We report a transition from the ferroelectric nematic liquid crystal (NF) phase to a lower-temperature, apolar fluid phase having reentrant isotropic symmetry (IR), in the liquid crystal compound RM734 doped with small concentrations of the ionic liquids 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) or 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI). Even a trace amount of ionic liquid dopant facilitates the kinetic pathway for the transition from the NF to the IR, enabling simple cooling to produce this isotropic fluid phase rather than resulting in immediate crystallization. The IR 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. Ionic liquid doping also stabilizes the smectic ZA, an additional birefringent antiferroelectric phase having the director parallel to fluid smectic layers, significantly increasing its temperature range between the paraelectric and ferroelectric nematic phases with increasing BMIM concentration.

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.

Electronic electro-optic (EEO) phase modulation is a key emerging technology for the chip-scale inter-conversion of signals between the electronic and photonic domains. The recent discovery of the ferroelectric nematic (N_F) liquid crystal phase, a three dimensional fluid of rod-shaped organic molecules having near-perfect equilibrium polar molecular orientational order, offers attractive opportunities for the creation of second-order nonlinear optical materials for EEO. Here we propose and realize a design motif for NF EEO molecules in which few-nanometer-long molecular rods are functionalized both for electro-static end-to-end association, facilitating NF phase formation, and for chromophoric optical nonlinearity, enabling high EEO efficiency, a combination enabling an active second-order nonlinear EEO medium that is 100

The recently discovered ferroelectric nematic phase draws great interest in the soft condensed matter community. The author appreciates the opportunity to participate in the early research of the discovery of ferroelectric nematic phase and the following discovery of NF*, SmZA, SmAF phase. The author is deeply honoured to receive the Glenn Brown prize in 2024, and the invited paper is a summary of author's Ph.D. research under professor Noel Clark's guidance, focused on the ferroelectric nematic realm.

We show that stable, freely suspended liquid crystal films can be made from the ferroelectric nematic (NF) phase and from the recently discovered polar, lamellar SmZA and SmAF phases. The NF films display two-dimensional, smectic-like parabolic focal conic textures comprising director/polarization bend that are a manifestation of the electrostatic suppression of director splay in the film plane. In the SmZA and SmAF phases, the smectic layers orient preferentially normal to the film surfaces, a condition never found in typical thermotropic or lyotropic lamellar LC phases, with the SmZA films exhibiting focal-conic fan textures mimicking the appearance of typical smectics in glass cells when the layers are oriented normal to the plates, and the SmAF films showing a texture of plaquettes of uniform in-plane orientation where both bend and splay are suppressed, separated by grain boundaries. The SmAF phase can also be drawn into thin filaments, in which X-ray scattering reveals that the smectic layer planes are normal to the filament axis. Remarkably, the filaments are mechanically stable even if they break, forming free-standing, fluid filaments supported only at one end. The unique architectures of these films and filaments are stabilized by the electrostatic self-interaction of the liquid crystal polarization field, which enables the formation of confined, fluid structures that are fundamentally different from those of their counterparts made using previously known liquid crystal phases.

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 P s 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 (N F ), evidenced by a single-peak polarization reversal current response, a giant imaginary dielectric permittivity on the order of 10 3 , and the absence of any smectic layer X-ray diffraction peaks. The ordinary nematic phase N and the ferroelectric nematic phase N F 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 Z A (SmZ A ) 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, SmZ A and N F —which may shed new light on the understanding of polar and antipolar order in these phases.

Numerous measurements of the dielectric constant $\epsilon$ of the recently discovered ferroelectric nematic ($N_F$) liquid crystal (LC) phase report extraordinarily large values of $\epsilon^\prime$ (up to ~30,000). We show that what is in fact being measured in such experiments is the high capacitance of the non-ferroelectric, interfacial, insulating layers of nanoscale thickness that bound the $N_F$ material in typical cells. We analyze a parallel-plate cell filled with $N_F$ material of high-polarization $\mathbf{P}$, oriented parallel to the plates at zero applied voltage. Minimization of the dominant electrostatic energy renders $\mathbf{P}$ spatially uniform and orients it to make the electric field in the $N_F$ as small as possible, a condition under which the voltage applied to the cell appears almost entirely across the high-capacity interfacial layers. This coupling of orientation and charge creates a combined polarization-external capacitance (PCG) Goldstone reorientation mode requiring applied voltages orders of magnitude smaller than that of the $N_F$ layer alone to effectively transport charge across the $N_F$ layer. The $N_F$ layer acts as a low-value resistor and the interfacial capacitors as reversible energy storage reservoirs, lowering the restoring force (mass) of the PCG mode and producing strong reactive dielectric behavior. Analysis of data from several experiments on ferroelectric liquid crystals (chiral smectics C, bent-core smectics, and the $N_F$ phase supports the PCG model, showing that deriving dielectric constants from electrical impedance measurements of high-polarization ferroelectric LCs, without properly accounting for the self-screening effects of polarization charge and the capacitive contributions of interfacial layers, can result in overestimation of the $\epsilon^\prime$ values of the LC by many orders of magnitude.

Recently discovered ferroelectric nematic liquid crystals (FNLCs) offer the opportunity to make liquid crystalbased, high-speed electro-optic devices. The lack of a center of symmetry combined with having the polar axis oriented parallel to the long, polarizable molecular axis allows for large second-order nonlinear optical susceptibility and therefore a large Pockels effect. The electro-optic response at high frequencies is purely electronic, making possible high-speed modulators with bandwidths limited only by device architecture. Facile and thermodynamically stable alignment of the polar axis over large areas makes FNLCs an attractive alternative to organic crystals and poled polymers, which have been pursued for decades as Pockels materials. A novel methodology for characterizing the electro-optic coefficient (r33) of this new class of Pockels material was developed. Using this methodology, FNLCs engineered to have large nonlinearities were demonstrated to have r33 values approaching that of lithium niobate.

We have structurally characterized the liquid crystal (LC) phase that can appear 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-y-old void in the taxonomy of smectic LCs and which we term the "smectic ZA," is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole-dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-SmZA-ferroelectric nematic phase sequence.

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.

Significance Liquid crystal science grows in richness and applicability with each new phase that is found or created. The recent discovery of the ferroelectric nematic was both thrilling and unexpected, since it appeared in new molecules not much different in structure from many similar materials studied over the last 100 years. Clearly, significant secrets remain to be discovered in the complexities of organic molecular architecture and interaction. A fundamental question following the ferroelectric nematic discovery was whether there could also be a ferroelectric smectic A, the nematic-companion phase obtained when molecules spontaneously position to form planar, fluid layers normal to their molecular long axes. Here, we report such a phase, broadening the ferroelectric nematic realm.

The combination of large spontaneous polarization and fluidity makes the newly discovered ferroelectric nematic liquid crystalline phase (NF) responsive to electric fields in ways that have no counterpart in other materials. We probe this sensitive field response by confining a NF fluid in microchannels that connect electrodes through straight and curved paths. We find that by applying electric fields as low as E c.a. 0.5 V/mm, the NF phase orders with its polarization smoothly following the winding paths of the channels even when oriented antiparallel to the line connecting positive to negative electrodes, implying analogous behavior of the electric field. Upon inversion of E, the polar order undergoes a complex multistage switching process dominated by electrostatic interactions. Multistage polarization switching dynamics is also found in numerical simulations of a quasi-2D continuum model of NF liquid crystals in microchannels, which also clarify the conditions under which the electric field is guided by the microchannels. Experiments and theory indicate that all observations are direct consequences of the prompt effective screening of electric field components normal to the channel walls. This electric "superscreening" effect emerges as a distinctive property of the NF phase, capable of inducing conditions in which both the polarization and the electric field are guided by microchannels.

Significance The devices of the portable computing revolution are being made possible by nematic liquid crystal display (LCD) technology. The optical changes viewed in a dynamic LCD image are based on reorienting molecules by coupling electronically generated electric fields to molecular dielectric anisotropy. This takes place in appropriate fluid electro-optic structures stabilized by nonpolar orientational coupling of molecules to surfaces. The recent observation of ferroelectric nematics having spontaneous macroscopic electric polarization density has introduced a much stronger polar coupling of electric field to molecular reorientation in nematics. This development opens opportunities for advanced electro-optics, but these will require polar control of molecular orientation by surfaces. The generation of polar-structured surfaces and their coupling to nematic polarity is demonstrated in this paper. 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 π-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 from the cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in antiparallel-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 ∼3 × 10−3 J/m2.

This article presents the design and characteristics of new wideband polarization transformer based on a square waveguide with diaphragms. Matching and polarization characteristics of the polarization transformer have been simulated and optimized. Frequency dependences of the simulated characteristics are presented. Developed polarization transformer can be applied in modern satellite antennas.

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.