Free residual DC voltage for nematic liquid crystals on solution-derived lanthanum tin oxide film

We present the liquid crystal (LC) alignment properties of solution-derived lanthanum tin oxide (LaSnO) films cured at various temperatures and exposed to ion-beam (IB) irradiation. Using a solution process, LaSnO films were deposited on the indium-tin-oxide glass substrates and IB irradiation was used as an alignment method. Homogeneous and uniform LC alignment was achieved and observed by cross-polarised optical microscopy. Pre-tilt angle results with low standard deviation supported the notion of uniform LC alignment. The LaSnO film cured at 300°C showed nearly zero capacitance–voltage hysteresis. The change of the surface morphology of the LaSnO film due to IB irradiation was observed by atomic force microscopy. The effects of IB irradiation on the LC alignment layer were further demonstrated by X-ray photoelectron spectroscopy. The strong IB irradiation broke the metal–oxide bonds present, which in turn induced an increased number of oxygen vacancies on the whole surface. Uniform LC alignment was attributed to surface reformation and van der Waals forces.     

Homogeneous liquid crystal alignment on poly(vinylidene fluoride-trifluoroethylene) films subjected to ion-beam irradiation

We demonstrate homogeneous and uniform liquid crystal (LC) alignment on poly(vinylidene fluoride-trifluoroethylene) [PVDF-TrFE] films using ion-beam (IB) irradiation and a performance improvement of twisted nematic (TN) cells using IB-irradiated PVDF-TrFE films. Spontaneous ferroelectricity of the PVDF-TrFE films was modified by IB irradiation, which affected the LC alignment properties. The variation in the pre-tilt angles of the LC molecules on the IB-irradiated PVDF films is attributed to surface reformation, including defluorination and oxidation because the pre-tilt angles of LC molecules can be controlled by adjusting the fluorine content. The results of contact angle measurements supported this phenomenon. A 58% reduction in the switching voltage was observed for TN cells, indicating that the IB-irradiated PVDF-TrFE films are a promising candidate for use as an alignment layer.     

Novel alignment mechanism of liquid crystal on a hydrogenated amorphous silicon oxide

The mechanism of liquid crystal (LC) alignment has been investigated during the last few decades for inorganic materials as well as for organic materials; however, it has not been clearly confirmed for some alignment materials. Inorganic alignment materials such as amorphous silicon oxide (a-SiOx) and hydrogenated amorphous silicon oxide (a-SiOx:H) are deposited on indium tin oxide (ITO) films on glass by reactive sputtering deposition. After deposition, the inorganic alignment materials are irradiated using an Ar+ ion beam (IB) for LC alignment. On the basis of the experimental results, a-SiOx films deposited by the sputtering do not align the LC, but a-SiOx:H films treated with varying IB energies, IB incident angles, IB doses, and IB irradiation times have excellent alignment properties and electrooptical properties, identical to those of polyimide (PI). These results imply that inorganic alignment layers irradiated by IB can be adopted as an LC alignment layer instead of rubbed PI. Additionally, hydrogen plays an important role in LC alignment because of the difference in alignment properties between a-SiOx films and a-SiOx:H films. We investigate the mechanism of IB-treated inorganic alignment layers and suggest that LCs are aligned by chemical effects, such as van der Waals interaction, more than by physical effects, such as morphology effects, in the inorganic alignment layer irradiated by IB.     

Homogeneously aligned liquid crystal molecules on unidirectional buckle pattern of polyurethane films

We present the fabrication of an anisotropic structure on a polyurethane (PU) film for aligning liquid crystal (LC) molecules with ion beam (IB) irradiation at an incident angle. The obtained anisotropic structure assembles the LC cells in a layer that aligns LC molecules uniformly. Polarised optical microscopy images of an LC cell fabricated with IB-irradiated PU were captured to confirm the LC alignment state and compared with those fabricated with non-treated PU. To analyse the effects of the IB irradiation, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy were used to investigate the chemical and morphological modifications, respectively. IB irradiation modifies the chemical structure of PU, which indicates that a new skin layer is formed on the PU films. This skin layer generates an in-plane compressive strain, thereby creating buckles on the PU films. Simultaneously, the physical collision of the reactive Ar⁺ ions during IB irradiation induces a directional strain on the surface, thereby forming a unidirectional structure of buckles along the direction of IB irradiation. The PU film annealed at 200°C showed the high average transmittance of 88.9%, which is appropriate as an alignment layer.     

Homogeneous alignment of liquid crystals on low-temperature solution-derived gallium oxide films via IB irradiation method

In this paper, solution-derived gallium oxide (GaO) films are fabricated for the homogeneous alignment of liquid crystals (LCs) after an ion-beam (IB) irradiation process. GaO thin films are prepared under a variety of temperatures and different IB irradiation intensities, and the physicochemical performances of the fabricated GaO thin films are analysed using a UV-vis spectrometer, an atomic force microscope, and X-ray photoelectron spectroscopy. A higher transmittance of 85.40% from GaO thin film is obtained compared with that of polyimide (PI) film (83.52%), which indicates the feasibility for a GaO thin layer to substitute for a conventional PI layer as an alignment layer. LCs are found to align on the GaO thin film after pre-baking at 100°C and homogeneous and uniform low-IB intensity irradiation. We also determined the electro-optical (EO) characteristics of the twisted nematic (TN) cells fabricated with GaO thin layers and found them to be similar to those of cells fabricated with PI layers. Overall, GaO films achieved via the IB irradiation method are promising LC alignment layers due to the method’s low-temperature solution-derived process.     

Liquid crystal aligning capabilities on surface-reformed indium-doped zinc oxide films via ion-beam exposure

We investigated the characteristics of a solution-processed indium-doped zinc oxide (In:ZnO) film formed via ion-beam (IB) irradiation as a liquid crystal (LC) alignment layer. The In:ZnO film was deposited using solution processing and cured at various temperatures. Uniform LC alignment was observed at all curing temperatures in cross-polarised optical microscopy images. A regular pre-tilt angle supported these results and showed homogeneous LC alignment. Several surface analyses were conducted to evaluate the effect of IB irradiation on the In:ZnO film surface. X-ray diffraction analysis showed an amorphous structure both before and after IB irradiation, and physical surface reformation was observed using atomic force microscopy. Root mean square surface roughness was reduced and a smooth surface was achieved after IB irradiation. X-ray photoelectron spectroscopy was used to detect chemical surface reformation. It was found that the IB irradiation broke the metal-oxide bonds and increased the occurrence of oxygen vacancies, which affected the van der Waals forces between the LC molecules and the In:ZnO film surface. Electrical performance was observed to identify the possibility of using the In:ZnO film in LC applications. Enhanced electro-optical performance was measured and zero residual DC voltage which was verified using a capacitance-voltage curve was achieved.     

Liquid crystal alignment properties on surface-reformed solution-derived lanthanum-doped zinc oxide films

Liquid crystal (LC) alignment characteristics were investigated using a solution-derived lanthanum-doped zinc oxide (La:ZnO) film that was exposed to various intensities of ion-beam (IB) irradiation. At an IB intensity of 1700 eV, uniform and homogeneous LC alignment was achieved, as revealed by cross-polarized optical microscopy and pre-tilt angle measurement. Field-emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to verify that the IB irradiation induced physical and chemical surface reformation of the La:ZnO film that relate to LC alignment. FE-SEM and AFM revealed that the IB irradiation reformed the existing surface structure into a new structure with an altered surface roughness. The XPS results showed that the van der Waals force with anchoring energy increased as the IB intensity increased, and this profoundly affected the state of LC alignment. The capacitance-voltage (C-V) hysteresis curve was measured as a function of IB intensity to characterize the accumulated charge as a residual DC. Nearly zero C-V hysteresis was achieved at an IB intensity of 1700 eV. Therefore, a solution-derived La:ZnO film with an IB intensity of 1700 eV has great potential for high-quality LC applications.     

Homogeneous liquid crystal orientation on ion beam exposure TiO2 surfaces depending on an anisotropic dipole field

We studied homogeneous liquid crystal (LC) alignment properties on ion-beam (IB) irradiated TiO₂ films deposited by the electron beam evaporation method. Stable homogeneous LC alignment on a TiO₂ surface resulted from IB irradiation energy over 1800 eV. X-ray photoelectron spectroscopy analyses showed that Ti⁴⁺ 2p_3/2 and Ti⁴⁺ 2p_1/2 peaks were increased with increasing IB energy. Assuming that the increased peaks produced anisotropy dipole fields in the direction of the IB exposure process, we confirmed that the increasing IB energy induced strengthened the surface energy for entirely clear and stable LC molecule orientation. The voltage-transmittance characteristics of the twisted-nematic cell on the TiO₂ surface indicate that the TiO₂ film has potential for use as the LC alignment layer.     

Liquid crystal alignment on ion-beam irradiated bismuth-doped tin oxide films and their application to liquid crystal displays

Uniform and defect-free homogeneous alignment of liquid crystal (LC) molecules on solution-derived bismuth-doped tin oxide (TBO) films has been achieved using ion-beam (IB) irradiation. We performed measurements and physicochemical analysis to verify and establish the cause of the successful LC alignment. In addition, we measured the electro-optical characteristics of twisted-nematic cells with IB-irradiated TBO films to explore the suitability of this material for liquid crystal displays (LCDs). The results indicate that this approach will allow the fabrication of high-performance enhanced LCD devices.     

Physicochemical analysis of ion beam-induced surface modifications on polyethylene glycol films for liquid crystal alignment

ABSTRACT

We investigated the surface modification induced by the ion-beam (IB) irradiation of a polyethylene glycol (PEG) film and its liquid crystal (LC) alignment characteristics. The X-ray photoelectron spectroscopy analysis revealed the chemical modification; as the IB incidence angle increased, the number of surface C–O bonds decreased, inducing an anisotropic dipole moment on the PEG film surface. In addition, the physical modification was demonstrated via atomic force microscopy analysis using three-dimensional images as a function of the IB incidence angle. The surface roughness was analyzed; the modification with the smoothest surface was observed for an IB incidence angle of 45°. This modification affected the LC alignment state of the PEG film, as demonstrated by the polarized optical microscopy analysis with pre-tilt angle measurements. Furthermore, for the same IB incidence angle, the residual DC measured using the capacitance–voltage curves was extremely low. Hence, a PEG film irradiated with an IB incidence angle of 45° could be a suitable LC alignment layer.     

Electro-optical effects of anchoring transition in polymer dispersed liquid crystal films

Two groups of polymer dispersed liquid crystal films have been studied, one with a fixed cell thickness but varying liquid crystal (LC) concentrations and the other with a fixed LC concentration but varying cell thicknesses. A sudden decrease in transmittance with increasing temperature was observed for films whose LC domain sizes were comparable to their cell thicknesses. In particular, spontaneous alignment of LC directors was observed below ∼20°C when LC domains were formed spanning the space between upper and lower indium tin oxide-coated glass substrates. With increasing temperature, this axially aligned homeotropic configuration changed gradually into homogeneous configurations. We believe that the sudden decrease in transmittance originated from the anchoring transition at the glass substrates and polymer walls. In addition, it has been found that the intensity of ultra violet irradiation has a strong effect on the director configuration of LC domains, and that the cure temperature affects the anchoring transition temperature significantly.     

Light exposure dependence of molecular orientation of glassy polyfluorene layers formed on photo-aligned polyimide films

We have investigated the molecular orientation of glassy poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) layers formed on photo-aligned polyimide films with different in-plane anisotropy. The polyimide contains azobenzene in the backbone structure (Azo-PI), allowing us to control the in-plane anisotropy of the film by varying linearly polarized light (LP-L) exposure. The glassy PFO layers (30 nm thick) were obtained by annealing the samples at the liquid crystalline phase of PFO and then quenching them to room temperature. The degree of alignment of PFO was assessed by the polarization ratio of photoluminescence (PL). The PL polarization ratio increased rapidly with the LP-L exposure, and it reached 10 at 2.8 J/cm². Beyond this LP-L exposure, it became almost constant around 10.4. This PL polarization ratio was much higher than the absorption dichroic ratio of the underlying Azo-PI film. This result suggests that the degree of alignment of PFO is determined by its liquid crystalline nature. The saturation dependence of the degree of alignment is very useful for fabricating alignment patterns by a simple photo-mask exposure method. We have succeeded in fabricating 3 μm line-and-space alignment patterns of PFO.     

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.     

Twisted nematic LC mode with high electro-optical performance and high thermal endurance formed using IB-irradiated poly(methyl methacrylate) as an alignment layer

We obtained homogeneously aligned liquid crystals (LCs) on ion beam (IB) irradiated poly(methyl methacrylate) (PMMA) by controlling the IB energy. We then examined the LC alignment state using polarized optical microscopy and conducted thermal stability testing. We obtained homogeneous LC alignment at IB energies above 1,400 eV, indicating that strong IB energy facilitates the alignment of LCs on the PMMA surface. This surface was analyzed by atomic force microscopy, and the contact angles (CAs) were measured to elucidate the mechanism of LC alignment. The increased surface energy strengthened the van der Waals interaction between the surface and LCs, thereby inducing stable, homogeneous LC alignment. Electro-optical (EO) characteristics were measured using twisted nematic (TN) LC mode. Compared to LC cells with conventionally used rubbed polyimide (PI), the LC cells with IB-irradiated PMMA exhibited higher thermal budgets and good electro-optical characteristics. These new LC cells have promising potential for advanced LC displays.     

Synthesis and properties of photoalignable aromatic polyesters containing phenylenediacrylate units in their backbones and n‐alkyl moieties in their side groups

A series of poly[oxy(4‐n‐alkyl‐3,5‐benzoate)oxy‐1,4‐phenylenediacryloyl]s (PPDA‐CnBZ polymers) with high molecular weights was synthesized. These polymers exhibit excellent solubility in some common organic solvents and produce good quality films using conventional spin‐casting and drying processes. The polymers are thermally stable up to 357–362 °C in a nitrogen atmosphere; their glass transition temperatures are greater than 121 °C. The photoreactions and photoalignments of the polymers were investigated using ultraviolet‐visible and infrared spectroscopy, and their liquid crystal (LC) alignment properties were examined. The phenylenediacrylate (PDA) chromophores in the polyesters were found to mainly undergo photocyclization upon ultraviolet light irradiation. Irradiation of the polyester films with linearly polarized ultraviolet light (LPUVL) induces preferential orientation of the polymer main chains, while the unreacted PDA chromophores are aligned along the direction perpendicular to the electric vector of the LPUVL. All the films irradiated with LPUVL were found to align LCs in a direction perpendicular to the electric vector of the LPUVL. Moreover, these LC alignments persisted even on irradiated films annealed at temperatures up to 210 °C, which is much higher than the glass transition temperatures of the polyesters. These LC alignment characteristics are due to the anisotropic interactions of the LC molecules with the oriented polymer chains and with the unreacted PDA chromophores. LC alignments on the polyester film surfaces have homeotropic to homogeneous characteristics, depending on the length of the n‐alkyl side group, providing strong evidence that the n‐alkyl side groups of the polyesters play a critical role in determining the pretilt angles of the LCs. The LC pretilt angles were also found to be influenced by the thermal annealing history of the irradiated films. In summary, the excellent properties of the PPDA‐CnBZ polymers make them promising candidate materials for use as LC alignment layers in advanced LC display devices. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1322–1334, 2004     

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.     

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.     

Vertical alignment of liquid crystal on tocopherol-substituted polystyrene films

We synthesised a series of vitamin-based and renewable tocopherol-substituted polystyrene (PTOC#, # = 20, 40, 60, 80 and 100), where # is the molar content of tocopherol 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 higher molar content of tocopherol side group showed vertical LC alignment behaviour. The vertical alignment (VA) behaviour was well correlated with the surface energy value of these polymer films. For example, VA was observed when the surface energy values of the polymer were smaller than about 35.22 mJ/m² generated by the nonpolar tocopherol moiety having long and bulky carbon groups. Good electro-optical characteristics, such as voltage holding ratio and residual DC voltage, and aligning stabilities at 200°C and ultraviolet irradiation of 10 J/cm² were observed for the LC cells fabricated using PTOC100 as a LC alignment layer. Therefore, it was first found that the renewable tocopherol-based materials can produce an eco-friendly vertical LC alignment system.     

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.     

Effects of plasma treatments on correlation between chemical structures of DLC films and liquid crystal alignment

In an effort to obtain an improved liquid crystal (LC) alignment layer for liquid crystal display device applications, amorphous diamond‐like carbon thin films were deposited on ITO‐coated glass substrates by an rf magnetron sputtering technique at room temperature and then treated with plasma in various atmospheres. The polarized images and pretilt angles of the LC cells showed that LC alignment was enhanced by post‐plasma treatments of the films. In Raman and X‐ray photoelectron spectroscopy spectra of the films, an increase in the fraction of sp²‐bonding was observed after post‐plasma treatments of the films. In particular, H₂ plasma‐treated film had the largest fraction of sp²‐bonding at the film surface and showed much improved alignment capabilities. These results suggest that π‐bondings of the sp²‐structure at the surface rather than the bulk play an important role in LC alignment.