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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

Oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation, and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO{sub 2}) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo method has been used to investigate the kinetics of oxygen transport in UO{sub 2} under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable off-stoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO{sub 2−x}, oxygen transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO{sub 2+x}, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that di-interstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence, and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing an explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Implementation of density functional embedding theory within the projector-augmented-wave method and applications to semiconductor defect states

We report a new implementation of the density functional embedding theory (DFET) in the VASP code, using the projector-augmented-wave (PAW) formalism. Newly developed algorithms allow us to efficiently perform optimized effective potential optimizations within PAW. The new algorithm generates robust and physically correct embedding potentials, as we verified using several test systems including a covalently bound molecule, a metal surface, and bulk semiconductors. We show that with the resulting embedding potential, embedded cluster models can reproduce the electronic structure of point defects in bulk semiconductors, thereby demonstrating the validity of DFET in semiconductors for the first time. Compared to our previous version, the new implementation of DFET within VASP affords use of all features of VASP (e.g., a systematic PAW library, a wide selection of functionals, a more flexible choice of U correction formalisms, and faster computational speed) with DFET. Furthermore, our results are fairly robust with respect to both plane-wave and Gaussian type orbital basis sets in the embedded cluster calculations. This suggests that the density functional embedding method is potentially an accurate and efficient way to study properties of isolated defects in semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Deformation mechanisms, defects, heat treatment, and thermal conductivity in large grain niobium

The physical and mechanical metallurgy underlying fabrication of large grain cavities for superconducting radio frequency accelerators is summarized, based on research of 1) grain orientations in ingots, 2) a metallurgical assessment of processing a large grain single cell cavity and a tube, 3) assessment of slip behavior of single crystal tensile samples extracted from a high purity ingot slice before and after annealing at 800 °C / 2 h, 4) development of crystal plasticity models based upon the single crystal experiments, and 5) assessment of how thermal conductivity is affected by strain, heat treatment, and exposure to hydrogen. Because of the large grains, the plastic anisotropy of deformation is exaggerated, and heterogeneous strains and localized defects are present to a much greater degree than expected in polycrystalline material, making it highly desirable to computationally anticipate potential forming problems before manufacturing cavities.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Reduced defect density at the CZTSSe/CdS interface by atomic layer deposition of Al{sub 2}O{sub 3}

The greatest challenge for improving the power conversion efficiency of Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe)/CdS/ZnO thin film solar cells is increasing the open circuit voltage (V{sub OC}). Probable leading causes of the V{sub OC} deficit in state-of-the-art CZTSSe devices have been identified as bulk recombination, band tails, and the intertwined effects of CZTSSe/CdS band offset, interface defects, and interface recombination. In this work, we demonstrate the modification of the CZTSSe absorber/CdS buffer interface following the deposition of 1 nm-thick Al{sub 2}O{sub 3} layers by atomic layer deposition (ALD) near room temperature. Capacitance-voltage profiling and quantum efficiency measurements reveal that ALD-Al{sub 2}O{sub 3} interface modification reduces the density of acceptor-like states at the heterojunction resulting in reduced interface recombination and wider depletion width. Indications of increased V{sub OC} resulting from the modification of the heterojunction interface as a result of ALD-Al{sub 2}O{sub 3} treatment are presented. These results, while not conclusive for application to state-of-the-art high efficiency CZTSSe devices, suggest the need for further studies as it is probable that interface recombination contributes to reduced V{sub OC} even in such devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Search for giant magnetic anisotropy in transition-metal dimers on defected hexagonal boron nitride sheet

Structural and magnetic properties of many transition-metal dimers embedded in a defected hexagonal boron nitride monolayer are investigated through density functional calculations to search for systems with magnetic anisotropy energies (MAEs) larger than 30meV. In particular, Ir–Ir@Dh–BN is found to have both large MAE (∼126 meV) and high structural stability against dissociation and diffusion, and it hence can serve as magnetic unit in spintronics and quantum computing devices. This giant MAE mainly results from the spin orbit coupling and the magnetization of the upper Ir atom, which is in a rather isolated environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Influence of chemical disorder on energy dissipation and defect evolution in advanced alloys

We report that historically, alloy development with better radiation performance has been focused on traditional alloys with one or two principal element(s) and minor alloying elements, where enhanced radiation resistance depends on microstructural or nanoscale features to mitigate displacement damage. In sharp contrast to traditional alloys, recent advances of single-phase concentrated solid solution alloys (SP-CSAs) have opened up new frontiers in materials research. In these alloys, a random arrangement of multiple elemental species on a crystalline lattice results in disordered local chemical environments and unique site-to-site lattice distortions. Based on closely integrated computational and experimental studies using a novel set of SP-CSAs in a face-centered cubic structure, we have explicitly demonstrated that increasing chemical disorder can lead to a substantial reduction in electron mean free paths, as well as electrical and thermal conductivity, which results in slower heat dissipation in SP-CSAs. The chemical disorder also has a significant impact on defect evolution under ion irradiation. Considerable improvement in radiation resistance is observed with increasing chemical disorder at electronic and atomic levels. Finally, the insights into defect dynamics may provide a basis for understanding elemental effects on evolution of radiation damage in irradiated materials and may inspire new design principles of radiation-tolerant structural alloys for advanced energy systems.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Bubble Formation and Lattice Parameter Changes Resulting from He Irradiation of Defect-Fluorite Gd2Zr2O7

Pyrochlores have long been considered as potential candidates for advanced ceramic waste-forms for the immobilization of radioactive waste nuclides. This work provides evidence that Gd2Zr2O7, often considered the most radiation tolerant pyrochlore, could be susceptible to radiation damage in the form of bubble nucleation at the highest He doses expected over geological time. Ion irradiations were utilized to experimentally simulate the radiation damage and He accumulation produced by ..alpha..-decay. Samples were pre-damaged using 7 MeV Au3+ to induce the pyrochlore to defect-fluorite phase transformation, which would occur due to ..alpha..-recoil damage within several hundred years of storage in a Gd2Zr2O7 waste-form. These samples were then implanted to various He concentrations in order to study the long-term effects of He accumulation. Helium bubbles 1-3 nm in diameter were observed in TEM at a concentration of 4.6 at.% He. Some bubbles remained isolated, while others formed chains 10-30 nm in length parallel to the surface. GIXRD measurements showed lattice swelling after irradiating pristine Gd2Zr2O7 with 7 MeV Au3+ to a fluence of 2.2 x 1015 Au/cm2. An increase in lattice swelling was also measured after 2.2 x 1015 Au/cm2 + 2 x 1015 He/cm2 and 2.2 x 1015 Au/cm2 + 2 x 1016 He/cm2. A decrease in lattice swelling was measured after irradiation with 2.2 x 1015 Au/cm2 + 2 x 1017 He/cm2, the fluence where bubbles and bubble chains were observed in TEM. Bubble chains are thought to form in order to reduce lattice strain normal to the surface, which is produced by the Au and He irradiation damage.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phase transformations, microstructural refinement and defect evolution mechanisms in Al-Si alloys under non-hydrostatic diamond anvil cell compression

Non-hydrostatic compression of materials using a diamond anvil cell (DAC) can transform equilibrium microstructure of an alloy to novel, potentially metastable states. In this study, in situ synchrotron X-ray diffraction (XRD) during compression up to 24 GPa and subsequent ex situ, high resolution analytical electron microscopy (AEM) after decompression of an Al-Si alloy provided insight into the crystallographic changes during the compression as well as microstructural refinement, and defect structures caused by such a high pressure compression-decompression process. Pressure resolved in-situ synchrotron XRD was used to detail the phase transformation pathway of the eutectic Si phase in Al-Si alloy, from Si-I → Si-XI → Si-V during compression, and a final transformation predominantly to Si-III after decompression. Using scanning and transmission electron microscopy (S/TEM), site specific analysis of the alloy immediately underneath the anvil contact surface demonstrated a highly complex microstructure. A narrow region of thick amorphous Al oxide interspersed with nanocrystalline grains was found at the top surface. Underneath this Al oxide, while the majority the eutectic Si was transformed into highly-deformed, polycrystalline (PC) Si-III, a complex intermediate layer was discovered at the interface between Al and Si, comprised of a small fraction of Al nanocrystals and a majority of nanocrystalline Si-I. This combination of pressure resolved in-situ synchrotron XRD coupled with subsequent high resolution, electron microscopy resolved the phase transformation as well as non-equilibrium microstructures in a metallic alloy induced by a non-hydrostatic high pressure compression followed by decompression.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Strong Electron–Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A 3 M 2 I 9 (A = Cs, Rb; M = Bi, Sb)

The optical and electronic properties of Bridgman grown single crystals of the wide-bandgap semiconducting defect halide perovskites A3M2I9 (A = Cs, Rb; M = Bi, Sb) have been investigated. Intense Raman scattering was observed at room temperature for each compound, indicating high polarizability and strong electron–phonon coupling. Both low-temperature and room-temperature photoluminescence (PL) were measured for each compound. Cs3Sb2I9 and Rb3Sb2I9 have broad PL emission bands between 1.75 and 2.05 eV with peaks at 1.96 and 1.92 eV, respectively. The Cs3Bi2I9 PL spectra showed broad emission consisting of several overlapping bands in the 1.65–2.2 eV range. Evidence of strong electron–phonon coupling comparable to that of the alkali halides was observed in phonon broadening of the PL emission. Effective phonon energies obtained from temperature-dependent PL measurements were in agreement with the Raman peak energies. A model is proposed whereby electron–phonon interactions in Cs3Sb2I9, Rb3Sb2I9, and Cs3Bi2I9 induce small polarons, resulting in trapping of excitons by the lattice. The recombination of these self-trapped excitons is responsible for the broad PL emission. Rb3Bi2I9, Rb3Sb2I9, and Cs3Bi2I9 exhibit high resistivity and photoconductivity response under laser photoexcitation, indicating that these compounds possess potential as semiconductor hard radiation detector materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Comprehensive defect suppression in perovskite nanocrystals for high-efficiency light-emitting diodes

Electroluminescence efficiencies of metal halide perovskite nanocrystals (PNCs) are limited by a lack of material strategies that can both suppress the formation of defects and enhance the charge carrier confinement. Here we report a one-dopant alloying strategy that generates smaller, monodisperse colloidal particles (confining electrons and holes, and boosting radiative recombination) with fewer surface defects (reducing non-radiative recombination). Doping of guanidinium into formamidinium lead bromide PNCs yields limited bulk solubility while creating an entropy-stabilized phase in the PNCs and leading to smaller PNCs with more carrier confinement. Further, the extra guanidinium segregates to the surface and stabilizes the undercoordinated sites. Furthermore, a surface-stabilizing 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene was applied as a bromide vacancy healing agent. The result is highly efficient PNC-based light-emitting diodes that have current efficiency of 108 cd A –1 (external quantum efficiency of 23.4%), which rises to 205 cd A –1 (external quantum efficiency of 45.5%) with a hemispherical lens.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Large-scale experimental validation of thermochemical water-splitting oxides discovered by defect graph neural networks

Thermochemical water-splitting (TCH) based on 2-step thermal redox cycles in metal oxides is a promising approach to generating H 2 , but state-of-the-art (SOTA) CeO 2 has several practical limitations, which has motivated continued materials discovery efforts in this field. Here, in this study, we improve upon a SOTA defect graph neural network (dGNN) surrogate model's oxygen vacancy predictions and combine them with materials project phase diagrams to down-select and discover structurally diverse, experimentally known metal oxides whose TCH performance was previously unknown. Amongst twelve candidates selected based on our high-throughput screening and down-selection criteria, we achieved ∼80% accuracy in identifying materials with stable redox cycling and hydrogen production in stagnation flow reactor water-splitting experiments. Closer to 100% accuracy can be achieved if higher-accuracy, hybrid DFT-predicted vacancy formation energies were computed and used in lieu of the most uncertain dGNN-based screening predictions, as they correct false positives to true negatives. Notably, two discovered candidates, Sr 3 PrMn 2 O 8 and Ba 2 Fe 2 O 5 , display hydrogen yields greater than CeO 2 under specific redox conditions. In conclusion, these results demonstrate our ability to computationally predict and experimentally validate promising candidate TCH materials that have the potential to compete with CeO 2 .

08 HYDROGEN↗
DOE OSTI2015

Defect-band mediated ferromagnetism in Gd-doped ZnO thin films

Gd-doped ZnO thin films prepared by pulsed laser deposition with Gd concentrations varying from 0.02–0.45 atomic percent (at. %) showed deposition oxygen pressure controlled ferromagnetism. Thin films prepared with Gd dopant levels (<Gd 0.112 at. %) at low oxygen deposition pressure (<25 mTorr) were ferromagnetic at room temperature. Negative magnetoresistance, electric transport properties showed that the ferromagnetic exchange is mediated by a spin-split defect band formed due to oxygen deficiency related defect complexes. Mott's theory of variable range of hopping conduction confirms the formation of the impurity/defect band near the Fermi level.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗