Formation of High-Density Brush of Liquid Crystalline Polymer Block Associated with Dewetting Process on Amorphous Polymer Film

The understanding of polymer dewetting on solid surfaces is significant in both fundamental polymer physics and practical film technologies. When liquid crystalline (LC) polymers are dewetted, LC ordering is involved in the dewetting process. Here, we report on the characteristic dewetting processes of a diblock copolymer composed of a cyanobiphenyl side chain liquid crystalline polymer (SCLCP) block connected with polystyrene (PS) taking place on a PS base film. Thin films of the block copolymer were prepared by the water-floating method onto the PS film, and the dewetting process is observed in a softened state above the glass transition temperature of the PS. At the smectic A phase temperature of the SCLCP block, the dewetted surface layer generated a flat unique fingering pattern leading to a monolayered (two-dimensional) high-density LC polymer brush through the LC ordering. The important role of the anchoring PS block on the base PS film surface is suggested for the formation of highly stretched LC polymer brush. Above the isotropization temperature, in contrast, ordinary three-dimensional droplet morphologies with smooth round edges were observed. By photo-cross-linking the base PS film, the lateral diffusion rate was significantly reduced. This can be applied to an entropy-driven morphology patterning via dewetting. The polymer brush formation and its spatial controls are expected to provide new opportunities for the modification strategies of polymer surfaces.