Total Landscape of Charge Carrier Transport on Conjugated Polymer Backbones

• Project/Area Number: 18H03918
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 35:Polymers, organic materials, and related fields
• Research Institution: Kyoto University
• Principal Investigator: 関 修平 京都大学, 工学研究科, 教授 (30273709)
• Co-Investigator(Kenkyū-buntansha): 櫻井 庸明 京都大学, 工学研究科, 助教 (50632907) ; 酒巻 大輔 大阪府立大学, 理学(系)研究科(研究院), 助教 (60722741)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Project Status: Granted (Fiscal Year 2021)
• Budget Amount: ¥44,590,000 (Direct Cost: ¥34,300,000、Indirect Cost: ¥10,290,000); Fiscal Year 2021: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000); Fiscal Year 2020: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000); Fiscal Year 2019: ¥9,230,000 (Direct Cost: ¥7,100,000、Indirect Cost: ¥2,130,000); Fiscal Year 2018: ¥19,890,000 (Direct Cost: ¥15,300,000、Indirect Cost: ¥4,590,000)
• Keywords: 界面 / 共役高分子 / 電子輸送 / 移動度 / TRMC / スピン輸送 / FMR / 骨格構造 / FI-TRMC / ESR / マイクロ波 / 伝導度 / Ellipticine / 持続長 / 電荷移動度 / ポリアセチレン

Outline of Annual Research Achievements

本研究は、TRMC@Interfaces/TRMC@Transformation/TRMC-ESR複合計測の３つの完全実験的計測法の確立を目指して研究を進め，令和２年度は，新型コロナウィルスの影響により，国内・国際を問わず学会等における研究成果発表はほとんど見送ったが，一部オンラインによる研究発表に加え，研究目的４）伝導種・スピン状態と電子輸送特性の完全定量分析に対応する研究項目３－ESR-TRMC複合計測による伝導種と輸送能の相関解明について，従来のEU-UHMobコンソーシアムにおけるブリュッセル自由大学・ストラスブール大学等との共同研究に加え，新たに米国Princeton大学と，この手法を利用した新しい共役分子・高分子の構造－電子物性相関に関わる研究に着手した．
ESR-TRMC複合計測の展開においては，TRMC法による伝度計測の鍵過程であるキャリア注入に際し，特に電子還元反応を効率よく引き起こす新たな電子供与体の気体拡散法を用いてin situキャリア(スピン)注入を定量することに成功した．ドープされた検体としてポリフルオレンのマイクロ波空洞共振器中の最大磁場下において計測されるESR信号を用いて，注入スピン数の絶対定量を行い，同時にTRMC計測およびマイクロ波誘導強磁性共鳴を用いた金属高分子接触界面における高分子骨格の配列と電子伝導特性・スピン拡散距離の定量に成功した．特に，ポリフルオレン薄膜中においてはスピン拡散長は数100 nmに達する一方で，電子の並進輸送はこれに直交する方向に主に観測され，純スピン流生成媒体として有効であることを示した．また，共役２次元高分子：COF薄膜においてこれらの手法を適用し，界面における電子輸送特性と，金属ナノ構造への電子移動速度を迅速に定量することに成功し，電子による効率的な還元反応へと至る界面設計指針を得た．

Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

令和２年度の研究計画は，新型コロナウィルスの影響により国内・国際学会発表はほとんど見送ったものの，すでに基幹となるESR-TRMC複合計測における計測システムの構築は令和１年度にほぼ終えていたこともあり，国内外の研究機関との共同研究を含めて，予定以上に順調に推移した．特に当初の研究項目３－ESR-TRMC複合計測による伝導種と輸送能の相関解明の過程で，界面における共役分子・高分子構造の相関解明の中で，電荷の並進輸送に加えて，ほぼ純スピン流といえる共役高分子の非等方的電荷・スピン輸送特性を見出したことは大きく，研究目的４）の本格的な達成と利用を超えた成果につながっている．これらの計測システムをもとにした，国内外の研究機関，主に物質提供を中心とした共同研究も順調に進展しつつある．

Strategy for Future Research Activity

今後の研究推進における最大の問題点は，ほぼ新型コロナウィルスによる測定対象物質の開発遅延に集約される．これまでの標準となる対象物質は，その化学原料も含めてほぼ問題なく入手が可能であったが，これをさらに展開する物質群の設計と合成においては，地域的な感染状況の影響を直接被ると予想されている．現在，研究推進における新しい協力者を開拓しつつあり，本研究機関近傍で物質開発を完結させる・研究協力者の雇用を行う，以上２点によって研究の最終目標に至る予定である．

Research Products

• [Int'l Joint Research] Universidad Complutense de Madrid(スペイン)
• [Int'l Joint Research] Indian Institute of Science(インド)
• [Int'l Joint Research] Technische Universitat Dresden(ドイツ)
• [Int'l Joint Research] Northwestern University(米国)
• [Int'l Joint Research] Universidad Complutense de Madrid(スペイン)
• [Int'l Joint Research] Indian Institute of Science(インド)
• [Journal Article] Protein-directed crystalline 2D fullerene assemblies (2020)
  • Author(s): Mantas Liutkus, Alicia Lopez-Andarias, Sara Mejias, Javier Lopez-Andarias, David Gil-Carton, Ferran Feixas, Silvia Osuna, Wakana Matsuda, Tsuneaki Sakurai, Shu Seki, Carmen Atienza, Nazario Martin, Aitziber L. Cortajarena
  • Journal Title: Nanoscale Volume: 12 Pages: 3614-3622
  • DOI: 10.1039/c9nr07083d
  • NAID: 120006895411
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Fermi Level Pinning Induced by Doping in Air Stable n-Type Organic Semiconductor (2020)
  • Author(s): Shikha Sharma, S. Ghosh, Tanweer Ahmed, Suman Ray, Saurav Islam, Ulrike Salzner, Arindam Ghosh, S. Seki, Satish Patil
  • Journal Title: ACS Appl. Electron. Mater. Volume: 2 Pages: 66-73
  • DOI: 10.1021/acsaelm.9b00742
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Identification of Prime Factors to Maximize the Photocatalytic Hydrogen Evolution of Covalent Organic Frameworks (2020)
  • Author(s): Ghosh, S., Nakada, A., Springer, M.A., Kawaguchi, T., Suzuki, K., Kaji, H., Baburin, I., Kuc, A., Heine, T., Suzuki, H., Abe, R. and Seki, S.
  • Journal Title: Journal of the American Chemical Society Volume: - Pages: 9752-9762
  • DOI: 10.1021/jacs.0c02633
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Electrically Switchable Amplified Spontaneous Emission from Liquid Crystalline Phase of an AIEE‐Active ESIPT Molecule (2020)
  • Author(s): Tsutsui Yusuke、Zhang Wanying、Ghosh Samrat、Sakurai Tsuneaki、Yoshida Hiroyuki、Ozaki Masanori、Akutagawa Tomoyuki、Seki Shu
  • Journal Title: Adv. Opt. Mater. Volume: - Pages: 1902158-1902158
  • DOI: 10.1002/adom.201902158
  • Peer Reviewed
• [Journal Article] Porphyrin Nanowires Developed by High-Energy Single Particle-Triggered Intra-Track Polymerization: Design, Property, and Conjugation with Metal Nanoparticles (2020)
  • Author(s): Tsuneaki Sakurai, Shugo Sakaguchi, Yuki Takeshita, Kazuto Kayama, Akifumi Horio, Masaki Sugimoto, Tetsuya Yamaki, Atsuya Chiba, Yuichi Saitoh, G.B.V.S. Lakshmi, Devesh Kumar Avasthi, and Shu Seki
  • Journal Title: ACS Applied Nano Materials Volume: 3 Pages: 6043-6053
  • DOI: 10.1021/acsanm.0c01242
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Helical Pore Alignment on Cylindrical Carbon (2020)
  • Author(s): Jun Maruyama, Tsutomu Shinagawa, Mitsuru Watanabe, Yukiyasu Kashiwagi, Shohei Maruyama, Toru Nagaoka, Wakana Matsuda, Yusuke Tsutsui, Shu Seki, Hiroshi Uyama
  • Journal Title: Small Volume: 16 Pages: 1905916-1905916
  • DOI: 10.1002/smll.201905916
  • Peer Reviewed
• [Journal Article] Repurposing DNA-binding agents as H-bonded organic semiconductors (2019)
  • Author(s): Fengjiao Zhang, Vincent Lemaur, Wookjin Choi, Prapti Kafle, Shu Seki, Jerome Cornil, David Beljonne, Ying Diao
  • Journal Title: Nature Communications Volume: 10 Pages: 4217-4217
  • DOI: 10.1038/s41467-019-12248-9
  • NAID: 120006726160
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Impact of Unsymmetrical Alkyl-Fluoroalkyl Side Chains over Coil-to-Rod Transition of Soluble Polyacetylenes: Modulation of Electronic Conjugation of Isolated Chains and Their Self-Assembly (2019)
  • Author(s): Yoshihiro Motomura, Yusuke Hattori, Tsuneaki Sakurai, Samrat Ghosh, Shu Seki
  • Journal Title: Macromolecules Volume: 52 Pages: 4916-4925
  • DOI: 10.1021/acs.macromol.9b00629
  • Peer Reviewed / Open Access
• [Journal Article] Rod-like transition first or chain aggregation first? ordered aggregation of rod-like poly(p-phenyleneethynylene) chains in solution (2019)
  • Author(s): Hattori Yusuke、Nishimura Nozomi、Tsutsui Yusuke、Ghosh Samrat、Sakurai Tsuneaki、Sugiyasu Kazunori、Takeuchi Masayuki、Seki Shu
  • Journal Title: Chem. Commun Volume: 55 Pages: 13342-13345
  • DOI: 10.1039/c9cc06892a
  • Peer Reviewed / Open Access
• [Journal Article] Dicyanomethyl Radical-Based Near-Infrared Thermochromic Dyes with High Transparency in the Visible Region (2019)
  • Author(s): Okino Kohei、Sakamaki Daisuke、Seki Shu
  • Journal Title: ACS Materials Letters Volume: 1 Pages: 25-29
  • DOI: 10.1021/acsmaterialslett.9b00049
  • Peer Reviewed
• [Journal Article] Highly Miscible Hybrid Liquid-Crystal Systems Containing Fluorescent Excited-State Intramolecular Proton Transfer Molecules (2019)
  • Author(s): Zhang Wanying、Suzuki Satoshi、Cho SeongYong、Watanabe Go、Yoshida Hiroyuki、Sakurai Tsuneaki、Aotani Mika、Tsutsui Yusuke、Ozaki Masanori、Seki Shu
  • Journal Title: Langmuir Volume: 35 Pages: 14031-14041
  • DOI: 10.1021/acs.langmuir.9b02272
  • Peer Reviewed
• [Journal Article] Cold Crystallization of Ferrocene-Hinged pi-Conjugated Molecule Induced by Limited Conformational Freedom of Ferrocene (2019)
  • Author(s): Yuki Tsujimoto, Tsuneaki Sakurai, Yuichiro Ono, Shusaku Nagano, Shu Seki
  • Journal Title: The Journal of Physical Chemistry B Volume: 123 Pages: 8325-8332
  • DOI: 10.1021/acs.jpcb.9b06880
  • Peer Reviewed
• [Journal Article] Observation of dissociative quasi-free electron attachment to nucleoside via excited anion radical in solution (2019)
  • Author(s): Jun Ma, Anil Kumar, Yusa Muroya, Shinichi Yamashita, Tsuneaki Sakurai, Sergey A. Denisov, Michael D. Sevilla, Amitava Adhikary, Shu Seki, Mehran Mostafavi
  • Journal Title: Nature communications Volume: 10 Pages: 102-102
  • DOI: 10.1038/s41467-018-08005-z
  • NAID: 120006549300
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Impact of the position of the imine linker on the optoelectronic performance of マ?-conjugated organic frameworks (2019)
  • Author(s): S. Ghosh, Y. Tsutsui, K. Suzuki, H. Kaji, K. Honjo, T. Uemura, and S. Seki
  • Journal Title: Molecular Systems Design & Engineering Volume: 4(2) Pages: 325-331
  • DOI: 10.1039/c8me00079d
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Integrated Electromagnetic Wave Spectroscopy Techniques: A Powerful Tool for Optoelectronic and Biochemical Materials (2019)
  • Author(s): Shu SEKI
  • Organizer: The 4th Materials Chemistry Frontiers International Symposium
  • Int'l Joint Research / Invited
• [Presentation] CARBON-BASED ELECTRONIC MATERIALS AND INTERFACES: NON-CONTACT APPROACH (2018)
  • Author(s): Shu SEKI
  • Organizer: 2nd From Carbon-Rich Molecules to Carbon-Based Materials Conference
  • Int'l Joint Research / Invited
• [Presentation] Organic Semiconductor Molecules at the Interfaces: Non-Contact Assessment by Microwave Electrical Conductivity Measurements (2018)
  • Author(s): Shu SEKI
  • Organizer: 233rd ECS Meeting
  • Int'l Joint Research / Invited