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At least 37 records · Page 2

General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System

The pH dependence of proton-coupled electron transfer (PCET) reactions, which are critical to many chemical and biological processes, is a powerful probe for elucidating their fundamental mechanisms. Herein, a general, multichannel kinetic model is introduced to describe the pH dependence of both homogeneous and electrochemical PCET reactions. According to this model, a weak pH dependence can arise from the competition among multiple sequential and concerted PCET channels involving different forms of the redox species, such as protonated and deprotonated forms, as well as different proton donors and acceptors. The contribution of each channel is influenced by the relative populations of the reactant species, which often depend strongly on pH, leading to complex pH dependence of PCET apparent rate constants. This model is used to explain the origins of the experimentally observed weak pH dependence of the electrochemical PCET apparent rate constant for a ruthenium-based water oxidation catalyst attached to a tin-doped In2O3 (ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. Furthermore, this work highlights the importance of considering multiple competing channels simultaneously for PCET processes.

Catalysts↗

Photoelectron emission analysis of surface elements of the International Sun Earth Explorer

The photoemission was measured of engineering materials (aluminum; copper, plain; copper, abraded; copper-beryllium; magnesium; silver; In2O3 on silica; reflective coating on silica; teflon; kapton; and Pyre ML) associated with the International Sun Earth Explorer (ISEE) Satellite. The procedures used are described, including the experimental equipment; results of the program, the conclusions reached, and areas for further work are presented. Data regarding the measured yield of the 11 materials whose surface emission was determined is included in the form of plots of photoelectric yield versus incident light wavelength.

Spencer, W. T.↗

Glass-Si heterojunction solar cells

An increase in efficiency from 2% to over 7% was achieved by a solar cell that used polycrystal silicon heterojunction with SnO2 glass. For Single crystal substrates, efficiencies close to 10% were measured. These cells had the same structures as polycrystalline cells. Work on p+/n heterojunction using In2O3 glass resulted in cells of 3% efficiency on polycrystalline material and 4% efficiency on single crystal material.

Ahrons, R. W.↗

Fabrication of OSOS cells by neutral ion beam sputtering

Oxide semiconductor on silicon (OSOS) solar cells have been fabricated from various indium tin oxide (In2O3)x(SnO2)1-x compositions sputtered onto p-type single crystal silicon substrates with a neutralized argon ion beam. High temperature processing or annealing was not required. The highest efficiency was achieved with x = 0.91 and was 12 percent. The cells are environmentally rugged, chemically stable, and show promise for still higher efficiencies. Moreover, the ion beam sputtering fabrication technique is amenable to low cost, continuous processing.

Burk, D. E.↗

Transparent conductive coatings

Thin film transparent conductors are discussed. Materials with electrical conductivity and optical transparency are highly desirable in many optoelectronic applications including photovoltaics. Certain binary oxide semiconductors such as tin oxide (SnO2) and indium oxide (In2O3) offer much better performance tradeoff in optoelectronics as well as better mechanical and chemical stability than thin semitransparent films. These thin-film transparent conductors (TC) are essentially wide-bandgap degenerate semiconductors - invariably n-type - and hence are transparent to sub-bandgap (visible) radiation while affording high electrical conductivity due to the large free electron concentration. The principal performance characteristics of TC's are, of course, electrical conductivity and optical transmission. The TC's have a refractive index of around 2.0 and hence act as very efficient antireflection coatings. For using TC's in surface barrier solar cells, the photovoltaic barrier is of utmost importance and so the work function or electron affinity of the TC is also a very important material parameter. Fabrication processes are discussed.

Ashok, S.↗

Photoenhanced thermal oxidation of InP

The growth rate of laser-photoenhanced thermally grown native oxides of InP in a N2O ambient and its dependence on growth condition are presented. Increased laser power, substrate temperature, and N2O pressure are observed to increase the growth rate. The topography and the composition of these oxides have been studied using secondary electron microscopy and X-ray photoemission spectroscopy, respectively. The oxide layers contain In2O3 and a phosphate, probably InPO4. The enhanced growth appears to be caused by both excited oxidizing species and a photon-enhanced surface reaction.

Fathipour, M.↗

Investigation of buried homojunctions in p-InP formed during sputter deposition of both indium tin oxide and indium oxide

While dc magnetron sputter deposition of indium tin oxide leads to the formation of a buried homojunction in single crystal p-type InP, the mechanism of type conversion of the InP surface is not apparent. In view of the recent achievement of nearly 17-percent global efficiencies for cells fabricated solely by sputter deposition of In2O3, it is presently surmised that tin may not be an essential element in type conversion. A variety of electrical and optical techniques are presently used to evaluate the changes at both indium tin oxide/InP and indium oxide/InP interfaces. Such mechanisms as the passivation of acceptors by hydrogen, and sputter damage, are found to occur simultaneously.

Gessert, T. A.↗

Recent advances in the ITO/InP solar cell

It was demonstrated that Indium Tin Oxide (ITO)/InP solar cells can now be made on as-received p(-) bulk substrates which are of nearly equal quality to those which could previously only be made on epitaxially grown p(-) InP base layers. Although this advancement is due in part to both increases in substrate quality and a better understanding of back contact formation, it appears that the passivation/compensation effects resulting from having H2 in the sputtering gas tends to reduce significantly the performance differences previously observed between these two substrates. It is shown that since high efficiency ITO/InP cells can be made from as-received substrates, and since the type conversion process is not highly spatially dependent, large area ITO/InP cells (4 sq cm) with efficiencies approaching 17 percent (Global) can be made. Furthermore, the measured open circuit voltages (V sub OC) and quantum efficiencies (QEs) from these large cells suggest that, when they are processed using optimum grid designs, the efficiencies will be nearly equal to that of the smaller cells thus far produced. It has been shown, through comparative experiments involving ITO/InP and IO/InP cells, that Sn may not be the major cause of type conversion of the InP surface and thus further implies that the ITO may not be an essential element in this type of device. Specifically, very efficient photovoltaic solar cells were made by sputtering (Sn free) In2O3 showing that type conversion and subsequent junction formation will occur even in the absence of the sputtered SN species. The result suggests that sputter damage may indeed be the important mechanism(s) of type conversion. Finally, an initial study of the stability of the ITO/InP cell done over the course of about one year has indicated that the J(sub SC) (short circuit current) and the fill factor (FF) are measurably stable within experimental certainty.

Gessert, T. A.↗

Investigation of anodic and chemical oxides grown on p-type InP with applications to surface passivation for n(+)-p solar cell fabrication

Most of the previously reported InP anodic oxides were grown on a n-type InP with applications to fabrication of MISFET structures and were described as a mixture of In2O3 and P2O5 stoichiometric compounds or nonstoichiometric phases which have properties similar to crystalline compounds In(OH)3, InPO4, and In(PO3)3. Details of the compositional change of the anodic oxides grown under different anodization conditions were previously reported. The use of P-rich oxides grown either by anodic or chemical oxidation are investigated for surface passivation of p-type InP and as a protective cap during junction formation by closed-ampoule sulfur diffusion. The investigation is based on but not limited to correlations between PL intensity and X-ray photoelectron spectroscopy (XPS) chemical composition data.

Faur, Maria↗

Buried homojunction solar cells formed in p-InP during sputter deposition and hydrogen plasma processing

Although it is apparent that direct current (DC) magnetron sputter deposition of indium tin oxide (ITO) leads to the formation of a buried homojunction in single-crystal p-type InP, the actual mechanism of type conversion of the InP surface is not clear. Since sputter deposition of In2O3 has also led to high-quality cells, it appears that Sn is not the cause of type conversion. To investigate the junction formation process further, experiments involving the use of a pure hydrogen plasma have been performed, resulting in type conversion of Fe-doped InP surfaces and in solar cells with efficiencies over 16 percent (global). The results confirm that sputter deposition is not necessary to form this type of buried homojunction solar cell, and they suggest a fabrication process that may be used with other relevant photovoltaic materials.

Gessert, T. A.↗

Post-flight analyses of the crystals from the M0003-14 quartz crystal microbalance experiment

Quartz Crystal Microbalances constructed by QCM Research were flown on the leading and trailing edges of the Long Duration Exposure Facility (LDEF) as one of the sub-experiments of M0003. Response of the crystals coated with 150 A of IN2O3ZnS was recorded during the first 424 days of the mission. A second QCM with crystals coated with 150 A was also flown but not monitored. The flight data and temperature profiles will be presented. After the flight, the QCM's were disassembled and analyzed. The samples included the crystals from the leading and trailing edge samples of both types of coatings along with the reference crystals which were inside the QCM housing. Analyses were performed by scanning electron microscopy, energy dispersive x ray analysis, x ray photoelectron spectroscopy, ion microprobe mass analysis, and reflectance spectroscopy in the infrared and ultraviolet/visible region. The crystals were contaminated predominantly with silicone compounds. The contamination is higher on the leading edge than on the trailing edge, and higher on the exposed crystal than on the reference crystals. No significant differences in composition of the In2O3 crystals were noted. Differences in the reflectance and surface analysis of the Zns crystals will be discussed.

Stuckey, W. K.↗

Post-flight analyses of the crystals from the M0003-14 quartz crystal microbalance experiment

Quartz Crystal Microbalances constructed by QCM Research were flown on the leading and trailing edges of LDEF as one of the sub-experiments of M0003. Response of the crystals coated with 150 A of In2O3 was recorded during the first 424 days of the mission. A second QCM with crystals coated with 150 A of ZnS was also flown but not monitored. After the flight, the QCM's were disassembled and analyzed in The Aerospace Corporation laboratories. The samples included the crystals from the leading and trailing edge samples of both types of coatings along with the reference crystals, which were inside the QCM housing. Analyses were performed by scanning electron microscopy, energy dispersive x-ray analyses, x-ray photoelectron spectroscopy, ion microprobe mass analysis, and reflectance spectroscopy in the infrared and UV/visible regions. The crystals are contaminated predominantly with silicone compounds. The contamination is higher on the leading edge than on the trailing edge and higher on the exposed crystals than on the reference crystals.

Stuckey, W. K.↗

Synthesis and decomposition of a novel carboxylate precursor to indium oxide

Reaction of metallic indium with benzoyl peroxide in 4-1 methylpyridine (4-Mepy) at 25 C produces an eight-coordinate mononuclear indium(III) benzoate, In(eta(sup 2)-O2CC6H5)3(4-Mepy)2 4H2O (I), in yields of up to 60 percent. The indium(III) benzoate was fully characterized by elemental analysis, spectroscopy, and X-ray crystallography; (I) exists in the crystalline state as discrete eight-coordinate molecules; the coordination sphere around the central indium atom is best described as pseudo-square pyramidal. Thermogravimetric analysis of (I) and X-ray diffraction powder studies on the resulting pyrolysate demonstrate that this new benzoate is an inorganic precursor to indium oxide. Decomposition of (I) occurs first by loss of 4-methylpyridine ligands (100 deg-200 deg C), then loss of benzoates with formation of In2O3 at 450 C. We discuss both use of carboxylates as precursors and our approach to their preparation.

Hepp, Aloysius F.↗

ITO-MgF2 Film Development for PowerSphere Polymer Surface Protection

Multi-kilogram class microsatellites with a PowerSphere electric power system are attractive for fulfilling a variety of potential NASA missions. However, PowerSphere polymer surfaces must be coated with a film that has suitable electrical sheet resistivity for electrostatic discharge control, be resistant to atomic oxygen attack, be transparent to ultraviolet light for composite structure curing and resist ultraviolet light induced darkening for efficient photovoltaic cell operation. In addition, the film must be tolerant of polymer layer folding associated with launch stowage of PowerSphere inflatable structures. An excellent film material candidate to meet these requirements is co-sputtered, indium oxide (In2O3) - tin oxide (SnO2), known as 'ITO', and magnesium fluoride (MgF2). While basic ITO-MgF2 film properties have been the subject of research over the last decade, further research is required in the areas of film durability for space-inflatable applications and precise film property control for large scale commercial production. In this paper, the authors present film durability results for a folded polymer substrate and film resistance to vacuum UV darkening. The authors discuss methods and results in the area of film sheet resistivity measurement and active control, particularly dual-channel, plasma emission line measurement of ITO and MgF2 plasma sources. ITO-MgF2 film polymer coupon preparation is described as well as film deposition equipment, procedures and film characterization. Durability testing methods are also described. The pre- and post-test condition of the films is assessed microscopically and electrically. Results show that an approx. 500A ITO-18vol% MgF2 film is a promising candidate to protect PowerSphere polymer surfaces for Earth orbit missions. Preliminary data also indicate that in situ film measurement methods are promising for active film resistivity control in future large scale production. Future film research plans are also discussed.

Hambourger, Paul D.↗

Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

Alim, M. A.↗

Modification of Radiator Pigments by Atomic Layer Deposition (ALD)

The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. Other examples include the application of variable emittance coatings such as the use of VO2 to optimize radiator size, allowing for a decrease in heater power budget. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. Modification of these coatings can be accomplished during coating application preprocessing by using a deposition technique prevalent in the semiconductor micro processing industry called Atomic Layer Deposition (ALD). The preprocessing is rendered directly on the coating dry pigment before binding. ALD is a cost effective nano-manufacturing technique that allows for the conformal coating of substrates with atomic-level thickness control in a benign temperature and pressure environment. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano-structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. We have demonstrated a method for the ALD of In2O3 and ITO films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments (patent pending). The results indicate excellent growth of 4-22 nm thick films demonstrating an order of magnitude decrease in resistivity on the pigments.

ITO↗

Technology Development for the Modification of High Aspect Ratio Geometries for Thermal and Environmental Control

A key technology development driver in environmental control systems and next generation optics are discussed utilizing thin film development borrowed from the semiconductor industry. The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. The multi-billion-dollar semiconductor industry has adopted Atomic Layer Deposition (ALD) for self-assembly and atomic-scale placement. ALD is a cost-effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. By using ALD, modification of these coatings can be accomplished during coating application preprocessing. The preprocessing is rendered directly on the coating dry pigment before binding. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano- structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. A method has been demonstrated for the ALD of In2O3 and films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments resulting in a direct spaceflight application. Results will be presented that verify the chemical composition of ALD pigments and charge dissipation properties when the pigment goes through its binding and coating process and we present early results of ALD for carbon nanotube formation and encapsulation.

Dwivedi, Vivek H.↗

Application and Development of Atomic Layer Deposition Techniques to Improve Thermo-Optical Coatings for Spacecraft Thermal Control and Advanced Optical Instruments

A key technology development driver in environmental control systems and next generation optics are discussed utilizing thin film development borrowed from the semiconductor industry. The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. The multi-billion-dollar semiconductor industry has adopted Atomic Layer Deposition (ALD) for self-assembly and atomic-scale placement. ALD is a cost-effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. By using ALD, modification of these coatings can be accomplished during coating application preprocessing. The preprocessing is rendered directly on the coating dry pigment before binding. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano- structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. A method has been demonstrated for the ALD of In2O3 and films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments resulting in a direct spaceflight application. Results will be presented that verify the chemical composition of ALD pigments and charge dissipation properties when the pigment goes through its binding and coating process and we present early results of ALD for carbon nanotube formation and encapsulation.

Dwivedi, Vivek H.↗