Real-space visualization of intrinsic magnetic fields of an antiferromagnet.

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 atoms2. Here we show real-space visualization of magnetic field distribution inside antiferromagnetic haematite (α-Fe2O3) using atomic-resolution DPC STEM in a magnetic-field-free environment3. 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-Fe2O3 is realized. These results open a new possibility for real-space characterization of many magnetic structures.

An elastic metal-organic crystal with a densely catenated backbone.

What particular mechanical properties can be expected for materials composed of interlocked backbones has been a long-standing issue in materials science since the first reports on polycatenane and polyrotaxane in the 1970s1-3. Here we report a three-dimensional porous metal-organic crystal, which is exceptional in that its warps and wefts are connected only by catenation. This porous crystal is composed of a tetragonal lattice and dynamically changes its geometry upon guest molecule release, uptake and exchange, and also upon temperature variation even in a low temperature range. We indented4 the crystal along its a/b axes and obtained the Young's moduli of 1.77 ± 0.16 GPa in N,N-dimethylformamide and 1.63 ± 0.13 GPa in tetrahydrofuran, which are the lowest among those reported so far for porous metal-organic crystals5. To our surprise, hydrostatic compression showed that this elastic porous crystal was the most deformable along its c axis, where 5% contraction occurred without structural deterioration upon compression up to 0.88 GPa. The crystal structure obtained at 0.46 GPa showed that the catenated macrocycles move translationally upon contraction. We anticipate our mechanically interlocked molecule-based design to be a starting point for the development of porous materials with exotic mechanical properties. For example, squeezable porous crystals that may address an essential difficulty in realizing both high abilities of guest uptake and release are on the horizon.

Ultrahigh toughness zirconia ceramics.

The attainment of both high strength and toughness is the ultimate goal for most structural materials. Although ceramic material has been considered for use as a structural material due to its high strength and good chemical stability, it suffers from the limitation of low toughness. For instance, although Y2O3-stabilized tetragonal ZrO2 polycrystals (Y-TZPs) exhibit remarkable toughness among ceramics due to their phase transformation toughening mechanism, this toughness is still much weaker than that of metals. Here, we report Y-TZP-based ceramic materials with toughnesses exceeding 20 MPa m1/2, which is comparable to those of metals, while maintaining strengths over 1,200 MPa. The superior mechanical properties are realized by reducing the phase stability of tetragonal zirconia by tailoring the microstructure and chemistry of the Y-TZP. The proposed ceramic materials can further advance the design and application of ceramic-based structural materials.

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.

Nanoscale Localized Phonons at Al2O3 Grain Boundaries.

Nanoscale defects like grain boundaries (GBs) would introduce local phonon modes and affect the bulk materials' thermal, electrical, optical, and mechanical properties. It is highly desirable to correlate the phonon modes and atomic arrangements for individual defects to precisely understand the structure-property relation. Here we investigated the localized phonon modes of Al2O3 GBs by combination of the vibrational electron energy loss spectroscopy (EELS) in scanning transmission electron microscope and density functional perturbation theory (DFPT). The differences between GB and bulk obtained from the vibrational EELS show that the GB exhibited more active vibration at the energy range of <50 meV and >80 meV, and further DFPT results proved the wide distribution of bond lengths at GB are the main factor for the emergence of local phonon modes. This research provides insights into the phonon-defect relation and would be of importance in the design and application of polycrystalline materials.

One-dimensional van der Waals heterostructures: Growth mechanism and handedness correlation revealed by nondestructive TEM.

We recently synthesized one-dimensional (1D) van der Waals heterostructures in which different atomic layers (e.g., boron nitride or molybdenum disulfide) seamlessly wrap around a single-walled carbon nanotube (SWCNT) and form a coaxial, crystalized heteronanotube. The growth process of 1D heterostructure is unconventional-different crystals need to nucleate on a highly curved surface and extend nanotubes shell by shell-so understanding the formation mechanism is of fundamental research interest. In this work, we perform a follow-up and comprehensive study on the structural details and formation mechanism of chemical vapor deposition (CVD)-synthesized 1D heterostructures. Edge structures, nucleation sites, and crystal epitaxial relationships are clearly revealed using transmission electron microscopy (TEM). This is achieved by the direct synthesis of heteronanotubes on a CVD-compatible Si/SiO2 TEM grid, which enabled a transfer-free and nondestructive access to many intrinsic structural details. In particular, we have distinguished different-shaped boron nitride nanotube (BNNT) edges, which are confirmed by electron diffraction at the same location to be strictly associated with its own chiral angle and polarity. We also demonstrate the importance of surface cleanness and isolation for the formation of perfect 1D heterostructures. Furthermore, we elucidate the handedness correlation between the SWCNT template and BNNT crystals. This work not only provides an in-depth understanding of this 1D heterostructure material group but also, in a more general perspective, serves as an interesting investigation on crystal growth on highly curved (radius of a couple of nanometers) atomic substrates.

High-performance, semiconducting membrane composed of ultrathin, single-crystal organic semiconductors.

Thin film transistors (TFTs) are indispensable building blocks in any electronic device and play vital roles in switching, processing, and transmitting electronic information. TFT fabrication processes inherently require the sequential deposition of metal, semiconductor, and dielectric layers and so on, which makes it difficult to achieve reliable production of highly integrated devices. The integration issues are more apparent in organic TFTs (OTFTs), particularly for solution-processed organic semiconductors due to limits on which underlayers are compatible with the printing technologies. We demonstrate a ground-breaking methodology to integrate an active, semiconducting layer of OTFTs. In this method, a solution-processed, semiconducting membrane composed of few-molecular-layer-thick single-crystal organic semiconductors is exfoliated by water as a self-standing ultrathin membrane on the water surface and then transferred directly to any given underlayer. The ultrathin, semiconducting membrane preserves its original single crystallinity, resulting in excellent electronic properties with a high mobility up to 12 [Formula: see text] The ability to achieve transfer of wafer-scale single crystals with almost no deterioration of electrical properties means the present method is scalable. The demonstrations in this study show that the present transfer method can revolutionize printed electronics and constitute a key step forward in TFT fabrication processes.

Direct Observation of Atomistic Reaction Process between Pt Nanoparticles and TiO2 (110).

The catalytic activity and selectivity of heterogeneous catalysts are governed by atomic and electronic structures at the heterointerface between noble metal nanoparticles (NPs) and oxide substrates. In specific chemical reactions, it is well-known that the catalytic activity is strongly suppressed by annealing in a reducing atmosphere, so-called strong metal-support interaction (SMSI). However, it is still unclear the formation process and atomistic origin of the SMSI. By preparing well-defined platinum (Pt) NPs supported on atomically flat TiO2 (110) substrate, we directly show the formation of chemically ordered Pt-Ti intermetallic NPs and impregnation of NPs into TiO2 substrate at high temperatures by using atomic-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Furthermore, we observed negative charge transfer from the Pt-Ti intermetallic NPs to the TiO2 surface, which would strongly affect the catalytic activities.

Lithium Lanthanum Titanate Single Crystals: Dependence of Lithium-Ion Conductivity on Crystal Domain Orientation.

Lithium lanthanum titanate La2/3-xLi3xTiO3 (LLTO) has the potential to exhibit the highest Li-ion conductivity among oxide-based electrolytes because of the fast Li-ion diffusion derived from its crystal structure. Herein, bulk Li-ion conductivity of up to σbulk = 4.0 × 10-3 S/cm at 300 K, which is approximately three to four times higher than that of LLTO polycrystals, was demonstrated using LLTO single crystals, and their dependence on crystal domain orientation was examined. A change in the activation energy, which was previously obscured because of random crystal orientation, was observed at approximately 260 K. Furthermore, electron microscopy analysis indicated that the ionic conductivity of LLTOs remained higher because the region with the highest ionic conductivity was tilted away from the ideal conduction orientation. The results reported herein provide the highest conductivity in LLTO and important insights into their crystal structures, enabling higher conductivity in novel oxide-based electrolyte design.

Direct imaging of atomistic grain boundary migration.

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-Al2O3 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.

Stabilizing the metastable superhard material wurtzite boron nitride by three-dimensional networks of planar defects.

Wurtzite boron nitride (w-BN) is a metastable superhard material that is a high-pressure polymorph of BN. Clarifying how the metastable high-pressure material can be stabilized at atmospheric pressure is a challenging issue of fundamental scientific importance and promising technological value. Here, we fabricate millimeter-size w-BN bulk crystals via the hexagonal-to-wurtzite phase transformation at high pressure and high temperature. By combining transmission electron microscopy and ab initio molecular dynamics simulations, we reveal a stabilization mechanism for w-BN, i.e., the metastable high-pressure phase can be stabilized by 3D networks of planar defects which are constructed by a high density of intersecting (0001) stacking faults and {10[Formula: see text]0} inversion domain boundaries. The 3D networks of planar defects segment the w-BN bulk crystal into numerous nanometer-size prismatic domains with the reverse crystallographic polarities. Our findings unambiguously demonstrate the retarding effect of crystal defects on the phase transformations of metastable materials, which is in contrast to the common knowledge that the crystal defects in materials will facilitate the occurrence of phase transformations.

Atomistic Origin of Li-Ion Conductivity Reduction at (Li3xLa2/3-x)TiO3 Grain Boundary.

Lithium lanthanum titanate (LLTO) is one of the excellent candidates for an electrolyte in the all-solid-state Li-ion battery, owing to the high Li-ion conductivity in the bulk. However, the Li-ion conductivity at the grain boundary (GB) is largely reduced, and it is therefore important to reveal the origin of Li-ion conductivity reduction at the GB. Here, by using atomic-resolution scanning transmission electron microscopy combined with atomic force microscopy, we investigate the charge states, Li-ion conductivities, atomic and electronic structures at the LLTO Σ5 and Σ13 GBs. Although the Σ5 GB has no significant influence on Li-ion conductivity, the Σ13 GB shows the evident reduction of Li-ion conductivity. We further elucidate that the Σ13 GB is positively charged by the formation of oxygen vacancies at the GB. Such a positive charge would form the Li-ion depletion layers adjacent to the GB, which causes the significant reduction of Li-ion conductivity.

Unveiling the Electronic Structure of Grain Boundaries in Anatase with Electron Microscopy and First-Principles Modeling.

Polycrystalline anatase titanium dioxide has drawn great interest, because of its potential applications in high-efficiency photovoltaics and photocatalysts. There has been speculation on the electronic properties of grain boundaries but little direct evidence, because grain boundaries in anatase are challenging to probe experimentally and to model. We present a combined experimental and theoretical study of anatase grain boundaries that have been fabricated by epitaxial growth on a bicrystalline substrate, allowing accurate atomic-scale models to be determined. The electronic structure in the vicinity of stoichiometric grain boundaries is relatively benign to device performance but segregation of oxygen vacancies introduces barriers to electron transport, because of the development of a space charge region. An intrinsically oxygen-deficient boundary exhibits charge trapping consistent with electron energy loss spectroscopy measurements. We discuss strategies for the synthesis of polycrystalline anatase in order to minimize the formation of such deleterious grain boundaries.

Anataselike Grain Boundary Structure in Rutile Titanium Dioxide.

The formation of nanoscale phases at grain boundaries in polycrystalline materials has attracted much attention, since it offers a route toward targeted and controlled design of interface properties. However, understanding structure-property relationships at these complex interfacial defects is hampered by the great challenge of accurately determining their atomic structure. Here, we combine advanced electron microscopy together with ab initio random structure searching to determine the atomic structure of an experimentally fabricated Σ13 (221) [11̅0] grain boundary in rutile TiO2. Through careful analysis of the atomic structure and complementary electron energy-loss spectroscopy analysis we identify the existence of a unique nanoscale phase at the grain boundary with striking similarities to the bulk anatase crystal structure. Our results show a path to embed nanoscale anatase into rutile TiO2 and showcase how the atomic structure of even complex internal interfaces can be accurately determined using a combined theoretical and experimental approach.

Photoindentation: A New Route to Understanding Dislocation Behavior in Light.

It was recently found that extremely large plasticity is exhibited in bulk compression of single-crystal ZnS in complete darkness. Such effects are believed to be caused by the interactions between dislocations and photoexcited electrons and/or holes. However, methods for evaluating dislocation behavior in such semiconductors with small dimensions under a particular light condition had not been well established. Here, we propose the "photoindentation" technique to solve this issue by combining nanoscale indentation tests with a fully controlled lighting system. The quantitative data analyses based on this photoindentation approach successfully demonstrate that the first pop-in stress indicating dislocation nucleation near the surface of ZnS clearly increases by light irradiation. Additionally, the room-temperature indentation creep tests show a drastic reduction of the dislocation mobility under light. Our approach demonstrates great potential in understanding the light effects on dislocation nucleation and mobility at the nanoscale, as most advanced technology-related semiconductors are limited in dimensions.

Single-Dislocation Schottky Diodes.

Dislocations often exhibit unique physical properties distinct from those of the bulk material. However, functional applications of dislocations are challenging due to difficulties in the construction of high-performance devices of dislocations. Here we demonstrate unidirectional single-dislocation Schottky diode arrays in a Fe2O3 thin film on Nb-doped SrTiO3 substrates. Conductivity measurements using conductive atomic force microscopy indicate that a net current will flow through individual dislocation Schottky diodes under forward bias and disappear under reverse bias. Under cyclic bias voltages, the single-dislocation Schottky diodes exhibit a distinct resistive switching behavior containing low-resistance and high-resistance states with a high resistance ratio of ∼103. A combined study of transmission electron microscopy and first-principles calculations reveals that the Fe2O3 dislocations comprise mixed Fe2+ and Fe3+ ions due to O deficiency and exhibit a one-dimensional electrical conductivity. The single-dislocation Schottky diodes may find applications for developing ultrahigh-density electronic and memory devices.

Two-Dimensional Room-Temperature Giant Antiferrodistortive SrTiO_{3} at a Grain Boundary.

The broken symmetry at structural defects such as grain boundaries (GBs) discontinues chemical bonds, leading to the emergence of new properties that are absent in the bulk owing to the couplings between the lattice and other parameters. Here, we create a two-dimensional antiferrodistortive (AFD) strontium titanate (SrTiO_{3}) phase at a Σ13(510)/[001] SrTiO_{3} tilt GB at room temperature. We find that such an anomalous room-temperature AFD phase with the thickness of approximate six unit cells is stabilized by the charge doping from oxygen vacancies. The localized AFD originated from the strong lattice-charge couplings at a SrTiO_{3} GB is expected to play important roles in the electrical and optical activity of GBs and can explain past experiments such as the transport properties of electroceramic SrTiO_{3}. Our study also provides new strategies to create low-dimensional anomalous elements for future nanoelectronics via grain boundary engineering.

Direct Measurement of Electronic Band Structures at Oxide Grain Boundaries.

Grain boundaries (GBs) modulate the macroscopic properties in polycrystalline materials because they have different atomic and electronic structures from the bulk. Despite the progress on the understanding of GB atomic structures, knowledge of the localized electronic band structures is still lacking. Here, we experimentally characterized the atomic structures and the band gaps of four typical GBs in α-Al2O3 by scanning transmission electron microscopy and valence electron energy-loss spectroscopy (EELS). It was found that the band gaps of the GBs are narrowed by 0.5-2.1 eV compared with that of 8.8 eV in the bulk. By combing core-loss EELS with first-principles calculations, we elucidated that the band gap reductions directly correlate with the decrease of the coordination numbers of Al and O ions at the GBs. These results provide in-depth understanding between the local atomic and electronic band structures for GBs and demonstrate a novel electronic-structure analysis for crystalline defects.

Ferroelectric Oxide Thin Film with an Out-of-Plane Electrical Conductivity.

Ferroelectricity and electrical conductivity are two fundamentally incompatible properties that are difficult to simultaneously achieve in a material. Here, we combine these two contradictory properties by embedding conducting SrNbO3 micro/nanopillars into a ferroelectric SrNbO3.5 (i.e., Sr2Nb2O7) thin film. The high-Tc ferroelectric SrNbO3.5 thin film is epitaxially grown on a LaAlO3 substrate by pulsed laser deposition. The conducting SrNbO3 micro/nanopillars are introduced into the film via an electron-irradiation-induced SrNbO3.5-to-SrNbO3 phase transformation triggered by a focused electron beam. The sizes and distribution of the SrNbO3 micro/nanopillars can be accurately controlled through artificial manipulation of the electron-irradiation-induced SrNbO3.5-to-SrNbO3 phase transformation. The ferroelectric SrNbO3/SrNbO3.5 thin film with an in-plane polarization exhibits an electrical conductivity in the out-of-plane direction. Such conducting ferroelectric thin films may lead to the discovery of plentiful physical phenomena and have great potential for pyroelectric, photoelectric, and multiferroic applications.

Defect Engineering and Anisotropic Modulation of Ionic Transport in Perovskite Solid Electrolyte LixLa(1-x)/3NbO3.

Solid electrolytes, such as perovskite Li3xLa2/1-xTiO3, LixLa(1-x)/3NbO3 and garnet Li7La3Zr2O12 ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in LixLa(1-x)/3NbO3 (x = 0.1~0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications.