Capillary Force Lithography Pattern-Directed Self-Assembly (CFL-PDSA) of Phase-Separating Polymer Blend Thin Films

[Image: see text] We report capillary force lithography pattern-directed self-assembly (CFL-PDSA), a facile technique for patterning immiscible polymer blend films of polystyrene (PS)/poly(methyl methacrylate) (PMMA), resulting in a highly ordered phase-separated morphology. The pattern replication is achieved by capillary force lithography (CFL), by annealing the film beyond the glass transition temperature of both the constituent polymers, while confining it between a patterned cross-linked poly(dimethyl siloxane) (PDMS) stamp and the silicon substrate. As the pattern replication takes place because of rise of the polymer meniscus along the confining stamp walls, higher affinity of PMMA toward the oxide-coated silicon substrate and of PS toward cross-linked PDMS leads to well-controlled vertically patterned phase separation of the two constituent polymers during thermal annealing. Although a perfect negative replica of the stamp pattern is obtained in all cases, the phase-separated morphology of the films under pattern confinement is strongly influenced by the blend composition and annealing time. The phase-separated domains coarsen with time because of migration of the two components into specific areas, PS into an elevated mesa region and PMMA toward the substrate, because of preferential wetting. We show that a well-controlled, phase-separated morphology is achieved when the blend ratio matches the volume ratio of the elevated region to the base region in the patterned films. The proposed top-down imprint patterning of blends can be easily made roll-to-roll-compatible for industrial adoption.