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.     

Effect of an electric field applied during the injection procedure on the pretilt angle of a nematic liquid crystal

We examined the effect of an electric field applied during the injection procedure on the polar pretilt angle of a nematic liquid crystal (LC). The pretilt angle of the sample injected at 25°C gradually increased as the electric field was increased. On the other hand, the pretilt angle of a sample injected at 90°C (which is above the nematic-isotropic phase transition temperature of LC) showed a sudden increase in the presence of the electric field and also increased with a greater electric field. We think the alignment layer might be swollen with LC molecules, and the rotation of the immersed LC molecules by the electric field induces a deformation of the alignment layer. These results imply LC and the alignment layer were coupled, and their cooperation had an influence on determining the bulk pretilt angle.     

Polar and azimuthal alignment of a nematic liquid crystal by alkylsilane self-assembled monolayers: effects of chain-length and mechanical rubbing

Alkylsilane self-assembled monolayers (SAMs) on oxide substrates are commonly used as liquid crystal (LC) alignment layers. We have studied the effects of alkyl chain length, photolytic degradation, and mechanical rubbing on polar and azimuthal LC anchoring. Both gradient surfaces (fabricated using photolytic degradation of C18 SAMs) and unirradiated SAMs composed of short alkyl chains show abrupt transitions from homeotropic to tilted alignment as a function of degradation or chain length. In both cases, the transition from homeotropic to tilted anchoring corresponds to increasing wettability of the SAM surfaces. However, there is an offset in the critical contact angle for the transition on gradient vs unirradiated SAMs, suggesting that layer thickness is more relevant than wettability for LC alignment. Mechanical rubbing can induce azimuthal alignment along the rubbing direction for alignment layers sufficiently near the homeotropic-to-planar transition. Notably, mechanical rubbing causes a small but significant shift in the homeotropic-to-tilted transition, e.g., unrubbed C5 SAMs induce homeotropic anchoring, but the same surface after rubbing induces LC pretilt.     

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.     

The effect of surface polarity of glass on liquid crystal alignment

The effects of the surface polarity of a glass substrate on the orientation of nematic liquid crystals (LCs) were studied using the polarised optical microscope and Fourier-transform infrared spectroscopy. On the surface of oxygen plasma treated glass, a homeotropic alignment of LCs was induced for LCs with negative dielectric anisotropy. This suggests that vertical orientation of LCs could be induced on a polar glass substrate without using an LC alignment layer. Upon cooling towards the isotropic–nematic transition, E7 with positive dielectric anisotropy changes its LC arrangement to isotropic, homeotropic, planar orientations in order. The nematic LC anchoring transition of E7 was interpreted by considering the competition between van der Waals forces and dipole interactions that control the alignment of LC molecules on a polar glass surface.     

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.     

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 properties of poly(styrenesulphonate)/alkyltrimethylammonium complexes

We synthesised a series of poly(4-styrenesulphonate)/alkyltrimethylammonium (PSS-#Cx, # = 12, 14 and 16; x?=?80, 60, 40 and 20) complexes, where # is the number of carbon atoms in the alkyl groups in alkyltrimethylammonium bromide, and x is the molar content (%) of alkyltrimethylammonium moiety, using polymer analogous reactions to investigate their liquid crystal (LC) alignment properties. In general, the LC cell fabricated using the polymer film having a longer alkyl side group and a higher molar content of alkyl side group showed homeotropic LC alignment behaviour with a pretilt angle of about 90°. The homeotropic LC alignment behaviour was well correlated with the surface energy of the polymer films. Homeotropic LC alignment was observed when the surface energy values of the polymer were smaller than about 44.87 mJ/m².     

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.     

Factors in liquid crystal photoalignment on polymer films: photoorientation versus self-assembly

We demonstrate that photostimulated self-assembly, running in parallel with molecular photoorientation in the top layer of the aligning polymer film, breaks the bulk molecular order mainly determined by the symmetry of irradiation. This may substantially modify liquid crystal (LC) alignment. Depending on the chemical composition of the liquid crystal, the self-assembled layers may influence either homeotropic or planar LC alignment with extremely weak azimuthal anchoring. Effective self-assembly occurs in polymers having side chain chromophores with flexible spacers and polar terminal groups.     

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.     

Polymer-dispersed liquid crystal composites for bio-applications: thermotropic,surface and optical properties

Polymer-dispersed liquid crystal (PDLC) systems based on polysulfone as carrying matrix and 4-cyano-4?-pentylbiphenyl (5CB) liquid crystal (LC) were obtained as thin transparent films. The PDLC films were prepared by solvent- and thermally induced phase separation methods, with various compositions in the two components. Information on the phase separation was obtained by polarised light optical microscopy, differential scanning calorimetry and scanning electron microscopy. The PDLC composites show well-defined droplets of submicrometric size, around 650 nm for a medium content of LC and around 250 nm for a low one. The droplets show a radial configuration and a homeotropic alignment of the LC molecules within. By contact angle measurement and surface free energy calculations, it was established that self-assembling of aliphatic units of the two composite components, at droplet interface, is the driving force of the homeotropic alignment. Moreover, these data indicated the potential biocompatibility of the studied composites. The photophysical behaviour shows a better light emission of the PDLCs containing bigger droplets.     

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.     

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.     

Correlations between surface and bulk liquid crystal alignment observed with optical second-harmonic generation

Abstract

We report a direct experimental observation of surface-induced liquid crystal (LC) monolayer orientation and its relation to the LC bulk alignment. Using optical second-harmonic generation from these LC monolayers, adsorbed on rubbed polymer surfaces, we determined both the polar and azimuthal orientation of the LC molecules. A close correlation between the rubbing-induced azimuthal orientational distribution of the LC monolayers and the resulting LC bulk pretilt angle has been observed. A simple model based on epitaxial growth of the bulk LC on top of the first LC monolayer is proposed to explain this correlation.     

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.     

Alignment of liquid crystals using Langmuir‒Blodgett films of unsymmetrical bent-core liquid crystals

ABSTRACT

The properties of the thin films of liquid crystal (LC) molecules can be governed easily by external fields. The anisotropic structure of the LC molecules has a large impact on the electrical and optical properties of the film. The Langmuir monolayer (LM) of LC molecules at the air–water interface is known to exhibit a variety of surface phases which can be transferred onto a solid substrate using the Langmuir?Blodgett (LB) technique. Here, we have studied the LM and LB films of asymmetrically substituted bent-core LC molecules. The morphology of LB film of the molecules is found to be a controlling parameter for aligning bulk LC in the nematic phase. It was found that the LB films of the bent-core molecules possessing defects favour the planar orientation of nematic LC, whereas the LB films with fewer defects show homeotropic alignment. The defect in LB films may introduce splay or bend distortions in the nematic near the alignment layer which can govern the planar alignment of the bulk LC. The uniform layer of LB film facilitates the molecules of nematic to anchor vertically due to a strong van der Waals interaction between the aliphatic chains leading to a homeotropic alignment.     

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.     

Novel polypyromellitimides and their liquid crystal aligning properties

Various aromatic poly{3,6‐bis[(4‐n‐alkyloxy)phenyloxy]‐pyromellitimide}s [poly(Ar‐C_m‐PMDA)s, m = 1, 4, 8, 12] were prepared in film form by routine two‐step condensation of 3,6‐bis[(4‐n‐alkyloxy)phenyloxy]pyromellitic dianhydrides (C_m‐PMDAs) with various aromatic diamines. After characterization of their chemical structures their solution, thermal and liquid crystal (LC)‐aligning properties in terms of pretilt angle at various rubbing densities were measured and discussed with respect to their backbone structures. All polyimide films showed excellent thermal stability and homogeneous LC alignment, but the poly(p‐phenylene‐C₁₂‐PMDA) exhibited completely homeotropic alignment while the pretilt angle values of poly(p‐phenylene‐C₈‐PMDA) varied with varying rubbing density.     

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.