Improved Quantitative SERS Enabled by Surface Plasmon Enhanced Elastic Light Scattering.

Abstract

The application of surface-enhanced Raman spectroscopy (SERS) for everyday quantitative analysis is hindered by the point-to-point variability of SERS substrates that arises due to the heterogeneous distribution of localized electromagnetic fields across a suite of plasmonic nanostructures. Herein, we adopt surface-enhanced elastic scattering as a SERS internal standard. Both elastic and inelastic (i.e., Raman) scattering are simultaneously enhanced by a given “hot spot”, and thus, the surface-enhanced elastic scattering signal provides a localized intrinsic internal standard that scales across all of the plasmon-enhanced electromagnetic fields within a substrate. Elastically scattered light originates from the amplified spontaneous emission (ASE) of the commercial laser, leading to the formation of a low-wavenumber pseudo band that arises from the interaction of the ASE and the edge filter. A theoretical model was developed to illustrate the underlying mechanism supporting this normalization approach. The normalized Raman signals are independent of the incident laser intensity and the density of “hot spots” for numerous SERS substrates. Following “hot-spot” (HS) normalization, the coefficient of variation for the tested SERS substrates decreases from 10 to 60% to 2%–7%. This approach significantly improves SERS quantitation of four chloroanilines and enables collection of highly reproducible analyte adsorption results under both static and dynamic imaging conditions. Overall, this approach provides a simple means to improve SERS reproducibility without the need to use additional chemicals as internal standards.