Experimental Evidence of t_{2g} Electron-Gas Rashba Interaction Induced by Asymmetric Orbital Hybridization.

We report the control of Rashba spin-orbit interaction by tuning asymmetric hybridization between Ti orbitals at the LaAlO_{3}/SrTiO_{3} interface. This asymmetric orbital hybridization is modulated by introducing a LaFeO_{3} layer between LaAlO_{3} and SrTiO_{3}, which alters the Ti-O lattice polarization and traps interfacial charge carriers, resulting in a large Rashba spin-orbit effect at the interface in the absence of an external bias. This observation is verified through high-resolution electron microscopy, magnetotransport and first-principles calculations. Our results open hitherto unexplored avenues of controlling Rashba interaction to design next-generation spin orbitronics.

Controlled Sign Reversal of Electroresistance in Oxide Tunnel Junctions by Electrochemical-Ferroelectric Coupling.

The persistence of ferroelectricity in ultrathin layers relies critically on screening or compensation of polarization charges which otherwise destabilize the ferroelectric state. At surfaces, charged defects play a crucial role in the screening mechanism triggering novel mixed electrochemical-ferroelectric states. At interfaces, however, the coupling between ferroelectric and electrochemical states has remained unexplored. Here, we make use of the dynamic formation of the oxygen vacancy profile in the nanometer-thick barrier of a ferroelectric tunnel junction to demonstrate the interplay between electrochemical and ferroelectric degrees of freedom at an oxide interface. We fabricate ferroelectric tunnel junctions with a La_{0.7}Sr_{0.3}MnO_{3} bottom electrode and BaTiO_{3} ferroelectric barrier. We use poling strategies to promote the generation and transport of oxygen vacancies at the metallic top electrode. Generated oxygen vacancies control the stability of the ferroelectric polarization and modify its coercive fields. The ferroelectric polarization, in turn, controls the ionization of oxygen vacancies well above the limits of thermodynamic equilibrium, triggering the build up of a Schottky barrier at the interface which can be turned on and off with ferroelectric switching. This interplay between electronic and electrochemical degrees of freedom yields very large values of the electroresistance (more than 10^{6}% at low temperatures) and enables a controlled switching between clockwise and counterclockwise switching modes in the same junction (and consequently, a change of the sign of the electroresistance). The strong coupling found between electrochemical and electronic degrees of freedom sheds light on the growing debate between resistive and ferroelectric switching in ferroelectric tunnel junctions, and moreover, can be the source of novel concepts in memory devices and neuromorphic computing.

Probing plasmons in three dimensions by combining complementary spectroscopies in a scanning transmission electron microscope.

The nanoscale optical response of surface plasmons in three-dimensional metallic nanostructures plays an important role in many nanotechnology applications, where precise spatial and spectral characteristics of plasmonic elements control device performance. Electron energy loss spectroscopy (EELS) and cathodoluminescence (CL) within a scanning transmission electron microscope have proven to be valuable tools for studying plasmonics at the nanoscale. Each technique has been used separately, producing three-dimensional reconstructions through tomography, often aided by simulations for complete characterization. Here we demonstrate that the complementary nature of the two techniques, namely that EELS probes beam-induced electronic excitations while CL probes radiative decay, allows us to directly obtain a spatially- and spectrally-resolved picture of the plasmonic characteristics of nanostructures in three dimensions. The approach enables nanoparticle-by-nanoparticle plasmonic analysis in three dimensions to aid in the design of diverse nanoplasmonic applications.

Interface control of bulk ferroelectric polarization.

The control of material interfaces at the atomic level has led to novel interfacial properties and functionalities. In particular, the study of polar discontinuities at interfaces between complex oxides lies at the frontier of modern condensed matter research. Here we employ a combination of experimental measurements and theoretical calculations to demonstrate the control of a bulk property, namely ferroelectric polarization, of a heteroepitaxial bilayer by precise atomic-scale interface engineering. More specifically, the control is achieved by exploiting the interfacial valence mismatch to influence the electrostatic potential step across the interface, which manifests itself as the biased-voltage in ferroelectric hysteresis loops and determines the ferroelectric state. A broad study of diverse systems comprising different ferroelectrics and conducting perovskite underlayers extends the generality of this phenomenon.

Enhanced tunnelling electroresistance effect due to a ferroelectrically induced phase transition at a magnetic complex oxide interface.

The range of recently discovered phenomena in complex oxide heterostructures, made possible owing to advances in fabrication techniques, promise new functionalities and device concepts. One issue that has received attention is the bistable electrical modulation of conductivity in ferroelectric tunnel junctions (FTJs) in response to a ferroelectric polarization of the tunnelling barrier, a phenomenon known as the tunnelling electroresistance (TER) effect. Ferroelectric tunnel junctions with ferromagnetic electrodes allow ferroelectric control of the tunnelling spin polarization through the magnetoelectric coupling at the ferromagnet/ferroelectric interface. Here we demonstrate a significant enhancement of TER due to a ferroelectrically induced phase transition at a magnetic complex oxide interface. Ferroelectric tunnel junctions consisting of BaTiO3 tunnelling barriers and La(0.7)Sr(0.3)MnO3 electrodes exhibit a TER enhanced by up to ~10,000% by a nanometre-thick La(0.5)Ca(0.5)MnO3 interlayer inserted at one of the interfaces. The observed phenomenon originates from the metal-to-insulator phase transition in La(0.5)Ca(0.5)MnO3, driven by the modulation of carrier density through ferroelectric polarization switching. Electrical, ferroelectric and magnetoresistive measurements combined with first-principles calculations provide evidence for a magnetoelectric origin of the enhanced TER, and indicate the presence of defect-mediated conduction in the FTJs. The effect is robust and may serve as a viable route for electronic and spintronic applications.

Simulation of spatially resolved electron energy loss near-edge structure for scanning transmission electron microscopy.

Aberration-corrected scanning transmission electron microscopy yields probe-position-dependent energy-loss near-edge structure (ELNES) measurements, potentially providing spatial mapping of the underlying electronic states. ELNES calculations, however, typically describe excitations by a plane wave traveling in vacuum, neglecting the interaction of the electron probe with the local electronic environment as it propagates through the specimen. Here, we report a methodology that combines a full electronic-structure calculation with propagation of a focused beam in a thin film. The results demonstrate that only a detailed calculation using this approach can provide quantitative agreement with observed variations in probe-position-dependent ELNES.

Self-organized bimetallic Ag-Co nanoparticles with tunable localized surface plasmons showing high environmental stability and sensitivity.

We demonstrate a promising synthesis route based on pulsed laser dewetting of bilayer films (Ag and Co) to make bimetallic nanoparticle arrays. By combining experiment and theory we establish a parameter space for the independent control of composition and diameter for the bimetallic nanoparticles. As a result, physical properties, such as the localized surface plasmon resonance (LSPR), that depend on particle size and composition can be readily tuned over a wavelength range one order of magnitude greater than for pure Ag nanoparticles. The LSPR detection sensitivity of the bimetallic nanoparticles with narrow size distribution was found to be high-comparable with pure Ag (∼60 nm/RIU). Moreover, they showed significantly higher long-term environmental stability over pure Ag.

Observation of perfect diamagnetism and interfacial effect on the electronic structures in infinite layer Nd0.8Sr0.2NiO2 superconductors.

Nickel-based complex oxides have served as a playground for decades in the quest for a copper-oxide analog of the high-temperature superconductivity. They may provide clues towards understanding the mechanism and an alternative route for high-temperature superconductors. The recent discovery of superconductivity in the infinite-layer nickelate thin films has fulfilled this pursuit. However, material synthesis remains challenging, direct demonstration of perfect diamagnetism is still missing, and understanding of the role of the interface and bulk to the superconducting properties is still lacking. Here, we show high-quality Nd0.8Sr0.2NiO2 thin films with different thicknesses and demonstrate the interface and strain effects on the electrical, magnetic and optical properties. Perfect diamagnetism is achieved, confirming the occurrence of superconductivity in the films. Unlike the thick films in which the normal-state Hall-coefficient changes signs as the temperature decreases, the Hall-coefficient of films thinner than 5.5 nm remains negative, suggesting a thickness-driven band structure modification. Moreover, X-ray absorption spectroscopy reveals the Ni-O hybridization nature in doped infinite-layer nickelates, and the hybridization is enhanced as the thickness decreases. Consistent with band structure calculations on the nickelate/SrTiO3 heterostructure, the interface and strain effect induce a dominating electron-like band in the ultrathin film, thus causing the sign-change of the Hall-coefficient.

Electronic and magnetic reconstructions in La0.7Sr0.3MnO3/SrTiO3 heterostructures: a case of enhanced interlayer coupling controlled by the interface.

We report on the magnetic coupling of La0.7Sr0.3MnO3 layers through SrTiO3 spacers in La0.7Sr0.3MnO3/SrTiO3 epitaxial heterostructures. Combined aberration-corrected microscopy and electron-energy-loss spectroscopy evidence charge transfer to the empty conduction band of the titanate. Ti d electrons interact via superexchange with Mn, giving rise to a Ti magnetic moment as demonstrated by x-ray magnetic circular dichroism. This induced magnetic moment in the SrTiO3 controls the bulk magnetic and transport properties of the superlattices when the titanate layer thickness is below 1 nm.

Enhanced current transport at grain boundaries in high-T(c) superconductors.

Large-scale applications of high-transition-temperature (high-T(c)) superconductors, such as their use in superconducting cables, are impeded by the fact that polycrystalline materials (the only practical option) support significantly lower current densities than single crystals. The superconducting critical current density (J(c)) across a grain boundary drops exponentially if the misorientation angle exceeds 2 degrees -7 degrees. Grain texturing reduces the average misorientation angle, but problems persist. Adding impurities (such as Ca in YBa2Cu3O7-delta; YBCO) leads to increased J(c) (refs 9, 10), which is generally attributed to excess holes introduced by Ca2+ substituting for Y3+ (ref. 11). However, a comprehensive physical model for the role of grain boundaries and Ca doping has remained elusive. Here we report calculations, imaging and spectroscopy at the atomic scale that demonstrate that in poly-crystalline YBCO, highly strained grain-boundary regions contain excess O vacancies, which reduce the local hole concentration. The Ca impurities indeed substitute for Y, but in grain-boundary regions under compression and tension they also replace Ba and Cu, relieving strain and suppressing O-vacancy formation. Our results demonstrate that the ionic radii are more important than their electronic valences for enhancing J(c).

New views of materials through aberration-corrected scanning transmission electron microscopy.

The successful correction of third-order and, more recently, fifth-order aberrations has enormously enhanced the capabilities of the scanning transmission electron microscope (STEM), by not only achieving record resolution, but also allowing near 100% efficiency for electron energy loss spectroscopy, and higher currents for two-dimensional spectrum imaging. These advances have meant that the intrinsic advantages of the STEM, incoherent imaging and simultaneous collection of multiple complementary images can now give new insights into many areas of materials physics. Here, we review a number of examples, mostly from the field of complex oxides, and look towards new directions for the future.

Suppression of octahedral tilts and associated changes in electronic properties at epitaxial oxide heterostructure interfaces.

Epitaxial oxide interfaces with broken translational symmetry have emerged as a central paradigm behind the novel behaviors of oxide superlattices. Here, we use scanning transmission electron microscopy to demonstrate a direct, quantitative unit-cell-by-unit-cell mapping of lattice parameters and oxygen octahedral rotations across the BiFeO3-La0.7 Sr0.3 MnO3 interface to elucidate how the change of crystal symmetry is accommodated. Combined with low-loss electron energy loss spectroscopy imaging, we demonstrate a mesoscopic antiferrodistortive phase transition near the interface in BiFeO3 and elucidate associated changes in electronic properties in a thin layer directly adjacent to the interface.

Morphological evolution of InAs/InP quantum wires through aberration-corrected scanning transmission electron microscopy.

Evolution of the size, shape and composition of self-assembled InAs/InP quantum wires through the Stranski-Krastanov transition has been determined by aberration-corrected Z-contrast imaging. High resolution compositional maps of the wires in the initial, intermediate and final formation stages are presented. (001) is the main facet at their very initial stage of formation, which is gradually reduced in favour of [114] or [118], ending with the formation of mature quantum wires with {114} facets. Significant changes in wire dimensions are measured when varying slightly the amount of InAs deposited. These results are used as input parameters to build three-dimensional models that allow calculation of the strain energy during the quantum wire formation process. The observed morphological evolution is explained in terms of the calculated elastic energy changes at the growth front. Regions of the wetting layer close to the nanostructure perimeters have higher strain energy, causing migration of As atoms towards the quantum wire terraces, where the structure is partially relaxed; the thickness of the wetting layer is reduced in these zones and the island height increases until the (001) facet is removed.

Direct Observation of Dislocation Core Structures in CdTe/GaAs(001).

A strategy is presented for determining sublattice polarity at defects in compound semiconductors. Core structures of 60-degree and Lomer dislocations in the CdTe/GaAs(001) system have been obtained by the application of maximum-entropy analysis to Z-contrast images (Z is atomic number) obtained in a 300-kilovolt scanning transmission electron microscope. Sixty-degree dislocations were observed to be of the glide type, whereas in the case of Lomer dislocations, both a symmetric (Hornstra-like) core and an unexpected asymmetric structure made up of a fourfold ring were seen.

Crack-like sources of dislocation nucleation and multiplication in thin films.

With the combination of the height sensitivity of atomic force microscopy and the strain sensitivity of transmission electron microscopy, it is shown that near singular stress concentrations can develop naturally in strained epitaxial films. These crack-like instabilities are identified as the sources of dislocation nucleation and multiplication in films of high misfit. This link between morphological instability and dislocation nucleation provides a method for studying the basic micromechanisms that determine the strength and mechanical properties of materials.

Direct Determination of Grain Boundary Atomic Structure in SrTiO3.

An atomic structure model for a 25 degrees [001] symmetric tilt grain boundary in SrTiO(3) has been determined directly from experimental data with the use of high-resolution Z-contrast imaging coupled with electron energy loss spectroscopy. The derived model of the grain boundary was refined by bond-valence sum calculations and reveals candidate sites for dopant atoms in the boundary plane. These results show how the combined techniques can be used to deduce the atomic structure of defects and interfaces without recourse to preconceived structural models or image simulations.

Column-by-column compositional mapping by Z-contrast imaging.

A phenomenological method is developed to determine the composition of materials, with atomic column resolution, by analysis of integrated intensities of aberration-corrected Z-contrast scanning transmission electron microscopy images. The method is exemplified for InAs(x)P(1-x) alloys using epitaxial thin films with calibrated compositions as standards. Using this approach we have determined the composition of the two-dimensional wetting layer formed between self-assembled InAs quantum wires on InP(001) substrates.

Characterizing the two- and three-dimensional resolution of an improved aberration-corrected STEM.

The successful development of third-order aberration correctors in transmission electron microscopy has seen aberration-corrected electron microscopes evolve from specialist projects, custom built at a small number of sites to common instruments in many modern laboratories. Here we describe some initial results illustrating the two- and three-dimensional (3D) performance of an aberration-corrected scanning transmission electron microscope with a prototype improved aberration corrector designed to also minimize fifth-order aberrations and a new, higher brightness gun. We show that atomic columns separated by 0.63 A can be resolved and demonstrate detection of single dopant atoms with 3D sensitivity.

Image simulation for electron energy loss spectroscopy.

Aberration correction of the probe forming optics of the scanning transmission electron microscope has allowed the probe-forming aperture to be increased in size, resulting in probes of the order of 1 A in diameter. The next generation of correctors promise even smaller probes. Improved spectrometer optics also offers the possibility of larger electron energy loss spectrometry detectors. The localization of images based on core-loss electron energy loss spectroscopy is examined as function of both probe-forming aperture and detector size. The effective ionization is nonlocal in nature, and two common local approximations are compared to full nonlocal calculations. The affect of the channelling of the electron probe within the sample is also discussed.

Dipolar interactions and their influence on the critical single domain grain size of Ni in layered Ni/Al(2)O(3) composites.

Pulsed laser deposition has been used to fabricate Ni/Al(2)O(3) multilayer composites in which Ni nanoparticles with diameters in the range of 3-60 nm are embedded as layers in an insulating Al(2)O(3) host. At fixed temperatures, the coercive fields plotted as a function of particle size show well-defined peaks, which define a critical size that delineates a crossover from coherently rotating single domain to multiple domain behavior. We observe a shift in peak position to higher grain size as temperature increases and describe this shift with theory that takes into account the decreasing influence of dipolar magnetic interactions from thermally induced random orientations of neighboring grains.