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All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Ab initio Computations of the Electronic, Mechanical, and Thermal Properties of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2

Refractory materials such as metallic borides, often considered as ultra high temperature ceramics (UHTC), are characterized by high melting point, high hardness, and good chemical inertness. These materials have many applications which require high temperature materials that can operate with no or limited oxidation. Ab initio, first principles methods are the most accurate modeling approaches available and represent a parameter free description of the material based on the quantum mechanical equations. Using these methods, many of the intrinsic properties of these material can be obtained. We performed ab initio calculations based on density functional theory for the UHTC materials ZrB2 and HfB2. Computational results are presented for structural information (lattice constants, bond lengths, etc), electronic structure (bonding motifs, densities of states, band structure, etc), thermal quantities (phonon spectra, phonon densities of states, specific heat), as well as information about point defects such as vacancy and antisite formation energies.

Lawson, John W.↗
DOE OSTI2020

Coupling between interfacial charge and mechanical deformation at high temperatures in ceramics. Final report

Basic research, under this project, has led to new fundamental discoveries in the effect of electric field (and temperature) on diffusion kinetics, electroluminescence and electronic conductivity in ceramic materials. For example, yttria stabilized zirconia sinters in just seconds well below 1000°C, while, at the same time, exhibiting a highly non-linear rise in conductivity, and intense electroluminescence. The phenomenon has been shown to occur in nearly all ceramics whether they are ionic or electronic conductors, or insulators. The rise in conductivity leads to Joule heating but in-situ measurements with a platinum standard at APS and Brookhaven (NSLS-II) have shown that the temperatures are much below what would have been needed to sinter in a few seconds. We have explored the hypothesis that huge concentrations of Frenkel pairs of vacancies and interstitials are produced. While these point defects accelerate sintering (by the interstitials being transported to the pores and the vacancies to the grain boundaries), they may also produce electron-hole pairs which can impart high electrical conductivity or recombine to emit photons. Many measurements, including in-situ measurements of lattice expansion are consistent with this hypothesis. However, the energy barrier for generating Frenkels in zirconia for example is much larger than can be expected at temperature and electrical fields in these experiments. Most recent work suggests that short wavelength phonons play a critical role in the genesis of the “flash” phenomenon. For example, the Debye temperature has been shown to be the lower bound for initiating flash. Molecular dynamics simulations have shown that large concentrations of Frenkel pairs can form under the proliferation of “optical” phonons at the edge of the Brillouin zone, that is with a wavelength at or below the lattice parameter. This project has led to the development of new experimental techniques as well as a software hardware interface for process and control and data analysis in real time, with a time scale of less than one second. This approach spells a new paradigm in materials science research. It potential impact on high rate manufacturing is self evident.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nanoscale lattice strains in self-ion implanted tungsten

Developing a comprehensive understanding of the modification of material properties by neutron irradiation is important for the design of future fission and fusion power reactors. Self-ion implantation is commonly used to mimic neutron irradiation damage, however an interesting question concerns the effect of ion energy on the resulting damage structures. The reduction in the thickness of the implanted layer as the implantation energy is reduced results in the significant quandary: Does one attempt to match the primary knock-on atom energy produced during neutron irradiation or implant at a much higher energy, such that a thicker damage layer is produced? In this work, we address this question by measuring the full strain tensor for two ion implantation energies, 2 MeV and 20 MeV in self-ion implanted tungsten, a critical material for the first wall and divertor of fusion reactors. A comparison of 2 MeV and 20 MeV implanted samples is shown to result in similar lattice swelling. Multi-reflection Bragg coherent diffractive imaging (MBCDI) shows that implantation induced strain is in fact heterogeneous at the nanoscale, suggesting that there is a non-uniform distribution of defects, an observation that is not fully captured by micro-beam Laue diffraction. At the surface, MBCDI and high-resolution electron back-scattered diffraction (HR-EBSD) strain measurements agree quite well in terms of this clustering/non-uniformity of the strain distribution. However, MBCDI reveals that the heterogeneity at greater depths in the sample is much larger than at the surface. This combination of techniques provides a powerful method for detailed investigation of the microstructural damage caused by ion bombardment, and more generally of strain related phenomena in micro-volumes that are inaccessible via any other technique.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Doping transition-metal atoms in graphene for atomic-scale tailoring of electronic, magnetic, and quantum topological properties

Atomic-scale fabrication is an outstanding challenge and overarching goal for the nanoscience community. The practical implementation of moving and fixing atoms to a structure is non-trivial considering that one must spatially address the positioning of single atoms, provide a stabilizing scaffold to hold structures in place, and understand the details of their chemical bonding. Free-standing graphene offers a simplified platform for the development of atomic-scale fabrication and the focused electron beam in a scanning transmission electron microscope can be used to locally induce defects and sculpt the graphene. In this scenario, the graphene forms the stabilizing scaffold and the experimental question is whether a range of dopant atoms can be attached and incorporated into the lattice using a single technique and, from a theoretical perspective, we would like to know which dopants will create technologically interesting properties. Here in this paper, we demonstrate that the electron beam can be used to selectively and precisely insert a variety of transition metal atoms into graphene with highly localized control over the doping locations. We use first-principles density functional theory calculations with direct observation of the created structures to reveal the energetics of incorporating metal atoms into graphene and their magnetic, electronic, and quantum topological properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The underappreciated lone pair in halide perovskites underpins their unusual properties

The presence of 6s 2 (5s 2 ) lone-pair electrons on the B-site Pb (Sn) in all-inorganic and hybrid halide ABX 3 perovskites distinguishes these materials from the familiar tetrahedral semiconductors traditionally employed in optoelectronics and is key to many of their appealing properties. These electrons are stereochemically active, albeit often in a hidden fashion, resulting in unusual and highly anharmonic lattice dynamics that are linked to many of the special optoelectronic properties displayed by this material class. This article describes the connections between this atypical electronic configuration and the electronic structure and lattice dynamics of these compounds. We illustrate how the lone pair leads to favorable bandwidths and band alignments, mobile holes, large ionic dielectric response, large positive thermal expansion, and even possibly defect-tolerant electronic transport. Taken together, the evidence suggests that other high-performing semiconductors may be found among compounds with lone-pair-bearing cations in high symmetry environments and a high degree of connectivity between atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Inverted Metamorphic AlGaInAs/GaInAs Tandem Thermophotovoltaic Cell Designed for Thermal Energy Grid Storage Application

We demonstrate an inverted metamorphic multijunction (IMM) photovoltaic cell comprising lattice-mismatched 1.2 eV AlGaInAs and 1.0 eV GaInAs junctions optimized for high-temperature thermophotovoltaic (TPV) applications. This device differs from traditional IMM solar cells because the mismatched junctions are grown at a single lattice constant. This architecture enables removal of the compositionally graded buffer that otherwise filters light from the junctions below and absorbs sub-bandgap light via free-carrier absorption. Sub-bandgap absorption dramatically reduces the efficiency of TPV systems using high reflectivity cells to enable band edge spectrum filtering. Three components required development to enable this device: (1) a lattice-mismatched 1.2 eV AlGaInAs junction, (2) a metamorphic contact layer grown after the graded buffer, and (3) a transparent tunnel junction that sits in front of the 1.0 eV GaInAs junction. Growth conditions that minimize oxygen defect incorporation maximize AlGaInAs cell quality, enabling a 0.41 V bandgap open circuit voltage offset at 22 mA/cm2 under AM1.5D. A mismatched GaInAs:Se layer is developed as a low resistance contact. Lastly, we develop a GaAsSb:C/GaInP:Se tunnel junction suitable for high-power densities with more transparency than the GaAsSb:C/GaInAs:Se structure used in past IMM cells. We characterize the tandem device under a high-intensity spectrum that approximates the emission from a 2150°C blackbody radiator and deduce a projected ideal TPV efficiency of 39.9% at ~30% of the blackbody irradiance and 36% ideal TPV efficiency under the full 118 W/cm2 irradiance. Improvements to the back-surface reflectivity and series resistance are expected to increase the ideal TPV efficiency well above 40%.

25 ENERGY STORAGE↗
DOE OSTI2023

Frustrated Magnetism and Ferroelectricity in a Dy 3+ -Based Triangular Lattice

Triangular lattice magnets have attracted extensive research interest because they are potential hosts for geometrically frustrated magnetism and strong quantum fluctuations. Here, utilizing a laser floating zone technique, we report the first-time successful growth of a DyInO 3 sizable crystal, which contains Dy3+-based triangular layers. The fine-tuning of Indium stoichiometry was found to be the key factor in the stabilization of the desired hexagonal phase. The X-ray diffraction study of the crystal structure reveals a non-centrosymmetric P6 3mc space group. Switchable polarization, i.e., ferroelectricity, and ferroelectric domain configuration are experimentally demonstrated at room temperature. Anisotropic magnetic and thermodynamic measurements unveil antiferromagnetic interactions, the absence of long-range ordering down to 0.1 K, and a possible doublet ground state, indicating a strongly frustrated magnetism. Our findings suggest that the DyInO 3 crystal is an excellent platform for studying emergent phenomena and their interplay with coherent topological defects in the quantum realm.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electronic Structure Theory and Novel Materials

This grant supported research on electronic structure and materials theory, with focus on three main issues: (i) novel techniques to deal with correlation in the electronic ground-state, (ii) topological materials, (iii) the phase diagram of lattice spin models. Regarding (i), we applied to the homogeneous electron liquid an approach that we previously developed in the context of molecular systems. In this scheme the electronic occupation probabilities and the natural spin orbitals are used to construct an approximate two-body density matrix for the electronic ground-state. Regarding (ii) we used standard electronic structure methods based on density functional theory to model topological materials and interpret experimental observations. Finally, regarding (iii) we further developed a numerical approach to compute the renormalized couplings within real space renormalization group theory in the context of lattice spin models. The main findings were the following. (i) We found that with our approximate two-body density matrix, which works well for small molecules, is not sufficiently accurate for condensed phase systems. Missing a systematic way of improving on the adopted approximations, we decided not to pursue this approach. (ii) We performed two studies. In one, we investigated the influence of Te defects on the topological properties of a WTe2 monolayer, finding that while Te vacancies, even in modest concentration, destroy the topological character, Te adatoms do not, consistent with a recent experiment. In another study, we predicted Weyl semimetal character and strong anomalous Hall effect in the Heusler compensated ferrimagnet Ti2MnAl. (iii) We developed a new Monte Carlo method to do real space renormalization group calculations for lattice spin models. We subsequently extended the scheme to deal with lattice spin models in presence of quenched disorder, finding that the approach can distinguish systems with finite and strong disorder. In the finite disorder case, the method allows one to find with good approximation the critical coupling distribution and the critical exponents.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Stoichiometric Control and Optical Properties of BaTiO 3 Thin Films Grown by Hybrid MBE

BaTiO 3 is a technologically relevant material in the perovskite oxide class with above-room-temperature ferroelectricity and a very large electro-optical coefficient, making it highly suitable for emerging electronic and photonic devices. An easy, robust, straightforward, and scalable growth method is required to synthesize epitaxial BaTiO 3 thin films with sufficient control over the film's stoichiometry to achieve reproducible thin film properties. Here the growth of BaTiO 3 thin films by hybrid molecular beam epitaxy is reported. A self-regulated growth window is identified using complementary information obtained from reflection high energy electron diffraction, the intrinsic film lattice parameter, film surface morphology, and scanning transmission electron microscopy. Subsequent optical characterization of the BaTiO 3 films by spectroscopic ellipsometry revealed refractive index and extinction coefficient values closely resembling those of stoichiometric bulk BaTiO 3 crystals for films grown inside the growth window. Even in the absence of a lattice parameter change of BaTiO 3 thin films, degradation of optical properties is observed, accompanied by the appearance of a wide optical absorption peak in the IR spectrum, attributed to optical transitions involving defect states present. Therefore, the optical properties of BaTiO 3 can be utilized as a much finer and more straightforward probe to determine the stoichiometry level present in BaTiO 3 films.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synthesis, Processing, and Use of Isotopically Enriched Epitaxial Oxide Thin Films

Isotopic engineering has emerged as a key approach to study the nucleation, diffusion, phase transitions, and reactions of materials at an atomic level. It aims to uncover mass transport pathways, kinetics, and operational and failure mechanisms of functional materials and devices. Understanding these phenomena leads to deeper insights into important physical processes, such as the transport of ions in energy conversion and storage devices and the role of active sites and supports during heterogeneous catalytic reactions. Likewise, isotopic engineering is being pursued as a means of modifying functionality to enable future technological applications. In this Account, we summarize our recent work employing isotope labeling (e.g., 18 O 2 and 57 Fe) during thin film synthesis and postgrowth processing to reveal growth mechanisms, defect chemistry, and elemental diffusion under working and extreme conditions. Isotope-resolved analysis techniques with nanometer-scale spatial resolution, such as time-of-flight secondary ion mass spectrometry and atom probe tomography, facilitate the accurate quantification of isotopic placement and concentration in our well-defined heterostructures with precisely positioned, isotope-enriched layers. By measuring the nanometer-scale redistribution between natural abundance and isotopically enriched oxygen layers during the deposition of Fe 2 O 3 and Cr 2 O 3 by molecular beam epitaxy, we identified intermixing processes driven by surface adatoms occurring both at the film growth surface and within the first few layers below the surface. Further insights into synthesis mechanisms were gained by studying the tungsten oxide thin films grown by evaporating WO 3 powder in the presence of background 18 O 2 , revealing minimal incorporation of background oxygen during the film formation process. Thermal and radiation-enhanced diffusion in epitaxial Fe and Cr oxides were precisely tracked using 18 O and 57 Fe tracer layers incorporated into model epitaxial oxide thin films. This approach has allowed us to access thermal diffusion behavior at lower temperatures than previously measured, revealing a potential changeover in diffusion mechanism. Understanding radiation-enhanced diffusion in model oxides that represent the surface layers on the structural components of nuclear reactors informs our understanding of their corrosion behavior under irradiation. Isotopic labeling can also provide unique insights into the surface exchange reactions and defect chemistry of electrocatalysts. For instance, tracking the change in 18 O concentration at the surface of an epitaxial LaNiO 3 thin film after the electrocatalytic oxygen evolution reaction revealed the participation of lattice oxygen, confirming a hypothesis that had been proposed previously. Lastly, we highlight a new direction wherein we perform in situ processing studies utilizing isotopic tracers in conjunction with model epitaxial thin films within the atom probe tomography instrument. Additionally, this Account illustrates the great potential of isotopic engineering to enable fundamental mechanistic insights into physical processes and engineer functional properties in epitaxial films, heterostructures, and superlattices.

36 MATERIALS SCIENCE↗
DOE OSTI2026

First-principles thermodynamic assessment of Sr-containing secondary phase formation in strontium-substituted lanthanum manganites for solid oxide cell applications

Sr-secondary phase formation is a potentially significant degradation mode with direct impact upon solid-oxide cell (SOC) commercial viability. A first-principles based thermodynamic study was performed for La 1−x Sr x MnO 3±δ (LSM) perovskites to assess their stability against formation of different Sr-secondary phases, including SrO, SrCrO 4 , SrSO 4 , SrCO 3 , and Sr(OH) 2 , for SOC applications. The Sr-secondary phase formation reaction free energies were determined via a thermodynamic model by combining ab initio lattice dynamics calculations for the solid phases and ab initio thermodynamic data for the gas phases. The current approach expands the previously reported thermodynamic modeling studies by integrating first-principles based point defect equilibria into the thermodynamic analysis. The modeling results obtained using this new approach indicate an increased tendency to form the SrO oxide upon decreasing the oxygen partial pressure. Additionally, the enhancing factors to form the Sr-related secondary phase from the associated SrO activity in LSM are further quantified by considering the equilibrium of SrO reacting with the contaminant gas species as a function of temperature and pressure.

defect thermodynamics modeling↗
DOE OSTI2022

In Situ Nano-Indentation of a Gold Sub-Micrometric Particle Imaged by Multi-Wavelength Bragg Coherent X-ray Diffraction

The microstructure of a sub-micrometric gold crystal during nanoindentation is visualized by in situ multi-wavelength Bragg coherent X-ray diffraction imaging. The gold crystal is indented using a custom-built atomic force microscope. A band of deformation attributed to a shear band oriented along the (221) lattice plane is nucleated at the lower left corner of the crystal and propagates towards the crystal center with increasing applied mechanical load. After complete unloading, an almost strain-free and defect-free crystal is left behind, demonstrating a pseudo-elastic behavior that can only be studied by in situ imaging while it is invisible to ex situ examinations. The recovery is probably associated with reversible dislocations nucleation/annihilation at the side surface of the particle and at the particle-substrate interface, a behavior that has been predicted by atomistic simulations. The full recovery of the particle upon unloading sheds new light on extraordinary mechanical properties of metal nanoparticles obtained by solid-state dewetting.

36 MATERIALS SCIENCE↗
NASA NTRS2004

Homoepitaxial and Heteroepitaxial Growth on Step-Free SiC Mesas

This article describes the initial discovery and development of new approaches to SiC homoepitaxial and heteroepitaxial growth. These approaches are based upon the previously unanticipated ability to effectively supress two-dimensional nucleation of 3C-SiC on large basal plane terraces that form between growth steps when epitaxy is carried out on 4H- and 6H-SiC nearly on-axis substrates. After subdividing the growth surface into mesa regions, pure stepflow homoeptixay with no terrace nucleation was then used to grow all existing surface steps off the edges of screw-dislocation-free mesas, leaving behind perfectly on-axis (0001) basal plane mesa surfaces completely free of atomic-scale steps. Step-free mesa surfaces as large as 0.4 mm x 0.4 mm were experimentally realized, with the yield and size of step-free mesas being initally limited by substrate screw dislocations. Continued epitaxial growth following step-free surface formation leads to the formation of thin lateral cantilevers that extend the step-free surface area from the top edge of the mesa sidewalls. By selecting a proper pre-growth mesa shape and crystallographic orientation, the rate of cantilever growth can be greatly enhanced in a web growth process that has been used to (1) enlarge step-free surface areas and (2) overgrow and laterally relocate micropipes and screw dislocations. A new growth process, named step-free surface heteroepitaxy, has been developed to achieve 3C-SiC films on 4H- and 6H-SiC substrate mesas completely free of double positioning boundary and stacking fault defects. The process is based upon the controlled terrace nucleation and lateral expansion of a single island of 3C-SiC across a step-free mesa surface. Experimental results indicate that substrateepilayer lattice mismatch is at least partially relieved parallel to the interface without dislocations that undesirably thread through the thickness of the epilayer. These results should enable realization of improved SiC homojunction and heterojunction devices. In addition, these experiments offer important insights into the nature of polytypism during SiC crystal growth.

Neudeck, Philip G.↗
DOE OSTI2022

Triple-Junction III-V Solar Cells with 39.5% AM1.5G and 34.2% AM0 Efficiencies

III-V multijunction solar cells have the highest efficiencies of any PV technology. These devices are currently the dominant space PV technology, and are being investigated for a wide range of other applications where efficiency is a key metric. In this presentation, we describe a 3-junction cell with the highest 1-sun efficiency to date: 39.5% under the global spectrum, which is higher than previous 6-junction devices. When tuned for the space spectrum, the cell achieves 34.2% beginning-of-life efficiency, without consideration for radiation hardness. These efficiency improvements are enabled by combining advances in device architectures and extended-defect control strategies. This latest 3-junction device includes a high-performance front-junction GaInP top cell, an optically-thick strain-balanced quantum well middle cell, and a lattice-mismatched GaInAs bottom cell with record performance despite dislocations. These advances not only allow high efficiency photovoltaics for both space and terrestrial PV applications, but also help enable new applications of III-V materials.

GaInAs↗
DOE OSTI2020

Development of Lattice-Mismatched GaInAsP for Radiation Hardness

We develop lattice-mismatched GaInAsP as an alternative alloy to pure As-based alloys currently used in III-V multijunction solar cells. Increasing the alloy phosphorous and indium content while maintaining an optimal bandgap may allow high efficiency multijunction devices with increased radiation hardness. Here, 1.0-eV GaInAsP is developed and implemented into single and multijunction solar cell devices. The lattice-mismatched GaInAsP must be grown strain free, and the subcell thickness must be maintained below the thickness where surface-driven phase separation occurs. As observed in transmission electron microscopy and cathodoluminescence imaging, phase separation strengthens in the GaInAsP layer and leads to interfacial defect formation when the cell thickness is too great. We show single junction 1.0-eV Ga 0.5 In 0.5 As 0.7 P 0.3 with excellent carrier collection and a bandgap-voltage offset of 0.40 V. This material quality approaches that of 1.0-eV Ga 0.7 In 0.3 As used in inverted metamorphic multijunction devices, but has increased phosphorus content and consequently is expected to have a higher radiation resistance. We incorporate the 1.0-eV GaInAsP subcell into a 3-junction inverted metamorphic solar cell to test the performance of the subcell in a multijunction. No additional loss is observed upon integration into a multijunction cell: both the carrier collection and voltage of the GaInAsP subcell are unchanged from single junction devices. While further materials development and radiation testing is still required, these preliminary results indicate that lattice-mismatched GaInAsP can be effectively used in multijunction solar cells to replace radiation-soft materials.

14 SOLAR ENERGY↗
DOE OSTI2025

First-Principles Thermodynamic Assessments of Sr-Containing Secondary Phase Formation in La1-xSrxMnO3±δ Perovskites for Solid Oxide Cell Applications

Sr-secondary phase formation is a potentially significant degradation mode threatening solid-oxide cell (SOC) commercial viability. A first-principles thermodynamic study was performed for rhombohedral perovskite (La1-xSrx) MnO3±δ (LSM) to assess its stability against Sr secondary phase formation in SOC applications. In this work, the Sr secondary phase formation reaction free energies were determined by combining ab initio lattice dynamics calculations for the solid phases and an ab initio thermodynamics approach for the gas phases. Furthermore, this approach goes beyond previous thermodynamic modeling studies by integrating first-principles based point-defect equilibria into the analyses. The modeling results indicate an increased tendency to form SrO oxide from LSM upon decreasing the oxygen partial pressure. Additionally, enhancing factors to form the Sr-related secondary phase from the associated SrO activity in LSM are further quantified by considering the equilibrium of SrO reacting with contaminant gas species as a function of temperature and gas pressure.

Defect and phase stability↗
DOE OSTI2020

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO 3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗