We investigated the response of symmetric poly(styrene-block-4-vinylpyridine) P(S-b-4VP) diblock copolymer micelles to surface fields of variable strength at free surfaces and substrate interfaces when the micelles as spun were subjected to solvent annealing. Free surface interactions were controlled with solvent annealing in solvents of varied selectivity. On exposure to vapors of a solvent strongly selective for PS, a the micelles retained their spherical shape but grew into cylindrical micelles or lamellar nanostructures via fusion on exposure to slightly selective or neutral solvent vapors. Giant 2D disks that completely wetted PS-grafted substrates resulted when spherical micelles were exposed to vapors of a highly selective solvent for P4VP. The interfacial interactions were controlled through subjecting them to UV/ozone (UVO) substrates initially coated with an end-grafted layer of short PS chains, with which the grafted PS chains became oxidized, degraded, or totally removed through UVO treatment for a controlled duration. When thin films were annealed in vapors of THF, the structural transition from spherical to cylindrical micelles depended on the interfacial field. On applying selective UVO exposure of optimal duration, we fabricated a substrate with two interfacial chemistries that promoted varied micellar species (spherical and cylindrical micelles) with a sharp boundary developed within thin films through solvent annealing for a controlled duration.
