Macroscopic Monograin Nano‐Gyroid Thin Films in 4‐inch Scale Through Shear‐Rolling and Subsequent Solvent Annealing

Abstract The gyroid structure from self‐assembly is highly attractive for optical applications such as photonic crystals and metamaterials. However, due to the direction‐dependent nature of these applications, achieving a monograin‐level structure over a large area has remained challenging. In this study, the fabrication of unidirectionally oriented anisotropic nanocylinders of polystyrene‐ block ‐polydimethylsiloxane (PS‐ b ‐PDMS) is reported block copolymer thin films up to a 4‐inch scale via a shear‐rolling process, followed by solvent annealing to induce phase transition to nearly monograin gyroid structures. Grazing‐incidence small‐angle X‐ray scattering (GISAXS) analysis and cross‐sectional scanning electron microscope (SEM) images in the direction parallel to the shear‐rolling direction reveal the preferential orientation with the (111) plane onto the YZ axis of the film, while only the (110) plane on the YZ axis of the film is observed in the perpendicular direction, with grain sizes approaching single‐grain levels. For metamaterial applications, the PDMS domain is selectively removed, and gold is electroplated to produce monograin gold gyroid films.