Surface-Enhanced Raman Spectroscopy on Amorphous Semiconducting Rhodium Sulfide Microbowl Substrates
Anran Li,
Jie Lin,
Zhongning Huang,
Xiaotian Wang,
Lin Guo
Affiliations
Anran Li
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China; Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing 100191, P. R. China
Jie Lin
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China; Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing 100191, P. R. China
Zhongning Huang
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China; Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing 100191, P. R. China
Xiaotian Wang
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China; Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing 100191, P. R. China; Corresponding author
Lin Guo
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China; Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing 100191, P. R. China; Corresponding author
Summary: Exploring highly surface-enhanced Raman scattering (SERS)-active semiconductors is urgently required for practical applications. Here, with the guidance of theoretical calculations, amorphous rhodium sulfide microbowls with high enhancement factor (1 × 105) and low limit of detection (10−7 M) for rhodamine 6G are successfully developed. This remarkable sensitivity is attributed to quasi-resonance Raman effect and multiple light scattering. The first-principles calculations show that the energy gap of 4-nitrobenzenethiol adsorbed on Rh3S6 is greatly decreased by shifting its lowest unoccupied molecular orbital (LUMO) energy level close to the LUMO of Rh3S6, enabling quasi-resonance Raman effect by visible light. The finite-difference time-domain simulations demonstrate the efficient photon trapping ability enabled by multiple light scattering. The optimum wavelength of ∼633 nm for SERS is predicted in simulations and confirmed in experiments. Our results provide both a deep insight of the photo-driven charge transfer process and an important guidance for designing SERS-active semiconductors. : Chemistry; Analytical Chemistry; Materials Science; Amorphous Material Subject Areas: Chemistry, Analytical Chemistry, Materials Science, Amorphous Material
