Article

Plasmonic coupling at a metal/semiconductor interface

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Abstract

Integrating plasmonic nanoparticles with semiconductor substrates introduces strong optical resonances that extend and enhance the spectrum of photocatalytic and photovoltaic activity. The effect of plasmonic resonances has been variously attributed to the field nanoconfinement, plasmon–exciton coupling, hot electron transfer, and so on, based on action spectra of enhanced photoactivity. It remains unclear, however, whether energized carriers in the substrate are generated by the transfer of plasmonically generated hot electrons from the metal, as broadly believed, or directly by dephasing of the plasmonic field at the interface. Here, we demonstrate the importance of the direct plasmonic coupling across the chemical interface for hot electron generation at a prototypical Ag nanocluster/TiO2 heterojunction by direct probing of the coherence and hot electron dynamics with two-photon photoemission spectroscopy. Energy, time and material distributions of excitations in the Ag nanocluster/TiO2 heterojunction indicate that dielectric coupling with the substrate renormalizes the plasmon resonance of the Ag nanoparticle, and its dephasing directly generates hot electrons in TiO2 on a <10 fs timescale.

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Acknowledgements

The experimental research was supported by a grant from the NSF (CHE-1414466) and the theory by grants from the NSFC (11620101003, 21421063, 91421313), and National Key Basic Research Program of China (2016YFA0200604, 2017YFA0204904). A.A. was supported by a Fellowship from the Pittsburgh Quantum Institute. The calculations were performed at the Supercomputer Center and Environmental Molecular Sciences Laboratory at PNNL, a user facility sponsored by the DOE Office of Biological and Environmental Research, and the supercomputing centre at USTC. The authors thank A. Sirjoosingh, G. Schatz and R. Lazzari for discussion on the dielectric interactions between Ag nanoclusters and TiO2 substrate.

Author information

Affiliations

  1. Department of Physics and Astronomy and Pittsburgh Quantum Institute, University of Pittsburgh, Pittsburgh, PA, USA

    • Shijing Tan
    • , Adam Argondizzo
    • , Jindong Ren
    • , Jin Zhao
    •  & Hrvoje Petek
  2. ICQD/Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei, Anhui, China

    • Jin Zhao
  3. Key Laboratory of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, University of Science and Technology of China, Hefei, Anhui, China

    • Jin Zhao
  4. Department of Physics, University of Science and Technology of China, Hefei, Anhui, China

    • Liming Liu
    •  & Jin Zhao
  5. Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui, China

    • Jin Zhao

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Contributions

S.T. performed the experiments and wrote the first draft of the manuscript. A.A. set up the experimental apparatus and assisted in the laser operation. J.R. performed the analysis of STM measurements. L.L. performed the theoretical calculations. J.Z. supervised and helped to interpret the calculations. H.P. conceived the experiment, supervised its execution, and finalized the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Jin Zhao or Hrvoje Petek.

Electronic supplementary material

  1. Supplementary Information

    Supplementary characterization and analysis information