Rafael S. Zola

Light-Driven Reversible Handedness Inversion in Self-Organized Helical Superstructures

We report here a fast-photon-mode reversible handedness inversion of a self-organized helical superstructure (i.e., a cholesteric liquid crystal phase) using photoisomerizable chiral cyclic dopants. The two light-driven cyclic azobenzenophanes with axial chirality show photochemically reversible trans to cis isomerization in solution without undergoing thermal or photoinduced racemization. As chiral inducing agents, they exhibit good solubility, high helical twisting power, and a large change in helical twisting power due to photoisomerization in three commercially available, structurally different achiral liquid crystal hosts. Therefore, we were able to reversibly tune the reflection colors from blue to near-IR by light irradiation from the induced helical superstructure. More interestingly, the different switching states of the two chiral cyclic dopants were found to be able to induce a helical superstructure of opposite handedness. In order to unambiguously determine the helical switching, we employed a new method that allowed us to directly determine the handedness of the long-pitched self-organized cholesteric phase.

Light‐Directing Omnidirectional Circularly Polarized Reflection from Liquid‐Crystal Droplets

Constructing and tuning self-organized three-dimensional (3D) superstructures with tailored functionality is crucial in the nanofabrication of smart molecular devices. Herein we fabricate a self-organized, phototunable 3D photonic superstructure from monodisperse droplets of one-dimensional cholesteric liquid crystal (CLC) containing a photosensitive chiral molecular switch with high helical twisting power. The droplets are obtained by a glass capillary microfluidic technique by dispersing into PVA solution that facilitates planar anchoring of the liquid-crystal molecules at the droplet surface, as confirmed by the observation of normal incidence selective circular polarized reflection in all directions from the core of individual droplet. Photoirradiation of the droplets furnishes dynamic reflection colors without thermal relaxation, whose wavelength can be tuned reversibly by variation of the irradiation time. The results provided clear evidence on the phototunable reflection in all directions.

Thermally, photochemically and electrically switchable reflection colors from self-organized chiral bent-core liquid crystals

We report the synthesis and characterization of two new chiral 1,3-phenylene based five ring bent-core mesogens that combine the unique electro-optic characteristics of banana-shaped molecules with chiroptic properties. Azobenzene moiety incorporated as a linking unit in one of the rigid arms renders trans–cis isomerization property to the molecules while chirality is introduced by tethering chiral aliphatic terminal chains. Both compounds can self-organize into helical superstructure, i.e. cholesteric mesophase, which can selectively reflect light. The novelty of the helical self-organized superstructure reported here lies in its low molecular weight single component molecular system that is truly multifunctional so that the reflection band is tunable by three different external stimuli, i.e. temperature, light and electric field. A red shift in reflection colors is obtained by changing the temperature on cooling and by UV irradiation while a blue shift is seen by electrical field application. Due to the high applicability of azobenzene-doped liquid crystalline systems, we also evaluated the efficiency of these chiral bent-core molecules as chiral transfer agents and found that they behave similar to rod-shaped dopants whose chirality is a consequence of the presence of one chiral center.

Elastic continuum theory: Towards understanding of the twist-bend nematic phases

The twist-bend nematic phase, N_{TB}, may be viewed as a heliconical molecular arrangement in which the director n precesses uniformly about an extra director field, t. It corresponds to a nematic ground state exhibiting nanoscale periodic modulation. To demonstrate the stability of this phase from the elastic point of view, a natural extension of the Frank elastic energy density is proposed. The elastic energy density is built in terms of the elements of symmetry of the new phase in which intervene the components of these director fields together with the usual Cartesian tensors. It is shown that the ground state corresponds to a deformed state for which K_{22}>K_{33}. In the framework of the model, the phase transition between the usual and the twist-bend nematic phase is of second order with a finite wave vector. The model does not require a negative K_{33} in agreement with recent experimental data that yield K_{33}>0. A threshold is predicted for the molecular twist power below which no transition to a twist-bend nematic may occur.

Thermally reversible full color selective reflection in a self-organized helical superstructure enabled by a bent-core oligomesogen exhibiting a twist-bend nematic phase

A self-organized helical superstructure was found to exhibit thermally tunable, reversible selective reflection of light across the whole visible region upon doping with an achiral bent-core hybrid trimer having a twist-bend nematic phase.

Bandwidth broadening induced by ionic interactions in polymer stabilized cholesteric liquid crystals

Cholesteric liquid crystals (CLCs) are selectively reflective materials that can exhibit a number of dynamic optical responses. We recently reported on electrically-induced, seven-fold increase in bandwidth in polymer stabilized CLCs (PSCLCs) subjected to DC electric fields. Here, the underlying mechanism of the electrically-controllable bandwidth broadening in PSCLCs is isolated by employing a variety of electro-optic experiments. We conclude that the mechanism is ionic charge trapping by the polymer network which subjects the material system to pitch expansion near the positive electrode and pitch compression near the negative electrode resulting in approximately linear pitch variation throughout the cell thickness.

Controllable Dynamic Zigzag Pattern Formation in a Soft Helical Superstructure

Zigzag pattern formation is a common and important phenomenon in nature serving a multitude of purposes. For example, the zigzag-shaped edge of green leaves boosts the transportation and absorption of nutrients. However, the elucidation of this complicated shape formation is challenging in fluid mechanics and soft condensed matter systems. Herein, a dynamically reconfigurable zigzag pattern deformation of a soft helical superstructure is demonstrated in a photoresponsive self-organized cholesteric liquid crystal superstructure under the simultaneous influence of an applied electric field and light irradiation. The zigzag-shaped pattern can not only be generated and terminated repeatedly on demand, but can also be easily manipulated by alternating irradiation of ultraviolet and visible light while under the influence of a sustained electric field. This unique behavior results from a delicate balance among the variable experimental parameters. The evolution of the zigzag-shaped pattern is successfully modeled by numerical simulations and has been monitored through diffraction of a probe laser. Interestingly, this fascinating zigzag-shaped pattern yields crescent-shaped diffraction pattern. The reversibly controllable dynamic zigzag pattern could enable the fabrication of novel photonic devices and architectures, besides greatly advancing the fundamental understanding of temporal behavior of ordered soft materials under combined stimuli.

Alignment Layers with Variable Anchoring Strengths from Polyvinyl Alcohol

In the study of polyvinyl alcohol (PVA) alignment layers for liquid crystal devices, we found that the anchoring strength can be greatly varied by changing the alignment film thickness. Both the polar and azimuthal anchoring strengths increased with increasing film thickness; however, they had different film thickness dependences. It was also noticed that the quartic term in the expansion of the Rapini-Papoular anchoring energy was important for describing the polar anchoring. In the experiment, solid PVA was dissolved in a thinner and spin-coated on glass substrates to create alignment layers. The substrates were assembled to make electrically-controlled birefringence liquid crystal cells. The polar anchoring strength of the alignment layer was measured using the high field method and the azimuthal anchoring strength using the twist angle method.

Effect of surface alignment layer and polymer network on the Helfrich deformation in cholesteric liquid crystals

We show that the Helfrich deformation can be used for fast response time, low driving voltage reflective displays by using cholesteric liquid crystals under short voltage pulses (∼10 ms). Rather than turning planar domains into focal conic domains through a nucleation process, as used in bistable modes, the fast voltage pulse only deforms the cholesteric planar layers to form wrinkled layers. Since the deformed state is formed through a homogeneous process, quick response times and low operating voltage can be achieved. We studied the effects of alignment layer and dispersed polymer on the stability of the Helfrich deformed cholesteric layers, and found that homogeneous alignment layer and polymer network can inhibit the nucleation process responsible for breaking the layers.

Polymer Stabilized VA Mode Liquid Crystal Display

We used a polymer network to improve the response time of a vertical aligned (VA) mode liquid crystal display (LCD). The polymer network was anisotropic and was oriented in the same direction as the liquid crystal in the dark state. We studied the effect of pretilt angle and polymer concentration and measured the transmittance as well as scattering. With the polymer network, the turn-off time of VA-LCD significantly improved while the contrast ratio remained high.