Sequence control of phase separation and dewetting in PS/PVME blend thin films by changing molecular weight of PS

The morphology evolution mechanism of polystyrene (PS)/poly (vinyl methyl ether) (PVME) blend thin films with different PS molecular weights (M_w) was studied. It was found that the morphology evolution was closely related to the molecular weight asymmetry between PS and PVME. In the film where M_w(PS) ≈ M_w(PVME), dewetting happened at the interface between the bottom layer and substrate after SD phase separation. While in the film where M_w(PS) >> M_w(PVME), dewetting happened at the interface between the middle PS/PVME blend layer and bottom PVME layer near the substrate prior to phase separation. The different sequences of phase separation and dewetting and different interface for dewetting occurrence were studied by regarding the competitive effects of viscoelasticity contrast between polymer components and preferential wetting between PVME and the substrate. The viscoelastic nature of the PS component played a crucial role in the sequence of phase separation and dewetting.