Phase behavior in thin films of weakly segregated block copolymer/homopolymer blends

Abstract

We have demonstrated the phase behavior of substrate-supported films of a symmetric weakly segregated polystyrene-block-poly (methyl methacrylate), P(S-b-MMA), block copolymer and its blends with homopolymer polystyrene (PS) at different compositions. Upon increasing the content of added PS in the blends, lamellae (L), perforated layers (PL), double gyroid (DG) and cylinders (C) are obtained in sequence for films. Among these nanodomains, PL and DG only exist in a narrow ϕ_PS region (ϕ_PS denotes the volume fraction of PS). At ϕ_PS = 64%, tuning film thickness and annealing temperature can produce parallel PL or DG with {121}_DG lattice planes being parallel to the substrate surface. The effects of annealing temperature and film thickness on the formation of PL and DG are examined. In thin films with n ≈ 3 (n denotes the ratio of initial film thickness to inter-domain spacing), the PL phase solely exists regardless of temperature. However, for thick films with n ≈ 6 and 10, thermal annealing at the most accessible temperature produces films containing both PL and DG of various fractions, but a low temperature tends to favor a greater fraction of PL. The PL phase becomes the only discernible phase if thick films are shortly annealed at 230 °C.