特異な分子特性/集合構造の混成による新しい電子系の開拓

• Project/Area Number: 15073214
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 佐藤 直樹 Kyoto University, 化学研究所, 教授 (10170771)
• Co-Investigator(Kenkyū-buntansha): 吉田 弘幸 京都大学, 化学研究所, 助教 (00283664)
• Project Period (FY): 2003 – 2007
• Project Status: Completed(Fiscal Year 2007)
• Budget Amount: ¥30,300,000 (Direct Cost : ¥30,300,000); Fiscal Year 2007 : ¥4,600,000 (Direct Cost : ¥4,600,000); Fiscal Year 2006 : ¥4,700,000 (Direct Cost : ¥4,700,000); Fiscal Year 2005 : ¥7,900,000 (Direct Cost : ¥7,900,000); Fiscal Year 2004 : ¥7,500,000 (Direct Cost : ¥7,500,000); Fiscal Year 2003 : ¥5,600,000 (Direct Cost : ¥5,600,000)
• Keywords: 分子特性 / 分子集合構造 / 電子系 / 有機薄膜 / フロンティア電子構造 / 分子極性 / 静電挙動 / 電子物性 / 集合構造 / 薄膜 / 誘電率 / 多形 / エネルギー分散 / 両性極性分子 / 熱相転移 / 両性イオン分子 / 自発分極 / フタロシアニン / 電荷担体 / 格子エネルギー / 静電分極 / 電子構造 / 価電子状態 / 空状態 / 広域電子構造 / 大環状π電子錯体 / 電荷分離特性 / 光励起 / 分子場

Research Abstract

本研究は、特異な分子特性と集合構造の混成による新しい電子系の開拓を念頭に置き、1)新奇な分子場が期待できる特徴的な分子の探索・調製、2)特徴的分子の集合化制御による分子場の形成・評価、3)特徴的分子の固有集合状態の光誘起等による外場効果の探査、4)新奇分子場や外場効果に基づく電子系の特性挙動の把握解明、を目指して薄膜、フロンティア電子構造、電子状態特性を軸にして展開した。
1)として、大環状π電子錯体のフタロシアニン化合物、ヘテロ環鎖状縮合分子に加え、分子性導体の分野ではこれまで取り上げられなかった両性極性分子、両性イオン分子などにも着目し、合成・精製を経て結晶・薄膜を作製し、構造-電子構造相関について、フロンティア電子状態の直接的観測を軸にして調べた。2)については、有機電界効果トランジスタの活性層材料に用いられるペンタセンの蒸着薄膜が自然酸化シリコン基板上で示す単結晶相、バルク相、薄膜相の多形に関し、後二者の構造を解析して分子の相対配置と分子間相互作用の相違を明らかにした。その結果を用いて密度汎関数法によるバンド計算を行い、各多形のエネルギー分散の特徴を捉え、電子物性の差異を解明した。フタロシアニン化合物や両性極性分子についても特徴ある結晶・薄膜多形を分子の集合化制御により実現した。3)に関して、両性極性分子の多形間にユニークな相転移を見いだすとともに、非中心対称性の分極結晶構造を導いた両性イオン分子の薄膜が、その表面電位を吸収光の照射により解消することも発見した。4)1〜3で対象とした系の特性や挙動を把握・解明するため、格子エネルギー、誘電特性などについて結晶中の分子の電子分極を考慮した第一原理計算を適宜行い、それぞれの電子系の特徴を捉えさらに新しい分子システムの構築に資する情報を総括した。

Research Products

• [Journal Article] Electronic structure of l, 3, 5-trithia-2, 4, 6-triazapentalenyl on gold surfaces (2008)
  • Author(s): K. Iketaki, K. Kanai, W. Fujita, K. Awaga, J. Tsutsumi, H. Yoshida, N. Sato, M. Knupfer, Y. Ouchi, K. Seki
  • Journal Title: Chem. Phys. Lett. 451 Pages : 58-62
  • Peer Reviewed
• [Journal Article] Aluminum diffusion and reaction in thin films of perylene-3, 4, 9, 10-tetracarboxylic dianhydride : depth profiles and time-dependent diffusion coefficients (2007)
  • Author(s): H. Yoshida, N. Sato
  • Journal Title: Appl. Phys. Lett 91 Pages : 141915
  • Peer Reviewed
• [Journal Article] Synthesis of a donor molecule with metal coordination sites toward multifunctional complexes (2007)
  • Author(s): K. Katoh, T. Sasamori, N. Tokitoh, N. Sato
  • Journal Title: Chem. Lett. 36 Pages : 1122-1123
  • Peer Reviewed
• [Journal Article] X-ray diffraction reciprocal space mapping study of the thin film phase of pentacene (2007)
  • Author(s): H. Yoshida, K. Inaba, N. Sato
  • Journal Title: Appl. Phys. Lett. 90 Pages : 181930
  • Peer Reviewed
• [Journal Article] X-ray diffraction reciprocal space mapping study of the thin film phase of pentacene (2007)
  • Author(s): H. Yoshida, K. Inaba and N. Sato
  • Journal Title: Appl. Phys. Lett. 90 Pages : 1819303
  • Peer Reviewed
• [Journal Article] Synthesis of a donor molecule with metal coordination sites toward multifunctional complexes (2007)
  • Author(s): K. Katoh, T. Sasamori, N. Tokitoh and N. Sato
  • Journal Title: Chem. Lett. 36 Pages : 1122-1123
  • Peer Reviewed
• [Journal Article] Aluminum diffusion and reaction in thin films of perylene-3,4,9,10-tetracarboxylic dianhydride: depth profiles and time-dependent diffusion coefficients (2007)
  • Author(s): H. Yoshida, and N. Sato
  • Journal Title: Appl. Phys. Lett. 91 Pages : 1419153
  • Peer Reviewed
• [Journal Article] Grazing-incidence x-ray diffraction study of pentacene thin films with the bulk phase structure (2006)
  • Author(s): H. Yoshida, N. Sato
  • Journal Title: Appl. Phys. Lett. 89 Pages : 101919
  • Peer Reviewed
• [Journal Article] Frontier electronic structures in fluorinated copper phthalocyanine thin films studied using ultraviolet and inverse photoemission spectroscopies (2006)
  • Author(s): R. Murdey, N. Sato, M. Bouvet
  • Journal Title: Mol. Cryst. Liq. Cryst. 455 Pages : 211-218
  • Peer Reviewed
• [Journal Article] Deposition of acrylonitrile cluster ions on solid substrates : Thin film formation by intracluster polymerization products (2006)
  • Author(s): H. Yoshida, N. Sato
  • Journal Title: J. Phys. Chem. B 110 Pages : 4232-4239
  • Peer Reviewed
• [Journal Article] Dicyanoaurate(I) salts with 1-alkyl-3-methylimidazolium : luminescent properties and room-temperature liquid forming (2006)
  • Author(s): Y. Yoshida, J. Fujii G. Saito, T. Hiramatsu, N. Sato
  • Journal Title: J. Mater. Chew. 16 Pages : 724-727
  • Peer Reviewed
• [Journal Article] Dicyanoaurate(I) Salts with 1-AIkyl-3-methylimidazolium : Luminescent Properties and Room-Temperature Liquid Forming (2006)
  • Author(s): Y.Yoshida, J.Fujii, G.Saito, T.Hiramatsu, N.Sato
  • Journal Title: J.Mater.Chem. 16 Pages : 724-727
• [Journal Article] Deposition of Acrylonitrile Cluster Ions on Solid Substrates : Thin Film Formation by Intracluster Polymerization Products (2006)
  • Author(s): H.Yoshida, N.Sato
  • Journal Title: J.Phys.Chem.B 110 Pages : 4232-4239
• [Journal Article] Frontier Electronic Structures in Fluorinated Copper Phthalocyanine Thin Films Studied Using Ultraviolet and Inverse Photoemission Spectroscopies (2006)
  • Author(s): R.Murdey, M.Bouvet, N.Sato
  • Journal Title: Mol.Cryst.Liq.Cryst. 455 Pages : 211-218
• [Journal Article] Grazing-Incidence X-ray Diffraction Study of Pentacene Thin Films with the Bulk Phase Structure (2006)
  • Author(s): H.Yoshida, N.Sato
  • Journal Title: Appl Phys.Lett. 89 Pages : [101919-1]-[101919-3]
• [Journal Article] Dicyanoaurate(I) Salts with 1-Alkyl-3-methylimidazolium : Luminescent Properties and Room-Temperature Liquid Forming (2006)
  • Author(s): Y.Yoshida, J.Fujii, G.Saito, T.Hiramatsu, N.Sato
  • Journal Title: J.Mater.Chem. 16 Pages : 724-727
• [Journal Article] Deposition of Acrylonitrile Cluster Ions on Solid Substrates : Thin Film Formation by Intracluster Polymerization Products (2006)
  • Author(s): Y.Yoshida, N.Sato
  • Journal Title: J.Phys.Chem.B (印刷中)
• [Journal Article] Frontier Electronic Structures in Fluorinated Copper Phthalocyanine Thin Films Studied Using Ultraviolet and Inverse Photoemission Spectroscopies (2006)
  • Author(s): R.Murdey, M.Bouvet, N.Sato
  • Journal Title: Mol.Cryst.Liq.Cryst. (印刷中)
• [Journal Article] Study of thin films of carrier-doped strontium titanate with emphasis on their interfaces with organic thin films (2005)
  • Author(s): N. Sato, Y. Harada, T. Terashima, R. Kanda, M. Takano
  • Journal Title: Appl. Surf. Sci. 244 Pages : 588-592
  • Peer Reviewed
• [Journal Article] Study of Thin Films of Carrier-Doped Strontium Titanate with Emphasis on Their Interfaces with Organic Thin Films (2005)
  • Author(s): N.Sato, Y.Harada, T.Terashima, R.Kanda, M.Takano
  • Journal Title: Appl.Surf.Sci. 244 Pages : 588-592
• [Journal Article] Study of thin films of carrier-doped strontium titanate with emphasis on their interfaces with organic thin films (2005)
  • Author(s): N.Sato, Y.Harada, T.Terashima, R.Kanda, M.Takano
  • Journal Title: Appl.Surf.Sci. (in press)
• [Presentation] Structures and surface electronic properties of evaporated thin films of a series of zwitterionic molecules (2007)
  • Author(s): J. Tsutsumi, H. Yoshida, N. Sato, S. Kato
  • Organizer: The 4th Workshop on Advanced Spectroscopy of Organic Materials for Electronic Applications
  • Place of Presentation: 千葉
  • Year and Date: 2007-11-11
• [Presentation] IPES and UPS Studies on Frontier Electronic States in Organic Semiconductor Thin Films (2006)
  • Author(s): N. Sato, H. Yoshida, R. J. Murdey
  • Organizer: Asian Pacific Conference on Surface Science and Engineering
  • Place of Presentation: Hong Kong (China)
  • Year and Date: 2006-12-19
• [Presentation] Observation of Electronic Structure of Frontier States in Organic Semiconductor Thin Films (2006)
  • Author(s): N. Sato, H. Yoshida, R. J. Murdey
  • Organizer: Workshop on Charge Carrier Injection $ TransportPhenomena in Organic Thin Films and the 10th European Conference on Organised Films
  • Place of Presentation: Riga (Latvia)
  • Year and Date: 2006-08-20
• [Book] 「有機トランジスタ材料の評価と応用II」中の第3編/第1章「薄膜構造解析」 (2008)
  • Author(s): 吉田弘幸, 佐藤直樹, 稲葉克彦
  • Total Pages: 14
  • Publisher: シーエムシー出版
• [Book] 「有機トランジスタ材料の評価と応用II」中の第3編/第1章「薄膜構造解析」 (2008)
  • Author(s): 吉田弘幸、佐藤直樹、稲葉克彦
  • Total Pages: 14
  • Publisher: シーエムシー出版
• [Book] 「表面物性工学ハンドブック第2版」中の第4章2「逆光電子分光法」 (2007)
  • Author(s): 佐藤直樹
  • Total Pages: 7
  • Publisher: 丸善
• [Book] 表面物性工学ハンドブック 第2版 (2007)
  • Author(s): 佐藤直樹, (小間篤, 青野正和, 石橋幸治, 塚田捷, 常行真司, 長谷川修司, 八木克道, 吉信淳 編)
  • Total Pages: 7
  • Publisher: 丸善
• [Book] 「化学便覧基礎編改訂5版」中の14.1.1、14.1.2、15.9.1、15.9.2、15.9.3 (2004)
  • Author(s): 佐藤直樹
  • Total Pages: 17
  • Publisher: 丸善
• [Remarks] 研究代表者・研究分担者の研究内容・研究成果に関するwebページのURL:
  • URL: http://www.scl.kyoto-u.ac.jp/~yoshida/kenkyugaiyou.htm.
• [Publications] N.Sato, H.Yoshida, K.Tsutsumi: "Unoccupied electronic states in phthalocyanine thin films studied by inverse photoemission spectroscopy"Synth.Metals. 133-134. 673-674 (2003)
• [Publications] N.Sato, H.Yoshida, K.Tsutsumi, M.Sumimoto, H.Fujimoto, S.Sakaki: "Electronic structures of unoccupied states in lithium phthalocyanine thin films of different polymorphs studied by IPES"Appl.Surf.Sci.. 212-213. 438-440 (2003)