Post-deposition ageing reactions differ markedly between plasma polymers deposited from siloxane and silazane monomers

Abstract

Plasma polymer coatings deposited from hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDSA) were monitored by XPS, FTIR and contact angle (CA) measurements as they aged in air after fabrication. Of particular interest was the influence of the monomer structure on the long term properties of the plasma deposited materials: in conventionally synthesized organosilicon materials, the siloxane unit provides very good long-term stability whereas the silazane structure is prone to hydrolytic attack. During plasma deposition of both coatings, abstraction of methyl groups was the major activation mechanism and the monomer structure was retained to a substantial extent. In the case of plasma polymerised (pp) HMDSA, however, other reactions such as Si–N bond cleavage resulted in considerably more structural diversity. During storage in air, the ppHMDSO film underwent minor chemical changes such as incorporation of additional siloxane cross-links and a small extent of loss of methyl groups. The chemical structure of both the freshly deposited material and the aged coating were unusually homogeneous, compared with the broad range of chemical structures typically found in most other plasma polymers. The structure of the ppHMDSA coating, in contrast, changed dramatically on ageing: almost all silazane moieties were lost after one year and substantial amounts of oxygen incorporated, mainly in the form of siloxane links. In spite of the initial chemical differences, the two materials became more similar over time, with the final structures of the aged materials based on a cross-linked siloxane backbone. The wettability data reflected the structural differences between the two materials. However, correlations between structures and surface properties were not predictable. The overall wettability of these surfaces was determined by a complex balance of several factors such as chemical structure, topography and mobility.