Elastic modulus, oxidation depth and adhesion force of surface modified polystyrene studied by AFM and XPS

AFM and XPS have been used to investigate the surface and near-surface properties of polystyrene (PS) substrates which have been subjected to one of three controlled surface modification processes performed in situ in a specially constructed cell. The cell was fitted to a Digital Instruments Nanoscope III AFM measuring head and allowed close control of the gaseous environment and made it possible to UV irradiate the sample during AFM measurements. Treatments were carried out using UV at 184.9 and 253.7 nm wavelengths, in oxygen (UV-ozone), and in nitrogen (UV-only). Polystyrene surfaces were also modified by an exposure to an atmosphere of ozone in the absence of UV (ozone-only). Data show that adhesion force is highest between tip and sample for the UV-ozone exposed surfaces and that the adhesion force increases with sample exposure time. Exposure to UV-only or ozone alone results in lower ultimate adhesion levels with a slower rate of increase with exposure time. Evaluation of Youngʹs modulus for unmodified PS gave a value of 3.37 (±0.52) GPa which agrees well with the textbook value which ranges from 2 to 4 GPa depending on the measurement technique. A 60 s exposure to combined UV-ozone resulted in the formation of a surface layer with a modulus at the surface of 1.25 (±0.19) GPa which increased to 2.5 (±0.37) GPa at a depth of 3.5 nm. The sample exposed for 60 s to UV-only had a Youngʹs modulus of 2.6 (±0.39) GPa but showed no reduced modulus layer at the surface. The modulus of the ozone-only treated material was the least affected with a decrease of around 0.75 GPa with some evidence for a surface layer with a modulus ranging from 2.6 (±0.39) GPa at the surface to 3.2 (±0.48) GPa at a depth of 2 nm. XPS analyses reveal that the oxygen content of the modified surfaces decreased in the order of UV-ozone > UV > ozone with approximate concentrations for a 60 s exposure of 5, 0.7 and 0.05 at.%, respectively. Friction force imaging of patterned surfaces reveals chemical heterogeneity. Statistical analysis of the friction force data shows that the resolution attainable with UV irradiation in nitrogen was higher than surfaces patterned by UV-ozone treatment.