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At least 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Fast lithium ion diffusion in brownmillerite Li x Sr 2 Co 2 O 5

Transition metal oxides not only exhibits novel magnetic properties but also provides outstanding ionic transports. Ionic conductors have great potential for interesting tunable physical properties via ionic liquid gating and novel energy storage applications such as all-solid-state lithium batteries. In particular, low migration barriers and high hopping attempt frequency are the keys to achieve fast ion diffusion in solids. Taking advantage of the oxygen-vacancy channel in Li x Sr 2 Co 2 O 5 , we show that migration barriers of lithium ion are as small as 0.28–0.17 eV depending on the lithium concentration rates. Our first-principles calculation also investigated hopping attempt frequency and concluded the room temperature ionic diffusivity and ion conductivity are high as 10 −7 –10 −6 cm 2 s −1 and 10 −3 –10 −2 Scm −1 , respectively, which outperform most of perovskite-type, garnet-type, and sulfide Li-ion solid-state electrolytes. This work proves Li x Sr 2 Co 2 O 5 as a promising super-ionic conductor.

Crystallographic defects↗
NASA NTRS1999

Solidification of II-VI Compounds in a Rotating Magnetic Field

This project is aimed at using a rotating magnetic field (RMF) to control fluid flow and transport during directional solidification of elemental and compound melts. Microgravity experiments have demonstrated that small amounts of residual acceleration of less than a micro-g can initiate and prolong fluid flow, particularly when there is a static component of the field perpendicular to the liquid solid interface. Thus a true diffusion boundary layer is not formed, and it becomes difficult to verify theories of solidification or to achieve diffusion controlled solidification. The RMF superimposes a stirring effect on an electrically conducting liquid, and with appropriate field strengths and frequencies, controlled transport of material through a liquid column can be obtained. As diffusion conditions are precluded and complete mixing conditions prevail, the technique is appropriate for traveling solvent zone or float zone growth methods in which the overall composition of the liquid can be maintained throughout the growth experiment. Crystals grown by RMF techniques in microgravity in previous, unrelated missions have shown exceptional properties. The objective of the project is two-fold, namely (1) using numerical modeling to simulate the behavior of a solvent zone with applied thermal boundary conditions and demonstrate the effects of decreasing gravity levels, or an increasing applied RMF, or both, and (2) to grow elements and II-VI compounds from traveling solvent zones both with and without applied RMFs, and to determine objectively how well the modeling predicts solidification parameters. Numerical modeling has demonstrated that, in the growth of CdTe from a tellurium solution, a rotating magnetic field can advantageously modify the shape of the liquid solid interface such that the interface is convex as seen from the liquid. Under such circumstances, the defect structure is reduced as any defects which are formed tend to grow out and not propagate. The flow of liquid, however, is complex due to the competing flow induced by the rotating magnetic field and the buoyancy driven convection. When the acceleration forces are reduced to one thousandth of gravity, the flow pattern is much simplified and well controlled material transport through the solvent zone can be readily achieved. Triple axis diffractometry and x-ray synchrotron topography have demonstrated that there is no significant improvement in crystal quality for HgCdTe grown on earth from a tellurium solution when a rotating magnetic field is applied. However, modeling shows that the flow in microgravity with a rotating magnetic field would produce a superior product.

Gillies, D. C.↗
DOE OSTI2025

Applications of Nickelate perovskites for neuromorphic computing from electronic structure and Machine Learning

While the limit of Moore's law is presently being reached with current microelectronic technologies, we need to develop new paradigms that overcome this limitation. In that respect, neuromorphic computing is a concept that emulates the neural behavior and response of the human brain, and it has been recognized as a promising alternative approach. In this research project, we will perform multi-fidelity scale bridging to explore the potential use of materials with metal to insulator transition for neuromorphic applications. In particular, rare earth nickelates are promising for such purposes, as the transition in these materials is quite sensitive to a broad set of different external stimuli. Our multi-fidelity approach will bridge the high-fidelity electronic structure calculations with classical potentials. We will bridge dynamical mean field theory with a classical atomistic representation via a deep learning force field. The neural network is trained with energies, charges, and forces obtained by accurate electronic structure theories based on Dynamical Mean Field Theory. The configurational space is generated from known crystal phases, ab initio molecular dynamics with exchange-correlation functionals corrected with the Hubbard model, disordered phases with different concentrations of oxygen vacancies, and nonsymmetrical positions and induced strain by grain interfaces or contact with a substrate. Strategies to train the model with a reduced number of training examples are obtained from active learning methods, and new structures for improving the learning process are generated by using machine learning autoencoders. This classical potential will be validated through a diversity of electronic structure methods and represents an important step to combine the flexibility and accuracy of first-principles with the speed of classical potentials. The generated multi-fidelity surrogate model will be used to understand the role of strain, oxygen vacancies, proton doping, the variation of the crystal phase, substrate effects, vibrational effects as the octahedral rotation, grain boundaries and defect effects on the response of a Metal to Insulator Transition (MIT) in correlated materials. Long time and large-scale simulations will help understand the role of different stimuli to control the hysteresis of the MIT, as it has been experimentally suggested. Selected configurations will be analyzed with higher-level theories to provide an accurate electronic description and to study how the orbitals and charges are rearranged under different conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Extreme Temperature Cryptography Based On Nitrogen-Incorporated Ultrananocrystalline Diamond

Physical entropy sources that remain stable under extreme temperatures are essential for cryptography in emerging technological frontiers in deep space exploration, geothermal energy harvesting, and nuclear energy. However, conventional semiconductor platforms fail to generate stable and reliable cryptographic keys above 200 degrees C due to performance degradation. Here, we report a diamond-based cryptographic primitive that exploits the defect-rich sp 2 -bonded grain boundary network in nitrogen-incorporated ultrananocrystalline diamond (n-UNCD) film as a robust entropy source to generate cryptographic keys that remain operationally stable even after enduring extreme temperatures of 700 degrees C for 54 h while also surviving thermal cycling between room temperature and 700 degrees C for 48 h. The strength of the generated keys is assessed through several cryptographic metrics such as bit uniformity, entropy, hamming distances, and correlation coefficients, all of which are found to be near their respective ideal values. Moreover, the generated keys pass the NIST SP 800 and SP 800-90B tests and are also resilient to supply bias variations and a regression-based machine learning attack model based on the Fourier series. The robustness of the keys is attributed to the better thermal stability and chemical inertness of the n-UNCD film. This is supported by high-resolution energy-dispersive X-ray spectroscopy (EDS), which shows no significant lateral diffusion of metal atoms into the n-UNCD layer, and by Raman spectroscopy, which reveals no significant changes in the bonding configuration of the n-UNCD structure. Our findings highlight the remarkable potential of n-UNCD film for extreme environment cryptography by expanding the operational limits of conventional hardware security platforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ab initio prediction of rapid kinetics of Fe impurities in δ -Pu

Here, we study the formation energies of iron impurities in δ-Pu within spin–orbital-polarized density functional theory (SOP-DFT). The thermodynamic solubility limit of iron in δ-Pu is calculated, indicating low miscibility. We show that surprisingly, Fe impurities at equilibrium are almost equally likely to occupy octahedral interstitial sites or substitutional sites, with slight preference for the former. In contrast, we find the energy of the tetrahedral interstitial Fe to be nearly 1 eV higher than the octahedral one. We explore the energy landscape for Fe impurity hopping diffusion and conclude that Fe impurities in δ-Pu are divided into two populations: (i) Immobile substitutional Fe impurities and (ii) highly mobile interstitial Fe impurities. The latter, (ii), migrate between octahedral interstitial sites with an energy barrier of around 0.2 eV. The energy barrier for exchange between the two populations is calculated to exceed 0.7 eV. Finally, we discuss the role of magnetic order on the impurity energetics.

Atomic structure↗
DOE OSTI2024

Elucidating the role of Cr migration in Ni-Cr exposed to molten FLiNaK via multiscale characterization

Structural materials used in nuclear reactor environments are subjected to coupled extremes such as high temperature, irradiation, and corrosion which act in concert to degrade their functional performance. Connecting alloy microstructure such as grain boundaries, and accumulating point defects with corrosion attack and pore morphology is critical to understanding underlying mechanisms. We uncover the compositional variations and morphology at multiple length scales in corrosion-damaged Ni-Cr alloy after exposure to oxidants in molten fluoride salts. A complex network of dense corrosion pores is detected by surface-level SEM observations. The corrosion pores take on a 1-dimensional morphology and are enriched with Ni and depleted of Cr 1–5 µm from the pore surface. STEM-EDS and 4D-STEM strain maps acquired simultaneously highlight the local variations in composition and structure of a ≤ 200 nm Cr-rich layer identified from a cross-section taken at the bottom of an isolated corrosion pore between the Ni-Cr alloy matrix and the embedded salt. However, the absence of an observed interface between the Ni-Cr alloy matrix and the FCC-structured Cr-rich layer suggests that Cr plating from the salt did not transpire. These findings support a proposed Cr lattice diffusion mechanism rather than Cr-precipitation from the salt to accommodate temperature transient conditions during sample cooling. Through the development of a 1D phase field model, these results are rationalized by formation energies for the Ni- and Cr-oxidation into the molten salt. This study reveals the locally altered microstructure caused by high temperature corrosion in non-steady-state molten salt nuclear reactor environments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mechanical and Thermophysical Properties of 3D-Printed SiC before and after Neutron Irradiation – FY21

This report presents the mechanical and thermophysical properties of 3D-printed SiC before and after neutron irradiation that have been evaluated to assess the fuel matrix material for the Transformational Challenge Reactor (TCR). The TCR fuel form consists of an additively-manufactured silicon carbide (SiC) matrix and uranium nitride tristructural isotropic (UN TRISO) fuel particles, which is manufactured through a newly developed processing route combining binderjet 3D printing, TRISO fuel particle loading, and chemical vapor infiltration (CVI). Because the fuel matrix is a primary component of the TCR core and its response to mechanical and thermal loads during operation is one of the most influential factors on the integrity of TCR core, testing and evaluation have focused on producing mechanical and thermophysical properties data for the binderjet/CVI SiC. Baseline mechanical and thermophysical properties were measured from the disk specimens printed for different and sizes orientations, which included equibiaxial flexural failure strength, elastic constants, thermal diffusivity and conductivity, density, and the coefficient of thermal expansion. Flexural failure strength datasets showed similar Weibull distributions regardless of sample variants including different orientations. The mean failure strengths of the 3D-printed SiC variants were in the range of 280–310 MPa, which are slightly lower than that of the chemical vapor deposition (CVD) SiC. Thermophysical test results showed that specific heat and thermal expansion are not sensitive to the build direction of SiC samples, while thermal conductivity is highly dependent on the build direction and can be correlated to the anisotropic character of the 3D-printed SiC. Neutron irradiation tests were carried out on the 3D-printed 6-mm diameter SiC disk specimens. Irradiation was carried to 2.3 dpa over a temperature range of 360–880°C. No significant degradation in strength was observed in SiC after irradiations in various conditions and with different orientations. Anisotropy that had been observed in the thermal conductivity of 3D-printed SiC prior to irradiation vanished after irradiation as the irradiation defect thermal resistivity accumulated in the material. Electron microscopy of the microstructure after neutron irradiation showed distinct defect morphologies in the heterogenous material, but no evidence for irradiation-induced cracking or degradation in the microstructure was observed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Experimental validation of the mechanistic scale-up methodology of gas–solid spouted beds using radioactive particle tracking (RPT)

The very high-temperature reactors (VHTRs) are highly ranked among candidates of Generation IV of nuclear reactors due to their high efficiency, safety, the resistance to proliferation, and reliability. The VHTRs are preferentially fueled by Tristructural-isometric (TRISO) coated fuel particles which has fuel kernels of fissile material coated by four coating layers: a porous buffer pyrolysis carbon layer (buffer PyC), an inner dense pyrolysis carbon layer (IPyC), a silicon carbide layer (SiC) and an outer dense pyrolysis carbon layer (OPyC). The heart of the operation and safety of the VHTRs significantly depends on the reliability of the coating layers of TRISO particles to retain metallic and gaseous fission products within the particles. The technique used for coating TRISO particles are gas-solids spouted beds via chemical vapor deposition (CVD). Fabrication of high-quality low-defect TRISO fuel particles fuel at larger scale spouted beds is required to support the commercialization of the VHTRs. In this work, our new developed mechanistic scale-up methodology of gas-solids spouted beds based on matching the radial profile of gas-holdup has been demonstrated and validated using radioactive particle tracking (RPT). Two spouted beds of small and larger scales were used in the study. Three sets of conditions were carried out which include the conditions of the reference case in the large scale, conditions that provide similar gas holdup radial profile to that of the reference case and conditions that provided dissimilar gas holdup radial in the small-scale spouted beds. The results confirm the validation of the scale-up methodology in terms of the dimensionless values of the spout diameter, cumulative probability distribution of the solids particles penetration into the spout, fraction of cycle time in each region of the bed, the radial profiles of the dimensionless values of the root-mean-square particle velocities and solids eddy diffusivity. Finally, the results further advance the knowledge and understanding of the gas-solids spouted beds provide deeper insight into their solids dynamics and presenting important benchmarking data for validating computational fluid dynamics codes and models. At last, procedures are established for the implementation of the new scale-up methodology.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2021

Elemental segregation to lattice defects in the CrMnFeCoNi high-entropy alloy during high temperature exposures

The influence of small plastic pre-strains on the elevated-temperature stability and microstructure of the equiatomic CrMnFeCoNi FCC solid solution is investigated. Particular attention is given to whether any of the alloy elements segregate to individual dislocations. To that end, CrMnFeCoNi samples were first deformed in tension at room temperature to plastic strains of 0.2 and 2.3%, and subsequently annealed at 973 K for 800 hours. The pre-strains activated planar slip of 1/2<110>-type dislocations on {111}-type glide planes. Interactions of this planar slip with special Σ3 grain boundaries formed a large number of dislocation segments with a <110>-type crystallographic orientation suitable for a credible end-on analysis of dislocation cores in HR-STEM. The cores of the 1/2<110> dislocations pushed up against the investigated grain boundaries were found to be close to the compact configuration. Within the sensitivity of the Super-X EDS mapping, no concentration gradient was detected near dislocations that would indicate enrichment at dislocation cores of any of the elemental constituents of the alloy after the pre-deformation and annealing. However, a Cr-rich tetragonal sigma phase nucleated and grew at grain boundary triple junctions during this anneal, processes that were not accelerated by the enhanced dislocation density present after pre-strain. A clear chromium gradient was observed in the Cr-depleted zones near grain boundaries suggesting that Cr transport occurred by relatively slow diffusion from the bulk to the grain boundaries and then by relatively fast diffusion along the grain boundaries to the precipitates. Accompanying the Cr depletion near grain boundaries is a simultaneous Ni and Mn enrichment, which promotes formation of the L1 0 NiMn phase that is observed on the grain boundaries after prolonged annealing.

36 MATERIALS SCIENCE↗
NASA NTRS2007

Fabrication of Buried Nanochannels From Nanowire Patterns

A method of fabricating channels having widths of tens of nanometers in silicon substrates and burying the channels under overlying layers of dielectric materials has been demonstrated. With further refinement, the method might be useful for fabricating nanochannels for manipulation and analysis of large biomolecules at single-molecule resolution. Unlike in prior methods, burying the channels does not involve bonding of flat wafers to the silicon substrates to cover exposed channels in the substrates. Instead, the formation and burying of the channels are accomplished in a more sophisticated process that is less vulnerable to defects in the substrates and less likely to result in clogging of, or leakage from, the channels. In this method, the first step is to establish the channel pattern by forming an array of sacrificial metal nanowires on an SiO2-on-Si substrate. In particular, the wire pattern is made by use of focused-ion-beam (FIB) lithography and a subsequent metallization/lift-off process. The pattern of metal nanowires is then transferred onto the SiO2 layer by reactive-ion etching, which yields sacrificial SiO2 nanowires covered by metal. After removal of the metal covering the SiO2 nanowires, what remains are SiO2 nanowires on an Si substrate. Plasma-enhanced chemical vapor deposition (PECVD) is used to form a layer of a dielectric material over the Si substrate and over the SiO2 wires on the surface of the substrate. FIB milling is then performed to form trenches at both ends of each SiO2 wire. The trenches serve as openings for the entry of chemicals that etch SiO2 much faster than they etch Si. Provided that the nanowires are not so long that the diffusion of the etching chemicals is blocked, the sacrificial SiO2 nanowires become etched out from between the dielectric material and the Si substrate, leaving buried channels. At the time of reporting the information for this article, channels 3 m long, 20 nm deep, and 80 nm wide (see figure) had been fabricated by this method.

Choi, Daniel↗
DOE OSTI2023

Mesoporous CuFe 2 O 4 Photoanodes for Solar Water Oxidation: Impact of Surface Morphology on the Photoelectrochemical Properties**

Abstract Metal oxide‐based photoelectrodes for solar water splitting often utilize nanostructures to increase the solid‐liquid interface area. This reduces charge transport distances and increases the photocurrent for materials with short minority charge carrier diffusion lengths. While the merits of nanostructuring are well established, the effect of surface order on the photocurrent and carrier recombination has not yet received much attention in the literature. To evaluate the impact of pore ordering on the photoelectrochemical properties, mesoporous CuFe 2 O 4 (CFO) thin film photoanodes were prepared by dip‐coating and soft‐templating. Here, the pore order and geometry can be controlled by addition of copolymer surfactants poly(ethylene oxide)‐ block ‐poly(propylene oxide)‐ block ‐poly(ethylene oxide) (Pluronic® F‐127), polyisobutylene‐ block ‐poly(ethylene oxide) (PIB‐PEO) and poly(ethylene‐ co ‐butylene)‐ block ‐poly(ethylene oxide) (Kraton liquid™‐PEO, KLE). The non‐ordered CFO showed the highest photocurrent density of 0.2 mA/cm 2 at 1.3 V vs. RHE for sulfite oxidation, but the least photocurrent density for water oxidation. Conversely, the ordered CFO presented the best photoelectrochemical water oxidation performance. These differences can be understood on the basis of the high surface area, which promotes hole transfer to sulfite (a fast hole acceptor), but retards oxidation of water (a slow hole acceptor) due to electron‐hole recombination at the defective surface. This interpretation is confirmed by intensity‐modulated photocurrent (IMPS) and vibrating Kelvin probe surface photovoltage spectroscopy (VKP‐SPS). The lowest surface recombination rate was observed for the ordered KLE‐based mesoporous CFO, which retains spherical pore shapes at the surface resulting in fewer surface defects. Overall, this work shows that the photoelectrochemical energy conversion efficiency of copper ferrite thin films is not just controlled by the surface area, but also by surface order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

In Situ High-Temperature Ultrafast Electron Diffraction through Integrated Furnace and MEMS Platforms

Temperature fundamentally governs phase stability, defect evolution, and transport behavior in materials. Despite its central role, direct measurements of structural evolution at elevated temperatures on ultrafast timescales have remained limited. Here, we report the design, integration, and validation of 2 complementary in situ heating platforms that substantially extend the thermal operating range of ultrafast electron diffraction (UED). A compact furnace-type heating stage enables stable diffraction measurements from room temperature to 800 K with ±0.1 K stability under ultrahigh vacuum, achieved through multi-sensor feedback control, dual air-cooling channels, and a thermally isolated motion stage. In parallel, a microelectromechanical system (MEMS)-based heating platform provides rapid thermal response and access to extreme temperatures ≥1,373 K with ±0.1 K stability over hundreds-micrometer regions while supporting simultaneous electrical biasing for electrothermal coupling studies. Absolute temperature calibration is established using diffraction-based thermometry via aluminum lattice expansion and independently validated through in situ melting of bismuth thin films. UED measurements further reveal pronounced temperature-dependent nonequilibrium lattice dynamics in bismuth, including modifications to electron–phonon coupling and Debye–Waller behavior, as well as enhanced ultrafast diffuse scattering in aluminum at elevated temperatures. Together, these developments establish a practical framework for quantitative, time-resolved studies of temperature-driven kinetics and nonequilibrium structural dynamics under extreme thermal environments.

Bai, Qianqian [Chinese Academy of Sciences (CAS), ↗
NASA NTRS1995

Hydrogen Passivation of N(+)P and P(+)N Heteroepitaxial InP Solar Cell Structures

Dislocations and related point defect complexes caused by lattice mismatch currently limit the performance of heteroepitaxial InP cells by introducing shunting paths across the active junction and by the formation of deep traps within the base region. We have previously demonstrated that plasma hydrogenation is an effective and stable means to passivate the electrical activity of such defects in specially designed heteroepitaxial InP test structures to probe hydrogen passivation at typical base depths within a cell structure. In this work, we present our results on the hydrogen passivation of actual heteroepitaxial n(+)p and p(+)n InP cell structures grown on GaAs substrates by metalorganic chemical vapor deposition (MOCVD). We have found that a 2 hour exposure to a 13.56 MHz hydrogen plasma at 275 C reduces the deep level concentration in the base regions of both n(+)p and p(+)n heteroepitaxial InP cell structures from as-grown values of 5 - 7 x 10(exp 14)/cc, down to 3 - 5 x 10(exp 12)/cc. All dopants were successfully reactivated by a 400 C, 5 minute anneal With no detectable activation of deep levels. I-V analysis indicated a subsequent approx. 100 fold decrease In reverse leakage current at -1 volt reverse bias, and an improved built in voltage for the p(+)n structures. ln addition to being passivated,dislocations are also shown to participate in secondary interactions during hydrogenation. We find that the presence of dislocations enhances hydrogen diffusion into the cell structure, and lowers the apparent dissociation energy of Zn-H complexes from 1.19 eV for homoepitaxial Zn-doped InP to 1.12 eV for heteroepitaxial Zn-doped InP. This is explained by additional hydrogen trapping at dislocations subsequent to the reactivation of Zn dopants after hydrogenation.

Chatterjee, B.↗
DOE OSTI2023

Modeling and Characterization of Surface Discharges in Insulating Material for Spacers: Electrode Shape, Discharge Mode, and Revision of the Creepage Concept

In the design of MV AC and DC spacers, the predominant factors are surface and interface conditions. Design is generally carried out on specifications and standards which are based on long-term experience and lab testing. However, the diffusion of power electronics with a trend to increase electric field, switching frequency, and rise time to achieve higher power density calls for an innovative, global approach to optimized insulation system design. A new methodology, based on field simulation, discharge modeling, and partial discharge inception measurements, called the three-leg approach, can form the basis to optimize insulation design for any type of supply voltage waveform. This paper focuses on the influence of the type of electrode on the inception and phenomenology of surface discharges and, as a consequence, on the interpretation of the results used for application of the three-leg approach. It is demonstrated that a typical electrode system used for insulating material testing can generate both gas and surface discharges at the triple point, when the electrodes have a smooth profile that is used to avoid corona or flashover. Hence, testing partial discharge may not provide a straightforward indication of the surface discharge inception and, thus, be partially misleading for insulation design. Another takeover is that such analysis must benefit from PD testing tools endowed with analytics able to provide automatic identification of the type of defect generating PD, i.e., internal, surface, and corona, since design and remedy actions can be taken, and adequate insulating materials developed, only knowing the type of source generating PD. Hence, testing partial discharge may not provide a straightforward indication of surface discharge inception and, thus, be partially misleading for insulation design. In addition to the importance of the three-leg approach to favor reliable and optimized design of insulation systems, there is a clear need to have a PD testing tool endowed with analytics. It should preferably be able to provide automatic identification of the type of defect generating PD, i.e., internal, surface, and corona.

36 MATERIALS SCIENCE↗
NASA NTRS1996

Hydrogen passivation of N(+)-P and P(+)-N heteroepitaxial InP solar cell structures

Dislocations and related point defect complexes caused by lattice mismatch currently limit the performance of heteroepitaxial InP cells by introducing shunting paths across the active junction and by the formation of deep traps within the base region. We have previously demonstrated that plasma hydrogenation is an effective and stable means to passivate the electrical activity of such defects in specially designed heteroepitaxial InP test structures to probe hydrogen passivation at typical base depths within a cell structure. In this work, we present our results on the hydrogen passivation of actual heteroepitaxial n-p and p-n InP cell structures grown on GaAs substrates by metalorganic chemical vapor deposition (MOCVD). We have found that a 2 hour exposure to a 13.56 MHz hydrogen plasma at 275 C reduces the deep level concentration in the base regions of both n(+)-p and p(+)-n heteroepitaxial InP cell structures from as-grown values of 5-7 x 10(exp 14) cm(exp -3), down to 3-5 x 10(exp 12) cm(exp -3). All dopants were successfully reactivated by a 400 C, 5 minute anneal with no detectable activation of deep levels. One to five analysis indicated a subsequent approximately 100 fold decrease in reverse leakage current at -1 volt reverse bias, and an improved built in voltage for the p(+)-n structures. In addition to being passivated, dislocations are also shown to participate in secondary interactions during hydrogenation. We find that the presence of dislocations enhances hydrogen diffusion into the cell structure, and lowers the apparent dissociation energy of Zn-H complexes from 1.19 eV for homoepitaxial Zn-doped InP to 1.12 eV for heteroepitaxial Zn-doped InP. This is explained by additional hydrogen trapping at dislocations subsequent to the reactivation of Zn dopants after hydrogenation.

Chatterjee, Basab↗
DOE OSTI2020

Role of shell composition and morphology in achieving single-emitter photostability for green-emitting “giant” quantum dots

The use of the varied chemical reactivity of precursors to drive the production of a desired nanocrystal architecture has become a common method to grow thick-shell graded alloy quantum dots (QDs) with robust optical properties. Conclusions on their behavior assume the ideal chemical gradation and uniform particle composition. In this work, advanced analytical electron microscopy (high-resolution scanning transmission electron microscopy coupled with energy dispersive spectroscopy) is used to confirm the nature and extent of compositional gradation and these data are compared with performance behavior obtained from single-nanocrystal spectroscopy to elucidate structure, chemical-composition, and optical-property correlations. In particular, the evolution of the chemical structure and single-nanocrystal luminescence was determined for a time-series of graded-alloy “CdZnSSe/ZnS” core/shell QDs prepared in a single-pot reaction. In a separate step, thick (~6 monolayers) to giant (>14 monolayers) shells of ZnS were added to the alloyed QDs via a successive ionic layer adsorption and reaction (SILAR) process, and the impact of this shell on the optical performance was also assessed. By determining the degree of alloying for each component element on a per-particle basis, we observe that the actual product from the single-pot reaction is less “graded” in Cd and more so in Se than anticipated, with Se extending throughout the structure. The latter suggests much slower Se reaction kinetics than expected or an ability of Se to diffuse away from the initially nucleated core. It was also found that the subsequent growth of thick phase-pure ZnS shells by the SILAR method was required to significantly reduce blinking and photobleaching. However, correlated single-nanocrystal optical characterization and electron microscopy further revealed that these beneficial properties are only achieved if the thick ZnS shell is complete and without large lattice discontinuities. Thus, we identify the necessary structural design features that are required for ideal light emission properties in these green-visible emitting QDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Cadmium Selective Etching in CdTe Solar Cells Produces Detrimental Narrow-Gap Te in Grain Boundaries

Recent advances in design and processing technology have made possible commercialization of polycrystalline (px)-CdTe as a photovoltaic absorber. Grain boundaries (GBs) are the most prominent structural defects in these devices and undergo significant changes during device fabrication. However, the effects of device fabrication processes on these GBs are not entirely understood. Prevailing models of GBs in thin-film photovoltaics consider individual GBs to have homogeneous properties in their area. Here, using an aberration-corrected scanning transmission electron microscope (STEM)-based low-loss and core-loss electron energy-loss spectroscopy (EELS), we show that back-surface etching of CdTe leads to inhomogeneity within individual grain boundaries. We observe that etching the back surface leads to the conversion of a region of GBs from CdTe to an elemental Te, which has an only 0.33 eV band gap, as deep as 1 μm from the back surface. The presence of elemental Te in GBs this deep into the absorber layer will increase recombination in the absorber layer and limit the extractable open-circuit voltage, thus reducing device efficiency. However, additive methods for back contact formation such as deposition of Te, ZnTe, or other materials preserve the CdTe stoichiometry of the GBs. Thus, especially for the next generations of CdTe-based cells having longer minority carrier diffusion length and/or thinner absorber layers, additive back contacting methods are superior.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Tailoring Carbide Dispersed Steels: A Path to Increased Strength and Hydrogen Tolerance

The use of transition metal carbides is reported for use as a hydrogen trapping mechanism for ferritic and austenitic steel materials. The program combined computational modeling and simulations to guide experiments towards candidate metal carbide traps, both for interfacial and interior trapping. It was found that interfacial trapping is less effective than interior trapping, with the group IVB transition metal carbides being the most effect internal traps with a loss of carbon. The sub-stoichiometric rocksalt structure accommodate the hydrogen atoms in its octahedral interstices. Using percolation theory, carbon loss of approximately 25% or more was sufficient to ensure an interconnected network of vacancies for such trapping from the surface to the internal sites within the carbide. Using this as a guide, the program developed a means to provide a uniform dispersion of ZrC nanoparticles with either Fe or 304L micron-scale powders which was then consolidated by direct current sintering. Electrolytic hydrogen diffusivity studies confirmed the reduction of hydrogen diffusion in the matrix with increasing ZrC content, which was a linear response over the sample range studied (0.01 to 1.0 wt.%). The consolidated material was micro-tensile tested in either a non-hydrogen or hydrogen charge condition and compared to a control with no carbides. Additions up to 0.05 wt.% ZrC increased the yield strength with no loss in ductility in either the non-hydrogen or hydrogen tested condition. ZrC concentrations above this amount further increased the yield strength at the expense of ductility. While these samples had a lower absolute ductility value prior to failure, the relative change in ductility between the non-hydrogen and hydrogen charge states was less for the carbides than that of the control. Metal-rich ZrC nanoparticles were fabricated through a conformal coating process yielding ZrC0.66 particles that were then incorporated into a metal matrix. Notch fatigue testing in a hydrogen environment was conducted where the number of cycles to failure was found to be less in the control than that of the carbide addition. However, the spread in experimental data and the number of samples tested limits a conclusive outcome based on defects noticed in the gauge section of all the powder processed samples. The collective outcomes of this report provide further insight into the mechanisms by which carbides act as hydrogen traps; a means to process such carbides through powder metallurgy; and their associated mechanical performance in either a non-hydrogen or hydrogen-charged condition.

08 HYDROGEN↗