Development of oxidized sulfur polymer films through a combination of plasma polymerization and oxidative plasma treatment.

A novel two-step process consisting of plasma polymerization and oxidative plasma treatment is introduced in this article for the first time for the fabrication of -SO(x)(H)-functionalized surfaces. Plasma-polymerized thiophene (PPT) was initially deposited onto silicon wafers and subsequently SO(x)(H)-functionalized using air or oxygen plasma. The effectiveness of both air and oxygen plasma treatments in introducing sulfur-oxygen groups into the PPT film was investigated as the plasma input specific energy and treatment time were varied. The surface chemistries of untreated and treated PPT coatings were analyzed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS), whereas spectroscopic ellipsometry was used to evaluate the film thickness and ablation rate. Surface chemistry analyses revealed that high concentrations of -SO(x)(H) functionalities were generated on the surface upon either air or oxygen plasma treatment. It was found that, at low plasma input energies, the oxidation process was dominant whereas, at higher energies, ablation of the film became more pronounced. The combination of thiophene plasma polymerization and air/oxygen plasma treatment was found to be a successful approach to the fabrication of -SO(x)(H)-functionalized surfaces.