“…Surface-enhanced Raman scattering (SERS) is an increase in Raman efficiency due to extremely localized electromagnetic fields at the surface of, for instance, Au and Ag nanoparticles . These fields can be excited using visible radiation and are tightly confined to only certain areas, known as “plasmonic hotspots”. − Molecules in these hotspots experience enhanced excitation and scattering when probed with the proper laser wavelength and/or polarization. , In recent years, there have been several spectroscopic studies of SERS hotspots consisting of either random structures − or nanofabricated plasmonic antennas. − Plasmonic hotspots are widely explored not only for chemical analysis via SERS, but also for particle/molecule trapping, , enhanced photochemistry, − and even nanolithography. , Images of plasmonic hotspots have been obtained with ∼10 nm resolution by near-field scanning optical microscopy − and with higher resolution by scanning (transmission) electron microscopes using electron energy-loss spectroscopy. − However, while many experiments concentrate on the average optical properties (e.g., the extinction spectrum from a nanoparticle suspension or the transmission spectrum from a nanofabricated substrate) to predict SERS performance, fewer experiments directly probe Raman scattering from single nanostructures (e.g., imaging of subnanoparticle interactions ,− ). Moreover, most reports do not completely explore the time evolution or local origin of fluctuations in the SERS signal.…”