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At least 19 records

Titanium in silicon as a deep level impurity

Titanium inserted in silicon by diffusion or during Czochralski ingot growth is electrically active to a concentration level of about 4 x 10 to the 14th per cu cm. It is reported that Hall measurements after diffusion show conversion of lightly doped p-type Si to n-type due to a Ti donor level at E sub c -0.22 eV. In addition, in DLTS measurements of n(+)p structures this level shows as an electron (minority carrier) trap at E sub c -0.26 eV with an electron capture cross section of about 3 x 10 to the -15th per sq cm at 300 K. Finally, a Ti electrically active concentration of about 1.35 x 10 to the 13th per cu cm in p type Si results in a minority carrier (electron) lifetime of 50 nsec at 300 K.

Chen, J.-W.↗

Growth of CdZnTe Crystals for Radiation Detector Applications by Directional Solidification

Advances in Cadmium Zinc Telluride (Cd(sub 1-x)Zn(sub x)Te) growth techniques are needed for the production of large-scale arrays of gamma and x-ray astronomy. The research objective is to develop crystal growth recipes and techniques to obtain large, high quality CdZnTe single crystal with reduced defects, such as charge trapping, twinning, and tellurium precipitates, which degrade the performance of CdZnTe and, at the same time, to increase the yield of usable material from the CdZnTe ingot. A low gravity material experiment, "Crystal Growth of Ternary Compound Semiconductors in Low Gravity Environment", will be performed in the Material Science Research Rack (MSRR) on International Space Station (ISS). One section of the flight experiment is the melt growth of CdZnTe ternary compounds. This talk will focus on the ground-based studies on the growth of Cd(sub 0.80)Zn(sub 0.20)Te crystals for radiation detector applications by directional solidification. In this investigation, we have improved the properties that are most critical for the detector applications (electrical properties and crystalline quality): a) Electrical resistivity: use high purity starting materials (with reproducible impurity levels) and controlled Cd over pressure during growth to reproducibly balance the impurity levels and Cd vacancy concentration b) Crystalline quality: use ultra-clean growth ampoule (no wetting after growth), optimized thermal profile and ampoule design, as well as a technique for supercool reduction to growth large single crystal with high crystalline quality

Su, Ching-Hua↗

Chemical Characterization and Thermal Stressing Studies of Perfluorohexane Fluids for Space-Based Applications

Perfluorohexane (PFH), C6F14, is a perfluorocarbon fluid. Several PFH fluids with different isomer concentrations were evaluated for use in an upcoming NASA space experiment. Samples tested included two commercially obtained high-purity n-perfluorohexane (n-PFH) fluids and a technical grade mixture of C6F14 branched and linear isomers (FC-72(TradeMark)). These fluids were evaluated for exact chemical composition, impurity purity and high temperature degradation behavior (pyrolysis). Our investigation involved simulated thermal stressing studies of PFH fluids under conditions likely to occur in the event of an atmospheric breach within the International Space Station (ISS) and subsequent exposure of the vapors to the high temperature and catalyst present in its Trace Contaminant Control Subsystem (TCCS). Exposure to temperatures in the temperature range of 200-450 C in an inert or oxidizing atmosphere, with and without the presence of catalyst was investigated. The most aggressive conditions studied were exposure of PFH vapors to 450 C in air and in the presence of TCCS (palladium) catalyst. Gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC) analyses were conducted on the perfluorohexane samples before and after pyrolysis. The FC-72 and n-PFH samples showed no significant degradation following pyrolysis even under the most aggressive study conditions. Some trace level impurities associated with the PFH samples such as linear perfluorocarbon monohydrides or monoiodides were destroyed by pyrolysis at the upper limit. Other trace level impurities such as olefinic or cycloolefinic perfluorocarbons were converted into oxidation products by pyrolysis. The purity of PFH following pyrolysis actually increased slightly as a consequence since these trace contaminants were effectively scrubbed from the samples. However, since the initial concentrations of the thermally-impacted impurities were so low, the net effect was trivial. A potential byproduct of exposure of perfluorohexane fluids to high temperatures is the production of perfluoroisobutene (PFiB), which is extremely toxic. An ultra-high sensitivity PFiB-specific analysis based on GC-MS with negative ion chemical ionization (NICI) detection was used to evaluate the samples following thermal stressing. The perfluorohexanes examined here under conditions reflective of the ISS TCCS environment showed no signs of PFiB production with an analytical detection limit of 10 part per billion (ppb v/v).

Arnold, William A.↗

NaK Plugging Meter Design for the Feasibility Test Loops

The design and predicted performance of a plugging meter for use in the measurement of NaK impurity levels are presented. The plugging meter is incorporated into a Feasibility Test Loop (FTL), which is a small pumped-NaK loop designed to enable the rapid, small-scale evaluation of techniques such as in situ purification methods and to permit the measurement of bulk material transport effects (not mechanisms) under flow conditions that are representative of a fission surface power reactor. The FTL operates at temperatures similar to those found in a reactor, with a maximum hot side temperature of 900 K and a corresponding cold side temperature of 860 K. In the plugging meter a low flow rate bypass loop is cooled until various impurities (primarily oxides) precipitate out of solution. The temperatures at which these impurities precipitate are indicative of the level of impurities in the NaK. The precipitates incrementally plug a small orifice in the bypass loop, which is detected by monitoring changes in the liquid metal flow rate.

Pearson, J. Boise↗

Laboratory Instruments Available to Support Space Station Researchers at Marshall Space Flight Center

A number of research instruments are available at NASA's Marshall Space Flight Center (MSFC) to support ISS researchers and their investigations. These modern analytical tools yield valuable and sometimes new informative resulting from sample characterization. Instruments include modern scanning electron microscopes equipped with field emission guns providing analytical capabilities that include angstron-level image resolution of dry, wet and biological samples. These microscopes are also equipped with silicon drift X-ray detectors (SDD) for fast yet precise analytical mapping of phases, as well as electron back-scattered diffraction (EBSD) units to map grain orientations in crystalline alloys. Sample chambers admit large samples, provide variable pressures for wet samples, and quantitative analysis software to determine phase relations. Advances in solid-state electronics have also facilitated improvements for surface chemical analysis that are successfully employed to analyze metallic materials and alloys, ceramics, slags, and organic polymers. Another analytical capability at MSFC is a mganetic sector Secondary Ion Mass Spectroscopy (SIMS) that quantitatively determines and maps light elements such as hydrogen, lithium, and boron along with their isotopes, identifies and quantifies very low level impurities even at parts per billion (ppb) levels. Still other methods available at MSFC include X-ray photo-electron spectroscopy (XPS) that can determine oxidation states of elements as well as identify polymers and measure film thicknesses on coated materials, Scanning Auger electron spectroscopy (SAM) which combines surface sensitivity, spatial lateral resolution (approximately 20 nm), and depth profiling capabilities to describe elemental compositions in near surface regions and even the chemical state of analyzed atoms. Conventional Transmission Electron Microscope (TEM) for observing internal microstructures at very high magnifications and the Electron Probe Micro-analyzer (EPMA) for very precise microanalysis are available as needed by the researcher. Space Station researchers are invited to work with MSFC in analyzing their samples using these techniques.

Panda, Binayak↗

Cryogenic Laser Calorimetry for Impurity Analysis

The results of a one-year effort to determine the applicability of laser-calorimetric spectroscopy to the study of deep-level impurities in silicon are presented. Critical considerations for impurity analysis by laser-calorimetric spectroscopy are discussed, the design and performance of a cryogenic laser calorimeter is described, and measurements of background absorption in high-purity silicon are presented.

Swimm, R. T.↗

Solar silicon via improved and expanded metallurgical silicon technology

A completed preliminary survey of silica sources indicates that sufficient quantities of high-purity quartz are available in the U.S. and Canada to meet goals. Supply can easily meet demand for this little-sought commodity. Charcoal, as a reductant for silica, can be purified to a sufficient level by high-temperature fluorocarbon treatment and vacuum processing. High-temperature treatment causes partial graphitization which can lead to difficulty in smelting. Smelting of Arkansas quartz and purified charcoal produced kilogram quantities of silicon having impurity levels generally much lower than in MG-Si. Half of the goal was met of increasing the boron resistivity from 0.03 ohm-cm in metallurgical silicon to 0.3 ohm-cm in solar silicon. A cost analysis of the solidification process indicate $3.50-7.25/kg Si for the Czochralski-type process and $1.50-4.25/kg Si for the Bridgman-type technique.

Hunt, L. P.↗

Characterization of zinc selenide single crystals

ZnSe single crystals of high quality and low impurity levels are desired for use as substrates in optoelectronic devices. This is especially true when the device requires the formation of homoepitaxial layers. While ZnSe is commercially available, it is at present extremely expensive due to the difficulty of growing single crystal boules with low impurity content and the resultant low yields. Many researchers have found it necessary to heat treat the crystals in liquid Zn in order to remove the impurities, lower the resistivity and activate the photoluminescence at room temperature. The physical vapor transport method (PVT) has been successfully used at MSFC to grow many single crystals of II-VI semiconducting materials including ZnSe. The main goal at NASA has been to try to establish the effect of gravity on the growth parameters. To this effect, crystals have been grown vertically upwards or horizontally. Both (111) and (110) oriented ZnSe crystals have been obtained via unseeded PVT growth. Preliminary characterization of the horizontally grown crystals has revealed that Cu is a major impurity and that the low temperature photoluminescence spectra is dominated by the copper peak. The ratio of the copper peak to the free exciton peak is being used to determine variations in composition throughout the crystal. It was the intent of this project to map the copper composition of various crystals via photoluminescence first, then measure their electrical resistivity and capacitance as a function of frequency before proceeding with a heat treatment designed to remove the copper impurities. However, equipment difficulties with the photoluminescence set up, having to establish a procedure for measuring the electrical properties of the as-grown crystals and time limitations made us re-evaluate the project goals. Vertically grown samples designated as ZnSe-25 were chosen to be measured electrically since they were not expected to show as much variation in their composition through their cross-section as the horizontally grown samples.

Gerhardt, Rosario A.↗

Dyakonov-Perel Effect on Spin Dephasing in n-Type GaAs

A paper presents a study of the contribution of the Dyakonov-Perel (DP) effect to spin dephasing in electron-donor-doped bulk GaAs in the presence of an applied steady, moderate magnetic field perpendicular to the growth axis of the GaAs crystal. (The DP effect is an electron-wave-vector-dependent spin-state splitting of the conduction band, caused by a spin/orbit interaction in a crystal without an inversion center.) The applicable Bloch equations of kinetics were constructed to include terms accounting for longitudinal optical and acoustic phonon scattering as well as impurity scattering. The contributions of the aforementioned scattering mechanisms to spin-dephasing time in the presence of DP effect were examined by solving the equations numerically. Spin-dephasing time was obtained from the temporal evolution of the incoherently summed spin coherence. Effects of temperature, impurity level, magnetic field, and electron density on spin-dephasing time were investigated. Spin-dephasing time was found to increase with increasing magnetic field. Contrary to predictions of previous simplified treatments of the DP effect, spin-dephasing time was found to increase with temperature in the presence of impurity scattering. These results were found to agree qualitatively with results of recent experiments.

Ning, C. Z.↗

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Smialek, James L.↗

Chemical, Structural, and Microstructural Changes in Metallic and Silicon-Based Coating Materials Exposed to Iodine Vapor

The chemical, structural and microstructural behavior of steels (304, 316 and A36), titanium-aluminum alloy (Ti-Al, (6Al-4V)), aluminum-magnesium alloy (Al-Mg, 6061), and coatings (Silcolloy and Dursan (SilcoTek Corporation)) were probed after exposure to iodine laminar flow. Exposures were carried out in a custom-built Iodine Vapor RIG (IVR) at 300 degrees C to an iodine laminar vapor flow of 1 mg min(exp. -1), carried by 145 mL-min(exp. -1) argon gas, for 5, 15 and 30 days. Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction (XRD) and cross section electron microscopy analysis coupled with energy dispersive X-ray spectroscopy (EDS). All steels exposed for 30 days formed scales consisting mainly of metal (Cr, Fe, Ni) oxides showing different chemistry, microstructure and crystalline phases. Elemental iodine was only detected by EDS analysis in the scales of stainless steels 304 and 316. After 30 days, the Ti-Al exhibited no detectable scale, suggesting only a very thin film was formed. A scale consisting mainly of aluminum, iodine, and oxygen formed on the Al-Mg sample exposed to 30 days. Some pockets rich in magnesium, iodine and oxygen also formed in this Al-Mg alloy. Stainless steel 316, low carbon steel A36 and Ti-Al alloy coated with Silcolloy and stainless steel 304 coated with Dursan that were exposed for 30 days exhibited no oxidation. Stainless steel 304 coated with Silcolloy exposed for 30 days did not exhibit corrosion although the sample gained weight and the coating exhibited expansion. The weight gain per area performance of the materials exposed in iodine lamina flow containing oxygen at impurity level for 10, 15 and 30 days are reported from the lowest to the highest weight gain per area as follows: Steels: Less than 316 less than 304 less than A36; Ti-Al-Mg based alloys: Al-Mg less than Ti-Al: Considering the experimental uncertainties, no weight change was observed for Stainless steel 316, low carbon steel A36 and Ti-Al alloy coated with Silcolloy and stainless steel 304 coated with Dursan. The corrosion of the alloys is catalyzed by iodine in the presence of oxygen as impurity.

Costa, Gustavo C. C.↗

Analysis of Base Metal Microstructures and Mechanical Properties of a Single-Piece, Spin-Formed Forward Pressure Vessel Bulkhead

In 2012, a pathfinder forward pressure vessel bulkhead (FPVBH) for the Orion Multi-Purpose Crew Vehicle (MPCV) was fabricated using aluminum (Al) alloy 2219. The demonstration article was offered as a replacement for the baseline configuration, which at that time was a multi-piece welded construction using aluminum-lithium (Al-Li) alloy 2195. In 2014, the NASA Engineering and Safety Center (NESC) funded a Phase I effort to explore spin-forming as a manufacturing method to produce a complex-shaped, single-piece FPVBH for the crew module (CM) [1]. The primary focus of the NESC effort was to expand spin-forming technology to the fabrication of an Al-Li 2195 FPVBH. As a result, limited testing and analysis was performed on the original Al 2219 article. In this study, a sufficiently large plate of Al 2219 was not available for the fabrication of a FPVBH. Therefore, the forming blank comprised two plates (from different lots) butt welded together using a single friction stir weld. The welded forming blank was then spin formed into the FPVBH configuration and heat treated to the T62 temper. Mechanical property testing of the spin-formed 2219-T62 FPVBH revealed that the tensile properties were comparable to the Metallic Material Properties Development and Standardization (MMPDS) A-basis allowable for Al 2219-T6 wrought products. However, post-spin forming application of the standard heat treatment produced large, recrystallized grains in the material. The response varied within the two plates; one plate lot exhibited nearly complete recrystallization, while the other lot contained bands of recrystallization. Although no reduction in tensile properties was observed due to these microstructural variations, a more detailed investigation was recommended to better understand the effect of spin forming on the recrystallization mechanism and the impact on other material properties. The current study examined the microstructure and mechanical properties of the fully processed Al 2219-T62 FPVBH with emphasis on comparing differences between the two plates. Testing was limited to the cone region of the FPVBH. The two specific tasks in this study were: a) Characterization of the microstructure and mechanical properties in the two plates used in the FPVBH. b) Isolation of the impact of each step in the thermo-mechanical processing (TMP) sequence of the FPVBH on recrystallization and grain growth. Mechanical property testing sampled regions containing both large, recrystallized and small, unrecrystallized grains. Tensile strengths and elongations were equivalent in both regions and exceeded MMPDS A-basis allowables. Fracture toughness was equivalent in both regions and fracture morphology was typical of aluminum alloys. The fatigue precrack region of the fracture toughness specimens appeared more faceted in the recrystallized plate. This suggests that property testing that is more sensitive to grain size, such as fatigue crack growth rate and stress corrosion cracking, may be warranted. Alcoa reviewed the production records for the two plate lots and confirmed that composition of both plates was within the allowable range for Al 2219 and that plate processing steps were all performed within production limits. However, the Fe content was notably higher in the fully recrystallized plate, resulting in a greater volume fraction of large Fe-bearing inclusions and Al-Cu constituent particles. Alcoa did not provide details regarding plate processing variables for the two plate lots. It was surmised that deformation by hot rolling was the most accurate TMP simulation of commercial spin forming within a laboratory setting. Both hot rolling and spin forming comprise combinations of shear and compressive deformation. The through-thickness strain caused by hot rolling is symmetrical about the mid-plane, as the rollers contact both sides of the material. Shear strains are maximum at the inner and outer surfaces and trend toward zero at the mid-thickness. In contrast, spin forming utilizes a single roller on the outer surface, producing a gradient in shear stress through the thickness. Shear strains in spin-formed material are highest at the outer surface due to direct contact with the roller, and trend toward zero at the inner surface. Consequently, there will undoubtedly be some discrepancies in the mechanical response of hot-rolled and spin-formed products in the through-thickness direction. Interrupted TMP simulations were performed on remnant plate from the FPVBH forming blank in order to isolate the effects of a post-weld anneal, spin-forming deformation/thermal cycling, and solution heat treatment (SHT) on development of the recrystallized microstructures. Analysis confirmed that large, recrystallized grains formed exclusively during SHT and only after a certain deformation level was exceeded. Remnant plate from both lots that received thermal processing only did not exhibit recrystallization but exhibited fully recrystallized microstructures when processed by hot rolling. This indicates that (1) the level of deformation exceeded the critical level for recrystallization in both plates and (2) that the level of deformation during hot rolling was greater than that which accumulated during spin forming of the FPVBH. Comparison of the hot-rolled plate with the spin-formed material showed that the recrystallized grain size was larger in the FPVBH, providing further evidence that deformation levels were lower in the FPVBH. The most plausible explanation for the differing degrees of recrystallization in the two plates is particle stimulated nucleation (PSN) at the Fe-bearing inclusions and large Al-Cu constituent particles. In the plate with higher solute content, the greater volume fraction of these particles reduces the deformation level required to promote recrystallization. During spin forming the critical deformation level was likely exceeded for the higher Fe content plate resulting in a fully recrystallized microstructure. The lower Fe content plate developed a microstructure that exhibited bands of recrystallization due to the combination of a non-uniform distribution of particles and deformation. The critical deformation required for recrystallization was likely only exceeded during spin forming in regions of higher particle content. While there were differences in Fe content between these lots of Al 2219 plate, the composition of both was within defined alloy limits and Alcoa reported no anomalies during plate production. The observed differences in recrystallization after spin forming may reflect the inherent variability between these two lots of plate. The spin-forming vendor, Spincraft, reported that similar variations in recrystallized microstructures have been observed during examination of multiple spin-forming trials of a different 2xxx series aluminum alloy. Hence, tighter chemical specification limits on impurity levels in Al 2219 plate may help ensure uniform, predictable microstructures. Finally, the tensile and fracture toughness properties were not affected by the microstructural variations noted.

single-piece↗

Advanced development of double-injection, deep-impurity semiconductor switches

Deep-impurity, double-injection devices, commonly refered to as (DI) squared devices, represent a class of semiconductor switches possessing a very high degree of tolerance to electron and neutron irradiation and to elevated temperature operation. These properties have caused them to be considered as attractive candidates for space power applications. The design, fabrication, and testing of several varieties of (DI) squared devices intended for power switching are described. All of these designs were based upon gold-doped silicon material. Test results, along with results of computer simulations of device operation, other calculations based upon the assumed mode of operation of (DI) squared devices, and empirical information regarding power semiconductor device operation and limitations, have led to the conculsion that these devices are not well suited to high-power applications. When operated in power circuitry configurations, they exhibit high-power losses in both the off-state and on-state modes. These losses are caused by phenomena inherent to the physics and material of the devices and cannot be much reduced by device design optimizations. The (DI) squared technology may, however, find application in low-power functions such as sensing, logic, and memory, when tolerance to radiation and temperature are desirable (especially is device performance is improved by incorporation of deep-level impurities other than gold.

Hanes, M. H.↗

High-temperature, long-term drift of platinum-rhodium thermocouples

Contamination of thermocouples is minimized by use of pure alumina insulators and a controlled low-impurity-level high-vacuum environment. Average thermal electromotive force change for platinum-rhodium thermocouples was -2.8 deg K after 3700 hours exposure to a mean temperature of 1530 deg K.

Szaniszlo, A. J.↗

Nonequilibrium ionization measurements in hydrogen-helium mixtures

Time-resolved emission measurements of several atomic line and continuum radiation channels were made behind the incident shock wave of an electric arc shock tube. Test times and nonequilibrium ionization times were obtained for shock velocities up to 2.5 X 10,000 m/sec in a 0.2 H2 - 0.8 He gas mixture. The shock-heated test gas was found to be free from driver gas contamination, and the test times were adequate to achieve steady state conditions. An activation energy of 4 eV was obtained from the nonequilibrium ionization time measurements. Modifications of experimental technique to determine the effect of test gas impurity level on ionization time measurements are discussed.

Leibowitz, L. P.↗