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At least 163 records · Page 9

Interaction between antimony atoms and micropores in silicon

The interaction between Sb atoms and micropores of a getter layer in silicon is studied. The getter layer was obtained via implantation of Sb{sup +} ions into silicon and subsequent heat treatment processes. The antimony atoms located in the vicinity of micropores are captured by micropores during gettering annealing and lose its electrical activity. The activation energy of capture process to the pores for antimony is lower than that of antimony diffusion in silicon deformation fields around microvoids on the diffusion process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Degradation & Performance Studies of ALD-Stabilized Nano-Composite SOFC Cathodes

This work showed, definitively, for the first time, that zirconia Atomic Layer Deposited (ALD) overcoats improve the stability of Solid Oxide Fuel Cell (SOFC) cathodes by chemically gettering interfacial Sr that has segregated out of lanthanum strontium cobalt iron oxide (LSCF). The optimum ALD ZrO 2 overcoat thickness was found to be ≥5 nm and <10 nm. Gadolinium doped ceria (GDC) pre-infiltration was also shown, for the first time, to improve SOFC cathode stability through the chemical getting of Sr at the LSCF-backbone and LSCF-gas interfaces. Due to the fact that it can be performed easily in air on large-area electrodes, GDC pre-infiltration is likely more commercially viable than ALD ZrO 2 overcoating as an interfacial Sr gettering technique. Combining ZrO 2 overcoating with GDC pre-infiltration was not successful because the GDC nano-particles gettered the ZrO 2 overcoat instead of the interfacial Sr.

30 DIRECT ENERGY CONVERSION↗

Fundamental Studies of Tritium Diffusivity and Formation on the Surfaces of Defective LiAlO 2 Pellets

One of the important components of tritium-producing burnable absorber rods (TPBAR) is the γLiAlO 2 layer used in the form of an annular ceramic pellet enriched with the 6 Li isotope. Within TPBAR architecture, this oxide is located between the zircaloy-4 liner and nickel-plated zircaloy-4 tritium getter. When irradiated in a pressurized water reactor (PWR), the 6 Li pellets absorb neutrons, simulating the nuclear characteristics of a burnable absorber rod, and produce tritium ( 3 H, T). The 3 H specie chemically reacts with the metal getter, leading to the formation of a metal hydride. Accurate analysis of the 3 H transport through the ceramic pellets and the barrier/cladding system is hampered by the lack of fundamental data about the hydrogen isotope solubility and diffusivity. In TPBAR architecture, between the γ-LiAlO 2 pellet and the Ni-plated Zircaloy-4 getter (or liner), there is a gas gap. After 3 H diffuses from bulk γ-LiAlO 2 to its surface, it is possible that different 3 H species (such as T, T 2 , T 2 O, and OT, etc.) are formed on this surface which can then get into the gas gap region. Furthermore, upon recombination and desorption molecular tritium can be formed on the γ-LiAlO 2 surface. Therefore, exploring the formation of 3 H-related species on γ-LiAlO 2 surface becomes very important as an integral part of the study of 3H solubility and diffusivity in the pellets.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Solid state NMR Investigation of Structural Differences in Pelletized DEB Samples

Upon hydrogenation of DEB pellets, which are composed of 75% virgin DEB and 25% of nanometer scale Pd catalysts on activated carbon, the uptake rate is strong, and the hydrogenation process is fast. However, the last batch of DEB pellets from KCNSC uptakes 10 times slower than traditional DEB pellets after ~ 50% consumption. In addition, the last batch of DEB getter pellets also became partially molten/wet during the hydrogenation process. This molten/wet phase during hydrogenation has only been observed with DPB and never with DEB formulation. DRIFT (diffuse reflection infrared Fourier transform) and XRD (x-ray diffraction) confirm that the questionable batch of DEB pellets from KCNSC are truly 100% DEB and not a mixture of DEB and DPB. So, there must be something different in the composition (like concentration and distribution of Pd) or interaction between the DEB molecules with the surrounding environment (activated carbon spreading medium). The possibility of some chemical contamination in the processing of this batch of questionable DEB getter pellets also comes to mind. Due to the ability of NMR to detect intermolecular interaction and sensitivity to small chemical concentration, NMR investigation was requested for this questionable batch of DEB getter pellets from KCNSC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New implantation techniques for improved solar cell junctions

Ion implantation techniques offering improved cell performance and reduced cost have been studied. These techniques include non-mass-analyzed phosphorus implantation, argon implantation gettering, and low temperature boron annealing. It is found that cells produced by non-mass-analyzed implantation perform as well as mass-analyzed controls, and that the cell performance is largely independent of process parameters. A study of argon implantation gettering shows no improvement over non-gettered controls. Results of low temperature boron annealing experiments are presented.

Spitzer, M. B.↗

Oxygen and carbon impurities and related defects in silicon

Oxygen and carbon are the predominant impurities in Czochralski-grown silicon. The incorporation of oxygen and carbon during crystal growth is reviewed and device effects are discussed. Methods for controlling oxygen and carbon incorporation during crystal growth are discussed and results supporting a segregation coefficient of k=0.5 for oxygen are presented. The nucleation and precipitation behavior of oxygen is complex. Temperature and doping level effects which add insight into the role of point defects in the nucleation process are highlighted. In general, precipitation is found to be retarded in N+ and P+ silicon. The types and quantities of defects resulting from the oxygen precipitates is of interest as they are technologically useful in the process called intrinsic gettering. A comparison is made between the available defect sites and the quantities of metallic impurities present in a typical wafer which need to be gettered. Finally, a discussion of the denuded-zone, intrinsic-gettered (DZ-IG) structure on device properties is presented.

Pearce, C. W.↗

Oxygen and carbon in silicon

The properties of the early transistors were determined by the minority-carrier lifetime, as is the silicon photovoltaic solar cell. Most of the devices on the modern integrated circuits are majority carrier devices, in part to avoid this lifetime dependence. The micro-electronics industry typically starts with wafers with a minority-carrier lifetime of 1000 micro-seconds, but during device fabrication this lifetime is reduced to beflow 1 micro-second, in spite of extraordinary cleanliness and precautions. Process-induced defects (PID) include point defects, defect complexes, line defects, and bulk precipitates. One of the aspects that needs to be better understood is the nature of minority carrier recombination at line defects and at precipitates. Some of the PIDs are known to be related to the fast-diffusers of the iron-series transition elements. One of the common techniques of dealing with these elements is intrinsic gettering by the oxygen precipitates. But even in the gettered state, there may be a residual effect on the lifetime. Oxygen is an almost ubiquitous impurity in silicon and plays an important role in both integrated circuits and solar cells. The isolated oxygen interstitial is electrically inactive, but in its various aggregated forms it has a variety of electrical activities. The agglomeration and precipitation of oxygen, including impurity gettering and the complicating role of carbon, is discussed.

Corbett, J. W.↗

Buffer Gas Experiments in Mercury (Hg+) Ion Clock

We describe the results of the frequency shifts measured from various buffer gases that might be used as a buffer gas to increase the loading efficiency and cooling of ions trapped in a small mercury ion clock. The small mass, volume and power requirement of space clock precludes the use of turbo pumps. Hence, a hermetically sealed vacuum system, incorporating a suitable getter material with a fixed amount of inert buffer gas may be a practical alternative to the groundbased system. The collision shifts of 40,507,347.996xx Hz clock transition for helium, neon and argon buffer gases were measured in the ambient earth magnetic field. In addition to the above non-getterable inert gases we also measured the frequency shifts due to getterable, molecular hydrogen and nitrogen gases which may be used as buffer gases when incorporated with a miniature ion pump. We also examined the frequency shift due to the low methane gas partial pressure in a fixed higher pressure neon buffer gas environment. Methane gas interacted with mercury ions in a peculiar way as to preserve the ion number but to relax the population difference in the two hyperfine clock states and thereby reducing the clock resonance signal. The same population relaxation was also observed for other molecular buffer gases (N H ,) but at much reduced rate.

mercury ion clock↗

Heat Switches Providing Low-Activation Power and Quick-Switching Time for Use in Adiabatic Demagnetization Refrigerators

An adiabatic demagnetization refrigerator (ADR) is a solid-state cooler capable of achieving sub-Kelvin temperatures. It neither requires moving parts nor a density gradient in a working fluid making it ideal for use in space-based instruments. The flow of energy through the cooler is controlled by heat switches that allow heat transfer when on and isolate portions of the cooler when off. One type of switch uses helium gas as the switching medium. In the off state the gas is adsorbed in a getter thus breaking the thermal path through the switch. To activate the switch, the getter is heated to release helium into the switch body allowing it to complete the thermal path. A getter that has a small heat capacity and low thermal conductance to the body of the switch requires low-activation power. The cooler benefits from this in two ways: shorter recycle times and higher efficiency. We describe such a design here.

Kimball, Mark O.↗

Heat Switches Providing Low-Activation Power and Quick-Switching Time for Use in Cryogenic Multi-Stage Refrigerators

An adiabatic demagnetization refrigerator (ADR) is a solid-state cooler capable of achieving sub-Kelvin temperatures. It neither requires moving parts nor a density gradient in a working fluid making it ideal for use in space-based instruments. The flow of energy through the cooler is controlled by heat switches that allow heat transfer when on and isolate portions of the cooler when off. One type of switch uses helium gas as the switching medium. In the off state the gas is adsorbed in a getter thus breaking the thermal path through the switch. To activate the switch, the getter is heated to release helium into the switch body allowing it to complete the thermal path. A getter that has a small heat capacity and low thermal conductance to the body of the switch requires low-activation power. The cooler benefits from this in two ways: shorter recycle times and higher efficiency. We describe such a design here.

Kimball, Mark O.↗

Active Gas-Gap Heat Switch with Fast Thermal Response

An active gas-gap heat switch may significantly reduce the time required to transition between the open and closed states, reduce the heat require to warm the getter, and reduce the heat that leaks from the getter to the switch body. A thermal interface at one end of the active gas-gap heat switch may include a plurality of fins. A getter assembly may be hermetically attached to the thermal interface and a containment tube may surround and house the plurality of fins.

Shirron, Peter J.↗

Role of Zr in strengthening MoSi 2 from density functional theory calculations

MoSi 2 is an important intermetallic with excellent oxidation resistance at high temperatures above1000C. However, its application at lower temperatures is limited by oxygen embrittlement, a phenomenon known as “pesting”. In this work, we comprehensively investigate the role of Zr in mitigating pesting in MoSi2using density functional theory calculations. We show that Zr dopants reduce the embrittling effects of oxygen interstitials at MoSi 2 grain boundaries by being a charge donor to oxygen. However, a more substantial effect is observed when Zr is present as a secondary getter nanoparticle phase. Oxygen interstitials have a strong thermodynamic driving force to migrate into the Zr subsurface at the Zr/MoSi 2 interface, and the work of separation of the clean and oxygen-contaminated Zr/MoSi 2 interfaces are much higher than that of MoSi 2 grain boundaries. So we present an efficient screening approach to identify other potential getter elements using simple thermodynamic descriptors, which can be extended to other alloy systems of interest. These findings provide crucial fundamental insight s and further avenues to optimize Mo and other alloys.

36 MATERIALS SCIENCE↗

Solar cell efficiency and high temperature processing of n -type silicon grown by the noncontact crucible method

The capital expense (capex) of conventional crystal growth methods is a barrier to sustainable growth of the photovoltaic industry. It is challenging for innovative techniques to displace conventional growth methods due the low dislocation density and high lifetime required for high efficiency devices. One promising innovation in crystal growth is the noncontact crucible method (NOC-Si), which combines aspects of Czochralski (Cz) and conventional casting. This material has the potential to satisfy the dual requirements, with capex likely between that of Cz (high capex) and multicrystalline silicon (mc-Si, low capex). In this contribution, we observe a strong dependence of solar cell efficiency on ingot height, correlated with the evolution of swirl-like defects, for single crystalline n -type silicon grown by the NOC-Si method. We posit that these defects are similar to those observed in Cz, and we explore the response of NOC-Si to high temperature treatments including phosphorous diffusion gettering (PDG) and Tabula Rasa (TR). The highest lifetimes (2033 us for the top of the ingot and 342 us for the bottom of the ingot) are achieved for TR followed by a PDG process comprising a standard plateau and a low temperature anneal. Further improvements can be gained by tailoring the time-temperature profiles of each process. Lifetime analysis after the PDG process indicates the presence of a getterable impurity in the as-grown material, while analysis after TR points to the presence of oxide precipitates especially at the bottom of the ingot. Uniform lifetime degradation is observed after TR which we assign to a presently unknown defect. Lastly, future work includes additional TR processing to uncover the nature of this defect, microstructural characterization of suspected oxide precipitates, and optimization of the TR process to achieve the dual goals of high lifetime and spatial homogenization.

14 SOLAR ENERGY↗

THE ABSORPTION OF HYDROGEN ON LOW PRESSURE HYDRIDE MATERIALS

For this study, hydrogen getter materials (Zircaloy-4 and pure zirconium) that have a high affinity for hydrogen (and low overpressure) have been investigated to determine the hydrogen equilibrium pressure on Zircaloy-4 and pure zirconium. These materials, as with most getter materials, offered significant challenges to overcome given the low hydrogen equilibrium pressure for the temperature range of interest. Hydrogen-zirconium data exists for pure zirconium at 500 C and the corresponding hydrogen overpressure is roughly 0.01 torr. This manuscript presents the results of the equilibrium pressures for the absorption and desorption of hydrogen on zirconium materials at temperatures ranging from 400 C to 600 C. The equilibrium pressures in this temperature region range from 150 mtorr at 600 C to less than 0.1 mtorr at 400 C. It has been shown that the Zircaloy-4 and zirconium samples are extremely prone to surface oxidation prior to and during heating. This oxidation precludes the hydrogen uptake, and therefore samples must be heated under a minimum vacuum of 5 x 10{sup -6} torr. In addition, the Zircaloy-4 samples should be heated at a sufficiently low rate to maintain the system pressure below 0.5 mtorr since an increase in pressure above 0.5 mtorr could possibly hinder the H{sub 2} absorption kinetics due to surface contamination. The results of this study and the details of the testing protocol will be discussed.

08 HYDROGEN↗

The origin and formation of oxygen inclusions in austenitic stainless steels manufactured by laser powder bed fusion

The origins of nano-scale oxide inclusions in 316L austenitic stainless steel (SS) manufactured by laser powder bed fusion (L-PBF) was investigated by quantifying the possible intrusion pathways of oxygen contained in the precursor powder, extraneous oxygen from the process environment during laser processing, and moisture contamination during powder handling and storage. When processing the fresh, as-received powder in a wellcontrolled environment, the oxide inclusions contained in the precursor powder were the primary contributors to the formation of nano-scale oxides in the final additive manufactured (AM) product. These oxide inclusions were found to be enriched with oxygen getter elements like Si and Mn. By controlling the extraneous oxygen level in the process environment, the oxygen level in AM produced parts was found to increase with the extraneous oxygen level. The intrusion pathway of this extra oxygen was found to be dominated by the incorporation of spatter particles into the build during processing. Moisture induced oxidation during powder storage was also found to result in a higher oxide density in the AM produced parts. SS 316L powder free of Si and Mn oxygen getters was processed in a well-controlled environment and resulted in a similar level of oxygen intrusion. Finally, microhardness testing indicated that the oxide volume fraction increase from extraneous oxygen did not influence hardness values. However, a marked decrease in hardness was found for the humidified and Si-Mn free AM processed parts.

36 MATERIALS SCIENCE↗

Fracture behavior of a melt-infiltration-processed SiC/Si composite at 900°C in argon, air, and steam

The fracture behavior of a melt-infiltration-processed SiC/Si composite, used to mimic the matrices of industrial fiber-reinforced ceramic composites, was examined in different atmospheres and temperatures. Specimens tested in four-point bending at 900 °C in oxygen-gettered argon, dry air, or steam-rich atmospheres exhibited higher average fracture strengths than specimens tested at 25°C. Higher mean fracture strength values were obtained for specimens tested in dry air or in a steam-rich atmosphere at 900°C than for specimens tested in high-purity, oxygen-gettered argon at this temperature. The increased fracture strengths obtained in air and in steam-rich atmospheres coincided with increased specimen oxidation and apparent oxide filling and blunting of flaws in these composites. Further, a transition in the location of catastrophic failure, from sites of preexisting damage created by Vickers indentations for tests in argon to other locations for tests in air or steam-rich atmospheres, was also consistent with such apparent oxide filling/blunting of indentation-induced flaws.

36 MATERIALS SCIENCE↗

Pelletization with Spark Plasma Sintering and Characterization of Metal Iodides: An Assessment of Long-Term Radioiodine Immobilization Options

Four promising iodine “getter” materials (Ag, Cu, Bi, and Sn) for radioiodine capture were assessed in their pure metal-iodide (MI x ) pelletized forms to compare relative chemical durabilities. To study chemical durability, commercial MI x compounds of AgI, BiI 3 , BiOI, CuI, and SnI 4 were converted to dense monolithic pellets using spark plasma sintering. Semidynamic leach testing in the form of modified ASTM C1308 tests was then performed on the pellets in two different forms including unmounted (as-pressed) specimens (i.e., “U”) and epoxy-mounted specimens (i.e., “M”) with polished surfaces. The chemical durability results and sample characterizations showed that three of the five MI x compounds tested (i.e., AgI, CuI, and BiOI) displayed moderate to high leach resistances. Further, the remaining two MI x compounds (i.e., BiI 3 and SnI 4 ), which are both desirable iodine waste forms due to their high iodine loading capacities, readily decomposed during leach testing, indicated by crystallographic changes in the specimens as well as large amounts of iodine detected in the leachate solutions. The instabilities of BiI 3 and SnI 4 raise uncertainties for using the base metals/cations (i.e., Bi 0 /Bi 3+ and Sn 0 /Sn 4+ , respectively) as viable getters for radioiodine capture due to likely poor waste form chemical durabilities after capture and consolidation into waste forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of nitrogen on lithium-induced corrosion and cracking of RAFM steel

The emergence of private fusion enterprises, combined with advancements in U.S. and EU ITER-TBM as well as EU DEMO liquid breeder blanket concepts, has renewed focus on the materials challenges. This study examines the compatibility of reduced activation ferritic/martensitic (RAFM) steel in liquid Lithium (Li) containing various Nitrogen (N) concentrations, tested at 600 and 700 °C for 500 and 1000 h under static conditions. Microstructural characterization revealed the corrosion-induced dissolution and precipitation in Li containing 0.082 and 0.17 wt.% N at 600 °C, while limited dissolution and precipitation were observed in N-gettered Li using zirconium (Zr) and titanium (Ti) foils at 600 °C. Tensile testing at room temperature after Li exposure revealed a decrease in strength and ductility of the RAFM steel as a function of N content in Li. Severe embrittlement was observed after 500 h in Li containing 0.17 wt.% N at 600 °C and after 500 h in hot-gettered Li at 700 °C. Chromium (Cr) depletion from the steel matrix was observed, leading to the formation of M6C-type carbides on the surface identified by electron microscopy (SEM), X-ray diffraction (XRD), in agreement with thermodynamic calculations. These findings highlight the critical materials challenges posed by liquid Li breeder blanket concepts, emphasizing the need for improved strategies to address Li-induced dissolution, precipitation, and steel embrittlement due to N contamination of the coolant.

Romedenne, Marie [ORNL] (ORCID:0000000317936561)↗