Practical spatial resolution of electron energy loss spectroscopy in aberration corrected scanning transmission electron microscopy

The resolution of electron energy loss spectroscopy (EELS) is limited by delocalization of inelastic electron scattering rather than probe size in an aberration corrected scanning transmission electron microscope (STEM). In this study, we present an experimental quantification of EELS spatial resolution using chemically modulated 2×(LaMnO(3))/2×(SrTiO(3)) and 2×(SrVO(3))/2×(SrTiO(3)) superlattices by measuring the full width at half maxima (FWHM) of integrated Ti M(2,3), Ti L(2,3), V L(2,3), Mn L(2,3), La N(4,5), La N(2,3) La M(4,5) and Sr L(3) edges over the superlattices. The EELS signals recorded using large collection angles are peaked at atomic columns. The FWHM of the EELS profile, obtained by curve-fitting, reveals a systematic trend with the energy loss for the Ti, V, and Mn edges. However, the experimental FWHM of the Sr and La edges deviates significantly from the observed experimental tendency.     

The Electronic Structure of Pristine and Doped (100) Tilt Grain Boundaries in SrTiO3

To understand the electronic properties of doped grain boundaries, we reviewed the atomic scale techniques currently available to study the electronic structure at pristine SrTiO₃ grain boundaries. The knowledge gained from the pristine boundaries is used to interpret experimental and theoretical results from a Mn doped 5 SrTiO₃ grain boundaries. Mn atoms are shown to preferentially substitute at specific Ti sites at the grain boundary core. Furthermore, the formal oxidation state of the Mn atoms at the grain boundary core was found to be reduced compared to the Mn atoms substituting for Ti in the bulk. This change of valence did not, however, significantly affect the atomic structure of the grain boundary, as determined by Z-contrast imaging and electron energy-loss spectroscopy, which revealed similar fine-structure features at both the doped and pristine grain boundary. We conclude, therefore, that composition and atomic structure have different effects on the local electronic structure and should be treated separately in any segregation and electrical conductivity models for grain boundaries.     

On the correlation between the X‐ray absorption chemical shift and the formal valence state in mixed‐valence manganites

Here the correlation between the chemical shift in X‐ray absorption spectroscopy, the geometrical structure and the formal valence state of the Mn atom in mixed‐valence manganites are discussed. It is shown that this empirical correlation can be reliably used to determine the formal valence of Mn, using either X‐ray absorption spectroscopy or resonant X‐ray scattering techniques. The difficulties in obtaining a reliable comparison between experimental XANES spectra and theoretical simulations on an absolute energy scale are revealed. It is concluded that the contributions from the electronic occupation and the local structure to the XANES spectra cannot be separated either experimentally or theoretically. In this way the geometrical and electronic structure of the Mn atom in mixed‐valence manganites cannot be described as a bimodal distribution of the formal integer Mn³⁺ and Mn⁴⁺ valence states corresponding to the undoped references.     

Resonant inelastic X-ray scattering (RIXS) spectroscopy at the Mn K absorption pre-edge—a direct probe of the 3d orbitals

A study of the Mn K absorption pre-edges in oxides using resonant inelastic X-ray scattering (RIXS) spectroscopy is presented. The energy transfer dimension enhances the separation of the pre-edge (predominantly 1s to 3d transitions) from the main K-edge and a detailed analysis is thus possible. The RIXS spectra are sensitive to the Mn spin state. The technique thus yields detailed information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, showing the importance of (2p,3d) two-electron interactions that give rise to the spin-sensitivity.     

Chevron defect at the intersection of grain boundaries with free surfaces in Au

We have identified a new defect at the intersection between grain boundaries and surfaces in Au using atomic resolution transmission electron microscopy. At the junction line of 90 degrees <110> tilt grain boundaries of (110)-(001) orientation with the free surface, a small segment of the grain boundary, about 1 nm in length, dissociates into a triangular region with a chevronlike stacking disorder and a distorted hcp structure. The structure and stability of these defects are confirmed by atomistic simulations, and we point out the relationship with the one-dimensional incommensurate structure of the grain boundary.     

Diffusion and segregation along grain boundary at the electrolyte-anode interface in IT-SOFC

The atomic level chemical and microstructural features of grain boundaries in gadolinium-doped ceria (GDC) electrolyte thin film supported by Ni-GDC cermet anode were characterized by high resolution transmission electron microscope (HR-TEM) and scanning TEM (STEM). It was found that metallic Ni can diffuse from the anode into the thin film electrolyte along grain boundaries. In addition, Ce and Gd can also diffuse and segregate at grain boundaries between Ni grains in the anode substrate. HR-TEM observations revealed that Ni diffusion and segregation at grain boundaries between GDC grains enhanced the inhomogeneity and led to microstructural changes at grain boundary regions, i.e. the formation of superstructure. The observations also indicated that enhanced inhomogeneity at grain boundaries might play a significant role in the conductivity of GDC electrolyte film in solid oxide fuel cells.     

LaAlO3/SrTiO3界面的电子结构及光学性质的第一性原理研究

采用基于密度泛函理论框架下的第一性原理平面波超软赝势方法,结合局域密度近似（LDA）研究了钙钛矿结构氧化物LaAlO3 /SrTiO3界面的电子结构及光学性质。能带结构分析表明当形成(AlO2)-/(TiO2)0界面时其禁带宽度为1.888 eV,呈现绝缘体的性质,当形成(LaO)+/(SrO)0界面时其禁带宽度为0.021 eV,呈现半导体或半金属性质。同时,对不同界面的光学性质也进行了研究,结果表明纯相的LaAlO3和SrTiO3的吸收系数、反射系数及能量损失谱强度明显高于由这两种单质形成不同界面的强度。     

Photoemission from buried interfaces in SrTiO3/LaTiO3 superlattices

We have measured photoemission spectra of SrTiO3/LaTiO3 superlattices with a topmost SrTiO3 layer of variable thickness. A finite coherent spectral weight with a clear Fermi cutoff was observed at chemically abrupt SrTiO3/LaTiO3 interfaces, indicating that an "electronic reconstruction" occurs at the interface between the Mott insulator LaTiO3 and the band insulator SrTiO3. For SrTiO3/LaTiO3 interfaces annealed at high temperatures (approximately 1000 degrees C), which leads to Sr/La atomic interdiffusion and hence to the formation of La(1-x)Sr(x)TiO3-like material, the intensity of the incoherent part was found to be dramatically reduced whereas the coherent part with a sharp Fermi cutoff was enhanced due to the spread of charge. These important experimental features are well reproduced by layer dynamical-mean-field-theory calculation.     

铌酸钾钠基(KNN基)无铅铁电薄膜的低温铁电性能

在 SrTiO3 (001 ) 衬 底 上 生 长 SrRuO3 后, 外 延 生 长 的 0. 95 ( K0 .49 Na0 .49Li0 .02 ) ( Ta0 .02 Nb0 .8 ) O3 -0.05CaZrO3 (额外掺杂了2 wt% MnO2 ) 无铅铁电薄膜 ( 简称 KNNLT-CZM) 被系统研究. X 射线衍射结果说明KNNLT-CZM 薄膜具有较高的质量. X 射线光电子能谱 (XPS) 表明部分 K 元素没有进入 KNNLT-CZM 钙钛矿结构晶格中, Mn 元素主要以 Mn2 + 形式存在. 变温电滞回线(P-E) 表明 KNNLT-CZM 薄膜在78 K 到300 K 范围内都拥有极好的铁电性. 以上结果表明此类薄膜在电子器件应用方面具有极大的潜力.     

Cooperative Jahn-Teller phase transition in LaMnO3 studied by X-ray absorption spectroscopy

The local structure of LaMnO3 across the Jahn-Teller (JT) transition at T(JT)=750 K was studied by means of x-ray absorption near edge structure and extended x-ray absorption fine structure at the Mn K-edge. Our results indicate a similar electronic local structure for Mn atoms above and below T(JT) and a dynamical tetragonal JT distortion of MnO6 octahedra above T(JT). The structural transition is originated by the ordering of tetragonally distorted octahedra. The entropy content of the transition is analyzed within the framework of the three-state Potts model with nearest neighbor antiferrodistortive coupling.     

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.     

Dynamic evanescent phonon coupling across the La(1-x)Sr(x)MnO3/SrTiO3 interface

The transport and magnetic properties of correlated La0.53Sr0.47MnO3 ultrathin films, grown epitaxially on SrTiO3, show a sharp cusp at the structural transition temperature of the substrate. Using a combination of experiment and first principles theory we show that the cusp is a result of evanescent cross-interface coupling between the charge carriers in the film and a soft phonon mode in the SrTiO3, mediated through linked oxygen octahedral motions. The amplitude of the mode diverges at the transition temperature, and phonons are launched into the first few atomic layers of the film, affecting its electronic state.     

Atomic-scale analysis of the oxygen configuration at a SrTiO3 dislocation core

The atomic structure of a SrTiO3 dislocation is revealed directly by phase-retrieval electron microscopy. In particular, atomic columns of light oxygen are observed simultaneously with the columns of considerably heavier Sr and Ti. A distinct structural modification of the oxygen octahedra at the dislocation core as well as a significant nonstoichiometry, including a deficiency of oxygen, are observed. Deviations from the bulk chemical concentration are quantified column by column by means of structure modeling and quantum-mechanical simulations of the electron scattering process.     

Nonstoichiometry and the electrical activity of grain boundaries in SrTiO3

A combination of experiments and first-principles calculations is used to show that grain boundaries in SrTiO3 are intrinsically nonstoichiometric. Total-energy calculations reveal that the introduction of nonstoichiometry into the grain boundaries is energetically favorable and results in structures that are consistent with atomic-resolution Z-contrast micrographs. Electron energy-loss spectra provide direct evidence of nonstoichiometry. These results and calculations for nonstoichiometric grain boundaries provide an explanation of the microscopic origin of the "double Schottky barriers" that dominate the electrical behavior of polycrystalline oxides.     

Assessment of the electronic conductivity of core-shell, Fe-doped LSGM ceramics by impedance spectroscopy

The structure, microstructure and low-temperature electrical properties of core-shell-type mixed conductors based on lanthanum gallate with Fe-doped grain boundaries are analyzed in depth. Electron probe microanalysis revealed that the iron concentration in the grain-boundary regions (shell) is below 1 at.% and their thickness is no more than 1.5 μm. The low-temperature (< 400 °C) electronic conductivity is enhanced by up to 2-3 orders of magnitude with respect to the corresponding undoped ceramics, as revealed by the analysis of impedance spectra combined with microstructural information. The electronic transport numbers lie in the range between 0.35 and 0.1 at 275 to 400 °C, decreasing at higher temperatures, where the influence of grain boundaries on the overall transport properties vanishes and the ionic conductivity increases.     

Atomic structure of grain boundaries in YBa2Cu3O7-δ as observed by Z-contrast imaging

Determination of the atomic structure of grain boundaries is the key to fundamental understanding of the critical current density in polycrystalline superconductors. High-resolution images with incoherent characteristics, obtained using a high-angle annular detector on an atomic resolution scanning transmission electron microscope, are used to study the atomic arrangements of these technologically important boundaries. The incoherent Z-contrast images do not experience contrast reversals with defocus or sample thickness and display no Fresnel Fringe effects at boundaries. Observed rigid shifts of atomic columns at grain boundaries are independent of sample thickness and objective lens defocus. These characteristics allow unambiguous and intuitive interpretations of the generated images. We find the atomic structures at grain boundaries in YBa₂Cu₃O_7-δ are strongly influenced by the strong tendency of this compound to exist only as complete unit cells terminated at {001} and {100} planes. The weak-link behavior associated with high-angle grain boundaries may follow from this structure in which there is no clear connection between the {100} facets of adjacent grains. Symmetric grain boundaries where adjacent grains share a common boundary plane have also been observed in YBa₂Cu₃O_7-δ. In these boundaries partial structural coupling of the grains is maintained. There is evidence that these two boundary forms produce junctions with very different superconducting properties.     

Monitoring of the process of formation of epitaxial films with the use of ultrasoft x-ray spectroscopy

The distinctive features of the atomic and electronic structure of thin surface layers of substances in the process of formation of epitaxial silicon films on silicon are studied using the procedures of reflection and scattering of ultrasoft x-ray radiation. The angular distribution of the scattered x-ray radiation (the scattering indicatrices) and the near fine structure of SiL_2,3 spectra of reflection are investigated. The assumption of the sensitivity of the observed peak of anomalous scattering (the Yoneda peak) of x-ray radiation to the presence, in the surface regions of the materials, of extended double-boundary defects, the defects of packing, grain boundaries, dislocations, etc. is made. It is shown that the experimental procedure used makes it possible to obtain information on the surface layers of substances. Translated from Zhurnal Priklaldnoi Spektroskopii, Vol. 67, No. 4, pp. 496–498, July–August, 2000.     

Atomic many-body effects for the p-shell photoelectron spectra of transition metals

Ab initio theoretical results for the 2p- and 3p-hole states of an Mn(2+) ion are reported in order to determine the importance of atomic contributions to the photoelectron spectra of bulk MnO. A combined treatment of relativity and electron correlation reveals important physical effects that have been neglected in virtually all previous work. The many-body and relativistic effects included in the atomic model are able, without any ad hoc empirical parameters, to explain most of the features of the MnO photoelectron spectra. In particular, it is not necessary to invoke charge transfer to explain the complex p-level spectra.     

Origin of metallic states at the heterointerface between the band insulators LaAlO3 and SrTiO3

We have studied the electronic structure at the heterointerface between the band insulators LaAlO3 and SrTiO3 using in situ photoemission spectroscopy. Our experimental results clearly reveal the formation of a notched structure on the SrTiO3 side due to band bending at the metallic LaAlO3/TiO2-SrTiO3 interface. The structure, however, is absent at the insulating LaAlO3/SrO-SrTiO3 interface. The present results indicate that the metallic states originate not from the charge transfer through the interface on a short-range scale but from the accumulation of carriers on a long-range scale.     

Theoretical aspects of solute segregation to high-angle grain boundaries

A high-angle grain boundary is modeled as a planar defect characterized by its thickness and atomic density. We successively examine the elastic and electronic contributions to the solute/grain boundary binding energy. We deduce the effect of the grain boundary physical parameters on its propensity for segregation. The thickness of high-angle grain boundaries is not a fundamental parameter for segregation. The atomic density in the grain boundary controls the electronic binding energy. The rate of change of elastic constants with the density is the important factor in the elastic contribution to segregation. We conclude that segregation to boundaries with small excess volumes is not precluded.