3D oxygen vacancy distribution and defect-property relations in an oxide heterostructure.

Oxide heterostructures exhibit a vast variety of unique physical properties. Examples are unconventional superconductivity in layered nickelates and topological polar order in (PbTiO3)n/(SrTiO3)n superlattices. Although it is clear that variations in oxygen content are crucial for the electronic correlation phenomena in oxides, it remains a major challenge to quantify their impact. Here, we measure the chemical composition in multiferroic (LuFeO3)9/(LuFe2O4)1 superlattices, mapping correlations between the distribution of oxygen vacancies and the electric and magnetic properties. Using atom probe tomography, we observe oxygen vacancies arranging in a layered three-dimensional structure with a local density on the order of 1014 cm-2, congruent with the formula-unit-thick ferrimagnetic LuFe2O4 layers. The vacancy order is promoted by the locally reduced formation energy and plays a key role in stabilizing the ferroelectric domains and ferrimagnetism in the LuFeO3 and LuFe2O4 layers, respectively. The results demonstrate pronounced interactions between oxygen vacancies and the multiferroic order in this system and establish an approach for quantifying the oxygen defects with atomic-scale precision in 3D, giving new opportunities for deterministic defect-enabled property control in oxide heterostructures.

Composite Spin Hall Conductivity from Non-Collinear Antiferromagnetic Order.

Non-collinear antiferromagnets (AFMs) are an exciting new platform for studying intrinsic spin Hall effects (SHEs), phenomena that arise from the materials' band structure, Berry phase curvature, and linear response to an external electric field. In contrast to conventional SHE materials, symmetry analysis of non-collinear antiferromagnets does not forbid non-zero longitudinal and out-of-plane spin currents with x ̂ , z ̂ $\hat{x},\hat{z}$ polarization and predicts an anisotropy with current orientation to the magnetic lattice. Here, multi-component out-of-plane spin Hall conductivities σ xz x , $\sigma _{{\rm{xz}}}^{\rm{x}},$ σ xz y , σ xz z $\sigma _{{\rm{xz}}}^{\rm{y}},\ \sigma _{{\rm{xz}}}^{\rm{z}}$ are reported in L12 -ordered antiferromagnetic PtMn3 thin films that are uniquely generated in the non-collinear state. The maximum spin torque efficiencies (ξ  = JS  /Je  ≈ 0.3) are significantly larger than in Pt (ξ  ≈  0.1). Additionally, the spin Hall conductivities in the non-collinear state exhibit the predicted orientation-dependent anisotropy, opening the possibility for new devices with selectable spin polarization. This work demonstrates symmetry control through the magnetic lattice as a pathway to tailored functionality in magnetoelectronic systems.

Limits to the strain engineering of layered square-planar nickelate thin films.

The layered square-planar nickelates, Ndn+1NinO2n+2, are an appealing system to tune the electronic properties of square-planar nickelates via dimensionality; indeed, superconductivity was recently observed in Nd6Ni5O12 thin films. Here, we investigate the role of epitaxial strain in the competing requirements for the synthesis of the n = 3 Ruddlesden-Popper compound, Nd4Ni3O10, and subsequent reduction to the square-planar phase, Nd4Ni3O8. We synthesize our highest quality Nd4Ni3O10 films under compressive strain on LaAlO3 (001), while Nd4Ni3O10 on NdGaO3 (110) exhibits tensile strain-induced rock salt faults but retains bulk-like transport properties. A high density of extended defects forms in Nd4Ni3O10 on SrTiO3 (001). Films reduced on LaAlO3 become insulating and form compressive strain-induced c-axis canting defects, while Nd4Ni3O8 films on NdGaO3 are metallic. This work provides a pathway to the synthesis of Ndn+1NinO2n+2 thin films and sets limits on the ability to strain engineer these compounds via epitaxy.

Liberating a hidden antiferroelectric phase with interfacial electrostatic engineering.

Antiferroelectric materials have seen a resurgence of interest because of proposed applications in a number of energy-efficient technologies. Unfortunately, relatively few families of antiferroelectric materials have been identified, precluding many proposed applications. Here, we propose a design strategy for the construction of antiferroelectric materials using interfacial electrostatic engineering. We begin with a ferroelectric material with one of the highest known bulk polarizations, BiFeO3. By confining thin layers of BiFeO3 in a dielectric matrix, we show that a metastable antiferroelectric structure can be induced. Application of an electric field reversibly switches between this new phase and a ferroelectric state. The use of electrostatic confinement provides an untapped pathway for the design of engineered antiferroelectric materials with large and potentially coupled responses.

Superconductivity in a quintuple-layer square-planar nickelate.

Since the discovery of high-temperature superconductivity in copper oxide materials1, there have been sustained efforts to both understand the origins of this phase and discover new cuprate-like superconducting materials2. One prime materials platform has been the rare-earth nickelates and, indeed, superconductivity was recently discovered in the doped compound Nd0.8Sr0.2NiO2 (ref. 3). Undoped NdNiO2 belongs to a series of layered square-planar nickelates with chemical formula Ndn+1NinO2n+2 and is known as the 'infinite-layer' (n = ∞) nickelate. Here we report the synthesis of the quintuple-layer (n = 5) member of this series, Nd6Ni5O12, in which optimal cuprate-like electron filling (d8.8) is achieved without chemical doping. We observe a superconducting transition beginning at ~13 K. Electronic structure calculations, in tandem with magnetoresistive and spectroscopic measurements, suggest that Nd6Ni5O12 interpolates between cuprate-like and infinite-layer nickelate-like behaviour. In engineering a distinct superconducting nickelate, we identify the square-planar nickelates as a new family of superconductors that can be tuned via both doping and dimensionality.

Dimensionality-Induced Change in Topological Order in Multiferroic Oxide Superlattices.

We construct ferroelectric (LuFeO_{3})_{m}/(LuFe_{2}O_{4}) superlattices with varying index m to study the effect of confinement on topological defects. We observe a thickness-dependent transition from neutral to charged domain walls and the emergence of fractional vortices. In thin LuFeO_{3} layers, the volume fraction of domain walls grows, lowering the symmetry from P6_{3}cm to P3c1 before reaching the nonpolar P6_{3}/mmc state, analogous to the group-subgroup sequence observed at the high-temperature ferroelectric to paraelectric transition. Our study shows how dimensional confinement stabilizes textures beyond those in bulk ferroelectric systems.

Topological Defects in Hexagonal Manganites: Inner Structure and Emergent Electrostatics.

Diverse topological defects arise in hexagonal manganites, such as ferroelectric vortices, as well as neutral and charged domain walls. The topological defects are intriguing because their low symmetry enables unusual couplings between structural, charge, and spin degrees of freedom, holding great potential for novel types of functional 2D and 1D systems. Despite the considerable advances in analyzing the different topological defects in hexagonal manganites, the understanding of their key intrinsic properties is still rather limited and disconnected. In particular, a rapidly increasing number of structural variants is reported without clarifying their relation, leading to a zoo of seemingly unrelated topological textures. Here, we combine picometer-precise scanning-transmission-electron microscopy with Landau theory modeling to clarify the inner structure of topological defects in Er1-xZrxMnO3. By performing a comprehensive parametrization of the inner atomic defect structure, we demonstrate that one primary length scale drives the morphology of both vortices and domain walls. Our findings lead to a unifying general picture of this type of structural topological defects. We further derive novel fundamental and universal properties, such as unusual bound-charge distributions and electrostatics at the ferroelectric vortex cores with emergent U(1) symmetry.

Enhanced Electrical Resistivity and Properties via Ion Bombardment of Ferroelectric Thin Films.

A novel approach to on-demand improvement of electronic properties in complex-oxide ferroelectrics is demonstrated whereby ion bombardment - commonly used in classic semiconductor materials - is applied to the PbTiO3 system. The result is deterministic reduction in leakage currents by 5 orders of magnitude, improved ferroelectric switching, and unprecedented insights into the nature of defects and intergap state evolution in these materials.

Atomically engineered ferroic layers yield a room-temperature magnetoelectric multiferroic.

Materials that exhibit simultaneous order in their electric and magnetic ground states hold promise for use in next-generation memory devices in which electric fields control magnetism. Such materials are exceedingly rare, however, owing to competing requirements for displacive ferroelectricity and magnetism. Despite the recent identification of several new multiferroic materials and magnetoelectric coupling mechanisms, known single-phase multiferroics remain limited by antiferromagnetic or weak ferromagnetic alignments, by a lack of coupling between the order parameters, or by having properties that emerge only well below room temperature, precluding device applications. Here we present a methodology for constructing single-phase multiferroic materials in which ferroelectricity and strong magnetic ordering are coupled near room temperature. Starting with hexagonal LuFeO3-the geometric ferroelectric with the greatest known planar rumpling-we introduce individual monolayers of FeO during growth to construct formula-unit-thick syntactic layers of ferrimagnetic LuFe2O4 (refs 17, 18) within the LuFeO3 matrix, that is, (LuFeO3)m/(LuFe2O4)1 superlattices. The severe rumpling imposed by the neighbouring LuFeO3 drives the ferrimagnetic LuFe2O4 into a simultaneously ferroelectric state, while also reducing the LuFe2O4 spin frustration. This increases the magnetic transition temperature substantially-from 240 kelvin for LuFe2O4 (ref. 18) to 281 kelvin for (LuFeO3)9/(LuFe2O4)1. Moreover, the ferroelectric order couples to the ferrimagnetism, enabling direct electric-field control of magnetism at 200 kelvin. Our results demonstrate a design methodology for creating higher-temperature magnetoelectric multiferroics by exploiting a combination of geometric frustration, lattice distortions and epitaxial engineering.

High-quality EuO thin films the easy way via topotactic transformation.

Epitaxy is widely employed to create highly oriented crystalline films. A less appreciated, but nonetheless powerful means of creating such films is via topotactic transformation, in which a chemical reaction transforms a single crystal of one phase into a single crystal of a different phase, which inherits its orientation from the original crystal. Topotactic reactions may be applied to epitactic films to substitute, add or remove ions to yield epitactic films of different phases. Here we exploit a topotactic reduction reaction to provide a non-ultra-high vacuum (UHV) means of growing highly oriented single crystalline thin films of the easily over-oxidized half-metallic semiconductor europium monoxide (EuO) with a perfection rivalling that of the best films of the same material grown by molecular-beam epitaxy or UHV pulsed-laser deposition. As the technique only requires high-vacuum deposition equipment, it has the potential to drastically improve the accessibility of high-quality single crystalline films of EuO as well as other difficult-to-synthesize compounds.

Magnetic structure and ordering of multiferroic hexagonal LuFeO_{3}.

We report on the magnetic structure and ordering of hexagonal LuFeO_{3} films of variable thickness grown by molecular-beam epitaxy on YSZ (111) and Al_{2}O_{3} (0001) substrates. These crystalline films exhibit long-range structural uniformity dominated by the polar P6_{3}cm phase, which is responsible for the paraelectric to ferroelectric transition that occurs above 1000 K. Using bulk magnetometry and neutron diffraction, we find that the system orders into a ferromagnetically canted antiferromagnetic state via a single transition below 155 K regardless of film thickness, which is substantially lower than that previously reported in hexagonal LuFeO_{3} films. The symmetry of the magnetic structure in the ferroelectric state implies that this material is a strong candidate for linear magnetoelectric coupling and control of the ferromagnetic moment directly by an electric field.

Controlling band alignments by artificial interface dipoles at perovskite heterointerfaces.

The concept 'the interface is the device' is embodied in a wide variety of interfacial electronic phenomena and associated applications in oxide materials, ranging from catalysts and clean energy systems to emerging multifunctional devices. Many device properties are defined by the band alignment, which is often influenced by interface dipoles. On the other hand, the ability to purposefully create and control interface dipoles is a relatively unexplored degree of freedom for perovskite oxides, which should be particularly effective for such ionic materials. Here we demonstrate tuning the band alignment in perovskite metal-semiconductor heterojunctions over a broad range of 1.7 eV. This is achieved by the insertion of positive or negative charges at the interface, and the resultant dipole formed by the induced screening charge. This approach can be broadly used in applications where decoupling the band alignment from the constituent work functions and electron affinities can enhance device functionality.

Visualizing the interfacial evolution from charge compensation to metallic screening across the manganite metal-insulator transition.

Electronic changes at polar interfaces between transition metal oxides offer the tantalizing possibility to stabilize novel ground states yet can also cause unintended reconstructions in devices. The nature of these interfacial reconstructions should be qualitatively different for metallic and insulating films as the electrostatic boundary conditions and compensation mechanisms are distinct. Here we directly quantify with atomic-resolution the charge distribution for manganite-titanate interfaces traversing the metal-insulator transition. By measuring the concentration and valence of the cations, we find an intrinsic interfacial electronic reconstruction in the insulating films. The total charge observed for the insulating manganite films quantitatively agrees with that needed to cancel the polar catastrophe. As the manganite becomes metallic with increased hole doping, the total charge build-up and its spatial range drop substantially. Direct quantification of the intrinsic charge transfer and spatial width should lay the framework for devices harnessing these unique electronic phases.

Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics.

The miniaturization and integration of frequency-agile microwave circuits--relevant to electronically tunable filters, antennas, resonators and phase shifters--with microelectronics offers tantalizing device possibilities, yet requires thin films whose dielectric constant at gigahertz frequencies can be tuned by applying a quasi-static electric field. Appropriate systems such as BaxSr1-xTiO3 have a paraelectric-ferroelectric transition just below ambient temperature, providing high tunability. Unfortunately, such films suffer significant losses arising from defects. Recognizing that progress is stymied by dielectric loss, we start with a system with exceptionally low loss--Srn+1TinO3n+1 phases--in which (SrO)2 crystallographic shear planes provide an alternative to the formation of point defects for accommodating non-stoichiometry. Here we report the experimental realization of a highly tunable ground state arising from the emergence of a local ferroelectric instability in biaxially strained Srn+1TinO3n+1 phases with n ≥ 3 at frequencies up to 125 GHz. In contrast to traditional methods of modifying ferroelectrics-doping or strain-in this unique system an increase in the separation between the (SrO)2 planes, which can be achieved by changing n, bolsters the local ferroelectric instability. This new control parameter, n, can be exploited to achieve a figure of merit at room temperature that rivals all known tunable microwave dielectrics.

Tuning oxygen reduction reaction activity via controllable dealloying: a model study of ordered Cu3Pt/C intermetallic nanocatalysts.

A promising electrocatalyst prototype of low Pt mole fraction, intermetallic nanoparticles of Cu(3)Pt, has been prepared using a simple impregnation-reduction method, followed by a post heat-treatment. Two dealloying methods (electrochemical and chemical) were implemented to control the atomic-level morphology and improve performance for the oxygen reduction reaction (ORR). The morphology and elemental composition of the dealloyed nanoparticles were characterized at angstrom resolution using an aberration-corrected scanning transmission electron microscope equipped with an electron energy loss spectrometer. We found that the electrochemical dealloying method led to the formation of a thin Pt skin of ca. 1 nm in thickness with an ordered Cu(3)Pt core structure, while chemical leaching gave rise to a "spongy" structure with no ordered structure being preserved. A three-dimensional tomographic reconstruction indicated that numerous voids were formed in the chemically dealloyed nanoparticles. Both dealloying methods yielded enhanced specific and mass activities toward the ORR and higher stability relative to Pt/C. The spongy nanoparticles exhibited better mass activity with a slightly lower specific activity than the electrochemically dealloyed nanoparticles after 50 potential cycles. In both cases, the mass activity was still enhanced after 5000 potential cycles.

Quantum many-body interactions in digital oxide superlattices.

Controlling the electronic properties of interfaces has enormous scientific and technological implications and has been recently extended from semiconductors to complex oxides that host emergent ground states not present in the parent materials. These oxide interfaces present a fundamentally new opportunity where, instead of conventional bandgap engineering, the electronic and magnetic properties can be optimized by engineering quantum many-body interactions. We use an integrated oxide molecular-beam epitaxy and angle-resolved photoemission spectroscopy system to synthesize and investigate the electronic structure of superlattices of the Mott insulator LaMnO(3) and the band insulator SrMnO(3). By digitally varying the separation between interfaces in (LaMnO(3))(2n)/(SrMnO(3))(n) superlattices with atomic-layer precision, we demonstrate that quantum many-body interactions are enhanced, driving the electronic states from a ferromagnetic polaronic metal to a pseudogapped insulating ground state. This work demonstrates how many-body interactions can be engineered at correlated oxide interfaces, an important prerequisite to exploiting such effects in novel electronics.

Data processing for atomic resolution electron energy loss spectroscopy.

The high beam current and subangstrom resolution of aberration-corrected scanning transmission electron microscopes has enabled electron energy loss spectroscopy (EELS) mapping with atomic resolution. These spectral maps are often dose limited and spatially oversampled, leading to low counts/channel and are thus highly sensitive to errors in background estimation. However, by taking advantage of redundancy in the dataset map, one can improve background estimation and increase chemical sensitivity. We consider two such approaches--linear combination of power laws and local background averaging--that reduce background error and improve signal extraction. Principal component analysis (PCA) can also be used to analyze spectrum images, but the poor peak-to-background ratio in EELS can lead to serious artifacts if raw EELS data are PCA filtered. We identify common artifacts and discuss alternative approaches. These algorithms are implemented within the Cornell Spectrum Imager, an open source software package for spectroscopic analysis.

Three-dimensional tracking and visualization of hundreds of Pt-Co fuel cell nanocatalysts during electrochemical aging.

We present an electron tomography method that allows for the identification of hundreds of electrocatalyst nanoparticles with one-to-one correspondence before and after electrochemical aging. This method allows us to track, in three-dimensions, the trajectories and morphologies of each Pt-Co nanocatalyst on a fuel cell carbon support. In conjunction with the use of atomic-scale electron energy loss spectroscopic imaging, our experiment enables the correlation of performance degradation of the catalyst with changes in particle/interparticle morphologies, particle-support interactions, and the near-surface chemical composition. We found that aging of the catalysts under normal fuel cell operating conditions (potential scans from +0.6 to +1.0 V for 30,000 cycles) gives rise to coarsening of the nanoparticles, mainly through coalescence, which in turn leads to the loss of performance. The observed coalescence events were found to be the result of nanoparticle migration on the carbon support during potential cycling. This method provides detailed insights into how nanocatalyst degradation occurs in proton exchange membrane fuel cells (PEMFCs) and suggests that minimization of particle movement can potentially slow down the coarsening of the particles and the corresponding performance degradation.

Atomic-resolution spectroscopic imaging of ensembles of nanocatalyst particles across the life of a fuel cell.

The thousand-fold increase in data-collection speed enabled by aberration-corrected optics allows us to overcome an electron microscopy paradox: how to obtain atomic-resolution chemical structure in individual nanoparticles yet record a statistically significant sample from an inhomogeneous population. This allowed us to map hundreds of Pt-Co nanoparticles to show atomic-scale elemental distributions across different stages of the catalyst aging in a proton-exchange-membrane fuel cell, and relate Pt-shell thickness to treatment, particle size, surface orientation, and ordering.