表面分子アーキテクト技術を用いる新規グラフェン細線の合成

• Project Area: Molecular Architectonics: Orchestration of Single Molecules for Novel Function
• Project/Area Number: 16H00967
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 坂口 浩司 京都大学, エネルギー理工学研究所, 教授 (30211931)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2017: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2016: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
• Keywords: ナノ材料

Outline of Annual Research Achievements

グラフェンナノリボン(GNR)は、分子幅やエッジ構造に依存した優れた半導体的性質を持つことが理論的に予測され、高性能デバイス応用が期待される新物質である。しかし分子幅や化学構造を規定した、特にジグザグエッジ型GNRの合成法が未開拓であり、その確立が世界的に望まれている。そこで本提案では、我々が開発した２ゾーン型ラジカル重合化学気相成長法を用い、分子設計した原料分子を気化させ、金属表面で重合・脱水素縮環することにより、従来にない新材料創成を目指した。また、走査トンネル顕微鏡を用いた化学構造の可視化・電子状態計測やナノギャップ電極を用いた分子電導計測を行い、未知なる物性を明らかにすることを目的とした。本研究では、新しい気相成長技術を開発し、従来得られなかったGNRを表面合成することに成功した。具体的には、従来用いられてきたGNR気相合成法である超高真空蒸着に対して、我々はラジカル発生帯とGNR成長帯を分離し独立に温度制御する新しい気相成長技術“２ゾーン化学気相成長法”を開発した。この手法を用いて1nm以下の幅を持つ理論的に予測された３種類全てのGNRを高収率で表面上に合成することに初めて成功した。更に、柔軟で且つ対称性の高い“Z型前駆体分子”を設計・合成し気相成長を行い、表面上で非対称構造に変形し、従来報告されていない表面キラル高分子を形成し、この特殊な分子の“形”が効率良い段階的な脱水素縮環反応を行う“新しい触媒機構”を初めて見出した。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] 金属表面を巧みに利用したグラフェンナノリボンの合成-ボトムアップ法による精密合成 (2018)
  • Author(s): 小島崇寛，坂口浩司
  • Journal Title: 化学 Volume: 73(2) Pages: 68-69
  • Peer Reviewed
• [Journal Article] Chiral Discrimination and Manipulation of Individual Heptahelicene Molecules on Cu(001) by Noncontact Atomic Force Microscopy (2018)
  • Author(s): Shiotari Akitoshi, Tanaka Koichi, Nakae Takahiro, Mori Shigeki, Okujima Tetsuo, Uno Hidemitsu, Sakaguchi Hiroshi, Sugimoto Yoshiaki
  • Journal Title: The Journal of Physical Chemistry C Volume: 122 Issue: 9 Pages: 4997-5003
  • DOI: 10.1021/acs.jpcc.8b00487
  • Peer Reviewed
• [Journal Article] On-surface synthesis of graphene clusters from a Z-bar-linkage precursor with quaterphenylbranches (2018)
  • Author(s): Z. Xu, T. Kojima, W. Wang, K. Kaushik, A. Saliniemi, T. Nakae, H. Sakaguchi
  • Journal Title: Materials Chemistry Frontiers Volume: 2(4) Issue: 4 Pages: 775-779
  • DOI: 10.1039/c7qm00577f
  • Peer Reviewed
• [Journal Article] Formation of Dibenzopentalane-linking Polymers under the Two-Zone CVD and Wet Conditions (2017)
  • Author(s): M. Saito, Y. Suda, S. Furukawa, T. Nakae, T. Kojima, H. Sakaguchi
  • Journal Title: Chemistry Letters Volume: 46(8) Issue: 8 Pages: 1099-1101
  • DOI: 10.1246/cl.170396
  • NAID: 130005906995
  • Peer Reviewed
• [Journal Article] Wide graphene nanoribbons produced by interchain fusion of poly(p-phenylene) via two-zone chemical vapor deposition (2017)
  • Author(s): S. Song, T. Kojima, T. Nakae, H. Sakaguchi
  • Journal Title: Chemical Communications Volume: 53 Issue: 52 Pages: 7034-7036
  • DOI: 10.1039/c7cc02849k
  • Peer Reviewed
• [Journal Article] Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface (2017)
  • Author(s): Shiotari Akitoshi, Nakae Takahiro, Iwata Kota, Mori Shigeki, Okujima Tetsuo, Uno Hidemitsu, Sakaguchi Hiroshi, Sugimoto Yoshiaki
  • Journal Title: Nature Communications Volume: 8 Issue: 1 Pages: 16089-16089
  • DOI: 10.1038/ncomms16089
  • NAID: 120006329156
  • Peer Reviewed / Open Access
• [Journal Article] Interchain-linked Graphene Nanoribbons from Dibenzo[g,p]chrysene via Two-zone Chemical Vapor Deposition (2017)
  • Author(s): S. Song, G. Huang, T. Kojima, T. Nakae, H. Uno, H. Sakaguchi
  • Journal Title: Chemistry Letters Volume: 46(10) Issue: 10 Pages: 1525-1527
  • DOI: 10.1246/cl.170614
  • NAID: 130006140003
  • Peer Reviewed / Open Access
• [Journal Article] Orientation and Electronic Structures of Multilayered Graphene Nanoribbons Produced by Two-Zone Chemical Vapor Deposition (2017)
  • Author(s): T. Kojima, Y. Bao, C. Zhang, S. Liu, H. Xu, T. Nakae, K. P. Loh, H. Sakaguchi
  • Journal Title: Langmuir Volume: 33(40) Issue: 40 Pages: 10439-10445
  • DOI: 10.1021/acs.langmuir.7b01862
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 機能性有機分子創成のための分子ひずみを駆使した表面合成法 (2017)
  • Author(s): 塩足亮隼，中江隆博，宇野英満，坂口浩司，杉本宜昭
  • Journal Title: 機能材料 Volume: 37(12) Pages: 60-67
  • Peer Reviewed
• [Journal Article] Effect of Gold Nanoparticle on Photon Upconversion based on Sensitized Triplet-Triplet annihilation in Polymer Films (2017)
  • Author(s): H. Yonemura, Y. Naka, M. Nishino, H. Sakaguchi, S. Yamada
  • Journal Title: Molecular Crystals and Liquid Crystals Volume: 654(1) Issue: 1 Pages: 196-200
  • DOI: 10.1080/15421406.2017.1358044
  • Peer Reviewed
• [Journal Article] Effect of Silver Nanoparticle on Singlet Exciton Fission in Rubrene Films (2017)
  • Author(s): H. Yonemura, Y. Futaoka, T. Taniguchi, H. Sakaguchi, S. Yamada
  • Journal Title: Molecular Crystals and Liquid Crystals Volume: 654(1) Issue: 1 Pages: 209-213
  • DOI: 10.1080/15421406.2017.1358046
  • Peer Reviewed
• [Journal Article] Homochiral polymerization-driven selective growth of graphene nanoribbons (2017)
  • Author(s): H. Sakaguchi, S. Song, T. Kojima, T. Nakae
  • Journal Title: Nature Chemistry Volume: 9(1) Issue: 1 Pages: 57-63
  • DOI: 10.1038/nchem.2614
  • Peer Reviewed
• [Journal Article] Effects of Silver Nanoparticle on Singlet Exciton Fission in Rubrene Films (2017)
  • Author(s): H. Yonemura, Y. Futaoka, T. Taniguchi, H. Sakaguchi, S. Yamada
  • Journal Title: Molecular Crystals and Liquid Crystals Volume: 印刷中
  • Peer Reviewed
• [Journal Article] Switch of the magnetic field effect on photon upconversion based on sensitized triplet-triplet annihilation (2016)
  • Author(s): H. Yonemura, Y. Naka, M. Nishino, H. Sakaguchi, S. Yamada
  • Journal Title: Photochemical & Photobiological Sciences Volume: 15(12) Issue: 12 Pages: 1462-1467
  • DOI: 10.1039/c6pp00264a
  • Peer Reviewed
• [Journal Article] Aggregation-Induced Orange-to-Red Fluorescence of 2,5-Bis(diarylamino)terephthalic Acid Dithioesters (2016)
  • Author(s): M. Shimizu, H. Fukui, M. Nakatani, H. Sakaguchi
  • Journal Title: European Journal of Organic Chemistry Volume: 36 Issue: 36 Pages: 5950-5956
  • DOI: 10.1002/ejoc.201601067
  • Peer Reviewed
• [Presentation] Synthesis of functional nanocarbon molecules by surface-induced conformation-controlled mechanism (2018)
  • Author(s): T. Nakae, H. Sakaguchi
  • Organizer: International Congress on Pure & Applied Chemistry (ICPAC) 2018
  • Int'l Joint Research / Invited
• [Presentation] 生物模倣型金属触媒作用を用いた幅制御したグラフェンナノリボンの合成 (2017)
  • Author(s): 小島崇寛, 宋 少堂, 中江隆博 ,坂口浩司
  • Organizer: 日本化学会第97春季年会（ATPポスター）
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県横浜市）
  • Year and Date: 2017-03-16
• [Presentation] 生物模倣型金属触媒作用を用いた幅制御したグラフェンナノリボンの合成 (2017)
  • Author(s): 小島崇寛, 宋 少堂, 中江隆博 ,坂口浩司
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県横浜市）
  • Year and Date: 2017-03-16
• [Presentation] Fabrication of Acene-Type Graphene Nanoribbons on Au(111) (2017)
  • Author(s): S. Song, T. Kojima, T. Nakae, H. Sakaguchi
  • Organizer: Symposium on Surface Science & Nanotechnology -25th Anniversary of SSSJ Kansai-
  • Place of Presentation: Kyoto International Community House (kokoka)（京都府京都市）
  • Year and Date: 2017-01-24
  • Int'l Joint Research
• [Presentation] 生物模倣触媒を用いる機能性ナノ炭素細線の合成 (2017)
  • Author(s): 坂口浩司
  • Organizer: 応用物理学会関西支部平成29年度第1回 講演会「マテリアルデザインとグリーンデバイスの最前線～関西発、イノベーションと若手研究者からの発信～」
  • Invited
• [Presentation] Conformation-assisted synthesis of acene-type graphene nanoribbons on Au(111) (2017)
  • Author(s): T. Kojima, T. Nakae, H. Sakaguchi
  • Organizer: International Symposium on Pure & Applied Chemistry (ISPAC)2017
  • Int'l Joint Research / Invited
• [Presentation] 生物模倣触媒によるグラフェンナノリボンの表面合成 (2017)
  • Author(s): 坂口浩司
  • Organizer: 第53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
  • Invited
• [Presentation] Biomimetic on-surface synthesis of graphene nanoribbons (2017)
  • Author(s): H. Sakaguchi
  • Organizer: Global Research Efforts on Energy and Nanomaterials (GREEN 2017)
  • Int'l Joint Research / Invited
• [Presentation] Observation of azulene-to-fulvalene rearrangement by AFM (2016)
  • Author(s): A. Shiotari, K. Iwata, T. Nakae, Y. Shinagawa, S. Mori, T. Okujima, H. Uno, H. Sakaguchi, Y. Sugimoto
  • Organizer: 24th International Colloquium on Scanning Probe Microscopy (ICSPM24)
  • Place of Presentation: Honolulu, Hawaii（USA）
  • Year and Date: 2016-12-14
  • Int'l Joint Research
• [Presentation] Surface Synthesis of graphene nanoribbons by conformation-controlled mechanism (2016)
  • Author(s): T. Nakae, H. Sakaguchi
  • Organizer: International Symposium on Pure & Applied Chemistry（ISPAC2016)
  • Place of Presentation: Kuching（Malaysia）
  • Year and Date: 2016-08-15
  • Int'l Joint Research / Invited
• [Presentation] AFM/STM observation of azulene-to-fulvalene rearrangement in a small molecule (2016)
  • Author(s): A. Shiotari, K. Iwata, T. Nakae, Y. Shinagawa, S. Mori, T. Okujima, H. Uno, H. Sakaguchi, Y. Sugimoto
  • Organizer: 19th International Conference on Non-Contact Atomic Force Microscopy
  • Place of Presentation: Nottingham（U.K.）
  • Year and Date: 2016-07-25
  • Int'l Joint Research
• [Presentation] Novel Nanographene Material Synthesized via Chemical Vapor Deposition (2016)
  • Author(s): S. Song, G. Huang, T. Nakae, T. Kojima, H. Sakaguchi
  • Organizer: The 2nd International Symposium on Synthetic Two-Dimensional Polymers (S2DP-2)
  • Place of Presentation: Todaiji Temple Cultural Center（奈良県奈良市）
  • Year and Date: 2016-06-02
  • Int'l Joint Research
• [Presentation] Bottom-up Synthesis of Graphene Nanoribbon with Precise Chiral Edge (2016)
  • Author(s): G. Huang, T. Nakae, T. Kojima, H. Sakaguchi
  • Organizer: The 2nd International Symposium on Synthetic Two-Dimensional Polymers (S2DP-2)
  • Place of Presentation: Todaiji Temple Cultural Center（奈良県奈良市）
  • Year and Date: 2016-06-02
  • Int'l Joint Research
• [Presentation] CVD Synthesis of Acene-Type Graphene Nanoribbons by Surface-Conformation-Driven Mechanism (2016)
  • Author(s): T. Nakae, S. Song, T. Kojima, H. Sakaguchi
  • Organizer: The 2nd International Symposium on Synthetic Two-Dimensional Polymers (S2DP-2)
  • Place of Presentation: Todaiji Temple Cultural Center（奈良県奈良市）
  • Year and Date: 2016-06-02
  • Int'l Joint Research
• [Presentation] Conformation-controlled Selective Growth of Carbon Nanoribbons (2016)
  • Author(s): H. Sakaguchi
  • Organizer: The 2nd International Symposium on Synthetic Two-Dimensional Polymers (S2DP-2)
  • Place of Presentation: Todaiji Temple Cultural Center（奈良県奈良市）
  • Year and Date: 2016-06-02
  • Int'l Joint Research / Invited
• [Presentation] Bottom-up Growth Mechanism of Graphene Nanoribbon on Au(111) Surface (2016)
  • Author(s): S. Song, T. Nakae, T. Kojima, H. Sakaguchi
  • Organizer: The 2nd International Symposium on π-System Figuration
  • Place of Presentation: Community Center Urawa（埼玉県さいたま市）
  • Year and Date: 2016-04-14
  • Int'l Joint Research
• [Book] Molecular Archtectonics: The Third Stage of Single Molecule Electronics (2017)
  • Author(s): T. Nakae, H. Sakaguchi
  • Total Pages: 539
  • Publisher: Springer
  • ISBN: 9783319570952
• [Book] Molecular Archtectonics: The Third Stage of Single Molecule Electronics (2017)
  • Author(s): T. Nakae, H. Sakaguchi, (Ed. by T. Ogawa)
  • Publisher: Springer