In Situ Identification of Spherical Ag Monomers and Dimers at Zeptomole Adsorbate Concentrations by Surface-Enhanced Raman Scattering Correlation Spectroscopy

[Image: see text] We have developed a bright optical setup, especially optimized for surface-enhanced Raman scattering (SERS) correlation spectroscopy. We show that the brightness of the experiment combined with the correlation approach permits in situ access to the size and shape of the SERS-active aggregates in solution despite a very weak SERS signal of the adsorbed molecules. As a result, we demonstrate that dimers and larger SERS-active aggregates can be identified through the temporal fluctuations of the SERS signal of only a few hundred of adsorbed molecules, that is, at zeptomole adsorbate concentrations. Monomers covered by a monolayer of MBA were also identified. These results open a way for single nanoparticle sensing, for single-molecule SERS-active aggregate characterization, or for quantitative monitoring of functionalization processes on metallic objects.