Pathways toward Photoinduced Alignment Switching in Liquid Crystalline Block Copolymer Films

The pathways toward linearly polarized light (LPL)-induced alignment switching in a diblock copolymer film composed of liquid crystalline (LC) azobenzene (Az) and amorphous poly­(butyl methacrylate) (PBMA) blocks were studied in detail using polarized UV–vis absorption spectroscopy, grazing incidence small-angle X-ray scattering measurements, and polarized optical microscopy and transmission electron microscopy observations. The hierarchical structures of microphase-separated cylinders of PBMA in a smectic LC Az layer matrix were prealigned by LPL and then irradiated by orthogonal LPL, which resulted in alignment switching to the orthogonal direction. In this process, the large prealigned domains were divided into substantially smaller domains at the submicrometer level, and then the structures were realigned in the orthogonal direction in a strongly cooperative manner, most likely through the domain rotation mechanism. The alignment change consisted of three stages: (i) fluctuations in the smectic layer of LC Az side chains in the initial state and breaking up of smaller grains to the submicrometer level before the orientation change (induction period), (ii) actual rotation of the divided domains driven by the photoinduced reorientation of Az mesogens (action period), and (iii) slower fusion and growth of smaller domains in the orthogonally realigned direction (postgrowth period). New aspects of dynamic self-assembly behavior in which different hierarchical structures are involved are proposed.