Search NASA⌕ Search

SEARCH · Search NASA

Results for “complex oxide interfaces”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6

Interface creation on a mixed-terminated perovskite surface

In the field of complex oxide heterostructures, understanding of the initial substrate surface can be critical to fundamental studies regarding the development of emergent properties at the film–substrate interface. For this reason, a considerable amount of effort has gone into the development of techniques to achieve surfaces with single termination for a variety of perovskite single crystals. However, a decisive understanding of how an interface is created when epitaxial growth occurs on a mixed terminated surface remains lacking. Employing in situ synchrotron X-ray scattering during thin film growth by molecular beam epitaxy, we investigate the initial stages of growth on (LaAlO 3 )(Sr 2 AlTaO 6 ) (001) substrates with mixed termination. Using LaNiO 3 as a model system, we find that the surface layers of the substrate restructure during deposition such that while a NiO 2 monolayer is weakly bound, a LaO monolayer bonds strongly, effectively incorporating with (Al, Ta)O 2 from the surface and forming a La(Al, Ta)O 3 ultrathin film. <!--/abstract content--><!--fulltext content--> With regard to the synthesis of high-quality complex oxide heterostructures, it is important that the substrate meet an array of criteria related to the crystal structure, lattice parameter, thermodynamic properties, electrical and optical properties, and so on. In particular, the surface of the substrate should be atomically smooth and exhibit the step-terrace structure ideal for epitaxial thin film growth. Perovskite oxides with the formula ABO 3 have two possible (001) surfaces: AO (A-site termination) and BO 2 (B-site termination). The ability to consistently achieve one of these surface terminations on SrTiO 3 , i.e., TiO 2 , has helped SrTiO 3 become the predominant oxide in the field.

36 MATERIALS SCIENCE↗

Metallic interface in non-SrTiO{sub 3} based titanate superlattice

We report on the fabrication of all perovskite Mott insulator/band insulator YTiO{sub 3}/CaTiO{sub 3} superlattices by pulsed laser deposition. The combination of in situ reflection high energy electron diffraction, X-ray diffraction, and X-ray reflectivity confirms the high quality of the films grown in a layer-by-layer mode. Electrical transport measurements reveal that a non-SrTiO{sub 3} based two-dimensional electron gas system has formed at the YTiO{sub 3}/CaTiO{sub 3} interface. These studies offer another route in the pursuit of complex oxide two-dimensional electron gas systems, which allows to obtain greater insights into the exotic many-body phenomena at such interfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

High-Temperature Oxidation of Stellite 12 Hardfacings: Effect of Mo on Characteristics of Oxide Scale

This study aims to understand the oxide scale formation on the surfaces of commercial and Mo (10 wt.%)-modified Stellite 12 hardfacings deposited on 4140 steel. For this purpose, samples of the hardfacings were isothermally oxidized in air at various temperatures in between 500 and 900 °C for 30 h. As a result of changes in the microstructure upon Mo addition, about 50% higher mass gain at all oxidation temperatures was observed. The characteristics of the developed oxide scales were examined by utilizing Raman spectroscopy, scanning electron microscopy and x-ray diffraction analysis. The oxide scale formed over Stellite 12 consisted of CoO-, Co{sub 3}O{sub 4-} and Cr{sub 2}O{sub 3}-type oxides, while additionally CoMoO{sub 4}-type complex oxide was detected on Mo-modified hardfacing, more likely at the alloy–scale interface. On the basis of findings of isothermal oxidation tests, the formation mechanisms of this complex oxide imposing better wear resistance as reported in our previous studies were explained during high-temperature wear testing, i.e., dynamic oxidation conditions.

36 MATERIALS SCIENCE↗

Disorder-induced transition from grain boundary to bulk dominated ionic diffusion in pyrochlores

In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion, while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.

36 MATERIALS SCIENCE↗

Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis /metal-oxide/water interfaces

Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al 2 O 3 (1 –1 0 2) and α-Fe 2 O 3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO 3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (≥10 –5 M), more than 99% of these ions partitioned into the biofilms at S. oneidensis /α-Al 2 O 3 (1 –1 0 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Furthermore, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (≤10 –6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al 2 O 3 (1 –1 0 2) substantially (~52% to ~13% at 10 –7 M, and ~23% to ~5% at 10–6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al 2 O 3 (1 –1 0 2) surfaces (~15% to ~28% at 10 –7 M, and ~1% to ~7% at 10 –6 M) .The higher observed partitioning of Zn(II) (~28%) at the α-Al 2 O 3 (1 –1 0 2) surfaces compared to Pb(II) (~13%) in the mixed-metal-ion systems at the lowest concentration (10 –7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al 2 O 3 (1 –1 0 2) surfaces under our experimental conditions.

58 GEOSCIENCES↗

Exploring possible ferromagnetism of the LaAl O 3 / SrTi O 3 interface

We report on extensive investigations of magnetism at the n -type LaAl O 3 / SrTi O 3 interface performed by utilizing a spectrum of local and integrative analytical techniques: Scanning superconducting quantum interference device microscopy, polar Kerr magnetometry, ferromagnetic resonance, and magnetic torque magnetometry. The samples originated from the same wafers. For nominally fully oxidized samples, we find that the mere presence of the conducting interface does not induce magnetism to values exceeding already present magnetic signals originating from the substrates, irrespective of the measurement technique. With the controlled introduction of oxygen vacancies, however, the different analytical techniques with their inherently different sensitivities and potential interactions with possible magnetic moments in the samples yield different results concerning the existence of magnetism. These unexpected differences obtained with the various measurement techniques are a possible source of the disagreement in the literature about the existence of ferromagnetism at LaAl O 3 / SrTi O 3 interfaces.

36 MATERIALS SCIENCE↗

Perspective: Rapid synthesis of complex oxides by combinatorial molecular beam epitaxy

In this study, the molecular beam epitaxy(MBE) technique is well known for producing atomically smooth thin films as well as impeccable interfaces in multilayers of many different materials. In particular, molecular beam epitaxy is well suited to the growth of complex oxides, materials that hold promise for many applications. Rapid synthesis and high throughput characterization techniques are needed to tap into that potential most efficiently. We discuss our approach to doing that, leaving behind the traditional one-growth-one-compound scheme and instead implementing combinatorial oxide molecular beam epitaxy in a custom built system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probing Perovskite Interfaces and Superlattices with X-ray Photoemission Spectroscopy

Complex oxides exhibit an exceedingly wide range of electronic, magnetic and optical properties, giving these materials considerable potential for interesting basic science investigations, as well as possible utility in a range of technological applications. Complex oxides have been vigorously investigated as epitaxial films over the past two decades, in part because of the discovery of high-Tc superconductivity in cuprates . A second reason for this interest is the rich and varied property set, including colossal magnetoresistance , exhibited by the doped manganites, AExRE1-xMnO3, where AE and RE represent alkaline earth and rare earth metals, respectively. The observations of many interesting and often unexpected phenomena have captured the attention and imagination of a growing community of condensed matter scientists who wants to explore the fundamental physics of these materials, as well as novel technological concepts.

Environmental Molecular Sciences Laboratory↗

Electrically coupling complex oxides to semiconductors: A route to novel material functionalities

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. In this paper, we discuss how composition of the perovskite A- and B-site cations can be manipulated to control the physical and electronic structure of semiconductor—complex oxide heterostructures. Two prototypical heterostructures, Ba 1-x Sr x TiO 3 /Ge and SrZr x Ti 1-x O 3 /Ge, will be discussed. In the case of Ba 1-x Sr x TiO 3 /Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZr x Ti 1-x O 3 /Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Finally, analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e., band-gap engineering, provides a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.

36 MATERIALS SCIENCE↗

Valence-state reflectometry of complex oxide heterointerfaces

Emergent phenomena in transition-metal-oxide heterostructures such as interface superconductivity and magnetism have been attributed to electronic reconstruction, which, however, is difficult to detect and characterise. Here we overcome the associated difficulties to simultaneously address the electronic degrees of freedom and distinguish interface from bulk effects by implementing a novel approach to resonant X-ray reflectivity (RXR). Our RXR study of the chemical and valance profiles along the polar (001) direction of a LaCoO 3 film on NdGaO 3 reveals a pronounced valence-state reconstruction from Co 3+ in the bulk to Co 2+ at the surface, with an areal density close to 0.5 Co 2+ ions per unit cell. An identical film capped with polar (001) LaAlO 3 maintains the Co 3+ valence over its entire thickness. As a result, we interpret this as evidence for electronic reconstruction in the uncapped film, involving the transfer of 0.5e – per unit cell to the subsurface CoO 2 layer at its LaO-terminated polar surface.

36 MATERIALS SCIENCE↗

The Formation Mechanism of Fluorescent Metal Complexes at the Li x Ni 0.5 Mn 1.5 O 4-δ /Carbonate Ester Electrolyte Interface

Electrochemical oxidation of carbonate esters at the Li x Ni 0.5 Mn 1.5 O 4-δ /electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of Li x Ni 0.5 Mn 1.5 O 4-δ positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of Mn II/III and Ni II complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at Li x Ni 0.5 Mn 1.5 O 4-δ , form a surface film that partially dissolves in the electrolyte. The dissolved Mn III complexes are reduced to their Mn II analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li + transport kinetics in Li-ion batteries.

energy storage (including batteries and capacitors↗

Single crystal functional oxides on silicon

Single-crystalline thin films of complex oxides show a rich variety of functional properties such as ferroelectricity, piezoelectricity, ferro and antiferromagnetism and so on that have the potential for completely new electronic applications. Direct synthesis of such oxides on silicon remains challenging because of the fundamental crystal chemistry and mechanical incompatibility of dissimilar interfaces. Here we report integration of thin (down to one unit cell) single crystalline, complex oxide films onto silicon substrates, by epitaxial transfer at room temperature. In a field-effect transistor using a transferred lead zirconate titanate layer as the gate insulator, we demonstrate direct reversible control of the semiconductor channel charge with polarization state. These results represent the realization of long pursued but yet to be demonstrated single-crystal functional oxides on-demand on silicon.

36 MATERIALS SCIENCE↗

NiO/Fe(001): Magnetic anisotropy, exchange bias, and interface structure

The magnetic and structural properties of NiO/Fe epitaxial bilayers grown on MgO(001) were studied using magnetooptic Kerr effect (MOKE) and conversion electron Moessbauer spectroscopy (CEMS). The bilayers were prepared under ultra high vacuum conditions using molecular beam epitaxy with oblique deposition. Two systems were compared: one showing the exchange bias (100ML-NiO/24ML-Fe), ML stands for a monolayer, and another where the exchange bias was not observed (50ML-NiO/50ML-Fe). For both, the magnetic anisotropy was found to be complex, yet dominated by the growth-induced uniaxial anisotropy. The training effect was observed for the 100ML-NiO/24ML-Fe system and quantitatively described using the spin glass model. The composition and magnetic state of the interfacial Fe layers were studied using {sup 57}Fe-CEMS. An iron oxide phase (Fe{sup 3+}{sub 4}Fe{sup 2+}{sub 1}O{sub 7}), as thick as 31 A, was identified at the NiO/Fe interface in the as-deposited samples. The ferrimagnetic nature of the interfacial iron oxide film explains the complex magnetic anisotropy observed in the samples.

36 MATERIALS SCIENCE↗

Epitaxial growth of (111)-oriented LaAlO{sub 3}/LaNiO{sub 3} ultra-thin superlattices

The epitaxial stabilization of a single layer or superlattice structures composed of complex oxide materials on polar (111) surfaces is severely burdened by the reconstructions at the interface that commonly arise to neutralize the polarity. We report on the synthesis of high quality LaNiO{sub 3}/mLaAlO{sub 3} pseudo cubic (111) superlattices on polar (111)-oriented LaAlO{sub 3}, the proposed complex oxide candidate for a topological insulating behavior. Comprehensive X-Ray diffraction measurements, reflection high energy electron diffraction, and element specific resonant X-ray absorption spectroscopy affirm their high structural and chemical quality. The study offers an opportunity to fabricate interesting interface and topology controlled (111)-oriented superlattices based on ortho-nickelates.

36 MATERIALS SCIENCE↗

The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores

Pyrochlores, a class of complex oxides with formula A 2 B 2 O 7 , are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound. We also find that pyrochlore/pyrochlore bicrystals A 2 B 2 O 7 /A 2 'B 2 'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement Error in Atomic-Scale Scanning Transmission Electron Microscopy—Energy-Dispersive X-Ray Spectroscopy (STEM-EDS) Mapping of a Model Oxide Interface

Abstract With the development of affordable aberration correctors, analytical scanning transmission electron microscopy (STEM) studies of complex interfaces can now be conducted at high spatial resolution at laboratories worldwide. Energy-dispersive X-ray spectroscopy (EDS) in particular has grown in popularity, as it enables elemental mapping over a wide range of ionization energies. However, the interpretation of atomically resolved data is greatly complicated by beam–sample interactions that are often overlooked by novice users. Here we describe the practical factors—namely, sample thickness and the choice of ionization edge—that affect the quantification of a model perovskite oxide interface. Our measurements of the same sample, in regions of different thickness, indicate that interface profiles can vary by as much as 2–5 unit cells, depending on the spectral feature. This finding is supported by multislice simulations, which reveal that on-axis maps of even perfectly abrupt interfaces exhibit significant delocalization. Quantification of thicker samples is further complicated by channeling to heavier sites across the interface, as well as an increased signal background. We show that extreme care must be taken to prepare samples to minimize channeling effects and argue that it may not be possible to extract atomically resolved information from many chemical maps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ , in vivo , and in operando imaging and spectroscopy of liquids using microfluidics in vacuum

This review offers a succinct overview of the development of a vacuum-compatible microfluidic reactor system for analysis at the liquid vacuum interface (SALVI), and its diverse applications in in situ, in vivo, and in operando imaging of liquid surfaces as well as the air-liquid (a-l), liquid-liquid (l-l), and solid-liquid (s-l) interfaces in the past decade. SALVI is one of the first microfluidics-based reactors that has enabled direct analysis of volatile liquids in vacuum surface tools such as scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Its integration into ambient and vacuum spectroscopy and microscopy is illustrated. Several applications are highlighted including (1) imaging nanoparticles in liquid using in situ SEM; (2) mapping the evolving l-l interface using in situ x-ray absorption spectroscopy and ToF-SIMS; (3) following complex a-l interfacial oxidation reaction products using in situ ToF-SIMS; (4) capturing biological interfaces of cells and microbes via in vivo multimodal and correlative imaging; and (5) monitoring the dynamic solid electrode and liquid electrolyte interface using in operando molecular imaging. Finally, outlook and recommendations are presented. Besides showing the holistic information volume obtained by real-time multiplexed imaging, this review intends to convey the importance of tool development in revolutionizing surface and interface analysis using vacuum platforms previously limited to solid surfaces. Microfluidics is manifested to be not limited to ambient conditions in many examples in this review. Moreover, fundamental interfacial phenomena underpinning mass and charge transfer can now be pursued in real time via innovated chemical imaging and spectroscopy.

42 ENGINEERING↗

Electron Trapping and Ion Leaching at the Li-Modified Quartz–Water Interface

Electrons and ions at metal oxide-water interfaces have a critical role in many phenomena and applications, thus making their properties of considerable interest. We here investigate the behavior of a lithium impurity at the water interface with Li-doped SiO 2 using hybrid density functional based ab initio molecular dynamics simulations. We find that the excess electron donated by the lithium dopant localizes on a surface silicon atom and is partially solvated at the aqueous interface. While the position of the excess electron does not change during our ~60 ps simulation, the lithium cation diffuses from its initial position in the SiO 2 subsurface toward the interface and eventually leaches out of the oxide surface and becomes solvated by four water molecules, forming an aqueous Li+- electron complex at the interface. The degree of interaction between the localized electron and the lithium ion controls not only the energy level of the excess electron but also the extent of structural distortion and hydrogen-bonding at the interface. The results of our study can be relevant for understanding the initial stages of glass corrosion, where alkali ions are leached from the surface region by interactions with water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗