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At least 649 records · Page 36

Method for fabricating semiconductor devices

A process for fabricating gold/gallium arsenide structures, in situ, on molecular beam epitaxially grown gallium arsenide. The resulting interface proves to be Ohmic, an unexpected result which is interpreted in terms of increased electrode interdiffusion. More importantly, the present invention surprisingly permits the fabrication of Ohmic contacts in a III-V semiconductor material at room temperature. Although it may be desireable to heat the Ohmic contact to a temperature of, for example, 200 degrees Centigrade if one wishes to further decrease the resistance of the contact, such low temperature annealing is much less likely to have any deleterious affect on the underlying substrate. The use of the term in situ herein, contemplates continuously maintaining an ultra-high vacuum, that is a vacuum which is at least 10.sup.-8 Torr, until after the metallization has been completed. An alternative embodiment of the present invention comprising an additional step, namely the termination of the gallium arsenide by a two monolayer thickness of epitaxial aluminum arsenide as a diffusion barrier, enables the recovery of Schottky barrier behavior, namely a rectified I-V characteristic. The present invention provides a significant breakthrough in the fabrication of III-V semiconductor devices wherein excellent Ohmic contact and Schottky barrier interfaces to such devices can be achieved simply and inexpensively and without requiring the high temperature processing of the prior art and also without requiring the use of exotic high temperature refractory materials as substitutes for those preferred contact metals such as gold, aluminum and the like.

Kaiser, William J.↗

Multiphysics Modeling for Dimensional Analysis of a Self-Heated Molten Regolith Electrolysis Reactor for Oxygen and Metals Production on the Moon and Mars

The technology of direct electrolysis of molten lunar regolith to produce oxygen and molten metal alloys has progressed greatly in the last few years. The development of long-lasting inert anodes and cathode designs as well as techniques for the removal of molten products from the reactor has been demonstrated. The containment of chemically aggressive oxide and metal melts is very difficult at the operating temperatures ca 1600 C. Containing the molten oxides in a regolith shell can solve this technical issue and can be achieved by designing a self-heating reactor in which the electrolytic currents generate enough Joule heat to create a molten bath. In a first phase, a thermal analysis model was built to study the formation of a melt of lunar basaltic regolith irradiated by a focused solar beam This mode of heating was selected because it relies on radiative heat transfer, which is the dominant mode of transfer of energy in melts at 1600 C. Knowing and setting the Gaussian-type heat flux from the concentrated solar beam and the phase and temperature dependent thermal properties, the model predicts the dimensions and temperature profile of the melt. A validation of the model is presented in this paper through the experimental formation of a spherical cap melt realized by others. The Orbitec/PSI experimental setup uses an 3.6-cm diameter concentrated solar beam to create a hemispheric melt in a bed of lunar regolith simulant contained in a large pot. Upon cooling, the dimensions of the vitrified melt are measured to validate the thermal model. In a second phase, the model is augmented by multiphysics components to compute the passage of electrical currents between electrodes inserted in the molten regolith. The current through the melt generates Joule heating due to the high resistivity of the medium and this energy is transferred into the melt by conduction, convection and primarily by radiation. The model faces challenges in two major areas, the change of phase as temperature increases, and the dominance of radiative heat flux as heat transfer mechanism within the melt the change of phase concerns the regolith itself which is present in states ranging from a fine grain regolith with low thermal conductivity and low density to a vitrified melt with much higher thermal conductivity, and higher density. As the regolith is heated, it starts to soften around 1300 C the melt iS very viscous and evolving gas bubbles out in thick, lava-like fashion. By 1600 C the regolith is completely melted and the viscosity is low The second challenge resides in the proper modeling of the radiative heat flux requiring the addition of the computing-demanding radiative-heat-transfer function to the general heat transfer equation. The model Includes temperature-dependent properties (density, thermal conductivity, heat capacity, and viscosity, and absorption coefficients) and solves the radiative heat flux equation assuming gray (fine grains) and semi-transparent (melt) media and using an absorption coefficient spectral found in the literature for terrestrial minerals similar in composition to those of lunar regolith simulant

Dominguez, Jesus A.↗

Extending Ion Engine Technology to NEXT and Beyond

Extending ion engine technology beyond the current state-of-the art primary interplanetary electric propulsion system, the 2.3-kW NASA Solar Electric Propulsion Technology and Applications Readiness (NSTAR) system, will require thrusters with improved propellant throughput and total impulse capability. Many of the design choices that culminated in the NSTAR thrusters must be revisited, and their application to next generation ion engine technology must be evaluated. The concept of derating, which was successfully employed in NSTAR, has been applied to the 40 cm NASA Evolutionary Xenon Thruster (NEXT) currently under development at NASA Glenn Research Center (GRC). At 5-kW, NEXT operates with the same average beam current density as NSTAR, and at 10-kW, the peak beam current density is only ten percent greater than NSTAR. The result is that similar Ion optics technology is expected to yield comparable lifetime. Thick-accelerator- grid ion optics are also being tested to realize additional lifetime benefits. A 40-A discharge cathode is being developed for NEXT based on scaling the NSTAR design. Nevertheless, the experiences of the NSTAR ground tests and the thruster on the Deep Space One spacecraft indicate that the discharge cathode wear must be studied experimentally and theoretically to ensure that it meets the lifetime requirements. Although NEXT is in its infancy, investigations have already begun to examine possible modifications to engine design for even higher-power and higher-specific impulse engines. Ion optics using alternate materials such as titanium, graphite, or carbon-carbon composite are currently being investigated due to their low sputter yields at high voltage. To avoid the difficulties encountered using electrodes at high-currents, the use of a microwave-based ion thruster is under investigation for potential high-power ion thruster systems requiring long lifetimes. Additionally, alternative propellants are being considered for applications requiring high-specific impulse (>> 5000 s) and extremely long-life (>> 15,000 hr). Testing requirements make condensable propellants attractive for high-power engines. Although the NSTAR ion engine demonstrated the flight maturity of ion thruster technology, many challenges remain for the development of thrusters with improved propellant throughput and power handling capabilities.

Domonkos, Matthew T.↗

Fabrication and testing of carbon-carbon grids for ion optics

Ion optics measuring 16.5 cm in diameter and 1.0 mm in thickness were fabricated from carbon-carbon composites that were woven from a high-tensile-modulus carbon fiber. Plate flatness varied by less than 0.05 mm. Several methods were investigated for forming ion-extraction apertures in the carbon-carbon plates, including laser machining, mechanical drilling, and conventional electric discharge machining. Tests conducted using a quartz dilatometer indicated that the coefficient of thermal expansion of the carbon-carbon plates varied between -0.51 to -1.8 x 10 exp -6/degree C at plate temperatures between 173-773 K. Sputter-erosion experiments indicate that carbon-carbon erodes at a rate approximately 25 percent below molybdenum under the same conditions. These material properties indicate that carbon-carbon may be superior to molybdenum for use as ion optics electrodes for ion engines.

Garner, Charles E.↗

Impact of direct exchange coupling via the insulator on the magnetic tunnel junction based molecular spintronics devices with competing molecule induced inter-electrode coupling

The magnetic tunnel junction (MTJ) based molecular spintronics device (MTJMSD) approach is suitable for mass production. This approach provides solutions to fabrication difficulties related to reliably connecting molecular device elements to the ferromagnets (FMs). To producing MTJMSD, the molecular channels are bridged across the insulator of an MTJ testbed with exposed side edges. In an MTJMSD, two FMs are simultaneously connected by an insulator film and the molecular channels along the exposed sides. In our prior experimental studies, we observed that molecules could produce strong coupling between ferromagnets in the presence of the competing coupling via an insulator. In this paper, our Monte Carlo Simulation (MCS) was used to study the impact of coupling variation via insulator (a.k.a. Ji) on the magnetic properties of an MTJMSD. We studied the effect of Ji while varying the molecule induced antiferromagnetic exchange coupling. The ferromagnetic or antiferromagnetic nature and magnitude of Ji determined the resultant effect. Antiferromagnetic Ji enhanced the pre-existing antiferromagnetic molecular coupling effect. Ferromagnetic Ji competed with the opposite nature of antiferromagnetic molecular coupling. Our MCS may help to understand the impact of insulator thickness and defects on the molecular spintronics device performance and design process.

36 MATERIALS SCIENCE↗

Effect of two synthetic lubricants on life of AISI 9310 spur gears

Spur-gear fatigue tests were conducted with two lubricants using a single lot of consumable-electrode vacuum-melted (CVM) AISI 9310 spur gears. The gears were case carburized and hardened to Rockwell C60. The gear pitch diameter was 8.89 cm. The lot of gears was divided into two groups, each of which was tested with a different lubricant. The test lubricants can be classified as synthetic polyol-ester-based lubricants. One lubricant was 30 percent more viscous that the other. Both lubricants have similar pressure viscosity coefficients. Test conditions included a bulk gear temperature of 350 K, a maximum Hertz stress of 1.71 GPa at the pitch line, and a speed of 10,000 rpm. The surface fatigue life of gears tested with one lubricant was approximately 2.4 times that for gears tested with the other lubricant. The lubricant with the 30 percent higher viscosity gave a calculated elastohydrodynamic (EHD) film thickness that was 20 percent higher than the other lubricant. This increased EHD film thickness is the most probable reason for the improvement in surface fatigue life of gears tested with this lubricant over gears tested with the less viscous lubricant.

Townsend, Dennis P.↗

Making AlN(x) Tunnel Barriers Using a Low-Energy Nitrogen-Ion Beam

A technique based on accelerating positive nitrogen ions onto an aluminum layer has been demonstrated to be effective in forming thin (<2 nm thick) layers of aluminum nitride (AlN(x)) for use as tunnel barriers in Nb/Al-AlN(x)/Nb superconductor/insulator/ superconductor (SIS) Josephson junctions. AlN(x) is the present material of choice for tunnel barriers because, to a degree greater than that of any other suitable material, it offers the required combination of low leakage current at high current density and greater thermal stability. While ultra-thin AlN films with good thickness and stoichiometry control are easily formed using techniques such as reactive molecular beam epitaxy and chemical vapor deposition, growth temperatures of 900 C are necessary for the dissociative adsorption of nitrogen from either nitrogen (N2) or ammonia (NH3). These growth temperatures are prohibitively high for the formation of tunnel barriers on Nb films because interfacial reactions at temperatures as low as 200 to 300 C degrade device properties. Heretofore, deposition by reactive sputtering and nitridation of thin Al layers with DC and RF nitrogen plasmas have been successfully used to form AlN barriers in SIS junctions. However, precise control over critical current density Jc has proven to be a challenge, as is attaining adequate process reproducibility from system to system. The present ion-beam technique is an alternative to the plasma or reactive sputtering techniques as it provides a highly controlled arrival of reactive species, independent of the electrical conditions of the substrate or vacuum chamber. Independent and accurate control of parameters such as ion energy, flux, species, and direction promises more precise control of film characteristics such as stoichiometry and thickness than is the case with typical plasma processes. In particular, the background pressure during ion-beam nitride growth is 2 or 3 orders of magnitude lower, minimizing the formation of compounds with contaminants, which is critical in devices the performance of which is dictated by interfacial characteristics. In addition, the flux of incoming species can be measured in situ using ion probes so that the dose can be controlled accurately. The apparatus used in the present ion-beam technique includes a vacuum chamber containing a commercial collimated- ion-beam source, a supply of nitrogen and argon, and an ion probe for measuring the ion dose. Either argon or nitrogen can be used as the feed gases for the ion source, depending on whether cleaning of the substrate or growth of the nitride, respectively, is desired. Once the Nb base electrode and Al proximity layer have been deposited, the N2 gas line to the ion beam is vented and purged, and the ion-source is turned on until a stable discharge is obtained. The substrate is moved over the ion-beam source to expose the Al surface layer to the ion beam (see figure) for a specified duration for the formation of the nitride tunnel barrier. Next, the Nb counter-electrode layer is deposited on the nitride surface layer. The Nb/Al- AlN(x)/Nb-trilayer-covered substrate is then patterned into individual devices by use of conventional integrated-circuit processing techniques.

Kaul, Anupama↗

Understanding implications of cathode architecture on energy density of solid-state batteries

Next generation solid-state batteries (SSB) will need to leverage high voltage cathodes, as well as metallic anodes to achieve the realistic performance targets necessary to replace liquid electrolyte-based batteries in cutting-edge applications including electric vehicles. However, limitations arising from mass and charge transports, kinetics and chemo-mechanical degradation at the electrode | electrolyte interface limit the performance of present day SSBs. Optimizing composite cathode architecture, which is an integral part of solid-state batteries, is vital to realize the high-energy density and high-performance goals for next-generation solid-state batteries. Additionally, cathode architecture needs to be optimized for high loadings of active material, well-percolated ion and electron transport pathways and increased resilience against electrochemical stresses. This paper provides a first report of framework for geometric modeling of composite cathode architectures and evaluates the impact of cathode architecture on cell-level energy density using hierarchical models. Packing around primary and secondary active material particles are simulated for a range of active material particle size and solid electrolyte size distributions in the composite cathode. Impact of packing architecture on processing parameters of a given cathode composition and thickness, as well as on achievable energy density is evaluated for a range of commonly used solid electrolyte and cathode materials. Overall, the proposed framework offers a facile exploratory methodology for establishing initial metrics for scalable processing of practical and competent SSBs.

25 ENERGY STORAGE↗

The Effect of Proton Conductivity of Fe–N–C–Based Cathode on PEM Fuel cell Performance

A model–based impedance spectroscopy is used to determine proton conductivity, oxygen transport parameter, double layer capacitance and oxygen reduction reaction (ORR) Tafel slope in the Fe–N–C cathode catalyst layer (CCL) of a PEM fuel cell. Experimental spectra of two cells differing by the membrane thickness only are processed using a physics–based model for PEMFC impedance. The spectra have been measured in the range of current densities from 25 to 800 mA cm -2 . The ORR Tafel slope of both the cells shows almost linear growth with the current density. In one of the cells, the CCL proton conductivity σp strongly decays at the current density of 100 mA cm -2 ; this decay is accompanied by the step growth of the double layer capacitance. Other minor variations of proton conductivity and double layer capacitance with the cell current occur also in a counterphase; presumed origin of this effect is discussed. The oxygen diffusion coefficient in the cathode exhibits explosive growth with the cell current. We attribute this effect to formation of temperature and pressure gradients in the CCL due to strongly non–uniform distribution of ORR rate in the electrode.

25 ENERGY STORAGE↗

xLi2MnO3 (1-x)LiMeO2 and Li4Ti5O12 Cell Chemistry for Behind-the-Meter Storage Applications

Li- and Mn-rich layered oxide material (xLi2MnO3 (1-x)LiMeO2, Me = Ni, Mn, and etc., LMR-NM) is paired with Li4Ti5O12 (LTO) in a full cell and evaluated for the Behind-the-Meter Storage (BTMS) applications. The LMR-NM/LTO full cell shows very high capacities and excellent long-term cycle life. It delivers 192 mAh g-1 after 500 cycles at C/2 and 45 degrees C with a capacity retention of 75% and coulombic efficiency higher than 99.95%. It also has impressive rate capabilities. A capacity of 220 mAh g-1 is achieved at 2C which is 88 % of the initial capacity at C/10. The high cycling temperature clearly enhances electrochemical kinetics and activates more Li2MnO3 component, which gives high capacities, low cell impedance, and better rate capabilities. Moreover, it helps to form a relatively thick cathode-electrolyte interphase (CEI) film to suppress transition metal dissolution from the cathode surface. The upper cut-off voltage (UCV) of 3.0 V keeps the structural integrity of the cathode during cycling. A higher UCV of 3.2 V accelerates structural instabilities of the cathode as well as growth of the solid-electrolyte interphase (SEI) via transition metal dissolution and deposition on the anode surface. It results in higher cell impedance, worse capacity retention and faster capacity fade.

behind-the-meter storage↗

Spin Solar Cell Phenomenon on a Single-Molecule Magnet (SMM) Impacted CoFeB-Based Magnetic Tunnel Junctions

The single-molecule magnet (SMM) is demonstrated here to transform conventional magnetic tunnel junctions (MTJs), a memory device used in present-day computers, into solar cells. For the first time, we demonstrated an electronic spin-dependent solar cell effect on an SMM-transformed MTJ under illumination from unpolarized white light. We patterned cross-junction-shaped devices to form a CoFeB/MgO/CoFeB-based MTJ. The MgO barrier thickness at the intersection between the two exposed junction edges was less than the SMM extent, which enabled the SMM molecules to serve as channels to conduct spin-dependent transport. The SMM channels yielded a region of long-range magnetic ordering around these engineered molecular junctions. Our SMM possessed a hexanuclear [Mn 6 (μ 3 -O) 2 (H 2 N-sao) 6 (6-atha) 2 (EtOH) 6 ] [H 2 N-saoH = salicylamidoxime, 6-atha = 6-acetylthiohexanoate] complex and thioesters end groups to form bonds with metal films. SMM-doped MTJs were shown to exhibit a solar cell effect and yielded ≈80 mV open-circuit voltage and ≈10 mA/cm 2 saturation current density under illumination from one sun equivalent radiation dose. A room-temperature Kelvin Probe AFM (KPAFM) study provided direct evidence that the SMM transformed the electronic properties of the MTJ’s electrodes over a lateral area in excess of several thousand times larger in extent than the area spanned by the molecular junctions themselves. As a result, the decisive factor in observing this spin-photovoltaic effect is the formation of SMM spin channels between the two different ferromagnetic electrodes, which in turn is able to catalyze the long-range transformation in each electrode around the junction area.

14 SOLAR ENERGY↗

Precious metal oxygen-evolving anodes for electrolytic reduction of metal oxides in molten LiCl-Li 2 O electrolyte

Understanding the electrochemical stability of oxygen-evolving anode materials in molten salt electrolytes is essential to enable decarbonized electrolytic reduction of metal oxides (e.g., used nuclear oxide fuels). Here, this work investigated three precious metals (Ir, Ru, and Pt) as oxygen-evolving anodes in molten LiCl-Li 2 O (99.0-1.0 wt%) at 650 °C. For consistent measurements, this work employed a three-electrode cell comprised of a two-phase Li-Bi (65-35 at%) reference electrode and a NiO counter electrode. Anodic polarization behavior of each anode was investigated via cyclic voltammetry (CV) and chronoamperometry. The onset potential for oxygen evolution was observed at E > 2.9 V (vs. Li/Li + ) for the Ir and Ru anodes and anodic current density was as high as 1.0 A cm -2 at 3.23 V. The dimensional stability of each anode was evaluated from long-term electrolysis experiments (10.0-32.1 h) at 3.23 V. Rapid consumption of the Pt anode was observed after the application of 26,453 C cm -2 with a reduction in diameter of about 15.8% due to the formation of a non-protective Li 2 PtO 3 compound. The formation of this compound was also observed during CV measurements as additional anodic waves at potentials more negative than that of oxygen evolution. In contrast, both the Ir and Ru anodes exhibited excellent dimensional stability with a reduction in diameter or thickness of less than 1.5% even after applying greater charge density of ~41,100 C cm -2 , demonstrating superior stability during oxygen evolution in the LiCl-Li 2 O electrolyte.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Structure of Layers Formed by [2-(3,6-Disubstituted-9 H -carbazol-9-yl)ethyl]phosphonic Acids on Metal Oxides

[2-(9 H -Carbazol-9-yl)ethyl]phosphonic acid (2PACz) and its derivatives are being used extensively as hole-transport layers in organic and perovskite solar cells due to their ability to modify electrode work function, surface wettability, and in some cases, to improve active-layer adhesion, while minimizing interfacial energy losses. The orientation and coverage of surface modifiers significantly impact these functional properties; however, the detailed structure and packing in these overlayers are challenging to investigate, leading to a lack of understanding of how this structure and packing influence performance and limiting the ability to rationally design molecular modifiers. Here, we investigate monolayers of 2-(9 H -carbazol-9-yl)ethyl phosphonic acid derivatives (from here on referred to as X-2PACz) on indium tin oxide (ITO) and alpha phase aluminum oxide (α-Al 2 O 3 ) using a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and X-ray reflectivity (XRR). By correlating elemental ratios, molecular orientation, and electron density profiles, we directly quantify surface coverage, layer thickness, and molecular tilt across a series of chemically related monolayers. We find that 2PACz and the X-2PACz derivatives form dense monolayers on α-Al 2 O 3 and ITO, with similar surface coverages on either substrate that are inversely proportional to molecular steric bulk. These surface coverage results indicate that X-2PACz is sterically limited in its monolayer surface packing density, as opposed to site limited. Despite surface packing density differences between molecules, the NEXAFS data show a constant average molecular orientation of 61° to 65° between the plane of the carbazole and the substrate for all the molecules on both substrates. These results increase our general understanding of 2PACz derivatives as they become increasingly useful in high performance solar cells.

NEXAFS↗

Combined, time-resolved, in situ neutron reflectometry and X-ray diffraction analysis of dynamic SEI formation during electrochemical N 2 reduction

One means of improving performance for electrochemical ammonia production through the Li-mediated N 2 reduction reaction (Li-NRR) is by cycling the current driving the reaction between open-circuit conditions and periods of applied current density. Herein, we have investigated the dynamics of the electrode–electrolyte interface under Li-NRR conditions during current cycling using in situ time-resolved neutron reflectometry and grazing-incidence synchrotron X-ray diffraction. During cycling, measured neutron reflectivity curves indicated bilayer formation in which Li-containing species such as LiOH, Li 2 O, and small quantities of Li 3 N and metallic Li primarily appeared in a thin layer at the cathode surface, above which formed a much larger, porous, ‘solid–electrolyte interface’ (SEI) layer. Upon return to open-circuit conditions, Li-containing species quickly moved out of the thin layer, leaving a compact, stable layer of decomposition products underneath the SEI layer. This SEI layer concomitantly filled with electrolyte or dissolved, becoming indistinguishable from the electrolyte via contrast in scattering-length density (SLD). During the second current cycle, Li-containing species again preferentially deposited directly atop the cathode, with the thick SEI-like layer again appearing within a minute. This SEI layer exhibited a lower SLD more quickly than in the first cycle, which might suggest that Li-containing species become distributed within the porous SEI layer. Furthermore, these time-resolved observations of SEI and plated layers during current cycling suggest that benefits associated with return to open-circuit conditions between periods of applied current density may be related to the concomitant loss of Li-containing species from a thin layer at the cathode surface into a porous SEI layer that becomes filled with electrolyte or dissolves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dendrite Growth Morphology Modeling in Liquid and Solid Electrolytes

The main goal of this project is to develop a multi-scale modeling approach that connects micron-scale phase-field models and atomic-scale density functional theory (DFT)-based simulations via parameter- and relationship-passing in order to predict Li-metal dendrite morphology evolution, in both liquid and solid electrolytes. The key hypothesis of the DFT-informed phase-field multiscale modeling approach is that it can capture the electrochemical-mechanical driving forces and incorporate the roles of nano-meter-thin solid electrolyte interphase (SEI) in liquid electrolytes as well as of the microstructures of micro-meter-thick solid electrolytes (SEs) for all-solid-state batteries. In this project, we have formulated and implemented phase-field models to incorporate the electrochemical driving forces in liquid electrolytes and then incorporate mechanical driving forces to simulate dendrite growth in solid electrolytes with resolved microstructures. We have implemented two treatments for the SEI: an explicit model to include the microstructure of the SE or SEI in the phase field model and an implicit model to simulate the impact of nano-meter thick SEI in liquid electrolytes by varying the electrode/electrolyte interfacial properties. The key interfacial properties, including the electronic and ionic transport properties, the charge transfer reaction kinetics, and mechanical properties, were computed by DFT-based calculations. At the DFT-based model, one key advancement is to directly predict the charge transfer reaction kinetics at a complex Li/SEI/electrolyte interface by linking DFT with density functional tight binding (DFTB) calculations. As the main accomplishments, we have demonstrated two successful predictions in both solid electrolyte and liquid electrolyte based on this multiscale approach. The predicted intergranular Li dendrite growth in LLZO revealed the importance of trapped electrons at internal interfaces in the microstructure of LLZO. The predicted electroplating morphology of mossy Li and faceted Mg agreed well with experiments. The insights provided by the multiscale model and the model enabled electrolyte and SEI design will accelerate the development of Li-metal electrode for high energy density batteries, that meet DOE’s target on cell density (>350 Wh/kg) and cost below $100/kWhuse for EV applications.

25 ENERGY STORAGE↗

Resonant tunneling IR detectors

Researchers propose a novel semiconductor heterojunction photodetector which would have a very low dark current and would be voltage tunable. A schematic diagram of the device and its band structure are shown. The two crucial components of the device are a cathode (InGaAs) whose condition band edge is below the conduction band edge of the quantum wells and a resonant tunneling filter (GaAs-AlGaAs). In a standard resonant tunneling device the electrodes are made of the same material as the quantum wells, and this device becomes highly conducting when the quantum levels in the wells are aligned with the Fermi level in the negatively biased electrode. In contrast, the researchers device is essentially non-conducting under the same bias conditions. This is because the Fermi Level of the cathode (InGaAs) is still well below the quantum levels so that no resonant transport occurs and the barriers (AlGaAs) effectively block current flow through the device. However, if light with the same photon energy as the conduction-band discontinuity between the cathode and the quantum wells, E sub c3-E sub c1, is shone on the sample, free carriers will be excited to an energy corresponding to the lowest quantum level in the well closest to the cathode (hv plue E sub c1 = E sub o). These electrons will resonantly tunnel through the quantum wells and be collected as a photocurrent in the anode (GaAs). To improve the quantum efficiency, the cathode (InGaAs) should be very heavily doped and capped with a highly reflective metal ohmic contact. The thickness of the device should be tailored to optimize thin film interference effects and afford the maximum absorption of light. Because the device relies on resonant tunneling, its response should be very fast, and the small voltages needed to change the responsivity should allow for very high frequency modulation of the photocurrent. In addition, the device is tuned to a specific photon energy so that it can be designed to detect a fairly narrow range of wavelengths. This selectivity is important for reducing the photocurrent due to spurious light sources.

Woodall, Jerry M.↗

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Lastly, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Reliability Model for Ni-BaTiO3-Based (BME) Ceramic Capacitors

The evaluation of multilayer ceramic capacitors (MLCCs) with base-metal electrodes (BMEs) for potential NASA space project applications requires an in-depth understanding of their reliability. The reliability of an MLCC is defined as the ability of the dielectric material to retain its insulating properties under stated environmental and operational conditions for a specified period of time t. In this presentation, a general mathematic expression of a reliability model for a BME MLCC is developed and discussed. The reliability model consists of three parts: (1) a statistical distribution that describes the individual variation of properties in a test group of samples (Weibull, log normal, normal, etc.), (2) an acceleration function that describes how a capacitors reliability responds to external stresses such as applied voltage and temperature (All units in the test group should follow the same acceleration function if they share the same failure mode, independent of individual units), and (3) the effect and contribution of the structural and constructional characteristics of a multilayer capacitor device, such as the number of dielectric layers N, dielectric thickness d, average grain size r, and capacitor chip size S. In general, a two-parameter Weibull statistical distribution model is used in the description of a BME capacitors reliability as a function of time. The acceleration function that relates a capacitors reliability to external stresses is dependent on the failure mode. Two failure modes have been identified in BME MLCCs: catastrophic and slow degradation. A catastrophic failure is characterized by a time-accelerating increase in leakage current that is mainly due to existing processing defects (voids, cracks, delamination, etc.), or the extrinsic defects. A slow degradation failure is characterized by a near-linear increase in leakage current against the stress time; this is caused by the electromigration of oxygen vacancies (intrinsic defects). The two identified failure modes follow different acceleration functions. Catastrophic failures follow the traditional power-law relationship to the applied voltage. Slow degradation failures fit well to an exponential law relationship to the applied electrical field. Finally, the impact of capacitor structure on the reliability of BME capacitors is discussed with respect to the number of dielectric layers in an MLCC unit, the number of BaTiO3 grains per dielectric layer, and the chip size of the capacitor device.

reliability↗