Chiral Nematic Liquid Crystal Research Articles

Circularly Polarized Luminescence in Composite Films: A Combination of Perovskites and Chiral Nematic Liquid Crystals

Chiral inorganic nanomaterial-based circularly polarized luminescence (CPL) materials have shown substantial promise in multiple research areas. However, the luminescence dissymmetry factor (glum), a key parameter for CPL, is far from satisfactory, especially for inorganic molecules with high luminescent quantum efficiency and diverse shapes and sizes. Obtaining large glum values is an urgent and crucial task in the field of CPL research. Among different approaches, the combination of inorganic nanomaterials and chiral nematic liquid crystals (N*-LCs) offers distinct advantages in achieving high glum values due to their distinctive optical characteristics and remarkable versatility. This concise review systematically investigates the recent advancements in CPL-active materials consisting of perovskites and N*-LCs. It elaborates on their preparation techniques, optical characteristics, and potential applications. Additionally, a brief outlook on their future development is offered. It is expected that this combination will assume an increasingly significant role in the CPL research field and attract more researchers to explore this area.

Three-Level Chirality Transfer and Amplification in Liquid Crystal Supramolecular Assembly for Achieving Full-Color and White Circularly Polarized Luminescence.

Chiral liquid crystal supramolecular assembly provides an ideal strategy for constructing excellent circularly polarized luminescence (CPL) materials. However, the chirality transfer in chiral liquid crystals normally occurs at two levels from the configurational chirality to the supramolecular phase chirality. The more precise and more levels of chirality transmission are fascinating but remain challenging. The present work reports the first success of three-level chirality transfer and amplification from configurationally point chirality of small molecules to conformationally helical chirality of helical polymers and finally to supramolecular phase chirality of cholesteric liquid crystals composed of chiral nonfluorescent polymers (P46) and nematic liquid crystals. Noticeably, the helical twisting power of P46 is five-fold larger than its monomer. Full-color and white CPL with maximum luminescence dissymmetry factor up to 1.54 and photoluminescence quantum yield up to 63.8% are realized utilizing helical supramolecular assembly combined with selective reflection mechanism. Also significantly, the electrically stimuli-responsive CPL switching device as well as anti-counterfeiting security, information encryption, and chiral logic gate applications are developed. This study deepens the understanding of chirality transfer and amplification across different hierarchical levels.

Imaging with a twist: Three-dimensional insights of the chiral nematic phase of cellulose nanocrystals via SHG microscopy.

Cellulose nanocrystals (CNCs) are bio-based nanoparticles that, under the right conditions, self-align into chiral nematic liquid crystals with a helical pitch. In this work, we exploit the inherent confocal effect of second-harmonic generation (SHG) microscopy to acquire highly resolved three-dimensional (3D) images of the chiral nematic phase of CNCs in a label-free manner. An in-depth analysis revealed a direct link between the observed variations in SHG intensity and the pitch. The highly contrasted 3D images provided unprecedented detail into liquid crystal's native structure. Local alignment, morphology, as well as the presence of defects are readily revealed, and a provisional framework relating the SHG response to the orientational distribution of CNC nanorods within the liquid crystal structure is presented. This paper illustrates the numerous benefits of using SHG microscopy for visualizing CNC chiral nematic systems directly in the suspension-liquid phase and paves the road for using SHG microscopy to characterize other types of aligned CNC structures, in wet and dry states.

Flowing Liquid Crystal Torons Around Obstacles

Liquid crystal torons, localized topological structures, are known for their stability and dynamic behaviour in response to external stimuli, making them attractive for advanced material applications. In this study, we investigate the flow of torons in chiral nematic liquid crystals around obstacles. We simulate the fluid flow and director field interactions using a hybrid numerical method combining lattice Boltzmann and finite difference techniques. Our results reveal that the toron dynamical behaviour depends strongly on the impact parameter from the obstacle. At impact parameters smaller than half cholesteric pitch, the flowing toron is destabilized by the interaction with the obstacle; otherwise, the flowing toron follows a trajectory with a deflection which decays exponentially with the impact parameter. Additionally, we explore the scattering of torons by multiple obstacles, providing insights into how the dynamics of these structures respond to complex environments.

Widely tunable reflection by a hybrid ion-doped positive-negative chiral nematic liquid crystal under an electric field.

In this study, a new methodology, in which the cation and chiral agent are doped in positive and negative nematic liquid crystal mixture to form cation-doped positive-negative chiral nematic liquid crystals (PN-CNLCs), is proposed. These PN-CNLCs are capable of achieving a wide wavelength tuning range close to 90 nm under the action of a high-frequency electric field. The dielectric interaction between these two liquid crystals with different dielectric anisotropies in the electric field allows for the effective change of the pitch of the CLCs. We discovered the tilting of the pitch in the PN-CNLCs by a series of well-designed validation experiments. The experimental results prove the symmetrical helix is formed along the alignment direction in PN-CNLCs. Furthermore, the experiments demonstrated that an increase in voltage does not directly affect the pitch, but it increases the tilt angle of the helix axis with respect to the normal of the LC cell. This study offers, to our knowledge, a novel perspective on the tuning performance of CLCs under electric field conditions, by integrating the properties of positive and negative liquid crystals. This finding not only contributes to the understanding of the electric field response mechanism of CLCs but also provides new avenues for the application of CLCs in fields such as wavelength tuning.

Self‐Assembled Biconvex Microlens Array Using Chiral Ferroelectric Nematic Liquid Crystals

AbstractRecently, it is shown (Popov et al, Sci. Rep, 2017, 7, 1603) that chiral nematic liquid crystal films adopt biconvex lens shapes underwater, which may explain the formation of insect eyes, but restrict their practical application. Here it is demonstrated that chiral ferroelectric nematic liquid crystals, where the ferroelectric polarization aligns parallel to the air interface, can spontaneously form biconvex lens arrays in air when suspended in submillimeter‐size grids. Using Digital Holographic Microscopy, it is shown that the lens has a paraboloid shape and the curvature radius at the center decreases with increasing chiral dopant concentration, i.e., with decreasing helical pitch. Simultaneous measurements of the imaging properties of the lenses show the focal length depends on the pitch, thus offering tunability. The physical mechanism of formation of the self‐assembled ferroelectric nematic microlenses is also discussed.

Electrically Tunable Chiral Ferroelectric Nematic Liquid Crystal Reflectors

AbstractManipulating light is an important area of optical research and development. To that end, tunable dichroic devices in which the reflectivity at differing wavelengths can be adjusted, are particularly valuable. This work is motivated by recent studies of the optical properties of chiral ferroelectric nematic liquid crystals (FNLCs). Here electro‐optical studies are presented on two room temperature, FNLC materials that demonstrate electrically tunable reflectivity when subject to a field below 0.2 V µm−1. Moreover, under appropriate conditions, the reflectivity can also be electrically (and reversibly) tuned (without change of color) from 0% to 40%. Reversible, low voltage tunable mirrors, having miniscule power consumption and operable around ambient temperature are expected to be useful in diverse applications ranging from energy‐saving, smart windows to virtual reality interfaces.

Topologically frustrated structures in inkjet printed chiral nematic liquid crystal droplets - experiments and simulations.

Director field alignment in inkjet printed droplets of chiral nematic liquid crystalline materials is investigated using both experiments and numerical simulations. Experimental investigations are performed by depositing droplets of varying sizes and pitches on homeotropic alignment layers. The competition between the bulk behaviour of the chiral nematic liquid crystal and the boundary conditions imposed by the droplet surface leads to the formation of a range of possible internal director configurations. Numerical investigations are performed using a free energy minimisation approach, and the resultant simulated polarising optical microscope images are found to agree well with experimental observations.

From Chitin Nanowhisker Colloidal Dispersions to Anisotropic Microfibers: Structural Evolution in Its Transformation Process as Revealed by Synchrotron Wide-Angle X-ray Diffraction Measurements.

Nanowhiskers in a colloidal dispersion are known to form chiral nematic liquid crystals (CNLC), as seen in a cellulose nanowhisker or so-called cellulose nanocrystal and chitin nanowhisker. In our related work, we clarified that once the thus-created chitin nanowhiskers with surface modified by chitosan (CTWK-CS) in CNLC phase were wet-spun, we could directly obtain anisotropic microfibers containing the highly ordered CTWK-CS. This drastic structural transformation from CNLC to anisotropic microfibers might relate to several important stages, i.e., stage (i) is the alignment of CTWK-CS initiated by a specific concentration and flow to create aggregation in the CNLC state, stage (ii) is the coagulation of CTWK-CS in CNLC to transform to microfibers, and stage (iii) is the drying of the thus-extruded microfibers to allow CTWK-CS alignment. The present work sets up the experimental systems simulating stages (i) and (iii) to reveal the orientational behavior of CTWK-CS and the structural evolution, respectively, by synchrotron 2D WAXD measurement. In stage (i), the high degree of the parallel alignments of CTWK-CS with the chain axis oriented along the flow direction of the colloidal dispersions confirms that the flow and concentration synergistically controlled CTWK-CS alignment. In contrast, for stage (iii), the poor c-axial orientation of CTWK-CS in as-spun wet microfibers gradually changed to the high degree of c-axial orientation along the fiber direction during drying process, indicating a reorientation of CTWK-CS along with dehydration. The present study declares an in situ observation of the direct wet spinning of nanowhiskers about their remarkable alignments in the sheared colloidal dispersions (stage (i)) and their random-to-high reorientation during the drying process of the as-spun wet microfiber (stage (iii)).

Multifaceted regulation of chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers

AbstractThe multifaceted regulation of the chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve. Herein, a series of novel salen‐based chiral fluorescent polymers with aggregation‐induced emission and varied substitution manners were facilely and efficiently synthesized. Multiple factors were systematically investigated on the chiroptical properties and self‐assembly performance of these polymers, which include molecular structures, solvent environments, metal coordination, and liquid crystal (LC) assemblies. Sutle change in the solvent composition can lead to diverse assembly morphologies of all these chiral polymers, from single‐handed helical fibers, helical toroids or loops, to spherical structures, consequently leading to an aggregation‐reduced circular dichroism (CD) phenomenon. The polymers bearing salen units show highly selective and reversible coordination with Zn2+ and can also induce multiple responses in the absorption, luminescence, CD, and circularly polarized luminescence (CPL) of these chiral fluorescent polymers via a coordination‐ and dissociation‐initiated self‐assembly tuning. Furthermore, a small amount of the chiral fluorescent polymer in can induce achiral nematic 4‐cyano‐4′‐n‐pentylbiphenyl (5CB) to form ordered chiral nematic LC phase with significant improvement in their CD and CPL signal. The absolute absorption and luminescent dissymmetry factors of the resulting supramolecular assemblies can reach the order of 10−1.

Heteroatom doped cellulose nanocrystals (CNC) with chiral nematic liquid crystal interface for high efficiency removal of ciprofloxacin

The increasing contamination of water systems by ciprofloxacin (CIP) has become a growing concern. The photocatalysis approach offers a promising strategy for the effective removal of CIP. In this study, MSx/CNC (MSx, M = Co, Ni, Cu) binary composites with chiral catalytic interfaces were prepared by chemical precipitation and the composite M0-MSy/CNC was prepared by energetic β-particle bombardment. The XPS results confirmed the successful construction of C–O−M bonds. TEM results clearly revealed the generation of sulfur vacancies (Sv) in the composites. The M0-MSy/CNC/peroxymonosulfate (PMS) photocatalytic system was also constructed in this study. The results of the application experiments showed that the Co0-CoSy/CNC/PMS system had an excellent degradation effect on CIP, which reached 100 % at 1.5 h of open light. The degradation kinetic constants of Co0-CoSy/CNC/PMS were 4.26 times higher than those of CoSx/CNC/PMS. In addition, EPR showed that the Co0-CoSy/CNC/PMS system generates ‧OH, ‧SO4−, ‧O2−, and h+ radicals to co-remove CIP. This study also elucidated the major intermediates of photocatalytic degradation of CIP at the chiral catalytic interface using LC-MS analysis. This work provides insights into the coupled application of photocatalysis and PMS activation in the remediation of aqueous environments.

Chiral ferroelectric nematic liquid crystals as materials for versatile laser devices

We present a liquid-crystal laser device based on the chiral ferroelectric nematic phase (NF*). The laser medium is obtained by mixing a ferroelectric nematic material with a chiral agent and a small proportion of a fluorescent dye. Notably, in the NF* phase very low electric fields perpendicular to the helical axis are able to reorient the molecules, giving rise to a periodic structure whose director profile is not single harmonic but contains the contribution of various Fourier components. This feature induces the appearance of several photonic bandgaps whose spectral ranges depend on the field, which can be exploited to build tunable laser devices. Here we report the characterization of home-made NF* lasers that can be tunable under low electric fields and present laser action in two of the photonic bands of the material. The obtained results open a promising route for the design of new and more versatile liquid-crystal based lasers.

Effect of different surface alignment layers and temperature changes on bandwidth of Bragg reflection in chiral nematic liquid crystal

In recent years, the practical properties of cholesteric liquid crystals (CLCs) have been widely studied due to their unique feature of selective Bragg reflection. In this study, we investigated the following aspects: (i) the effect of surface alignment using polyvinyl alcohol, polyamide, and polyimide as covering substrate, (ii) the impact of temperature changes on the reflection bandwidth and, consequently, variations in the cholesteric pitch. Furthermore, we extended Li’s four-parameter model to the cholesteric environment using Haller’s assumption and Vuk’s equations for nematic liquid crystals (NLCs) and Fergason’s theory for CLCs. The fit of the experimental data with this model demonstrated an excellent agreement. The experimental data revealed that the S5011 chiral dopant, with left-handedness, used in the NLC environment of the host, exhibits a significant helical twist power (HTP). This leads to the narrowing of the reflection band width with increasing temperature, without causing a noticeable change in the wavelength of the central reflection. This feature highlights the high potential of these types of chiral materials as thermally stable materials for creating selective-reflective optical filters that remain stable with temperature changes, particularly away from the cholesteric to isotropic transition point.

Anti-UV Passive Radiative Cooling Chiral Nematic Liquid Crystal Films for Thermal Management.

Passive radiative cooling (PRC) can spontaneously dissipate heat to outer space through atmospheric transparent windows, providing a promising path to meet sustainable development goals. However, achieving simultaneously high transparency, color-customizable, and thermal management of PRC anti ultraviolet (anti-UV) films remains a challenge. Herein, a simple strategy is proposed to utilize liquid crystalline polymer, with high mid-infrared emissive, forming customizable structural color film by molecular self-assembly and polymerization-induced pitch gradient, which guarantees the balance of transparency in visible spectrum and sunlight reflection, rendering anti-UV colored window for thermal management. By performing tests, temperature fall of 5.4 and 7.9°C are demonstrated at noon with solar intensity of 717Wm-2 and night, respectively. Vivid red-, green-, blue-structured colors, and colorless films are designed and implemented to suppress the solar input and control the effective visible light transmissivity considering the efficiency function of human vision. In addition, temperature rise of 11.1°C is achieved by applying an alternating current field on the PRC film. This study provides a new perspective on the thermal management and aesthetic functionalities of smart windows and wearables.

Sunlight-Driven Smart Windows with a Wide Temperature Range of Optical Switching Based on Chiral Nematic Liquid Crystals.

Photoresponsive liquid crystals are promising materials for sunlight-driven smart windows, which can automatically change their optical states in response to sunlight and control energy flow between the inside and outside of a building. Herein, liquid-crystalline systems are developed that show a transparent-scattering transition upon irradiation with sunlight in a wide temperature range. Push-pull azobenzenes with axial chirality have been newly developed as photochromic chiral dopants to allow changes in mesostructures of liquid crystals in response to sunlight. To realize optical switching, photochromic and photoinert chiral compounds with opposite handedness of helical twisting are doped in liquid crystals. This liquid crystalline sample with a compensated nematic phase is transparent in its initial state. Upon irradiation with sunlight, this sample transforms to a scattering state due to the formation of helical mesostructures along with photoisomerization of azobenzene moieties and the change in the helical twisting power. After the cease of irradiation, the sample reverts to the transparent state through thermal back isomerization of azobenzene moieties. This system significantly improves the operating temperature range of sunlight-driven smart windows based on liquid crystals: the transparent-scattering transition is observed at 4-42 °C. The present mechanism allows development of autonomous and wireless smart windows adaptable to various environments.

Effects of ion doping on the dielectric and electro-optical properties of chiral nematic liquid crystal

This study presents experimental findings pertaining to the use of the cationic surfactant cetyltrimethylammonium bromide (CTAB) as a dopant dispersed in cholesteric liquid crystal. The impact of the additive on the electrical and dielectric properties was investigated by dielectric spectroscopy. Compared with that in the pure counterpart, the dielectric relaxation frequency increased due to the added ions in the cholesteric liquid crystals impregnated with 0.01–0.5-wt% CTAB. Furthermore, by analyzing the dielectric spectra in a specific frequency range, the DC conductivity, ion density, and diffusion coefficient were calculated and compared. By fitting the experimental data into the Arrhenius equation, the activation energy was obtained as well. Our experimental results illustrated that all these physical properties were strongly dependent on the CTAB concentration and the temperature. This work also involved the electro-optical measurement in combination with the observation of optical texture. The ion addition provoked electrohydrodynamic flows in a surfactant-dispersed mixture, generating a homogeneous and transparent uniform lying helix state between two low-transmission optical states—the focal conic and dynamic scattering states. The operating frequency range of the dynamic scattering state was significantly broadened by the ionic dopant.

Structural, Optical, and Mechanical Insights into Cellulose Nanocrystal Chiral Nematic Film Engineering by Two Assembly Techniques.

Iridescent cellulose nanocrystal (CNC) films with chiral nematic nanostructures exhibit great potential in optical devices, sensors, painting, and anticounterfeiting applications. CNCs can assemble into a chiral nematic liquid crystal structure by evaporation-assisted self-assembly (EISA) and vacuum-assisted self-assembly (VASA) techniques. However, there is a lack of comprehensive examinations of their structure-property correlations, which are essential for fabricating materials with unique properties. In this work, we gained insights into the optical, mechanical, and structural differences of CNC films engineered using the two techniques. In contrast to the random self-assembly at the liquid-air interface in EISA, the continuous external pressure in the VASA process forces CNCs to assemble at the filter-liquid interface. This results in fewer defects in the interfaces between tactoids and highly ordered cholesteric phases. Owing to the distinct CNC assembly behaviors, the films prepared by these two methods show great differences in the nanostructure, microstructure, and macroscopic morphology. Consequently, the highly ordered cholesteric structure gives VASA-CNC films a more uniform structural color and enhanced mechanical performance. These fundamental understandings of the relationship of structure-property nanoengineering through various assembly techniques are essential for designing and constructing high-performance chiral iridescent CNC materials.

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.

Electro-optic characteristics of chiral nematic layers deformed by in-plane electric field

ABSTRACT Deformations of twisted and super-twisted layers composed of chiral and nonchiral nematic liquid crystals induced by in-plane electric field were studied numerically. The right-hand twisted structures with twist angles equal to 90°, 120°, 150°, 180°, 210°, 240° and 270° placed between crossed polarisers were considered. The optical transmission due to electro-optic effect which occurred in such systems was studied as a function of applied electric field strength. Steep and linear electro-optic characteristics were found in the case of nonchiral nematic confined in cells twisted by 90°. Such characteristics were favoured by large twist elastic constant, large dielectric anisotropy and weak azimuthal anchoring. In the case of super-twisted layers, useful characteristics were found for twist angles 210°, 240° and 270°, small twist elastic constant, strong azimuthal anchoring and large dielectric anisotropy.

Dynamics and Topology of Symmetry Breaking with Skyrmions.

We observe that pretransitional order parameter fluctuations of a skyrmion-forming chiral nematic liquid crystal are slowed down for 4 orders of magnitude, if confined to ≲100 nm thin layers. Fluctuating fragments of half-skyrmions are observed in a narrow temperature interval and are explained by thermally activated hopping between the various energy states. Skyrmion fluctuations are accompanied by imbalanced topological charge: positive charges appear at higher temperatures and dominate in the fluctuating region until skyrmions fully condense and negative charges appear at lower temperatures.