Surface-Mediated Photoalignment of Discotic Liquid Crystals on Azobenzene Polymer Films

This paper describes a simple strategy for the formation of photoaligned and micropatterned discotic liquid crystal (DLC) film on the surface of photoirradiated azobenzene-containing polymer thin film. The key material for the surface-mediated photoalignment of the DLCs was poly[4-(4-cyanophenylazo)phenyl methacrylate] (pMAzCN). Optical anisotropy was generated in a pMAzCN film by oblique exposure to nonpolarized light which resulted in angle-selective photoisomerization and reorientation of the azobenzenes. Subsequent annealing of the film at 240 °C enhanced the photoaligned state of the p-cyanoazobenzenes due to strong intermolecular dipole−dipole interaction and semicrystalline nature of the pMAzCN. This combination of photoirradiation and subsequent annealing of the pMAzCN film made it possible to realize the surface-assisted orientation control of a DLC molecule, which displays both columnar (Col) and discotic nematic (ND) phases over 152 °C. When the pMAzCN film was exposed to linearly polarized light from the surface normal, the DLC molecules showed homeotropic orientation with the director perpendicular to the substrate surface. In the contrast, oblique irradiation of the pMAzCN film with nonpolarized light gave rise to tilted DLC orientation with well-ordered optical birefringence at the ND phase. Rapid cooling from the ND phase produced a well-aligned glassy ND state at room temperature, which was adequately stable for 10 months even though no covalent cross-linking among the DLCs was performed. The spatial orientation of photoaligned DLCs in both their bulk film and in their interface region was characterized by means of optical birefringence, X-ray diffraction, and fluorescence measurements. At the ND phase, the DLC molecules were aligned in a hybrid manner such that their tilt angles varied throughout the thickness of DLC film. The direction of tilted DLCs was opposite to the propagation of the actinic nonpolarized light. The photoaligned DLC films exhibited polarized fluorescence emission with an s-polarized/p-polarized intensity ratio of 4.1, despite the nonpolarized excitation of only DLC at outmost surface. These results indicate that the three-dimensionally aligned azobenzene moieties of the pMAzCN thin film were transferred to the tilted DLC molecules at air/DLC interface. Finally, we demonstrated micrometer-scale photopatterned orientation of DLC molecules on the pMAzCN surface by oblique nonpolarized irradiation of the film through a p