Cholesteric Helix Research Articles

Amplification of Light‐Induced Helix Inversion of Intrinsically Chiral Diarylethene Molecular Switches

AbstractPhotonics and tunable optics are rapidly developing fields that require materials with programmable properties and advanced functionalities. Cholesteric liquid crystals (CLCs) are unique materials that exhibit selective light reflection and can be tuned using stimuli‐responsive small organic molecules. The challenge lies in designing molecules that can convert external signals, such as light, into dynamic and invertible chiral states, which can be transduced to the CLC supramolecular structures inducing large differences in helicity and eventually to macroscopic properties. Here, novel intrinsically chiral phenanthrene‐based diarylethenes as light‐responsive chiral dopants for controlling the supramolecular helical architectures of CLCs are introduced. The substitution pattern and light‐invertible axial chirality of these diarylethenes make them highly compatible with liquid crystals and provide high twisting power. The light‐induced cyclization and molecular chirality transformation result in a wide tunability of the cholesteric helix pitch (reflection colors) and reversible inversion of helical handedness. These findings provide a powerful tool for controlling and manipulating the macroscopic properties of CLCs, opening new avenues for a range of applications, including diffractive optics and photonics, anticounterfeiting tags, and displays.

Response of helielectric nematics under an in-plane electric field.

In traditional chiral nematic liquid crystals, the apolar cholesterics, the dielectric effect is the main driving force for responding to an electric field. The emerging polar chiral nematics, dubbed helielectric nematics, are the polar counterparts of the cholesterics. The head-to-tail symmetry breaking of the new matter state enables it to respond sensitively to the polarity of an electric field. Here, we report on the observation of a sequential polar winding/unwinding process of polarization helices under an electric field applied perpendicular to the helical axes, which behaves distinctly from the unwinding of the apolar cholesteric helices. Understanding the helix-unwinding behaviors provides insights for developing switchable devices based on helielectric nematics.

Instability of cholesteric bridge in isotropic environment with break-up and satellite droplet formation

ABSTRACT We investigate quasi-two-dimensional coalescence of domains of isotropic liquid in chiral liquid crystal in flat optical cells. It is demonstrated that coalescence can be accompanied by instability of the liquid crystal bridge separating the domains. We analyse the transformation of the bridge for materials in a wide range of the pitch of the cholesteric helix and different spatially modulated structures: planar cholesteric, one-dimensional stripe structure, focal conic structure and Blue Phases. The instability is followed by cascade break-up and formation of satellite cholesteric droplets. This picture differs from the standard three-dimensional coalescence scenario, where only a bridge between the droplets forms and grows. Studies of thinning dynamics in the bridge region showed that at the final stage of instability the width of the cholesteric bridge decreased linearly with time. In cholesteric with high chirality and small helical pitch the bridge thinning occurs substantially slower than in cholesteric with large helical pitch.

Pre-Smectic Ordering and the Unwinding Helix in Monte Carlo Simulations of Cholesteric Liquid-Crystals.

In this paper, molecular chirality is studied for liquid-crystal fluids represented by hard rods with the addition of an attractive chiral dispersion term. Chiral forces between molecular pairs are assumed to be long-ranged and are described in terms of the pseudotensor of Goossens [W. J. A. Goossens, Mol. Cryst. Liq. Cryst. 1971, 12, 237-244]. Following Varga and Jackson [S. Varga and G. Jackson, Chem. Phys. Lett. 2003, 377, 6-12], this is combined with a hard-spherocylinder core. We investigate the relationship between molecular chirality and the helical pitch of the system, which occurs in the absence of full three-dimensional periodic boundary conditions. The dependence of the wavenumber of this pitch on the thermodynamic variables, temperature, and density is measured. We also explore the use of a novel surface boundary interaction model. As a result of this approach, we are able to lower the temperature of the system without the occurrence of nematic droplets, which would interfere with the formation of a uniaxial pitch. Regarding the theoretical predictions of Wensink and Jackson [H. H. Wensink and G. Jackson, J. Chem. Phys. 2009, 130, 234911], on the one hand, we have qualitative agreement with the observed non-monotonic density dependence of the wavenumber. Initially increasing with density, the wavenumber reaches a maximum, before falling as the density moves toward the point of phase transition from cholesteric to smectic. However, further analysis for shorter rods, in the presence of novel boundary conditions, reveals some disagreement with the theory, at least in this case; the unwinding of the cholesteric helix in the cholesteric phase occurs simultaneously with subtle increases in smectic ordering. These pre-smectic fluctuations have not been accounted for so far in theories on cholesterics but turn out to play a key role in controlling the pitch of cholesteric phases of rod-shaped mesogens with a small to moderate aspect ratio.

Multiresponsive Cylindrically Symmetric Cholesteric Liquid Crystal Elastomer Fibers Templated by Tubular Confinement.

Cylindrically symmetric cholesteric liquid crystal elastomer (CLCE) fibers templated by tubular confinement are reported, displaying mechanochromic, thermochromic, and thermomechanical responses. The synthesis inside a sacrificial tube secures radial orientation of the cholesteric helix, and the ground state retroreflection wavelength is easily tuned throughout the visible spectrum or into the near-infrared by varying the concentration of a chiral dopant. The fibers display continuous, repeatable, and quantitatively predictable mechanochromic response, reaching a blue shift of more than -220 nm for 180% elongation. The cylindrical symmetry renders the response identical in all directions perpendicular to the fiber axis, making them exceptionally useful for monitoring complex strains, as demonstrated in revealing local strain during tying of different knots. The CLCE reflection color can be revealed with high contrast against any background by taking advantage of the circularly polarized reflection. Upon heating, the fibers respond-fully reversibly-with red shift and radial expansion/axial contraction. However, there is no transition to an isotropic state, confirming a largely forgotten theoretical prediction by de Gennes. These fibers and the easy way of making them may open new windows for large-scale application in advanced wearable technology andbeyond.

Massive, soft, and tunable chiral photonic crystals for optical polarization manipulation and pulse modulation

Photonic crystals enable modulation of light waves in space, time, and frequency domains; in particular, chiral photonic crystals are uniquely suitable for polarization rotation and switching of complex vector fields. Current development of chiral photonic crystals, nevertheless, are still confronted with limitations of one form or the other such as large optical losses, limited or absence of tunability, narrow operation bandwidth, and/or insufficient optical thickness for practical implementation. In this work, we show that cholesteric liquid crystals as 1D tunable chiral photonic crystals are promising alternatives to not only address all these issues and deficiencies but also enable new photonic applications in wider temporal and spectral realms. Our work entails a detailed study of the dynamical evolution of cholesteric helical self-assembly and defect formation in the bulk of thick cholesteric liquid crystals under various applied electric field conditions and a thorough exploration of how applying fields of vastly different frequencies can eliminate and/or prevent the formation of unremovable defects and to control the alignment of cholesteric helices in the entire bulk. We have developed a dual-frequency field assembly technique that enables robust room-temperature fabrication of stable well-aligned cholesteric liquid crystals to unprecedented thickness (containing thousands of grating periods) demanded by many photonic applications. The resulting chiral photonic crystals exhibit useful much-sought-after capabilities impossible with other existing or developing chiral photonic crystals—compactness (single, flat, millimeter-thick optical element), high transmission, dynamic tunability, large polarization rotation, and various switching/modulation possibilities for ultrafast and continuous-wave lasers in the visible, near- and mid-infrared regimes.

The Effect of the Degree of Polymerization and Polymer Composition on the Temperature Responsiveness of Cholesteric Semi-Interpenetrating Networks

Cholesteric liquid crystal oligomers and polymers are promising materials for creating materials and devices with stimuli-responsive structural color, and the cholesteric to smectic pre-transition effect is of particular interest as it leads to a strong redshift in the reflected color upon cooling. Cholesteric polymers can be stabilized by the formation of semi-interpenetrating networks to obtain more robust photonic materials, but this tends to strongly suppress the pre-transition effect. Here, we show that the pre-transition effect in semi-interpenetrating networks based on main-chain cholesteric oligomers can be amplified by incorporating a smectic monomer and by increasing the degree of polymerization of the oligomers. This amplification counteracts the suppressing effect of the semi-interpenetrating network, and the resulting materials still show a significant band shift upon cooling. Presumably, both methods lead to the formation of more smectic domains in the cholesteric helix, which causes an amplified pre-transitional effect. The results bring us closer to the use of cholesteric semi-interpenetrating cholesteric networks for applications in smart sensing, healthcare, and safety devices.

Light-controllable chiral dopant based on azo-fragment: synthesis and characterisation

ABSTRACT We present the synthesised chiral dopant 2-[(2-isopropyl-5-methylcyclohexyl)oxy]-2-oxoethyl 4-{(E)-[4-(decyloxy)phenyl]diazenyl}benzoate (ChD-3501), consisting of azo- and aliphatic fragments together with a chiral centre based on l-menthol as a reversible light-controllable chiral dopant. To assess the effects of UV–vis irradiation and temperature in the isotropic and liquid crystalline (LC) states, we studied the spectral kinetics of ethanol solution of ChD-3501, as well as induction of the cholesteric helix when it was dissolved in nematic LC (E7) as a chiral dopant. The concentration dependence of the helical pitch of the induced cholesterics was studied by means on Grandjean–Cano method, and the helical twisting power of ChD-3501 in the nematic host E7 was determined. The reversible trans-cis isomerisation of chiral dopant ChD-3501 in E7 under UV–vis irradiation was studied, and it has been found that the storage of the cis-isomer at certain constant temperature also leads to the reversible isomerisation. Possible applications of the studied system are discussed.

Observation and simulation of toron polymorphism: Effects of surface anchoring, elasticity and electric field in cholesterics with smectic-A phase beneath

Toron is one of the fundamental chiral topological textures appearing in many spintronic and soft matter systems. Here we report on the observation of torons in cholesteric liquid crystals with positive dielectric anisotropy (Δε > 0). In addition, the materials show smectic-A phase beneath the cholesteric phase, enabling us to see the pretransitional effect on the formation of the torons. In detail, we investigated the relation of toron formability and the external stimuli in terms of temperature and electric field. Importantly, the divergence of the elastic constants (K22 and K33) in the vicinity of the nematic-smectic-A phase transition causes the transition from the toron to the homeotropic alignment. The results reveal that both the homeotropic anchoring strength and the frustrated confinement of the cholesteric helix are important to determine whether the toron texture is selected among other textures like fingers. The confinement ratio, i.e. the ratio of cell thickness to cholesteric pitch, for the incidence of torons was found to be in a wide range of about 0.82 ∼ 1.5. We also show that the torons can be polymer-stabilized so that they retain over a wide temperature window. Even more importantly, the orientational state of the polymer-stabilized toron can be changed by an electric field, realizing fast switching between the dark and bright states. The system may find applications in electric-driven diffraction gratings or privacy protection films with a sub-millisecond response time.

Effect of Amorphous Crosslinker on Phase Behavior and Electro-Optic Response of Polymer-Stabilized Blue Phase Liquid Crystals.

Blue phase liquid crystals (BPLCs) composed of double-twisted cholesteric helices are promising materials for use in next-generation displays, optical components, and photonics applications. However, BPLCs are only observed in a narrow temperature range of 0.5–3 °C and must be stabilized with a polymer network. Here, we report on controlling the phase behavior of BPLCs by varying the concentration of an amorphous crosslinker (pentaerythritol triacrylate (PETA)). LC mixtures without amorphous crosslinker display narrow phase transition temperatures from isotropic to the blue phase-II (BP-II), blue phase-I (BP-I), and cholesteric phases, but the addition of PETA stabilizes the BP-I phase. A PETA content above 3 wt% prevents the formation of the simple cubic BP-II phase and induces a direct transition from the isotropic to the BP-I phase. PETA widens the temperature window of BP-I from ~6.8 °C for BPLC without PETA to ~15 °C for BPLC with 4 wt% PETA. The BPLCs with 3 and 4 wt% PETA are stabilized using polymer networks via in situ photopolymerization. Polymer-stabilized BPLC with 3 wt% PETA showed switching between reflective to transparent states with response times of 400–500 μs when an AC field was applied, whereas the application of a DC field induced a large color change from green to red.

Topological barriers to defect nucleation generate large mechanical forces in an ordered fluid

Common fluids cannot sustain static mechanical stresses at the macroscopic scale because they lack molecular order. Conversely, crystalline solids exhibit long-range order and mechanical strength at the macroscopic scale. Combining the properties of fluids and solids, liquid crystal films respond to mechanical confinement by both flowing and generating static forces. The elastic response, however, is very weak for film thicknesses exceeding 10 nm. In this study, the mechanical strength of a fluid film was enhanced by introducing topological defects in a cholesteric liquid crystal, producing unique viscoelastic and optomechanical properties. The cholesteric was confined under strong planar anchoring conditions between two curved surfaces with sphere-sphere contact geometry similar to that of large colloidal particles, creating concentric dislocation loops. During surface retraction, the loops shrank and periodically disappeared at the surface contact point, where the cholesteric helix underwent discontinuous twist transitions, producing weak oscillatory surface forces. On the other hand, new loop nucleation was frustrated by a topological barrier during fluid compression, creating a metastable state. This generated exceptionally large forces with a range exceeding 100 nm as well as extended blueshifts of the photonic bandgap. The metastable cholesteric helix eventually collapsed under a high compressive load, triggering a stick-slip-like cascade of defect nucleation and twist reconstruction events. These findings were explained using a simple theoretical model and suggest a general approach to enhance the mechanical strength of one-dimensional periodic materials, particularly cholesteric colloid mixtures.

Twist-bend nematics and heliconical cholesterics: a physico-chemical analysis of phase transitions and related specific properties

ABSTRACT Certain nematic liquid crystals, for example, those formed by banana-shaped molecules, can exhibit a low-temperature twist-bend nematic (Ntb) phase. Upon addition of chiral dopants, a chiral version of the twist-bend phase (N*tb) can be observed below the conventional chiral nematic (N*) phase, while under electric field the N* phase is transformed into a specific state known as ‘oblique helicoidal cholesteric’. In this work, we have studied the well-known Ntb-forming system CB7CB:CB6OCB with addition of 5CB and chiral dopants (ChDs) using optical microscopy, differential scanning calorimetry (DSC), and measurements of temperature-dependent optical transmission using optical microscopy. Effects of 5CB and different chiral dopants (of steroid or non-steroid nature) upon thermal stability of Ntb phase were analysed, and selective reflection in the visible range could be observed in the N* phase with a sufficiently high ChD content. As a peculiar feature, sharp unwinding of the cholesteric helix was observed at lower temperatures when approaching the N*tb phase, which appears to be similar to the helix unwinding close to the smectic-A transition.

Flow-assisted self-healing of the helical structure in a cholesteric liquid crystal.

We employ nonequilibrium molecular dynamics simulations to investigate the structure and dynamics of a cholesteric liquid crystal confined between atomically corrugated solid walls. By choosing walls normal to the helical axis, we can study systems with an arbitrary cholesteric pitch without exposing the cholesteric helix to a spurious stress. We investigate the effects of local heating and flow and their joint effects. A steady-state laminar Poiseuille flow is initiated by means of an external body force. Flow alone (i.e., without local heating) in a direction normal to the helical axis does not affect the cholesteric pitch. If the liquid crystal is heated in a small region, the cholesteric helix becomes unstable and melts locally. However, if local heating and flow are combined, a nontrivial synergistic effect is observed in that the helical structure recuperates the better, the higher the speed of the flow is.

Generation of hard twisted photons by charged particles in cholesteric liquid crystals

We study the radiation from charged particles crossing a cholesteric plate in the shortwave approximation when the wavelength of photons is much smaller than the pitch of the cholesteric helix, whereas the escaping angle of the photon and the anisotropy of the permittivity tensor can be arbitrary. The radiation of photons is treated in the framework of quantum electrodynamics with classical currents. The radiation of the plane-wave photons and the photons with definite projection of the angular momentum (the twisted photons) produced by charged particles crossing the cholesteric plate and moving rectilinearly and uniformly is considered. The explicit expressions for the average number of radiated photons and their spectra with respect to the energy and the projection of the angular momentum are obtained in this case. It turns out that in the paraxial approximation the projection of the orbital angular momentum, l, of radiated twisted photons is related to the harmonic number n∈Z as l=2n+1, i.e., the given system is a pure source of twisted photons as expected. It is shown that in the paraxial shortwave regime the main part of radiated photons is linearly polarized with l=±1 at the harmonics n={-1,0}. The applicability conditions of the approach developed are discussed. As the examples, we consider the production of 6.3eV twisted photons from uranium nuclei and the production of x-ray twisted photons from 120 MeV electrons.

Cholesteric layers with tangential-conical surface anchoring for an electrically controlled polarization rotator

The voltage dependences of polarization characteristics of light passed through the cholesteric layers with tangential-conical boundary conditions have been investigated. It has been shown that such layers allow turning the polarization azimuth more than 70 ∘ because of the unique untwisting effect of the cholesteric helix, due to free azimuthal rotation of the director on the substrate with conical anchoring. Optical cells under study have some advantages (low control voltage, smooth variation of polarization azimuth, simplicity of design) and can be used as an electrically controlled polarization rotator of white light.

Resettability of Cholesteric Liquid Crystal Helix Pitch Using Self-Assembled Dendrimer with Lysine Groups

Resettability of Cholesteric Liquid Crystal Helix Pitch Using Self-Assembled Dendrimer with Lysine Groups

Consequences of Chirality in Directing the Pathway of Cholesteric Helix Inversion of π-Conjugated Polymers by Light.

Control over main-chain motion of chiral π-conjugated polymers can lead to unexpected new functionalities.Here, it is shown that by combining photoswitchable azobenzene units in conjugation with chiral fluorene comonomers and appropriate plasticizers, the polymer organization and chiroptical properties of these alternating copolymers steered by light and its state of polarization can be dynamically controlled. The configuration of the stereogenic centers in the side chains of the fluorene units determines the handedness of the cholesteric organization in thermally annealed films, indicating cooperative behavior. The polymer alignment and helicity of the supramolecular arrangement can be switched by irradiating with linearly and circularly polarized light, respectively.Intriguingly, when switching the handedness of thermally induced cholesteric organizations by illuminating with circularly polarized light that is opposite to the handedness of the cholesteric phases, a nematic-like intermediate state is observed during helix interconversion. By the sequence of irradiation with left and right circularly polarized light followed by thermal annealing, an asymmetric motion, reminiscent of that seen in molecular motors is observed. These findings suggest that functional conjugated polymers can exhibit emergent properties at mesoscopic scale.

Optical Textures and Orientational Structures in Cholesteric Droplets with Conical Boundary Conditions.

Cholesteric droplets dispersed in polymer with conical boundary conditions have been studied. The director configurations are identified by the polarising microscopy technique. The axisymmetric twisted axial-bipolar configuration with the surface circular defect at the droplet’s equator is formed at the relative chirality parameter . The intermediate director configuration with the deformed circular defect is realised at , and the layer-like structure with the twisted surface defect loop is observed at . The cholesteric layers in the layer-like structure are slightly distorted although the cholesteric helix is untwisted.

Facile Anisotropic Deswelling Method for Realizing Large‐Area Cholesteric Liquid Crystal Elastomers with Uniform Structural Color and Broad‐Range Mechanochromic Response

AbstractCholesteric liquid crystal elastomers (CLCEs) are soft and dynamic photonic elements that couple the circularly polarized structural color from the cholesteric helix to the viscoelasticity of rubbers: the reflection color is mechanically tunable (mechanochromic response) over a broad range. This requires uniform helix orientation, previously realized by long‐term centrifugation to ensure anisotropic deswelling, or using sacrificial substrates or external fields. The present paper presents a simple, reproducible, and scalable method to fabricate highly elastic, large‐area, millimeters thick CLCE sheets with intense uniform reflection color that is repeatably, rapidly, and continuously tunable across the full visible spectrum by stretching or compressing. A precursor solution is poured onto a substrate and allowed to polymerize into a 3D network during solvent evaporation. Pinning to the substrate prevents in‐plane shrinkage, thereby realizing anisotropic deswelling in an unprecedentedly simple manner. Quantitative stress–strain–reflection wavelength characterization reveals behavior in line with theoretical predictions: two linear regimes are identified for strains below and above the helix unwinding threshold, respectively. Up to a doubling of the sample length, the continuous color variation across the full visible spectrum repeatedly follows a volume conserving function of the strain, allowing the CLCE to be used as optical high‐resolution strain sensor.

Rotation and propulsion in 3D active chiral droplets

Chirality is a recurrent theme in the study of biological systems, in which active processes are driven by the internal conversion of chemical energy into work. Bacterial flagella, actomyosin filaments, and microtubule bundles are active systems that are also intrinsically chiral. Despite some exploratory attempt to capture the relations between chirality and motility, many features of intrinsically chiral systems still need to be explored and explained. To address this gap in knowledge, here we study the effects of internal active forces and torques on a 3-dimensional (3D) droplet of cholesteric liquid crystal (CLC) embedded in an isotropic liquid. We consider tangential anchoring of the liquid crystal director at the droplet surface. Contrary to what happens in nematics, where moderate extensile activity leads to droplet rotation, cholesteric active droplets exhibit more complex and variegated behaviors. We find that extensile force dipole activity stabilizes complex defect configurations, in which orbiting dynamics couples to thermodynamic chirality to propel screw-like droplet motion. Instead, dipolar torque activity may either tighten or unwind the cholesteric helix and if tuned, can power rotations with an oscillatory angular velocity of 0 mean.