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We present a new ferroelectric nematic material, 4-((4′-((trans)-5-ethyloxan-2-yl)-2′,3,5,6′-tetrafluoro-[1,1′-biphenyl]-4-yl)difluoromethoxy)-2,6-difluorobenzonitrile (AUUQU-2-N) and its higher homologues, the molecular structures of which include fluorinated building blocks, an oxane ring, and a terminal cyano group, all contributing to a large molecular dipole moment of about 12.5 D. We observed that AUUQU-2-N has three distinct liquid crystal phases, two of which were found to be polar phases with a spontaneous electric polarization Ps of up to 6 µC cm–2. The highest temperature phase is a common enantiotropic nematic (N) exhibiting only field-induced polarization. The lowest-temperature, monotropic phase proved to be a new example of the ferroelectric nematic phase (NF), evidenced by a single-peak polarization reversal current response, a giant imaginary dielectric permittivity on the order of 103, and the absence of any smectic layer X-ray diffraction peaks. The ordinary nematic phase N and the ferroelectric nematic phase NF are separated by an antiferroelectric liquid crystal phase which has low permittivity and a polarization reversal current exhibiting a characteristic double-peak response. In the polarizing light microscope, this antiferroelectric phase shows characteristic zig-zag defects, evidence of a layered structure. These observations suggest that this is another example of the recently discovered smectic ZA (SmZA) phase, having smectic layers with the molecular director parallel to the layer planes. The diffraction peaks from the smectic layering have not been observed to date but detailed 2D X-ray studies indicate the presence of additional short-range structures including smectic C-type correlations in all three phases—N, SmZA and NF—which may shed new light on the understanding of polar and antipolar order in these phases. [ABSTRACT FROM AUTHOR]

The organic mesogens RM734 and DIO are members of separate molecular families featuring distinct molecular structures. These families are the first ones known to exhibit a ferroelectric nematic liquid crystal phase. Here, we present an experimental investigation of the phase diagram and electro-optics of binary mixtures of RM734 and DIO. We observe paraelectric nematic and ferroelectric nematic phases in both materials, each of which exhibits complete miscibility across the phase diagram, showing that the paraelectric and ferroelectric are the same phases in RM734 and DIO. Remarkably, these molecules form ideal mixtures with respect to both the paraelectric–ferroelectric nematic phase behaviour and the ferroelectric polarisation density of the mixtures, the principal order parameter of the transition. Ideal mixing is also manifested in the orientational viscosity, and the onset of glassy dynamics at low temperature. This behaviour is attributable in part to the similarity of their overall molecular shape and net longitudinal dipole moment, and to a common tendency for head-to-tail molecular association. In contrast, the significant difference in molecular structures leads to poor solubility in the crystal phases, enhancing the stability of the ferroelectric nematic phase at low temperature in the mixtures and enabling room-temperature electro-optic effects. [ABSTRACT FROM AUTHOR]

We investigated the electrostatic behavior of ferroelectric liquid droplets exposed to the pyroelectric field of a lithium niobate ferroelectric crystal substrate. The ferroelectric liquid is a nematic liquid crystal, in which almost complete polar ordering of the molecular dipoles generates an internal macroscopic polarization locally collinear to the mean molecular long axis. Upon entering the ferroelectric phase by reducing the temperature from the nematic phase, the liquid crystal droplets become electromechanically unstable and disintegrate by the explosive emission of fluid jets. These jets are mostly interfacial, spreading out on the substrate surface, and exhibit fractal branching out into smaller streams to eventually disrupt, forming secondary droplets. We understand this behavior as a manifestation of the Rayleigh instability of electrically charged fluid droplets, expected when the electrostatic repulsion exceeds the surface tension of the fluid. In this case, the charges are due to the bulk polarization of the ferroelectric fluid, which couples to the pyroelectric polarization of the underlying lithium niobate substrate through its fringing field and solid-fluid interface coupling. Since the ejection of fluid does not neutralize the droplet surfaces, they can undergo multiple explosive events as the temperature decreases. [ABSTRACT FROM AUTHOR]

In high-resolution adiabatic scanning calorimetry (ASC) experiments, data for the temperature dependence of the specific enthalpy, h(T), and of the specific heat capacity, cp(T), are simultaneously obtained, from which the order of the phase transition and critical behaviour can be evaluated. ASC was applied to study the nematic to ferroelectric nematic phase transition (N–NF) in the liquid crystal molecule 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). The N–NF was found to be very weakly first order with a latent heat Δh = 0.115 ± 0.005 J/g. The pretransitional specific heat capacity behaviour is substantially larger in the high-temperature N phase than in the low-temperature NF phase. In both phases the power-law analysis of cp(T) resulted in a critical exponent α = 0.50 ± 0.05 and amplitude ratio ANF/AN = 0.42 ± 0.03. The very small latent heat and the value of α indicate that the N–NF transition is close to a tricritical point. This is confirmed by a value of the order parameter exponent β ≈ 0.25, recently obtained from electric polarisation measurements. Invoking two-scale-factor universality, it follows from the low value of ANF/AN ratio that the size of the critical fluctuations is much larger in the NF phase than in the N phase. [ABSTRACT FROM AUTHOR]

We show that surface interactions can vectorially structure the three-dimensional polarization field of a ferroelectric fluid. The contact between a ferroelectric nematic liquid crystal and a surface with in-plane polarity generates a preferred in-plane orientation of the polarization field at that interface. This is a route to the formation of fluid or glassy monodomains of high polarization without the need for electric field poling. For example, unidirectional buffing of polyimide films on planar surfaces to give quadrupolar in-plane anisotropy also induces macroscopic in-plane polar order at the surfaces, enabling the formation of a variety of azimuthal polar director structures in the cell interior, including uniform and twisted states. In a p-twist cell, obtained with antiparallel, unidirectional buffing on opposing surfaces, we demonstrate three distinct modes of ferroelectric nematic electro-optic response: intrinsic, viscosity-limited, field-induced molecular reorientation; field-induced motion of domain walls separating twisted states of opposite chirality; and propagation of polarization reorientation solitons fromthe cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in antiparallelrubbed cells produce Grandjean textures of helical twist that can be unwound via field-induced polar surface reorientation transitions. Fields required are in the 3-V/mm range, indicating an in-plane polar anchoring energy of wP ~3 × 10-3 J/m². [ABSTRACT FROM AUTHOR]

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 ferro-electrics 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 ultra-low applied field (E ~ 1 V/cm), produced by the coupling of the large polarization to nematic birefringence and flow. Electrostatic selfinteraction 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. [ABSTRACT FROM AUTHOR]

We produced controlled heliconical structures of a twist-bend nematic (NTB) liquid-crystal (LC) phase in nanoconfinement in a porous anodic aluminium oxide (AAO) film. The structural parameters of the NTB phase such as conical angle and helical pitch can be modulated by varying the surface energy of the inner surface of the porous AAO film, done by using different self-assembled monolayers (SAMs). The LC molecules tend to be more freely packed, thus forming a larger conical angle, when placed on the tri-deca-fluoro-1,1,2,2-tetrahydrooctyl-trichlorosilane (FOTS)-treated substrate, which has a relatively low surface energy. In contrast, the molecules form a more tightly packed structure, and thus a smaller conical angle, when placed on the 2-(methoxy(polyethyleneoxy)-propyl)trimethoxysilane (PEG 6/9)-treated substrate, which has higher surface energy. This work improves our collective understanding of self-assembled heliconical structures in the NTB phase. [ABSTRACT FROM AUTHOR]

We report the synthesis and properties of several new heliconical twist-bend nematic (NTB) bimesogens possessing “classic” bent-core benzylideneaniline wings combined with oligomethylene spacers of odd parity. While short alkoxy tails combined with a resorcinol diester core in the classic system appear to give SmA phases (not B2 phases), in the present system, methoxy or ethoxy tails exhibit the NTBphase as evidenced by textural analysis. Several of these compounds also exhibit microscopic helical defect structures in the NTBphase, which have been reported in other lamellar and pseudo-lamellar liquid crystal phases, but not in the NTBphase. [ABSTRACT FROM AUTHOR]

Freeze-fracture transmission electron microscopy study of the nanoscale structure of the so-called "twist-bend" nematic phase of the cyanobiphenyl (CB) dimer molecule CB(CH2)7CB reveals stripe-textured fracture planes that indicate fluid layers periodically arrayed in the bulk with a spacing of d ∼ 8.3 nm. Fluidity and a rigorously maintained spacing result in long-range-ordered 3D focal conic domains. Absence of a lamellar X-ray reflection at wavevector q ∼ 2π/d or its harmonics in synchrotron-based scattering experiments indicates that this periodic structure is achieved with no detectable associated modulation of the electron density, and thus has nematic rather than smectic molecular ordering. A search for periodic ordering with d ∼ in CB(CH2)7CB using atomistic molecular dynamic computer simulation yields an equilibrium heliconical ground state, exhibiting nematic twist and bend, of the sort first proposed by Meyer, and envisioned in systems of bent molecules by Dozov and Memmer. We measure the director cone angle to be ϑTB ∼ 25° and the full pitch of the director helix to be pTB ∼ 8.3 nm, a very small value indicating the strong coupling of molecular bend to director bend. [ABSTRACT FROM AUTHOR]

The chiral, heliconical (twist-bend) nematic ground state is reported in an achiral, rigid, bent-core mesogen (UD68). Similar to the nematic twist-bend (/VTB) phase observed in bent molecular dimers, the NTB 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 NTB helical pitch is pTB~ 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. [ABSTRACT FROM AUTHOR]