Surface morphology control of immiscible polymer-blend thin films

The effects of the molecular weights (molecular weight of polystyrene, M_w,PS, varying from 2.9 to 129 k) on the surface morphologies of spin-coated and annealed polystyrene/poly (methyl methacrylate) (PS/PMMA=50/50, w/w) blend films were investigated by atomic force microscopy and X-ray photoelectron spectroscopy. For the spin-coated films, when the M_w,PS varied from 2.9 to 129 k, three different kinds of surface morphologies (a nanophase-separated morphology, a PMMA cellular or network-like morphology whose meshes filled with PS, a sea-island like morphology) were observed and their formation mechanisms are discussed, respectively. Upon annealing, two different morphology-evolution processes were observed. It is found that a upper PS-rich phase layer is formed when M_w,PS<4 k, and this behavior is mainly attributed to the low interfacial tension between PS and PMMA component. When M_w,PS>4 k, the PS-rich phase forms droplets on top of the PMMA-rich phase layer which wets the SiO_x substrate. These results indicate that the surface morphology of the polymer blend films can be controlled by the polymer molecular weight and annealing conditions.