Phase transition behavior and molecular orientation of oligo(9,9 '-dioctylfluorene-alt-bithiophene)

A novel conjugated oligomer, oligo(9,9'-dioctylfluorene-alt-bithiophene) (OF8T2), was found to exhibit a unique phase transition between crystalline and liquid-crystalline states, and a liquid-crystalline glass was easily generated, offering better TFT device performance. In thin films, upon annealing the OF8T2 molecules oriented preferentially with their planes of conjugation being normal to the substrate, and both film thickness and annealing temperature were critical to the film morphology and the molecular orientation. When the OF8T2 film was deposited on a rubbed polyimide surface and annealed, the molecules aligned their long axes along the rubbing direction.

Film Morphology and Molecular Orientation in Oligothiophene-fluorene Films

The effects of processing conditions on film morphology and molecular orientation were studied for a novel conjugated fluorene-bithiophene oligomer, oligo(9,9-dioctylfluorene-alt-bithiophene) (OF8T2). Depending on the method of film preparation, OF8T2 molecules adopt different orientations in the films. X-ray diffraction peak at 4.9 degrees of the OF8T2 film deposited from petroleum ether/dichloromethane mixture is attributed to a layering distance between sheets of OF8T2 chains, which are separated by the octyl side chains. Preferred orientation is clearly inferred through the absence of peaks corresponding to pi-pi stacking.

Effect of end substitution on optical properties and molecular orientation of distyrylbenzene derivatives in thin film

Three distyrylbenzene (DSB) derivatives were vacuum-evaporated on a (001) surface of KBr. DSB derivative molecules formed nuclei by interaction between the electron donative methoxyl group and Br- ion of the substrate crystal and oriented their longitudinal axis obliquely to the substrate surface. The peak shift between the emission peaks of solution and film decreased depending on the number of substituent. This phenomenon was originated to reduction of molecular interaction between neighboring molecules by steric hindrance of end substituents. (C) 2000 Elsevier Science S.A. All rights reserved.

Molecular orientation of copper phthalocyanine in thin films and their gas-sensing properties

Copper phthalocyanine derivative Langmuir-Blodgett (LB) films were prepared by vertical dipping and horizontal lifting methods. Molecular orientation of copper phthalocyanine derivative in thin films was studied by polarized UV-Vis spectra. The relationship between the molecular orientation of copper phthalocyanine in LB films and their gas-sensing properties was investigated.

Molecular orientation of copper phthalocyanine derivative ins copper phthalocyanine-Fe2O3 nanoparticles alternating LB films

Copper phthalocyanine-Fe2O3 nanoparticles alternating thin films were fabricated by Langmuir-Blodgett technique. Molecular orientation of [4-(4'-benzyloxy phenyl sulfonyl)phenoxy]-tris-4-(2,4-di-t-phenoxy) phthalocyanine copper (II) in its alternating LB films, deposited at different conditions,was studied by polarized UV-Vis spectra. The tilt extent of the copper phthalocyanine molecule omits LB films increases with the surface pressure of the subphase increasing on the same subphase, or with Fe2O3 concentration decreasing at the same pressure. The orientation of the copper phthalocyanine derivative is important for the gas-sensing properties. The bigger the tilt extent of the phthalocyanine molecule is, the greater the sensitivity of the film is.

Study of molecular orientation in Langmuir-Blodgett films by FTIR

The structure information of orientation and packing of molecular chains can be obtained from infrared transmission and reflection-absorbance (RA) spectra. In the present paper, on the basis of Umemura et al., their FORTRAN program of minicomputer was developed and can be run on 486 personal computer. By comparison of infrared transmission and RA intensities, surface enhancement factors and molecular orientation angle were calculated using the above program, and the influence of complex refractive index, angle of incidence, and thickness of LB film were discussed. These results are consistent with that of Umemura et al.

DETERMINATION OF THE MOLECULAR-ORIENTATION OF A PHTHALOCYANINE DERIVATIVE IN A LANGMUIR-BLODGETT-FILM BY POLARIZED UV VIS SPECTRA

Langmuir-Blodgett (LB) films of (p-carboxyphenoxy)-tri(2,4-di-tert-pentyl phenoxy)phthalocyanine copper(II) (asyCuPc) are prepared; the associated forms of the compound in chloroform solution and the particular orientation of asyCuPc molecular macrocycles in LB films is determined by polarized UV-VIS.

Electric-field-induced molecular alignment of side-chain liquid-crystalline polyacetylenes containing biphenyl mesogens

Electric-field-induced molecular alignments of side-chain liquid-crystalline polyacetylenes [-{HC=C[(CH2)(m)OCO-biph-OC7H15]}-, where biph is 4,4'-biphenylyl and m is 3 (PA3EO7) or 9 (PA9EO7)] were studied with X-ray diffraction and polarized optical microscopy. An orientation as high as 0.84 was obtained for PA9EO7. Furthermore, the molecular orientation of]PA9EO7 was achieved within a temperature range between the isotropic-to-smectic A transition temperature and 115 degreesC, and this suggested that the orientational packing was affected by the thermal fluctuation of the isotropic liquid and the mobility of the mesogenic moieties. The maximum achievable orientation for PA9EO7 was much greater than that for PA3EO7. This was the first time that the electric-field-induced molecular orientation of a side-chain liquid-crystalline polymer with a stiff backbone was studied.

Theoretical study of determining orientation and alignment of symmetric top molecule using laser-induced fluorescence

General expressions used for extracting the orientation and alignment parameters of a symmetric top molecule from laser-induced fluorescence (LIF) intensity are derived by employing the density matrix approach. The molecular orientation and alignment are described by molecular state multipoles. Excitation and detection are circularly and linearly polarized lights, respectively. In general cases, the LIF intensity is a complex function of the initial molecular state multipoles, the dynamic factors and the excitation-detection geometrical factors. It contains a population, ten orientation and fourteen alignment multipoles. The problem of how to extract the initial molecular state multipoles from the resolved LIF intensity is discussed.

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Study on the Single Crystals of Poly(3-octylthiophene) Induced by Solvent-Vapor Annealing

Needle-like single crystals of poly(3-octylthiophene) (P3OT) have been prepared by tetrahydrofuran-vapor annealing. The morphology and structure of the crystals were characterized with optical microscopy, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and wide-angle X-ray diffraction. It is observed that the P3OT molecules are packed with the backbones parallel to the length axis of the crystal and the alkyl side chains perpendicular to the substrate. The field effect transistor based on the P3OT single crystal exhibited a charge carrier mobility of 1.54 x 10(-4) cm(2)/(Vs) and on/off current ratio of 37, and the molecular orientation of the crystal is ascribed to account for the device performance. The time-dependent morphological evolution demonstrated that the crystals underwent Ostwald ripening when annealed.

Morphology and structure of poly(di-n-butylsilane) single crystals prepared by controlling kinetic process of solvent evaporation

The silicon backbone conformation in poly(di-n-butylsilane) (PDBS) has been shown to be a 7/3 helix at ambient conditions, which is in marked contrast to the near-planar conformation of its homologous polymers with side chain lengths of one to three or six to eight carbon atoms. In this work, both the 7/3 helical and near-planar chain conformations are achieved by controlling the solvent evaporation rate around room temperature. The chain conformation and crystal structure obtained in this method have been correlated to the crystal morphology by wide-angle X-ray diffraction, transmission electron microscopy, electron diffraction, optical microscopy, atomic force microscopy, and UV absorption spectrum. The lath-shaped single crystals obtained at 12 degreesC correspond to an orthorhombic form with near-planar chain conformation whereas the lozenge-shaped single crystals obtained at 30 degreesC (in coexistence with the lath-shaped crystals) are orthohexagonal with a 7/3 helix.

Morphology and structures of self-assembled symmetric poly(di-n-alkylsilanes)

The self-assembly of poly(di-n-butylsilane) (PDBS) and poly(di-n-hexylsilane) (PDHS) on the surfaces of amorphous carbon and highly oriented pyrolytic graphite (HOPG) have been investigated, respectively. The morphology and structures of these self-assembled thin films were studied by using atomic force microscopy, transmission electronic microscopy, and wide-angle X-ray diffraction. In the case of weak van der Waals interactions between absorbed molecules and substrate, i.e., on amorphous carbon, the self-assembly process was driven by absorbate-absorbate intermolecular interactions. For PDBS with weak absorbate-absorbate intermolecular interactions, the thin film showed organization lacking any measurable preferred orientation on the surface of amorphous carbon. While for PDHS with rigid backbone and strong intermolecular interactions, flat-on lamellae with silicon backbones perpendicular to the surface of amorphous carbon were formed. However, in the case of strong van der Waals interactions between absorbed molecules and substrate, i.e., on HOPG, the self-assembly process was tailored by the balance of absorbate-absorbate intermolecular interactions and molecule-substrate interactions. Both PDHS and PDBS thin films grew into edge-on lamellae on the surface of HOPG, which aligned according to a Mold symmetry.

Formation of mesophase mono-domains and micro-structures in thin films of a series of copolyethers containing both odd-numbered methylene units

The structural and morphological evolution of mono-domains in thin films has been investigated for a series of liquid crystalline (LC) copolyethers. The copolyethers studied were synthesized by the reaction of 1-(4-hydroxy-4 ' -biphenylyl)-2-(4-hydroxyl-phenyl)propane (TPP) with 1,7-dibromoheptane and 1,11-undecane at different compositions (coTPPs-7/11). In contrast to the solution-cast thin films without annealing, which exhibit the isotropic homogeneous molecular orientation, mono-domains with a homeotropic alignment were found in coTPP-7/11(5/5) after the thin films were annealed in the high-temperature columnar phase (Phi '). Similar to the nucleation process in polymer crystallization, transmission electron microscopic observations show that small mono-domains appear in the initial stage of annealing, where molecules form a uniaxial in-plane chain orientation. With increasing annealing time, the molecular orientation gradually became tilted with respect to the substrate surface, and finally, a uniaxial homeotropic molecular orientation was achieved after a prolonged annealing time. The lateral size of mono-domains was found to increase continuously with annealing time and grew into a circular shape, indicating an isotropic lateral growth scheme which implies a hexagonal molecular packing proved by the electron diffraction experiments.

Double twist in helical polymer "soft" crystals

In natural and synthetic materials having non-racemic chiral centers, chirality and structural ordering each play a distinct role in the formation of ordered states. Configurational chirality can be extended to morphological chirality when the phase, structures possess low liquid crystalline order. In the crystalline states the crystallization process suppresses the chiral helical morphology due to strong ordering interactions, In this Letter, we report the first observation of helical single lamellar crystals of synthetic non-racemic chiral polymers. Experimental evidence shows that the molecular chains twist along both the long and short axes of the helical lamellar crystals, which is the first time a double-twist molecular orientation in a helical crystal has been observed.