Tunable photonic band gap crystals based on a liquid crystal-infiltrated inverse opal structure

Composite materials comprised of nematic liquid crystals (LCs) and SiO(2) inverse opal films were fabricated. Their optical properties were quite different from those of inverse opal films without the LCs. The optical properties could be controlled by changing the refractive indices of the LCs, which vary with orientation, phase, and temperature. In particular, the optical properties were drastically changed by thermal or photoinduced isothermal phase transitions of the LCs. This means that the photonic band structure could be controlled, and tunable photonic crystals have been achieved, based on the inverse opal structure. The mechanism of this change was investigated by the evaluation of the effective refractive indices. As a result, it was found that the change in optical properties was derived from the orientation of the LC molecules in the voids in the inverse opal film. Furthermore, once the mechanism was understood, it was also possible to control the position of the reflection peak by changing the alignment of the LCs. Such materials have the possibility for practical use in optical devices and fundamental research systems.     

Temperature-dependent optical band structure and defect mode in a one-dimensional photonic liquid crystal

We analysed the propagation of an electromagnetic wave in a one-dimensional periodic system composed of a finite set of E7 liquid crystal mixture slabs in a twisted configuration alternated by homogeneous and isotropic dielectric layers. For different incident angles of the circularly polarised wave, we studied the optical band structure for reflectance and transmittance considering that the dielectric matrix of the device depends on temperature and wavelength. We demonstrated that the position of the band can be moved from visible to short-infrared spectrum region by increasing the thickness of the layers. We found that for a fixed incident angle, the band spectrum shifts towards the short-wavelength region as the temperature gets increasing, whereas, for a constant temperature, such a spectrum moves towards larger frequencies as the incident angle increases. We show that when one of the homogeneous and isotropic slabs has a different size compared with the remaining ones, a defect mode is induced in the band structure whose frequency can be thermally tuned.     

Influence of dimerization on the nematic-isotropic phase transition in strongly polar liquid crystals

A molecular theory of the nematic-isotropic phase transition is developed for the fluid composed of rod-like particles with large longitudinal dipoles. The equilibrium between the monomers and dimers with antiparallel dipoles is explicitly taken into account and the concentration of dimers is determined self-consistently together with the nematic order parameters. We show that for small central dipole moments the nematic-isotropic transition temperature increases with the increasing dipole. This is in accordance with the results of previous approaches. By contrast, for large values of the dipole the transition temperature decreases due to the growing concentration of dimers. This result enables one to explain the results of recent computer simulations that reveal a destabilization of the nematic phase in a system of hard rods with large central longitudinal dipoles. The temperature variation of the concentration of dimers is also analysed and the sign of the concentration discontinuity at the transition point is correlated with the qualitative influence of dimers on the transition temperature.     

Nematic-isotropic phase transition of binary liquid crystal mixtures

We experimentally studied the nematic-isotropic phase transition of (a) binary mixtures consisting of nematic and racemic liquid crystals and (b) binary mixtures consisting of positive and negative dielectric liquid crystals. We observed that the phase transition temperature is very sensitive to the chemical structures of the constituent components. We also used Maier-Saupe theory to calculate the transition temperature of binary mixtures. By fitting the experimental data, we obtained the interaction coupling constant between the constituent components.     

The structure of acrolein in a liquid crystal phase

The (1)H NMR spectrum of a sample of acrolein dissolved in the nematic liquid crystal phase I52 has been analysed to yield 18 dipolar couplings between all the magnetic nuclei in the molecule; moreover, the (13)C and (13)C{(1)H} NMR spectra of a sample of acrolein in CDCl(3) were recorded and analysed to determine the indirect J(ij) couplings. The data were used to obtain the relative positions of the carbon and hydrogen atoms, assuming that these are independent of the conformations generated by rotation around the C--C bond through an angle phi, and to obtain a probability distribution P(phi). It has been found that in the liquid phase, the distribution is a maximum at the trans form whereas the abundance of the cis form is significantly smaller compared with that found by microwave spectroscopy or high level quantum mechanical calculations. Such calculations produced also a suitable force field needed to develop suitable strategies for vibrational correction procedure in the case of flexible molecules.     

Modelling of the phase transition of nanoscale confined liquid crystal

By dividing the bulk melting entropy, a simple thermodynamic model without any adjustable parameter for the size-dependent melting transition temperature has been extended to interpret the melting and freezing transitions of liquid crystals (LCs) confined in nanopores. The results show that as the size of the nanopore decreases, the melting, clearing and freezing transition temperatures of LCs drop. The transition temperatures directly depend on the density of hydrogen bond at the interface between inner pore wall and LC molecules. The model predictions agree well with the corresponding experimental results of LCs p-azoxyanisole and 4-pentyl-4′-cyanobiphenyl confined in nanopores.     

Tuning of Photonic band gap via combined effect of electric and optical fields in a blue phase liquid crystal composite

ABSTRACT

Blue phase liquid crystals are soft 3D photonic crystals in which the liquid crystal molecules self-assemble to form a cubic structure with lattice spacing of a few hundred nanometers resulting in selective reflection of colours in the visible spectrum. The corresponding wavelength or the ‘photonic band gap’ can be tuned using various external stimuli such as thermal, electric, magnetic and optical fields. Here, we report efficient tuning of photonic band gap by utilising the combination of electric and optical fields in a blue phase liquid crystalline system. The studies indicate that the chirality of the medium has a direct bearing on the direction of the wavelength shift and the extent of the photonic band gap tunability. More importantly, the synergistic effect of the two fields helps in reversible tuning of the band gap.     

X-ray diffraction analysis of the layer structure in a ferroelectric liquid crystal with a chiral nematic-chiral smectic C phase transition

A half-V-shaped switching ferroelectric liquid crystal (FLC) is a promising candidate for fast response displays. In the half-V FLC display, a liquid crystal with a chiral nematic-chiral smectic C phase transition is used, and the smectic layer is formed by cooling from N* to SmC* with an applied d.c. field. We studied the layer structure by means of X-ray measurements for two axes (ω and χ). By using a point-focused X-ray tube and optimizing the slit width, we succeeded in the two-axis measurement with a commercial X-ray system. The ω-χ profile of the half-V FLC showed two broad peaks in an arc-shaped high-intensity area. Our interpretation of this result is that the major part of the layer consists of a tilted-bookshelf structure and that the minor part consists of a near-bookshelf structure. Since optical microscopy observations on the half-V FLC cells showed a stripe-shaped texture, we consider that the coexistence of the tilted-bookshelf and the near-bookshelf structures forms the stripe-shaped patterns. The radius of the arc-shaped high-intensity area was nearly equal to the molecular tilt angle. This result can explain why the half-V FLC showed a desirable black appearance in spite of the stripe-shaped texture.     

Depression of the crystal-nematic phase transition in thermotropic liquid crystal copolyesters

The crystal-nematic phase transition of a copolyester consisting of 20 mol% poly(ethylene terephthalate) and 80 mol% p-hydroxybenzoic acid (PHB) was characterized by depression of the crystal-nematic transition by the addition of a liquid crystal diluent. This copolyester contains blocks of crystalline PHB. Its transition behavior was compared with thatrandom copolyester with diluent of the same composition. From the extrapolated transition temperature depression data, the heat of transition per mole of p-oxybenzoate was calculated as about 1.3 kcal/mol, with an entropy of about 2 cal/deg mol. This assumes that only the p-oxybenzoate unit crystallized from the nematic state. The validity of the Flory-Huggins model for this transition point depression was confirmed graphically by comparison with two different thermotropic-liquid crystal polyesters. These results may represent the first reported crystal-nematic temperatures and heats generated by the dilution method for liquid crystal copolyesters of this type.     

On the mechanism of photoinduced phase transitions in ternary liquid crystal systems near thermal equilibrium

According to their phase diagram, polyalkyl glycol ether dissolved in ternary solutions (water, alcane, and cyclohexane) lead to the formation of either liquid crystal phases or microemulsion phases. By photosensitization of the ternary system with laser dyes and choosing the adequate concentration and temperature conditions of these lyotropic systems, it is possible to photoinduce the phase transitions from the microemulsion phase to the liquid crystal phase (and vice versa). The phototransformation conditions were chosen in such a way that the system is in thermal equilibrium during the entire phase transition. The method of photo small angle x-ray scattering has been applied to investigate the mechanism of photoinduced phase transition. Spectroscopically, the mechanism of photoinduced phase transition has been characterized by optical absorption and emission techniques.     

Barotropic phase transition between the lamellar liquid crystal phase and the inverted hexagonal phase of dioleoylphosphatidylethanolamine

The phase transition between the lamellar liquid crystal (Lalpha) phase and the inverted hexagonal (H(II)) phase of dioleoylphosphatidylethanolamine (DOPE) in aqueous NaCl solutions was observed by means of differential scanning calorimetry (DSC) under ambient pressure and light-transmittance technique under high pressure. The pressure dependence of the transition temperature (dT/dp) and the thermodynamic quantities for the Lalpha/H(II) transition were compared with those of another phase transition found in the DOPE bilayer membrane, which is the transition from the lamellar crystal (Lc) phase to the Lalpha phase. The dT/dp value of the Lalpha/H(II) transition was about 3.5 times as large as that of the Lc/Lalpha transition while the thermodynamic quantities were significantly smaller than those of the latter to the contrary. Comparing the enthalpy and volume behavior of the Lalpha/H(II) transition with that of the Lc/Lalpha transition, we concluded that the Lalpha/H(II) transition can be regarded as the volume-controlled transition for the reconstruction of molecular packing.     

Influence of pressure on the B2I phase transition of a banana-shaped liquid crystal

Employing a phenomenological mean field theory, we analyse the effect of high pressure on the B₂I phase transition properties of a bent-core liquid crystal. The basic idea of the work is to explain the phase transition behaviour of system by assuming that certain Landau coefficients associated with the order parameters coupling terms of the free-energy density expansion are pressure dependent. We observe excellent agreement between the theoretical and experimental results of mesogen PHDBB and that the B₂I transition remains first order even at the elevated pressures.     

A chiral induced ferroelectric liquid crystal phase transition with a vanishingly small enthalpy

Abstract

Information on molecular interactions that give rise to the stabilization of various ferroelectric, liquid-crystalline mesophases is important to the realization of their potential utility in a wide variety of optical devices. Understanding the roles that optical activity and optical purity play in the formation and properties of the various smectic phases is therefore of particular interest. In order to study this relationship three new liquid-crystalline materials were prepared, one as a racemic mixture, the other two as the optically active analogues. The optically active isomers appear to exhibit a different mesophase morphology from the racemate. The chiral compounds apparently possess two extra ferroelectric mesophases in comparison to the racemic mixture. The transitions to and from these phases have extremely small enthalpies. An attempt is made to explain the results for the chiral compounds in terms of differing dipolar couplings in the chiral ferroelectric phases. In the racemic mixture these interactions are compromised or scrambled by a loss of asymmetry thus destabilizing these extra phases.     

A chiral induced ferroelectric liquid crystal phase transition with a vanishingly small enthalpy

Information on molecular interactions that give rise to the stabilization of various ferroelectric, liquid-crystalline mesophases is important to the realization of their potential utility in a wide variety of optical devices. Understanding the roles that optical activity and optical purity play in the formation and properties of the various smectic phases is therefore of particular interest. In order to study this relationship three new liquid-crystalline materials were prepared, one as a racemic mixture, the other two as the optically active analogues. The optically active isomers appear to exhibit a different mesophase morphology from the racemate. The chiral compounds apparently possess two extra ferroelectric mesophases in comparison to the racemic mixture. The transitions to and from these phases have extremely small enthalpies. An attempt is made to explain the results for the chiral compounds in terms of differing dipolar couplings in the chiral ferroelectric phases. In the racemic mixture these interactions are compromised or scrambled by a loss of asymmetry thus destabilizing these extra phases.     

Nanoconfined heliconical structure of twist-bend nematic liquid crystal phase

We produced controlled heliconical structures of a twist-bend nematic (N_TB) liquid-crystal (LC) phase in nanoconfinement in a porous anodic aluminium oxide (AAO) film. The structural parameters of the N_TB 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 N_TB phase.     

Unlocking of interlocked heteropolymer gel by light: photoinduced volume phase transition in an ionic liquid from a metastable state to an equilibrium phase

An azobenzene-containing heteropolymer gel in an ionic liquid exhibits thermally reversible volume phase transition when the azobenzene moiety mainly exists in the cis-state, whereas the transition becomes irreversible when it is in the trans-state and an interlocked collapsed state is stabilized; however, the unlocking of the metastable state occurs by UV light irradiation.     

Dynamics of a low temperature phase transition in liquid crystal TB10A probed by Raman spectroscopy

Raman spectra of TB10A were recorded in the regions, 925-1000 and 1140-1220cm-1 from room temperature down to 20 K, during cooling and heating cycles. The subtle changes in the spectral features of the bands at 975 and 1195cm-1 at 47 K were attributed to a hitherto unreported stable-metastable phase transition in TB10A. The dynamics of the new phase transition have been explained in terms of splitting of the non-planar mode at 975cm-1 owing to strong intermolecular interaction due to close molecular packing in the low temperature phase. The spectral anomaly of the 975cm-1 band, in terms of variation of relative intensity with respect to temperature, also shows the hysterisis linked with the process of stable-metastable-stable modification in TB10A.