Liquid‐Crystal Composites Composed of Photopolymerized Self‐Assembled Fibers and Aligned Smectic Molecules

A new liquid‐crystal composite, composed of photopolymerizable self‐assembled fibers and a smectic liquid crystal, and its photopolymerized composite have been prepared. The fibers oriented along the smectic layers are obtained by self‐assembly of an amino acid derivative with terminal methacryloyl groups in the smectic liquid crystal. The oriented fibrous structures are fixed by photopolymerization, resulting in the formation of microgrooves on the substrate surfaces. The aligned direction of the liquid‐crystalline molecules is changed to the direction along the fibers after thermal annealing. The patterning of liquid‐crystal alignment is achieved for these liquid‐crystal composites by patterned photopolymerization.     

Electrochromic Polymer‐Dispersed Liquid‐Crystal Film: A New Bifunctional Device

Polymer‐dispersed liquid crystals (PDLCs) are liquid‐crystal dispersions within a polymer matrix. These films can be changed from an opaque to a transparent state by applying a suitable alternating‐current electric field. PDLCs have attracted the interest of researchers for their applications as light shutters, smart windows, and active displays. For such applications, electrochromic devices, which change color as a result of electrochemical reactions, have also become a recent focus of research. Herein, we report our preliminary results on bifunctional devices based on PDLCs that host electrochromic guest molecules. Such devices allow both an independent and fast switching from a scattering opaque state to a transmissive transparent state owing to liquid‐crystal reorientation and a color change from white (pale yellow) to dark blue, due to either oxidation or reduction of the electrochromic molecules.     

Liquid‐Crystalline Polymer with a Block Mesogenic Side Group: Photoinduced Manipulation of Nanophase‐Separated Structures

In this report, a novel type of photoresponsive liquid crystalline polymer with a block mesogenic side‐group is demonstrated. The block mesogene is an amphipathic molecule containing a hydrophobic mesogene (azotolane moiety) and hydrophilic oligooxyethylene moieties in the same unit. The block mesogene in the polymer plays a role in liquid crystalline, amphiphilic and photoresponsive properties. As expected, a film prepared from the polymer exhibits phase separation of a lamellar structure due to cooperative motion between liquid crystal assembly and nanophase separation. The morphology of the lamellae can be aligned upon irradiation of linearly polarized light. Moreover, a photochemical phase transition induced by unpolarized UV irradiation erases the surface morphology. The erased nanostructure can be recovered by annealing or irradiation of linearly polarized light, meaning that the surface morphology is rewritable via a photochemical process.     

Enhanced Hole‐Transporting Behavior of Discotic Liquid‐Crystalline Physical Gels

Discotic liquid‐crystalline (LC) physical gels have been prepared by combining the self‐assembled fibers of a low‐molecular‐weight gelator and semiconducting LC triphenylene derivatives. The hole mobilities of the discotic LC physical gels measured by a time‐of‐flight method become higher than those of LC triphenylenes alone. The introduction of the finely dispersed networks of the gelator in the hexagonal columnar phases may affect the molecular dynamics of the liquid crystals, resulting in the enhancement of hole transporting behavior in the LC gel state.     

Enhanced Electro‐Optic Behavior for Shaped Polymer Cholesteric Liquid‐Crystal Flakes Made Using Soft Lithography

Polymer cholesteric liquid‐crystal (PCLC) flakes were investigated for their electro‐optical behavior under an applied alternating‐current field. Shaped flakes, fabricated using soft lithography and suspended in dielectric‐fluid‐filled cells, reoriented more uniformly than randomly shaped flakes made by fracturing of PCLC films. Extensive characterization found shaped flakes to be smooth and uniform in size, shape, and thickness. Reorientation in applied fields as low as tens of mV_rms μm^–1 was fastest for flakes with lateral aspect ratios greater than 1:1, confirming theoretical predictions based on Maxwell–Wagner polarization. Brilliant reflective colors and inherent polarization make shaped PCLC flakes of interest for particle displays.     

Electrotunable Non‐reciprocal Laser Emission from a Liquid‐Crystal Photonic Device

A liquid crystal (LC) photonic device with an anisotropic optical heterojunction structure has been fabricated. The device has a phase‐retarding nematic LC (NLC) layer sandwiched between two polymer cholesteric LC films with right‐handed helices of different pitches. Electrotunable non‐reciprocal light transmittance and unidirectional circularly polarized (CP) lasing emission have been successfully demonstrated for this device structure. Two left CP (LCP) lasing emission peaks are observed at the edges of the overlapping region between the two photonic bands in the structure and are shifted upon the application of a voltage. In contrast, a non‐reciprocal right CP (RCP) lasing emission peak emerges at one of the band edges and diminishes upon the application of a voltage. These phenomena are interpreted based on the selective reflection of RCP light and the reorientation of the NLC molecules by the application of a voltage.     

Synthesis,Properties, and Photopolymerization of Liquid‐Crystalline Oxetanes: Application in Transflective Liquid‐Crystal Displays

Mixtures of liquid‐crystalline di‐oxetanes and mono‐oxetanes are made for the purpose of making birefringent films by photopolymerization. The composition of a di‐oxetane mixture that forms spin‐coated films of planarly aligned nematic monomers is reported. These films are photopolymerized in air. The molecular order of the monomers can be changed on the microscale to form thin films with alternating birefringent and isotropic parts by using a combination of photopolymerization and heating. The interface observed between the birefringent and isotropic 10 μm × 10 μm domains is very sharp and the films show hardly any surface corrugation. In addition, the polymerized films are thermally stable, making them very suitable for use as patterned thin‐film retarders in high‐performance transflective liquid‐crystal displays (LCDs) which satisfy customer demand for displays that are brighter and thinner and that deliver better optical performance than conventional LCDs with an external non‐patterned retarder.     

Alignment of a Perylene‐Based Ionic Self‐Assembly Complex in Thermotropic and Lyotropic Liquid‐Crystalline Phases

The thermotropic and lyotropic liquid‐crystalline (LC) phases of the ionic self‐assembled complex N,N′,‐bis(2‐(trimethylammonium)ethylene)‐perylene‐3,4,9,10‐tetracarboxyldiimide‐bis(2‐ethylhexyl)sulfosuccinate have been studied using polarizing microscopy, differential scanning calorimetry (DSC), and X‐ray scattering techniques. A two‐dimensional (2D) columnar thermotropic LC phase with π–π stacking of the perylene tectonic units and a lyotropic LC phase in dimethyl sulfoxide (DMSO) have been found. Different techniques have been applied to align both systems and included: surface interactions, electric and magnetic fields, shear force, and controlled domain formation at the LC–isotropic phase‐transition front (PTF). Characterization of the alignment in films has been performed using polarized UV‐vis spectroscopy and transmission null‐ellipsometry. The best results have been obtained for alignment of the material in a lyotropic phase by controlled domain formation at the PTF of the LC–isotropic phase transition. In this case, a dichroic ratio of 18 is achieved with packing of columns of perylenediimide tectons perpendicular to the PTF.     

1,3,6,8‐Tetraphenylpyrene Derivatives: Towards Fluorescent Liquid‐Crystalline Columns?

Tetraphenylpyrene has been selected as a discotic core to promote liquid‐crystalline fluorescent columns in view of its high fluorescence quantum yield in solution and ease of substitution by flexible lateral side chains. The synthesis and characterization of ten new derivatives of pyrene have been carried out; the pyrene core has been substituted at the 1,3,6,8‐positions by phenylene rings bearing alkoxy, ester, thioether, or tris(alkoxy)benzoate groups on the para position; the compounds have been characterized by mass spectrometry and ¹H NMR and UV‐vis spectroscopies. In order to generate liquid‐crystalline phases, the nature, number, and size of the side chains as well as the degree of polarity around the tetraphenylpyrene core have been varied. However, the desired liquid‐crystalline behavior has not been observed. The supramolecular order together with the absorption and emission properties in solution and the solid state are discussed and compared to theoretical predictions. Quantum‐chemical calculations rationalize the high solid‐state fluorescence of a tetraphenylpyrene derivative for which the crystal structure has been determined.     

Cover Picture: Enhanced Electro‐Optic Behavior for Shaped Polymer Cholesteric Liquid‐Crystal Flakes Made Using Soft Lithography (Adv. Funct. Mater. 2/2005)

The cover shows a variety of shaped flakes fabricated from polymer cholesteric liquid‐crystal material using soft lithography. In work reported by Jacobs and co‐workers on p. 217, the micrometer‐sized flakes exhibit brilliant circularly polarized selective reflection colors without polarizers or color filters when placed in a fluid‐filled electro‐optic cell. With the application of a low‐magnitude alternating current field, the flakes reorient in hundreds of milliseconds and the colors disappear. Polymer cholesteric liquid‐crystal (PCLC) flakes were investigated for their electro‐optical behavior under an applied alternating‐current field. Shaped flakes, fabricated using soft lithography and suspended in dielectric‐fluid‐filled cells, reoriented more uniformly than randomly shaped flakes made by fracturing of PCLC films. Extensive characterization found shaped flakes to be smooth and uniform in size, shape, and thickness. Reorientation in applied fields as low as tens of mV_rms μm^–1 was fastest for flakes with lateral aspect ratios greater than 1:1, confirming theoretical predictions based on Maxwell–Wagner polarization. Brilliant reflective colors and inherent polarization make shaped PCLC flakes of interest for particle displays.     

Exploiting Microphase‐Separated Morphologies of Side‐Chain Liquid Crystalline Polymer Networks for Triple Shape Memory Properties

We report a new strategy to achieve triple shape memory properties by using side‐chain liquid crystalline (SCLC) type random terpolymer networks (XL‐ TP‐n), where n is the length of flexible methylene spacer (n = 5, 10, and 15) to link backbone and mesogen. A lower glass transition temperature (T_g = T_low) and a higher liquid crystalline clearing temperature (T_cl = T_high) of XL‐TP‐n serve as molecular switches to trigger a shape memory effect (SME). Two different triple shape creation procedures (TSCPs), thermomechanical treatments to obtain temporary shapes prior to the proceeding recovery step, are used to investigate the triple shape memory behavior of XL‐TP‐n. The discrete T_g and T_cl as well as unique microphase‐separated morphologies (backbone‐rich and mesogen‐rich domains) within smectic layers of XL‐TP‐n enables triple shape memory properties. Motional decoupling between backbone‐rich and mesogen‐rich domains is also critical to determine the resulting macroscopic shape memory properties. Our strategy for obtaining triple shape memory properties will pave the way for exploiting a broad range of SCLC polymers to develop a new class of actively moving polymers.     

Orientational Switching of Mesogens and Microdomains in Hydrogen‐Bonded Side‐Chain Liquid‐Crystalline Block Copolymers Using AC Electric Fields

In this report, we show that the microstructures of hydrogen‐bonded side‐chain liquid‐crystalline block copolymers can be rapidly aligned in an alternating current (AC) electric field at temperatures below the order–disorder transition but above the glass transition. The structures and their orientation were measured in real time with synchrotron X‐ray scattering. Incorporation of mesogenic groups with marked dipolar properties is a key element in this process. A mechanism related to the dissociation of hydrogen bonds is proposed to account for the fast orientation switching of the hydrogen‐bonded blends.     

Synthesis,Liquid‐Crystalline Properties,and Photo‐optical Studies of Photoresponsive Oligomeric Mesogens as Dopants in a Chiral Glassy Liquid Crystal

We have prepared photoresponsive oligomers that have molecular weights of ca. 4500, 8000, and 16 000 g mol^–1 via the free‐radical polymerization of 4‐[4‐alkylphenylazo]phenoxyalkyl acrylates. All of the oligomers possess bilayer smectic A (SmA) and smectic B (SmB) phases. Increasing the concentration of these oligomeric dopants in a glass‐forming cholesteric liquid crystal causes a dramatic red‐shift in the reflection wavelength. The pitch shifts are very dependent on the alkyl chain lengths and molecular weights of the dopants. The oligomer that contains octyl chains and an octyl spacer, and that has a molecular weight of 4500 g mol^–1 exhibits the largest shift in the reflection wavelength. UV exposure has been used to control the cholesteric reflection pitch of the oligomer‐cholesteric glassy liquid‐crystal mixture over the entire visible region of the electromagnetic spectrum and vitrifies the samples by rapid cooling from their cholesteric temperatures to 0 °C. Extremely stable, even at 70 °C, erasable, full‐color images have been created using this host–guest mixture.     

One‐ and Two‐Dimensionally Structured Polymer Networks in Liquid Crystals for Switchable Diffractive Optical Applications

We have created one‐ and two‐dimensionally structured polymer networks dispersed in a liquid‐crystal solvent using a holographic exposure technique. These structures have potential for electrically switchable, reverse‐mode, polarization selective and non‐selective diffractive optical elements. Using a simple phenomenological model to describe our diffraction measurements in conjunction with microscopic studies, we are able to estimate the structured polymer wall thickness as a function of monomer concentration.     

LaPO4 Mineral Liquid Crystalline Suspensions with Outstanding Colloidal Stability for Electro‐Optical Applications

Mineral liquid crystals are materials in which mineral's intrinsic properties are combined with the self‐organization behavior of colloids. However, the use of such a system for practical application, such as optical switching, has rarely been demonstrated due to the fundamental drawbacks of colloidal systems such as limited dispersion stability. Studying colloidal suspensions of LaPO₄ nanorods, it is found that drastic improvement of colloidal stability can be obtained through a transfer of particles from water towards ethylene glycol, thus enabling the investigation of liquid crystalline properties of these concentrated suspensions. Using polarization microscopy and small‐angle x‐ray scattering (SAXS), self‐organization into nematic and columnar mesophases is observed enabling the determination of the whole phase diagram as a function of ionic strength and rod volume fraction. When an external alternative electric field is applied, a very efficient orientation of the nanorods in the liquid‐crystalline suspension is obtained, which is associated with a significant optical birefringence. These properties, combined with the high colloidal stability, are promising for the use of such high transparent and athermal material in electro‐optical devices.     

Electro‐optical Materials: Switching of Electrically Responsive,Light‐Sensitive Colloidal Suspensions of Anisotropic Pigment Particles (Adv. Funct. Mater. 3/2011)

An unusual electro‐optical behavior of colloidal suspensions of dichroic, elongated (rod‐shaped) pigment particles is reported. These suspensions exhibit nematic liquid crystal order at low volume fraction of the suspended particles (<15 wt%) and show a strong electric and optical response to an external electric field. Additionally, the characteristics of the optical response can be reversibly manipulated by illuminating the sample with light in its absorption band. The suspensions show a number of interesting phenomena like homeotropic‐planar orientational transitions and light‐induced pattern formation.     

Electro‐Optical Study of Subphthalocyanine in a Bilayer Organic Solar Cell

Ultra‐thin films of subphthalocyanine (SubPc) were grown onto Si/SiO₂ substrates by organic molecular beam deposition and the complex refractive index has been characterized by spectroscopic ellipsometry. The peak maximum in the extinction coefficient is determined to be 1.6 at 590 nm and the dielectric constant equals 3.9 in the limit of long wavelength. These values are extraordinary high when compared to the well‐known metal‐phthalocyanines and will be beneficial for the performance in a photovoltaic cell. The amorphous SubPc structure on top of indium‐tin‐oxide (ITO) as well as quartz glass is imaged by atomic force microscopy and scanning electron microscopy and we have characterized the nearly flat surface topology. Next, subphthalocyanine films in combination with buckminsterfullerene (C₆₀) have been studied in a planar bilayer donor/acceptor heterojunction by current density‐voltage characterization under AM 1.5 simulated illumination at various light intensities. A power conversion efficiency of 3.0 % under 1 sun was measured. Finally, the external and internal quantum efficiencies demonstrated peak maxima at 590 nm of 46 % and 55 %, respectively. Considering the abrupt junction at the donor/acceptor interface, the electron transfer from SubPc to the acceptor material is thus determined to be highly efficient.     

Electropolymerization of a Bifunctional Ionic Liquid Monomer Yields an Electroactive Liquid‐Crystalline Polymer

The preparation and polymerization of a bifunctional imidazolium‐based ionic liquid (IL) monomer that incorporates both a vinyl group and a thiophene moiety is reported. Potentiodynamic electropolymerization of the monomer produces an optically birefringent polymer film that strongly adheres to the electrode surface. Fourier transform IR spectroscopy shows that polymerization occurs through both the vinyl and thienyl groups. Cylic voltammetry (CV) is used to determine the polymer oxidation potential (1.66 V) and electrochemical bandgap, E_g, of 2.45 eV. The polymer exhibits electrochromism, converting from yellow in the neutral form (λ_max = 380 nm) to blue in the polaronic state at 0.6 V (λ_max = 672 nm) and to blue‐grey in the bipolaronic state at 1.2 V (λ_max > 800 nm). Topographic atomic force microscopy (AFM) images reveal isolated (separated) fibrils. Grazing‐incidence small‐angle X‐ray scattering (GISAXS) studies indicate a lamellar structure with a lattice spacing of 3.2 nm. Wide‐angle X‐ray diffraction (WAXD) studies further suggest that the polymerized thiophene sheets are oriented perpendicular to the polymerized vinylimidazolium. The electrical conductivity, as determined by four‐probe dc conductivity measurements was found to be 0.53 S cm^?1 in the neutral form and 2.36 S cm^?1 in the iodine‐doped state, values higher than typically observed for polyalkylthiophenes. The structural ordering is believed to contribute to the observed enhancement of the electrical conductivity.     

Low‐Power and High‐Contrast Nanoscale All‐Optical Diodes Via Nanocomposite Photonic Crystal Microcavities

A novel nanoscale integrated all‐optical diode is reported, realized by combining the strong plasmonic responses of gold nanoparticles with the all‐optical tunable properties of polymeric photonic crystal microcavities. Non‐reciprocal transmission properties are achieved based on the effect of surface‐plasmon resonance enhancing the optical non‐linearity and dynamic coupling of asymmetrical microcavity modes. An ultralow‐threshold photon intensity of 2.1 MW cm^?2 and an ultrahigh transmission contrast over 10⁴ are realized simultaneously. Compared with previously reported all‐optical diodes, the operating power is reduced by five orders of magnitude, while the transmission contrast is enlarged by three orders of magnitude.