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.     

含氟基团对液晶垂直排列的作用

实验发现双酚A双肉桂酸酯和六氟双酚A双肉桂酸酯单体在线偏振紫外光作用下发生光交联,形成的薄膜对液晶分子的排列效果截然不同,分别诱导液晶分子沿面平行排列和垂直排列.红外光谱分析表明光交联的类型均为[2+2]环加成反应.利用原子力显微镜观察薄膜表面,没有发现明显的各向异性拓扑分布.通过测量非含氟和含氟两种交联膜的表面能大小,发现氟的引入使薄膜的表面能降低,同时表面能中的极性作用明显降低.实验结果表明,氟基团的引入导致液晶分子垂直排列.本文探讨了这种垂直排列的原因.     

Command surfaces, 10. Novel polymethacrylates with laterally attached azobenzene groups displaying photoinduced optical anisotropy

Polymethacrylates with laterally attached azobenzenes were prepared to cause molecular reorientation of this chromophore in their thin films by linearly polarized irradiation with an exposure energy of less than ca. 100 mJ/cm². A homogeneous alignment was induced by assembling a nematic liquid crystal cell using a substrate plate covered with the photoirradiated films. The alignment direction of the cell was controlled by changing the electric vector of the actinic light.     

Photo-induced liquid crystal alignment on polyimide containing fluorinated groups

Polyimides were prepared from pyromellitic dianhydride, 4,4'-bis[2-(4-aminophenyl)hexafluoroprop-2-yl]diphenyl ether and 4,4'-diamodiphenyl ether (PMDA-BDAF-ODA) and used for liquid crystal alignment using linearly polarized UV exposure. The alignment properties of a LC on the polyimide films were found to depend on the fluorine content in the PMDA-BDAF-ODA alignment layer and on the UV exposure time. Pretilt angles were obtained in the range 0° to 90° dependent upon the fluorine content in the polyimide film and the UV exposure time. These effects seem to be closely related to the surface energy of the photo-alignment layer.     

Influence of molecular mass on the liquid crystal alignment of photosensitive fluorinated polyester films

Photosensitive fluorinated polyesters (polymer-n) of varying molecular mass M _n (number-average molecular mass) were synthesized. The thin films formed from polymer-n samples could induce liquid crystal (LC) alignment after irradiation by linearly polarized ultraviolet light. The LC alignment direction on the irradiated films was investigated in detail by linearly polarized infrared spectroscopy and polarizing optical microscopy. It was found that LC alignment behaviour changed with change in the molecular mass of polymer-n: irradiated films with lower or higher M _n induced homeotropic or homogenous alignment, respectively. There was no clear morphological anisotropy in these aligned films, as observed by atomic force microscopy. The surface energies of the irradiated films were also measured using the indirect contact angle method, where both surface energy and its polar component increased with increasing M _n. The variation in M _n could be considered as a main reason for varying alignment behaviour.     

UV-driven switching of chain orientation and liquid crystal alignment in nanoscale thin films of a novel polyimide bearing stilbene moieties in the backbone

A novel photosensitive polyimide, poly(4,4'-stilbenylene 4,4'-oxidiphthalimide) (ODPA-Stilbene PSPI) was newly synthesized. The most surprising feature of this PSPI is that the PSPI films irradiated with linear polarized ultraviolet light (LPUVL) can favorably induce a unidirectional alignment of liquid crystals (LCs) in contact with the film surface and further switch the director of the unidirectionally aligned LCs from a perpendicular direction to a parallel direction with respect to the polarization direction of LPUVL by simply controlling the exposure dose in the irradiation process. These LPUVL-irradiated films were found to provide high anchoring energy to LCs, always giving very stable, homogeneous cells with unidirectionally aligned LCs regardless of the LC alignment directions. In the films, the PSPI polymer chains were found to undergo favorably unidirectional orientation via a specific orientation sequence of the polymer chain segments led by the directionally selective trans-cis photoisomerization of the stilbene chromophore units in the backbone induced by LPUVL exposure. Such unidirectionally oriented polymer chains of the films induce alignment of the LCs along the orientation direction of the polymer chains via favorable anisotropic molecular interactions between the oriented polymer chain segments and the LC molecules. In addition, the PSPI has an excellent film formation processibility; good quality PSPI thin films with a smooth surface are easily produced by simple spin-coating of the soluble poly(amic acid) precursor and subsequent thermal imidization process. In summary, this new PSPI is the promising LC alignment layer candidate with rubbing-free processing for the production of advanced LC display devices, including LC display televisions with large display areas.     

Synthesis of a liquid crystalline azobenzene monomer for photoalignment of ferroelectric liquid crystals

A liquid crystalline dimethacrylate-based monomer containing an azobenzene group was synthesized. The miscibility of the azo monomer and its crosslinked polymer network with ferroelectric liquid crystals (FLCs) was improved by the liquid crystallinity of the monomer. By performing thermal polymerization of the azo monomer dissolved in a FLC host under linearly polarized visible light irradiation, following a pre-irradiation with unpolarized UV light at room temperature, bulk alignment of the FLC could be induced in the absence of surface orientation layers, as a result of the photo-orientation of azobenzene moieties related to the reversible trans-cis photoisomerization of the chromophore. The optical and rubbing-free alignment of a FLC could be achieved with as few as 0.5 wt % of the azo polymer network. This represents a step toward the preparation of uniform samples of photoaligned FLC by reducing the amount of the azo polymer network that may be phase-separated from the FLC host.     

Anisotropic surface morphology of azopolymer films generated by polarized UV light irradiation

X-ray reflectivity measurements reveal anisotropy of the vertical surface roughness caused by exposure to linearly polarized UV (LPUV) light in the films of two azopolymers. The irradiated surface is found to have higher roughness in the direction parallel to the direction of polarization than in the orthogonal direction. The photo-modification of the surface morphology is caused by spatial changes induced in polymer films by LPUV irradiation. The important role of surface roughness anisotropy in determining the alignment of liquid crystals is discussed.     

Anisotropic surface morphology of azopolymer films generated by polarized UV light irradiation

X-ray reflectivity measurements reveal anisotropy of the vertical surface roughness caused by exposure to linearly polarized UV (LPUV) light in the films of two azopolymers. The irradiated surface is found to have higher roughness in the direction parallel to the direction of polarization than in the orthogonal direction. The photo-modification of the surface morphology is caused by spatial changes induced in polymer films by LPUV irradiation. The important role of surface roughness anisotropy in determining the alignment of liquid crystals is discussed.     

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.     

Alignment control of liquid crystals on surface relief gratings

Liquid crystal alignment layers of a high T _g polymer containing an azobenzene moiety are prepared by photofabrication of a surface relief grating (SRG). The interference pattern of a circular and linearly polarized Ar⁺ laser beam generated the surface relief grating and the morphology was detected by atomic force microscope. The optical anisotropy of the films was investigated by polarizing optical microscopy. The orientation of the optical axis of the film mainly depends on the direction of the initial polarization plane. Nematic liquid crystals were aligned parallel to the direction of the grating, but the pretilt angles of the liquid crystals were nearly zero. Irradiation with homogeneous linearly polarized light could also align liquid crystals, but this alignment capability was weaker than that of the SRG film.     

Alignment control of liquid crystals on surface relief gratings

Liquid crystal alignment layers of a high T_g polymer containing an azobenzene moiety are prepared by photofabrication of a surface relief grating (SRG). The interference pattern of a circular and linearly polarized Ar⁺ laser beam generated the surface relief grating and the morphology was detected by atomic force microscope. The optical anisotropy of the films was investigated by polarizing optical microscopy. The orientation of the optical axis of the film mainly depends on the direction of the initial polarization plane. Nematic liquid crystals were aligned parallel to the direction of the grating, but the pretilt angles of the liquid crystals were nearly zero. Irradiation with homogeneous linearly polarized light could also align liquid crystals, but this alignment capability was weaker than that of the SRG film.     

Photoinduced orientation in poly(vinylcinnamate) and poly(7-methacryloyloxycoumarin) thin films and the consequences on liquid crystal alignment

Thin films of poly(vinylcinnamate) and poly(7-methacryloyloxycoumarin) have been exposed to linearly polarized UV light. The resulting anisotropic films have been characterized by using UV, conventional and polarization modulation FTIR spectroscopies. In particular, several internal vibrational modes have been used as structural probes to examine the orientation of groups in the irradiated polymers. These experiments provide new information about the photoinduced anisotropy in these photocrosslinkable polymers upon irradiation with linearly polarized UV light, and an orientation mechanism is proposed. This mechanism is confirmed by studying the liquid crystal alignment induced by PVCi and poly(7-methacryloyloxycoumarin). Finally, the stability of the photoalignment process is discussed.     

Photoinduced orientation in poly(vinylcinnamate) and poly(7-methacryloyloxycoumarin) thin films and the consequences on liquid crystal alignment

Thin films of poly(vinylcinnamate) and poly(7-methacryloyloxycoumarin) have been exposed to linearly polarized UV light. The resulting anisotropic films have been characterized by using UV, conventional and polarization modulation FTIR spectroscopies. In particular, several internal vibrational modes have been used as structural probes to examine the orientation of groups in the irradiated polymers. These experiments provide new information about the photoinduced anisotropy in these photocrosslinkable polymers upon irradiation with linearly polarized UV light, and an orientation mechanism is proposed. This mechanism is confirmed by studying the liquid crystal alignment induced by PVCi and poly(7-methacryloyloxycoumarin). Finally, the stability of the photoalignment process is discussed.     

Linearly polarized ultraviolet photoreaction of photocrosslinkable polymers comprising the p-phenylenediacrylate group and photoalignment control of liquid crystals on the resultant film

We present (1) the linearly polarized (LP) ultraviolet (UV) photoreaction of block copolyesterethers comprising a hard segment of polyester and soft segment of poly(tetramethylene ether) (PTMG) and (2) the alignment behavior of liquid crystals (LCs) on the resultant photoreacted polymer films. Two kinds of copolyesterethers with different polyester segments of poly(hexamethylene p-phenylenediacrylate) (1a) or poly(hexamethylene p-phenylenediacrylate)-co-poly(hexamethylene 1,4-dibenzoate) (1b) were used in this study. The LP–UV irradiation resulted in a negative optical anisotropy for both polymer films, and a homogeneous photoalignment of LCs was achieved on the photoreacted polymer film. The LC alignment was perpendicular to the electric vector of the incident polarized light for 1a, whereas a reversion of the alignment from parallel to perpendicular was observed for 1b, depending on the irradiation doses. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4000–4006, 1999     

Molecular orientation and liquid crystal alignment properties of new cinnamate-based photocrosslinkable polymers

Isotropic thin films of three original phenyl substituted cinnamate-based polymers, here-after referred to as 'Para', 'Meta' and 'Metamet' have been exposed to linearly polarized UV light and their photoinduced molecular orientations have been studied. The resulting photocrosslinked anisotropic polymer films were characterized using UV, conventional and polarization modulation (PM) FTIR spectroscopies. From UV and PM-IR linear dichroism measurements, at least two simultaneous orientation processes appear to play a key role in these phenyl substituted cinnamate-based systems. On the one hand, isomerization reactions deplete chromophores along the polarization direction (P) of the UV light and induce a preferential orientation of remaining 'trans'-isomers perpendicular to P; on the other hand, cycloaddition reactions lead to the formation of either head to head or head to tail photodimers aligned preferentially along P in the 'Para' and to a lesser extent in the 'Meta' and 'Metamet' systems. These last results are related to the different liquid crystal alignment properties of the films, and the influences of the chemical structure of the chromophores are discussed.     

UV tuning of the electro-optical and morphology properties in polymer-dispersed liquid crystals

Polymer-dispersed liquid crystal (PDLC) films operating in reverse mode are transparent electro-optical devices, which can be turned into an opaque state by application of a suitable electric field. The effect was investigated of different UV powers, used during the polymerization process, on the electro-optical and morphology properties of PDLCs, working in reverse mode operation. Films were obtained by UV polymerization of mixtures of a low molecular weight nematic liquid crystal and a photopolymerizable liquid crystal monomer, homeotropically aligned by rough conductive surfaces. The electro-optical and morphology properties of samples were related to the polymerization conditions. Samples polymerized by lower UV powers exhibited “polymer ball” morphology and an electro-optical response due to the liquid crystal director reorientation, whereas samples obtained at higher UV powers showed a “Swiss cheese” morphology and an electro-optical response due to dynamic scattering. In addition, we observed by conductivity and IR measurements that UV exposure induces a degradation of the nematic liquid crystal.     

Highly sensitive photoalignment of calamitic and discotic liquid crystals assisted by axis-selective triplet energy transfer

Highly sensitive photoalignment of liquid crystals (LCs) can be realized by axis-selective triplet energy transfer. Addition of a triplet photosensitizer (phosphorescent donor) into a photocrosslinkable polymer tethering E-cinnamate side chains ensures dramatic enhancement of photosensitivity to generate the optical anisotropy of polymer film and surface-assisted LC photoalignment. Photoirradiation of triplet photosensitizer-doped polymer films with linearly polarized 365 nm light for the selective excitation of triplet sensitizer gives rise to optical anisotropy of cinnamates as a result of axis-selective triplet energy transfer. By analyzing phosphorescence spectra with theoretical Perrin's formula, we find that triplet energy transfer is efficient within a radius of ～0.3 nm from the triplet photosensitizer. Such photoaligned polymer films can be used for the surface-assisted orientation photocontrol of not only calamitic LC, but also discotic LC, even for extremely low exposure energies. The present procedure would be greatly advantageous for high-throughput fabrication of optical devices by photoalignment techniques.     

Photoinduced alignment of polymerisable liquid crystals on photoreactive polymers containing 2,6-bis(benzylidene)-1-cyclohexanone units in the main chain

Photoreactive polymers containing 2,6-bis(benzylidene)-1-cyclohexanone (bisBC) units were synthesised and investigated as a photoalignment layer for polymerisable liquid crystals (PLCs) and liquid crystalline polymers (LCPs). The liquid crystalline materials were aligned homogeneously on the photoalignment layers in a wide range of irradiation dose of linearly polarised UV light (LPUVL). Specifically, for the photoalignment layer baked at 80°C, order parameters of the liquid crystalline materials were low due to the disturbance of oriented-photoreactive polymer caused by the contact with the solvent of liquid crystalline materials. However, the liquid crystalline materials were aligned homogeneously even at low irradiation doses on the thermally cured photoalignment layer baked at 180°C. In addition, the liquid crystalline materials were aligned perpendicular to the LPUVL electric field. The alignment mechanism is discussed by comparing the retardation of photoalignment layer with anisotropic polarisabilities of model molecules calculated by density functional theory (DFT). It is suggested that the liquid crystalline materials aligned along the unreacted chromophores in the photoreactive polymer.     

Rollable ferroelectric liquid crystal devices monostabilized with molecularly aligned polymer walls and networks

This paper describes a flexible monostabilized ferroelectric liquid crystal (FLC) device using molecularly aligned polymer walls and networks, which are sequentially formed with a two-step photopolymerization-induced phase separation. When ultraviolet (UV) light was irradiated through a photomask onto a heated nematic phase solution of FLC and monomer, monomer molecules that had flowed into the irradiated areas were photopolymerized, and polymer walls aligned along the rubbing direction of the polyimide alignment layers on plastic film substrates were formed. After uniform UV irradiation without a photomask, polymer networks aligned along the rubbing direction were formed in the FLC. The FLC molecules were monostabilized in the rubbing direction by the strong anchoring of the polymer networks. The device, which was sandwiched between crossed polarizers, exhibited a monostable electro-optic characteristic with a high contrast ratio of over 100:1 and a response time of less than 1 ms. The FLC device exhibited spatially uniform operation even when it was rolled up with a radius of curvature of 1.5 cm.