SERS spectra of polyaniline thin films deposited on rough Ag, Au and Cu. Polymer film thickness and roughness parameter dependence of SERS spectra

Surface-enhanced Raman scattering (SERS) has lately proved to be an effective technique which has led to its increasing application for studying the structural properties of conducting polymer thin films. It is generally accepted that the enhancement process has an electromagnetic origin arising from the excitation of surface plasmons (SPs) in the metal support on which the polymer film is deposited. However, the electromagnetic enhancement is also accompanied by a chemical process, on which only scarce experimental data are available at present. The chemical process originates in an increased polarizability of the molecules at the metal surface under the action of an incident radiation, as a result of which new chemical bonds are formed with the atoms of the metal support. This paper is devoted to the study of the SERS spectra under 1064 nm excitation for two forms of polyaniline, one of the emeraldine base type and the other of the emeraldine salt type. Our purpose has been to identify the chemical effects at the polymer/metal interface that are involved in specific modifications of the SERS spectra. The following results concerning SERS spectrum variation with metal support type (Ag, Au and Cu) have been obtained. An oxidation of emeraldine base taking place at the polymer/metal interface has been revealed. In the case of emeraldine salt, an oxidized form of polyaniline, the SERS spectra remain unchanged regardless of the changes in the metal support, which proves the stability of this form. A new result has been obtained as SERS spectroscopy revealed an electron delocalization process taking place in the emeraldine salt molecule as a result of an electron transfer from metal to the polymer molecule occurring on the level of quinoid rings. The concept of a rough Raman-active surface has been clarified by using a parameter ha, similar to the grating groove depth/grating periodicity ratio which occurs when a diffraction grating is used as optic coupler.