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NASA NTRS2014

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI] and [EMIM][BF4]

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

lithium batteries↗

NASA NTRS2009

Proton and Gamma Radiation Effects in Undoped, Single-doped and co-doped YLiF4 and LuLiF4

Proton and gamma radiation effects in various YLiF4 and LuLiF4 crystals have been investigated. The radiation induced color centers compared with six different kinds of crystal samples in ranges up to 200 krads and 200 MeV. The radiation induced absorption coefficients are strongly dependent on polarization and concentration of rare-earth ions.

Lee, Hyung↗

NASA NTRS2006

Semiconductor Bolometers Give Background-Limited Performance

Semiconductor bolometers that are capable of detecting electromagnetic radiation over most or all of the infrared spectrum and that give background-limited performance at operating temperatures from 20 to 300 K have been invented. The term background-limited performance as applied to a bolometer, thermopile, or other infrared detector signifies that the ability to detect infrared signals that originate outside the detector is limited primarily by thermal noise attributable to the background radiation generated external to the bolometer. The signal-to-noise ratios and detectivities of the bolometers and thermopiles available prior to this invention have been lower than those needed for background-limited performance by factors of about 100 and 10, respectively. Like other electrically resistive bolometers, a device according to the invention exhibits an increase in electrical resistance when heated by infrared radiation. Depending on whether the device is operated under the customary constant- current or constant-voltage bias, the increase in electrical resistance can be measured in terms of an increase in voltage across the device or a decrease in current through the device, respectively. In the case of a semiconductor bolometer, it is necessary to filter out visible and shorter-wavelength light that could induce photoconductivity and thereby counteract all or part of the desired infrared- induced increase in resistance. The basic semiconductor material of a bolometer according to the invention is preferably silicon doped with one or more of a number of elements, each of which confers a different variable temperature coefficient of resistance. Suitable dopants include In, Ga, S, Se, Te, B, Al, As, P, and Sb. The concentration of dopant preferably lies in the range between 0.1 and 1,000 parts per billion.

Goebel, John↗

NASA NTRS1987

Effect of high temperature annealing on the thermoelectric properties of GaP doped SiGe

Silicon-germanium alloys doped with GaP are used for thermoelectric energy conversion in the temperature range 300-1000 C. The conversion efficiency depends on Z = S-squared/rho lambda, a material's parameter (the figure of merit), where S is the Seebeck coefficient, rho is the electrical resistivity and lambda is the thermal conductivity. The annealing of several samples in the temperature range of 1100-1300 C resulted in the power factor P (= S-squared/rho) increasing with increased annealing temperature. This increase in P was due to a decrease in rho which was not completely offset by a drop in S-squared suggesting that other changes besides that in the carrier concentration took place. SEM and EDX analysis of the samples indicated the formation of a Ga-P-Ge rich phase as a result of the annealing. It is speculated that this phase is associated with the improved properties. Several reasons which could account for the improvement in the power factor of annealed GaP doped SiGe are given.

Vandersande, Jan W.↗

NASA NTRS1982

Convective and interfacial instabilities during solidification of succinonitrile containing ethanol

Even though slow convective flow is difficult to detect in solidifying metals, it can readily be observed in transparent materials by observing the motion of small neutrally buoyant particles. Succinonitrile, which solidifies with an unfaceted solid/liquid interface and has well characterized physical properties, is considered an excellent material for such studies. For studies of solute-induced convection, ethanol is a useful addition to succinonitrile since it has a lower density and a somewhat similar molecular structure. Samples of high purity and ethanol-doped succinonitrile are unidirectionally solidified in a vertical temperature gradient. Latex mimcrospheres 2 microns in diameter are suspended in the liquid to reveal the convective flow. Convective and morphological stability is observed as a function of solute concentration and growth velocity. These measurements are compared with theoretical calculations that predict the transition from stability to instability as a function of solidification conditions. The predicted transitions occur at low concentrations and solidification velocities; for this reason, extreme care must be taken in order to eliminate the effects of impurities or thermally induced convection.

Schaefer, R. J.↗

NASA NTRS2007

Crystal Growth and Characterization of CdTe Grown by Vertical Gradient Freeze

In this study, crystals of CdTe were grown from melts by the unseeded vertical gradient freeze method. The quality of grown crystal were studied by various characterization techniques including Synchrotron White Beam X-ray Topography (SWBXT), chemical analysis by glow discharge mass spectroscopy (GDMS), low temperature photoluminescence (PL), and Hall measurements. The SWBXT images from various angles show nearly strain-free grains, grains with inhomogeneous strains, as well as twinning nucleated in the shoulder region of the boule. The GDMS chemical analysis shows the contamination of Ga at a level of 3900 ppb, atomic. The low temperature PL measurement exhibits the characteristic emissions of a Ga-doped sample. The Hall measurements show a resistivity of 1 x l0(exp 7) ohm-cm at room temperature to 3 x 10(exp 9) ohm-cm at 78K with the respective hole and electron concentration of 1.7 x 10(exp 9) cm(exp -3) and 3.9 x 10(exp 7) cm(exp -3) at room temperature.

Su, Ching-Hua↗

NASA NTRS1985

Microhardness of carbon-doped (111) p-type Czochralski silicon

The effect of carbon on (111) p-type Czochralski silicon is examined. The preparation of the silicon and microhardness test procedures are described, and the equation used to determine microhardness from indentations in the silicon wafers is presented. The results indicate that as the carbon concentration in the silicon increases the microhardness increases. The linear increase in microhardness is the result of carbon hindering dislocation motion, and the effect of temperature on silicon deformation and dislocation mobility is explained. The measured microhardness was compared with an analysis which is based on dislocation pinning by carbon; a good correlation was observed. The Labusch model for the effect of pinning sites on dislocation motion is given.

Danyluk, S.↗

NASA NTRS1970

Current conduction in junction gate field effect transistors

The internal physical mechanism that governs the current conduction in junction-gate field effect transistors is studied. A numerical method of analyzing the devices with different length-to-width ratios and doping profiles is developed. This method takes into account the two dimensional character of the electric field and the field dependent mobility. Application of the method to various device models shows that the channel width and the carrier concentration in the conductive channel decrease with increasing drain-to-source voltage for conventional devices. It also shows larger differential drain conductances for shorter devices when the drift velocity is not saturated. The interaction of the source and the drain gives the carrier accumulation in the channel which leads to the space-charge-limited current flow. The important parameters for the space-charge-limited current flow are found to be the L/L sub DE ratio and the crossover voltage.

Kim, C.↗

NASA NTRS1983

Development and fabrication of a high current, fast recovery power diode

A high voltage (VR = 1200 V), high current (IF = 150 A), fast recovery ( 700 ns) and low forward voltage drop ( 1.5 V) silicon rectifier was designed and the process developed for its fabrication. For maximum purity, uniformity and material characteristic stability, neutron transmutation n-type doped float zone silicon is used. The design features a hexagonal chip for maximum area utilization of space available in the DO-8 diode package, PIN diffused junction structure with deep diffused D(+) anode and a shallow high concentration n(+) cathode. With the high temperature glass passivated positive bevel mesa junction termination, the achieved blocking voltage is close to the theoretical limit of the starting material. Gold diffusion is used to control the lifetime and the resulting effect on switching speed and forward voltage tradeoff. For solder reflow assembly, trimetal (Al-Ti-Ni) contacts are used. The required major device electrical characteristics were achieved. Due to the tradeoff nature of forward voltage drop and reverse recovery time, a compromise was reached for these values.

Berman, A. H.↗

NASA NTRS2001

Measurement of Microscopic Growth Rates in Float-Zone Silicon Crystals

Time dependent convective flows during crystal growth of doped semiconductors lead to fluctuations of the composition, so called dopant striations. In general, it is difficult to decide which is the main mechanism for the generation of these striations, it might be either the fluctuation of the concentration field in the melt and the extent of the solute boundary layer ahead of the solid-liquid interface or a variation of the growth velocity. Direct access to the concentration field is rather complicated to achieve, especially considering the high process temperature and the chemical activity of liquid silicon. The contribution of growth rate fluctuations to the formation of compositional fluctuations can be determined by measuring microscopic growth rates. The classical method of current pulses requires electrical feed-throughs and good electrical contacts, both are critical issues for the growth of high purity silicon crystals. Using a radiation based heating system, the heating power can be modulated very fast and effectively. We added to the normal heater power a sinusoidal off-set in the frequency range of 1 to 10 Hz, generating a narrow spaced weak rippling in the grown crystals which are superposed to the dopant striations caused by natural and by thermocapillary convection. The pulling speed was varied between 1 and 4mm/min. The microscope images of etched crystals slices have been analyzed by peak-search algorithms (measuring the spacing between each artificially induced marker) and by FFT. Performing growth experiments under a time-dependent flow regime, fluctuations of the microscopic growth velocity of Delta(v)/v(sub average) up to 50% have been measured. Damping the time-dependent convection by the use of an axial, static magnetic field of 500mT, the microscopic growth rate became constant within the resolution limit of this method. The results will be discussed using analytical methods for the calculation of microscopic growth velocity and by comparing them with measurements of temperature fluctuations in the melt during growth experiments itself.

Dold, P.↗

NASA NTRS2006

Impact of Solar Array Designs on High Voltage Operations

As power levels of advanced spacecraft climb above 25 kW, higher solar array operating voltages become attractive. Even in today s satellites, operating spacecraft buses at 100 V and above has led to arcing in GEO communications satellites, so the issue of spacecraft charging and solar array arcing remains a design problem. In addition, micrometeoroid impacts on all of these arrays can also lead to arcing if the spacecraft is at an elevated potential. For example, tests on space station hardware disclosed arcing at 75V on anodized A1 structures that were struck with hypervelocity particles in Low Earth Orbit (LEO) plasmas. Thus an understanding of these effects is necessary to design reliable high voltage solar arrays of the future, especially in light of the Vision for Space Exploration of NASA. In the future, large GEO communication satellites, lunar bases, solar electric propulsion missions, high power communication systems around Mars can lead to power levels well above 100 kW. As noted above, it will be essential to increase operating voltages of the solar arrays well above 80 V to keep the mass of cabling needed to carry the high currents to an acceptable level. Thus, the purpose of this paper is to discuss various solar array approaches, to discuss the results of testing them at high voltages, in the presence of simulated space plasma and under hypervelocity impact. Three different types of arrays will be considered. One will be a planar array using thin film cells, the second will use planar single or multijunction cells and the last will use the Stretched Lens Array (SLA - 8-fold concentration). Each of these has different approaches for protection from the space environment. The thin film cell based arrays have minimal covering due to their inherent radiation tolerance, conventional GaAs and multijunction cells have the traditional cerium-doped microsheet glasses (of appropriate thickness) that are usually attached with Dow Corning DC 93-500 silicone adhesive. In practice, these cover glasses and adhesive do not cover the cell edges. Finally, in the SLA, the entire cell and cell edges are fully encapsulated by a cover glass that overhangs the cell perimeter and the silicone adhesive covers the cell edges providing a sealed environment. These three types of blanket technology have been tested at GRC and Auburn. The results of these tests will be described. For example, 15 modules composed of four state-of-the-art 2x4 cm GaAs solar cells with 150 pm cover glasses connected in two-cell series strings were tested at high voltage, in plasma under hypervelocity impact. A picture of one of the modules is shown in figure 1. These were prepared by standard industry practice from a major supplier and had efficiencies above 18%. The test results and other fabrication factors that influenced the tests will be presented. In addition, results for SLA segments tested under the same conditions will be presented. Testing of thin film blankets at GRC will also be presented. Figure 1 : Typical GaAs Solar Cell Module These results will show significant differences in resistance to arcing that are directly related to array design and manufacturing procedures. Finally, the approaches for mitigating the problems uncovered by these tests will be described. These will lay the foundation for future higher voltage array operation, even including voltages above 300-600 V for direct drive SEP applications.

Brandhorst, Henry W., Jr.↗

NASA NTRS1986

Transit time and charge storage measurements in heavily doped emitters

A first direct measurement of the minority-carrier transit time in a transparent heavily doped emitter layer is reported. The value was obtained by a high-frequency conductance method recently developed and used for low-doped Si. The transit time coupled with the steady-state current enables the determination of the quasi-static charge stored in the emitter and the quasi-static emitter capacitance. Using a transport model, from the measured transit time, the value for the minority-carrier diffusion coefficient and mobility is estimated. The measurements were done using a heavily doped emitter of the Si p(+)-n-p bipolar transistor. The new result indicates that the position-averaged minority-carrier diffusion coefficients may be much smaller than the corresponding majority-carrier values for emitters having a concentration ranging from about 3 x 10 to the 19th per cu cm to 10 to the 20th per cu cm.

Neugroschel, A.↗

NASA NTRS1988

Automatic Replenishment Of Dopant In Silicon Growth

Dopant incorporated feed pellets to maintain required concentration. Technique of continuous replenishment of dopant in silicon melt helps ensure correct resistivity in solid silicon grown from melt. Technique used in dendritic-web growth process in which ribbon of silicon continously pulled from molten material. Providing uniform doping and resistivity in ribbon technique enables production of high-quality silicon ribbon at high yields for use in semiconductor devices.

Kochka, E. L.↗

NASA NTRS1996

Observations of Dynamic Strain Aging in Polycrystalline NiAl

Dynamic strain aging has been investigated at temperatures between 77 and 1100 K in eight polycrystalline NiAl alloys. The 0.2% offset yield stress and work hardening rates for these alloys generally decreased with increasing temperature. However, local plateaus or maxima were observed in conventional purity and carbon doped alloys at intermediate temperatures (600-900 K). This anomalous behavior was not observed in low interstitial high-purity, nitrogen doped, or in titanium doped materials. Low or negative strain rate sensitivities (SRS) were also observed in all eight alloys in this intermediate temperature range. Coincident with the occurrence of negative SRS was the occurrence of serrated flow in conventional purity alloys containing high concentrations of Si in addition to C. These phenomena have been attributed to dynamic strain aging (DSA). Chemical analysis of the alloys used in this study suggests that the main species causing strain aging in polycrystalline NiAl is C but indicate that residual Si impurities can enhance the strain aging effect.

Weaver, M. L.↗

NASA NTRS1988

Polyimide/metal composite films via in situ decomposition of inorganic additives - Soluble polyimide versus polyimide precursor

Polyimide-metal oxide (Co3O4 or CuO) composite films have been prepared via in situ thermal decomposition of cobalt (II) chloride or bis(trifluoroacetylacetonato)copper(II). A soluble polyimide (XU-218) and its corresponding prepolymer (polyamide acid) were individually employed as the reaction matrix. The resulting composites exhibited a greater metal oxide concentration at the air interface with polyamide acid as the reaction matrix. The water of imidization that is released during the concurrent polyamide acid cure and additive decomposition is believed to promote metal migration and oxide formation. In contrast, XU-218 doped with either HAuCl4.3H2O or AgNO3 yields surface gold or silver when thermolyzed (300 C).

Rancourt, J. D.↗

NASA NTRS1984

New electron trap in p-type Czochralski silicon

A new electron trap (acceptor level) was discovered in p-type Czochralski (CZ) silicon by current transient spectroscopy. The behavior of this trap was found to be similar to that of the oxygen thermal donors; thus, 450 C annealing increases the trap concentration while high-temperature annealing (1100-1200 C) leads to the virtual elimination of the trap. The new trap is not observed in either float-zone or n-type CZ silicon. Its energy level depends on the group III doping element in the sample. These findings suggest that the trap is related to oxygen, and probably to the acceptor impurity as well.

Mao, B.-Y.↗

NASA NTRS1991

A model for the high-temperature transport properties of heavily doped n-type silicon-germanium alloys

A model is presented for the high-temperature transport properties of large-grain-size, heavily doped n-type silicon-germanium alloys. Electron and phonon transport coefficients are calculated using standard Boltzmann equation expressions in the relaxation time approximation. Good agreement with experiment is found by considering acoustic phonon and ionized impurity scattering for electrons, and phonon-phonon, point defect, and electron-phonon scattering for phonons. The parameters describing electron transport in heavily doped and lightly doped materials are significantly different and suggest that most carriers in heavily doped materials are in a band formed largely from impurity states. The maximum dimensionless thermoelectric figure of merit for single-crystal, n-type Si(0.8)Ge(0.2) at 1300 K is estimated at ZT about 1.13 with an optimum carrier concentration of n about 2.9 x 10 to the 20th/cu cm.

Vining, Cronin B.↗

NASA NTRS1984

Material growth and characterization for solid state devices

During the reporting period, InGaAs was grown on Fe-doped (semi-insulating) (100) InP substrates by current controlled liquid phase epitaxy (CCLPE) at 640 C and current densities of 2.5A sq/cm to 5 A/sq cm for periods from 5 to 30 minutes. Special efforts were made to reduce the background carrier concentration in the grown layers as much as possible. The best layers exhibited carrier concentrations in the mid-10 to the 15th power/cu cm range and up to 10,900 sq cm/V-sec room temperature mobility. InGaAsP quaternary layers of energy gap corresponding to wavelengths of approximately 1.5 microns and 1.3 microns were grown on (100) InP substrates by CCLPE. In the device fabrication area, work was directed toward processing MISFET's using InGaAs. SiO2, Si3N4 and Al2O3 were deposited by ion beam sputtering, electron beam evaporation and chemical vapor reaction on Si, GaAs, and InGaAs substrates. SiO2 and Si3N4 sputtered layers were found to possess a high density of pinhole defects that precluded capacitance-voltage analysis. Chemical vapor deposited Al2O3 layers on Si, GaAs and InGaAs substrates also exhibited a large number of pinhole defects. This prevented achieving good MIS devices over most of the substrate surface area.

Stefanakos, E. K.↗