Polyimide-Free Planar Alignment of Nematic Liquid Crystals: Sequential Interfacial Modifications through Dual-Wavelength in Situ Photoalignment.

High-quality alignment control of liquid crystals (LCs) for ultrahigh-definition large-sized display is a challenging task. A conventional rubbing method has obvious limitations for fabricating large-sized displays with a small pixel size and an uneven inner surface. To comply with the current trend, we propose a simple and reliable polyimide-less in situ photoalignment. It was achieved using a visible-light-sensitive azo-dye and a mesogenic acrylate, both doped to host LCs. Without using a pretreated alignment layer, mono- and multidomain uniaxial alignments of LC molecules were induced by linearly polarized visible light (LPVL) and subsequently stabilized by unpolarized UV-light irradiation. The stepwise process was monitored by adopting a fluorescent indicator. By loading the mixture into a confined cell, azo-dyes were spontaneously adsorbed at inner surfaces of the cell, whereas reactive mesogens (RMs) were homogeneously dissolved in an LC host. The molecular orientational anisotropy of dyes at the surface, induced by LPVL, aligned the LC director perpendicular to the polarization direction. Upon the second step, UV-irradiation, the RMs in an LC host were photopolymerized into thin interfacial layers, stabilizing the aligned LC director. The overlaid cross-linked RM layers secured a thermal and a radiative stability of LC alignment. The RM layers completely screened the effect of azo-dyes, which can be easily randomized by heat and irradiation. The interfacial RM layer functioned as a permanently stable alignment layer. It provided sufficient azimuthal anchoring strength together with heat and light stabilities, which are essential for practical applications. Such sequential interfacial modifications through dual-wavelength processes can completely avoid interference between forming alignment and stabilization layers, inevitable if the same wavelength light is used. The proposed method provides a simple fabrication process and reliable alignment characteristics by employing effective in situ photoalignment and without using a traditional alignment layer. Therefore, it meets a current trend in the display market toward ultrahigh-resolution and large-area displays.

Azobenzene Molecular Machine: Light-Induced Wringing Gel Fabricated from Asymmetric Macrogelator.

To develop light-triggered wringing gels, an asymmetric macrogelator (1AZ3BP) was newly synthesized by the chemically bridging a photoisomerizable azobenzene (1AZ) molecular machine and a biphenyl-based (3BP) dendron with a 1,4-phenylenediformamide connector. 1AZ3BP was self-assembled into a layered superstructure in the bulk state, but 1AZ3BP formed a three-dimensional (3D) network organogel in solution. Upon irradiating UV light onto the 3D network organogel, the solvent of the organogel was squeezed and the 3D network was converted to the layered morphology. It was realized that the metastable 3D network organogels were fabricated mainly due to the nanophase separation in solution. UV isomerization of 1AZ3BP provided sufficient molecular mobility to form strong hydrogen bonds for the construction of the stable layered superstructure. The light-triggered wringing gels can be smartly applied in remote-controlled generators, liquid storages, and sensors.

Silica-supported Au@hollow-SiO2 particles with outstanding catalytic activity prepared via block copolymer template approach.

Catalytically active Au@hollow-SiO2 particles embedded in porous silica support (Au@hollow-SiO2@PSS) were prepared by using spherical micelles from poly(styrene)-block-poly(4-vinyl pyridine) block copolymer as a sacrificial template. Drastic increase of the shell porosity was observed after pyrolytic removal of polymeric template because the stretched poly(4-vinyl pyridine) chains interpenetrating with silica shell acted as an effective porogen. The embedding of Au@hollow-SiO2 particles in porous silica support prevented their fusion during pyrolysis. The catalytic activity of Au@hollow-SiO2@PSS was investigated using a model reaction of catalytic reduction of 4-nitrophenol and reductive degradation of Congo red azo-dye. Significantly, to the best of our knowledge, Au@hollow-SiO2@PSS catalyst shows the highest activity among analogous systems reported till now in literature. Such high activity was attributed to the presence of multiple pores within silica shell of Au@hollow-SiO2 particles and easy accessibility of reagents to the catalytically active sites of the ligand-free gold surface through the porous silica support.

A photo-responsive metallomesogen for an optically and electrically tunable polarized light modulator.

A palladium(ii)-based metallomesogen with azobenzene was synthesized for the fabrication of an optically and electrically tunable polarized light modulator. Owing to the extended molecular geometry constructed by organometallic chemistry, the photo-responsive metallomesogen showed an excellent orientation in liquid crystal media.

Syntheses of D-A-A Type Small Molecular Donor Materials Having Various Electron Accepting Moiety for Organic Photovoltaic Application.

Small molecular donor, DTDCTB achieved a high power conversion efficiency (PCE) value of 6.6 ± 0.2% in vacuum-deposited planar mixed heterojunction (PMHJ) structure. However, the same material just recorded PCE of 0.34% in solution processed small molecule based bulk heterjunction (BHJ) organic photovoltaic cells. For the improvement of organic photovoltaic cells (OPVs), In this study, we designed and synthesized several D-A-A (donor-acceptor-acceptor) type molecular electron donating materials. Ditolylaminothienyl moiety as an electron donating group connected to 1,2,5-benzothiadiazole as a conjugated electron accepting unit, simultaneously with an electron accepting terminal group such as cyano alkyl acetate and N-alkyl rhodanine. The thermal, photophysical, and electrochemical properties of prepared small molecules were investigated by DSC, UV/Vis spectroscopy and Cyclic Voltametry, respectively. As a result, 0.89% of PCE can be obtained from OPV using a mixture of DTATBTER and PCBM as an active layer with a Voc of 0.87 V, a Jsc of 3.20 mA/cm2, and a fill factor of 31.9%.

Flexible and Patterned Thin Film Polarizer: Photopolymerization of Perylene-based Lyotropic Chromonic Reactive Mesogens.

A perylene-based reactive mesogen (DAPDI) forming a lyotropic chromonic liquid crystal (LCLC) phase was newly designed and synthesized for the fabrication of macroscopically oriented and patterned thin film polarizer (TFP) on the flexible polymer substrates. The anisotropic optical property and molecular self-assembly of DAPDI were investigated by the combination of microscopic, scattering and spectroscopic techniques. The main driving forces of molecular self-assembly were the face-to-face π-π intermolecular interaction among aromatic cores and the nanophase separation between hydrophilic ionic groups and hydrophobic aromatic cores. Degree of polarization for the macroscopically oriented and photopolymerized DAPDI TFP was estimated to be 99.81% at the λmax = 491 nm. After mechanically shearing the DAPDI LCLC aqueous solution on the flexible polymer substrates, we successfully fabricated the patterned DAPDI TFP by etching the unpolymerized regions selectively blocked by a photomask during the photopolymerization process. Chemical and mechanical stabilities were confirmed by the solvent and pencil hardness tests, and its surface morphology was further investigated by optical microscopy, atomic force microscopy, and three-dimensional surface nanoprofiler. The flexible and patterned DAPDI TFP with robust chemical and mechanical stabilities can be a stepping stone for the advanced flexible optoelectronic devices.

Oxygen adsorption-induced surface segregation of titanium oxide by activation in carbon nanofibers for maximizing photocatalytic performance.

This research demonstrates a simple method for synthesizing titanium dioxide nanoparticle-decorated carbon nanofibers. These nanofibers showed highly efficient degradation of methylene blue under UV light because of the synergistic effects of the large surface-active sites of titanium dioxide nanoparticles and the carbon nanofibers on the photocatalytic properties.

Film patterned retarder for stereoscopic three-dimensional display using ink-jet printing method.

We propose a film patterned retarder (FPR) for stereoscopic three-dimensional display with polarization glasses using ink-jet printing method. Conventional FPR process requires coating of photo-alignment and then UV exposure using wire-grid mask, which is very expensive and difficult. The proposed novel fabrication method utilizes a plastic substrate made of polyether sulfone and an alignment layer, poly (4, 4' - (9, 9 -fluorenyl) diphenylene cyclobutanyltetracarboximide) (9FDA/CBDA) in which the former and the latter aligns reactive mesogen along and perpendicular to the rubbing direction, respectively. The ink-jet printing of 9FDA/CBDA line by line allows fabricating the cost effective FPR which can be widely applied for 3D display applications.

Thermal- and photo-induced phase-transition behaviors of a tapered dendritic liquid crystal with photochromic azobenzene mesogens and a bicyclic chiral center.

A ribbon-shaped chiral liquid crystalline (LC) dendrimer with photochromic azobenzene mesogens and an isosorbide chiral center (abbreviated as AZ3 DLC) was successfully synthesized and its major phase transitions were studied by using differential scanning calorimetry (DSC) and linear polarized optical microscopy (POM). Its ordered structures at different temperatures were further identified through structure-sensitive diffraction techniques. Based on the experimental results, it was found that the AZ3 DLC molecule exhibited the low-ordered chiral smectic (Sm*) LC phase with 6.31 nm periodicity at a high-temperature phase region. AZ3 DLC showed the reversible photoisomerization in both organic solvents and nematic (N) LC media. As a chiral-inducing agent, it exhibited a good solubility, a high helical-twisting power, and a large change in the helical-twisting power due to its photochemical isomerization in the commercially available N LC hosts. Therefore, we were able to reversibly "remote-control" the colors in the whole visible region by finely tuning the helical pitch of the spontaneously formed helical superstructures.

Solvent-free directed patterning of a highly ordered liquid crystalline organic semiconductor via template-assisted self-assembly for organic transistors.

Highly ordered organic semiconductor micropatterns of the liquid-crystalline small molecule 2,7-didecylbenzothienobenzothiophene (C10 -BTBT) are fabricated using a simple method based on template-assisted self-assembly (TASA). The liquid crystallinity of C10 -BTBT allows solvent-free fabrication of high-performance printed organic field-effect transistors (OFETs).

In situ homeotropic alignment of nematic liquid crystals based on photoisomerization of azo-dye, physical adsorption of aggregates, and consequent topographical modification.

In situ homeotropic alignment is achieved by photochromic trans- to cis-isomerization of an azo-dye doped in a nematic host. The augmented dipole moment of the cis-isomer formed under UV-irradiation expedites molecular assembly into crystalline aggregates. Subsequent deposition of the aggregates creates a roughened surface and induces an anchoring transition from the initial planar to a homeotropic alignment of the LCs.

Phase behaviors and structures of a symmetrically tapered biphenylamide.

A symmetrically tapered N,N'-bis[tris[(2-dodecylaminocarbonyl)ethyl]methyl]]-4,4'-biphenylamide (d-C(n)PhA, where n is the number of carbon atoms in the alkyl chains, n = 12), was newly designed and synthesized in order to investigate the supramolecular ordered structures induced by phase separation, hydrogen (H)-bonding, and pi-pi stacking interaction. This symmetrically tapered d-C(12)PhA biphenylamide consists of three different parts: H-bondable hydrophilic amide moieties, a rigid hydrophobic biphenyl aromatic core, and three flexible hydrophobic alkyl chains at each end of the core. Major phase transitions and supramolecular structures in d-C(12)PhA biphenylamide were characterized by differential scanning calorimetry (DSC), one-dimensional (1D) wide-angle X-ray diffraction (WAXD), 1D and 2D Fourier-transform infrared spectroscopy (FT-IR), and solid-state (13)C nuclear magnetic resonance (NMR). The symmetrically tapered d-C(12)PhA biphenylamide formed a hexagonal columnar (Phi(H)) liquid crystalline (LC) mesophase at a cooling process and a highly ordered columnar (Phi(HK)) crystalline phase at a subsequent heating process. Selected area electron diffractions (SAED) from single crystals combined with the results of WAXD and POM suggest that discotic building blocks are constructed by three d-C(12)PhA biphenylamides rotating 60 degrees with respect to neighboring ones and the ABC stacked discotic building blocks further self-assemble into columns and then these columns are laterally close-packed to give nanorods. Furthermore, it was identified that the long axis of column is parallel to the long axis of rods.

Dielectrophoretic and electrophoretic force analysis of colloidal fullerenes in a nematic liquid-crystal medium.

This research focuses on the electrokinetic motion of fullerenes suspended in liquid crystal host medium, which are investigated in the homogeneously aligned nematic liquid crystal cells driven by in-plane field. We investigated the effect of electrophoretic and dielectrophoretic forces and related parameters of the colloidal fullerenes in liquid crystals. The electrophoretic mobility, zeta potential, and critical voltage have been evaluated. Fullerenes suspended in liquid crystal medium migrated toward the positive electrode, but were pulled back in the opposite direction when the polarity was reversed especially at low frequency range (<5 Hz) . At higher electric field and higher frequency ranges, the net displacement of fullerenes has been observed. We demonstrate that the dielectrophoretic force dominated the motion in the colloidal fullerenes by a proper analysis of different electrophoretic parameters. In addition, the electrodynamics of fullerenes was explained by applying the theory of the dielectrophoresis and Schwarz's formula. We propose a model to estimate the density of fullerenes suspended in liquid crystal medium.

Zero-birefringence photosensitive polyimides for optical waveguides.

Zero-birefringence (delta n < 1 x 10(-6)) photosensitive fluorinated polyimides are synthesized for use in polymer optical waveguides. To obtain zero birefringence, the UV exposure time and copolymer content of photosensitive polyimides are controlled. Zero birefringence combined with photoprocessing of the material has excellent potential for applications in high-performance wavelength division multiplexing components such as polarization-independent arrayed waveguide gratings and Bragg wavelength filters.