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Orbital-resolved visualization of single-molecule photocurrent channels

Author

Listed:
  • Miyabi Imai-Imada

    (RIKEN)

  • Hiroshi Imada

    (RIKEN
    Japan Science and Technology Agency (JST))

  • Kuniyuki Miwa

    (RIKEN
    Institute for Molecular Science)

  • Yusuke Tanaka

    (RIKEN
    The University of Tokyo)

  • Kensuke Kimura

    (RIKEN)

  • Inhae Zoh

    (RIKEN
    Seoul National University)

  • Rafael B. Jaculbia

    (RIKEN)

  • Hiroko Yoshino

    (RIKEN)

  • Atsuya Muranaka

    (RIKEN)

  • Masanobu Uchiyama

    (RIKEN
    The University of Tokyo)

  • Yousoo Kim

    (RIKEN)

Abstract

Given its central role in utilizing light energy, photoinduced electron transfer (PET) from an excited molecule has been widely studied1–6. However, even though microscopic photocurrent measurement methods7–11 have made it possible to correlate the efficiency of the process with local features, spatial resolution has been insufficient to resolve it at the molecular level. Recent work has, however, shown that single molecules can be efficiently excited and probed when combining a scanning tunnelling microscope (STM) with localized plasmon fields driven by a tunable laser12,13. Here we use that approach to directly visualize with atomic-scale resolution the photocurrent channels through the molecular orbitals of a single free-base phthalocyanine (FBPc) molecule, by detecting electrons from its first excited state tunnelling through the STM tip. We find that the direction and the spatial distribution of the photocurrent depend sensitively on the bias voltage, and detect counter-flowing photocurrent channels even at a voltage where the averaged photocurrent is near zero. Moreover, we see evidence of competition between PET and photoluminescence12, and find that we can control whether the excited molecule primarily relaxes through PET or photoluminescence by positioning the STM tip with three-dimensional, atomic precision. These observations suggest that specific photocurrent channels can be promoted or suppressed by tuning the coupling to excited-state molecular orbitals, and thus provide new perspectives for improving energy-conversion efficiencies by atomic-scale electronic and geometric engineering of molecular interfaces.

Suggested Citation

  • Miyabi Imai-Imada & Hiroshi Imada & Kuniyuki Miwa & Yusuke Tanaka & Kensuke Kimura & Inhae Zoh & Rafael B. Jaculbia & Hiroko Yoshino & Atsuya Muranaka & Masanobu Uchiyama & Yousoo Kim, 2022. "Orbital-resolved visualization of single-molecule photocurrent channels," Nature, Nature, vol. 603(7903), pages 829-834, March.
  • Handle: RePEc:nat:nature:v:603:y:2022:i:7903:d:10.1038_s41586-022-04401-0
    DOI: 10.1038/s41586-022-04401-0
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    Cited by:

    1. Katharina Kaiser & Leonard-Alexander Lieske & Jascha Repp & Leo Gross, 2023. "Charge-state lifetimes of single molecules on few monolayers of NaCl," Nature Communications, Nature, vol. 14(1), pages 1-10, December.

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