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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
Organic materials have received considerable attention because of their large dipole moments and optical nonlinearities. The optically induced switching of material properties is important for studying the optoelectronic effects including second harmonic generation. Organic materials for photonic applications contain chromophore dipole which consist of acceptor and donor groups bridged by a delocalized pi-electron system. Both theoretical and experimental data show a reversible highly dipolar photoinduced intra molecular charge transfer in betaine type molecules accompanied by change of the sign and the value of the dipole moment. The arrangement of polar molecules in films is studied both by atom force microscopy and surface potential measurements. To understand the photo response of these materials, their spectroscopic and electrical properties are studied. The morphology and photoinduced surface potential switching of the self-assembled monolayers and polymer films are investigated. (c) 2005 Elsevier B.V. All rights reserved
We have formed Y layers of perfluorododecanoic acid CF3(CF2)10COOH by thermal evaporation in vacuo and of perfluorotetradecanoic acid CF3(CF2)12COOH by thermal evaporation and by the Langmuir-Blodgett (LB) technique. We have obtained the bilayer spacing of both these materials by X-ray diffraction and have also studied the in-plane structure of these materials by means of grazing incidence diffraction (GID). Computer modelling was used to interpret the results obtained. For the perfluorododecanoic acid, we find two stable untwisted phases at 25°C and a combination of these two predicts both the Bragg peaks arising from the layer structure and the GID results. Our experimental results show that the perfluorotetradecanoic acid exists in the generally accepted helical structure. Computer modelling leads to the conclusion that closely packed perfluorinated chains with 12 or less carbon atoms should exist in an untwisted state while molecules having more than 12 carbon atoms show the onset of the helical conformation.
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
Surface light emitting diodes SLEDs , in which previously microfabricated electrodes were coated with a conjugated polymer, were made with greatly different electrode spacings 250 nm and 10 or 20 mm and with different electrode material combinations. The fabrication process allowed us to compare several electrode materials. The SLED structures also enabled imaging of the light emission zone with fluorescence video microscopy. Conventional sandwich structures were also made for comparison electrode separation 50 nm. In this study, the emitting layer was poly[3- (2',5'-bis(1'',4'',7''trioxaoctyl)phenyl)-2,2'-bithiophene] (EO-PT), a conjugated polymer based on polythiophene with oligo ethyleneoxide side chains. The current-voltage (I(V)) and light-voltage (L(V)) characteristics of the SLEDs were largely insensitive to electrode separation except at high voltages, at which the current in the devices with the largest separations was limited. Sandwich structures had the same light output at a given current. Light could be obtained in forward and reverse bias from indium tin oxide ITO -aluminum, gold silicide-aluminum, and gold silicide-gold SLEDs, but the turn-on voltages were lowest with the ITO-aluminum devices, and these were also the brightest and most reliable. Adding salt to the EO-PT increased the current and brightness, decreased the turn-on voltages, and made the I(V) characteristics symmetric; thus, a device with an electrode separation of 10 mm had the extraordinarily low turn-on voltage of 6 V. The location of the light emission was at the electron-injecting contact.
Surface light emitting diodes (SLEDs) with a polymer-on-top geometry were used to study the sensitivity of light emission to oxygen. In these devices, pre-fabricated electrodes were coated with a conjugated polymer, which was thus directly exposed to the environment. Oxygen caused an immediate ten-to hundred fold decrease in electroluminescence efficiency relative to that in nitrogen or argon. Above the voltage for light emission, there was a sharp increase in current. Removing the oxygen led to recovery of the light intensity over a period of minutes, but the current returned immediately to its lower, original level. The electroluminescence and photoluminescence spectra were identical and were unaltered in shape by oxygen exposure (only decreasing in size). However, photoluminescence was unaffected by oxygen alone. This result indicates that oxygen does not affect excitons directly, but rather influences an intermediate species on the path to exciton formation, one that is significant only in electroluminescence and not in photoluminescence. Under simultaneous exposure to oxygen and UV light, the photoluminescence irreversibly decreased, presumably due to photo-oxidation
New substituted 2,5-diphenyl-1,3,4-oxadiazoles are reported as luminescent materials in light emitting diodes LEDs . The investigated new oxadiazoles show efficient blue and green emission in single layer devices. The combination with a hole transporting and red emitting polythiophene led to a white emission with higher quantum efficiency (QE).
The work presents low signal dielectric spectra of gold/copper phthalocyanine/magnesium and gold/copper phthalocyanine/gold sandwich systems in the 25 Hz-1 MHz frequency range. The performed analysis enables us to distinguish the electrode resistance and the lattice polarization from processes related with electric transport, such as charge carrier relaxation at space charge region of a barrier and charge carrier injection in dielectric response.
Dielectric properties of zinc phthalocyanine thin films : effects of annealing in air and in N-2
(2005)
This work presents the effects of ambient conditions, in particular oxygen and humidity, on the dielectric spectra of thin zinc phthalocyanine (ZnPc) films equipped with interdigitated electrodes and the effect of annealing in dry N-2 or in ambient air. The measurements were performed in the frequency range 10(-2)-10(5) Hz. The results indicate that the electric properties of ZnPc films are not only affected by oxygen but also by water vapour the presence of which always leads to the drop in alternating current conductance (ac-conductance). Moreover, at room temperature, the ac-conductance of ZnPc films previously exposed to air exhibits a reversible change with humidity, which makes these films attractive for humidity sensing applications. (C) 2004 Elsevier B.V. All rights reserved
The surfaces of ordered films formed from an amphiphilic derivative of 2,5-diphenyl-1,3,4-oxadiazole by the Langmuir-Blodgett (LB) technique and organic molecular beam deposition (OMBD) were investigated by the use of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. For the assignment of the spectral features of the C, N, and O K- edge absorption spectra, fingerprint spectra of poly(p-phenylene terephthalamide)(Kevlar), poly(ethylene terephthalate), poly(p-phenylene-1,3,4-oxadiazole), and 2,5-di- (pentadecyl)-1,3,4-oxadiazole, which contain related chemical moieties, were recorded. Ab initio molecular orbital calculations, performed with explicit treatment of the core hole, are used to support the spectral interpretations. Angle-resolved NEXAFS spectroscopy at the C, N, and O K-edges suggests a preferentially upright orientation of the oxadiazole derivative in the outermost layer of the films. X-ray specular reflectivity data and molecular modeling results suggest a similar interpretation.
Grazing incidence x-ray diffraction (GIXD) measurements of uranyl arachidate (UO2A2) LB films
(1998)
By means of pyroelectrical measurements and dielectric spectroscopy as well as structural information from differential scanning calorimetry, it is shown that, in a poly(vinyl alcohol) with azobenzene-alkoxy side chains, pyroelctricity and dielectric hysteresis which are usually related to each other have different origins. The pyroelectric effect is explained with reversible dipole-density changes upon thermal expansion, whereas the dielectric hysteresis is proposed to result from a charge-carrier polarisation.
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
Feuchtesensor
(1994)