Surface Plasmon Enhanced Vibrational Spectra of Monolayer Assemblies on Gratings and Rough Metal Surfaces

Abstract

Abstract The vibrational spectra of monolayer assemblies of cadmium arachidate on smooth and rough silver substrates were obtained by surface infrared and surface plasmon enhanced Raman spectroscopy. The assemblies were laid down by the Langmuir-Blodgett deposition technique. For Raman scattering the intensity of the incident light was enhanced by grating coupling to surface plasmon optical modes of the metal or to localized plasmon modes in the case of rough surfaces. It was found that the different vibrational frequency regions corresponding, for example, to C-C and C-H stretching modes, were enhanced by selecting different scattering angles for collecting the inelastically scattered light. The Raman spectra of monolayer assemblies in contact with silver islands showed evidence of conformational disorder, i.e., the alkyl chains of some molecules were not in the all-trans configuration. In contrast, the infrared spectra did not show evidence of similar disorder. These observations were explained by assuming that the infrared photons sensed the majority undistorted molecular species, while the Raman photons came from a distorted minority species located in regions where optical electromagnetic fields were enhanced by shape plasmon resonances of the rough silver surface.