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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.
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.
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.
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.
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.
Preparation and characterization of ordered thin films based on aromatic poly(1,3,4-oxadiazole)s
(1995)
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.
Preparation and characterization of ordered thin films based on aromatic poly(1,3,4-oxadiazole)s
(1995)
In this second paper we describe the comprehensive structure investigations on multilayers of uranyl arachidate formed by Langmuir-Blodgett deposition from subphases of different pH on solid substrates by means of a combination of infrared spectroscopy, X-ray specular reflection, ellipsometry, and scanning force microscopy, The structure of these multilayers and their stability are obviously influenced by the subphase pH. The pH range of the acid to salt conversion determined for the Langmuir films is confirmed by the infrared spectroscopic data of the multilayers. While arachidic acid films, deposited from an uranyl acetate subphase of low pH, are found to have strongly distorted rough surface, the films of uranyl structure, The influence of the counterions on the alkyl chain conformation, chain packing, reorganization probability, and stability of the multilayer is discussed.
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.
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.
New aromatic poly(1,3,4-oxadiazole)s were synthesized having excellent film forming properties due to their solubility in common organic solvents. The investigated new polyoxadiazoles can be used as emission material in single layer LED. The poly- oxadiazoles show an emission in the range of blue to yellow light. The external quantum efficiency as well as the turn-on voltage of the devices are influenced when blends of the polyoxadiazole with hole transport materials are used.
The molecular in-plane structure of uranyl arachidate Langmuir-Blodgett (LB) films formed at different subphase pH values was analysed by means of X-ray grazing-incidence diffraction. For multilayers formed at low subphase pH a reorganisation of the arachidic acid film structure is confirmed. At appropriate subphase pH values, reorganisation of the film structure, e.g. via the formation of three-dimensional crystallites, is prevented by the presence of the uranyl ions and by the subsequent introduction of conformational disorder (gauche defects) in the alkyl chains. The observation of a macroscopic flow-induced in-plane texture in these uranyl arachidate LB films has profound implications for the design of ordered, supramolecular structures by the Langmuir-Blodgett technique.
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.
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.
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.
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
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.
Grazing incidence x-ray diffraction (GIXD) measurements of uranyl arachidate (UO2A2) LB films
(1998)
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
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