Structural "δ Doping" to Control Local Magnetization in Isovalent Oxide Heterostructures.

Modulation and δ-doping strategies, in which atomically thin layers of charged dopants are precisely deposited within a heterostructure, have played enabling roles in the discovery of new physical behavior in electronic materials. Here, we demonstrate a purely structural "δ-doping" strategy in complex oxide heterostructures, in which atomically thin manganite layers are inserted into an isovalent manganite host, thereby modifying the local rotations of corner-connected MnO_{6} octahedra. Combining scanning transmission electron microscopy, polarized neutron reflectometry, and density functional theory, we reveal how local magnetic exchange interactions are enhanced within the spatially confined regions of suppressed octahedral rotations. The combined experimental and theoretical results illustrate the potential to utilize noncharge-based approaches to "doping" in order to enhance or suppress functional properties within spatially confined regions of oxide heterostructures.

Big Data Analytics for Scanning Transmission Electron Microscopy Ptychography.

Electron microscopy is undergoing a transition; from the model of producing only a few micrographs, through the current state where many images and spectra can be digitally recorded, to a new mode where very large volumes of data (movies, ptychographic and multi-dimensional series) can be rapidly obtained. Here, we discuss the application of so-called "big-data" methods to high dimensional microscopy data, using unsupervised multivariate statistical techniques, in order to explore salient image features in a specific example of BiFeO3 domains. Remarkably, k-means clustering reveals domain differentiation despite the fact that the algorithm is purely statistical in nature and does not require any prior information regarding the material, any coexisting phases, or any differentiating structures. While this is a somewhat trivial case, this example signifies the extraction of useful physical and structural information without any prior bias regarding the sample or the instrumental modality. Further interpretation of these types of results may still require human intervention. However, the open nature of this algorithm and its wide availability, enable broad collaborations and exploratory work necessary to enable efficient data analysis in electron microscopy.

Ferroelectrics. Observation of a periodic array of flux-closure quadrants in strained ferroelectric PbTiO3 films.

Nanoscale ferroelectrics are expected to exhibit various exotic domain configurations, such as the full flux-closure pattern that is well known in ferromagnetic materials. Here we observe not only the atomic morphology of the flux-closure quadrant but also a periodic array of flux closures in ferroelectric PbTiO3 films, mediated by tensile strain on a GdScO3 substrate. Using aberration-corrected scanning transmission electron microscopy, we directly visualize an alternating array of clockwise and counterclockwise flux closures, whose periodicity depends on the PbTiO3 film thickness. In the vicinity of the core, the strain is sufficient to rupture the lattice, with strain gradients up to 10(9) per meter. Engineering strain at the nanoscale may facilitate the development of nanoscale ferroelectric devices.

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.

Exploring mesoscopic physics of vacancy-ordered systems through atomic scale observations of topological defects.

Vacancy-ordered transition metal oxides have multiple similarities to classical ferroic systems including ferroelectrics and ferroelastics. The expansion coefficients for corresponding Ginzburg-Landau-type free energies are readily accessible from bulk phase diagrams. Here, we demonstrate that the gradient and interfacial terms can quantitatively be determined from the atomically resolved scanning transmission electron microscopy data of the topological defects and interfaces in model lanthanum-strontium cobaltite. With this knowledge, the interplay between ordering, chemical composition, and mechanical effects at domain walls, interfaces and structural defects can be analyzed.

Atomic-scale evolution of modulated phases at the ferroelectric-antiferroelectric morphotropic phase boundary controlled by flexoelectric interaction.

Physical and structural origins of morphotropic phase boundaries (MPBs) in ferroics remain elusive despite decades of study. The leading competing theories employ either low-symmetry bridging phases or adaptive phases with nanoscale textures to describe different subsets of the macroscopic data, while the decisive atomic-scale information has so far been missing. Here we report direct atomically resolved mapping of polarization and structure order parameter fields in a Sm-doped BiFeO(3) system and their evolution as the system approaches a MPB. We further show that both the experimental phase diagram and the observed phase evolution can be explained by taking into account the flexoelectric interaction, which renders the effective domain wall energy negative, thus stabilizing modulated phases in the vicinity of the MPB. Our study highlights the importance of local order-parameter mapping at the atomic scale and establishes a hitherto unobserved physical origin of spatially modulated phases existing in the vicinity of the MPB.

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.

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.

Aberration-corrected scanning transmission electron microscopy: from atomic imaging and analysis to solving energy problems.

The new possibilities of aberration-corrected scanning transmission electron microscopy (STEM) extend far beyond the factor of 2 or more in lateral resolution that was the original motivation. The smaller probe also gives enhanced single atom sensitivity, both for imaging and for spectroscopy, enabling light elements to be detected in a Z-contrast image and giving much improved phase contrast imaging using the bright field detector with pixel-by-pixel correlation with the Z-contrast image. Furthermore, the increased probe-forming aperture brings significant depth sensitivity and the possibility of optical sectioning to extract information in three dimensions. This paper reviews these recent advances with reference to several applications of relevance to energy, the origin of the low-temperature catalytic activity of nanophase Au, the nucleation and growth of semiconducting nanowires, and the origin of the eight orders of magnitude increased ionic conductivity in oxide superlattices. Possible future directions of aberration-corrected STEM for solving energy problems are outlined.

Spectroscopic imaging of single atoms within a bulk solid.

The ability to localize, identify, and measure the electronic environment of individual atoms will provide fundamental insights into many issues in materials science, physics, and nanotechnology. We demonstrate, using an aberration-corrected scanning transmission electron microscope, the spectroscopic imaging of single La atoms inside CaTiO3. Dynamical simulations confirm that the spectroscopic information is spatially confined around the scattering atom. Furthermore, we show how the depth of the atom within the crystal may be estimated.