Polar Displacements Research Articles

Boosting Energy-Storage in High-Entropy Pb-Free Relaxors Engineered by Local Lattice Distortion.

The high-entropy strategy has shown potential in advancing the energy-storage performance of dielectric capacitors, offering benefits to a range of electronic and electrical systems. However, designing high-performance high-entropy relaxor ferroelectrics (RFEs) presents challenges due to the unclear correlation between their core effects and local polarization heterogeneity. Here, we demonstrate that by engineering the local lattice distortion, a core effect in high-entropy systems, to manipulate the local polarization configuration, a giant energy density (Wrec) of 18.7 J cm-3 and high efficiency (η) of 85% can be achieved in (Bi0.5K0.5)TiO3-based high-entropy bulk RFE ceramics. Atomic-level local structural analysis unveils that the local lattice distortion field can be flattened by introducing ions with less size mismatch. The increase in configurational entropy from 1.54 to 2.06R is associated with a smoother polar displacement vector field and a reduction in the size of polar clusters to several unit-cell sizes with weak coupling. Consequently, a substantial decrease in hysteresis and an enhancement in the breakdown field strength can be obtained, leading to a significant improvement in energy density by over 6 times and efficiency by 3 times. Our research establishes a relationship between local lattice distortion, atomic polar displacement, and energy-storage performance in complex high-entropy systems, providing insights for enhancing energy-storage performance via a local structure design.

Interrogating Explicit Solvent Effects on the Mechanism and Site-Selectivity of Aryl Halide Oxidative Addition to L2Pd(0).

We report a study of solvent effects on the rate, selectivity, and mechanism of (hetero)aryl (pseudo)halide oxidative addition to Pd(PCy3)2 as an exemplar of L2Pd(0) species. First, 2-chloro-3-aminopyridine is observed to undergo faster oxidative addition in toluene compared to more polar solvents, which is not consistent with the trend we observe with many other 2-halopyridines. We attribute this to solvent basicity hydrogen bonding between solvent and substrate. Greater hydrogen bond donation from the substrate leads to a more electron-rich aromatic system, and therefore slower oxidative addition. We demonstrate how this affects rate and site-selectivity for hydrogen bond donating substrates. Second, electron-deficient multihalogenated pyridines exhibit improved site-selectivity in polar solvents, which we attribute to different C-X sites undergoing oxidative addition by two different mechanisms. The C-X site that favours the more polar nucleophilic displacement transition state is preferred over the site that favours a less-polar 3-centered transition state. Finally, (hetero)aryl triflates consistently undergo faster oxidative addition in more polar solvents, which we attribute to highly polar nucleophilic displacement transition states. This leads to improved site-selectivity for C-OTf oxidative addition, even in the presence of highly reactive 2-pyridyl halides.

Stabilizing Phosphorene‐Like Group IV–VI Compounds via van der Waals Imprinting for Multistate Ferroelectricity and Tunable Spin Transport

AbstractLayered group IV–VI compounds (i.e., SnSe, SnS, GeSe, and GeS) in the puckered structure resembling black‐phosphorene (BlackP) have attracted increasing interest because of their intriguing ferroic orders and outstanding thermoelectric properties. By invoking the guiding principles of isovalency and isomorphism for promoting van der Waals epitaxy, and based on comprehensive first‐principles calculations, here it is shown that the typically metastable BlackP‐like GeTe can be readily stabilized on the (001) surface of isostructural SnSe. Importantly, the ferroelectricity of such a BlackP‐like GeTe monolayer can be substantially enhanced compared to the freestanding state, due to the substrate enlarged in‐plane polar displacements. The GeTe/SnSe heterobilayer exhibits multiple ferroelectric/ferrielectric polarization states, which can be exploited for high‐density memory devices. These mutually switchable polarization states are also shown to be internally locked with the spin polarization of the valence/conduction bands with pronounced Rashba spin‐orbit splitting and Berry curvature dipole. These findings highlight the intuitive yet enabling power of van der Waals imprinting in growing novel 2D materials for enriched functionalities.

The role of local non-tetragonal polar displacements in the temperature- and pressure-induced phase transitions in PbTiO3-BiMeO3 ferroelectrics

In situ high-pressure/high-temperature Raman-scattering analyses on PbTiO3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}, 0.92PbTiO3-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3-$$\\end{document}0.08Bi(Zn0.5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{0.5}$$\\end{document}Ti0.5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{0.5}$$\\end{document})O3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document} and 0.83PbTiO3-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3-$$\\end{document}0.17Bi(Mg0.5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{0.5}$$\\end{document}Ti0.5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{0.5}$$\\end{document})O3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document} single crystals reveal an intensity transfer between the fine-structure components of the A1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_1$$\\end{document}(TO) soft mode. The enhancement of the lowest-energy subpeak, which stems from intrinsic local non-tetragonal polar distortions, along with the suppression of the tetragonal A1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_1$$\\end{document}(1TO) fundamental mode with increasing pressure and temperature indicates the key role of the local polarization fluctuations in transformation processes and emphasizes the significance of the order-disorder phenomena in both the pressure- and temperature-induced phase transitions of pure PbTiO3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document} and its solid solutions with complex perovskites. Moreover, the temperature and pressure evolution of the fraction of the local non-tetragonal polar distortions is highly sensitive to the type of B-site substituent.

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.

Unexpected Competition between Ferroelectricity and Rashba Effects in Epitaxially Strained SrTiO_{3}.

The Rashba parameter α_{R} is usually assumed to scale linearly with the amplitude of polar displacements by construction of the spin-orbit interaction. On the basis of first-principles simulations, ferroelectric phases of SrTiO_{3} reached under epitaxial compressive strain are characterized by (i)large Rashba effects at the bottom of the conduction band near the paraelectric-ferroelectric boundary and (ii)an unexpected suppression of the phenomena when the amplitude of polar displacements increases. This peculiar behavior is ascribed to the inverse dependence of the Rashba parameter with the crystal field Δ_{CF} induced by the polar displacements that alleviates the degeneracy of Ti t_{2g} states and annihilates the Rashba effects. Although α_{R} has intrinsically a linear dependance on polar displacements, the latter becomes antagonist to Rashba phenomena at large polar mode amplitude. Thus, the Rashba coefficient may be bound to an upper value.

Comparison of carrier doping in ZnSnO3 and ZnTiO3 from first principles.

Ferroelectric materials have attracted increasing attention due to their rich properties. Unlike perovskite ferroelectric oxides, in the LiNbO3-type ferroelectric oxides of ABO3, ferroelectrically active cations are not necessary. While the effects of carrier doping on perovskite ferroelectric oxides have been extensively studied, the studies on LiNbO3-type ferroelectric oxides are rare. We consider two LiNbO3-type ferroelectric oxides ZnSnO3 and ZnTiO3, where the former has no ferroelectrically active cation and the latter has ferroelectrically active cation Ti4+, and study the effect of carrier doping by performing first-principles calculations. Comparison results indicate that the B-site cation has significant effects on the polar distortion in LN-type ferroelectrics. Our studies show that LN-type materials can maintain the coexistence of ferroelectricity and conductance over a very wide range of concentrations. The polar displacement is even enhanced under hole doping. More importantly, ZnSnO3 can be doped by electrons up to a high level to realize the conducting ferroelectrics of high mobility due to its isolated s conduction band.

Engineering polar distortions in multiferroic Sr1−xBaxMnO3−δ thin films

The physical properties of perovskite oxide thin films are governed by the subtle interplay between chemical composition and crystal symmetry variations, which can be altered by epitaxial growth. In the case of perovskite-type multiferroic thin films, precise control of stoichiometry and epitaxial strain allows for gaining control over the ferroic properties through selective crystal distortions. Here, we demonstrate the chemical tailoring of the polar atomic displacements by tuning the stoichiometry of multiferroic Sr1−xBaxMnO3−δ (0 ≤ x ≤ 0.5) epitaxial thin films. A combination of x-ray diffraction and aberration-corrected scanning transmission electron microscopy enables unraveling the local polarization orientation at the nanoscale as a function of the film’s composition and induced crystalline structure. We demonstrate experimentally that the orientation of polarization is intimately linked to the Ba doping and O stoichiometry of the films and, with the biaxial strain induced by the substrate, it can be tuned either in-plane or out-of-plane with respect to the substrate by the appropriate choice of the post-growth annealing temperature and O2 atmosphere. This chemistry-mediated engineering of the polarization orientation of oxide thin films opens new venues for the design of functional multiferroic architectures and the exploration of novel physics and applications of ferroelectric textures with exotic topological properties.

Stratosphere–troposphere synergetic effect on the extreme low-temperature event over China in late November 2022

In late November 2022, most regions in China were hit by a strong northwest-path cold wave, bringing a high-hazard extreme low-temperature event (ELTE). Several parts of Northwest China experienced extremely low temperatures and record-breaking snow depths. A stratosphere–troposphere synergetic effect was suggested to be closely related to the ELTE according to a diagnostic analysis. On the one hand, the concurrent establishment of two blockings in Europe–Northeast Atlantic and North Pacific led to a polar vortex split at the tropopause, and the Arctic Oscillation phase subsequently turned negative. An airflow with high potential vorticity (PV) was squeezed out of the Arctic. Meanwhile, a high-PV air that originated from the lower stratospheric Arctic was conveyed southwards to the western Siberian Plain along the sloping isentropic surface. This condition triggered a tropospheric response in which the East Asia trough deepened due to the intensified cyclonic circulation induced by the high-PV intrusion. On the other hand, downward propagation of stratospheric anomalies accompanied by stratospheric polar vortex displacement and split was observed in mid- and late November, respectively. Changes in stratospheric circulation contributed to enhanced blockings over Europe–Northeast Atlantic in the lower stratosphere or upper troposphere. As a result, the inverted omega-shaped circulation pattern was formed in the middle to upper troposphere, and it consisted of the intensified East Asia trough and two blockings in the upstream and downstream regions. The high-PV air upstream of the East Asia trough was advected to China, which directly led to the outbreak of the ELTE. The establishment of double blockings and the displacement or split of the stratospheric polar vortex can be efficient signals for cold-event prediction in China. This study provides novel insights into the cause of ELTEs under warming climates in the future.

Magnetoelastic and Magnetoelectric Coupling in Two-Dimensional Nitride MXenes: A Density Functional Theory Study.

Two-dimensional multiferroic (2D) materials have garnered significant attention due to their potential in high-density, low-power multistate storage and spintronics applications. MXenes, a class of 2D transition metal carbides and nitrides, were first discovered in 2011, and have become the focus of research in various disciplines. Our study, utilizing first-principles calculations, examines the lattice structures, and electronic and magnetic properties of nitride MXenes with intrinsic band gaps, including V2NF2, V2NO2, Cr2NF2, Mo2NO2, Mo2NF2, and Mn2NO2. These nitride MXenes exhibit orbital ordering, and in some cases the orbital ordering induces magnetoelastic coupling or magnetoelectric coupling. Most notably, Cr2NF2 is a ferroelastic material with a spiral magnetic ordered phase, and the spiral magnetization propagation vector is coupled with the direction of ferroelastic strain. The ferroelectric phase can exist as an excited state in V2NO2, Cr2NF2, and Mo2NF2, with their magnetic order being coupled with polar displacements through orbital ordering. Our results also suggest that similar magnetoelectric coupling effects persist in the Janus MXenes V8N4O7F, Cr8N4F7O, and Mo8N4F7O. Remarkably, different phases of Mo8N4F7O, characterized by orbital ordering rearrangements, can be switched by applying external strain or an external electric field. Overall, our theoretical findings suggest that nitride MXenes hold promise as 2D multiferroic materials.

Local Chemical Clustering Enabled Ultrahigh Capacitive Energy Storage in Pb-Free Relaxors.

Designing Pb-free relaxors with both a high capacitive energy density (Wrec) and high storage efficiency (η) remains a remarkable challenge for cutting-edge pulsed power technologies. Local compositional heterogeneity is crucial for achieving complex polar structure in solid solution relaxors, but its role in optimizing energy storage properties is often overlooked. Here, we report that an exceptionally high Wrec of 15.2 J cm-3 along with an ultrahigh η of 91% can be achieved through designing local chemical clustering in Bi0.5Na0.5TiO3-BaTiO3-based relaxors. A three-dimensional atomistic model derived from neutron/X-ray total scattering combined with reverse Monte Carlo method reveals the presence of subnanometer scale clustering of Bi, Na, and Ba, which host differentiated polar displacements, and confirming the prediction by density functional theory calculations. This leads to a polar state with small polar clusters and strong length and direction fluctuations in unit-cell polar vectors, thus manifesting improved high-field polarizability, steadily reduced hysteresis, and high breakdown strength macroscopically. The favorable polar structure features also result in a unique field-increased η, excellent stability, and superior discharge capacity. Our work demonstrates that the hidden local chemical order exerts a significant impact on the polarization characteristic of relaxors, and can be exploited for accessing superior energy storage performance.

Mapping Polar Distortions using Nanobeam Electron Diffraction and a Cepstral Approach.

Measuring local polar ordering is key to understanding ferroelectricity in thin films, especially for systems with small domains or significant disorder. Scanning nanobeam electron diffraction (NBED) provides an effective local probe of lattice parameters, local fields, polarization directions, and charge densities, which can be analyzed using a relatively low beam dose over large fields of view. However, quantitatively extracting the magnitudes and directions of polarization vectors from NBED remains challenging. Here, we use a cepstral approach, similar to a pair distribution function, to determine local polar displacements that drive ferroelectricity from NBED patterns. Because polar distortions generate asymmetry in the diffraction pattern intensity, we can efficiently recover the underlying displacements from the imaginary part of the cepstrum transform. We investigate the limits of this technique using analytical and simulated data and give experimental examples, achieving the order of 1.1 pm precision and mapping of polar displacements with nanometer resolution.

Chemical Design of Pb-Free Relaxors for Giant Capacitive Energy Storage.

Dielectric capacitors have captured substantial attention for advanced electrical and electronic systems. Developing dielectrics with high energy density and high storage efficiency is challenging owing to the high compositional diversity and the lack of general guidelines. Herein, we propose a map that captures the structural distortion (δ) and tolerance factor (t) of perovskites to design Pb-free relaxors with extremely high capacitive energy storage. Our map shows how to select ferroelectric with large δ and paraelectric components to form relaxors with a t value close to 1 and thus obtaining eliminated hysteresis and large polarization under a high electric breakdown. Taking the Bi0.5Na0.5TiO3-based solid solution as an example, we demonstrate that composition-driven predominant order-disorder characteristic of local atomic polar displacements endows the relaxor with a slushlike structure and strong local polar fluctuations at several nanoscale. This leads to a giant recoverable energy density of 13.6 J cm-3, along with an ultrahigh efficiency of 94%, which is far beyond the current performance boundary reported in Pb-free bulk ceramics. Our work provides a solution through rational chemical design for obtaining Pb-free relaxors with outstanding energy-storage properties.

Ferroelectricity in Low-Permittivity SrZrO3 Epitaxial Films

Bulk SrZrO3 has an orthorhombic perovskite structure (Pbnm) with a central symmetry but exhibits a low dielectric constant. In this study, we reported a room-temperature ferroelectric SrZrO3 thin film with a low dielectric constant, induced by compressive strain from the SrTiO3 substrate. The presence of an out-of-phase boundary structure allows SrZrO3 with a large lattice mismatch to grow epitaxially on SrTiO3 substrates. The apparent atomic displacements in the lattice are revealed by scanning transmission electron microscopy imaging. Compressive strain induces an orthorhombic-to-monoclinic phase transition, evidenced by both the atomic structure obtained from the annular bright-field image and the structure optimized with first-principles calculation. Further first-principles calculations demonstrated that compressive strain causes a polar displacement of the Zr atom inside the ZrO6 octahedron, which is the origin of the ferroelectricity. Our work shows a way to design novel ferroelectrics from conventional non-ferroelectric materials, which is of significant importance to robust, stable, and lead-free ferroelectrics applications.

Superior Capacitive Energy-Storage Performance in Pb-Free Relaxors with a Simple Chemical Composition

Chemical design of lead-free relaxors with simultaneously high energy density (Wrec) and high efficiency (η) for capacitive energy-storage has been a big challenge for advanced electronic systems. The current situation indicates that realizing such superior energy-storage properties requires highly complex chemical components. Herein, we demonstrate that, via local structure design, an ultrahigh Wrec of 10.1 J/cm3, concurrent with a high η of 90%, as well as excellent thermal and frequency stabilities can be achieved in a relaxor with a very simple chemical composition. By introducing 6s2 lone pair stereochemical active Bi into the classical BaTiO3 ferroelectric to generate a mismatch between A- and B-site polar displacements, a relaxor state with strong local polar fluctuations can be formed. Through advanced atomic-resolution displacement mapping and 3D reconstructing the nanoscale structure from neutron/X-ray total scattering, it is revealed that the localized Bi enhances the polar length largely at several perovskite unit cells and disrupts the long-range coherent Ti polar displacements, resulting in a slush-like structure with extremely small size polar clusters and strong local polar fluctuations. This favorable relaxor state exhibits substantially enhanced polarization, and minimized hysteresis at a high breakdown strength. This work offers a feasible avenue to chemically design new relaxors with a simple composition for high-performance capacitive energy-storage.

Emergence of high piezoelectricity from competing local polar order-disorder in relaxor ferroelectrics

Relaxor ferroelectrics are known for outstanding piezoelectric properties, finding a broad range of applications in advanced electromechanical devices. Decoding the origins of the enhanced properties, however, have long been complicated by the heterogeneous local structures. Here, we employ the advanced big-box refinement method by fitting neutron-, X-ray-based total scattering, and X-ray absorption spectrum simultaneously, to extract local atomic polar displacements and construct 3D polar configurations in the classical relaxor ferroelectric Pb(Mg1/3Nb2/3)O3–PbTiO3. Our results demonstrate that prevailing order-disorder character accompanied by the continuous rotation of local polar displacements commands the composition-driven global structure evolution. The omnidirectional local polar disordering appears as an indication of macroscopic relaxor characteristics. Combined with phase-field simulations, it demonstrates that the competing local polar order-disorder between different states with balanced local polar length and direction randomness leads to a flattening free-energy profile over a wide polar length, thus giving rise to high piezoelectricity. Our work clarifies that the critical structural feature required for high piezoelectricity is the competition states of local polar rather than relaxor.

Incommensurate Modulation and Competing Ferroelectric/Antiferroelectric Modes in Tetragonal Tungsten Bronzes

The nanoscale structure of Sr0.61Ba0.39Nb2O6, a classic uniaxial relaxor ferroelectric crystallizing with the tetragonal tungsten bronze (TTB) structure and exhibiting an incommensurate modulation, has been determined by atomistic refinements using combined data from variable-temperature neutron total scattering, extended X-ray absorption fine structure, and three-dimensional single-crystal diffuse scattering. We found the modulation to arise from the intergrowth of structural slabs featuring distinct types of octahedral rotations directed to minimize octahedral deformations. This modulation involves displacements of the A cations (Sr and Ba) but exerts no significant effect on the polar displacements of Nb. Our results demonstrated the coexistence of competing polar Γ3– and antipolar Γ2– modes for off-centering of Nb above the nominal ferroelectric transition temperature of 350 K. The nanoscale-correlated antipolar distortions, which exhibit their largest amplitudes at 425 K, are suppressed below the transition. We identified coupling between the polar off-centering of Nb on its two symmetrically distinct sites as a fundamental characteristic controlling the ferroelectric-to-relaxor crossover in TTBs. We then used it to propose a simple microscopic interpretation for the previously established empirical trend that links crystal–chemical parameters in these systems to their polar response.

Bi2CoO2F4-A Polar, Ferrimagnetic Aurivillius Oxide-Fluoride.

Aurivillius oxides have been a research focus due to their ferroelectric properties, but by replacing oxide ions by fluoride, divalent magnetic cations can be introduced, giving Bi2 MO2F4 (M = Fe, Co, and Ni). Our combined experimental and computational study on Bi2CoO2F4 indicates a low-temperature polar structure of P21 ab symmetry (analogous to ferroelectric Bi2WO6) and a ferrimagnetic ground state. These results highlight the potential of Aurivillius oxide-fluorides for multiferroic properties. Our research has also revealed some challenges associated with the reduced tendency for polar displacements in the more ionic fluoride-based systems.

Possible influence of sudden stratospheric warmings on the atmospheric environment in the Beijing–Tianjin–Hebei region

Abstract. Using European Centre for Medium-Range Weather Forecasts fifth-generation (ERA5) and second Modern-Era Retrospective analysis for Research and Applications (MERRA-2) reanalysis and surface meteorological observation data, this study explores the possible impact of sudden stratospheric warming (SSW) events on air quality in the Beijing–Tianjin–Hebei (BTH) region. Major SSW events are divided into polar vortex displacement SSW and polar vortex split SSW. As the duration of split SSW events is longer and the stratospheric signal pulses propagate further downward than displacement SSWs, subseasonal variability of the atmospheric particulates in the BTH is larger during split SSWs. The air particulate concentration is light before the SSW onset due to the enhanced perturbation in the troposphere associated with strengthened planetary waves. The air particulate concentration around the SSW onset dates begins to rise due to weakening of the tropospheric disturbance as the enhanced planetary waves enter the stratosphere. In the decaying period of the SSW, the air particulate concentration decreases as the stratospheric negative northern annular mode (NAM) signal propagates downward. Specifically, in the pre-SSW period of displacement (split) SSW events, a wavenumber-1-like (wavenumber-2-like) anomaly pattern is strengthened. The East Asian winter monsoon intensifies as the East Asian trough is deepened, especially before the split SSW event onset, leading to a cleaning period. Around the SSW onset period as the tropospheric perturbation diminishes and the East Asian winter monsoon weakens, a surge of air particulate concentration is observed. After the SSW onset, due to the downward propagation of the stratospheric negative NAM signal, cold anomalies form in northeastern East Asia, especially for split SSWs, corresponding to a cleaning period in the BHT region. The local meteorological conditions during the SSWs are also discussed.

Design of superior electrostriction in BaTiO3‐based lead‐free relaxors via the formation of polarization nanoclusters

AbstractElectrostrictive materials have wide applications in modern high‐precision electronic devices. Driven by growing environmental concerns, there is demand for lead‐free materials with superior electrostriction behaviors. In this study, we demonstrate a record‐high electrostrictive coefficient of ~0.0712 m4 C−2 in perovskite ferroelectric ceramics, along with hysteresis‐free strain as well as excellent frequency and thermal stabilities, in lead‐free BaTiO3‐based ceramics through a polarization nanocluster design. By appropriately introducing Li+ and Bi3+ into the BaTiO3 lattice matrix, the long‐range ferroelectric ordering can be broken, and polarization nanoclusters can be formed, resulting in a relaxor state with concurrently suppressed polarization and maintained electro‐strain. A three‐dimensional atomic model constructed using advanced neutron total‐scattering data combined with the reverse Monte Carlo method indicates the existence of Bi and Li segregations at the subnanometer scale, which confirms the prediction made by density functional theory calculations. Such a short‐range chemical order destroys the long‐range ferroelectric order of the off‐centered Ti polar displacements and leads to the embedding of Li+/Bi3+‐rich polar nanoregions in the Ba2+‐rich polarization disorder matrix. Further, a completely reversible electric‐field‐induced lattice strain is observed, giving rise to pure electrostriction without hysteresis behavior. This work provides a novel strategy for developing lead‐free relaxor ferroelectrics with high electrostriction performance.image