Mechanistic reaction pathway for hexafluoropropylene oxide pulsed plasma deposition of PTFE-like films

The pulsed plasma deposition of PTFE-like thin films using hexafluoropropylene oxide (HFPO) precursor has been investigated by time-resolved in situ mass spectrometry. Electron-impact and electron-attachment ionisation modes have been employed to monitor neutral plasma species; whilst electrical discharge negative and positive ions have been detected by switching-off the mass spectrometer electron-impact ionisation source. The relative concentrations of neutral versus ionic plasma species were found to rise for shorter pulse duty cycles. Mechanistically, HFPO molecules undergo pulsed plasma-initiated decomposition to form difluorocarbene (:CF₂) radical species, and these can combine to form tetrafluoroethylene (CF₂ = CF₂) molecules, which subsequently polymerise leading to the growth of PTFE-like ([–CF₂–]_n) perfluoroalkyl chains. Shorter pulsed plasma duty cycles enhance the growth of linear PTFE-like perfluoroalkyl chains. (paper)