Alignment methods of nematic liquid crystals (LCs) by surface photoreactions on substrate surfaces were initially proposed around 1990, and the photoalignment technology of nematic LCs has recently been integrated into the LC device fabrication industry due to its profitable features. Accumulated efforts in this field have revealed that applications of photoalignment processes are not limited to conventional nematic LCs but that a variety of functional materials can also be manipulated according to this principle. Target materials have now been extended to thermotropic smectic LCs, discotic LCs, LC polymers, block copolymers, gel networks, conjugated polymers, and organic semiconductors and lyotropic systems including chromonic LCs and inorganic–organic mesostructured hybrids. Through these photochemical approaches, many types of photopatterning for both topographical and orientational modulations have become feasible. This article reviews photoalignment processes applied to a wide range of materials, surveying relatively recent work. Some important related alignment and patterning processes are also introduced to clarify the significance of these photoalignment techniques

The orientation of liquid crystal molecules is very sensitive towards contacting surfaces, and this phenomenon is critical during the fabrication of liquid crystal display panels, as well as optical and memory devices. To date, research has focused on designing and modifying solid surfaces. Here we report an approach to control the orientation of liquid crystals from the free (air) surface side: a skin layer at the free surface was prepared using a non-photoresponsive liquid crystalline polymer film by surface segregation or inkjet printing an azobenzene-containing liquid crystalline block copolymer. Both planar-planar and homoeotropic-planar mode patterns were readily generated. This strategy is applicable to various substrate systems, including inorganic substrates and flexible polymer films. These versatile processes require no modification of the substrate surface and are therefore expected to provide new opportunities for the fabrication of optical and mechanical devices based on liquid crystal alignment.