Ji Hyun Park

Macroscopic Control of Helix Orientation in Films Dried from Cholesteric Liquid-Crystalline Cellulose Nanocrystal Suspensions

The intrinsic ability of cellulose nanocrystals (CNCs) to self-organize into films and bulk materials with helical order in a cholesteric liquid crystal is scientifically intriguing and potentially important for the production of renewable multifunctional materials with attractive optical properties. A major obstacle, however, has been the lack of control of helix direction, which results in a defect-rich, mosaic-like domain structure. Herein, a method for guiding the helix during film formation is introduced, which yields dramatically improved uniformity, as confirmed by using polarizing optical and scanning electron microscopy. By raising the CNC concentration in the initial suspension to the fully liquid crystalline range, a vertical helix orientation is promoted, as directed by the macroscopic phase boundaries. Further control of the helix orientation is achieved by subjecting the suspension to a circular shear flow during drying.

Ultralong Ordered Nanowires from the Concerted Self-Assembly of Discotic Liquid Crystal and Solvent Molecules.

The realization of long, aligned molecular wires is a great challenge, and a variety of approaches have been proposed. Interestingly, hexapentyloxytriphenylene (HAT5) discotic liquid crystal molecules, a model system of molecules with flat and aromatic cores, can spontaneously form well-aligned, micrometer long, yet only tens of nanometers thick, nanowires on solid surfaces. We have investigated the formation mechanism of these wires using different solvents with selected characteristics, including chemical structure, boiling point, vapor pressure, and surface tension. When casting from toluene and benzene solutions, atomic force microscopy reveals that the discotics spontaneously form very long and thin wires, self-aligning along a common orientation. If instead dodecane or heptane are used, different and in general thicker structures are obtained. The chemical structure of the solvent appears to have a key role, coupling to the liquid crystal self-assembly by allowing solvent molecules to enter the ordered structure if their design matches the core of HAT5 molecules, thereby guiding the assembly. However, other aspects are also relevant in the assembly, including the nature of the substrate and the rate of solvent evaporation, and these can favor or interfere with the self-assembly into long structures. The use of solvents with aromatic structure is advantageous not only because it affects the geometry of the assembly, promoting long wire formation, but it is also compatible with good quality of the intermolecular order, as suggested by a high anisotropy of the Raman spectra of the nanowires formed from these solvents. Finally, the electrical properties of ordered systems show a clearly higher electrical conductivity compared to the disorganized aggregates.

Molecular wires from discotic liquid crystals

Discotic liquid crystal (LC) can arrange in columnar structures along which electrical conduction occurs via π-π interaction between adjacent molecular cores. The efficiency of the conductivity is strongly dependent on the overlap of the orbitals of neighbor molecules and, in general, on the structural arrangements. The understanding of the factors that influence the organization is crucial for the optimization of the final conductive properties of the self-assembled columns. In this paper we present a study on the self-organization into molecular wires of a discotic LC using a solution based method. In particular, we focus on the effect of solvents used for preparing the LC solution. The resulting morphologies were investigated by atomic force microscopy (AFM) and optical microscopy, showing that diverse structures result from different solvents. With suitable conditions, we were able to induce very long fibers, with several tents of micrometer in length that, in turn, self-organize assuming a common orientation on a macroscopic scale.

Graphene: a new liquid crystal for high performance electro-optic applications

Graphene, a monoatomically thick film made by carbon atoms arranged in honeycomb lattice, for its exceptional electrical, thermal and mechanical properties is one of the most attractive materials to be incorporated in electronic devices and in composites. New interest has been recently arisen from water suspensions of flakes of graphene oxide (GO), obtained from chemical exfoliation of graphite, since they form liquid crystal (LC) phases, for the easiness of handling graphene, otherwise forming aggregates, and their high yield. Interestingly, GO LC suspensions are responsive to electric fields with an extremely high Kerr coefficient resulting in an induced birefringence at macroscopic scale, achieved with very low electric fields. The LC phase formation and its responsiveness to electric fields are dependent on suspension characteristics such as flake average dimension, aqueous matrix and flake properties. In particular, bare graphene flakes have larger response to electric fields, due to their higher polarizability, than GO flakes. As it will be described, this results in improved electro-optic performance of reduced-graphene compared to GO LC with remarkably higher optical transmission for the same field strength thanks to a more efficient flake reorientation enabling a larger optical modulation.

Solvent effect on columnar formation in solar-cell geometry

The efficiency of the conduction of photocurrent in discotic liquid crystals is known to depend on the quality of the columnar organization. Solvents have shown to be able to influence the formation of wire structures on substrates promoting very long and ordered wired formations or bulkier structures depending on the affinity of the solvent with parts of the molecular structure of discotics. Here we present a study on the effect of solvents when the liquid crystal is confined between two substrates with the columns running perpendicular to them, geometry used in solar cells. We focused on toluene and dodecane, solvents that have shown to promote on substrates the formation of aligned and long nanowires and bulk large and isolated fibers, respectively. The phase transition behavior indicates that toluene does not interfere with the columnar formation while dodecane strongly influence increasing the disorder in the structure.

Study of liquid crystal formation of graphene oxide flakes (Withdrawal Notice)

Graphene can be produced with chemical method and this process goes through the formation of an oxidative form of graphene, called graphene oxide (GO), useful for mass production of graphene, obtained by reduction. Interestingly, graphene oxide is dispersible in water due to its hydrophilic functional groups and this allows the formation of liquid crystal phases above certain threshold concentration. GO shows a discotic nematic phase above a certain concentration threshold. Due to the diversity of GO flake average size, as a result of variations in production methods, the value of the threshold and the width of the region of coexistence of the isotropic and liquid crystal phase can strongly vary from samples to samples. We have observed the appearance of a nematic liquid crystal phase at very low concentration and a co-existence region form 0.1mg/ml to 1.0mg/ml by final GO obtained from synthesis. We have controlled the size of the flakes by ultra-sonication. With smaller flakes the transition concentration shifted towards much higher concentrations since the aspect ratio of the flakes has decreased. We report a detailed study of the size distribution of the GO flakes, together with UV-VIS spectroscopic and polarized dynamic light scattering, for understanding the liquid crystal phase formation.

Self-assembling of molecular nanowires for enhancing the conducting properties of discotic liquid crystals

The self-organization of discotic liquid crystal molecules in columns has enormous interest for soft nanoelectronic applications. A great advantage of discotic liquid crystal is that defects can be self-annealed in contrast to typical organic materials. Through the overlap of molecular orbitals, the aromatic cores assemble into long range ordered one-dimensional structures. Very thin structured films can be obtained by spin-coating from solution and the resulting morphologies are strongly dependent on the interaction between discotics and solvent molecules. Toluene produces films formed by very long nanowires, spontaneously aligned along a common direction and over fairly large areas. These nanostructured films are a result of the interplay between liquid crystal self-organization and solvent driven assembly. The ordered nanowire structures exhibit improvement in the electrical properties compared to misaligned structures and even to pristine HAT5, deposited without the aid of solvent. In this study we show that the toluene-based deposition of discotic liquid crystals is advantageous because it allows a uniform coverage of the substrate, unlike pristine HAT5 but also thanks to the type of induced structures exhibiting one order of magnitude higher conductivity, in the aligned nanowire films, compared to bare HAT5 ones.