Effective Viscosity of Lightly UVO-Treated Polystyrene Films on Silicon with Different Molecular Weights

Abstract

Recently, we found that a brief, 1 s exposure to ultraviolet ozone (UVO) can cause the effective viscosity, ηeff, of polystyrene films supported by oxide-coated silicon (PS-SiOx) to increase by more than 100 times. In this experiment, we study the phenomenon with different PS molecular weights, Mw, from 2.4 to 451 kg/mol. We found that ηeff was increased for all Mw’s when the film thickness, h0, was decreased below an onset thickness comparable to the radius of gyration, Rg, of the polymer. For h0 greater than the onset thickness, the ηeff versus h0 dependence varies with Mw. Specifically, for Mw ≥ 60K g/mol ηeff was constant, equal to the bulk viscosity. For Mw < 60K g/mol, ηeff decreased with decreasing h0 in the same way as that of the pristine counterparts. X-ray photoelectron spectroscopy (XPS) shows that oxygenated groups are formed in the films after the UVO treatment. We propose that the oxygenated groups can interact with the OH groups on the SiOx surface to produce increases in ηeff. Correspondingly, we found that the ηeff data could fit well to a three-layer model containing a dynamically dead layer on the substrate. Results of the fit are consistent with a surface layer with a thickness of ∼Rg and the following attributes. Below entanglement, the mobility of this layer is enhanced relative to the bulk polymer. Above entanglement, couplings between the surface chains and the chains in the inner, bulklike region force the surface chains to flow as the inner chains. As a result, enhanced mobility can only be found in short-range, local motions over depths of the order of the average distance between entanglements. This picture explains a variety of surface relaxation phenomena reported in the literature.