First-principles experimental demonstration of ferroelectricity in a thermotropic nematic liquid crystal: Polar domains and striking electro-optics.

We report the experimental determination of the structure and response to applied electric field of the lower-temperature nematic phase of the previously reported calamitic compound 4-[(4-nitrophenoxy)carbonyl]phenyl2,4-dimethoxybenzoate (RM734). We exploit its electro-optics to visualize the appearance, in the absence of applied field, of a permanent electric polarization density, manifested as a spontaneously broken symmetry in distinct domains of opposite polar orientation. Polarization reversal is mediated by field-induced domain wall movement, making this phase ferroelectric, a 3D uniaxial nematic having a spontaneous, reorientable polarization locally parallel to the director. This polarization density saturates at a low temperature value of ∼6 µC/cm2, the largest ever measured for a fluid or glassy material. This polarization is comparable to that of solid state ferroelectrics and is close to the average value obtained by assuming perfect, polar alignment of molecular dipoles in the nematic. We find a host of spectacular optical and hydrodynamic effects driven by ultralow applied field (E ∼ 1 V/cm), produced by the coupling of the large polarization to nematic birefringence and flow. Electrostatic self-interaction of the polarization charge renders the transition from the nematic phase mean field-like and weakly first order and controls the director field structure of the ferroelectric phase. Atomistic molecular dynamics simulation reveals short-range polar molecular interactions that favor ferroelectric ordering, including a tendency for head-to-tail association into polar, chain-like assemblies having polar lateral correlations. These results indicate a significant potential for transformative, new nematic physics, chemistry, and applications based on the enhanced understanding, development, and exploitation of molecular electrostatic interaction.

Chiral Incommensurate Helical Phase in a Smectic of Achiral Bent-Core Mesogens.

An achiral, bent-core mesogen forms several tilted smectic liquid crystal phases, including a nonpolar, achiral de Vries smectic A which transitions to a chiral, ferroelectric state in applied electric fields above a threshold. At lower temperature, a chiral, ferrielectric phase with a periodic, supermolecular modulation of the tilt azimuth, indicated by a Bragg peak in carbon-edge resonant soft x-ray scattering, is observed. The absence of a corresponding resonant umklapp peak identifies the superlayer structure as a twist-bend-like helix that is only weakly modulated by the smectic layering.

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.

Topological ferroelectric bistability in a polarization-modulated orthogonal smectic liquid crystal.

We report a bent-core liquid crystal (LC) compound exhibiting two fluid smectic phases in which two-dimensional, polar, orthorhombic layers order into three-dimensional ferroelectric states. The lower-temperature phase has a uniform polarization field which responds in an analog fashion to applied electric field. The higher-temperature phase is a new smectic state with periodic undulation of the polarization, structurally modulated layers, and a bistable response to applied electric field which originates in the periodically splay-modulated bulk of the LC rather than by surface stabilization at the cell boundaries.

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.

Triclinic fluid order.

Among the condensed phases, those of lowest point group symmetry are the triclinic crystals, which have only the identity element or the identity and inversion elements. Such low symmetry is stabilized by the specificity of molecular interaction, which is weakened with increasing disorder, so that known phases with fluid degrees of freedom are more symmetric. Here we report triclinic order, appearing as a broken symmetry in a single, isolated, fluid smectic liquid crystal layer freely suspended in air, showing that none of its principal dielectric axes lies either normal or parallel to the layer plane.

A main-chain de vries smectic liquid crystal polymer prepared by hoveyda-grubbs catalyst initiated acyclic diene metathesis polymerization.

A main-chain liquid crystalline polymer has been obtained by applying a Hoveyda-Grubbs 2nd generation catalyst in acyclic diene metathesis polymerization (ADMET) of a monomer containing on one end a terminal dimethylvinylsilyl group and at the other end a terminal CC double bond. This material showed an interesting Iso-de Vries SmA* - SmC* - Glass phase transition with a very small layer shrinkage on progressing from the SmA* phase into the SmC* phase. Will this material present a helical structure along the fiber axis in the SmC* temperature range? Several physical characterization methods including XRD, optical observation, and microtome technique have been used to investigate the internal structural organization in this liquid crystalline fiber.

New SmAPF Mesogens Designed for Analog Electrooptics Applications.

We have previously reported the first realization of an orthogonal ferroelectric bent-core SmAPF phase by directed design in mesogens with a single tricarbosilane-terminated alkoxy tail. Given the potentially useful electrooptic properties of this phase, including analog phase-only electrooptic index modulation with optical latching, we have been exploring its "structure space", searching for novel SmAPF mesogens. Here, we report two classes of these-the first designed to optimize the dynamic range of the index modulation in parallel-aligned cells by lowering the bend angle of the rigid core, and the second expanding the structure space of the phase by replacing the tricarbosilane-terminated alkyl tail with a polyfluorinated polyethylene glycol oligomer.

Fabrication of Liquid Crystalline Polyurethane Networks with a Pendant Azobenzene Group to Access Thermal/Photoresponsive Shape-Memory Effects.

Herein, we report a novel thermal/photoresponsive shape-memory polyurethane network with a pendant azobenzene group by utilizing its anisotropic-isotropic phase transitions and photoresponsive feature concurrently. To achieve this goal, the side-chain liquid crystalline polyurethane networks based on the pendant azobenzene group [SCLCPU(AZO)-Ns] were developed in a well-defined architecture. The smectic C nature of an LC phase in the polyurethane networks was confirmed by differential scanning calorimetry, polarized optical microscopy, and one-dimensional and two-dimensional wide-angle X-ray diffraction. The well-defined architecture-made SCLCPU(AZO)-N displays two distinct transition temperatures (Ttrans) (Tg and Tcl), with a difference of about 40 °C. Consequently, the excellent triple-shape-memory effect in this network was demonstrated by cyclic thermomechanical analysis. By making full use of the trans-cis photoisomerization of azobenzene, the reversible bending and unbending behaviors were realized under the light irradiation with wavelengths of 450 and 550 nm, respectively.

Field control of the surface electroclinic effect in chiral smectic-A liquid crystals.

The surface electroclinic effect, which causes an azimuthal deviation of the layer normal from the surface rubbing direction in cells of chiral smectic- A liquid crystals, can be eliminated (and even reversed) by applying an electric field during cooling from the isotropic phase. The observed dependence of layer orientation on field strength leads to a model in which the surface electroclinic tilt results from an effective surface electric field. The experiements suggest a general method for controlling the azimuthal layer alignment of chiral smectic cells.

An electric-field-responsive discotic liquid-crystalline hexa-peri-hexabenzocoronene/oligothiophene hybrid.

A novel hexa-peri-hexabenzocoronene/oligothiophene hybrid is shown to self-assemble into a hexagonal columnar liquid crystalline phase, and respond to applied electric fields resulting in uniform homeotropic or parallel alignment depending upon the electrode structure. Furthermore, the columnar orientation can be maintained even after removal of the electric field unless the material is heated above the clearing temperature.

Cybotactic behavior in the de Vries smectic-A* liquid-crystal structure formed by a silicon-containing molecule.

We have identified a metastable liquid-crystal (LC) structure in the de Vries smectic-A* phase (de Vries Sm-A*) formed by silicon-containing molecules under certain boundary conditions. The phase transition with the metastable structure was observed in a LC droplet placed on a planar aligned substrate and LCs confined in the groove of a silicon microchannel. During the rapid cooling step, a batonnet structure was generated as an intermediate and metastable state prior to the transition that yielded the thermodynamically stable toric focal conic domains. This distinctive behavior was characterized using depolarized reflection light microscopy and grazing incidence x-ray diffraction techniques. We concluded that the silicon groups in the molecules that formed the de Vries phase induced the formation of layered clusters called cybotactic structures. This observation is relevant to an exploration of the physical properties of cybotactic de Vries phases and gives a hint as to their optoelectronic applications.

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.

Generalized Langevin-Debye model of the field dependence of tilt, birefringence, and polarization current near the de Vries smectic-A* to smectic-C* liquid crystal phase transition.

In chiral smectic-A (Sm-A) liquid crystals, an applied electric field induces a tilt of the optic axis from the layer normal. When these materials are of the de Vries type, the electroclinic tilt susceptibility is unusually large, with the field-induced director reorientation accompanied by a substantial increase in optical birefringence with essentially no change in the smectic layer spacing. In order to account for the observed electro-optic behavior, we assume that the molecular orientation distribution in the Sm-A has two degrees of freedom: azimuthal orientation and tilt of the molecular long axis from the layer normal, with the tilt confined to a narrow range of angles. We present a generalized Langevin-Debye model of the response of this orientational distribution to applied field that gives a field-induced optic axis tilt, birefringence, and polarization dependence that agrees well with experimental measurements and reproduces the double-peaked polarization current response characteristic of a first-order Sm-A(*)-Sm-C(*) transition. Additionally, we find that the measured field-induced polarization and the Langevin-Debye model predictions can be quantitatively described as pre-transitional behavior near the tricritical point of a recently published generalized 3D XY model of interacting hard rods confined to reorient on a cone in the presence of an applied field.

Electro-optic response of the anticlinic, antiferroelectric liquid-crystal phase of a biaxial bent-core molecule with tilt angle near 45∘.

We describe the unusual electro-optic response of a biaxial bent-core liquid crystal molecule that exhibits an anticlinic, antiferroelectric smectic phase (Sm-C(A)P(A)) with a molecular tilt angle close to 45°. In the ground state, the sample shows very low birefringence. A weak applied electric field distorts the antiferroelectric ground state, inducing a small azimuthal reorientation of the molecules on the tilt cone. This results in only a modest increase in the birefringence but an anomalously large (∼40°) analog rotation of the extinction direction. This unusual electro-optic response is shown to be a consequence of the molecular biaxiality.

Effective conductivity due to continuous polarization reorientation in fluid ferroelectrics.

A smectic-A (SmA) liquid crystal phase of fluid layers with in-plane polarization P is shown to exhibit effective conductivity in the semiconducting range during electric-field-induced polarization reorientation, but becomes insulating once the polarization is aligned with the field. Such fluid ferroelectrics sandwiched between highly insulating layers enable electro-optic devices with long-term dc electrostatic control of polarization and optic axis orientation.

Spontaneous ferroelectric order in a bent-core smectic liquid crystal of fluid orthorhombic 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 SmAP(F), 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.