Defluorination of polytetrafluoroethylene (PTFE) surface film is a suitable technique for tailoring its surface properties. The influence of discharge parameters on the surface chemistry was investigated systematically using radio-frequency inductively coupled H2 plasma sustained in the E- and H-modes at various powers, pressures and treatment times. The surface finish was probed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The measurements of water contact angles (WCA) showed increased wettability of the pristine PTFE; however, they did not reveal remarkable modification in the surface chemistry of the samples treated at various discharge parameters. By contrast, the combination of XPS and ToF-SIMS, however, revealed important differences in the surface chemistry between the E- and H-modes. A well-expressed minimum in the fluorine to carbon ratio F/C as low as 0.2 was observed at the treatment time as short as 1 s when plasma was in the H-mode. More gradual surface chemistry was observed when plasma was in the E-mode, and the minimal achievable F/C ratio was about 0.6. The results were explained by the synergistic effects of hydrogen atoms and vacuum ultraviolet radiation.
