X-ray photoelectron spectroscopy and differential capacitance study of thiol-functional polysiloxane films on gold supports

Polymeric molecules containing multiple thiol groups (polythiols) provide tenacious attachment to metal surfaces such as gold. Polythiol films are also well suited for subsequent derivatization with biomacromolecules through remnant free thiol groups of the film. In this study, 1-3 nm thick layers of a commercial polythiol, poly((mercaptopropyl)methylsiloxane) (PMPMS), are investigated with X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy. XPS is used to reveal the surface coverage of thiolate-Au bonds between the polythiol and the metal support, which is found to be approximately 30% lower than that in alkanethiol self-assembled monolayers. The surface density of thiolate-Au bonds did not depend on film thickness provided sufficient PMPMS material was present. Differential capacitance measurements show that the effective dielectric barrier presented by PMPMS films under aqueous environments corresponds closely to their physical thickness, with even approximately 1 nm films remaining impermeable to electrolyte species. Modification of the films with an oligoethylene glycol compound was also examined, in anticipation of future applications in label-free, impedance-based biomolecular diagnostics.