Crystalline interfaces in materials often govern the macroscopic functional properties owing to their complex structure and chemical inhomogeneity. For ionic crystals, however, such understanding has been precluded by the debatable local anion distribution across crystal interfaces. In this study, using yttria-stabilized zirconia as a model material, the oxygen vacancy distribution across individual grain boundaries was directly quantified by atomic-resolution scanning transmission electron microscopy with ultrahigh-sensitive energy-dispersive X-ray spectroscopy. Combined with dynamical scattering calculations, we unambiguously show that the relative oxygen concentrations increase in four high-angle grain boundaries, indicating that the oxygen vacancies are actually depleted near the grain boundary cores. These results experimentally evidence that the long-range electric interaction is the dominant factor to determine the local point defect distribution at ionic crystal interfaces.
We study the effects of specimen mistilt on the picometer-scale measurement of local structure by combing experiment and simulation in annular bright-field scanning transmission electron microscopy (ABF-STEM). A relative distance measurement method is proposed to separate the tilt effects from the scan noise and sample drift induced image distortion. We find that under a typical experimental condition a small specimen tilt (∼6 mrad) in 25 nm thick SrTiO along [001] causes 11.9 pm artificial displacement between O and Sr/TiO columns in ABF image, which is more than 3 times of scan noise and sample drift induced image distortion ∼3.2 pm, suggesting the tilt effect could be dominant for the quantitative analysis of ABF images. The artifact depends on the crystal mistilt angle, specimen thickness, defocus, convergence angle and uncorrected aberration. Our study provides useful insights into detecting and correcting tilt effects during both experiment operation and data analysis to extract the real structure information and avoid mis-interpretations of atomic structure as well as the properties such as oxygen octahedral distortion/shift.
Probing the charge density distributions in materials at atomic scale remains an extremely demanding task, particularly in real space. However, recent advances in differential phase contrast-scanning transmission electron microscopy (DPC-STEM) bring this possibility closer by directly visualizing the atomic electric field. DPC-STEM at atomic resolutions measures how a sub-angstrom electron probe passing through a material is affected by the atomic electric field, the field between the nucleus and the surrounding electrons. Here, we perform a fully quantitative analysis which allows us to probe the charge density distributions inside atoms, including both the positive nuclear and the screening electronic charges, with subatomic resolution and in real space. By combining state-of-the-art DPC-STEM experiments with advanced electron scattering simulations we are able to map the spatial distribution of the electron cloud within individual atomic columns. This work constitutes a crucial step toward the direct atomic scale determination of the local charge redistributions and modulations taking place in materials systems.
The near-edge fine structure of an ionization edge in electron energy-loss spectroscopy provides bonding and elemental information. We investigate the fine structure of the O K edge in SrTiO 3 , where the oxygen atoms have identical local bonding environments in three dimensions but differ in their two-dimensional projection. By removing the effects of elastic and thermal diffuse scattering in experimental data, we demonstrate a small difference between the O columns that are nonequivalent in projection, which was not evident before the removal of scattering of the probing electrons. We explore the robustness of this method to the uncertainty in various experimental parameters.
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