ABSTRACTWe have successfully synthesised silver quantum dots (Ag QDs) via chemical method. We have studied Ag QDs doped 4-(trans-4-n hexylcyclohexyl) isothiocyanatobenzoate (6CHBT) LC hybrid system and their associated structural and optoelectronic properties using both experimental and theoretical methods. The QDs with sizes 4.27 nm−9.56 nm self-assemble to form nano-micro scale hierarchical structures. Theoretical NMR study has been performed using three different methods HF, B3LYP, and wB97XD for pure and Ag NPs doped LC system. NMR data greatly helps us to explore the phenomenological description of the hybrid system by giving us molecular scale insights. Optical microscope, RAMAN, UV, FTIR, HR-XRD, FESEM-EDX, and Fluorescence data confirm the structural and physio-chemical properties of QDs, LC molecules and as well as their hybrid system. We use a nanoscale predictive model to estimate the effective size to which the bandgap value of Ag QDs in a hybrid system corresponds. The bandgap value of pure Ag QDs is found to be 5.32 eV, whereas upon doping these Ag QDs in LC media, their bandgap falls to a value of 4.08 eV. The estimated size (i.e. corresponding to effective confinement) using a hexahedral or octahedral-shaped particle model comes out to be ~15 nm.

ABSTRACTControlling objects with body language is an extremely interesting ability for human beings. Recognizing different gestures is an effective way to collect valuable information, which is used to switch the radiation characteristic of beam scanning antennas. However, most existing beam scanning antennas are wire-connected and manually controlled by users. Thereby, a novel framework of gesture-controlled antennas is proposed in this paper. Rather than DC voltages supplied by powers or AC voltages supplied by signal generators, the beam scanning antenna can be effectively controlled by different gesture commands collected in real time from the user. On this basis, considering the advantages of the low cost and wide frequency band of liquid crystal (LC) materials, a LC-based fixed-frequency beam scanning leaky wave antenna (LWA) with gesture-controlled systems is demonstrated as one example. Different gestures can be recognised as controlled information to supply corresponding output signals by field programmable gate arrays (FPGAs) for the LC-based LWA. Based on the proposed framework, a verification system is tested, which demonstrates that the radiation characteristic can be effectively controlled by the user’s gesture. This work supplies a novel way for intelligent beam scanning antennas with potential applications in the internet of things (IoT), satellite and 5 G/6 G communications.

ABSTRACTPolymer-stabilised cholesteric liquid crystal (PSCLC) films attracted much attention in decoration and anti-counterfeiting. Herein, the PSCLC films were prepared using the mixtures of epoxy monomers through cationic photopolymerisation. The structural colour was tunable by changing the concentration of chiral dopant in the reaction mixture and polymerisation temperature. Due to polymerisation shrinkage, microcracks were formed at the surfaces of the PSCLC films, which originated from the oily streak defects of the CLC mixtures. Colourful patterns were prepared by controlling the polymerisation temperature. In addition, since light can leak out through the microcracks, the tetraphenylethylene-doped patterns can be applied in anti-counterfeiting.

ABSTRACTChiral liquid crystal mixtures are an important field of research in the development of these materials. The main advantage of chiral liquid crystal mixtures is their ability to produce an optically active three-dimensional structure. Moreover, 1,3,4-oxadiazoles have been widely used as electron-transporting/hole-blocking materials or emitting layers in electroluminescent diodes and nonlinear optical materials owing to their interesting properties. Here, we investigate the phase transitions in a mixture of a chiral oxadiazole derivative liquid crystal, EOS-12, and a traditional nematic liquid crystal, E7. EOS-12 is miscible with the E7 matrix at all concentrations. The mesomorphic properties of these mixtures were studied using differential scanning calorimetry (DSC), polarised optical microscopy (POM) and digital colourimetry analysis. In addition, the cholesteric pitch is measured using the Grandjean-Cano technique and photophysical studies were performed in solutions and films. Mixtures show polymorphism depending on the concentration and temperature: nematic, chiral nematic, TGBA*, and smectic phases. A temperature-concentration phase diagram was established using POM. Stabilisation of the SmA phase is observed with a greater temperature range than the constituents of the mixture. According to these results, the properties of the mixture can be used to create various material functionalities, depending on the composition of the mixture.

ABSTRACTWe investigated the properties of linear and circular dichroisms of cholesteric liquid crystal layer in external static magnetic field directed along helix axis. We showed that when the direction of light propagation and the direction of external magnetic field coincide, increasing the latter magnitude leads to a decrease in the linear dichroism, whereas when these directions are opposite, increasing the external magnetic field (BextBextBext) magnitude leads an increase in the linear dichroism. The presence of external magnetic field leads to the shift of circular dichroism curves both along wavelength axis and along dichroism axis. Then, we investigated the peculiarities of dichroism dependencies on BextBextBext for different wavelengths of incident light. We compared the dependence of circular dichroism on Bext for a magnetically active cholesteric liquid crystal layer and an isotropic magnetically active layer and showed that while these dependencies are similar for wavelengths away from the photonic band gap, diffraction significantly affects these dependencies for wavelengths near and inside the photonic band gap. We investigated the evolution of spectra of linear and circular dichroisms at the change in Bext, too. The results obtained can find application in the design of innovative polarised optoelectronic devices.

Published in Liquid Crystals (Vol. 50, No. 3, 2023)

ABSTRACTEmbedding of nanoparticles in nematic liquid crystalline materials has received huge attention in recent years. In most of the work, nanoparticles decrease nematic-isotropic transition temperature along with an undesired increase in conductivity. Interestingly, there are few reports where nematic-isotropic transition temperature has increased along with improvement in other relevant properties due to presence of ferroelectric and/or functionalised nanoparticles of small size. Here, we are reporting enhanced nematic-isotropic transition temperature of 4-pentyl-4′-cyanobiphenyl (5CB) due to dispersion of metallic copper nanoparticles (CuNPs). Low concentrations (0.2 and 0.5 weight%) of CuNPs have been dispersed in 5CB to prepare nanocomposites. Thermodynamic results on unaligned samples and dielectric results on planar and homeotropic aligned samples show enhancement of isotropic to nematic transition temperature of 5CB in the presence of CuNPs without any substantial change of conductivity. Optical studies show a marginal decrease in the band gap of the dispersed samples as compared to those of the pure 5CB which validates conductivity results. The relaxation frequency corresponding to the rotation of molecules about their short axes has increased due to the presence of CuNPs in the nematic matrix of 5CB. These observed results are useful for the electro-optical applications as well as for fundamental aspects.

ABSTRACTA series of new luminescent liquid crystals (LLCs) comprised of difluoromethoxy and substituted 2-cyano-pyrrole (CN-Py) bridge with the molecular rigid core were synthesised. Their emission colours could be adjusted facilely and reversibly in a non-invasive manner by simply changing the excitation wavelength at room temperature. A simple and practical approach has been developed to avoid the use of hazardous and highly toxic elemental bromine to achieve a green and environmentally friendly synthesis pathway for difluoromethoxy-bridged liquid crystals. Notably, excitation-dependent multicolour luminescence has been realised in a single molecule of 5CC-CF2O-2Br-CN based on pure organic difluoromethoxy bridged liquid crystal, whose emission colours changes from yellow to blue with a blue shift of excitation wavelength. Interestingly, the CIE coordinates (0.29,0.33) of 5CC-CF2O-2Br-CN is very close to the white light coordinates (0.33, 0.33) under excitation at a wavelength of 335 nm. Therefore, 5CC-CF2O-2Br-CN can be a candidate of promising white light emitting luminescent liquid crystal. This protocol offers efficient access to single-molecule liquid crystal material with white light emission.

ABSTRACTA series of 4-(aroyloxybenzoyloxy)benzonitriles was synthesised and their thermal, mesomorphic and photophysical properties were characterised. The lower homologues show only nematic phase, whereas higher members of the series exhibit long-range smectic A phase with a pronounced homeotropic organisation. This alignment is desired for in-plane charge conduction, allowing applications as active layer in organic field effect transistors. The compounds showed an intense absorption band between 250 to 300 nm.

ABSTRACTWe study the transverse normal linear propagating modes within a cylindrical wave guide filled with a blue-phase liquid crystal, which is subjected to the cladding by means of soft anchoring boundary conditions. The axis of the two dimensional helical structure of the blue phase is taken parallel to the cylindrical wave guide axis. We establish the coupled governing equations consisting of the electromagnetic Maxwell’s equations in the presence of a blue phase and the equilibrium equations for the blue-phase texture resulting from the minimisation of both, the bulk and surface free energy. By assuming a low intensity electromagnetic field, we decouple the texture equation and solve it to obtain blue-phase configurations; parameterised for different anchoring energies from which calculate the band structure and electromagnetic fields associated to these textures. We find that the number of propagating modes in the blue-phase cored waveguide depends on the anchoring strength.

ABSTRACTIn this work, the morphology of nematic capillary nanobridges in slit pores separated by a vertical distance D will be characterised by Monte Carlo simulations for oblate molecules nematogen modelled by the Gay-Berne potential. Previous studies on droplets show that the molecules are arranged homeotropically at the nematic-vapour interface and form spherical droplets with an annular disclination located in their equatorial plane. In the presence of pores with attractive substrates that favour homeotropic anchoring, the formation of nanobridges characterised by anchoring angles that decrease with increasing particle-substrate interaction intensity is observed. When the orientational field in the nanobridge is analysed, the formation of an annular disclination of topological charge+1/2 located in the plane perpendicular to the z-axis that passes through the centre of mass of the nanobridge is observed for small D. However, when considering higher values of D, a change to a biaxial orientational profile within the nanobridge is observed, where now the annular disclination is arranged in a plane perpendicular to one direction of the xy plane. These results are indicative of the existence of an orientational phase transition for an intermediate D value between a uniaxial and a biaxial orientational configuration in the capillary nanobridge.

ABSTRACTLiquid crystalline materials that have been used in the display industry need to have a wide temperature-range nematic phase while remaining functioning in different climate conditions. In this work, a new binary mixture of thermotropic liquid crystal materials, particularly the nematic phase, has been studied. A widely used material 5CB (4-Cyano-4’−pentyl biphenyl), exhibiting nematics phase, and PA (4-Phenylbenzoic acid) were preferred. Mixtures of different concentrations of 5CB-PA were prepared and investigated using dielectric spectroscopy, phase transition and electro-optical responses techniques. It was found that not only was an improvement to the dielectric anisotropic achieved but also the nematic temperature range extended from 35 ºC to just above 50°C by adding 10 wt.%. On the other hand, the threshold voltage is increased by 10% for the same sample. In addition, elastic constants and response time showed similar behaviours upon increasing the loading concentration of PA, whereas the visco-elastic coefficient significantly declined. All the estimated values for the pure 5CB are in good agreement with the literature. This improvement in the operating temperature range is unique and suggests that the doping can lead to cheap and mass production of a stable liquid crystalline material for their application in the display industry.

ABSTRACTThe liquid crystal 2’,3’-difluro-4-nonyl-4”-heptyl-para-terphenyl (abbreviated as 7T9) was examined by differential scanning calorimetry, polarized optical microscopy, X-ray diffraction, Fourier-transform absorption infrared spectroscopy and broadband dielectric spectroscopy in order to describe its phase behaviour as well as vibrational and relaxation dynamics in appropriate thermodynamic states. The two-dimensional correlation analysis of infrared spectra was used to check changes of the arrangement and specific interactions of molecules during phase transitions. The compound under study formed two crystal phases and three liquid crystal phases, smectic C, smectic A and nematic. The absorption band associated with asymmetric C-H bending vibrations in methyl groups was sensitive to various intra- and intermolecular interactions related with the thermodynamic states of the 7T9 compound. The Arrhenius type low-frequency relaxation was detected in the high-temperature crystal phase.

ABSTRACTVibrated monolayers of granular particles confined into horizontal cavities form a variety of fluid patterns with orientational order that resemble equilibrium liquid-crystal phases. In some cases, one can identify nematic and smectic patterns that can be understood in terms of classical statistical mechanics of hard bodies. Low aspect ratio cylinders project as rectangles and form uniaxial, or 2-atic, and tetratic, or 4-atic, nematic phases. Other polygonal particles may exhibit different liquid-crystal phases, in general p-atic phases, of higher symmetries. We give a brief summary of theoretical work on rectangles and triangles, and provide some experimental results on vibrated monolayers. In the case of equilateral triangles, the theory predicts an exotic triatic phase, or 6-atic phase, with six-fold symmetry and three equivalent directors. The right-angled triangles exhibit a 4-atic phase with strong octatic (8-atic) correlations. Experiments on cylinders show 4-atic textures and, even more remarkable, geometric frustration caused by confinement excites topological defects, which seem to follow the same topological rules as standard liquid crystals. Some of our findings can be understood with the help of simulations of hard particles subject to thermal equilibrium, although standard Density-Functional Theories fail to account for the correct equilibrium phases in some cases.

ABSTRACTGlasses-free three-dimensional (3D) displays are being regarded as the key to the future of display that will redefine the display industry. Inspired by the curved screen, liquid crystal micro-lens arrays (LC MLAs) on flexible PET substrate with a radius of curvature of 5 cm was achieved. For demonstration, an integral imaging-based 2D/3D convertible display system is proposed by using the flexible LC MLAs (FLC MLAs) to switch its operation mode between 2D and 3D modes. When the FLC MLAs with an applied voltage are in the system, the prototype renders a matched 3D image and works in 3D mode. When the FLC MLAs do not have an applied voltage, the FLC MLAs are equivalent to glass, and the display system works in 2D mode. In addition, we also demonstrated that the FLC MLAs have a wider viewing angle than the flat integral imaging 3D display system. The depth of field ranges from 6.78 to 210.12 mm under low operating voltages of 3.4 to 3.1 Vrms, respectively. With its low voltage, thin structure, and adjustable focal length form factors, the developed display system can be integrated with off-the-shelf purchased flat panels, making it a promising option for portable electronics.

ABSTRACTThe liquid crystalline phase of spider silk is thought to enable for the silk protein to be stored at high concentration in the gland without gelation, facilitating the instant fibre formation at the spinning duct. Nevertheless, it has never been revealed whether the liquid crystalline state of the silk protein maintains after the fibre formation. In this study, we conducted the X-ray liquid crystal structure analysis to reveal the details of molecular assemblies of the native spider silk proteins. Based on the wide- and small angle X-ray scattering data using the uniaxial bundle of spider draglines, the spider dragline silk fibres maintain a rectangular columnar liquid crystalline phase with a P21/a (p2gg) symmetry. The liquid crystalline state of the spider silk fibre is not nematic, cholesteric, nor hexagonal columnar, as previously proposed, but rectangularly packed columnar liquid crystal. The movable silk molecular chains along the long fibre axis in the rectangular columnar liquid crystalline structure help to explain the mechanical strength of the native spider dragline silk fibres. The results obtained in this study will contribute to understanding the biological basis underlying the silk fibre formation and will be useful to the biomimicry of spider silk fibres.

ABSTRACTIn this study, novel achiral mesogens containing 4,4’-biphenyl central core connected on both sides through an ester function to 1-(4-(alkyloxy)phenyl)-1 H-[1,2,3]-triazolyl group have been synthesised and characterised. Different mesophases have been identified, with the appearance of both a periodic striped pattern and propeller-patterned droplets close to the transition between the nematic and the smectic-C phases. This periodic texture has been found to be independent of the geometry of the sample cell. These observations suggest a spontaneous symmetry breaking, which can result either from an intrinsic enantioselective self-sorting process with a chirality synchronisation mechanism, or from an extrinsic surface mechanism at the interface between the two phases.

ABSTRACTPhotonic crystal elastomers that can change colour upon stretching or compression have potential applications in mechanical sensors and optical coatings. However, facile synthetic strategies are required for these materials to be made on a commercially viable scale. To address this issue, we report a photoinitiated polymerisation method to prepare stretchable chiral nematic cellulose nanocrystal (CNC) elastomer composites that exhibit reversible visible colour upon the application of mechanical stress. The initial CNC-elastomer composite is colourless, but when it is stretched (or compressed), the helical pitch of the chiral nematic structure is reduced to lengths corresponding to the wavelengths of the visible region, resulting in colouration. By increasing the percentage elongation of the material (ca. 50–300%), the structural colour can be tuned from red to blue. The colour of the material was characterised by reflectance optical spectroscopy and reflectance circular dichroism to confirm the wavelength and polarisation of the reflected light.

ABSTRACTLyotropic liquid crystal gels (LLC gels) are versatile materials which combine the anisotropy of a liquid crystal with the mechanical stability of a gel. We succeeded in gelling the rare calamitic nematic NC phase of two different micellar LLC systems with the low molecular weight gelator (LMWG) 3,5-bis-(5-hexylcarbamoyl-pentoxy)-benzoic acid hexyl ester (BHPB-6). The systems of choice are: (1) a binary LLC system with the surfactant N,N-dimethyl-N-ethyl-1-hexadecylammonium bromide (CDEAB) and water; (2) a ternary LLC system with the surfactant N,N,N-trimethyl-N-tetradecylammonium bromide (C14TAB), n-decanol, and water. The obtained gels show optical birefringence and no macroscopic flow. Freeze fracture electron microscopy (FFEM) images show ribbon-like gel fibres that form the gel network and can stack into thicker bundles, while small-angle X-ray scattering (SAXS) confirms the coexistence of the nematic NC phase and the gel network. The growth of the gel network was monitored with time-resolved SAXS measurements. Additionally, significant gel ageing effects were observed in rheology measurements, showing that the gel strengthens with time. With this study, we considerably broaden the pool of available surfactant-based LLC gels and pave a way to macroscopically aligned LLC gels with the goal to apply them as stimuli-responsive actuators and sensors.

ABSTRACTWe theoretically study nematic-isotropic phase transitions and phase separations in aqueous rodlike polymer solutions, such as rigid DNA (or rodlike polymer) in water. By taking into the hydrogen bonding between a rodlike polymer and solvent molecules, we predict novel phase diagrams, such as overhang-type coexistence curves with isotropic-nematic (I+N) phase separations and re-entrant I+N separations. We demonstrate that the hydrogen bonding between molecules of different components stabilises the nematic phase at lower polymer concentrations and temperatures.