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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Corrosion mechanisms for metal alloy waste forms: experiment and theory Level 4 Milestone M4FT-14LA0804024 Fuel Cycle Research & Development

This document meets Level 4 Milestone: Corrosion mechanisms for metal alloy waste forms - experiment and theory. A multiphysics model is introduces that will provide the framework for the quantitative prediction of corrosion rates of metallic waste forms incorporating the fission product Tc. The model requires a knowledge of the properties of not only the metallic waste form, but also the passive oxide films that will be generated on the waste form, and the chemistry of the metal/oxide and oxide/environment interfaces. in collaboration with experimental work, the focus of this work is on obtaining these properties from fundamental atomistic models. herein we describe the overall multiphysics model, which is based on MacDonald's point-defect model for passivity. We then present the results of detailed electronic-structure calculations for the determination of the compatibility and properties of Tc when incorporated into intermetallic oxide phases. This work is relevant to the formation of multi-component oxides on metal surfaces that will incorporate Tc, and provide a kinetic barrier to corrosion (i.e. the release of Tc to the environment). Atomistic models that build upon the electronic structure calculations are then described using the modified embedded atom method to simulate metallic dissolution, and Buckingham potentials to perform classical molecular dynamics and statics simulations of the technetium (and, later, iron-technetium) oxide phases. Electrochemical methods were then applied to provide some benchmark information of the corrosion and electrochemical properties of Technetium metal. The results indicate that published information on Tc passivity is not complete and that further investigation is warranted.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Effect of lithium diffusion into Ga 2 O 3 thin films

The integration of lithium based compounds (e.g., Li:NiO/Ga 2 O 3 , LiGa 5 O 8 /Ga 2 O 3 ) in Ga 2 O 3 based pn-heterojunctions raises concerns about interface stability, i.e., Li diffusion effects on Ga 2 O 3 properties. In this work the ex-situ diffusion of Li is investigated in three different Ga 2 O 3 epilayers systems [(001) κ-Ga 2 O 3 and (−201) β-Ga2O3 heteroepitaxy on (001) α-Al 2 O 3 , and (010) β-Ga 2 O 3 homoepitaxy] at relevant temperatures for the synthesis / processing of Li-based epilayers. It is here experimentally demonstrated and quantified the Li diffusion in all the investigated Ga 2 O 3 epilayers systems and Li bulk (D Li,bulk ) and 2D defects (D Li,2D ) diffusion coefficients are provided. In the case of the (010) β-Ga 2 O 3 homoepitaxial layer (nominally free of structural defects), hybrid functional theory calculations foresee a diffusion mechanism mediated by Ga vacancies (VGa). Moreover, in the (010) β-Ga 2 O 3 homo-layer a significant effect on its functional properties (e.g., additional Raman vibrational modes, induced conductivity in an otherwise insulating sample) upon the Li-diffusion process is experimentally highlighted and tentatively related to the passivation of acceptor defects (i.e., formation of V Ga -nLi complexes).

Defects↗
DOE OSTI2019

Passivation of Germanium by Graphene for Stable Graphene/Germanium Heterostructure Devices

The scalable integration of graphene onto semiconductor platforms is an important step towards utilizing the exceptional structural, electronic, thermal, and mechanical properties of graphene in state-of-the-art technologies. Specifically, graphene films grown on Ge are an exciting materials system for high-performance electronics; however, the device performance depends sensitively on the structural, electronic, and chemical nature of the graphene/Ge interface. We have recently discovered that graphene grown directly on Ge via chemical vapor deposition (CVD) can passivate the Ge surface, preventing its oxidation for months—longer than alternate passivation methods reported in the literature. Yet, the factors that govern passivation are not understood. Here, we elucidate how the CVD growth conditions and Ge surface orientation affect Ge oxidation below graphene. We find that growing graphene with a high H2:CH4 flux ratio minimizes formation of defects in graphene, enhancing Ge passivation. While minimizing defects is important, surprisingly, we find that passivation depends much stronger on the Ge surface orientation. These results provide a route for the integration of graphene films with a pristine graphene/substrate interface on Ge, an important step towards stabilizing the Ge surface and realizing graphene-based or hybrid graphene/Ge heterostructure devices integrated directly on conventional semiconductor wafers.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

BiasMDP: Carrier lifetime characterization technique with applied bias voltage

A characterization method is presented, which determines fixed charge and interface defect densities in passivation layers. This method bases on a bias voltage applied to an electrode on top of the passivation layer. During a voltage sweep, the effective carrier lifetime is measured by means of microwave detected photoconductivity. When the external voltage compensates the electric field of the fixed charges, the lifetime drops to a minimum value. This minimum value correlates to the flat band voltage determined in reference impedance measurements. This correlation is measured on p-type silicon passivated by Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}/HfO{sub 2} stacks with different fixed charge densities and layer thicknesses. Negative fixed charges with densities of 3.8 × 10{sup 12 }cm{sup −2} and 0.7 × 10{sup 12 }cm{sup −2} are determined for Al{sub 2}O{sub 3} layers without and with an ultra-thin HfO{sub 2} interface, respectively. The voltage and illumination dependencies of the effective carrier lifetime are simulated with Shockley Read Hall surface recombination at continuous defects with parabolic capture cross section distributions for electrons and holes. The best match with the measured data is achieved with a very low interface defect density of 1 × 10{sup 10 }eV{sup −1} cm{sup −2} for the Al{sub 2}O{sub 3} sample with HfO{sub 2} interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Mechanochemical topological defects in an active nematic

We propose a reaction-diffusion system that converts topological information of an active nematic into chemical signals. We show that a curvature-activated reaction dipole is sufficient for creating a system that dynamically senses topology by producing a concentration field possessing local extrema coinciding with ±$\frac{1}{2}$ defects. The enabling term is analogous to polarization charge density seen in dielectric materials. We demonstrate the ability of this system to identify defects in both passive and active nematics. Our results illustrate that a relatively simple feedback scheme, expressed as a system of partial differential equations, is capable of producing chemical signals in response to inherently nonlocal structures in anisotropic media. Here, we posit that such coarse-grained systems can help generate testable hypotheses for regulated processes in biological systems, such as morphogenesis, and motivate the creation of bio-inspired materials that utilize dynamic coupling between nematic structure and biochemistry.

42 ENGINEERING↗
DOE OSTI2017

Placing single atoms in graphene with a scanning transmission electron microscope

We demonstrate that the sub-atomically focused beam of a scanning transmission electron microscope (STEM) can be used to controllably manipulate individual dopant atoms in a 2D graphene lattice. We demonstrate the manipulation of adsorbed source materials and the graphene lattice with the electron beam such that individual vacancy defects can be controllably passivated by Si substitutional atoms. We further demonstrate that these Si defects may be directed through the lattice via e-beam control or modified (as yet, uncontrollably) to form new defects which can incorporate new atoms into the graphene lattice. Furthermore, these studies demonstrate the potential of STEM for atom-by-atom nanofabrication and fundamental studies of chemical reactions in 2D materials on the atomic level.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Gold-doped graphene: A highly stable and active electrocatalysts for the oxygen reduction reaction

In addressing the growing need of renewable and sustainable energy resources, hydrogen-fuel-cells stand as one of the most promising routes to transform the current energy paradigm into one that integrally fulfills environmental sustainability. Nevertheless, accomplishing this technology at a large scale demands to surpass the efficiency and enhance the cost-effectiveness of platinum-based cathodes, which catalyze the oxygen reduction reaction (ORR). In this work, our first-principles calculations show that Au atoms incorporated into graphene di-vacancies form a highly stable and cost-effective electrocatalyst that is, at the same time, as or more (dependently of the dopant concentration) active toward ORR than the best-known Pt-based electrocatalysts. We reveal that partial passivation of defected-graphene by gold atoms reduces the reactivity of C dangling bonds and increases that of Au, thus optimizing them for catalyzing the ORR and yielding a system of high thermodynamic and electrochemical stabilities. We also demonstrate that the linear relation among the binding energies of the reaction intermediates assumed in computational high-throughput material screening does not hold, at least for this non-purely transition-metal material. We expect Au-doped graphene to finally overcome the cathode-related challenge hindering the realization of hydrogen-fuel cells as the leading means of powering transportation and portable devices.

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

Explicit analytical modeling of the low frequency a-Si:H/c-Si heterojunction capacitance: Analysis and application to silicon heterojunction solar cells

We develop a fully analytical model in order to describe the temperature dependence of the low frequency capacitance of heterojunctions between hydrogenated amorphous silicon (a-Si:H) and crystalline silicon (c-Si). We demonstrate that the slope of the capacitance-temperature (C-T) curve is strongly enhanced if the c-Si surface is under strong inversion conditions compared to the usually assumed depletion layer capacitance. We have extended our analytical model to integrate a very thin undoped (i) a-Si:H layer at the interface and the finite thickness of the doped a-Si:H layer that are used in high efficiency solar cells for the passivation of interface defects and to limit short circuit current losses. Finally, using our calculations, we analyze experimental data on high efficiency silicon heterojunction solar cells. The transition from the strong inversion limited behavior to the depletion layer behavior is discussed in terms of band offsets, density of states in a-Si:H, and work function of the indium tin oxide (ITO) front electrode. In particular, it is evidenced that strong inversion conditions prevail at the c-Si surface at high temperatures down to 250 K, which can only be reproduced if the ITO work function is larger than 4.7 eV.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Influence of Bulky Organo-Ammonium Halide Additive Choice on the Flexibility and Efficiency of Perovskite Light-Emitting Devices

Perovskite light-emitting diodes (LEDs) require small grain sizes to spatially confine charge carriers for efficient radiative recombination. As grain size decreases, passivation of surface defects becomes increasingly important. Also, polycrystalline perovskite flms are highly brittle and mechanically fragile, limiting their practical applications in flexible electronics. Here, the introduction of properly chosen bulky organo-ammonium halide additives is shown to be able to improve both optoelectronic and mechanical properties of perovskites, yielding highly efficient, robust, and flexible perovskite LEDs with external quantum efficiency of up to 13% and no degradation after bending for 10 000 cycles at a radius of 2 mm. Moreover, insight of the improvements regarding molecular structure, size, and polarity at the atomic level is obtained with first-principles calculations, and design principles are provided to overcome trade-offs between optoelectronic and mechanical properties, thus increasing the scope for future highly efficient, robust, and flexible perovskite electronic device development.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Mixed cation FA x PEA 1- x PbI 3 with enhanced phase and ambient stability toward high-performance perovskite solar cells

In this study, different from the commonly explored strategy of incorporating a smaller cation, MA + and Cs + into FAPbI 3 lattice to improve efficiency and stability, it is revealed that the introduction of phenylethylammonium iodide (PEAI) into FAPbI 3 perovksite to form mixed cation FA x PEA 1–x PbI 3 can effectively enhance both phase and ambient stability of FAPbI 3 as well as the resulting performance of the derived devices. From our experimental and theoretical calculation results, it is proposed that the larger PEA cation is capable of assembling on both the lattice surface and grain boundaries to form quais-3D perovskite structures. The surrounding of PEA + ions at the crystal grain boundaries not only can serve as molecular locks to tighten FAPbI 3 domains but also passivate the surface defects to improve both phase and moisture stablity. Consequently, a high-performance (PCE:17.7%) and ambient stable FAPbI 3 solar cell could be developed

14 SOLAR ENERGY↗
DOE OSTI2018

Effect of Material Structure on Photoluminescence of ZnO/MgO Core-Shell Nanowires

Zinc oxide (ZnO) nanowires are widely studied for use in ultraviolet optoelectronic devices, such as nanolasers and sensors. Nanowires (NWs) with an MgO shell exhibit enhanced band-edge photoluminescence (PL), a result previously attributed to passivation of ZnO defects. However, we find that processing the ZnO NWs under low oxygen partial pressure leads to an MgO-thickness-dependent PL enhancement owing to the formation of optical cavity modes. Conversely, processing under higher oxygen partial pressure leads to NWs that support neither mode formation nor band-edge PL enhancement. High-resolution electron microscopy and density-functional calculations implicate the ZnO m-plane surface morphology as the key determinant of core-shell structure and cavity-mode optics. A ZnO surface with atomic steps along the m-plane in the c-axis direction stimulates the growth of a smooth MgO shell that supports guided-wave optical modes and enhanced UV PL. On the other hand, a smoother ZnO surface leads to nucleation of a rough cladding layer which supports neither enhanced UV PL nor optical cavity modes. Finite-element analysis shows a clear correlation between allowed Fabry-Perot and whispering gallery modes and enhanced UV-PL. Finally, these results point the way to fabricating ZnO/MgO core-shell nanowires for more efficient UV nanolasers, scintillators, and sensors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

The Itinerant 2D Electron Gas of the Indium Oxide (111) Surface: Implications for Carbon‐ and Energy‐Conversion Applications

Abstract Transparent conducting oxides (TCO) have integral and emerging roles in photovoltaic, thermoelectric energy conversion, and more recently, photocatalytic systems. The functional properties of TCOs, and thus their role in these applications, are often mediated by the bulk electronic band structure but are also strongly influenced by the electronic structure of the native surface 2D electron gas (2DEG), particularly under operating conditions. This study investigates the 2DEG, and its response to changes in chemistry, at the (111) surface of the model TCO In 2 O 3 , through angle resolved and core level X‐ray photoemission spectroscopy. It is found that the itinerant charge carriers of the 2DEG reside in two quantum well subbands penetrating up to 65 Å below the surface. The charge carrier concentration of this 2DEG, and thus the high surface n‐type conductivity, emerges from donor‐type oxygen vacancies of surface character and proves to be remarkably robust against surface absorbents and contamination. The optical transparency, however, may rely on the presence of ubiquitous surface adsorbed oxygen groups and hydrogen defect states that passivate localized oxygen vacancy states in the bandgap of In 2 O 3 .

Jovic, Vedran↗
DOE OSTI2021

Interfacial stabilization for inverted perovskite solar cells with long-term stability

Perovskite solar cells (PSCs) commonly exhibit significant performance degradation due to ion migration through the top charge transport layer and ultimately metal electrode corrosion. Here, we demonstrate an interfacial management strategy using a boron chloride subphthalocyanine (Cl 6 SubPc)/fullerene electron-transport layer, which not only passivates the interfacial defects in the perovskite, but also suppresses halide diffusion as evidenced by multiple techniques, including visual element mapping by electron energy loss spectroscopy. As a result, we obtain inverted PSCs with an efficiency of 22.0% (21.3% certified), shelf life of 7000 h, Τ 80 of 816 h under damp heat stress (compared to less than 20 h without Cl 6 SubPc), and initial performance retention of 98% after 2000 h at 80 °C in inert environment, 90% after 2034 h of illumination and maximum power point tracking in ambient for encapsulated devices and 95% after 1272 h outdoor testing ISOS-O-1. Our strategy and results pave a new way to move PSCs forward to their potential commercialization solidly.

14 SOLAR ENERGY↗
DOE OSTI2017

Germanium–Tin/Cadmium Sulfide Core/Shell Nanocrystals with Enhanced Near-Infrared Photoluminescence

Ge 1–x Sn x alloy nanocrystals and Ge 1–x Sn x /CdS core/shell nanocrystals were prepared via solution phase synthesis, and their size, composition, and optical properties were characterized. We found that the diameter of the nanocrystal samples ranged from 6 to 13 nm. Furthermore, the crystal structure of the Ge 1–x Sn x materials was consistent with a cubic diamond phase, while the CdS shell was consistent with the zinc blende polytype. Inclusion of Sn alone does not result in enhanced photoluminescence intensity; however, adding an epitaxial CdS shell onto the Ge 1–x Sn x nanocrystals does enhance the photoluminescence up to 15-fold versus that of Ge/CdS nanocrystals with a pure Ge core. There is more effective passivation of surface defects, and a consequent decrease in the level of surface oxidation, by the CdS shell as a result of improved epitaxy (smaller lattice mismatch) is the most likely explanation for the increased photoluminescence observed for the Ge 1–x Sn x /CdS materials. With enhanced photoluminescence in the near-infrared region, Ge 1–x Sn x core/shell nanocrystals might be useful alternatives to other materials for energy capture and conversion applications and as imaging probes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An Atomic-Scale Understanding of UO 2 Surface Evolution during Anoxic Dissolution

Our present understanding of surface dissolution of nuclear fuels such as uranium dioxide (UO 2 ) is limited by the use of non-local characterization techniques. In this paper, we discuss the use of state-of-the-art scanning transmission electron microscopy (STEM) to reveal atomic–scale changes occurring to UO 2 thin films subjected to anoxic dissolution in deionised water. No amorphisation of the UO 2 film surface during dissolution is observed, and dissolution occurs preferentially at surface reactive sites that present as surface pits which increase in size as the dissolution proceeds. Using a combination of STEM imaging modes, energy-dispersive X-ray spectroscopy (STEM-EDS), and electron energy loss spectroscopy (STEM-EELS), we investigate structural defects and oxygen passivation of the surface that originates from the filling of the octahedral interstitial site in the centre of the unit cells and its associated lattice contraction. Taken together, our results reveal complex pathways for both the dissolution and infiltration of solutions into UO 2 surfaces.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Understanding the Effect of Lead Iodide Excess on the Performance of Methylammonium Lead Iodide Perovskite Solar Cells

The presence of unreacted lead iodide in organic-inorganic lead halide perovskite solar cells is widely correlated with an increase in power conversion efficiency. We investigate the mechanism for this increase by identifying the role of surfaces and interfaces present between methylammonium lead iodide perovskite films and excess lead iodide. We show how type I and II band alignments arising under different conditions result in either passivation of surface defects or hole injection. Through first-principles simulations of solid-solid interfaces, we find that lead iodide captures holes from methylammonium lead iodide and modulates the formation of defects in the perovskite, affecting recombination. Using surface-sensitive optical spectroscopy techniques, such as transient reflectance and time-resolved photoluminescence, we show how excess lead iodide affects the diffusion and surface recombination velocity of charge carriers in methylammonium lead iodide films. Our coupled experimental and theoretical results elucidate the role of excess lead iodide in perovskite solar cells.

14 SOLAR ENERGY↗
DOE OSTI2019

Modulating Carrier Transport via Defect Engineering in Solar Water Splitting Devices

Developing sustainable solar water splitting devices requires efficient separation and transport of photogenerated carriers. In this Perspective, we examine carrier transport in semiconductor photoelectrodes using bismuth vanadate as a primary model system and highlight strategies to significantly improve carrier delivery through defect engineering. To improve electron transport in low-mobility semiconductors, we introduce two distinct bulk doping methods, by homogeneously enhancing the bulk defect level or by forming distributed homojunctions with graded doping. Next, we demonstrate the use of structural boundaries as extrinsic pathways for fast electron transport, thus providing novel insights to engineer materials’ macroscopic conductivity. Third, we describe the importance of interface design in terms of structural, chemical, and electronic matching at the back contact to suppress carrier recombination. Lastly, we highlight the methods for surface defect control via passivation and catalysis and give a brief outlook of research challenges and opportunities for solar water splitting.

77 NANOSCIENCE AND NANOTECHNOLOGY↗