xiaojun Wei1, Masahiro Matsunaga1, Kenji Maeda1, Tatsurou Yahagi1, Nobuyuki Aoki1,
Jonathan P. Bird2, Koji Ishibashi3 and Yuichi Ochiai11Graduate School of Advanced Integration Science, Chiba University
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan2
Department of Electrical Engineering, University at Buffalo,
SUNY, Buffalo, New York 14260-1920, USA
3
Advanced Device Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
Carbon nanotubes (CNTs) have recently received extensive attention due to theirnanoscale dimensions and outstanding materials properties such as ballistic electronic
conduction, immunity from electromigration effects at high current densities, andtransparent conduction. However, the local operation mechanism of field effect transistor(FET) composed of single wall carbon nanotubes (SWNTs) network has not been wellevaluated yet. Scanning gate microscopy (SGM) is one of such techniques to establish aspatially resolved local gate study in semiconductor nano-structures. It has also been
applied to investigate FET structures consisting of a SWNT. SGM responses related to amodulation of defects in a SWNT [1], Schottky barrier formed between the metallic
electrode and a SWNT [2], and quantum states related to Coulomb blockade [3], havebeen visualized directly as the images in comparison to topographic scans.
In this paper, ring-shape response was observed at intra-tube positions corresponding
semiconducting enriched by density gradient ultracentrifuge (DGU) process showed inFig. 1. This is different from the former experiments using CoMoCAT SWNTs, SGM
response was observed at specific inter-tube junctions suggesting a Schottky junction
formed with semiconducting and metallic SWNTs in the network [4]. When the carrier
density is enough by applying a negative back gate voltage, the response appears as one
bright spot. However, it becomes multiple concentric rings near the sub-threshold region.
The diameter of the rings depends on the back gate voltage and increases with increasing
the voltage. Multiple concentric rings response
would be related to a kind of quantum
mechanical transports due to a formation of
discrete energy levels by close defects in the
SWNT at room temperature. Although theorigin has not been clarified yet, resonant
tunneling effect could be expected due to aconfinement effect from close defects in the Fig.1 AFM image (left) and the corresponding
SGM image (right) within the channel
SWNT introduced during the GDU process.
corresponding DGU process.

[1] M. Bockrath et al, Science 291, 283 (2001).
[2] M. Freitag et al, Appl. Phys. Lett. 79, 3326 (2001).
[3] M. T. Woodside and P. L. McEuen, Science. 296, 1098 (2002).
[4] X. Wei et al, Jpn. J. Appl. Phys.51, 04DN05 (2012).
Corresponding Author: X. Wei
Tel: +81-43-290-3430, Fax: +81-43-290-3427, E-mail: weixiaojun@graduate.chiba-u.jp- 53 -

1P-10
Polymer Solar Cells with PEDOT:PSS / SWCNTs and MWCNTs Composite
as Hole Transport Layer○Naoki Kishi1, Junki Hayashi1, Takeshi Saito2, Tetsuo Soga1, Takashi Jimbo3
1

Department of Frontier Materials, Nagoya Institute of Technology,
Nagoya 466-8555, Japan
2
Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565, Japan
3
Research Center for Nano-Device and System, Nagoya Institute of Technology,
Nagoya 466-8555, Japan
Polymer solar cells have attracted much attention in recent years for their potential
application as a low cost approach to solar energy conversion. Hole transport layer, which isformed between a hole correcting anode and a photovoltaic layer in the solar cell structure,
plays an important roll on the controlling the hole injection to the anode electrode. Several
kinds of polymer materials such as poly(3,4-ethylenedioxythiophene) : poly(styrenesulfonate)(PEDOT:PSS) have been investigated as hole transport materials for organic solar cells.
Recently, we reported that the device performance of polymer solar cells can be improved byintroducing SWCNTs into the hole transport layer [1]. However, further studies on
PEDOT:PSS/CNT composite hole transport layer are required to develop photovoltaic devices
with high photo conversion efficiency.
In this study, we reported the effects of incorporating different types of CNTs (SWCNTs
and MWCNTs) into PEDOT:PSS hole transport layer on the solar cell performance. The
optimum solar cell structure with SWCNTs incorporation shows improved short circuitcurrent density and fill factor. On the other hand, the addition of MWCNTs decreased photo
conversion efficiency due to increment of the leakage current of the devices. The performanceof the solar cells will be discussed in detail.
[1] N. Kishi et al., Nano, 6 (2011) 583.
Corresponding Author : Naoki Kishi
E-mail : kishi.naoki@nitech.ac.jp
Tel&Fax : 052-735-5147- 54 -

1P-11High efficiency carbon nanotube/silicon heterojunction solar cells
fabricated using high quality carbon nanotube network film
Feijiu Wang 1, Daichi Kozawa1, Yuhei Miyauchi1,2,
Shinichiro Mouri1, Yutaka Ohno3, and Kazunari Matsuda1
1

2

3

Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama
332-0012, Japan

Department of Quantum Engineering, Nagoya University, Furocho, Chikusa-ku, Nagoya
464-8603, Japan

Single-walled carbon nanotubes (SWNT) have attracted a great deal of attention forphotovoltaic applications due to their excellent properties such as high carrier mobility,
high-efficiency carrier multiplication effects, and tunable band gap by controlling theirdiameters. Recently, the heterostructures of SWNTs and Si have been extensively studied forhighly efficient photovoltaic cells [1, 2]. It was found that the key to realize the highly
efficient solar cell is the use of high quality SWNTs network film with both low resistivity
and high transparency from the analysis of photovoltaic properties of SWNTs/Si solar cells[3]. We have fabricated the SWNTs/Si solar cells using the high quality SWNTs network filmand evaluated the photovoltaic properties of the cells.
The high quality SWNTs network films fabricated by the floating catalytic CVD method[4] was used for the cells. Figure 1 shows the current density voltage (J-V) characteristics of
SWNT/Si heterojunction solar cell with high photovoltaic conversion efficiency. From thisJ-V curve, the conversion efficiency (), current density (JSC), fill factor (FF) and open circuit
voltage (VOC) are 10.6 %, 29 mA/cm2, 67 % and 0.549 V, respectively. This photovoltaic
conversion efficiency is greater than previously reported highest value of SWNT/Si solar cells
without doping treatment [2]. This high conversion efficiency is attributed to the greatly
decrease of power loss due to lower inter-nanotube series resistance of the high quality
network film with very longer nanotube [4]. We also evaluated the photovoltaic conversion
efficiency during 10 days for the check of stability of the devices, and only the small decreaseof efficiency (1.5 %) was observed, which is much
η = 10.6 % Jsc = 29 mA/cm2
FF = 67 % Voc = 0.549 V
smaller than the previously reported value ( 6 %)during 6 days [1].
12
η (%)

9

[1] E. Shi et al., Sci. Rep. 2, 884 (2012).
[2] P. Wadhwa et al., Nano Lett. 10, 5001 (2010).
[3] D. Kozawa et al., Appl. Phys. Exp. 5, 042304 (2012).
[4] A. Kaskela et al., Nano Lett. 10, 4349 (2010).

6
3
0

0 2 4 6 8 10
Days

Corresponding Author: Kazunari Matsuda
Tel: +81-774-38-3460, Fax: +81-774-38-3460

Fig. 1: J–V curve of SWNTs/Si solar cell.
Inset shows the stability of this solar cell.

E-mail: matsuda@iae.kyoto-u.ac.jp- 55 -

1P-12
P-N junction in Carbon Nanotube Electric Double Layer Transistor○Ryo Shimizu1, Yijin Zhang 2, Kazuhiro Yanagi 3, Yoshihiro Iwasa 2, Taishi Takenobu 1
1

Department of Applied Physics, Waseda University, Shinjuku 169-8555, Japan
2
Quantum-Phase Electronics Centre and Department of Applied Physics,
The University of Tokyo,Tokyo 113-8656, Japan3
Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
Single-walled carbon nanotubes (SWCNTs) are next-generation semiconducting materials
due to their extraordinary properties such as high mobility, flexibility, and ambipolartransistor operation. Moreover SWCNTs are prospective materials for optoelectronics ininfrared region owing to their narrow energy bandgap. The fundamental optoelectronicelements such as LED and solar cell require p-n junction and it is already realized bychemical doping [1] and ambipolar transistor operation. However, it is very difficult to obtainstable p-n junction by chemical method. Moreover, p-n junction based on ambipolar
characteristics always needs gate voltage application and it is not realistic method for futureapplications. To solve these problems, we realized pseudo stable p-n junction on the channelof SWCNT ambipolar electric double layer transistor (EDLT) by fixing ions in liquid-gate
insulator with low temperature.
Ionic gel was adopted as gate insulator which consists of 1-Ethyl-3methylimidazoliumbis(trifluoromethylsulfonyl)imide and polystyrene-poly(methyl methacrylate)-polystyrene.
Figure 1 describes an ambipolar carrier accumulation using EDLT. Both holes and electrons
can be accumulated at the same time by controlling electric voltage between electrodes. A p-njunction is formed in between hole-accumulated region and electron-accumulated region. To
fix this p-n junction, we froze the ionic gel by low temperature with applying VGS = -1.0 V
and VDS = -2.0 V. Figure 2 shows current-voltage characteristics of the device after fixing p-njunction. Inset represents I-V curve before freezing ionic gel. As shown by these plots,
rectification behavior has appeared by fixing ions in gel. Furthermore, photocurrent wasobserved by irradiating white light to the device. These results indicate that p-n junction has
formed successfully.
In summary, we have demonstrated pseudo stable p-n junction on the channel of SWCNT
ambipolar EDLT by coinstantaneous accumulation of holes and electrons. This result can bebuilding block of next-generation optoelectronic devices.

Fig.1 Ambipolar carrier accumulationand formation of p-n junction

Fig.2

I-V characteristics after freezing ionic gel[1] C. Biswas, S. Y. Lee, T. H. Ly, A. Ghosh, Q. N. Dang, and Y. H. Lee, ACS Nano 5, 9817 (2011).
Corresponding Author: Taishi Takenobu, Tel&Fax: +81-3-5286-2981, E-mail: takenobu@waseda.jp- 56 -

1P-13High-mobility, filexible, n-type carbon nanotube thin-film transistors○Tomohiro Yasunishi, Yutaka Ohno, Shigeru Kishimoto, and Takashi Mizutani
Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, JapanThe control of the conduction type (p/n control) of carbon nanotube thin-film transistors(CNT TFTs) is an issue that must be addressed for the various circuit applications. Techniques
for p/n control have been proposed by utilizing chemical doping [1,2]; however, the mobilityof the n-type devices are still poor. Here, we realized high-mobility n-type carbon nanotube
TFTs on a plastic film, on the basis of the transfer process and chemical doping technique.
Bottom-gate TFTs were fabricated on a PEN substrate. After forming of gate electrodes(Ti/Au: 10/100 nm) with conventional photolithography, electron-beam evaporation, andlift-off process, a 50-nm Al2O3 insulator layer was deposited on the substrate by an atomic
layer deposition technique. Contact windows for the gate electrodes were then opened byphotolithography and reactive-ion etching. Then, the CNT film was transferred from themembrane filter to the substrate having patterned electrodes as previous work [3].
Subsequently, source and drain electrodes were formed by the lift-off process. CNTs outside
the channel area were removed by oxygen plasma. The channel length and width are both 100
m. We used polyethylenimine (PEI, MW 800) for electron donor as reported previously [1].
PEI was dissolved in methanol (0.8 vol%) and dropped on the substrate. Before the solvent
evaporated, the solution was removed by nitrogen blow.
Figure 1 shows the ID-VGS characteristics of a fabricated device. Device measurement was
performed in ambient air. Before chemical doping with PEI, the device showed p-typecharacteristics with an on/off ratio of ~106 and a mobility of 85 cm2/Vs for the rigorous model.
After chemical doping with PEI, the device
polarity changes to n-type, whose mobility is 57
cm2/Vs with a high on/off ratio of ~106. The
obtained mobility is the highest value compared
to previous n-type CNT TFTs to our knowledge.
Acknowledgments: This work was partially
supported by '08 NEDO Grant, R&D promotion
scheme funding international joint researchpromotedby
NICT,
ALCA-JST,
and
Grant-in-Aid of JSPS.

[1] Y. X. Zhou et al., Nano Lett., 4, 2031 (2004).
[2] Y. H. Lee et al., Acs Nano, 5, 2369 (2011).
[3] D.-M. Sun, et al., Nature Nanotech. 6, 156 (2011).
Corresponding Author: Y. Ohno
Tel: +81-52-789-5387, Fax: +81-52-789-5387,
E-mail: yohno@nuee.nagoya-u.ac.jp- 57 -

Fig. 1 ID-VGS characteristics of a CNT
TFT measured at |VDS| = 0.5 V before
and after chemical doping with PEI.

1P-14
Functionalization of Carbon Nanotubes with Antibody for Immunoassay
Yoko Iizumi1, Toshiya Okazaki1, Yuzuru Ikehara2, Mutsuo Ogura3, ○Masako Yudasaka1
1

3

Nanotube Research Center, 2 Research Center for Medical Glycoscience
Nanotsystem Research Institute, National Institute of Advanced Industrial Science andTechnology, Tsukuba, Ibaraki, Japan

Optical absorption, fluorescence, and Raman scattering of single-walled carbon nanotubes(CNT) in near infrared (NIR) range are potentially useful for imaging diseased sites in the
body because the NIR lights have high transparency for the biological materials. Recently, themouse blood vessels are visualized by the CNT NIR fluorescence [1]. The advantages of
CNTs optical properties are potentially useful in biosensors to increase the detection limit of
the objective materials. In our proof of principle study, the CNTs were used as a fluorescentlabel for immunoassay: IgG antibody was labeled with CNT and the usefulness of CNT label
was demonstrated via specific coupling of IgG with protein G.

Intensity (counts)

The CNTs (CoMoCAT) were dispersed inphosphate buffer by coating the CNT surface with
8.0k
phospholipid PEG (PLPEG). Rabbit IgG was
attached to PLPEG by the reaction of IgG with
6.0k
NHS, an end group of PLPEG. The obtained
4.0k
complex was designated as CNT-IgG. The
CNT-IgG dispersed in phosphate buffer
2.0k
homogenously and stably. It showed the0.0
fluorescence spectrum and Raman scattering
1000
1100
1200
1300
Wavelength (nm)spectrum characteristic of CNTs. Following atypical immunoassay process, the CNT-IgG was
mixed with protein G magnetic beads (Pr.G-beads), Figure 1. Fluorescence spectrum ofand the CNT-IgG/Pr.G-beads were taken out and
CNT-IgG/Pr.G-beads. (Ex.660 nm)
washed. The CNT-IgG/Pr.G-beads showed
fluorescence spectra and Raman spectra of CNTs, indicating IgG, Pr.G, and magnetic beads
did not alter the optical properties of CNTs. At the last stage, CNT-PEG was eluted from
Pr.G-beads. The eluted solution showed the CNT fluorescence spectra. These results suggestthat the CNTs will become useful as the NIR fluorescent label for immunoassay.
[1] G. Hong et al. Nature Medicine 18, 1841(2012).
Corresponding Authors:
T. Okazaki, E-mail: toshi.okazaki@aist.go.jp,
M. Yudasaka, E-mail: m-yudasaka@aist.go.jp- 58 -

1P-15
Arc Production of SWNTs under Controlled He Gas Temperature○Tetsu Mieno, Takashi Suzuki
Dept. Physics, Shizuoka University, 836 Ooya, Suruga-ku, Shizuoka 422-8529, Japan
By means of the arc discharge method, single-walled carbon nanotubes (SWNTs) and othercarbon nano-materials can be produced.

However, as the control of production condition is difficult,it is hard to produce high-quality and long SWNTs.

In order to develop applications of SWNTs andother carbon nano-material, study of the arc production process is important.

When SWNTs are arc-produced in He gas, strong thermal convection flows up the He gas andsublimated gaseous carbons, and the carbon reaction-time under hot He gas is limited.

When thisthermal convection is suppressed under the gravity-free condition, carbons thermally diffuse and longreaction-time can be realized, where the hot gas region becomes much larger and spherical.
cooling rate of carbons is also much smaller. [1]The

In order to realize this convection-free reaction, theparabolic flight experiments were carried out using a jet plane.

During20 sec of the gravity-freetimes, SWNTs were produced, by which production of SWNTs was considerably improved. [2-4]Here, we have developed an arc reactor as a gournd experiment, in which gas temperature can becontrolled by an electric furnace, and the gradient of gas temperature can be decreased. In a vertical andcylindrical metal chamber (50 mm in diameter), two arc electrodes are set, and the arc discharge can begenerated (Fig. 1).

By using a carbon/Ni/Y composite rod, SWNTs are arc-produced, where p(He)= 50

kPa, Id= 50 A. Figure 2 shows a typical TEM image of produced SWNTs under furnace temperature of
700 C. It can be observed that content of SWNTs increases by increasing the gas temperature.
1) T. Mieno, Plasma Phys. Controlled Fusion, 46 (2004) 211.

2) T. Mieno, M. Takeguchi, J. Appl. Phys. 99 (2006) 104301.

3) T. Mieno, New Diamond and Frontier Carbon Technol., 16 (2006) 139.

4) T. Mieno, G-D Tan, ÒCarbon NanotubesÒ, ed. S. Yellampalli, INTECH, 2011, pp. 61-76.

TEL & FAX: +81-54-238-4750, E-mail: sptmien@ipc.shizuoka.ac.jp

Fig. 1 (left):Photo of the reactor.
Fig. 2 (right):
A TEM image of SWNTs.
Tgas= 700 C.

- 59 -

1P-16
Electric-field-induced layer formation of metallic and semiconducting
single-wall carbon nanotubes in D2O – H2O mixtures°Fusako Sasaki1, Hideaki Numata1, 2, Takeshi Saito1, 3, Fumiyuki Nihey1, 2

1

Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba 305-8565, Japan
2
Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
3
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8565, Japan

Separation of metallic and semiconducting single-wall carbon nanotubes (SWCNTs) has
been intensively studied both for fundamental interests and for electronic applications such as
thin-film transistors. We have proposed a method to separate metallic and semiconducting
SWCNT solution by electric-field-induced layer formation (ELF) method [1, 2]. Previously,
deuterium oxide (D2O) has been used as solvent to disperse SWCNTs. Ihara et al. pointed outthat the density gradient established in the solvent plays an important role for ELF [1]. In thispresentation, ELF of SWCNTs in D2O – H2O mixtures was studied to elucidate the role of thesolvent density. From a technological point of view, the reduction of D2O consumption would
make the ELF method cost-effective.
Several sets of polyoxyethylene (100) stearyl ether (Brij 700) solution (1 wt %) wereprepared by using the mixtures of D2O and H2O with different ratios to obtain solutions withdifferent densities (1.0 – 1.1 g/cm3). SWCNTs (eDIPS, 1.0 nm in diameter) were dispersed ineach of the solutions by sonication and ultracentrifugation. Each solution was introduced intoa modified separation cell [2] and applied by the voltage of 90 V for 190 hours. Figure 1
shows the initial (a) and final (b) images of the separation cell with SWCNTs in H2O solution.
Semiconductor-rich (lower) and metal-rich (upper) layers were successfully formed as shownin Fig. 1 (b) and (c). Similar results were obtained for SWCNTs in the D2O:H2O mixtureswith different ratios. We also found that the purity of separated SWCNTs depends on the
difference between the densities at the top and bottom of the cell, regardless of the density ofsolution itself (Fig. 2). We expect our present study paves the way for low-cost separation of
metallic and semiconducting SWCNTs by ELF method.
This work was supported by New Energy and Industrial Technology Development
Organization (NEDO).

Lower
layer
Initial

Final

0.8

10

lower layer(semiconductor-rich)

3

upper layer(metal-rich)-3

1.2
Upper (c)1layerd bottom - d top (10 g/cm )(b)

Absorbance (arb. unit)

(a)

0.6
0.4
0.2
0

pristine
400

800
Wavelength (nm)1200

Fig. 1 (a) Initial and (b) final images of a separation cell with
SWCNTs in H2O solution. (c) Absorption spectra of the separated
SWCNTs.

5090
Purity (%)

95

100

Fig. 2 Relationship between the density differencesin the cell and semiconducting SWCNT purities.

References:[1] K. Ihara, H. Endoh, T. Saito, and F. Nihey, J. Phys. Chem. C 115, 22827 (2011).
[2] F. Sasaki, T. Saito, and F. Nihey, The 43th Symposium Abstract, p.85 (2012).
Corresponding Author: Fumiyuki Nihey
E-mail: nihey@tasc-nt.or.jp, Tel: +81-29-861-3772, Fax: +81-29-858-6330- 60 -

85

1P-17Development of Substrate Heater System of Cold-Wall Chemical
Vapor Deposition Equipment for Improvement of Single-Walled
Carbon Nanotubes Quality○Yusaku Tsuda１, Satoshi Doi1 , Koji Ishii2, Nobuyuki Iwata1 , Hirofumi Yajima2,
and Hiroshi Yamamoto1
1

Department of Electronics & Computer Science,College of Science & Technology,
Nihon University, 7-24-1 Narashinodai, Funabashi, Chiba 274-8501 Japan2
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3
Kagurazaka, Shinjyuku-ku, Tokyo 162-0826, Japan
In our previous report, position selective growth of single-walled carbon nanotubes(SWNTs) is carried out on a surface treated SiO2 (300nm)/Si substrate between
electrodes by cold-wall chemical vapor deposition (CC-CVD) method in μm-scale[1].
The SWNTs grow at the intermediate area between electrodes. In addition, chirality
controlled growth of the SWNTs is also done by irradiating free electron laser (FEL)
during CC-CVD growth. The grown SWNTs are all semiconducting investigated by amulti excited laser Raman analysis. However, the grown SWNTs length is limited toapproximately 500 nm, and the value of the G/D ratio is still low around 30 using 532
nm excitation laser, probably due to the degradation of growth
front by too much
走査エリア 2×2μm
feeding carbon source. In this study we develop the newheater system and change a CC-CVD growth process,resulting in over 400 in the value of G/D ratio.
The new heater used in the CC-CVD process was SiC(EIG, NIKKATO Co.). The reaching temperature at theheater surface is approximately 1300ºC. The heater was
surrounded by a thermal insulating material, and thesubstrate holder was set above the heater with the distance ofabout 51.5mm.
The heater system, including heaternm
7.23
substrate, thermal insulating material, and thermal reflecting 0Fig.1 The previous
surfacemetals, was annealed in air to get rid of deposited carbon in image after CC-CVD processadvance. Surface treated substrate SiO2(300nm)/Si in O3 with the size of 2μm×2μm
a ceramic heater.
atmosphere was dipped in Mo dissolved solution followed by using
走査エリア 2×2μm
Co dissolved solution. The dipped substrate was annealed
at 400ºC after each dipping. The CC-CVD process was
carried out at 700 ºC, measured at the substrate surface by athermocouple.
Figures 1 and 2 show surface images of the grown SWNTs
using a ceramic heater and the new SiC heater, respectively.
The length was more than about 1μm as shown in Fig.2.
The value of G/D ratio was over 400 with 532 nm excitation
laser. RBM peaks indicated the presence of SWNTs with
nm
0
24.53
Fig.2
The
surface
image after
1.0 ~ 1.7 nm in diameter. Particles, probably catalysts
CC-CVD process with thecovered by amorphous carbon, was also observed. The size of 2μm×2μm using new
SiC heater.
details will be discussed.

[1] K.Sakai, et al., IEICE TRANS. Electron, E94-C (2011) 1861.

- 61 -

1P-18
Nitrogen-doped single-walled carbon nanotubes andtheir growth mechanismżTheerapol Thurakitseree1, Christian Kramberger1, Akihito Kumamoto2, Shohei Chiashi1,
Erik Einarsson1, Shigeo Maruyama1
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
Institute of Engineering Innovation School of Engineering, The University of Tokyo,
Tokyo 113-8656, Japan

An ongoing challenge in the field of nanotechnology is the controlled synthesis ofsingle-walled carbon nanotubes (SWNTs). In particular, synthesis of SWNTs with uniform
diameters or chiralities is critical for applications that rely on the SWNT optical properties.
The presence of nitrogen during nanotube synthesis has been shown to strongly influence thenanotube diameter [1], making it a promising
approach to controlling nanotube properties at thesynthesis stage. We have recently demonstrated
this effect is very strong when acetonitrile(CH3CN) is introduced into ethanol feedstock, but
the mechanism is not yet clear [2].
In the present study, we address the role ofnitrogen on influencing the SWNT diameter. The
mean diameter of vertically aligned SWNTs can be
modulated along the nanotube array by simply
switching between pure ethanol feedstock and a
5% acetonitrile mixture in ethanol [3]. The mean
diameter changes from 2.1 nm for ethanol-grown
SWNTs to approximately 1 nm when acetonitrile isadded. This diameter change is reversible (Fig. 1),
suggesting that nitrogen affects only the surface ofthe catalyst particle. We hypothesize that the Fig.1 Scanning electron microscope images
presence of nitrogen reduces the effective flux of of triple-layered VA-SWNT array withcarbon into the catalyst nanoparticle, resulting in a different diameters along nanotubes
change from a tangential to perpendicular growth synthesized from ethanol (blue) and 5%
acetonitrile mixture in ethanol (red). Yellow
mode [4], which results in a smaller diameter.
arrows point at interface between layers.

[1] P. Ayala et al., Carbon. 48, 575 (2010).
[2] T. Thurakitseree et al., Carbon. 50, 2635 (2012).
[3] T. Thurakitseree et al., under review.
[4] M.-F. C. Fiawoo et al., Phys. Rev. Lett. 108, 195503 (2012).
Corresponding Author: Prof. Shigeo Maruyama
Tel: +81-3-5841-6408, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 62 -

1P-19Selective synthesis of large amount of (6, 5) single-walled carbon nanotubes
using pulse plasma CVD○Koshi Murakoshi, Toshiaki Kato, Rikizo Hatakeyama, Toshiro Kaneko
Department of Electronic Engineering, Tohoku University, Sendai, 980-8579 JapanOne dimensional single-walled carbon nanotubes (SWNTs) are potential materials for
future nanoelectronics. Since the electronic and optical properties of SWNTs strongly dependon their diameter and chirality, the selective synthesis of SWNTs with desired chiralities is
one of the major challenges in nanotube science and applications. Recently, we havedemonstrated a narrow-chirality distributed growth of SWNTs by time-programmed plasma
CVD [1]. In this method, we used very short time growth of SWNTs. Based on the systematicinvestigations, it has been revealed that there is a close correlation between incubation time(ti) and SWNT structures. Since ti of the small diameter (or specific chirality) SWNTs isshorter than that of the larger (or other chiralities) one, selective growth of narrow-chirality
distributed SWNTs has been realized by adjusting the growth time during plasma CVD. Dueto the short growth time, however, only small amount of narrow-chirality distributed SWNTs
can be grown with this method.
In this study, we have improved previous time-programmed plasma CVD and established a
new strategy to realize the mass production of narrow-chirality distributed SWNTs using
pulse plasma CVD. In the pulse plasma CVD, multiple short time growth of SWNTs is
possible by repeating the plasma generation. In order to compare before and after pulse
plasma irradiation at the same region, we carry out the mapping analysis. The amount of
SWNTs is also estimated by the intensity of G-band, which is normalized by the intensity of
Si. Chirality distribution of SWNTs is analyzed by optical measurements such as
photoluminescence excitation-emission (PLE) spectroscopy and UV-vis-NIR absorption
spectroscopy.
When we carry out the pulse plasma CVD for SWNTs growth, it is found that the amountof SWNTs increases with an increase in the total growth time. Interestingly, it is also revealed
that the initial narrow-diameter distribution of SWNTs can be maintained even after the longtime pulse plasma CVD. We think this is because that only specific diameter or chirality
SWNTs can be grown during each pulse of plasma CVD due to their very short ti. The resultsof optical measurements indicate the (6, 5) SWNTs are selectively synthesized by pulse
plasma CVD. When we adjust the growth conditions, we can improve the purity of (6, 5)
SWNTs up to 36%. These results indicate that it should be possible to realize the mass
production of narrow-chirality distributed SWNTs with our established novel approach.
[1] T. Kato and R. Hatakeyama, ACS Nano 4, 7395 (2010).
Corresponding Author: K. Murakoshi
Tel: +81-22-795-7046, Fax: +81-22-263-9225,
E-mail: murakoshi10@ecei.tohoku.ac.jp- 63 -

1P-20

○Kenta Nakamura, Takanori Umino, Shohei Chiashi and Shigeo Maruyama



Structurecontrolled synthesis of singlewalled carbon nanotubes (SWNTs) can make abreakthrough in applications of SWNTs. Carbon materials in nanosize such as diamondnanoparticles and fullerenes are good candidates for the catalyst of the structurecontrolled
synthesis, because they can be controlled in size and hardly aggregate even at hightemperatures. C60 is one of those carbon materials, and was reported to act as catalysts for
SWNT synthesis by CVD [1].
We performed CVD synthesis using C60 as the catalyst. C60 crystals were made on Si/SiO2
substrate by dropping C60toluene solution on the substrate. Ethanol gas was used as a carbon
source. The CVD temperature was 650㹼950 °C and the pressure of ethanol gas was 1.3 kPa.
The samples were inserted into an electric furnace after the temperature reached 800 °C. Our
CVD process does not include any oxidation or watertreatment which were used for SWNT
growth from C60 in previous reports [1, 2].
An SEM image of grown SWNTs is shown in Fig. 1. The SEM image indicates that
SWNTs are grown from an agglomeration with size of approximately 5 m. Although theagglomerations come from C60, typical Raman signal of C60 could not be observed from them.
It suggested that C60 clusters were thermallypolymerized or deform. Raman spectrum of grown
SWNTs is shown in Fig. 2. The split peak of Gband
around 1590 cm1 proves the existence of SWNTs.
Moreover, if the samples were located in the furnace
during temperature elevation, no SWNTs weresynthesized probably because of sublimation of C60.
These results indicate that the SWNTs grow fromm
C60 or carbon material generated from C60 during
CVD.
Fig.1 SEM image of SWNTs synthesized
In addition, we examined the effect of from C60.
temperatures and ethanol gas pressures of CVD on
the production yield and structures of SWNTs
grown from C60. The tendency was compared withthat of SWNTs synthesized from Co/Mo catalysts.
[1] X. Yu . Nano Lett , 3343 (2010).
[2] I. Ibrahim . ACS Nano , 10825 (2012).
Corresponding Author: Shigeo Maruyama
Tel: +81358416421, Fax: +81358006983,
Email: maruyama@photon.t.utokyo.ac.jp










 

Fig.2 Raman scattering spectrum
SWNTs synthesized from C60.

- 64 -

of1P-21
Characterization of Horizontally Aligned Single-Walled Carbon Nanotubes
Grown on Crystal Quartz by Using Scanning Microscopy○Daisuke Hasegawa, Taiki Inoue, Keigo Otsuka, Saifullah Badar,
Shohei Chiashi and Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo, 113-8656, Japan
Characterization of single-walled carbon nanotubes (SWNTs) is of great importanceespecially for understanding of growth mechanism toward electronic applications such as
field effect transistors. Scanning electron microscopy (SEM) has the advantage of facile
observation in a wide range of magnifications, and atomic force microscopy (AFM) can
measure surface nanostructure. Specific peaks, such as G-band or radial breathing mode(RBM), in a Raman spectrum of SWNTs provide information of quality, diameter andchirality. Horizontally aligned SWNTs (HASWNTs) have been reported to grow along aparticular orientation on the single crystal quartz substrates with several cutting angles [1, 2].
Low density, little entanglement and high straightness of HASWNTs compared to othermorphologies have the advantage of easier characterization of individual SWNTs in the axial
direction.
In this study, we used scanning Raman spectroscopy, AFM and SEM to investigate asgrown HASWNTs synthesized by alcohol catalytic chemical vapor deposition on crystal
quartz in the exact same measurement area. Raman scattering, AFM and SEM images areshown in (a-c), (d) and (e) of Fig. 1, respectively. Through comparison of thesemeasurements, G-band, RBM, height profiles and length of each SWNT can be assigned eachother. Approximately 40% and 10% of HASWNTs seen in SEM images can be observed in
Raman images of G-band and RBM signals using a 532 nm excitation laser, respectively.

Fig. 1 Images of HASWNTs observed by using (a-c) Raman spectroscopy, (d) AFM and (e) SEM. Intensity
mapping of (a) G-band and (b) RBM using a 532 nm excitation laser and (c) RBM using a 785 nm excitation laser
are shown. Note that holes and scratch lines clearly seen in (d) come from the fabrication process of quartz
substrates.
[1] C. Kocabas et al. Small 1, 1110 (2005).
[2] S. Chiashi et al. J. Phys. Chem. C 116, 6805 (2012).

- 65 -

Corresponding Author: S. Maruyama
TEL: +81-3-5841-6421, FAX: +81-3-5800-6983
Email: maruyama@photon.t.u-tokyo.ac.jp

1P-22String-like Aggregates of Aligned (6,5) Single Wall Carbon Nanotubes○H. Kawai1, K. Hasegawa¹, T. Nakatsu2, Y. Naitou3, Y. Takagi4, T. Takenobu4, K. Yanagi1
1

Tokyo Metropolitan Univ., 2Kyoto Univ., 3AIST, 4Waseda Univ.

Single wall carbon nanotubes (SWCNTs) show various properties dependingon their chiralities. Recently, it becomes possible to obtain high-purity
SWCNTs with a single chirality by density gradient ultracentrifugation and gel
chromatography and so on. Those techniques enable us to investigate thephysical properties of SWCNTs with uniform electronic structure, however,typical properties of such high-purity SWCNTs have been often investigatedin randomly distributed networks. How to obtain aligned purified SWCNTs
systems is an important subject to improve device performances.
In our study, we investigated to control aggregation processes of SWCNTs,
which are enriched (6, 5) chirality, dispersed in solutions with surfactants.
We found that temperature of the solutions and reaction time significantly
influenced their aggregation processes andmorphologies of the aggregates. Fig. 1 shows
pictures of solutions when the vial washeated at several different temperaturesand reaction times. If the temperature was
below 70 degrees, no aggregation wasobserved. When the temperatures were set
at 80~100 degrees for over 3 hours,
disorderedaggregations(alga-likeaggregations) were dominantly generated.
However when the temperature and the Fig1. (a) Temperatures at 10 ℃
reaction time were adjusted to a proper ~70℃, reaction time more than 1
condition, string-like aggregates were day. (b) at 80℃~100℃ for morethan 3 hours. (c) at 80℃~100℃
formed.
Micro-Raman measurementfor 1 hour.
clearly shows that the (6, 5) SWCNTs werealigned to string axis in the aggregates. In
addition, clear alignments of SWCNT
bundles were observed in SEM images.
Moreover, we succeeded to control
conductance of the string-aggregates byelectric double layers techniques. This
result will be a first step toward
crystallization of SWCNTs.
Fig2. G-band intensities ofaggregates and buckypaper as afunction of polarization angles of
excitation light.

Corresponding Author: K. Yanagi
Tel: +81-42-677-2494, Fax: +81-42-677-2483,
E-mail: yanagi-kazuhiro@tmu.ac.jp- 66 -

1P-23
Super Growth: Unexpectedly High Yield Carbon Nanotube
Synthesis from Low Activity Carbon Feedstocks at High
Concentrations○Hiroe Kimura1,3, Jundai Goto1, Satoshi Yasuda1, Shunsuke Sakurai1 , Motoo Yumura1 ,Don N. Futaba*1 and Kenji Hata*1,2,3
Nanotube Research Center, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba,

1

305-8565, Japan.
2

Japan Science and Technology Agency (JST), Kawaguchi, 332-0012, Japan.

3

Tsukuba University, Department of Pure and Applied Sciences, Tsukuba University, Tsukuba, 305-8573, Japan

When a carbon feedstock is delivered into the reaction chamber of a CVD system, the concentration isa critical parameter because for a given growth process (i.e. flow rate, temperature, catalyst composition,
catalyst amount, etc.) an optimum carbon feedstock concentration exists for the yield. In general, it iswell-known that as the carbon feedstock concentration increases, the yield increases, peaks, and thendrops. This is because at low feedstock concentrations, the rate-limiting factor is the supply of carbon.
while at high feedstock concentrations, the rate limiting factor is the short catalyst lifetime. Therefore, thecurrent trend for CNT synthesis is the use of highly active carbon feedstocks, such as acetylene, ethylene
at low concentrations. However, when a growth enhancer is added at even ~100 ppm levels, this optimum
carbon concentration can be greatly increased which leads to a dramatic increase in growth yield as
exemplified by water-assisted CVD (Super-growth method [1]).
Here, we report an entirely different approach using the Super Growth CVD method, where, in contrast
to using highly active carbon feedstocks at low concentrations, low activity carbon feedstocks are used inhigh concentrations, exceeding the saturation concentrations for active sources, to achieve unprecedented
and superior CNT growth yields. We found that when an unsaturated, chain feedstock, such as butane,
was used as the carbon feedstock, the yield linearly increased with carbon concentration, and did notshow saturation or a peak as observed with the other groups of hydrocarbons. As a result, we could
achieve 2.5-fold optimum growth yield higher than using ethylene. We propose that the mechanisms forthe growth kinetics for high and low reactivity carbon feedstocks are fundamentally different where thelatter benefits from a longer catalyst lifetime because of a relatively low production rate of carbon
impurities.
References:[1] K. Hata et al, Science, 306, 1241 (2004)*Corresponding Author: Kenji Hata, Don N. Futaba
TEL: (029) 861-4654, FAX: (029) 861-4851, E-mail: kenji-hata@aist.go.jp, d-futaba@aist.go.jp- 67 -

1P-24Pressure dependence of High-temperature Pulsed-arc DischargeżHayato Kikuchi1, Katsuhide Terada2, Toshiki Sugai 1
1

2

Department of Chemistry, Toho University, Chiba 274-8510, Japan
Faculty of Pharmaceutical Sciences, Toho University, Chiba 274-8510, Japan

A high-temperature pulsed-arc discharge (HTPAD) has been developed to produce
nanocarbon materials. The system utilizes width controlled pulsed arc discharge for thevaporization of electrode in temperature controlled ambient rare gas. With this width andtemperature control, novel materials have been produced by the system such as high-quality
double wall carbon nanotubes[1]. Furthermore by utilizing the low energy consumption ofpulse mode operation we can shrink the system size and increase the working pressurecompared to the standard steady arc discharge around 2 atm[2]. Here, we present the pressure
dependence of production of carbon nanotubes by the pulsed arc discharge up to 4 atm.
The system consists of a furnace with a ceramic tube inside, an Ar gas flow and pressure
control system, an HV pulse voltage controller, and a water cooling trap. Electrodes made ofgraphite containing catalytic metals (Ni/Y 4.2/0.5 at. %:Toyo Tanso Co. Ltd.) were located in
the ceramic tube. The pulsed arc discharges (0.6 ms, 50 Hz, and 100 A) vaporized theelectrodes and produced nanotubes in the high-temperature (1250 Υ) and high-pressure (upto 4 atm) Ar gas in the ceramic tube. The products were collected on the trap and werecharacterized by Raman spectroscopy with excitation
laser of 633 nm together with weight analyses.
Figure 1 shows the pressure dependence of G/Dratio of the Raman spectra. The ratio increases as thepressure increases showing the graphitization of the
produced nanotubes is enhanced by the pressure.
Figure 2 shows the ratio between the mass of trapped
product and that of the vaporized electrodes. Since theproduced nanotubes are selectively collected on thetrap, the result shows that concentration of nanotubes inthe vaporized materials is also increased by thepressure. These results clarified that the production Fig. 1 Pressure Dependence of G/D ratio
processes are controlled by the pressure and that there
exists some frontier to improve the productivity
through the high pressure of 4 atm which have been not
utilized by the steady arc discharge[2].
[1] T. Sugai et al., Nano Lett. 3, 769 (2003).
[2] Y. Saito, Y. Tani, and A. Kasuya, J. Phys. Chem. B.
104, 2495 (2000).
Corresponding Author: T. Sugai Tel: 047-472-4406 E-mail:sugai@chem.sci.toho-u.ac.jp- 68 -

Fig. 2 Pressure Dependence of Trap vs.
Vaporization Ratio

1P-25ESR Measurements of N@C60 with [10]Cycloparaphenylene in Solution○Mitsuhiro Okamoto1, Takahiro Iwamoto2, Shigeru Yamago2, and Tatsuhisa Kato 1, 3
1

Department of Interdisciplinary Environment, Graduate School of Human andEnvironmental Studies, Kyoto University, Kyoto 606-8501, Japan
2
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan
3
Institute for the Promotion of Excellence in Higher Education, Kyoto University, Kyoto 6068501, Japan
Cycloparaphenylenes (CPPs) are molecules with the simplest structure unit of armchaircarbon nanotubes in which paraphenylene structures are linked in a cyclic manner. The
concave cavity of the CPPs should act as a host for π-conjugated molecules with a convex
surface, such as fullerenes. Yamago group of author succeeded in syntheses of [n]CPPs (n=813)[1] and reported the size selective encapsulation of C60 by [10]CPP [2]. We report here ESR
studies of N@C60 encapsulated complex by [10]Cycloparaphenylene in solution by using a X
band-ESR spectrometer
The ESR spectra of N@C60[10]CPP complex in toluene-d8
solution are shown in Fig.1.
Spectra were recorded attemperatures above and below
the freezing point of solvent,
Tfreezing =178K. Comparing
with spectra of intact N@C60 intoluene-d8 solution, it isnoticeable that the sharp triplet
peaks are still observed evenbelow the freezing temperatureof solvent. The rotation of
N@C60 within the encapsulated
complex should reflect on theprominent feature of the sharp
line width of ESR spectra
below the freezing point ofsolvent.

[1] T. Iwamoto et al. J. Am. Chem.
Soc. 133, 8354 (2011).
[2] T. Iwamoto et al. Angew. Chem.
Int. Ed. 50, 8342 (2011).

Fig.1 ESR spectra of N@C60-[10]CPP complex and intact N@C60
in toluene-d8 solution at the temperatures above and below thefreezing point of 178K.

Corresponding Author: T. Kato
Tel: +81-75-753-6695, Fax: +81-75-753-6695,
E-mail: kato.tatsuhisa.6e@kyoto-u.a.cjp- 69 -

1P-26
Polythiophene encapsulated in carbon nanotubes
as a high-throughput Raman imaging marker○Kenshi Miyaura, Yasumitsu Miyata, Ikuya Wakamori, Boanerges Thendie,
Ryo Kitaura, Hisanori Shinohara
Department of Chemistry & Institute for Advanced Research, Nagoya University,
Nagoya 464-8602, Japan
Raman imaging of carbon nanotubes is one of the most powerful tools for thehigh-throughput measurement of nanotube location, density, and orientation on arbitrary
substrates and even in living cells [1,2]. However, complete Raman imaging of
nanotubes requires multiple-wavelength laser excitations because the resonanceenergies of CNTs vary sensitively depending on the chirality. To solve this problem, we
have focused our attention to the use of encapsulated molecules inside nanotubes as an
imaging marker. In our previous study [2], we reported the encapsulation ofpolythiophene (PT, Fig.1a), a representative pi-conjugated polymer, and its high fillingyield, a single resonance band, and strong Raman signals. These findings have tempted
us to further investigate the optical properties of individual nanotubes encapsulating PT.
Here, we demonstrate that the encapsulated PT can be used as an efficient marker ofindividual CNTs for Raman imaging with a single-wavelength laser excitation. PT/CNT
complexes were obtained by a vapor-phase doping of oligothiophenes and were purified
with density gradient ultracentrifugation. The individual nanotubes were then deposited
on a SiO2/Si substrate and measured on confocal Raman imaging with a 488 nm
excitation laser. As shown in Figs.1b-c, as compared with the G-band intensity image of
nanotubes (Fig.1b), the Raman image of PT shows more points in the same area
(Fig.1c). In some locations, only the PT-derived peaks can be observed because ofoff-resonance of outer nanotubes at the present excitation wavelength (Fig.1d). These
results indicate that the present nanotube system possesses a high potential of PT
markers for versatile imaging of CNTs in electronics and biological applications.

Figure 1. (a) Schematic illustration of the PT/CNT complex. Raman images of (b) G-band intensity of CNTs and(c) PT-derived peak intensity. (d) Raman spectra at different points marked by circles of A and B in Fig.1c.
[1] R. Haverner et al., ACS Nano 6, 373 (2011), [2] J. W. Kang et al., Nano Lett. 12, 6170 (2012),[3] K. Miyaura et al. The 43th FNTG General Symposium.
Corresponding Author: Hisanori Shinohara
Tel: 052-789-2482, Fax: 052-747-6442, E-mail: noris@nagoya-u.jp,- 70 -

1P-27
Biodegradation of Single-Wall Carbon Nanohorns○Minfang Zhang1, Mei Yang1, Cyrill Bussy2, Hanene Ali-Boucetta2, Sumio Iijima1, 3,
Kostas Kostarelos2, Masako Yudasaka1
1

Nanotube Research Center, National Institute of Advanced Industrial Science and Technology,
1-1-1 Higashi, Tsukuba 305-8565, Japan
2
Nanomedicine Lab, University College London (UCL) School of Pharmacy,
London WC1N 1AX, United Kingdom
3
Department of Materials Science and Engineering, Meijo University, 1-501 Shiogamaguchi,
Tenpaku, Nagoya 468-8502, Japan

With the rapid development in the applications of nanocarbons, such as carbon nanohorn(CNH), carbon nanotube and nanographene in biomedicine, the concerns of long-term fate,excretion, and degradation of these materials are very important. Recently, some reports haveshown that carbon nanotubes and graphene can be biodegraded under certain conditions [1],but the biodegradation of CNH has still remained unclear. In this study, we have investigatedthe biodegradation of CNHs in ex vitro and in vitro experiments.
CNHs treated with light assisted oxidation (LAOx-CNHs) [2] were incubated with a low
concentration of hydrogen peroxide (40μM) supplemented with two simulated biologicalsolutions. One was enzyme of human myeloperoxidase (hMPO) solution and another was
phagolysosomal stimulant fluid (PSF). PSF is a medium that mimics the acidic oxidizing
environment typically presented in endosomes and phagolysosomes. Our results showed that
CNHs degraded slowly in PSF solution and about 50% CNHs were removed after 2 months. On
the other hand, about 40% CNHs were removed in 5 days when hMPO was used.
In order to investigate the cellular degradation of CNHs, we incubated human leukemia
macrophage cells (THP-1) with LAOx-CNHs (10μg/ml). Quantities of CNHs in the cells were
estimated from optical absorption intensities (700 nm) of CNHs in the cell-lysis. The amountsof CNHs in the cells decreased with longer incubation periods and about 30 % CNHs weredegraded after 9 days.
The small-sized (20-50 nm) CNHs [3] having more carboxylic groups than LAOx-CNHs(sizes ca. 100 nm) were prepared and their biodegradation was similarly studied. The degreeof degradation for small-sized CNHs was about 12% in ex vivo studies and 20% in cell
cultures using the THP-1 cell line. The reason why the kinetics of degradation for thesmall-sized CNHs seemed to be slower than the large-sized CNHs has been revealed and will
be further investigated as will be discussed in the presentation.
[1] B. L. Allen et al. Nano let. 8, 3899 (2008); J. Am. Chem. Soc. 131, 17194 (2009); V. E. Kagan, et al. Nat.
Nanotechnol.5, 354 (2010). X. Liu, et al. Carbon 48, 1961 (2010).
[2] M. Zhang, et al. ACS Nano 1, 265 (2007). [3] M. Zhang, et al. Small (2012).
Corresponding Author: M. Zhang, K. Kostarelos, M. Yudasaka
E-mail: m-zhang@aist. go.jp; k.kostarelos@ucl.ac.uk, m-yudasaka@aist.go.jp- 71 -

1P-28Carbon nanohorns induced RAW264.7 apoptosis: Lysosomal membrane
destabilization caused reactive oxygen species generation, leading cell
apoptosis○Mei Yang1, Minfang Zhang1, Yoshio Tahara1, Sumio Iijima1, 2, Masako Yudasaka1
1

2

Nanotube Research Center, AIST 5-2, Tsukuba, Japan
Department of Material Science and Engineering, Meijo University, Nagoya, Japan

In recent years, nanocarbons have gained enormous popularity and offered a wide range ofpotential applications. With increasing industrial productions of nanocarbons, public concern
on their environmental and health effects is growing rapidly. Animal studies show that
intravenously injected nanocarbons are easily captured by tissue macrophages and retained in
the tissues for long periods. This accumulation in macrophages could potentially lead to
long-term toxicity, which may limit the bio-application of nanocarbons. In this context,
negative effects, such as inflammatory response, oxidative stress and thrombus induction
have been found both in vitro and in vivo studies [1-3]. Recently, in vitro experiments showthat nanocarbons causes apoptosis at high uptake conditions [4-5], but its mechanism of how
the nanocarbons induce apoptosis has not been clarified. Therefore, we have studied themechanism of apoptosis induced by single-walled carbon nanohorns (SWNHs), a type ofnanocarbons, in macrophages.
We used SWNHs treated by light-assisted oxidation with hydrogen peroxide. They weredispersed in cell culture medium without using any dispersants, and used for the cell
experiments of RAW264.7 macrophage. It was found that SWNH caused cell proliferation
inhibition, reactive oxygen species (ROS) generation and caspase activation in a SWNH
concentration and incubation time dependent manner. Lysosomal membrane destabilization
was determined by acridine orange staining method. Lysosomal membrane destabilization
occurred just 1 hour after SWNHs treatment and enhanced gradually for 6 hours, while ROS
generation started 1 h after SWNHs treatment and kept low level, but suddenly increased after
24 hours. Cathepsins (lysosomal enzymes) inhibitors suppressed ROS generation. The results
suggest that the high accumulation of SWNHs in lysosomes caused the lysosomal membrane
destabilization, which induced the ROS generation, leading to the cell apoptosis.
[1] AA Shvedova, et al. Am. J. Physiol. Lung Cell. Mol. Physiol., 289, L698, (2005).
[2] G Jia, et al. Environ. Sci. Technol, 39, 1378(2005).
[3] S K Singh, et al. ACS nano, 5, 4987(2011).
[4] Y Tahara, et al. Biomaterials, 33, 2762(2012)[5] WW Cheng, et al. Int. J. Biochem. Cell Biol., 43, 564(2011).
Corresponding Author: M. Yang and M. Yudasaka.
Tel:029-861-4818, TEL/Fax: +81-29-861- 6290
E-mail: m-yan@aist.go.jp (M. Yang), m-yudasaka@aist.go.jp (M. Yudasaka).

- 72 -

1P-29
Nitrogen-doped carbon nanohorn aggregates with electrocatalytic activity
for oxygen reduction○Ryota Yuge1, Takashi Manako1, Shunji Bandow4, Masako Yudasaka2, Kiyohiko Toyama1,
Takashi Yamaguchi3, Sumio Iijima4, and Kaichiro Nakano1
1

2

Smart Energy Research Laboratories, NEC Corporation, Tsukuba 305-8501, Japan
Nanotube Research Center, National Institute of Advanced Science and Technology (AIST),
Tsukuba, 305-8565, Japan
3
Institute for Advanced Research, Nagoya University, Nagoya, 464-8602, Japan
4
Department of Materials Science and Engineering, Meijo University, Nagoya 468-8502,
Japan

Single-wall carbon nanohorns (SWNHs) [1] are a kind of nano-carbon materials such ascarbon nanotubes, and graphenes, which are attractive due to their excellent properties as
support for metal particles [2]. Recently, it has been reported that non-metallic nitrogen-dopedcarbon nanotubes have the intrinsic catalytic properties for oxygen reduction reaction (ORR)[3]. This achieves not only the potentially low cost for noble metal free but also their betterstability against CO poisoning compared to traditional platinum catalysts [3]. In this study, we
tried to incorporate the nitrogen atom in graphene sheets of SWNHs and control the quantityof the nitrogen atoms. We also investigated the ORR electrocatalytic activity of them.
SWNHs were prepared by the CO2 laser ablation, which was operated at 3.5 kW at room
temperature. During 30 seconds laser ablation, the target was rotated at 2 rpm. The buffer
gases were N2, Ar, and N2/Ar mixture. The gas flow rate and pressure were 10 L/min and 760
Torr, respectively. The obtained samples are denoted as N2-SWNHs, Ar-SWNHs, andN2/Ar-SWNHs.
Shapes of N2-SWNHs, Ar-SWNHs, and N2/Ar-SWNHs observed by a scanning electron
microscopy and scanning transmission electron microscopy were quite similar. However,from XPS, and ESR results, we found that the nitrogen atoms are incorporated in the carbon
network of N2-SWNHs and behave as acceptors. In oxygen-saturated 0.1 molar potassiumhydroxide, electrocatalytic activity of N2-SWNHs was superior to that of Ar-SWNHs,
indicating that nitrogen atoms incorporated in graphene network acted as active sites of ORR.
The details are shown in the presentation.
[1] S. Iijima et al. Chem. Phys. Lett. 309, 165 (1999).
[2] T. Yoshitake et al. Physica B 323, 124 (2002).
[3] K. Gong et al. Science 323, 760 (2009).
Corresponding Author: R. Yuge
Tel: +81-29-850-1566, Fax: +81-29-856-6137
E-mail: r-yuge@bk.jp.nec.com- 73 -

1P-30CVD Growth of Bernal Stacked Bilayer Grapheneon +HWHURHSLWD[LDO&X  )LOP

○6KRWD7DQRXH Kenji Kawahara, 0DVDKDUX7VXML

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Fig. 2 Optical microscope images of graphene with the different hydrogen concentrations, (a) 7.0%,(b) 7.5%, and (c) 8.0%. Inset of (b) shows the Raman 2D band of the BLG area. SLG: single-layer
graphene, MLG: multi-layer graphene.
References: [1] Y. Zhang et al., Nature, 459, 820 (2009). [2] L. Liu et al., ACS Nano, 6, 8241 (2012). [3] Z.
Sun et al., ACS Nano, 6, 9790 (2012). [4] A. C. Ferrari et al., Phys. Rev. Lett., 97, 187401 (2006). [5] C. M.
Orofeo et al., Carbon, 50, 2189 (2012).
&RUUHVSRQGLQJ$XWKRU+LURNL$JR 7HO )D[(PDLODJR#FPN\XVKXXDFMS- 74 -

1P-31
Scalable processing of crystallographic etching for graphite powder using
supercritical fluid○Takaaki Tomai, Naoki Tamura, Itaru Honma
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai
980-8577, JapanThe characteristics of finite-sized graphene, which is strongly affected by the edge type,such as armchair and zigzag, have attracted much attention. Crystallographic etching ofgraphene/graphite is one of the most promising methods for selective introduction of zigzag
edge to the graphene/graphite surface [1]. Crystallographic etching of graphite surface isconducted by Ni, Co nanoparticle under reductive environment and by Ag nanoparticle underoxidative environment.
Recently, we succeeded in the crystallographic etching of graphite surface in supercriticalwater (SCW, critical point of water: 374 °C, 22 MPa) environment. The Ag-supported
graphite was treated in SCW with oxygen. The treated temperature and time was 500 °C and
10 min, respectively. In the case of usage of graphite substrate, we confirmed many straight
trenches formed on the surface by etching due to catalytic oxidation by SEM observation. We
also observed an apparent increase in the etching rate with increasing water density when wevaried the water density from 0 to 0.2 g/ml. This result indicates that the water contributes tothe enhancement of the etching reaction. Although the mechanism is still not fully understood,
efficient removal of adsorbed gaseous products (CO, CO2) from the catalyst surface by the
SCW might promote the catalytic carbon gasification. Moreover, after supercritical treatment,
suspened materials in the water are observed. It is highly supposed that theanisotropically-etched graphene layer was isolated from the surface of graphite due to theexfoliation effect of supercritical fluid [2]. By using transmission electron microscopy (TEM),
it is revealed that the graphene with zigzag edges which is introduced.
To check the scalability, we applied this method to dispersed graphite powder. To verify
that the treatment progressed efficiently for the bulk, we conducted a Raman spectroscopic
analysis. It has been reported that the D band at around 1350 cm‒1 and the Dʹ band at around
1620 cm‒1 can be attributed to the defects and the graphite edges. Moreover, the D band
intensity from a zigzag edge is weaker than that from an armchair edge, while the Dʹ band
intensity doesn’t show the dependence on the edge type [3]. In the case of the graphite powder
with Ag nanoparticles after SCW treatment, the average intensity ratio between the D bandand the Dʹ band (ID/IDʹ) value was smaller than that in the case of SCW-treated graphite
powder without Ag nanoparticles. This result indicates that zigzag edges are effectively
introduced by crystallographic etching in SCW even to the dispersed graphite powder.
Further details of process and the characteristics of zigzag-edge-introduced graphite
powder will be presented in FNTG44.
[1] L. Ci et al. Nano Res. 1, 116 (2008).
[2] T. Tomai, Y. Kawaguchi and I. Honma, Appl. Phys. Lett. 100, 233110 (2012).
[3] L. G. Cancado et al. Phys. Rev. Lett. 93, 247401 (2004).
Corresponding Author: T. Tomai
Tel: +81-22-217-5816, Fax: +81-22-217-5828,
E-mail: tomai@tagen.tohoku.ac.jp- 75 -

1P-32In situ RHEED Study on Growth Process of Graphene by
Chemical Vapor Deposition○Takuro Minato, Hitoshi Nakahara, Koji Asaka, and Yahachi Saito
Department of Quantum Engineering, Nagoya University, Furo-cho, Nagoya 464-8603
In situ observations of graphene growth have been carried out by SEM and LEEM. In thesepreviously reports, the segregation of graphene on metal substrates with high solubility of carbon
was observed during cooling process after chemical vapor deposition (CVD). In this study,
graphene growth process during CVD was studied by in situ reflection high energy electron
diffraction (RHEED).
Graphene was synthesized by CVD using ethanol gas. In order to investigate the effect ofcarbon solubility, vacuum deposited films of copper (Cu), which has low carbon solubility of
0.04 at.% at 1000 ℃, and cobalt (Co), which has high carbon solubility of 3.41 at.% at 1000 ℃,
were used as catalyst metal. These films were prepared using electron beam deposition on
silica-coated silicon substrates. The base pressure of CVD chamber was at 5 × 10-6 Pa tominimize the effect of the residual gas on the graphene growth. The substrate was heated at
900 ℃, and the ethanol pressure was kept at 0.1 Pa for 5 minutes during CVD. After CVD, thesubstrates were taken out from the CVD chamber followed by Raman spectroscopy and atomic
force microscopy (AFM) characterization.
Figures 1(a),(b) show electron diffraction patterns of the Cu and Co films during CVD,
respectively. Streaks due to graphene reflections 10 were observed in both Cu (Fig. 1(a)) and Co
films (Fig. 1(b)), suggesting that graphene has already grown on the substrates before cooling thesubstrates. It took 60 and 10 seconds until these streaks appeared in CVD process on Cu and Co
films, respectively. It is considered that this difference was due to the higher catalytic activity ofCo than Cu films. After cooling the substrates, electron diffraction patterns of Cu and Co films
changed (Figs. 1(c),(d)); For Cu, Debye rings due to graphene appeared, and for Co, streaks due
to graphene became clearer.
(a)

(b)

(c)

(d)

Fig. 1. RHEED patterns from (a) Cu film during CVD. (b) Co film during CVD.
(c) Cu film after CVD. (d) Co film after CVD. Insets in each figure illustrated
graphene growth process.
Corresponding Author: T. Minato
Tel&Fax&E-mail: +81-52-789-3714, +81-52-789-3703, minato@surf.nuqe.nagoya-u.ac.jp- 76 -

1P-33
Influence of applied potentials for electrochemical exfoliation of graphite○Haruya Okimoto, Syun Takabayashi, Yuhei Sobe, Masahito Sano1

Department of Polymer Science and Engineering, Yamagata University, Yonezawa,
992-8510, Japan

Chemical exfoliation of graphite, such as Hummers method, is an attractive technique forthe synthesis of graphene at room temperature. However, it needs several strong oxidants(KMnO4, NaNO2) and a reductant (N2H2). Recently, we have reported a new method ofelectrochemical exfoliation of graphite without strong oxidants. It is known thatelectrochemical reactions on graphite involve many processes such as intercalation, anodic
oxidation, and electrolysis, depending on the applied potential. It is important to elucidate areaction at a given potential to control chemical characteristics of the resulting graphene. In
this study, we report a systematic study of exfoliation of graphite over several applied
potentials.
All electrochemical measurements were recorded in a conventional three-electrodepotentiostat (working electrode: Grafoil as a raw material for graphene, counter electrode: Pt
plate, and reference electrode : Ag/AgCl). Sulfuric acid system (H2SO4 or NaSO4) and nitricacid system (HNO3 and NaNO3) were used as anelectrolyte
for
exfoliationofgraphite.
Chlonoamperometry were used for constant-voltage
electrochemical exfoliation. After electrochemical
exfoliation for 20 min, the exfoliated graphene wasdispersed in DMF. The solution was cast on silicon
and dried to measure the thickness, size, andfunctional moiety by AFM, SEM, XPS.
Figure 1 shows a cyclic voltammogram in Na2SO4
solution. A small peak at +1.8 V is known as anintercalation reaction in the case of H2SO4. This
result suggested that the Na2SO4 is also intercalated
to graphite at the same potential as H2SO4. Fig 1 Cyclic voltammogram
Exfoliation of graphite is estimated to occur at the recorded at Grafoil in 1 M Na2SO4.
potentials +1.7, +1.8, and +2.1 V in Na2SO4 solution.
2.1 V
40
The graphite electrode does not react below +1.7 V,
which is just beneath the intercalation potential. On
20
the other hands, the graphite is expanded andexfoliated over +1.8 V. Figure 2 shows the0
1.8 V
histograms of graphene thickness measured by AFM.
40
The thickness of exfoliated graphene is not affectedby the applied voltage. This result means that +1.8 V
20
is a threshold value for the electrochemical
0
exfoliation of graphene.
0
2
4
6
50

40

Frequency (％)

30

20

B

10

600

0

1

2

3

4

5

6

0

1

2

3

4

5

6

50

40

30

20

10

0

Thickness (nm)Corresponding Author: H. Okimoto
Tel/Fax: +81-238-26-3074
E-mail: haruya@yz.yamagata-u.ac.jp

Fig 2 Histograms of graphene
thicknessmadeatdifferent
potentials.

- 77 -

1P-34CVD synthesis of shape-controlled
graphene and boron nitride heterostructures○Eriko Maeda, Yasumitsu Miyata, Ryo Kitaura, and Hisanori Shinohara*
Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya
Atomic-layer lateral heterostructures of graphene and hexagonal boron nitride (hBN)have attracted much attention because of their unique interface-originated properties aswell as applications in electronics. Recently, the synthesis of such heterostructures has
been reported by three different groups including the presentgroup [1-3]. These works
demonstrate that firstly-grown graphene can be used as a patterning mask and its edges
behave as nucleation site of secondary-grown hBN in chemical vapor deposition(CVD).
Here, we show ashape-controlled growth of graphene/hBN heterostructures usinghydrogen etching process of graphene. Individual grains of single-layer graphene are
first grown from methane on a copper foil, and then the graphene is etched underhydrogen atmosphere. This etching process can produce hexagonal-shape hole andribbon-shape gap in graphene grains depending on etching conditions. Shape-controlled
hBN is then synthesized in the patterned graphene grains using ammonia borane CVD.
The samples obtained are characterized by using optical spectroscopy and imaging,scanning and transmission electron microscope observations. As shown in Fig.1, thepresent process results in the growth of hexagonal and ribbon-shape hBN in eachgraphene grains. In the presentation, the detail of growth process and structure of the
products will be discussed.

Fig.1 (a,b) Scanning electron microscope images of CVD-grown hBN/graphene heterostructures.
[1] Y. Miyata et al. Appl. Phys. Express 5 (2012) 085102.,[2] M. Levendorf et al. Nature, 488 (2012) 627., [3] P. Sutter et al. Nano Lett., 12 (2012) 4869.
Corresponding Author: Hisanori Shinohara
Tel: 052-789-2482, Fax: 052-747-6442, E-mail: noris@nagoya-u.jp- 78 -

1P-35
Orientation Controlled Growth of NbS2 Nanosheets on CVD Graphene
Wanyin Ge, Kenji Kawahara, Masaharu Tsuji, and ○Hiroki Ago*
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8580
Recent development of graphene trigged the extensive interest in a new class of
two-dimensional materials.
In particular, quasi-two-dimensional transition metal
chalcogenides show unique physical properties, and many chemical or physical approaches
have been proposed to prepare the chalcogenide nanosheets. The primary emphasis so far
has been put on semiconductor chalcogenides, such as MoS2 and WS2. On the contrary, very
few works have been reported for metallic chalcogenide nanosheets. Niobium disulfide(NbS2) is a metallic chalcogenide having a layered structure and shows superconductivity attransition temperatures of 1.7-6.3 K as well as unique anisotropic optical and magnetic
properties [1]. Layered NbS2 has been applied to a cathode material in secondary batteries,
catalyst for the purification of petroleum, and humidity sensors. The preparation ofnanosheets of NbS2 is particularly important not only in these applications, but also in thefundamental research for the quasi-two-dimensional chalcogenide materials.
Here, we report ambient pressure chemical vapor deposition (CVD) growth of
single-crystalline NbS2 nanosheets with a controllable orientation. On SiO2 substrates, NbS2
nanosheets grow almost perpendicular to the substrate surface. However, when we use thetransferred CVD graphene on SiO2 substrate,
NbS2 nanosheets grow laterally lying on thegraphene, as shown in Fig. 1. The as-grown
NbS2 sheets show mainly triangular shapeswith the thickness of about 20-200 nm andseveral hundreds to micrometres in the lateraldimension.
Analyses based on X-ray
diffraction and Raman spectroscopy indicatethat the NbS2 nanosheets are single
crystalline with a rhombohedra structure(3R-type) [2]. Our finding on the formationof highly aligned NbS2 nanosheets ongraphene gives new insight on the formation Figure 1 (a) SEM images of NbS2 nanosheetsgrown on transferred graphene. The density ofmechanism of NbS2 and would contribute to NbS2 nanosheets is much lower than that on
the templated growth of various layered graphene. (b,c) NbS2 nanosheets on graphene.
(d) NbS2 nanosheets grown on plain SiO2 surface.
materials.
References:[1] W. G. Fisher, M. J. Sienko, Inog. Chem., 19, 39 (1980).
[2] W. Ge, K. Kawahara, M. Tsuji, H. Ago, submitted.
Corresponding Author: Hiroki Ago (Tel&Fax: +81-92-583-7817, E-mail: ago@cm.kyushu-u.ac.jp)- 79 -

1P-36
Nanocolumnar Crystal Growth of Organic Semiconductor Molecules
on a Graphene-Modified Surface○Satoshi Okada, Shunsuke Furukawa, Hideyuki Tanaka, Koji Harano, Eiichi Nakamura
Department of Chemistry, The University of Tokyo, Tokyo 113-0033, Japan
Morphological control of organic semiconductor molecules are important in organic solar
cells to increase current density and enhance performance. Here, we solution-processednanocolumnar structure of donor material tetrabenzoporphyrin (BP)[1] onto graphitic sheets(reduced graphene oxide: rGO)-coated poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS). The nanocolumns are formed by sparsely rGO-covered PEDOT:PSS
surface, which initiated nucleation of BP via acid-base interaction (Fig. 1). Graphitic sheets
were synthesized by HummersÕ method followed by reaction with isocyanate, and was spincoated on PEDOT:PSS and thermally reduced (Fig. 2) [2] to obtain ca. 30%-covered surface.
On rGO-coated PEDOT:PSS, BP was solution processed from its soluble precursor CP
followed by thermal treatment to obtain BP film. Flat domain structure was obtained on
PEDOT:PSS (Fig. 3 left), while nanocolumnar structure with the height of 50-150 nm wasformed on rGO-coated PEDOT:PSS (Fig. 3 right). The obtained nanocolumnar BP wasapplied for BP/C60 p-n devices by thermally evaporating C60 to obtain devices with 1.08-foldenhanced performance. The increase in performance was attributed to 1.16-fold increase incurrent density and 1.2-fold enlargement in surface area of BP.
CP
spin-coatingrGO
PEDOT:PSS
ITO

1500 rpm
30 secheatingCP
PEDOT:PSS
ITO

Crystal nucleiof BP

180 ¡C PEDOT:PSS
ITO
20 minNBPhen/Al
C60
BP

BP

PEDOT:PSS
ITO

150 nm(C60)

PEDOT:PSS
ITO

Fig. 1. Formation of nanocolumnar donor BP on rGO-masked PEDOT:PSS and solar cell fabrication(a)
O O

BP on PEDOT:PSS

O
NHPhthermalreduction

O
O

(b)

O

NHPh
NHPh

250 ¡COOO
Ph-iGOrGO

NH N

180 ¡C

NH N

N HN

ÐC2H4

N HN

CP

BP on rGO-coated PEDOT:PSS

BP

Fig. 2. Materials used in this study. (a)Preparation of graphitic sheets. (b) Preparationof BP from soluble precursor CP.

1 µm

1 µm

500 nm

500 nmFig. 3. SEM images of BP film. (left) BP on
PEDOT:PSS.
(right)BPonrGO-coated
PEDOT:PSS.
(top)
Top
view.
(bottom)
Cross-section image.

[1] Aramaki, S. et al. Appl. Phys. Lett. 84, 2085 (2004).
[2] Stankovich, S. et al. Carbon 44, 3342 (2006).
Corresponding Author: Eiichi Nakamura
Tel: +81-3-5841-1475, Fax: +81-3-5841-1475,
E-mail: nakamura@chem.s.u-tokyo.ac.jp- 80 -

1P-37
Imaging graphene lattice by the helium ion microscope:
A prediction by ab initio simulationsżYoshiyuki Miyamoto
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Central 2, 1-1-1 Umezono, Tsukuba 305-8568, Japan
In the last general meeting, I introduced the feasibility of Helium ion microscope (HIM) as
a new tool for getting image of suspended graphene. HIM can take images by secondary
emitted electron induced by collision of high-speed helium ion to the samples. The amount of
the emitted electrons depends on the position of the collision, thus ion-beam scanning can
induce contrast of the intensity of the secondary emitted electron that makes the HIM image.
The mechanism of the secondary electron emission was fond to be impact ionization upon thecollision by performing ab initio simulations based on the time-dependent density functional
theory [1]. Further analysis considering finite beam-size of helium has been made to examine
accessible experimental conditions to challenge for lattice image of graphene.
First, the similarity between the profile of secondary electron intensity as a function of
He-ion-beam impact point and the profile of the valence charge density is demonstrated, seeFig. 1. Second, the guess of HIM image of graphene ribbon from the charge distribution isdemonstrated considering possible focusing size of the He ion beam. The charge density
profile has been modified by the Gaussian broadening technique mimicking the finite
beam-size and necessary conditions for taking lattice image will be discussed [1].
This work was performed by using the Earth Simulator. The author is indebted tocollaboration with Prof. H. Zhang and Prof. A. Rubio
and to support by the Research organization for
Information Science and Technology (RIST), Tokyo
office.
[1] H. Zhang, Y. Miyamoto, and A. Rubio, Phys. Rev. Lett. 109,
265505 (2012).
.
Corresponding Author: Yoshiyuki Miyamoto
Tel: +81-29-849-1498, Fax: +81-29-861-3171,
E-mail: yoshi-miyamoto@aist.go.jp- 81 -

Fig.1 (a)Simulated HIM image and(b)charge density of graphene.

1P-38AndersonAnderson
Localization
Localizationof Edge-Disorderedof Edge-Disordered
Graphene
Graphene
Nanoribbons
Nanoribbons
1
1
2
1,2
1,2
○Kengo○Kengo
Takashima
Takashima, Yukihiro, Yukihiro
Takada2Takada, Takahiro, Takahiro
Yamamoto
Yamamoto1

Dept. of1Dept.
Electricalof ElectricalEngineering,Engineering,Tokyo Univ.
Tokyoof Science,
Univ. of Science,
Chiyoda-ku,
Chiyoda-ku,
Tokyo 102-0073,
Tokyo 102-0073,
Japan Japan

2

Dept. of2Dept.
LiberalofArts,Liberal
Tokyo
Arts,
Univ.
Tokyo
of Univ.
Science,of Science,
Chiyoda-ku,
Chiyoda-ku,
Tokyo 102-0073,
Tokyo 102-0073,
Japan Japan

Graphene
Grapheneis a potential
is a potential
candidatecandidate
for channel
for channelmaterials
materialsof field ofeffectfieldtransistors
effect transistors(FETs) because(FETs) becauseofof
their hightheircarrierhigh mobility
carrier mobility[1]. However,[1]. However,metallicmetallic
behaviorbehaviorof grapheneof graphene
is a major
is ahurdle
majortohurdleutilizetoitutilize itto the channel
to the channelof FETs,of because
FETs, because
high on-off
highratios
on-offareratiosnot areachievable
not achievable
without without
an energy-band
an energy-bandgap. gap.
One possible
One possible
way to overcome
way to overcome
the gap-opening
the gap-opening
problemproblem
is to process
is to process
the graphene
the graphenein the formin theofform ofnanoribbon
nanoribbon
with nanometerwith nanometer
width. Graphene
width. Graphene
nanoribbons
nanoribbons
has an energy
has an energy
gap andgap
theyandhave
theybeen
have beensuccessfully
successfully
applied applied
to FETsto
with
FETs
high
with
on-offhighratio
on-off[2].ratio [2].
The channel
The channel
length oflengthcutting-edgeof cutting-edge
GNR-FETs
GNR-FETsis less thanis less
100nm
than (the100nmminimum(the minimum
length islength~1nm).
is ~1nm).
BecauseBecausesuch channelsuch channel
lengths lengths
are shorterare shorter
than thethan
typicalthe coherent
typical coherent
length oflengthGNRs,of GNRs,
the GNRs
the isGNRs is
expectedexpected
to exhibit
to exhibit
remarkableremarkableelectronic
electronictransporttransport
properties
properties
originating
originatingfrom thefrom
wave
thenature
wave ofnature ofelectrons.
electrons.
A recentA experiment
recent experimentreportedreported
that thethat
resistancethe resistanceof GNRsof increases
GNRs increases
exponentiallyexponentiallywith with
their length
their evenlengthat eventhe room
at thetemperatureroom temperature[3]. This[3].
non-Ohmic
This non-Ohmic
behaviorbehavior
is believed
is believed
to be due
to be
to due toAnderson’sAnderson’s
localization
localization
caused causedby the byinterference
the interference
betweenbetween
coherentcoherent
electronselectrons
scatteredscatteredby the by thedisordereddisorderededges ofedges
GNRs.
of However,
GNRs. However,the detailtherelation
detail relation
betweenbetween
the edgetheroughnessedge roughness
and the andcoherent
the coherent
GNRs
not hasbeennot
clarifiedbeen clarified
yet.
yet.
length Llength
Lφ ofhasφ of GNRs
In this Instudy,
this westudy,
have
we computationallyhave computationallyinvestigatedinvestigatedthe coherent
the coherent
electronic
electronictransporttransport
ininedge-disorderededge-disorderedarmchairarmchair
GNRs (AGNRs).
GNRs (AGNRs).
The edge
Thedisorderedge disorderhas been
hastreatedbeen treatedas randomly
as randomly
distributed
distributedcarbon-paircarbon-pairvacancies
vacancies
on the edges
on theofedges
AGNR
of AGNR(Fig.1). (Fig.1).
We clarified
We clarified(i) a relation(i) a relation
betweenbetween
amountthe amountof edge ofcarbon-pairedge carbon-pairvacancies,
vacancies,(ii) the chemical-potential(ii) the chemical-potential
dependence
dependenceof Lφ, andof Lφ, andLφ and theLφ and(iii) the (iii)ribbon-width
the ribbon-width
dependence
dependenceof Lφ. of Lφ.
[1] Novoselov,[1] Novoselov,
et al., Science
et al., Science
306, 666306,(2004).
666 (2004).
[2] Schwierz,[2] Schwierz,
Nature Nanotech.
Nature Nanotech.
5, 487 (2010).
5, 487 (2010).
[3] Xu et[3]al.,
XuNanoet al.,Lett.
Nano
11,Lett.
108211,(2011).
1082 (2011).
[4] Roche,[4] Phys.
Roche,Rev.
Phys.
B 59,
Rev.2284
B 59,(1999).
2284 (1999).

Fig.1: AFig.1:
schematic
A schematic
view of aview
edge-disorderedof a edge-disordered
GNR GNR

Corresponding
Corresponding
Authors:Authors:
TakahiroTakahiro
Yamamoto
Yamamoto
TEL&FAX:TEL&FAX:+81-3-5213-0990+81-3-5213-0990
E-mail: E-mail:takahiro@rs.tus.ac.jp
takahiro@rs.tus.ac.jp- 82 -

1P-39Gapped and gapless graphene and graphene-nanoribbon/nanotube complex
Shota Kizukuri, Takashi Koretsune and Susumu Saito
Department of Physics, Tokyo Institute of Technology,
2-12-1 Oh-okayama, Meguro-ku, Tokyo 152-8551, Japan
Nanostructured carbon materials are of high importance as future device materials becauseof their variety of electronic properties. Here, we focus on graphene and armchair-edgegraphene nanoribbon (AGNR)/carbon nanotube (CNT) complex. It is expected that theinterlayer interaction between graphene and the periodically placed AGNRs/CNTs may
modify the linear dispersion around the K point and open up the band gap. So, we study theband structure of graphene and AGNR complex by first-principles calculation. It is found thata gap actually appears in some cases depending on the stacking way of AGNR on graphene aswell as the width of AGNRs and the stacking distance. Although, the graphene part in thiscomplex system deforms from a flat-geometry sheet, its band structure is still gapless.
However the whole complex system shows semiconducting property (Fig. 1), indicating theimportance of interlayer interaction. Furthermore, by changing interlayer distance, the size ofthe band gap can be controlled. By calculating the total energy as a function of interlayer
distance, we estimate the pressure value to be necessary for the band gap modulation.
We also study the band structure of graphene complex with thick CNTs. In the optimized
system, the graphene deforms to fit the shape of collapsed CNTs. In addition, to consider
more realistic systems, we also discuss the wiggle-like shaped AGNRs complex and AB-AC
stacking AGNR complex.

Fig. 1: Band structure of deformed graphene (G) and the GNRs-on-graphene complex(G-AGNR) around the K point.

- 83 -

1P-40
SGM investigation of graphene nano structure○Souhei Furuya, Kazuyuki Takai, Yoshiaki Sato, and Toshiaki Enoki
Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo
152-8551, Japan
Nano-structured graphene such as the graphene point contact is one of the mostinteresting systems in view of a study on the effect of potential barrier of the edge region of
the sample and the carrier puddling at Dirac point on the transport properties of graphene.
Scanning Gate Microscopy (SGM) is a powerful tool to investigate the effect of the local
electronic structure on the transport properties [1]. In SGM, the effect of the local electrostatic
modulation on the transport is obtained as the 2D conductance mapping as a function of theposition of the scanning gate. In this study, the SGM instrument able to operate under UHV, at
low temperature down to 2 K, in the magnetic field up to 8 T, is developed based on existing
LT-STM system as schematically shown in Fig.1. Graphene point contact structure ischaracterized toward SGM investigation on graphene.
The point contact structure of few layer graphene was fabricated by annealing of SiC at
1750 ℃ and following photolithography and oxygen plasma etching processes, where theinfluence of the local potential by the scanning gate significantly affects on the electron
scattering at a narrow bridging region between two electrodes. To compare the behavior of
carriers in graphene with those in ordinary metals, we employed the Au point contact device
on SiC as reference. SGM measurement was performed in lift-up manner, where tip went over
10 nm above the height mode scanned trajectory.
The point contact structure of graphene and Au having 700 nm channel width and 40 nm
height was successfully fabricated as shown Fig. 2 a). SGM image of Au point contact
showed no variation in the conductance, being consistent with the short mean free path andthe higher Fermi energy of Au electron system.

a)b)

75.04 nm

SiC

SiC

Au
A

Au
V

5 µm
0.00 nmFig. 1 Schematic diagram for SGM measurement

Fig. 2 a) Optical microscope image of Au point contactb) STM height image of square region of a)[1] M. A. Topinka, et al. SCIENCE 289,
289 2323 (2000)
Corresponding Author: Souhei Furuya
Tel: +81-3-5734-2610, Fax: +81-3-5734-2242, E-mail: furuya.s.ab@m.titech.ac.jp- 84 -

1P-41
Raman spectroscopy of mechanically strained chemically functionalizedgraphene○Mark A. Bissett, Masaharu Tsuji, and Hiroki Ago*
Institute of Materials Chemistry and Engineering, Kyushu University, Fukuoka, 816-8580
The unique properties of graphene make it an ideal candidate for applications in flexible
electronics such as touch screens and displays. These properties include high conductivity, as
well as transparency and mechanical flexibility. However, pristine graphene exists as a
zero-band gap material and this must be overcome before being applicable to many functional
devices. Previously, it has been shown that mechanical strain as well as chemicalfunctionalization can alter the electronic structure of graphene and possibly introduce a bandgap [1]. Thus, for optimizing the performance of graphene devices it is important to gain athorough fundamental understanding of the effects of both strain and chemicalfunctionalization on the electronic structure of graphene. In this work we utilize Raman
spectroscopy to investigate the effect of mechanical strain on both pristine single-layer
polycrystalline graphene on a flexible polydimethylsiloxane (PDMS) substrate and also
graphene that has been chemically functionalized by an aryl diazonium molecule (4-NBD), as
seen in Fig. 1a.
Our previous work has investigated the effect of strain on polycrystalline graphene andfound that the presence of domain boundaries can affect the Raman spectra which indicate achange in electronic structure [2]. The reactivity of polycrystalline graphene was found to begreatly increased due to these domain boundaries compared to exfoliated single crystalline
graphene. This high reactivity can be seen in Fig. 1b where we see an increase in the D/Gratio as well as a shift in the Raman peak positions. This shift in peak position is indicative ofa doping effect taking place. Figure 1c shows the plots of the 2D peak width with increasing
values of strain. The pristine graphene exhibits the expected linear trend; however, thefunctionalized graphene exhibits an unusual v-shaped trend. This unusual behavior is
attributed to a combination of phonon splitting caused by the chemical functionalization andalso morphological changes to the graphene lattice caused by the covalent bond formation [3].

Figure 1: (a) Schematic of functionalized polycrystalline graphene on flexible PDMS. (b) Raman
spectra with increasing 4-NBD functionalization times. (c) Plot of 2D bandwidth with increasing strain
for both pristine and functionalized graphene. Inset shows peak fitting for each sample.
[1] Zhan, D. et al., Adv. Mater., 24, 4055 (2012).
[2] Bissett, M. A. et al., ACS Nano, 6, 10229 (2012).
[3] Bissett, M. A. et al., J. Phys. Chem. C, submitted.
Corresponding Author: H. Ago, Tel: +81-92-583-7817, Fax: +81-92-583-7817, E-mail: ago@cm.kyushu-u.ac.jp- 85 -

1P-42Magnetic Interactions between Nanographite and Oxygen MoleculeżKazuyuki Takai1, Alexander. I. Shames2, Vladimir Yu. Osipov3, Alexander Ya. Vul'3,
Yutaka Kaburagi4, Takuya Hayashi5, Toshiaki Enoki1
1

Department of Chemistry, Tokyo Institute of Technology, 2-12-1 Oh-okayama,
Meguro-ku,Tokyo 152-8551, Japan, 2 Department of Physics, Ben-Gurion University of the
Negev, 84105, Be’er-Sheva, Israel, 3 Ioffe Physical-Technical Institute, Polytechnicheskaya
26, 194021, St. Petersburg, Russia, 4 Faculty of Engineering, Tokyo City University, 1-28-2,
Tamazutsumi, Setagaya-ku, 158-8557 Tokyo, Japan, 5Faculty of Engineering, Shinshu
University, 4-17-1 Wakasato, Nagano 380-8553, Japan
In nanographene, the edge state spins given by the presence of edges with S-electron
nature form ferrimagnetic spin structure, where the exchange interactions among spins are
meditated by conduction carriers [1]. In this view point, carbon onions (CO) derived fromdetonation nanodiamonds by prolonged heat treatment was interesting material, which iscomposed of well separated nanographene sheets and featured by its defective and hollow
nature, giving mangetic interactions between edge-state spin and guest adsorbed molecules[2][3]. In this study, S-electronic edge-localized spin magnetism in CO was investigated in termsof the molecular oxygen adsorption and microwave (MW) irradiation effect.
The linewidth of ESR spectra of CO under air atmosphere (oxygen pressure ~ 200 mbar) at
low incident MW power (PMW d 200 PW) shows progressive broadening of the edge-spinsignal (g = 2.0014(2) ) as the temperature decreases. At T < 140 K, the edge-spin EPR signal
becomes unobservable, revealing weak narrow ESR signal with g = 2.0022(1) ascribed tospins of localized defects(“Old”). Within the low temperature region (T < 60 K), the lattersignal demonstrates unusual enhancement in the intensities and line width upon the irradiationof the larger MW power (PMW > 20 mW) accompanied with a drastic upward deviations fromthe conventional saturation behavior. On abrupt reduction of PMW back to low power (PMW < 1mW), the new intensive narrow EPR signal with the same g = 2.0022(1) is observed with a
non-Curie-Weiss behavior in the temperature range less than 60 K (“New”), where it turns
back to the weak narrow signal (Old) (Fig. 1). The observed new magnetic entities in theoxygen adsorbed CO is explained by the antiferromagnetic coupling between the edge spinsand negatively charged O2- oxygen molecules, which is generated through the charge transfer
between nanographite and oxygen molecules in the process of desorption / adsorption ofoxygen molecules caused by high power MW-irradiation and subsequent abrupt reduction of
PMW. The antiferromagnetic dimer model well explains the observed temperature-dependenceof the ESR intensities.
Fig.1 The temperature dependence of ESR
intensities for new and old signal in CO. Solidlines indicates the fitting results with the modelof antiferromagnetic dimers.
[1] T Enoki and K Takai, Solid State Communications 149
1144 (2009)[2] V. Yu. Osipov, T. Enoki, K. Takai, et al, Carbon 44 1225
(2006)[3] A. Shames, A. M. Panich, V. Yu. Osipov, et al, J. Appl.
Phys. 107 014318 (2010)- 86 -

1P-43A new stage in the detonation nanodiamond research
Shuichi Sasaki, Ryoko Yamanoi, Eiji Ōsawa
NanoCarbon Research Institute, AREC, Faculty of Textile Science and Technology, Tokida 3-15-1,
Ueda, Nagano, ₸386-8567, Japan
Optimization of operation conditions in the disintegration of crude detonation
nanodiamond agglutinates by means of attrition milling with 30 m zirconia beads according to
Taguch’s method of the quality engineering, led to significant decrease in the average diameter ofparticle-size distribution from 4.8 to 3.7 nm in the primary particles of detonation nanodiamond(PPDN).1) We report here subsequent developments in our endeavor to develop a standard method to
obtain ensemble of polydisperse PPDNs of potentially the most useful and interesting among the
known nanocarbons from 4.8 to 3.7 nm carbons. A decisive improvement occurred when old beads
were replaced with a new batch and a few runs have been completed to reach new low diameters of
3.0 to 3.3 nm. In view of the large difference in diameters between beads and PPDN (104:1), weinterpret this high performance of new beads as the effect of being well-covered and adhered withthe primary diamond particles, which are actually responsible for disintegration of nanodiamondagglutinates. This new mechanism of disintegration will be discussed in the presentation in moredetail. The final diameter corresponds to an ensemble consisting of only the primary particles, while
the larger diameters mean persistence of small agglutinates like dimers and trimmers.
In such a small size-range, the colloidal solution of PPDN looks clearer and acquiresconsistencies in the values of pH (5.8, 5 %), viscosity (2 cps, 5%) and ζ-potential (+53 mV). In
addition to these expected behaviors of well-distributed ensemble, one remarkable size-effect wasobserved. Diamond-graphite transition in the 4.8 nm PPDN is known to occur at 800-900℃,
considerably lower than that of bulk diamond (3000-4000℃). However, the 3.0 nm PPDN
transformed quickly under irradiation of electron beam in a conventional TEM operating at 200KeV,
to give well-dispersed 5-6 layered nano-onions. The transformation seems very fast as we could notrecognize original nanodiamond particles at all in the TEM examination but completely transformed
masses of nano-onion particles (Photo 1). Quantum confinement
limit of the size of smaller nanoparticles has long been
considered to be around 1nm, but this behavior of PPDM
indicates the limiting size could be larger, around 2 nm.
(1) “Optimized de-agglomeration of detonation nanodiamond,” Sasaki, S.;
Yamanoi,R.;Ōsawa,

E.

Presented

beforethePhoto. 1. TEM
photograph
of
3nm
PPDN
immediately after
starting the TEM
observation.

42nd

Fullerenes-Nanotubes-Graphenes General Symposium, University of Tokyo,
March 6-8, 2012, Abstract Book, p. 40.

- 87 -

1P-44
Biomimetic approach toward tough nanodiamond materials○Keita Fujiwara, Toshiki Ikami, Tadamasa Ito, Masaki Ozawa
Department of Materials Science and Engineering,Meijo University, Aichi 468-8502, Japan
Nacre is composed of alternating calcium carbonate layers and protein layers well known
as “brick-and-mortar” structures. The former occupies about 93 %, while the latter about 5 %.
Despite the brittleness of the main constituent, nacre shows outstanding toughness partly
because of the characteristic structures. In addition, another mechanism was found working ata nanoscale. Each bricks are made of nanoparticles of calcium carbonate bound by proteins,
and they rotate to dissipate stresses applied. These mechanisms working at different lengthscales make nacre 1000 times tougher than calcium carbonate alone [1]. In this study,
fabrication of tough materials inspired by nacre were investigated by substituting
nanodiamonds for calcium carbonate as well as polymer networks for proteins.
As we have an unique technique to facilitate surface functionalization of nanodiamondprimary particles by using a powerful microtip-type sonicator in the presence of hard ceramicbeads [2], detonation nanodiamond derivatives thus functionalized were at first examined to
be incorporated in a polymer hydrogel, and then dried up to give nacreous bricks havingnanostructures. Carboxylated or sulfonated nanodiamonds [3] were successfully integrated ina gel of polyacrylamide or gelatin, while they showed phase separation with, for example, apoly(2-acrylamido-2-methyl-1-propanesulfonic acid)] gel. As even sulfonated nanodiamonds
are excluded from a polymer network having sulfo groups, integration is likely driven not bysimilarity of functional groups between diamonds and polymers, but by electrostatic attraction
between them. Fig. 1 displays a composite gel with polyacrylamide. The product obtained
after drying the gel was reasonably, but not outstandingly, tough, presumably due to the sizeof the particles being off the optimal values or to pores developed during the drying process.
On the other hand, the directional freezing technique [4] was employed to organize
microscale nacreous structures. Ice grains are known to be utilized as templates upon freezingof colloids. A nanodiamond colloid mixed withmonomers were directionally frozen prior topolymerization, and then a resultant composite
gel was dried up to give a material consistingof nanodiamonds and polymer networks
arranged like brick-and-mortars. Despite low
nanodiamond concentration examined so far
Fig.1
Composites of nanodiamonds withand considerable amount of pores developed inpolymer networks. A puddingy hydrogel ofthe product, a lamellar structure waspolyacrylamide with nanodiamonds (a), and adried nanodiamond-gelatin composite preparedsuccessfully obtained as in Fig. 1(b).
using directional freezing (b).

[1] X. Li et al. Nano Lett. 6, 2301 (2006)[2] Y. Liang et al.ACS Nano 3, 2288 (2009).
[3] Y. Liang et al. J. Colloid Interface Sci. 354, 23 (2011).
[4] W. Mahler, M. F. Bechtold Nature 285, 27 (1980).
Corresponding Author: T. Ito
Tel: +81-52-838-2410, Fax: +81-52-831-1170,
E-mail: 123434005@ccalumni.meijo-u.ac.jp- 88 -

1P-45
Kinetic consideration on the formation of polyyne-iodine
complex by photoinduced reaction○Yoriko Wada and Tomonari Wakabayashi
Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering,
Kinki University, Higashi-Osaka 577-8502, Japan
Polyynes are linear hydrocarbon molecules which have sp-hybridized carbon chains.
Hydrogen-end-capped polyynes, H(C≡C)nH, are the simplest model compounds for linear
carbon chain molecules. These molecules exhibit absorption bands for the allowed transitionin the UV region and those for the forbidden transition in the near UV region [1,2]. We havereported that the absorption bands for the allowed transition disappeared and those for theforbidden transition are intensified by addition of iodine molecules into the polyyne solution
under illumination with visible light. These spectral changes indicate that the formation of themolecular complex with polyyne and iodine molecules is proceeding [3]. The composition of
the polyyne-iodine complex was determined to be 1:3 for polyyne:iodine molecules fromiodine concentration dependence experiments.
In this work, we investigated the formation mechanism of the polyyne-iodine molecularcomplex by a reaction kinetic analysis. Mixed solutions of polyyne and iodine which havedifferent concentrations of iodine were prepared. The 532 nm cw-laser light irradiates themixed solution. Then, absorption spectra of the mixed solution were recorded. Figure 1 shows
temporal changes in the UV/Vis absorption spectra of mixed solution of polyyne and iodine
molecules (2.3 molar equivalent of I2/C10H2 in hexane) upon irradiation for 0-136 s. Fig 1 a)shows UV absorption spectra for C10H2 and b) visible ones for I2. The insert shows the
spectral component of C10H2 in a). The absorption band of I2 at 520 nm decreased by 17% at
136 s. If the corresponding amount of I2 wasconverted to C10H2I6, the depletion in the C10H2
absorption should be 18%. However, the observed
decrease in the C10H2 absorption was 54%. In orderto understand this photoinduced decay process, we
model chemical reactions, 1) I2 + h I2*, 2) I2* 
I2, 3) C10H2 + I2*  D + I2*. Reaction 1 represents
photoexcitation of an iodine molecule, reaction 2
represents relaxation of the active molecular iodine
I2*, and reaction 3 represents degradation of C10H2.
Based on this model, reaction kinetics wasconsidered for the observed temporal changes in the
UV/Vis absorption spectra. As a result, it wasclarified that the active molecular iodine I2* degrades
C10H2 in the case of low concentrations of I2 for the
initial concentration.

[1] E. Kloster-Jensen et al., Helv. Chem. Acta. 57 (1974) 1731.
[2] T. Wakabayashi et al., Chem. Phys. Lett. 446 (2007) 65.
[3] Y. Wada et al., J Phys. Chem. B 115 (2011) 54.
Corresponding Author: T. Wakabayashi
Tel: +81-6-6730-5880 (ex. 4101), Fax: +81-6-6723-2721,
E-mail: wakaba@chem.kindai.ac.jp- 89 -

Figure 1. Temporal changes in UV/Vis
absorption spectra of the mixture solutionof polyyne and iodine (2.3 molar
equivalent of I2/C10H2 in hexane) upon
irradiation for 0-136 s.

1P-46
Improved Mechanical Property of Bucky Paper by Adding Carbon
Nanocoil○Koji Maruyama1, Yoshiyuki Suda1, Hideto Tanoue1, Hirofumi Takikawa1,
Hitoshi Ue2, Kazuki Shimizu3, Yoshito Umeda4
1

Department of Electrical and Electronic Information Engineering,
Toyohashi University of Technology, Toyohashi, 441-8580 Japan
2
Fuji Research Laboratory, Tokai Carbon Co., Ltd.
3
Shonan Plastic Mfg. Co., Ltd.
4
Toho Gas Co., Ltd., Tokai, Aichi 476-8501 Japan.

Bucky paper which is made of carbon nanotube（CNT）is expected for application of electric
double layer capacitor（EDLC）electrode, because of high electrical conductivity and large
specific surface area of CNT . Although EDLC using bucky paper electrode has high specificcapacitance, the mechanical property of the electrode is weak. The approach in this work is toimprove the mechanical property of bucky paper by combining CNT with carbon nanocoil（CNC）.
To prepare the electrode, different amounts of multi-walled CNT（MWCNT）（10－15 nm
diameter, 3 m length）and CNC（500－800 nm coil diameter, 20－30 m length）wereultrasonicated separately in the aqueous（SDC 1 wt% solution）and mixed. The solution was
filtered through a 0.22m cellulose membrane and rinsed with deionized water to obtain theelectrodes. Fig. 1 shows the fracture surface of the CNT/CNC electrode. To measure themechanical property, we conducted testing of the electrode in tension （Fig. 2）. Young’s
modulus was calculated from slopes of the lines in Fig. 2. The results show that Young’s
modulus was improved from 1.4 GPa to 1.81 GPa by adding CNC.
This work has been partly supported by the Research Project of the Venture BusinessLaboratory from Toyohashi University of Technology (TUT); the Core University Programs(JSPS-CAS program in the field of "Plasma and Nuclear Fusion") from the Japan Society for
the Promotion of Science (JSPS); and a Grand-in-Aid for Scientific Research from JSPS.
1.2

Stress (GPa)

1.0
0.8
0.6

1.81GPa

1.4GPa

CNT
CNT/CNC

0.4
0.2
0.0
0.0

Fig. 1 SEM image of fructure surface of
CNT/CNC electrode.

0.5

1.0

1.5

2.0

Strain (%)

Fig. 2 Tensile stress curve of CNT and CNT/CNC
electrodes.

Corresponding Author: Yoshiyuki Suda
Tel: +81-532-44-6726, Fax: +81-532-44-6757, E-mail: suda@ee.tut.ac.jp- 90 -

1P-47
Measurement of electric resistance of a single carbon nanocoil○Ryuji Kunimoto 1, Taiichiro Yonemura1, Yoshiyuki Suda1, Hideto Tanoue1,
Hirofumi Takikawa1, Hitoshi Ue2, Kazuki Shimizu3, Yoshito Umeda4
1

Department of Electrical and Electronic Information Engineering,
Toyohashi University of Technology, Toyohashi 441-8580, Japan
2
Fuji Research Laboratory, Tokai Carbon, Co., Ltd., Oyama 410-1431, Japan
3
Development Department, Shonan Plastic Mfg. Co., Ltd., Hiratsuka 254-0807, Japan
4
Toho Gas Co., Ltd., Tokai, Aichi 476-8501, Japan
Carbon nanocoil (CNC) is predicted to have a high mechanical strength [1], and we focus on
the elongation behavior of CNC. The purpose of this study is to measure the electricalresistance of CNC when it is elongated under the tensile load. CNC was synthesized in ourlaboratory by chemical vapor deposition [2]. Fig. 1 shows that the SEM image of a preparedsample. We have prepared a CNC sample using focused ion beam (FIB), and fixed the end of
CNC to Au film on SiO2/Si substrate. Silver paste was used to bond Au film with a stage of
SEM. The stage of SEM was connected to the manipulator tip through a source meter. We
approached the manipulator tip to the CNC and measured the electrical resistance of CNC.
Table 1 shows the measurement results of the electrical resistances of CNC. Electricalresistance measurements were carried out by making the tip contact point A and point B in Fig.
1. Measured value of the former is a resistance of the whole measurement system without
CNC. Therefore, the resistance of CNC was obtained by subtracting the value of the former
from that of the latter. It was measured that the electrical resistance of CNC is in the order ofseveral hundred kΩ.
This work has been partly supported by the Research Project of the Venture BusinessLaboratory from Toyohashi University of Technology (TUT); the Core University Programs(JSPS-CAS program in the field of "Plasma and Nuclear Fusion") from the Japan Society for
the Promotion of Science (JSPS); JSPS KAKENHI Grant Number 24360108; and MEXT
KAKENHI Grant Number 24110708.
Table 1 Measurement of electrical resistance of three CNC samples.

Point B

Sample 1

Sample 2

Sample 3

Coil length [m]

11.7

5.5

12.5

Coil diameter [nm]

730

1400

1240

Wire diameter [nm]

600

500

677

Resistance [kΩ]

290

80

621

SiO2film

CNC

Pt

Point AAu film

Fig. 1 Preparation of measurement
sample of CNC[1] S. Motojima, et al: Diamond & Related Materials, 13, 1989 (2004)[2] K. Takimoto, et al., The 37th Fullerene-Nanotubes General Symposium (2009) 3P-30
Corresponding Author: Yoshiyuki Suda
Tel: +81-532-44-6726, Fax: +81-532-44-6757, E-mail: suda@ee.tut.ac.jp- 91 -

2P-1
ESR Measurements of Series of [n]Cycloparaphenylene Cation Radicals in
Solution○Takahiko Kouyama1, Eiichi Kayahara2, Shigeru Yamago2, and Tatsuhisa Kato 1, 3
1

Department of Interdisciplinary Environment, Graduate School of Human andEnvironmental Studies, Kyoto University, Kyoto 606-8501, Japan
2
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan
3
Institute for the Promotion of Excellence in Higher Education, Kyoto University, Kyoto 6068501, Japan
Cycloparaphenylenes (CPPs) are molecules with the simplest structure unit of armchaircarbon nanotubes. Yamago group of author succeeded in selective syntheses of [n]CPPs.[1]The systematic study of the electric structure of the series of CPPs would attract thetheoretical attention. We report here ESR studies of radical cations prepared by the oxidationof [n]CPPs (n=6,8,10,12) with SbCl5 in CH2Cl2 solvent by using a X band- ESR spectrometer.
The ESR spectra of [n]CPPs (n=6,8,10,12) radical cations in CH2Cl2 solution wereobtained at 293K. All observed spectra were well reproduced by the computer simulation, as
shown in Fig 1. The ESR parameters of g factors, 1H hyperfine coupling (hfc) constants, andline widths ΔHpp determined by
Table 1. g factors and hfc constants obtained by simulation
the simulation are tabulated ing factor
hfc
ΔHpp
Table 1. It is noticeable that the gconstant
factors are greater than the value[6]CPP
2.00280.0429 /0.0128 /of free electron, ge = 2.0023, andmT
mT
that the smaller 1H hfc constants[8]CPP
2.00230.03430.0194are obtained for the bigger size of[10]CPP2.00310.02930.0180paraphenylene ring.
[12]CPP2.00300.02490.0156
Observed[6]CPP

Simulated[8]CPP

Observed
Simulated[10]CPP

Observed

Simulated[12]CPP

Observed
Simulated

327.5

328.0

328.5

329.0

329.5

Magnetic Field / mT

Fig.1 ESR spectra of [n]CPPs (n=6 - 12) radical cations in CH2Cl2 solution recorded at 293K.
[1] T. Iwamoto et al. J. Am. Chem. Soc., 133, 8354 (2011).
Corresponding Author: T. Kato
Tel: +81-75-753-6695, Fax: +81-75-753-6695,
E-mail: kato.tatsuhisa.6e@kyoto-u.ac.jp- 92 -

2P-2
Isolation and Properties of a Cyclopentadiene Adduct ofLithium-ion Encapsulated [60]Fullerene○Hiroki Kawakami, Hiroshi Okada, Yutaka Matsuo
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan
There have so far been many reports on functionalization of fullerene by the Diels-Alderreaction [1]. Cyclopentadiene (CpH), which is a conjugated diene used in the Diels-Alderreaction, reacts with [60]fullerene smoothly to give an adduct C60-CpH [2]. Its thermal
stability and kinetic parameter have been reported [3]. In the endohedral metallofullerene
research field, the reversible and regioselective addition of CpH to La@C82 has been reported
in 2005 [4].
We investigated reactivity between lithium-ion-encapsulated fullerene (Li+@C60) and CpH.
The reaction of [Li+@C60]PF6Ð with CpH immediately proceeded and produced amono-adduct([Li+@C60(CpH)]PF6Ð)andbis-adducts([Li+@C60(CpH)2]PF6Ð).
[Li+@C60(CpH)]PF6Ð was isolated with electrolyte-associated HPLC technique. The HPLC
charts before and after isolation are shown in figure 1. Then, the behavior of desorption andaddition of CpH was compared with that of empty C60 adduct (C60(CpH)). Light absorption
and electrochemical properties of [Li+@C60(CpH)]PF6Ð will be also presented.
PF6Ð

PF6Ð

Li+



+

PF6Ð
Li+

Li+

Ð

+

PF6Ð

Ð

[Li @C60(CpH)2]PF6 [Li @C60(CpH)]PF6

+

Li+

+

Ð



Ð

[Li @C60(CpH)]PF6[Li @C60]PF6

Isolation
time

time
+

Figure 1. Analytical HPLC charts of [Li @C60]-CpH adducts before and after isolation
Buckyprep column with an eluent system of o-dichlorobenzene and acetonitrile (95:5 v/v)
containing 30 mM tetrabutylammonium hexafluorophosphate (Bu4NPF6)[1] Śliwa, W. Full. Sci. Techn. 1997, 5, 1133Ð1175.
[2] Rotello, V. M. et al. Tetrahedron Lett. 1993, 1561-1562.
[3] a) Pang, L. S. I.; Wilson, M. A. J. Phys. Chem. 1993, 97, 6761Ð6763. b) Howard. B. J.; Rotello. M. V. et al. J.
Phys. Chem. 1993, 97, 8560Ð8561.
[4] Hasegawa, T.; Akasaka, T.; Nagase, S. et al. J. Am. Chem. Soc. 2005. 127. 12190Ð12191.
Corresponding Author: Y. Matsuo
Tel: 03-5841-1476, Fax: 03-5841-1476, E-mail: matsuo@chem.s.u-tokyo.ac.jp- 93 -

2P-3
Solution-phase Synthesis of Dumbbell-Shaped Dimer C120 by the Use of
FeCl3
Masahiko Hashiguchi1, ○Hiroshi Inada2 and Yutaka Matsuo2
1

Fullerene Development Group, Performance Products Division, Mitsubishi Chemical
Corporation, 1-1 Kurosakishiroishi, Yahatanishi-ku, Kitakyushu 806-0004, Japan2
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan

Fullerene chemists and carbon cluster scientists have devoted much attention to fullerene
dimers, because of their unique structures that are thought to be intermediates in fullerenepolymerization. Among them, special attention has been paid to buckminsterfullerene dimer,
C120, which is composed of only carbon atoms [1]. The first reported C120 synthesis usedhigh-speed vibration milling [2-4]. On the other hand, a solution-phase synthesis of the dimer
C120 has yet to be reported. Solution-phase synthesis offers certain advantages: the synthesis
can be conducted by using common laboratory glassware and etc.
C60 was converted into C120 in the presence of FeCl3 in 1,1,2,2-tetrachloroethane at 150 ¡Cunder nitrogen atmosphere. Aromatic organic solvents such as toluene and xylene are often
used in synthesis of fullerene derivatives. However they are not suitable for this reaction
because they cause a side reaction [5-9].
C120 was characterized with electrospray ionization mass spectrometry, attenuated totalreflection fourier transform infrared spectrometry, and X-ray crystal structure analysis. We
will discuss the proposed reaction mechanism in this presentation. These findings will provide
opportunities for further investigation to obtain polymeric structures of fullerenes in thesolution phase as well as to expand applied research on C120.
[1] J. L. Segura et al. Chem. Soc. Rev. 29 13 (2000).
[2] G-W. Wang et al. Nature. 387 583 (1997).
[3] K. Komatsu et al. J. Org. Chem. 63 9358 (1998).
[4] K. Komatsu et al. Carbon 38 1529 (2000).
[5] G. A. Olah et al. J. Am. Chem. Soc. 113 9387 (1991).
[6] A. Iwashita et al. Angew. Chem. Int. Ed. 46 3513 (2007).
[7] S. H. Hoke II et al. Rapid Commun. Mass Spectrometry 5 472 (1991).
[8] M. Hashiguchi et al. Org. Biomol. Chem. 9 6417 (2011).
[9] M. Hashiguchi et al. Org. Lett. 14 3276 (2012).
Corresponding Author: Y. Matsuo
Tel: +81-3-5841-1476, Fax: +81-3-5841-1476
E-mail: matsuo@chem.s.u-tokyo.ac.jp- 94 -

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2P-5
Cycloadditions to La2 @C80 and vibronic coupling density analysis◦ Naoki Haruta1 , Tohru Sato1,2 , Kazuyoshi Tanaka1
1 Department of Molecular Engineering, Graduate School of Engineering,

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

Nishikyo-ku, Kyoto 615-8510, JapanThe frontier orbitals of large molecules such as fullerenes are sometimes delocalized throughout the molecules. In such a case, the frontier orbital theory has diﬃculty in predicting theirreactivity. To overcome this diﬃculty, we have clariﬁed that it is eﬀective to consider an electronic state as well as molecular vibrations [1, 2]. In this study, we discuss the reactivity of an
endohedral metallofullerene La2 @C80 from the view of vibronic (electron-vibration) couplings.
Vibronic coupling density and its integration, a vibronic coupling constant are discussed
as reactivity indices. Vibronic coupling means the interaction between electrons and molecular vibrations. The vibronic coupling constant Vs and the vibronic coupling density ηs (r) are
expressed by∫Vs =ηs (r)d3 r, whereηs (r) = ∆ρ(r) × vs (r).

∆ρ(r) is the change of electron density in a reaction process. For example, for nucleophilic
attacks, it is the electron density diﬀerence between neutral and anionic states. vs (r) is thepotential derivative with respect to vibrational mode s. According to the Hellman–Feynman
theorem, Vs is exactly equal to the gradient of the potential surface with an electronic statechanged in a reaction process. Vs has therefore the physical meaning of the driving force todeform the molecule along the vibrational mode s in the early stage of a chemical reaction.
ηs (r) can be regarded as the local picture of a chemical reaction, which is illustrated on thebasis of an electronic structure ∆ρ(r) and a vibrational structure vs (r).
In this study, we performed the DFT calculations (BP86functional; all electron basis sets C: TZ2P, La: TZP) for
the neutral and charge-transfer (ionic) states of La2 @C80 including relativistic eﬀects as ZORA with the ADF 2012.01
package. La2 @C80 has a much unstable D5d isomer, andD2h , D3d , C2h and Ci isomers whose energy diﬀerences areless than 50 meV. At the room temperature, all the D2h , D3d ,C2h and Ci isomers are possible and averaged to be observed.
Therefore, we here analyzed the reactivity of a D3d isomer
which has the highest symmetry of them. Fig. 1 shows thepotential derivative vs (r) caused by an eﬀective vibration for
nucleophilic attacks. The double bonds indicated by arrows
are more reactive than others, that is consistent with exper- Fig. 1: The potential derivative
imental facts [3]. In the present work, we will discuss the vs (r) caused by an eﬀective vivibronic couplings on the basis of the electronic and vibra- bration for nucleophilic attacks.
tional structures in more detail.
[1] T. Sato et al, Chem. Phys. Lett. 531, 257 (2012).
[2] N. Haruta et al, J. Org. Chem. 77, 9702 (2012).
[3] M. Yamada et al, J. Am. Chem. Soc. 128, 1402 (2006).
Corresponding Author: T. Sato
Tel: +81-75-383-2803, Fax: +81-75-383-2556,
E-mail: tsato@moleng.kyoto-u.ac.jp- 96 -

2P-6
A Novel Non-IPR Endohedral Metallofullerene: La2@Cs(17490)-C76○Mitsuaki Suzuki,1 Naomi Mizorogi,1 Zdenek Slanina,1 Xing Lu,1,2
Shigeru Nagase,3 and Takeshi Akasaka1
1Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
State Key Laboratory of Materials Processing and Die & Mould Technology, School ofMaterials Science and Engineering, Huazhong University of Science and Technology (HUST),
3
Fukui Institute for Fundamental Chemistry, Kyoto University.
2

Fullerenes are pure-carbon molecules consisting of exactly 12 pentagonal carbon
rings and a varied number of hexagons, which depend on the cage size. Thus, fullerene
chemistry has the very important experimental rule, that is, the isolated pentagon rule (IPR).
The search for fullerene structures violating the IPR is of particular importance and of wide
interest because non-IPR cages might exhibit different properties from those of IPR-compliant
structures. Two strategies have shown practical effectiveness in generating non-IPR fullerene
cages. One of them is the encapsulation of metallic species inside the fullerene cages, which
generates hybrid molecules known as endohedral metallofullerenes (EMFs). Until now, agreat number of endohedral metallofullerenes (EMFs) have been discovered. EMFs have very
unique structures and properties because of the electron transfer from encapsulated species tofullerene cage. This also results in several prominent examples of EMFs that do not satisfy the
IPR with cage sizes spreading from C72 to C84. This serves as a solution for stabilizing
non-IPR fullerene cages which seems more effective because many more examples of
non-IPR EMFs have been obtained.1
Herein, we report the isolation andsystematic characterization of a new non-IPR EMF,
i.e. La2@Cs(17490)-C76, including the firstsingle-crystal X-ray diffraction crystallographic
result of a non-IPR EMF possessing a C76 cage.
Moreover, the motion of the two encapsulated La
ions has been examined using variable-temperature
139
La NMR, providing new insights into the Fig. 1. X-ray structure of La2@C76·
metal-cage interactions in these types of Ni(OEP)·2(benzene)·CS2. Solvent molecules
and hydrogen atoms are omitted for clarity.
unconventional EMFs.
[1] (a) Endofullerenes: A New Family of Carbon Clusters, Akasaka, T.; Nagase, S. Eds.; Kluwer: Dordrecht, The
Netherlands, 2002. (b) Yang, S.; Dunsch, L. Endohedral Fullerenes, in Nanomaterials: Inorganic andBioinorganic Perspectives, Lukehart, C. M. and Scott, R. A. Eds. John Wiley & Sons: Chichester, United
Kingdom, 2008, pp189-214. (c) Chemistry of Nanocarbons, Akasaka, T;. Wudl, F.; Nagase, S. Eds.;
Wiley-Blackwell: London, 2010. (d) Lu, X.; Akasaka, T.; Nagase, S. Rare Earth Metals Trapped inside
Fullerenes−Endohedral Metallofullerenes, in Rare Earth Coordination Chemistry: Fundamentals andApplications, Huang, C. H. Ed. John Wiley & Sons: Singapore, 2010, pp 273-308.
Corresponding Author: T. Akasaka
Tel: +81-29-853-6409, Fax: +81-29-853-6409,
E-mail: akasaka@tara.tsukuba.ac.jp- 97 -

2P-7
Magnetic Properties of Gd@C82-PEG-b-PAMA-complexed Nanoparticle○Toshihiro Aizawa1, Yukichi Horiguchi2, Yukio Nagasaki2, 3, 4, Hisanori Shinohara5, andTatsuhisa Kato 1, 6
1

Department of Interdisciplinary Environment, Graduate School of Human andEnvironmental Studies, Kyoto University, Kyoto 606-8501, Japan
2
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573,
Japan
3
MasterÕs School of Medical Sciences, University of Tsukuba, Tsukuba 305-8573, Japan
4
Satellite Laboratory of International Center for Materials Nanoarchitectonics, National
Institute of Materials Science, Tsukuba 305-8573, Japan
5
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
6
Institute for the Promotion of Excellence in Higher Education, Kyoto University, Kyoto 6068501, Japan
Gadolinium is a promising candidate for MRI contrast agent because of the significant
variations in the water relaxation time. Nagoya group of author has reported that gadolinium
fullerenol Gd@C82(OH)n exhibited the efficient reduction of relaxation time.[1] Tsukuba groupof author reported the solubilization of Gd@C82 in water by synthetic block copolymers,poly( ethylene glycol)-b-poly [N,N-(dimethylamino) ethyl methacrylate] (PEG-b-PAMA).[2]We report here the magnetic properties of Gd@C82-PEG-b-PAMA by ESR spectroscopy.
The electron spin state of intact Gd@C82 has been reported by Kyoto group.[3] The chargetransfer of three electrons of gadolinium outer electron shell gave the electronic state of
Gd3+@C823-. And the spin (S = 1/2) on the π orbital of the fullerene cage was coupled with theoctet spin (S = 7/2) of the encapsulated gadolinium in an antiferromagnetic manner, then the
ground state of Gd@C82 was characterized by an integer spin quantum number S = 3. In thesolid powder form of Gd@C82 , the radical electrons canceled upon dimeraization, and theresultant spin state of the dimer was described by two independent octet (S = 7/2) spins of thegadolinium. Thus the radical spin on the cage contributed to the peculiar spin state of
Gd@C82.
The ESR spectra of Gd@C82-PEG-bPAMA were obtained by X band ESR
measurement in frozen solution of water withvarious pH at 5K, as shown in Fig.1. The
sharp peak at the magnetic field of 3500
Gauss was prominent feature in the spectrum,
whose line width varies with pH of solution.
[1] H. Kato et al. J. Am. Chem. Soc. 125, 4391 (2003).
[2] Y. Horiguchi et al. Sci. Technol. Adv. Mater. 12,044607 (2011).
[3] K. Furukawa et al. J. Phys. Chem. A 107, 10933(2003).
Corresponding Author: T. Kato
Tel: +81-75-753-6695, Fax: +81-75-753-6695,
E-mail: kato.tatsuhisa.6e@kyoto-u.ac.jp- 98 -

Fig.1 ESR spectra of Gd@C82-PEG-b-PAMA infrozen solution of water with different pH at 5K.

2P-8
Synthesis of C70 Nanosheets
by Liquid-Liquid Interfacial Precipitation Method○Kana Osonoe, Ryosuke Kano and Masaru Tachibana
Department of Nanosystem Science, Yokohama City University, Yokohama 236-0027, Japan
C70, one of the higher fullerenes, has narrow band gap than C60. So C70 is very interesting forthe application to a nanoelectronic device. However, it is difficult to get a high quality C70
crystal because C70 has some phase transitions near room temperature and symmetry being
lower than C60. Therefore there are fewer studies on solid state properties of C70 than C60.
Recently, for the control of the crystal shape, much attention has been paid for the solution
growth. A liquid–liquid interfacial precipitation method (LLIP method) leads to not only thecontrol of crystal shapes but also the short time growth for the crystals [1]. The LLIP method
is expected as an effective method for practical use. In this paper, we report the synthesis of
C70 nanosheets by LLIP method.
C70 nanosheets were prepared by LLIP method with an interface between C70-saturated toluene with ferrocene and IPA. Fig. 1 shows optical microscopic image of the crystals grownfor 24 hours by LLIP method. They exhibit hexagonal shapes with ~200 nm in thickness and10 µm in diameter. Fig. 2 shows XRD pattern of C70 nanosheets. From the XRD pattern, thestructure of C70 nanosheets exhibits a monoclinic structure including ferrocene (a = 27.15Å, b= 10.21Å, c = 19.25Å, β = 121.73°). In addition, it should be noted that the monoclinic structure of C70 nanosheets change to a face-centered cubic one with annealing. We present thegrowth method of C70 nanosheets and the structural characteristic.

Fig. 1 The optical microspopepic image

Fig.2 The XRD pattern of C70 nanosheetsof C70nanosheets.

[1] T. Wakahara et al. J. Am. Chem. Soc 131 (2009) 6372
Corresponding author: Masaru Tachibana, YokohamaCity University, 22-2 Seto, Kanazawa-ku,
Yokohama 2360027, Japan, Tel &Fax: +81-45-787-2360, E-mail: tachiban@yokohama-cu.ac.jp- 99 -

2P-9Synthesis of C60 Derivatives Having a Sulfur-containing Opening and
X-ray Structure of N2 Encapsulated MoleculeżTsukasa Futagoishi,1 Michihisa Murata,1 Yasujiro Murata1,21Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
2
JST-PRESTO

We have already established methods to synthesize endohedral fullerenes encapsulating
helium1, dihydrogen2, and water3, based on skeletal modifications of fullerenes by organic
reactions.4 In order to further extend our research to the encapsulation of larger molecules,
development of a method to enlarge the opening is required. In this work, we prepared C60
derivatives with a large opening by using sulfur insertion as a key reaction.

A sulfur insertion was carried out to tetraketo-C60 derivative 13 with a 16-membered-ring
opening under the presence of a reducing agent. This reaction afforded a novel open-cage C60
derivative 2 having a 17-membered-ring opening by insertion of a sulfur atom to the rim of
the opening. Furthermore, we unexpectedly found that new sulfur-containing compounds also
formed in this reaction; an insertion of two sulfur atoms to the opening of 1 gave 3 andsubsequent loss of one carbonyl group gave 4 (Scheme 1). 1H NMR and X-ray structural
analysis showed that a water molecule was encapsulated in 2-4.
Then an insertion of dinitrogen to 2 was studied. After powder of 2/H2O@2 was heatedunder vacuum, the powder was subjected to nitrogengas (10 atm). In order to inhibit the release ofdinitrogen, one of the carbonyl groups of 2 wasimmediately reduced (Scheme 2).5 Although the
product was a mixture of 5 encapsulating dinitrogenor water, N2@5 was found to be separated from the
mixture by HPLC (Buckyprep column). X-ray
structural analysis of N2@5 clearly showed that
dinitrogen was present at the center of the C60 cageof 5 (Fig. 1).
[1] Y. Morinaka, F. Tanabe, M. Murata, Y. Murata, K.
Komatsu, Chem. Commun. 2010, 4532. [2] K. Komatsu, M.
Murata, Y. Murata, Science 2005, 307, 238. [3] K. Kurotobi, Y.
Murata, Science 2011, 333, 613. [4] M. Murata, Y. Murata, K.
Komatsu, Chem. Commun. 2008, 6083. [5] S.-C. Chuang, Y.
Murata, M. Murata, K. Komatsu, Chem. Commun. 2007, 1751.
Corresponding Author: Y. Murata Tel: +81 774-38-3172, Fax:
+81 774-38-3178, E-mail: yasujiro@scl.kyoto-u.ac.jp- 100 -

2P-10
Polymerization in C60 thin films deposited under in situ UV light irradiation○Daijiro Arai1,2, Hisanori Tanimoto1, Manabu Ohtomo2, Shiro Entani2, Yoshihiro
Matsumoto2, Seiji Sakai2
1

Institute of Materials Science, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki
305-8573, Japan
2
Advanced Science Research Center, Japan Atomic Energy Agency, Shirakata-Shirane 2-4,
Tokai, Ibaraki 319-1195, Japan[Introduction] Polymerized C60 film is of interest for some attractive property, such as highelectrical conductivity due to the unique electronic structure[1]. While there have been several
reports on the polymerization method of C60, light irradiation has advantages of simplicity andcontrollability for nano-scale fabrication. However, since the light penetration depth into C60
films is limited to ~100 nm, it is difficult to fabricate homogeneous C60 films essential forelectronic applications. In the present study, microstructures are investigated for the C60 films
deposited under in situ UV light irradiation by using X-ray diffraction (XRD), micro-Raman
spectroscopy and X-ray photoelectron spectroscopy (XPS). It is demonstrated that the in situ
UV light irradiation leads to a growth of FCC crystal with high polymerization degree of C 60
comparable to that in the high-pressure phase through the entire thickness.
[Experimental] C60 films of 100’s nm thichness were deposited on Si substrates at room
temperature. To perform in situ UV light (λ = 365 nm) irradiation, the substrate was tilted
with respect to the directions of a Knudsen-Cell and incident light source. After the deposition,
the lattice parameter and degree of polymerization were estimated from the XRD data. The
thermal stability of the C60 photopolymer was investigated for the change of the Raman
spectrum by thermal annealing. The electronic structures were also investigated by XPS.

Intensity(a.u.)(111)(220) (311) (222)[Result & Discussion] Figs. 1(a) and 1(b) show
the XRD patterns obtained for the C60 films(a) pristine C60
deposited without and with UV light irradiation(pristine and in situ UV irradiated C60 film),
respectively. For the in situ UV irradiated films,(b) in situ UVlight irradiation
the diffraction peaks due to the (111), (220), and(310) reflections of the FCC lattice are observed;
however, the peak positions are shifted to higher(c) after annealing
at 403K
angles compared with the pristine C60 film. The
estimated lattice constant is 1.355 nm, which is
10
15
20
25
4% smaller than that of pristine C60. From the2θ(deg.)micro-Raman measurements, it is also confirmedthat C60 molecules in the in situ UV irradiated Fig. 1 XRD patterns of the C60 films. (a) pristine
films are uniformly polymerized. The number of C60 film, (b) in situ UV light irradiated C60 film
2
the covalently-bonded C60 around a C60 molecule (80 mW/cm , 300 nm thick), (c) and the same
was estimated to be about 6 from the lattice film after annealing at 403 K.
constant, which is larger than that reported for the C60 photopolymer by post lightirradiation[2] and comparable to that in the high-pressure phase[1]. More details including the
XPS results will be reported on the presentation.

[1] T. L. Makarova, Semiconductors 35, 243(2001)[2] E. Kovats et al. J. Phys. Chem B 109,11913(2005)- 101 -

2P-11Chirality dependence of exciton diffusion in air-suspended single-walledcarbon nanotubes○A. Ishii, A. Yokoyama, M. Yoshida, T. Shimada, Y. K. Kato
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
In single-walled carbon nanotubes, exciton diffusion affects the photoluminescencequantum efficiency through substrate- and defect-induced nonradiative decay of the excitons,
and therefore quantitative characterization of exciton diffusion is important. In the case of
air-suspended nanotubes, exciton diffusion lengths can be determined by analyzing thedependence of photoluminescence intensity on nanotube length [1]. As this method requires~30

nanotubes

foraparticularchirality,

we

have

constructedanautomated

micro-photoluminescence system which allows us to characterize over five hundredindividual carbon nanotubes in a day. A three-dimensional programmable stage is used toautomatically locate and list the positions of bright nanotubes. Excitation wavelength,
intensity, and polarization angle are automatically controlled to fully characterize thesenanotubes. Using this system, hundreds of as-grown air-suspended carbon nanotubes arecharacterized, and data from high quality individual tubes are selected to investigate thechirality dependence of exciton diffusion length.
This work is supported by SCOPE, KAKENHI, KDDI Foundation, The Sumitomo
Foundation, and the Photon Frontier Network Program of MEXT, Japan. The samples arefabricated at the Center for Nano Lithography & Analysis at The University of Tokyo.
[1] S. Moritsubo et al., Phys. Rev. Lett. 104, 247402 (2010).
Corresponding Author: Y. K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 102 -

2P-12
Electric Double Layer Transistors using Thick Films in Single Chiral Statesof (6,5) and (11,10) Single-Wall Carbon Nanotubes○Kudo Hikaru1, M. Kawai1, H. Tomoyuki1 ,Yuki Nobusa2, Taishi Takenobu2, Kazuhiro Yanagi1
Tokyo Metropolitan Univ.1, Waseda Univ.2
Recent progress of purification techniques enables us to obtain metallic, semiconducting and single
chiral SWCNTs, and then purified semiconducting SWCNTs have been used as field effect transistor
applications. In the case of typical SWCNT thin film transistors, device performances have beensignificantly influenced by the morphologies of the networks of the semiconducting SWCNTs. Thus, how
the electronic structures of the semiconducting SWCNTs affect the performances has not been wellrevealed. In the case of electric double layer transistors (EDLT), transistor performances depend on theelectronic structures of SWCNTs because quantum capacitance, which is related to the density of states of
SWCNTs, influences the capacitance of the channel at low voltages. Thus we investigated device propertiesof EDLTs of (6,5) and (11,10) SWCNTs, which were obtained by gel and ultracentrifugation purifications[1], and clarified their differences.
Figure 1 shows transfer characteristics of (6,5) and (11,10) SWCNTs EDLT. The on/off ratios of bothtransistors were more than 104, and motilities were 50 to
80 cm2 V-1s-1. As shown in Fig. 1, distinct differences wereobserved in the threshold voltages of EDLTs. Thresholdvoltages of (11, 10) was smaller than those of (6,5),
reflecting the band-gap widths of the SWCNTs. The
backgrounds of the distinct threshold voltages aredifferences in their capacitance characteristics (Fig. 2).
Quantum capacitance due to the densities of states of (6,5)
and (11,10) SWCNTs influenced the threshold voltages ofFig. 1 Transfer characteristics of EDLTs of(6,5) and (11,10) SWCNTs

the EDLTs of the SWCNTs.

[1] H. Liu et al., Phys. Stat. Solidi B 248,

2524 （2011）, M.

Kawai et al., J. Am. Chem. Soc. 134, 9545 (2012).
Corresponding Author: K. Yanagi
Tel: +81-42-677-2494,
Fax: +81-42-677-2483,
E-mail: yanagi-kazuhiro@tmu.ac.jp

Fig. 2 Capacitances of EDLTs of (6,5) and(11,10) SWCNTs- 103 -

2P-13
Existence of two distinct equilibrium states in the exchange reaction of
sodium cholate and oligo DNA on single-walled carbon nanotubes○Yuichi Kato1, Yasuro Niidome1,2, Naotoshi Nakashima1,2,3

1

Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
2
WPI-I2CNER, Kyushu University, Fukuoka 819-0395, Japan
3
JST-CREST, Chiyoda-ku, Tokyo 102-0075, JapanA deep understanding of the solubilization of the single-walled carbon nanotubes (SWNTs)
is essential from the viewpoints of fundamental science and applications. Although surfactant
micelles are the most typical SWNT solubilizers, quantitative analysis on the concentration
dependence of surfactant on the SWNTs has been very limited. In general, SWNT
solubilization requires a certain concentration of surfactants. These concentrations do notcoincide with the critical micelle concentration (CMC) in some cases.[1]Previously, based on thermodynamics, we provided the equilibrium constants (Kexchange)
and thermodynamical parameters of the exchange reactions of DNAs and sodium cholate(SC) (concentration below the CMC) on the SWNTs.[2,3] Here, we describe the finding thattwo distinct equilibrium states exist in the exchange reaction of sodium cholate and DNAs on
the surfaces of the SWNTs.
We prepared SC dispersed SWNT solutions by sonication and centrifugation. The
SC-SWNT solutions, DNA solutions and buffer solutions were mixed. The DNA
concentration ([DNA]) was adjusted from 0 to 0.14 mM. The SC concentration ([SC]) was
adjusted from 1.2 to 4.8 mM. The absorption spectra were measured. In order to compare theexchange reactions with different SC concentrations, we plotted the [DNA] where the surface
coverage of the SC (θSC) equals the surface
coverage of the DNA (θDNA) as a function of [SC](Fig. 1). Note that the plots showed a linear
relation; however, two slopes were observed in the
different [SC] range. Fig. 1 represents the existenceof two states of the SC-SWNTs. The transition in
the two states occurs in a very small [SC] range.
The surface tensions of the SC solutions
revealed that the CMC is approximately 14 mM,
which is much higher than the observed breakpoints in Fig. 1. Both absorption peak wavelengths
and zeta potentials of the SC-SWNTs with different[SC] values do not show any signs. These results Fig. 1 Plots of DNA concentrations as asuggest the transitions of the adsorption structure at function of the SC concentrations in which
the surface coverages (θSC and θDNA) werecertain SC concentrations with different equivalent.
chiral-types of SWNTs under the CMC of SC.
[1] A. Ishibashi, N. Nakashima, Chem. Eur. J. 12, 7595–7602 (2006).
[2] Y. Kato, Y. Niidome, N. Nakashima, Chem. Lett. 40, 730–732 (2011).
[3] Y. Kato, A. Inoue, Y. Niidome, N. Nakashima, Sci. Rep. 2, art. no. 733 (2012).
Corresponding Author: N. Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 104 -

2P-14Control of UV Optical Absorption of Single-Wall Carbon Nanotubes Using
Electro-chemical Doping Techniques○Toru Igarashi1, Kai Hasegawa1, Tomoyuki Funabasama1, Shimpei Ono2, Kazuhiro Yanagi 1
1

Department of Physics, Tokyo Metropolitan University, 2. CRIEPI

Steep optical absorption line-shapes of single-wall carbon nanotubes (SWCNTs) are due to
one-dimensional characteristics, quantized conditions along circumference direction, andexcitonic effects in the SWCNTs. However, the physical backgrounds of a broad opticalline-shape, which is sometimes observed in bundled SWCNTs and has absorption maximum
at about 4.5 eV (here the band is termed as U-band), have still been under discussion. In
previous studies, the detailed investigations of the U-band are sometimes prohibited by thepresence of un-identified amorphous carbon species and different chiralities. However,high-purity SWCNTs in a single-chiral state have been obtained by recent purification
techniques, and made it possible to discuss the details of the U-band. Figure 1 shows opticalabsorption spectra of (6,5) SWCNTs in a solution and their films. In the solution, although
there were absorption bands in UV region, which will be due to the -* transitions, U-band
was not significant. However, in a film where the SWCNTs were bundled, the absorbance ofU-band became dominant in the spectra. Therefore, it is clear that physical phenomena in the
SWCNT-bundles play important roles for the U-band.
The presence of the U-band is a bottle-neck forelectrochromic applications of SWCNTs,1 and also
understanding of the background of the U-band is offundamental interest Therefore, in this study, weinvestigated the physical backgrounds of the U-bands
using electro-chemical doping techniques. To reduce
chemical reactions during electro-chemical doping, we
performed opto-electrochemical measurements at  26
C˚. Figure 2 shows the optical absorption spectra of(6,5) SWCNTs upon different potentials. Remarkably,
the line-shape of U-band is changed when the potential
is shifted, in addition to the disappearance of S11 and Fig. 1 Optical absorption spectra of (6,5)
S22, and the shift of S33. Such changes were stable and SWCNTs in a solution and in a film
reversible because the measurements were performed
at a low temperature. The broadening of U-band by
doping, which was expected from Fano-mechanisms,
was not observed, thus contributions from free-carrierstates will be small. The results suggest that opticalabsorption bands originated from -* transitions canbe controllable even if the bands are located at
UV-region.
[1] Yanagi et al., Adv. Mater. 23, 2811 (2011)
Corresponding Author: K. Yanagi
Tel: +81-42-677-2494, Fax: +81-42-677-2483
E-mail: yanagi-kazuhiro@tmu.ac.jp

Fig. 2 Changes of optical absorption
spectra of (6,5) SWCNTs byelectrochemical doping at -26 C˚- 105 -

2P-15
Thermodynamics for the exchange reaction of sodium cholate
and double-stranded DNA on single-walled carbon nanotubes○Akiko Tsuzuki1, Ayaka Inoue1, Yuichi Kato1, Yasuro Niidome1,2,
and Notoshi Nakashima1,2,3
1

Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
2
WPI I2CNER, 3JST-CREST

DNA is one of the well-known solubilizers for single-walled carbon nanotubes (SWNTs).
DNA-SWNT hybrids are useful materials for studies on biosensors, electron transfer, length
fractionation, and chirality separation of SWNTs. Previously, we have reported
thermodynamis on soluble SWNTs, in which the exchange of sodium cholate (SC) and single
stranded DNAs (ssDNA) was analyzed[1,2].
In
this
work,
we
focusedonthermodynamics on the exchange reactionof double-stranded DNA (dsDNA) and SC
on SWNTs.
CNTs that were individually solubilized ina SC solution (2 mM) were mixed withvarious concentrations of ssDNA (d(G)20,
0-800 M) and dsDNA (d(G)20-d(C)20,0-400 M). After keeping the samples forthree days at 14 ° C, the near-IR absorption
spectra were measured at 22 and 30 °C Figure 1 Semi-log plots of the normalized absorbanceafter 24 h-incubation.
at 1190 nm. The absorbance changes indicated fractions
Absorbance changes at 1190 nm that of DNA-wrapped SWNTs in the presence of d(G)20 andrepresent the fraction of the (8,6)SWNTs d(G)20-d(C)20. Temperatures were 14, 22, and 30 °C.
wrapped with ssDNA were plotted against
the concentration of the ssDNA (Fig. 1). From the analysis of the plots, we could calculate theequilibrium constants (K) of the exchanges of the solubilizers. Temperature dependences ofd(G)20 (dotted lines) indicated that the exchange of SC with d(G)20 was endothermic. It wasreported that d(C)20 also showed endothermic reaction [1]. For the use of dsDNA, smaller K
was found to obtain at the higher temperature (solid lines in Fig. 1), indicating that theexchange of SC with dsDNA was exothermic. Thus, the exchanges of SC with ssDNAs occur
in a different manner from that using dsDNA. The thermodynamic parameters (H, S),
which were obtained from the temperature dependence of K, suggested that thedsDNA-wrapped SWNTs remain the double stranded structure.
[1] Y. Kato, Y. Niidome, N. Nakashima, Chem. Lett., 40, 730 (2011).
[2] Y. Kato, Ayaka Inoue, Y. Niidome, N. Nakashima, Scientific Reports, 2,733 (2012).
Corresponding Author: N. Nakashima
Tel: +81-92-802-2841, Fax: +81-92-802-2841
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 106 -

2P-16
Improvement of CNT Properties through a Post Synthetic Treatment○Naoyuki Matsumoto1, Azusa Oshima1, Motoo Yumura1,2, Don N. Futaba1,2,
and Kenji Hata1,2
1Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba
305-8565, Japan
2
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba
305-8565, Japan

Single-wall carbon nanotubes (SWCNTs) have attracted intense interest in numerous
applications from MEMS devices, composites, sensors, filters to capacitor electrodes due totheir unique inherent properties. However, despite great advances in synthesis, there remains alimitation with regards to the level of synthetic structural control and therefore the SWCNT
properties. For example, floating catalyst CVD [1] can grow highly crystalline and small
diameter SW- and DWCNTs, but cannot grow CNTs with great length, which is advantageous
for long-range electrical, thermal, and strain transfer in macroscopic assemblies. In contrast,
water-assisted CVD (Super-growth method [2]) has demonstrated the synthesis of high purity
and millimeter-long SWCNTs in a forest but do not possess the high crystallinity of floating
catalyst CVD. Therefore, effort has been placed on alternative approaches to overcome thesesynthetic limitations.
Here, we report the three-fold increase in electrical and thermal properties of Super-growth
SWCNTs using a post-synthetic treatment to induce CNT structural change and improve
crystallinity. This process consists of thermal annealing of the SWCNTs at high temperatures(1500-2000oC) in a neutral (argon) gas ambient based on the method reported by Yudasaka etal. [3],[4] to induce the improvement in crystallinity for improved thermal properties and/or
the conversion of low purity SWCNTs into high purity MWCNTs for improved electricalconductivity. Detailed structural examination of the SWCNTs before and after treatment using
Raman and TEM clarified the structural change to the individual nanotubes, which explains
the improvement in the observed properties. Finally, this simple method affords several
advantages: 1) high reproducibility, 2) the homogeneous treatment of gram-scale (or larger)
SWCNT samples, and 3) no required vacuum, and therefore this method possesses thepotential to integrate into a SWCNT mass production line.
[1] T. Saito et al. J. Nanosci. Nanotechnol., 8, 6153 (2008).
[2] K. Hata et al. Nature, 306, 1362 (2004).
[3] M. Yudasaka et al. Nano. Lett. 1, 487 (2001).
[4] M. Yudasaka et al. Carbon 41, 1273 (2003).

Corresponding Author: Don N. Futaba
Tel: +81-29-861-4656, Fax: +81-29-861-4851,
E-mail: d-futaba@aist.go.jp- 107 -

2P-17
Tensile strength of individual multi-walled carbon nanotube constituting
MWCNT fiber○Hideaki Suzuki1, Yoshinori Sato1, Go Yamamoto2, Kenichi Motomiya1, Toshiyuki Hashida2,
Kazuyuki Tohji1
1

Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan
2
Graduate school of Engineering, Tohoku University, Sendai 980-8579, Japan

Carbon nanotube (CNT) is an attractive one-dimensional nanomaterial withextremely high tensile strength and Young’s modulus [1, 2]. An issue remains concerning how
to constitute macroscale CNT assemblies that can fully utilize the mechanical properties ofindividual CNT itself. As a means to solve this issue, binder-free multi-walled carbon
nanotube (MWCNT) fibers have been produced twisting MWCNTs from vertically aligned
MWCNT arrays (MWCNT forest) [3] in our laboratory. The tensile strength of MWCNT
fibers is, however, not high enough because MWCNTs synthesized by chemical vapor
deposition (CVD) are considered to have many defects. In this study, we measured the tensile
strength of individual MWCNT constituting MWCNT fibers and evaluated the strength ratioof fiber to individual MWCNT.
Individual MWCNT was picked up from MWCNT forest
which has the ability for fiber formation, and tensile tests ofindividual MWCNT were performed with a nanomanipulator insidea scanning electron microscope (SEM). Individual MWCNT was
picked up by pushing up half of a copper transmission electron
microscope (TEM) grid to the MWCNT forest (Fig. 1). The bothside of the MWCNT was fixed to a cantilever and the TEM grid(Fig. 2), and then the cantilever was moved backward during
tensile test. In the result, average tensile strength and specifictensile strength were 22.0 GPa and 10.1 GPa/g/cm3, respectively.
The specific strength ratio of fiber to individual MWCNT was
7.3%. Hence, the reason for low strength of MWCNT fiber is due
to not the low strength of individual MWCNT but the slippage
between individual MWCNTs and/or the condition for spinningfiber.

Fig.1 TEM image ofindividual MWCNT.

Fig.2 SEM photograph ofindividual MWCNT between
cantilever and TEM grid.

[1] S. L. Mielke et al. Chem. Phys. Lett. 390, 413-420 (2004).

Corresponding Author: Y. Sato[2] B. Peng et al. Nat. Nanotech. 3, 626-631 (2008).

Tel: +81-22-795-3215, Fax: +81-22-795-3215[3] M. Zhang et al. Science 306, 1358-1361 (2004).

E-mail: hige@ncsimd.kankyo.tohoku.ac.jp- 108 -

2P-18
Bending Properties of Single-Walled Carbon Nanotube Film Transistors○Hiroki Hamahata1,Yuki Nobusa1, Yohei Yomogida1, Kazuhiro Yanagi2,
Yoshihiro Iwasa3 and Taishi Takenobu1
1

Department of Applied Physics, Waseda University, Shinjuku 169-8555, Japan
Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan
3
QPEC, School of Engineering, The University of Tokyo, Bunkyo 113-8656, Japan2

The recent technique for the separation of metallic and semiconducting SWCNTs
opened a new route to high-performance SWCNT TFTs without the effect of metallic
nanotubes [1,2]. However, the trade-off behavior between carrier mobility and on/off ratio
was still a big open question. Very recently, we found clear answer for this longstanding issue,
and realized very high-performance transistors with mobility of more than 100 cm2/Vs andon/off ratio of 104-105 using one of the solid electrolytes, ion gel [3]. For practicalapplications in flexible electronics, the co-existence of high performance and excellent
flexibility is strongly required. Importantly, because both SWCNT high-density film and ion
gel seem to be highly flexible materials, the obtained high-performance SWCNT transistors
might have enough durability against extreme flexure strain. Therefore, in this study, wefabricated flexible SWCNT transistors using ion gel, and investigated the flexibility of thesedevices. Moreover, we also tested stretchability for same transistors on PDMS substrate.
We fabricated ion-gel gated SWCNT film transistors on flexible kapton film andrealized high on/off ratio of 104. We have tested bending durability of this device (composedof Au electrode, ion gel and semiconducting SWCNT film) up to bending angle of 180 degree(mountain and valley fold for tension and compression of SWCNT film, respectively, as
shown in Fig.1) and any degradation was not observed. During the bending test, both on/off
ratio and mobility of SWCNT ion-gel transistor were almost constant, and transistor kept
on/off ratio of 104 and mobility of 100 cm2/Vs even at 180 degree. Under the angle of 180
degree, the directly measured curvature radius of SWCNT film was 270 μm for tension and400 μm for compression. For the stretching test as shown in Fig.2, no degradation wasobserved by 14 % of strain. These results obviously show the ultra-high flexibility of ionic-gel
gated SWCNT transistors and open the route to bendable and stretchable electronics based on
SWCNT thick film and ion gel.

Fig.1 Schematic of bending device

Fig.2 Schematic of stretching device[1] M.S. Arnold et al. Nat. Nanotechnol. 1, 60 (2006).
[2] K. Yanagi et al. Appl. Phys. Express. 1, 034003 (2008).
[3] Y. Yomogida et al. The 42nd FNTGraphene General Symposium.
Corresponding Author: Taishi Takenobu
TEL/FAX: +03-5286-2981,
E-mail: takenobu@waseda.jp- 109 -

2P-19High-performance, flexible carbon nanotube transparent conductive filmsof double layered structure○Norihiro Fukaya 1, Yusuke Kataoka 2, Dong Young Kim 2,3, Shigeru Kishimoto 1,
Takashi Mizutani 1, Suguru Noda 2,3, and Yutaka Ohno 1
12

Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
Department of Chemical System Engineering, The University of Tokyo, Tokyo 113-8656,
Japan
3
Department Applied Chemistry, Waseda University, Tokyo 169-8555, Japan

Carbon nanotubes (CNTs) are quite promising material for transparent conductive films(TCFs) without resource problems because of various advantages such as good flexibility, andchemical stability, less haze, and so on. However, the resistance of CNT TCFs are still higher
than other TCFs. In this study, we propose a novel CNT TCFs with double layered structure to
reduce the sheet resistance. The double layered structure consists of a uniform layer and a gridlayer of single-walled CNTs.
We fabricated the double layered CNT TCFs by utilizing the dry transfer technique basedon floating-catalyst chemical vapor deposition technique (FC-CVD) 1. CNTs grown by
FC-CVD were collect with a membrane filter and transferred on a polyethylenenaphthalete
film with thickness of 100m. For the grid formation, we used a membrane filter on which aphotoresist layer was patterned as a grid. The patterned membrane filter was able to be used
multiple times for the filtration and transfer process. After transferring both layers, thedensification of CNTs with isopropanol and the chemical doping with nitric acid were carriedout.
Figure 1 shows the transmittance at a wavelength of 550 nm versus sheet resistance. The
closed and open circles represent CNT TCFs with and without the grid structured layer,
respectively. The solid line is the fitted data using an equation2, T  exp   / R  , where and  are an absorption coefficient and resistivity of CNT film, showing a tradeoff between
the transmittance and sheet resistancedetermined by the material. By adding thegrid structured layer, the performance of
CNT TCFs were improved over the
tradeoff curve. The sheet resistance at atransmittance of 80 % was reduced by
46 % from 95 /sq. to 53 /sq. This value
is among the best data of CNT TCFs.
Acknowledgment: This work was
supported by JST/ALCA.
.
[1] A. Moisala et al., Chem. Eng. Science 61, 4393
(2006).
[2] A. Kaskela et al., Nano Lett. 10, 4349 (2010).
Corresponding Author: Y. Ohno
Tel: +81-52-789-5387, Fax: +81-52-789-5387,
E-mail: yohno@nuee.nagoya-u.ac.jp

Fig.1 Transmittance versus sheet resistance for CNT
TCF without (open circles) and with (closed circles) agrid structured layer.
Insert: Schematic of proposed double layered CNT TCF.

- 110 -

2P-20Evaluation of the contact resistivity at CNT/SiC interface
using conductive AFM○Megumi Shibuya1, Masafumi Inaba1, Kazuyoshi Oohara1, Takumi Ochiai1, Yoshiho
Masuda2, Atsushi Hiraiwa1, Michiko Kusunoki2, Hiroshi Kawarada1
1

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

1. Introduction

CNT synthesized with SiC surface decomposition method (CNTon SiC)[1][2] exhibits the most densely packed CNT forest (~1013cm-2) and is suitable for electrodes with high current density
durability. CNTs can be important material for SiC, promisingmaterials of power semiconductors, in cooperation with its highthermal conductivity and heat resistance. It is necessary for
application as electrodes to evaluate the contact resistivity, we haverevealed that CNT-metal contact resistivity is lower than ~3×10-9cm2[3]. In this study, we estimated the contact resistivity at
CNT/SiC interface.

Fig.1 Schematic image of current paths at
CNT/SiC system.

2. Lateral conduction blocking by focused ion beam (FIB)

CNT on SiC is synthesized on the C-face () of on-axis n-type 4Hor 6H-SiC substrate (Nitrogen donor density: ~ND~1018 cm-3 and 1019 cm-3)
with SiC surface decomposition method. In general, vertical conduction(parallel to CNT axis) is dominant comparing to lateral conduction. As
shown in Fig.1 however, lateral conduction also coexists in the CNT on
SiC because of its high tubedensity (~1013 cm-2). For confining lateral
conduction to a certain area to estimate the contact resistivity at CNT/SiC
interface, conducting islands were electrically isolated by FIB (Fig.2).
Current-voltage property was measured by conductive AFM.

3. Estimation of the contact resistivity at CNT/SiC interface

Fig.2 Islands formed by FIB tolimitlateral conduction within them.

CNT-AFM probe contact area isfixed, so CNT-AFM probe
contact resistance is constant. Changing the island size to restrict
conduction area makes it possible to estimate CNT/SiC interface
contact resistance. Fig.3 shows the relationship between series
resistance of CNT and area of islands within minimal isolated areas.
Slope of approximate line at each CNT length represents the sumof the contact resistivity at CNT/SiC interface and the product of
CNT-SiC CNT CNT+ρ ･l ). The
CNT length and resistivity component (ρC
CNT-probe, the contact
intercept of that line corresponds to ρCresistivity of probe-CNT, and it is the same order as our previous
work[3]. The contact resistivities at CNT/SiC interface are ~10-2
Fig.3 Resistance of CNT versus size of islandscm2 and ~10-3 cm2 at NDof 1018 and 1019 cm-3, respectively The
corresponding Schottky barrier heights at CNT/SiC interface are ~0.5 eV and ~0.45 eV.
[1] M. Kusunoki et al., Appl. Phys. Lett.77, 531 (2000)[3] M. Inaba, H. Kawarada et al., submitted[2] M. Kusunoki et al., Appl. Phys. Lett. 87, 103105 (2005)
Corresponding Author: M. Shibuya/Tel: 03-5286-3391, Fax: 03-5286-3391,
E-mail: seal_1030@fuji.waseda.jp- 111 -

2P-21High-mobility carbon nanotube thin-film transistors fabricatedon transparent plastic film by flexographic printing technique○Kentaro Higuchi 1, Yuta Nakajima 2, Takuya Tomura 2, Masafumi Takesue 2,
Shigeru Kishimoto 1, Takashi Mizutani 1, Katsuhiko Hata 2 and Yutaka Ohno 1
12

Department of Quantum Engineering, Nagoya University, Nagoya 464-8603, Japan
Research and Development Center, Bando Chemical Industries, LTD., Kobe 650-0047,
Japan

Among many kinds of thin film transistors, carbon nanotube thin-film transistors(CNT-TFTs) have attractive features such as high mobility, flexibility, and transparency. In theprevious work, we realized high performance CNT TFTs and functional integrated circuits(ICs) on a transparent plastic substrate by the simple gas-phase filtration and transfer process[1]. In this work, we introduce flexographic printing technique in the fabrication process of
CNT TFTs. The devices are fabricated by fully lithography free and ambient pressure
processes.
We fabricated bottom-gate-type CNT TFTs on a polyethylene naphthalate (PEN) film withthe flexographic printing technique, which is a kind of high-speed typographic prints with aflexible relief plate made of photopolymer. The inks of silver nanoparticles and polyimide
were respectively used for the electrodes and insulator. First, the gate electrode and insulator
were printed by a flexographic printer. A carbon nanotube thin film grown by thefloating-catalyst CVD was transferred as our previous work [1]. Then, the source and drainelectrodes were printed. After printing the resist material, CNTs outside the channel region
were etched by the ambient pressure plasma with O2.
Figure 1 shows (a) an array of CNT TFTs fabricated on a 15-cm-square PEN film, (b)optical micrograph of a CNT TFT, and (c) ID-VGS characteristic of a device. The channel
length and channel width were 115 μm and 130 m, respectively. The device showed highmobility of 157 cm2/Vs for the rigorous model (112 cm2/Vs for parallel plate model) with
on/off ratio of about 104. The obtained
mobility is the highest value for printed
TFTs to our knowledge.
This work was partially supported by '08
NEDO Grant, R&D promotion scheme
funding international
joint
researchpromoted by NICT, ALCA-JST, andGrant-in-Aid of MEXT.
[1] D.-M. Sun, et al. Nature Nanotech. 6, 156 (2011).
Corresponding Author: Y. Ohno
Tel: +81-52-789-5387, Fax: +81-52-789-5387,
E-mail: yohno@nuee.nagoya-u.ac.jp

Fig. 1 (a) CNT TFT array printed on 15-cm-square
PEN film. (b) optical micrograph and (c) ID-VGS
characteristic of CNT TFT.

- 112 -

2P-22
Effect of gas atmosphere on the photovoltaic characteristics ofsemiconducting single-walled carbon nanotubes/Si heterojunction
photovoltaic cells○Mao Shoji1,3, Atsushi Nakano2 and Hironori Ogata 1,2,3
1

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

Single-walled carbon nanotubes (SWNTs) are expected to the application to various kindsof the electronic devices, because the high carrier mobility of the SWNTs. Especially, The useof semiconducting SWNTs (S-SWNTs) in photovoltaic applications is attractive because theoptical bandgap of S-SWNTs can be varied by controlling the nanotube diameter.1) S-SWNTs
are reported to show unipolar p-type behavior under ambient conditions. Various chemical
doping have been reported to convert from p-type to n-type.2) In this study, we report theeffects of the electronic energy level evolution of S-SWNTs films by exposed to air or oxygenon the photovoltaic characteristics of both p-type SWNTs/n-Si and chemically doped (n-type)
SWNTs/p-Si heterojunction photovoltaic cells.
The SWNTs (CoMoCAT method, 0.8 ± 0.1 nm in diameter) dispersed in
1,2-dichlorobenzene at 0.5 mg/mL by ultrasonication and SWNTs thin film was fabricatedusing airbrush on the Si substrate. N-type doping of the S-SWNTs was performed by dropped
reduced benzyl viologen (BV) solution (5 mM) on the SWNTs thin films. The schematic of
SWNTs/Si device is showed in Figure 1. The current density-voltage (J-V) characteristics
were measured in the dark and under light (AM1.5G, 100 mW/cm2) condition in the vacuum(44 Pa), oxygen (760 Torr) and air (ambient atmospheric pressure) conditions.
Figure 2 shows the time dependences of PCE for p-type (undoped) SWNTs/n-Si or
viologen doped-SWNTs/p-Si devices under each gas atmosphere. The value of power
conversion efficiency (PCE) increases gradually for the p-type SWNTs/n-Si device. However,that decreases for viologen doped-SWNTs/p-Si device by exposed to oxygen. The detailed
results will be presented.
0.06
0.05

0.04

Figure 1

The structure of SWNTs/Si device.

PCE (%)PCE (%)(a) Undoped-SWNTs/n-Si (b) 5 mM BV-SWNTs/n-Si
0.07
0.006

0 25 50 75 100
Time (min)

0.004

Oxy

0.002

0.000

Vac

Air
0 25 50 75100
Time (min)Figure 2 Time dependences of PCE of (a) p-type
SWNTs/n-Si or (b) viologen doped SWNTs/p-Si
devices in each gas atmosphere.

1) P.-L. Ong, et al., Nanotechnology 21 (2010) 105203.
2) S. M. Kim et al., J. Am. Chem. Soc. 131 (2009) 327.
Corresponding Author: Hironori Ogata,Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 113 -

2P-23




            
            
                                        
    
           㻌       㻋
                               



              
      
             
      




      

 㻌 


                                         −


- 114 -

2P-24
CNT Synthesis by Laser Ablation Method
Using Carbon and Nickel Double Target○Koji Ishii1, Nobuyuki Iwata2, Hiroshi Yamamoto2 and Hirofumi Yajima 1
1

Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3
Kagurazaka, Shinjyuku-ku, Tokyo 162-0826, Japan2
Department of Electronics & Computer Science, College of Science & Technology, Nihon
University, 7-24-1 Narashinodai, Funabashi, Chiba 274-8501, Japan
Carbon nanotubes (CNTs) have potential for application to nano-scale devices because of
the physical and chemical properties. Practically, a large amount of high quality CNTs are
required for application. Conventional laser ablation method has a disadvantage of a low
synthesis rate because of the molar ratio of carbon to catalyst at the target surface. The ratio
gradually changes as proceeding the synthesis1). We propose the novel laser ablation method,
called double laser ablation (DLA) method, as shown in Fig.1. In the DLA method, twoablated plasma plumes, including both of carbon and catalytic metal particles, are merged to
be introduced into the furnace to synthesize CNTs. In this work, single walled carbon
nanotubes (SWNTs) were synthesized by the DLA apparatus with two separated double target,
graphite target and Ni catalyst target. The quartz tube was filled with 66.6kPa argon gas andthe flow was 100ccm. The electric heater was controlled up to 1000°C at the rate of
10°C/min. The second harmonics of YAG laser pulse was focused on the targets andsynthesized for 30 minutes.
Figure 2 shows the typical Raman spectrum ofobtained deposits with 532nm excitation laser.
The spectrum revealed G-band at 1582 cm-1 andD-band at 1350cm-1, respectively. Howeverradial breathing mode (RBM) was not detected.
Figure 3 shows the image of transmission
electron microscopy (TEM).
It wasdemonstrated that tubular materials was
synthesized by the DLA apparatus.
Fig.1. The schematic DLA apparatus

Intensity(arb. units)

1500
1000
500
20nm

0
0

500 1000 1500
Raman Shift(cm-1)

2000

Fig.2. The typical Raman spectrum of deposits
obtained by the DLA method with excitation
wavelength of 532nm.

Fig.3. The TEM image of sample
synthesized by the DLA method.

[1] M. Yudasaka, T. Komatsu, T. Ichihashi, and S. Iijima, chem phys lett 278(1997)102-106.
Tel and Fax : +81-469-5457
E-mail : chem_spdf_orbital@yahoo.co.jp- 115 -

2P-25
Solubilization of single-walled carbon nanotubes using a flavin derivative inorganic solvents○Yuichi Kato1, Yasuro Niidome1,2, Naotoshi Nakashima1,2,3
1

Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan2
WPI Research Center I2CNER, Kyushu University, Fukuoka 819-0395, Japan
3
JST-CREST, Chiyoda-ku, Tokyo 102-0075, Japan

We synthesized a flavin derivative as a solubilizer of single-walled carbon nanotubes(SWNT), and revealed that the compound showed a unique SWNT chiral selective dissolution
behavior.
Due to the difficulty in the synthesis of single-walled carbon nanotubes(SWNTs) with a specific chiral indices (n,m), SWNT chirality sorting has been an
anticipated technique for realizing practical applications of SWNTs, especially inthe field of nano-electronic devices. Recently, several papers describing the separation of
the chiral mixtures of semiconducting/metallic SWNTs.[1] One of interestingchirality-sorting method is a selective extraction using polyfluorenes (PFOs) withlong alkyl-chains and their derivatives which are known to dissolve only semiconducting
SWNTs. [2] This method is simple and powerful for the chirality-sorting; however, the removalof the PFO in the PFH/SWNT hybrids is difficult. The development of a method that allows
easy removal of the solubilizers from the hybrids is thus required.
10-Dodecyl-7,8-dimethyl-10H-benzo[g]pteridine-2,4-dione(Fig. 1) is a small molecule that solubilizes SWNTs in organic
solvents such as acetone or toluene.[3] Here, we report that thecompound shows a unique SWNT chiral selective dissolution
behavior, which was revealed by vis-near IR absorption,
photoluminescence, and Raman spectroscopies. Removal of
the flavin from the nanotube hybrid will also be reported at theFig. 1 Chemical structure ofmeeting.
10-Dodecyl-7,8-dimethyl-10Hbenzo[g]pteridine-2,4-dione.

[1] M. C. Hersam, Nature Nanotech. 3, 387–94 (2008).
[2] a) F. Chen, B. Wang, Y. Chen, L.-J. Li, Nano Lett. 7, 3013-3017 (2007).
b) H. Ozawa, T. Fujigaya, Y. Niidome, N. Hotta, M. Fujiki, N. Nakashima, J. Am. Chem. Soc. 133, 2651–2657(2011).
[3] S. Ju, W. P. Kopcha, F. Papadimitrakopoulos, Science 323, 1319–23 (2009).
Corresponding Author: N. Nakashima
Tel: +81-92-802-2840, Fax: +81-92-802-2840
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 116 -

2P-26
SWNT growth from Pt catalysts on Al2Ox buffer layer
by Alcohol Gas Source Method in High VacuumżNaoya Fukuoka, Hiroki Kondo, Yuya Sawaki, Ranajit Ghosh, Shigeya Naritsuka,
Takahiro Maruyama
Department of Materials Science and Engineering, Meijo University, Nagoya 468-8502, Japan䎬䏑䏗䏈䏑䏖䏌䏗䏜䎃䎋䏄䎑䏘䎑䎌䎬䏑䏗䏈䏑䏖䏌䏗䏜䎃䎋䏄䎑䏘䎑䎌Single-walled carbon nanotubes (SWNTs) have been anticipated for applications in a lotof future nanodevices. To fabricate SWNT devices in a conventional LSI process, it isimportant to obtain SWNTs having homogeneous structures in high yield. To increase the
SWNT yield, Al2Ox have been widely used as buffer layers for transition metal catalysts in the
CVD growth. Recently, we reported SWNTs having a narrow diameter distribution could beobtained from Pt catalysts on SiO2/Si substrates. However, the Al2Ox buffer layers have neverbeen utilized for Pt. In this study, we carried out SWNT growth on Pt catalysts on Al2Ox andinvestigated the effects of Al2Ox on Pt catalysts.
Al2Ox buffer layers were formed on SiO2/Si substrates by oxidation of Al thin layers (3-30nm). After deposition of Pt catalysts (0.2 nm) on the Al2Ox using a pulsed arc plasma gun, the
SWNT growth was carried out using alcohol gas source method in a high vacuum [1, 2]. The
growth temperature was 700ºC, and the ethanol pressure was 1×10-3 Pa. The grown SWNTs
were characterized by SEM and Raman spectroscopy.
Figure 1 shows the Raman spectra of SWNTs grown(a)from Pt catalysts on SiO2/Si substrates and Al2Ox buffer
W/O Al O buffer
layers (Al thickness: 3nm). On the Al2Ox buffer layer, the Gband intensity was small, compared to that on the SiO2/Si
substrate, indicating that the SWNT yield was reduced on
With Al O buffer
the Al2Ox buffer layer. The Raman spectra in the RBM
region shows that Raman shifts of SWNTs on the Al2Ox
䎔䎓䎓
䎕䎓䎓
䎖䎓䎓
䎗䎓䎓
䎐䎔
were smaller than those on SiO2/Si, suggesting that the䎵䏄䏐䏄䏑䎃䎶䏋䏌䏉䏗䎃䎋䏆䏐 䎌
diameters of SWNTs on the Al2Ox were smaller than those(b)on the SiO2/Si. These results indicate that the effects of
Al2Ox buffer layers on Pt catalysts were fairly different from
W/O Al O buffer
those on transition metal catalysts.
This work was partially supported by the Japan
With Al O buffer
Society for the Promotion of Science (JSPS), Grant-in-aid䎔䎕䎓䎓 䎔䎗䎓䎓 䎔䎙䎓䎓 䎔䎛䎓䎓for Scientific Research (c) 21510119 and the Instrument䎐䎔䎵䏄䏐䏄䏑䎃䎶䏋䏌䏉䏗䎃䎋䏆䏐 䎌
Center of the Institute for Molecular Science (IMS).
References[1] T. Maruyama et al., J. Nanosci. Nanotechnol. 10 (2010) 1.
[2] T. Maruyama et al. Mater. Express 1 (2011) 267.
Corresponding author: Takahiro Maruyama
Phone: +81-52-838-2386, Fax: +81-52-832-1172
E-mail: takamaru@meijo-u.ac.jp- 117 -

2

x

2

2

x

x

2

x

Fig. 1 Raman spectra of (a) RBM
region and (b) high frequency region
for SWNTs grown from Pt catalyst on
Al2Ox buffer layers and SiO2/Si
substrates.

2P-27
Low temperature growth of dense carbon nanotube arrays
on conductive underlayersżNuri Na1,2, Yeong-Gi So3, Yuichi Ikuhara3 and Suguru Noda2,4,*
1
2

Department of Chemical System Engineering, The University of Tokyo, Japan
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
3
Institute of Engineering Innovation, The University of Tokyo, Japan
4
PRESTO, JST, Japan

Carbon nanotubes (CNTs) have been studied as a candidate for via interconnects in future
large-scale integrated circuits (LSIs) because they have attractive electrical and thermal
properties [1]. Rapid growth of millimeter-tall CNT arrays has been realized by chemical
vapor deposition (CVD), however, such growth is achieved on insulating underlayer at hightemperatures (~ 800 ºC) with a porosity > 90% in CNT arrays. Dense CNT growth at 1u1012
cm-2 on conductive underlayer at 450 ºC [2] and at 15u1012 cm-2 on insulating underlayer at
700 ºC [3] are reported recently, which are not satisfactory for practical application yet.
In this work, we prepared Ni particles densely on conductive TiN layers on SiO2/Si by
sputter-deposition through their nucleation and growth and by stopping deposition prior totheir percolation. We obtained a particulate structure as deposited by depositing nominally0.6-nm-thick Ni at 400 qC slowly (8.1 pm/s) under a substrate bias of -20 V, which kept aparticulate structure with a density as high as ~ 2.8×1012 cm-2 after annealing in H2/Ar at 400
qC (Fig. 1). We then performed CVD at 400 qC by feeding C2H2 at a pressure as low as 1-10
mTorr so as not to kill the catalyst and obtained CNT arrays, whose density proved as high as
1.1 g cm-3 by energy dispersive X-ray analysis byscanning electron microscopy (SEM). The CNT
films were transferred to SiO2/Si or transmission
electron microscope (TEM) grids by etching SiO2
layers and analyzed by atomic force microscopy(AFM) and high resolution transmission electron
microscopy (HRTEM). The number density ofFig. 1. AFM images of Ni particles.
CNTs and CNT walls were as high as 1.5×1012
-2
12
-2
(a)
As deposited and (b) after annealing.
cm and 12×10 cm , respectively (Fig. 2).

Fig. 2. (a) Cross-sectional SEM, bottom-view SEM (b) and AFM (c), and (d) plan-view TEM of CNT arrays.
[1] Y. Awano, et al., Phys. Stat. Sol. A 203, 3611 (2006).
[2] Y. Yamazaki, et al., Appl. Phys. Express 3, 055002 (2010).
[3] G. Zhong, et al., ACS Nano 4, 2893 (2012).
*Corresponding Author: Suguru Noda, Tel&Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 118 -

2P-28
Selective Removal of Metallic Single-Walled Carbon Nanotubes
Utilizing Thermal Lithography of Molecular Glass Thin FilmsżKeigo Otsuka, Taiki Inoue, Daisuke Hasegawa, Shohei Chiashi, Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
Tokyo, Japan
Single-walled carbon nanotubes (SWNTs) are a promising material for future electronics
such as field effect transistors (FETs) due to their extraordinary electrical properties. For therealization of practical SWNT devices, it is one of the most important demands to obtainaligned arrays composed only of semiconducting SWNTs. Recently, selective etching of
metallic SWNTs using a molecular glass film was reported [1]. The method could beapplicable to the large-scale fabrication because it enables removal of whole length ofmetallic SWNTs in contrast to partial cutting of metallic SWNTs by electrical breakdown [2].
In this study, we attempted to remove metallic SWNTs using the method and considered its
mechanism in order for improved processing.
Horizontally-aligned SWNTs grown on quartz substrates were transferred onto silicon
substrates and used as channels of back-gated FETs. An SEM image of a fabricated FET
device is shown in Fig. 1 (a). The current-voltage (ID-VGS) characteristic of the device (Fig. 2)
shows that on/off ratio is 2.6, and this indicates the existence of metallic SWNTs along withsemiconducting SWNTs. A thin film of molecular glass was fabricated on the FET byspin-coating, and a drain voltage of -4 V and a gate voltage of +10 V were applied to the FET
for about 35 hours. After the application of the voltage, some trench structures along SWNTs
were observed by AFM on the molecular glass film (Fig. 1(b)), which means that some of
SWNTs originally embedded in the molecular glass were exposed. After oxygen plasma
etching of the exposed SWNTs and dissolution of the molecular glass film (Fig. 1 (c)), thedevice shows on/off ratio of 34.5 (Fig. 2). The increase in on/off ratio indicates that metallic
SWNTs were preferentially removed. The viscosity of the molecular glass around metallic
SWNTs was considered to decrease with a temperature increase resulting from Joule heatingof metallic SWNTs, and the trench structures were formed along metallic SWNTs.

Fig. 1 (a) SEM image of an as-fabricated FET. (b) AFM image ofthe molecular glass film-coated FET after voltage application. (c)SEM image of the FET after oxygen plasma etching and dissolutionof the molecular glass film.
[1] J. Xiao et al. MRS Spring Meeting (2012).
[2] P. G. Collins et al. Science 292, 706 (2001).
Corresponding Author: S. Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983
E-mail: maruyama@photon.t.u-tokyo.ac.jp

Fig. 2 Current-voltage characteristicsof the FET before and after the treatment.

- 119 -

2P-29Effects of discharge current direction and magnetic field for the productionof single-walled carbon nanotubes in the arc discharge method○Mohammad Jellur Rahman1, Tetsu Mieno2
1

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

2

Mass production of high-quality and diameter-controlled single-walled carbon nanotubes(SWNTs) are required to realize their various applications [1]. In the arc discharge method,
SWNTs are produced in the hot He gas region near the arc plasma, where heat convection
blows hot carbon species upward, and the reaction time is limited [2]. Therefore, if thedischarge direction relative to gravity is changed, the production conditions of SWNTs in the
hot gas region will be changed. When a magnetic field is applied perpendicular to thedischarge current, the arc plasma jets out in the J  B direction and leads to the efficient
production of SWNTs [2-4]. Therefore, SWNTs are synthesized by the arc discharge method
in He gas where three directions of discharge current relative to gravity are selected. The sootproduction rate is larger for the upward discharge current. The qualities of the produced
SWNTs for the three cases are almost the same. A steady magnetic field (3.0 mT),
perpendicular to the discharge current direction (J  B arc discharge) increases the sootproduction rate for all the three discharge current directions. The estimated ratio of thenumber of SWNT bundles to the number of carbon particles is higher for the upward
discharge current in the case of B = 0. This ratio increases significantly for the horizontal anddownward discharge currents when a magnetic field is applied.

Fig.1 Three discharge current directions and magnetic field.
30

Nntb /Ncp

Wsoot (mg/min)

0.6
0.5

20
15
10

0.4
0.3
0.2

5
0

B=0
J xB

0.7

B=0
J xB

25

0.1
0.0
Horizontal

UpwardDownward

Current direction

Horizontal

UpwardDownward

Current direction

Fig.2 Variation of the soot production rate, and nanotube
bundles to carbon particles ratio in the three currents.
[1] T. Yamamoto et al. in Carbon Nanotubes-Top. Appl.
Phys., eds. A. Jorio, et al. (Springer, Berlin, 2008).
Fig.3 TEM images of the soot for the B = 0[2] T. Mieno, et al. Jpn. J. Appl. Phys. 43, L1527 (2004).
(a)-(c) and J  B (d)-(f) in the three discharge[3] S. P. Doherty et al. Carbon 44, 1511 (2006).
currents.
[4] Y. Su et al. Carbon 50, 2556 (2012).
Corresponding Author: T. Mieno, Tel. and Fax: + 81-54-238-4750, E-mail: sptmien@ipc.shizuoka.ac.jp- 120 -

2P-30Chirality separation of metallic single-wall carbon nanotubes by gel column
chromatography
Takeshi Tanaka1, Yasuko Urabe1,2 and Hiromichi Kataura1,2
1

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8562, Japan
2
JST, CREST, Kawaguchi, Saitama, 332-0012, Japan

As-produced single-wall carbon nanotubes (SWCNTs) contains various kind of structure(chirality). Recently we reported single chirality separation of semiconducting (S-) SWCNTs
using dextran-based gel (Sephacryl S200) column chromatography [1]. In this separation,
metallic (M-) SWCNTs were not adsorb to the gel and not separated each other. In this study
we report chirality separation of metallic SWCNTs.
Proceeding chirality separation of M-SWCNTs, M/S separation of SWCNTs wereconducted. HiPco-SWCNTs/0.5 % sodium dodecyl sulfate (SDS) aqueous solution wereprepared by sonication and ultracentrifugation.
The dispersion was applied to Sephacryl S200
column equilibrated with 0.5% SDS, andhigh-purity M-SWCNTs were obtained as
unbound fraction (Fig. 1, bottom spectrum).
The separated M-SWCNTs mixture werediluted twice with water and applied to longcolumn (60 cm in length) packed with
Sephacryl S200 equilibrated with 0.3% SDS.
After flowing 0.3 % SDS, the concentrationof elution solution changed to 0.4 and 0.5
SDS and 1% sodium cholate. From theoptical adsorption spectra of eluted fractions(Fig. 1), clear difference of adsorption peaks
were observed, indicating chirality separationof M-SWCNTs. The early and late eluted
fractions tended to contain M-SWCNTs with
optical absorption peaks of longer and shorter
wavelengths, respectively. Detailed analyses
containing the result of Raman spectroscopy
will be presented.

Metallic SWCNTs
mixture before separation

References:[1] H. Liu et al., Nature commun., 2011, 2, 309
Corresponding Author: T. Tanaka
E-mail: tanaka-t@aist.go.jp

Fig. 1
Optical absorption spectra of chirality
separated M-SWCNTs by Sephacryl S200 column (60cm in length). The bottom spectrum is that of
M-SWCNTs mixture before chirality separation.

- 121 -

2P-31
Encapsulation of superconductive metal carbide in the inner space ofcarbon nanotubes by template methodżKeita Kobayashi1, Takeshi Saito2,3, Masaharu Kiyomiya3, Hidehiro Yasuda1
1

Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, 7-1
Mihogaoka, Ibaraki, Osaka 567-0047, Japan
2
Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565 Japan
3
Technology Research Association for Single Wall Carbon Nanotubes (TASC),
Tsukuba305-8562, JapanThe density of integrated circuits (ICs) should be increased for development of next-generationelectric devices. However, the miniaturization of metal interconnections in ICs increases theirrisk of disconnection by electro migration [1]. Therefore, development of alternative materials
to metal interconnections is crucial for producing ultra-fine wiring boards. Carbon nanotubes(CNTs) is expected as one of the candidates for the alternative materials due to their stability
and structure [1]. Moreover, CNTs have been widely used as a template for producing
one-dimensional nano-wires by encapsulating guest materials in their inner space [2]. Sincewall of CNT prevents migration of the guest materials [3], it is expected to be applied to an
useful ultra-fine conducting wire to develop further dense IC by encapsulation of good
conductor in the inner space of CNT. Encapsulated superconductor materials in CNTs are
particularly desirable, because they should produce high-efficiency ICs. However, fusion orvaporization of guest materials is necessary for encapsulation of the materials into inner spaceof CNT by the template method. Although the encapsulation of Pb (Tc: 7.2 K) and Sn (Tc: 3.7
K) in CNTs has been reported [4], any super conducting ceramics has not been encapsulated
into CNTs by the method due to their higher melting point. The arc discharge method [5] andthe laser vaporization method [6] have been used to synthesize multi-wall CNTs (MWCNTs)
encapsulating refractory metals. However, these obtained products are not suitable fordevelopment of further dense IC because diameters of these MWCNT and guest materials are
too large (>10 nm) for use as ultra-fine conducting wires. Therefore, development of novel
method for encapsulating such refractory guest materials into CNTs is required.
Based on these backgrounds, we have tried to encapsulate superconductive guest
materials with higher melting point to CNT having thinner diameter. Consequently, wedeveloped a simple method for encapsulating niobium carbide (NbC; melting point: ~3000 K;
Tc: 10.5 K) in the inner space of CNTs with diameter of 1-3 nm. In this presentation, we willreport synthesis method of the NbC-encapsulated CNT and will outline their properties.
[1] in Handobook of Carbon Nanotubes and Graphene, The Fullerenes, Nanotubes and Graphene ResearchSociety (Ed) (Corona Publishing, Tokyo, 2011).
[2] J. Sloan et al. Inorg. Chim. Acta, 330, 1 (2002).
[3] K. Kobayashi et al. Adv. Maters. 22, 3156 (2010).
[4] K. Kobayashi et al. Small 6, 1279 (2010).
[5] A. Koshio, J. Surf. Finish. Soc. Jpn. 58, 725 (2007).
[6] F. Kokai et al. Appl. Phys. A 97, 55 (2009).
Corresponding Author: K. Kobayashi
Tel: +81-6-6879-7941, Fax: +81-6-6879-7942,
E-mail: kobayashi-z@uhvem.osaka-u.ac.jp- 122 -

2P-32
Energetics and Electronic Structures of C60 Rolled in the Shortest Zigzag
Carbon Nanotubes
Shota Kigure and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
Carbon nanotubes inherently possess nanometer scale space inside their one-dimensional
covalent network. Such space can accommodate foreign atoms and molecules resulting ininteresting hybrid structures with mixed dimensionality. Indeed, it has been demonstrated thatfullerenes are encapsulated into inner space of carbon nanotubes exhibiting interesting
electronic and structural properties. Recently, an experiment has reported that C60 is rolled incyclic-polyphenyl leading to interesting hybrid structures consisting of nano-scale materials
with different topology. The hybrid structures can be regarded as sliced carbon peapods. In
the present work, we aim to elucidate energetics and electronic structures of C60 rolled in the

shortest zaigzag carbon nanotubes (cyclic polyacenes) whose diameters are 1.24 nm to1.55 nm based on density functional theory with local density approximation.
Figure 1 show an energy gain upon the encapsulation of C60 inside the cyclic polyacenes as afunction of their diameter. For all polyacenes studied
here, encapsulation reactions are exothermic indicating
the fact that these short peapods are energeticallystable. The calculated encapsulation energy strongly
depends on the diameter of polyacenes. For the C60,
(17,0) nanotube (heptadecacene) give the largest
encapsulation energy of about 1.3 eV which is thealmost same as that for the peapods with infinite length.
Encapsulation of C60 leads to decrease the energy gap
between the highest occupied and the lowest
unoccupied states for the thick nanotubes.

Fig. 1: Encapsulation energy of
C60 as a function of tube diameter.

Corresponding Author: S.Kigure
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 123 -

2P-33
Effect of inert gas on the growth of epitaxial grapheneon Si-terminated SiC (0001)○Akkawat Ruammaitree, Hitoshi Nakahara, Yahachi Saito
Department of Quantum Engineering, Graduate School of Engineering,
Nagoya University, Nagoya 464-8601, Japan
Graphene on SiC has a potential for technological application devices. In order to apply it
to such devices, the uniform and ordered growth of graphene on SiC substrate is necessary. In
this report, we have studied the growth of epitaxial graphene on Si-terminated SiC (0001) byannealing the SiC substrates in helium, neon and argon at pressure of 0.05 atm.
In the case of annealing the substrate in helium gas, AFM images (fig.1 (a) and (b)) show
there are many pits at lower step edges and triangular graphene islands. For annealing thesubstrate in neon gas (fig.1 (c) and (d)), the pits at lower step edge still remain but thetriangular graphene islands disappear from the terrace. In addition, the number of steps
increases as compared with the sample annealed in helium gas. In the case of the substrateannealed in argon gas (fig.1 (e) and (f)), all of the pits at the lower step edge disappear. The
triangular monolayer graphene islands are formed and enlarged until they merge with othergraphene regions. The SEM image (Fig.2 (a))(a)(b)
reveals that the triangular monolayer grapheneislands will be formed on the wide terrace (>1.5
m). The direction of triangular graphene which
was formed on the same terrace pointed to thesame direction. Fig. 2 (b) and (c) show moiré
pattern at a triangular monolayer graphene islandand the Fourier transform of Fig.2 (a),(c)(d)
respectively.
Annealing in argon at 0.05 atm can be a
candidate for creation of uniform and orderedmonolayer graphene on SiC by merging grapheneislands with graphene stripes at step edges before
the formation of graphene bilayer.
(a)

(b)

(e)

(c)

Fig.2 SEM (a), 50×50 nm2 STM (b) and Fourier transform(c) images of the sample which annealed in Ar gas
Corresponding Author: A. Ruammaitree
Tel: +8180-3823-3199
E-mail: akkawat@surf.nuqe.nagoya-u.ac.jp- 124 -

(f)

Fig.1 AFM 10×10m2 topographic (a, c, e) andphase (b, d, f) images of the samples annealed
in He (a and b), Ne (c and d) and Ar (e and f)gas. Bright regions in phase images represent
graphene. Arrows indicate the pits at lower stepedge. Circles indicate triangular grapheneislands.

2P-34Structural characterization of graphene edges using dark-field TEM○Miho Fujihara, Yasumitsu Miyata, Ryo Kitaura, Eriko Maeda, Hisanori Shinohara*
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
Graphene has attracted much attention for future electronics and spintronics applications
due to their high carrier mobility and unique magnetism. Because the electrical and magnetic
properties of graphene strongly depend on the edge structure [1], it is important to develop a
preparation method of graphene with desired edge structure. Hydrogen etching is one of themost promising methods to produce clean edge with zigzag structure [2]. However, it is still
unclear how grain boundary and morphology are affected by the etching process. In this work,
we have investigated the edge structure of hydrogen-etched graphene by using dark fieldtransmission electron microscopy (DF-TEM).
Graphene was grown on copper foil by chemical vapor deposition of methane. The
hydrogen etching was then conducted by flowing Ar/H2 at 1,050 °C. The etched graphene wastransferred to a SiN grid for DF-TEM observation as reported previously [3]. DF-TEM
observation was carried out a JEM-2100F operated at 80 kV.
As shown in Figs.1a-c, DF-TEM observations reveal that the hydrogen etching generates
two different types of the etching pattern including polygonal and ribbon shape. In the former
case, hexagonal and septagonal holes are located in single grain and at grain boundary,respectively (Figs.1a and b). Almost all edges observed correspond to zigzag type as
confirmed by electron diffraction. In contrast, the latter can be found in single grains rather
than at grain boundaries and has various types of edge structures including zigzag, armchairand chiral types. This suggests that the ribbon-shaped gaps are derived from the preferential
etching of graphene wrinkle, which should have high reactivity due to its large C-C bondcurvature. The present results provide a useful basis to prepare well-defined graphene edges
with a desired structure.

Fig.1 (a-c) DF-TEM images of graphene after hydrogen etching at different positions.
[1] M. Fujita et al. J. Phys. Soc. Jpn. 65, 1920 (1996).
[2] R. Yang et al. Adv. Mater. 22, 4014 (2010).
[3] P. Y. Huang et al. Nature 469, 389 (2011).

Corresponding Author: H. Shinohara
Tel: +81-52-789-2482, Fax: +81-52-789-1169,
E-mail: noris@cc.nagoya-u.a.jp- 125 -

2P-35Synthesis of Nitrogen-doped Carbon Materials Controlled Nitrogen
Bonding Configuration○Satoshi Yasuda 1,2, Li Yu 1, Kei Murakoshi 1
1

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

Nitrogen-doped carbon materials exhibit oxygen reduction reaction (ORR) catalytic
activity, and paid attention to the metal free catalytic material for fuel cells [1]. There havemainly three common nitrogen bonding configurations within carbon, which are quaternary,pyridinic and pyrrolic nitrogen bonding configurations, and they are responsible for the ORR
catalytic activities due to the reduced adsorption energy. However, in spite of numerous
studies, it is still uncertain which configurations play important role in the actual activity forpromoting ORR. To clarify the nitrogen configuration effect and realize high effective ORR
catalytic material, development of selective synthesis technique of each nitrogenconfiguration in the carbon becomes a great challenge. Chemical vapor deposition (CVD) has
been widely used as synthesis technique of conventional nitrogen-doped carbon materials.
However, such high temperature process does not possess selective synthesis of the nitrogenconfigurations in carbon. In this study, we developed low temperature synthesis process basedon surface polymerization of nitrogenous aromatic ring compounds as precursors, resulting inpossibility of selective nitrogen configuration synthesis reflected on the molecular structure.
Low temperature CVD was employed below 500 oC to inhibit thermal decomposition of
the feedstock molecule and polymerize them. As feedstock molecules, we used two kinds ofnitrogenous aromatic ring compounds which are pyridine and julolidine molecules (Fig. (a)).
The thermal polymerizations of each molecule are expected to allow selective synthesis ofpyridinic and quaternary nitrogen configurations in carbon, respectively (Fig. (b)).
Nitrogen-doped carbon sheets were synthesized on Cu foil below 500 oC for 30 ~ 120 min
growth time at ambient pressure. Raman spectra for both samples made from pyridine andjulolidine showed distinguishable D- and G-bands,
indicating graphitic carbon formation. X-ray
photoelectron spectra of both samples confirmed theexistence of nitrogen in the carbon sheet with the N/Catomic ratio of 8 %. The binding energy of N1s peak ofpyridine-made sheet was 398.2 eV, indicating a mainly
pyridinic configuration, while julolidine-made sheet
showed 401.4 eV of N1s peak, which is identical toquaternary one (Fig. (c)). These results indicate that thesurface polymerization technique has potential tosynthesize nitrogen-doped graphene contained desired
nitrogen configuration in the graphitic carbon for ORR Fig. (a) Schematics of feedstock
catalyst.
molecules and (b) synthesized structures.
(c) XPS spectra of N1s.

[1] K. P. Gong et al. Science 324, 760 (2009).
Corresponding Author: S. Yasuda
TEL & FAX: +81-(0)11-706-4811
E-mail: satoshi-yasuda@sci.hokudai.ac.jp- 126 -

2P-36
Preparation of High-Density Graphene Nanoribbons
by Anisotropic Catalyst Cutting
1

2

Kazuma Yoshida,1and Hiroki Ago1,2,*○Yasumichi Kayo, Pablo Solís-Fernández,
1,2Masaharu Tsuji,

1

2

Graduate School of Engineering Sciences, Kyushu University, Fukuoka 816-8580
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8580

Graphene, a two-dimensional sheet of carbon hexagons,
is an attractive material for electronic applications, such as
field-effect transistors, integrated circuits, and sensors, due
to its unique structure and extraordinary high carrier
mobility [1]. However, since graphene has no band gap,
opening the band gap is a critical issue when one tries to Fig. 1 Schematic of metal
apply graphene to semiconductor devices. Theoretical and catalyzed anisotropic cutting ofgraphene to create GNR array.
experimental works have demonstrated that quantum
confinement in one dimensional structure, so called graphene nanoribbons (GNRs), canpotentially open the band gap [2,3]. Top-down lithography has been widely used to obtain
GNRs, but the GNR edges are damaged by O2 plasma treatment. The GNRs prepared byunzipping carbon nanotubes can be also damaged by gas phase or liquid phase oxidation
processes [4,5]. Therefore, a new method based on bottom-up approach is expected.
Here, we developed a processing method to catalytically cut graphene along anisotropic
crystalline orientation of underlying substrate, as illustrated in Fig. 1. This is similar to the
CVD growth of horizontally-aligned single-walled carbon nanotubes (SWNTs) on crystalline
sapphire and quartz [5], as Tsukamoto et al. showed recently [6]. We systematicallyinvestigated the anisotropic cuttings at different temperatures and different gas atmospheresfor single-layer graphene grown by CVD. Various metal nanoparticles including Ni, Fe, andCu gave anisotropic cutting lines, as seen in Fig. 2, and Ni nanoparticles were found to givethe highest cutting density with more than 20 lines/µm. Moreover, we also observed that a
cutting density is strongly dependent on the annealing temperature and H2 concentration.
Our results can be applied to large area fabrication of dense, highly aligned GNR arrays thatcan be developed to future carbon-based electronics.

Fig. 2 SEM images of single-layer graphene measured after metal-catalyzed cutting using (a) Ni, (b) Fe, and (c)Cu. In (a), the cutting lines appear black and remaining graphene is gray. In (b) and (c), cutting lines appear as
bright contrast.
References: [1] A. K. Geim, Nat. Mater., 6, 183 (2007). [2] K. Tanaka et al., Synth. Met., 17, 143 (1987). [3] X.
Li. et al., Science 319, 1229 (2008). [4] D. V. Kosynkin et al., Nature, 458, 872 (2009). [4] L. Jiao et al., Nat.
Nanotechnol. 5, 321 (2010). [5] H. Ago et al., Chem. Phys. Lett., 408, 433 (2005). [6] T. Tsukamoto et al., J.
Phys. Chem. C, 115, 8580 (2011).
Corresponding Author: Hiroki Ago (Tel&Fax: +81-92-583-7817, E-mail: ago@cm.kyushu-u.ac.jp)- 127 -

2P-37
Transparent graphitic tiles synthesized from carbon nanowalls
by shock compression○Kazutaka Nakamura1, Toshiyuki Atou2, Keisuke Niwase3, Kazutaka G. Nakamura2
and Masaru Tachibana1
1

Department of Nanosystem Science, Yokohama City University, Yokohama 236-0027,
Japan.
2
Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama, 226-8503,
Japan.
3
Hyogo University of Teacher Education, Hyogo 673-1494, Japan.
The transformation of graphite to diamond under high pressure is a long time issue. Shockcompression and rapid quenching (SCARQ) technique is an effective method to obtainmetastable carbon phase, transformed from the initial carbon phase in a short period of theshock compression [1]. The nature of transformed carbon phase, transition pressure andtransition temperature should depend on the initial state of the starting material. For theunderstanding of the transformation mechanism, it is important to investigate thetransformation of various kinds of carbon materials under high pressure.
Carbon nanowalls (CNWs) are two dimensional graphitic sheets vertically oriented to thesubstrate surface [2]. The nanostructure is composed of small and uniform graphite domains
or crystallites with several tens of nanometers [3]. Such structural feature has been also
demonstrated by transport properties such as Anderson weak localization [4] and novel
electrochemical properties for fuel cells [5]. Thus, CNWs with such unique structure are alsoof great interest as a starting material for high-pressure transformation of graphite. Here we
report the synthesis of transparent graphitic tiles from CNWs by the SCARQ method.
The transparent tiles (Fig. 1) are included in samples recovered from shock pressures morethan 57 GPa [6]. They exhibit strong photoluminescence but no diamond Raman peak, similar
to the case of amorphous diamond [7]. However, the electron energy-loss spectroscopy
exhibits relatively intense π* peak associated with graphite, that is inconsistent with thetransparency. From these results, it is suggested that the transparent tile is a mixture ofamorphous diamond and superhard graphitic material with the transparency [6]. Such carbon
phase may come from the unique structural feature of CNWs as the starting material for theshock compression.
[1] K. Kondo, Diam. Relat. Mater. 5, 13 (1996).
[2] S. Kurita et al., J. Appl. Phys. 97, 104320 (2005).
[3] K. Kobayashi et al., J. Appl. Phys. 101, 094306 (2007).
[4] S. Yamada et al., J. Phys. Soc. Jpn. 79, 054708 (2010).
[5] S. C. Shin et al., J. Appl. Phys. 110, 104308 (2011).
[6] K. Nakamura et al., J. Appl. Phys. (in press)[7] K. Niwase et al., Phys. Rev. Lett. 102, 116803 (2009).
Corresponding Author: M. Tachibana
Tel & Fax: +81-45-787-2307
E-mail: tachiban@yokohama-cu.ac.jp

Fig. 1- 128 -

2P-38Water-Soluble Graphene through Polyglycerol Grafting○Toku Yasuda1,2, Li Zhao1, Gang Liu1, Shuji Aonuma2, Takahide Kimura1, Naoki Komatsu1
1
2

Department of Chemistry, Shiga University of Medical Science, Otsu, 520-2192, Japan
Department of Materials Chemistry, Osaka Electro-Communication University, Osaka,
572-8530, JapanFor applications of nanocarbons in biology and medicine, such as imaging probe and drug
carrier, they have to be well solubilized in a physiological environment. In this context,
surface chemical functionalization has been extensively investigated to impart stronghydrophilicity to nanocarbons. We found recently that polyglycerol-grafted nanodiamond(ND-PG) exhibited very high solubility in phosphate buffer (16 mg/mL) [1]. In this paper, we
will present our recent result of PG grafting at the periphery of exfoliated graphene throughring-opening
polymerizationofglycidoltopreparePG-functionalized graphene (G-PG) soluble in PBS. We carriedout the PG-functionalization of exfoliated graphene under similar
reaction conditions to those of the ND-PG [1], but used graphene
was prepared through wet-process of graphite exfoliation as astarting material. The strong Tyndall effects were observed in the
aqueous solutions as shown in Fig. 1, suggesting that G-PG issolubilized both in the water and PBS. The existence of G-PG in Fig. 1 Aqueous solutions ofthese solutions was confirmed by UV and Raman spectroscopies. PG - functionalized graphene
In the Raman spectra shown in Fig. 2, both G and G’ bands are in water (left) and PBS (right).
detected in the dried samples
from water and PBS solutions.
From the ratio of G’ / G andthe symmetrical shape of G’band, a few-layer graphene isconsidered to be dominant in
the G-PG. In addition, theintensity of the D band isvery low, indicating that the
G-PG does not have number Fig. 2 Raman spectra of polyglycerol - functionalized grapheneof defects and that theprocess to prepare G-PG causes little damage to graphene.
[1] L. Zhao, T. Takimoto, M. Ito, N. Kitagawa, T. Kimura, N. Komatsu, Angew. Chem. Int. Ed., 50, 1388 (2011).

Corresponding Author: Naoki Komatsu
Tel: +81-77-548-2102, Fax: +81-77-548-2405, E-mail: nkomatsu@shiga-med.ac.jp- 129 500 nm

500 nm2P-39Relationship between morphology, electric properties and field emission
characteristics of carbon nanosheets films by microwave plasma-enhanced
chemical vapor deposition○1Shohei Hayase, 2Zhipeng Wang and 1,3Hironori Ogata
1

Department of Chemical Science and Technology, Hosei University, Koganei 184-8584,
Japan
2
Institution for Sustainability Research and Education, Hosei University, 2-17-1, Fujimi,
Chiyoda-ku, 102-8160 Tokyo, Japan
3
Research Center for Micro-Nano Technology, Hosei University, Koganei 184-0003, Japan
Carbon nanosheets (CNSs) consist of two-dimensional networks of almost vertically-aligned
graphitic walls with sharp edges and a few to some tens of nanometers thick. Due to the highaspect ratio and the high in-plane continuity of the wall structures, CNSs are expected as thecandidate for field emitters. As is well known, field emission (FE) properties strongly dependon the electric properties of the emitters and their morphological structures. Thus, themodification of the electronic structure or morphology of CNSs provides a possibility toenhance the FE performance of the CNSs. In this work, CNSs with various morphologies
were fabricated by changing H2 gas flow ratio and their FE properties were investigated. We
also investigate the effect of nitrogen plasma treatments on the structure and FE properties of
CNSs. The electron field emission properties of the films on NiFe substrate were measured ina parallel-plate configuration with ITO coated glass anode and a Teflon(100μm) interelectrodespacer at room temperature in high vacuum (below 10-3 Pa).
Figure 1 shows the FE-SEM image of the CNSs film before nitrogen plasma treatment.
Figure 2 shows the J-E characteristic curve of FE from the CNSs. The turn-on electric field
for the onset of emission at a J=10-5mA/cm2 was found to be 5.2V/μm, the β value was fitted
to be 2090. In this presentation, the detailed results will be presented.

Figure 1. FE-SEM image of the CNSs.

Figure 2. J-E characteristic curve ofFE from the CNSs film.

Corresponding Author: Hironori Ogata,Tel: +81-42-387-6229, Fax: +81-42-387-6229, E-mail: hogata@hosei.ac.jp- 130 -

2P-40Characterization of Electrical Properties
for Graphene Film Deposited by Microwave Plasma CVD○Yuki Okigawa1,2, Kazuo Tsugawa2, Takatoshi Yamada1,2
Masatou Ishihara1,2, and Masataka Hasegawa1,2
1

Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba 305-8565, Japan
2
Technology Research Association for Single Wall Carbon Nanotubes (TASC), Tsukuba
305-8565, Japan
We have developed the microwave plasma graphene CVD technique combined with theroll-to-roll process. In this method, a continuous deposition process of graphene film is
expected at low temperature and few ten seconds [1]. Although higher quality of the graphenefilm is required, the electrical property of the graphene film deposited by plasma CVD
technique is not fully understood. Hall effect measurement using van der Pauw devices isuseful to measure the electrical property for graphene, which is expected to understand themechanism of the electrical conductivity of graphene film. In addition, it is necessary tomeasure the electrical property for the different size of graphene, such as micrometer andcentimeter size of graphene. In this study, we have measured the hall mobility by Hall effectmeasurement with van der Pauw devices.
The graphene film was deposited by microwave plasma CVD technique on Cu foil. Then,it was transferred to the quartz substrate. After that, the van der Pauw device was fabricatedusing conventional photolithography, metal deposition and lift-off processes. Figure 1(a)shows the optical microscopy image for a micrometer size of the device. For a centimeter sizeof device, the four electrodes were deposited using the silver paste, as shown in Fig. 1(b).
These devices show that the mobility is estimated to be from 10 to 100 cm2/Vs. And theseshow the p-type conduction.
(a)

(b)

100 mm10 mm

Figure 1 Optical microscopy images for van der Pauw devices.
(a) micrometer size (b) centimeter size.
[1] T. Yamada et al., Carbon, 50, 2615 (2012).
Corresponding Author: Yuki Okigawa
Tel: +81-29-861-2747, Fax: +81-29-861-4565,
E-mail: okigawa.yuki@aist.go.jp- 131 -

2P-41
Host-guest Interactions between Nanographene and Gas molecules○Junichi Takashiro1, Kazuyuki Takai1, Manabu Kiguchi1, Toshiaki Enoki1
Takeo Yamada2, Kenji Hata2, Takafumi Ishii3, Takashi Kyotani3
1

Department of Chemistry, Tokyo Institute of Technology, Meguro, Tokyo, 152-8551, Japan
2
Nanotube Research Center, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, 305-8565, Japan
3
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
Sendai, 980-8577, JapanThe electronic properties of nano-sized graphene(nanographene) are influenced by the edges. Especially,in zigzag edges a non-bonding  state called “edgestate” is created. Nanoporous activated carbon fibers(ACFs, Fig.1), which consist of 3D disordered networkof nanographene sheets with their edges terminated by
Fig.1 Activated Carbon Fibers (ACFs)
oxygen-containing functional groups, are good model
system to investigate the effect of adsorbed guest chemical species on the electronic
properties of nanographene [1]. In this work, we investigated the interaction between ACFs
and gas species (O2, He, Ar and Xe) in terms of physisorption, charge-transfer, and chemical
reaction.
Pristine ACFs were pre-heat-treated at 1000℃ to eliminate the foreign species terminating
the nanographene edge. The time evolution of the resistivity was measured after 1atm of gas
species was introduced to ACFs at room temperature. To investigate the details of interaction
between nanographene and oxygen atoms, ACFs were exposed to O2 atmosphere of 1-100Paat Ttreat; 600-1300℃ (oxidation). The oxidized samples were investigated by the resistivity,
thermogravimetry, XPS, NEXAFS and thermal desorption measurements.
The resistivity increases upon gas adsorption, where the increment is in the order of O2 >Ar > He  Xe. The large increase in the resistivity is caused by chemisorptions of O2 tonanographene accompanied by charge transfer. For chemically inert noble gas species, thephysisorption of larger diameter noble gas molecules except Xe works to expand the nanopore
space to a larger extent, resulting in the resistivity increase owing to the elongation ofinter-nanographene-sheet distance. Xe, whose diameter is larger than the nanopore size,shows only a small resistivity increase, as it cannot be accommodated into the nanopores.
Fig.2 shows (a) edge state intensities in C K-edge NEXAFS and (b) the atomic ratio ofedge carbon atoms to total carbon atoms in nanographene (Cedge/Ctotal) obtained from TG for
oxidized and non-oxidized ACFs. The(a)(b)
NEXAFS intensity of the edge state
originatingfrom zigzag edges
decreases with increasing in Ttreat,irrespective of the increasing ofCedge/Ctotal. This is explained by thehigher reactivity of zigzag edge than Fig.2 (a) Edge state intensity and (b) Cedge/Ctotal normalizedarmchair edge due to its energeticallywith the value in the pristine state for ACFs at Ttreat (■),
and non-oxidized ACFs (□)
unstable nature, suggesting thatoxidation process in nanographene transforms zigzag edge into armchair edge.
[1] T.Enoki and K.Takai et al. Solid State Communications 149 1144 (2009)
Corresponding Author: T.Enoki
E-mail: enoki.t.aa@m.titech.ac.jp- 132 -

2P-42
Linear Dispersion Bands on Partially H-Terminated (111) Surfaces of
Diamond Structure○Junki Sone, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan

Ever since exfoliation of graphene from bulk graphite,
graphene has been attracting a lot of attentions due totheir interesting electronic properties arising from theircharacteristic geometry. Graphene has a planerhoneycomb structure due to sp2 hybridization of carbon
atoms. On this atomic sheet, π electrons are extended
through out the network leading to the peculiar electronic
structure at the Fermi level: A pair of linear dispersion
bands emerges at the Fermi level. Such characteristic
electronic structures result in a rich variety of physicalproperties and allow us to apply for electronic devices in
the next generation. Besides the honeycomb sheet of C
Fig.1 Geometric structure of
atoms, recently, a hexagonal atomic sheet consisting of Si partially H-terminated (111)
has been synthesized. In the present work, we aim tosurface of diamond. Circles
denoted black and white are theexplore the possibility of the emergence of liner
atoms with hydrogenated anddispersion bands on semiconductor surfaces. Here, we
without hydrogenated.
focus on the (111) surfaces of diamond structure of C andSi, whose topmost atoms are partially terminated by H
atoms. In accord with the partial termination, unsaturated
surface bonds form hexagonal network ( Fig. 1). On thesesurfaces, we perform first-principles calculations based on
density functional theory to elucidate their geometric andelectronic structures.
Since a unit cell contains two dangling bonds, we find that
two surface associated states emerge in the gap between
valence and conduction bands. Due to the large spacing
between the dangling bonds, these states have small dispersion
of a few hundred meV. By focusing at K point, surprisingly,
these states have linear dispersion as in the case of graphene(Fig. 2). In sharp contrast, calculated Fermi velocities of C and
Si dangling bonds are 10 % of that of graphene. Thus, bycontrolling surface morphologies of semiconductors withappropriate adsorbates, we can easily obtained Dirac fermion
systems on surface of matters and tune their electron
Fig.2 Electronic structure ofcorrelation.

dangling bond states ofpartially hydrogenated (111)
surface of diamond near K
point.

Corresponding Author: J.Sone
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 133 -

2P-43
Influence of mechanical deformation on thermal properties ofgraphene○Takashi Funatani 1 , Takahiro Yamamoto 2 , Matsuto Ogawa 1 , Satofumi Souma 1
1

Dept. of Electrical and Electronic Engineering, Kobe University, Kobe, 657-8501,
Japan
2
Dept. of Liberal Arts, Tokyo University of Science, Chiyoda, Tokyo 102-0073, Japan
Recent rapid development of semiconductor technologies have been
mainly achieved by the miniaturization of silicon MOSFET and theirintegration based on the Moore’s law. However, as the device size isaggressively scaled down, the heat production in the device influencesmore seriously the device performance. As one of strategies to resolve
such problem, graphene is attracting great attention since it has highthermal conductivity and thus useful for dissipating heat. On the other
hand, from the view point of effective utilization of heat given off,
thermoelectric devices are also drawing many attentions, where thematerial with low thermal conductivity is preferable. Therefore, it isinteresting to explore the possibility to control the thermal conductivity ofgraphene.
With such motivation, in the present study we theoretically examine
the effect of mechanical deformation on “phonon specific heat” ingraphene, which is one of physical quantities that dominate its thermal
conductivity. Our calculations have shown that the tensile strain appliedalong the zigzag direction (Fig. 1) modulates essentially the temperaturedependence of the specific heat, where the specific heat is found to be
increased by applying the strain when the temperature is higher than thethreshold value (Fig. 2), meaning that the thermal conductivity ofgraphene is expected to be enhanced by the mechanical deformation. The
detail of our analyses will be given in the prese ntation.

Fig. 1. Conceptual diagram of graphenestrained along the zigzag direction

Fig. 2. Temperature dependence ofphonon specific heat in graphene with
0 [%] and 20 [%] strain.

Corresponding Author: Satofumi Souma
Tel&FAX: +81-78-803-6087 E-mail: ssouma@harbor.kobe-u.ac.jp- 134 -

2P-44First-principles study of edge-modified armchair graphene nanoribbons○Hideyuki Jippo and Mari Ohfuchi
Fujitsu Laboratories Ltd., 10-1 Morinosato-wakamiya, Atsugi, Kanagawa 243-0197, Japan
Graphene nanoribbons (GNRs) have attracted attention as hopeful semiconducting
nanostructures for electronic applications of graphene. Recently a bottom-up approach toatomically precise fabrication of armchair GNRs (AGNRs) has been reported [1]. Thisapproach might also enable us to produce AGNRs with various edge terminations.
OH-terminated AGNRs (OH-AGNRs) have been theoretically studied and shown to haverippled edges and different energy band gaps from H-terminated AGNRs (H-AGNRs) [2]. Fand Cl-terminated AGNRs (F- and Cl-AGNRs) have also shown rippled edges [2], but theirelectronic structures are still unclear. In this article, we investigate the electronic structures of
the F- and Cl-AGNRs using first-principles methods.
We examine H-, F-, Cl- and OH-AGNRs with widths N = 7 and 19. They are most likely tobe realized by the bottom-up approach. The most stable geometries of H-AGNRs have planar
configurations, but those of F-, Cl- and OH-AGNRs have rippled edges as shown in Fig. 1.
The ripples stem from steric hindrance between neighboring pairs of the termination atoms orgroups and are strongly localized to the edges. We have found that F-AGNRs are the moststable owing to the strong C-F bonds despite their rippled edge structures. As shown in Fig. 2,
the energy band gaps of F- and Cl-AGNRs are narrower than those of H-AGNRs. We havefound that this is due to the structural deformations rather than the chemical effect. For
OH-AGNRs, the chemical interactions between the adjacent OH groups further reduce theband gaps.
In summary, the energy band gaps of AGNRs have been shown to vary with the edge
terminations. This seems to show the possibility of controlling their electronic properties byedge modifications.

Fig.1. (a) Perspective and (b) side views of the moststable geometry for Cl-terminated armchair graphene
nanoribbon with a width N = 7. The light and dark grayspheres represent C and Cl atoms, respectively. The
symbols of u and d represent the edge moves “up” and“down” from the ribbon plane, respectively. The dottedlines indicate the unit cell.
[1] J. Cai et al., Nature 466, 470 (2010).

Fig.2. Energy band gaps of H-, F-, Cl and
OH-terminated armchair graphene nanoribbons
with widths N = 7 and 19.

[2] P. Wagner, et al., Phys. Rev. B 84, 134110 (2011).

Corresponding Author: H. Jippo
Tel: +81-46-250-8843, Fax: +81-46-250-8274, E-mail: jippo.hideyuki@jp.fujitsu.com- 135 -

2P-45Enhancement of photo-induced current in the complex ofiron oxide nanotubes and fullerenols
Yuki Shiraki, żYuki Mishina, Shunji Bandow
Department of Materials Science and Engineering, Meijo University,
1-501 Shiogamaguchi, Tenpaku, Nagoya 468-8502, Japan

2

I (PA/cm )2

I (PA/cm )Dye sensitized solar cell is most promising
120
OFF
OFF
candidate for an effective absorber of thea : visible
OFF
100
visible light. The principle of this composite
is based on the charge transfer from the visible
80
ONON
light excited electrons to the conduction bandON
60
Fe-oxNT/C60-OHof the dye molecule to the conduction band of
Fe-oxNT
the host materials of metal oxides such as
40
Fe-oxNT + C60-OH
TiO2 and WO3, etc. Since such charge
20transfer would take place at the interfacial
C60-OH0
region, it is effective to have a large surface
0.4
0.6
0.8
1.0
1.2
area for the host material. A tube structure is
E (V) vs. Ag/AgCla candidate for realizing such large surface
area and we focus a material of iron-oxide or120
titanium oxide nanotube.
b : UV100
Since the metal oxides normally haveONhydrophilic nature, hydrophobic fullerene isON
Fe-oxNT/C60-OH
80
not suitable for making the complex. In
order to avoid this problem, we prepared
60
OFF
OFF
fullerenols, C60(OH)n, by the patent method
Fe-oxNT40[1]. Metal oxides nanotubes were preparedFe-oxNT + C60-OH
C60-OHby the sol-gel (Fe-oxide NT) and strong
20
alkaline reflux (Ti-oxide NT) methods0
reported [2,3].
0.4
0.6
0.8
1.0
1.2
E (V) vs. Ag/AgCl
The samples were made by mixing thecolloidal solutions of metal-oxide NTs andfullerenols and kept for 1 day at RT. Fig. 1 Photo-induced current measured in anelectrolyte of a 0.2 mol KHCO3 aq. under irradiating
Responses of photo-induced current are in a) visible light (halogen lamp) andb) UV (Hg lamp).
Figs. 1a (visible light) and 1b (UV) with the Remarkable enhancement of the current and lightsamples of 1) fullerenols only (C60-OH), 2) irradiation effects can be seen in a Fe-oxNT/C60-OH
iron-oxide nanotube only (Fe-oxNT), 3) just complex under a visible light.
after mixing Fe-oxNT and C60-OH (Fe-oxNT+ C60-OH) and 4) after 1 day reaction (Fe-oxNT/C60-OH). As shown in the figure, anenhancement of the photo current and a remarkable visible light response can be identified
only in the sample after 1 day reaction. Comparison of the light irradiation responses
between the mixtures of Ti-oxNT/C60-OH and Fe-oxNT/C60-OH will be discussed.
[1] P2007-031090[2] Y. Mishina et al., The 41st FNTG (2011), 3P-10.
[3] Y. Shiraki and S. Bandow, The 42nd FNTG (2012), 3P-49 and 43rd FNTG (2012), 3P-38.
Corresponding Author: Shunji Bandow, E-mail: bandow@meijo-u.ac.jp, Tel : +81-52-838-2404- 136 -

2P-46Development of Multi-stage Ion Trap Mobility System.
żToshiki Sugai
Department of Chemistry, Toho University, Miyama 2-2-1 Funabashi, 274-8510, Japan
Ion mobility measurements have been utilized to analyze structures of nanocarbon
materials[1]. Structures of Metal-fullerene show significant dependence on the number ofmetal atoms and the cage size. To study further, we have been developing an ion trap mobility
system and structural changes of salt solution particles and solid polystyrene particles weremonitored for more than 2 hours[2]. The measurements have revealed the stability and thesensitivity of the system. The salt water solution particles absorb water vapor in air and growto larger particles whereas the rigid polystyrene particles keep their structures. Despite ofthese advantages, the trap system has low mobility resolution because of the small size of the
trap. To improve the resolution, we have been developing the multi-stage ion trap mobility
system. The details of the system will be presented.
[1] T. Sugai et al., J. Am. Chem. Soc. 123, 6427 (2001).
[2] T. Sugai et al., The 38th symposium (2010) and The 44th symposium (2012).
TEL: +81-47-472-4406, FAX: +81-47-472-4406, E-mail: sugai@chem.sci.toho-u.ac.jp- 137 -

3P-1
Thermal Reactions of C60 with Siliranes: Formation of Carbosilylated
Fullerenes○Ryosuke Iida1, Kentaro Takagi1, Masahiro Kako1,Tadashi Hasegawa2, Yutaka Maeda2,
Michio Yamada2, Takeshi Akasaka3
1

Department of Engineering Science, The University of Electro-Communications, Chofu,
Tokyo 182-8585, Japan2
Department of Chemistry, Tokyo Gakugei University, Koganei, Tokyo 184-8501, Japan
3
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki, 305-8577, Japan

Many research groups have investigated derivatization of fullerenes with various functionalgroups from both mechanistic and synthetic viewpoints. It has been demonstrated that
introduction of heteroatoms such as electropositive silicon has induced remarkable changes inthe electronic characteristics of fullerenes. In fact, the facile silylation reactions of fullerenes
have been described using reactive silicon compounds such as disiliranes, silylenes, and silyl
radicals [1]. These silylated derivatives have more negative charge on the cage than the parent
fullerenes as revealed by electrochemical analyses and theoretical calculations. Neverthelesssuch silylation procedures are hitherto limited under photolytic conditions, and thedecomposition of the silylated products were frequently observed under the photolytic
conditions. Therefore, it is worthwhile to investigate alternative procedures for silylation offullerenes without photoirradation. Recently, we reported the photochemical carbosilylationof C60 using siliranes indicating the production of the novel 1,2- and 1,4-adducts [1]. In ourcontinuing research of silylation of fullerenes, we are investigating thermal reactivities ofsiliranes with C60 for comparison with those of the photoreactions. Because siliranes are
established as the precursors of silylenes, it is noteworthy that silylene addition and formal[2+3] cycloaddition are possible for siliranes. In addition, we also examined the thermal
reactions of siliranes and fullerenes catalyzed by transition metal complexes as an alternative
procedure for silylation.
Dmt
When a toluene solution of C60 and
Dmt
Si
Si
Dmt
silirane 1a was heated at 110¡C for 24 h,
Dmt
a carbosilylated product compound 2a
1a
was obtained in 68 % yield. Based on the
spectroscopic
analyses,
2a
was
2a
!
determined to be a 1,2-addcut on the [6,6] C60
Dep
OH
Dep
bond junction of C60. On the other hands,
Si H
Si
Dep
Dep
the reaction of silirane 1b and C60
1bafforded the corresponding hydrolyzed
silylene adduct. These results and related
Dep =
Dmt =
transition-metal catalyzed reactions will
be discussed in detail.
                          Scheme 1.
[1] Nagatsuka, J.; Sugitani, S.; Kako, M.; Nakahodo, T.; Mizorogi, N.; Ishitsuka, M. O.; Maeda, Y.; Tsuchiya, T.;
Akasaka, T.; Gao, X.; Nagase, S. J. Am. Chem. Soc. 2010, 132, 12106-12120, and references cited therein.
Corresponding Author: Masahiro Kako Tel: +81-42-442-5570  E-mail: kako@e-one.uec.ac.jp- 138 -

3P-2
Construction of an Opening on Fullerene C70 and     
Encapsulation of a Water MoleculeżRui Zhang,1 Michihisa Murata,1 Yasujiro Murata1,21Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
2
JST–PRESTO

We have reported a synthetic method to produce endohedral fullerene C60 encapsulating awater molecule.1 In this work, by applying the similar procedure to C70 with a larger innerspace, open-cage C70 derivative 1 with a 13-membered-ring opening was synthesized as a key
compound for the insertion of a water molecule. We also studied the insertion of a watermolecule by heating a solution of 1 under the presence of water.
We first prepared
open-cage C70 derivative 4with a 12-membered-ring
openingvia
thermalreaction of C70 withpyridazine
2
andsubsequent photo-oxidationof compound 3 (Scheme
1).2 Then, by following thesynthetic
methodfor
H2O@C60, we tried toenlarge the opening of 4 byusing N-methylmorpholine
N-oxide (NMO) as anoxidant.1 This reaction
resulted in a formation ofcomplex mixture and desired product 1 was not isolated. Thus, we used N-pyridine oxide 5 asa milder nucleophilic oxidant than NMO and succeeded in obtaining 1 in 78% yield. The
plausible mechanism of this reaction is shown in Scheme 2. First a thermal reaction of 4 with
5 gives epoxide 6, which again reacts with 5 to produce tetraketone 7. Then a water molecule
adds to one of the carbonyl groups of 7 to afford 1.
Insertion of water molecule to 1 was achieved by heating a solution of 1 under thepresence of water. 1H NMR of the product showed a new singlet signal at G = –18.16 ppm in
CDCl3. Considering that the water molecule inside the corresponding open-cage C60
derivative gave a singlet signal at G = –9.87 ppm in CDCl3,1 the water molecule encapsulated
in 1 was subjected to the strong shielding effect from the C70 cage. We will also present
results of closing the opening toward the synthesis of endohedral fullerene H2O@C70.
[1] K. Kurotobi, Y. Murata, Science 333, 613 (2011).
[2] Y. Murata, S. Maeda, M. Murata, K. Komatsu, J. Am. Chem. Soc. 130, 6702 (2008).
Corresponding Author: Yasujiro Murata
Tel: +81-774-38-3172, Fax: +81-774-38-3178
E-mail: yasujiro@scl.kyoto-u.ac.jp- 139 -

3P-3
Thermal [2+2] cycloaddition of C60 with aryl dienamines○Naohiko Ikuma, Hiroyuki Yamamoto, Tsubasa Mikie, Ken Kokubo, Takumi Oshima
1

Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita,
Osaka, 565-0871, Japan
Facile and highly selective functionalizations of C60 without any undesirable by-products

are required to obtain a variety of fullerene derivatives in reasonable costs. We are interested
in the development of novel methodology in which the mono-addition of C60 drasticallyreduces the further multi-additions due to the raise of its LUMO energy. In this context, wereported that reaction of C60 with some morpholinoenamines proceeds via single electrontransfer (SET) to gives selectively monoadducts in very high yield[1].
Here, we extend this reaction to diaryl dienamines 1 derived from cycloamines and variously
substituted acetophenones and report the successful formation of new [2 + 2] adduct 2 of C60
with 1 in relatively high yields (up to 60%), depending on the aromatic substituents. On aradical trapping experiment with nitrosobenzene, this reaction seems to proceed via SET in asimilar manner as morpholinoenamines. The NMR analysis of 2 indicated the occurrence of
1,3-proton transfer of primary [2 + 2] adducts probably catalyzed by basic morpholino group.

[1] T. Mikie, H. Asahara, K. Nagao, N. Ikuma, K. Kokubo, T.Oshima, Org. Lett. 13, 4244 (2011).
Corresponding Author: N. Ikuma
Tel&Fax: +81-6-6879-4593,
E-mail: ikuma@chem.eng.osaka-u.ac.jp- 140 -

3P-4
Transport Characteristics of C60 Photo-Polymers Fabricatedby Focused Optical Vortex Irradiation○Naoto Toriumi1, Tatsuya Doi1, Daiki Momiyama1, Wataru Akiyama1, KatsuhikoMiyamoto1, Takashige Omatsu1, Jonathan P. Bird2, Yuichi Ochiai1, and Nobuyuki Aoki1
1

Graduate School of Advanced Integration Science, Chiba University,
Chiba, 263-8522 Japan2
Department of Electrical Engineering, University at Buffalo, SUNY, Buffalo, NY
14260-1920, USA
Recently, a state of the art photo-polymerization of a C60 thin film has been realized byirradiation of topological laser beam namely optical vortex (OV). Since the beam has a helical
wavefront and a torque appears along the tangential direction, a confinement force can be
expected along the peripheral direction of the beam and the polymerization takes a progresswith a compressive photon-pressure under a high-beam-power density. Therefore, it can be
expected to achieve a highly-packed and uniform photo-polymerization in a C60 thin film.
Moreover, combining with circular polarization, total angular momentum of light can becontrolled [1].
In our study, thermally evaporated C60 thin film was deposited 50 nm on a SiO2 layer on top ofa heavily doped Si substrate. A continuous-wave 532 nm laser beam was used for the opticalsource. The OV was produced by using a spiral phase plate and irradiated onto the sample
through an objective lens.
We observed electric properties of C60 thin film polymerized by OV irradiation and a peak shiftof Raman spectrum corresponding to Ag(2) mode suggests a polymerization of the C60 molecule[2]. Moreover, no significant cracks were confirmed in the polymerized region by OV.
Therefore, non-conventional polymerization regime can be expected in the photo-polymer by
OV irradiation. However, these characteristics have been confirmed in air after soaked intoluene for 3 minutes to remove non-polymerized C60 films on the sample surface.
As the following step, we are trying to have in-site measurements of electric conduction
properties just after the OV irradiation. Moreover, dose amount dependence of the transport
properties and the thickness of the polymerized region will be discussed in the presentation.
[1] T. Omatsu et al., Opt. Express 18 (2010) 17967.
[2] S. J. Duclos et al., Solid State Commun. 80 (1991) 481.
Corresponding Author: N. Aoki
Tel: +81-43-290-3430, Fax:+81-43-290-3427,
E-mail: n-aoki@faculty.chiba-u.jp

Fig1. Circular pattern on a C60
thin film by OV irradiation.

- 141 -

3P-5
Fabrication of bulk-heterojunction organic solar cells using PCBM andmixed donors of P3HT and phenylene–thiophene oligomerżShunjiro Fujii1,2, Zongfan Duan3, Takanori Okukawa4, Yuichiro Yanagi4,
Akira Yoshida4, Takeshi Tanaka1, Yasushiro Nishioka4, and Hiromichi Kataura1,2*
1

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Ibaraki 305-8562, Japan 2JST, CREST, Kawaguchi 330-0012,
Japan 3School of Materials Science and Engineering, Xi'an University of Technology,
Xi'an 710048, China 4Nihon University, Funabashi, Chiba 274-0851, Japan

IPCE (%)

Organic solar cells (OSCs) are of special interest owing to their advantages of
low-cost and solution-processable fabrications. Each material for OSCs has different
spectral sensitivity characteristics. Since the spectral distribution of sunlight has the
maximum intensity around the wave lenghth of 450 nm, OSCs are expected to havemaximum incident photon-to-current conversion efficiency (IPCE) around 450 nm.
Recently, we have reported the OSCs using a new phenylene-thiophene oligomer (PTO
shown in Figure 1) as an electron donor [1]. The bulk-hetero junction (BHJ) OSCs
fabricated from PTO and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) showed amaximum IPCE around 400 nm. To improve the perfomance, the wavelength range of
IPCE spectra is required to be widen and adjusted to the sunlight spectra. In this study,
we fabricated BHJ-OSCs using two donors of PTO and poly(3-hexylthiophene) (P3HT),
which have the maximum IPCE around 400 nm and 500 nm [2], respectively.
The active layers of BHJ-OSCs were
fabricated by spincoating mixed
solutions of chloroform solvent. The
Figure 1 Molecular structure of oligomer
measured IPCE spectra of the OSCs using the20
two donars showed the maximum sensitivity
around 450 nm, and had a wider sensitivity range(Figure 2). As a reslut, the OSC using the blend
15
film of mixed donars and PCBM showed a power
conversion efficiency of 0.90%, which was higher
10than that of PTO and PCBM (0.47%) or P3HT
‫ۂ‬P3HT:PCBM
and PCBM (0.65%). In this presentation, detailed
5
PTO:PCBM‫ە‬characteristics of the OSCs will be discussed.
‫ڧ‬Mixed donors:PCBM[1] Z. Duan et al., Chem. Lett. 41, 363 (2012)[2] F. Padinger et al., Adv. Funct. Mater., 13, 85 (2003)
Corresponding Author: Hiromichi Kataura
Tel: +81-29-861-2551, Fax: +81-29-861-2786,
E-mail: h-kataura@aist.go.jp- 142 -

0
300

400

500

600

700

Wavelength (nm)800

Figure 2 IPCE spectra of the OSCs withdifferent active layers in the configuration of
Glass/ITO/ PEDOT:PSS/active layer/Al.

3P-6
Reaction of Trimetallic Nitride Template-endohedral Metallofullerene(TNT-EMFs) with Aziridine○Masato Kimura1, Chihiro Ueda2, Michio Yamada2, Yutaka Maeda2, Tadashi Hasegawa2,
Takeshi Akasaka1
1Life Science center of Tsukuba Advanced Research Alliance, University of Tsukuba,
Tsukuba, Ibaraki 305-8577, Japan2
Department of Chemistry, Tokyo Gakugei University,Koganei, Tokyo 184-8501, Japan
Endohedral Metallofullerenes (EMFs) have attracted interest for specific physical andchemical properties, as the result of electron transfer between the encapsulated metal species
and the fullerene cage. Especially, TNT-EMFs, which encapsulated M3N cluster, e.g.
Sc3N@C80, are promising candidates for practical application in material science andbiological science, because of its higher production yield than any other EMFs. For practicalapplication, such as organic photovoltaic cells, it is essential to control its solubility orelectronic properties by chemical modification. Prato et al. reported the reaction of C60 or
SWNTs with azirizine afford corresponding adducts. [1] We focus on the azirizine, precursor ofazomethyne ylide, for functionalization of metallofullerens, because of the convenientsynthesis of aziridine with various functional groups.
Herein, we report the reaction of TNT-EMFs, Sc3N@C80 with aziridine derivatives andcharacterization of 2, 3 by HPLC, MALDI-TOF Mass, Vis-NIR, NMR, and electrochemicalmeasurements.
Scheme 1

Reference[1] Prato et al. J. Am. Chem. Soc. 2007, 129, 14580.
Corresponding Author: Takeshi Akasaka
Tel: +81-29-853-6409, Fax: +81-29-853-5881, E-mail: akasaka@tara.tsukuba.ac.jp- 143 -

3P-7
Extraction of unstable di-metallofullerenes using a mixed solvent oftriethylamine and acetone
Aimi Togashi, Takeshi Kodama, Wataru Fujita, Koichi Kikuchi, Yohji Achiba
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
C80(Ih) fullerene cage has been well known to be stabilized by transferring 6 electrons
from the multiple metal atoms encapsulated inside the cage such as La2 or Ce2. Actually,
La2@C80 or Ce2@C80 species is easily extracted by conventional organic solvents such as CS2
or 1,2,4-trichlorobenzene (TCB). However, until quite recently, the presence of Y2@C80 and
Sc2@C80 has never been distinguished by the usual extraction method. In 2011, Kodama et al.
have demonstrated for the first time that even Y2@C80 is able to be extracted by using amixed solvent consisting of triethylamine (TEA) and acetone[1]. The differences in electronic properties of the C80(Ih) common cage have strongly been suggested to give asignificant influence on the extraction behaviors observed between La and Y systems. In thisstudy, with use of a mixed solvent mentioned above, we have intended to extract LaY@C80 as
well as Sc2@C80 those have never been extracted so far by conventional organic solvents.
Soot containing metallofullerenes was produced by direct-current (60 A) arc dischargeof La/Y/C composite rods (La:Y:C=1:1:98) or Sc/C composite rods (Sc:C=2:98) under a 500
torr He atmosphere. The raw soot was divided into two parts and each part was extracted for
8h with a mixed solvent of TEA and acetone or with TCB, respectively. Fig. 1 shows the
typical LD-TOF-MS spectra of the mixed solvent extract and the TCB extract for
LaY-metallofullerenes, and Fig. 2 shows the ones for Sc-metallofullerenes. The signals of
LaYC80 or Sc2C80 are found in the mixed solvent extract, not in the TCB extract. Therefore, it
is suggested that the two metal atoms are encapsulated in C80(Ih) for LaYC80 and Sc2C80.

Fig. 1 LD-TOF-MS spectra of extracts
for LaY-metallofullerenes.

Fig. 2 LD-TOF-MS spectra of extracts
for Sc-metallofullerenes.

[1] T. Kodama, et al. The 41st Fullerenes-Nanotubes-Graphene General Symposium 31 (2011).
Corresponding Author: Takeshi Kodama
E-mail: kodama-takeshi@tmu.ac.jp
Tel:+81-42-677-2530, Fax:+81-42-677-2525- 144 -

3P-8
Spin Configurations of Three Radicals on Fullerenes○Susumu Okada(a) and Takahiro Yamamoto(b)(a) Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba
305-8577, Japan(b) Department of Liberal Arts (Physics), Faculty of Engineering, Tokyo University of
Sciences, Kudanshita, Chiyoda Ku, Tokyo 102-0073, Japan
Electronic structure of carbon allotropes with three-fold coordination is known to dependon their morphology, dimensionality, size, and boundary condition. Indeed, chemical
modifications on fullerenes result in interesting π electron systems on the spherical networks.
For instance, C60 derivatives with conical shape have been synthesized by attaching fivearomatic molecules to C60. Furthermore, deca-organo C60 have been also synthesized. In thesematerials, the aromatic molecules attached to C60 certainly modify the spherical π electron
system of C60. In the case of deca-organo C60, attached aromatic molecules divide spherical πelectron system into three parts: a short armchair nanotube and two pentagonal rings
surrounded by molecules. According to these two pentagonal rings, this C60 derivative has
two radical spins localized at these pentagonal, which are expected to posses interesting
mutual arrangements. In this work, we aim to investigate the spin configuration of a radical
spin trimer on fullerene surfaces by using both first-principles total-energy calculations andanalytic calculations.
Our first-principles calculations show that the three radical spins exhibit peculiar
spin-density distributions that are difficult to understand in terms of a classical spin picture.
To reveal physical origin, we have analyzed the peculiar spin-density distributions based on aquantum spin model consisting of S=1/2 spins localized at the corners of a triangle. As aresult, the spin-density distributions obtained by the first-principles calculations were well
reproduced by the quantum spin model. In addition, we found from the model analysis thatthe modulation of exchange coupling between the spins induces a rich variety of spin
configurations.

Corresponding Author: S. Okada
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 145 -

3P-9
Magnetic Properties of Deca-Methyl Fullerenes○Haruna Nittaa, Yutaka Matsuob, Eiichi Nakamurab, Susumu OkadaaaGraduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japanb
Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

It is known that electronic states of nanoscale materials consisting of sp2 carbon atoms,
such as grapheme nanoribbons, carbon nanotubes and fullerenes, strongly depend on their
network topologies and dimensionalities. In addition to the intrinsic diversity of electronic
structure of these carbon allotropes, both physical and chemical modifications also lead tounusual electronic properties on resultant systems. Indeed, C60 derivatives with conical shapes
have been synthesized under controlled modifications of C60 by attaching five aromatic
molecules [1] and have been reported to possess peculiar electronic structures. In addition to
the penta-organo C60, selective multiadditions of organic molecules to C60 and large fullerenes
lead to many fullerene derivatives with interesting morphologies [2]. In this work, we study
geometric and electronic structures of deca-methyl fullerenes, (Me)10C60, (Me)10C70,(Me)10C80, based on density functional theory. To investigate the interaction between radical
spins on these deca-methyl fullerenes, we use local spin density approximation (LSDA) forthe exchange correlation potential among the interacting electrons.
Our calculations clarified that the chemical adsorption of methyl groups results insegmentation of a spherical π electron system of fullerenes: Two pentagonal rings are isolated
from the remaining sp2 network leading to the spin polarization which are coupled in parallel
and antiparallel arrangements. Further calculations unraveled that the antiparallel spinarrangement is the ground state for deca-methyl C60s. With increase the size of fullerene,energy difference between the parallel and antiparallel arrangements decreases. In the case of
the deca-methyl C70, these two states almost degenerate each other indicating that the radical
spins are freely arranged. Further increase the size, in the case of the deca-methyl C80, theparallel arrangement is energetically favorable due to the substantial hybridization with the πstates on a hexagonal network at the C80 equator. The facts indicate that the radical spin
interaction on deca-methyl fullerenes is tunable by controlling the chemisorption site and thefullerene size.
References[1] M. Sawamura, K. Kawai, Y. Matsuo, K. Kanie, T. Kato, and E. Nakamura: Nature 419, (2003) 702.
[2] Y. Matsuo and E. Nakamura: Chem. Rev. 108 (2008) 3016.
Corresponding Author: H.Nitta
Tel: +81-29-853-5921, Fax: +81-29-853-5924,
E-mail: sokada@comas.frsc.tsukuba.ac.jp- 146 -

3P-10Synthesis of non-IPR fullerenes from C60 in liquid phaseby irradiation of intense femtosecond laser pulses○Takeshi Kodama, Tatsuya Fujino, Haruo Shiromaru, Yohji Achiba
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
Recently, the use of ultrashort pulsed lasers with extremely high intensity electric field
have been started for the study of a new type of chemical reaction. In the field of carbon
cluster science, polyynes were successfully synthesized by the femtosecond laser irradiation
to organic solvents without any additional introduction of carbon sources[1,2]. Under suchextreme laser condition, it has been believed that the atomization of solvent molecules andreconstruction of new C-C network formation take place very efficiently, resulting in the
production of polyynes even in liquid phase. So the questions might arise what would happen
when the ultrashort pulsed laser is irradiated to the fullerene cage in liquid phase.
According to our previous experiment[3], the irradiation of the femtosecond laser to the
C70 toluene solution , the black powder-like materials were generated and the mass
spectroscopic analysis of these materials revealed that the C68, C66 and C64 species weregenerated. Therefore, it was suggested that the successive C2-loss process occurs and theresulting chemically unstable C68, C66 and C64 would be easily changed into insoluble
aggregates. In this study, we try to synthesize non-IPR fullerenes, C58, from C60 in liquid
phase, because the isomer (#1205) with C3v symmetry is expected as an energetically stable
non-IPR fullerene via a C2 ejection from C60.
Fig. 1 shows the absorption spectra of C60 before and after laser irradiation in toluene
solution. After 10 min irradiation, characteristic peaks of C60 almost disappear and thebaseline becomes to be risen. Further 20 min
irradiation gives rise of returning the baselineback to almost zero and black powder-likematerials start to appear. The phenomenon of
the rise of base line before 10 min irradiationsuggests that some soluble non-IPR fullerenes
Fig. 1 Absorption spectral changes of C60
are generated at the initial state.
before and after irradiation in toluene solution.
[1] A. Hu, et al. Carbon 46, 1823 (2008).
[2] Y. Sato, et al. Carbon 48, 1673 (2010).
[3] T. Kodama, et al. The 40th Commemorative Fullerenes-Nanotubes General Symposium 187 (2011).
Corresponding Author: Takeshi Kodama
E-mail: kodama-takeshi@tmu.ac.jp
Tel:+81-42-677-2530, Fax:+81-42-677-2525- 147 -

3P-11
Interaction of carbon nanotubes with homopolypeptides○Atsushi Hirano 1, Tomoshi Kameda 2, Takeshi Tanaka 1, Hiromichi Kataura 1
1

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology, Tsukuba, Ibaraki 305-8562, Japan
2
Computational Biology Research Center, Advanced Industrial Science and Technology,
Koto, Tokyo 135-0064, JapanWith
theprogressofnanotechnology,
nanoparticles including carbon nanotubes have raised
concerns regarding the environmental and healthissues. It is known that nanoparticles are associatedwith protein molecules in the biological systems once
they are taken into the systems. The complexes ofnanoparticles with proteins are termed “protein
coronas” which are considered to be related withcytotoxicities [1]. Clarifying the mechanism of theformation of protein coronas is one of the importantFig. 1 Interaction of lysozyme withsubjects in the development of the nanotechnology.
carbon nanotubes. Side chains ofSeveral recent studies have showed that carbon
arginine are depicted by black sticks.
nanotubes are associated with proteins and dispersedby them [2]. In particular, lysozyme, which is a
protein from egg white, was found to interact withcarbon nanotubes mainly through arginine residues bymolecular dynamics (MD) simulation [3]. We also
obtained a similar result about the interaction of thearginine residues with carbon nanotubes using MD
simulation as a preliminary study (Figure 1). Thus,
arginine is considered to play an important role in theinteraction of protein with carbon nanotubes.
In this study, we compared the effect ofpoly-L-arginine (poly-R) on the dispersion of carbon
nanotubes to that of poly-L-lysine (poly-K) for
Fig. 2 Absorption spectra of carbon
nanotubes
dispersedbytheclarifying the side chain effect of arginine. Figure 2
homopolypeptides.
shows spectra of carbon nanotubes dispersed bypoly-R and poly-K. The amount of carbon nanotubes
dispersed by poly-R was more than that by poly-K in the molecular weight range studied,indicating the affinity of arginine with carbon nanotubes. We will show the molecularmechanism of the interaction of arginine with carbon nanotubes obtained by experiments andMD simulations.
[1] T. Cedervall et al. Proc. Natl. Acad. Sci. USA 104, 2050 (2007)[2] A. Hirano et al. Langmuir 26, 17256 (2010)[3] M. Calvaresi et al. Chem. Eur. J. 18, 4308 (2012)
Corresponding Author: T. Tanaka
Tel: +81-29-861-2903, Fax: +81-29-861-2786,
E-mail: tanaka-t@aist.go.jp- 148 -

3P-12
Molecular recognition of external grooves on bundled surfaces ofsingle-walled carbon nanotubes○JongTae Yoo1, Tsuyohiko Fujigaya1,2, and Naotoshi Nakashima1,2,3
Department of Applied Chemistry, Graduate School of Engineering, Kyushu University,
744 Motooka, Fukuoka 819-0395, Japan
2World Premier International (WPI), International Institute for Carbon-Neutral Energy
Research, Kyushu University 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
3Japan Science and Technology Agency, CREST, 5 Sanbancho, Chiyoda-ku, Tokyo,
102-0075, Japan

1

Cylindricalandcurvature
structureofsingle-walled carbon nanotubes (SWNTs) often
makes clear difference over planer analogues.
Recently, one-dimensional nano-spaces in the bundleof SWNTs such as interstitial channel and externalgroove attract attentions in experimentally andtheoretically due to their intense van der Waals
interaction with molecules. Here, we investigated aneffect of SWNT bundle for SWNT-molecularinteraction using the affinity chromatography [1]incorporating SWNT bundles as a stationary phase.
In a preparation of the stationary phase, different
concentrations of SWNT dispersions in 1-methyl-2pyrrolidinone (NMP) were mixed with silica sphereand the precipitates were collected [2]. As shown in
SEM images, bundled structures of SWNTs wereobserved on the silica surface prepared from higher
concentration (Fig. 1B), while such a structure was
hardly seen on that from lower one (Fig. 1A).
Quite interestingly, we noticed the changes of theorder of retentions between isolated and bundled
SWNTs caused by the unusual behavior of
p-terphenyl in the chromatograms (Fig. 2) and theresult suggests the specific recognition of bundled
SWNTs for p-terphenyl. We consider that p-terphenyl
strongly interacts with the one-dimensional externalgroove in the SWNT bundle due to its structure.
We believe that this unique aspect will provide a
promising feature for new applications of SWNTs.
[1] J. Yoo et al., Nanoscale 2011, 3, 2517.
[2] T. Fujigaya et al., Carbon 2011, 49, 468.
Corresponding Author: Naotoshi Nakashima
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp
Tel & Fax: +81-92-802-2842- 149 -(A)

(B)

Fig. 1 SEM images of silica gel coated by(A) isolated and (B) bundled SWNTs. Scalebars: 1 m.

(A)

(B)

Fig. 2 Chromatograms of PAHs using (A)isolated and (B) bundled SWNTs asstationary phase at flow rates of (A) 0.1 and(B) 0.7 mL/min.

3P-13
Enhancement of photoluminescence from single-walled carbon nanotubes
by photonic crystal nanocavities
Ryosuke Watahiki1, żTakashi Shimada1, Pei Zhao2, Shohei Chiashi2, Satoshi Iwamoto3,
Yasuhiko Arakawa3, Shigeo Maruyama2, and Yuichiro K. Kato1
1
2

Institute for Engineering Innovation, The University of Tokyo, Tokyo 113-8656, Japan
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
3
Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, Japan

Single-walled carbon nanotubes are bright nanoscale emitters, whereas photonic crystal
nanocavities offer the possibility for efficient optical coupling at the nanoscale because of
their small mode volumes and high quality factors. Here we report on the enhancement ofphotoluminescence from single-walled carbon nanotubes by L3 cavities in hexagonal latticephotonic crystals [1]. Free-standing photonic-crystal membranes are fabricated fromsilicon-on-insulator substrates, and micelle-encapsulated carbon nanotubes are dispersed on
the devices. We observe sharp peaks with a typical spectral width of a 0.37 nm whichcorresponds to a quality factor of 3,800. As the peaks appear at wavelengths longer than thoseof Si photoluminescence, they are attributed to carbon nanotube emission coupled to themicrocavity modes. We find that the photoluminescence intensity is enhanced by more than afactor of 50 compared to luminescence from a slab area.
This work is supported by SCOPE, Casio Science Promotion Foundation, Global COE andPhoton Frontier Network Programs of MEXT, Japan.
[1] R. Watahiki et al., Appl. Phys. Lett. 101, 141124 (2012).
Corresponding Author: Yuichiro K. Kato
Tel: +81-3-5841-7702, Fax: +81-3-5841-7772,
E-mail: ykato@sogo.t.u-tokyo.ac.jp- 150 -

3P-14
Effect of Solvents on Electrochemical Band Gaps ofSingle-Walled Carbon Nanotubes○Daigo Miyazaki 1, Yasuhiko Hirana1, Yasuro Niidome 1,2, Naotoshi Nakashima1,2,3
Department of applied Chemistry, Graduate School of Engineering, Kyushu University, 744
Motooka, Fukuoka 819-0395, Japan
2WPI-I2CNER, Kyushu University, 744 Motooka, Fukuoka 819-0395, Japan
3CREST, Japan Science and Technology Agency, 5 Sanbancho, Chiyoda-ku,
Tokyo 102-0075, JapanThe electronic properties of single-walled carbon nanotubes (SWNTs) are one of the mostfundamental properties. The redox properties (i.e. electronic densities, the Fermi levels, redox
potentials) of SWNTs are related to the structures of SWNTs that have a specified diameter andchiral angle uniquely related to a pair of integers (n,m); the so-called chiral index. The redox
properties of SWNTs are also strongly affected by the change of microenvironment conditions[1].
In this study, we have found that the electrochemical band gaps (ΔEelectr) of (n,m)SWNTs
were strongly affected by the change of solvents. To determine the redox properties of SWNTs,

no solvent dependence. Such a strong solvent
dependence of ΔEelectr is due to the difference in thesolvation energy of the charged SWNTs produced
during the electrochemical oxidation or reduction of
SWNTs. The present study provides useful
information for a deep understanding of thefundamental electronic properties of isolatedElectrochemical band gap / eVin situ photoluminescence (PL) spectroelectrochemistry [2] of the films containing fifteen
isolated (n,m)SWNTs cast on ITO electrodes was carried out in organic solvents to obtain
ΔEelectr and Fermi levels of the (n,m)SWNTs (Fig.1). We have discovered that the ΔEelectr of the(n,m)SWNTs became greater as the solvent dipole
1.5FA
moment of the SWNTs increased, which is in sharp
(7,5)
1.4
(10,2)
NMF
contrast to the optical band gaps that show virtually
DMF(11,1)
1.3(10,3)

1.2
1.1
1
0.9
0.8
0.7
0.7

(9,5)

DMAc
NMP

(8,3)
(6,5)

(10,6)

(8,4)
(7,6)

(9,4)

(8,6)

(10,5)

0.8
0.9
1
SWNT diameter / nm

(9,7)

1.1

Fig. 1 Electrochemical band gaps of isolated(n,m)SWNTs in solvents and is a key to the(n,m)SWNTs in given solvents.
modulation of ΔEelectr of (n,m)SWNTs.

[1] Y. Hirana, Y. Tanaka, Y. Niidome, N. Nakashima et al. J. Am. Chem. Soc. 2010, 132, 13073-13077.
[2] Y. Tanaka, Y. Hirana, Y. Niidome, K. Kato, S. Saito, N. Nakashima, Angew. Chem. Int. Ed. 2009, 48, 76557659
Corresponding Author: Naotoshi Nakashima
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp
Tel&Fax: +81-92-802-2840- 151 -

3P-15
Effects of OPO Laser Irradiation on the Structural Characteristics ofSingle- and Double-Walled Carbon Nanotubes
Tetsuya Oto, Akira Kumazawa, Yuka Nagaya, Koji Tsuchiya, Tadahiro Ishii, andHirofumi Yajima
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science
1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
As-synthesized single-walled carbon nanotubes (SWNTs) consist of various chiralstructures responsible for metallic (m) and semiconducting (s) SWNTs. Selective
separations of m- and s-SWNTs have been requested for practical and advanced
applications. Thus, we have developed a new and promising selective separation
technique for m-SWNTs with nanosecond pulsed optical parametric oscillator (OPO)
laser operated with wavelength tunability.1) In the previous Conference, we havepresented the effects of the laser wavelength and power on the selective separations of
m-SWNTs from individually dispersed SWNTs with the dispersants such ascarboxymethylcellulose (CMC) and sodium dodecylbenzenesulfonate (NaDDBS) in
aqueous solutions.2) Individually dispersed SWNTs exhibited the UV-vis-NIR
absorption spectra with the characteristic peaks in three band regions (400-1600 nm)
corresponding to m-SWNTs first transitions (M11), and s-SWNTs first (S11) and second(S22) transition bands, respectively. The OPO laser with a peak wavelength in the S11
or S22 region brought merely about the destruction of the dispersed s-SWNTs throughphoto-thermal conversion process, while the m-SWNTs remained unchanged owing totheir high thermal conductivity function. In the CMC dispersion system, themaximum collection efficiencies for m-SWNTs were achieved under the condition of alaser fluence of 6.4 MW/cm2 at 778 nm (S22) and 19.1 MW/cm2 at 989 nm (S11).2) In thepresent study, in order to gain further insight into the effectivity of OPO laser irradiation
for selective chirality separation of SWNTs and DWNTs, we focus on the resonancetransition effect of the laser irradiation on SWNTs and DWNTs in their dispersion andsolid states. Consequently, the 507 nm (M11)-laser irradiation to the solid state ofas-synthesized SWNTs induced a decrease in the absorption peaks corresponding tom-SWNTs, while the peaks corresponding to s-SWNTs hardly changed. This result
suggests that the separation of s-SWNTs from as-synthesized SWNTs can be achieved
through the laser irradiation to the solid state of SWNTs.
1. I. Tajima et al. The 36th Fullerenes-Nanotubes General General Symposium (2009) 3P-5.
2. A. Kumazawa et al., The 40th Fullerenes-Nanotubes General General Symposium (2011) 2P-24.

*Corresponding Author: Hirofumi Yajima
TEL: +81-3-3260-4272(ext.5760), FAX: +81-3-5261-4631, E-mail: yajima@rs.kagu.tus.ac.jp- 152 -

3P-16
Vernier spectrum in finite-length armchair carbon nanotubes○Yuki Tatsumi, Wataru Izumida, Riichiro Saito
Department of Physics, Tohoku University, Sendai, 980-8578, Japan
Many experiments of the transport through single-wall carbon nanotubes exhibit four-folddegeneracy reflecting the combination of the spin degeneracy and the valley degeneracy of
the K and K’ points in the Brillouin zone. However, some of the experiments show a gate
voltage dependence of the degeneracy, for instance, two- and four-fold degeneracies
alternately appear[1]. The recent theoretical study shows that the Fermi velocity of theright-going wave is different from that of left-going wave because of the curvature of thenanotube surface[2]. It has been argued that an effect of the velocity difference would
appear as a vernier spectrum in a finite-length nanotube, in which the two- and four-folddegeneracies alternately appear as a function of the energy. The scenario of the vernier
spectrum is as follows. A standing wave as a linear combination of a right- (left-) goingwave in the K valley and a left- (right-) going wave in the K’ valley would be an
eigenfunction for the finite-length nanotube. The wave number is quantized because of thefinite length and then the linear bands are quantized. There are two level separations
reflecting the two different velocities. Therefore the system shows a vernier-like energy
spectrum. However, it is not clear what conditions, for instance, which chirality and what
type of the boundary conditions, are needed for the above scenario of the wavefunction.
Here we perform a numerical calculation for finite-length armchair nanotubes, in which large
difference of the velocities is expected, to study conditions of appearance of the vernier
spectrum.
Energy spectrum, {n}, for (5,5)-armchair nanotube near the half-filling is shown in Fig. 1(a). The calculation is done for a tight-binding model with the nanotube length of 200nm.
The ends of the nanotube areterminated by hydrogen atoms. The
vernier-like spectrum is clearly seen:
large and small peak separations
appear alternately. Addition energy,n+1=n+1-n, shown in Fig. 1 (b)clearly exhibits the oscillatory
behavior of the peak separation. It
is confirmed that each wavefunction
consists of a right- (left-) going wave
in the K valley and a left- (right-)
going wave in the K’ valley. The Fig. 1 (a) Energy spectrum for (5,5) armchair nanotube ofvernier spectrum is also observed for length 200nm, near the half-filling, =0, and (b) additiona capped nanotube. An effective energy. Each level is labeled by an integer number fromone-dimensional model explains the HOMO of n=0 with ascending order of the energy. Note that
 =0 for every two levels because of the two-fold degeneracy
microscopic mechanism of the energy ofn the spin degree of freedom.
spectrum in finite-length armchair
nanotubes.
[1] A. Makarovski et al. Phys. Rev. B 74, 155431 (2006), [2] W. Izumida et al. Phys. Rev. B 85, 165430 (2012).
Corresponding Author: W. Izumida,
Tel: +81-22-795-6475, Fax: +81-22-795-6447, E-mail: izumida@cmpt.phys.tohoku.ac.jp- 153 -

3P-17First-principles study of radial breathing modes
in small-diameter carbon nanotubes○Takashi Koretsune and Susumu Saito
Department of Physics, Tokyo Institute of Technology, Tokyo 152-8551, Japan
Radial breathing modes (RBMs) in carbon nanotubes (CNTs) play important roles forcharacterizing individual CNTs. There are several well-known empirical relations between
frequencies of RBMs and diameters of CNTs. In small-diameter nanotubes, however, each
RBM can deviate from the relations due to the curvature effect. Therefore, it is important tostudy this deviation from first principles. Furthermore, even in large-diameter nanotubes, it is
not well understood to what extent the first-principles study can explain the empirical
relations for all the nanotubes. To discuss RBMs in various situations such as carrier doping
or encapsulation of molecules, it is of great importance to clarify the ability of predicting
RBMs from first principles. Here, we demonstrate that the first-principles study based on thedensity-functional theory can actually predict RBMs in quite good accuracy by using two
methods: the conventional plane-wave based method for small-diameter tubes and the method
utilizing helical symmetry for large-diameter tubes.
Figure 1 shows the calculated RBMs for small-diameter nanotubes. It is found that theRBMs actually deviate from the empirical relations. In general, tubes with larger chiral angle
have larger RBMs. We will discuss the reason of this chiral angle dependence.

700

248/d
217.8/d + 15.7

Frequency (cm-1)

650
600
550
500
450
400
350
300
0.3

0.4

0.5
0.6
Diameter (nm)Fig. 1 Frequencies of RBMs for small-diameter nanotubes.
E-mail: koretune@stat.phys.titech.ac.jp- 154 -

0.7

3P-18
Electronic Properties of Capped Carbon Nanotubes with AccumulatedElectrons by a Parallel Electric Field○Ayaka Yamanaka, Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai, Tsukuba
305-8577, Japan
In this decade, carbon nanotubes are attracting much attention due to its possible
application for semiconductor electronic devices in the next generation. Therefore it is urging
us to unravel fundamental properties of carbon nanotubes under an electric field for designingand fabricating nanotube-based electronic devices. In this work, we study the electronic
properties of finite-length carbon nanotubes whose edges are capped by C60 hemispheres tounravel the effects of the external electric field on charge accumulation.
All calculations are performed by using the density functional theory. To express theexchange correlation potential among interacting electrons, we apply the local density
approximation. We use an ultrasoft pseudopotential to describe the interaction between
valence electrons and ions. The effective screening medium (ESM) method is applied toinvestigate behaviors of carbon nanotubes under the electric field in the framework of thefirst-principles calculations.
We study the electronic properties of capped finite-length armchair and zigzag nanotubes
with 7-angstrom diameter under an electric field parallel to the nanotubes as shown in Fig. 1.
We analyze the electrostatic potential and accumulated electrons to uncover how thenanotubes response to the electric field. By analyzing the calculated potential, we find that thepotential modulation only occurs around the cap region (Fig. 2). We also find that injected
electrons are accumulated around the cap region. The analyses unravel that there is acorrelation between electrostatic potential and distribution of accumulated electrons.

Fig.1 A structural model of nanotubes underthe electric field.
Fig.2 Plane-averaged electrostatic potential and electricfield of capped carbon nanotube.
Corresponding Author: A. Yamanaka
Tel: +81-29-853-5600 (ext. 8233), Fax: +81-29-853-5924,
E-mail: ayamanaka@comas.frsc.tsukuba.ac.jp- 155 -

3P-19
Electronic Raman scattering and origin of the Fano resonance in metallic
carbon nanotubes○ Eddwi H. Hasdeo, Ahmad R.T. Nugraha, Kentaro Sato, and Riichiro Saito
Department of Physics, Tohoku University, Sendai 980-8578, Japan
Although most of excitonic physics in the Raman spectra of SWNTs has been investigated intensively,
the origin of the asymmetric Breit-Wigner-Fano (BWF) lineshape of G-band in the metallic SWNTs(m-SWNTs) is still not well explained theoretically. Fano pointed out that the asymmetric feature of abroadened spectrum comes from interference between a discrete excitation spectrum with continuum
spectra [1]. In m-SWNTs, electrons in the linear energy band plays an important role to give rise to thecontinuum spectra. However, the detailed mechanism remains a debatable topic [2-4]. Some reportssuggest that the coupling of collective excitation (plasmon) with phonon could explain the origin of
BWF asymmetry [2], and some others argue that the electron-hole pair and phonon coupling via Kohn
anomaly is more dominant [3]. Farhat et al. have observed a new feature of the continuum spectra
exclusively in m-SWNTs which is ascribed to the electronic Raman scattering (ERS) [4]. Compared to
the G band, the ERS feature has broader spectral width (~ 60 cm-1,~ 10 cm-1) and smaller

peak intensity (IERS ~ 0.6 IG). The energy of inelastic scattered light in phonon Raman spectra changes
as a function of excitation energy, while the ERS peak position does not; it keeps constant at Mii (i-thvan-Hove singularity transition energy). Therefore, instead of the phonon Raman contribution, theCoulomb interaction is relevant to the ERS. The calculated result shows that zero momentum transfer(q = 0) vanishes in the direct Coulomb interaction because of the symmetry of the wave-function, thus
a higher order Raman process is relevant to the ERS. By considering the second-order Raman process,we are able to reproduce experimental results for the ERS spectra consistently. Finally, the asymmetric
BWF feature, i.e. an interference result between the G band and the ERS spectra is presented as afunction of nanotube diameter and of laser excitation energy. We also theoretically predict a newfeature that the RBM spectra of m-SWNTs give a similar asymmetric lineshape which requires anexperimental confirmation.
[1] U. Fano, Phys. Rev. 124, 1866–1878 (1961).
[2] S. D. M. Brown et al., Phys. Rev. B 63, 155414 (2001), S. M. Bose et al. Phys. Rev. B 72, 153402 (2005).
[3] M. Lazzeri et al., Phys. Rev. B 73, 155426 (2006), Y.Wu et al. Phys. Rev. Lett. 99, 027402 (2007).
[4] H. Farhat et al., Phys. Rev. Lett. 107, 157401 (2011).
Corresponding Author: E. H. Hasdeo
TEL: +81-22-795-6442, FAX: +81-22-795-6447, E-mail: hasdeo@flex.phys.tohoku.ac.jp- 156 -

3P-20
Selective Dispersion of Single-Walled Carbon Nanotubes into Nano-Cage of
Helical Conformation of Poly(m-phenylene-ethynylene) Derivatives
Fumito Kobayashi1, Yuki Moriyama1, ○Masahiro Takahashi1,
Masayoshi Tange2, Toshiya Okazaki2, Keiki Kishikawa1, Shigeo Kohmoto1
1

Faculty of Engineering, Chiba University, Chiba, 263-8522, Japan
2
Nanotube Research Center, AIST, Tsukuba, 305-8565, Japan

As-synthesized single-walled carbon nanotubes(SWNTs) contain mixture of different diameters andchiralities. So separation of SWNTs is especially
important for applications.
Diphenyl acetylene unit (alias Tolan) possesses smallinternal-rotational
barrier.
Corresponding
Poly(phenylene-ethynylene)
derivatives
canberecognized as repetition of Tolan unit. Accordingly thepolymers can transform into various high order
structures, i.e. -helix and zigzag, and random coil.
Especiallythea-helix
structureofpoly(phenylene-ethynylene) is attractive in recent years
for supra molecular chemistry. The helical structure
can construct at nano-cage at inner space of the helicalstructure. For example, polymer 1 can form nano-cagewith ca. 0.9 nm in diameter at helical structure (Fig. 2).
The nano-cage may include nano scale molecules, i.e.
SWNTs. Further, an outside of the helical structure canbe functionalized without degradation.
Poly(phyenylene-ethynylene) 1 was obtained asorange solid by co-polymerization with dibromo anddiehynyl compounds using of Sonogashira coupling
reaction with Pd catalyst (Fig. 1, Table 1).
Table 1. Properties of polymer 1.
Mwa)
PDI a)
n3
1.55
9.7
5.1×10a) Measured by GPC with polystyrene standard.

Polymer 1 could stably disperse SWNTs(CoMoCAT) into THF solution.
The dispersed
solution show typical absorption spectra for highdispersed SWNTs. A TEM image of the cast film
from the solution showed the SWNTs which was
disaggregated and straightly extended for several
micro meters (Fig. 3). We will report and discuss aselectivityofdispersed
SWNTs
with
photoluminescence map.

Fig.1 Poly(phenylene ethynylene)
derivative 1

Fig. 2.
Molecular modeling ofoligomer of 1 (n = 3) optimized with
MM2 calculation.

Fig. 3. TEM image of dispersed SWNTs(CoMoCAT) with 1.

Corresponding Author: M. Takahashi
Tel: +81-43-290-3397, Fax: +81-43-290-3401,E-mail: masahiro@faculty.chiba-u.jp- 157 -

3P-21Chromatographic Separation of Highly Soluble SWNTs Prepared by
Polyglycerol Grafting○Keisuke Nakamura1,2, Li Zhao1, Shuji Aonuma2, Takahide Kimura1, Naoki Komatsu1
1
2

Department of Chemistry, Shiga University of Medical Science, Otsu, 520-2192, Japan
Department of Materials Chemistry, Osaka Electro-Communication University, Osaka,
572-8530, JapanFor applications of nanocarbons in biology and medicine, such as imaging probe and drug
carrier, they have to be solubilized in a physiological environment. Recently, we have foundthat surface functionalization with polyglycerol (PG) afford very good hydrophilicity tovarious nanocarbons (nanodiamond [1] and graphene [2]) as well as metal oxides (ZnO [3] orFe3O4 [4]). In this paper, we will report PG functionalization, solubilization, andchromatographic separation of SWNTs. After cutting SWNTs through mixed acid treatment,
they were functionalized with PG through ring opening polymerization of glycidol [1]. The
SWNT-PG was solubilized in pure water (>8.5 mg/mL) and phosphate buffer (>8.5 mg/mL).
Since these solutions were very stable without any precipitation for more than one month,they were subjected to size exclusion chromatography (SEC) to separate the SWNT-PG
according to the size. Four fractions including SWNT-PG were collected and analyzed withSTEM (Fig. 1) and DLS. Both the median size determined by DLS and the average length
determined by STEM decreased from the fraction 1 to 4 in the SEC (Table 1).
Table. 1 Size and length of SEC-separated SWNT-PG
determined by DLS and STEM, respectively.

Fraction

Median size

Average length(Retention time, min)(nm) in DLS(nm) in STEM

1 (19-20)

69-

2 (20-21)

66

118

3 (21-22)

54

99

4 (22-23)

43

72

Fig. 1 STEM image of SWNT-PG after
SEC separation (fraction 2).
[1] L. Zhao, N. Komatsu, et al. Angew. Chem. Int, Ed., 50, 1388-1392 (2011)[2] T. Yasuda, N. Komatsu, et al. The 43rd Fullerenes-Nanotubes-Graphene General Symposium, 1-14
[3] L. Zhao, N. Komatsu, et al. J. Indian Chem. Soc., 88, December, 1787-1790 (2011)[4] L. Zhao, N. Komatsu, et al. Adv. Funct. Mater., 22, 5107-5117 (2012).
Corresponding Author: Naoki Komatsu
Tel: +81-77-548-2102, Fax: +81-77-548-2405, E-mail: nkomatsu@shiga-med.ac.jp- 158 -

3P-22
Electric double layer transistors of aligned carbon nanotube thin film
○Yoshifumi Wada1, Jiang Pu 2, Yuki Takagi 2, Kazuhiro Yanagi 3, and Taishi Takenobu 1,2
12

Department of Physics, Waseda University, Tokyo 169-8555, Japan
Department of Applied Physics, Graduate School of Advanced Science and Engineering,
Waseda University, Tokyo 169-8555, Japan3
Department of Physics, Tokyo Metropolitan University, Hachioji 192-0397, Japan

Electric double layer capacitors (EDLCs), which is consist from two electrodes andelectrolyte (fig.1), have huge capacitance [1]. This huge capacitance is due to very thin double
charge layers formed with ions in electrolyte and carriers in electrode, which corresponds tocapacitor with nano meter gap. We call this thin layer as electric double layer. Recently thisEDLC is applied to MOS transistors as gate dielectric layer, which named as electric double
layer transistors (EDLTs). It realized low voltage operation (< 3 V) of transistor and highcarrier density at the semiconductor/electrolyte interface [2]. However, because ion movement
in electrolyte is necessary to operate EDLTs, high speed operation is extremely difficult,which prevent them from actual use in electronic devices. Here we tried to investigate the ion
motion in EDLC from electrochemical impedance spectroscopy (EIS) and realize 100 kHz
response speed in EDLCs. Finally, we apply this structure to single-walled carbon nanotube(SWCNT) EDLTs, which is aligned by recent reported solution process [3].
We measured EIS of laminate structure EDLC using ionic liquid,
1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]) , and gold
electrode. In particularly, we could get high-speed response using asymmetric size electrodepair, which has different size of each electrode. With applying this structure, we realized
response speed more than 100 kHz, which is very fast as EDLC.
Because we have succeeded in the fabrication of high speed EDLCs, we applied thistechnique into transistors. For this purpose, asymmetric structure is very important and, tofabricate asymmetric EDLTs, we used the aligned SWCNT film (fig. 2) as transistor channel
because of its small channel area. Using the aligned SWCNT films and EDLT structure, we
finally obtained high-response also in EDLTs, which might be 1st step for future high-speed
electronics based on electrolyte.
[1] K. H. Lee et al., J. Phys. Chem. B. 115, 3315 (2011)[2] S. H. Kim et al., Adv. Mater. 17, 1 (2012)[3] H. Y. Li et al., J. Am. Chem. Soc. 134 , 2760 (2012)

Fig.1 Electric double layer- 159 -

Fig.2 Aligned SWCNT film

3P-23
Photo-thermoelectric power of single-walled carbon nanotube films
○Hajime Sakakibara1, Yoshinori Sato1, Kosuke Ino1, Akihiko Ito2,
Tomokazu Matsue1, Takashi Goto2, Kenichi Motomiya1, Kazuyuki Tohji1
1

Graduate school of Environmental studies, Tohoku University, Sendai 980-8579, Japan
2
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Single-walled carbon nanotubes (SWCNTs) possess spike like density of states derived
from one-dimensional van Hove singularity. The optical transitions occur between matchingvan Hove singularities in conduction and valence bands. In particular, semiconducting
SWCNTs show several absorption peaks in the near-infrared light region, whereas metallic
SWCNTs in the visible light region. Using their unique electric and optical characteristics,
SWCNTs have been applied to photovoltaic devices as basic researches [1, 2].
Recently, it was reported that photovoltaic powers of thin SWCNT films arose when thefilms were asymmetrically illuminated by a near-infrared light. This photo-thermoelectric
power was attributed to the temperature gradient of both ends of the film [3]. The thermal
conductivity of an individual SWCNT is nearly 3500 Wm-1K-1 at room temperature [4]; on
the other hand, the SWCNT mat is 35 Wm-1K-1 at room temperature [5]. Therefore, numerous
tube-tube junctions are due to the dominant barriers to thermal transport in CNT mats. In thisstudy, we investigated the influence of the different film thickness on photo-thermoelectric
power of SWCNT films. In addition, we prepared thin/thick half SWCNT films with aninterface of different film thickness in order to increase photo-thermoelectric power.
We prepared two type SWCNT films to measure the properties of photo-thermoelectric
power of the films. One was uniform SWCNT films (Fig.1a) and the other was thin/thick halfones (Fig.1b). SWCNT films were prepared spraying SWCNTs/ethanol dispersion on a glass
slide with Ag electrodes. We measured the photo-voltage and temperature difference of bothends of SWCNT films under asymmetrically solar light irradiation using an AM1.5 solar
simulator with 100 mW/cm2. We will report the details of the results in this presentation.
(a)

(b)

Light irradiation

Light irradiation

Thermocouples
Thermocouple

Thermocouple
Ag

SWCNTsAg

Ag

Glass slide

SWCNTsAg

Glass slide

Fig.1 Schematic illustrations of (a) uniform SWCNT films cell and (b) thin/thick half ones.
[1] K. Suzuki et al. Chem. Lett. 32, 28 (2003).
[2] Y. Jia et al. Adv. Mater. 20, 4594 (2008).
[3] M. Omari et al. Appl. Phys. Lett. 98, 243113 (2011).
[4] E. Pop et al. Nano Lett. 6, 96 (2006).
[5] J. Hone et al. Phys. Rev. B 59, 2514 (1999).
Corresponding Author: Yoshinori Sato
Tel: +81-22-795-3215, Fax: +81-22-795-3215, E-mail: hige@ncsimd.kankyo.tohoku.ac.jp- 160 -

3P-24
Specific biosensor based on
biotin-labeled double-walled carbon nanotube FET
1,2

1

1

2

○Akihiro Kuno , Yuka Nagaya , Koji Tsuchiya , Akira Hida

Koji Ishibashi2, and Hirofumi Yajima1
1

Department of Applied chemistry, Tokyo University of Science, Tokyo 162-8601, Japan
2
Advanced Device Laboratory, RIKEN, Saitama 351-0198, Japan

Biosensor devices based on carbon nanotube field effect transistors (CNT-FETs) are
expected to be used as highly sensitive biosensing. Biosensing using CNTs hasvarious advantages such as one-dimensional channel, high carrier mobility, and large
surface area to volume ratio. Thus, highly sensitive and various types of single-walled
CNT-FET biosensors have been reported [1]. Double-walled carbon nanotubes(DWCNTs) also have a potential for biosensors because of their unique inner-outer
structure. Even if the outer layer is damaged due to surface modification, the electricalproperties of the inner layer are protected by the outer layer.
In this study, we report the biosensing based on biotin-labeled DWCNT-FET.
DWCNTs were oxidized by mixture of sulfuric acid and nitric acid (3:1) to createcarboxyl groups on their surface. The oxidized
DWCNTs were then allowed to react with
5-(biotinamido)pentylamine through amine
coupling using 1-ethyl-3-(3-dimethylamin
opropyl) carbodiimide hydrochloride (EDC) andsulfo-NHS.
Electrical property for the biotin-labeled
DWCNT was largely changed when streptavidin
solution was added (Fig.1), while nothing is detectedwith streptavidin by tiny changes of the electricalFig.1 Gate characteristics ofbiotin-labeled DWCNT-FET

property for non-biotin-labeled DWCNT. This result biosensor.
revealed that the biotin-labeled DWCNT-FET device obtained in the present study had
specific biosensing ability to streptavidin.
[1] Brett Lee Allen, Padmakar D. Kichambare, and Alexander Star, Adv. Mater, 19, 1439, (2007)*Corresponding Author: Hirofumi Yajima
Tel: +81-3-3260-4272(ext.5760), Fax: +81-3-5261-4631,
E-mail: yajima@rs.kagu.tus.ac.jp- 161 -

3P-25
Selective Solubilization of Semiconducting-Carbon Nanotubes by Using
Weak-Bond Connecting Fluorene-Based Polymers○Fumiyuki Toshimitsu1, Fujigaya Tsuyohiko 1, Naotoshi Nakashima 1,2
1

Department of Chemistry, Graduate School of Engineering, Kyusyu University, Fukuoka
819-0395, Japan
2
JST-CREST, 5 Sanbancho, Chiyoda-ku, Tokyo 102-0075, Japan

Selective separation of single-walled carbon nanotubes (SWNTs) from various chiralitey is
crucial issue for fundamental studies and applications toward next-generation nanotechnology.
SWNTsÕ unique optical and electrical properties [1,2] would be accomplished efficiently only when
they are separated into certain chirality portions. It is desirable to develop strategic purification
methods of separating SWNTs according to thier chirality. We have previously reported polymer
wrapping techniques which efficiently solubilize/extract semiconducting SWNTs with highchiral-selectivity by developing polyfluorene derivatives [3, 4, 5, 6]. In order to expand this into moreutilizable method, we introduced weak-bond connections, such as hydrogen-bond or
metal-coordination-bond, which make polymers tunable for recognizing various chirality, andbreakable so as to detachable from SWNTs.
In this study, a series of fluorene-besed ligands were
designed and synthesized to afford weak bond connected12polymers. Ligand 1 and 2 recognized each other to formhydrogen-bond polymer in aprotic solvents. On the other
hand, ligand 3 assembled into coordination polymers bytreating with various metal ions. Each polymers
3
solubilized/extracted SWNTs and exhibited different
selectivity on SWNT chirality depending on the solvents,
metal ions, and counter anions. The solubilized SWNT was
confirmed by UV-Vis-NIR absorption and Raman
spectroscopies. In order to ratiocinate these chiral specificrecognition of the polymers on SWNT, conformation
analysis of polymers on SWNTs by scanning tunneling
1. Chemical structures of ligands
microscopy (STM) direct observation and molecular Figurein this study (1, 2 and 3), and simulated
mechanics simulation were performed upon the SWNTs wrapping conformation on SWNT.
wrapped with each polymers.
H2N

HOOC

COOH

C8H17

C8H17

C8H17

N

N

NH2

N

C8H17

N

N

C8H17

C8H17

N

Referneces[1] J. Bernholc, D. Brenner, M. Buongiorno Nardelli, V. Meunier, and C. Roland, Annu. Rev. Mater. Res. 32, 347 (2002).
[2] H. J. Dai, Acc. Chem. Res. 35, 1035 (2002).
[3] H. Ozawa, N. Ide, T. Fujigaya, Y. Niidome, and N. Nakashima, Chem. Lett. 40, 239 (2011).
[4] H. Ozawa, T. Fujigaya, Y. Niidome, N. Hotta, M. Fujiki, and N. Nakashima, J. Am. Chem. Soc., 133, 2651 (2011).
[5] K. Akazaki, F. Toshimitsu, H. Ozawa, T. Fujigaya, and N. Nakashima, J. Am. Chem. Soc., 134, 12700 (2012).
Corresponding Author: T. Tokyo
Tel: +81-42-677-1111, Fax: +81-42-677-2525,
E-mail: nakashima-tcm@mail.cstm.kyushu-u.ac.jp- 162 -

3P-26Chirality Analysis of Single-walled Carbon Nanotubes Growth
in Molecular Dynamics SimulationżTomoya Kawasuzuki, Kaoru Hisama, Yuki Takaki, Shohei Chiashi, and Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
It is highly important to understand the growth mechanism of single-walled carbon
nanotubes (SWNTs) in order to develop chirality-controlled growth techniques. For thispurpose, we have performed classical molecular dynamics simulation (MD) of
catalyst-nucleated SWNT growth process [1, 2]. However, the SWNTs obtained in MD
simulation have defect structure so far and it is difficult to define their chirality (n,m).
Therefore, we tried analyze the “local chirality” of SWNTs in MD simulation by calculating
the distribution of angle between carbon-carbon bond and the “local axis”. As shown in Fig. 1,
the tangential plane at a carbon atom has contact with SWNT on line. Here, the line is definedas the local axis of the carbon atom.
Figure 2 shows the probability density of the bonds against the angle between the C-C
bond and the local axis of a grown SWNT in MD simulation (Co catalyst, 1600 K, after 220ns). The structure and local axes are shown in the insert. This distribution has two peaks near
0° and 60°, which indicates that the part of this SWNT shows zigzag-like structure. Since thismethod can be applied widely to the SWNT structures of MD growth simulation, the relation
between this local chirality and SWNT growth condition in MD simulation will be discussed.

Probability Density [%]1000Fig. 1 Schematic diagram of the local axis
and the tangential plane

30

60

90

Angle between bonds and local axes [deg]Fig. 2 Probability density of angle between C-C
bond and the local axis.

[1] T. Matsuo et al., to be submitted.
[2] Y. Shibuta and S. Maruyama, Chem. Phys. Lett., 382 (2003) 381.
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 163 -

3P-27
Methane-assisted CVD yielding
millimeter-tall single-wall carbon nanotubes of smaller diametersżZhongming Chen 1,2, Dong Young Kim 2, Kei Hasegawa 2, Suguru Noda 2, *1
2

Department of Chemical System Engineering, The University of Tokyo, Japan
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan

Growing taller carbon nanotubes (CNTs) with smaller diameters is an ever-lasting
challenge. The rapid growth of millimeter-tall vertically aligned SWCNTs (VA-SWCNTs) bychemical vapor deposition (CVD) on substrates was realized in 2004, which attracted great
attention [1], however the resulting SWCNTs proved to have rather large diameters of 3-4 nm[1,2]. Small catalyst particles are unstable and easily get coarsened during CVD, resulting in
the gradual diameter increase in SWCNTs during their growth and abrupt growth termination[2,3]. In this work, we examined the use of low purity H2 (96 vol% H2 with 4 vol% CH4 as a
stimulant gas) for the low cost H2 and unexpectedly found the dramatic effect of CH4.
SWCNTs grew to millimeter-scale and formed vertically aligned arrays by CVD using
C2H2/ H2/ H2O/ Ar gas and Fe/Al-Si-O catalyst (Fig. 1). We found that the small CH4 addition
significantly improved their height (Figs. 1a,b). The sharp G-band peak (originating fromgraphitic structure) and radial breathing mode (RBM) peaks are characteristic for SWCNTs(Fig. 2). The small CH4 addition significantly improved the quality of SWCNTs, as shown by
the increased intensity ratio of G-band to D-band (originating from defects). Atomic force
microscope analysis revealed that the smaller Fe particles formed at higher density whenannealed under H2 with CH4. Real-time growth monitoring revealed that the growth lifetime
was longer when CVD was carried out with CH4. X-ray photoelectron spectroscopy revealed
the annealing in CH4/ H2 resulted in the carbon deposition at a small content on Fe particles
without any CNT growth. The thin carbon layer formed on Fe particles possibly prevented the
Fe particles from coarsening by reducing their surface energy while allowing them to grow
SWCNTs from highly reactive C2H2. Further study is ongoing to clarify the underlying
mechanism.
Intensity [a.u.]

at 488 nm

GRBM(b) w/ CH4, IG/ID = 12.6 D(a) w/o CH4, IG/ID = 5.4

0Fig. 1. Photographs (a, b) and SEM images (c, d)of the SWCNT arrays synthesized using (a, c) H2
without CH4 and (b, d) H2 with CH4. SEM
images were taken at the middle of the arrays.㩷

1000

-1

1500

Fig. 2. Raman spectra of the SWCNT
arrays taken at their top using an
excitation wavelength of 488 nm㩷

[1] K. Hata, et al., Science 306, 1362 (2004).
[2] K. Hasegawa and S. Noda, ACS Nano, 5, 975 (2011).
[3] K. Hasegawa and S. Noda, Carbon, 49, 4497 (2011).
Corresponding Author: S. Noda
Tel: +81-3-5286-2769, Fax: +81-3-5286-2769, E-mail: noda@waseda.jp- 164 -

500

Raman shift [cm ]3P-28Pyrene-based nanocalipaers for selective extraction of metallic SWNTs
Gang Liu, ○Naoki Komatsu, Takahide Kimura
Department of Chemistry, Shiga University of Medical Science, Seta, Otsu 520-2192, Japan.
H3C(OCH2CH2)4(CH2CH2O)4CH3

NN
We have been working on separation of SWNTs
with chiral nanotweezers through molecular
recognition [1]. Quite recently, chiral porphyrinbased nanocalipers, a newly designed host molecule
next to nanotweezers, have been found to
discriminate not only diameter and handedness, but
C(CH )
C(CH )
also metallicity [2]. In this paper, we modified theFig 1. Structures of dipyrene nanocalipers
porphyrin-based nanocalipers to pyrene-based ones aby replacing porphyrin moieties to 2-pyrenes (Fig.
1) and applied to the extraction of HiPco SWNTs.
After bath-sonication of the suspension of
ES22
ES11
HiPco and the nanocalipers, the extract wasconcentrated, washed, and dispersed in D2O/SDBS
EM11
by use of a rosette cooling cell [3]. The Raman andabsorption spectra of the washed solid and the D2O
dispersion, respectively, were measured as shown in
Fig. 2. While semiconducting SWNTs were more babundant than metallic ones in the absorption
spectrum of the HiPco, metallic SWNTs were
Semiconducting
significantly enriched after the extraction with
nanocalipers (Fig. 2a). The metallic enrichment is
supported by the Raman spectra (Fig. 2b, c); after
the extraction, the peak in the metallic region in the
RBM were almost dominant and BWF feature in the
Metallic
G band was more pronounced. The pyrene-based
nanocalipers are found to exhibit preference forcmetallic SWNTs as the porphyrin-based ones.
3 3

3 3

[1] G. Liu, N. Komatsu, in Handbook of carbon nano materials(Eds.: F. D'Souza, K. M. Kadish), World Scientific, 2012, vol.
3, pp. 203-232; X. Peng, F. Wang, A. F. M. M. Rahman, A.
Bauri, N. Komatsu, Chem. Lett., 2010, 39, 1022.
[2] G. Liu, N. Komatsu, et. al., submitted.
[3] T. Yasumitsu, G. Liu, J.-M. Levêque, S. Aonuma, L.
Duclaux, T. Kimura, N. Komatsu, Ultrason. Sonochem., 2013,
Fig. 2 Absorption (a) and Raman (b. c) spectraof SWNTs before and after the extraction

20, 37.
Corresponding Author: Naoki Komatsu

Tel: +81-77-548-2102, Fax: +81-77-548-2405. E-mail: nkomatsu@belle.shiga-med.ac.jp- 165 -

3P-29In situ Raman monitoring formation of SWNTs: process optimization andlow temperature synthesis○Ming Liu1, Yuquan Su1, Rong Xiang1 , Zikang Tang1,2
12School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275, China
Department of Physics, Hong Kong University of Science and Technology, Clear Water Bay,
Hong Kong, China

Raman scattering is a powerful approach to characterize single-walled carbon nanotubes(SWNTs). In principle, real time Raman monitoring the chemical vapor deposition (CVD)synthesis of SWNTs can give insights into both formation dynamics and structure evolution.
However, since the very pioneer work,[1] there have been limited progress on in situ Raman
measurement. One, if not the most, critical reason is that a Raman spectrum taken at a hightemperature during the growth process usually has a low intensity, unable to provide enoughsignal-to-noise ratio to explicit the fingerprints of the obtained material (e.g. shape of G- peakor even radial breathing modes).
In this work, we are devoted to explore the possibility of increasing Raman signal using
metal nano-particles mediated surface enhance Raman scattering (SERS). Unlike
conventional SERS of SWNTs that has been extensively investigated, SERS during a CVD
process involves high growth temperature, which brings more technical and scientificchallenges. We perform a systematic study on the configuration, metal type, particle size. An
enhancement up to ten is achieved at high temperature after this preliminary attempts.[2]After further optimization of the growth and measurement, RBM change during the CVD isobtained.[3] Also, we will report the formation of SWNTs at -196°C, the lowest temperature
as far as we know. The formation process is clearly evidenced by in situ Raman, benefited
from the clean background at this low temperature. [4][1] Chiashi S et al., Chem. Phys. Lett., 386, 89 (2004).
[2] Liu M et al., submitted (2013)[3] Xiang R et al., submitted (2013)[4] Su YQ et al., submitted (2013)
Corresponding Author: Rong Xiang
E-mail: xiangr2@mail.sysu.edu.cn- 166 -

3P-30One-Step Catalyst-Free Mist Flow CVD Growth of Single-Wall Carbon
Nanotubes using C60 Fullerenes○Yun Sun, Ryo Kitaura, Jinying Zhang, Yasumitsu Miyata and Hisanori Shinohara
Department of Chemistry, Nagoya University, Nagoya 464 -8601, JapanDue to their unique structural and electronic properties, single-walled carbon nanotubes(SWCNTs) have extensively studied during the past couple of decades. However, most of thetechniques for the synthesis of SWCNTs are centered on metal catalysts supported CVD,
which oftentimes leads to concomitant complicated purification processes. Contaminations
can alter the quality and the intrinsic properties of as-grown SWCNTs. Because of this,catalyst-free growth of SWCNTs has been reported during the past decade. For example,
various all-carbon routes have been developed, such as cloning SWCNTs from open-end
SWCNT seeds [1]. The growth of SWCNTs via opened fullerenes as the nucleation is feasible
in light of the previous study [2].
The so-called floating catalyst CVD, in contrast, is capable of continuously synthesizing
SWCNTs from the gas phase onto a substrate by simultaneously supplying the catalyst
precursor and carbon source.
Here a one-step catalyst-free CVD growth of SWCNTs has been investigated by using a
colloidal aqueous C60 solution [4] directly on the basis of the mist flow method [4]. It seems
that C60 fullerenes are considered as “the seed” during the formation of SWCNTs (Fig.1). Cap
opening, nucleation and growing SWCNTs might be occurring successively during the growth.
Consequently, under the optimum CVD reaction condition, the diameter distribution of
as-grown SWCNTs becomes fairly narrow (from 1.0 to 1.5 nm) and a typical mean diameteris 1.28 nm, which is rather close to the diameter of individual C60 molecules. Meanwhile, theuniform diameter of SWCNTs can be distinguished by the Raman spectra within RBM region
measured at different positions of corresponding SEM image of as-grown products (Fig.2).

2 nm

Fig.1 HRTEM images of cap structures.

Fig.2 (a) SEM image and (b) corresponding Raman spectra, respectively.

References:[1] J. Liu et al. Nat. Commun. 3, 1 (2012).
[2] I. Ibahim et al. ACS Nano 6, 10825 (2012).
[3] Andrievsky et al. Chem. Phys. Lett. 300, 392 (1999).
[4] Y. Sun et al. NANO 7, 1250045 (2012).
Corresponding Author: R. Kitaura and H. Shihohara
Tel: +81-52-789-2482, Fax: +81-52-747-6442,
E-mail: r.kitaura@nagoya-u.jp and noris@nagoya-u.ac.jp- 167 -

3P-31Modeling the catalyst formation process to achieve diameter and density
control of single-wall carbon nanotube forestsżShunsuke Sakurai1,2, Don N Futaba1,2, Motoo Yumura1,2, and Kenji Hata1,2
1Nanotube Research Center, National Institute of Advanced Industrial Scienceand Technology (AIST), Tsukuba 305-8565, Japan
2
Technology Research Association for Single Wall Carbon Nanotubes (TASC),
Tsukuba 305-8565, Japan

dr/dt (a.u.)

Catalyst particle array for single-walled nanotube (SWNT) forest requires small particle sizes (<3 nm) and high particle density (below 20 nm spacing) at high temperature typically above 700 ºC.
The most widely used method to satisfy the above requirements is to use an AlOx layer to support the
Fe catalysts. In this method, H2 annealing immediately prior to CNT growth (denoted as catalyst
formation process), invoke the transformation of Fe thin film into a very high density array of small Fe
catalysts array suited for SWNT forest growth.
Previously, we found essentially any Fe compounds spanning from Fe salts, nanoparticles andbuckyferrocene could serve as catalysts for SWNT with nearly identical diameters (2.8-3.1 nm) [1].
Recently, we succeeded in continuously controlling the diameter of SWNT forest in the range of 1.9
nm to 3.2 nm, by changing temperature and gas flow rate during catalyst formation process [2].
These results indicate the understanding of the catalyst
formation process is one of the key to control the SWNT
A §
dr
r·
forest growth. We found that subsurface diffusion of Fe 3s ¨¨1  ¸¸  jS / wn wr
dtr © rc ¹
atoms into the AlOx support induced by hydrogen annealing
induce the reconfiguration of remaining Fe atoms into small
Ostwald
Subsurfaceripening
diffusion
nanoparticles suitable for SWNT growth. In this paper, we
present the model for the growth of catalyst particle duringformation process, considering the offsetting effects of
r2
r1
Ostwald ripening and subsurface diffusion. From this model,0
the growth of the particles stops at a specific size, where theeffects of subsurface diffusion and Ostwald ripening arebalanced (Figure 1). From analyses using this model, we
0
1
34
rr 2/r(a.u.)
c0
conclude H2 exposure increased catalyst surface energy and
Figure 1: Calculation of the growthdecreased diameter while increased temperature led torate of catalyst particles.
increased diffusion on the surface and to an increase indiameter.
2[1] S. Sakurai, H. Nishino, D. N. Futaba, S. Yasuda, T. Yamada, A. Maigne, Y. Matsuo, E. Nakamura, M. Yumura,and K. Hata J. Am. Chem. Soc., 134, 2148 (2012). [2] S. Sakurai, M. Inaguma, D. N. Futaba, M. Yumura, K.
Hata submitted
Corresponding Author: Don Futaba
TEL: +81-29-861-6205, FAX: +81-29-861-1169, E-mail: d-futaba@aist.go.jp- 168 -

3P-32
Simultaneous Growth Control of Position, Chirality,
and in-plane Orientation of Single-Walled Carbon Nanotubes
by Cold-Wall Chemical Vapor Deposition Method○Takumi Sagara1, Satoshi Doi1, Nobuyuki Iwata1, Hirofumi Yajima2, and Hiroshi Yamamoto1
1

Department of Electronics & Computer Science,College of Science & Technology, Nihon
University, 7-24-1 Narashinodai, Funabashi, Chiba 274-8501 Japan2
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3
Kagurazaka, Shinjyuku-ku, Tokyo 162-0826, Japan

In our previous report, position selective growth of single-walled carbon nanotubes(SWNTs) is carried out on a surface treated SiO2 (300nm)/Si substrate between electrodes by
cold-wall chemical vapor deposition (CC-CVD) method in μm-scale[1]. The SWNTs grow at
the intermediate area between electrodes. In addition, chirality controlled growth of the
SWNTs is also done by irradiating free electron laser (FEL) during CVD growth. The
grown SWNTs are all semiconducting investigated by a multi excited laser Raman analysis.
The possible chirality is (14,0), (13,2), (10,6), (9,7), (13,0), (12,2), (10,5), and (8,7). The
remained issue for applications of the field effect transistor (FET) using just one SWNTs is
the in-plane alignment synthesis process. In this study, the CC-CVD growth was carried out
on the r-cut sapphire substrate for the purpose of the in-plane alignment. The substrate wasannealed in advance to obtain a step-terraces structure. The Co/Mo catalysts were adheredby dipping technique on the annealed substrate followed by firing.
Figure 1 shows the Raman spectrum of the SWNTs grown on sapphire substrates. The G
and D peaks were observed around 1580 cm-1 and 1350 cm-1, respectively. The G/D ratio
was 12. The observed radial breathing mode (RBM) around 160 cm-1 mode indicated thegrowth of SWNTs with the diameter of 1.1 ~ 1.8 nm. Figure 2 shows the surface image ofgrown SWNTs. The observed needles are expected bundled-SWNTs bundles with adiameter of 3 ~ 5 nm. Position as well as chirality control growth of SWNTs on the r-cut
sapphire substrate will be also discussed.

Intensity (arb. units)

90000
80000
70000

G/D ratio 12

60000
50000
40000
30000
20000

250

500

750 1000 1250 1500
-1

Wavenumber [ cm ]Fig1. The Raman spectrum of obtained SWNTs

Fig2. The AFM image of the sample surface[1] K. Sakai, S. Doi, N. Iwata, H. Yajima, and H. Yamamoto, IEICE Trans. Electron. E94-C (2011) 1861-1866.
Corresponding Author: T. Sagara
TEL/FAX: 047-469-5457, E-mail: cstu12010@g.nihon-u.ac.jp- 169 -

3P-33
Diameter Dependent Interaction between Single-Walled Carbon Nanotubes
and Encapsulated Ferrocenes
ʊHironori Suzuki,1,2 Yoko Iizumi2 and Toshiya Okazaki,2,1,*
1

Department of Chemistry, Tsukuba University, Tsukuba 305-8577, Japan
2

Nanotube Research Center, AIST, Tsukuba 305-8565, Japan,

Doping molecules to the inner spaces of single-walled carbon nanotubes (SWCNTs) is expected to bea useful technique for achieving realistic applications of SWCNTs. Organometallic compounds,
ferrocenes, have been doped in SWCNTs by many researchers. However, the interaction between
SWCNTs and the encapsulated ferrocenes, and their doping effects on the electronic and opticalproperties of SWCNTs are still controversial [1,2]. In this study, we characterize ferrocenes
encapsulating SWCNTs (ferrocenes@SWCNTs) by photoluminescence (PL) spectroscopy over a wide
range of tube diameters (0.95 nm < d < 1.5 nm). Figure 1 shows the two-dimensional PL maps offerrocenes@SWCNTs and the empty SWCNTs (KH chemicals), respectively. Interestingly, the PL
properties strongly depend on the tube diameter. In the smaller diameter region (d < ~1.05 nm), theintensity of the PL signal is severely decreased. In the middle (~1.05 nm < d < ~1.3 nm), the observed
PL peak positions are shifted compared with those the original SWCNTs. For larger diameter tubes (d> ~1.3 nm), their PL peak positions become similar to each other. The observed PL behaviors shouldreflect the difference in the interaction between SWCNTs and the encapsulated ferrocences.

(a)

(b)

Fig. 1. Two dimensional PL maps of (a) ferrocenes@SWCNTs and (b) the original SWCNTs.
[1] H. Shiozawa et al., Phys. Rev. B, 77, 153402 (2008). [2] X. Liu et al., Adv. Funct. Mater., 22, 3202 (2012).
Corresponding author: Toshiya Okazaki (toshi.okazaki@aist.go.jp)- 170 -

3P-34
Spectroscopic studies of single-wall boron nitride nanotubes
synthesized in single-wall carbon nanotubes○Ryo Nakanishi1, Ryo Kitaura1, Yuta Yamamoto2, Shigeo Arai2, Jamie H Warner3,
Yasumitsu Miyata1 and Hisanori Shinohara1
1

Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya,2464-8602, Japan
Ecotopia Science Institute, Nagoya University, Nagoya, 464-8603, Japan3
Department of Materials, University of Oxford, Oxford, OX1 3PH, UK

Boron nitride nanotubes (BNNTs) are nano-scale cylindrical tubes same as carbon
nanotubes (CNTs), except that they are consisting of hexagonal boron nitride sheets. One of
the most important features of BNNTs is that they possess a large band gap (~ 6.0 eV)
irrespective of the chiralities [1]. Therefore, single-wall BNNTs (SWBNNTs) with narrow
diameters can be considered as an ideal nano-scale vessel to explore physical properties of
one-dimensional materials such as atomic wires. However, their selective and bulk synthesis
is still in its infancy. Previously, we reported a novel synthesis method of SWBNNTs using
single-wall CNTs (SWCNTs) with narrow diameter distribution (1.40.1 nm) as anano-template, from which SWBNNTs (0.70.1 nm) with quite small and uniform diameter
could be obtained selectively. Here, to explore the details of the reaction such as the efficiency,
we have focused on spectroscopic studies of the SWBNNTs inside SWCNTs.
We have synthesized SWBNNTs inside SWCNTs
according to the procedures previously reported: (a)ammonia-borane complex (ABC) was used as a BN
source, which was sealed into a glass tube with
cap-opened SWCNTs under high vacuum (10 -6 Torr)and encapsulated into them with heating at 823 K for
3 days. After capping those ends with C60 andwashing with deionized water, ABC encapsulated
SWCNTs (ABC@SWCNTs) were annealed at 1,673
K for 3 days. From the analyses on electronenergy-loss spectroscopy (EELS) inside transmission (b)electron microscope (TEM), the B:C:N ratio of
SWBNNT inside SWCNTs (SWBNNT@SWCNTs)
is 14:71:15, whose B and N ratios are somewhat
higher than that of ABC@SWCNTs (B:C:N =10:81:9). Considering the yield of SWBNNTs(~50 %) obtained by TEM observation, this result
suggests that the reaction efficiency from ABCs to
SWBNNTs is extremely high (ca. 100 %). Further Figure 1. EELS spectra of (a) ABC@EELS analysis, Raman and absorption spectroscopy SWCNTs and (b) SWBNNT@SWCNTs
taken at each inset region.
results will also be discussed in this presentation.
[1] N. G. Chopra et al., Science 269, 966 (1995).
Corresponding Author: Ryo Kitaura and Hisanori Shinohara
Tel: +81-52-789-2483, Fax: +81-52-747-6442, E-mail: r.kitaura@nagoya-u.jp, noris@nagoya-u.jp- 171 -

3P-35
Molecular Dynamics Simulation of Multi-layer Graphene Growth
by Catalytic CVD Method
Yuki Takaki, Kaoru Hisama, Tomoya Kawasuzuki, Shohei Chiashi, Shigeo Maruyama
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan
Toward utilization of graphene in various applications, it is quite important to control thelayer number of graphene in chemical vapor deposition (CVD) method. In order to understandthe growth mechanism of graphene in atomic scale, we have performed molecular dynamics
simulations. We adopted a newly developed Tersoff-type classical potential for carbon andseveral metal atoms, such as Co, Fe and Ni [1].
We annealed metal substrates (17 × 17 × 15 nm) for 100 ps, and supplied carbon atoms
every 10 ps to keep constant pressure of carbon vapor at various temperatures; 1600, 1800
and 2000 K. We succeeded in the growth of single-layer graphene, as shown in Fig. 1. Figure
1 shows a snapshot of single-layer graphene grown on the iron substrate at 1800 K. The ratioof 6 membered rings indicates the quality of graphene. This ratio depends on growthtemperature, and it shows the highest value at 1800 K in case of the iron substrate.
After the growth of the 1st graphene layer, we simulated the growth process of multi-layer
graphene by directly supplying carbon atoms into metal substrates. This simulation
reproduces the segregation of carbon atoms from metal substrates in cooling process inexperimental graphene growth [2]. When the amount of carbon atoms in metal substrates
excess the saturation point, carbon atoms appear in the interface between the 1st graphene
layer and the metal surface, and form the 2nd graphene layer as shown in Fig. 2. Figure 2 show
a snapshot of double-layer graphene grown on the iron substrate at 2000 K.

Fig. 1 Snapshot of single-layer graphene grown at
1800 K.

Fig. 2 Snapshot of double-layer graphene grown at2000 K.

[1] T. Matsuo et al, to be submitted.
[2] M. Liu et al. ACS Nano 6, 10581 (2012).
Corresponding Author: Shigeo Maruyama
Tel: +81-3-5841-6421, Fax: +81-3-5800-6983,
E-mail: maruyama@photon.t.u-tokyo.ac.jp- 172 -

3P-36
Synthesis and characterization oflarge sized-grain, single-layer BN-doped graphene○Yu Kobayashi, Yasumitsu Miyata, Eriko Maeda, Ryo Kitaura, and Hisanori Shinohara*
Department of Chemistry & Institute for Advanced Research, Nagoya University, Nagoya
Graphene has been considered as one of the promising candidates for various
device applications in electronics and optics because of its excellent carrier mobility andoptical transparency. However, due to the absence of a band gap in graphene, it is still
highly required to develop cutting-edge methods to control its electronic structure. For
this purpose, the substitutional doping of hetero atoms like boron and nitrogen provides
a powerful way to modulate electronic properties of materials, which has been applied
to the synthesis of boron and nitrogen-doped graphene (BN-doped graphene) [1,2].
Here, we report the synthesis and characterization of large sized-grain andsingle-layer BN-doped graphene produced by a thermal chemical vapor deposition(CVD). The doped graphene with large grain size was obtained through simultaneous
supply of small amounts of methane and ammonia borane precursors. Interestingly,
unlike the case of undoped graphene with hexagonal shape (Fig.1a), the BN-doped
graphene is irregular in grain shape even though they have similar grain size of around
10 µm (Fig.1b). Raman spectra clearly present asignificant increase of intensity ratio of
D-mode to G-mode for the BN-doped graphene (Fig.1c). These results suggest that theatomic structural disorder leads to the change of microscopic grain shape, providing animportant insight into the synthesis of high-quality BN-doped graphene.

Fig.1 Optical microscope images of (a) undoped and (b) BN-doped graphenes. (c) Raman spectraof undoped and BN-doped graphenes.
[1] L Ci et al. Nat. Mater. 9 (2011) 430, [2] C. Chang et al. ACS Nano, in press.
Corresponding Author: Hisanori Shinohara,
E-mail: noris@nagoya-u.jp, Tel&Fax: 052-789-2482 & 052-747-6442- 173 -

3P-37
Synthesis and Characterization of Intercalated Graphite andGraphene for Room Temperature Superconductivity○Shogo Sato, Hiroaki Ichikawa, Nobuyuki Iwata, Hiroshi Yamamoto
College of Science &Technology, Nihon University, 7-24-1 Narashinodai, Funabashi-shi,
Chiba 2748501
Graphite intercalation compounds (GIC) is prepared on various substances.
Superconducting transition temperature Tc of GIC with Ca are reported at 11.5K[1].
Furthermore, recently, room temperature superconductivity (RTS) was demonstrated in thewater-treated graphite powder, where clear typical superconducting diamagnetic hysteresis
loop is observed[2]. In this study we aim at realizing the RTS in a FeCl3 or a metalintercalated graphite (FeCl3-GIC), double layers graphene, and/or a few layers graphene
according to the BCS theory. The Tc is expected to be higher than room temperature as longas a disorder and a roughness of the graphite/graphene layers are much reduced.
Figure 1 shows the magnified Raman spectra between 1500 and 1700 cm-1 after the
800
FeCl3 was intercalated to a few layers graphene.
1585cmThe G peak was split to two peaks, indicating
1607cm600
the presence of interacted graphenes. The
lower intensity peak at 1607 cm-1 than that of400
the bare G peak corresponds to the intercalation
200of one layer of FeCl3 more or less every fivelayer graphene sheets, so-called stage 5 [3].
-1Intensity[arb units]-1graphene grown using Cu, Ni, Co and Fe foil bychemical vapor deposition will be discussed.

0

1560

Fig.1.

- 174 -

1600

1620

1640

Wavenumber[cm ]Magnified Raman spectra of the stage 5

FeCl3 intercalated graphene.
25
20
15
10
5
0
100

150

200

250

Temperture[K][1] N. Emery et al., Phys. Rev. Lett. 95 (2005) 087003[2] T. Scheike et al., Adv. Mater, 24(2012) 5826-5836[3] F. Kang et al., Carbon, 36(1998) 383

1580

-1

Resistivity[・m]

Figure 2 shows a resistivity of the stage 5
FeCl3 intercalated graphene as a function oftemperature. Resistivity lineally decreased as
decreasing temperature with the remarkablechange in resistivity behavior around 200K.
The reason of the change is unclear at thismoment, but it is speculated that the crystal
structure transition is present. The intercalated
double layers graphene, and/or a few layers

Fig.2.

Temperature Resistivity characterization at

265 ~ 90 K.

3P-38
Directional growth of graphene over Cu catalyst
by face-to-face configuration CVDżTatsuya Masuda1,2, Kenji Kawahara3, Hiroki Ago3, Suguru Noda2,4*
1

Department of Chemical System Engineering, The University of Tokyo, Japan2
Department of Applied Chemistry, Waseda University, Japan
3
Institute for Materials Chemistry and Engineering, Kyushu University, Japan
4
PRESTO, JST, Japan

Chemical vapor deposition (CVD) on Cu catalyst yields monolayer graphene owing to its
self-terminating reaction [1]. Resulting graphene is, however, polycrystalline with grainboundaries at random positions. Epitaxial growth of graphene on epitaxial Cu or Co catalysts
on single-crystalline sapphire or MgO substrates [2] is a promising approach, however it isstill challenging to unify the grains without seams. Such problem arises from the nucleation at
random positions and growth to random directions of graphene.
We have developed a face-to-face configuration (F2FC) preventing Cu sublimation during
CVD by limiting the diffusion of Cu vapor to the bulk stream [3] (Fig. 1). When a less active
reactant such as CH4 is fed through a sub-millimeter gap (Fig. 1a), it is less consumed by the
Cu catalyst and diffuses uniformly from the edge to the center of Cu [3]. If an active reactant
such as C2H2 is fed through a sub-micrometer gap (Fig. 1b), it should be consumed by the Cu
catalyst and graphene should selectively nucleate at the edge of Cu. When the graphene cover
the edge of Cu, C2H2 should be fed and graphene should grow to inner region of Cu.
In this work, we used the epitaxial Cu catalyst on sapphire [2, 3] and prepared the counter
substrate by partially etching the thermal oxide on Si substrates (Fig. 1b). The
F2FC-substrates were set in the tubular
CVD reactor, annealed under H2/ Ar at 25
Torr and 1050 °C for 10 min, and CVD
was carried out by flowing C2H2/ H2/ Ar at
25 Torr and 1050 °C for 2 min. Typicalresults are shown in Fig. 2 with that with
CH4 as a reference. When CH4 was used,graphene nucleate randomly, resulted in a
Fig.1 Schematics of F2FC-CVD.
number of grain boundaries in scanningelectron microscopy (SEM) and a D-bandin a Raman spectrum. Whereas when C2H2
was used, graphene selectively nucleated at
the edge of Cu and grew inward andD-band was absent. We are now examining
grain boundary distributions.
[1] X. Li, et al., Science 324, 1312 (2009).
[2] Y. Ogawa, et al., J. Phys. Chem. Lett.3, 219(2011)[3] T. Masuda and S. Noda, The 43rd Fall Meetingof the Society of Chemical Engineers, Japan, U319
(2011).
*Tel&Fax:03-5286-2769, noda@waseda.jp

Fig.2 Raman spectra and SEM images of graphene on
epitaxial Cu after F2FC-CVD.

- 175 -

3P-39Monte Carlo Particle Simulations of Local Heating Properties
in Graphene-channel nano-FETs○Shusuke Oki, Taichi Misawa and Yuji Awano
1

Department of Electronics and Electrical Engineering, Keio University, Yokohama
223-8522, JapanDue to high density integration of LSIs, thermal management becomes more and more
important. Besides, Graphene has received much attention as an emerging research material
for future nano-scale FETs and interconnects, because of its excellent electrical and thermal
properties. In this paper, we report computer simulations on the electrical and thermal
properties of Single layer Graphene (SLG) nano-FETs for the first time, using Monte Carloparticle model for both electron and phonon transport.
Start
In devices scaled below or comparable to the size of electron
Initialize variables
mean-free path, Monte Carlo particle method would be the mostreliable and accurate method of quantitative evaluation of
Perform Monte Carloelectron transport [1]. Meanwhile, heat dissipation in the
Method(drift, scattering)macro-scale devices has been analyzed as diffusion phenomena,
Solve Poisson’s equation
Calculate phonon spatial
while in nano-scale devices, cannot be treated the same way
distribution
because the mean-free-path of the phonon becomes comparable
No
T=T+ΔTto the size of device. Thus, we employed Monte Carlo particle
Yesmethod for not only electron but also phonon transport inGraphene-channel nano-scale FETs simulation. This simulation
Calculate phonon transport fromconsists of two parts; the first part is electron transport simulation
spatial distribution
to obtain spatial distributions of phonons generated byelectron-phonon interactions, the second part is phonon transport
Calculate local temperature in
the channel of nano-FET
simulation in order to estimate local heating in the device (thisphonon transport is then being feedback as a scattering rate to
T=T+nΔT
recalculate electron transport). We succeeded in calculating bothn>1000electron and phonon transport phenomena self-consistently for aEndreasonable computing time by introducing two different time Fig. 1 Algorithm of a new model
steps for electron and phonon transport simulations.
The phonon velocity is derived from the phonon
dispersion curve of SLG [2].
Using our new method, we succeeded in analyzing
local heating phenomena in nano-scale SLG FETsquantitatively. Figure 2 shows the peak temperature ofnano-scale SLG FET, comparing with that of GaAs.
Although the heat generation rate of SLG is higher
than that of GaAs because of higher optical phonon
energy, the peak channel temperature in SLG is lower
than that of GaAs, which is probably due to high speed
Fig. 2 Peak temperature in FET channel
optical and acoustic phonons in SLG. Our method can beapplied for power devices in which local heating is more crucial in determining device
performance.
Electron transport for short period of time(5 ps)

Phonon transport for long period of time(100 ps~)Feed back as
scattering rate

[1] N. Harada, et al., APEX1 (2008) 024002.
[2] D. L. Mafra, et al., Phys. Rev. B 76 (2007), 233407.
Corresponding Author: Y. Awano Tel, Fax: +81-45-566-1506, E-mail: awano@elec.keio.ac.jp- 176 -

3P-40Electrically driven ultra-high-speed black body emitters based on graphene○Tomoya Yokoi1, Yusuke Takayama1, Tatsuya Mori1, Daiju Tsuya2, Hideyuki Maki1
1

Department of Applied Physics and Physico-Informatics, Faculty of Science and Technology,
Keio University, Yokohama 223-8522, Japan
2
NIMS Nanofabrication Platform, Tsukuba 305-0047, Japan[1] M. H. Bae, Z. Y. Ong, D. Estrada, and E. Pop, Nano Lett. 10, 4787(2010).
Corresponding Author: H. Maki
Tel: +81-45-566-1643, Fax: +81-45-566-1587, E-mail: maki@appi.keio.ac.jp- 177 -

Voltage(V)Intensity(a.u.)

Intensity(a.u.)Graphene is an ideal two-dimensional materials with interesting electrical, optical andthermal properties, and these unique properties have been utilized for the novel application in
optoelectronics and photonics [1]. In this study, we fabricated a graphene-based emitter, andfirstly observed high-speed blackbody emission with the response speed of > 1 GHz, which is> 106 times higher than that of a conventional incandescent emitter with a filament and ishigher or comparable to a light-emitting diode (LED) and a laser diode (LD).
1.0
We used mechanical exfoliation techniqueExperimental result(with a tape) to deposit graphene onto SiO2
0.8
Fitting
1132.5K(90nm)/Si substrate, and the Ti/Pd(5/40nm)
0.6electrodes were deposited on it. Figure 1 shows1039.8K
0.4
the emission spectra under DC bias. Since these
947.1K
spectra can be fitted to Planck’s law, these
0.2
emissions can be explained by the blackbody
0.0
radiation by Joule heating. The graphene
900
1000
1100
1200
1300
1400
1500
Wavelength(nm)temperature obtained from the fitting increased
Fig. 1. Infrared spectrum of graphene black bodywith increasing bias voltage.
radiation and temperature of graphene estimated
The response speed of the emission from this from Planck’s law fitting at Vds = 11, 13 and 15 V.
device was evaluated by the time-resolved
Emission
1600
emission measurement under applying pulsed
7
Voltage
1400
voltage. As shown in Fig. 2, the observed
1200
emission intensities quickly respond to the
61000
applied pulse voltage. In addition, we also
5800
experimentally demonstrated 1-ns-width pulsed
600
light generation. We note that an emitter with a4
400
thick graphite (~3000 layers) has quite slow
0
5
10
15
speed (~100kHz). This high-speed response inTime(ns)graphene is explained by the extremely short Fig. 2. Optical response of graphene black bodytemperature response time dominated by the radiation under applying pulse voltage (4 - 6 V).
high heat dissipation to the substrate owing to the direct heat dissipation to the substrate andthe small heat capacity per unit area of graphene. This electrically driven, small footprint andultra-high speed emitter may open novel applications of blackbody emission such as anintegrated light source for integrated photonic or optoelectronic circuit, an ultrafast white lightsource (like a supercontinuum light) and so on.
This work was partially supported by Grants-in-Aid for the Encouragement of Young
Scientists (no. 23686055) from the MEXT, Japan, by the A-STEP (no. AS242Z01485J ) from
JST, Japan and by NIMS Nanofabrication Platform in "Nanotechnology Platform Project" by
MEXT, Japan..

3P-41Few-layer Graphene/silicon Heterojunction Photovoltaic Cells by Microwave
Plasma-Enhanced Chemical Vapor Deposition○Zhipeng Wang1, Shohei Hayase2, Mao Shoji2, Hironori Ogata1,2,3
1

Institute for Sustainability Research and Education, Hosei University, fujimi, 102-8160, Japan
2
Graduate School of Engineering, Hosei University, koganei, 184-8584, Japan
3
Research Center for Micro-Nano Technology, Hosei University, koganei, 184-0003, Japan

Graphene, a single layer of carbon atoms in a hexagonal lattice, has attracted great attention due
to its outstanding and fascinating properties [1] and a wide range of interesting potential
applications [2]. Recently, the graphene-based Schotty junction solar cells have been extensively
investigated to optimize their power efficiencies [3, 4]. The graphene films used in their studies
were usually grown on metal folis (eg. Cu, Ni) by chemical vapor deposition in Ar/H2/CH4 systemat high temperatures (above 900 oC). Besides them, few-layer graphene (FLG) films which were
fabricated by flame synthesis technique could be used to form a p-n junction solar cell with n-typesilicon [5]. Recently, we have obtained the FLG films on the various metal substrates by
microwave plasma enhanced chemical vapor deposition (MPECVD, 2.45GHz) with a solid carbon
source. Fig. 1 shows the example of the FLG films consist of bi- or trilayer by MPECVD with asolid carbon source. In this presentation, we will present the fabrication and the optimized
photovoltaic properties of FLG/n-type silicon heterojunction photovoltaic cells. The detailed
results will be discussed in the presentation.

Fig. 1 Typical TEM image of few-layer graphene loading on the Cu mesh
[1] K. S. Novoselov et al., Science 306, 666 (2004).
[2] P. Avouris et al., MRS Bulletin. 37, 1225 (2012).
[3] X. Li et al., Adv. Mater. 22, 2743 (2010).
[4] X. Miao et al., Nano Lett. 12, 2745(2012).
[5] Z. Li et al., Chem. Commun. 47, 3520 (2011).
[6] Z. Wang et al. preparing
Corresponding Author: H. Ogata. Tel/fax: +81-42-387-6229. E-mail: hogata@hosei.ac.jp.

- 178 -

3P-42Degree of oxidation of centrifuged graphene oxideżHiroyuki Yokoi1,2, Michio Koinuma1,2, Kazuto Hatakeyama1,2, Takaaki Taniguchi1,2,
Yasumichi Matsumoto1,2
1

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

Graphene oxide (GO) is single-layered graphene modified with functional groups
including oxygen. GO can be dispersed stably in water and become base material for many
applications such as polymer composites, sensors, biomedical applications. As it is possible tosynthesize GO in a large scale, this material has potential to utilize some of excellent featuresof graphene for industrial applications cost-effectively and massively. Though typical GO has
low electrical conductivity, several approaches to reduce GO have been developed to improvethe conductivity[1]. The reduced GO (rGO), however, looses dispersiveness instead, which
spoils the handiness of GO. In this paper, we present a method to separate GO with the degreeof oxidation comparable to rGO and the dispersiveness comparable to conventional GO.
In the experiments, GO was prepared following the Hummers’ method from pure graphite
powder (New Metals and Chemicals Ltd., 99.9999%) and washed several times with distilledwater and then dried in an oven. The obtained GO was sonicated in distilled water with anultrasonic bath for 2 h, and centrifuged at 15kG for 0.5 h to remove any aggregated GO. The
supernatant liquid was centrifuged again at 11kG for 0.25 h. This two-stage centrifugation
produced precipitation in spite that the centrifugal force and duration were smaller at thesecond stage than at the first stage. We mixed the precipitation with a small amount of thesupernatant by shaking with a hand lightly and found that the precipitation dispersed very
well in the liquid. We applied X-ray photoelectron spectroscopy (XPS) analysis to theprecipitation and found that the precipitation was GO with the lower degree of oxidation thanthat of original GO as shown in Fig. 1. The XPS spectrum of precipitated GO (p-GO) was
similar to that of rGO. Despite that the apparent degree of oxidation of p-GO is comparable tothat of rGO, the dispersion has been stable for 5 months. Further studies on the Zeta potential
and the electric properties of p-GO will be presented.
(a)

(b)

Fig. 1 XPS spectra of (a)precipitation of centrifuged
GO suspension and (b)original GO[1] Y. Matsumoto et al. ACS Appl. Mater. Interfaces, 2, 3461 (2010).
Corresponding Author: H. Yokoi
Tel: +81-96-342-3727, Fax: +81-96-342-3710,
E-mail: yokoihr@kumamoto-u.ac.jp- 179 -

3P-43Spin polarization of hexagonal boron nitride/Ni(111) interface
studied by spin-polarized metastable de-excitation spectroscopy.
○Manabu Ohtomo1, Yasushi Yamauchi2, Pavel V. Avramov1, Shiro Entani1,
Yoshihiro Matsumoto1, Hiroshi Naramoto1, and Seiji Sakai1
1Advanced Science Research Center, Japan Atomic Energy Agency, Ibaraki 319-1195, Japan
2
National Institute of Materials Science, Ibaraki 305-0047, Japan

1.

Introduction
Hexagonal boron nitride (h-BN) has a large band gap (~5 eV) and a honeycomb
lattice which makes it a promising insulating material for graphene spintronics. In thisstudy, we present spin-polarized metastable de-excitation spectroscopy (SPMDS) of
h-BN / Ni(111) “spinterface” in order to elucidate the spintronic structure and enhance
the spin injection efficiency from Ni magnetic electrode into graphene overlayer through
h-BN.

2.

Experimental procedure
Substrate was a W(110) single crystal on which a Ni(111) film with thickness of 15
nm was epitaxially grown by molecular beam epitaxy (MBE) method. The h-BN wasgrown by ultra-high vacuum chemical vapor deposition technique (UHV-CVD) at thesubstrate temperature of 850oC. The precursor for UHV-CVD was borazine which has
an analogous structure to benzene.
The SPMDS detect the de-excitation process of polarized metastable helium atoms(23S), which is governed by the Pauli principle and sensitive to surface spins. The spinpolarized atom of the triplet states was produced by the optical pumping of metastable
helium atom beam with circularly polarized light. All measurements and fabrication
processes were performed in-situ conditions.

3.

Results and discussion
As previously suggested by core-level excitation spectroscopy [1], it was confirmedthat the 3d hybridization of Ni and N induces new electronic states in the band gap ofh-BN. The SPMDS study revealed that the de-excitation process, which was mainly
Auger neutralization (AN) in pristine Ni(111), changed into AN mixed with Augerde-excitation (AD) upon the formation of h-BN. This result indicates that the density ofstates around the Fermi level was significantly reduced. The spin asymmetry of
SPMDS spectra showed that the induced gap states were spin-polarized along the Ni
majority spins near the Fermi energy, which agrees well with the density functional
theory (DFT) calculations of spin dependent band structure. According to the DFT
calculations, the exchange splitting of the gap states were sufficiently large (0.6 eV).
This result suggests that the splitting was mainly induced by coupling with Ni atoms.
[1] N. Mårtensson et al., Phys. Rev. B 70, 165404 (2004).

Corresponding Author: Dr. M. Ohtomo
Tel: +81-29-284-3802, Fax: +81-29-284-3802,
E-mail: ohtomo.manabu@jaea.go.jp- 180 -

3P-44
Tetragonal C4 Polymer: A Two-dimensional Metallic sp2 Carbon Allotrope○Mina Maruyama and Susumu Okada
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8571, Japan
Carbon molecules are known to form various polygonal conformations due toflexibility of its bonding angle and length. These polygons can be a constituent unit for thevarious molecular patchworks with zero-, one-, two- and three-dimensions by sewing thesepolygons. In addition to graphene, it is interested in exploring the possibility of the other two
dimensional carbon allotropes consisting of carbon polygons. Among the polygons, tetragons(cyclobutadiene: C4) can completely cover up a two-dimensional plane. Althoughcyclobutadiene molecule is unstable under ambient condition, two-dimensional polymerized
cyclobutadiene is expected to be stable due to the intermolecular covalent bonds. We study
the geometric and electronic structures of a two-dimensionally polymerized C4 based on thedensity functional theory with local density approximation.
We find that the polymerized C4 is stable and keeps its tetragonal bonding network
under the equilibrium lattice parameter of a=0.34 nm as shown in Fig. 1. Under theequilibrium lattice constant, the C4 unit almost retains its tetragonal and planer structures: The
optimized bond lengths for intra- and inter-unit are found to be 0.142 nm and 0.131 nm,
respectively, and the bond angle in the unit is about 90 degree. Calculated total energy ishigher than that of grapheme by 0.6 eV/atom. As shown Fig. 2, the polymerized C4 is a metal
with linear dispersion bands at the Fermi level.
5Energy (eV)

0 
-5
-10
-15

a
-20


X

M



Fig. 2 Electronic structure ofpolymerized C4. Energies are measured
from that of the Fermi level.

Fig. 1 The optimized structure of
the polymerized C4.

Corresponding Author: Mina Maruyama
E-mail: mmaruyama@comas.frsc.tsukuba.ac.jp
Tel: +81-29-853-5600(ext: 8233)- 181 -

3P-45Graphene-based nanomaterials prepared by laser ablation of graphite○Maki Nakamura 1, Takazumi Kawai 2, Michiko Irie 1, Ryota Yuge 2, Sumio Iijima 1,2,3,
Shunji Bandow 3, Masako Yudasaka 1
1

Nanotube Research Center, AIST, 1-1-1 Higashi, Tsukuba 305-8565, Japan
2
NEC Corporation, 34 Miyukigaoka, Tsukuba 305-8501, Japan
3
Meijo University, 1-501 Shiogamaguchi, Nagoya 468-8502, Japan

Graphene-based nanomaterials are expected to have many applications in the fields ofelectrochemistry, biomedicine, and so on. We previously reported the oxidation of sphericalgraphene-based aggregates containing thin graphene sheets (TGSs) and single-walled carbon
nanohorns (SWNHs) (Fig. 1) under mild condition, i.e., with hydrogen peroxide at room
temperature for a certain period (from 1 hour to 56 days) [1]. By using high resolution
thermogravimetric analysis (HR-TGA), we revealed the existence of two types of TGSs; one
type (TGS1) was easily oxidized, while the other type was more resistant to oxidation (TGS2).
The weight ratio of TGS1 and TGS2 was estimated to be 2:1, but their structures were notclear. In this report, we investigated the characteristics of TGSs, in terms of layer numbers,inter-layer distances, and structure of TGS1 and TGS2.
The spherical aggregates containing TGSs and
SWNHs were prepared by CO2 laser ablation ofgraphite in Ar (~760 Torr) without auxiliary heating.
The weight ratio of TGSs and SWNHs determined by
HR-TGA was 45:55. The layer numbers and inter-layer
distances of TGSs were determined by usingtransmission electron microscopy (TEM) images.
The layer number histogram of TGSs showed adistinctive distribution: even-number layered graphenes(2-, 4-, 6- and 8-layers) were preferentially formed
Fig.1 A TEM image of a spherical(~90%), and their population decreased as the layer
aggregate containing thin graphene
number increased. Especially, bi-layers formed most
sheets and carbon nanohorns.
abundantly (~60%). Assuming that TGS1 and TGS2
are attributed to surface layers and inner layers, respectively, the ratio of TGS1 and TGS2
(2:1) estimated in a previous study largely agreed with the layer number counting results.
Therefore, it can be concluded that surface-selective oxidation on TGSs occurred by mildoxidation. The inter-layer distances estimated by TEM images were about 15% larger thanthat of bulk graphite (0.335 nm) in the bi-layer TGSs, and they approached the bulk value as
the layer number increased. Supposed growth mechanism of even layer-number preferential
growth is that single-layer graphenes are firstly formed, but they are unstable and bends toform bi-layers, and the bi-layers then go on to stack and form thicker TGSs (4-, 6- and8-layers).
[1] M. Nakamura et al. The 42th Fullerenes-Nanotubes-Graphene General Symposium, 2012.
Corresponding Author: M. Nakamura, M. Yudasaka
Tel: +81-29-861-6290, Fax: +81-29-861-6290,
E-mail: ma-ki-nakamura@aist.go.jp, m-yudasaka@aist.go.jp- 182 -

3P-46
Effects of etchant and synthesis temperature on the sheet-resistivity ofnitrogen doped graphene film
Takahiro Mizuno, ż Shunji Bandow
Department of Materials Science and Engineering, Meijo University,
1-501 Shiogamaguchi, Tenpaku, Nagoya 468-8502, Japan

Normalizerd Rsq (k:sq per sheet)

Normalized Rsq (k:sq per sheet)

Number of graphene layers

A graphene film can be easily formed on the Cu substrate25
by the thermal chemical vapor deposition of methanol. In
CuSO4 etching20
the previous study, we demonstrated that the nitrogen doping
15
FeCl3 etchingeffectively lowered the magnitude of the sheet-resistivity by
10
1/4. However, actual value of the sheet-resistivity for a5
single sheet of N-doped graphene was still in the order0~10-20 k:/(sq y sheet), which is not low enough level.
0.0
0.2
0.4
0.6
0.8
Liq. supplying rate (cc/min)
Hence, we study here that the effect of etching method on the
sheet-resistivity and also the effects of methanol supplying
Fig. 1 Number of graphene layers
rate and synthesis temperature on the sheet-resistivity.
after etching away the Cu. Neither
First we checked the etchant effect on the sheet-resistivity etchant gives serious destruction tofor pristine un-doped graphene. Two kinds of etchants the garaphene layer.
were used. One is ca. 6M-HCl/H2SO4 solution of CuSO4
80(CuSO4 etchant) and the other is ca. 0.5M-HCl solution of
60
CuSO4 etching
FeCl3 (FeCl3 etchant). Same batch of a graphene formed on
40
the Cu foil at 925 ºC for 2 min was used, and various
FeCl3 etchinggraphene samples were prepared by changing the liquid20
supplying rate between 0.1 and 0.8 cc/min. Figure 1 is a0result of the number of graphene layers, which clearly
0.0
0.2
0.4
0.6
0.8
Liq. supplying rate (cc/min)indicates a decrease of the number of layers with decreasing
the liquid supplying rate, and the number of layers does not Fig. 2 Liq. supplying rate dependence
depend on the etchants or acid concentrations. On the other on the normalized Rsq. A CuSO4
may give the atomic defects
hand, the magnitude of the sheet-resistivity per one graphene etchantin the surface layer of graphene.
layer (normalized Rsq) was definitely different as indicated in
25
Fig. 2. This suggests that the strong acid (CuSO4 etchant)20
may destroy a one surface layer of stacked graphene and15
makes the defects, while FeCl3 etchant does not give such10
significant effect to the graphene layer.
0.03 % melamine containing MeOH
5
Next, we checked a synthesis temperature effect on thenormalized Rsq between 900 and 1000 ºC (Tmp of Cu is 1083
0
900
925
950
975
1000
Synth T (°C)ºC) with a liquid supplying rate 0.16 cc/min. In addition,
we used a 0.03 % melamine containing MeOH for the Fig. 3 Synthesis temperature
N-doping. Results are in Fig. 3. Although the magnitude dependence on the normalized Rsq.
of the normalized Rsq does not indicate a distinct dependence,
obvious drop of the normalized Rsq down to ~5 k:/(sqysheet) can be seen when a small
amount of melamine was added in the liquid source. Hence when we prepare a 5 layered
N-doped graphene film, it can be realized the visible light transparency of ~90 % and the
sheet resistivity of ~1 k:/sq.
Corresponding Author: Shunji Bandow, E-mail: bandow@meijo-u.ac.jp, Tel : +81-52-838-2404- 183 -

Ⓨ⾲⣴ᘬAuthor Index

Author Index<A>
Achiba, Yohji
Ago, Hiroki
Aizawa, Toshihiro
Akasaka, Takeshi
Akiyama, Wataru
Akizuki, Naoto
Ali-Boucetta, Hanene
Antipina, Liubov
Aoki, Nobuyuki
Aonuma, Shuji
Aoyagi, Shinobu
Arai, Daijiro
Arai, Miho
Arai, Shigeo
Arakawa, Yasuhiko
Aroua, Safwan
Asaka, Koji
Atou, Toshiyuki
Avramov, Pavel
Awano, Yuji
<B>
Baba, KeisukeBaba, Yuji
Badar, Saifullah
Bandow, Shunji
Bird, Jonathan P.
Bissett, MarkBussy, Cyrill<C>
Caiyu, Qiu
Chan, M.Y.
Chaunchaiyakul, Songpol
Chen, Zhongming
Chiashi, Shohei

Chiba, Takaaki
Cui, Kehang

3-10, 3P-7, 3P-10
1P-30, 1P-35, 1P-41,
2-11, 2P-36, 3P-38
2P-7
1S-1, 1-1, 2P-6,
3P-1, 3P-6
3P-4
1P-8
㻌
1P-27
㻌
2-9
㻌
1P-9, 3P-4 㻌
2P-38, 3P-21 㻌
3-11
2P-10
3S-8
3P-34
3P-13
1-2
1P-32
2P-37
2-9, 3P-43
3P-39

1-5
2-9
1P-21
1P-29, 2P-45, 3P-45,
3P-46
1P-9, 3P-4
1P-41
1P-27

1-10
2S-6
2-4
3P-27
1P-18, 1P-20, 1P-21,
2-2, 2P-28, 3-2,
3-6, 3P-13, 3P-26,
3P-35
3-2
3-2

- 185 -

<D>
Doi, Satoshi
Doi, Tatsuya
Duan, Zongfan<E>
Eda, Goki
Einarsson, Erik
Enoki, Toshiaki
Entani, Shiro<F>
Fedorov, Alexander
Ferreira, A.A.
Fujigaya, Tsuyohiko
Fujihara, Miho
Fujii, Shunjiro
Fujino, Tatsuya
Fujita, Wataru
Fujiwara, Keita
Fukaya, Norihiro
Fukuoka, Naoya
Fukuzumi, Shunichi
Fumiyuki, Toshimitsu
Funabasama, Tomoyuki
Funatani, Takashi
Furukawa, Ko
Furukawa, Shunsuke
Furuya, Souhei
Futaba, Don N.

1P-17, 3P-32
3P-4
3P-5

1S-3
1P-18, 3-2, 3-6
1P-40, 1P-42, 2-8,
2P-41
2-9, 2P-10, 3P-43

Futagoishi, Tsukasa
Fuyuno, Naoto

1-6
2S-6
3P-12, 3P-25
2P-34
3-1, 3P-5
3P-10
3P-7
1P-44
2P-19
2P-26
3-12
3P-25
2P-14
2P-43
1-1
1P-36
1P-40
1P-23, 2P-16, 3P-31,
3-4
2P-9
1-7

<G>
Ge, Wanyin
Ghosh, Ranajit
Goto, Jundai
Goto, Takashi

1P-35
2P-26
1P-23
3P-23

<H>
Hamahata, Hiroki
Harano, Koji
Harish, Sivasankaran
Haruta, Naoki
Hasdeo, Eddwi

2P-18
1P-36
3-6
2P-5
3-8, 3P-19

Hasegawa, Daisuke
Hasegawa, Kai
Hasegawa, Kei
Hasegawa, Masataka
Hasegawa, Shigeki
Hasegawa, Tadashi
Hashida, Toshiyuki
Hashiguchi, MasahikoHashimoto, Kenro
Hata, KatsuhikoHata, Kenji
Hatakeyama, Kazuto
Hatakeyama, Rikizo
Hayakawa, Yoshio
Hayase, Shohei
Hayashi, Junki
Hayashi, Takuya
Hida, Akira
Higuchi, Kentaro
Hino, Shojun
Hirai, Daisuke
Hiraiwa, Atsushi
Hirana, Yasuhiko
Hirano, Atsushi
Hirao, Norie
Hisama, Kaoru
Hitosugi, Shunpei
Homma, Naoki
Homma, Yoshikazu
Honda, Kazumasa
Honma, Itaru
Horiguchi, Yukichi
Hunabasama, Tomoyuki<I>
Ichikawa, Hiroaki
Igarashi, Toru
Iguchi, Kazuyuki
Iida, Ryosuke
Iijima, Sumio
Iizuka, Ryosuke
Iizumi, Yoko
Ikami, Toshiki
Ikehara, Yuzuru
Ikuhara, Yuichi
Ikuma, Naohiko
Imamura, Saneyuki

1P-21, 2P-28
1P-22, 2P-14
2P-23, 3P-27
2P-40
3-3
3P-1, 3P-6
2P-17
2P-3
3-10
2P-21
1P-23, 2P-16, 2P-41,
3-4, 3P-31
3P-42
1P-19, 2-10
1P-4
2P-39, 3P-41
1P-10
1P-42
3P-24
2P-21
3-13
1P-5
2P-20
2-1, 3P-14
3P-11
2-9
3P-26, 3P-35
1-3
2-2
2-2
1P-4
1P-31
2P-7
2P-12

3P-37
2P-14
3S-8
3P-1
1P-27, 1P-28, 1P-29,
2-3, 3P-45
1-3
1P-14, 3P-33
1P-44
1P-14
2P-27
3P-3
1P-1

- 186 -

Izumi, Noriko
Izumida, Wataru

3-3
2P-20
2P-3
3P-23
2-5, 2P-15
1P-21, 2P-28, 3-2
3P-45
1-6, 3-7, 3-11
1P-9, 3P-24
2P-40
1P-3, 2P-11
1P-17, 2P-24, 3P-32
3P-15
2P-41
3-6
1-3
3P-23
1P-44, 2-7
3-1
3P-13
1P-25
1P-8
1P-12, 2P-18
1P-17, 2P-4, 2P-24,
3P-32, 3P-37
3-11
3P-16

<J>
Jimbo, Takashi
Jippo, Hideyuki

1P-10
2P-44

Imanishi, Masahiro
Inaba, Masafumi
Inada, Hiroshi
Ino, Kosuke
Inoue, Ayaka
Inoue, Taiki
Irie, MichikoIrle, Stephan
Ishibashi, Koji
Ishihara, Masatou
Ishii, A.
Ishii, Koji
Ishii, Tadahiro
Ishii, Takafumi
Ishikawa, Kei
Isobe, Hiroyuki
Ito, AkihikoIto, Tadamasa
Ito, Yasuhiro
Iwamoto, Satoshi
Iwamoto, Takahiro
Iwamura, Munechiyo
Iwasa, Yoshihiro
Iwata, Nobuyuki<K>
Kaburagi, Yutaka
Kako, Masahiro
Kameda, Tomoshi
Kaneko, ToshiroKano, Ryosuke
Kataoka, Yusuke
Kataura, Hiromichi
Kato, Tatsuhisa
Kato, Teppei
Kato, Toshiaki
Kato, Yuichi
Kato, Yuichiro K.

1P-42
3P-1
3P-11
1P-19, 2-10
2P-8
2P-19
1P-2, 2P-30, 3-1,
3P-5, 3P-11
1-1, 1P-25, 2P-1,
2P-7
3-5
1P-19, 2-10
2-5, 2P-13, 2P-15,
2P-25
1P-1, 1P-3, 2P-11,
3P-13

Katsuno, Shunsaku
Kawahara, Kenji
Kawai, Hideki
Kawai, Masatoshi
Kawai, Takazumi
Kawakami, Hiroki
Kawarada, Hiroshi
Kawashima, Yuki
Kawasuzuki, Tomoya
Kayahara, Eiichi
Kayo, Yasumichi
Kiguchi, Manabu
Kigure, Shota
Kikuchi, Hayato
Kikuchi, Koichi
Kim, Dong Young
Kimura, Hiroe
Kimura, Masato
Kimura, Takahide
Kinoshita, Hidenori
Kishi, Naoki
Kishikawa, Keiki
Kishimoto, Shigeru
Kitaura, Ryo
Kiyomiya, Masaharu
Kizukuri, Shota
Kobayashi, Fumito
Kobayashi, Keita
Kobayashi, Yu
Kodama, Takeshi
Kohmoto, Shigeo
Koinuma, Michio
Kokubo, Ken
Koma, Kazunari
Komatsu, Katsuyoshi
Komatsu, Koichi
Komatsu, Naoki
Konabe, Satoru
Kondo, Hiroki
Koretsune, Takashi
Kostarelos, Kostas
Kouyama, Takahiko
Kowalczyk, Tim
Kozawa, Daichi

2-7
1P-30, 1P-35, 2-11,
3P-38
1P-22
2P-12
3P-45
2P-2
2P-20
3-12
3P-26, 3P-35
2P-1
2P-36
2P-41
2P-32
1P-24
3P-7
2P-19, 3P-27
1P-23
3P-6
2-4, 2P-38, 3P-21,
3P-28
3-2
1P-10
3P-20
1P-13, 2P-19, 2P-21
1-7, 1P-26, 1P-34,
2P-34, 3-9, 3-11,
3P-30, 3P-34, 3P-36
2P-31
1P-39
3P-20
2P-31
3P-36
3-10, 3P-7, 3P-10
3P-20
3P-42
3P-3
2-6
2-11
1S-2, 1-1, 2S-6
1-7, 2-4, 2P-38,
3P-21, 3P-28
1-9
2P-26
1P-39, 3P-17
1P-27
2P-1
3-11
1-7, 1P-11- 187 -

Kramberger, ChristianKudo, Hikaru
Kumamoto, Akihito
Kumazawa, Akira
Kunimoto, Ryuji
Kuno, Akihiro
Kusunoki, Michiko
Kuwahara, Yuji
Kyakuno, Haruka
Kyotani, Takashi

1P-18
2P-12
1P-18
3P-15
1P-47
3P-24
2P-20
2-4
1P-2
2P-41

<L>
Li, S.-L.
Liu, Gang
Liu, Ming
Lu, Xing

2S-6
2-4, 2P-38, 3P-28
3P-29
2P-6

<M>
Machida, Tomoki
Maeda, Eriko
Maeda, Kenji
Maeda, Yutaka
Maki, Hideyuki
Manako, Takashi
Maniwa, Yutaka
Maruyama, Koji
Maruyama, Mina
Maruyama, Shigeo
Maruyama, Takahiro
Mase, Kentaro
Masubuchi, Satoru
Masuda, Tatsuya
Masuda, Yoshiho
Matsuda, Kazunari
Matsue, Tomokazu
Matsumoto, Naoyuki
Matsumoto, Yasumichi
Matsumoto, Yoshihiro
Matsunaga, Masahiro
Matsuo, Yutaka
Mieno, Tetsu
Mikie, Tsubasa
Minato, Takuro
Misawa, Taichi
Mishina, Yuki
Miura, Ryohei

3S-8
1P-34, 2P-34, 3P-36
1P-9
3P-1, 3P-6
3P-40
1P-29
1P-2
1P-46
3P-44
1P-18, 1P-20, 1P-21,
2P-28, 3-2, 3-6,
3P-13, 3P-26, 3P-35
2P-26
3-12
3S-8
3P-38
2P-20
1-7, 1-8, 1P-8,
1P-11, 2-1
3P-23
2P-16
3P-42
2-9, 2P-10, 3P-43
1P-9
2P-2, 2P-3, 3S-9
1P-15, 2P-29
3P-3
1P-32
3P-39
2P-45
1P-1

Murakoshi, Kei
Murakoshi, Koshi
Murata, Michihisa
Murata, Shigeaki
Murata, Yasujiro

3P-4
1P-37
2-11
1P-2, 1P-26, 1P-34,
2P-34, 3-9, 3P-30,
3P-34, 3P-36
1-7, 1-8, 1P-8,
1P-11, 2-1
1P-26
3P-14
2S-6
3-13
1-1, 2P-6
3P-46
1P-13, 2P-19, 2P-21
3P-4
3P-40
3S-8
1-1
1-4
3P-20
2P-17, 3P-23
1-7, 1-8, 1P-8,
1P-11, 2-1
2P-35
1P-19
1-1, 2P-9, 3P-2
3-3
1-1, 2P-9, 3P-2

<N>
Na, NuriNagasaki, Yukio
Nagase, Shigeru
Nagaya, Yuka
Naitou, Yasuhisa
Nakahara, Hitoshi
Nakaharai, S.
Nakai, Yusuke
Nakajima, Yuta
Nakamura, Eiichi
Nakamura, Kazutaka
Nakamura, Keisuke
Nakamura, Kenta
Nakamura, Maki
Nakanishi, Ryo
Nakanishi, Yusuke
Nakano, Atsushi
Nakano, Kaichiro

2P-27
2P-7
1-1, 2P-6
3P-15, 3P-24
1P-22
1P-32, 2P-33
2S-6
1P-2
2P-21
1P-36
2P-37
3P-21
1P-20
3P-45
3P-34
3-13
2P-22
1P-29

Miyamoto, KatsuhikoMiyamoto, Yoshiyuki
Miyashita, Masahiro
Miyata, Yasumitsu
Miyauchi, Yuhei
Miyaura, Kenshi
Miyazaki, Daigo
Miyazaki, H.
Miyazaki, Takafumi
Mizorogi, Naomi
Mizuno, Takahiro
Mizutani, Takashi
Momiyama, Daiki
Mori, Tatsuya
Morikawa, Sei
Morinaka, Yuta
Moriyama, Hiroshi
Moriyama, Yuki
Motomiya, Kenichi
Mouri, Shinichiro

Nakashima, Naotoshi
Nakatsu, Touru
Namba, Ryoichi
Naramoto, Hiroshi
Narita, Ayumi
Naritsuka, Shigeya
Nihey, Fumiyuki
Niidome, Yasuro
Nikawa, Hidefumi
Nishi, Tatsuhiko
Nishibori, Eiji
Nishimura, Yoshifumi
Nishioka, Yasushiro
Nitta, HarunaNiwa, Hiroyuki
Niwase, Keisuke
Nobusa, Yuki
Noda, Shoko
Noda, Suguru
Nugraha, Ahmad
Numata, Hideaki<O>
Ochiai, Takumi
Ochiai, Yuichi
Ogata, H.
Ogata, Hironori
Ogawa, Matsuto
Ogawa, Yui
Ogura, Mutuo
Ohfuchi, Mari
Ohkubo, Kei
Ohno, Yutaka
Ohta, Kazutoku
Ohta, Tomona
Ohtomo, Manabu
Okada, Hiroshi
Okada, Satoshi
Okada, Susumu
Okamoto, Mitsuhiro
Okazaki, Toshiya
Oki, Shusuke- 188 -

2S-5, 2-1, 2-5,
2P-13, 2P-15, 2P-25,
3P-12, 3P-14, 3P-25
1P-22
3-3
2-9, 3P-43
2-9
2P-26
1P-16
2-5, 2P-13, 2P-15,
2P-25, 3P-14
1-1
3-13
3-11
1-6, 3-7
3P-5
3P-9
3-13
2P-37
2P-12, 2P-18
3-13
2P-19, 2P-23, 2P-27,
3P-27
3-8, 3P-19
1P-16

2P-20
1P-9, 3P-4
3P-41
1-5, 2P-22, 2P-39
2P-43
2-11
1P-14
2P-44
3-12
1P-11, 1P-13, 2P-19,
2P-21
1P-4
3-13
2-9, 2P-10, 3P-43
2P-2
1P-36
1-9, 2P-32, 2P-42,
3P-8, 3P-18, 3P-44
1P-25
1P-14, 2-3, 3P-20,
3P-33
3P-39

Okigawa, Yuki
Okimoto, Haruya
Okukawa, Takanori
Omatsu, Takashige
Ono, Shimpei
Ono, Taizo
Onuki, Masahiro
Oohara, Kazuyoshi
Osawa, Eiji
Oshima, Azusa
Oshima, Takumi
Oshima, Yugo
Osipov, Vladimir Yu
Osonoe, Kana
Oto, Tetsuya
Otsuka, Keigo
Ozawa, Masaki

2P-40
1P-33
3P-5
3P-4
2P-14
1P-4
3S-8
2P-20
1P-43
2P-16
3P-3
1P-6
1P-42
2P-8
3P-15
1P-21, 2P-28
1P-44, 2-7<P>Pu, Jiang

3P-22

<R>
Rahman, Mohammad Jellur
Ruammaitree, Akkawat

2P-29
2P-33

<S>
Sado, Yuki
Sagara, Takumi
Saito, Riichiro
Saito, Susumu
Saito, Takeshi
Saito, Yahachi
Sakai, Seiji
Sakakibara, Hajime
Sakamoto, Shingo
Sakurai, Shunsuke
Sano, Masahito
Sasaki, Fusako
Sasaki, Shuichi
Sasaki, Yuki
Sato, Kentaro
Sato, Satoru
Sato, Shintaroh
Sato, Shogo
Sato, Tohru
Sato, Yoshiaki
Sato, Yoshinori
Sawaki, Yuya

2-9
1P-42
2-6
2P-20
2P-11, 3P-13
1P-47
3-1
1P-12
2-9
1-7, 1P-26, 1P-34,
2P-7, 2P-34, 3-9,
3-11, 3-13, 3P-30,
3P-34, 3P-36
3-6
Shiomi, Junichiro
2P-45
Shiraki, Yuki
3-10, 3P-10
Shiromaru, Haruo
2P-22, 3P-41
Shoji, Mao
1P-46
Simizu, Kazuki
2P-6
Slanina, Zdenek
2P-27
So, Yeong-Gi
1P-33
Sobe, Yuhei
1P-10
Soga, Tetsuo
2P-36
Solís-Fernández, Pablo
2P-42
Sone, Junki
2-9
Sorokin, Pavel
2P-43
Souma, Satofumi
3P-29
Su, Yuquan
Subramaniam, Chandramouli 3-4
1P-46, 1P-47
Suda, Yoshiyuki
1P-24, 2P-46
Sugai, Toshiki
3-11
Sugimoto, Kunihisa
3P-38
Suguru, Noda
3P-30
Sun, Yun
3P-9
Susumu, Okada
2P-17
Suzuki, Hideaki
3P-33
Suzuki, Hironori
2P-6
Suzuki, Mitsuaki
1P-15
Suzuki, Takashi

Sekiguchi, Tetsuhiro
Shames, Alexander. I.
Shibata, Okinaga
Shibuya, Megumi
Shimada, Takashi
Shimizu, Kazuki
Shimizu, Maki
Shimizu, Ryo
Shimoyama, Iwao
Shinohara, Hisanori

3-11
3P-32
1-10, 3-8, 3P-16,
3P-19
1P-39, 3P-17
1P-10, 1P-16, 2P-31
1P-32, 2P-33
2-9, 2P-10, 3P-43
3P-23
1P-7
1P-23, 3P-31
1P-33
1P-16
1P-43
3-13
3P-19
1-1
2-2
3P-37
2P-5
1P-40, 2-8
2P-17, 3P-23
2P-26- 189 -

<T>
Tachibana, Masaru
Tadera, Shin
Tahara, Yoshio
Takabayashi, Syun
Takada, Yukihiro
Takagi, Kentaro
Takagi, Yuki
Takahashi, Masahiro

2P-8, 2P-37
1P-2
1P-28
1P-33
1P-38
3P-1
1P-6, 1P-22, 3P-22
3P-20

Tsukagoshi, Kazahito
Tsuya, Daiju
Tsuzuki, Akiko

1P-40, 1P-42, 2-8,
2P-41
3P-26, 3P-35
1P-38
2P-41
3P-40
1P-6, 1P-12, 1P-22,
2P-12, 2P-18, 3S-7,
3P-22
2P-21
1P-46, 1P-47
1P-31
1-1
1P-36
2P-5
2P-30, 3-1, 3P-5,
3P-11
3P-29
2-3, 3P-20
3P-42
3S-8
2P-10
1P-46, 1P-47
1P-30
3P-16
1P-24
1P-26
1P-18, 3-2
1-10
3P-7
2P-17, 3P-23
1P-31
1P-7
2P-21
3P-4
1P-29
3P-15, 3P-24
1P-17
2P-40
1P-30, 1P-35, 1P-41,
2-11, 2P-36
2S-6, 2-11
3P-40
2P-15

<U>
Uchiyama, Kouya
Ue, Hitoshi
Ueda, Chihiro

1-4
1P-46, 1P-47
3P-6

Takai, Kazuyuki
Takaki, Yuki
Takashima, Kengo
Takashiro, Junichi
Takayama, Yusuke
Takenobu, Taishi
Takesue, Masafumi
Takikawa, Hirofumi
Tamura, Naoki
Tanabe, Fumiyuki
Tanaka, Hideyuki
Tanaka, Kazuyoshi
Tanaka, Takeshi
Tang, Zikang
Tange, Masayoshi
Taniguchi, Takaaki
Taniguchi, Takashi
Tanimoto, Hisanori
Tanoue, Hideto
Tanoue, Shota
Tatsumi, Yuki
Terada, Katsuhide
Thendie, Boanerges
Thurakitseree, Theerapol
Ting, Yu
Togashi, Aimi
Tohji, Kazuyuki
Tomai, Takaaki
Tominaga, Masato
Tomura, Takuya
Toriumi, Naoto
Toyama, Kiyohiko
Tsuchiya, Koji
Tsuda, Yusaku
Tsugawa, Kazuo
Tsuji, Masaharu

Umeda, Yoshito
Umino, Takanori
Urabe, Yasuko
Uruchida, Katsuya
Usui, Shinji

1P-46, 1P-47
1P-20
2P-30
2P-4
3-5

<V>
Vul' Alexander, Ya

1P-42

<W>
Wada, Yoriko
Wada, Yoshifumi
Wakabayashi, Tomonari
Wakamiya, Atsushi
Wakamori, Ikuya
Wang, Feijiu
Wang, Feng
Wang, Jian
Wang, Zhipeng
Warner, Jamie
Watahiki, Ryosuke
Watanabe, Kenji
Watanabe, Satoshi
Wei, Xiaojun
Witek, Henryk

1P-45, 2-6
3P-22
1P-45, 2-6
1-1
1P-26
1P-11
2-4
3-11
2P-39, 3P-41
3P-34
1P-1, 3P-13
3S-8
1P-5
1P-9
1-6, 3-7<X>
Xiang, Rong

3P-29

<Y>
Yahagi, Tatsurou
Yajima, Hirofumi
Yamada, Michio
Yamada, Takatoshi
Yamada, Takeo
Yamago, Shigeru
Yamaguchi, Takashi
Yamaguchi, Takehiro
Yamakoshi, Yoko
Yamamoto, Go
Yamamoto, Hiroshi
Yamamoto, Hiroyuki
Yamamoto, Kazuhiro
Yamamoto, Takahiro
Yamamoto, Yuta
Yamanaka, Ayaka- 190 -

1P-9
1P-17, 2P-24, 3P-15,
3P-24, 3P-32
3P-1, 3P-6
2P-40
2P-41, 3-4
1P-25, 2P-1
1P-29
3S-8
1-2
2P-17
1P-17, 2P-4, 2P-24,
3P-32, 3P-37
3P-3
1P-4
1P-5, 1P-38, 2-2,
2P-43, 3-5, 3P-8
3P-34
3P-18

Yamanoi, Ryoko
Yamasaki, Takashi
Yamauchi, Yasushi
Yamawaki, Hiroshi
Yanagi, Kazuhiro
Yanagi, Yuichiro
Yang, Mei
Yasuda, Hidehiro
Yasuda, Satoshi
Yasuda, Toku
Yasunishi, Tomohiro
Yokoi, Hiroyuki
Yokoi, Tomoya
Yokoyama, A.
Yomogida, Yohei
Yonemura, Taiichiro
Yoo, JongTae
Yoshida, Akira
Yoshida, Kazuma
Yoshida, M.
Yoza, Kenji
Yu, Li
Yudasaka, Masako
Yuge, Ryota
Yumura, Motoo<Z>
Zhang, Jinying
Zhang, Minfang
Zhang, Rui
Zhang, Yijin
Zhao, LiZhao, PeiZhao, Sihan
Zheng, Ming

1P-43
1-3
3P-43
1P-4
1P-2, 1P-6, 1P-12,
1P-22, 2P-12, 2P-14,
2P-18, 3P-22
3P-5
1P-27, 1P-28
2P-31
1P-23, 2P-35
1-7, 2P-38
1P-13
3P-42
3P-40
1P-3, 2P-11
2P-18
1P-47
3P-12
3P-5
2P-36
1P-3, 2P-11
1-4
2P-35
1P-14, 1P-27, 1P-28,
1P-29, 3P-45
1P-29, 3P-45
1P-23, 2P-16, 3P-31,
3-4

3P-30
1P-27, 1P-28
3P-2
1P-12
2P-38, 3P-21
3-2, 3P-13
3-9
2S-4

- 191 -

」෗ࢆࡈᕼᮃࡢ᪉࡬
ࣇ࣮࣭ࣛࣞࣥࢼࣀࢳ࣮ࣗࣈ࣭ࢢࣛࣇ࢙ࣥᏛ఍ࡣࠊᮏㄅᥖ㍕ⴭస≀ࡢ」෗࡟㛵ࡍࡿᶒ฼ࢆ୍⯡♫ᅋἲேᏛ⾡ⴭసᶒ༠఍࡟ጤクࡋ࡚࠾ࡾࡲࡍࠋ
ᮏㄅ࡟ᥖ㍕ࡉࢀࡓⴭస≀ࡢ」෗ࢆࡈᕼᮃࡢ᪉ࡣࠊ
㸦♫㸧Ꮫ⾡ⴭసᶒ༠఍ࡼࡾチㅙࢆཷࡅ࡚ୗࡉ࠸ࠋ
ణࡋࠊ௻ᴗ➼ἲே࡟ࡼࡿ♫ෆ฼⏝┠ⓗࡢ」෗࡟ࡘ࠸࡚ࡣࠊᙜヱ௻ᴗ➼ἲேࡀ♫ᅋἲே᪥ᮏ」෗ᶒࢭ
ࣥࢱ࣮㸦㸦♫㸧Ꮫ⾡ⴭసᶒ༠఍ࡀ♫ෆ฼⏝┠ⓗ」෗࡟㛵ࡍࡿᶒ฼ࢆ෌ጤクࡋ࡚࠸ࡿᅋయ㸧࡜ໟᣓ」෗チㅙዎ⣙ࢆ⥾⤖ࡋ࡚࠸ࡿሙྜ࡟࠶ࡗ࡚ࡣࠊࡑࡢᚲせࡣࡈࡊ࠸ࡲࡏࢇ㸦♫እ㡺ᕸ┠ⓗࡢ」෗࡟ࡘ࠸
࡚ࡣࠊチㅙࡀᚲせ࡛ࡍ㸧ࠋᶒ฼ጤクඛ㸸୍⯡♫ᅋἲேᏛ⾡ⴭసᶒ༠఍
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TEL㸸03-3475-5618  FAX㸸03-3475-5619
E-mail㸸info@jaacc.jp
ὀព㸸」෗௨እࡢチㅙ㸦ⴭస≀ࡢᘬ⏝ࠊ㌿㍕࣭⩻ヂ➼㸧࡟㛵ࡋ࡚ࡣࠊ㸦♫㸧Ꮫ⾡ⴭసᶒ༠఍࡟ጤク⮴ࡋ࡚࠾ࡾࡲࡏࢇࠋ┤᥋ࠊࣇ࣮࣭ࣛࣞࣥࢼࣀࢳ࣮ࣗࣈ࣭ࢢࣛࣇ࢙ࣥᏛ఍࡬࠾ၥ࠸ྜࢃࡏࡃࡔࡉ࠸ࠋ 

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2013 ᖺ 3 ᭶ 11 ᪥ Ⓨ⾜

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ㅮ₇せ᪨㞟㸺ࣇ࣮࣭ࣛࣞࣥࢼࣀࢳ࣮ࣗࣈ࣭ࢢࣛࣇ࢙ࣥᏛ఍㸼
ࠛ113-8656 ᮾி㒔ᩥி༊ᮏ㒓 7-3-1
ᮾி኱Ꮫ ኱Ꮫ㝔ᕤᏛ⣔◊✲⛉ ᶵᲔᕤᏛᑓᨷ
୸ᒣ◊✲ᐊෆ
TEL / FAX 㸸 03-3830-4848
E-mail㸸fntg@photon.t.u-tokyo.ac.jp
URL㸸http://fullerene-jp.org/
༳ๅ / 〇ᮏ 㸦ᰴ㸧๰ᚿ௻⏬

グリーンイノベーションに貢献する革新的で実用向きの材料

カーボンナノホーン

20 nm

10 nm

サンプル販売中！
日本電気株式会社
共通ソリューション開発本部〒108-8423 東京都港区芝五丁目21－6（芝ダイビル）
TEL : 03-3798-6402
E-Mail : info@embedded.jp.nec.co

1グラムからサンプルをご用意しています。
詳しくは、ホームページを御覧ください。
カーボンナノホーン サンプル販売ホームページ
http://www.nec.co.jp/embedded/products/cnh/

溶液中の粒子のナノレベル微細化・分散に

ホーン先端部の振幅の安定性を、より高めた Advance タイプ になりました。
近年のナノテクノロジーの発展及び粉体関連技術の向上により、より微細な粒子に対する乳化分散処理の要望が増えてまいりました。
超音波ホモジナイザーを使用し、均質な乳化分散処理を行い、安定させることにより製品の機能は向上します。
ブランソン社では 20kHz 機と、40kHz 機の 2 タイプを用意しております。
1 次粒子の凝集力にも拠りますが、20kHz 機では 100nm 程度までの分散
力があります。40kHz 機は、さらに細かいレベルで分散ができる可能性があります。

20KHz 超音波ホモジナイザー
BRANSON SONIFIER シリーズ

高周波 40KHz 超音波ホモジナイザー
BRANSON SLPe シリーズ

ブランソン社の製品は、ホーン先端部の振幅の安定性が高く、強力なキャビテーションが得られ、効率良く、再現性の高い分散処理が行えます。

主なアプリケーション
分散
カーボンナノチューブ
磁性粉
ポリマー

粉末冶金

有機顔料

酸化鉄

ラテックス

研磨剤

電池

半導体

電子基盤

金属酸化物

製紙

フィラー
液晶

無機顔料

セラミック

シリカ

セメント

アルミナ

感光体

記録材料

カーボンブラック

ファンデーション

光触媒

触媒

ワクチン

貴金属

金属

宝石

体外診断薬

タイヤ

発酵菌類

歯磨き粉

シャンプー

その他

乳化
エマルジョン製剤 農薬 トナー ラテックス 界面活性剤 クリーム 乳液 クリーム 等------------------------------------------------------

ࢼࣀࣛࣉࢱ࣮

ἢỶỼỉ২ᘐửἜἠἘἁồ
本装置はカーボンナノチューブ・グラフェンや燃料電池用触媒を始めとする
各種ナノ粒子を分散させる事を目的に開発いたしました。

実施例：カーボンナノチューブ・グラフェンの分散、燃料電池触媒評価
納入実績：各大学、自動車メーカー、光学機器メーカー、電子部品メーカー

回転機構付破砕槽

高効率新型破砕槽

標準50mlチューブ

15mlチューブ

ॖ
ửắဇ
Ἑἴೞ
ẇ
ụộẴ
Ẳềấ
Ệ
ấൢ᠉
Ễạẹ
ỪẶ
բẟӳ
ẟẇ
ẪẻẰ
ｴﾈﾙｷﾞｰ収束装置付破砕槽

対象試料 / 特長ṼỽὊἮὅἜἠἓἷὊἨẆ ἧἻὊἾὅẆ ἂἻἧỹὅሁἜἠቩ‫܇‬
Ṽᴾ݅᧍ϼྸ ίἜἠἼἋἁ˯ถὸ ᾉ ๋‫ۥ‬ỉᔕႆ Ὁ ੱ૝ởἅὅᴾᴾᴾᴾᴾἑἱầẝụộẶỮẇᴾ
Ṽᴾ‫ٶ‬౨˳ӷ଺ϼྸ ᵆᵏᵎᵎ᷈ᶊ ῍ ᵐᵎᶋᶊὸ ᾉ ᚾ૰ἓἷὊἨỉᢠ৸ỆợụẆ ᙐૠᚾ૰ửӷ଺ỆϼྸỂẨộẴẇ
Ṽᴾϐྵࣱᑣ‫ ڤ‬ᾉ ‫᠃ׅ‬ೞನỉ੔ဇỆợụ‫ר‬ɟễឬ᪦ඬༀ‫ݧ‬ầӧᏡỂẴẇ
Ṽᴾ˯ᬳ᪦ ᾉ ᭗ࣱᏡ᧸᪦ረỉ੔ဇỆợụẆ ឬ᪦ඬཎஊỉᬳ᪦ử᧸ഥẇṼภࡇСࣂầܾତ ᾉ ἢἋἑἨࡸễỉỂ˯ภẦỤ ᵒᵎḥộỂ˓ॖỆᚨ‫ܭ‬ӧᏡ ίỼἩἉἹὅὸẇ

品名

品 番

包 装 希望販売価格

超音波密閉式分散装置
50 mL チューブ用チップ

NR-350 １UNIT
MM-50WS １SET

￥1,950,000￥54,000-

ギヤー板
冷水循環器

NG350-50
１PC
CP80-R
１UNIT￥9,000￥264,000-

冷水循環器接続ﾁｭｰﾌﾞ

TU-100

使用可能チューブ：マルエム社製 50 mL ねじ口試験管

１PC￥15,000-

1.5mlチューブ

NR-350仕様（予告無く変更する場合があります）
品番
品名
超音波周波数
超音波出力
電源
最低設置スペース概寸
発振ユニット概寸
処理ユニット概寸
消音箱概寸
NR-350 全体重量
ランタイマー
インターバルタイマー (ON)
インターバルタイマー (OFF)
処理本数
付属品
備考

NR-350密閉式超音波分散装置 Nanoruptor
20 ｋＨz380,300,250,130 W（切替式）
100 Ｖ、50/60 Hz、5.5 A
400 (W) × 350 (D) × 680 (H) mm
400 (W) × 280 (D) × 160 (H) mm
250(W) × 200 (D) × 300 (H) mm
400 (W) × 350 (D) × 520 (H) mm
36 Kg
599 サイクル
0 〜 59 秒、デジタル
0 〜 59 秒、デジタル
1 本 (50 mL チューブ ) 〜各種
高性能消音箱、電源ケーブル
接続ケーブル、排水ポンプ取り扱い説明書、ユー ザー登録カード
NR-350 は機器のみです。別途処理量に応じたアクセサリー ( ギヤ - 板 + チップ )をお買い求め下さい。

ᮾ•㟁ᶵᰴᘧ఍♫㈍኎ᨭ᥼㒊ᰩཎࠉPNXULKDU#FRVPRELRFRMS㛤Ⓨ㒊ࠉࠉࠉ➲ཎࠉNVDVDKDU#FRVPRELRFRMS

Create The Next Polymer Analysis

分取 HPLC のスタンダード 好評の NEXT シリーズ
JAI のリサイクル分取 HPLC は発売以来４０年
特に国内外の有機合成研究室で活躍しています。

高性能

使いやすさ

メンテナンス性能

３つの要素を徹底的に追求したNEXTシリーズがあなたのラボの作業効率を飛躍的に向上。 ンパクト＆スマートコ

FeatureGPCリサイクルによるMacrocyclic Oligothiophenesの分離

・ 液晶タッチパネルインターフェイス

次の時代へ
NEXTシリーズ

・ 溶媒置換に便利な自動洗浄機能
・ PCコントロールで遠隔操作・ 同一試料の重ね打ち注入

1st Cycle
2nd Cycle

・ 全自動で繰返し注入＆分取が可能
3rd Cycle

4th Cycle

5th Cycle
6th Cycle

・ 独自のリサイクル（特許）を標準装備

Column: JAIGEL-2.5H+JAIGEL-3H
Eluent: Chloroform
Detector: UV-310B @ 254nm

GPCリサイクルによる位置異性体の分離

1st Cycle
2nd Cycle

37th Cycle

3rd Cycle

38th Cycle

Column: JAIGEL-2H+JAIGEL-2.5H
Eluent: Chloroform
Detector: UV-310B @ 254nm

最大流量・LC-9110NEXT 10ml/min MAX
・LC-9130NEXT 30ml/min MAX

LC-9110NEXT / LC-9130NEXT■ 本社・工場： 〒190-1213■ 大阪営業所： 〒532-0002

東京都西多摩郡瑞穂町武蔵 208
大阪市淀川区東三国 5-13-8-303

TEL 042-557-2331
TEL 06-6393-8511

FAX 042-557-1892
FAX 06-6393-8525■ 名古屋営業所： 〒465-0025

愛知県名古屋市名東区上社 3-609-3D

TEL 052-709-5400

FAX 052-709-5403

誘導体化フラーレン用HPLCカラム

COSMOSIL Buckyprep-D
R● 誘導体化フラーレン用HPLCカラム● トルエン移動相中で誘導体化フラーレンが分離可能■C60インデン付加体の分析例
C60インデンは誘導体化フラーレンの一種であり、有機薄膜太陽電池のn型半導体材料として注目されている化合物です。
コスモシール Buckyprep-Dを用いることにより高い分離性能が得られます。

COSMOSIL Application Data
Buckyprep

Buckyprep-D

Column:Column size: 4.6mmI.D.-250mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30qC
Detection:
UV 325nm
Sample:Inj.Vol.:

C60 [Indene]2 (1.0mg/ml)
1.0Pl

NACALAI TESQUE, INC

Data courtesy of Yusuke Tajima, Dr. Sci.
Organic Optoelectronics Laboratory, RIKEN (Institute of Physics and Chemistry)■Buckyprepシリーズの用途

フラーレン分離のスタンダードカラム

COSMOSIL Buckyprep

誘導体化フラーレンの分離

COSMOSIL Buckyprep-D

金属内包フラーレンの分離

COSMOSIL Buckyprep-M・誘導体化フラーレン (Buckyprep-D)

・金属内包フラーレン (Buckyprep-M)

COSMOSIL Application DataCOSMOSIL Application Data

Column:Buckyprep-D
Column size: 4.6mmI.D.-50mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30qC
Detection:
UV325nmColumn:Buckyprep-M
Column size: 4.6mmI.D.-250mm
Mobile phase: Toluene
Flow rate:
1.0 ml/min
Temperature: 30qC
Detection:
UV312nmSample:Inj.Vol.

(0.125mg/ml)
1; C602; C70(0.250mg/ml)
3; [6,6]-Phenyl-C61 Butyric Acid Methyl Ester[PCBM](0.125mg/ml)
4; [6,6]-Phenyl-C71 Butyric Acid Methyl Ester[ [70]PCBM ](0.375mg/ml)
1.0Pl
NACALAI TESQUE, INC

Sample:Sc2@C76(I)Sc2@C78
Sc2@C80(I)C86

Sample courtesy of Prof. H.Shinohara,
Department of chemistry, Nagoya University

C86

Sc
Sc2@C76(I)C84
C84

Sc2@C78
Sc2@C80(I)NACALAI TESQUE, INC

詳しい情報はWeb siteをご覧ください。

ナカライテスク株式会社〒604-0855

京都市中京区二条通烏丸西入東玉屋町498

価格 ・ 納期のご照会 フリーダイヤル 0120-489-552
製品に関するご照会 TEL : 075-211-2746 FAX : 075-211-2710

Web site :http://www.nacalai.co. jp

書籍のご案内カーボンナノチューブ・
グラフェンハンドブック

カーボンナノチューブの基礎

フラーレン・ナノチューブ・
グラフェン学会 編
B5判／368頁
定価10,500円

齋藤弥八・坂東俊治
共著
A5判／220頁
定価2,940円

本ハンドブックでは，カーボンナノチューブの基本的事項を解説しながら，エレクトロニクスへの応用，近赤外発光と吸収によるナノチューブの評
価と光通信への応用の可能性を概観。最近嘱目のグラフェンやナノリスクについても触れた。

カーボンナノチューブはC 60フラーレンに次ぐ新しい炭素材料であり，エレクトロニクスやエネル
ギー分野への応用が注目されている。本書は，ナノチューブとその関連物質の作製法，構造，物性および応用を平易に述べた入門書である。

カーボンナノチューブの材料科学入門

シミュレーション辞典

齋藤弥八 編著
坂東俊治・中山喜萬・
春山純志・久保佳実
共著
A5判／250頁
定価3,570円

日本シミュレーション学会 編
A5判／452頁
定価9,450円

材料科学に新分野を創出し，エレクトロニクスからエネルギー分野まで広範囲な応用が期待される
ナノテクノロジー材料の典型物質「カーボンナノチューブ」について，その製法から物性，実用の可能性までを解説した。

シミュレーションの内容を共通基礎，電気・電子，
機械，環境，生命，社会，可視化，通信の八つに区分し，シミュレーションの学理と技術に関する広範囲の内容について，1ページを1項目として
約380項目をまとめた。

科学技術と共に歩む

株式
会社

コロナ社

〒１
１２-０
０
１
１ 東京都文京区千石４-４
６１- ０ 振替０
０
１
４
０-８１
-４８
４
４
TEL（０
３）
３
９
４
１-３
１
３
１
（代）
，-３
１
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１
３３
（営業部直通）http://www.coronasha.co.jp
FAX（０
３）
３
９４
１-３
１
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E-mail eigyo@coronasha.co.jp

リ チ ウ ム 内 包 フ ラ ー レ ン は L i + @ C 60
L i ĸȤȪɳȟю୞Ǹೄ۳ǢǨǬ A60 ȟܺǰǳτෟࡱՙ൓ࢦǑࣵ‫ޑ‬ȟయǕǬࢡǤǑĥಠ݄ĥǙ‫ݱ‬ĕǵ‫ܬ‬Ȍ߾ǢșǳǑȋǦÿ

㼇㻸㼕+䠜㻯60㼉 䞉 㻼㻲6䠉㻿㻚㻭㼛㼥㼍㼓㼕㻘㻌㻴㻚㻿㼔㼕㼚㼛㼔㼍㼞㼍㻌㼑㼠㻚㼍㼘㻚㻘㻌㻭㼚㼓㼑㼣㻚㻯㼔㼑㼙㻚㻵㼚㼠㻚㻱㼐㻚㻌㻞㻜㻝㻞㻘㻡㻝㻘㻟㻟㻣㻣㻙㻟㻟㻤㻝㻌㉸ศᏊ㘒య䛾㛗ᑑ࿨ග㟁Ⲵศ㞳≧ែ㻲㼡㼗㼡㼦㼡㼙㼕㻘㻌㻿㻚㻌㼍㼚㼐㻌㼀㼍㼚㼕㻘㻌㻲㻚㻌㼑㼠㻌㼍㼘㻚㻘㻌㻯㼔㼑㼙㻚㻌㻿㼏㼕㻚㻌㻞㻜㻝㻟㻘㻌㻡㻘㻌㼕㼚㻌㼜㼞㼑㼟㼟㼟ᕧ኱䛺㟁Ẽ཮ᴟᏊ䝰䞊䝯䞁䝖䜢ᣢ䛴
㻸㼕+@C60 䞉 㻼㻲6- 䜲䜸䞁ᑐ䞊ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷Ḓᇆ┦ඛ⏕䞊䜲䜸䞁䛻䜘䜛㟁Ꮚ⛣ື 㻻㻺㻛㻻㻲㻲 ไᚚ㻲㼡㼗㼡㼦㼡㼙㼕㻘㻌㻿㻚㻌㼑㼠㻌㼍㼘㻚㻌㻶㻚㻌㻭㼙㻚㻌㻯㼔㼑㼙㻚㻌㻿㼛㼏㻚㻌㻞㻜㻝㻝㻘㻌㻝㻟㻟㻘㻌㻝㻡㻥㻟㻤ึ䜑䛶䝸䝏䜴䝮䜲䜸䞁䛾ෆໟ໬䜢ド᫂䛧䛯 㼇㻸㼕+@C60](SbCl6㻕 ༢⤖ᬗ㻿㻚㻌㻭㼛㼥㼍㼓㼕㻘㻌㻴㻚㻿㼍㼣㼍㻘㻌㻴㻚㼀㼛㼎㼕㼠㼍㻌㼑㼠㻌㼍㼘㻚㻘㻺㼍㼠㼡㼞㼑㻌㻯㼔㼑㼙㼕㼟㼠㼞㼥㻘㻌㻞㻘㻌㻢㻣㻤㻌㻔㻞㻜㻝㻜㻕㻚㻴㻚㻌㼁㼑㼚㼛㻘㻌㻷㻚㻌㻷㼛㼗㼡㼎㼛㻘㻌㼀㻚㻌㻻㼟㼔㼕㼙㼍㻌㼑㼠㻌㼍㼘㻚㻌㻺㼍㼚㼛㼟㼏㼍㼘㼑㻘㻌㻞㻜㻝㻟㻘㻌㻡㻘㻌㼕㼚㻌㼜㼞㼑㼟㼟㻚

㼇㻸㼕+䠜㻼㻯㻮㻹㼉㻼㻲6㼅㻚㻹㼍㼠㼟㼡㼛㻘㻌㻴㻚㻻㼗㼍㼐㼍㻌㼑㼠㻚㼍㼘㻚㻘㻌㻻㼞㼓㻚㻸㼑㼠㼠㻌㻞㻜㻝㻞㻘㻝㻠㻘㻟㻣㻤㻠㻚

001B01 リチウム内包フラーレンクラスター
L i +@ C 6 0 を 中 心 に 据 え て そ の 周 囲 を 十 数 個 のC 60 が取り囲むように凝集した粉末
001D04 リチウム内包フラーレン PF
化学式 ： [Li@C

1,000

mg

500,000

円

500

mg

250,000円

10mg210,000円

20mg390,000円

30

mg

570,000円

40mg

747,000円

50mg930,000円

18,600円

6 塩

6 0] （ P F 6 )L i +@ C 6 0 と P F 6 - が 1 : 1 で 対 を 成 す
微結晶の粉末50mg 以上の mg 当たりの単価
TS001 リチウム内包フラーレンクラスター特別試作品
L i +@ C 6 0 , L i , C 6 0 , の 混 成 体 粉 末 を A r
雰囲気中で梱包したもの

1,000

mg

400,000

円

500

mg

200,000円㻸㼕㻬㻯 60 䛾 〇 㐀 䞉 ㈍ ኎e-mai l : info@ide a - i . j p
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Part of Thermo Fisher Scientific䝣䝻䞁䝔䜱䜰䜹䞊䝪䞁䛾䝣䝷䞊䝺䞁〇ရ⣧ᗘ㻔㻴㻼㻸㻯㠃✚䠂䚸௦⾲್䠅
ෆᐜ௚

᭱పᩘ㔞
䠄䡃䠅
10
2
2
1
1

ST

99
99.5
99.5/ ᪼⳹⢭〇ရ
99.9/ ᪼⳹⢭〇ရ
99.9/ ᪼⳹⢭〇/ ༢⤖ᬗရ97SU98/ ᪼⳹⢭〇ရ

0.5

ศᏊᵓ㐀

㖭䚷䚷᯶
ST
TL
SU
SUH
SC

nanom purple䝣䝷䞊䝺䞁 C60

nanom orange䝣䝷䞊䝺䞁 C70

nanom mix
nanom spectra[60]PCBM(phenyl C61-butyric acid methyl
ester)䚷䚷䚷 C60,C70, 䛭䛾௚㧗ḟ䚷䚷䚷䝣䝷䞊䝺䞁䛾ΰྜ≀䚷䚷䚷 䈜ᚤ⢏໬ရ䠄 ST-F䠅䜒䛒䜚䜎䛩
99

STΰྜ䝣䝷䞊䝺䞁

E100

O
O

50
1

E100H

99.5

1

E102

99.9

0.5

98/ ␗ᛶయ䝖䞊䝍䝹1

nanom spectra䚷E400
bis[60]PCBM䈜఩⨨␗ᛶయ䛾ΰྜ≀(bis-phenyl C61-butyric acid methyl ester)

nanom spectra䚷E123

O

O
O

O

[60,70]PCBM

nanom spectra

E110(phenyl C71-butyric acid methyl
ester)

E112[70]PCBM

1㼇㻢㻜㼉㻼㻯㻮㻹䚸㼇㻣㻜㼉㻼㻯㻮㻹䛾ΰྜ≀

199/ ␗ᛶయ䝖䞊䝍䝹

0.5

O
O

䈜఩⨨␗ᛶయ䛾ΰྜ≀99.5/␗ᛶయ䝖䞊䝍䝹୺ᡂศ

nanom spectra䚷Q100[60]䜲䞁䝕䞁௜ຍయnanom spectra䚷㻽㻠㻜 㻜2[60]䜲䞁䝕䞁䠎௜ຍయ

2+
2+ n/20.5

99/ ␗ᛶయ䝖䞊䝍䝹

1

C60OHn䚷n=10䜢୺ᡂศ䛸䛩䜛ΰྜ≀(n = ca.10)

2+nanom spectra䚷A100Ỉ⣲໬䝣䝷䞊䝺䞁

99䈜఩⨨␗ᛶయ䛾ΰྜ≀nanom spectra䚷D100Ỉ㓟໬䝣䝷䞊䝺䞁

0.5

䈜఩⨨␗ᛶయ䛾ΰྜ≀+n/2

C60Hn䚷 n=30䜢୺ᡂศ䛸䛩䜛ΰྜ≀11(n = ca. 30)

㖭᯶䚸ྲྀᢅᩘ㔞➼䛿ண࿌↓䛟ኚ᭦䛩䜛ሙྜ䛜䛤䛦䛔䜎䛩䚹ண䜑䛤஢ᢎୗ䛥䛔䚹

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