Scanning wave photopolymerization enables dye-free alignment patterning of liquid crystals

Hierarchical control of two-dimensional (2D) molecular alignment patterns over large areas is essential for designing high-functional organic materials and devices. However, even by the most powerful current methods, dye molecules that discolor and destabilize the materials need to be doped in, complicating the process. We present a dye-free alignment patterning technique, based on a scanning wave photopolymerization (SWaP) concept, that achieves a spatial light-triggered mass flow to direct molecular order using scanning light to propagate the wavefront. This enables one to generate macroscopic, arbitrary 2D alignment patterns in a wide variety of optically transparent polymer films from various polymerizable mesogens with sufficiently high birefringence (>0.1) merely by single-step photopolymerization, without alignment layers or polarized light sources. A set of 150,000 arrays of a radial alignment pattern with a size of 27.4 μm × 27.4 μm were successfully inscribed by SWaP, in which each individual pattern is smaller by a factor of 10⁴ than that achievable by conventional photoalignment methods. This dye-free inscription of microscopic, complex alignment patterns over large areas provides a new pathway for designing higher-performance optical and mechanical devices.