Atomistic Investigation of Grain Boundary Fracture in Alumina

Grain boundary (GB) fracture is a major mechanism of material failure in polycrystalline ceramics. However, the intricate atomic arrangements of GBs have impeded our understanding of the atomistic mechanisms of these processes. In this study, we investigated the atomic-scale crack propagation behavior of an α-Al2O3 ∑13 grain boundary, using a combination of in situ transmission electron microscopy (TEM) and scanning TEM. The atomic-scale fracture path along the GB core was directly determined by the observation of the atomic structures of the fractured surfaces, which is consistent with density functional theory calculations. We found that the GB fracture can be attributed to the weaker local bonds and a smaller number of bonds along the fracture path. Our findings provide atomistic insights into the mechanisms of crack propagation along GBs, offering significant implications for GB engineering and the toughening of ceramics

Atomistic Investigation of Grain Boundary Fracture in Alumina

Grain boundary (GB) fracture is a major mechanism of material failure in polycrystalline ceramics. However, the intricate atomic arrangements of GBs have impeded our understanding of the atomistic mechanisms of these processes. In this study, we investigated the atomic-scale crack propagation behavior of an α-Al2O3 ∑13 grain boundary, using a combination of in situ transmission electron microscopy (TEM) and scanning TEM. The atomic-scale fracture path along the GB core was directly determined by the observation of the atomic structures of the fractured surfaces, which is consistent with density functional theory calculations. We found that the GB fracture can be attributed to the weaker local bonds and a smaller number of bonds along the fracture path. Our findings provide atomistic insights into the mechanisms of crack propagation along GBs, offering significant implications for GB engineering and the toughening of ceramics

Patterning Oxide Nanopillars at the Atomic Scale by Phase Transformation

Phase transformations in crystalline materials are common in nature and often modify dramatically properties of materials. The ability to precisely control them with a high spatial precision represents a significant step forward in realizing new functionalities in confined dimensions. However, such control is extremely challenging particularly at the atomic scale due to the intricacies in governing thermodynamic conditions with a high spatial accuracy. Here, we apply focused electron beam of a scanning transmission electron microscope to irradiate SrNbO_3.4 crystals and demonstrate a precise control of a phase transformation from layered SrNbO_3.4 to perovskite SrNbO₃ at the atomic scale. By purposely squeezing O atoms out of the vertex-sharing NbO₆ octahedral slabs, their neighboring slabs zip together, resulting in a patterning of SrNbO₃ nanopillars in SrNbO_3.4 matrix. Such phase transformations can be spatially manipulated with an atomic precision, opening up a novel avenue for materials design and processing and also for advanced nanodevice fabrication

Stable Magnetic Skyrmion States at Room Temperature Confined to Corrals of Artificial Surface Pits Fabricated by a Focused Electron Beam

Stable confinement of elemental magnetic nanostructures, such as a single magnetic domain, is fundamental in modern magnetic recording technology. It is well-known that various magnetic textures can be stabilized by geometrical confinement using artificial nanostructures. The magnetic skyrmion, with novel spin texture and promise for future memory devices because of its topological protection and dimension at the nanometer scale, is no exception. So far, skyrmion confinement techniques using large-scale boundaries with limited geometries such as isolated disks and stripes prepared by conventional microfabrication techniques have been used. Here, we demonstrate an alternative technique confining skyrmions to artificial nanostructures (corrals) built from surface pits fabricated by a focused electron beam. Using aberration-corrected differential phase contrast scanning transmission electron microscopy, we directly visualized stable skyrmion states confined at a room temperature to corrals made of artificial surface pits on a thin plate of Co₈Zn₈Mn₄. We observed a stable single-skyrmion state confined to a triangular corral and a unique transition into a triple-skyrmions state depending on the perpendicular magnetic field. Furthermore, we made an array of stable single-skyrmion states by using concatenated triangular corrals. Artificial control of skyrmion states with the present technique should be a powerful way to realize future nonvolatile memory devices using skyrmions

Atomic-Scale Tracking of a Phase Transition from Spinel to Rocksalt in Lithium Manganese Oxide

For the intercalation type cathode in lithium-ion batteries, the structural framework of electrode is expected to remain unchanged during lithium insertion and extraction. Unfavorable phase transition in electrode materials, which has been frequently observed, modifies the structural framework, which leads to capacity loss and voltage decay. Here, we track atoms motion/shift in lithium manganese oxide during a phase transition from spinel to rocksalt by using atomically resolved aberration corrected scanning transmission electron microscopy and spectroscopy. We find that when given energy, the transition metal cation can readily hop between oxygen tetrahedral and octahedral sites in oxygen deficient lithium manganese oxide similar to lithium diffusion behavior, which leaves the anion structure framework almost unchanged. During this phase transition, the intermediate state, migration length, and atomic structure of phase boundaries are revealed, and the mechanism is discussed. Our observations help us to understand the past experimental phenomena and provide useful information to stabilize the structure of electrode materials and thus improve the cycling life of lithium-ion batteries

Direct Observation of Impurity Segregation at Dislocation Cores in an Ionic Crystal

Dislocations, one-dimensional lattice defects, are known to strongly interact with impurity atoms in a crystal. This interaction is generally explained on the basis of the long-range strain field of the dislocation. In ionic crystals, the impurity–dislocation interactions must be influenced by the electrostatic effect in addition to the strain effect. However, such interactions have not been verified yet. Here, we show a direct evidence of the electrostatic impurity–dislocation interaction in α-Al₂O₃ by visualizing the dopant atom distributions at dislocation cores using atomic-resolution scanning transmission electron microscopy (STEM). It was found that the dopant segregation behaviors strongly depend on the kind of elements, and their valence states are considered to be a critical factor. The observed segregation behaviors cannot be explained by the elastic interactions only, but can be successfully understood if the electrostatic interactions are taken into account. The present findings will lead to the precise and quantitative understanding of impurity induced dislocation properties in many materials and devices

High Electron Mobility of Nb-Doped SrTiO₃ Films Stemming from Rod-Type Sr Vacancy Clusters

Achieving high electron mobility in SrTiO₃ films is of significant interest, particularly in relation to technological applications such as oxide semiconductors, field-induced superconductors, and thermoelectric generators. One route to achieving high electron mobility is growth of high quality SrTiO₃ films with low defect concentrations. Another approach for mobility enhancement is applying a strain to the crystal. However, the maximum mobilities obtainable by these approaches are limited both by external and internal factors (currently available fabrication techniques, and maximum crystal strain, for example). In this paper, we demonstrate a unique crystal engineering approach to alter the strain in Nb-doped SrTiO₃ films based on the deliberate introduction of Sr vacancy clusters. Nb-doped SrTiO₃ films produced in this manner are found to exhibit remarkably enhanced electron mobilities (exceeding 53 000 cm² V^–1 s^–1). This method of defect engineering is expected to enable tuning and enhancement of electron mobilities not only in SrTiO₃ films, but also in thin films and bulk crystals of other perovskite-type materials

Atomic-Scale Identification of Individual Lanthanide Dopants in Optical Glass Fiber

Various dopants are added in commercially available optical glass fibers. The specific atomic species and charge state of lanthanide dopants are known to significantly influence the fiber’s optical properties. For understanding the role of dopants on the optical properties, atomic-scale identification of the lanthanide dopants in the optical fiber is crucial. Aberration-corrected scanning transmission electron microscopy (STEM) is especially powerful for visualizing individual atoms of heavy elements buried in a matrix composed of light elements. Here, we apply aberration-corrected high-angle annular dark field (HAADF)-STEM to directly visualize individual erbium (Er) dopants buried in the optical glass fiber. Molecular dynamics and image simulations are used to interpret the experimental images and draw quantitative conclusions. The visibility of the buried Er atoms in the amorphous glass is strongly dependent on the defocus and specimen thickness, and only Er atoms in very thin regions can be reliably identified

Atomic-Scale Observations of (010) LiFePO₄ Surfaces Before and After Chemical Delithiation

The ability to view directly the surface structures of battery materials with atomic resolution promises to dramatically improve our understanding of lithium (de)­intercalation and related processes. Here we report the use of state-of-the-art scanning transmission electron microscopy techniques to probe the (010) surface of commercially important material LiFePO₄ and compare the results with theoretical models. The surface structure is noticeably different depending on whether Li ions are present in the topmost surface layer or not. Li ions are also found to migrate back to surface regions from within the crystal relatively quickly after partial delithiation, demonstrating the facile nature of Li transport in the [010] direction. The results are consistent with phase transformation models involving metastable phase formation and relaxation, providing atomic-level insights into these fundamental processes

Full Determination of Individual Reconstructed Atomic Columns in Intermixed Heterojunctions

Heterojunctions offer a tremendous opportunity for fundamental as well as applied research, ranging from the unique electronic phases in between oxides to the contact issues in semiconductor devices. Despite their pivotal roles, determining individual building atom of matter in heterojunctions is still challenging, especially for those between highly dissimilar structures, in which breaking of symmetry, chemistry, and bonds may give rise to complex reconstruction and intermixing at the junction. Here, we combine electron microscopy, spectroscopy, and first-principles calculations to determine individual reconstructed atomic columns and their charge states in a complex, multicomponent heterojunction between the delafossite CuScO₂ and spinel MgAl₂O₄. The high resolution enables us to demonstrate that the reconstructed region can accommodate a highly selective intermixing of Cu cations at specific Sc cation sites with half atomic density, forming a complex ordered superstructure. Such ability to resolve reconstructed heterojunctions to the atomic dimensions helps elucidate atomistic mechanisms and discover novel properties with applications in a diverse range of scientific disciplines