Topologically Distinct Lamellar Block Copolymer Morphologies Formed by Solvent and Thermal Annealing

Solvent annealing produces ordered assemblies in thin films of block copolymers and, in contrast to uniform thermal annealing, can be used to tune the self-assembled morphology, control the domain orientation with respect to the substrate, and, as demonstrated here, reduce the defect density. The two-dimensional network topology of lamellae self-assembled by polystyrene-block-poly(methyl methacrylate) block copolymers in thin films was compared when processed by solvent and thermal annealing techniques. The mixed solvent annealing method described here reduced the overall defect density (e.g., dislocations with PMMA or PS cores) and thus the connectivity of the lamellar domains compared to thermal annealing; however, the long-range continuity of the networks was maintained and depended primarily on the copolymer composition. In addition, the persistence length of the lamellar domains for solvent annealed films was found to be 2-3 times that of the corresponding thermally annealed systems.