Research on digital transducer principles. Volume 8 - Electrical conduction mechanisms in metal-semiconductor-polymer thin film structures, 1 July - 30 June 1968
Charge transport mechanism in metal semiconductor polymer thin films
Hartwig, W. H.↗
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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Halide perovskite-polymer composite film for bright and stable light-emitting devices
Stability is the primary hindrance for the application of halide perovskite material in light-emitting devices, solar cells, and other devices. In this work, halide perovskite and polymer composite film have been prepared for stable and bright light-emitting devices. Pure-phase Cs4PbBr6 crystals have been synthesized, and their photoluminescence (PL) properties and fluorescence lifetimes have been investigated. The Cs 4 PbBr 6 crystals exhibited high uniformity but underwent rapid photodegradation under light irradiation. To address this issue, we prepared bright light-emitting devices using composite of Cs 4 PbBr 6 crystals and polyethylene oxide (PEO) as the emission layer. The aim was to improve the optical and physical properties of halide perovskites, such as photodegradation and stability. PEO, with its excellent film-forming ability, created a uniform and dense film on the halide perovskite surface, filling microscopic defects and providing a protective barrier. FTIR, morphology, and PL analyses confirmed the protective role of the halide perovskite and polymer composite film. The composite film light-emitting devices demonstrated improved stability and higher PL brightness, with a peak brightness approaching 3 × 10 8 cd/m 2 , which was approximately 75% higher than the pure halide perovskite devices.
Composite film↗
New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells
Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been produced and which incorporates strongly acidic (proton donating) functional groups into the polymer backbone. Both of these polymer films have demonstrated significantly higher proton conductivity than Nafion at elevated temperatures and low relative humidities. An added advantage is that these polymers are very inexpensive to produce because their starting materials are commodity chemicals that are commercially available in large volumes.
Kinder, James D.↗
Strong thin membrane structure
A continuous process is described for producing strong lightweight structures for use as solar sails for spacecraft propulsion by radiation pressure. A thin reflective coating, such as aluminum, is applied to a rotating cylinder. A nylon mesh, applied over the aluminum coating, is then coated with a polymerizing material such as a para-xylylene monomer gas to polymerize as a film bound to the mesh and the aluminum. An emissivity increasing material such as chromium or silicon monoxide is applied to the polymer film to disperse such material colloidally into the growing polymer film, or to the final polymer film. The resulting membrane structure is then removed from the cylinder. Alternately, the membrane structure can be formed by etching a substrate in the form of an organic film such as a polymide, or a metal foil, to remove material from the substrate and reduce its thickness. A thin reflective coating (aluminum) is applied on one side of the substrate, and an emissivity increasing coating is applied on the reverse side of the substrate.
Frazer, R. E.↗
Low-gravity electrodeposition and growth of polymer thin films with large third-order optical nonlinearities by electrochemical processes for devices: Thiophene-based polymers
It has been proposed that NLO thin film properties may be improved by low-gravity processing. Strong candidates for NLO thin film applications are the polythiophenes. Polymeric thiophenes are attractive materials due to their ease of preparation, stability, and high X(exp 3). A simple and convenient method for preparation of polythiophenes is electrochemical oxidation. We will apply some of our experience and lessons learned in low-gravity metal, metal/cermet electrode position to improve the quality of polythiophene(s) thin films. In low gravity electrode position of Ni at a high rate on an Au substrate often results in the production of an x-ray non diffracting surface. Cobalt metal deposition does not give this result nor does Ni when deposited similarly on a glassy carbon substrate. Co/Ni alloy composition produced during electrode position is strongly dependent upon the amount of convection. Code position of neutral inert cermets with metals is influenced significantly by the presence of gravity and the size of the cermets. Tracks left in the 1-g surfaces by unsuccessful particle occlusion indicate suspension of the large particles is not the only reason for poor volume percentages of the larger particles in the deposits. All size particles are more homogeneously distributed in the deposits in low-gravity electrocodeposition than in 1-g. Low gravity gives larger volume percentages for the larger particles in the deposits, while 1-g gives larger volume percentages for the smaller particles. Intermediate size particles give mixed results. The experimental cells were constructed with flat electrode end plates such that 1-g bench reference electrode positions could be carried out at various orientations with respect to gravity. A series of bench studies using similar designed cells are suggested so that convection modification can be applied to electrochemical thin film preparation. Convection effects can then be coupled with other parameter variations in current, temperature, concentration, solvent, electrolyte, and anode substrates to optimize the properties of NLO thin films before resorting to low-gravity processing.
Penn, Benjamin G.↗
Strong thin membrane structure for use as solar sail comprising substrate with reflective coating on one surface and an infra red emissivity increasing coating on the other surface
Production of strong lightweight membrane structure by applying a thin reflective coating such as aluminum to a rotating cylinder, applying a mesh material such as nylon over the aluminum coating, coating the mesh overlying the aluminum with a polymerizing material such as a para-xylylene monomer gas to polymerize as a film bound to the mesh and the aluminum, and applying an emissivity increasing material such as chromium and silicon monoxide to the polymer film to disperse such material colloidally into the growing polymer film, or applying such material to the final polymer film, and removing the resulting membrane structure from the cylinder. Alternatively, such membrane structure can be formed by etching a substrate in the form of an organic film such as a polyimide, or a metal foil, to remove material from the substrate and reduce its thickness, applying a thin reflective coating such as aluminum on one side of the substrate and applying an emissivity increasing coating such as chromium and silicon monoxide on the reverse side of the substrate.
Frazer, Robert E.↗
Manufacturing polymer thin films in a micro-gravity environment
This project represents Venezuela's first scientific experiment in space. The apparatus for the automatic casting of two polymer thin films will be contained in NASA's Payload No. G-559 of the Get Away Special program for a future orbital space flight in the U.S. Space Shuttle. Semi-permeable polymer membranes have important applications in a variety of fields, such as medicine, energy, and pharmaceuticals and in general fluid separation processes, such as reverse osmosis, ultrafiltration, and electrodialysis. The casting of semi-permeable membranes in space will help to identify the roles of convection in determining the structure of these membranes.
Vera, Ivan↗
Increasing Volume in Conjugated Polymers to Facilitate Electrical Doping with Phosphomolybdic Acid
Molecular p-type electrical dopants have been proven useful to fine-tune the optoelectronic properties of bulk organic semiconductors and their interfaces. In this work, the volume in polymer films and its role in solution-based electrical p-type doping using phosphomolybdic acid (PMA) are studied. The polymer film volume was controlled using two approaches. One is based on heating both the PMA solution and the film prior to immersion. The second is based on coating the polymer film with a liquid blend that contains the PMA solution and a swelling solvent. 31 P NMR and FTIR experiments indicate that the Keggin structure appears to be preserved throughout the doping process. Results show that increasing the polymer volume facilitates the infiltration of the PMA Keggin structure, which results in an increased electrical p-type doping level.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Hydrophobic coating of solid materials by plasma-polymerized thin film using tetrafluoroethylene
Glass slides were coated with plasma-polymerized tetrafluoroethylene films of different thickness using the glow discharge technique in a tube-shaped chamber, and the plasma conditions, film growth rates, light permeability of the polymer films, and particle bond strength in the polymer films were studied. Ashed sections of mouse organs and ashed bacillus spores were also coated to give them hydrophobic treatment without damaging their shapes or appearance. The hydrophobic coating of the specimens was successful, and the fine ash patterns were strongly fixed onto the glass slides, making permanent preparations.
Hozumi, K.↗
Laboratory Analysis of Polymer Thin Films for Planetary Balloons and Gossamer Structures
Commercially available polymer thin fdms with thickness of 15 microns or less were evaluated for potential application as the gas envelope material of balloons and other inflated vehicles. Films on this thickness scale are of interest for Earth and Mars ballooning as well as many gossamer space structures. Due to the uniqueness of these missions relative to typical uses of these materials, application-specific materials properties measurements were made. We evaluated numerous polymer chemistries, plus a few variations within one chemistry. The data show that there are often trade-offs among the different materials, such as with polyesters and polyimides having greater stiffness (modulus) but lower tear propagation resistance than polyethylene. Sections of polyethylene films can be joined by heat sealing, while adhesives and their accompanying mass penalty must be used with polyesters and polyimides. When the analysis temperature is reduced to 190 K, polyethylenes display dramatically increased stiffness and yield point, while the increase for other materials is more modest. The data also show that manufacturing processes can significantly affect film properties. To emphasize the need for application-specific properties assessment, we discuss two recent applications using these materials.
Sterling, Jerry↗
Self-lubricating polymer composites and polymer transfer film lubrication for space applications
The use of self-lubricating polymers and polymer composites in space is somewhat limited today. In general, they are only used when other methods are inadequate. There is potential, however, for these materials to make a significant impact on future space missions if properly utilized. Some of the different polymers and fillers used to make self-lubricating composites are surveyed. The mechanisms of composite lubrication and wear, the theory behind transfer film lubricating mechanisms, and some factors which affect polymer composite wear and transfer are examined. In addition, some of the current space tribology application areas for self-lubricating polymer composites and polymer transfer are mentioned.
Fusaro, Robert L.↗
Ultrathin conformal OCVD PEDOT coatings on porous electrodes and applications thereof
The present disclosure relates to electrodes comprising a polymer film and a substrate, wherein the polymer film has a thickness of about 5 nm to about 600 nm. The present disclosure also relates to electrochemical cells and batteries comprising the electrodes disclosed herein. The present disclosure also relates to methods of making the electrodes disclosed herein.
Gleason, Karen K.↗
Controlling swelling in mixed transport polymers through alkyl side-chain physical cross-linking
Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Optical Sensors Based on Single on Arm Thin Film Waveguide Interferometer
Single-arm dual-mode optical waveguide interferometer utilizes interference between two modes of different order. Sensing effect results from the change in propagation conditions of the modes caused by the environment. The waveguide is made as an open asymmetric structure containing a dye-doped polymer film onto a quartz substrate. It is more sensitive to the change of environment than its conventional polarimetric analog using orthogonal modes (TE and TM) of the same order. The sensor still preserves the option of operating in polarimetric regime using a variety of mode combinations such as TE(sub 0)/TM(sub 0) (conventional) TE(sub 0)/TM(sub 1), TE(sub 1)/TM(sub 0), or TE(sub 1)/TM(sub 1) but can also work in nonpolarimetric regime using combinations TE(sub 0)/TE(sub 1) or TM(sub 0)/TM(sub 1). Utilization of different mode combinations simultaneously makes the device more versatile. Application of the sensor to gas sensing is based on doping polymer film with an organic indicator dye targeting a particular gaseous reagent. Change of the optical absorption spectrum of the dye caused by the gaseous pollutant results in change of the reactive index of the dye-doped polymer film that can be detected by the sensor. As indicator dyes we utilize Bromocresol Purple doped into polymer poly(methyl) methacrylate that is sensitive to small concentrations of ammonia. The indicator dye demonstrated an irreversible increase in optical absorption near the peak at 350 nm being exposed to 5% ammonia in pure nitrogen at 600 Torr. The dye also showed reversible growth of the absorption peak near 600 nm after exposure to a vapor of standard medical ammonia spirit (65% alcohol). We have built a breadboard prototype of the sensor with He-Ne laser as a light source and with a single mode fiber input and a multimode fiber output. The prototype showed a sensitivity to temperature change of the order of 2 C per 2pi phase shift. The sensitivity of the sensor to the presence of dTy ammonia is not less than 300 ppm per 2pi phase shift. The proposed sensor can be used as a robust stand-alone instrument for continuous environment pollution monitoring.
Sarkisov, S. S.↗
Optical Sensors Based on Single Arm Thin Film Waveguide Interferometer
Single-arm double-mode double-order optical waveguide interferometer utilizes interference between two propagating modes of different orders. Sensing effect results from the change in propagation conditions of the modes caused by the environment. The waveguide is made as an open asymmetric slab structure containing a dye-doped polymer film onto a fused quartz substrate. It is more sensitive to the change of environment than its conventional polarimetric analog using orthogonal modes (TE and TM) of the same order. The sensor still preserves the option of operating in polarimetric regime using a variety of mode combinations such as TE(sub 0)/TM(sub 0) (conventional), TE(sub 0)/TM(sub 1), TE(sub 1)/TM(sub 0), or TE(sub 1)/TM(sub 1) but can also work in nonpolarimetric regime using combinations TE(sub 0)/TM(sub 1) or TE(sub 0)/TM(sub 1). Utilization of different mode combinations simultaneously makes the device more versatile. Application of the sensor to gas sensing is based on doping polymer film with an organic indicator dye sensitive to a particular gas. Change of optical absorption spectrum of the dye caused by the gaseous pollutant results change of the reactive index of the dye-doped polymer film that can be detected by the sensor. As an indicator dyes, we utilize Bromocresol Purple doped into polymer poly(methyl) methacrylate, which shows a reversible growth of the absorption peak neat 600 nm after exposure to wet ammonia. We have built a breadboard prototype of the sensor with He-Ne laser as a light source and with a single mode fiber input and a multimode fiber output. The prototype showed sensitivity to temperature change of the order of 2 C per one full oscillation of the signal. The sensitivity of the sensor to the presence of wet ammonia is 200 ppm per one full oscillation of the signal. The further improvements include switching to a longer wavelength laser source (750-nm semiconductor laser), substitution of poly(methyl) methacrylate with hydrophilic high-temperature polyimide, and increase the doping rate of indicator dye. All these improvements are expected to bring sensitivity to 10 ppm of ammonia per one full oscillation of signal independent on the humidity of ambient air. The proposed sensor can be used as a robust and inexpensive stand-alone instrument for continuous environment pollution monitoring.
Sarkisov, S. S.↗
Mesoscale Polymer Surfactants: Photolithographic Production and Localization at Droplet Interfaces
Stabilization of fluid droplets, classically as oil-in-water or water-in-oil emulsions, is typically conducted using molecular surfactants or small particulates that localize at oil-water interfaces. In this paper, we describe a method whereby thin polymer films are converted photolithographically to ribbon-like mesoscale objects, which in turn adsorb to fluid inter-faces where they extend as appendages, or arms, from the droplet surface. These “mesoscale polymer surfactants”, or MPSs, were prepared from thin polymer films containing reactive functional moieties, including coumarin for photo-crosslinking, triphenylsulfonium for photoacid generation, and tert-butyl ester for solubility switching. The resultant MPSs, prepared initially on Si substrates, were released into water to reveal an exquisite shape sensitivity (forming straight, bent, or helical structures) and affinity for droplet interfaces based on their preparation conditions and the properties of the surrounding liquid. Notably, the lithographic techniques employed were amenable to differentiating the wettability of MPS segments, affording access to diblock-like MPSs which adhered to dispersed droplets via their hydrophobic segments, allowing their hydrophilic segments to extend into the continuous phase.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Supramolecular Control of Redox-Mediated Interactions for Ion-Selective Electroseparations
This report summarizes efforts from the Su Group at the University of Illinois at Urbana-Champaign in researching and developing materials and processes for the recovery of rare earth elements and other metal elements that are critical to the United States economy and national security, under DOE Award No. DE-SC0021409. This report highlights efforts in the recovery of: • Transition metal elements (including arsenic, chromium, molybdenum, rhenium, vanadium): Redox-active metallopolymers are able to capture these elements in their oxyanion form. Direct control of target ion capture/release through electrochemical-mediated switching of metallocene binding sites reduces chemical input and lowers generation of waste in element recovery processes. We study the effects of metallopolymer structure on targeted ion binding through a combination of experimental screening of ion selectivity from multi-component mixtures, computational efforts which elucidate the charge-transfer origins of metallocene binding and provide insight on how binding site structure influences selectivity, and state-of-the-art neutron reflectivity of metallocene polymer films to understand the interplay of polymer-ion (charge-transfer), polymer-solvent (polymer hydrophilicity/hydrophobicity), and ion-solvent (ion hydration) interactions with spatial resolution of polymer films. • Rare earth elements (including yttrium, neodymium, europium, gadolinium, dysprosium, cerium): Here we employ redox-copolymers for recovery of rare earth elements by electrochemically regenerated ion-exchange. Rare earth elements require an alternative route to capture/release than directly with metallopolymers since rare earth elements typically exist in cationic form in water. To address this, copolymerization of traditional ion-exchange moieties with metallocene moieties allowed for capture of rare earth elements with the ion-exchange moieties and electrochemical-mediated release of rare earth elements through oxidation of metallocene moieties.
36 MATERIALS SCIENCE↗
Understanding interfacial segregation in polymer blend films with random and mixed side chain bottlebrush copolymer additives
Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chain chemistries. Specifically, we synthesized bottlebrush polymers with either poly(styrene-ran-methyl methacrylate) side chains or with a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains. Furthermore, the bottlebrush additives were matched in terms of PS and PMMA compositions, and they were blended with linear PS or PMMA chains that ranged in length from shorter to longer than the bottlebrush side chains. Experiments revealed similar behaviors of the two types of bottlebrushes, with a slight preference for mixed side-chain bottlebrushes at the film surface. SCFT simulations were qualitatively consistent with experimental observations, predicting only slight differences in the segregation of bottlebrush additives driven by side chain microstructures. Specifically, these slight differences were driven by the chemistries of the bottlebrush polymer joints and side chain end-groups, which were entropically repelled and attracted to interfaces, respectively. Using SCFT, we also demonstrated that the interfacial behaviors were dominated by entropic effects with high molecular weight linear polymers, leading to enrichment of bottlebrush near interfaces. Surprisingly, the SCFT simulations showed that the chemistry of the joints connecting the bottlebrush backbones and side chains played a more significant role compared with the side chain end groups in affecting differences in surface excess of bottlebrushes with random and mixed side chains. This work provides new insights into the effects of side chain microstructure on segregation of bottlebrush polymer additives.
36 MATERIALS SCIENCE↗