Plasma polymerization of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl in a collisional, capacitively coupled radio frequency discharge.

Plasma polymerization of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) yields thin films containing stable nitroxide radicals that have properties analogous to that of nitric oxide (NO) without short lifetimes. This property gives TEMPO films a wide variety of potential applications. Typically, control of the final film chemistry is difficult and the plasma discharge conditions must be tailored to in order to maximize the retention of these nitroxide groups during the polymerization and deposition process. In this study, plasma diagnostics and surface analysis of the deposited films were carried out to determine the optimal plasma conditions for the retention of nitroxide groups. These techniques included energy-resolved mass spectrometry, heated planar probe ion current measurements, deposition rate measurements, and x-ray photoelectron spectroscopy (XPS). Results show that operating the plasma with a combination of low input powers and high pressures produces a collisional discharge in which fragmentation of the TEMPO molecule is suppressed, leading to good retention of nitroxide groups. Ion energy distribution functions and quartz crystal microbalance measurements support the soft landing theory of ion deposition on the substrate within this γ-mode, in which the flux of low energy, soft landed ions form the primary contribution to film growth. XPS analysis of deposited polymers shows 75.7% retention of N-O groups in the polymer films deposited in a 25 Pa 5 W discharge.