Uncovering the crystal defects within aragonite CaCO3.

Knowledge of deformation mechanisms in aragonite, one of the three crystalline polymorphs of CaCO3, is essential to understand the overall excellent mechanical performance of nacres. Dislocation slip and deformation twinning were claimed previously as plasticity carriers in aragonite, but crystallographic features of dislocations and twins have been poorly understood. Here, utilizing various transmission electron microscopy techniques, we reveal the atomic structures of twins, partial dislocations, and associated stacking faults. Combining a topological model and density functional theory calculations, we identify complete twin elements, characters of twinning disconnection, and the corresponding twin shear angle (∼8.8°) and rationalize unique partial dislocations as well. Additionally, we reveal an unreported potential energy dissipation mode within aragonite, namely, the formation of nanograins via the pile-up of partial dislocations. Based on the microstructural comparisons of biogenic and abiotic aragonite, we find that the crystallographic features of twins are the same. However, the twin density is much lower in abiotic aragonite due to the vastly different crystallization conditions, which in turn are likely due to the absence of organics, high temperature and pressure differences, the variation in inorganic impurities, or a combination thereof. Our findings enrich the knowledge of intrinsic crystal defects that accommodate plastic deformation in aragonite and provide insights into designing bioengineering materials with better strength and toughness.

Precisely Tailoring WSe2 Polarity via van der Waals Bismuth-Gold Modulated Contact.

Creating high-quality contacts between high-melting-point metals and delicate two-dimensional (2D) semiconductors poses a critical challenge to polarity control due to inevitable chemical disorder and Fermi-level pinning observed in the contact regions. Here, we report a van der Waals (vdW) integration strategy to precisely tailor the WSe2 polarity by meticulously modulating metal contact compositions. Controlling the low-melting-point bismuth (Bi) thickness effectively modulates the Bi/Au dominant contact with WSe2. This facilitates the precise polarity transformation between n-type, ambipolar, and p-type, with exceptional field-effect mobilities of 200 cm2 V-1 s-1 for electrons and 136 cm2 V-1 s-1 for holes. Within this vdW geometry, we further demonstrate the fundamental electrical components such as diodes and complementary inverters with enhanced rectification ratios and voltage gains. Our results showcase an effective and compatible with mass manufacturing method for precise polarity modulation of 2D semiconductors, providing a promising pathway toward large-scale high-performance 2D electronics and integrated circuits.

A Roadmap for Ferroelectric-Antiferroelectric Phase Transition.

Antiferroelectric materials have shown great potential in electronic devices benefiting from the reversible phase transition between ferroelectric and antiferroelectric phases. Understanding the dipole arrangements and clear phase transition pathways is crucial for design of antiferroelectric materials-based energy storage and conversion devices. However, the specific phase transition details remain largely unclear and even controversial to date. Here, we have grown a series of PbZrO3 on SrTiO3 substrates and elucidated the fine atom structures and phase transition pathways using atomic-resolution transmission electron microscopy. Specifically, a roadmap for ferroelectric to antiferroelectric phase transitions, here with increasing film thickness, is determined as ferroelectric rhombohedral (R3c)-ferroelectric monoclinic (Pc)-ferrielectric orthorhombic (Ima2)-antiferroelectric orthorhombic (Pbam), where Pc and Ima2 phases act as structural bridges. Moreover, the phase transition pathway is strongly related to the synergistic effect of oxygen octahedral tilting and cation displacement. These findings provide an insightful understanding for the theories and related properties of antiferroelectrics.

Large Polarization Near 50 µC/cm2 in a Single Unit Cell Layer SrTiO3.

The generally nonpolar SrTiO3 has attracted more attention recently because of its possibly induced novel polar states and related paraelectric-ferroelectric phase transitions. By using controlled pulsed laser deposition, high-quality, ultrathin, and strained SrTiO3 layers were obtained. Here, transmission electron microscopy and theoretical simulations have unveiled highly polar states in SrTiO3 films even down to one unit cell at room temperature, which were stabilized in the PbTiO3/SrTiO3/PbTiO3 sandwich structures by in-plane tensile strain and interfacial coupling, as evidenced by large tetragonality (∼1.05), notable polar ion displacement (0.019 nm), and thus ultrahigh spontaneous polarization (up to ∼50 µC/cm2). These values are nearly comparable to those of the strong ferroelectrics as the PbZrxTi1-xO3 family. Our findings provide an effective and practical approach for integrating large strain states into oxide films and inducing polarization in nonpolar materials, which may broaden the functionality of nonpolar oxides and pave the way for the discovery of new electronic materials.

Atomic Insight into the Successive Antiferroelectric-Ferroelectric Phase Transition in Antiferroelectric Oxides.

Antiferroelectrics characterized by voltage-driven reversible transitions between antiparallel and parallel polarity are promising for cutting-edge electronic and electrical power applications. Wide-ranging explorations revealing the macroscopic performances and microstructural characteristics of typical antiferroelectric systems have been conducted. However, the underlying mechanism has not yet been fully unraveled, which depends largely on the atomistic processes. Herein, based on atomic-resolution transmission electron microscopy, the deterministic phase transition pathway along with the underlying lattice-by-lattice details in lead zirconate thin films was elucidated. Specifically, we identified a new type of ferrielectric-like dipole configuration with both angular and amplitude modulations, which plays the role of a precursor for a subsequent antiferroelectric to ferroelectric transformation. With the participation of the ferrielectric-like phase, the phase transition pathways driven by the phase boundary have been revealed. We provide new insights into the consecutive phase transformation in low-dimensional lead zirconate, which thus would promote potential antiferroelectric-based multifunctional devices.

Low-oxygen rare earth steels.

Rare earth (RE) addition to steels to produce RE steels has been widely applied when aiming to improve steel properties. However, RE steels have exhibited extremely variable mechanical performances, which has become a bottleneck in the past few decades for their production, utilization and related study. Here in this work, we discovered that the property variation of RE steels stems from the presence of oxygen-based inclusions. We proposed a dual low-oxygen technology, and keeping low levels of oxygen content in steel melts and particularly in the raw RE materials, which have long been ignored, to achieve impressively stable and favourable RE effects. The fatigue life is greatly improved by only parts-per-million-level RE addition, with a 40-fold improvement for the tension-compression fatigue life and a 40% enhancement of the rolling contact fatigue life. We find that RE appears to act by lowering the carbon diffusion rate and by retarding ferrite nucleation at the austenite grain boundaries. Our study reveals that only under very low-oxygen conditions can RE perform a vital role in purifying, modifying and micro-alloying steels, to improve the performance of RE steels.

Direct Observation of Large-Scale Screw Dislocation Grids in Oxide Heteroepitaxies.

Screw dislocation is important not only for understanding plastic deformation of crystals but also for optical and electrical properties of materials. However, characterizations of screw dislocations are still challenging since there is almost no atom distortion when viewed along the dislocation line. In particular, although it is theoretically known that shear strains in heteroepitaxy systems may be relaxed via screw dislocation grids, the specific structures and thickness-dependent evolutions of these grids are still largely unknown. Here, by using orthorhombic [001]-oriented DyScO3 substrates we have directly observed large-scale screw dislocation grids in the DyScO3/BiFeO3 oxide heteroepitaxies exhibiting large shear strain. Pure screw dislocations with a[100] and a[01̅0] Burgers vectors were confirmed by multiscale transmission electron microscopy study. Our results directly confirm screw dislocation grids as a factor to tailor shear strains in epitaxial systems and suggest a practical platform for studying structures and induced responses corresponding to screw dislocations.

Real-Time Transformation of Flux-Closure Domains with Superhigh Thermal Stability.

Polar topologies have received extensive attention due to their exotic configurations and functionalities. Understanding their responsive behaviors to external stimuli, especially thermal excitation, is highly desirable to extend their applications to high temperature, which is still unclear. Here, combining in situ transmission electron microscopy and phase-field simulations, the thermal dynamics of the flux-closure domains were illuminated in PbTiO3/SrTiO3 multilayers. In-depth analyses suggested that the topological transition processes from a/c domains to flux-closure quadrants were influenced by the boundary conditions of PbTiO3 layers. The symmetrical boundary condition stabilized the flux-closure domains at higher temperature than in the asymmetrical case. Furthermore, the reversible thermal responsive behaviors of the flux-closure domains displayed superior thermal stability, which maintained robust up to 450 °C (near the Curie temperature). This work provides new insights into the dynamics of polar topologies under thermal excitation and facilitates their applications as nanoelectronics under extreme conditions.

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.

Atomic-Scale Tunable Flexoelectric Couplings in Oxide Multiferroics.

Flexoelectricity is an effective tool in modulating the crystallographic structures and properties of oxides for multifunctional applications. However, engineering the nonuniform strain to obtain tunable flexoelectric behaviors at the atomic scale remains an ongoing challenge in conventional substrate-imposed ferroelectric films. Here, the regulatable flexoelectric behaviors are demonstrated at atomic scale in [110]-oriented BiFeO3 thin films, which are triggered by the strain-field coupling of high-density interfacial dislocations. Using aberration-corrected scanning transmission electron microscopy, the asymmetric polarization rotation around the single dislocation is revealed, which is induced by the gradient strain fields of the single dislocation. These strain fields are highly correlated to generate huge strain gradients between neighboring dislocations, and thereby, serial flexoelectric responses are engineered as a function of dislocation spacings in thicker BiFeO3 films. This work opens a pathway for the modulation of flexoelectric responses in ferroelectrics, which could be extended to other functional materials to create exotic phenomena.

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.

Periodic Polarization Waves in a Strained, Highly Polar Ultrathin SrTiO3.

SrTiO3 is generally paraelectric with centrosymmetric structure exhibiting unique quantum fluctuation related ferroelectricity. Here we reveal highly polar and periodic polarization waves in SrTiO3 at room temperature, which is stabilized by periodic tensile strains in a sandwiched PbTiO3/SrTiO3/PbTiO3 structure. Scanning transmission electron microscopy reveals that periodic a/c domain structures in PbTiO3 layers exert unique periodic tensile strains in the ultrathin SrTiO3 layer and consequently make the highly polar and periodic states of SrTiO3. The as-received polar SrTiO3 layer features peak polar ion displacement of ∼0.01 nm and peak tetragonality of ∼1.07. These peak values are larger than previous results, which are comparable to that of bulk ferroelectric PbTiO3. Our results suggest that it is possible to integrate large and periodic strain state in oxide films with exotic properties, which in turn could be useful in optical applications and information addressing when used as memory unit.

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.

Grain Boundaries and Tilt-Angle-Dependent Transport Properties of a 2D Mo2C Superconductor.

The grain boundaries (GBs) of graphene and molybdenum disulfide have been extensively demonstrated to have a strong influence on electronic, thermal, optical, and mechanical properties. 2D transition-metal carbides (TMCs), known as MXenes, are a rapidly growing new family of 2D materials with many fascinating properties and promising applications. However, the GB structure of 2D TMCs and the influence of GB on their properties remain unknown. Here, we used aberration-corrected scanning transmission electron microscopy combined with electrical measurements to study the GB characteristic of highly crystalline 2D Mo2C superconductor, a newly emerging member of the 2D TMC family. The 2D Mo2C superconductor shows a unique tilt-angle-dependent GB structure and electronic transport properties. Different from the reported 2D materials, the GB of 2D Mo2C shows a peculiar dislocation configuration or sawtooth pattern depending on the tilt angle. More importantly, we found two new periodic GBs with different periodic structures and crystallographic orientations. Electrical measurements on individual GBs show that GB structure strongly affects the transport properties. In the normal state, an increasingly stronger electron localization behavior is observed at the GB region with increasing tilt angle. In the superconducting state, the magnitude of the critical current across the GBs is dramatically reduced, associated with local suppression of superconductivity at GBs. These findings provide new understandings on the GB structure of 2D TMCs and the influence of GB on 2D superconductivity, which would be helpful for tailoring the properties of 2D TMCs through GB engineering.

Local Enhancement of Polarization at PbTiO3/BiFeO3 Interfaces Mediated by Charge Transfer.

Ferroelectrics hold promise for sensors, transducers, and telecommunications. With the demand of electronic devices scaling down, they take the form of nanoscale films. However, the polarizations in ultrathin ferroelectric films are usually reduced dramatically due to the depolarization field caused by incomplete charge screening at interfaces, hampering the integrations of ferroelectrics into electric devices. Here, we design and fabricate a ferroelectric/multiferroic PbTiO3/BiFeO3 system, which exhibits discontinuities in both chemical valence and ferroelectric polarization across the interface. Aberration-corrected scanning transmission electron microscopic study reveals an 8% elongation of out-of-plane lattice spacing associated with 104%, 107%, and 39% increments of δTi, δO1, and δO2 in the PbTiO3 layer near the head-to-tail polarized interface, suggesting an over ∼70% enhancement of polarization compared with that of bulk PbTiO3. Besides that in PbTiO3, polarization in the BiFeO3 is also remarkably enhanced. Electron energy loss spectrum and X-ray photoelectron spectroscopy investigations demonstrate the oxygen vacancy accumulation as well as the transfer of Fe3+ to Fe2+ at the interface. On the basis of the polar catastrophe model, FeO2/PbO interface is determined. First-principles calculation manifests that the oxygen vacancy at the interface plays a predominate role in inducing the local polarization enhancement. We propose a charge transfer mechanism that leads to the remarkable polarization increment at the PbTiO3/BiFeO3 interface. This study may facilitate the development of nanoscale ferroelectric devices by tailing the coupling of charge and lattice in oxide heteroepitaxy.

Large Scale Two-Dimensional Flux-Closure Domain Arrays in Oxide Multilayers and Their Controlled Growth.

Ferroelectric flux-closures are very promising in high-density storage and other nanoscale electronic devices. To make the data bits addressable, the nanoscale flux-closures are required to be periodic via a controlled growth. Although flux-closure quadrant arrays with 180° domain walls perpendicular to the interfaces (V-closure) have been observed in strained ferroelectric PbTiO3 films, the flux-closure quadrants therein are rather asymmetric. In this work, we report not only a periodic array of the symmetric flux-closure quadrants with 180° domain walls parallel to the interfaces (H-closure) but also a large scale alternative stacking of the V- and H-closure arrays in PbTiO3/SrTiO3 multilayers. On the basis of a combination of aberration-corrected scanning transmission electron microscopic imaging and phase field modeling, we establish the phase diagram in the layer-by-layer two-dimensional arrays versus the thickness ratio of adjacent PbTiO3 films, in which energy competitions play dominant roles. The manipulation of these flux-closures may stimulate the design and development of novel nanoscale ferroelectric devices with exotic properties.

Unique Domain Structure of Two-Dimensional α-Mo2C Superconducting Crystals.

The properties of two-dimensional (2D) materials such as graphene and monolayer transition metal dichalcogenides are strongly influenced by domain boundaries. Ultrathin transition metal carbides are a class of newly emerging 2D materials that are superconducting and have many potential applications such as in electrochemical energy storage, catalysis, and thermoelectric energy conversion. However, little is known about their domain structure and the influence of domain boundaries on their properties. Here we use atomic-resolution scanning transmission electron microscopy combined with large-scale diffraction-filtered imaging to study the microstructure of chemical vapor deposited high-quality 2D α-Mo2C superconducting crystals of different regular shapes including triangles, rectangles, hexagons, octagons, nonagons, and dodecagons. The Mo atom sublattice in all these crystals has a uniform hexagonal closely packed arrangement without any boundaries. However, except for rectangular and octagonal crystals, the C atom sublattices are composed of three or six domains with rotational-symmetry and well-defined line-shaped domain boundaries because of the presence of three equivalent off-center directions of interstitial carbon atoms in Mo octahedra. We found that there is very small lattice shear strain across the domain boundary. In contrast to the single sharp transition observed in single-domain crystals, transport studies across domain boundaries show a broad resistive superconducting transition with two distinct transition processes due to the formation of localized phase slip events within the boundaries, indicating a significant influence of the boundary on 2D superconductivity. These findings provide new understandings on not only the microstructure of 2D transition metal carbides but also the intrinsic influence of domain boundaries on 2D superconductivity.

Large-area high-quality 2D ultrathin Mo2C superconducting crystals.

Transition metal carbides (TMCs) are a large family of materials with many intriguing properties and applications, and high-quality 2D TMCs are essential for investigating new physics and properties in the 2D limit. However, the 2D TMCs obtained so far are chemically functionalized, defective nanosheets having maximum lateral dimensions of ∼10 µm. Here we report the fabrication of large-area high-quality 2D ultrathin α-Mo2C crystals by chemical vapour deposition (CVD). The crystals are a few nanometres thick, over 100 µm in size, and very stable under ambient conditions. They show 2D characteristics of superconducting transitions that are consistent with Berezinskii-Kosterlitz-Thouless behaviour and show strong anisotropy with magnetic field orientation; moreover, the superconductivity is also strongly dependent on the crystal thickness. Our versatile CVD process allows the fabrication of other high-quality 2D TMC crystals, such as ultrathin WC and TaC crystals, which further expand the large family of 2D materials.

Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition.

The controlled growth of large-area, high-quality, single-crystal graphene is highly desired for applications in electronics and optoelectronics; however, the production of this material remains challenging because the atomistic mechanism that governs graphene growth is not well understood. The edges of graphene, which are the sites at which carbon accumulates in the two-dimensional honeycomb lattice, influence many properties, including the electronic properties and chemical reactivity of graphene, and they are expected to significantly influence its growth. We demonstrate the growth of single-crystal graphene domains with controlled edges that range from zigzag to armchair orientations via growth-etching-regrowth in a chemical vapor deposition process. We have observed that both the growth and the etching rates of a single-crystal graphene domain increase linearly with the slanted angle of its edges from 0° to ∼19° and that the rates for an armchair edge are faster than those for a zigzag edge. Such edge-structure-dependent growth/etching kinetics of graphene can be well explained at the atomic level based on the concentrations of the kinks on various edges and allow the evolution and control of the edge and morphology in single-crystal graphene following the classical kinetic Wulff construction theory. Using these findings, we propose several strategies for the fabrication of wafer-sized, high-quality, single-crystal graphene.