Smectic Layers Research Articles

Thermotropic reentrant isotropic symmetry and induced smectic antiferroelectricity in the ferroelectric nematic material RM734

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.

Vertically aligned polyimide prepared from a lyotropic precursor containing clay nanosheet that facilitates vertical stacking of smectic layer

Vertically aligned polyimide prepared from a lyotropic precursor containing clay nanosheet that facilitates vertical stacking of smectic layer

Structural and dynamical investigation of glassforming smectogen by X-ray diffraction and infra-red spectroscopy aided by density functional theory calculations.

Structural and dynamical investigation of glassforming smectogen by X-ray diffraction and infra-red spectroscopy aided by density functional theory calculations.

Macroscopic dynamics of the antiferroelectric smectic ZA phase and its magnetic analog ZM

We analyze the macroscopic dynamics of antiferroelectric smectic ZA and antiferromagnetic smectic ZM liquid crystals. The smectic ZA phase is characterized by antiferroelectric order in one direction in the planes of the smectic layers giving rise to an orthogonal biaxial overall symmetry without polar direction. Thus in sufficiently thick (bulk) samples without externally applied electric fields, globally D2h symmetry results. Therefore, the macroscopic dynamics of the smectic ZA is isomorphic to that of the McMillan phase and one can take over the corresponding results in the field-free limit. This also applies to the defect structure in the sense that one can expect the appearance of half-integer defects as they have also been observed for the McMillan phase. Based on the fact that ferromagnetic nematic liquid crystals are known for about a decade, it seems natural to investigate the antiferromagnetic analog of the smectic ZA phase, which we denote as ZM in the present paper. In this phase, one also has an in-plane preferred direction, which is, however, not like a director in an ordinary nematic, but odd under time reversal. It can be characterized by a staggered magnetization, N, just as in a solid antiferromagnet like MnO. As additional macroscopic variables when compared to a usual non-polar smectic A phase, we have the in-plane staggered magnetization and the magnetization M. As a consequence, we find that spin waves (frequently called anti-magnons in solids) become possible. Therefore, we have for the antiferromagnetic smectic phase, ZM, three pairs of propagating modes: first and ‘second’ sound as in usual smectic A phases and one pair of spin waves. The coupling between ‘second’ sound and spin waves is also analyzed leading to the possibility to excite spin waves by dynamic layer compressions and, vice versa, to generate ‘second’ sound by temporally varying magnetic fields. We note, however, that without additional mechanical or magnetic deformations, the coupling between spin waves on the one hand and first and second sound on the other is a higher order effect in the wave vector q. We also analyze the question of antiferroelectricity and antiferromagnetism for nematic liquid crystals.Graphical abstract

X-Ray Diffraction Reveals the Consequences of Strong Deformation in Thin Smectic Films: Dilation and Chevron Formation.

Smectic liquid crystals can be viewed as model systems for lamellar structures for which there has been extensive theoretical development. We demonstrate that a nonlinear energy description is required with respect to the usual Landau-de Gennes elasticity in order to explain the observed layer spacing of highly curved smectic layers. Using x-ray diffraction we have quantitatively determined the dilation of bent layers distorted by antagonistic anchoring (as high as 1.8% of dilation for the most bent smectic layers) and accurately described it by the minimal nonlinear expression for energy. We observe a 1° tilt of planar layers that are connected to the curved layers. This value is consistent with simple energetic calculations, demonstrating how the bending energy impacts the overall structure of a thin distorted smectic film. Finally, we show that combined x-ray measurements and theoretical modeling allow for the quantitative determination of the number of curved smectic layers and of the resulting thickness of the dilated region with unprecedented precision.

Freely suspended nematic and smectic films and free-standing smectic filaments in 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.

Effect of CsPbBr3 perovskite quantum dots on molecular alignment, dielectric and memory effect of a cyanobiphenyl based liquid crystal

Effect of CsPbBr3 perovskite quantum dots on molecular alignment, dielectric and memory effect of a cyanobiphenyl based liquid crystal

Thermal and structural analysis of binary mixtures of pyrimidine liquid crystals using Modulated Differential Calorimetry and Synchrotron X-ray Diffraction measurements.

We present a systematic experimental dataset on the temperature dependence of specific heat capacity in a binary mixture of the second and seventh homologous series of 5-alkyloxy-2-(4-nonyloxy-phenyl) pyrimidine(PhP) liquid crystal compound. These binary mixtures exhibit nematic, smectic-A, and smectic-C phases within a concentration range of xPhP1 = 0 to 0.45. The liquid crystalline phases are structurally characterized using synchrotron X-ray diffraction. We determine the apparent molecular length in the nematic phase, smectic layer spacing, average distance between the long axes of molecules, correlation length, and orientational order parameters (<P2> and <P4>) as functions of temperature. The tilt angle in the SmC phase is inferred from the layer spacing data. To examine the critical behavior near the nematic to smectic A(NA) and smectic A to the smectic C (AC) phase transitions, we evaluate the critical exponents: α from specific heat capacity, β from the fitting of the temperature-dependent tilt angle, and ν‖, ν⊥from the temperature-dependent longitudinal (ξ‖) and transverse (ξ⊥) correlation lengths. Modulated Differential Scanning Calorimetry (MDSC) measurements indicate the absence of phase shift, latent heat and imaginary specific heat capacity, suggesting that the AC transitions are second-order for all binary mixtures. The results obtained from heat capacity reveal that both the AC and NA transitions exhibit non-universal behaviours with effective exponents lying between the tricritical and 3D-XY values and follow nearly identical curve with decreasing width of the Sm-A and N phases. The Josephson hyperscaling relation is verified for both the NA and AC transitions in different mixtures. Moreover, knowing the heat capacity critical exponent α and the order parameter critical exponent β, the susceptibility critical exponent γ for the AC transition can be estimated from Rushbrooke equality α+2β+γ=2, with γ values ranging from 1.015 to 1.313, indicating the system's crossover character and apparently validating the Rushbrooke equality.

Structural investigation of the liquid crystalline phases of three homologues from the nOS5 series (n = 9, 10, 11) by X-ray diffraction

ABSTRACT Polarizing optical microscopy and differential scanning calorimetry are used to determine the phase sequence of three liquid crystalline 4-pentylphenyl-4’-n-alkyloxythiobenzoates with n = 9, 10, 11. The X-ray diffraction method is applied for structural characterisation of the liquid crystalline phases. The smectic layer spacing, tilt angle, average distance between the long axes of molecules and correlation length of the short-range order are determined as a function of temperature. For the crystal-like smectic phases with the hexagonal or herring-bone packing, the unit cell parameters are obtained. The presence of the tilted hexagonal phase for n = 10, 11 and tilted herring-bone phase for n = 9, 10 is indicated, although the direction of the tilt cannot be determined.

Smectic layer reorientation by surface mode in surface stabilized ferroelectric liquid crystal

Smectic layer reorientation by surface mode in surface stabilized ferroelectric liquid crystal

Estimations of the Thicknesses of Smectic Layer and Rigid Amorphous Layer in Mesomorphic Isotactic Polypropylene with Synchrotron Small‐Angle and Wide‐Angle X‐Ray Scattering

AbstractDespite extensive research, the stabilization mechanism of mesomorphic isotactic polypropylene (iPP) at room temperature has not been elucidated completely. To address this issue, nanoscale structural information is indispensable. In this study, mesomorphic‐α phase transition is studied with synchrotron wide‐angle diffraction and small‐angle X‐ray scattering. It is found that during phase transition, the mobile amorphous content remained unchanged, while rigid amorphous fraction (RAF) decreased constantly, accompanied by an increase in long period. Assuming that the increase in long period is induced by the extension of the rigid amorphous coil (RAC), the thickness of RAF (RRAF) is estimated, which is found to be 2.2 nm. This value is greater than the length of b axis in α crystal cell, which can be the reason that folded‐chain iPP clusters in mesomorphic iPP cannot approach closer to form α crystal at room temperature. Besides, with RRAF, the thickness of smectic layer is estimated, which is found to be 0.9 nm. At this thickness, bulk‐free energy cannot compensate for the folded‐surface free energy, which can be the other reason that mesomorphic iPP chains cannot transit into α crystal at room temperature. The information obtained in this study is favorable for understanding the stabilization mechanism of mesomorphic iPP.

Optical imaging of ferroelectric domains in periodically poled lithium niobate using ferroelectric liquid crystals

Ferroelectric liquid crystals exhibiting a chiral smectic C* phase are deposited on z cut periodically poled lithium niobate substrates and investigated by polarized optical microscopy. While the pure substrates placed between crossed polarizers and observed in transmission appear dark, uniformly aligned liquid crystal films deposited on these substrates show alternating domains with varying brightness. This effect can be attributed to the well-known coupling between the direction of the spontaneous polarization and the optical axis in the birefringent ferroelectric smectic C* phase. Quantitative measurements of the tilt angle between the local optical axis and the smectic layer normal confirm antiparallel orientations of spontaneous polarization of the liquid crystal from domain to domain, as expected by the periodic poling of the lithium niobate substrate. This effect provides a valuable non-destructive method of optical inspection of the quality of periodically poled ferroelectric substrates, which plays an important role in achieving quasi-phase-matching in non-linear optical applications.

Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound

The experimental IR spectra of (S)-4′-(1-methylheptyloxycarbonyl) biphenyl-4-yl 4-[2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethyl-1-oxy]-2-fluorobenzoate in the crystal phase are analyzed with the help of dispersion-corrected density functional theory (DFT+D3) calculations for isolated molecular monomer and dimer models, and a periodic model computed at the extended density functional tight-binding (xTB) level of theory. It is found that the frequency scaling coefficients obtained with the results of the molecular calculations are good matches for the crystal phase, being close to 1. The molecular and periodic models both confirm that varied intra- and intermolecular interactions are crucial in order to reproduce the broadened shape of the experimental band related to C=O stretching; the key factors are the conjugation of the ester groups with the aromatic rings and the varied intermolecular chemical environments, wherein the C=O group that bridges the biphenyl and F-substituted phenyl groups seems particularly sensitive. The C=O stretching vibrations are investigated as a function of temperature, covering the range of the crystal, smectic CA*, smectic C* and isotropic liquid phases. The structure changes are followed based on the X-ray diffraction patterns collected in the same temperatures as the IR spectra. The experimental and computational results taken together indicate that the amount of weak C=O…H-C hydrogen bonds between the molecules in the smectic layers decreases with increasing temperature.

Revealing the antipolar order in the antiferroelectric SmZA phase by means of circular alignment

Many ferroelectric nematic liquid crystals, like one of the archetype materials, DIO, do not have a direct paraelectric N to ferroelectric NF phase transition, but exhibit yet another phase between N and NF. This phase has recently been proposed to be antiferroelectric, with a layered structure of alternating polarization normal to the average director and is sometimes referred to as Smectic ZA (SmZA). We have examined the SmZA phase in circularly rubbed (CR) cells, known to discriminate between the polar NF and the non-polar N phase from the configuration of disclination lines formed. We find that the ground state of SmZA has the same disclination configuration as the non-polar N phase, demonstrating that the SmZA phase is also non-polar, i.e., it has no net ferroelectric polarization. At the same time, the SmZA texture generally has a grainy appearance, which we suggest is partly a result of the frustration related to layered order combined with the imposed twist in CR cells. We discuss possible orientations of the smectic layers, depending on the alignment conditions. While a horizontal SmZA layer structure is always compatible with surface-induced twist, a vertical layer structure would tend to break up in a twisted bookshelf structure to match non-parallel alignment directions at the two surfaces.

Multiple Phase Structures and Enhanced Dielectric Properties of Side-Chain Liquid Crystalline Polymer Containing Unique Biaxial Mesogen with Large Dipole Moment

Multiple Phase Structures and Enhanced Dielectric Properties of Side-Chain Liquid Crystalline Polymer Containing Unique Biaxial Mesogen with Large Dipole Moment

Investigation of glass transition and polymorphism of smectogenic, partially fluorinated chiral compound by X-ray diffraction and infra-red spectroscopy

Investigation of glass transition and polymorphism of smectogenic, partially fluorinated chiral compound by X-ray diffraction and infra-red spectroscopy

Confinement and magnetic-field effect on chiral ferroelectric nematic liquid crystals in Grandjean-Cano wedge cells.

We explore the structure and magnetic-field response of edge dislocations in Grandjean-Cano wedge cells filled with chiral mixtures of the ferroelectric nematic mesogen DIO. Upon cooling, the ordering changes from paraelectric in the cholesteric phase N^{*} to antiferroelectric in the smectic SmZ_{A}^{*} and to ferroelectric in the cholesteric N_{F}^{*}. Dislocations of the Burgers vector b equal to the helicoidal pitch P are stable in all three phases, while dislocations with b=P/2 exist only in the N^{*} and SmZ_{A}^{*}. The b=P/2 dislocations split into pairs of τ^{-1/2}λ^{+1/2} disclinations, while the thick dislocations b=P are pairs of nonsingular λ^{-1/2}λ^{+1/2} disclinations. The polar order makes the τ^{-1/2} disclinations unstable in the N_{F}^{*} phase, as they should be connected to singular walls in the polarization field. We propose a model of transformation of the composite τ^{-1/2} line-wall defect into a nonsingular λ^{-1/2} disclination, which is paired up with a λ^{+1/2} line to form a b=P dislocation. The SmZ_{A}^{*} behavior in the in-plane magnetic field is different from that of the N_{F}^{*} and N^{*}: the dislocations show no zigzag instability, and the pitch remains unchanged in the magnetic fields up to 1 T. The behavior is associated with the finite compressibility of smectic layers.

Domain reorientation due to smectic layer instability in high tilt angle-based surface stabilized ferroelectric liquid crystal cell

High tilt angle (45°) ferroelectric liquid crystal (FLC) in surface stabilized geometry, having no chiral smectic A (SmA∗) phase, has been studied for the reorientation of the smectic layers near the transition temperature (Tc). The electro-optical studies have shown the stripe domain formation in which the liquid crystal molecules are aligned along the rubbing direction, but the smectic layers are tilted away from the rubbing direction at room temperature. In such high tilt angle FLCs, the molecular alignment and smectic layer formation start from bottom and top rubbed grooves at Tc. The domain formation of the FLC takes place in the middle of the top and bottom surfaces due to the frustration of the dipolar interaction. The smectic layer switching is observed by optical microscopy and confirmed by the dielectric spectroscopy method near Tc of SmC∗ and chiral nematic phases. Domain switching has shown a larger switching angle than the molecular tilt angle within the smectic layer. These studies are expected to be significant for understanding the smectic layer structure and the domain switching process, which may pave the way for large optical switching devices.

Layer topology of smectic grain boundaries

ABSTRACT Grain boundaries in extremely confined colloidal smectics possess a topological fine structure with coexisting nematic and tetratic symmetry of the director field. An alternative way to approach the problem of smectic topology is via the layer structure, which is typically more accessible in experiments on molecular liquid crystals. Here, we consider exemplary density functional theory results for two-dimensional hard rods to illustrate how the concept of endpoint defects, which appear as tetratic disclinations of quarter charge in director topology, translates to smectic layer topology built around the networks formed by density maxima and minima. By doing so, we elaborate on further advantages of a topological concept evolving around the layer structure rather than the director field, such as providing insight in the structure of edge dislocations or virtual defects at the confining walls.

Preferential ordering of incommensurate-length guest particles in a smectic host.

Using density functional theory, we study the preferential ordering of rod-like guest particles immersed in a smectic host fluid. Within a model of perfectly aligned rods and assuming that the guest particles do not perturb the smectic host fluid, simple excluded-volume arguments explain that guest particles that are comparable in length to the host particles order in phase with the smectic host density layering, whereas guest particles that are considerably shorter or longer order in antiphase. The corresponding free-energy minima are separated by energetic barriers on the order of the thermal energy kBT, suggesting that guest particles undergo hopping-type diffusion between adjacent smectic layers. Upon introducing a slight orientational mismatch between the guest particles and the perfectly aligned smectic host, an additional, smaller free-energy barrier emerges for a range of intermediate guest-to-host length ratios, which splits the free-energy minimum into two. Guest particles in this range occupy positions intermediate between in-phase ordering and in-antiphase ordering. Finally, we use Kramers' theory to identify slow, fast, and intermediate diffusive regimes for the guest particles as a function of their length. Our model is in qualitative agreement with experiment and simulation and provides an alternative, complementary explanation in terms of a free-energy landscape for the intermediate diffusive regime, which was previously hypothesized to result from temporary caging effects [M. Chiappini, E. Grelet, and M. Dijkstra, Phys. Rev. Lett. 124, 087801 (2020)]. We argue that our simple model of aligned rods captures the salient features of incommensurate-length guest particles in a smectic host if a slight orientational mismatch is introduced.