Development of tip-enhanced nonlinear and time-resolved spectroscopic methods at the single molecular level

• Project/Area Number: 19H00889
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 32:Physical chemistry, functional solid state chemistry, and related fields
• Research Institution: University of Hyogo
• Principal Investigator: TAKEUCHI SATOSHI 兵庫県立大学, 理学研究科, 教授 (50280582)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥46,800,000 (Direct Cost: ¥36,000,000、Indirect Cost: ¥10,800,000); Fiscal Year 2022: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2021: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2020: ¥10,270,000 (Direct Cost: ¥7,900,000、Indirect Cost: ¥2,370,000); Fiscal Year 2019: ¥30,030,000 (Direct Cost: ¥23,100,000、Indirect Cost: ¥6,930,000)
• Keywords: 走査型トンネル顕微鏡 / 単一分子 / プラズモン / ラマン散乱 / 吸着構造 / 分子構造 / 局在表面プラズモン / 発光 / フェムト秒パルス / 非線形分光

Outline of Research at the Start

原子スケールの撮像が可能な走査型トンネル顕微鏡技術と100兆分の1秒に迫る極短パルス光技術を融合することにより、高い時空間分解能を併せもつ新たな分光方法論を創出する。これにより、単一分子の非線形・時間分解分光という新たな分野を開拓するとともに、分子の置かれた局所環境と分子特性・振舞いとの相関を解明し、次世代ナノテクノロジーを牽引する分子素子研究の発展に資する知見と方向性を与えることをめざす。

Outline of Final Research Achievements

We pursued structural study of single organic semiconductor molecules adsorbed on a non-flat surface of a metallic tip by tip-enhanced Raman spectroscopy. We first developed a straightforward optical alignment protocol for pinpointing the nano-gap region, which greatly facilitates optical STM experiments. With this technique, we succeeded in observing Raman scattering from a single adsorbate on the tip surface, revealing its translational motions, adsorption dynamics, and charge-transfer interaction with the metal.

Academic Significance and Societal Importance of the Research Achievements

分子素子の実現・実用化には個々の分子が機能する精巧な機構と動作機序を分子科学に立脚し、単一分子レベルで解明することが欠かせない。本研究では、極低温・超高真空走査型トンネル顕微鏡のトンネル接合部位に光を照射することで、探針先端近傍に吸着させた有機半導体分子のラマン散乱信号を観測し、その構造情報と吸着ダイナミクスを明らかにした。これにより、分子の置かれた局所環境と分子の特性および振舞いとの相関を理解することができた。

Research Products

• [Journal Article] Spectroscopic mapping of the gold complex oligomers (dimer, trimer, tetramer, and pentamer) by excited-state coherent nuclear wavepacket motion in aqueous solutions (2023)
  • Author(s): M. Iwamura, R. Urayama, A. Fukui, K. Nozaki, L. Liu, H. Kuramochi, S. Takeuchi, T. Tahara
  • Journal Title: Physical Chemistry Chemical Physics Volume: 25 Issue: 2 Pages: 966-974
  • DOI: 10.1039/d2cp04823j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] General Design Strategy to Precisely Control the Emission of Fluorophores via a Twisted Intramolecular Charge Transfer (TICT) Process (2022)
  • Author(s): Hanaoka Kenjiro、Iwaki Shimpei、Yagi Kiyoshi、Myochin Takuya、Ikeno Takayuki、Ohno Hisashi、Sasaki Eita、Komatsu Toru、Ueno Tasuku、Uchigashima Motokazu、Mikuni Takayasu、Tainaka Kazuki、Tahara Shinya、Takeuchi Satoshi、Tahara Tahei、Uchiyama Masanobu、Nagano Tetsuo、Urano Yasuteru
  • Journal Title: Journal of the American Chemical Society Volume: 144 Issue: 43 Pages: 19778-19790
  • DOI: 10.1021/jacs.2c06397
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Single-Molecule Raman Spectroscopy of a Pentacene Derivative Adsorbed on the Nonflat Surface of a Metallic Tip (2022)
  • Author(s): Norihiro Aiga, Satoshi Takeuchi
  • Journal Title: The Journal of Physical Chemistry C Volume: 126 Issue: 38 Pages: 16227-16235
  • DOI: 10.1021/acs.jpcc.2c03067
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A straightforward optical alignment protocol for STM-based single molecule spectroscopy (2022)
  • Author(s): Norihiro Aiga, Satoshi Takeuchi
  • Journal Title: Applied Physics Letters Volume: 121 Issue: 9 Pages: 091601-091601
  • DOI: 10.1063/5.0107414
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Ultrafast dynamics of an azobenzene-containing molecular shuttle based on a rotaxane (2022)
  • Author(s): M. M. Sartin, M. Osawa, S. Takeuchi, T. Tahara
  • Journal Title: Chemical Communications Volume: 58 Issue: 7 Pages: 961-964
  • DOI: 10.1039/d1cc06093g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] フェムト秒時間分解インパルシブ誘導ラマン分光による光誘起結合生成ダイナミクスの実時間構造追跡 (2022)
  • Author(s): 倉持光、竹内佐年、岩村宗高、田原太平
  • Journal Title: 光学 Volume: 51 Pages: 1-7
  • Peer Reviewed
• [Journal Article] Femtosecond time-resolved absorption study of signaling state of a BLUF protein PixD from the cyanobacterium synechocystis: hydrogen bond rearrangement completes during forward proton-coupled electron transfer (2021)
  • Author(s): T. Fujisawa, S. Masuda, S. Takeuchi, T. Tahara
  • Journal Title: Journal of Physical Chemistry B Volume: 125 Issue: 44 Pages: 12154-12165
  • DOI: 10.1021/acs.jpcb.1c05957
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Excited-state proton transfer dynamics in LSSmOrange studied by time-resolved impulsive stimulated Raman spectroscopy (2021)
  • Author(s): P. Kumar, E. Fron, H. Hosoi, H. Kuramochi, S. Takeuchi, H. Mizuno, T. Tahara
  • Journal Title: Journal of Physical Chemistry Letters Volume: 12 Issue: 31 Pages: 7466-7473
  • DOI: 10.1021/acs.jpclett.1c01653
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Skeletal structure of the chromophore of photoactive yellow protein in the excited state investigated by ultraviolet femtosecond stimulated Raman spectroscopy (2021)
  • Author(s): H. Kuramochi, S. Takeuchi, H. Kamikubo, M. Kataoka, T. Tahara
  • Journal Title: Journal of Physical Chemistry B Volume: 125 Issue: 23 Pages: 6154-6161
  • DOI: 10.1021/acs.jpcb.1c02828
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Mode-specific vibrational analysis of exciton delocalization and structural dynamics in conjugated oligomers (2021)
  • Author(s): W. Kim, S. Tahara, H. Kuramochi, S. Takeuchi, T. Kim, T. Tahara, D. Kim
  • Journal Title: Angewandte Chemie International Edition Volume: 60 Issue: 31 Pages: 16999-17008
  • DOI: 10.1002/anie.202102168
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State (2020)
  • Author(s): Iwamura Munetaka、Fukui Airi、Nozaki Koichi、Kuramochi Hikaru、Takeuchi Satoshi、Tahara Tahei
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 51 Pages: 23154-23161
  • DOI: 10.1002/anie.202011813
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Time-domain observation of surface-enhanced coherent Raman scattering with 10^5 -10^6 enhancement (2020)
  • Author(s): P. Kumar, H. Kuramochi, S. Takeuchi, T. Tahara
  • Journal Title: Journal of Physical Chemistry Letters Volume: 11 Issue: 15 Pages: 6305-6311
  • DOI: 10.1021/acs.jpclett.0c01411
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Femtosecond Polarization Switching in the Crystal of a [CrCo] Dinuclear Complex (2020)
  • Author(s): Kuramochi Hikaru、Aoyama Genki、Okajima Hajime、Sakamoto Akira、Kanegawa Shinji、Sato Osamu、Takeuchi Satoshi、Tahara Tahei
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 37 Pages: 15865-15869
  • DOI: 10.1002/anie.202004583
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Tracking photoinduced Au-Au bond formation through transient terahertz vibrations observed by femtosecond time-domain Raman spectroscopy (2019)
  • Author(s): H. Kuramochi, S. Takeuchi, M. Iwamura, K. Nozaki, T. Tahara
  • Journal Title: Journal of American Chemical Society Volume: 141 Issue: 49 Pages: 19296-19303
  • DOI: 10.1021/jacs.9b06950
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Protein Dynamics Preceding Photoisomerization of the Retinal Chromophore in Bacteriorhodopsin Revealed by Deep-UV Femtosecond Stimulated Raman Spectroscopy (2019)
  • Author(s): S. Tahara, H. Kuramochi, S. Takeuchi, T. Tahara
  • Journal Title: Journal of Physical Chemistry Letters Volume: 10 Issue: 18 Pages: 5422-5427
  • DOI: 10.1021/acs.jpclett.9b02283
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Fifth-order time-domain Raman spectroscopy of photoactive yellow protein for visualizing vibrational coupling in its excited state (2019)
  • Author(s): H. Kuramochi, S. Takeuchi, H. Kamikubo, M. Kataoka, T. Tahara
  • Journal Title: Science Advances Volume: 5 Issue: 6
  • DOI: 10.1126/sciadv.aau4490
  • Peer Reviewed / Int'l Joint Research
• [Presentation] 針でなぞり、光でさぐる単一分子の構造と振舞い (2022)
  • Author(s): 竹内佐年
  • Organizer: 九州大学理学部化学教室公開講演会
  • Invited
• [Presentation] 走査型トンネル顕微鏡へのレーザー光の導入技術と単一分子ラマン分光研究 (2022)
  • Author(s): 長澤武範、相賀則宏、竹内佐年
  • Organizer: 兵庫県立大学 知の交流シンポジウム
• [Presentation] 探針増強電場を用いたペンタセン誘導体の単分子ラマン分光と吸着ダイナミクスの観測 (2022)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 第16回分子科学討論会
• [Presentation] 様々な濃度の溶液中におけるジシアノ金(I)錯体の2量体から5量体の核波束運動 (2022)
  • Author(s): 岩村宗高、野崎浩一、Li Liu、倉持光、竹内佐年、田原太平
  • Organizer: 第16回分子科学討論会
• [Presentation] 水溶液中におけるジシアノ金（I）錯体の励起２量体から５量体の吸収・発光および振動スペクトル (2022)
  • Author(s): 岩村宗高、浦山里奈、福井愛理、野崎浩一、Li Liu、倉持光、竹内佐年、田原太平
  • Organizer: 第33回配位化合物の光化学討論会
• [Presentation] STM探針増強電場を用いたペンタセン誘導体の単分子レベルのラマン分光 (2022)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 日本物理学会第77回年次大会
• [Presentation] 走査型トンネル顕微鏡を用いた単一分子レベルの電流誘起発光分光の試み (2021)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 兵庫県立大学 知の交流シンポジウム
• [Presentation] 走査型トンネル顕微鏡を用いたペンタセン誘導体の電流誘起発光の観測 (2021)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 第15回分子科学討論会
• [Presentation] 選択励起された白金(II)錯体会合体の超高速時間分解分光計測 (2021)
  • Author(s): 岩村宗高、渡邊ほのか、野崎浩一、高梨司、倉持光、竹内佐年、田原太平
  • Organizer: 第32回配位化合物の光化学討論会
• [Presentation] マイナーアクチノイド分離用抽出剤 HONTA の電子構造に関する研究 (2021)
  • Author(s): 益田遼太郎、大高咲希、下條竜夫、竹内佐年、足立純一、星野正光、樋川智洋、宮崎康典、佐野雄一、竹内正行
  • Organizer: 日本原子力学会2021年春の年会
• [Presentation] ペンタセン誘導体分子膜のトンネル電流誘起発光分光 (2021)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 日本物理学会第76回年次大会
• [Presentation] 中空ファイバーを用いた極短パルス光伝送の試み (2020)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 兵庫県立大学 知の交流シンポジウム2020
• [Presentation] 分子の構造ダイナミクス追跡とその極限化 (2020)
  • Author(s): 竹内佐年
  • Organizer: 第43回XFEL構造生物ミーティング
  • Invited
• [Presentation] 走査型トンネル顕微鏡の探針電場増強を用いた分光システムの構築 (2020)
  • Author(s): 相賀則宏、竹内佐年
  • Organizer: 日本物理学会 第７５回年次大会
• [Presentation] 水溶液中におけるテトラシアノ白金(II)錯体会合体のコヒーレント振動と励起状態ダイナミクス (2019)
  • Author(s): 岩村宗高、岡田莉奈、野崎浩一、倉持 光、竹内佐年、田原太平
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Ultrafast dynamics and coherent vibrations of [Au(CN)2-]n and [Pt(CN)42-]n oligomers in water (2019)
  • Author(s): M. Iwamura, K. Nozaki, H. Kuramochi, S. Takeuchi, T. Tahara
  • Organizer: 23rd International Symposium on the Photochemistry and Photophysics of Coordination Compounds
  • Int'l Joint Research
• [Presentation] Excited-state dynamics of metallophilic oligomers induced by bond formations among metal atoms (2019)
  • Author(s): M. Iwamura, K. Nozaki, H. Kuramochi, S. Takeuchi, T. Tahara
  • Organizer: The 2nd International Symposium on Soft Crystals
  • Int'l Joint Research / Invited
• [Presentation] Direct observation of ultrafast structural dynamics of the [Au(CN)2-] trimer upon photoinduced tight Au-Au bond formation (2019)
  • Author(s): H. Kuramochi, S. Takeuchi, M. Iwamura, K. Nozaki, T. Tahara
  • Organizer: 10th International Conference on Advanced Vibrational Spectroscopy
  • Int'l Joint Research / Invited
• [Presentation] Nuclear wavepacket motions of metallophilic oligomers in solution (2019)
  • Author(s): M. Iwamura, K. Nozaki, H. Kuramochi, S. Takeuchi, T. Tahara
  • Organizer: 10th International Conference on Advanced Vibrational Spectroscopy
  • Int'l Joint Research / Invited