Plasma–Induced Modification Mechanisms of PET Films: Correlated Evolution of Topographical Features and Surface Chemical States

The effects of RF plasma treatments using different gases (Ar, O2, and N2) and processing parameters on the surface wettability of polyethylene terephthalate (PET) films were systematically investigated. Atomic force microscopy (AFM) and X–ray photoelectron spectroscopy (XPS) were employed to characterize the evolution of surface topography and chemical composition. While all treatments enhanced hydrophilicity, the magnitude of improvement and the governing mechanisms were gas-dependent. Among them, O2 plasma treatment exhibited the most pronounced effect: under optimal conditions (20 W, 80 s), the water contact angle (WCA) was reduced to 3.7°, indicating a superhydrophilic surface. This enhancement was primarily attributed to a substantial increase in surface oxygen content (O/C ratio) and the incorporation of strongly polar oxygen-containing functional groups, such as C=O and COOH. N2 plasma offered moderate improvement via nitrogen-containing groups, while non-reactive Ar plasma relied primarily on physical etching, yielding the smallest enhancement. Analysis revealed that wettability evolution was dominated by increased polar surface energy from chemical functionalization, with surface roughness playing a synergistic role. These results demonstrate that optimizing plasma gas and parameters effectively controls PET wettability through the coupled regulation of surface chemistry and topography.