Analysis of phase distributions in the Li\u3csub\u3e2\u3c/sub\u3eO–Nb\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e5\u3c/sub\u3e–TiO\u3csub\u3e2\u3c/sub\u3e system by piezoresponse imaging

The M-phase solid solutions Li1+x-yNb1-x-3yTix+4yO3) (0.1 ≤ x ≤ 0.3, 0 ≤ y ≤ 0.175) in the Li2O–Nb2O5–TiO2 system have promising microwave dielectric properties. However, these compounds can contain small quantities of ferroelectric impurities that affect the polarization response of the material. Due to their low concentration and their chemical similarity to the host material, the impurities cannot be detected by x-ray diffraction or local elemental analysis. Scanning surface potential microscopy and piezoresponse imaging were used to analyze phase compositions in this system. Piezoresponse imaging demonstrated the presence of thin (\u3c200–300 nm) ferroelectric layers on the grain boundaries oriented along the c-axis of the M-phase. Differences between the surface potential and the piezoresponse of ferroelectric multicomponent systems are discussed

Finite size and intrinsic field effect on the polar-active properties of the ferroelectric-semiconductor heterostructures

Using Landau-Ginzburg-Devonshire approach we calculated the equilibrium distributions of electric field, polarization and space charge in the ferroelectric-semiconductor heterostructures containing proper or incipient ferroelectric thin films. The role of the polarization gradient and intrinsic surface energy, interface dipoles and free charges on polarization dynamics are specifically explored. The intrinsic field effects, which originated at the ferroelectric-semiconductor interface, lead to the surface band bending and result into the formation of depletion space-charge layer near the semiconductor surface. During the local polarization reversal (caused by the inhomogeneous electric field induced by the nanosized tip of the Scanning Probe Microscope (SPM) probe) the thickness and charge of the interface layer drastically changes, it particular the sign of the screening carriers is determined by the polarization direction. Obtained analytical solutions could be extended to analyze polarization-mediated electronic transport.Comment: 35 pages, 12 figures, 1 table, 2 appendices, to be submitted to Phys. Rev.

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 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.Comment: 4 pages and 3 figures. Accepted in Phys.Rev.Let

Suppression of Octahedral Tilts and Associated Changes of 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-La0.7Sr0.3MnO3 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 and elucidate associated changes in electronic properties in a thin layer directly adjacent to the interface

Theory-assisted determination of nano-rippling and impurities in atomic resolution images of angle-mismatched bilayer graphene

Ripples and impurity atoms are universally present in 2D materials, limiting carrier mobility, creating pseudo–magnetic fields, or affecting the electronic and magnetic properties. Scanning transmission electron microscopy (STEM) generally provides picometer-level precision in the determination of the location of atoms or atomic 'columns' in the in-image plane (xy plane). However, precise atomic positions in the z-direction as well as the presence of certain impurities are difficult to detect. Furthermore, images containing moiré patterns such as those in angle-mismatched bilayer graphene compound the problem by limiting the determination of atomic positions in the xy plane. Here, we introduce a reconstructive approach for the analysis of STEM images of twisted bilayers that combines the accessible xy coordinates of atomic positions in a STEM image with density-functional-theory calculations. The approach allows us to determine all three coordinates of all atomic positions in the bilayer and establishes the presence and identity of impurities. The deduced strain-induced rippling in a twisted bilayer graphene sample is consistent with the continuum model of elasticity. We also find that the moiré pattern induces undulations in the z direction that are approximately an order of magnitude smaller than the strain-induced rippling. A single substitutional impurity, identified as nitrogen, is detected. The present reconstructive approach can, therefore, distinguish between moiré and strain-induced effects and allows for the full reconstruction of 3D positions and atomic identities

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

Conductivity of twin walls - surface junctions in ferroelastics: interplay of deformation potential, octahedral rotations, improper ferroelectricity and flexoelectric coupling

Electronic and structural phenomena at the twin domain wall-surface junctions in the ferroelastic materials are analyzed. Carriers accumulation caused by the strain-induced band structure changes originated via the deformation potential mechanism, structural order parameter gradient, rotostriction and flexoelectric coupling is explored. Approximate analytical results show that inhomogeneous elastic strains, which exist in the vicinity of the twin walls - surface junctions due to the rotostriction coupling, decrease the local band gap via the deformation potential and flexoelectric coupling mechanisms. This is the direct mechanism of the twin walls static conductivity in ferroelastics and, by extension, in multiferroics and ferroelectrics. On the other hand, flexoelectric and rotostriction coupling leads to the appearance of the improper polarization and electric fields proportional to the structural order parameter gradient in the vicinity of the twin walls - surface junctions. The "flexo-roto" fields leading to the carrier accumulation are considered as indirect mechanism of the twin walls conductivity. Comparison of the direct and indirect mechanisms illustrates complex range of phenomena directly responsible for domain walls static conductivity in materials with multiple order parameters.Comment: 35 pages, 11 figures, 3 table, 3 appendices Improved set of rotostriction coefficients are used in calculation

Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide

The surfaces of transition-metal oxides with the perovskite structure are fertile grounds for the discovery of novel electronic and magnetic phenomena. In this article, we combine scanning transmission electron microscopy (STEM) with density functional theory (DFT) calculations to obtain the electronic and magnetic properties of the (001) surface of a ( LaFe O 3 ) 8 / ( SrFe O 3 ) 1 superlattice film capped with four layers of LaFe O 3 . Simultaneously acquired STEM images and electron-energy-loss spectra reveal the surface structure and a reduction in the oxidation state of iron from F e 3 + in the bulk to F e 2 + at the surface, extending over several atomic layers, which signals the presence of oxygen vacancies. The DFT calculations confirm the reduction in terms of oxygen vacancies and further demonstrate the stabilization of an exotic phase in which the surface layer is half metallic and ferromagnetic, while the bulk remains antiferromagnetic and insulating. Based on the calculations, we predict that the surface magnetism and conductivity can be controlled by tuning the partial pressure of oxygen