Plasmon Scanned Surface-Enhanced Raman Scattering Excitation Profiles

Since the discovery of surface-enhanced Raman spectroscopy (SERS) in 1977, scientists have come to understand the enhancement mechanism, but have been unable to consistently optimize the weak signals inherent in Raman experiments. Surface-enhanced Raman signals originate from excitation of the localized surface plasmon resonance (LSPR) of a nanostructured metal surface, thus producing concentrated electromagnetic fields at the surface of the nanostructure. Design of the nanostructured metal substrate plays an important role in understanding and optimizing SERS experiments. In this research, the size-dependent optical properties accessible by nanosphere lithography (NSL) are exploited to fabricate topographically predictable SERS-active substrates with systematically varying LSPRs. Correlated microextinction and micro-Raman measurements, as well as quantitative implementation of a Raman standard, allow significant improvements over the current method used to optimize SERS experiments. The knowledge gained in the novel plasmon scanned SERS excitation profiles clearly indicates the substrate parameters necessary for experimental optimization and promotes further understanding of the SERS enhancement mechanism.