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Poly(1,3,4-oxadiazole)s have been the focus of considerable interest with regard to the- production of high- performance materials, particularly owing to their high thermal stability in oxidative atmosphere and specific properties determined by the structure of 1,3,4-oxadiazole ring, which, from the spectral and electronic points of view, is similar to a p-phenylene structure.[1] Besides their excellent resistance to high temperature, polyoxadiazoles have many desirable characteristics, such as good hydrolytic stability, high glass transition temperatures, low dielectric constants, and tough mechanical properties. Some polyoxadiazoles have semiconductive properties, other structures can be electrochemically doped and thus made conductive, and other have liquid-crystalline properties, which make them very attractive for a wide range of high-performance applications. They exhibit excellent fiber- and film-forming capabilities, thus being considered for use as heat-resistant reinforcing fibers for advanced composite materials, highly resistant fabrics for the filtration of hot gases, special membranes for gas separation or reverse osmosis, precursors for highly oriented graphite fibers, films, and blocks to be used in the construction of electronic instruments based on X-rays, neutron beams, or a-particles, or in the construction of nuclear reactor walls. Since they were first reported in 1961,[2] a wide variety of polymers containing 1,3,4-oxadiazole rings have been synthesized, and their preparation, characterization, and physico-mechanical properties have been periodically reviewed .[3-8] This article will present a general overview of this class of polymers and will refer to the work carried out by different researchers in the last ten years with the emphasis on the potential uses of such polymers as advanced materials.
The formation of a Langmuir monolayer of an amphiphilic derivative of zinc phthalocyanine (Na[(ZnPcSO3)-S-t]) has been studied by means of surface potential technique and Brewster angle microscopy. The experiments were undertaken in order to understand the behaviour of this monolayer with a well-defined surface pressure isotherm. The floating film is described as a truly monomolecular layer formed by very rigid islands in which the phthalocyanine units tend to take on a preferential orientation with their planes perpendicular to the air-water interface, for high values of the surface pressure. (c) 2004 Elsevier B.V. All rights reserved
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.
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.
The structure of mono- and multilayers of amphiphilic disc-shaped pentaynes wa inbestigated by Brewsterangle microscopy, X-ray specular reflection and grazing incidence diffraction (GID). X-ray specular reflection experiments confirm the "edge on" arrangement of the molecular discs. The molecular modelling of the Langmuir-Blodgett (LB)- multilayers predicts a columnar in-plane packing of the molecules. A GID experiment with monochromatic synchrotron radiation was used to verify the predicted multilayer structure on molecular level, while the Brewsterangle microscopy gave a deeper insight in the monolayer in-plane structure on micron scale.
Changes of the molecular arrangenemt that can be induced by means of the LB technique in the multilayers of a disc-shaped multialkynyl amphiphile are monitored by means of small angle X-ray diffraction. Studies of the monolayers at the air-water interface reveal "edge-on" orientation of the discs. Specific effects of the counter- ions (Na+, Cd²+, Pb²+, and Ba²+) and sub-solution pH on the monolayer collapse pressure, transfer efficiency and molecular order in the multilayers are found. A correlation between the monolayer properties and the ability for formation of periodic discotic structures in the presence of divalent counterions is established. The discotic molecules retain their "edge-on" arrangement in the highly compressed transferred films with slight irregular interdigtation of the flexible wings and inclination to the substrate normal. The tilt and the inter- digitation are reduced when the discotic monolayers are deposited in alternating LB films with barium arachidate spacer layers.
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
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.
The differential approach is based on the determination of dimensionless differential slope, for instance, of current-voltage characteristics (IVC), I=f(V). This slope (a) is given by formula alpha=d(lgI)/d(lgV). With such definition the ranges of constancy of the a(V) dependency correspond to the part of IVC characterized by the power behaviour (I similar to V-alpha). The differential slope of alpha(V) dependency gamma = d(lg alpha)/dlgV determines the exponent behaviour of curve (I similar to exp {eV(y)/kT}). Processing by the differential approach of the investigated theoretical or experimental characteristics permits us to determine the peculiarity of charge flow mechanisms, temperature behaviour of conductivity, etc. The theoretical base and some applications of differential approach to the investigation of the current-voltage, temperature and degradation characteristics of the polyaniline and poly(p- phenilenevinilene) based structures have been shown. (c) 2005 Elsevier B.V. All rights reserved
Films of emeraldine base of polyaniline (PAni) doped by various transition metal salts have been prepared, and current-voltage characteristics of the indium-tin oxide (ITO)/PAni film/metal electrode heterostructures were investigated. It was found that the electrical characteristics of the heterostructures are greatly affected by the dopant used and the metal electrode used. Different dopants resulted in different current anomalies with asymmetric current-voltage characteristics. Depending on the dopant used, the exponential and power law of the current behavior can be distinguished. Depending on the metal electrode used, two different regimes of current passing have been found at low applied voltages, namely, a nearly ohmic regime for the indium electrode, and a diode regime for the aluminum electrode. The diode regime was found to accompany by a positive charge accumulation in the film near the film/metal interface, which creates a built-in potential in the film. The amount of positive charges accumulated at the interface and therefore the value of the built-in potential can be reversibly increased or reduced by successive runs of the applied voltage in the forward or reverse direction, respectively. (C) 2004 Elsevier B.V. All rights reserved
Langmuir-Blodgett(LB) multilayers were prepared from disc-shaped multiyne mesogens based on amphiphilic alkyl pentakis(aryl-ethynyl)benzene ethers. The two compounds used are characterized by five hydrophobic flexible chains and one hydrophilic substituent at the terminal position of the alkoxy chain. The LB films were analysed by X-ray scattering and spectroscopic measurements. An edge-on arrangement of the two discotic pentaalkynes within Y-type bilayers with a different packing density proved to be possible for the LB films of both compounds.
Einfluss des Transferverhältnisses auf die Monoschichtsymmetrie in Y-Typ Langmuir-Blodgett-Schichten
(1995)
Feuchtesensor
(1994)
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
Grazing incidence x-ray diffraction (GIXD) measurements of uranyl arachidate (UO2A2) LB films
(1998)
In this work, we report our investigations on the film-forming properties as well as the optical and electroluminescent characterisations of a series of lateral-substituted soluble oligo(phenylenevinylenes) of various conjugation length. Preliminary investigations show that these materials are potential candidates for use in organic light-emitting devices (OLEDs). Two types of OLEDs were fabricated: single layer (SL) and single heterostructure (SHS), with poly(p-phenylenevinylene) (PPV) as hole transporting layer. Our best results were obtained with single layer device emitting green light with a luminance of 0.18 cd m(-2) and 0.24 cd m(-2) at a driving voltage of 10 V. (c) 2004 Elsevier B.V. All rights reserved
On the basis of a stochastic model of hopping transport in disordered solids we present results of simulations of the dark discharge of surface charged thin films considering the energetic distribution of the localised states within the sheet. A non- linear differential equation with suitable boundary and initial conditions describes the time evolution of the space charge. We suppose a Gaussian distribution of energies for the carrier transporting states with a standard deviation s. The arrival time of carriers at the rear electrode of the sandwich sample is studied in dependence on film thickness, initial surface charge, and energetic disorder. Our calculations confirm that the transit time increases indirect proportional with initial surface charge and proportional with the square thickness. For standard deviations of energetic distribution of 0.05 eV up to 0.25 eV the normalised transit time grows as s1.44. We discuss this in terms of the stochastic transport model.
Langmuir monolayers of arachidic acid have been prepared on a subphase containing uranyl ions (O-U-O)ý+. The interaction between the uranyl ions and the monolayer of arachidic acid has been studied by means of surface pressure and surface potential isotherms and Brewster angle microscopy at different pH values (ranging from 1.5 to 8). A similar systematic study has been carried out in the presence of Cdý+ ions for comparison purposes. The surface pressure and surface potential isotherms demonstrate that the acid to salt conversion of arachidic acid in the presence of uranyl ions occurs at lower bulk pH values (pH=3.5) as compared with other bivalent metal counterions such as Cdý+. Changes in the surface morphology of the monolayer induced by the interaction with uranyl- and cadmium ions are analyzed and the correlation between the surface potential change and the morphology of the films is discussed.