可溶性聚酰亚胺液晶取向膜的制备与性能

液晶取向膜是液晶显示器中的关键材料,为了制得性能优良的液晶取向膜,我们通过铃木偶联反应制备了3种含有不同末端基团的3,5-二氨基联苯,将制得的3种二胺单体分别与环丁烷四甲酸二酐聚合得到3种新型的聚酰亚胺。 利用核磁氢谱对单体和聚合物的结构进行了表征,测试了聚合物的溶解性、热稳定性以及用作液晶取向膜的性能。 结果表明,所得的聚酰亚胺具有良好的溶解性和热稳定性,经过机械摩擦后,末端带有甲氧基的聚酰亚胺能使液晶分子平行于摩擦方向取向,末端带有苯氧羰基和联苯氧羰基的聚酰亚胺能使液晶分子垂直于摩擦方向取向。 此类可溶性的聚酰亚胺液晶取向膜将简化制备工艺并在柔性显示器件中具有较大的应用价值。     

Synthesis,photo-reaction and photo-induced liquid crystal alignment of soluble polyimide with pendant cinnamate group

In this paper, the synthesis, photo-reaction and photo-induced liquid crystal alignment of a polyimide with a pendant cinnamate group are reported. The polyimide was synthesized by the thermal imidization of the polyamic acid derived from 4,4'-(hexafluoro-isopropylidene)diphthalic anhydride and hydroxydiaminopropane, followed by the attachment of the cinnamate group to the main chain polyimide. The surface of thin layers of the polyimide was found to be preferentially occupied by the pendant cinnamate groups, and liquid crystal alignment on the polyimide thin film exposed to polarized UV was independent of the cinnamate content. The thermal stability of the photo-induced liquid crystal alignment was enhanced with decrease in the cinnamate content. This could be attributed to the strong interchain interaction of the polyimide chains which prevents thermal randomization of the photo-product of the pendant cinnamates. The dependences of the photo-reaction temperature and the annealing temperature of the alignment layer on the azimuthal anchoring energy of the photo-aligned liquid crystal suggest that the local stress developed during the UV irradiation profoundly influences the thermal stability of the liquid crystal alignment.     

Synthesis, photo-reaction and photo-induced liquid crystal alignment of soluble polyimide with pendant cinnamate group

In this paper, the synthesis, photo-reaction and photo-induced liquid crystal alignment of a polyimide with a pendant cinnamate group are reported. The polyimide was synthesized by the thermal imidization of the polyamic acid derived from 4,4'-(hexafluoro-isopropylidene)diphthalic anhydride and hydroxydiaminopropane, followed by the attachment of the cinnamate group to the main chain polyimide. The surface of thin layers of the polyimide was found to be preferentially occupied by the pendant cinnamate groups, and liquid crystal alignment on the polyimide thin film exposed to polarized UV was independent of the cinnamate content. The thermal stability of the photo-induced liquid crystal alignment was enhanced with decrease in the cinnamate content. This could be attributed to the strong interchain interaction of the polyimide chains which prevents thermal randomization of the photo-product of the pendant cinnamates. The dependences of the photo-reaction temperature and the annealing temperature of the alignment layer on the azimuthal anchoring energy of the photo-aligned liquid crystal suggest that the local stress developed during the UV irradiation profoundly influences the thermal stability of the liquid crystal alignment.     

Investigation on ion movement in the fringe-field switching mode depending on resistivity of alignment layer and dielectric anisotropic sign of liquid crystal

Adsorption and desorption of ions at interface between liquid crystal and alignment layer in liquid crystal displays play a crucial role in residual direct current voltage associated with image sticking. In this article, the dependency of such adsorption and desorption of ions on resistivity of alignment layer and sign of liquid crystal dielectric anisotropy in the fringe-field liquid crystal cell has been investigated. Our studies show that the time constant of ions during adsorption and desorption depends upon resistivity and dielectric constant of liquid crystal and alignment layer, and most strongly influenced by the resistivity of alignment layer such that the one with lower resistivity in two orders shows much faster adsorption and desorption at the interface than that of the one with higher resistivity.     

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.     

The polar anchoring energy of nematic liquid crystals with polyvinylidene fluoride alignment layer

It has been proved that the high dielectric polyvinylidene fluoride (PVDF) could be used as an alignment layer in liquid crystal device. In this paper, the transmittance, pretilt angle and the polar anchoring energy of the substrates with PVDF alignment layer were researched. Theoretical results and the experimental results about the reflectivity R_SS (polarisation-conserving signals) recorded by full-leaky guided mode in liquid crystal technique are analysed to evaluate the anchoring energy of PVDF alignment layer. The result shows that the polar anchoring energy between PVDF alignment layer and liquid crystal molecules is 2.80 × 10^?4 J/m².     

Liquid crystal alignment and pretilt angle generation on a photopolymer layer based on N-(phenyl)maleimide

A photopolymer based on N-(phenyl)maleimide was synthesized and the liquid crystal (LC) alignment effects of the photopolymer layer on homeotropic alignment were studied. Good LC alignment with UV exposure of PMI5CA (N-(phenyl)maleimide with a 5-carbon chain cinnamoyl group) was obtained. However, defective LC alignment was observed for PMI3CA (N-(phenyl)maleimide with a 3-carbon chain cinnamoyl group) and PMIF (N-(phenyl)maleimide including a fluoro-cinnamoyl group). Good LC alignment with UV exposure on the PMI5CA surface was observed with annealing temperature up to 150°C. It seems that the LC aligning ability of the photopolymer layers based on N-(phenyl)maleimide depends on the side chain length of the photopolymer.     

Characterization of the alignment of a nematic liquid crystal using half leaky guided modes

The excitation of half leaky guided optical modes to characterize fully the optical tensor profile in a thin liquid crystal layer has been used to evaluate the effect of rubbed polyimide aligning layers on the alignment of a nematic liquid crystal. A cell fabricated with rubbed polyimide alignment surfaces was studied at a wavelength of 632.8 nm. The liquid crystalline layer is sandwiched between a high refractive index top glass plate and a low refractive index glass substrate. Angular dependent reflectivities are recorded using a coupling prism and matching fluid with the same index as the top glass plate. Careful fitting of the predictions from multilayer optics theory to the observed angle dependent polarization conversion and reflectivity data yields the director profile within the liquid crystal layer in great detail.     

Alignment of polymer network-stabilized ferroelectric liquid crystal using a magnetic field

Polymer network-stabilized ferroelectric liquid crystals with homogeneous alignment have been produced in cells without a surface alignment layer. In this technique, a crosslinkable monomer is mixed into a ferroelectric liquid crystal and polymerized in a magnetic field to form a polymer network that will stabilize the alignment of the ferroelectric liquid crystal. The concentration of the monomer is an important factor in achieving alignment of the ferroelectric liquid crystal. Both the morphology of the final composite layer and the molecular alignment of the host FLC are affected by the curing temperature at which the UV curing of the sample is started.     

Alignment of polymer network-stabilized ferroelectric liquid crystal using a magnetic field

Polymer network-stabilized ferroelectric liquid crystals with homogeneous alignment have been produced in cells without a surface alignment layer. In this technique, a crosslinkable monomer is mixed into a ferroelectric liquid crystal and polymerized in a magnetic field to form a polymer network that will stabilize the alignment of the ferroelectric liquid crystal. The concentration of the monomer is an important factor in achieving alignment of the ferroelectric liquid crystal. Both the morphology of the final composite layer and the molecular alignment of the host FLC are affected by the curing temperature at which the UV curing of the sample is started.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Liquid crystal alignment induced by controllable surface wettability of BiFeO3 bumps thin layer

The alignment of liquid crystals (LCs) in LC-based optical devices determines the visual quality of devices, and a simple pretreatment is necessary for LC alignment. Here, we present a BiFeO₃ (BFO) thin layer working as an alignment layer, homogeneously aligning LCs after a pre-thermal annealing treatment. Dramatic BFO bumps were observed during the thermal annealing process, and a corresponding enhancement in wettability was detected from measurement of tunable contact angles. LCs in the BFO bump thin layer sandwiched TN cell were found to be perfectly homogeneously aligned due to the enhanced anisotropy and wettability caused by the morphology change of the thin layer.     

Fabrication of homogenously self-alignment fringe-field switching mode liquid crystal cell without using a conventional alignment layer

We propose a novel method to fabricate a uniaxially homogeneous alignment of liquid crystal (LC) molecules without using a conventional alignment layer such as polyimide film. The method produces the polymer alignment layer (PAL) by polymerisation of the monomer including in the LC layer above the T_NI of the LC material. The fringe-field switching (FFS) mode LC cell with the PAL (FFS-PAL-LC cell) produced from the monomer 4,4?-di-mehacryloyl-oxy chalcone (4,4?-DMOCh) exhibited enough level of alignment state and electro-optical property compared with the FFS-LC cell having the conventional polyimide-type alignment layer. We can expect that the FFS-PAL-LC cell is useful for next-generation displays such as flexible liquid crystal displays (LCDs) because the method does not need high-temperature process of over 200°C.     

Molecular dynamics simulations of liquid crystal molecules on a polyimide monolayer

Preliminary results are presented on the molecular dynamics simulations of alignment of the liquid crystal molecule, 4-n-octyl-4'-cyanobiphenyl (8CB), on a polyimide (pyromelltic dianhydride-p-phenylene diamine) oligomer monolayer. We actually simulated a three-layer system, i.e., liquid crystal molecule/polyimide oligomer/a basal plane of graphite. First, simulations of the oligomers adsorbed on graphite were done in order to obtain reasonable adsorption structures, as the pre-stage simulation of the three-layer system. Then, by placing a liquid crystal layer on top, the three-layer system was simulated. The stable liquid crystal alignment direction on the polyimide monolayer was found roughly to be the polyimide chain direction with zero pretilt in this combination of liquid crystal and polymer materials. The calculated adsorption energy of an 8CB molecule to the polyimide monolayer was 128 kJ mol^-1 and the carbonyl group of the polyimide was the main adsorption site.     

Photopolymerization induced orientation transition in a nematic liquid crystal cell

We report the observation of a liquid crystal tilt transition from homeotropic to planar orientation induced by photopolymerization of the alignment layer in the absence of liquid crystal. The alignment agent is a unique, polymerizable lecithin (DC₂₃PC), which induces homeotropic alignment before UV exposure. After non-polarized UV exposure, a tilted orientation is obtained. Moreover, further buffing of the UV treated substrate yields a homogeneous alignment. We believe that the conformation change in the lecithin array caused by solid state polymerization is primarily responsible for the transition. These results help to explain the mechanism of liquid crystal alignment and will lead to several potential applications.     

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.     

FT-IR study of liquid crystal molecules on alignment layers

Alignment control at the molecular level is crucial for realizing high-performance LCDs. In particular, the structure of the interface between the liquid crystal and the alignment layer must be clarified. By utilizing RAS (reflection-absorption spectroscopy), a highly sensitive FT-IR spectroscopic technique, we have obtained the following information about the orientation of liquid crystal molecules; (1) the cyano group in a liquid crystal molecule behaves like an electron donor with respect to an SiO layer, but like an electron acceptor with respect to a polyimide layer; (2) with the use of polarized IR spectroscopy, it was discovered that the liquid crystal 8CB is aligned with a slant away from the aligning direction, regardless of the type of alignment layer. The angle between the molecular short axis within the plane of the core and the surface normal was found to be smaller on polyimide layers than on SiO layers.     

Influence of the remanent polarisation on the liquid crystal alignment in composite films of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and a cyanobiphenyl-based liquid crystal

Polymer-dispersed liquid crystals (PDLCs) of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and nematic 4-cyano-4?-n-hexylbiphenyl (6CB) or 4-cyano-4?-n-pentylbiphenyl (5CB) were prepared to study the effect of the remanent polarisation of the polymer on the liquid crystal alignment. We measured the macroscopic alignment of the liquid crystal molecules in the thickness direction by means of Infrared Transition-Moment Orientational Analysis. Electrical poling at 100 V/µm caused an increased order parameter up to 0.15. After subsequent annealing above the nematic-to-isotropic phase-transition temperature, the order parameter was reduced to 0.02. Nevertheless, the order parameter was still higher than for non-poled film indicating a slight orientation in thickness direction. Both values are lower than those expected from model calculations. In agreement with dielectric measurements, we attribute this result to the shielding effect of mobile charge carriers within the liquid crystal inclusions.     

Polymer and azo-dye composite: a photo-alignment layer for liquid crystals

In this article, we disclose a method to fabricate polymer-stabilised azo-dye photo alignment layers for liquid crystal. The idea includes the introduction of polymer network in the alignment layer, in optimal concentration, followed by two-step irradiation. The stabilised photo-alignment layer has been explored for different aspects of the display-related parameters, viz. anchoring energy, stability for various display-related environments as a function of concentration of monomer and irradiation, residual DC and voltage holding ratio. The composite photo-alignment layer offers well-suited parameters for the liquid crystal alignment and therefore could find application in a variety of modern photonic and display devices.