Long-range nature of surface-enhanced Raman scattering

Abstract: The long-range action of surface-enhanced Raman scattering (SERS) is probed via distance-dependent measurements of molecular Raman spectra. To this end, identical SERS substrates composed of irregular silver nanoisland arrays were covered by dielectric spacer layers with variable thickness, and the strength of the SERS signal produced from analyte molecules deposited on top of the structure was analyzed. The obtained distance dependence of the signal strength exhibited a shelf-like behavior up to 30 nm away from the enhancing surface and then rapidly decreased further away. Thus, the observed behavior of the electromagnetic mechanism of SERS enhancement in metal island films contradicts the widely accepted picture of extremely rapid (2-3nm) decay of SERS-enhancement of 2D nanoparticle ensembles. Because of the observed steady enhancement factors at distances of ~30 nm from the surface, SERS can be used for probing the spectra of macromolecules or other objects relatively distant from the metal surface.