The observation of single molecule events using surface-enhanced Raman scattering (SERS) is a well-established phenomenon. These events are characterized by strong fluctuations in SERS intensities. High-speed SERS intensity fluctuations (in the microsecond time scale) have been reported for experiments involving single metallic particles. In this work, the high-speed SERS behavior of six different types of nanostructured metal systems (Ag nanoshells, Ag nanostars, Ag aggregated spheres, Au aggregated spheres, particle-on-mirror, and Ag deposited on microspheres) was investigated. All systems demonstrated high-speed SERS intensity fluctuations. Statistical analysis of the duration of the SERS fluctuations yielded tailed distributions with average event durations around 100 μs. Although the characteristics of the fluctuations seem to be random, the results suggest interesting differences between the system that might be associated with the strength distribution and density of the localized SERS hotspots. For instance, systems with more localized fields, such as nanostars, present faster fluctuation bursts compared to metallic aggregates that support spread-out fields. The results presented here appear to confirm that high-speed SERS intensity fluctuations are a fundamental characteristic of the SERS effect.
Plasmon Mapping in Metallic Nanostructures and its Application to Single Molecule Surface Enhanced Raman Scattering: Imaging Electromagnetic Hot-Spots and Analyte Location
