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At least 343 records · Page 19

First-principles elucidation of defect-mediated Li transport in hexagonal boron nitride

Hexagonal boron nitride (hBN) is a promising candidate as a protective membrane or separator in Li-ion and Li–S batteries, given its excellent chemical stability, mechanical robustness, and high thermal conductivity. In addition, hBN can be functionalized by introducing defects and dopants, or be directly integrated into other active components of batteries, which further augments its appeal to the field. Here, we use first-principles simulations to evaluate the role of atomic defects in hBN in regulating the Li-ion diffusion mechanism and associated kinetics. Specifically, the following four distinct types of vacancy defects are considered: isolated single B and N vacancies, a B–N vacancy pair, and a B 3 N vacancy cluster. It is found that these defect sites generally favor Li intercalation and out-of-plane diffusion but slow down in-plane Li-ion diffusion due to a strong Li trapping effect at the defect sites. Such a trapping effect is, however, highly local such that it does not necessarily affect the overall Li-ion conductivity in defected hBN layers. The present systematic evaluation of the impact of atomic defects on Li ion migration and accompanied charge analysis of hBN lattice in response to Li-ion diffusion provide a mechanistic understanding of Li-ion transport behavior in defected hBN and highlight the potential of defect engineering to achieve optimal material performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origins of epitaxial macro-terraces and macro-steps on GaN substrates

Localized lattice distortions in GaN substrates can serve as nucleation sites for epitaxial macro-steps and macro-terraces. These detrimental macro-scale features give rise to optically hazy homoepitaxial GaN surfaces. After nucleating, these macro-features grow laterally along the surface and coalesce, leading to significant coverage of the wafer surface. Dot-core GaN substrates consisting of a periodic array of cores were used as a defect-engineered system, where dislocations are intentionally concentrated at the cores. The high density of threading dislocations at the cores induced localized lattice distortions. Here, these distortions are associated predominantly with lattice tilt on the order of hundreds of arcsec across ~0.5 mm laterally along the wafer surface. The resulting macro-features that nucleated at these localized distorted sites were made up of macro-terraces with lengths ranging ~30–~150 μm and macro-step heights ranging ~200–~400 nm. Another source of localized distortion was threading screw dislocations or GaN nanopipes that resulted in spiral growth and hillock formation. Based on x-ray topography and optical microscopy measurements, we speculate that the coalescence of hillocks evolves into macro-terraces and macro-steps. While previous studies focused on the substrate miscut as a means to control macro-feature formation, we show that localized lattice tilt from defects is another important contributor to macro-feature formation.

36 MATERIALS SCIENCE↗

PdAu/YSZ composite hydrogen separation membranes with enhanced stability in the presence of CO

The effects of gold composition on the tolerance of palladium-based composite membranes to CO exposure was studied under the presence of high CO concentrations. Membranes with PdAu compositions ranging up to 41% by mass were exposed to binary 50/50 H 2 /CO gas atmospheres and both hydrogen flux and purity were monitored over time. It was observed that the highest gold composition (41%) suffered no degradation in membrane performance in terms of permeate hydrogen purity and hydrogen permeation flux during the 48 h exposure. Furthermore, for lower gold compositions, X-ray diffraction patterns suggested that carbon entered the film and could be removed by exposure to a non-CO containing gas mixture over time. However, removal of the carbon adversely affected purity; interestingly, some of the purity decline could be reversed upon re-exposure to the CO gas mixture. It is hypothesized that carbon loading in the palladium films causes lattice expansion and may even fill pore defects, thus lowering leaks through the Pd films. Furthermore, this study suggests that a membrane exposed to a CO mixture should not be cycled between CO and non-CO environments, but rather run continuously for best performance. Additionally, the choice of Pd-alloy and metal composition should be considered in regard to its carbon solubility to best predict lifetime performance.

08 HYDROGEN↗

Structural characterization of neutron irradiated hexagonal boron-10 nitride-15 single crystals

The negatively charged boron vacancy ($V$$^{–}_{⁠B}$⁠) in hexagonal boron nitride (hBN) is a promising quantum defect that can be used to sense pressure, temperature, and magnetic field with high spatial resolution. hBN enriched with the boron-10 and nitrogen-15 isotopes, denoted h 10 B 15 N, has good contrast and coherence for quantum sensing because nitrogen-15 has nuclear spin (1/2), reducing hyperfine interactions. Boron vacancies can be generated by neutron irradiation, which causes the transmutation of the boron-10 isotope to lithium-7. In this study, the ancillary structural, compositional, and mechanical properties of h 10 B 15 N crystals that have been subjected to neutron irradiation fluences from 1.4 × 10 16 to 8.4 × 10 17 n/cm 2 were thoroughly characterized. Besides creating $V$$^{–}_{⁠B}$⁠, the process also induces other defects that generate strain in the crystal lattice. In turn, the mechanical properties of these crystals change drastically. Investigated here are the visual changes, lattice integrity, composition, crystal strain, and elastic constants (C 33 and C 66 ) to assess how these characteristics change as a function of neutron fluence.

36 MATERIALS SCIENCE↗

Interplay of charge density wave states and strain at the surface of CeTe 2

in this work we use scanning tunneling microscopy (STM) to study charge density wave (CDW) states in the rare-earth ditelluride, CeTe 2 . Our STM measurements surprisingly detect a unidirectional CDW with q ~ 0.28 a * , which differs from previous experimental and first-principles studies of the rare-earth ditellurides, and which is very close to what is found in experimental measurements of the related rare-earth tritellurides. Furthermore, in the vicinity of an extended subsurface defect, we find spatially-separated as well as spatially-coexisting unidirectional CDWs at the surface of CeTe 2 . We quantify the nanoscale strain and its variations induced by this defect, and establish a correlation between local lattice strain and the locally-established CDW states; this suggests that lattice strain plays an important role in determining the specific characteristics of the established CDW state. Our measurements probe the fundamental properties of a weakly-bound two-dimensional Te sheet, which experimental and theoretical work has previously established as the fundamental component driving much of the essential physics in both the rare-earth di- and tritelluride compounds.

36 MATERIALS SCIENCE↗

Effect of iron vacancies on magnetic order and spin dynamics of the spin ladder BaFe 2-δ S 1.5 Se 1.5</sub

Quasi-one-dimensional iron chalcogenides possess various magnetic states depending on the lattice distortion, electronic correlations, and presence of defects. Here we present neutron diffraction and inelastic neutron scattering experiments on the spin ladder compound BaFe 2-δ S 1.5 Se 1.5 with ~6% iron vacancies. The data reveal that long-range magnetic order is absent, while the characteristic magnetic excitations that correspond to both the stripe- and block-type antiferromagnetic correlations are observed. First-principles calculations support the existence of both stripe- and block-type antiferromagnetic short-range orders in the experimental sample. The disappearance of long-range magnetic order may be due to the competition between these two magnetic orders, which is greatly enhanced for a certain concentration of iron vacancies, which we calculate to be about 6%, consistent with the measured iron vacancy concentration. Our results highlight how iron vacancies in the iron-based spin ladder system strongly influence the magnetic ground state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Estimates of Quantum Tunneling Effects for Hydrogen Diffusion in PuO 2

We detail the estimation of activation energies and quantum nuclear vibrational tunneling effects for hydrogen diffusion in PuO 2 based on Density Functional Theory calculations and a quantum double well approximation. We find that results are relatively insensitive to choice of exchange correlation functional. In addition, the representation of spin in the system and use of an extended Hubbard U correction has only a small effect on hydrogen point defect formation energies when the PuO 2 lattice is held fixed at the experimental density. We then compute approximate activation energies for transitions between hydrogen interstitial sites seeded by a semi-empirical quantum model and determine the quantum tunneling enhancement relative to classical kinetic rates. Our model indicates that diffusion rates in H/PuO 2 systems could be enhanced by more than one order of magnitude at ambient conditions and that these effects persist at high temperature. The method we propose here can be used as a fast screening tool for assessing possible quantum nuclear vibrational effects in any number of condensed phase materials and surfaces, where hydrogen hopping tends to follow well defined minimum energy pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Shock-implanted noble gases. II - Additional experimental studies and recognition in naturally shocked terrestrial materials

The process by which ambient gases can be implanted into silicates by shocks was investigated by analyzing the noble-gas content of several experimentally and naturally shocked silicate samples. The retentivity of shock-implanted gas during stepwise heating in the laboratory was defined in terms of two parameters, namely, the activation energy for diffusion and the extraction temperature at which 50 percent of the gas is released, both of which correlate with the shock pressure. The experiments indicate that, with increasing shock pressure, gas implantation occurs through an increasing production of microcracks/defects in the silicate lattice. The degree of annealing of these defects control the degree of diffusive loss of implanted gas.

Bogard, Donald↗

Flux flow and flux dynamics in high-T(sub c) superconductors

Because high temperature superconductors, including BYCO and BSCCO, are type 2 superconductors with relatively low H(sub c 1) values and high H(sub c 2) values, they will be in a critical state for many of their applications. In the critical state, with the applied field between H(sub c 1) and H(sub c 2), flux lines have penetrated the material and can form a flux lattice and can be pinned by structural defects, chemical inhomogeneities, and impurities. A detailed knowledge of how flux penetrates the material and its behavior under the influence of applied fields and current flow, and the effect of material processing on these properties, is required in order to apply, and to improve the properties of, these superconductors. When the applied field is changed rapidly, the time dependence of flux change can be divided into three regions, an initial region which occurs very rapidly, a second region in which the magnetization has a 1n(t) behavior, and a saturation region at very long times. A critical field is defined for depinning, H(sub c,p) as that field at which the hysteresis loop changes from irreversible to reversible. As a function of temperature it is found that H(sub c,p) is well described by a power law with an exponent between 1.5 and 2.5. The behavior of H(sub c,p) for various materials and its relationship to flux flow and flux dynamics are discussed.

Bennett, L. H.↗

Flux flow and flux dynamics in high-Tc superconductors

Because high temperature superconductors, including BYCO and BSSCO, are type 2 superconductors with relatively low H(sub c 1) values and high H(sub c 2) values, they will be in a critical state for many of their applications. In the critical state, with the applied field between H(sub c 1) and H(sub c 2), flux lines have penetrated the material and can form a flux lattice and can be pinned by structural defects, chemical inhomogeneities, and impurities. A detailed knowledge of how flux penetrates the material and its behavior under the influence of applied fields and current flow, and the effect of material processing on these properties, is required in order to apply, and to improve the properties of these superconductors. When the applied field is changed rapidly, the time dependence of flux change can be divided into three regions, an initial region which occurs very rapidly, a second region in which the magnetization has a 1n(t) behavior, and a saturation region at very long times. A critical field is defined for depinning, H(sub c,p) as that field at which the hysteresis loop changes from irreversible to reversible. As a function of temperature, it is found that H(sub c,p) is well described by a power law with an exponent between 1.5 and 2.5. The behavior of H(sub c,p) for various materials and its relationship to flux flow and flux dynamics are discussed.

Bennett, L. H.↗

Proton Effects and Test Issues for Satellite Designers: Displacement Effects - Section 4

Microelectronic and photonic systems in the natural space environment are bombarded by a variety of charged particles including electrons, trapped protons, cosmic rays, and solar particles (protons and other heavy ions). These incident particles cause both ionizing and non-ionizing effects when traversing a device, and the effects can be either transient or permanent. The vast majority of the kinetic energy of an incident proton is lost to ionization, creating the single event effects (SEES) and total ionizing dose (TID) effects described in section IVA. However, the small portion of energy lost in non-ionizing processes causes atoms to be removed from their lattice sites and form permanent electrically active defects in semiconductor materials. These defects, i.e., "displacement damage," can significantly degrade device performance. In general, most of the displacement damage effects in the natural space environment can be attributed to protons since they are plentiful and extremely energetic (and therefore not readily shielded against). For this reason, we consider only proton induced displacement damage in this course. (Nevertheless, we identify solar cells as an important example of a case where both electron and proton damage can be important since only very light shielding is feasible.) The interested reader is encouraged to explore the three previous NSREC and RADECS short courses [Srou88a, Summ92, Hopk97] which also treat displacement damage issues for satellite applications. Part A of this segment of the short course introduces the space environment, proton shielding issues, and requirements specifications for proton-rich environments. In order to exercise the displacement damage analysis tools for on-orbit performance predictions, the requirements document must provide the relevant proton spectra in addition to the usual total ionizing dose-depth curves.

Marshall, Cheryl J.↗

Proton Effects and Test Issues for Satellite Designers

Microelectronic and photonic systems in the natural space environment are bombarded by a variety of charged particles including electrons, trapped protons, cosmic rays, and solar particles (protons and other heavy ions). These incident particles cause both ionizing and non-ionizing effects when traversing a device, and the effects can be either transient or permanent. The vast majority of the kinetic energy of an incident proton is lost to ionization, creating the single event effects (SEES) and total ionizing dose (TID) effects. However, the small portion of energy lost in non-ionizing processes causes atoms to be removed from their lattice sites and form permanent electrically active defects in semiconductor materials. These defects, i.e., "displacement damage," can significantly degrade device performance. In general, most of the displacement damage effects in the natural space environment can be attributed to protons since they are plentiful and extremely energetic (and therefore not readily shielded against). For this reason, we consider only proton induced displacement damage in this course. (Nevertheless, we identify solar cells as an important example of a case where both electron and proton damage can be important since only very light shielding is feasible.) The interested reader is encouraged to explore the three previous NSREC and RADECS short courses which also treat displacement damage issues for satellite applications. Part A of this segment of the short course introduces the space environment, proton shielding issues, and requirements specifications for proton-rich environments. In order to exercise the displacement damage analysis tools for on-orbit performance predictions, the requirements document must provide the relevant proton spectra in addition to the usual total ionizing dose-depth curves. Ion-solid interactions and the nature of the displacement damage they generate have been studied extensively for over half a century, yet they still remain a subject of investigation. In this section, a description of the mechanisms by which displacement damage is produced will be followed by a summary of the major consequences for device performance in a space environment. Often the degradation of a device parameter can be characterized by a damage factor (measured in a laboratory using monoenergetic protons) that is simply the change in a particular electrical or optical parameter per unit proton fluence. In addition, we will describe the concept of a non-ionizing energy loss rate (NIEL) which quantifies that portion of the energy lost by an incident ion that goes into displacements. It has been calculated as a function of proton energy, and is analogous to (and has the same units as) the linear energy transfer (LET) for ionizing energy. We will discover that, to first order, the calculated NIEL describes the energy dependence of the measured device damage factors. This observation provides the basis for predicting proton induced device degradation in a space environment based on both the calculated NIEL and relatively few laboratory test measurements. The methodology of such on-orbit device performance predictions will be described, as well as the limitations. Several classes of devices for which displacement damage is a significant (if not the dominant) mode of radiation induced degradation will be presented.

Marshall, Cheryl J.↗

Single Junction InGaP/GaAs Solar Cells Grown on Si Substrates using SiGe Buffer Layers

Single junction InGaP/GaAs solar cells displaying high efficiency and record high open circuit voltage values have been grown by metalorganic chemical vapor deposition on Ge/graded SiGe/Si substrates. Open circuit voltages as high as 980 mV under AM0 conditions have been verified to result from a single GaAs junction, with no evidence of Ge-related sub-cell photoresponse. Current AM0 efficiencies of close to 16% have been measured for a large number of small area cells, whose performance is limited by non-fundamental current losses due to significant surface reflection resulting from greater than 10% front surface metal coverage and wafer handling during the growth sequence for these prototype cells. It is shown that at the material quality currently achieved for GaAs grown on Ge/SiGe/Si substrates, namely a 10 nanosecond minority carrier lifetime that results from complete elimination of anti-phase domains and maintaining a threading dislocation density of approximately 8 x 10(exp 5) per square centimeter, 19-20% AM0 single junction GaAs cells are imminent. Experiments show that the high performance is not degraded for larger area cells, with identical open circuit voltages and higher short circuit current (due to reduced front metal coverage) values being demonstrated, indicating that large area scaling is possible in the near term. Comparison to a simple model indicates that the voltage output of these GaAs on Si cells follows ideal behavior expected for lattice mismatched devices, demonstrating that unaccounted for defects and issues that have plagued other methods to epitaxially integrate III-V cells with Si are resolved using SiGe buffers and proper GaAs nucleation methods. These early results already show the enormous and realistic potential of the virtual SiGe substrate approach for generating high efficiency, lightweight and strong III-V solar cells.

Ringel, S. A.↗

Evaluations of Additively Manufactured Superalloy Lattice Blocks

Cast lattice block structures made up of high-temperature superalloys were previously shown to offer advantages in density, efficiency, and tailored properties. However, inconsistencies in casting die-fill, composition, and microstructure were identified as persistent issues with the casting process path. Three candidate lattice designs were screened through additive manufacturing of a superalloy. Laser powder bed fusion was applied with superalloy powder to produce lattice blocks for three-dimensional octahedral unit-cell designs of three heights. Properties of the structural designs versus additively manufactured lattices were compared, including structural dimensions, densities, defects, grain structures, crystallographic texture, and surface residual stresses. Findings indicate this concept could produce useful superalloy structures for high-temperature-capable static components requiring tailored density, and thermophysical and mechanical properties.

superalloy↗

Radiative capture rates at deep defects from electronic structure calculations

We present a methodology to calculate radiative carrier capture coefficients at deep defects in semiconductors and insulators from first principles. Electronic structure and lattice relaxations are accurately described with hybrid density functional theory. Calculations of capture coefficients provide an additional validation of the accuracy of these functionals in dealing with localized defect states. We also discuss the validity of the Condon approximation, showing that even in the event of large lattice relaxations the approximation is accurate. We test the method on GaAs:VGa-TeAs and GaN:CN, for which reliable experiments are available, and demonstrate very good agreement with measured capture coefficients.

36 MATERIALS SCIENCE↗

Precision Structure Engineering of High-Entropy Oxides under Ambient Conditions

High-entropy oxides (HEOs) have unveiled a unique frontier in the realm of heterogeneous catalysis, taking advantage of the entropic effect and increased complexities to deliver ultrahigh stability and large tuning capability. However, current HEO synthesis mainly relies on high-temperature annealing approaches affording HEOs possessing no or low surface area, inferior active site exposure efficiency, and low controllability over the structure tuning. The grand challenge lies in producing high-quality HEO catalysts with high active site utilization efficiency, which relies on precision structure engineering, preferably under mild conditions. In this work, an in situ lattice engineering approach was developed to afford a supported HEO catalyst under ambient conditions. The HEO compositions (CuCoFeNiMnO x ) were uniformly integrated into the lattice of CeO 2 driven by cavitation-induced nucleation being generated via ultrasonication. The as-afforded catalysts were featured by high surface area, atomically dispersed HEO compositions, active redox properties, abundant oxygen vacancies (O V ), antiagglomeration, and high phase stability under harsh conditions. Compared with the ex situ introduction of HEO on the surface, the in situ method provides dual benefits to maintain the dispersity of HEO via entropic and lattice confinement effects. Engineering the complex HEO within the lattice of fluorite-structured CeO 2 also yields abundant defects (e.g., O V ) and active metal sites with strong reducing properties (e.g., Ce 3+ and Cu + ), which greatly improves the activity of the lattice oxygen and tunability of the adsorption behavior of the guest molecules, especially in the presence of impurities (e.g., water and propane). The catalytic performance of the supported HEO catalyst in oxidative procedures surpasses the pure dense phase HEO as well as the ex situ-generated catalysts. Further, the synthesis approach being developed in this work, together with the fundamental understanding in structure evolution and reaction mechanism, showcases a facile pathway under ambient conditions to generate stable catalysts capable of maintaining structural robustness in high-temperature conditions while delivering enhanced catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computed Tomography (CT) Analysis of 3D Printed Lattice Structures

LATTICE structures are increasingly used in product design across different industries, including the Department of Energy (DOE), due to their high strength and lightweight properties. These structures possess qualities such as high stiffness, energy absorption, large surface area, and structural support. To ensure lattice structures' quality and symmetry, it is crucial to have defect-free structures. However, in some cases, traditional non-destructive evaluation methods may not be practical due to encasing lattice structures in material. To analyze the lattice structures' quality, this project will employ CT imaging to gain access to the encased structures and perform a detailed analysis of each section. Three 3D printed complex lattice cubes were created, with two exposed and one encased in material, for this project. The CT X-ray cabinet will be used to scan all three cubes, and the data collected will be reconstructed and evaluated using complex interpretation software. This analysis will allow for a detailed examination of the structure's porosity, inclusions, cracks, wall thickness, and symmetry in each section.

36 MATERIALS SCIENCE↗