Insertion of the Liquid Crystal 5CB into Monovacancy Graphene.

Interfacial interactions between liquid crystal (LC) and two-dimensional (2D) materials provide a platform to facilitate novel optical and electronic material properties. These interactions are uniquely sensitive to the local energy landscape of the atomically thick 2D surface, which can be strongly influenced by defects that are introduced, either by design or as a byproduct of fabrication processes. Herein, we present density functional theory (DFT) calculations of the LC mesogen 4-cyan-4'-pentylbiphenyl (5CB) on graphene in the presence of a monovacancy (MV-G). We find that the monovacancy strengthens the binding of 5CB in the planar alignment and that the structure is lower in energy than the corresponding homeotropic structure. However, if the molecule is able to approach the monovacancy homeotropically, 5CB undergoes a chemical reaction, releasing 4.5 eV in the process. This reaction follows a step-by-step process gradually adding bonds, inserting the 5CB cyano group into MV-G. We conclude that this irreversible insertion reaction is likely spontaneous, potentially providing a new avenue for controlling both LC behavior and graphene properties.

Large, Tunable Liquid Crystal Pretilt Achieved by Enhanced Out-of-Plane Reorientation of Azodye Thin Films.

In-plane, or azimuthal, photo-reorientation of azodye films using polarized exposure makes them promising alignment layers for a host of liquid crystal (LC) applications beyond displays including beam steering, q-plates, liquid crystal elastomer origami, and control of active matter. Out-of-plane, or polar, reorientation of azodye films, which dictates the liquid crystal pretilt, has received far less attention. Spatial control over the full polar and azimuthal orientation enables the generation of complex patterns that have broad interests and applications. In this paper, we describe an enhanced out-of-plane reorientation in Brilliant Yellow films utilizing a two-step exposure and demonstrate a liquid crystal pretilt angle that is tunable over a range of 0-33° with the associated anchoring strength of the alignment layer being unaffected by the inclusion of a pretilt. We report an order of magnitude increase in both amplitude and tunability of the pretilt angle in terms of previous results for single photoalignment films. This is a significant result for liquid crystal applications because it offers a simple, scalable, single-component solution with the potential to provide three-dimensional (3-D) patternability of the LC director at the surface.

Thermophoresis of colloids in nematic liquid crystal.

Thermophoresis, or the directional motion of colloidal particles in liquids driven by a temperature gradient, is of both fundamental interest and practical use. In this work we explore the thermophoresis of colloids suspended in nematic liquid crystals (LCs). We observe that the motion of these colloids is fundamentally different from that in isotropic systems as a result of elastic distortions in the director fields caused by the colloidal inclusions. In the case of a sufficiently large local temperature and gradient, the elastic energy drives negative thermophoresis of immersed particles, which has a strongly nonlinear dependence on temperature. We develop a theory that incorporates elastic energy minimization into the traditional thermophoretic formulation and demonstrated a good agreement with experimental observations. We also examine the temperature dependence of the effective viscosity of the colloids and highlight the large magnitude of the Soret coefficient (|ST| > 5000), which results from the inherent enhancement in thermophoresis due to elastophoretic considerations and suppression of Brownian diffusion in LC media.

Enhancing Charge Transport Using Boron and Nitrogen Substitutions into Triphenylene-Based Discotic Liquid Crystals.

The substitution of p-block heteroatoms into polyaromatic hydrocarbons offers the potential for introducing enhanced molecular properties and advancing material development for electro-optical applications. Using density functional theory, we characterize the substitution of boron and nitrogen atoms into a 2,3,6,7,10,11-hexakis(hexathiol)triphenylene (TTP) core, a precursor for a material with a discotic liquid crystal phase, to determine the strength of exciton dissociation and the influence doping has on the formation of a heterojunction with graphene. The substitution of nitrogen and boron into the TTP motif enables tunability of both electron and hole coupling between hetero- and homodyads. The coupling is found to far exceed that of TTP and varied transport behavior with different combinations of doped cores of nitrogen-TTP and boron-TTP is reported. Heterodyads of nitrogen-TTP with boron-TTP appear to be ambipolar in electron/hole coupling, whereas heterodyads of boron- or nitrogen-TTP with TTP form strong electron coupling dyads and homodyads of nitrogen-TTP and boron-TTP form strong hole coupling. Finally, we describe the heterojunction of nitrogen- or boron-TTP with monolayer graphene and observe Ohmic contacts with large hole transport barriers. The presence of induced dipoles occurs at the interface in all heterojunctions, suggesting the possibility of tuning the junction with external potentials and improving exciton dissociation.

Simultaneous Large Optical and Piezoelectric Effects Induced by Domain Reconfiguration Related to Ferroelectric Phase Transitions.

Electrical switching of ferroelectric domains and subsequent domain wall motion promotes strong piezoelectric activity, however, light scatters at refractive index discontinuities such as those found at domain wall boundaries. Thus, simultaneously achieving large piezoelectric effect and high optical transmissivity is generally deemed infeasible. Here, it is demonstrated that the ferroelectric domains in perovskite Pb(In1/2 Nb1/2 )O3 -Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 domain-engineered crystals can be manipulated by electrical field and mechanical stress to reversibly and repeatably, with small hysteresis, transform the opaque polydomain structure into a highly transparent monodomain state. This control of optical properties can be achieved at very low electric fields (less than 1.5 kV cm-1 ) and is accompanied by a large (>10 000 pm V-1 ) piezoelectric coefficient that is superior to linear state-of-the-art materials by a factor of three or more. The coexistence of tunable optical transmissivity and high piezoelectricity paves the way for a new class of photonic devices.

Thermotropic liquid crystal (5CB) on two-dimensional materials.

We present ground-state electronic properties of the liquid crystal 4-cyano-4^{'}-pentylbiphenyl (5CB) on the two-dimensional materials monolayer graphene, hexagonal boron nitride, and phosphorene. Our density functional theory results show that the physisorption is robust on all surfaces with the strongest binding of 5CB on phosphorene. All surfaces exhibit flexural distortion, especially monolayer graphene and hexagonal boron nitride. While we find type-I alignment for all three substrates, meaning the Fermi level of the system is in the HOMO-LUMO gap of 5CB, the band structures are qualitatively different. Unlike for graphene and phosphorene, the HOMO-LUMO of 5CB appear as localized states within the band gap of boron nitride. In addition, we find that the valence band for boron nitride is sensitive to the orientation of 5CB relative to the surface. The qualitatively different band structures demonstrate the importance of substrate selection for tailoring the electronic and optoelectronic properties of nematic liquid crystals on two-dimensional materials.