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NASA NTRS1987

The localization and crystallographic dependence of Si suboxide species at the SiO2/Si interface

X-ray photoemission spectroscopy has been used to examine the localization and crystallographic dependence of Si(+), Si(2+), and Si(3+) suboxide states at the SiO2/Si interface for (100)and (111)-oriented substrates with gate oxide quality thermal oxides. The Si(+) and Si(2+) states are localized within 6-10 A of the interface while the Si(3+) state extends about 30 A into the bulk SiO2. The distribution of Si(+) and Si(2+) states shows a strong crystallographic dependence with Si(2+) dominating on (100) substrates and Si(+) dominating on (111) substrates. This crystallographic dependence is anticipated from consideration of ideal unreconstructed (100) and (111) Si surfaces, suggesting that (1) the Si(+) and Si(2+) states are localized immediately within the first monolayer at the interface and (2) the first few monolayers of substrate Si atoms are not significantly displaced from the bulk. The total number of suboxide states observed at the SiO2/Si interface corresponds to 94 and 83 percent of a monolayer for these (100) and (111) substrates, respectively.

Grunthaner, P. J.↗

NASA NTRS1987

Shallow n(+) diffusion into InP by an open-tube diffusion technique

Very shallow n(+) layers have been obtained in InP by using gallium sulfide as a source for sulfur diffusion, and chemically vapor-deposited SiO2 as a cap. Diffusions were carried out from 585 to 725 C in an open-tube system with a nitrogen ambient. The doping profile of sulfur in InP is estimated to be of the complementary error function type with a surface concentration of 5.6 x 10 to the 18th/cc and a diffusion constant of 1.1 x 10 to the -14th sq cm/s at 670 C. Diodes made on n(+)-p junctions obtained by this diffusion technique show ideality factors close to unity and saturation current densities as low as 3.4 x 10 to the -15th A/sq cm, signifying the presence of a defect-free junction. These diffusions, with junction depths in the 400-700 A range, are ideal for solar cell applications.

Ghandhi, Sorab K.↗

NASA NTRS1986

Mantle heterogeneity and crustal recycling in Archean granite-greenstone belts - Evidence from Nd isotopes and trace elements in the Rainy Lake area, Superior Province, Ontario, Canada

Crustal evolution in the Rainy Lake area, Ontario is studied in terms of geochemical characteristics. The Nd isotope data are examined for heterogeneity of the Archean mantle, and the Sm/Nd depletion of the mantle is analyzed. The Nd isotope systematics of individual rock suites is investigated in order to understand the difference between crust and mantle sources; the precursors and petrogenetic processes are discussed. The correlation between SiO2 content and Nd values is considered. Rapid recycling of crustal components, which were previously derived from depleted mantle sources, is suggested based on the similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks.

Shirey, Steven B.↗

NASA NTRS1987

Barred olivine chondrules in ordinary chondrites

The characteristics of 125 barred olivine chondrules identified in polished thin sections of 26 H-L-LL3-6 chondrites were studied, using an electron microprobe for determining mineral abundances and a broad-beam electron microprobe for determining bulk compositions. Compared with all chondrule types in the H-L-LL3 ordinary chondrites, the barred olivine chondrules were found to be enriched in FeO, Al2O3, Na2O, and K2O and depleted in SiO2 and MgO; they were also found to be enriched in the feldspathic component. It is concluded that the precursor components of barred olivine chondrules consisted of a mixture of an olivine-rich component, a refractory-rich component containing Al2O3, TiO2, and CaO, and a volatile-rich alkalic component. This unusual combination implies high temperatures of melting for the refractory component and low temperatures for the volatile component, supporting the hypothesis of Grossman and Wasson (1983) that the alkalies condensed on the alumina already available.

Weisberg, Michael K.↗

NASA NTRS1987

Tektite-like bodies at Lonar Crater, India - Implications for the origin of tektites

Homogeneous dense glass bodies (both irregular and splash form) with high silica contents (about 67 pct SiO2) occur in the vicinity of Lonar Crater, India. Their lack of microlites and mineral remnants and their uniform chemical composition virtually preclude a volcanic origin. They are similar to tektites reported in the literature. While such a close association of tektite-like bodies with impact craters is already known (Aouelloul Crater, Mauritania; Zhamanshin Crater, U.S.S.R.), the tektite-like bodies at Lonar Crater are unique in that they occur in an essentially basaltic terrain. Present geochemical data are consistent with these high silica glass bodies being impact melt products of two-thirds basalt and one-third local intertrappean sediment (chert). The tektite-like bodies of the impact craters Lonar, Zhamanshin, and Aouelloul are generally similar. Strong terrestrial geochemical signatures reflect the target rock REE patterns and abundance ratios and demonstrate their terrestrial origin resulting from meteorite impact, as has been suggested by earlier workers.

Murali, A. V.↗

NASA NTRS1987

Oxygen measurements in thin ribbon silicon

The oxygen content of thin silicon ribbons grown by the dendritic web technique was measured using a modification of the ASTM method based on Fourier transform infrared spectroscopy. Web silicon was found to have a high oxygen content, ranging from 13 to 19 ppma, calculated from the absorption peak associated with interstitial oxygen and using the new ASTM conversion coefficient. The oxygen concentration changed by about 10 percent along the growth direction of the ribbon. In some samples, a shoulder was detected on the absorption peak. A similar shoulder in Czochralski grown material has been variously interpreted in the literature as due to a complex of silicon, oxygen, and vacancies, or to a phase of SiO2 developed along dislocations in the material. In the case of web silicon, it is not clear which is the correct interpretation.

Hyland, S. L.↗

NASA NTRS1987

Rb-Sr and Sm-Nd systematics of cherts and other siliceous deposits

An analysis of marine and lacustrine cherts demonstrates that Rb-Sr and Sm-Nd systems may be used in elucidating the origin and evolution of cherts, and that the Rb-Sr system may be used for dating. All samples have high Rb/Sr ratios, and though the site of these elements in cherts was not established, they appear to be correlated with Al content. Sm/Nd ratios were typical of continental sources, and the results show the Rb-Sr system in cherts to be isolated from the associated carbonate, with little Sr exchange. Data suggest that in many cases cherts are formed by dissolved SiO2 nucleating on clay-like material which preserves the isotropic characteristics of the detrital source, while in some cases it is possible that cherts were formed from silica-saturated waters from a nonmarine source.

Weis, D.↗

NASA NTRS1987

A vaporization model for iron/silicate fractionation in the Mercury protoplanet

A study has been carried out on the vaporization of a totally molten silicate magma of chondritic composition heated into the range 2500-3500 K. The motivation for this was to determine the changes in the composition of the mantle that would occur in the Mercury protoplanet should that body have been subjected to the high-temperature phase in the evolution of the primitive solar nebula, but the results are of more general interest. An empirical model based on ideal mixing of complex components was used to describe the nonideal magma. It is found that vaporization of about 70-80 percent of the original amount of silicate from a chondritic planet is required to produce an iron-rich body with a mean uncompressed density equal to that deduced for Mercury. At this point the silicate is depleted in the alkalis, FeO, and SiO2, and enriched in CaO, MgO, Al2O3, and TiO2 relative to chondritic material.

Fegley, Bruce, Jr.↗

NASA NTRS1987

Durability characterization of ceramic materials for gas turbines

The strength retention of ceramic materials during extended high-temperature cyclic exposure is critical to their widespread application in gas turbine engines. During a continuing NASA funded program initated in 1979, reaction bonded silicon nitride (RBSN), sintered silicon carbide (SSC), reaction sintered silicon carbide (RSSC), and sintered silicon nitride (SSN) materials were evaluated following simulated gas turbine engine exposures. Exposures were performed by cycling specimens five times per hour between a high velocity burner discharge and a rapid air quench. The retained flexural strengths were determined following up to 3500 hours of exposure at temperatures up to 1370 C. Post-exposure strengths have been correlated with fractography and surface examination using SEM. Results illustrate excellent strength retention of SSC materials after 3500 hours of exposure to 1370 C. At 1200 C, RBSN and RSSC also demonstrate significant strength retention. Although SSN materials typically suffer significant strength losses during exposures at 1200 C, a new composition, which has improved high-temperature strength, also shows improved durability. In the majority of the materials, strength loss is typically associated with flaw formation in the protective SiO2 layer.

Carruthers, W. D.↗

NASA NTRS1987

NDE reliability and process control for structural ceramics

The reliability of microfocus X-radiography and scanning laser acoustic microscopy for detecting microvoids in silicon nitride and silicon carbide was statistically evaluated. Materials- and process-related parameters that influenced the statistical findings in research samples are discussed. The use of conventional X-radiography in controlling and optimizing the processing and sintering of an Si3N4-SiO2-Y2O3 composition designated NASA 6Y is described. Radiographic evaluation and guidance helped develop uniform high-density Si3N4 modulus-of-rupture bars with improved four-point flexural strength (857, 544, and 462 MPa at room temperature, 1200 C, and 1370 C, respectively) and reduced strength scatter.

Baaklini, G. Y.↗

NASA NTRS1986

Crystallization of baria-titania-silica glasses

The critical cooling rate for glass formation, Rc, and the crystallization kinetics of the compositions (1/2)(100-x)BaO-(1/2)(100-x)TiO2-(x)SiO2 with x = 20, 25, 30, 33.3, and 40 mol pct were studied using a thermal image furnace. Crystallization was studied under nonisothermal conditions, and the data were analyzed using the Johnson-Mehl-Avrami equation. The Rc and activation energy for crystallization both decrease with increasing silica content. Fresnoite, Ba2TiSi2O8, crystallized from all of the glasses when they were reheated. The infrared absorption spectra of the glasses and crystals show that they both contain (Si2O7) and square pyramidal (TiO5) groups.

Ray, Chandra S.↗

NASA NTRS1988

Friction and Wear of Monolithic and Fiber Reinforced Silicon-Ceramics Sliding Against IN-718 Alloy at 25 to 800 C in Atmospheric Air at Ambient Pressure

The friction and wear of monolithic and fiber reinforced Si-ceramics sliding against the nickel base alloy IN-718 at 25 to 800 C was measured. The monolithic materials tested were silicon carbide (SiC), fused silica (SiO2), syalon, silicon nitride (Si3N4) with W and Mg additives, and Si3N4 with Y2O3 additive. At 25 C fused silica had the lowest friction while Si3N4 (W,Mg type) had the lowest wear. At 800 C syalon had the lowest friction while Si3N4 (W,Mg type) and syalon had the lowest wear. The SiC/IN-718 couple had the lowest total wear at 25 C. At 800 C the fused silica/IN-718 couple exhibited the least total wear. SiC fiber reinforced reaction bonded silicon nitride (RBSN) composite material with a porosity of 32 percent and a fiber content of 23 vol percent had a lower coefficient of friction and wear when sliding parallel to the fiber direction than in the perpendicular at 25 C. The coefficient of friction for the carbon fiber reinforced borosilicate composite was 0.18 at 25 C. This is the lowest of all the couples tested. Wear of this material was about two decades smaller than that of the monolithic fused silica. This illustrates the large improvement in tribological properties which can be achieved in ceramic materials by fiber reinforcement. At higher temperatures the oxidation products formed on the IN-718 alloy are transferred to the ceramic by sliding action and forms a thin, solid lubricant layer which decreases friction and wear for both the monolithic and fiber reinforced composites.

Deadmore, Daniel L.↗

NASA NTRS1988

Microwave dielectric spectrum of rocks

A combination of several measurement techniques was used to investigate the dielectric properties of 80 rock samples in the microwave region. The real part of the dielectric constant, epsilon', was measured in 0.1 GHz steps from 0.5 to 18 GHz, and the imaginary part, epsilon'', was measured at five frequencies extending between 1.6 and 16 GHz. In addition to the dielectric measurements, the bulk density was measured for all the samples and the bulk chemical composition was determined for 56 of the samples. The study shows that epsilon' is frequency-dependent over the 0.5 to 18 GHz range for all rock samples, and that the bulk density rho accounts for about 50 percent of the observed variance of epsilon'. For individual rock types (by genesis), about 90 percent of the observed variance may be explained by the combination of density and the fractional contents of SiO2, Fe2O3, MgO, and TiO2. For the loss factor epsilon'', it was not possible to establish statistically significant relationships between it and the measured properties of the rock samples (density and chemical composition).

Ulaby, F. T.↗

NASA NTRS1986

Improved processing of Si3N4

A sintered Si3N4-SiO2-Y2O3 composition, NASA 6Y, was developed that reached four-point flexural average strength/standard deviation values of 857/36, 544/33, and 462/59 MPa at room temperature, 1200, and 1370 C, respectively. These strengths represented improvements of 56, 38, and 21 percent over baseline properties at the three test temperatures. At room temperature the standard deviation was reduced by more than a factor of three. These accomplishments were realized by the iterative utilization of conventional X-radiography to characterize structural (density) uniformity as affected by systematic changes in powder processing and sintering parameters. Accompanying the improvement in mechanical properties was a change in the type of flaw causing failure from a pore to a large columnar beta-Si3N4 grain typically 40 to 80 microns, 10 to 30 microns wide, and with an aspect ratio of 5:1.

Sanders, William A.↗

NASA NTRS1988

Sulfur as a surface passivation for InP

The use of liquid and gas phase sulfur pretreatment of the surface of InP as a way to form a near-ideal passivated surface prior to chemical vapor deposition of SiO2 was investigated. Results of high-frequency and quasi-static capacitance-voltage measurements, as well as enhancement mode insulated gate field-effect transistor (FET) transductance and drain current stability studies, all support the efficacy of this approach for metal-insulator-semiconductor application of this semiconductor. In particular, surface state values in the range of 10 to the 10th to a few 10 to the 11th/sq cm per eV and enhancement mode FET drain current drifts of less than 5 percent over a 12 h test period were measured.

Iyer, R.↗

NASA NTRS1988

The origin of type C inclusions from carbonaceous chondrites

The origin of type C inclusions found in carbonaceous chondrites and the relationship of the type C inclusions to other Ca- and Al-rich chondrules are discussed on the basis of major-element composition of these objects. The results on bulk composition analysis of primary phase assemblages in eight Allende-type inclusions and an Allende glass-spinel inclusion were found to be consistent with the following scenario: (1) the condensation of melilite + spinel + perovskite +/- hibonite +/- CaAl4O7; (2) the reaction of melilite + spinel with SiO2(g); (3) the removal of inclusions from further interaction with the reacting gas; (4) melting with little or no volatilization; (5) crystallization; (6) alteration; and (7) incorporation of inclusions into host meteorite. Type C inclusions are considered to be precursors to Al-rich chondrules in ordinary and enstatite chondrites, i.e., they are considered to be a spinel-rich class of type A that reacted with silica from a coexisting gas to produce anorthite plus diopside.

Beckett, John R.↗

NASA NTRS1988

Sol-gel synthesis of magnesium oxide-silicon dioxide glass compositions

MgO-SiO2 glasses containing up to 15 mol pct MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol pct MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol pct MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol pct) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗

NASA NTRS1989

Improved Method For Making Infrared Imagers

Properties of thin dielectric layer adjusted precisely. Deposition technique found to improve fabrication of infrared imaging devices. Applied to dielectric layer of SiO and SiO2, critical to operation of device. For imager to work properly, thickness of dielectric layer adjusted precisely in coordination with absorption coefficient and wavelength of light imaged. New deposition process enables adjustment of thickness and index of refraction of critical dielectric layer to within plus or minus 1 percent.

Kaganowicz, G.↗