Local Electronic Structure and Dynamics of Muon-Polaron Complexes in Fe_{2}O_{3}.

We perform detailed muon spin rotation (µSR) measurements in the classic antiferromagnet Fe_{2}O_{3} and explain the spectra by considering dynamic population and dissociation of charge-neutral muon-polaron complexes. We show that charge-neutral muon states in Fe_{2}O_{3}, despite lacking the signatures typical of charge-neutral muonium centers in nonmagnetic materials, have a significant impact on the measured µSR frequencies and relaxation rates. Our identification of such polaronic muon centers in Fe_{2}O_{3} suggests that isolated hydrogen (H) impurities form analogous complexes, and that H interstitials may be a source of charge carrier density in Fe_{2}O_{3}.

Erratum: Dynamic Multiferroicity of a Ferroelectric Quantum Critical Point [Phys. Rev. Lett. 122, 057208 (2019)].

This corrects the article DOI: 10.1103/PhysRevLett.122.057208.

Unconventional Spin Relaxation Involving Localized Vibrational Modes in Ho Single-Atom Magnets.

We investigate the spin relaxation of Ho single atom magnets on MgO/Ag(100) as a function of temperature and magnetic field. We find that the spin relaxation is thermally activated at low field, while it remains larger than 1000 s up to 30 K and 8 T. This behavior contrasts with that of single molecule magnets and bulk paramagnetic impurities, which relax faster at high field. Combining our results with density functional theory, we rationalize this unconventional behavior by showing that local vibrations activate a two-phonon Raman process with a relaxation rate that peaks near zero field and is suppressed at high field. Our work shows the importance of these excitations in the relaxation of axially coordinated magnetic atoms.

The ultrathin limit of improper ferroelectricity.

The secondary nature of polarization in improper ferroelectrics promotes functional properties beyond those of conventional ferroelectrics. In technologically relevant ultrathin films, however, the improper ferroelectric behavior remains largely unexplored. Here, we probe the emergence of the coupled improper polarization and primary distortive order parameter in thin films of hexagonal YMnO3. Combining state-of-the-art in situ characterization techniques separately addressing the improper ferroelectric state and its distortive driving force, we reveal a pronounced thickness dependence of the improper polarization, which we show to originate from the strong modification of the primary order at epitaxial interfaces. Nanoscale confinement effects on the primary order parameter reduce the temperature of the phase transition, which we exploit to visualize its order-disorder character with atomic resolution. Our results advance the understanding of the evolution of improper ferroelectricity within the confinement of ultrathin films, which is essential for their successful implementation in nanoscale applications.

Depolarizing-Field Effects in Epitaxial Capacitor Heterostructures.

We identify a transient enhancement of the depolarizing field, leading to an unexpected quench of net polarization, during the growth of a prototypical metal-ferroelectric-metal epitaxial system made of BaTiO_{3} and SrRuO_{3}. Reduced conductivity and, hence, charge screening efficiency in the early growth stage of the SrRuO_{3} top electrode promotes a breakdown of ferroelectric BaTiO_{3} into domains. We demonstrate how a thermal annealing procedure can recover the single-domain state. By tracking the polarization state in situ, using optical second harmonic generation, we bring new understanding to interface-related electrostatic effects in ferroelectric capacitors.

Dynamic Multiferroicity of a Ferroelectric Quantum Critical Point.

Quantum matter hosts a large variety of phases, some coexisting, some competing; when two or more orders occur together, they are often entangled and cannot be separated. Dynamical multiferroicity, where fluctuations of electric dipoles lead to magnetization, is an example where the two orders are impossible to disentangle. Here we demonstrate an elevated magnetic response of a ferroelectric near the ferroelectric quantum critical point (FE QCP), since magnetic fluctuations are entangled with ferroelectric fluctuations. We thus suggest that any ferroelectric quantum critical point is an inherent multiferroic quantum critical point. We calculate the magnetic susceptibility near the FE QCP and find a region with enhanced magnetic signatures near the FE QCP and controlled by the tuning parameter of the ferroelectric phase. The effect is small but observable-we propose quantum paraelectric strontium titanate as a candidate material where the magnitude of the induced magnetic moments can be ∼5×10^{-7} µ_{B} per unit cell near the FE QCP.

Advances in magnetoelectric multiferroics.

The manipulation of magnetic properties by an electric field in magnetoelectric multiferroic materials has driven significant research activity, with the goal of realizing their transformative technological potential. Here, we review progress in the fundamental understanding and design of new multiferroic materials, advances in characterization and modelling tools to describe them, and the exploration of devices and applications. Focusing on the translation of the many scientific breakthroughs into technological innovations, we identify the key open questions in the field where targeted research activities could have maximum impact in transitioning scientific discoveries into real applications.

Evidence of Incoherent Carriers Associated with Resonant Impurity Levels and Their Influence on Superconductivity in the Anomalous Superconductor Pb_{1-x}Tl_{x}Te.

We present a combined experimental and theoretical study of the evolution of the Fermi surface of the anomalous superconductor Pb_{1-x}Tl_{x}Te as a function of thallium concentration, drawing on a combination of magnetotransport measurements (Shubnikov-de Haas oscillations and the Hall coefficient), angle resolved photoemission spectroscopy, and density functional theory calculations of the electronic structure. Our results indicate that for Tl concentrations beyond a critical value, the Fermi energy coincides with resonant impurity states in Pb_{1-x}Tl_{x}Te, and we rule out the presence of an additional valence band maximum at the Fermi energy. A comparison to nonsuperconducting Pb_{1-x}Na_{x}Te implies that the presence of these impurity states at the Fermi energy provides the enhanced pairing interaction and thus also the anomalously high temperature superconductivity in this material.

Functional electronic inversion layers at ferroelectric domain walls.

Ferroelectric domain walls hold great promise as functional two-dimensional materials because of their unusual electronic properties. Particularly intriguing are the so-called charged walls where a polarity mismatch causes local, diverging electrostatic potentials requiring charge compensation and hence a change in the electronic structure. These walls can exhibit significantly enhanced conductivity and serve as a circuit path. The development of all-domain-wall devices, however, also requires walls with controllable output to emulate electronic nano-components such as diodes and transistors. Here we demonstrate electric-field control of the electronic transport at ferroelectric domain walls. We reversibly switch from resistive to conductive behaviour at charged walls in semiconducting ErMnO3. We relate the transition to the formation-and eventual activation-of an inversion layer that acts as the channel for the charge transport. The findings provide new insight into the domain-wall physics in ferroelectrics and foreshadow the possibility to design elementary digital devices for all-domain-wall circuitry.

Ultrafast Structure Switching through Nonlinear Phononics.

We describe a mechanism by which nonlinear phononics allows ultrafast coherent and directional control of transient structural distortions. With ErFeO_{3} as a model system, we use density functional theory to calculate the structural properties as input into an anharmonic phonon model that describes the response of the system to a pulsed optical excitation. We find that the trilinear coupling of two orthogonal infrared-active phonons to a Raman-active phonon causes a transient distortion of the lattice. In contrast to the quadratic-linear coupling that has been previously explored, the direction of the distortion is determined by the polarization of the exciting light, introducing a novel mechanism for nonlinear phononic switching. Since the occurrence of the coupling is determined by the symmetry of the system we propose that it is a universal feature of orthorhombic and tetragonal perovskites.

Separating different contributions to the crystal-field parameters using Wannier functions.

We discuss the calculation of crystal-field splittings using Wannier functions and show how contributions to the crystal-field splitting that are due to hybridization with different ligand states can be separated from the bare Coulomb contribution by constructing sets of Wannier functions incorporating different levels of hybridization. We demonstrate this method using SrVO3 as a generic example of a transition metal oxide. We then calculate trends in the crystal-field splitting for two series of hypothetical tetragonally distorted perovskite oxides and discuss the relation between the calculated 'electrostatic' contribution to the crystal field and the simple point charge model. Finally, we apply our method to the charge disproportionated 5d electron system CsAuCl3. The proposed procedure elucidates the way in which the negative charge transfer energy in this material leads to a reversal of the p-d ligand contribution to the crystal-field splitting such that the eg states of the nominally Au(3+) cation are energetically lower than the corresponding t2g states.

Large resistivity modulation in mixed-phase metallic systems.

In numerous systems, giant physical responses have been discovered when two phases coexist; for example, near a phase transition. An intermetallic FeRh system undergoes a first-order antiferromagnetic to ferromagnetic transition above room temperature and shows two-phase coexistence near the transition. Here we have investigated the effect of an electric field to FeRh/PMN-PT heterostructures and report 8% change in the electrical resistivity of FeRh films. Such a 'giant' electroresistance (GER) response is striking in metallic systems, in which external electric fields are screened, and thus only weakly influence the carrier concentrations and mobilities. We show that our FeRh films comprise coexisting ferromagnetic and antiferromagnetic phases with different resistivities and the origin of the GER effect is the strain-mediated change in their relative proportions. The observed behaviour is reminiscent of colossal magnetoresistance in perovskite manganites and illustrates the role of mixed-phase coexistence in achieving large changes in physical properties with low-energy external perturbation.

Nonlinear lattice dynamics as a basis for enhanced superconductivity in YBa2Cu3O6.5.

Terahertz-frequency optical pulses can resonantly drive selected vibrational modes in solids and deform their crystal structures. In complex oxides, this method has been used to melt electronic order, drive insulator-to-metal transitions and induce superconductivity. Strikingly, coherent interlayer transport strongly reminiscent of superconductivity can be transiently induced up to room temperature (300 kelvin) in YBa2Cu3O6+x (refs 9, 10). Here we report the crystal structure of this exotic non-equilibrium state, determined by femtosecond X-ray diffraction and ab initio density functional theory calculations. We find that nonlinear lattice excitation in normal-state YBa2Cu3O6+x at above the transition temperature of 52 kelvin causes a simultaneous increase and decrease in the Cu-O2 intra-bilayer and, respectively, inter-bilayer distances, accompanied by anisotropic changes in the in-plane O-Cu-O bond buckling. Density functional theory calculations indicate that these motions cause drastic changes in the electronic structure. Among these, the enhancement in the character of the in-plane electronic structure is likely to favour superconductivity.

Linear magnetoelectric effect by orbital magnetism.

We use symmetry analysis and first-principles calculations to show that the linear magnetoelectric effect can originate from the response of orbital magnetic moments to the polar distortions induced by an applied electric field. Using LiFePO(4) as a model compound we show that spin-orbit coupling partially lifts the quenching of the 3d orbitals and causes small orbital magnetic moments (µ((L)) ≈ 0.3 µ(B)) parallel to the spins of the Fe(2+) ions. An applied electric field E modifies the size of these orbital magnetic moments inducing a net magnetization linear in E.

Anisotropic conductance at improper ferroelectric domain walls.

Transition metal oxides hold great potential for the development of new device paradigms because of the field-tunable functionalities driven by their strong electronic correlations, combined with their earth abundance and environmental friendliness. Recently, the interfaces between transition-metal oxides have revealed striking phenomena, such as insulator-metal transitions, magnetism, magnetoresistance and superconductivity. Such oxide interfaces are usually produced by sophisticated layer-by-layer growth techniques, which can yield high-quality, epitaxial interfaces with almost monolayer control of atomic positions. The resulting interfaces, however, are fixed in space by the arrangement of the atoms. Here we demonstrate a route to overcoming this geometric limitation. We show that the electrical conductance at the interfacial ferroelectric domain walls in hexagonal ErMnO(3) is a continuous function of the domain wall orientation, with a range of an order of magnitude. We explain the observed behaviour using first-principles density functional and phenomenological theories, and relate it to the unexpected stability of head-to-head and tail-to-tail domain walls in ErMnO(3) and related hexagonal manganites. As the domain wall orientation in ferroelectrics is tunable using modest external electric fields, our finding opens a degree of freedom that is not accessible to spatially fixed interfaces.

A multiferroic material to search for the permanent electric dipole moment of the electron.

We describe the first-principles design and subsequent synthesis of a new material with the specific functionalities required for a solid-state-based search for the permanent electric dipole moment of the electron. We show computationally that perovskite-structure europium barium titanate should exhibit the required large and pressure-dependent ferroelectric polarization, local magnetic moments and absence of magnetic ordering at liquid-helium temperature. Subsequent synthesis and characterization of Eu(0.5)Ba(0.5)TiO(3) ceramics confirm the predicted desirable properties.

A strain-driven morphotropic phase boundary in BiFeO3.

Piezoelectric materials, which convert mechanical to electrical energy and vice versa, are typically characterized by the intimate coexistence of two phases across a morphotropic phase boundary. Electrically switching one to the other yields large electromechanical coupling coefficients. Driven by global environmental concerns, there is currently a strong push to discover practical lead-free piezoelectrics for device engineering. Using a combination of epitaxial growth techniques in conjunction with theoretical approaches, we show the formation of a morphotropic phase boundary through epitaxial constraint in lead-free piezoelectric bismuth ferrite (BiFeO3) films. Electric field-dependent studies show that a tetragonal-like phase can be reversibly converted into a rhombohedral-like phase, accompanied by measurable displacements of the surface, making this new lead-free system of interest for probe-based data storage and actuator applications.

Conduction at domain walls in oxide multiferroics.

Domain walls may play an important role in future electronic devices, given their small size as well as the fact that their location can be controlled. Here, we report the observation of room-temperature electronic conductivity at ferroelectric domain walls in the insulating multiferroic BiFeO(3). The origin and nature of the observed conductivity are probed using a combination of conductive atomic force microscopy, high-resolution transmission electron microscopy and first-principles density functional computations. Our analyses indicate that the conductivity correlates with structurally driven changes in both the electrostatic potential and the local electronic structure, which shows a decrease in the bandgap at the domain wall. Additionally, we demonstrate the potential for device applications of such conducting nanoscale features.

Ferrodistortive instability at the (001) surface of half-metallic manganites.

We present the structure of the fully relaxed (001) surface of the half-metallic manganite La0.7Sr0.3MnO3, calculated using density functional theory. Two relevant ferroelastic order parameters are identified and characterized. The known tilting of the oxygen octahedra, which is present in the bulk phase, decreases towards the surface. A ferrodistortive Mn off-centering, triggered by the surface and not reported before, decays monotonically into the bulk. This distortion affects neither the half-metallicity nor the zero-temperature magnetization, but does change the effective spin-spin interactions, and thus the temperature dependence of the magnetic properties.

Electrical control of antiferromagnetic domains in multiferroic BiFeO3 films at room temperature.

Multiferroic materials, which offer the possibility of manipulating the magnetic state by an electric field or vice versa, are of great current interest. In this work, we demonstrate the first observation of electrical control of antiferromagnetic domain structure in a single-phase multiferroic material at room temperature. High-resolution images of both antiferromagnetic and ferroelectric domain structures of (001)-oriented multiferroic BiFeO3 films revealed a clear domain correlation, indicating a strong coupling between the two types of order. The ferroelectric structure was measured using piezo force microscopy, whereas X-ray photoemission electron microscopy as well as its temperature dependence was used to detect the antiferromagnetic configuration. Antiferromagnetic domain switching induced by ferroelectric polarization switching was observed, in agreement with theoretical predictions.