Signal reproducibility in surface-enhanced Raman scattering (SERS) remains a challenge, limiting the scope of the quantitative applications of SERS. This drawback in quantitative SERS sensing can be overcome by incorporating internal standard chemicals between the core and shell structures of metal nanoparticles (NPs). Herein, we prepared a SERS-active core Raman labeling compound (RLC) shell material, based on Au–Ag NPs and assembled silica NPs (SiO2@Au@RLC@Ag NPs). Three types of RLCs were used as candidates for internal standards, including 4-mercaptobenzoic acid (4-MBA), 4-aminothiophenol (4-ATP) and 4-methylbenzenethiol (4-MBT), and their effects on the deposition of a silver shell were investigated. The formation of the Ag shell was strongly dependent on the concentration of the silver ion. The negative charge of SiO2@Au@RLCs facilitated the formation of an Ag shell. In various pH solutions, the size of the Ag NPs was larger at a low pH and smaller at a higher pH, due to a decrease in the reduction rate. The results provide a deeper understanding of features in silver deposition, to guide further research and development of a strong and reliable SERS probe based on SiO2@Au@RLC@Ag NPs.
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