Simple strategy to improve surface-enhanced Raman scattering based on electrochemically prepared roughened silver substrates

We develop an easy and effective pathway to improve surface-enhanced Raman scattering (SERS) effects of probe molecules of Rhodamine 6G (R6G) adsorbed on electrochemically prepared roughened Ag substrates. In general SERS studies, SERS-active metal substrates are first prepared. Then probe molecules are adsorbed on them to evaluate the relative SERS effects. In this study, we employ electrochemical oxidation-reduction cycle (ORC) treatments in 0.1 M KCl solutions containing probe molecules of 2×10^-5 M R6G to prepare R6G-adsorbed SERS-active Ag substrates for one step. Encouragingly, based on this strategy, the SERS intensity of adsorbed R6G can be increased by 1 order of magnitude, as compared with that of R6G adsorbed on a roughened Ag substrate beforehand, which was generally shown in the literature. Moreover, this improved SERS effect based on this strategy is also effective for 2×10 ^-9 M probe molecules, which is at a level of single molecule detection based on Ag colloids. It is also effective for probe molecules of ClO₄^- with low Raman cross section and for other electrochemically prepared SERS-active substrates of Au. Further analyses indicate that the increase in SERS activity in this new method is most likely due to the incorporation of more chloride ions into the substrate.