Direct and Indirect Interfacial Electron Transfer at a Plasmonic p-Cu7S4/CdS Heterojunction

Yang, Zhicheng; Ghorai, Nandan; Wu, Shengxiang; He, Sheng; Lian, Tianquan

doi:10.1021/acsnano.4c14556

Direct and Indirect Interfacial Electron Transfer at a Plasmonic p-Cu₇S₄/CdS Heterojunction

Journal Article · Wed Jan 01 00:00:00 EST 2025 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.4c14556· OSTI ID:2500392

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Emory University, Atlanta, GA (United States)

Plasmonic semiconductors exhibit significant potential for harvesting near-IR solar energy, although their mechanisms of plasmon-induced hot electron transfer (HET) are poorly understood. We report a transient absorption study of plasmon-induced HET in p-Cu₇S₄/CdS type II heterojunctions. Near-IR excitation of the p-Cu₇S₄ plasmon band at ~1400 nm leads to ultrafast HET into the CdS conduction band with a time constant of <150 fs and a quantum efficiency of ~0.054%. The injected hot electrons remain in CdS with an amplitude-weighted average lifetime of 1.9 ± 0.5 ns, significantly longer than that in Au/CdS heterostructures, suggesting that plasmonic semiconductors can slow down charge recombination due to the presence of a bandgap. The excited near-IR plasmon does not decay by coupling to the interfacial charge transfer transition, likely due to its energy mismatch. This study provides a detailed mechanistic understanding and possible directions for improving plasmonic HET in plasmonic semiconductor heterojunctions.

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Research Organization:: Emory University, Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008798

OSTI ID:: 2500392

Alternate ID(s):: OSTI ID: 2500320

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 1 Vol. 19; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Direct and Indirect Interfacial Electron Transfer at a Plasmonic p-Cu7S4/CdS Heterojunction

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Direct and Indirect Interfacial Electron Transfer at a Plasmonic p-Cu₇S₄/CdS Heterojunction