Renfan Shao

Twist-bend heliconical chiral nematic liquid crystal phase of an achiral rigid bent-core mesogen.

The chiral, heliconical (twist-bend) nematic ground state is reported in an achiral, rigid, bent-core mesogen (UD68). Similar to the nematic twist-bend (N(TB)) phase observed in bent molecular dimers, the N(TB) phase of UD68 forms macroscopic, smecticlike focal-conic textures and exhibits nanoscale, periodic modulation with no associated modulation of the electron density, i.e., without a detectable lamellar x-ray reflection peak. The N(TB) helical pitch is p(TB) ∼ 14 nm. When an electric field is applied normal to the helix axis, a weak electroclinic effect is observed, revealing 50-μm-scale left- and right-handed domains in a chiral conglomerate.

Spontaneous ferroelectric order in a bent-core smectic liquid crystal of fluid orthorhombic layers.

The ferroelectric properties of bent-core liquid crystalline molecules emerge from ordering within the smectic layers. Macroscopic polarization density, characteristic of ferroelectric phases, is stabilized by dipolar intermolecular interactions. These are weakened as materials become more fluid and of higher symmetry, limiting ferroelectricity to crystals and to smectic liquid crystal stackings of fluid layers. We report the SmAPF, the smectic of fluid polar orthorhombic layers that order into a three-dimensional ferroelectric state, the highest-symmetry layered ferroelectric possible and the highest-symmetry ferroelectric material found to date. Its bent-core molecular design employs a single flexible tail that stabilizes layers with untilted molecules and in-plane polar ordering, evident in monolayer-thick freely suspended films. Electro-optic response reveals the three-dimensional orthorhombic ferroelectric structure, stabilized by silane molecular terminations that promote parallel alignment of the molecular dipoles in adjacent layers.

Electro-optic characteristics of de Vries tilted smectic liquid crystals: Analog behavior in the smectic A* and smectic C* phases

Chiral smectic A liquid crystal materials of the de Vries type (with molecules tilted relative to the layer normal) exhibit analog field-induced (electroclinic) optic axis rotation accompanied by an increase in birefringence. We identify two such de Vries smectic A* materials and use them to develop and test models for these characteristic electro-optic effects. These materials also exhibit colossal analog field-induced optic axis rotation in the lower temperature smectic C* phase, a consequence of polarization charge stabilization, and of polarization screening of the applied field in the liquid crystal.

An Approach to the Design of Ferroelectric Liquid Crystals with Large Second Order Electronic Nonlinear Optical Susceptibility

Abstract Ferroelectric liquid crystal thin films in the Clark-Lagerwall surface-stabilized geometry exhibit well known spontaneous polar orientation of functional groups. The symmetry of the system thus allows the existence of bulk electronic second order nonlinear hyperpolarizability x(2) within thc context of the simple dipolar model. For all FLC materials examined to date, however, the magnitude of x(2) is small, presumably since the particular functional group arrays oriented along the polar axis possess small molecular hyperpolarizdbility β. Using the Boulder Model for the molecular origins of the polar order occurring in FLC films, it is possible to design materials with functionalized aromatic rings oriented along the polar axis of the film. Since such functional arrays may show respectable values of β, it should be possible to obtain FIX films (both low molecular weight and polymeric) with useful magnitude of x(2) using this approach. Results of initial experiments aimed at design of FLC materials...

Chirality-Preserving Growth of Helical Filaments in the B4 Phase of Bent-Core Liquid Crystals

The growth of helical filaments in the B4 liquid-crystal phase was investigated in mixtures of the bent-core and calamitic mesogens NOBOW and 8CB. Freezing-point depression led to nucleation of the NOBOW B4 phase directly from the isotropic phase in the mixtures, forming large left- and right-handed chiral domains that were easily observed in the microscope. We show that these domains are composed of homochiral helical filaments formed in a nucleation and growth process that starts from a nucleus of arbitrary chirality and continues with chirality-preserving growth of the filaments. A model that accounts for the observed local homochirality and phase coherence of the branched filaments is proposed. This model will help in providing a better understanding of the nature of the B4 phase and controlling its growth and morphology for applications, such as the use of the helical nanophase as a nanoheterogeneous medium.

The case of thresholdless antiferroelectricity: polarization-stabilized twisted SmC* liquid crystals give V-shaped electro-optic response

We have studied the three-component liquid crystal mixture reported to exhibit ‘thresholdless antiferroelectricity’ [Inui et al., J. Mater. Chem., 1996, 6, 671]. We find that the thresholdless or V-shaped switching is obtained in the absence of antiferroelectricity. This analog electro-optic response is due to the field-induced switching of a twisted smectic C* structure stabilized by polar surface interactions and by electrostatic bulk polarization charge interactions. The latter confine the director twist to thin surface regions leaving the bulk of the cell uniform, which gives good extinction at zero field. In sufficiently thin cells, such thresholdless switching can in fact be followed down to much lower temperatures, where the bulk would be antiferroelectric, but is maintained in the cells in the ferroelectric state by hysteresis from surface action.

Organization of the polarization splay modulated smectic liquid crystal phase by topographic confinement

Recently, the topographic patterning of surfaces by lithography and nanoimprinting has emerged as a new and powerful tool for producing single structural domains of liquid crystals and other soft materials. Here the use of surface topography is extended to the organization of liquid crystals of bent-core molecules, soft materials that, on the one hand, exhibit a rich, exciting, and intensely studied array of novel phases, but that, on the other hand, have proved very difficult to align. Among the most notorious in this regard are the polarization splay modulated (B7) phases, in which the symmetry-required preference for ferroelectric polarization to be locally bouquet-like or “splayed” is expressed. Filling space with splay of a single sign requires defects and in the B7 splay is accommodated in the form of periodic splay stripes spaced by defects and coupled to smectic layer undulations. Upon cooling from the isotropic phase this structure grows via a first order transition in the form of an exotic array of twisted filaments and focal conic defects that are influenced very little by classic alignment methods. By contrast, growth under conditions of confinement in rectangular topographic channels is found to produce completely new growth morphology, generating highly ordered periodic layering patterns. The resulting macroscopic order will be of great use in further exploration of the physical properties of bent-core phases and offers a route for application of difficult-to-align soft materials as are encountered in organic electronic and optical applications.

Four-ring achiral unsymmetrical bent core molecules forming strongly fluorescent smectic liquid crystals with spontaneous polar and chiral ordered B7 and B1 phases

Achiral molecules based on a novel four-ring core with an ester linkage at the molecular bend are shown to exhibit smectic liquid crystal phases with spontaneously chiral and polar layers (SmCP phases), including their polarization splay modulated and layer undulated (PMLU) variants, B7 and B1. Additionally, these compounds exhibit strong photoluminescence, the first family of SmCP phases to do so.

The measurement of second‐harmonic generation in novel ferroelectric liquid crystal materials

We present the analysis of experimental results on second‐harmonic generation in a novel ferroelectric liquid crystal (FLC) material, o‐ nitroalkoxyphenyl biphenylcarboxylate 1, synthesized specifically for large nonlinear coefficients. All nonzero dij coefficients have been measured, with the largest being d22 = 0.6 ± 0.3 pm/V. Relative values of refractive indices are also given suggesting uniaxial optical properties with large birefringence (nz − nx≊ 0.20 at λ=1.064 μm). This material demonstrates the flexibility of FLC molecular synthesis to form thermodynamically stable macroscopically aligned materials for second‐order nonlinear optics applications.

Design and synthesis of ferroelectric liquid crystals. 15.1 FLC materials for nonlinear optics applications

Abstract We have recently reported the first FLCs designed specifically for large second order nonlinear optical (NLO) susceptibility χ(2); a series of o-nitro-1-methylheptyloxy biphenylbenzoates and phenyl biphenylcarboxylates. Properties of a stable room-temperature C* mixture of two such components (1:1 W316/W317 = MX5679) are presented. The nonlinear susceptibility, as evidenced by the Type 1 eeo deff for second harmonic generation (SHG) from 1,064 nm light for MX5679 is indeed large relative to other FLCs which have been evaluated for χ(2) (deff (ZLI3654) = 0.0016 pm/V, deff (SCE9) = 0.0037 pm/V, deff (MX5679) = 0.16 pm/V). The synthesis and some properties of second-generation FLCs designed for NLO applications is also described.