Hyperbranched polyimide application in liquid crystal alignment layers

Several hyperbranched polyimides (HBPIs) were applied in liquid crystal (LC) alignment layers and exhibited outstanding performance for LC alignment. The maximum pretilt angle was above 8°, and the minimum pretilt angle was 4.2°. The results of atomic force microscope measurement disclosed that a lot of grooves were aligned parallel to the rubbing direction and found that the grooves were not main factor for LC alignment. The LC alignment and pretilt angles are unambiguously associated with the intrinsic HBPI chemical structures. The results of thermal gravimetric analysis and ultraviolet–visible spectra showed that the HBPIs had good thermal stability and excellent transmittance. T₅ and T₁₀ were higher than 360°C and 400°C, respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

Pretilt angle generation by UV exposure during imidization of polyimide

We investigated pretilt angle generation and liquid crystal (LC) alignment by ultraviolet exposure during the imidization of polyimide (PI). The generated pretilt angle of a nematic (N) LC using an in situ photo-alignment method is smaller than that using a conventional photo-alignment method on a surface of PI having side chains. The NLC pretilt angles using an in situ photo-alignment method injected at isotropic phase increased with annealing were observed.     

Pretilt angle generation by UV exposure during imidization of polyimide

We investigated pretilt angle generation and liquid crystal (LC) alignment by ultraviolet exposure during the imidization of polyimide (PI). The generated pretilt angle of a nematic (N) LC using an in situ photo-alignment method is smaller than that using a conventional photo-alignment method on a surface of PI having side chains. The NLC pretilt angles using an in situ photo-alignment method injected at isotropic phase increased with annealing were observed.     

Synthesis and Characterization of a Soluble Polyimide Containing a Photoreactive 4‐Styrylpyridine Derivative as the Side Group

An aromatic polyimide bearing photoreactive 4‐(2‐(4‐oxyethylenyloxyphenyl)vinyl)pyridine side groups was synthesized and characterized. The polymer is stable up to 300°C and soluble in organic solvents, giving thin films in good quality. When exposed to UV light, it reorients favorably with an angle of 98° with respect to the electric vector of linearly polarized UV light. UV‐exposed films align liquid‐crystals (LCs) homogeneously along the preferential orientation of the polymer chains on the surface. The pretilt angle of the LCs is 0.32–0.92°, depending on the exposure dose and annealing. LC alignment is retained up to 210°C. Based on the optical retardation behavior and spectroscopic measurements, a photoalignment mechanism is proposed.     

Control of liquid crystal pretilt angles by chemical derivatization reaction of polyvinyl alcohol films

A chemical derivatization technique was used to control the pretilt angle of a liquid crystal. A polyvinyl alcohol (PVA) alignment layer, which gives a very low pretilt angle when in contact with the liquid crystal (LC), was reacted with trifluoroacetic anhydride (TFAA) in the gas phase to change polar -OH groups to -OCOCF₃ groups. By introduction of the -OCOCF₃ groups in to the PVA, we obtained homeotropic alignment of the E7 LC molecules. The homeotropic alignment of E7 LC molecules in contact with the derivatized PVA alignment layer was confirmed by FTIR and microscopy with crossed polarizers. The change of liquid crystal molecules from homogeneous to homeotropic alignment may be caused by the decrease in surface tension of the PVA alignment layer, due to substitution of the polar -OH groups by -OCOCF₃ groups in the gas phase derivatization reaction.     

Control of liquid crystal pretilt angles by chemical derivatization reaction of polyvinyl alcohol films

A chemical derivatization technique was used to control the pretilt angle of a liquid crystal. A polyvinyl alcohol (PVA) alignment layer, which gives a very low pretilt angle when in contact with the liquid crystal (LC), was reacted with trifluoroacetic anhydride (TFAA) in the gas phase to change polar –OH groups to –OCOCF₃ groups. By introduction of the –OCOCF₃ groups in to the PVA, we obtained homeotropic alignment of the E7 LC molecules. The homeotropic alignment of E7 LC molecules in contact with the derivatized PVA alignment layer was confirmed by FTIR and microscopy with crossed polarizers. The change of liquid crystal molecules from homogeneous to homeotropic alignment may be caused by the decrease in surface tension of the PVA alignment layer, due to substitution of the polar –OH groups by –OCOCF₃ groups in the gas phase derivatization reaction.     

偶氮聚合物表面起伏光栅用于液晶定向研究

液晶显示具有低功耗、高画质、轻巧等优点，广泛应用于各种平板显示装置．使液晶分子能在显示器中均匀的定向排列是液晶显示的关键技术之一．液晶定向技术的主要方法有摩擦法、SiOx等氧化物或Au、Pt等金属蒸镀法、紫外偏振光(或激光)辐照法等．所谓摩擦法，即通过将基片在均匀移动的丝绒布表面摩擦来实现的．一般认为摩擦法是通过摩擦在基板表面形成的微沟槽来诱导     

Preliminary communication Investigation of pretilt angle generation in nematic liquid crystal with oblique non-polarized UV light irradiation on polyimide films

We investigated new rubbing-free techniques for liquid crystal (LC) alignment with non- polarized ultraviolet (UV) light irradiation on plates coated with two kinds of the polyimide (PI) films. It was found that monodomain alignment of nematic (N) LC is obtained in the cell having a PI surface without a side chain. We successfully observed that the generated pretilt angle of the NLC is about 3 with an angle of incidence of 70 on the PI surface without side chains. This pretilt angle generation is attributed to interaction between the LC molecules and the polymer surfaces; the uniform alignment of NLC is attributed to anisotropic dispersion force effects due to photo-depolymerization of polymer on PI surfaces.     

In situ control of surface molecular order in liquid crystals using a localised polymer network and its application to electro-optical devices

A liquid crystal (LC) alignment technique has been developed that allows local control of the polar pretilt angle over the range of 0–90°. This was achieved through the formation of a polymer network localised in the vicinity of the LC cell substrates. The network was formed as a result of in situ UV-induced polymerisation of a photo-reactive monomer added at concentrations of 0.5–1%. Localisation of the polymer network at the LC–substrate boundary was achieved by the application of a high voltage before polymerisation. The resultant pretilt angle was determined by the voltage applied during the polymerisation and/or the duration of the voltage application before the polymerisation step. The desired pretilt angle could be set over a small area of the sample, which allows the fabrication of LC devices with spatially variable optical retardation. Using this method we fabricated a converging lens, a bi-prism, and a phase diffraction grating with resolution greater than 50 lines mm^?1.     

Synthesis of new aromatic polyimides with various side chains containing a biphenyl mesogen unit and their abilities to control liquid-crystal alignments on the rubbed surface

New poly(m-phenylene 4,4′-oxydiphthalimide)s containing various side chains, such as 6-(4-biphenylmethoxy)hexyloxy group and 6-(phenylphenoxy)hexyloxy isomers, were synthesized, giving thin films of a high quality. All the polyimides apparently were almost amorphous, but exhibited short-range ordering in some extent, depending on the side chains. By incorporating side chains, the thermal properties, including stability, thermal expansivity, and glass transition temperature, were generally degraded, whereas the optical and dielectric properties were improved. All the polyimides exhibited a good rubbing processability and excellent performance in the controlling of both the alignment and the pretilt of LC molecules in the LC cell. The pretilt angle of LC molecules was easily achieved in a wide-angle range of 8–27°, depending upon the rubbing density as well as the incorporated side chains. The pretilting of LC molecules was very sensitive to all the molecular parameters (namely, the flexibility of polymer chain backbone as well as the isomeric structure of biphenyl mesogen end group, spacer length, and spacer conformation in the side chain) in the polyimide, in addition to the rubbing process. In particular, the side chains, which are much shorter in length than the long alkyl side chains in the polyimides being used widely as LC alignment layers, were evident to involve effectively in the alignment of and the pretilt of LC molecules, which are highly desired in the LC display industry. This might mainly be attributed to a strong interaction between the biphenyl mesogen end group of the side chain and the LC molecule. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2909–2921, 1999     

Influence of the surface pretilt angle on spatially periodic deformations in nematic layers

The deformations induced by electric field in twisted or untwisted flexoelectric nematic layers can be homogeneous (i.e. one-dimensional) or spatially periodic (i.e. two-dimensional). The periodic deformations are undesirable from an applicative point of view since they destroy the homogeneous appearance of the area of an excited pixel of a display. They are particularly favoured when the nematic material possesses flexoelectric properties. In order to check whether the unwanted periodic deformations can be eliminated by means of suitable surface pretilt angle, the small deformations arising just above the corresponding threshold voltage were investigated numerically. The nematic materials exhibiting both weak and strong flexoelectricity were taken into account. The surface pretilt angles ranging from 0° to 30° were adopted. It was shown that the periodic patterns, arising in the case of planar surface alignment, disappear if sufficiently large surface pretilt angle is applied.     

Synthesis and properties of photoalignable aromatic polyesters containing phenylenediacrylate units in their backbones and n‐alkyl moieties in their side groups

A series of poly[oxy(4‐n‐alkyl‐3,5‐benzoate)oxy‐1,4‐phenylenediacryloyl]s (PPDA‐CnBZ polymers) with high molecular weights was synthesized. These polymers exhibit excellent solubility in some common organic solvents and produce good quality films using conventional spin‐casting and drying processes. The polymers are thermally stable up to 357–362 °C in a nitrogen atmosphere; their glass transition temperatures are greater than 121 °C. The photoreactions and photoalignments of the polymers were investigated using ultraviolet‐visible and infrared spectroscopy, and their liquid crystal (LC) alignment properties were examined. The phenylenediacrylate (PDA) chromophores in the polyesters were found to mainly undergo photocyclization upon ultraviolet light irradiation. Irradiation of the polyester films with linearly polarized ultraviolet light (LPUVL) induces preferential orientation of the polymer main chains, while the unreacted PDA chromophores are aligned along the direction perpendicular to the electric vector of the LPUVL. All the films irradiated with LPUVL were found to align LCs in a direction perpendicular to the electric vector of the LPUVL. Moreover, these LC alignments persisted even on irradiated films annealed at temperatures up to 210 °C, which is much higher than the glass transition temperatures of the polyesters. These LC alignment characteristics are due to the anisotropic interactions of the LC molecules with the oriented polymer chains and with the unreacted PDA chromophores. LC alignments on the polyester film surfaces have homeotropic to homogeneous characteristics, depending on the length of the n‐alkyl side group, providing strong evidence that the n‐alkyl side groups of the polyesters play a critical role in determining the pretilt angles of the LCs. The LC pretilt angles were also found to be influenced by the thermal annealing history of the irradiated films. In summary, the excellent properties of the PPDA‐CnBZ polymers make them promising candidate materials for use as LC alignment layers in advanced LC display devices. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1322–1334, 2004     

Anisotropic reactive mesogens transfer onto polyimides-mixture layer via imprinting method for continuous pretilt angle control

We present a new approach for the alignment process to orient liquid crystal (LC) molecules. The process consists of fabrication of a stamp composed of reactive mesogens (RMs), transfer of RM from the stamp onto polyimide (PI) layers, and LC device fabrication using the resulting RM/PI layers. The RM stamp was made anisotropic by a rubbing treatment, and this anisotropy was transferred to the PI layers via contact imprinting, leading to an achievement of uniform LC alignment. In addition, the pretilt angle of the LC molecules could be controlled by varying the content of homogeneous PI in the PI layers. We describe the effects of high pretilt angle upon the electro-optical (EO) characteristics of twisted-nematic (TN) cells based on the RM transfer film/blended PI layers.     

Liquid crystal alignment behaviours on poly(methyl methacrylate) having polyhedral oligomeric silsesquioxane groups

A series of poly(methyl methacrylate) derivatives containing polyhedral oligomeric silsesquioxane (POSS) groups (MCP#) were synthesised via free radical polymerisation (FRP) using methacryl isobutyl POSS (MA-POSS) and methyl methacrylate as monomers to investigate liquid crystal (LC) alignment property of these polymer films. The LC cells made from the films of the polymers having 100 mol% of MA-POSS units (MCP100) showed vertical LC alignment having a pretilt angle of about 90°. The vertical LC alignment behaviour on the MCP100 film was ascribed to the very hydrophobic MCP100 surface having the surface energy value smaller than about 23 mJ/m² generated by the nonpolar bulky POSS group. Good electro-optical characteristics, such as voltage holding ratio (VHR) and residual DC voltage (R-DC), were observed for the LC cells fabricated using MCP100 as a LC alignment layer.     

Homogeneously aligned liquid crystal molecules on unidirectional buckle pattern of polyurethane films

We present the fabrication of an anisotropic structure on a polyurethane (PU) film for aligning liquid crystal (LC) molecules with ion beam (IB) irradiation at an incident angle. The obtained anisotropic structure assembles the LC cells in a layer that aligns LC molecules uniformly. Polarised optical microscopy images of an LC cell fabricated with IB-irradiated PU were captured to confirm the LC alignment state and compared with those fabricated with non-treated PU. To analyse the effects of the IB irradiation, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy were used to investigate the chemical and morphological modifications, respectively. IB irradiation modifies the chemical structure of PU, which indicates that a new skin layer is formed on the PU films. This skin layer generates an in-plane compressive strain, thereby creating buckles on the PU films. Simultaneously, the physical collision of the reactive Ar⁺ ions during IB irradiation induces a directional strain on the surface, thereby forming a unidirectional structure of buckles along the direction of IB irradiation. The PU film annealed at 200°C showed the high average transmittance of 88.9%, which is appropriate as an alignment layer.     

Control of surface anchoring properties of liquid crystal by thermo-transfer printing of siloxane oligomers

We presented the results for the surface anchoring properties of a nematic liquid crystal (LC) in a wide range of the substrate wettability through thermo-transfer printing of siloxane oligomers. For the modification of the surface energy, poly(dimethylsiloxane) (PDMS) oligomers were directly transferred onto a glass substrate from a bulk PDMS plate by contact printing at elevated temperatures. The hydrophobicity of the PDMS-modified surface was found to increase with the temperature of the substrate during transfer printing. The LC alignment on the PDMS-modified substrate exhibited continuous variations of the pretilt angle from nearly 0° to 90° and the polar anchoring strength according to the surface energy.     

Relationship between alignment layer polymer surface structures and liquid crystal display parameters

The polar alignment layer (AL) surface provided relatively small liquid crystal (LC) pretilt angles while polyimides with long alkyl side chains gave relatively large LC pretilt angles. The results suggest that LC pretilt angles, in addition to an anchoring effect, are greatly affected by both electronic and steric interactions between LC molecules and a polyimide alignment layer surface. Rubbing with a cotton cloth induces functional groups, side chains, and repeat units at the surface of a liquid crystal polyimide AL to re-orient. It was discovered that rubbing induced polar functional groups and repeat units to re-orient out-of-the-plane of the surface, and it made non-polar aliphatic side chains partially re-orient inwards, toward the bulk of the film.     

Liquid crystal alignment properties of 2-naphthoxymethyl-substituted polystyrenes

The liquid crystal (LC) alignment properties of LC cells fabricated with films of 2-naphthoxymethyl-substituted polystyrenes with different contents of naphthoxymethyl side groups were investigated. The polymer films exhibited good optical transparency in the visible light region (400–700 nm). The LC cells made from the unrubbed films of polymers having more than 57 mol%?of 2-naphthoxymethyl containing monomeric units showed homeotropic LC alignment with a high pretilt angle of about 90^o. Good electro-optical characteristics, such as the threshold voltage, response time, voltage holding ratio and residual DC voltage were observed for the LC cells fabricated with the polymer having 100 mol%?of 2-naphthoxymethyl containing monomeric units as an LC alignment layer.     

Photo-alignment of liquid crystals using a crosslinked discotic film

A new photo-alignment layer using a crosslinked discotic compound was demonstrated. This discotic compound exhibits excellent solubility in common organic solvents, the possibility of low temperature processing and good thermal stability. A linearly polarized long wavelength ultraviolet (LPUV) light (λ = 350 nm) was used to initiate the crosslinking process and induce liquid crystal alignment on the discotic film surface. The induced LC directors were found parallel to the electric field direction of the LPUV light. A 1.2° pre-tilt angle was achieved using a single exposure at a 30° oblique angle.     

Physicochemical analysis of ion beam-induced surface modifications on polyethylene glycol films for liquid crystal alignment

ABSTRACT

We investigated the surface modification induced by the ion-beam (IB) irradiation of a polyethylene glycol (PEG) film and its liquid crystal (LC) alignment characteristics. The X-ray photoelectron spectroscopy analysis revealed the chemical modification; as the IB incidence angle increased, the number of surface C–O bonds decreased, inducing an anisotropic dipole moment on the PEG film surface. In addition, the physical modification was demonstrated via atomic force microscopy analysis using three-dimensional images as a function of the IB incidence angle. The surface roughness was analyzed; the modification with the smoothest surface was observed for an IB incidence angle of 45°. This modification affected the LC alignment state of the PEG film, as demonstrated by the polarized optical microscopy analysis with pre-tilt angle measurements. Furthermore, for the same IB incidence angle, the residual DC measured using the capacitance–voltage curves was extremely low. Hence, a PEG film irradiated with an IB incidence angle of 45° could be a suitable LC alignment layer.