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Complex oxides: Intricate disorder

In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore, how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations 1 . Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder 2, 3 . These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought 4 .

36 MATERIALS SCIENCE↗

Impact of electric-field dependent dielectric constants on two-dimensional electron gases in complex oxides

High-density two-dimensional electron gas (2DEG) can be formed at complex oxide interfaces such as SrTiO{sub 3}/GdTiO{sub 3} and SrTiO{sub 3}/LaAlO{sub 3}. The electric field in the vicinity of the interface depends on the dielectric properties of the material as well as on the electron distribution. However, it is known that electric fields can strongly modify the dielectric constant of SrTiO{sub 3} as well as other complex oxides. Solving the electrostatic problem thus requires a self-consistent approach in which the dielectric constant varies according to the local magnitude of the field. We have implemented the field dependence of the dielectric constant in a Schrödinger-Poisson solver in order to study its effect on the electron distribution in a 2DEG. Using the SrTiO{sub 3}/GdTiO{sub 3} interface as an example, we demonstrate that including the field dependence results in the 2DEG being confined closer to the interface compared to assuming a single field-independent value for the dielectric constant. Our conclusions also apply to SrTiO{sub 3}/LaAlO{sub 3} as well as other similar interfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Permittivity of complex oxide crystals with allowance for spatial dispersion

The temporal and spatial dispersions of the permittivity of complex oxide crystals, which have numerous branches of dipole active oscillations, is considered. Formulas for calculating the susceptibility spectra of complex oxides in the terahertz region with allowance for both types of dispersion are obtained in the resonance approximation of photon-phonon interaction using quantum Green's functions. The calculation results are used to discuss the well-known experimental data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Complex oxides useful for thermoelectric energy conversion

The invention provides for a thermoelectric system comprising a substrate comprising a first complex oxide, wherein the substrate is optionally embedded with a second complex oxide. The thermoelectric system can be used for thermoelectric power generation or thermoelectric cooling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron molecular beam epitaxy: Layer-by-layer growth of complex oxides via pulsed electron-beam deposition

Complex oxide epitaxial film growth is a rich and exciting field, owing to the wide variety of physical properties present in oxides. These properties include ferroelectricity, ferromagnetism, spin-polarization, and a variety of other correlated phenomena. Traditionally, high quality epitaxial oxide films have been grown via oxide molecular beam epitaxy or pulsed laser deposition. Here, we present the growth of high quality epitaxial films using an alternative approach, the pulsed electron-beam deposition technique. We demonstrate all three epitaxial growth modes in different oxide systems: Frank-van der Merwe (layer-by-layer); Stranski-Krastanov (layer-then-island); and Volmer-Weber (island). Analysis of film quality and morphology is presented and techniques to optimize the morphology of films are discussed.

36 MATERIALS SCIENCE↗

Visualizing quantum phenomena at complex oxide interfaces: An atomic view from scanning transmission electron microscopy

Complex oxide interfaces have been one of the central focuses in condensed matter physics and material science. Over the past decade, aberration corrected scanning transmission electron microscopy and spectroscopy has proven to be invaluable to visualize and understand the emerging quantum phenomena at an interface. In this paper, we briefly review some recent progress in the utilization of electron microscopy to probe interfaces. Furthermore, we discuss several important challenges for electron microscopy to advance our understanding on interface phenomena, from the perspective of variable temperature, magnetism, electron energy loss spectroscopy analysis, electronic symmetry, and defects probing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ferroelectric Domain Wall Motion in Freestanding Single-Crystal Complex Oxide Thin Film

Ferroelectric domain walls in single-crystal complex oxide thin films are found to be orders of magnitude slower when the interfacial bonds with the heteroepitaxial substrate are broken to create a freestanding film. This drastic change in domain wall kinetics does not originate from the alteration of epitaxial strain; rather, it is correlated with the structural ripples at mesoscopic length scale and associated flexoelectric effects induced in the freestanding films. In contrast, the effects of the bond-breaking on the local static ferroelectric properties of both top and bottom layers of the freestanding films, such as domain wall width and spontaneous polarization, are modest and governed by the change in epitaxy-induced compressive strain.

36 MATERIALS SCIENCE↗

Effects of the Inverse Trans-Influence in a Berkelium(III) Phosphine Oxide Complex

An example of a 249 Bk 3+ phosphine oxide complex has been prepared to examine and quantify the effects of the inverse trans-influence (ITI) on a late actinide complex. This has been accomplished through a comparison of cis and trans Bk-ligand bonds in the meridional berkelium(III) complex, BkBr 3 (OPCy 3 ) 3 (OPCy 3 = tricyclohexylphosphine oxide). A detailed bond metric analysis was completed that includes the shortest published distance for a Bk 3+ −O bond, attributed to the smaller coordination number of Bk 3+ of six in mer-BkBr 3 (OPCy 3 ) 3 . ITI calculations of the trans Bk 3+ −O bond provide an ITI value (98.5(2)%) comparable to that of mer-AmBr 3 (OPCy 3 ) 3 (98.2(2)%) and indicate a small 5f orbital contribution to bonding. This effect is discussed in the context of the isomorphous lanthanide(III) series where the ITI is calculated to be higher for mer-BkBr 3 (OPCy 3 ) 3 than in most Ln 3+ analogues.

Actinides↗

Electrical characterization of freestanding complex oxide ferroelectrics: Artifacts and experimental precautions

Recently, freestanding complex oxide ferroelectric materials have gained attention due to their tremendous potential in electronic and mechanical engineering applications. Whether these materials in a freestanding form exhibit intrinsically different behavior than in a strongly bonded as-grown state is a topic of ongoing exploration. Several factors such as circuit configuration, substrates, and electronic measurement conditions can affect probing the intrinsic properties of these materials and complicate the conclusive outcome of such exploration. The importance of maintaining the same experimental conditions for a comparative study of these materials in as-grown and freestanding states is discussed here

36 MATERIALS SCIENCE↗

Alleviating polarity-conflict at the heterointerfaces of KTaO{sub 3}/GdScO{sub 3} polar complex-oxides

We have synthesized and investigated the heterointerfaces of KTaO{sub 3} (KTO) and GdScO{sub 3} (GSO), which are both polar complex-oxides along the pseudo-cubic [001] direction. Since their layers have the same, conflicting net charges at interfaces, i.e., KO(−1)/ScO{sub 2}(−1) or TaO{sub 2}(+1)/GdO(+1), forming the heterointerface of KTO/GSO should be forbidden due to strong Coulomb repulsion, the so-called polarity conflict. However, we have discovered that atomic reconstruction occurs at the heterointerfaces between KTO thin-films and GSO substrates, which effectively alleviates the polarity conflict without destroying the hetero-epitaxy. Our result demonstrates one of the important ways to create artificial heterostructures from polar complex-oxides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Tailoring Spin Textures in Complex Oxide Micromagnets

Engineered topological spin textures with submicron dimensions in magnetic materials have emerged in recent years as the building blocks for various spin-based memory devices. Examples of these magnetic configurations include magnetic skyrmions, vortices, and domain walls. Here in this paper, we show the ability to control and characterize the evolution of spin textures in complex oxide micromagnets as a function of temperature through the delicate balance of fundamental materials parameters, micromagnet geometries, and epitaxial strain. These results demonstrate that in order to fully describe the observed spin textures, it is necessary to account for the spatial variation of the magnetic parameters within the micromagnet. This study provides the framework to accurately characterize such structures, leading to efficient design of spin-based memory devices based on complex oxide thin films.

36 MATERIALS SCIENCE↗

In-situ observation of single-phase compositionally-complex oxide formation during high-pressure and high-temperature synthesis

Compositionally-complex oxides (CCOs) with equal or non-equal atomic ratios of multi-principal cations are single-phase solid solutions and possess unique structural characteristics and correlated possibilities for tailorable and exceptional functionalities. However, breakdown of single-phase structure and phase separation impair widespread adoption of CCOs under in-service environments. Here, in-situ phase transformation during high-pressure and high-temperature synthesis of an exemplary CCO (CeZrHf) 0.852 (YbY) 0.148 O 2-δ is for the first time clarified by using synchrotron X-ray energy dispersive diffraction. During synthesizing at ~4.5 GPa inside a large-volume press, ZrO 2 and HfO 2 gradually initiate lattice diffusion as monoclinic (022) and (220) peaks collapse and merge completely at 973 K; CeO 2 starts diffusing as the dramatic intensity change of cubic (220) peak above 1073 K, causing a metastable phase formation; single-phase solid solution ultimately forms at 1673 K. Importantly, the results revealed provide in-depth understanding of phase transformation dynamics and insights for novel design paradigm of CCOs.

36 MATERIALS SCIENCE↗

Direct observation of charge mediated lattice distortions in complex oxide solid solutions

Using aberration corrected scanning transmission electron microscopy combined with advanced imaging methods, we directly observe atom column specific, picometer-scale displacements induced by local chemistry in a complex oxide solid solution. Displacements predicted from density functional theory were found to correlate with the observed experimental trends. Further analysis of bonding and charge distribution was used to clarify the mechanisms responsible for the detected structural behavior. By extending the experimental electron microscopy measurements to previously inaccessible length scales, we identified correlated atomic displacements linked to bond differences within the complex oxide structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Speciation and diffusive dynamics in hydrated grain boundaries of complex oxide Gd2Ti2O7

Abstract Grain boundaries in polycrystalline materials significantly affect their properties, such as ionic transport, corrosion, and chemical durability. The pyrochlore compound (Gd 2 Ti 2 O 7 ) is employed as a model for complex oxides and is known for its diverse applications, including nuclear waste immobilization. Density functional theory-based first-principles molecular dynamics simulations were performed at different temperatures on the hydrated grain boundary system. The results show extensive transformations within the grain boundaries among hydrous water species (OH − , H 2 O, and H 3 O + ). The temperature dependence of self-diffusion coefficients follows Arrhenius behavior, with an activation energy of 35.9 kJ/mol for hydrogen and 46.3 kJ/mol for oxygen. The lifetime of OH − is about three to four times longer than that of H 2 O at temperatures from 800 to 2100 K, suggesting the greater stability of OH − over H 2 O, a unique characteristic of the grain boundaries. The estimated lifetime of the hydrous species decreases as the temperature increases, with an activation energy of 9.9 kJ/mol for OH − and 13.4 kJ/mol for H 2 O. While Gd 3 + is more mobile than Ti 4+ , both the Gd 3 + and Ti 4+ cations are orders of magnitude less mobile than the water species. The results suggest that water species are much more mobile within grain boundaries than in the bulk crystal and have the potential to penetrate deep into polycrystalline materials through grain boundaries, leading to grain boundary degradation and dissolution. The different mobilities of cations in complex oxides can lead to leaching of certain cations and incongruent dissolution during the chemical weathering of Earth and industrial materials.

B. Ghosh, Dipta↗

Interfacial Magnetism in Complex Oxide Heterostructures Probed by Neutrons and X-rays

Magnetic complex-oxide heterostructures are of keen interest because a wealth of phenomena at the interface of dissimilar materials can give rise to fundamentally new physics and potentially valuable functionalities. Altered magnetization, novel magnetic coupling and emergent interfacial magnetism at the epitaxial layered-oxide interfaces have all been intensively investigated, which shapes our understanding on how to utilize those materials, particularly for spintronics. Neutron and x-ray based techniques have played a decisive role in characterizing interfacial magnetic structures and clarifying the underlying physics in this rapidly developing field. Here we review some recent experimental results, with an emphasis on those studied via polarized neutron reflectometery and polarized x-ray absorption spectroscopy. We conclude with some perspectives.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Step-by-step growth of complex oxide microstructures

The synthesis of complex and hybrid oxide microstructures is of fundamental interest and practical applications. However, the design and synthesis of such structures is a challenging task. We developed a solution phase process to synthesize complex silica and silica titania hybrid microstructures by exploiting the emulsion droplet based shape control and step by step growth. The strategy is robust and can be extended to make complex hybrid structures made of two or more materials while each having its own shape.

36 MATERIALS SCIENCE↗

Magnetism of Complex Oxide Interfaces

This chapter reviews theoretical studies focused on interfaces or heterostructures of complex oxides such as perovskite transition-metal oxides (TMO). It describes examples of such theoretical studies of TMO interfaces employing a variety of methods. The chapter explains theoretical work at the interfaces of a ferroelectric and a magnetic manganite and provides rules to judge the type of coupling between the spins at opposite sides of the interfaces. It shows how the electric field of the ferroelectric component affects the electronic density of the other component, typically a metallic manganite, thus altering its transport properties and sometimes even inducing a phase transition. The chapter explores the puzzling exchange bias effect is addressed for the interfaces involving a ferromagnet on one side and a G-type antiferromagnetic state on the other. If the interfacial carrier density is modulated away from the region, the ferromagnetism and transport will become worse.

Okamoto, Satoshi↗