Investigation of alignment mechanism of liquid crystal on polyimide Langmuir-Blodgett films by scanning tunnelling microscopy

The homogeneous alignment of a liquid crystal material, 4'-n-octyl-4-cyanobiphenyl (8CB), was achieved by polyimide Langmuir-Blodgett (LB) films. Scanning electron microscopy and scanning tunnelling microscopy measurements show that the alignment of the polyimide LB films with a grooveless surface occurs due to the orientation of the polyimide chains. We directly observe 8CB monolayers on oriented polyimide LB films. We find that the monolayers form a two dimensional crystalline structure and the 8CB molecules are always aligned along the chain direction of the polyimide. The results show that the alignment of 8CB molecules arises by an epitaxial growth on the oriented polyimide LB films.     

Investigation of alignment mechanism of liquid crystal on polyimide Langmuir-Blodgett films by scanning tunnelling microscopy

Abstract

The homogeneous alignment of a liquid crystal material, 4′-n-octyl-4-cyanobiphenyl (8CB), was achieved by polyimide Langmuir-Blodgett (LB) films. Scanning electron microscopy and scanning tunnelling microscopy measurements show that the alignment of the polyimide LB films with a grooveless surface occurs due to the orientation of the polyimide chains. We directly observe 8CB monolayers on oriented polyimide LB films. We find that the monolayers form a two dimensional crystalline structure and the 8CB molecules are always aligned along the chain direction of the polyimide. The results show that the alignment of 8CB molecules arises by an epitaxial growth on the oriented polyimide LB films.     

Textures and defects in lyotropic liquid crystals of ethyl-cyanoethyl cellulose

Textures and defects in ethyl-cyanoethyl cellulose [(E-CE)C]/dichloroacetic acid (DCA) cholesteric liquid crystalline solutions and in (E-CE)C/polyacrylic acid (PAA) composites were observed and studied by polarizing microscopy and electron microscopy. The existence of χ, λ and τ disclinations were observed in the mesophase with disk-like and band-like textures. Pairs of disclinations with different signs were also found in the mesophase with the band-like texture. Domain walls were observed in (E-CE)C/PAA composite films with cholesteric order by TEM. The orientation of polymer chains in the vicinity of the core of the disclinations is discussed.     

INFLUENCE OF THE SOLVENT SWELLING ON MACROMOLECULAR CHOLESTERIC LIQUID CRYSTALLINE STRUCTURE*

Ethyl-cyanoethyl cellulose [(E-CE)C]/cross-linked polyacrylic acid [PAA] molecular compositeswith cholesteric order were prepared. It was found that the macromolecular cholesteric structure was changedwith the swelling of PAA in the composites. The selective reflection of the cholesteric phase shifted to thelonger wavelength and the X-ray diffraction angle shifted to the high angle direction during swelling, whichsuggested that the cholesteric pitch and the number of the layers of ordered (E-CE)C chains in the cholestericphase were increased.     

Macromolecular cholesteric order observed by electron microscopy

The macromolecular cholesteric structure in the ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid [AA] cholesteric liquid crystalline solutions is studied by directly observing the morphology and structure of the ethyl-cyanoethyl cellulose [(E-CE)C]/polyacrylic acid [PAA] using electron microscopy. A periodical lamellar structure is observed in ultrathin slices of the composites with cholesteric order by both transmission electron microscopy (TEM) and low-voltage scanning electron microscopy (LVSEM). It is suggested that the periodical lamellar structure is induced by the twist of the molecular orientation in the cholesteric phase and reflects the structural features of the macromolecular cholesteric phase. The macromolecular cholesteric phase exhibits the twisted ring morphology in the initial stage of the formation of the liquid crystalline phase. The swelling of the ultrathin slices with cholesteric order in water is heterogeneous, which suggests the tight packing of the (E-CE)C chains in the direction of the helix axis in the macromolecular cholesteric phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 439–445, 1998     

UV-driven switching of chain orientation and liquid crystal alignment in nanoscale thin films of a novel polyimide bearing stilbene moieties in the backbone

A novel photosensitive polyimide, poly(4,4'-stilbenylene 4,4'-oxidiphthalimide) (ODPA-Stilbene PSPI) was newly synthesized. The most surprising feature of this PSPI is that the PSPI films irradiated with linear polarized ultraviolet light (LPUVL) can favorably induce a unidirectional alignment of liquid crystals (LCs) in contact with the film surface and further switch the director of the unidirectionally aligned LCs from a perpendicular direction to a parallel direction with respect to the polarization direction of LPUVL by simply controlling the exposure dose in the irradiation process. These LPUVL-irradiated films were found to provide high anchoring energy to LCs, always giving very stable, homogeneous cells with unidirectionally aligned LCs regardless of the LC alignment directions. In the films, the PSPI polymer chains were found to undergo favorably unidirectional orientation via a specific orientation sequence of the polymer chain segments led by the directionally selective trans-cis photoisomerization of the stilbene chromophore units in the backbone induced by LPUVL exposure. Such unidirectionally oriented polymer chains of the films induce alignment of the LCs along the orientation direction of the polymer chains via favorable anisotropic molecular interactions between the oriented polymer chain segments and the LC molecules. In addition, the PSPI has an excellent film formation processibility; good quality PSPI thin films with a smooth surface are easily produced by simple spin-coating of the soluble poly(amic acid) precursor and subsequent thermal imidization process. In summary, this new PSPI is the promising LC alignment layer candidate with rubbing-free processing for the production of advanced LC display devices, including LC display televisions with large display areas.     

PREPARATION AND PROPERTIES OF ETHYL-CYANOETHYL CELLULOSE/POLYACRYLIC ACID COMPOSITE FILMS WITH REFLECTION COLORS*

Ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) becomes a cholesteric liquid crystalline solution withvivid colors when the (E-CE)C concentration is 42 wt%～52 wt%. (E-CE)C/polyacrylic acid (PAA) composites withcholesteric structure were prepared by polymerzing AA in (E-CE)C/AA liquid crystalline solutions. The layers of orderedpolymer chains in the cholesteric phase were inclined during polymerization and the degree of the inclination depended onthe polymerization temperature and the concentration of the solution before polymerization. The cholesteric structure in thecomposites could not be changed when temperature was lower than 100℃. Cross-linking of the PAA in compositesimproved their water-resistance. The cholesteric order of the composites without cross-linking was destroyed when theywhere immersed in water. The color derived from the selective reflection of the cholesteric phase of the cross-linkedcomposites turned from blue to red after the composites absorbed water. The color of the composites could be returned to theoriginal one when the absorbed water was removed from the swollen composites.     

Is the alignment of nematics on a polymer slab always along the rubbing direction? A molecular dynamics study

ABSTRACT

We have studied the alignment and molecular organisation within a thin film of the popular nematic 5CB sandwiched between two flat polymer slabs, examining the effect of polymer chemical nature and morphology with atomistic molecular dynamics simulations. We have chosen two common polymers: polystyrene (PS) and polymethylmethacrylate (PMMA), either with their chains in random coil conformation (disordered) or with chains unidirectionally stretched (ordered). We found that, independently on the arrangement of the chains, both surfaces align planarly the liquid crystal, in accord with experimental observation. Moreover, while 5CB molecules align along the chains stretching direction of the PMMA ordered surface, on the combed PS surface they arrange on average perpendicularly to the stretching direction. This behaviour is attributed to the chemically specific interactions between the respective aromatic moieties of PS and 5CB.     

Effects of external fields on macromolecular cholesteric phase

Effects of external fields such as magnetic field and boundary conditions on supramolecular structure, molecular arrangement and the texture of the ethyl-cyanoethyl cellulose cholesteric liquid crystalline solutions were investigated. It was found that the molecules of (E-CE)C are oriented to perpendicular to the magnetic field and the diamagnetic anisotropy of (E-CE)C is negative. With homeotropic anchoring boundary condition, the molecules are aggregated with focal-conics arrangement the molecules are aggregated with planar arrangement with homogeneous anchoring boundary condition. The effects of the external field on the orientation of the cholesteric phase were influenced by the concentration of the solution because the twist power of the cholesteric was varied with the concentration. And the effects are also restrains by the surface tension of the interphase.     

Influence of the remanent polarisation on the liquid crystal alignment in composite films of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and a cyanobiphenyl-based liquid crystal

Polymer-dispersed liquid crystals (PDLCs) of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and nematic 4-cyano-4?-n-hexylbiphenyl (6CB) or 4-cyano-4?-n-pentylbiphenyl (5CB) were prepared to study the effect of the remanent polarisation of the polymer on the liquid crystal alignment. We measured the macroscopic alignment of the liquid crystal molecules in the thickness direction by means of Infrared Transition-Moment Orientational Analysis. Electrical poling at 100 V/µm caused an increased order parameter up to 0.15. After subsequent annealing above the nematic-to-isotropic phase-transition temperature, the order parameter was reduced to 0.02. Nevertheless, the order parameter was still higher than for non-poled film indicating a slight orientation in thickness direction. Both values are lower than those expected from model calculations. In agreement with dielectric measurements, we attribute this result to the shielding effect of mobile charge carriers within the liquid crystal inclusions.     

乙基氰乙基纤维素/交联聚丙烯酸复合物膜的溶胀行为

研究了乙基氰乙基纤维素 [(E CE)C] 交联聚丙烯酸 [PAA]胆甾相液晶复合物膜的厚度以及膜的组成对膜在水中的溶胀行为的影响 .复合物膜越厚则达到溶胀平衡所需要的时间越长 ,但是其最大溶胀率是相同的 .复合物膜的最大溶胀率先是随着 (E CE)C浓度的增加而增加 ,当 (E CE)C的浓度大于 5 1wt%的时候 ,复合物膜的最大溶胀率几乎不再发生变化 .复合物膜的交联密度越大 ,其最大溶胀率越小 ,溶胀速率也随着膜的交联 (点 )密度的增加而减小 .研究还发现复合物膜的交联 (点 )密度越大 ,其溶胀前后最大选择性反射光波长的位移也越小 .     

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.     

Crystal structure of friction-transferred poly(2,5-dioctyloxy-1,4-phenylenevinylene)

Poly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV) was found to form a highly oriented film by a friction-transfer technique. Structural investigation of friction-transferred DOPPV was studied by means of polarized ultraviolet-visible (UV-vis) absorption spectroscopy, polarized photoluminescence (PL) spectroscopy, and synchrotron-sourced grazing incident X-ray diffraction (GIXD) analysis. The polarized UV-vis absorption and PL spectra indicate clear axial alignment. DOPPV backbones in friction-transferred film are highly aligned along the drawing direction of the friction-transfer. Further information of the molecular arrangement in friction-transferred DOPPV film was investigated by both the out-of-plane and the in-plane GIXD analyses with synchrotron source. The DOPPV molecules in friction-transferred films were perfectly arranged three-dimensionally: the backbones aligned along the drawing direction of friction-transfer, the alkyl side chains lay in the film plane, and the planar backbones were arranged parallel to the film surface. Additionally, two neighboring DOPPV molecules along the direction of inter-backbones separation by alkyl side chains were found to be shifted with respect to one another by the mean distance of half of a monomeric repeat.     

Optical anisotropy in solution-cast film of cellulose triacetate

The out-of-plane birefringence and its wavelength dispersion are studied employing solution-cast films of cellulose triacetate (CTA). In solution-cast process, CTA molecules are induced to align in the film plane. Although refractive index is the lowest in the oriented direction for the CTA films stretched more than 110 %, refractive index is found to be the lowest in the normal direction for the unstretched cast film. Attenuated total reflection measurements reveal that in-plane alignment of the acetyl group which provides strong polarizability anisotropy is responsible for the phenomenon. Furthermore, the out-of-plane birefringence is found to increase with increasing wavelength, i.e. extraordinary wavelength dispersion, whereas a stretched CTA film shows ordinary wavelength dispersion. The level of the out-of-plane birefringence in cast films depends on the preparation conditions, which is predictable considering the evaporation rate. Moreover, it is demonstrated for the first time that the out-of-plane birefringence and its wavelength dispersion can be modified by addition of a certain plasticizer such as tricresyl phosphate (TCP). During the evaporation, TCP molecules orient in the film plane accompanying the orientation of CTA chains by intermolecular orientation correlation, called nematic interaction. This technique will widen the scope of material design of retardation films because there are numerous liquid compounds having strong polarizability anisotropy.     

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.     

Ca+RBr→CaBr+R(R=CH3,C2H5,n-C3H7)反应的矢量相关和产物的转动取向

The quasiclassical trajectory method is used to study the vector correlations of the reactions Ca+RBr (R=CH3, C2H5 and n-C3H7Br) and the rotational alignment of product CaBr. The product rotational alignment parameters at di?erent collision energies and the vector correlations between the reagent and product are numerically calculated. The vector correlations are described by using the angle distribution functions P(θr),P(φr), P(θr, φr) and the polarization-dependent differential cross sections (PDDCSs). The peak values of P(θr) of the product CaBr from Ca+CH3Br are larger than those from Ca+C2H5Br and Ca+n-C3H7Br. The peak of P(θr) atφr = 3π/2 is apparently stronger than that at φr= π/2 for the three reactions Ca+RBr. The calculation results show that the rotational angular momentum of the product CaBr is not only aligned, but also oriented along the direction which is perpendicular to the scattering plane.The product CaBr molecules are strongly scattered forward. The orientation and alignment of the product angular momentum will affect the scattering direction of the product molecules to varying degrees.     

Effects of temperature on the alignment and electrooptical responses of a nematic nanoscale liquid crystalline film

The surface-induced alignment and electrooptical (EO) dynamics of a 50-nm-thick liquid crystalline (4-n-pentyl-4'-cyanobiphenyl; 5CB) film were studied at three temperatures: 25 and 33 degrees C (near the crystalline-nematic and nematic-isotropic transition temperatures, respectively) and 29 degrees C (a median temperature in the stability region of the nematic phase). The ZnSe surfaces that entrap the liquid crystal (LC) film have been polished unidirectionally to produce a grooved surface presenting nanometer-scale corrugations, a structure that induces a planar and homogeneous orientation in the nematic phase. The present work attempts to understand the influences of temperature on the surface-induced alignment and corresponding EO dynamics of the material. Step-scan time-resolved spectroscopy measurements were made to determine the rate constants for the electric-field-induced orientation and thermal relaxation of the 5CB film. The field-driven orientation rates vary sensitively with temperature across a range that spans the stability limits of the nematic phase; the relaxation rates, however, vary very little across this same temperature range. We propose that these differences in LC behavior arise as consequence of the interplay of the temperature dependence of the elastic constants, viscosity, and degree of orientational order of the LC medium. A simple theoretical model provides some understanding of these behaviors.     

Controlled growth of micropatterned, oriented calcite films on a self-assembled multilayer film

A micropatterned multilayer film, which was fabricated from layer-by-layer electrostatic self-assembly of nitrodiazoresin (NDR)/poly(acrylic acid) (PAA) followed by photolithography, was utilized as a structured template for the biomimetic mineralization of calcium carbonate. Micropatterned CaCO3 films consisting of regularly aligned calcite crystals oriented in the <104> direction were selectively deposited on the patterned NDR/PAA multilayer film.     

Ordering rigid rod conjugated polymer molecules for high performance photoswitchers

Molecules of a rigid rod conjugated polymer, a derivative of poly(para-phenylene ethynylene)s with thioacetyl end groups (TA-PPE), were well aligned by drop-casting the polymer solution onto the friction-transferred poly(tetrafluoroethylene) substrates. TA-PPE molecules were found to be exactly oriented with their conjugated backbones along the PTFE sliding direction. Photoresponse characteristics based on the uniaxially ordered film were significantly improved compared to those of devices with the disordered film. For example, the switch on/off ratio of the photoswitchers with aligned molecules was as high as 330-400, while that of devices without alignment was only 8-12. It was due to the efficient carrier transport along the highly aligned polymer films, in which the molecules of TA-PPE oriented along the carrier transport direction of the devices.     

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.