A TEM and electron energy loss spectroscopy (EELS) investigation of active and inactive silver particles for surface enhanced resonance Raman spectroscopy (SERRS)

A number of silver particles and aggregates of particles were studied using surface enhanced resonance Raman spectroscopy (SERRS), high resolution transmission electron microscopy (HRTEM) and electron energy-loss spectroscopy (EELS). The SERRS mapping/TEM collage method developed previously in our group allows each SERRS active or inactive species to be reliably identified and analysed by each of the techniques in three different instruments. Our aim is to correlate SERRS activity, particle microstructure, chemical composition and electronic properties of each species to gain an insight into the enhancement mechanism. To date, our findings do not reveal any clear link between particle microstructure and SERRS activity. Additionally, the direction of the polarisation of the incident excitation or the presence of interparticle junctions between aggregated particles was not correlated with SERRS activity. However, spectral variations in the EELS data from structurally similar particles and SERRS active and inactive particles suggest that each species is chemically/electronically distinct. Differences in the spectra of single particles, dimers and clusters were also observed. Further analysis of the data, including extraction of the complex dielectric function from the EELS data, will provide an insight into the relationship between these observations and SERRS activity.