Polarity Effect near the Surface and Interface of Thin Supported Polymer Films: X-ray Reflectivity Study

Four homopolymer films (poly(methyl methacrylate) (PMMA), poly(4-vinylpyridine) (P4VP), polystyrene (PS), and poly(alpha-methyl styrene) (PAMS)) with different interactions with native Si oxide on Si wafers and three random copolymer films (PS-ran-PMMA) with different mole fractions were investigated with the X-ray reflectivity (XRR) method. The electron density profile of each film was obtained by fitting the results of the XRR measurements. A new data correction technique that uses the vertical real beam profile and a fitting method that uses the distorted wave Born approximation were combined to overcome the sensitivity limitations of XRR analysis. The results show that the chemical structures of polymer pendant groups and the interactions between the polymer films and the native Si oxide layer are strongly correlated with the density profiles of the films near the surfaces and interfaces. Two general types of electron density profiles were found that are characterized by the polarity of the pendant group of the polymer. The reproducibility and credibility of the fitting technique were also thoroughly tested.