Surface enhanced Raman scattering enhancement factors: a comprehensive study

This paper presents an in-depth study of Surface Enhanced Raman Scattering (SERS) enhancement factors (EFs) and cross-sections, including several issues often overlooked. In particular, various possible rigorous definitions of the SERS EFs are introduced and discussed in the context of SERS applications, such as analytical chemistry and single molecule SERS. These definitions highlight the importance of a careful characterization of the non-SERS cross-sections of the probes under consideration. This aspect is illustrated by experimental results for the non-SERS cross-sections of representative SERS probes along with average SERS EFs for the same probes. In addition, the accurate experimental determination of single molecule enhancement factors is tackled with two recently developed techniques, namely: bi-analyte SERS (BiASERS) and temperature-dependent SERS vibrational pumping. We demonstrate that SERS EFs as low as 10(7), as opposed to the figure of 10(14) often claimed in the literature, are sufficient for the observation of single molecule SERS signals, with maximum single molecule EFs typically on the order of similar to 10(14).