Thermodynamically Anchoring-Frustrated Surface to Trigger Bulk Discontinuous Orientational Transition

Surface-specific liquid crystal (LC) nanostructures provide a unique platform for studying surface-wetting phenomena and also for technological applications. The most important studies on LC properties are related to bulk alignment, surface anchoring, and so on. Here, we study an LC system with a nematic liquid crystal (NLC) on a perfluoropolymer-coated substrate, in which a discontinuous bulk orientational transition has recently been found. Using free-energy analysis based on experimental results of the newly-conducted grazing-incidence X-ray diffraction (GI-XRD) measurements, we have confirmed a thermodynamic growth process of smectic liquid crystalline wetting nanosheets on the surface and successfully explained that a frustrated surface of planar and vertical anchoring states accompanied by an elastic energy cost kinetically triggers the bulk reorientation in the first-order manner. This interfacial bottom-up process may offer a general insight into how interfacial hierarchical molecular architectures alter the bulk properties of matter thermodynamically.