Electronic and vibrational surface-enhanced Raman scattering: from atomically defined Au(111) and (100) to roughened Au

In surface-enhanced Raman spectra, vibrational peaks are superimposed on a background continuum, which is known as one major experimental anomaly. This is problematic in assessing vibrational information especially in the low Raman-shift region below 200 cm(-1), where the background signals dominate. Herein, we present a rigorous comparison of normal Raman and surface-enhanced Raman spectra for atomically defined surfaces of Au(111) or Au(100) with and without molecular adsorbates. It is clearly shown that the origin of the background continuum is well explained by a local field enhancement of electronic Raman scattering in the conduction band of Au. In the low Raman-shift region, electronic Raman scattering gains additional intensity, probably due to a relaxation in the conservation of momentum rule through momentum transfer from surface roughness. Based on the mechanism for generation of the spectral background, we also present a practical method to extract electronic and vibrational information at the metal/dielectric interface from the measured raw spectra by reducing the thermal factor, the scattering efficiency factor and the Purcell factor over wide ranges in both the Stokes and the anti-Stokes branches. This method enables us not only to analyse concealed vibrational features in the low Raman-shift region but also to estimate more reliable local temperatures from surface-enhanced Raman spectra.