Light-Responsive Microstructures in Droplets of the Twist-Bend Nematic Phase.

We report on the structure and optical manipulation of the director configurations in emulsions of liquid-crystalline droplets of a compound exhibiting the nematic (N) and the twist-bend nematic (NTB) phases. We demonstrate a decrease in the ratio of the bent elastic constant K33 to the splay constant K11 by nearly 2 orders of magnitude with decreasing temperature in the N phase. The director structures in liquid-crystal droplets doped with a photoswitchable surfactant without and under ultraviolet (UV) light are discussed in light of the strong elastic anisotropy of the investigated compound. We also compare our findings with the results obtained in doped nematic droplets of a conventional 4-cyano-4'-pentylbiphenyl (5CB) liquid crystal. The dynamics of droplets in the NTB phase by UV light irradiation are also studied using polarizing and confocal microscopies.

Optically driven translational and rotational motions of microrod particles in a nematic liquid crystal.

A small amount of azo-dendrimer molecules dissolved in a liquid crystal enables translational and rotational motions of microrods in a liquid crystal matrix under unpolarized UV light irradiation. This motion is initiated by a light-induced trans-to-cis conformational change of the dendrimer adsorbed at the rod surface and the associated director reorientation. The bending direction of the cis conformers is not random but is selectively chosen due to the curved local director field in the vicinity of the dendrimer-coated surface. Different types of director distortions occur around the rods, depending on their orientations with respect to the nematic director field. This leads to different types of motions driven by the torques exerted on the particles by the director reorientations.

Photomanipulation of the anchoring strength using a spontaneously adsorbed layer of azo dendrimers.

We systematically studied the photoinduced anchoring transition in a nematic liquid crystal containing azo dendrimers. Because the azo dendrimers in the trans-isomer state were spontaneously adsorbed at substrate surfaces, which was confirmed by optical second-harmonic generation (SHG), a homeotropic orientation was established at the first stage. Ultraviolet (UV) light irradiation triggered a transition into a planar state which was accompanied by a suppression of the SH generation. The monotonic decrease of the effective scalar order parameter with increasing UV light intensity was determined by polarized attenuated total reflection infrared (ATR-IR) spectroscopy. The variation of anchoring strength and extrapolation length was evaluated by observing the Fréedericksz transition as a function of UV light intensity at a certain visible (VIS) light intensity. Such a photoinduced variation can be interpreted as a variation of the anchoring strength depending on the trans/cis ratio at the surfaces based on a modified Rapini-Papoular model. Thus, this system provides the opportunity for a controlled change in the anchoring strength.

Lasing properties of polymerized chiral nematic Bragg onion microlasers.

Dye doped photocurable cholesteric liquid crystal was used to produce solid Bragg onion omnidirectional lasers. The lasers were produced by dispersing and polymerizing chiral nematic LC with parallel surface anchoring of LC molecules at the interface, extracted and transferred into another medium. Lasing characteristics were studied in carrier medium with different refractive index. The lasing in spherical cholesteric liquid crystal was attributed to two mechanisms, photonic bandedge lasing and lasing of whispering-gallery modes. The latter can be suppressed by using a higher index carrier fluid to prevent total internal reflection on the interface of the spheres. Pulse-to-pulse stability and threshold characteristics were also studied and compared to non-polymerized lasers. The polymerization process greatly increases the lasing stability.

Thermodynamically Anchoring-Frustrated Surface to Trigger Bulk Discontinuous Orientational Transition.

Surface-specific liquid crystal (LC) nanostructures provide a unique platform for studying surface-wetting phenomena and also for technological applications. The most important studies on LC properties are related to bulk alignment, surface anchoring, and so on. Here, we study an LC system with a nematic liquid crystal (NLC) on a perfluoropolymer-coated substrate, in which a discontinuous bulk orientational transition has recently been found. Using free-energy analysis based on experimental results of the newly-conducted grazing-incidence X-ray diffraction (GI-XRD) measurements, we have confirmed a thermodynamic growth process of smectic liquid crystalline wetting nanosheets on the surface and successfully explained that a frustrated surface of planar and vertical anchoring states accompanied by an elastic energy cost kinetically triggers the bulk reorientation in the first-order manner. This interfacial bottom-up process may offer a general insight into how interfacial hierarchical molecular architectures alter the bulk properties of matter thermodynamically.

Circular flow formation triggered by Marangoni convection in nematic liquid crystal films with a free surface.

We demonstrate circular flow formation at a surface in homeotropically oriented nematic liquid crystals with a free surface using focused laser beam irradiation. Under a weak laser power, a pit together with an associated circular bulge is formed: the Marangoni effect. Here a diverging molecular flow from the pit (thermocapillary flow) also induces director tilt in the radial direction. Upon increasing the laser power, the pit becomes deeper, and eventually evolves into a circular flow associated with a deeper pit and a subsidiary circular bulge or valley structure. This phenomenon is induced by escaping from excess deformation energy due to a bend deformation of the director. Actually, we confirmed that the circular flow is never formed in the isotropic phase. The handedness of the vortex cannot be controlled by circular polarisation, but is controllable by doping with chiral molecules. This rotational motion (a nematic micro-rotor) is a unique phenomenon only exhibited by anisotropic liquids, and is expected to be applied for novel devices.

Enhancing and reducing chirality by opposite circularly-polarized light irradiation on crystalline chiral domains consisting of nonchiral photoresponsive W-shaped liquid crystal molecules.

We found possible chirality enhancement and reduction in chiral domains formed by photoresponsive W-shaped molecules by irradiation with circularly polarized light (CPL). The W-shaped molecules exhibit a unique smectic phase with spontaneously segregated chiral domains, although the molecules are nonchiral. The chirality control was generated in the crystalline phase, which shows chiral segregation as in the upper smectic phase, and the result appeared to be as follows: for a certain chiral domain, right-CPL stimuli enhanced the chirality, while left-CPL stimuli reduced the chirality, and vice versa for another chiral domain. Interestingly, no domain-size change could be observed after CPL irradiation, suggesting some changes in the causes of chirality. In this way, the present system can recognize the handedness of the applied chiral stimuli. In other words, the present material can be used as a sensitive chiral-stimuli-recognizing material and should find invaluable applications, including in chiroptical switches, sensors, and memories as well as in chiral recognition.

Monolayer Filaments versus Multilayer Stacking of Bent-Core Molecules.

Bent-core materials exhibiting lamellar crystals (B4 phase), when dissolved in organic solvents, formed gels with helical ribbons made of molecular monolayers and bilayers, whereas strongly deformed stacks of 5-6 layers were found in the bulk samples. The width and pitch of the helical filaments were governed by molecular length; they both increased with terminal-chain elongation. It was also found that bulk samples were optically active, in contrast to the corresponding gels, which lacked optical activity. The optical activity of samples originated from the internal structure of the crystal layers rather than from the helicity of the filaments. A theoretical model predicts a strong increase in optical activity as the number of layers in the stack increases and its saturation for few layers, thus explaining the smaller optical activity for gels than for bulk samples. A strong increase and redshift in fluorescence was detected in gels as compared to the sol state.

Photoresponsive stripe pattern in achiral azobenzene liquid crystals.

A periodic stripe pattern is found in the nematic phase close to the smectic phase of photoresponsive achiral liquid-crystalline compounds. The origin of the stripe patterns can be ascribed to an extremely large bent elastic constant K33 . In addition, we succeeded in controlling the pattern by the following two methods: 1) the stripe disappears by a trans-cis photoisomerization upon UV light irradiation and reappears upon light termination, and 2) the stripe pattern is stabilized over the whole nematic phase, at approximately 10 °C, by polymerization of the compounds.

Thermal diffusivity anisotropy measured by a temperature wave method in the homologous series of (p-alkoxybenzylidene)-p'-octylaniline (nO.8).

The anisotropy of thermal diffusivity in four homologues of (p-alkoxybenzylidene)-p'-octylaniline (nO.8, n = 4 - 7) was measured using a temperature wave method. The results show that the thermal diffusivity component along the director (α(∥)) is considerably larger than that perpendicular to the director (α(⊥)) in all mesophases, i.e., nematic (N), smectic A (SmA), smectic B (SmB), and smectic G (SmG) phases. Both components of the thermal diffusivity show a dip at the second- or weakly first-order N-SmA phase transition due to the heat capacity anomaly. In contrast, at the first-order SmA-SmB phase transition, thermal diffusivity exhibits a stepwise increase. The x-ray and calorimetric measurements enable a calculation of the thermal conductivity and the study of the effect of the molecular length on the thermal conductivity and diffusivity in the SmA and SmB phases. For the homologues n = 4, 5, and 6, which exhibit the same phase sequence upon cooling, the parallel component of the thermal conductivity k(∥) in the SmA and SmB phases systematically increases with increasing length of the molecular tails, while no such increase is observed in the thermal diffusivity α(∥). We thus conclude that the molecular model [Urbach et al., J. Chem. Phys. 78, 5113 (1983)] is valid for the qualitative prediction of the effect of the molecular length on the magnitude of the thermal conductivity.

A Twist-Bend Nematic (NTB ) Phase of Chiral Materials.

New chiral dimers consisting of a rod-like and cholesterol mesogenic units are reported to form a chiral twist-bend nematic phase (NTB *) with heliconical structure. The compressibility of the NTB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the NTB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non-chiral compounds (ca. 10 nm).

Optical manipulation of the nematic director field around microspheres covered with an azo-dendrimer monolayer.

We report here the optical manipulation of the director and topological defect structures of nematic liquid crystals around a silica microparticle with azobenzene-containing dendrimers (azo-dendrimers) on its surface. We successfully demonstrate the successive switching processes from hedgehog, to boojum, and further to Saturn ring configurations by ultraviolet (UV) light irradiation and termination. The switching time between these defect structures depends on the UV light intensity and attains about 50 ms. Since the pretreatment of microparticles is not necessary and the surface modification is spontaneously performed just by dissolving the azo-dendrimers in liquid crystals, this dendrimer supplies us with a variety of possible applications.

Discontinuous thermal diffusivity change due to the anchoring transition of a liquid crystal on a perfluoropolymer surface.

Thermal diffusivity of a liquid crystal, 4'-butyl-4-heptyl-bicyclohexyl-4-carbonitrile, was measured using a temperature wave method. The liquid crystal was sandwiched by two glass substrates, which were treated with three different surface agents for providing distinct molecular orientations. Here, we demonstrate that: 1) a large thermal diffusivity anisotropy arising from different orientations, that is, planar and homeotropic states, was found in the nematic and smectic A phases; 2) when substrates were coated with a perfluoropolymer, abrupt changes of the thermal diffusivity were observed in the nematic phase both on cooling and heating due to the discontinuous anchoring transition between planar and homeotropic states. The temperature dependence of the thermal diffusivity anisotropy was well described by a power law, with an exponent of 0.27 according to the mean-field theory.

Pattern-stabilized decorated polar liquid-crystal fibers.

Geometric frustration gives rise to new fundamental phenomena and is known to yield the formation of exotic states of matter, such as incommensurate crystals, modulated liquid-crystalline phases, and phases stabilized by defects. In this Letter, we present a detailed study of polar structure of freely suspended fluid filaments in a polarization modulated liquid-crystal phase. We show that a periodic pattern of polarization-splay stripes separated by defect boundaries and decorating smectic layers can stabilize the structure of fluid fibers against the Rayleigh-Plateau instability. The instability is suppressed by the resistance of the defect structure to a radial compression of the cylindrical fibers. Our results provide direct experimental observation of a link between the stability of the liquid fibers, internal polar order, and geometrical constraints. They open a new perspective on a wide range of fluid polar fiber materials.

Observation of two isotropic-nematic phase transitions near a surface.

Using specified conditions, we succeeded in observing the isotropic-nematic (Iso-N) liquid crystal phase transition at surfaces followed by that in bulk for the first time. An additional heat anomaly peak was found at a higher temperature side of a main phase transition peak using highly sensitive differential scanning calorimetry (HS-DSC). The peak is pronounced particularly in the cooling process, since the transition starts at surfaces on cooling. The temperature dependence of retardation allows us to safely conclude that the higher temperature peak that appeared in HS-DSC is attributed to the Iso-N transition at surfaces. These measurements also indicate that the surface transition is of first order. These behaviors were theoretically explained by generalized Maier-Saupe theory.

Columnar liquid crystal with a spontaneous polarization along the columnar axis.

A fan-shaped molecule (2), carrying hydrogen-bonding amide groups in proximity to its polar aromatic core, self-assembles into a columnar liquid crystalline mesophase, which unprecedentedly possesses a spontaneous macroscopic polarization along the columnar axis. Due to its polar nature, the mesophase displays a signal of second harmonic generation (SHG), which disappears on phase transition to an isotropic melt and then retrieves its original intensity on subsequent cooling.

Color-temperature tunable white reflector using bichiral liquid crystal films.

We have demonstrated multicolored reflections showing various whitish colors from a bichiral liquid crystal (LC) film. The bichiral LC film was fabricated by using left-handed and right-handed polymeric cholesteric liquid crystal (CLC) films with two different helical pitches and an isotropic polymer film in between. Color temperatures of the multiple reflections are controlled from ~4000 K to ~10000 K by changing linear polarization directions of normally incident and reflected lights. This characteristic can extend practical applications of CLCs to illuminant devices.

Low threshold lasing from dye-doped cholesteric liquid crystal multi-layered structures.

We fabricated novel hybrid structures composed of a dye-doped low-molecular-weight cholesteric liquid crystal sandwiched by multi-layered polymer cholesteric liquid crystal films and evaluated their lasing characteristics. Lasing was observed with an extremely reduced threshold (12 nJ/pulse) by a factor of 10 compared with that in a simple dye-doped low-molecular-weight cholesteric liquid crystal cell. Lasing characteristics experimentally obtained were discussed by comparing them with the simulated photonic density of states spectra.

Carrier transport simulation in a model liquid crystalline system with the biaxial Gay-Berne potential.

In this paper, we performed carrier transport simulation to understand the unusual temperature dependence of the carrier mobility observed in nematic liquid crystals. For this purpose, we made a model liquid crystalline system consisting of biaxial Gay-Berne particles, and then we simulated hopping transport between these particles. The hopping rate was formulated suitably for the biaxial Gay-Berne particles based on the investigation of the electronic overlaps between actual aromatic molecules. The carrier transport simulation was performed by master equation method on the model system prepared by N-P-T ensemble Monte Carlo simulation. We reproduced gradual mobility increase in the nematic phase as a result of the change in the short range molecular order.

Enhanced optical activity by achiral rod-like molecules nanosegregated in the B4 structure of achiral bent-core molecules.

Chirality in a mixture system consisting of bent-core 1,3-phenylene bis[4-(4-8-alkoxyphenyliminomethyl)benzoates] (P8-O-PIMB) and rod-like n-pentyl-cyanobiphenyl (5CB) molecules has been studied. Precise circular dichroism (CD) spectra using thin sample cells indicate mainly two characteristics: (1) the origin of CD signals is due to chiral-segregated bent-core molecules in the B(4) phase, where 5CB is in the isotropic phase; (2) the enhanced CD signal is detected in the B(X) phase, where 5CB is in the nematic phase. These results suggest that 5CB molecules are embedded in the network of helical nanofilaments formed by P8-O-PIMB and form helical superstructure with the same handedness as the helical nanofilaments in the B(X) phase, resulting in the giant CD signals.