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The search for alternative routes of organic thin film formation is stimulated by the outstanding properties of these films in such fields as nonlinear optics, photonic data processing and molecular electronics. The formation of highly ordered multilayer structures by thermal vacuum deposition (VD) of organic compounds is an essential step toward the application of supramolecular organic architectures in technical systems. The VD of an amphiphilic substituted 2,5- diphenylene-1,3,4-oxadiazole 1 onto silicon substrates at defined temperature was used for the formation of ultrathin films. The structural data obtained for the VD-films of oxadiazole 1 by means of X-ray reflectivity, X-ray grazing incidence diffraction and atomic force microscopy (AFM) investigations indicate the formation of well ordered oxadiazole multilayers. The structure of the VD-multilayers is compared with that of Langmuir-Blodgett (LB) films and thermally treated LB-multilayers prepared from the same compound.
This paper describes the formation and structure investigation of Langmuir monolayers and Langmuir-Blodgett multilayers formed from amphiphilic derivatives of 2,5-diphenyl-1,3,4-oxadiazole. The 2,5-diphenyl-1,3,4-oxadiazole group as a functional unit with interesting physical and chemical properties is maintained, while the head group, the length of the alkyl chain and the structure of the coupling unit between aromatic and aliphatic part of these linear short-chain amphiphiles is systematically varied in order to explore the influence of this change on the film forming properties and the stability of Langmuir and Langmuir-Blodgett films. Molecular mechanics simulations are shown by these systematic variations to be suitable for the prediction of optimal chemical structures allowing for a stable stratified molecular packing. The combination of a detailed structure investigation of the multilayers based on scanning force microscopy and X-ray data with molecular mechanics simulations yields an insight into the packing of the molecules and the intermolecular interactions.
Study of gas transport through composite membranes with a stabilised Langmuir-Blodgett skin layer
(1995)
The Langmuir-Blodgett (LB-) technique is used to deposit molecular reinforced separation layers on porous polymer substrates resulting in composite membranes for gas separation. The adsorption of a polycation to the arachidic acid Langmuir layer and the subsequent transfer of the highly ordered and stabilised monolayer onto a polypropylene membrane (Cellgard 2400) yields a laminated separation layer combining the advantageous high degree of order of fatty acid films and the stability of thin polymeric films. X-ray reflectivity data of these films confirm the transfer of the assembled polymer layer together with the fatty acid monolayer and the formation of ordered Y-type LB-films. SFM pictures show a dense film without pinholes completely covering the porous support. Gas permeation measurements are used to study the transport process of different gases through the composite membrane.
The thermal treatment of Y-type Langmuir-Blodgett (LB) films formed from the amphiphilic derivative of 2,5- diphenyl-1,3,4-oxadiazole 1 results in changes of the molecular packing. These changes have been analysed by a combination of X-ray specular reflectivity data, X-ray grazing incidence diffraction data and scanning force microscopy images, On the basis of these experimental data we have simulated possible supramolecular structures, These simulations provide insight into the intermolecular interactions giving rise to the observed structural transitions. The crystalline structure induced by thermal treatment of the LB films is characterized by a uniaxial texture, which is correlated with the dipping direction during deposition of the LB film.
Langmuir-Blodgett films of bolaamphiphiles with reactive head groups can be used for the surface modification of composite membranes for gas separation processes. The scope of our investigations was to get a detailed insight in the monolayer behaviour and LB film structure of previously synthesized bisaroyl azide bolaamphiphiles. The layers have been analyses by means of surface potential measurements and Brewster angle microscopy. Furthermore parameters for a successful LB Film deposition were found. As expected for a molecule with two hydrophilic ends the transfer ratio on upstroke was close to one and on downstroke no transfer occurred. The multilayer structure was analysed by scanning force microscopy and X-ray reflectivity measurements. The SFM images revealed a periodic in plane structure on molecular level. Based on a combination of the X-ray data with results of other methods two possible models of the multilayer structure are presented
The complexation of highly ordered fatty acid monolayers with polyelectrolytes is expected to yield well- ordered Langmuir films suitable for the formation of Langmuir-Blodgett multilayers with improved long-term stability. Studies of the surface pressure-area isotherms and of the surface potential kinetics yield detailed information regarding the influence of these polymeric counterions on the monolayer properties. The injection of bivalent metal salts into the subphase after the complexation was used to improve the order and stability of the mono- and multilayers. The corresponding Langmuir-Blodgett films were investigated by means of X-ray reflectivity measurements and scanning force microscopy. The polyion complex multilayers show a strongly increased mechanical stability compared with films of fatty acid salts formed with bivalent metal ions. These structures are expected to be suitable as ultrathin separation layer for gas separation or ultrafiltration membranes.
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
Polypropylene membranes with deposited ultrathin "siin" layers are attractive for separation and cleaning of gaseous mixtures. In the present study, the surface morphology and wetting hysteresis of composite membranes consisting of a microporous polypropylene support and Langmuir-Blodgett ("skin") films, are investigated. The effect of the interlayer molecular interactions and the substrate features on the integrity and homogeneity of the "skin" layers is examined. Langmuir-Blodgett films of arachidic acid and cadmium and calcium arachidate are characterized both on smooth silicon and on porous polypropylene supports. Contact angle measurements and scanning force microscopy (SFM) are applied for investigations of the membrane surface modification upon transfer of a different number of monolayers. It was found that the contact angle hysteresis of the bare membrane decreases after the LB-deposition of close-packed monolayers. Smoothing of the membrane surface is also evidenced by the SFM images, on different length scales, confirming a good coverage of the membrane pores.
Lead island films were obtained via vacuum vapor deposition on glass and ceramic substrates at 80 K. Electrical conductance was measured during vapor condensation and further annealing of the film up to room temperature. The resistance behavior during film formation and atomic force microscopy of annealed films were used as information sources about their structure. A model for the quenched growth, based on ballistic aggregation theory, was proposed. The nanostructure, responsible for chemiresistive properties of thin lead films and the mechanism of sensor response are discussed. (C) 2003 Elsevier B.V. All rights reserved
Preparation and characterization of ordered thin films based on aromatic poly(1,3,4-oxadiazole)s
(1995)
Preparation and characterization of ordered thin films based on aromatic poly(1,3,4-oxadiazole)s
(1995)
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
The photoalignment ability of poly[methyl(phenyl)silylene] (PMPSi) films makes it possible to use them as hole- transporting substrates for the preparation of organic oriented films. A PMPSi layer prepared by spin coating was irradiated, after drying, with linearly polarized UV light. Then, water-soluble hydroxyaluminium phthalocyaninesulfonate [Al(OH)Pc(SO3Na)(1-2)] was deposited by casting. The cell ITO/PMPSi/AI(OH)Pc(SO3Na)(1-2)/Al showed non-linear current- voltage characteristics. For applied voltages higher than 10 V, polarized electroluminescence was observed. Its spectral characteristic consisted of two peaks with maxima at about 320 and 700 nm; their polarized anisotropies R-EL = Phi(parallel to) / Phi(perpendicular to) were ca. 15 and 0.5, respectively
Conjugated polymers are organic semiconducting materials that can emit light. These polymers have the advantages of being light, cheap, and easy to process, and in addition the band gap can be tailored. We report the microfabrication of surface light emitting diodes (SLEDs) on silicon substrates in which the electrodes are underneath the organic electroluminescent layer. Patterned electrodes are separated by a 2500Å-thick insulating layer of silicon oxide or are interdigitated with a separation of 10 or 20 µm; the luminescent polymer is spin-coated or solvent cast on top of the electrodes. This fabrication method is completely compatible with conventional silicon processing because the polymer is deposited last and the light is emitted from the upper surface of the diodes. Despite the large spacing between electrodes, and despite the absence of an evaporated top contact, the voltages required for light emission were not much greater than those used in conventional sandwich-type structures
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
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).
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
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.