Preliminary communication: Novel method for uniform orientation of liquid crystal molecules by a polyimide surface exposed to a water flow

A novel technique for surface-induced orientation of liquid crystal (LC) molecules is proposed, using a polyimide surface exposed to a unidirectional water flow. The LC molecules director was unidirectionally oriented along the water flow direction on the polyimide surface. The orientational state of the LC director was strongly dependent upon whether the water flow exposure was carried out before or after thermal curing for imidization, and also upon the temperature of water flow.     

Determination of the molecular orientation of very thin films on solid substrates: surface liquid crystal layers and rubbed polyimide films

The molecular orientation of very thin films on solid substrates can be determined quantitatively by measuring the polarized infrared (IR) absorption spectra of samples as a function of angle of incidence. The quantitative molecular orientation is derived by fitting the incident angle dependence and the dichroic ratio with theoretical calculations. We applied this method to a technologically important system: liquid crystal (LC)/rubbed polyimide film. To understand the alignment mechanism of LC molecules in contact with rubbed polyimide films, we have quantitatively determined the molecular orientation of rubbed polyimide films and a surface LC layer in contact with a rubbed polyimide film. In this paper two relations are discussed: (1) correlation between the inclination angle of polyimide backbone structures in rubbed films and the pretilt angle of bulk LC in contact with them, and (2) relation among the molecular orientation of a rubbed polyimide film and those of surface and bulk LC layers in contact with it.     

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.     

新型可溶性偶氮聚酰亚胺及其作为液晶光定向层应用的初步研究

以 4 ,4′ 二 (1,2 苯二酸酐 4 羧酸酯 )偶氮苯为二酐单体 ,4 十六烷氧基 4′ ,4″ 二氨基三苯甲烷为二胺单体 ,通过缩聚反应合成了可溶性偶氮聚酰亚胺 .采用红外光谱、氢核磁共振、紫外光谱和热分析等手段 ,对产物的结构、热性能及光学性能等进行了表征 .在紫外光辐照下 ,上述聚合物表现出明显的光色效应 .经线性偏振紫外光 (LPUV)辐射后的上述偶氮聚酰亚胺定向层能诱导液晶盒中液晶分子发生定向沿面排列 ,且取向均匀 .上述实验表明 ,合成的偶氮聚酰亚胺是一类潜在的液晶光定向材料 .     

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.     

Alignment mechanism of a nematic liquid crystal on a pre-rubbed polyimide film with laser-induced periodic surface structure

A periodic surface structure was prepared on a pre-rubbed polyimide (PI) film surface with a pulsed UV laser polarized perpendicular to the rubbing direction. The experimental results demonstrate that the rubbing-induced molecular anisotropic orientation was relaxed by the pulsed laser irradiation, and the laser induced molecular orientation was perpendicular to the line of the laser-induced periodic structure. The dichroism of the anisotropy of molecular orientation increased with the increase of laser energy. Since the direction of the laser-induced molecular anisotropy was perpendicular to the surface groove direction of the pre-rubbed PI surface, the effects of surface microgroove and anisotropic molecular orientation of the PI chain on liquid crystal (LC) alignment can be distinguished from each other. LC alignment was investigated by evaluating the anchoring energy of the PI surface, which was calculated according to Berreman's theory using the twist angle of the LC in the cells. The experimental results demonstrate that the exact alignment direction of the LC molecules is determined by the relative strength of both factors.     

Response time mechanism for a photo-aligned vertical-alignment liquid crystal display on a homeotropic alignment layer

The electro-optical characteristics of the photo-aligned vertical-alignment liquid crystal display (VA-LCD) with a non-polarized UV exposure of 45° on homeotropic polyimide (PI) surface was investigated. The domain size of the photo-aligned VA-LCD increases proportionately with the UV exposure time. The LC alignment of the photo-aligned VA-LCD is attributed to photo-dissociation of the polymer by UV exposure on the homeotropic PI surface. Good voltage-transmittance characteristics of the photo-aligned VA-LCD without negative compensation film was measured. The response time of the photo-aligned VA-LCD was slow compared with a rubbing-aligned VA-LCD; this is considered to be due to the alignment of LC molecules.     

Response time mechanism for a photo-aligned vertical-alignment liquid crystal display on a homeotropic alignment layer

The electro-optical characteristics of the photo-aligned vertical-alignment liquid crystal display (VA-LCD) with a non-polarized UV exposure of 45° on homeotropic polyimide (PI) surface was investigated. The domain size of the photo-aligned VA-LCD increases proportionately with the UV exposure time. The LC alignment of the photo-aligned VA-LCD is attributed to photo-dissociation of the polymer by UV exposure on the homeotropic PI surface. Good voltage-transmittance characteristics of the photo-aligned VA-LCD without negative compensation film was measured. The response time of the photo-aligned VA-LCD was slow compared with a rubbing-aligned VA-LCD; this is considered to be due to the alignment of LC molecules.     

Pretilt angle of liquid crystals and liquid-crystal alignment on microgrooved polyimide surfaces fabricated by soft embossing method

In this study, the soft embossing method is proposed to fabricate periodical microgrooved structure on polyimide surfaces. These microgrooved polyimide surfaces are assembled to form liquid-crystal cells. It is found that the director of liquid crystals uniformly aligns along the groove direction even when the groove width is as high as 3 microm. The anchoring energy of these microgrooved polyimide surfaces is higher than that of the typical rubbed surfaces. The pretilt angle of liquid crystals is adjusted by tuning the surface polarity of the polyimide alignment layer, which is identified by the advancing contact angle of water. The surface polarity of polyimide alignment layers is manipulated by simply mixing two kinds of polyimide: a more hydrophilic one and a more hydrophobic one. It is found that the pretilt angle of liquid crystals increases along with the advancing contact angle of water on the alignment layer under the condition of a fixed surface topography.     

Alignment mechanism of a nematic liquid crystal on a pre-rubbed polyimide film with laser-induced periodic surface structure

A periodic surface structure was prepared on a pre-rubbed polyimide (PI) film surface with a pulsed UV laser polarized perpendicular to the rubbing direction. The experimental results demonstrate that the rubbing-induced molecular anisotropic orientation was relaxed by the pulsed laser irradiation, and the laser induced molecular orientation was perpendicular to the line of the laser-induced periodic structure. The dichroism of the anisotropy of molecular orientation increased with the increase of laser energy. Since the direction of the laser-induced molecular anisotropy was perpendicular to the surface groove direction of the pre-rubbed PI surface, the effects of surface microgroove and anisotropic molecular orientation of the PI chain on liquid crystal (LC) alignment can be distinguished from each other. LC alignment was investigated by evaluating the anchoring energy of the PI surface, which was calculated according to Berreman's theory using the twist angle of the LC in the cells. The experimental results demonstrate that the exact alignment direction of the LC molecules is determined by the relative strength of both factors.     

Orientation of liquid crystal molecules in polydimethylsiloxane micro-channels

The orientation of liquid crystal (LC) molecules confined in polydimethylsiloxane micro-channels, which are produced using mould-replica technique, with a rectangular cross section, is studied. The rod-like molecules of the LC adopt the vertical anchoring at every surface of the channels. The macroscopic alignment of the confined LC can be changed by altering the aspect ratio of the channels. The change in the macroscopic alignment of the LC is attributed directly to the restructuring of the proportion of the number of molecules anchored to the respective surfaces due to the changes in specific area of the bounding surface of the channels. Solutions for the elastic energy function obtained using conformal mapping method were used to predict director profile of the LC in the confinement.     

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.     

Orientational and electro-optical properties of liquid crystal aligned with a directly spinnable carbon nanotube web

We investigated the orientational and electro-optical properties of a nematic liquid crystal (LC) aligned with a directly spinnable carbon nanotube (CNT) web functioning both as an electrode and as an alignment layer. The LC molecules were uniformly oriented along the drawing direction of the CNT web and the spatially averaged birefringence was comparable to a rubbed polyimide sample. The CNT web sample also showed smaller residual DC and hysteresis compared to the polyimide sample.     

Light-induced LC director freezing on a chalcogenide surface

First observations of permanent light-induced director patterning in a transparent liquid crystal (LC) are reported. The patterning was observed in an LC cell with one of the substrates covered with a chalcogenide film. Concentric director ring pattern appears following the irradiation of the chalcogenide surface through the LC layer by a Gaussian beam. The experimental results are explained in terms of the heat transfer from the chalcogenide film to the LC after the light absorption by the chalcogenide film. Heating the LC changes its birefringence according to the spatial intensity distribution of the Gaussian beam. This in turn leads to the spatially oscillating changes of the polarisation state of light in the plane of the chalcogenide film. The oscillating changes of the light polarisation result in producing the light-induced easy orientation axis and the oscillating changes of the anchoring energy. It causes the spatial modulation of the director on the chalcogenide surface and the formation of the concentric ring twist structures in the cell.     

Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment

The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.     

A dielectric study on the relaxation and switching behaviour of liquid crystals confined within a colloidal network

The molecular ordering and dynamics of a liquid crystal (LC E7) in the presence of a three-dimensional network of submicron particles have been studied by dielectric relaxation spectroscopy. The field-dependent orientation of the LC was quantified by the director order parameter and modelled by use of a three-phase model. The influence of the colloidal network on the molecular dynamics was assessed from the dielectric spectra, e.g. from the position of relaxation peaks as well as from the strength of the two principal relaxations (α and γ). The spectra changed noticeably upon application of an increasing d.c. bias. A reduction of the threshold field was observed upon addition of colloidal particles to the LC. This was associated with a switching between two metastable states induced by anchoring on the filler particles. Modelled spectra were found to be in good agreement with the experimental data. The modelling showed that the confined LC phase is composed of two fractions, viz. an ordered and a disordered one with different molecular mobilities. Furthermore, switching experiments were conducted at various temperatures in order to evaluate the impact of the colloidal network on the (temperature-dependent) orientational behaviour of the LC molecules. For the colloid-filled LC higher conductivities were found, which gave rise to longer switch-off times.     

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.     

High-transmittance liquid crystal cell fabricated using nanoparticle-doped polyimide

We found that we can increase the transmittance of a liquid crystal (LC) cell by doping the alignment material with nanoparticles. We fabricated an LC cell using indium–tin–oxide glass substrates coated with SiO₂-doped polyimide. We confirmed that the transmittance of LC cells fabricated using SiO₂-doped polyimide was higher than that of LC cells fabricated using pure polyimide. To account for the increase of transmittance, we measured the order parameter of the fabricated LC cells and investigated the surface morphology of the alignment layer using atomic force microscopy.     

Zigzag defect-free alignment of surface stabilized ferroelectric liquid crystal cells with a polyimide irradiated by polarized UV light

Zigzag defect-free surface stabilized ferroelectric liquid crystal (SSFLC) cells were prepared using a photodegradable polyimide (PI) having a cyclobutane ring in the backbone. The PI layers were irradiated by polarized ultraviolet light (PUVL) at normal incidence to the surface, and characterized by UV and FTIR spectroscopy. The anisotropy originates from preferential cleavage of PI chains oriented parallel to the polarization direction of the irradiating PUVL. After the polarized UV light irradiation, the PI surface was much flatter than that after rubbing, but it induced a similar order parameter of dye-doped nematic LC molecules to that for a rubbed cell. Alignment of both the FLC molecules and the layer structure is important in SSFLC. After 40 min irradiation, the FLC molecules were well aligned homogeneously, and the FLC cells showed a uniform texture without zigzag defects which also indicates a well aligned layer structure. Zigzag defect-free alignment may result from the flatter surface, the much smaller and more constant pretilt angles, and the bigger cone angle than those achieved by rubbing.     

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