Anisotropy and Raman absorption of the polyimide surface irradiated by the ion beam for liquid crystal alignment

In this paper, polyimide surfaces irradiated by an ion-beam for liquid crystal alignment are investigated by using atomic force microscopy, Raman spectroscopy, and spectroscopic ellipsometry. A liquid crystal cell aligned homogeneously through the ion-beam exposure exhibits electro-optic switching behavior similar to that of a rubbing-aligned liquid crystal cell. However, we found that the surface morphology and bonding molecules of ion-beam-treated polyimide surfaces show properties very different from mechanically-rubbed ones. Experimental results show that optical anisotropy of ion-beam-treated polyimide surfaces results in the formation of hydrogenated amorphous carbon-like structure with a short main-chain, while mechanical rubbing has little effect on structural and compositional variations of polyimide layers.     

Photo-induced liquid crystal alignment of poly(vinyl cinnamate) and fluorinated polyimide blends

Liquid crystal(LC) alignment properties were mainly affected by surface properties of alignment layers. In our previous work, we prepared poly(vinyl cinnamate) (PVCi) and polyimide blend alignment layer for thermally stable LC alignment. In this work, we utilized fluorinated polyimide for blend alignment layers in order to modify surface properties of alignment layers. For this purpose, polyimides containing fluorine unit were synthesized and used for the blend alignment layers. Fluorine containing diamine, 4,4′-bis[2-(4-aminophenyl)hexafluoropropyl]-diphenyl ether(BDAF), is used for the polyimide synthesis. We prepared the fluorinated polyimide and PVCi blend alignment layers and investigated the effect of fluorine on the LC alignment properties and pretilt angle of LC.     

Polyimide film containing ultra-fine particles

We have succedded in fabricating a polyimide film with a molecular alignment superior to that obtainable by the conventional rubbing treatment. This phenomenon is realized by means of the dispersion of ultra-fine particles such as carbon and titanium dioxide in the polyimide precursor prior to the fabrication of the polyimide film and the rubbing treatment. The molecular alignment was evaluated with birefringence and infrared dichroism measurements. Further experiments establishe that the adsorption of polyimide molecules on ultra-fine particles is a significant factor in achieving a large orientational anisotropy. A model of the alignment is presented in which the rubbing treatment induces the particles to traverse the surface of the film, causing polyimide molecules adsorbed on them to be elongated in the rubbing direction. A potential application of oriented polymide films is the homogeneous alignment of nematic and smectic liquid crystals.     

Chain flexibility versus molecular entanglement response to rubbing deformation in designing poly(oxadiazole-naphthylimide)s as liquid crystal orientation layers

Four poly(oxadiazole-imide)s containing naphthalene rings, with different flexibility and molecular weight, are investigated with respect to their rheological properties to establish the optimal processing conditions from solution phase to film state for liquid crystal orientation purposes. The film uniformity and strength are determined by monitoring the flow behavior and chain entanglements. The solution rheological data are in agreement with film tensile testing, revealing that higher molecular weight favors chain entanglements and implicitly the film mechanical resistance. In order to analyze the suitability of these films as alignment layers their surface is patterned by rubbing with two types of velvet. Liquid crystal alignment of 4′-pentyl-4-biphenylcarbonitrile nematic is tested by polarized light microscopy. The resulting behavior is correlated with the polyimide malleability and characteristics of the textile fibers, namely their polarity, size, and mechanical features. The competitive effects between chain flexibility and entanglements, together with the interactions occurring between the polymer and velvet are analyzed in order to explain the surface regularity, which influences the uniformity of the liquid crystal alignment. The contrast between dark and bright states recorded on the liquid crystal cell indicates that some of these polynaphthalimides are promising candidates for liquid crystal display devices.     

Anomalous light transmission by nematic liquid crystal cells

Light transmission through nematic liquid crystal (NLC) cells with a planar alignment and various boundary conditions has been studied as a function of the bias voltage in the regimes of maximum transmittance and complete extinction. The phenomenon of anomalous light leakage in the regime of complete extinction has been observed in the NLC sells with alignment layers of amorphous hydrogenated carbon (a-C:H) and poly(vinyl alcohol) (PVA), in which an anisotropy was induced by rubbing the electrode surface (for a-C:H) and the alignment layer (for PVA). The anomalous transmission is caused by the deformation of nematic molecules, which are situated near the surface, in the direction perpendicular to the direction of rubbing. The magnitude of anomalous transmission increases with the bias voltage. This behavior is explained by the anisotropy of the surface anchoring energy of nematic molecules at the interface.     

Molecular-scale soft imprint lithography for alignment layers in liquid crystal devices

We describe molecular-scale soft nanoimprint lithographic replication of rubbed polyimide substrates to form alignment layers for liquid crystal devices. Systematic studies of the surface relief morphology of the polyimide and molded structures in three different polymers illustrate good lithographic fidelity down to relief heights of several nanometers, and with some capabilities at the level of approximately 1 nm. Collective results of experiments with several polymer formulations for molds and molded materials and process conditions indicate that this molecular-scale fidelity in replication can be used to produce surfaces that will effectively align liquid crystal molecules. Good electro-optical responses from liquid crystal light modulators that are formed in this manner suggest utility for fundamental studies and potential practical application.     

Polyimide photo-alignment layers for inclined homeotropic alignment of liquid crystal molecules

We have succeeded in realizing an inclined homeotropic alignment of liquid crystal (LC) molecules by using photo-aligned films of a polyimide containing azobenzene in the backbone structure. To induce such an LC alignment, a side chain structure was introduced into the backbone structure. The LC pretilt angle, measured from the surface normal, could be controlled up to 1.75° by varying the light exposure in oblique angle irradiation with unpolarized light. Its thermal stability was examined by annealing the LC cell at 100 °C. No change was observed in the pretilt angle even after annealing for 36 h, indicative of its excellent thermal stability. Since photo-alignment has patterning capability, the photo-aligned polyimide film is expected as a promising alignment film for multi-domain vertical alignment mode LC displays.     

基于1,2,4-三羧基-3-羧甲基环戊烷二酐的可溶性聚酰亚胺垂直取向剂的制备及性能

采用1,2,4-三羧基-3-羧甲基环戊烷二酐（TCA）、4,4’-二氨基二苯甲烷（MDA）及长侧链二胺4-十二烷氧基苯甲酸酯联苯酚-3’,5’-二胺基苯甲酸酯（DBPDA）共聚制备了一系列的聚酰亚胺。并对其溶解性能、透光性能及取向性能进行了测试。结果显示,聚酰亚胺在有机溶剂中可溶,成膜后紫外透光率较高,在波长400 n...     

Use of polydimethylsiloxane thin film as vertical liquid crystal alignment layer

The possibility of the use of polydimethylsiloxane to align liquid crystals is studied. The polydimethylsiloxane thin films coated on glass substrates exhibit a very low surface free energy, and are found to be capable of vertical liquid crystal alignment. Comparing to thin films made using a typical polyimide polydimethylsiloxane films possess a more stable surface energetic state. The pretilt angle of the calamitic liquid crystal molecules sandwiched between the silicon elastomer thin films was virtually 90°, and the molecular tilt can be maintained in a wide temperature range. Liquid crystal sandwiched between the silicon-based polymer thin films can operate in the in-plane-switching mode.     

The development of self-assembled liquid crystal display alignment layers

From simple pocket calculators to mobile telephones and liquid crystal display (LCD)-TV, over the past few decades, devices based on LCD technology have proliferated and can now be found in all conceivable aspects of everyday life. Although used in cutting-edge technology, it is surprising that a vital part in the construction of such displays, namely the alignment layer, relies essentially on a mechanical rubbing process, invented almost 100 years ago. In this paper efforts to develop alignment layers (also called command layers) by processes other than rubbing, namely self-assembly of molecular and macromolecular components will be discussed. Two topics will be presented: (i) tuneable command layers formed by stepwise assembling of siloxane oligomers and phthalocyanine dyes on indium tin oxide surfaces and (ii) command layers formed by self-assembly of porphyrin trimers. The potential use of these layers in sensor devices will also be mentioned.     

Magnetic-field-assisted formation of alignment polymer coatings in liquid crystal cells

We describe a new method for obtaining liquid crystal (LC) layers with planar orientation in plane-parallel cells, which is based on the technology of LC-polymer interface formation in solution under the action of an applied magnetic field. The azimuthal anchoring energy of LC at the polymer surface has been determined by measuring the angle of orientation of the nematic LC director on the substrate surface as a function of the magnetic field. The LC orientation provided by the proposed method is stable, and the anisotropy of LC anchoring is comparable with that achieved using well-known methods of alignment polymer film preparation by rubbing.     

Nano-engineering of the anchoring of liquid crystals on solid surfaces

The solid surface in the conventional liquid crystal displays, being responsible for the liquid crystal alignment in the absence of external fields, is playing only a passive role in the switching of the liquid crystal layer. Recently, we have shown that the anchoring strength and the easy axis, two important parameters characterizing the liquid crystal alignment, can effectively be controlled by light via photo-induced nano-scale changes of the solid surface properties. We have also introduced two novel concepts of commanded anchoring, the electrically commanded surfaces (for mediating switching of the liquid crystal) and the high performance alignment layers (for facilitating the switching of the liquid crystal) realized practically by means of a proper nano-engineering of the alignment layer. Electrically commanded anchoring concepts are strong candidates for implementation in a new generation of advanced liquid crystal displays and devices.     

Surface alignment of liquid crystal multilayers evaporated on photoaligned polyimide film observed by surface profiler

The investigation of the surface alignment of liquid crystal (LC) multilayers evaporated on photoaligned polyimide vertical alignment (PI-VA) film was carried out by means of the novel three-dimensional (3D) surface profiler. We report the first use of the surface profiler to visualize a microscopic image of the monolayer arrangement of LC molecules in contact with the surface of photo-treated PI-VA film. The photoinduced anisotropy of partially UV-exposed PI-VA film can be visualized as a topological image of LC multilayers. It seems that the topology of LC multilayers is indicating the orientational distribution of LC molecules on the treated film. It was found that the periodically photoaligned PI-VA film surface can align an adsorbed LC monolayer and the LC molecular alignment can be extended to the bulk via the epitaxylike LC–LC interaction, i.e. a short-range molecular interaction. With regard to the unexposed PI-VA film surface, noticeable anisotropy in the monolayer alignment was not observed, indicating that the long-range elastic interaction may be responsible for the bulk alignment. The appearance of small droplets in the masked region may be presumably related to the dewetting phenomena.     

Surface alignment of liquid crystal multilayers evaporated on photoaligned polyimide film observed by surface profiler

The investigation of the surface alignment of liquid crystal (LC) multilayers evaporated on photoaligned polyimide vertical alignment (PI-VA) film was carried out by means of the novel three-dimensional (3D) surface profiler. We report the first use of the surface profiler to visualize a microscopic image of the monolayer arrangement of LC molecules in contact with the surface of photo-treated PI-VA film. The photoinduced anisotropy of partially UV-exposed PI-VA film can be visualized as a topological image of LC multilayers. It seems that the topology of LC multilayers is indicating the orientational distribution of LC molecules on the treated film. It was found that the periodically photoaligned PI-VA film surface can align an adsorbed LC monolayer and the LC molecular alignment can be extended to the bulk via the epitaxylike LC–LC interaction, i.e. a short-range molecular interaction. With regard to the unexposed PI-VA film surface, noticeable anisotropy in the monolayer alignment was not observed, indicating that the long-range elastic interaction may be responsible for the bulk alignment. The appearance of small droplets in the masked region may be presumably related to the dewetting phenomena.     

Effects of backbone conformation and surface texture of polyimide alignment film on the pretilt angle of liquid crystals

Polyimides (PIs) with different inclination angle of polymer backbones, together with polar hydroxyl group and/or nonpolar trifluoromethyl group at various sites of the backbone were synthesized and used as liquid crystal alignment layers. The molecular conformation, surface chemistry, surface energy, surface morphology, and pretilt angle of the PI film were investigated. The distributions of fluorinated group and hydroxyl group at different depths of the PI surfaces were analyzed by X-ray photoelectron spectroscopy. Effects of the conformation of the PI molecular backbone on the surface morphology of the rubbed PI layer, the pretilt angle and surface energy of the alignment film were studied. The PI which contains both nonpolar fluorinated groups sticking out of the surface and the polar hydroxyl groups on the surface exhibits high pretilt angle.     

Improvement in device performance from a mixture of a liquid crystal and photosensitive acrylic prepolymer with the photoinduced vertical alignment method

Abstract

In a multicomponent nematic liquid crystal (NLC) mixture of a liquid crystal (negative-type NLC) and a photosensitive acrylic prepolymer, photopolymerization upon UV irradiation induces the separation of the LC and photosensitive acrylic prepolymer layers, thereby leading to a vertical arrangement of LC molecules. In this study, we propose a simple vertical alignment method for LC molecules, by adding a chiral smectic A (SmA?) liquid crystal having homeotropic texture characteristics to an NLC mixture solution. Measurements of electro-optical properties revealed that the addition of the SmA? LC not only strengthened the anchoring force of the copolymer alignment film surface, but also significantly enhanced the contrast ratio (～73%), response time and grayscale switching performance of the device.     

Improvement in device performance from a mixture of a liquid crystal and photosensitive acrylic prepolymer with the photoinduced vertical alignment method

In a multicomponent nematic liquid crystal (NLC) mixture of a liquid crystal (negative-type NLC) and a photosensitive acrylic prepolymer, photopolymerization upon UV irradiation induces the separation of the LC and photosensitive acrylic prepolymer layers, thereby leading to a vertical arrangement of LC molecules. In this study, we propose a simple vertical alignment method for LC molecules, by adding a chiral smectic A (SmA∗) liquid crystal having homeotropic texture characteristics to an NLC mixture solution. Measurements of electro-optical properties revealed that the addition of the SmA∗ LC not only strengthened the anchoring force of the copolymer alignment film surface, but also significantly enhanced the contrast ratio (∼73%), response time and grayscale switching performance of the device.     

Alignment and Graphene‐Assisted Decoration of Lyotropic Chromonic Liquid Crystals Containing DNA Origami Nanostructures

Composites of DNA origami nanostructures dispersed in a lyotropic chromonic liquid crystal are studied by polarizing optical microscopy. The homogeneous aqueous dispersions can be uniformly aligned by confinement between two glass substrates, either parallel to the substrates owing to uniaxial rubbing or perpendicular to the substrates using ozonized graphene layers. These opportunities of uniform alignment may pave the way for tailored anisometric plasmonic DNA nanostructures to photonic materials. In addition, a decorated texture with nonuniform orientation is observed on substrates coated with pristine graphene. When the water is allowed to evaporate slowly, microscopic crystal needles appear, which are aligned along the local orientation of the director. This decoration method can be used for studying the local orientational order and the defects in chromonic liquid crystals.     

Fullerene-containing liquid crystal spatiotemporal light modulators with surface-electromagnetic-wave-treated conducting layers

We have studied the switching characteristics of multilayer electrooptical structures comprising quartz substrates, transparent conducting layers, and an oriented nematic liquid crystal (NLC) film doped with photosensitive charge-transfer complexes based on electrooptically active organic monomer or polymer molecules and fullerenes. The transparent conducting layers treated with surface electromagnetic waves are used for the orientation of NLC molecules. The surface relief with variable permittivity, which is created by this treatment, not only ensures the alignment of NLC molecules, but also significantly influences the relaxation times of the electrooptical mesophase, thus making possible effective control over the switching times of the electrooptical light modulator within 1–1.5 ms.     

Orientations of liquid crystals on mechanically rubbed films of bovine serum albumin: a possible substrate for biomolecular assays based on liquid crystals

We report the uniform planar anchoring of thermotropic liquid crystals on films of bovine serum albumin (BSA) covalently immobilized on the surface of glass microscope slides and mechanically rubbed using a cloth. The azimuthal orientations of the liquid crystals were measured to be parallel to the direction of rubbing. Following immersion and removal of these rubbed films of BSA from aqueous solutions containing either BSA, fibrinogen, lysozyme, anti-FITC immunoglobulin G (IgG), or antistreptavidin IgG, we measured liquid crystals placed onto these surfaces to largely retain their uniform alignment. In contrast, following immersion of a rubbed film of BSA into an aqueous solution of anti-BSA IgG, we observed liquid crystals on these surfaces to assume nonuniform orientations. We conclude that specific binding of anti-BSA IgG to the film of rubbed BSA erased anisotropy induced within the film of BSA by rubbing. This result suggests that the spatial scale of anisotropy within the rubbed film of BSA is comparable to or smaller than the size of the IgG molecule. Because the anisotropy within a rubbed film of a protein can be erased by specific binding of a second protein, we believe these types of substrates (rubbed films of proteins) have the potential to be useful in a variety of label-free biomolecular assays where specific binding of a target species to its ligand can be imaged through observation of the optical appearance of liquid crystal placed onto the surface.