Wetting of Liquid-Crystal Surfaces and Induced Smectic Layering at a Nematic-Liquid Interface: An X-ray Reflectivity Study

Abstract

We report the results of a synchrotron x-ray reflectivity study of bulk liquid-crystal surfaces that are coated by thin wetting films of an immiscible liquid. The liquid-crystal subphase consisted of the nematic or isotropic phase of 4-octyl-4′-cyanobiphenyl (8CB), and the wetting film was formed by the fluorocarbon perfluoromethylcyclohexane (PFMC), a volatile liquid. The thickness of the wetting film was controlled by the temperature difference ΔTμ between the sample and a reservoir of bulk PFMC, contained within the sealed sample cell. Phase information on the interfacial electron density profiles has been extracted from the interference between the scattering from the PFMC-vapor interface and the surface-induced smectic order of the 8CB subphase. The liquid-crystal side of the nematic-liquid (8CB-PFMC) interface is characterized by a density oscillation whose period corresponds to the smectic layer spacing and whose amplitude decays exponentially toward the underlying nematic subphase. The decay length ξ of the smectic amplitude is independent of the PFMC film thickness but increases as the nematic–smectic-A transition temperature TNA is approached, in agreement with the longitudinal correlation length ξ∥∝(T−TNA)−0.7 for the smectic fluctuations in the bulk nematic. The results indicate that the homeotropic orientation of the 8CB molecules is preferred at the 8CB-PFMC interface and that the observed temperature dependence of the smectic layer growth is consistent with the critical adsorption mechanism. The observed ΔTμ dependence of the PFMC film thickness, L∝(ΔTμ)−1/3, implies that PFMC completely wets the 8CB surface and is dominated by the nonretarded dispersion interactions between hydro- and fluorocarbons. The complete wetting behavior of PFMC is nearly independent of the degree of interfacial smectic order in the subphase.