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.     

Smectic C* layer directional instabilities in cells with twist geometry

We have investigated the formation and structure of horizontal chevrons, as well as the reorientation dynamics of smectic layers under applied asymmetric electric fields in cells with a twist geometry. The tilted layer structure of horizontal chevron domains is found to be rotated by an angle approximately equal to the twist angle alpha, as compared with parallel rubbed substrates, alpha = 0°. The time of horizontal chevron formation decreases slightly with increasing twist angle. The smectic layer reorientation under application of time-asymmetric electric fields is found to be enhanced for reorientation into the direction of twist, while it is hindered for reorientation out of the direction of layer twist. Increasing the twist angle results in a basically linear increase/decrease in the reorientation velocity, depending on field asymmetry direction. The electro-optic behaviour of twist cells with inclined smectic layers is outlined and compared with measurements performed on cells with monostable, parallel anchoring conditions.     

Smectic C* layer directional instabilities in cells with twist geometry

We have investigated the formation and structure of horizontal chevrons, as well as the reorientation dynamics of smectic layers under applied asymmetric electric fields in cells with a twist geometry. The tilted layer structure of horizontal chevron domains is found to be rotated by an angle approximately equal to the twist angle alpha, as compared with parallel rubbed substrates, alpha = 0°. The time of horizontal chevron formation decreases slightly with increasing twist angle. The smectic layer reorientation under application of time-asymmetric electric fields is found to be enhanced for reorientation into the direction of twist, while it is hindered for reorientation out of the direction of layer twist. Increasing the twist angle results in a basically linear increase/decrease in the reorientation velocity, depending on field asymmetry direction. The electro-optic behaviour of twist cells with inclined smectic layers is outlined and compared with measurements performed on cells with monostable, parallel anchoring conditions.     

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.     

Influence of rubbing conditions of polyimide alignment layer on optical anisotropy of immobilized liquid crystal film

The relationship between the molecular orientation of a rubbed polyimide film (alignment layer) and that of mesogens in a photopolymerized liquid crystal (LC) coated on the film has been investigated using optical measurements. LC monomers were deposited on the alignment layer and were aligned in one direction. The LC monomers were subsequently photocured. Alignment layers under various rubbing conditions were prepared. It was found that the inclination angle of the refractive index ellipsoid and the optical retardation of photopolymerized LC films are strongly related to the optical anisotropy of the rubbed polyimide film. The photopolymerized LC film exhibited high optical anisotropy when alignment layers with an inclination angle of the refractive index ellipsoid smaller than 6° were used.     

Flow behaviours of liquid crystal droplets on polyimide alignment layers

The flow behaviours of liquid crystal droplets on polyimide alignment layers and during assembling between two substrates have been directly observed. The droplet shape became elliptical with time on the rubbed polyimide layer, where the major axis of the elliptical droplet was parallel to the rubbing direction. Rubbing enhanced the wettability between the liquid crystal and the polyimide layer. During the assembling process, the liquid crystal droplets elliptically splayed out between two substrates assembled antiparallel. The liquid crystal molecules preferentially flowed parallel to the rubbing direction in a two-step flow mode; the droplet diameter slowly increased at the first step, and then it rapidly increased at the second step. The two-step flow of the droplet proved to be due to the thickness of the droplet dependent on the rubbing strength.     

Molecular orientation and alignment of rubbed poly(vinyl cinnamate) surfaces

We observed that weakly and strongly rubbed polyvinyl-cinnamate surfaces align liquid crystal films perpendicular and parallel to the rubbing direction, respectively. Surface-specific sum-frequency vibrational spectroscopy was used to probe molecular orientations and alignments of the rubbed surfaces and provide a molecular-level understanding of the observation.     

Characterization of the alignment of a nematic liquid crystal using half leaky guided modes

The excitation of half leaky guided optical modes to characterize fully the optical tensor profile in a thin liquid crystal layer has been used to evaluate the effect of rubbed polyimide aligning layers on the alignment of a nematic liquid crystal. A cell fabricated with rubbed polyimide alignment surfaces was studied at a wavelength of 632.8 nm. The liquid crystalline layer is sandwiched between a high refractive index top glass plate and a low refractive index glass substrate. Angular dependent reflectivities are recorded using a coupling prism and matching fluid with the same index as the top glass plate. Careful fitting of the predictions from multilayer optics theory to the observed angle dependent polarization conversion and reflectivity data yields the director profile within the liquid crystal layer in great detail.     

Pretilt angle of liquid crystals and liquid-crystal alignment on microgrooved polyimide surfaces fabricated by soft embossing method

In this study, the soft embossing method is proposed to fabricate periodical microgrooved structure on polyimide surfaces. These microgrooved polyimide surfaces are assembled to form liquid-crystal cells. It is found that the director of liquid crystals uniformly aligns along the groove direction even when the groove width is as high as 3 microm. The anchoring energy of these microgrooved polyimide surfaces is higher than that of the typical rubbed surfaces. The pretilt angle of liquid crystals is adjusted by tuning the surface polarity of the polyimide alignment layer, which is identified by the advancing contact angle of water. The surface polarity of polyimide alignment layers is manipulated by simply mixing two kinds of polyimide: a more hydrophilic one and a more hydrophobic one. It is found that the pretilt angle of liquid crystals increases along with the advancing contact angle of water on the alignment layer under the condition of a fixed surface topography.     

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.     

Oriented growth of crystalline pentacene films with preferred a-b in-plane alignment on a rubbed crystalline polymethylene surface

We have achieved a growth of highly oriented crystalline pentacene thin films, with preferred a-b in-plane orientation with respect to the rubbing direction of a rubbed polymethylene surface. The polymethylene thin film, generated on a gold surface by gold-catalyzed decomposition of diazomethane, was annealed and gently rubbed in a fixed direction by a flannelette cloth to serve as an alignment layer during the deposition of pentacene molecules. Various surface analysis techniques, including reflection absorption IR spectroscopy (RAIRS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, grazing incidence X-ray diffraction (GIXD), and atomic force microscopy were used to elucidate the structural details of the polymethylene and the pentacene thin films deposited on it. Two crystalline morphologies of pentacene thin film were observed: the minor one of rod-like molecular crystals having their long axes of the crystals perpendicular to the rubbing direction, and the dominant one of platelet-like and layered crystals having the molecular axes stand near vertical to the surface. Moreover, GIXD revealed that the rubbing on polymethylene indeed induced a preferential azimuthal alignment of pentacene crystallites. The deposition of pentacene at 25 degrees C led to a twin growth of crystallites with the [110] direction predominately aligned perpendicular to the rubbing direction. In contrast, the pentacene deposition at 50 degrees C produced twinned crystallites of lower twin angle and the [120] direction aligned parallel to the rubbing direction.     

Liquid crystal alignment capabilities on rubbed organic solvent soluble polyimide surfaces with trifluoromethyl moieties

High pretilt angles, polar anchoring energy (out of plane-tilt), and surface ordering in the nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) were investigated on rubbed organic solvent soluble polyimide (PI) surfaces with a helical backbone structure and trifluoromethyl moieties. It was found that the pretilt angle of 5CB is about 15° in the wide rubbing region of rubbed soluble PI surfaces with trifluoromethyl moieties attached to the lateral benzene rings. It is suggested that the microscopic surface structure of the polymer contributes to the LC pretilt angle generation at the surface. Also, the polar anchoring energy of 5CB is dependent on the molecular structure of these unidirectionally rubbed soluble PI surfaces. The polar anchoring strength of 5CB on rubbed soluble PI surfaces is as weak with trifluoromethyl moieties attached to the lateral benzene rings weak as when the trifluoromethyl moieties are attached to the polymer backbone. Finally, the polar anchoring energy of 5CB strongly depends on the surface ordering of rubbed soluble PI surfaces.     

Liquid crystal alignment capabilities on rubbed organic solvent soluble polyimide surfaces with trifluoromethyl moieties

High pretilt angles, polar anchoring energy (out of plane-tilt), and surface ordering in the nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) were investigated on rubbed organic solvent soluble polyimide (PI) surfaces with a helical backbone structure and trifluoromethyl moieties. It was found that the pretilt angle of 5CB is about 15° in the wide rubbing region of rubbed soluble PI surfaces with trifluoromethyl moieties attached to the lateral benzene rings. It is suggested that the microscopic surface structure of the polymer contributes to the LC pretilt angle generation at the surface. Also, the polar anchoring energy of 5CB is dependent on the molecular structure of these unidirectionally rubbed soluble PI surfaces. The polar anchoring strength of 5CB on rubbed soluble PI surfaces is as weak with trifluoromethyl moieties attached to the lateral benzene rings weak as when the trifluoromethyl moieties are attached to the polymer backbone. Finally, the polar anchoring energy of 5CB strongly depends on the surface ordering of rubbed soluble PI surfaces.     

Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains

Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2'-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis[omega-[4-(4-cyanophenyl)phenoxy]hexyl] 4,4'-diamino-2,2'-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA--6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39 degrees to 43 degrees, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-theta(c)) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (theta(c)) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -theta(c) pretilt angle with respect to the rubbing direction.     

Liquid crystalline polyfluorenes for blue polarized electroluminescence

A series of 9,9‐dialkyl‐poly(fluorene‐2,7‐diyl)s containing linear and branched alkyl substituents with a M_n of up to 200000 g/mol has been synthesized. Moreover, some of the polymers were end capped with a suitable hole transport functionality, such as a triphenylamine derivative, to improve their charge transport properties and to control the molecular weight. The thermal alignment of these novel polymers on a rubbed polyimide layer led to highly anisotropic film formation with dichroic ratios (absorption parallel and perpendicular to the rubbing direction) of up to 26 in absorption and 21 in emission.     

Effect of pretilt angle on the polar anchoring energy in NLCs on weakly rubbed polyimide surfaces

The polar anchoring strength and pretilt angle generation in nematic liquid crystals (NLCs), on three kinds of rubbed polyimide (PI) surfaces, were investigated. The pretilt angle generated in 4-n-pentyl-4'-cyanobiphenyl (5CB) is large compared with ZLI-4792 (a fluorinated mixture type NLC) for all rubbed PI surfaces. The high pretilt angle in 5CB is attributed to a much larger birefringence and much larger perpendicular component of permittivity. The polar anchoring energy of ZLI-4792 is high compared with 5CB on all rubbed PI surfaces for a weak rubbing strength. It is suggested that the high anchoring energy of ZLI-4792 may be attributed to the low NLC pretilt angle.     

The alignment of nematic liquid crystals on photolithographic micro-groove patterns

Abstract

The alignment of nematic liquid crystals on micro-groove patterns was studied. It has been found that the order of the alignments is determined by the edge shape, spacing, and line pitch of the micro-groove patterns. On coarse patterns, with pitches greater than 2 μm, striped patterns of the liquid crystal alignment were observed using polarized light which manifested different orientations of the liquid crystals on the top, edge, and bottom of the grooves, respectively. On fine patterns, with pitches less than 2 μm, a uniform device-quality alignment has been realized, with which twisted nematic cells were constructed in combination with the rubbed alignment layer on the opposite substrate. Their viewing angle characteristics and tilt orientations of the director were also investigated.     

The alignment of nematic liquid crystals on photolithographic micro-groove patterns

The alignment of nematic liquid crystals on micro-groove patterns was studied. It has been found that the order of the alignments is determined by the edge shape, spacing, and line pitch of the micro-groove patterns. On coarse patterns, with pitches greater than 2 μm, striped patterns of the liquid crystal alignment were observed using polarized light which manifested different orientations of the liquid crystals on the top, edge, and bottom of the grooves, respectively. On fine patterns, with pitches less than 2 μm, a uniform device-quality alignment has been realized, with which twisted nematic cells were constructed in combination with the rubbed alignment layer on the opposite substrate. Their viewing angle characteristics and tilt orientations of the director were also investigated.     

Cell processing on polyimide surface patterned by rubbing

In this study, we prepared a novel rubbed fluorinated polyimide film using a rubbing machine with a rubbing cloth and determined the surface properties of the rubbed film using an atomic force microscope and contact angle measurements. In addition, we evaluated the cell adhesion behavior on the rubbed polyimide film using a phase contrast microscope. Interestingly, a rubbed polyimide surface having a micrometer‐scale grooved pattern was prepared by the rubbing method, and the morphologies of rat primary hepatocytes and human liver cell lines attached to the rubbed surface were three‐dimensional multicellular spheroids, while the cells on an unrubbed surface showed two‐dimensional monolayers. This initial study indicates that the rubbing method without any chemical modification is simple and can easily produce large surface areas, suggesting that the rubbing may become a novel cell culture method. Copyright © 2008 John Wiley & Sons, Ltd.