Summary: Plasma deposited allylamine films were studied by “in situ” ToF‐SSIMS, XPS and NEXAFS Spectroscopy before exposure to ambient air. The influence of external plasma parameters such as duty cycle, plasma power, and monomer flow rate on (i) unsaturation, (ii) branching and cross‐linking, (iii) nitrogen surface concentration and (iv) retention of amino groups was investigated. Harder plasma conditions, which can be obtained when high duty cycles, high plasma power, and low monomer flow rates are employed, increase the unsaturated, branched and cross‐linked character of the plasma deposited films, while the surface concentration of N as well as the retention of the monomer's amino group decrease. As proven by NEXAFS findings and cross‐checked by ToF‐SSIMS results, the allylamine monomer's primary amino groups are partially transformed into other nitrogen functionalities during its plasma polymerization. Amongst them imines and nitriles are the conversion products with the highest probabilities of formation. Another conversion channel is the formation of nitrogen species not participating in the film growth. This is the reason for an increased N loss in plasma deposited allylamine films as observed independently by XPS and ToF‐SSIMS when the plasma parameters are changed from mild to hard.

Summary: Pulsed‐plasma‐deposited ethylene films were studied by time‐of‐flight static secondary ion mass spectrometry (ToF‐SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma‐deposited ethylene films was investigated. From these data, information on the chemical character of the plasma‐deposited ethylene films was derived. The investigation of the effect of external plasma parameters on the chemical character of the plasma‐deposited ethylene films revealed that there were some drastic changes in the secondary ion mass spectra of the films. It was found that fragmentation and re‐arrangement of the monomer molecules in the plasma, which affects the chemical character of the deposited films, vary according to the external plasma parameters. When the plasma polymers are exposed to air, extensive oxygen incorporation occurs. The oxygen uptake is high at the beginning and then it levels of. Some indications for the formation and decay of peroxy radicals (COO•) and, subsequently, hydroperoxides (COOH) are found. It was observed that the oxygen uptake of the plasma deposited ethylene films increase when the plasma conditions become harder.

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Summary: Pulsed plasma‐deposited polystyrene films were studied by time‐of‐flight static secondary ion mass spectrometry (ToF‐SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma‐deposited polystyrene films was investigated. From these data, information on the chemical character of the plasma polystyrene films was derived. In the range of deposition conditions applied in this study, the fragmentation of styrene is a minor process. The main process is probably the radical chain propagation to polymers. All the polystyrene plasma polymers, relying on ToF‐SIMS, seem to be rather similar to a reference polystyrene oligomer sample. When the plasma polymers are exposed to air, extensive oxygen incorporation occurs. Oxygen uptake was found to alter the emission probabilities of secondary ions. A relation between the regularity of the plasma polymers and the amount of oxygen incorporation was found. The result was that the chemical regularity of the plasma polystyrene decreases when the effective power in the plasma is increased.

Summary: XPS and NEXAFS spectroscopy results were used for chemical characterization of pulsed plasma deposited allyl alcohol films before and after exposure to ambient air. The influence of the composite plasma parameter, effective plasma power (P) to monomer flow rate (F) ratio on the spectroscopic results was investigated. From this data, information about the chemical character of the plasma polymerized films, such as retention of the hydroxyl groups in the deposited sample, the amount of long living radicals and branching and/or crosslinking was derived. A high degree of hydroxyl retention was observed, which, however, decreased along with the oxygen content of the film, as the P/F ratio increased. A trend in the extent of the oxygen loss according to the variation of the P/F ratio was deduced, which agrees with earlier ToF‐SSIMS findings (Plasma Process. Polym. 2005, 2, 563).