Spiral Hierarchical Superstructures from Twisted Ribbons of Self-Assembled Chiral Block Copolymers.

Spiral hierarchical superstructures were found in the self-assembly of chiral block copolymers (BCPs*) composed of a chiral poly(l-lactide) (PLLA) and an achiral polystyrene (PS) as major and minor blocks, respectively. The PLLA helical chain with semiflexible rod-like character as compared to the random coil of PS results in self-assembly with a conformational asymmetry effect overwhelming the compositional one. Consequently, instead of the forming PS cylinder microdomains in the PLLA matrix, a smectic liquid-crystal-like bilayer sandwiched with PLLA and PS microdomains will be formed. Owing to twisting and bending due to the chiral cholesteric liquid-crystal-like force field combined with steric hindrance at the chiral interface, the forming bilayers (twisted ribbon) will develop into either a concentric lamellar texture from scrolling or roll-cake textures from spiraling. This study might bring a concept for the formation of spiral hierarchical superstructures from self-assembled bilayers for device application.