Plasma polymer films were deposited from hexamethyldisiloxane (HMDSO) in a low-pressure discharge. The influence of the energetic conditions in the gas phase as well as at the surface on the densification/cross-linking of the hydrophobic films was studied. The fragmentation of the monomer in the plasma seems to be of similar importance for film densification as the energetic particle interactions at the surface. A map of fragmentation chemical pathways can thus be proposed for HMDSO. The aging and hydration of the HMDSO films were studied and hydration history effects related to the energetic conditions applied in the plasma process were observed. Effective water penetration was possible as evidenced by silver release studies.

Functional plasma polymers were deposited from pure ethylene discharges and with the addition of carbon dioxide or ammonia. The incorporation of oxygen and nitrogen-containing functional groups depends on the fragmentation in the gas phase as well as on the densification during film growth. While a minimum energy per deposited carbon atom is required for cross-linking, the densification and accompanying reduction of functional group incorporation was found to scale linearly with momentum transfer through ion bombardment during film growth.

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 ppSiOx 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.

Vertical chemical gradients extending over a few nanometers were explored. The gradients are based on plasma-polymerized oxygen-containing ethylene (ppOEt) films. Using plasma conditions with low CO2/C2H4 ratio and high energy input, cross-linked films were deposited as base layer, while increasing CO2 and lowering energy input resulted in less cross-linked yet highly functional films as applied as top layer. Aging studies indicate that, in particular, for very thin gradient structures, the cross-linked subsurface zone effectively hinders reorientation of the surface functional groups, thus restricting hydrophobic recovery and oxidation effects.