Gyroid Structures in Solvent Annealed PS‑b‑PMMA Films: Controlled Orientation by Substrate Interactions

We investigated the orientation of gyroid structures in thin films of high-molecular-weight (HMW) polystyrene-b-poly­(methyl methacrylate) (PS-b-PMMA) upon a solvent vapor annealing (SVA) process with tetrahydrofuran nonselective to the PS and PMMA blocks. During the SVA process, the swollen PS-b-PMMA films produced the gyroid structures that were developed through a cylindrical morphology from a poorly ordered structure. The interfacial interactions exerted by the substrates significantly influenced the orientation of cylinders, like the parallel and perpendicular orientations on the selective and neutral substrates, respectively, while the solvent vapor generated perpendicular cylinders at the surface. In the final formation of gyroid structures, we identified the two distinct [211] and [111] planes on the surface throughout the interior of the films, which were directed from cylinders on the selective and neutral substrates, respectively. To provide the insight of the molecular mechanisms taking place during the order–order transition, we further performed coarse-grained simulations of a block copolymer model. Our results based on experiments and simulations suggest a simple route for the directed orientation of well-defined gyroid structures.