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Terahertz dynamics of electron–vibron coupling in single molecules with tunable electrostatic potential


Clarifying electronic and vibronic properties at the individual molecule level provides key insights for future chemistry, nanoelectronics and quantum information technologies. However, information obtained by conventional single-molecule transport measurements is based on time-averaged properties. Here, we report on terahertz (THz) spectroscopy of single fullerene molecules by using a single-molecule transistor geometry. From the time-domain THz autocorrelation measurements, we obtained THz spectra associated with the THz-induced centre-of-mass oscillation of the molecules. The observed spectra reflect the potential profile experienced by the molecule on the metal surface when the number of electrons on the molecule fluctuates by one during the single-electron tunnelling process. Such an ultra-high sensitivity to the electronic/vibronic structures of a single molecule on the addition/removal of a single electron has been achieved as a result of using THz spectroscopy in the single-molecule transistor geometry. This scheme provides an opportunity to investigate the ultrafast THz dynamics of subnanometre-scale systems.

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Fig. 1: Set-up for single-molecule terahertz spectroscopy.
Fig. 2: Teraherz autocorrelation measurements of a single C60 molecule.
Fig. 3: Vibron-assisted tunnelling in a C60 single-molecule transistor.
Fig. 4: Calculated interaction energy for a C60 molecule on a gold surface.

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We thank Y. Arakawa for discussions on single-molecule spectroscopy and S. Ishida for his technical help in the fabrication process. This work is supported by KAKENHI (Grant-in-Aid for Scientific Research) on Innovative Areas ‘Science of hybrid quantum systems’ (15H05868) from the Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT), KAKENHI from Japan Society for the Promotion of Science (JSPS) (16H06709 and 17H01038), the Project for Developing Innovation Systems of MEXT, and the Canon Science Foundation.

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S.Q.D. fabricated the single-molecule transistor samples and carried out the THz measurements. K.H. conceived and supervised the project. K.Y. supported the transport measurements and Y.Z. provided assistance with the THz spectroscopy. I.H. carried out the DFT calculations. S.Q.D., I.H. and K.H. wrote the manuscript with contributions from all authors. All authors contributed to discussions.

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Correspondence to Shaoqing Du or Kazuhiko Hirakawa.

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Du, S., Yoshida, K., Zhang, Y. et al. Terahertz dynamics of electron–vibron coupling in single molecules with tunable electrostatic potential. Nature Photon 12, 608–612 (2018).

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