4.8 Article

Manipulating Hot-Electron Injection in Metal Oxide Heterojunction Array for Ultrasensitive Surface-Enhanced Raman Scattering

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 43, Pages 51618-51627

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c11977

Keywords

surface-enhanced Raman scattering; heterojunction array; localized surface plasmon resonance; plasmon-induced charge transfer; direct interfacial charge transfer; photoinduced charge transfer

Funding

  1. National Natural Science Foundation of China [11874108, 22004016]
  2. Fundamental Research Funds for the Central Universities [2242021R41069, 2242021R10100, 2242021R20036]

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By using the hot-electron injection strategy, a heterojunction array composed of plasmonic MoO2 and semiconducting WO3-x was designed to achieve unprecedented enhanced PICT efficiency between substrates and molecules. This approach not only achieved a record Raman enhancement factor among metal oxide substrates, but also enabled the ultrasensitive detection of target molecules.
Efficient photoinduced charge transfer (PICT) resonance is crucial to the surface-enhanced Raman scattering (SERS) performance of metal oxide substrates. Herein, we venture into the hot-electron injection strategy to achieve unprecedented enhanced PICT efficiency between substrates and molecules. A heterojunction array composed of plasmonic MoO2 and semiconducting WO3-x is designed to prove the concept. The plasmonic MoO2 generates intense localized surface plasmon resonance under illumination, which can generate near-field Raman enhancement as well as accompanied plasmon-induced hot-electrons. The hot-electron injection in direct interfacial charge transfer and plasmon-induced charge transfer process can effectively promote the PICT efficiency between substrates and molecules, achieving a record Raman enhancement factor among metal oxide substrates (2.12 x 10(8)) and the ultrasensitive detection of target molecule down to 10(-11) M. This work demonstrates the possibility of hot-electron manipulation to realize unprecedented Raman enhancement in metal oxides, offering a cutting-edge strategy to design high-performance SERS substrates.

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