Morphology of Poly(styrene-co-butadiene) Random Copolymer Thin Films and Nanostructures on a Graphite Surface

We studied the morphology of poly(styrene-co-butadiene) random copolymers on a graphite surface. Polymer solutions were spin coated onto graphite, at various concentrations and molecular weights. The polymer films and nanostructures were imaged using atomic force microscopy. Above the overlap concentration, thin films formed. However, total wetting did not occur, despite the polymers being well above their Tg. Instead, dewetting was observed, suggesting the films were in a state of metastable equilibrium. At lower concentrations, the polymers formed networks, nanoislands, and nanoribbons. Ordered nanopatterns were observed on the surface; the polymers orientated themselves due to π–π stacking interactions reflecting the crystalline structure of the graphite. At the lowest concentration, this ordering was very pronounced. At higher concentrations, it was less defined but still statistically significant. Higher degrees of ordering were observed with poly(styrene-co-butadiene) than polystyrene and polybutadiene homopolymers as the copolymer’s aromatic rings are distributed along a flexible chain, which maximizes π–π stacking. At the two lowest concentrations, the size of the nanoislands and nanoribbons remained similar with varying molecular weight. However, at higher concentrations, the polymer network features were largest at the lowest molecular weight, indicating that in this case, a large proportion of shorter chains stay on top of the adsorbed ones. The contact angles of the polymer nanostructures remained mostly constant with size, which is due to the strong polymer/graphite adhesion dominating over line tension and entropic effects.