Polyimide aligned ferroelectric smectic C liquid crystals

27 alkyl-aromatic polyimides have been synthesized and tested as alignment layers for surface stabilized ferroelectric liquid crystals with a number of room temperature ferroelectric mixtures. The cone angles are used as a quantitative measure of the bistability obtained in these cells. The effect of the structure of the polyimides on the cone angles obtained and the stability of the alignment is discussed.     

Polyimide aligned ferroelectric smectic C liquid crystals

Abstract

27 alkyl-aromatic polyimides have been synthesized and tested as alignment layers for surface stabilized ferroelectric liquid crystals with a number of room temperature ferroelectric mixtures. The cone angles are used as a quantitative measure of the bistability obtained in these cells. The effect of the structure of the polyimides on the cone angles obtained and the stability of the alignment is discussed.     

Computer simulations of interactions between liquid crystal molecules and polymer surfaces II. Alignment of smectic C-forming mesogens

Computer simulations have been performed to examine the behaviour of the liquid crystalline molecule 4-n-heptyl-2-fluoro-phenyl 4-n-octyloxybiphenyl-4-carboxylate (MBF) when in contact with crystalline polymer surfaces. The simulations form part of a study of the alignment interactions that are found in liquid crystal displays. MBF forms several smectic phases including a chiral smectic C* phase when suitably doped. In this paper we examine the way that layers of MBF molecules interact with the structure of the crystalline polymer surface, with the aim of understanding how molecular level interactions give rise to macroscopic phenomena such as the cone angle in ferroelectric liquid crystal devices. Molecular dynamics simulations consisting of a fixed crystalline polymer surface in contact with either a single MBF molecule or up to two layers of them (48 molecules) have been performed. A variety of simple polymer surfaces have been examined and the simulations show that the cone angle is highly dependent on the geometry of both the liquid crystal molecule and the polymer substrate. For molecules of MBF on polyethylene substrates, a cone angle of 20 is predicted, in line with experimental findings.     

The relationship between liquid crystal alignment in the nematic and smectic C* phases

The pretilt angle in the nematic phase is related to two different surface dependent factors, while the quality of surface stabilized ferroelectric liquid crystal (SSFLC) devices is dependent on only one of them. We have synthesized two series of polyalkyleneimides and found that the pretilt angles for thick nematic cells are not related to the cone angles in SSFLC cells.     

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.     

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.     

Cone motion viscosity and optical second harmonic generation of ferroelectric liquid crystalline dendrimers

We report second harmonic generation in a ferroelectric liquid crystalline trimer and ferroelectric liquid crystalline dendrimers of first, second and third generation. Thin cells were filled with the compounds by capillary forces at elevated temperature, and cooled from the surface stabilized ferroelectric state to below the glass transition temperature, while kept in an electric field. The cone motion viscosity and the threshold electric field for unwinding of the helix axis of the chiral tilted smectic mesophases were studied separately at elevated temperature, and these data were used to optimize the preparation of the films. The measured response time was between 0.3 and 3ms, which corresponds to a cone motion viscosity between 0.5 and 50 Pa s. Second harmonic generation was studied both at elevated temperature with an electric field and at room temperature with and without electric field. The first generation dendrimer exhibited a strong increase in the second order non-linear optical response with time at room temperature. The d₂₃-coefficient of this dendrimer was approximately four times larger than for the other macromolecules and was 0.045 pm V^-1. The relatively large d-coefficient of the first generation dendrimer is ascribed to crystallization, which improved the orientation of the molecular dipoles.     

Helical unwinding in polymer-dispersed ferroelectric liquid crystals

We demonstrate that ferroelectric liquid crystals dispersed in a polymer matrix can form uniaxially aligned elliptical droplets. The alignment is controlled by mechanical shear during the polymerization of a UV-curable adhesive. The possibility of prealignment makes polymer-dispersed ferroelectric liquid crystals suitable for application in flexible electro-optical displays. In contrast to surface stabilized ferroelectric liquid crystal displays, the electro-optical effect in our system is due to the deformed-helix ferroelectric (DHF) effect.     

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.     

Cone motion viscosity and optical second harmonic generation of ferroelectric liquid crystalline dendrimers

We report second harmonic generation in a ferroelectric liquid crystalline trimer and ferroelectric liquid crystalline dendrimers of first, second and third generation. Thin cells were filled with the compounds by capillary forces at elevated temperature, and cooled from the surface stabilized ferroelectric state to below the glass transition temperature, while kept in an electric field. The cone motion viscosity and the threshold electric field for unwinding of the helix axis of the chiral tilted smectic mesophases were studied separately at elevated temperature, and these data were used to optimize the preparation of the films. The measured response time was between 0.3 and 3ms, which corresponds to a cone motion viscosity between 0.5 and 50 Pa s. Second harmonic generation was studied both at elevated temperature with an electric field and at room temperature with and without electric field. The first generation dendrimer exhibited a strong increase in the second order non-linear optical response with time at room temperature. The d ₂₃-coefficient of this dendrimer was approximately four times larger than for the other macromolecules and was 0.045 pm V^-1. The relatively large d-coefficient of the first generation dendrimer is ascribed to crystallization, which improved the orientation of the molecular dipoles.     

Electro-optic characteristics of surface-stabilized ferroelectric liquid crystal devices with the stripe-shaped domain structure

The stripe-shaped domain (SSD) structure has been obtained in the initial ferroelectric liquid crystal (FLC) alignment after the doping of a naphthalocyanine compound into rubbed polyimide films. Pre-tilt angles on the aligning films have been measured. The memory capability of aligned SSFLC cells has been enhanced nearly to completion, and contrast ratios reached 86:1 with the appearance of the SSD structure. Thus fabricated, 64 64 electrically controlled FLC spatial light modulator has better electro-optic characteristics and stability than a non-doped device.     

Contrast ratio and switching of zigzag defect-free surface stabilized FLCD by photoinduced alignment

The contrast ratio and electro-optical switching behaviours of surface stabilized ferroelectric liquid crystal cells with alignment layers of a photodegradable polyimide prepared by polarized ultraviolet light irradiation have been investigated. The higher contrast ratio was obtained for a zigzag defect-free sample obtained by the photo-induced alignment method than by the rubbing method. The switching behaviours of the FLC, such as spontaneous polarization and response time, were measured. Higher spontaneous polarization and faster response times were obtained with cells prepared by the photoinduced alignment method. In addition, response times of the order of microseconds, which are fast enough to realize high quality moving images with video-frame rate, were obtained.     

The optical tensor configuration in a surface stabilized ferroelectric liquid crystal determined by using half leaky guided modes

The optic tensor configuration in a surface stabilized ferroelectric liquid crystal cell is investigated using optical excitation of half leaky guided modes. A thin ferroelectric liquid crystal layer is confined between a high index pyramid, with an index greater than the maximum of the liquid crystal, and a glass substrate having an index less than the minimum of the liquid crystal. Using standard attenuated total reflection experimental procedures, over a small angle range a series of sharp resonant peaks are recorded in the s-polarized reflectivity using p-polarized incident light. These peaks are extraordinarily sensitive to details of the optical tensor configuration within the cell. Fitting theoretically modelled reflectivities from multilayer Fresnel theory to the data allows determination of near surface alignment, bending of the chevron, surface tilt angle and biaxiality. To give a clear physical explanation for the great sensitivity of the technique, the electromagnetic field component distributions in the cell are also presented and analysed. The results confirm that the half leaky guided mode method has enormous potential for the study of the optic tensor configuration in liquid crystal layers.     

Contrast ratio and switching of zigzag defect-free surface stabilized FLCD by photoinduced alignment

The contrast ratio and electro-optical switching behaviours of surface stabilized ferroelectric liquid crystal cells with alignment layers of a photodegradable polyimide prepared by polarized ultraviolet light irradiation have been investigated. The higher contrast ratio was obtained for a zigzag defect-free sample obtained by the photo-induced alignment method than by the rubbing method. The switching behaviours of the FLC, such as spontaneous polarization and response time, were measured. Higher spontaneous polarization and faster response times were obtained with cells prepared by the photoinduced alignment method. In addition, response times of the order of microseconds, which are fast enough to realize high quality moving images with video-frame rate, were obtained.     

Restricted polymer-stabilised electrically suppressed helix ferroelectric liquid crystals

The electrically suppressed helix ferroelectric liquid crystal (ESHFLC) electro-optical mode is characterised by the high contrast and fast response time at low driving voltage. However, the ESHFLC demands several constraints on the alignment layer and the cell gap. However, due to the fundamental characteristics of the ferroelectric liquid crystals, the cone angle decreases at higher temperatures, which is the biggest hurdle for this electro-optical mode to find the real application. In this article, we disclose a restricted polymer stabilisation (with very small polymer concentration in the mixture) for the ESHFLC without pushing other vital parameters out of the range of the constraints for ESHFLCs. The restricted polymer-stabilised ESHFLC shows large temperature range with stable high contrast, fast response time and low driving voltage, thus, it could find application in a range of the modern display and photonic devices.     

The effect of thermal treatment of the alignment layer on the electro-optical response of SSFLCs

Annealing the polyimide alignment layer affected the IR spectra of the alignment layer and correspondingly the electro-optic effect of surface stabilized ferroelectric liquid crystal displays. It was found that with proper annealing a smectic C* liquid crystal with a spontaneous polarization as high as 30 nC/cm² can show good stability towards disturbing pulses. The optimum annealing conditions consisted of a rather narrow temperature band. A model where amorphous regions in an otherwise crystalline polymer act as islands of instability is proposed.     

Ferroelectric polysiloxane liquid crystals with 'de Vries'-type smectic A*-smectic C* transitions

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*-smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the optical tilt angle in the SmC* phases reaches values up to 30°, temperature-dependent SAXS measurements clearly reveal that the smectic layer spacing is basically conserved during the A*-C* transition as well as in the subsequent C* phase. Connected with the A*-C* transition we further observed a significant increase in birefringence, hence reflecting an increase of orientational order. The practical absence of layer shrinkage and the enhanced orientational ordering are consistent with the de Vries diffuse cone model of smectic A-smectic C transitions.     

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.     

旋光性聚合物的铁电性能

旋光性高分子在结构上具有一定的空间特异性,因而可以有多种应用。根据铁电材料所必需具备的条件,经过特定的分子结构设计,可以使之具备铁电性能,据此,人们已合成了许多不同类型的铁电聚合物。本文按照铁电聚合物所处的聚集态不同,分别综述了具有铁电特性的晶态和液晶态旋光性聚合物的种类、结构特点及其铁电性能,分析讨论了影响液晶态旋光性聚合物的自发极化率和响应时间的因素。