Reversal of the magnetoelectric effect at a ferromagnetic metal/ferroelectric interface induced by metal oxidation

Multiferroic materials composed of ferromagnetic and ferroelectric components are interesting for technological applications due to sizable magnetoelectric coupling allowing the control of magnetic properties by electric fields. Due to being compatible with the silicon-based technology, HfO2-based ferroelectrics could serve as a promising component in the composite multiferroics. Recently, a strong charge-mediated magnetoelectric coupling has been predicted for a Ni/HfO2 multiferroic heterostructure. Here, using density functional theory calculations, we systematically study the effects of the interfacial oxygen stoichiometry relevant to experiments on the magnetoelectric effect at the Ni/HfO2 interface. We demonstrate that the magnetoelectric effect is very sensitive to the interface stoichiometry and is reversed if an oxidized Ni monolayer is formed at the interface. The reversal of the magnetoelectric effect is driven by a strong Ni−O bonding producing exchange-split polarization-sensitive antibonding states at the Fermi energy. We argue that the predicted reversal of the magnetoelectric effect is typical for other 3d ferromagnetic metals, such as Co and Fe, where the metal-oxide antibonding states have an opposite spin polarization compared to that in the pristine ferromagnetic metals. Our results provide an important insight into the mechanism of the interfacial magnetoelectric coupling, which is essential for the physics and application of multiferroic heterostructures.

Perspectives on Pyrochlores, Defect Fluorites, and Related Compounds: Building Blocks for Chemical Diversity and Functionality

In this article we provide some perspectives on a range of pyrochlore and defect fluorite type compounds with nominal A2B2O7, A2BO5, ABC2O7, and other stoichiometries. Typically, the phase transformations and stability fields in these systems are mapped as a function of the ionic radii of the A and B-site cations, e.g., the A/B cation radius ratio (rA/rB). This provides a useful guide to compatible structures and compositions for the development of advanced materials. Pyrochlore commonly transforms to a defect fluorite structure at high temperature in many systems; however, it is not uncommon to observe defect fluorite as the initial metastable phase at low temperature. The patterns of order-disorder observed in these materials are primarily due to the energetics of layer stacking, the defect formation and migration energies of cations and anions, or modulations of the parent cubic structure in 3 + n dimensional space. The first lead to predominantly non-cubic derivatives of the parent defect fluorite structure (e.g., zirconolite polytypes), the second control the order-disorder processes, and the latter lead to a variety of subtle additional scattering features within the cubic parent structure. Although the energetics of cation disorder and anion-vacancy disorder have become more accessible via atomistic approaches (e.g., MD and DFT), we continue to find interesting physical-chemical problems in these materials. For example, although there are significant differences in composition (Tb/Zr ratio and O content) between Tb2Zr2O7 and Tb2ZrO5, both of which are defect fluorites, we note that the modulations found in these two compounds by electron scattering are virtually identical with regard to the direction and magnitude of displacement from the normal Bragg diffracted beams. This suggests that neither the A/B cation ratio nor the oxygen stoichiometry have a significant effect on the modulations. The general observations on the systems of compounds noted in this paper rest primarily in the context of industrial materials for nuclear waste disposal, potential applications in inert matrix fuel designs, and other important technological applications such as ionic conductivity, electrical conductivity, and magnetism. Scientific advances in these areas have been underpinned by recent advances in ion irradiation, synchrotron X-ray, neutron scattering, and modelling and simulation capabilities. Furthermore, there has been some renewed interest in natural samples, e.g., Th-U zirconolite and pyrochlore as analogues for potential host phases in nuclear waste forms. In particular, the natural pyrochlores have provided additional details with regard to radiation damage ingrowth, percolation transitions, and the relationships between accumulated dose and physical properties including hardness, elastic modulus. Specific details of the thermal annealing of these samples have also been elucidated in considerable detail.

Synthesis and Structure of Oxygen Deficient Lead-Technetium Pyrochlore, the First Example of a Valence V Technetium Oxide

The structure of lead-technetium pyrochlore has been refined in space group Fd3¯m with a = 10.36584(2) Å using a combination of synchrotron X-ray and neutron powder diffraction data and confirmed via Electron Diffraction. The oxide is found to be oxygen deficient with a stoichiometry of Pb2Tc2O7-d. Displacive disorder of the Pb cations is evident from the refinements, as has been observed in Bi2Tc2O7-d. X-ray absorption spectroscopic measurements at the Tc K-edge demonstrate the valence of the Tc is greater than 4.0 as anticipated from the refined oxygen stoichiometry. Raman spectroscopy confirms the presence of disorder leading us to conclude that this pyrochlore is the first example of a valence V technetium oxide.

Tuning the Electrical Properties of NiO Thin Films by Stoichiometry and Microstructure

Here, the electrical properties of NiO thin films grown on glass and Al2O3 (0001) substrates have been investigated. It was found that the resistivity of NiO thin films strongly depends on oxygen stoichiometry. Nearly perfect stoichiometry yields extremely high resistivity. In contrast, off-stoichiometric thin films possess much lower resistivity, especially for oxygen-rich composition. A side-by-side comparison of energy loss near the edge structure spectra of Ni L3 edges between our NiO thin films and other theoretical spectra rules out the existence of Ni3+ in NiO thin films, which contradicts the traditional hypothesis. In addition, epitaxial NiO thin films grown on Al2O3 (0001) single crystal substrates exhibit much higher resistivity than those on glass substrates, even if they are deposited simultaneously. This feature indicates the microstructure dependence of electrical properties.

Thermodynamic Stability and Microscopic Behavior of BaxSr1-xCo1-yFeyO3-δ Perovskites

The mixed conducting perovskite-type oxides BaxSr1-xCo1-yFeyO3-δ (BSCF) are intensively studied as potential high-performance solid oxide fuel cell cathode materials. The effect of different compositional variables and oxygen stoichiometry on the structure and thermodynamic stability of the BaxSr1-xCo1-yFeyO3-δ (x = 0.2, 0.4, 0.5, 0.6, 0.8; y = 0.2, 0.4, 0.6, 0.8, 1) perovskite-type compositions were investigated by solid electrolyte electrochemical cells method and scanning electron microscopy (SEM). The thermodynamic quantities represented by the partial molar free energies, enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressures of oxygen were obtained in the temperature range of 823–1273 K. The in situ change of oxygen stoichiometry and the determination of thermodynamic parameters of the new oxygen-deficient BSCF compositions were studied via coulometric titration technique coupled with electromotive force (EMF) measurements. The effect of A- and B-site dopants concentration correlated to the variation of oxygen stoichiometry on the thermodynamic stability and morphology of the BSCF samples was evidenced.