Surface Depth Analysis of Chemical Changes in Random Copolymer Thin Films Composed of Hydrophilic and Hydrophobic Silicon-Based Monomers Induced by Plasma Treatment as Studied by Hard X-ray Photoelectron Spectroscopy and Neutron Reflectivity Measurements

In this study, a silicon-based copolymer, poly(tris(trimethylsiloxy)-3-methacryloxypropylsilane)- co -poly( N, N -dimethyl acrylamide), thin film was subjected to plasma surface treatment to make its surface hydrophilic (biocompatible). Neutron reflectivity (NR) measurement of the plasma-treated thin film showed a decrease in the film thickness (etching width: ∼20 nm) and an increase in the scattering length density (SLD) near the surface (∼15 nm). The region with a considerably high SLD adsorbed water (D 2 O) from its saturated vapor, indicating its superior surface hydrophilicity. Nevertheless of the hydrophilicity, the swelling of the thin film was suppressed. Hard X-ray photoelectron spectroscopy (HAXPES) performed at various takeoff angles revealed that the thin-film surface (∼20 nm depth) underwent extensive oxidation. NR and HAXPES analysis quantitatively yielded the depth profiling of elemental compositions in a few tens of nm scale. Si oxidation and hydrogen elimination (probably CH 3 groups) in the vicinity of the surface region increased the SLD and decreased the hydrophobicity. A combination of Soft X-ray photoelectron spectroscopy and NR measurements revealed the surface chemical composition and mass density. It was considered that the surface near the film was chemically composed close to SiO 2, forming a gel-like (three-dimensional network) structure that is hydrophilic and suppresses swelling due to moisture, indicating it can be expected to maintain stable hydrophilicity on the film surface.