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It is well known that the performance of solar cells based on a blend of hole-accepting and electron-accepting conjugated polymers as the active material depend crucially on the length scale of the resulting phase separated morphology. However, a direct control of this morphology is difficult if the layer is prepared from an organic solvent. To circumvent this difficulty, recently a universal method to fabricate defined nano-structured blend layer using nanoparticles dispersed in water was demonstrated. These nanoparticles were prepared with the miniemulsion method, which allows for the preparation of semiconducting polymer nanospheres (SPNs) with diameters in the range of 30 to 300 nanometres. Since the process starts from the active material dissolved in a common solvent, it can be applied to the fabrication of nanoparticles of blends of polymers with oligomers or even with inorganic materials. We present here for the first time scanning near field optical microscopy (SNOM) investigations on these novel nanostructured polymer layers. We show that by spin-coating a mixture of two different dispersions a nanoparticle monolayer with a statistically distribution of the nanoparticles can be obtained. Mixing conjugated polymer nanoparticles with some inert particles like polystyrene beads may allow for the preparation of nano-sized light emitters
Electron beam irradiation of poly(vinyl methyl ether) films : 1. Synthesis and film topography
(2005)
Temperature-sensitive hydrogel layers on silicon (Si) substrates were synthesized by electron beam irradiation of spin-coated poly(vinyl methyl ether) (PVME) films. The influences of the used solvent, the polymer concentration, and the spinning velocity on the homogeneity and the thickness of the PVME film were investigated. In the range of concentration c(p) = 1-15 wt% PVME in ethanol solution, homogeneous films with a thickness between d = 50 nm and 1.7 mu m were obtained. The films were cross-linked by electron beam irradiation under inert atmosphere and analyzed by sol-gel- analysis. The results were compared with bulkgels formed by electron beam irradiation of PVME in the dry state. The film topography was analyzed by high-resolution field emission scanning electron microscopy and atomic force microscopy. An islandlike structure in the dry, swollen, and shrunken state of the hydrogel films was observed
An increase in random molecular vibrations of a solid owing to heating above the melting point leads to a decrease in its long-range order and a loss of structural symmetry. Therefore conventional liquids are isotropic media. Here we report on a light-induced isothermal transition of a polymer film from an isotropic solid to an anisotropic liquid state in which the degree of mechanical anisotropy can be controlled by light. Whereas during irradiation by circular polarized light the film behaves as an isotropic viscoelastic fluid, it shows considerable fluidity only in the direction parallel to the light field vector under linear polarized light. The fluidization phenomenon is related to photoinduced motion of azobenzene-functionalized molecular units, which can be effectively activated only when their transition dipole moments are oriented close to the direction of the light polarization. We also describe here how the photofluidization allows nanoscopic elements of matter to be precisely manipulated
Three series of semiflexible and rigid main-chain polyesters containing photoreactive mesogenic units derived from p-phenylenediacrylic acid (PDA) and cinnamic acid have been synthesized by high-temperature polycondensation. The thermal and mesomorphic properties of the polymers have been determined. The photochemical behavior of polymer P-[1]-T, which contains a PDA unit, has been studied both in solution and in films. In solution, [2+2] photocycloaddition, E/Z photoisomerization, and photo-Fries rearrangement can take place. In contrast, the dominant process in spin-coated films is the [2+2] photocycloaddition reaction, which causes crosslinking of the polymer. In films, the photochemistry and induction of anisotropy are strongly influenced by the aggregation of the PDA phenylester unit. A dichroism of about 0.2 has been induced in films by irradiation with linearly polarized UV light, and thus the capability of these films to induce optical anisotropy and align liquid crystals has been demonstrated. Liquid-crystalline cells have been made with polarized irradiated films of P[1]-T as aligning layers. A commercial liquid-crystalline mixture has been used for this study, and a similar liquid-crystalline order determined by polarized Fourier transform infrared to a commercial cell with rubbed polyimide as an aligning layer has been detected. Because of crosslinking of the irradiated P[1]-T photoaligning layer, the photoinduced anisotropy is stable at high temperatures, and the liquid-crystalline molecules are insoluble in the irradiated polymer. (c) 2005 Wiley Periodicals, Inc
Two basic morphologies of emeraldine base of polyaniline-transition metal salt complex films cast from N- methylpyrrolidinone solutions are described. The first morphology consists of grains and the other consists of loose aggregates, respectively. The correlation of the film morphology with formation of precipitate in the complex solution, kinetics of solvent evaporation from the cast film, amount of solvent entrapped in the film, film conductivity, and IR absorption spectra is shown. Two different mechanisms of the complex formation as a result of competition in the polymer- inorganic salt-solvent trio interactions are discussed; the first mechanism results in folding of macromolecules into compact coils being then a core of grains in the complex films, and the second mechanism leads to blending of the polymer chains with solvent giving rise to formation of loose aggregates. (c) 2005 Elsevier B.V. All rights reserved
Non-linear optical and electrical properties of polymer films obtained by dipole orientation of active units are reported. Novel polar oligomer with N-(indan-1,3-dion-2-yl)pyridinium betaine (IPB) as a side group is studied. Orientation of polar groups in oligomer thin films causes an increase of the photo-induced change of surface potential on irradiation in the region of photo-induced electron transfer (PIET) where the IPB group exhibits a reversible change of the value and sign of the dipole moment. At longer wavelengths, the value of the surface potential of the oligomer may be determined by transport of photo-generated charge carriers
Tuning of the excited-state properties and photovoltaic performance in PPV-based polymer blends
(2008)
The surface structures of crystals based on aromatic oxadiazoles were investigated by AFM. The crystal structure for 2,5-di(p-tolyl)-1,3,4-oxadiazole (DTO) differs from that of 2,5-di (4-methoxycarbonyl-phenyl)-1,3,4- oxadiazole (DMPO). In DMPO all molecules show parallel orientation to the surface in such a way that the surface is formed as well as by the nitrogen atoms of the heterocyclic rings and the methyl groups of the ester substituents. By contrast, the oxadiazole molecules in DTO crystals are oriented perpendicular to the crystal surface. The experimental data are interpreted by molecular modelling. It is shown that there is a difference between molecular structure of the surface, as detected by AFM, and the bulk structure determined by X-ray diffraction.
New aromatic poly(amide-ether)s (II) have been synthesized by solution polycondensation of various aromatic diamines having two ether bridges (I) with a diacid chloride containing silicon, namely bis(chlorocarbonylphenyl)- diphenyIsilane. These polymers are easy soluble in polar amidic solvents such as N-methylpyrrolidinone or dimethylformamide and can be cast into thin flexible films or coatings from such solutions. They show high thermal stability with initial decomposition temperature being above 400 °C. Their glass transition temperatures lie in the range of 220-250 °C, except for polymer He which did not show a clear Tg when heated in a differential scanning calorimetry experiment up to 300 °C. The large interval between the glass transition and decomposition temperatures of pnlymers Ia-Id could be advantageous for their processing via compression molding. The polymer coatings deposited by the spincoating, technique onto silicon wafers showed a very smooth, pinhole-free surface in atomic force microscopy investigations. The free-standing films of 20-30 mm thickness show low dielectric constant, in the range of 3.65-3.78, which is promising for future application as high performance dielectrics.