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.     

Silica‐Based,Organically Modified Host Material for Waveguide Structuring by Two‐Photon‐Induced Photopolymerization

The three‐dimensional fabrication of optical waveguides has gained increasing interest in recent years to establish interconnections between electrical components on a very small scale where copper circuits encounter severe limitations. In this work the application of optically clear, organically modified porous silica monoliths and thin films as a host material for polymeric waveguides to be inscribed into the solid host structure by two‐photon‐induced photopolymerization is investigated. Porosity is generated using a lyotropic liquid crystalline surfactant/solvent system as a template for the solid silica material obtained by a sol–gel transition of a liquid precursor. In order to reduce the brittleness of the purely inorganic material, organic–inorganic co‐precursor molecules that contain poly(ethylene glycol) chains are synthesized and added to the mixture, which successfully suppresses macroscopic cracking and leads to flexible thin films. The structure of the thus‐obtained porous organic–inorganic hybrid material is investigated by atomic force microscopy. It is shown that the modified material is suitable for infiltration with photocurable monomers and functional polymeric waveguides can be inscribed by selective two‐photon‐induced photopolymerization.     

Grayscale Photopatterning of an Amorphous Polymer Thin Film Prepared by Photopolymerization of a Bisanthracene‐Functionalized Liquid‐Crystalline Monomer

A method for grayscale photopatterning of an amorphous polymer film derived from a bisanthracene‐functionalized liquid‐crystalline monomer is developed. Solution photopolymerization of a monomer with two anthracene moieties, one at each end, affords an amorphous polymer. A combination of irradiation with patterned UV light and heating results in photopatterning on thin films prepared from the polymer. On non‐irradiated areas of the film, the polymer reverts to the monomer owing to the thermal back‐reaction of the anthracene photodimer, forming an ordered phase. On irradiated areas remaining in the amorphous phase, the thermal back‐reaction is suppressed. This phenomenon results in a clear contrast and visual images on the film under polarized light. Grayscale photopatterning is also made possible for the solution‐polymerized polymer by controlling the intensity of exposure. In addition, rewritable photopatterning can be achieved by melt photopolymerization of the monomer. The new photopatterning is essentially nondestructive because it needs neither image development nor anthracene‐excitation light for reading.     

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.     

Rapid Prototyping for Soft‐Matter Electronics

A series of rapid and inexpensive methods to produce elastically soft sensors and circuits in minutes using a CO₂ laser (10.6 μm wavelength) are introduced. These soft‐matter electronics are composed of laser‐patterned films of conductive poly(dimethylsiloxane) (cPDMS) and liquid‐phase gallium–indium (GaIn) alloy embedded in a thin sheet of soft silicone elastomer. Direct laser patterning eliminates the need for photolithography, replica molding, and customized inkjet or microcontact (μCP) printing, and allows conductive traces of cPDMS and liquid GaIn to be rapidly integrated into a single soft‐matter circuit. The versatility of this fabrication method is demonstrated by the production of a variety of electrically functional soft‐matter sensors and circuit elements that contain features with >150 μm planar dimensions. It is postulate that in the case of GaIn alloy patterning occurs when the recoil force of the escaping vapor exceeds the liquid's surface tension. This mechanism exploits the unique “moldability” of liquid GaIn alloy, which forms a surface oxide of Ga₂O₃ that allows the patterned film to maintain its shape.     

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.     

Photo‐ and Rubbing‐Alignable Brush Polyimides Bearing Three Different Chromophores

Three new photoreactive brush polyimides (PSPIs), each bearing a different type of chromophore (cinnamoyl (CA), 3‐(2‐furyl)acryloyl (FA), and methacryloyl (MA)) in their bristles (i.e., side groups), are successfully synthesized, and are found to produce good‐quality films with smooth surfaces through conventional spin‐casting and drying processes. These PSPI polymers are thermally stable up to 320 °C. This is the first quantitative investigation of the photoaligning and rubbing‐aligning processabilities of PSPI polymer films, and of the abilities of the resultant films to control the orientation and anchoring of liquid‐crystal (LC) molecules. The chromophores of both poly(1‐cinnamoyloxy‐2,4‐phenylene hexafluoroisopropylidenediphthalimide) (6F‐DAP‐CA) and poly(1‐3‐(2‐furyl)acryloyloxy‐2,4‐phenylene hexafluoroisopropylidenediphthalimide) (6F‐DAP‐FA) PSPIs are found to undergo photodimerization in thin films and, to a lesser extent, photoisomerization, resulting in insoluble, crosslinked films. The MA chromophores of 6F‐DAP‐MA PSPI are found to undergo photopolymerization in thin films, which might include photodimerization to a lesser extent, resulting in insoluble, crosslinked films. Thin films of the PSPI polymer chains are found to have excellent unidirectional orientation ability as a result of either photoexposure with linearly polarized UV light (LPUVL) or rubbing. Both the photoaligned and the rubbing‐aligned polymer chains in the PSPI films are demonstrated to effectively induce the alignment of nematic LCs along their orientation directors by anisotropic interactions between the preferentially oriented polymer chain segments and the LCs. The contribution to LC alignment of the microgrooves developed in the rubbed films is found to be very low. The anchoring energies of the LCs on the photoaligned film surfaces are comparable to those on the rubbing‐aligned film surfaces; the anchoring energies are found to be in the range 0.45–2.25 × 10^–5 J m^–2, and to depend on which film treatment process is used and which chromophore bristle is present. In summary, the new PSPIs reported in this paper are promising LC alignment‐layer candidates with rubbing‐free processing for the production of advanced LC‐display (LCD) devices, including LCD televisions with large display areas.     

Masked Deposition of Gallium‐Indium Alloys for Liquid‐Embedded Elastomer Conductors

A fabrication method is introduced that utilizes masked deposition and selective wetting to produce hyperelastic electronic circuits that are composed of a thin elastomer film embedded with microchannels of liquid‐phase gallium‐indium (Ga‐In) alloy. This method exploits the low melting‐point and controllable wetting dynamics of Ga‐In alloys, as well as the ability for Ga‐In alloys to form irregularly‐shaped, free‐standing, micrometer‐scale structures via gallium surface oxidation. Masked deposition eliminates the need for manual injection filling, which enables certain geometries that cannot be produced by injection and allows for the automated, high‐volume production of Ga‐In based “liquid‐embedded elastomer electronics” (LE3). With this approach, LE3 circuits can be produced with isolated features that have planar dimensions of less than 200 μm and edge‐to‐edge feature separations as small as 25 μm.     

Nematic Anisotropic Liquid‐Crystal Gels—Self‐Assembled Nanocomposites with High Electromechanical Response

The uniqueness of liquid crystals (LCs) lies in the large anisotropies of their properties, which can be utilized to generate high electromechanical responses. In a properly oriented LC polymer system, an external electric field can induce reorientation of the mesogenic units possessing a dielectric anisotropy, which, when coupled with the shape anisotropy of the mesogenic units, can in turn produce large mechanical strain. Anisotropic LC gels, which can be obtained by in‐situ photopolymerization of the reactive LC molecules in the presence of non‐reactive LC molecules in an oriented state, are an example of such liquid‐crystal polymer systems. It is shown here that a homeotropically aligned LC gel in its nematic phase exhibits high electrically induced strain (> 2 %) with an elastic modulus of 100 MPa and a high electromechanical conversion efficiency (75 %) under an electric field of 25 MV/m. These anisotropic LC polymeric materials could provide a technologically compatible system for such applications as artificial muscles and as microelectromechanical devices.     

Ultrawide-view liquid crystal displays

The wide viewing angle technologies for liquid crystal displays (LCDs) are reviewed. The most promising liquid crystal modes for wide view technologies, such as in-plane switching, multidomain vertical alignment, patterned vertical alignment, and advanced-super-view are compared. By optimizing the phase-compensation films and their device configurations, the ultrawide-view LCDs with a contrast ratio higher than 100:1 at /spl plusmn/85/spl deg/ viewing cone are demonstrated.     

Self‐Assembled Shape‐Memory Fibers of Triblock Liquid‐Crystal Polymers

New thermoplastic liquid‐crystalline elastomers have been synthesized using the telechelic principle of microphase separation in triblock copolymers. The large central block is made of a main‐chain nematic polymer renowned for its large spontaneous elongation along the nematic director. The effective crosslinking is established by small terminal blocks formed of terphenyl moieties, which phase separate into semicrystalline micelles acting as multifunctional junction points of the network. The resulting transient network retains the director alignment and shows a significant shape‐memory effect, characteristic and exceeding that of covalently bonded nematic elastomers. Its plasticity at temperatures above the nematic–isotropic transition allows drawing thin well‐aligned fibers from the melt. The fibers have been characterized and their thermal actuator behavior—reversible contraction of heating and elongation on cooling—has been investigated.     

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.     

Sub‐3 V ZnO Electrolyte‐Gated Transistors and Circuits with Screen‐Printed and Photo‐Crosslinked Ion Gel Gate Dielectrics: New Routes to Improved Performance

A facile, high‐resolution patterning process is introduced for fabrication of electrolyte‐gated transistors (EGTs) and circuits using a photo‐crosslinkable ion gel and stencil‐based screen printing. The photo‐crosslinkable gel is based on a triblock copolymer incorporating UV‐sensitive terminal azide functionality and a common ionic liquid. Using this material in conjunction with conventional photolithography and stenciling techniques, well‐defined 0.5–1 μm thick ion gel films are patterned on semiconductor channels as narrow as 10 μm. The resulting n‐type ZnO EGTs display high electron mobility (>2 cm² Vs^?1) and on/off current ratios (>10⁵). Further, EGT‐based inverters exhibit static gains >23 at supply voltages below 3 V, and five‐stage EGT ring oscillator circuits display dynamic propagation delays of 50 μs per stage. In general, the screen printing and photo‐crosslinking strategy provides a clean room‐compatible method to fabricate EGT circuits with improved sensitivity (gain) and computational power (gain × oscillating frequency). Detailed device analysis indicates that significantly shorter delay times, of order 1 μs, can be obtained by improving the ion gel conductance.     

Liquid‐Crystalline Phase Behavior in a Zwitterionic Tetraazapentacene

A 5,7‐dioctadecylquinoxalinophenazine zwitterion 1 has been investigated to determine its thermal phase behavior. A combination of differential scanning calorimetry (DSC), variable temperature low‐ and high‐angle X‐ray diffraction (XRD), and deuterium solid‐state NMR spectroscopy were used to characterize the different phases of the tetraazapentacene 1 . This molecule is found to exist in a variety of crystalline solid phases between room temperature and 167 °C, with different room‐temperature phases resulting from crystallization from solution compared with cooling from the melt. Interestingly, the molecule exhibits liquid‐crystalline behavior at high temperatures, between 167 °C and 186 °C, above which it becomes an isotropic fluid. The presence of liquid‐crystalline behavior in a zwitterionic system opens up the potential for the use of these or related molecules in optoelectronic switching.     

Patterning of Flexible Transparent Thin‐Film Transistors with Solution‐Processed ZnO Using the Binary Solvent Mixture

Flexible transparent thin‐film transistors (TTFTs) have emerged as next‐generation transistors because of their applicability in transparent electronic devices. In particular, the major driving force behind solution‐processed zinc oxide film research is its prospective use in printing for electronics. Since the patterning that prevents current leakage and crosstalk noise is essential to fabricate TTFTs, the need for sophisticated patterning methods is critical. In patterning solution‐processed ZnO thin films, several points require careful consideration. In general, as these thin films have a porous structure, conventional patterning based on photolithography causes loss of film performance. In addition, as controlling the drying process is very subtle and cumbersome, it is difficult to fabricate ZnO semiconductor films with robust fidelity through selective printing or patterning. Therefore, we have developed a simple selective patterning method using a substrate pre‐patterned through bond breakage of poly(methyl methacrylate) (PMMA), as well as a new developing method using a toluene–methanol mixture as a binary solvent mixture.     

Liquid‐Metal Electrode for High‐Performance Triboelectric Nanogenerator at an Instantaneous Energy Conversion Efficiency of 70.6%

Harvesting ambient mechanical energy is a key technology for realizing self‐powered electronics, which has tremendous applications in wireless sensing networks, implantable devices, portable electronics, etc. The currently reported triboelectric nanogenerator (TENG) mainly uses solid materials, so that the contact between the two layers cannot be 100% with considering the roughness of the surfaces, which greatly reduces the total charge density that can be transferred and thus the total energy conversion efficiency. In this work, a liquid‐metal‐based triboelectric nanogenerator (LM‐TENG) is developed for high power generation through conversion of mechanical energy, which allows a total contact between the metal and the dielectric. Due to that the liquid–solid contact induces large contacting surface and its shape adaptive with the polymer thin films, the LM‐TENG exhibits a high output charge density of 430 μC m^?2, which is four to five times of that using a solid thin film electrode. And its power density reaches 6.7 W m^?2 and 133 kW m^?3. More importantly, the instantaneous energy conversion efficiency is demonstrated to be as high as 70.6%. This provides a new approach for improving the performance of the TENG for special applications. Furthermore, the liquid easily fluctuates, which makes the LM‐TENG inherently suitable for vibration energy harvesting.     

Polymer‐Stabilized Chromonic Liquid‐Crystalline Polarizer

Robust coatable polarizer is fabricated by the self‐assembly of lyotropic chromonic liquid crystals and subsequent photo‐polymerizing processes. Their molecular packing structures and optical behaviors are investigated by the combined techniques of microscopy, scattering and spectroscopy. To stabilize the oriented Sunset Yellow FCF (H‐SY) films and to minimize the possible defects generated during and after the coating, acrylic acid (AA) is added to the H‐SY/H₂O solution and photo‐polymerized. Utilizing cross‐polarized optical microscopy, phase behaviors of the H‐SY/H₂O/AA solution are monitored by varying the compositions and temperatures of the solution. Based on the experimental results of two‐dimensional wide angle X‐ray diffraction and selected area electron diffraction, the H‐SY crystalline unit cell is determined to be a monoclinic structure with the dimensions of a = 1.70 nm, b = 1.78 nm, c = 0.68 nm, α = β = 90.0° and γ = 84.5°. The molecular arrangements in the oriented H‐SY films were further confirmed by polarized Fourier‐transform infrared spectroscopy. The polymer‐stabilized H‐SY films show good mechanical and chemical stabilities with a high polarizability. Additionally, patterned polarizers are fabricated by applying a photo‐mask during the photo‐polymerization of AA, which may open new doors for practical applications in electro‐optic devices.     

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.     

High‐Speed,Low‐Voltage,and Environmentally Stable Operation of Electrochemically Gated Zinc Oxide Nanowire Field‐Effect Transistors

Single‐crystal, 1D nanostructures are well known for their high mobility electronic transport properties. Oxide‐nanowire field‐effect transistors (FETs) offer both high optical transparency and large mechanical conformability which are essential for flexible and transparent display applications. Whereas the “on‐currents” achieved with nanowire channel transistors are already sufficient to drive active matrix organic light emitting diode (AMOLED) displays; it is shown here that incorporation of electrochemical‐gating (EG) to nanowire electronics reduces the operation voltage to ≤2 V. This opens up new possibilities of realizing flexible, portable, transparent displays that are powered by thin film batteries. A composite solid polymer electrolyte (CSPE) is used to obtain all‐solid‐state FETs with outstanding performance; the field‐effect mobility, on/off current ratio, transconductance, and subthreshold slope of a typical ZnO single‐nanowire transistor are 62 cm²/Vs, 10⁷, 155 μS/μm and 115 mV/dec, respectively. Practical use of such electrochemically‐gated field‐effect transistor (EG FET) devices is supported by their long‐term stability in air. Moreover, due to the good conductivity (≈10^?2 S/cm) of the CSPE, sufficiently high switching speed of such EG FETs is attainable; a cut‐off frequency in excess of 100 kHz is measured for in‐plane FETs with large gate‐channel distance of >10 μm. Consequently, operation speeds above MHz can be envisaged for top‐gate transistor geometries with insulator thicknesses of a few hundreds of nanometers. The solid polymer electrolyte developed in this study has great potential in future device fabrication using all‐solution processed and high throughput techniques.     

Controlling the Color of Cholesteric Liquid‐Crystalline Films by Photoirradiation of a Chiroptical Molecular Switch Used as Dopant

Using thin films of a cholesteric mixture of acrylates 2 and 3 doped with the chiroptical molecular switch (M)‐trans‐ 1 , photocontrol of the reflection color between red and green is possible. This doped liquid‐crystal (LC) film can be used for photoinduced writing, color reading, and photoinduced locking (via polymerization) of chiral, optically written information.