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Semiconductor nanomaterial is a kind of important enhancement substrate in surface-enhanced Raman scattering (SERS), and the charge-transfer (CT) process contributes dominantly when they are used as the enhancement substrate for SERS. Doping has significant effect on the CT process of semiconductor nanomaterials. Yet till now, none attempts have been made to explore how doping affects the CT process between the semiconductor and probe molecules. For the first time, this paper investigates the effect of gallium (Ga) doping on the CT process between ZnO nanoparticles and 4-mercaptobenzoic acid (4-MBA) monolayer. In this paper, a series of Ga-doped ZnO nanoparticles (NPs) with various ratio of Ga and Zn are synthesized and their SERS performances are studied. The study shows that the doped Ga can cause the band gap shrinkage of ZnO NPs and then affect the CT resonance process form the valence band (VB) of ZnO NPs to the LUMO of 4-MBA molecules. The band gap of Ga-doped ZnO NPs is gradually narrowed with the increasing doping concentration, and a minimum value (3.16 eV) is reached with the Ga and Zn ratio of 3.8%, resulting in the maximum degree of CT. This work investigates the effects of doping induced band gap shrinkage on CT using SERS and provides a new insight on improving the SERS performance of semiconductor NPs.

frontiers in chemistry

Investigation of the Charge-Transfer Between Ga-Doped ZnO Nanoparticles and Molecules Using Surface-Enhanced Raman Scattering: Doping Induced Band-Gap Shrinkage