Surface Composition, Chemistry, and Structure of Polystyrene Modified by Electron-Beam-Generated Plasma

Polystyrene (PS) surfaces were treated by electron-beam-generated plasmas in argon/oxygen, argon/nitrogen, and argon/sulfur hexafluoride environments. The resulting modifications of the polymer surface energy, morphology, and chemical composition were analyzed by a suite of complementary analytical techniques: contact angle goniometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and reflection electron energy loss spectroscopy (REELS). The plasma treatments produced only minimal increases in the surface roughness while introducing the expected chemical modifications: oxygen-based after Ar/O(2) plasma, oxygen- and nitrogen-based after Ar/N(2) plasma, and fluorine-based after Ar/SF(6) plasma. Fluorinated PS surfaces became hydrophobic and did not significantly, change their properties over time. In contrast, polymer treated in Ar/O(2) and Ar/N(2) plasmas initially became hydrophilic but underwent hydrophobic recovery after 28 days of aging. The aromatic carbon chemistry in the top 1 nm of these and surfaces clearly indicated that the hydrophobic recovery was produced by reorientation/diffusion of undamaged aromatic polymer fragments from the bulk rather than by contamination. Nondestructive depth profiles of aged plasma-treated PS films were reconstructed from parallel angle-resolved XPS (ARXPS) measurements using a maximum-entropy algorithm. The salient features of reconstructed profiles were confirmed by sputter profiles obtained with 200 eV Ar ions. Both types of depth profiles showed that the electron-beam-generated plasma modifications are confined to the topmost 3-4 nm of the polymer surface, while valence band measurements and unsaturated carbon signatures in ARXPS and REELS data indicated that much of the PS structure was preserved below 9 nm.