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.     

Theoretical modeling of the benzoic acid adsorption on the GaAs (001)-β2(2 × 4) oxidized surface

We describe a computational model of benzoic acid adsorbed on the most abundant and technologically important GaAs surface. The performances of many electronic devices based on organic layers deposited on semiconductor surfaces, critically depend on the quality of the layer, and thus on the features of the organic/inorganic bonds. Since very few is known about the atomic structure of such interfaces, theoretical modeling plays a central role in understanding these systems at the microscopic scale. We have optimized the structures of several clusters mimicking the unoxidized and oxidized GaAs (001) surface, using them to study the preferred arrangements of adsorbed benzoic acid molecules. The largest clusters were also used to investigate the cooperative effects between two adsorbed molecules, obtaining the most likely structure for a perfectly packed layer. Finally, we show the correlation of a microscopic observable, namely the energy of the lowest lying empty orbital concentrated on the organic moiety, with the electron affinity measured for para-substituted benzoic acids adsorbed on GaAs.     

2-D array photonic crystal sensing motif

We have developed the first high-diffraction-efficiency two-dimensional (2-D) photonic crystals for molecular recognition and chemical sensing applications. We prepared close-packed 2-D polystyrene particle arrays by self-assembly of spreading particle monolayers on mercury surfaces. The 2-D particle arrays amazingly diffract 80% of the incident light. When a 2-D array was transferred onto a hydrogel thin film showing a hydrogel volume change in response to a specific analyte, the array spacing was altered, shifting the 2-D array diffraction wavelength. These 2-D array photonic crystals exhibit ultrahigh diffraction efficiencies that enable them to be used for visual determination of analyte concentrations.     

Surface characterization and liquid crystal alignment behavior of comb-like poly(oxyethylene)/poly(3-hexylthiophene) blend films

The blend surfaces of poly[oxy(n-decylsulfonylmethyl)ethylene] (CH(3)-10SE) and poly (3-hexylthiophene) (P3HT) with different weight ratios were prepared by spin coating the polymer solution mixtures. In this study, their surface properties such as surface morphology, chemical composition, molecular structure, and wettability were systematically studied and correlated with liquid crystal (LC) alignment behaviors on the blend films. Therefore, we found that CH(3)-10SE part with a well-ordered side chain structure predominantly affects the both of wettability and LC alignment behavior of the blend films while there was no clear association between the wettability and the LC alignment behavior.     

Photoswitching properties of photonic band gap material containing azo-polymer liquid crystal

A photochemically tunable photonic crystal was prepared by infiltration of the polymer liquid crystal (LC) having azo-chromophores in a SiO₂ inverse opal structure. The SiO₂ inverse opal film infiltrated with the polymer LC reflected a light corresponding to the periodicity as well as the refractive indices of the inverse opal structure. Linearly polarized light irradiation caused the shift of the reflection band to longer wavelength more than 15 nm. This is caused by the formation of uniaxially anisotropic molecular orientation of the polymer LC. The switched state was stable under interior light, and reversible switching of the reflection band can be achieved by the linearly and circularly polarized light irradiation. This photoswitching property will be suitable not only for various optical materials, but also for introduction of defects in the photonic crystals.     

Photo-reversible liquid crystal alignment using azobenzene-based self-assembled monolayers: comparison of the bare monolayer and liquid crystal reorientation dynamics

Photosensitive surfaces treated to have in-plane structural anisotropy by illumination with polarized light can be used to orient liquid crystals (LCs). Here we report a detailed study of the dynamic behavior of this process at both short and long times, comparing the ordering induced in the bare active surface with that of the LC in contact with the surface using a high-sensitivity polarimeter that enables detailed characterization of the anisotropy of the active surface. The experiments were carried out using self-assembled monolayers (SAMs) made from dimethylaminoazobenzene covalently bonded to a glass surface through a triethoxysilane terminus. This surface gives planar alignment of the liquid crystal director with an azimuthal orientation that can be controlled by the polarization of actinic light. We find a remarkable long-term collective interaction between the orientationally ordered SAM and the director field of the LC: while an azobenzene based SAM in contact with an isotropic gas or liquid relaxes to an azimuthally isotropic state in the absence of light due to thermal fluctuations, an orientationally written SAM in contact with LC in the absence of light can maintain the LC director twist permanently, that is, the SAM is capable of providing azimuthal anchoring to the LC even in the presence of a torque about the surface normal. We find that the short-time, transient LC reorientation is limited by the weak azimuthal anchoring strength of the SAM and by the LC viscosity.     

Nematic liquid crystal gyroids as photonic crystals

ABSTRACT

We demonstrate nematic and cholesteric liquid crystal (LC) gyroids and show their photonic properties as photonic crystals by using numerical modelling. The LC gyroids are designed as composite optical materials, where we take one labyrinth of passages to be a solid dielectric, whereas the other (complementing) labyrinth of passages is taken to be filled by chiral or achiral nematic LC, with the intermediate gyroid surface imposing homeotropic (perpendicular) surface anchoring. The nematic inside the gyroid matrix is shown to exhibit a variety of possible orientational profiles which are characterised by complex networks of topological defects – from ordered, semi-ordered, to completely disordered. The diversity of possible nematic states is shown to lead to a rich structure of photonic bands, which can be tuned by the LC volume fraction and the cholesteric pitch, including control over full – direct and indirect – band gaps.     

A Chiral Self‐Assembled Monolayer Derived from a Resolving Agent and its Performance as a Crystallization Template for an Organic Compound from Organic Solvents

A new chiral nonracemic thiol derived from a popular acidic resolving agent that incorporates a cyclic disubstituted phosphate group (phencyphos) has been prepared in enantiomerically pure form. The stereochemistry and absolute configuration were established by performing a single‐crystal X‐ray structural analysis of a synthetic intermediate. The thiol compound was used for the preparation of self‐assembled monolayers (SAMs) on both monocrystalline and polycrystalline metallic gold, which have very different surface roughness. The monolayers were used to promote the nucleation and growth of crystals from nonaqueous solutions of an organic molecule (the parent phencyphos) of similar structure to the compound present in the monolayer. The template layers influence the nucleation and growth of the phencyphos crystals despite the lack of two‐dimensional order in the surfaces. Heterogeneous nucleation of phencyphos takes place upon evaporation of either CHCl₃ or isopropanol solutions of the compound on the SAM surfaces, where the evaporation rate merely influences the size and homogeneity of the crystals. The roughness of the surface also plays an important role; the polycrystalline gold produces more homogeneous samples because of the greater number of nucleation sites. Clear evidence for nucleation and growth on the surfaces is shown by scanning electron microscopy. The variation in crystal form achieved by using different surfaces and solvents suggests that the layers are applicable for the preparation of organic crystals from organic solutions.     

Transportation of a microdroplet on an oriented liquid crystal surface

Wetting phenomena play important roles in several technological applications and in many physical and biological thin‐film phenomena, such as wetting, adhesion and friction. One of key issues of these studies is to control the surface energy (or wettability) dynamically for liquid transportation. We have developed a liquid crystal (LC) surface for use as a transport substrate since we expected that the surface energy of an LC surface can be controlled rapidly using an electric field. The rapid control of the polarisability (or wettability) of a liquid crystalline surface by an electric field has been demonstrated, together with the transportation of a liquid microdroplet.     

Dynamics of vacancy defects in 2-D crystalline monolayers under chiral smectic thin films studied by scanning tunnelling microscopy

Scanning tunnelling microscopy (STM) can be used to image adsorbed organic molecules in real space and real time. The technique seems especially well suited for imaging 2-D crystalline monolayers formed under liquid crystal films. In addition to observing perfect 2-D crystals, STM provides the ability to observe crystal defects, and to observe how these defects evolve over time. In this study two different vacancy defects in 2-D lamellar monolayers of chiral liquid crystal molecules under bulk smectic films were observed in situ. Both vacancies showed dynamic behaviour and an unexpected transport anisotropy.     

In situ self-assembled homeotropic alignment layer for fast-switching liquid crystal devices

We propose a novel method for homeotropic alignment of liquid crystals (LCs) utilising in situ self-assembly of a low concentration of 4-(4-heptylphenyl)benzoic acids that form hydrogen bond with the indium tin oxide (ITO) substrates. Stable homeotropic alignment in the LC device is achieved with a simple mixing process of benzoic acid derivative in LC media, and it yields electro-optical performance similar to that achieved with the conventional alignment method using polyimides. It is experimentally confirmed that an ultrathin self-assembled molecular layer of 4-(4-heptylphenyl)benzoic acid formed by hydrogen bonding on ITO substrate makes it possible to attain a reliable homeotropic alignment of LCs. Furthermore, this simple approach provides a cost-effective and stable LC alignment layer with fast response time and thermal stability.     

Weak surface anchoring energy of 4-cyano-4'-pentyl-1,1'-biphenyl on perfluoropolyether Langmuir-Blodgett films

Functional director alignment layers are needed for high performance liquid crystal displays (LCDs). Reported herein is a novel polymer material for LC alignment, namely, perfluoropolyether (PFPE), which exhibits a weak surface anchoring energy for bend deformation and is amenable to simple fabrication of grooved surfaces by soft lithography, a surface topography desired for multistable LCDs. Liquid crystal optical cells fabricated using Langmuir-Blodgett films of PFPE (of variable thickness) exhibited weak surface anchoring energies on the order of 10(-5) Jm2 for the nematic liquid crystal 4-cyano-4'-pentyl-1,1'-biphenyl with no dependence on film thickness.     

pH-Driven adsorption and desorption of fatty acid at the liquid crystal–water interface

The pH-driven adsorption and desorption of fatty acid monolayers at the liquid crystal (LC)–water interface were studied. We doped fatty acids (stearic acid, palmitic acid, myristic acid, dodecanoic acid, and decanoic acid) into 4-cyano-4′-pentylbiphenyl (5CB), and employed sessile LC droplets as our experimental platform. Under a crossed polariser, the LC droplets displayed a bright flower bud-shaped texture at low pH, whereas at high pH, they exhibited a bright four-brush appearance due to desorption of the adsorbed fatty acids at the LC–water interface. Furthermore, we identified the critical transition pH of various concentrations of stearic acid and other fatty acids featuring distinct tail lengths. Based on the interfacial behaviour, we propose a new method to estimate the pK_a of fatty acids, which opens up new possibilities for simple, precise, and reliable measurement of the pK_a of other carboxylic acids. The findings presented herein will greatly facilitate the understanding of the interfacial behaviour of amphiphiles at the oil–water interface.     

Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface

Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data are discussed.     

Smectic liquid crystal alignment using mechanically rubbed n-octadecylsiloxane self-assembled monolayers

In recent years a variety of techniques has appeared for the fabrication and manipulation of self-assembled monolayers (SAMs). This development now offers new tools for the study and control at the molecular level of the interaction of liquid crystals (LCs) with solid surfaces, a research area of great importance for liquid crystal applications. In this paper we show that mechanically rubbed octadecylsiloxane SAMs generate a novel surface alignment of LCs in which the in-plane surface anisotropy usually accompanying rubbing is operative, but only for smectics in which the mean molecular long axis, [ncirc], is tilted from the layer normal. On our SAMs smectic phases align with the layers parallel to the SAM surface, and in tilted smectics the surface component of [ncirc] is along the rubbing direction. This anisotropy is absent in the nematic phases which align with [ncirc] strictly normal to the surface. This behaviour can be understood in terms of a rubbed SAM monolayer surface, which is low energy, molecularly smooth, and rendered anisotropic by the rubbing. UV irradiation of rubbed SAMs gave excellent planar alignment ([ncirc] parallel to the surface). This type of control over LC alignment has not been previously reported.     

带隙可调各向同性蛋白石光子晶体的制备与研究

用旋涂法将聚苯乙烯微球组装成光子晶体,研究了此光子晶体的特点,并分析了在单一微球粒径下旋涂参数对光子带隙的影响.结果表明:旋涂法制备的光子晶体具有各向同性特点,其光子带隙由旋涂参数决定.光子晶体的反射波段取决于乳液中微球的质量分数,而反射强度取决于旋涂层数.因此,在设计光子晶体时,可以根据需要,通过微球的质量分数和旋涂...     

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.     

Anchoring energies of liquid crystals measured on surfaces presenting oligopeptides

We report a methodology that permits quantitation of the azimuthal anchoring energy of the nematic liquid crystal 4-cyano-4'-pentyl-biphenyl on surfaces patterned with oligopeptides. The oligopeptide (IYGEFKKKC), an optimized substrate for the Src protein kinase, was covalently immobilized via the terminal cysteine to monolayers of amine-terminated tetra(ethylene glycol) formed on gold films. The measurements of anchoring energies, which were based on a torque-balance method, revealed a systematic decrease in anchoring energy from 3.7 +/- 0.6 microJ/m2 with increasing surface density of oligopeptide. We calculate that a mass density of oligopeptide of less than 1 ng/cm2 can lead to a measurable change in the anchoring energy of the nematic liquid crystal. These results suggest that measurements of anchoring energies of liquid crystals on surfaces may offer the basis of quantitative and label-free methods for detecting biomolecules on surfaces.     

Brewster angle microscopy of calcium oxalate monohydrate precipitation at phospholipid monolayer phase boundaries

The precipitation of calcium oxalate monohydrate (COM) at phospholipid monolayers confined to the air/water interface is observed in situ with the aid of Brewster angle microscopy. COM crystals appear as bright objects that are easily identified and quantified to assess the effects of different conditions on crystallization. Crystal precipitation was monitored at monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in liquid condensed (LC) and liquid expanded (LE) phases. Within the LC phase, higher pressures reduce the incidence of crystallization at the interface, implying that within this phase precipitation is enhanced by higher compressibility or fluidity of the monolayer. Precipitation at biphasic LC/LE and LE/gas (G) monolayers was also studied. COM appears preferentially at phase boundaries of the DPPC LC/LE and LE/G monolayers. However, when an LC/LE phase boundary is created by two different phospholipids that are phase segregated, such as DPPC and 1,2-dimyristoyl-sn-glycero-3-phosphocholine, crystal formation occurs away from the interface within the DPPC LC phase. It is suggested that COM growth at phase boundaries is preferred only when there is molecular exchange between the phases.     

Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment

The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.