摘要： Self-assembly of metal nanocrystals is capable to create a gap of sub-nanometer distance for concentrating the incoming light by the strong coupling of surface plasmon resonance, known as “hot spot”. Although the plasmonic property of silver is better than the other metals in the visible range, the superior Raman enhancement of silver comparing to gold is still under debate. To provide direct evidence, in this work, we studied the silver adsorption on assembled gold nanorods (AuNRs) by in situ surface-enhanced Raman scattering (SERS) measurement. The self-assembled AuNR multimers were used as the SERS substrate, where the 4-mercaptophenol (MPh) molecules in our experiment played dual roles as both probe molecules for the Raman scattering and linking molecules for the AuNR assembly in a basic environment. Silver atoms were adsorbed on the surface of gold nanorod assemblies by reduction of Ag+ anions. The stability of the adsorbed silver was guaranteed by the basic environment. We monitored the SERS signal during the silver adsorption with a home-built in situ Raman spectroscopy, which was synchronized by recording the UV-vis absorption spectra of the reaction solution to instantly quantify the plasmonic effect of the silver adsorption. Although a minor change was found in plasmonic resonance wavelength or intensity, the measured SERS signal at specific modes faced a sudden increase by 2.1 folds during the silver adsorption. The Finite element method (FEM) simulation confirmed that the silver adsorption corresponding to the plasmonic resonance variation gave little change to the electric field enhancement. We attributed the mode-specific enhancement mechanism of the adsorption of silver to the chemical enhancement from charge transfer (CT) for targeting molecules with a specific orientation. Our findings provided new insights to construct SERS substrates with higher enhancement factor (EF), which hopefully would encourage new applications in the field of surface-enhanced optical spectroscopies.