Self-template-assisted micro-phase segregation in blended liquid-crystalline block copolymers films toward three-dimensional structures.

In-plane mesopatterns derived from block-copolymer (BCP) micro-phase segregation in thin films have attracted much interest in practical applications as well as fundamental research programs. However, phase segregation along the film-normal direction has been less studied. Here, we describe a strategy to concurrently, yet independently, control in-plane micro-phase and out-of-plane macro-phase segregation in multiblended films composed of liquid-crystalline BCPs (LCBCPs), affording spontaneously layered three-dimensional (3D) mesostructures. This strategy relies on sequential liquid crystallization during the cooling process in thermal annealing as follows. The constituent LCBCP with the highest isotropic-transition temperature (T iso) first liquid-crystallizes and segregates from the other LCBCP mixture remaining in isotropic states to form a noncontaminated layer at the top surface. This preformed LCBCP layer preserves its inherent in-plane pattern and acts as a template guiding the subsequent micro-phase segregations of the other low-T iso LCBCPs underneath. This self-template-assisted micro-phase segregation (STAMPS) readily provides 3D mesostructures, the potential toward rational material design of which is also demonstrated in water-separation applications.