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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Computational Screening of Supported Metal Oxide Nanoclusters for Methane Activation: Insights into Homolytic versus Heterolytic C–H Bond Dissociation

Since its discovery in zeolites, the [CuOCu] 2+ motif has played an important role in our understanding of selective methane activation over supported metal oxide nanoclusters. Although there are two known C-H bond dissoci-ation mechanisms, namely homolytic and heterolytic cleavage, most computational studies on optimizing metal oxide nanoclusters for improved methane activation reactivity have focused only on the homolytic mechanism. In this work, both mechanisms were examined for a set of 21 mixed metal oxide complexes of the form of [M 1 OM 2 ] 2+ (M 1 , M 2 = Mn, Fe, Co, Ni, Cu, Zn). Except for pure copper, heterolytic cleavage was found to be the dominant C-H bond activation pathway for all systems. Furthermore, mixed systems including [CuOMn] 2+ , [CuONi] 2+ , and [CuOZn] 2+ are predicted to possess similar methane activation activity as pure [CuOCu] 2+ . Furthermore, these results suggest that both homolytic and heterolytic mechanisms should be considered in computing methane activation energies on supported metal oxide nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Understanding the p-doping of spiroOMeTAD by tris(pentafluorophenyl)borane

The solid-state organization of photoabsorber, hole and electron transporting layers, and interfaces between them plays an important role in governing the performance and stability of emerging optoelectronic devices such as perovskite solar cells (PSCs). The molecular organic semiconductor (OSC) 2,2' ,7,7' -tetrakis [N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiroOMeTAD) is a promising hole-transporting material (HTM) for PSCs, which is p-doped by molecular dopants to augment the charge carrier mobility. Here, the p-type doping of spiroOMeTAD by tris(pentafluorophenyl)borane (BCF) is investigated by a combination of techniques including optical spectroscopy, X-ray diffraction, Fourier transform infrared (FTIR), solid-state (ss)NMR, and electron paramagnetic resonance (EPR) spectroscopy. BCF molecules interact with traces of water molecules to form BCF-water complexes. Optical spectroscopy analysis suggests that the BCF/BCF-water complexes oxidize spiroOMeTAD molecules and facilitate p-type doping of spiroOMeTAD molecules. The different distributions of BCF and BCF-water molecules in doped spiroOMeTAD are characterized by FTIR and 11B NMR spectroscopy. An NMR crystallography approach which combines two-dimensional (2D) ssNMR and crystallography modeling is employed to unravel the packing interactions in spiroOMeTAD, and this analysis is extended to probe the morphological and structural changes in spiroOMeTAD:BCF blends. The hyperfine interactions are characterized by 2D hyperfine sub-level correlation (HYSCORE) spectroscopy. In this way, insight into the complex spiroOMeTAD:BCF blend morphology is obtained and compared for different dopant concentrations. Further, molecular-level analysis of doped HTMs enabled by this study has much wider relevance for further investigation, for example, chemical design and interfacial engineering of p-type doped HTMs for stable and efficient hybrid perovskite photovoltaics.

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

Impeding 99 Tc(IV) mobility in novel waste forms

Technetium ( 99 Tc) is a long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state1. Immobilization of Tc in mineral substrates is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels2, 3 has been proposed as a novel method to increase Tc retention in glass waste forms. However, experiments with Tc-magnetite under high temperature and oxic conditions showed re-oxidation of Tc(IV) to volatile pertechnetate Tc(VII)O4-.4, 5 Here we address this problem with large-scale ab initio molecular dynamics simulations and propose that elevated temperatures, 1st row transition metal dopants can significantly enhance Tc retention in the order Co > Zn > Ni. Experiments with doped spinels at T=700 ºC provided quantitative confirmation of increased Tc retention in the same order predicted by theory. This work highlights the power of modern state-of-the-art simulations to provide essential insights and generate bottom-up design criteria of complex oxide materials at elevated temperatures.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Adsorption of carbon monoxide on small aluminum oxide clusters: Role of the local atomic environment and charge state on the oxidation of the CO molecule

We present extensive density functional theory (DFT) calculations dedicated to analyze the adsorption behavior of CO molecules on small Al{sub x}O{sub y}{sup ±} clusters. Following the experimental results of Johnson et al. [J. Phys. Chem. A 112, 4732 (2008)], we consider structures having the bulk composition Al{sub 2}O{sub 3}, as well as smaller Al{sub 2}O{sub 2} and Al{sub 2}O units. Our electron affinity and total energy calculations are consistent with aluminum oxide clusters having two-dimensional rhombus-like structures. In addition, interconversion energy barriers between two- and one-dimensional atomic arrays are of the order of 1 eV, thus clearly defining the preferred isomers. Single CO adsorption on our charged Al{sub x}O{sub y}{sup ±} clusters exhibits, in general, spontaneous oxygen transfer events leading to the production of CO{sub 2} in line with the experimental data. However, CO can also bind to both Al and O atoms of the clusters forming aluminum oxide complexes with a CO{sub 2} subunit. The vibrational spectra of Al{sub x}O{sub y} + CO{sub 2} provides well defined finger prints that may allow the identification of specific isomers. The Al{sub x}O{sub y}{sup +} clusters are more reactive than the anionic species and the final Al{sub 2}O{sup +} + CO reaction can result in the production of atomic Al and carbon dioxide as observed from experiments. We underline the crucial role played by the local atomic environment, charge density distribution, and spin-multiplicity on the oxidation behavior of CO molecules. Finally, we analyze the importance of coadsorption and finite temperature effects by performing DFT Born-Oppenheimer molecular dynamics. Our calculations show that CO oxidation on Al{sub x}O{sub y}{sup +} clusters can be also promoted by the binding of additional CO species at 300 K, revealing the existence of fragmentation processes in line with the ones experimentally inferred.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

What is in a name: Defining “high entropy” oxides

High entropy oxides are emerging as an exciting new avenue to design highly tailored functional behaviors that have no traditional counterparts. Study and application of these materials are bringing together scientists and engineers from physics, chemistry, and materials science. The diversity of each of these disciplines comes with perspectives and jargon that may be confusing to those outside of the individual fields, which can result in miscommunication of important aspects of research. In this Perspective, we provide examples of research and characterization taken from these different fields to provide a framework for classifying the differences between compositionally complex oxides, high entropy oxides, and entropy stabilized oxides, which is intended to bring a common language to this emerging area. We highlight the critical importance of understanding a material’s crystallinity, composition, and mixing length scales in determining its true definition.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Surface Chemistry, Passivation, and Electrode Performance in Core–Shell Architectures of LiCoO 2 Nanoplates

Core–shell structures offer opportunities to overcome challenges to the durability of Li-ion batteries with high energy density due to instability at the cathode/electrolyte interface. Achieving complete stability requires fundamental understanding of the role of the shell in providing passivation without compromising carrier transport, by tuning surface chemistry and structural features in a highly conformal barrier layer. Here, individual LiCoO 2 nanoplates were employed as the core, and passivating shells were grown at a tailored thickness and composition, through different Al loadings and annealing temperatures. Depending on the annealing conditions, the sub-5 nm shells were shown to vary from amorphous aluminum oxide layers to LiAl x Co 1–x O 2 gradients, resulting in an Al-rich outer layer on a Co-rich core. This control revealed the differing balance between effective minimization of redox-active Co 3+ at the surface and transport properties of the two types of shell. Based on correlations with electrode performance, the requirements in thickness of the layers were proposed to critically depend on their chemical composition, with epitaxial shells based on surface substitution being favored. As a result, the outcomes of the study simultaneously advance the ability to assemble complex oxides into heterostructures and refine the rules of design for tunable passivation through a barrier layer, so as to maximize electrode properties in practical batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Atomic-Scale Control of Magnetism at the Titanite-Manganite Interfaces

Complex oxide thin-film heterostructures often exhibit magnetic properties different from those known for bulk constituents. This is due to the altered local structural and electronic environment at the interfaces, which affects the exchange coupling and magnetic ordering. The emergent magnetism at oxide interfaces can be controlled by ferroelectric polarization and has a strong effect on spin-dependent transport properties of oxide heterostructures, including magnetic and ferroelectric tunnel junctions. In this work, using prototype La 2/3 Sr 1/3 MnO 3 /BaTiO 3 heterostructures, we show that ferroelectric polarization of BaTiO 3 controls the orbital hybridization and magnetism at heterointerfaces. We observe changes in the enhanced orbital occupancy and significant charge redistribution across the heterointerfaces, affecting the spin and orbital magnetic moments of the interfacial Mn and Ti atoms. Notably, we find that the exchange coupling between Mn and Ti atoms across the interface is tuned by ferroelectric polarization from ferromagnetic to antiferromagnetic. Our findings provide a viable route to electrically control complex magnetic configurations at artificial multiferroic interfaces, taking a step toward low-power spintronics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

In-situ synthesis of oxides by reactive process atmospheres during L-PBF of stainless steel

Traditionally, reactive gases such as oxygen (O 2 ) and carbon dioxide (CO 2 ) have been avoided during laser powder bed fusion (L-PBF) of metals and alloys based on the notion that it may lead to defect formation and poor properties. Here, in this work, we show that instead, these gases can be used to form sub-μm-sized oxide particles in-situ during the L-PBF process in an Fe-Cr-Al-Ti stainless steel and lead to improved room temperature and high-temperature mechanical properties. We manufactured cube samples using pure Ar and various reactive gas atmospheres, namely an O 2 /Argon (Ar) mixture containing 0.2 % O 2 and CO 2 /Ar mixtures containing up to 100 % CO 2 . Co-axial measurements of infrared radiation emitted from the melt pool showed correlation to the presence of O 2 or CO 2 in the gas mixture. Builds produced under CO 2 -containing atmosphere contained complex oxides with an average diameter of ~40 nm, an Al-rich core and a Ti-rich shell. Due to the high cooling rates typical to L-PBF, agglomeration of oxides and slag formation on the surface of the samples could almost be entirely avoided. Compression tests at temperatures up to 800 °C showed that the samples produced in 100 % CO 2 have about 20 % higher yield stress compared to samples produced in Ar. The paper concludes with a discussion of the formation mechanism of the observed oxides. Our results show that in-situ reactions during additive manufacturing processes are a promising pathway to the synthesis of particle-reinforced alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Realization of a Hole-Doped Mott Insulator on a Triangular Silicon Lattice

The physics of doped Mott insulators is at the heart of some of the most exotic physical phenomena in materials research including insulator-metal transitions, colossal magnetoresistance, and high-temperature superconductivity in layered perovskite compounds. Advances in this field would greatly benefit from the availability of new material systems with a similar richness of physical phenomena but with fewer chemical and structural complications in comparison to oxides. In this paper, using scanning tunneling microscopy and spectroscopy, we show that such a system can be realized on a silicon platform. The adsorption of one-third monolayer of Sn atoms on a Si(111) surface produces a triangular surface lattice with half filled dangling bond orbitals. Modulation hole doping of these dangling bonds unveils clear hallmarks of Mott physics, such as spectral weight transfer and the formation of quasiparticle states at the Fermi level, well-defined Fermi contour segments, and a sharp singularity in the density of states. These observations are remarkably similar to those made in complex oxide materials, including high-temperature superconductors, but highly extraordinary within the realm of conventional $sp$-bonded semiconductor materials. Finally, it suggests that exotic quantum matter phases can be realized and engineered on silicon-based materials platforms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Probing Electron Correlations in 1D Electronic Materials Using Single Quantum Channels (Final Technical Report)

This research focuses on the investigation of strong electron correlations in quasi-one-dimensional oxide nanostructures. The archetypical system consisting of heterostructures formed from an ultrathin layer of LaAlO 3 and TiO 2 -terminated SrTiO 3 offers a unique laboratory for probing strong correlations due to intrinsic richness of the physical system and its ability to be modulated at extreme nanoscale dimensions. Under suitable conditions, SrTiO 3 is known to exhibit a variety of important properties associated with strong electronic correlations, especially superconductivity, magnetism. Understanding the nature of these electronic correlations at fundamental scales, and in reduced spatial dimensions, will provide the scientific basis for new energy technologies, information technologies, and materials. The research program is motivated by recent discoveries and technical advances in the PIs' lab, specifically, (1) pioneering work to create conductive nanostructures to be created in LaAlO 3 /SrTiO 3 heterointerfaces with 2 nm spatial resolution, (2) the discovery of a novel correlated electronic phases in which electrons pair without forming a superconductor, and (3) the demonstrated ability to form high-quality quantum point contacts (QPCs) and achieve ballistic electron transport over micrometer-scales in LaAlO 3 /SrTiO 3 nanowires. The program has three major components. First, we have press forward to develop a full microscopic understanding of the mechanism for electron pairing in LaAlO 3 /SrTiO 3 nanostructures. Understanding the “glue” that leads to pairing and superconductivity in a doped semiconductor will help to form a scientific basis for the correlated oxide nanoelectronics platform being developed. Second, we have used their ability to create well-defined quantum channels in nanowires allows to allow novel “scattering” experiments to be performed that probe fundamentally new quasiparticle excitations using an unprecedented combination of experimental methodologies. Experiments already underway with artificially defined superlattices (5 nm period) demonstrate the feasibility of this approach. Third, we have investigated 1D correlations in proximally coupled nanowires, which are predicted exhibit Majorana-like zero modes in the absence of superconductivity or spin-orbit coupling. These studies provide insight not only into new and emergent phenomena in the rich class of complex oxides, but also fundamental mechanisms of superconductivity and magnetism. Thematically, the research aims to combine some of the most important and interesting challenges in the physics of semiconductor nanostructures and correlated electronic materials. The increased understanding of electron correlations can pave the way to the development of new materials with outstanding or novel properties, which could be relevant for energy-related technologies such as low-power high performance computing, quantum computation, or the development of novel materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Atomic-scale 3D imaging of individual dopant atoms in an oxide semiconductor

The physical properties of semiconductors are controlled by chemical doping. In oxide semiconductors, small variations in the density of dopant atoms can completely change the local electric and magnetic responses caused by their strongly correlated electrons. In lightly doped systems, however, such variations are difficult to determine as quantitative 3D imaging of individual dopant atoms is a major challenge. We apply atom probe tomography to resolve the atomic sites that donors occupy in the small band gap semiconductor Er(Mn,Ti)O 3 with a nominal Ti concentration of 0.04 at. %, map their 3D lattice positions, and quantify spatial variations. Our work enables atomic-level 3D studies of structure-property relations in lightly doped complex oxides, which is crucial to understand and control emergent dopant-driven quantum phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Emerging Diluted Ferromagnetism in High- T c Superconductors Driven by Point Defect Clusters

Here, defects in ceramic materials are generally seen as detrimental to their functionality and applicability. Yet, in some complex oxides, defects present an opportunity to enhance some of their properties or even lead to the discovery of exciting physics, particularly in the presence of strong correlations. A paradigmatic case is the high–temperature superconductor YBa 2 Cu 3 O 7–δ (Y123), in which nanoscale defects play an important role as they can immobilize quantized magnetic flux vortices. Here previously unforeseen point defects buried in Y123 thin films that lead to the formation of ferromagnetic clusters embedded within the superconductor are unveiled. Aberration–corrected scanning transmission microscopy has been used for exploring, on a single unit–cell level, the structure and chemistry resulting from these complex point defects, along with density functional theory calculations, for providing new insights about their nature including an unexpected defect–driven ferromagnetism, and X–ray magnetic circular dichroism for bearing evidence of Cu magnetic moments that align ferromagnetically even below the superconducting critical temperature to form a dilute system of magnetic clusters associated with the point defects.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Through the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn 2 O 5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi 3+ Mn 3+ Mn 4+ O 5 phase, we identify electronic analogues to the well-known BiVO 4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Lastly, our suite of experimental and computational characterization indicates that BiMn 2 O 5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.

14 SOLAR ENERGY↗
DOE OSTI2018

Beyond electrostatic modification: design and discovery of functional oxide phases via ionic-electronic doping

A new research field of functional materials and device physics is emerging that combines ionic transport with charge carrier modulation to realize emergent physical properties and discovery of metastable phases. The paradigm for enabling function extends far beyond carrier accumulation or depletion in band semiconductors or simply moving ions through an insulating electrolyte. Rather, by careful selection of electronically or structurally fragile materials, one can collapse or open band gaps via extreme ionic dopant concentration, or reconfigure their entire crystal structure to create new phases. Electron-electron and electron-lattice interactions can be coupled or controlled independently in such systems via electric fields without thermal constraints by use of ionic dopants. The unifying theme across these studies is to introduce ions and electrons via electric fields through interfaces with electrochemistry playing a dominant role. In this review, we briefly summarize this nascent field of iontronics and discuss principal results to date with examples from binary and complex oxides as well as selected 2D materials systems. Here, we conclude the review by highlighting gaps in fundamental scientific understanding and prospects for the use of such novel devices in future electronic, photonic and energy technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancing anomalous Hall effect with suppressed ferromagnetism in the SrTiO 3 -confined bilayer heterostructure of ultrathin SrRuO 3 and SrIrO 3

Ferromagnetism is an essential ingredient for anomalous Hall effect. SrRuO 3 is a representative ferromagnetic oxide that exhibits anomalous Hall effect even down to the monolayer confinement limit. Paramagnetic metal SrIrO 3 , on the other hand, becomes an antiferromagnetic insulator when confined to a monolayer. Here, in this study, we show that, by forming a confined bilayer structure of SrRuO 3 and SrIrO 3 monolayers with SrTiO 3 spacers, the anomalous Hall effect is significantly enhanced while the ferromagnetism as well as the perpendicular magnetic anisotropy are suppressed. These effects originate from interfacial Ru–Ir hybridization that modifies the electronic structure in the vicinity of the Fermi level. Our work demonstrates that confined bilayer heterostructure is an useful design for exploring the synergistic combination of interfacial coupling and quantum confinement of complex oxides.

anomalous hall effect↗
DOE OSTI2018

Prediction of perovskite and other ternary oxide multilayers as mirrors for soft X-rays

Highlights: • Theoretical framework to identify optimal multilayers for high x-ray reflectivity. • Perovskite oxide multilayers are proposed as soft x-ray mirrors. • High soft x-ray reflectivity up to 33% are expected in perovskite multilayers. - Abstract: We propose multilayers of perovskite and related ternary oxides with a general formula of ABO{sub 3} as high reflectivity mirrors, especially for use in water window region (2.3–4.4 nm). The high reflectivity combinations of oxide multilayers were deduced using evolutionary search algorithms such as genetic algorithms, and the calculation speed was accelerated via parallel computing methods We also propose a figure of merit for X-ray reflectivity in periodic multilayers systems, which can simplify the future efforts on identifying material combinations, and the search through this multi-dimensional parameter space. The highest reflectivity value was found to be over 33% at 3.1 nm in the water window region. The effect of interface roughness was simulated and the decrease in reflectivity was found to be modest for practically achievable roughness values. This work establishes the foundation for future experimental and theoretical studies towards achieving high reflectivity x-ray mirrors of complex oxide multilayers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Theory and application of the vector pair correlation function for real-space crystallographic analysis of order/disorder correlations from STEM images

Deviations of local structure and chemistry from the average crystalline unit cell are increasingly recognized to have a significant influence on the properties of many technologically important materials. Here, we present the vector pair correlation function (vPCF) as a new real-space crystallographic analysis method, which can be applied to atomic-resolution scanning transmission electron microscopy (STEM) images to quantify and analyze structural order/disorder correlations. Our STEM-based vPCFs have several advantages over radial PCFs and/or 3D pair distribution functions from x-ray total scattering: vPCFs explicitly retain crystallographic orientation information, are spatially resolved, can be applied directly on a sublattice basis, and are suitable for any material that can be imaged with STEM. To show the utility of our approach, we measure partial vPCFs in Ba 5 SmSn 3 Nb 7 O 30 (BSSN), a tetragonal tungsten bronze (TTB) structured complex oxide. Many TTBs are known to be classical or relaxor ferroelectrics, and these properties have been correlated with the presence of superlattice ordering. BSSN, specifically, exhibits relaxor behavior and an incommensurate structural modulation. From the vPCF data, we observe that, of the cation sites, only the Ba (A2) sublattice is structurally modulated. We then infer the local modulation vector and reveal a marked anisotropy in its correlation length. Finally, short-range correlated polar displacements on the B2 cation sites are observed. This work introduces the vPCF as a powerful real-space crystallography technique, which enables direct, robust quantification of short-to-long range order on a sublattice-specific basis and is applicable to a wide range of complex material types.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

An antisite defect mechanism for room temperature ferroelectricity in orthoferrites

Single-phase multiferroic materials that allow the coexistence of ferroelectric and magnetic ordering above room temperature are highly desirable, motivating an ongoing search for mechanisms for unconventional ferroelectricity in magnetic oxides. Here, we report an antisite defect mechanism for room temperature ferroelectricity in epitaxial thin films of yttrium orthoferrite, YFeO 3 , a perovskite-structured canted antiferromagnet. A combination of piezoresponse force microscopy, atomically resolved elemental mapping with aberration corrected scanning transmission electron microscopy and density functional theory calculations reveals that the presence of Y Fe antisite defects facilitates a non-centrosymmetric distortion promoting ferroelectricity. This mechanism is predicted to work analogously for other rare earth orthoferrites, with a dependence of the polarization on the radius of the rare earth cation. Our work uncovers the distinctive role of antisite defects in providing a mechanism for ferroelectricity in a range of magnetic orthoferrites and further augments the functionality of this family of complex oxides for multiferroic applications.

36 MATERIALS SCIENCE↗