Single molecule spectroscopy of conjugated polymer chains in an electric field-aligned liquid crystal

Using single molecule polarization spectroscopy, we investigated the alignment of a polymer solute with respect to the liquid crystal (LC) director in an LC device while applying an external electric field. The polymer solute is poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (or MEH-PPV), and the LC solvent is 5CB. The electric field induces a change in the LC director orientation from a planar alignment (no electric field) to a perpendicular (homeotropic) alignment with an applied field of 5.5 x 103 V/cm. We find that the polymer chains align with the LC director in both planar and homeotropic alignment when measured in the bulk of the LC solution away from the device interface. Single molecule polarization distributions measured as a function of distance from the LC device interface reveal a continuous change of the MEH-PPV alignment from planar to homeotropic. The observed polarization distributions are modeled using a conventional elastic model that predicts the depth profile of the LC director orientation for the applied electric field. The excellent agreement between experiment and simulations shows that the alignment of MEH-PPV follows the LC director throughout the LC sample. Furthermore, our results suggest that conjugated polymers such as MEH-PPV can be used as sensitive local probes to explore complex (and unknown) structures in anisotropic media.     

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.     

X-ray study of substrate-induced alignment of a smectic A liquid crystal

Abstract

We have performed a structural study of the liquid crystal (LC) octylcyanobiphenyl (8CB), deposited on gratings and flat surfaces, using high resolution X-ray scattering as a function of film thickness. 8CB is a room temperature smectic A₂, with a layer spacing of 31·6 Å. Glass was used as substrate and treated with either one of the organic surfactants MAP or DMOAP. Surface tension forces cause the liquid crystal molecules to align perpendicularly with respect to the plane of the substrate at the air interface. Competing with the LC-air interface, which is a strong aligner, a grating at the LC-substrate interface produces distortions in the smectic layering with an excess of elastic energy, which favours alignment parallel to the substrate and the grooves. Our purpose was to detect the onset and evolution of parallel alignment as a function of film thickness. The studies used 9 keV (1·403 Å) X-rays focused to a spot size of 2 mm² at the sample position. In-plane scans, which detect the smectic layers perpendicular to the plane of the substrate, were done at angles φ = 0° and 90° with respect to the gratings to ascertain the molecular orientation, at a nominal X-ray incidence angle of α = 0°. In order to observe regions of varying smectic layer orientation within the film, we performed a series of scans where the out-of-plane tilt angle χ changed from 0°, corresponding to scattering in the plane of the film, to 90°, which corresponds to scattering normal to the surface of the film. The results from these scans were fitted to a multilayer model where the orientation of the smectic layers varies as a function of film depth. The analysis confirmed our earlier observations that surface tension at the air interface plays a dominant role in the alignment of the LC molecules.     

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.     

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.     

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.     

Phase separation of polymer-dispersed liquid crystals on a chemically patterned substrate

The surface-induced structure formation of polymer-dispersed liquid crystals (PDLCs) on a chemically patterned substrate was studied for the first time. The patterns on the substrate were successfully transferred to the PDLC film, resulting in alternating LC-rich and polymer-rich phases. This simple approach offers a new means of organizing micrometer-sized LC domains into well-ordered structures in a polymer matrix of PDLCs.     

Langmuir films of flexible polymers transferred to aqueous/liquid crystal interfaces induce uniform azimuthal alignment of the liquid crystal

We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that: (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous–LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir–Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4′-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4′-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous–5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous–5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous–air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones.     

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.     

Study of poly[bis(p-toluene sulfonate) diacetylene] films prepared by a modification of the Langmuir–Blodgett technique

Coherent this films of poly[bis(p-toluene sulfonate) diacetylene] were successfully formed by modified Langmuir–Blodgett techniques using two methods: (i) Photopolymerization of the monomer film at the gas/liquid interface and then transfer to a solid substrate, and (ii) transfer of the monomer film to the solid substrate and subsequent photopolymerization on the substrate itself. The films thus obtained were characterized by traditional force–area isotherms while on pure water subphases. Segments were transferred at either 1 or 10 dyn/cm surface pressure, in different stages of photopolymerization, to glass or germanium substrates. The films on the substrate were characterized by the methods of multiple attenuated-internal-reflection infrared spectroscopy, ellipsometry, contact-potential measurement, and laser Raman spectroscopy. Our results show that the films are multimolecular and about 100 Å thick. Of special interest were the observation of significant anisotropy of oriented dipoles and the ability to obtain excellent spectral data for these very thin oriented films. Raman spectroscopic features are similar to those observed for the bulk polymer, even in the low-frequency region. Polarized Raman spectroscopy confirmed the presence of local anisotropy in these films.     

Growth of highly oriented crystalline polyaniline films by self-organization

Silicon substrates with (100) orientation were modified with amino-silane self-assembled monolayer (SAM) to provide amino (NH(2)) moieties at the substrate surface. Self-organization of polyaniline during chemical polymerization, on this modified surface, leads to the growth of highly oriented films at the substrate-polymer interface. The morphology studied using scanning electron microscopy and atomic force microscopy revealed the formation of polymer film with well faceted pyramidal crystallites. XPS and FTIR spectroscopy were used to analyze the chemical structure of the film. X-ray diffraction measurements show the crystalline nature of the polyaniline, whose lattice parameters are in agreement with the reported values. This study underlines the importance of a SAM in deciding the structure and morphology of the deposited polymer.     

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.     

Liquid crystal-gold nanoparticle composite-modified indium tin oxide (ITO) substrates and their electrochemical characterisation

A simple efficient strategy for the simultaneous synthesis and anchoring of liquid crystal (LC)-stabilised gold nanoparticles (NPs) on indium tin oxide (ITO) substrate is described. A monolayer of 3-mercaptopropyltrimethoxy silane (MPS) compound was formed on ITO and quality of the monolayer was assessed using electrochemical techniques namely cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Gold NP preparation was carried out on this monolayer-modified substrate (and on bare ITO), in a single-step reaction, simply by drop-casting a solution containing an appropriate amount of chloroauric acid and a LC compound possessing a terminal amino group, on the MPS monolayer-modified substrate and heating (70degree) for 2-3 min.. The LC compound served as a reducing agent as well as a capping ligand. LC-capped NPs were chemically anchored onto the ITO substrate through bonding to thiol moiety of the MPS. The CV and EIS analysis of the MPS monolayer showed a complete blocking behaviour for the electron transfer across the electrode/electrolyte interface confirming the formation of a high-quality dense compact monolayer. On the other hand, upon immobilisation of LC-gold NP composite on self-assembled monolayer-modified ITO substrates, both CV and impedance studies showed a small current indicating the gold NP-mediated electron transfer, thus confirming the successful immobilisation of NPs.     

Polarised UV-induced homogeneous alignment for fringe-field switching liquid crystal display with a new azobenzene monomer

A novel preparation method of homogeneous alignment polymer film (HAPF) was proposed by polymerisation of the monomer, 4,4?-di-methacryloyl-oxy azobenzene (4,4?-DMOAz), being dissolved in the liquid crystal (LC) material of positive dielectric anisotropy. For obtaining the homogeneous alignment, exposure of the polarised UV light was carried out to the LC cell above the nematic to isotropic transition temperature of the LC material. The fringe-field switching (FFS) mode LC cell with the HAPF formed from the monomer 4,4?-DMOAz (FFS-HAPF-LC cell) exhibited enough level of alignment state, electro-optical and response properties compared with the FFS-LC cell carrying the conventional polyimide-type alignment layer. FFS-HAPF-LC cell can be expected to be useful for next-generation displays such as flexible LC displays.     

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.     

Fabrication of vertically aligned liquid crystal cell without using a conventional alignment layer

We propose a novel method to fabricate a vertical alignment (VA) of liquid crystal (LC) molecules without using a conventional alignment layer such as polyimide film. The method produces the vertical alignment polymer layer (VAPL) by polymerisation of a monomer or mixed monomers including in the LC layer above T_NI of the LC material. The VA mode LC cell with the VAPL (VAPL-LC cell) produced from the mixed monomers of acrylic acid 4-(4?-octyloxy-biphenyl-4-yloxy)-butyl ester and 1,2-bis-(4-methacryloxy-phenyl)-2,2-dimethoxy-ethane-1-one exhibited enough level of alignment state and electro-optical property with high voltage holding ratio. We can expect that the VAPL-LC cell is useful for next-generation displays such as flexible liquid crystal displays because the method does not need the process including high temperature over 200°C.     

Study of polymer-stabilised blue phase liquid crystal on a single substrate

One outstanding feature of the polymer-stabilised blue phase (PSBP) is that it is unnecessary to form an alignment film, which requires a high-temperature baking process. Therefore, PSBPs may enable flexible liquid crystal displays (LCDs) on plastic substrates. In this study, polymer stabilisation of a blue phase (BP) on a single substrate was performed without using a conventional sandwich-type cell, and the electro-optical properties are demonstrated to be similar to those of a sandwich-type PSBP LCD cell. It was experimentally shown that the oxygen which inhibits radical polymerisation is required to be excluded in order to complete the polymer stabilisation in blue phase.     

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.     

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.     

An electrically light-transmittance-switchable film with a low driving voltage based on liquid crystal/polymer composites

ABSTRACT

As a typical class of electrically light-transmittance-switchable (ELTS) composites materials, polymer dispersed liquid crystal (PDLC) films have been widely used in displays, smart windows, light shutters, etc. However, the commercialised PDLC film still requires a comparatively high voltage to maintain its transparent state, leading to huge power consumption and even a potential safety risk. In this regard, we proposed a ‘heat followed UV’ stepwise polymerisation strategy for preparing a kind of ELTS film with a low driving voltage (~20.7 V) through constructing a coexistent system of polymer dispersed and polymer stabilised liquid crystal (PD&SLC). In this new PD&SLC system, vertically orientated polymer networks were formed within LC domains to induce the vertical alignment of LC, thereby reducing the driving voltage. Also, the as-made PD&SLC film exhibited good flexibility due to the high content of polymer. Moreover, the effects of the liquid crystalline polymerisable monomers content on the polymer morphologies as well as the electro-optical properties of the as-made PD&SLC films were elaborately investigated.