Towards complete photonic band gap in a high refractive index nanoparticle-doped blue phase liquid crystal.

Three-dimensional (3D) photonic crystals with complete photonic band gap (PBG) are fascinating due to the possibility of controlling light in all directions. Realizing such photonic crystals is nontrivial due to symmetry requirements and associated fabrication challenges. Liquid crystalline cubic blue phases (BPs) are soft 3D photonic crystals with an incomplete PBG due to the low refractive index contrast (<0.1). The present work attempts to drive a cubic BP towards a complete PBG via a simple approach of high refractive index nanoparticle-doping. The photonic band diagrams and reflection spectra of the nanoparticle-doped BP simulated using the finite element method show an increased PBG width, a parameter that quantifies the complete PBG. The reflection spectra obtained from UV-Vis-NIR spectroscopy show an increase (by a factor of >2) in PBG width for the nanoparticle-doped BP, validating the simulations. The findings are explained based on increased refractive index contrast (∼1.4) due to the nanoparticles getting trapped in the cores of disclination lines that make up the BP lattice. The simulations also indicate effective confinement of electric field eigenmodes in the nanoparticle-doped BP leading to high attenuation of the incident light. Further, the iso-frequency contours extracted from the band diagrams exhibit self-collimation and negative refraction of light.

Effect of Photonic Band Gap on Photoluminescence in a Dye-Doped Blue Phase Liquid Crystal.

Tunability of fluorescence intensity is an essential parameter for enhancing the versatility of devices like emissive displays and solar cells. Soft photonic crystals, with their tunable photonic band gap (PBG), are highly sought-after systems for such purposes. Here, we report modulation of photoluminescence (PL) intensity in a fluorescent dye-doped blue phase liquid crystal, a 3D soft photonic crystal. On cooling, from the isotropic fluid phase, the PL intensity gets enhanced due to the overlapping of the emission wavelength of the dye with the photonic band edge. However, the PL intensity decreases on the application of an electric field, despite both thermal and electric fields having a similar effect (red shift) on the PBG. The contrasting behavior of PL intensity, also observed in composites obtained by varying the dye and the chiral dopant (handedness), is discussed in terms of scattering pathways for the emitted photons. The time-resolved PL studies show a reduction in the lifetime of the excited species upon cooling, validating the thermal dependence of PL intensity modulation due to Purcell effect. The facile modulation of PL intensity in the dye-doped blue phase system makes it appealing from the point of view of high-performance photonic applications.

Photo-tunable epsilon-near-zero behavior in a self-assembled liquid crystal - nanoparticle hybrid material.

Dynamic tuning of electromagnetic response is an important parameter to realize exotic applications of optical metamaterials. Self-assembly achieved via the incorporation of soft materials is an attractive approach to achieve tunable optical properties. Among the soft materials, liquid crystals are highly sought after due to the inherent soft-stimuli responsiveness. This article reports experimental evidence of tunable epsilon-near-zero (ENZ) behavior brought about by an optical field in a self-assembled liquid crystal - nanoparticle system. The material consists of Au nanoparticles capped with a photo-active chiral liquid crystal ligand. In the liquid crystalline state, the system self-assembles into a helical lamellar superstructure, confirmed by polarizing optical microscopy, HRTEM, XRD, and circular dichroism studies. Upon irradiation with UV light, the localized surface plasmon resonance peak of Au red-shifts by ∼10 nm and gets restored with white light illumination. The effective permittivity of the system obtained from ellipsometry indicates ENZ behavior in the visible spectrum with a bandwidth of ∼45 nm which gets enhanced by a factor of 1.6 on UV illumination. Theoretical calculations, carried out using the effective medium approach, support the experimental findings, making the system an efficient ENZ metamaterial in the optical regime.

Effect of gelation on the Frank elastic constants in a liquid crystalline mixture exhibiting a twist bend nematic phase.

We report studies on the Frank elastic constant behaviour of a liquid crystal gel system exhibiting the twist bend nematic (Ntb) phase. Physical gelation is observed to ease the splay and stabilize the twist deformations in the nematic phase preceding the Ntb. More importantly, the ultra-low bend elastic constant (K33) of the system is enhanced by an order of magnitude on gelation. The magnitude of K33 remains high even in the vicinity of the Ntb phase, which otherwise is susceptible to bend deformations. This phenomenon is explained from the point of view of polar interactions in the Ntb system. XRD and dynamic rheology along with the elastic constant data validate this argument. Another salient feature of the system is that gel fibers grown in the direction orthogonal to the helical axis vanish in the Ntb phase as observed from polarizing optical microscopy. A possible reason for this is discussed on the basis of ordering developed in the surrounding medium. This feature gives the possibility of using the Ntb phase as a tool to imprint directional microstructures with a gel network.

Giant enhancement and facile tuning of photoluminescence in a soft anisotropic magneto-gel.

A soft photoluminescent composite, prepared using a nematic liquid crystal and a fluorescent gelator, exhibits a nearly two orders of magnitude increase in fluorescence on addition of superparamagnetic nanoparticles. The internal magnetic field generated leading to an increase in the population of singlet excitons which affects the radiative efficiency, and enhanced ordering of the LC environment are proposed to be responsible for the large increase seen in fluorescence. Also, the nematic nature of the host liquid crystal medium aids in switching of the fluorescence intensity between its anisotropic limits on application of an external electric field with the switch-off time being faster compared to the field-driven switch-on time.

Electrically Tunable Soft Photonic Gel Formed by Blue Phase Liquid Crystal for Switchable Color-Reflecting Mirror.

We report a robust soft photonic crystal system, fabricated using blue phase (BP) liquid crystal, which can efficiently filter the visible light. The BP gel system is obtained without surface treatment or polymerization, and thus is facile and cost effective to fabricate. Perfect monodomain with vivid color is achieved with a low electric field, which can be further tuned to reflect a second color. Most importantly, apart from the field-induced color switching, a dark/transparent state is also achieved due to complete unwinding of the BP helical structure. A potential application as a tunable color-reflecting mirror, which can be switched between "reflecting" and "transparent" states, is proposed.

Dynamic Orthogonal Switching of a Thermoresponsive Self-Organized Helical Superstructure.

Controllable manipulation of self-organized dynamic superstructures of functional molecular materials by external stimuli is an enabling enterprise. Herein, we have developed a thermally driven, self-organized helical superstructure, i.e., thermoresponsive cholesteric liquid crystal (CLC), by integrating a judiciously chosen thermoresponsive chiral molecular switch into an achiral liquid crystalline medium. The CLC in lying state, in both planar and twisted nematic cells, exhibits reversible in-plane orthogonal switching of its helical axis in response to the combined effect of temperature and electric field. Consequently, the direction of the cholesteric grating has been observed to undergo 90° switching in a single cell, enabling non-mechanical beam steering along two orthogonal directions. The ability to reversibly switch the cholesteric gartings along perpendicular directions by appropriately adjusting temperature and electric field strength could facilitate their applications in 2D beam steering, spectrum scanning, optoelectronics and beyond.

Effect of Atomic-Scale Differences on the Self-Assembly of Thiophene-based Polycatenars in Liquid Crystalline and Organogel States.

Two series of polycatenars are reported that contain a central thiophene moiety connected to two substituted oxadiazole or thiadiazole units. The number, position, and length of the peripheral chains connected to these molecules were varied. The oxadiazole-based polycatenars exhibited columnar phases with rectangular and hexagonal or oblique symmetry, whereas the thiadiazole-based polycatenars exhibited columnar phases with rectangular and/or hexagonal symmetry. All of the compounds exhibited bright emission in the solution and thin-film states. Two oxadiazole-based molecules and one thiadiazole-based molecule exhibited supergelation ability in hydrocarbon solvents, which is mainly supported by attractive π-π interactions. These gels showed aggregation-induced enhanced emission, which is of high technological importance for applications in solid-state emissive displays. X-ray diffraction studies of the xerogel fibers of oxadiazole-based polycatenars revealed a columnar rectangular organization, whereas a hexagonal columnar arrangement was observed for thiadiazole-based polycatenars. Rheological measurements carried out on the samples quantitatively confirmed the formation of gels and showed that these gels are mechanically robust. The impact of an atomic-scale difference (oxygen to sulfur, <2 % of the molecular weight) on the self-assembly and the macroscopic properties of those self-assembled structures are clearly visualized.

Optically Biaxial, Re-entrant and Frustrated Mesophases in Chiral, Non-symmetric Liquid Crystal Dimers and Binary Mixtures.

Sixteen optically active, non-symmetric dimers, in which cyanobiphenyl and salicylaldimine mesogens are interlinked by a flexible spacer, were synthesized and characterized. While the terminal chiral tail, in the form of either (R)-2-octyloxy or (S)-2-octyloxy chain attached to salicylaldimine core, was held constant, the number of methylene units in the spacer was varied from 3 to 10 affording eight pairs of (R & S) enantiomers. They were probed for their thermal properties with the aid of orthoscopy, conoscopy, differential scanning calorimetry and X-ray powder diffraction. In addition, the binary mixture study was carried out using chiral and achiral dimers with the intensions of stabilizing optically biaxial phase/s, re-entrant phases and important phase sequences. Notably, one of the chiral dimers as well as some mixtures exhibited a biaxial smectic A (SmAb ) phase appearing between a uniaxial SmA and a re-entrant uniaxial SmA phases. The mesophases such as chiral nematic (N*) and frustrated phases viz., blue phases (BPs) and twist grain boundary (TGB) phases, were also found to occur in most of the dimers and mixtures. X-ray diffraction studies revealed that the dimers possessing oxybutoxy and oxypentoxy spacers show interdigitated (SmAd ) phase where smectic periodicity is over 1.4 times the molecular length; whereas in the intercalated SmA (SmAc ) phase formed by a dimer having oxydecoxy spacer the periodicity was found to be approximately half the molecular length. The handedness of the helical structure of the N* phases formed by two enantiomers was examined with the aid of CD measurements; as expected, these enantiomers showed optical activities of equal magnitudes but with opposite signs. Overall, it appears that the chiral dimers and mixtures presented herein may serve as model systems in design and developing novel materials exhibiting the apolar SmAb phase possessing D2h symmetry and nematic-type biaxiality.

Diminished Splay Stiffening in Weak Gels of Calamitic-Bent-Core Nematic Composites.

Composites of calamitic and bent-core nematic molecules exhibiting a nematic to nematic-gel transformation have been investigated using thermal, electrical, X-ray, and mechanical probes. The studies focusing on the Frank elastic behavior show a surprising result that the thermal behavior of the threshold voltage and the dependent splay elastic constant (K11) are remarkably different in temperature regions identified as weak and strong gels. In the former gel, the parameters exhibit values significantly smaller than the higher-temperature fluid nematic, effectively canceling out the underlying thermal variation due to the order parameter. This is especially attractive from the viewpoint of display devices. The X-ray diffraction data suggest that the fibers have a plastic nature in the weak gel and 3D-crystalline ordering in the strong gel. We argue that the different elastic behavior in the two gel phases is caused by the nature of the fibers; they are stiff in both gels but the interfiber interaction is weaker in the weak gel allowing the splay elastic constant to be lowered. The X-ray and rheological data lend support to the characterization of the fibers.

Influence of polarization-tilt coupling on the ferroelectric properties of smectic gels.

We have studied composites of a ferroelectric liquid crystal mixture with a simple organic gelating agent, employing structural, thermal, electrical and mechanical probes, investigating the influence of the coupling between the polarization and the tilt angle on the ferroelectric properties of smectic gels. The calorimetric data, presenting clear signatures of the gelation occurring in the smectic A (SmA) phase or the isotropic phase, depending on the concentration of the gelator, help in constructing a rich diagram in the temperature-gelator concentration phase space. The atomic force microscopy imaging brings out the interesting feature of the transfer of chirality from the ferroelectric liquid crystal (FLC) to the gel strands, as exemplified by the creation of nanorope structures which have attracted much attention in recent times. The influence of gelation on the magnitude of the tilt angle appears to be dependent on the probe employed: there is no change in the values obtained by X-ray diffraction, which looks at the projection of the entire molecular length onto the layer normal. In contrast, the value from the electro-optic method, wherein the molecular-core is responsible for the results, diminishes with gelator concentration. The latter feature is copied by the magnitude of the polarization also. Dielectric spectroscopy shows that gelation weakly influences the soft mode in the SmA phase. However, the Goldstone mode behaviour is strongly dependent on the gelator concentration, with the appearance of two modes in the smectic C* (SmC*) phase of higher gel concentrations. With information obtained upon application of DC bias, the origin of the two relaxations is discussed. These data are analyzed in terms of the predictions of the Landau model proposed for the ordinary (non-gel) SmA-SmC* transition showing that the gel network enhances the linear polarization-tilt coupling over the biquadratic one. Upon gelation the system becomes mechanically strong with a large increase in the elastic moduli.

Anchoring transition induced by gelation in a liquid crystal system.

We report a novel type of anchoring transition (ANT) in a liquid crystal driven by the physical gelation of the system. The ANT manifests as anomaly in the thermal behaviour of the dielectric permittivity. Data from X-ray studies suggest that ANT is caused by the ability of the gel fibres to compete with the substrate-driven orientation conditions. It is further found that the molecular reorientation is possible only in cases where the gel is weak, the difference between weak and strong gels being established by rheological measurements.

Soft glass rheology in liquid crystalline gels formed by a monodisperse dipeptide.

Thermal and extensive rheological characterization of a nematic liquid crystal gelated with a novel monodisperse dipeptide, also a liquid crystal, has been carried out. For certain concentrations, the calorimetric scans display a two-peak profile across the chiral nematic-isotropic (N*-I) transition, a feature reminiscent of the random-dilution to random-field crossover observed in liquid crystal gels formed with aerosil particles. All samples show shear thinning behavior without a Newtonian plateau region at lower shear rates. Small deformation oscillatory data at lower frequencies exhibit a frequency dependence of the storage (G') and loss (G'') moduli that can be described by a weak power-law, characteristic of soft glassy rheological systems. At higher frequencies, while lower concentration composites have a strong frequency dependence with a trend for possible crossover from viscoelastic solid to viscoelastic liquid behavior, the higher-concentration gels show frequency-independent rheograms of entirely elastic nature G' > G''. The plateau modulus of G' is described by a power-law with an exponent again common to soft materials, such as foams, slurries, etc. Other features which are a hallmark of such materials observed in the present study are: (i) above a critical strain, a strain softening of the moduli with a peak in the loss modulus, (ii) power-law variation of the storage modulus in the nonlinear viscoelastic regime, and (iii) absence of Cox-Merz superposition for the complex viscosity. An attractive feature of these gels is the fast recovery upon removal of large strain and qualitatively different temporal behavior of the recovery between the low and high concentration composites, with the latter indicating the presence of two characteristic time scales.

Electric-field-dictated phase diagram and accelerated dynamics of a reentrant nematic liquid crystal under photostimulation.

In a system consisting of photoactive molecules that exhibit light-driven isomerization transformations, actinic light can diminish or enhance ordering to the extent that transitions from the equilibrium to a more disordered phase can be brought about isothermally. This feature enables light to be used as a thermodynamiclike parameter to investigate phase behavior and adds another dimension to the studies owing to the nonequilibrium character of the isothermal transitions. We have carried out experiments which exploit the combination of two recent findings, viz., an electric field can accelerate the return to the nematic liquid crystalline phase from a photodriven isotropic phase; and in a reentrant mesogen, the photoinduced phase can be more ordered. To photostimulate the nonequilibrium transitions a low power uv radiation (0.1 mW cm(-2)) has been used. Unique temperature-electric-field phase diagrams of a liquid crystal exhibiting isotropic-nematic-smectic- A -reentrant nematic sequence, mapped using light transmission as probe reveal that the electric field influences all the transitions, but the effect is maximum on the equilibrium reentrant nematic to the photoinduced smectic- A transition. Temporal measurements have been performed under nonequilibrium conditions to study the dynamics of both the photochemical and the back relaxation processes across the different transitions. The electric field is indeed observed to accelerate the thermal back relaxation in each case, and especially the recovery of the reentrant phase is hastened by three orders of magnitude in time. We explore possible causes for the acceleration and present a finding which can be associated with one of the predictions of density-functional calculations for isomerization of azobenzenes.

Fast responding robust nematic liquid crystalline gels formed by a monodisperse dipeptide: electro-optic and rheological studies.

Realization of mechanically robust electrically fast responding liquid crystal devices with low operating voltage is one of the current research interests. Here we report a gel system comprising a commercially available nematic liquid crystal material and a new monodisperse dipeptide liquid crystalline organogelator that results in these properties. The gels exhibit nearly 2 orders of magnitude faster switching response than the pure nematic liquid crystal while having 3 orders of magnitude higher zero shear rate viscosity, and with the attractive feature that the switching threshold voltage is hardly altered. Electro-optic and rheological studies of this system are described here.

Evidence of wormlike micellar behavior in chromonic liquid crystals: rheological, X-ray, and dielectric studies.

We report rheological, X-ray, and dielectric investigations on a chromonic liquid-crystalline system formed by aqueous solutions of a food coloring agent, Sunset Yellow, in the absence and upon addition of salt. The salt-concentration dependence of the steady-state viscosity at low shear rates has a non-monotonic variation and is qualitatively similar to the behavior seen in wormlike micellar systems, a surprising result since chromonic systems are expected to be non-micellar in character. More interestingly, for a particular low concentration of the salt (20 mM), the viscosity increases by 3 orders of magnitude in comparison with that of the pure chromonic material. The dynamic (oscillatory) rheological data bring out features which can be described in terms of a microstructure formation. X-ray and dielectric studies show that certain characters of the aggregates formed by the Sunset Yellow molecules are not altered by the addition of salt.

Kinetics of the thermal back relaxation time of the photoinduced nematic-isotropic transition.

We report on the temperature dependence of the response time for the photochemical and thermal back relaxation processes observed in a material exhibiting a photostimulated, isothermal nematic-isotropic phase transition. It is found that the time required for the system to achieve the photostationary state as well as to recover the original state after photoirradiation with a uv beam is a smooth function of the absolute temperature of the sample, except in the vicinity of the transition. The duration of the recovery can be split into two parts: delay time and response time. Using a simple description based on the Maier-Saupe model, we show that the temperature dependence of the response time can be understood in terms of the order parameter excess between the equilibrium and photostimulated states.

Nonequilibrium liquid crystalline layered phase stabilized by light.

The ability of light to alter/stabilize a particular thermodynamic phase is a power tool to investigate condensed matter from a new dimension. This field of photoinduced phase transitions is currently an important area of research. Being elastically soft and having subtle changes between its many phases a liquid crystal material is an attractive medium to investigate such light-driven phase transitions. The attraction is partly due to the large birefringence changes accompanying these transitions that are useful in developing photonic devices. In all of the cases reported to date, the photoinduced transition always leads to a phase that in any case exists in the thermal cycle. Recently we reported the first exception to such an established phenomenon (Adv. Mater. 2005, 17, 2086). The guest-host ternary mixture consisting of the photoactive azobenzene guest molecules does not exhibit smectic A phase in the absence of UV radiation. However, the smectic A phase is induced and stabilized only in the presence of UV light. In this paper, we map out hitherto unexplored temperature versus UV intensity phase diagrams for various mixtures, which illustrate that light mimics, in a limited sense, the role of a thermodynamic parameter such as, for example, pressure. The threshold UV intensity required to photodrive the appearance of the smectic A phase is seen to have a strong concentration dependence. Our studies also suggest the possibility of observing a double critical point by employing the UV intensity as a fine-tuning parameter.

Photoinduced effects in the vicinity of the smectic-A-smectic-C*A transition: polarization, tilt angle, and response time studies.

We report detailed measurements of the photoinduced effects on the electric polarization, tilt angle, response time, and rotational viscosity in the vicinity of the smectic-A-antiferroelectric-smectic-C (Sm-C*(A)) transition of a guest-host system consisting of photoactive azobenzene-based guest molecules and nonphotoactive host molecules. In the Sm-C*(A) phase all the parameters, except the tilt angle, exhibit both the primary and secondary photoferroelectric effects. The tilt angle dependence of the polarization in the absence of light and in light-on conditions have been analyzed in terms of the predictions of the generalized mean-field and microscopic models.