Role of nanoparticle surface charge in surface-enhanced Raman scattering

In this work, the role of nanoparticle surface charge in surface-enhanced Raman scattering (SERS) is examined for the common case of measurements made in colloidal solutions of Ag and Au. Average SERS intensities obtained for several analytes (salicylic acid, pyridine, and 2-naphthalenethiol) on Ag and An colloids are correlated with the pH and zeta potential (xi) values of the nanoparticle solutions from which they were recorded. The consequence of the electrostatic interaction between the analyte and the metallic nanoparticle is stressed. The xi potentials of three commonly used colloidal solutions are reported as a function of pH, and a discussion is given on how these influence SERS intensity. Also examined is the importance of nanoparticle aggregation (and colloidal solution collapse) in determining SERS intensities, and how this varies with the pH of the solution. The results show that SERS enhancement is highest at xi potential values where the colloidal nanoparticle solutions are most stable and where the electrostatic repulsion between the particles and the analyte molecules is minimized. These results suggest some important criteria for consideration in all SERS measurements and also provide important insights into the problem of predicting SERS activities for different molecular systems.