LSP spectral changes correlating with SERS activation and quenching for R6G on immobilized Ag nanoparticles

In terms of chemical enhancement in Surface Enhanced Raman Scattering (SERS), we investigated the effect of halide and other anions to rhodamine 6G (R6G) adsorbed Ag particles that were immobilized on the substrates. The residual species on chemically prepared Ag particles such as citrate or a-carbon were thoroughly substituted by various anions, e. g., Cl-, Br-, I-, SCN-, CN-, or S2O32- anions, whose adsorption features are elucidated by the formation constants for AgX2 (m-1)-, here X denotes the above anions. In particular, Cl-, Br-, or SCN- ions activated SERS of R6G via intrinsic electronic interaction with Ag, whereas CN-, S2O32-, or I- anions quenched it due to their exclusive adsorption onto the Ag surfaces. We found that the activation process with the anions commonly yields a marked blue-shift of the coupled plasmon peak from ca. 650-700 to 500-550 nm in elastic scattering. It is rationalized by slight increase of the gap size between adjacent Ag nanoparticles by only ca. 1 nm based on theoretical simulations. This is probably caused by slight dissolution, oxidative etching, of the particles according to large formation constants of the complexes. Consequently, partly remaining negative charges on the Ag surface, and a slight increase in the gap size, providing huge electric field, facilitated R6G cations to adsorb on the nanoparticles, especially at the junction.