Composition and Stability of Plasma Polymer Films Exhibiting Vertical Chemical Gradients

Controlling the balance between stability and functional group density in grown plasma polymer films is the key to diverse applications such as drug release, tissue-engineered implants, filtration, contact lenses, microfluidics, electrodes, sensors, etc. Highly functional plasma polymer films typically show a limited stability in air or aqueous environments due to mechanisms like molecular reorganization, oxidation, and hydrolysis. Stabilization is achieved by enhancing cross-linking at the cost of the terminal functional groups such as −OH and −COOH, but also −NH₂, etc. To overcome such limitations, a structural and chemical gradient was introduced perpendicular to the surface plane; this vertical gradient structure is composed of a highly cross-linked base layer, gradually changing into a more functional nanoscaled surface termination layer. This was achieved using CO₂/C₂H₄ discharges with decreasing power input and increasing gas ratio during plasma polymer deposition. The aging behavior and stability of such oxygen-functional vertical gradient nanostructures were studied in air and in different aqueous environments (acidic pH 4, neutral pH ≈ 6.2, and basic pH 10). Complementary characterization methods were used, including angle-resolved X-ray photoelectron spectroscopy (ARXPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) as well as water contact angle (WCA) measurements. It was found that in air, the vertical gradient films are stabilized over a period of months. The same gradients also appear to be stable in neutral water over a period of at least 1 week. Changes in the oxygen depth profiles have been observed at pH 4 and pH 10 showing structural and chemical aging effects on different time scales. The use of vertical gradient plasma polymer nanofilms thus represents a novel approach providing enhanced stability, thus opening the possibility for new applications

Response of Plasma-Polymerized Hexamethyldisiloxane Films to Aqueous Environments

Thin plasma polymer films were deposited in hexamethyldisiloxane (HMDSO) and HMDSO/O₂ low-pressure discharges and their chemical structures analyzed using infrared (IR) spectroscopy and neutron reflectometry (NR). The (plasma-polymerized) ppHMDSO film exhibits hydrophobic, poly­(dimethylsiloxane)-like properties, while the retention of carbon groups is reduced by O₂ addition, yielding a more inorganic, hydrophilic ppSiO_<i>x</i> film. Both films show a minor (vertical) density gradient perpendicular to the substrate, where the exposed film surface seems to be more oxidized, indicating oxidative aging reactions upon contact with air. The hydration and water uptake abilities of the films in aqueous environments were investigated in humid environments using ellipsometry, NR in D₂O, and multiple transmission-reflection IR measurements after equilibration of the films in water