Quantifying Wavelength-Dependent Plasmonic Hot Carrier Energy Distributions at Metal/Semiconductor Interfaces

Yu, Yun; Wijesekara, Kanishka D.; Xi, Xiaoxing; Willets, Katherine A.

doi:10.1021/acsnano.9b00219

Quantifying Wavelength-Dependent Plasmonic Hot Carrier Energy Distributions at Metal/Semiconductor Interfaces

Journal Article · Tue Feb 26 00:00:00 EST 2019 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.9b00219· OSTI ID:1608032

^[1]; Wijesekara, Kanishka D. ^[2]; Xi, Xiaoxing ^[2]; ^[2]

Temple Univ., Philadelphia, PA (United States); Temple University
Temple Univ., Philadelphia, PA (United States)

Hot carriers generated from the nonradiative decay of localized surface plasmons are capable of driving charge-transfer reactions at the surfaces of metal nanostructures. Photocatalytic devices utilizing plasmonic hot carriers are often based on metal nanoparticle/semiconductor heterostructures owing to their efficient electron–hole separation ability. The rapid thermalization of hot carriers generated at the metal nanoparticles yields a distribution of carrier energies that determines the capability of the photocatalytic device to drive redox reactions. Here in this paper, we quantify the thermalized hot carrier energy distribution generated at Au/TiO₂ nanostructures using wavelength-dependent scanning electrochemical microscopy and a series of molecular probes with different redox potentials. We determine the quantum efficiencies and oxidizing power of the hot carriers from wavelength-dependent reaction rates and photocurrent across the metal/semiconductor interface. The wavelength-dependent reaction efficiency tracks the surface plasmon resonance spectrum of the Au nanoparticles, showing that the reaction is facilitated by plasmon excitation, while the responses from molecules with different redox potentials shed light on the energy distribution of the hot holes generated at metal nanoparticle/semiconductor heterostructures. The results provide important insight into the energies of the plasmon-generated hot carriers and quantum efficiencies of plasmonic photocatalytic devices.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)

Sponsoring Organization:: AFOSR; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012575

OSTI ID:: 1608032

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 3 Vol. 13; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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