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At least 145 records · Page 8

Photoemission measurements of interface barrier energies for tunnel oxides on silicon

Internal photoemission measurements of the Si/SiO2 and Al/SiO2 barrier heights on oxides of tunneling thickness (43-56 A) are compared with measurements on thick oxides (310 A and greater) and the barrier heights are found to be the same. The results suggest that substantially thinner oxides, grown by the same method, can be characterized by the same barrier heights. Limits to the experimental technique posed by photovoltaic and displacement currents, and transport of hot carriers in the tunnel oxide are discussed.

Dressendorfer, P. V.

To Produce Nutrients for Plant Growth

On July 1, 1979 a new research program entitled "Development of a Prototype Experiment for Treating CELSS and PCELSS Wastes to Produce Nutrients for Plant Growth" was undertaken by the Massachusetts Institute of Technology and the Georgia Institute of Technology under grant from the National Aeronautics and Space Administration's Ames Research Center. The program was designed to be completed over a five-year period, with the work divided into two phases. Phase I covers approximately two years and involves the development of necessary facilities, chemical methodologies and models to allow meaningful experiments during Phase II, which will involve interfacing waste oxidation with plant growth. Homogeneous samples of freeze-dried human feces and urine have been prepared to assure comparability of results among various CELSS waste treatment research groups. A model of food processing wastes within a PCELSS was developed, and an initial batch of waste was prepared. An automated gas chromatographic system to analyze oxidizer effluents was designed and is operational. A state-of-the-art quantitative elemental analysis capability, built around inductively coupled plasma emission spectroscopy and atomic absorption spectroscopy using electrothermal atomization, has been demonstrated. A continuous flow wet oxidation system was constructed and is now operational.

Michael Modell

An X-ray diffraction study of titanium oxidation

Titanium specimens of commercial purity were exposed at 1100 to 1400 F to laboratory air for times up to 100 hours. The extent of substrate contamination by interstitial oxygen was was determined by a new X-ray diffraction analysis involving transformation of X-ray diffraction intensity bands. The oxygen solid-solubility at the oxide-metal interfaces and its variation with time at temperature were also determined. Diffusion coefficients are deduced from the oxygen depth profiles.

Wiedemann, K. E.

Electrical characterization of plasma-grown oxides on gallium arsenide

Plasma-grown GaAs oxides and their interfaces have been characterized by measuring the electrical properties of metal-oxide-semiconductor capacitors and of Schottky junctions. The current transport mechanism in the oxide at high electrical field was found to be Frankel-Poole emission, with an electron trap center at 0.47 eV below the conduction band of the oxide. The interface-state density, evaluated from capacitance and conductance measurements, exhibits a U-shaped interface-state continuum extending over the entire band gap. Two discrete deep states with high concentration are superimposed on this continuum at 0.40 and 0.70 eV below the conduction band. The results obtained from measurements on Schottky junctions have excluded the possibility that these two deep states originate from plasma damage. Possible origins of these states are discussed in this paper.

Hshieh, F. I.

Microstructural aspects of zirconia thermal barrier coatings

Various combination of plasma-sprayed bond coatings and zirconia ceramic coatings on a nickel-based superalloy substrate were tested by static thermal exposure at 1200 C and cyclic thermal exposure to 1000 C. The bond coats were based on Ni-Cr-Al alloys with additions of rare earth elements and Si. The ceramic coats were various ZrO2-Y2O3 compositions, of which the optimum was found to be ZrO2-8.9 wt percent Y2O3. Microstructural analysis showed that resistance to cracking during thermal exposure is strongly related to deleterious phase changes. Zones depleted of Al formed at the bond coat/ceramic coat interface due to oxidation and at the bond coat/substrate interface due to interdiffusion, leading eventually to breakdown of the bond coat. The 8.9 percent Y2O3 coating performed best because the as-sprayed metastable tetragonal phase converted slowly into the low-Y2O3 tetragonal plus high-Y2O3 cubic-phase mixture, so that the deleterious monoclinic phase was inhibited from forming. Failure appeared to start with the formation of circumferential cracks in the zirconia, probably due to compressive stresses during cooling, followed by the formation of radial cracks due to tensile stresses during heating. Cracks appeared to initiate at the Al2O3 scale/bond coat interface and propagate through the zirconia coating. Comparisons were made with the behavior of bulk ZrO2-Y2O3 and the relationship between the microstructure of the tetragonal phase and the phase diagram. A separate investigation was also made of the ZrO2-Al2O3 interface.

Mitchell, T. E.

Effect of 0.1 at. pct Zirconium on the cyclic oxidation resistance of beta-NiAl

The effect of 0.1 at. pct Zr on the cyclic oxidation of hipped beta-NiAl was studied. Oxidation testing was performed in static air at 1100-1200 C, using 1-hr exposure cycles for test times up to 3000 hr. The weight change versus time data were modeled with the COSP computer program to analyze and predict cyclic-oxidation behavior. Zr additions significantly change the nature of the scale-spalling process during cooling, so that the oxide spalls near the oxide-air interface at a relatively low depth within the scale. Without Zr, the predominantly alpha-Al2O3 scale tends to spall randomly to bare metal at relatively high effective-scale-loss rates, particularly at 1150 C and 1200 C. This leads to higher rates of Al consumption for the Zr-free aluminide and much earlier depletion of Al, leading to eventual breakaway (i.e., failure).

Barrett, Charles A.

Process and Radiation Induced Defects in Electronic Materials and Devices

Process and radiation induced defects are characterized by a variety of electrical techniques, including capacitance-voltage measurements and charge pumping. Separation of defect type into stacking faults, displacement damage, oxide traps, interface states, etc. and their related causes are discussed. The defects are then related to effects on device parameters. Silicon MOS technology is emphasized. Several reviews of radiation effects and silicon processing exist.

Washington, Kenneth

Nonprotective Alumina Growth in Sulfur-Doped NiAl(Zr)

The 1200 C oxidation behavior of NiAl was examined at various levels of sulfur and zirconium dopants to test the possibility of a critical S/Zr ratio required for adhesion. Cyclic furnace testing for 200 1 -hr cycles and interrupted testing for 500 hr were used as screening tests. Pure NiAl and NiAl(Zr) with 0. 14 at.% Zr were chosen as model base compositions; they exhibited normal, slow-growing scales (3 Mg/sq cm) with excellent adhesion for the Zr-doped alloys. NiAl with about 120 ppma S exhibited a substantial weight loss (-20 Mg/sq cm) in cyclic tests and a very large weight gain (+60 Mg/sq cm) in interrupted tests. The major surface phase remained as alpha -Al2O3. Sulfur doping the NiAl(Zr) alloy caused massive weight gains of 80 - 100 Mg/sq cm, swelling, cracking, and nearly complete conversion into NiAl2O4, and alpha- Al2O3. The initial objective of determining critical S/Zr ratios for adhesion was therefore unattainable. Initiation of the catastrophic attack was examined after a 10 hr exposure, revealing a few sites of broad, raised, and cracked ridges. In cross-section, the ridges appeared as modular intrusions, with a complex, fractal, oxide-metal interface. They were primarily alumina (with occasional entrapped islands of NiAl2O4 or pure Ni metal). They possessed a unique microstructure consisting of 0.3 microns lamellae, separated by 0.1 microns open channels. This allowed for rapid growth controlled by gaseous diffusion. The microstructure is discussed in terms of SO2 evolution and a sulfur-driven de-passivation process.

Smialek, James L.

Recent Advances in the Development of Thick-Section Melt-Infiltrated C/SiC Composites

Using a pressureless melt infiltration and in situ reaction process to form the silicon carbide (SiC) matrix, Ultramet has been developing a means to rapidly fabricate ceramic matrix composites (CMCs) targeting thicker sections. The process also employs a unique route for the application of oxide fiber interface coatings designed to protect the fiber and impart fiber-matrix debond. Working toward a 12 inch diameter, 2.5 inch thick demonstrator component, the effect of various processing parameters on room temperature flexure strength is being studied with plans for more extensive elevated temperature mechanical strength evaluation to follow this initial optimization process.

Babcock, Jason R.

Moisture-Induced Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

Thermal expansion mismatch stresses and interfacial sulfur activity are the major factors producing primary Al2O3 scale spallation on high temperature alloys. However, moisture-induced delayed spallation appears as a secondary, but often dramatic, illustration of an additional mechanistic detail. A historical review of delayed failure of alumina scales and TBC s on superalloys is presented herein. Similarities with metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al+3H2O=Al(OH)3+3H(+)+3e(-), is the operative mechanism. This proposal was tested by standard cathodic hydrogen charging in 1N H2SO4, applied to Rene N5 pre-oxidized at 1150 C for 1000 1-hr cycles, and monitored by weight change, induced current, and microstructure. Here cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the electrolyte alone produced neither scale spallation nor alloy dissolution. These experiments thus highlight the detrimental effects of hydrogen charging on alumina scale adhesion. It is proposed that interfacial hydrogen embrittlement is produced by moist air and is the root cause of both moisture-induced, delayed scale spallation and desktop TBC failures.

Smialek, James L.

Moisture-Induced Delayed Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

While interfacial sulfur is the primary chemical factor affecting Al2O3 scale adhesion, moisture-induced delayed spallation appears as a secondary, but impressive, mechanistic detail. Similarities with bulk metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al(sub alloy)+3(H2O)(sub air) = Al(OH)(-) (sub 3) +3H(+) may be the operative mechanism. This proposal was tested on pre-oxidized Rene N5 by standard cathodic hydrogen charging in 1N H2SO4, as monitored by weight change, induced current, and microstructure. Cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the acid electrolyte produced neither scale spallation nor alloy dissolution. Thus, hydrogen charging was detrimental to alumina scale adhesion. Moisture-induced interfacial hydrogen embrittlement is concluded to be the cause of delayed scale spallation and desktop thermal barrier coating failures.

Smialek, James L.

On-Chip p-MOSFET Dosimetry

On-chip p-FETs were developed to monitor the radiation dose of n-well CMOS ICs by monitoring the threshold voltage shifts due to radiation induced oxide and interface charge.

FET's

A Multifunctional Isostructural Bilayer Oxygen Evolution Electrode for Durable Intermediate-Temperature Electrochemical Water Splitting

The overarching goal of the proposed research is to address SOEC’s degradation problem by advancing a new isostructural highly electrocatalytically active bilayer oxygen evolution reaction (OER) electrode, consisting of a LSCF (La 1-x Sr x Co 1-y Fe y O 3-δ ) core and a SCT (SrCo 0.9 Ta 0.1 O 3-δ ) shell, to achieve high and sustainable rate of oxygen evolution matching operating current densities without encountering delamination. To realize this goal, the project has adopted a combined experimental and theoretical approach to conduct research in the following six areas closely associated with SOPO tasks: 1) Development of electrocatalytically active bilayer oxygen electrodes (SOPO task-1) 2) Development of new symmetric three electrode cell (STEC) methodology to extract electrokinetic data of oxygen electrodes (SOPO task-2) 3) Quantification of electrokinetics of bilayer oxygen electrodes and correlation with degradation and delamination (SOPO task-2) 4) Performances of bilayer oxygen electrodes under fuel cells and electrolyzers modes (SOPO task-3) 5) Microscale modeling of oxygen electrode/electrolyte interface in solid oxide electrolysis cells (SOPO task-4) 6) Prediction of crack growth rate at oxygen electrode/electrolyte interface in solid oxide electrolysis cells (SOPO task-4)

08 HYDROGEN

Carbon-Mediated Oxygen Vacancy Creation at Hematite Interfaces

Nanoscale iron oxides (e.g., hematite (a-Fe 2 O 3 )) have unique properties, such as enhanced chemical reactivity and high surface area, when compared with their bulk counterparts. These nanoscale surfaces can be more reactive due to the presence of defects (e.g., oxygen vacancies). In this work, we probed the surface chemistry of bulk and nanoscale hematite via X-ray photoelectron spectroscopy, electron microscopy, and powder X-ray diffraction. Oxygen exposure and vacuum annealing experiments were conducted to add or remove oxygen vacancies and remove adventitious carbon. In the absence of the oxygen annealing step, vacuum annealing resulted in partial reduction of Fe(III) to Fe(II) on all hematite surfaces. This was a size-dependent effect with the extent of reduction increasing as the crystallite size decreased. In addition, the atomic concentrations of carbon increased on all iron oxide surfaces after vacuum annealing. Oxygen annealing almost completely removed carbon from sample surfaces, and no Fe(III) reduction was observed in the absence of carbon. Under these conditions, the results reveal that carbonaceous material enhances oxygen vacancy formation, which then facilitates the reduction of Fe(III) on hematite surfaces. We provide new insights into the mechanisms of Fe(III) reduction on both bulk and nanoscale hematite surfaces and establish the major role of carbon in oxygen vacancy formation.

Zengotita, Frances E. [University of Notre Dame, I

Transition Metal Oxides as Cathodes in Li-O2 battery: A First Principles Investigation

Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like Dimethyl ether (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of cathode and reduction of cyclability. In this work, we investigate some of the well-known oxides as cathodes with focus on the interface between the oxide surfaces and the discharge product: Li2O2, in the Li-O2 battery using first principles computations. Our results show that attention must be paid on choosing the appropriate surface of the oxides. We extend the analysis to suggest other possible oxide chemistries that should be investigated as cathodes in Li-O2 batteries.

Li-O2 battery

Obtaining bulk-like correlated oxide surfaces with protective caps

Functional oxides exhibit a diverse range of correlated electron phenomena, some of which are highly attractive for novel electronic, magnetic, and optical devices. Despite decades of advancement of our fundamental understanding of these materials, they consistently fall short of realizing their promise in functional devices. We identify a significant bottleneck toward device realization to be surface overoxidation. Protective caps can effectively prevent overoxidation, but their interfaces with functional oxides are not well understood. These interfaces are critical for effectively using functional oxides in field-effect devices, where “the interface is the device.” This work addresses the chemistry and physics of the interface between protective caps and the correlated metal SrVO3, a model functional oxide. Our comparison of five different cap materials reveals effective protection and similar SrVO3 surface chemistry in all cases. Systematic comparisons of surface and bulk-sensitive photoelectron spectra reveal that negligible interface redox takes place, elucidating the cap-SrVO3 interface chemistry. This work demonstrates a robust and simple solution to the surface overoxidation problem in vanadates, paving the way toward effectively using these materials in field-effect devices. Our conclusions are general and can be applied to numerous other systems, thus moving oxide electronics closer to the realization of functional devices.

Cohen, Amit (ORCID:0009000276477510)

Oscillations in MOS tunneling

Oscillatory deviations from Fowler-Nordheim tunneling currents were measured in MOS capacitors with oxide thicknesses ranging from 30 to 75 A. The observed variation of oscillation phases and amplitudes with oxide thickness indicates that the Si-SiO2 interface is independent of oxide thickness only for thicknesses greater than 65 A. At lower thicknesses, the barrier height at the interface decreases gradually with oxide thickness at a rate on the order of 10 mV/A. At higher thicknesses, the barrier height is 4.08 eV. The energy dispersion relation with the SiO2 conduction band is parabolic. The mean free path within the SiO2 conduction band is on the order of 13 A.

Lewicki, G.

Properties of silicon carbide fiber-reinforced silicon nitride matrix composites

The mechanical properties of NASA Lewis developed SiC/RBSN composites and their thermal and environmental stability havd been studied. The composites consist of nearly 30 vol pct of aligned 142 micron diameter chemically vapor-deposited SiC fibers in a relatively porous silicon nitride matrix. In the as-fabricated condition, the unidirectional and 2-D composites exhibited metal-like stress-strain behavior, graceful failure, and showed improved properties when compared with unreinforced matrix of comparable density. Furthermore, the measured room temperature tensile properties were relativley independent of tested volume and were unaffected by artifical notches normal to the loading direction or by thermal shocking from temperatures up to 800 C. The four-point bend strength data measured as a function of temperature to 1400 C in air showed that as-fabricated strength was maintained to 1200 C. At 1400 C, however, nearly 15 pct loss in strength was observed. Measurement of room temperature tensile strength after 100 hr exposure at temperatures to 1400 C in a nitrogen environment indicated no loss from the as-fabricated composite strength. On the other hand, after 100 hr exposure in flowing oxygen at 1200 and 1400 C, the composites showed approximately 40 pct loss from their as-fabricated ultimate tensile strength. Those exposed between 400 to 1200 C showed nearly 60 pct strength loss. Oxidation of the fiber/matrix interface as well as internal oxidation of the porous Si3N4 matrix are likely mechanisms for strength degradation. The excellent strength reproducibility, notch insensitivity, and high temperature strength of the composite makes it an ideal candidate for advanced heat engine applications provided coating or densification methods are developed to avoid internal oxidation attack.

Bhatt, Ramakrishna T.