Search

The idea that rod-like molecules possessing an electric dipole moment could exhibit a ferroelectric nematic phase was suggested more than a century ago. However, only recently such a phase has been reported for two quite different liquid crystals: RM734 (4-[(4-nitrophenoxy)carbonyl)]phenyl 2,4-dimethoxybenzoate) and DIO (2.3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2.6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate). For RM734 a direct ferroelectric nematic (NF) to classical nematic N transition was reported, whereas for DIO an intermediate phase Nx was discovered between the NF and the N phases. Here we present high-resolution calorimetric evidence that an intermediate Nx phase also exists in RM734 along a narrow temperature range between the NF and the N phases., Comment: 18 pages, 7 Figures

The current intense study of ferroelectric nematic liquid crystals was initiated by the observation of the same ferroelectric nematic phase in two independently discovered organic rod-shaped mesogenic compounds, RM734 and DIO. We recently reported that the compound RM734 also exhibits a monotropic, low-temperature, antiferroelectric phase having reentrant isotropic symmetry (the $I_A$ phase), the formation of which is facilitated to a remarkable degree by doping with small (below $1\%$) amounts of the ionic liquid ${\rm BMIM-PF}_6$. Here we report similar phenomenology in DIO, showing that this reentrant isotropic behavior is not only a property of RM734 but is rather a more general, material-independent feature of ferroelectric nematic mesogens. We find that the reentrant isotropic phases observed in RM734 and DIO are similar but not identical, adding two new phases to the ferroelectric nematic realm. The two $I_A$ phases exhibit similar, strongly peaked, diffuse x-ray scattering in the WAXS range $(1

We report a transition from the ferroelectric nematic liquid crystal ($N_F$) phase to a lower-temperature, antiferroelectric fluid phase having reentrant isotropic symmetry ($I_A$), in the liquid crystal compound RM734 doped with small concentrations of the ionic liquids BMIM or EMIM. Even a trace amount of ionic liquid dopant facilitates the kinetic pathway for the transition from the $N_F$ to the $I_A$, enabling simple cooling to produce this isotropic fluid phase rather than resulting in crystallization. The $I_A$ was also obtained in the absence of specific ionic liquid doping by appropriate temperature cycling in three distinct, as-synthesized-and-purified batches of RM734, two commercial and one from our laboratory. An additional birefringent, lamellar-modulated, antiferroelectric phase with the director parallel to the layers, resembling the smectic $Z_A$, is found between the paraelectric and ferroelectric nematic phases in RM734/BMIM mixtures., Comment: 45 pages, including Supplementary Information

We report the smectic $A_F$, a new liquid crystal phase of the ferroelectric nematic realm. The smectic $A_F$ is a phase of small polar, rod-shaped molecules which form two-dimensional fluid layers spaced by approximately the mean molecular length. The phase is uniaxial, with the molecular director, the local average long-axis orientation, normal to the layer planes, and ferroelectric, with a spontaneous electric polarization parallel to the director. Polarization measurements indicate almost complete polar ordering of the $\sim 10$ Debye longitudinal molecular dipoles, and hysteretic polarization reversal with a coercive field of about $2 \times 10^5$ V/m is observed. The smectic $A_F$ phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic ($N$) -- smectic $Z_A$ (Sm$Z_A$) -- ferroelectric nematic ($N_F$) -- smectic $A_F$ (Sm$A_F$) phase sequence; and 7N/DIO, exhibiting an $N$ -- Sm$Z_A$ -- Sm$A_F$ phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers., Comment: 26 pages, 6 figures

We have structurally characterized the liquid crystal phase that appears as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-year-old void in the taxonomy of smectics and which we term the "smectic $Z_A$", is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer. The period of this polarization wave ($\sim$180 A) is mesoscopic, corresponding to $\sim$40 molecules side-by-side, indicating that this lamellar structure is collectively stabilized. A Landau free energy, originally formulated to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-Sm$Z_A$-ferroelectric nematic phase sequence., Comment: main paper (with 7 figures) and supplement (with 12 figures) comprise 65 pages

The organic mesogens RM734 and DIO are members of separate molecular families featuring distinct molecular structures. These families, at the present time, are the only ones known to exhibit a ferroelectric nematic liquid crystal (LC) 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 (N) and ferroelectric nematic (NF) 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 as in DIO. Remarkably, these molecules form ideal mixtures with respect to both the paraelectric-ferroelectric nematic phase behavior and the ferroelectric polarization 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 behavior is attributable in part to the similarity of their overall molecular shape and net longitudinal dipole moment (~ 11 Debye), 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 making possible room temperature electro-optic effects. In the mixtures with excess DIO, an intermediate phase appears via an ultraweak, first-order transition from the N phase, in a narrow temperature range between the paraelectric and ferroelectric nematics., Comment: main paper has 24 pages with 5 figures; supplementary information has 14 pages with 8 figures

We show that surface interactions can vectorially structure the three-dimensional polariza-tion 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 mac-roscopic 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 {\pi}-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 twist-ed states of opposite chirality; and propagation of polarization reorientation solitons from the cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in anti-parallel-rubbed 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 ~ 3x10-3 J/m2., Comment: 34 pages, including 5 figures and bibliography

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 microcoulombs/cm-sqd, the largest ever measured for an organic material or for any fluid. 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 long axes in the nematic. We find a host of spectacular optical and hydrodynamic effects driven by ultra-low applied field (E~1V/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 science and technology based on the enhanced understanding, development, and exploitation of molecular electrostatic interaction., Comment: main paper: 23 pages; SI 34 pages

The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered macroscopically chiral heliconical winding of molecular scale pitch, in absence of positional ordering. Here we characterize the structure of the ground state of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB over a wide range of concentrations and temperatures, showing that the contour length along the molecular direction for a single turn of the helix is approximately equal to 2{\pi}Rmol, where Rmol is the radius of bend curvature of a single all-trans CB7CB molecule. This relation emerges from a model which simply relates the macroscopic characteristics of the helical structure, which is mostly biaxial twist and has little bend, to the bent molecular shape. This connection comes about through the presence in the fluid of self-assembled oligomer-like correlations of interlocking molecules, arising from the nanosegregation of rigid and flexible molecular subcomponents, forming a brickwork tiling of pairs of molecular strands into a duplex double-helical chain., Comment: Supplementary Information included

Binary mixtures of the twist-bend nematic-forming liquid crystal CB7CB with the prototypical rod-like liquid crystal 5CB exhibit a twist-bend nematic phase with properties similar to those reported for neat CB7CB. The mixtures appear homogeneous, with no micron- or nano-scale segregation evident at any concentration. The linear dependence of the phase transition temperature on concentration indicates that these binary mixtures are nearly ideal. However, a decrease in the viscosity with the addition of 5CB allows the characteristic twist-bend stripe textures to relax into a state of uniform birefringence. We confirm the presence of nanoscale modulations of the molecular orientation in the mixtures by freeze-fracture transmission electron microscopy (FFTEM), further evidence of their twist-bend nature. We devise and implement a statistical approach to quantitatively measure the ground state pitch of the twist-bend phase and its mixtures using FFTEM. The addition of 5CB generally shifts the measured ground-state pitch distributions towards larger pitch. Interestingly, the pitch appears to increase discontinuously by ~10 nm at the 50 wt% concentration of 5CB, indicating that the twist-bend phase undergoes a structural transition at higher 5CB concentrations., Comment: Supplementary information included

Freeze Fracture Transmission Electron Microscopy (FFTEM) study of the nanoscale structure of the so-called "twist-bend" nematic (NX) phase of the cyanobiphenyl (CB) dimer molecule CB(CH2)7CB reveals a stripe texture of fluid layers periodically arrayed with a bulk spacing of d ~ 8.3 nm. Fluidity and a rigorously maintained spacing produce long-range-ordered fluid layered focal conic domains. Absence of a lamellar x-ray reflection at wavevector q ~ 2{\pi}/8 nm-1 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 molecular ordering. A search for periodic ordering with d ~ 8nm in CB(CH2)7CB using atomistic molecular dynamic computer simulation yielded equilibration of a conical twist-bend helixed nematic ground state, of the sort first proposed by Meyer, and envisioned in systems of bent molecules by Dozov and Memmer, We identify {\theta} ~ 33 degree as the cone angle, and p ~ 8nm as the full pitch of the helix, the shortest ever found in a nematic fluid., Comment: 21 pages, 6 figures