基板表面における有機ハーフメタル物質の創出

• Project/Area Number: 15J11122
• Research Category: Grant-in-Aid for JSPS Fellows
• Allocation Type: Single-year Grants
• Section: 国内
• Research Field: Functional solid state chemistry
• Research Institution: Nagoya University
• Principal Investigator: 江口 敬太郎 名古屋大学, 物質科学国際研究センター, 特別研究員(PD)
• Project Period (FY): 2015-04-24 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: ポルフィラジン / X線吸収分光 / X線磁気円二色性 / 分子薄膜 / 磁性材料 / 単分子膜 / ラジカル

Outline of Annual Research Achievements

強磁性薄膜上に吸着した金属フタロシアニンや金属ポルフィリンは、強磁性薄膜との磁気相互作用により、バルクや薄膜に比べ強く磁化した状態が分子単層膜試料において報告されてきた。しかしながら、この強磁性薄膜と吸着分子界面における磁気相互作用の強さは、室温に比べて小さく、室温近傍で制御可能な強さの磁気相互作用を実現する必要がある。そのため、金属フタロシアニンと類似した分子骨格を持ち、外縁部が金属フタロシアニンに比べ化学的に活性な金属テトラキスチアジアゾールポルフィラジンの強磁性薄膜との磁気相互作用についてX線磁気円二色性分光法を用いて検討した。鉄、コバルト、ニッケル薄膜上にバナジルフタロシアニンが吸着した系については、測定温度5Kにおいて中心バナジウムイオンと鉄、コバルト薄膜が反強磁性磁気相互作用を示し、ニッケル薄膜上ではこの反強磁性磁気相互作用が極端に弱くなることをこれまでに報告している。一方、本研究において行った鉄およびニッケル薄膜上のバナジルテトラキスチアジアゾールポルフィラジンの系では、鉄およびニッケル薄膜と中心バナジウムイオンとの強い磁気相互作用は確認されなかった。この原因については、配位子と基板との相互作用がフタロシアニンの系に比べ強いため、VOの酸素を下にして吸着したこと、または、酸素を上にして吸着した場合には、外縁部と基板との距離が縮まる一方VOと基板との距離が離れた、分子骨格が歪んだ状態で吸着したことが考えられるが明らかにはできていない。そのため、基板上での吸着構造を考慮した配位子の検討が必要である。

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

• [Int'l Joint Research] Imperial College London(英国)
• [Int'l Joint Research] University of Windsor(カナダ)
• [Int'l Joint Research] Imperial Collage London(United Kingdom)
• [Int'l Joint Research] University of Windsor(Canada)
• [Int'l Joint Research] Imperial Collage London(英国)
• [Journal Article] Influence of Air Exposure on Photocarrier Generation in Amorphous and Phase II Thin Films of Titanyl Phthalocyanine (2018)
  • Author(s): Eguchi Keitaro、Imai Yoshiaki、Matsushita Michio M.、Awaga Kunio
  • Journal Title: The Journal of Physical Chemistry C Volume: 122 Issue: 14 Pages: 7731-7736
  • DOI: 10.1021/acs.jpcc.8b00290
  • Peer Reviewed
• [Journal Article] Multi-functional dithiadiazolyl radicals: Fluorescence, electro-luminescence and photo-conducting behavior in pyren-1′-yl-dithiadiazolyl (2018)
  • Author(s): Yassine Beldjoudi, Mitchell Nascimento, Yong Cho, Hyeonghwa Yu, Hany Aziz, Daiki Tonouchi, Keitaro Eguchi, Michio M. Matsushita, Kunio Awaga, Igor Osorio-Roman, Christos Constantinides and Jeremy Rawson
  • Journal Title: Journal of the American Chemical Society Volume: 印刷中 Issue: 20 Pages: 6260-6270
  • DOI: 10.1021/jacs.7b12592
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Templating effects of tetrakis(thiadiazole)porphyrazine on the structure and optical properties of copper phthalocyanine thin films (2017)
  • Author(s): Keitaro Eguchi, Sandrine Heutz, Kunio Awaga
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 21 Issue: 04-06 Pages: 1-5
  • DOI: 10.1142/s1088424617500171
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Highly-oriented molecular arrangements and enhanced magnetic interactions in thin films of CoTTDPz using PTCDA templates (2016)
  • Author(s): K. Eguchi, C. Nanjo, K. Awaga, H. H. Tseng, P. Robaschik and S. Heutz
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 18 Issue: 26 Pages: 17360-17365
  • DOI: 10.1039/c6cp01932c
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Soft X-ray Absorption Spectroscopy of 1,3,5-trithia-2,4,6-triazapentalenyl Thin Films on Ag(111) (2016)
  • Author(s): Keitaro Eguchi, Kunio Awaga, Yasumasa Takagi, TOshihiko Yokoyama
  • Journal Title: UVSOR ACTIVITY REPORT 2015 Volume: 43 Pages: 113-113
• [Presentation] Magnetic properties of magnetic ionic liquid thin films prepared on Cu(001) and ferromagnetic Co/Cu(001) (2018)
  • Author(s): Keitaro Eguchi, Toshihiko Yokoyama and Kunio Awaga
  • Organizer: The 17th International Conference on X-ray Absorption Fine Structure
  • Int'l Joint Research
• [Presentation] 有機薄膜電界効果トランジスタにおける膜厚依存性のIn-situ実時間測定 (2017)
  • Author(s): 江口敬太郎，阿波賀邦夫，Boldjoudi Yassine，Rawson Jeremy
  • Organizer: 日本化学会第97回春季年会
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2017-03-16
• [Presentation] Templating effects of tetrakis(thiadiazole)porphyrazine on the structure and morphology of copper phthalocyanine thin films (2017)
  • Author(s): Keitaro Eguchi, Sandrine Heutz and Kunio Awaga
  • Organizer: The 9th International Conference on Molecular Electronics and Bioelectronics
  • Int'l Joint Research
• [Presentation] Templating Effects Controlling Structure, Morphology and Magnetism in Porphyrazine Thin Films (2016)
  • Author(s): Peter Robaschik, Keitaro Eguchi, Hsiang-Han Tseng, Chihiro Nanjo, Kunio Awaga, Sandrine Heutz
  • Organizer: European Conference on Molecular Spintronics 2016
  • Place of Presentation: Bologna
  • Year and Date: 2016-11-15
  • Int'l Joint Research
• [Presentation] Highly-Oriented Molecular Arrangements in Thin Films of CoTTDPz Using PTCDA Templates (2016)
  • Author(s): Keitaro Eguchi, Chihiro Nanjo, Hsiang-Han Tseng, Peter Robaschik, Sandrine Heutz, Kunio Awaga
  • Organizer: The 12th Japan-China Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena
  • Place of Presentation: Tokyo
  • Year and Date: 2016-10-16
  • Int'l Joint Research
• [Presentation] 分子薄膜のin situ FET測定 (2016)
  • Author(s): 江口敬太郎，阿波賀邦夫，Boldjoudi Yassine，Rawson Jeremy
  • Organizer: 第10回分子科学討論会
  • Place of Presentation: 神戸ファッションマート
  • Year and Date: 2016-09-13
• [Presentation] Highly-Oriented Molecular Arrangements and Enhanced Magnetic Interactions in Thin Films of CoTTDPz Using PTCDA Templates (2016)
  • Author(s): Keitaro Eguchi, Chihiro Nanjo, Hsiang-Han Tseng, Peter Robaschik, Sandrine Heutz, Kunio Awaga
  • Organizer: The 15th International Conference on Molecule-Based Magnets
  • Place of Presentation: Sendai
  • Year and Date: 2016-09-04
  • Int'l Joint Research
• [Presentation] HIGHLY-ORIENTED MOLECULAR ARRANGEMENTS AND ENHANCED MAGNETIC INTERACTIONS IN THIN FILMS OF CoTTDPz USING PTCDA TEMPLATES (2016)
  • Author(s): Keitaro Eguchi, Chihiro Nanjo, Hsiang-Han Tseng, Peter Robaschik, Sandrine Heutz, and Kunio Awaga
  • Organizer: The 15th International Conference on Molecule-Based Magnets
  • Place of Presentation: Sendai International Center
  • Year and Date: 2016-09-04
  • Int'l Joint Research
• [Presentation] 1,3,5-トリチア-2,4,6-トリアザペンタレニル薄膜の構造と電子状態 (2016)
  • Author(s): 江口敬太郎、阿波賀邦夫
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-25
• [Presentation] PTCDA薄膜上CoTTDPz薄膜の分子配向と磁気特性 (2015)
  • Author(s): 江口敬太郎、Tseng Hsiang-Han、Robaschik Peter、Heutz Sandrine、阿波賀邦夫
  • Organizer: 第9回分子科学討論会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2015-09-18
• [Presentation] Magnetic Properties of Vanadyl Phthalocyanine Adsorbed on Ferromagnetic Iron, Cobalt, and Nickel Films (2015)
  • Author(s): Keitaro Eguchi, Yasumasa Takagi, Takeshi Nakagawa, and Toshihiko Yokoyama
  • Organizer: International Colloquium on Magnetic Films and Surfaces
  • Place of Presentation: Cracow (Poland)
  • Year and Date: 2015-07-14
  • Int'l Joint Research
• [Presentation] Electronic and Magnetic Structures of Vanadium Phthalocyanine Monolayer and Multilayer Films Prepared on Ag(111) (2015)
  • Author(s): Keitaro Eguchi, Takeshi Nakagawa, Yasumasa Takagi, and Toshihiko Yokoyama
  • Organizer: 20th International Conference on Magnetism
  • Place of Presentation: Barcelona (Spain)
  • Year and Date: 2015-07-06
  • Int'l Joint Research