Plasma polymer film designs through the eyes of ToF-SIMS.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used for the detailed chemical characterization of complex organic materials. Of particular interest in biointerface materials, it provides the accurate molecular information on their surface, a prerequisite for the understanding of subsequent interaction with biomaterials. Plasma polymer films are promising biointerface materials, as tuning the deposition parameters allows the control over film stability and density of surface functional groups. However, the optimization of these film properties not only requires a detailed characterization of the film chemistry, but also that of the deposition mechanisms. Here, ToF-SIMS is used within its different operation modes to investigate those on several plasma polymer film designs. The detailed information on surface molecular chemistry, interface conformation, vertical and lateral chemical and cross-linking gradients is gathered and linked to the underlying deposition mechanisms. In combination with other techniques, the interpretation and understanding of the final functional property of the films in terms of protein adsorption and site-specific binding is achieved.