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Grain boundary (GB) migration plays an important role in modifying the microstructures and the related properties of polycrystalline materials, and is governed by the atomistic mechanism by which the atoms are displaced from one grain to another. Although such an atomistic mechanism has been intensively investigated, it is still experimentally unclear as to how the GB migration proceeds at the atomic scale. With the aid of high-energy electron-beam irradiation in atomic-resolution scanning transmission electron microscopy, we controllably triggered the GB migration in α-Al 2 O 3 and directly visualized the atomistic GB migration as a stop motion movie. It was revealed that the GB migration proceeds by the cooperative shuffling of atoms on GB ledges along specific routes, passing through several different stable and metastable GB structures with low energies. We demonstrated that GB migration could be facilitated by the GB structural transformations between these low-energy structures. The atomic process of grain boundary migration has been directly observed by scanning transmission electron microscopy, revealing transformations between different stable or metastable grain boundary structures.

Impurity doping is a conventional but one of the most effective ways to control the functional properties of materials. In insulating materials, the dopant solubility limit is considerably low in general, and the dopants often segregate to grain boundaries (GBs) in polycrystals, which significantly alter their entire properties. However, detailed mechanisms on how dopant atoms form structures at GBs and change their properties remain a matter of conjecture. Here, we show GB structural transformation in α -Al 2 O 3 induced by co-segregation of Ca and Si aliovalent dopants using atomic-resolution scanning transmission electron microscopy combined with density functional theory calculations. To accommodate large-sized Ca ions at the GB core, the pristine GB atomic structure is transformed into a new GB structure with larger free volumes. Moreover, the Si and Ca dopants form a chemically ordered structure, and the charge compensation is achieved within the narrow GB core region rather than forming broader space charge layers. Our findings give an insight into GB engineering by utilizing aliovalent co-segregation. The effect of aliovalent doping on grain boundary is not yet fully understood at the atomic level. Here, the authors report grain boundary structural transformation in α-Al 2 O 3 is induced by co-segregation of multiple dopants using atomic-resolution electron microscopy and theoretical calculations.

Lithium-excess layered cathode materials such as Li 2 MnO 3 have attracted much attention owing to their high energy densities. It has been proposed that oxygen-release and cation-mixing might be induced by delithiation. However, it is still unclear as to how the delithiated-region grows. Here, by using atomic-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy, we directly observe the atomic structures at the interface between pristine and delithiated regions in the partially delithiated Li 2 MnO 3 single crystal. We elucidate that the delithiated regions have extensive amounts of irreversible defects such as oxygen-release and Mn/Li cation-mixing. At the interface, a partially cation disordered structure is formed, where Mn migration occurred only in the specific Mn/Li layers. Besides, a number of dislocations are formed at the interface to compensate the lattice mismatch between the pristine and delithiated regions. The observed oxygen-release and dislocations could govern the growth of delithiated-regions and performance degradation in Li 2 MnO 3 . The delithiation process in lithium excess cathode material of Li 2 MnO 3 has remained unclear. Here, the authors report that delithiation is governed by the climb motion of dislocations with the aid of oxygen-release, determined directly by atomic-resolution STEM imaging and spectroscopy.

Grain boundaries (GBs) are considered as the effective sinks for point defects, which improve the radiation resistance of materials. However, the fundamental mechanisms of how the GBs absorb and annihilate point defects under irradiation are still not well understood at atomic scale. With the aid of the atomic resolution scanning transmission electron microscope, we experimentally investigate the atomistic mechanism of point defects absorption by a ∑31 GB in α-Al 2 O 3 under high energy electron beam irradiation. It is shown that a disconnection pair is formed, during which all the Al atomic columns are tracked. We demonstrate that the formation of the disconnection pair is proceeded with disappearing of atomic columns in the GB core, which suggests that the GB absorbs vacancies. Such point defect absorption is attributed to the nucleation and climb motion of disconnections. These experimental results provide an atomistic understanding of how GBs improve the radiation resistance of materials. Grain boundaries can improve the radiation resistance of a material by annihilating point defects formed under irradiation, however the atomistic mechanism is still unclear. Here the authors demonstrate grain boundaries absorb point defects through the climb motion of disconnections.

Characterizing magnetic structures down to atomic dimensions is central to the design and control of nanoscale magnetism in materials and devices. However, real-space visualization of magnetic fields at such dimensions has been extremely challenging. In recent years, atomic-resolution differential phase contrast scanning transmission electron microscopy (DPC STEM) 1 has enabled direct imaging of electric field distribution even inside single atoms 2 . Here we show real-space visualization of magnetic field distribution inside antiferromagnetic haematite (α-Fe 2 O 3 ) using atomic-resolution DPC STEM in a magnetic-field-free environment 3 . After removing the phase-shift component due to atomic electric fields and improving the signal-to-noise ratio by unit-cell averaging, real-space visualization of the intrinsic magnetic fields in α-Fe 2 O 3 is realized. These results open a new possibility for real-space characterization of many magnetic structures. Real-space visualization of the magnetic fields in antiferromagnetic haematite is achieved using atomic-resolution differential phase contrast scanning transmission electron microscopy in a magnetic-field-free environment.

Space charge layers (SCLs) formed at grain boundaries (GBs) are considered to critically influence the properties of polycrystalline materials such as ion conductivities. Despite the extensive researches on this issue, the presence of GB SCLs and their relationship with GB orientations, atomic-scale structures and impurity/solute segregation behaviors remain controversial, primarily due to the difficulties in directly observing charge distribution at GBs. In this study, we directly observe electric field distribution across the well-defined yttria-stabilized zirconia (YSZ) GBs by tilt-scan averaged differential phase contrast scanning transmission electron microscopy. Our observation clearly reveals the existence of SCLs across the YSZ GBs with nanometer precision, which are significantly varied depending on the GB orientations and the resultant core atomic structures. Moreover, the magnitude of SCLs show a strong correlation with yttrium segregation amounts. This study provides critical insights into the complex interplay between SCLs, orientations, atomic structures and segregation of GBs in ionic crystals. Here the authors directly observe space-charge-induced electric fields at yttria-stabilized zirconia grain boundaries, revealing how space charge layers corelate with grain boundary orientations, core atomic structures, and yttrium segregation amounts.

In fracture processes, grain boundaries behave as preferential paths for crack propagation. These grain boundary fractures proceed by the atomic-bond rupture within the grain boundary cores, and thus grain boundary structures have crucial influence on the fracture properties. However, the relationship between grain boundary structures and atomic fracture processes has been a matter of conjecture, especially in the case of dopant-segregated grain boundaries which have complicated local structures and chemistries. Here, we determine the atomic-bond breaking path within a dopant-segregated Al 2 O 3 grain boundary core, via atomic-scale observations of the as-fractured surface and the crack tip introduced by in situ nanoindentation experiments inside a transmission electron microscope. Our observations show that the atomic fracture path is selected to produce less coordination-deficient oxygen polyhedra of dopant cations, which is rationalised using first-principles calculations. The present findings indicate that the atomic coordination geometry at the grain boundary core affects the fracture processes. Cracks propagate preferentially along grain boundaries, but what happens exactly at the atomic scale remains unclear. Here, the authors combine atomic-scale observations and first-principles calculations to show local coordination chemistry at a dopant-segregated alumina grain boundary core dictates the atomic bond-breaking path.

Mobile charge carriers are essential components in high-performance, nano-engineered semiconductor devices. Employing charge carriers confined to heterointerfaces, the so-called two-dimensional electron gas, is essential for improving device performance. The real-space visualization of a two-dimensional electron gas at the nanometre scale is desirable. However, it is challenging to accomplish by means of electron microscopy due to an unavoidable strong diffraction contrast formation at the heterointerfaces. We performed direct, nanoscale electric field imaging across a GaN-based semiconductor heterointerface using differential phase contrast scanning transmission electron microscopy by suppressing diffraction contrasts. For both nearly the lattice-matched GaN/Al 0.81 In 0.19 N interface and pseudomorphic GaN/Al 0.88 In 0.12 N interface, the extracted quantitative electric field profiles show excellent agreement with profiles predicted using Poisson simulation. Furthermore, we used the electric field profiles to quantify the density and distribution of the two-dimensional electron gas across the heterointerfaces with nanometre precision. This study is expected to guide the real-space characterization of local charge carrier density and distribution in semiconductor devices. Differential phase contrast scanning transmission electron microscopy probes the electric field distribution across a GaN-based semiconductor heterointerface.

Liquid crystals are mostly formed by self-assembly of organic molecules. In contrast, inorganic materials available as liquid crystals are limited. Here we report the development of liquid-crystalline (LC) hydroxyapatite (HAp), which is an environmentally friendly and biocompatible biomineral. Its alignment behavior, magneto-optical properties, and atomic-scale structures are described. We successfully induce LC properties into aqueous colloidal dispersions of rod-shaped HAp by controlling the morphology of the material using acidic macromolecules. These LC HAp nanorod materials are macroscopically oriented in response to external magnetic fields and mechanical forces. We achieve magnetic modulation of the optical transmission by dynamic control of the LC order. Atomic-scale observations using transmission electron microscopy show the self-organized inorganic/organic hybrid structures of mesogenic nanorods. HAp liquid crystals have potential as bio-friendly functional materials because of their facile preparation, the bio-friendliness of HAp, and the stimuli-responsive properties of these colloidal ordered fluids. Liquid crystals comprising inorganic species are far less common than their organic-based counterparts. Here, the authors report a magneto-optically responsive liquid crystal based on nanorods of the biomineral hydroxyapatite, representing a new type of biologically-based, dynamic inorganic material.

Grain boundary segregation is a critical issue in materials science because it determines the properties of individual grain boundaries and thus governs the macroscopic properties of materials. Recent progress in electron microscopy has greatly improved our understanding of grain boundary segregation phenomena down to atomistic dimensions, but solute segregation is still extremely challenging to experimentally identify at the atomic scale. Here, we report direct observations of atomic-scale yttrium solute segregation behaviours in an yttria-stabilized-zirconia grain boundary using atomic-resolution energy-dispersive X-ray spectroscopy analysis. We found that yttrium solute atoms preferentially segregate to specific atomic sites at the core of the grain boundary, forming a unique chemically-ordered structure across the grain boundary. Solute segregation is challenging to experimentally identify at the atomic scale. Here, the authors report the direct observation of atomic site-dependent solute segregation behaviour in an yttria-stabilized zirconia grain boundary by atomic-resolution energy-dispersive X-ray spectroscopy.