Realizing Outstanding Energy Storage Performance in KBT-Based Lead-Free Ceramics via Suppressing Space Charge Accumulation.

The great potential of K1/2Bi1/2TiO3 (KBT) for dielectric energy storage ceramics is impeded by its low dielectric breakdown strength, thereby limiting its utilization of high polarization. This study develops a novel composition, 0.83KBT-0.095Na1/2Bi1/2ZrO3-0.075 Bi0.85Nd0.15FeO3 (KNBNTF) ceramics, demonstrating outstanding energy storage performance under high electric fields up to 425 kV cm-1: a remarkable recoverable energy density of 7.03 J cm-3, and a high efficiency of 86.0%. The analysis reveals that the superior dielectric breakdown resistance arises from effective mitigation of space charge accumulation at the interface, influenced by differential dielectric and conductance behaviors between grains and grain boundaries. Electric impedance spectra confirm the significant suppression of space charge accumulation in KNBNTF, attributable to the co-introduction of Na1/2Bi1/2ZrO3 and Bi0.85Nd0.15FeO3. Phase-field simulations reveal the emergence of a trans-granular breakdown mode in KNBNTF resulting from the mitigated interfacial polarization, impeding breakdown propagation and increasing dielectric breakdown resistance. Furthermore, KNBNTF exhibits a complex local polarization and enhances the relaxor features, facilitating high field-induced polarization and establishing favorable conditions for exceptional energy storage performance. Therefore, the proposed strategy is a promising design pathway for tailoring dielectric ceramics in energy storage applications.

Thickness- and Field-Dependent Magnetic Domain Evolution in van der Waals Fe3GaTe2.

The discovery of room-temperature ferromagnetism in van der Waals (vdW) materials opens new avenues for exploring low-dimensional magnetism and its applications in spintronics. Recently, the observation of the room-temperature topological Hall effect in the vdW ferromagnet Fe3GaTe2 suggests the possible existence of room-temperature skyrmions, yet skyrmions have not been directly observed. In this study, real-space imaging was employed to investigate the domain evolution of the labyrinth and skyrmion structure. First, Néel-type skyrmions can be created at room temperature. In addition, the influence of flake thickness and external magnetic field (during field cooling) on both labyrinth domains and the skyrmion lattice is unveiled. Due to the competition between magnetic anisotropy and dipole interactions, the specimen thickness significantly influences the density of skyrmions. These findings demonstrate that Fe3GaTe2 can host room-temperature skyrmions of various sizes, opening up avenues for further study of magnetic topological textures at room temperature.

Ultrahigh-Efficiency Superior Energy Storage in Lead-Free Films with a Simple Composition.

Dielectric capacitors are highly desired in modern electronic devices and power systems to store and recycle electric energy. However, achieving simultaneous high energy density and efficiency remains a challenge. Here, guided by theoretical and phase-field simulations, we are able to achieve a superior comprehensive property of ultrahigh efficiency of 90-94% and high energy density of 85-90 J cm-3 remarkably in strontium titanate (SrTiO3), a linear dielectric of a simple chemical composition, by manipulating local symmetry breaking through introducing Ti/O defects. Atomic-scale characterizations confirm that these Ti/O defects lead to local symmetry breaking and local lattice strains, thus leading to the formation of the isolated ultrafine polar nanoclusters with varying sizes from 2 to 8 nm. These nanoclusters account for both considerable dielectric polarization and negligible polarization hysteresis. The present study opens a new realm of designing high-performance dielectric capacitors utilizing a large family of readily available linear dielectrics with very simple chemistry.

Low-k nano-dielectrics facilitate electric-field induced phase transition in high-k ferroelectric polymers for sustainable electrocaloric refrigeration.

Ferroelectric polymer-based electrocaloric effect may lead to sustainable heat pumps and refrigeration owing to the large electrocaloric-induced entropy changes, flexible, lightweight and zero-global warming potential. Herein, low-k nanodiamonds are served as extrinsic dielectric fillers to fabricate polymeric nanocomposites for electrocaloric refrigeration. As low-k nanofillers are naturally polar-inactive, hence they have been widely applied for consolidate electrical stability in dielectrics. Interestingly, we observe that the nanodiamonds markedly enhances the electrocaloric effect in relaxor ferroelectrics. Compared with their high-k counterparts that have been extensively studied in the field of electrocaloric nanocomposites, the nanodiamonds introduces the highest volumetric electrocaloric enhancement (~23%/vol%). The resulting polymeric nanocomposite exhibits concurrently improved electrocaloric effect (160%), thermal conductivity (175%) and electrical stability (125%), which allow a fluid-solid coupling-based electrocaloric refrigerator to exhibit an improved coefficient of performance from 0.8 to 5.3 (660%) while maintaining high cooling power (over 240 W) at a temperature span of 10 K.

Mechanical manipulation for ordered topological defects.

Randomly distributed topological defects created during the spontaneous symmetry breaking are the fingerprints to trace the evolution of symmetry, range of interaction, and order parameters in condensed matter systems. However, the effective mean to manipulate topological defects into ordered form is elusive due to the topological protection. Here, we establish a strategy to effectively align the topological domain networks in hexagonal manganites through a mechanical approach. It is found that the nanoindentation strain gives rise to a threefold Magnus-type force distribution, leading to a sixfold symmetric domain pattern by driving the vortex and antivortex in opposite directions. On the basis of this rationale, sizeable mono-chirality topological stripe is readily achieved by expanding the nanoindentation to scratch, directly transferring the randomly distributed topological defects into an ordered form. This discovery provides a mechanical strategy to manipulate topological protected domains not only on ferroelectrics but also on ferromagnets/antiferromagnets and ferroelastics.

Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer.

Topology created by quasi-continuous spatial variations of a local polarization direction represents an exotic state of matter, but field-driven manipulation has been hitherto limited to creation and destruction. Here we report that relatively small electric or mechanical fields can drive the non-volatile rotation of polar spirals in discretized microregions of the relaxor ferroelectric polymer poly(vinylidene fluoride-ran-trifluoroethylene). These polar spirals arise from the asymmetric Coulomb interaction between vertically aligned helical polymer chains, and can be rotated in-plane through various angles with robust retention. Given also that our manipulation of topological order can be detected via infrared absorption, our work suggests a new direction for the application of complex materials.

Surface Effect of Thickness-Dependent Polarization and Domain Evolution in BiFeO3 Epitaxial Ultrathin Films.

With the trend of device miniaturization, ultrathin ferroelectric films are gaining more and more attention. However, understanding ferroelectricity in this nanoscale context remains a formidable challenge, primarily due to the heightened relevance of surface effects, which often leads to the loss of net polarization. Here, the influence of surface effects on the polarization as a function of thickness in ultrathin BiFeO3 films is investigated using phase-field simulations. The findings reveal a notable increase in ferroelectric polarization with increasing thickness, with a particularly discernible change occurring below the 10 nm threshold. Upon accounting for surface effects, the polarization is marginally lower than the case without such considerations, with the disparity becoming more pronounced at smaller thicknesses. Moreover, the hysteresis loop and butterfly loop of the ultrathin film were simulated, demonstrating that the ferroelectric properties of films remain robust even down to a thickness of 5 nm. Our investigations provide valuable insights into the significance of ferroelectric thin films in device miniaturization.

Colossal electrocaloric effect in an interface-augmented ferroelectric polymer.

The electrocaloric effect demands the maximized degree of freedom (DOF) of polar domains and the lowest energy barrier to facilitate the transition of polarization. However, optimization of the DOF and energy barrier-including domain size, crystallinity, multiconformation coexistence, polar correlation, and other factors in bulk ferroelectrics-has reached a limit. We used organic crystal dimethylhexynediol (DMHD) as a three-dimensional sacrificial master to assemble polar conformations at the heterogeneous interface in poly(vinylidene fluoride)-based terpolymer. DMHD was evaporated, and the epitaxy-like process induced an ultrafinely distributed, multiconformation-coexisting polar interface exhibiting a giant conformational entropy. Under a low electric field, the interface-augmented terpolymer had a high entropy change of 100 J/(kg·K). This interface polarization strategy is generally applicable to dielectric capacitors, supercapacitors, and other related applications.

Stretchable polymer composites with ultrahigh piezoelectric performance.

Flexible piezoelectric materials capable of withstanding large deformation play key roles in flexible electronics. Ferroelectric ceramics with a high piezoelectric coefficient are inherently brittle, whereas polar polymers exhibit a low piezoelectric coefficient. Here we report a highly stretchable/compressible piezoelectric composite composed of ferroelectric ceramic skeleton, elastomer matrix and relaxor ferroelectric-based hybrid at the ceramic/matrix interface as dielectric transition layers, exhibiting a giant piezoelectric coefficient of 250 picometers per volt, high electromechanical coupling factor keff of 65%, ultralow acoustic impedance of 3MRyl and high cyclic stability under 50% compression strain. The superior flexibility and piezoelectric properties are attributed to the electric polarization and mechanical load transfer paths formed by the ceramic skeleton, and dielectric mismatch mitigation between ceramic fillers and elastomer matrix by the dielectric transition layer. The synergistic fusion of ultrahigh piezoelectric properties and superior flexibility in these polymer composites is expected to drive emerging applications in flexible smart electronics.

In situ activation of flexible magnetoelectric membrane enhances bone defect repair.

For bone defect repair under co-morbidity conditions, the use of biomaterials that can be non-invasively regulated is highly desirable to avoid further complications and to promote osteogenesis. However, it remains a formidable challenge in clinical applications to achieve efficient osteogenesis with stimuli-responsive materials. Here, we develop polarized CoFe2O4@BaTiO3/poly(vinylidene fluoridetrifluoroethylene) [P(VDF-TrFE)] core-shell particle-incorporated composite membranes with high magnetoelectric conversion efficiency for activating bone regeneration. An external magnetic field force conduct on the CoFe2O4 core can increase charge density on the BaTiO3 shell and strengthens the ß-phase transition in the P(VDF-TrFE) matrix. This energy conversion increases the membrane surface potential, which hence activates osteogenesis. Skull defect experiments on male rats showed that repeated magnetic field applications on the membranes enhanced bone defect repair, even when osteogenesis repression is elicited by dexamethasone or lipopolysaccharide-induced inflammation. This study provides a strategy of utilizing stimuli-responsive magnetoelectric membranes to efficiently activate osteogenesis in situ.

Polar Solomon rings in ferroelectric nanocrystals.

Solomon rings, upholding the symbol of wisdom with profound historical roots, were widely used as decorations in ancient architecture and clothing. However, it was only recently discovered that such topological structures can be formed by self-organization in biological/chemical molecules, liquid crystals, etc. Here, we report the observation of polar Solomon rings in a ferroelectric nanocrystal, which consist of two intertwined vortices and are mathematically equivalent to a [Formula: see text] link in topology. By combining piezoresponse force microscopy observations and phase-field simulations, we demonstrate the reversible switching between polar Solomon rings and vertex textures by an electric field. The two types of topological polar textures exhibit distinct absorption of terahertz infrared waves, which can be exploited in infrared displays with a nanoscale resolution. Our study establishes, both experimentally and computationally, the existence and electrical manipulation of polar Solomon rings, a new form of topological polar structures that may provide a simple way for fast, robust, and high-resolution optoelectronic devices.

Morphotropic Phase Boundary in Polarized Organic Piezoelectric Materials.

Designing the morphotropic phase boundary (MPB) has been the most sought-after approach to achieve high piezoelectric performance of piezoelectric materials. However, MPB has not yet been found in the polarized organic piezoelectric materials. Here, we discover MPB with biphasic competition of ß and 3/1-helical phases in the polarized piezoelectric polymer alloys (PVTC-PVT) and demonstrate a mechanism to induce MPB using the compositionally tailored intermolecular interaction. Consequently, PVTC-PVT exhibits a giant quasistatic piezoelectric coefficient of >32 pC/N while maintaining a low Young's modulus of 182 MPa, with a record-high figure of merit of piezoelectricity modulus of about 176 pC/(N·GPa) among all piezoelectric materials.

Ultralow Tip-Force Driven Sizable-Area Domain Manipulation through Transverse Flexoelectricity.

Deterministic control of ferroelectric domain is critical in the ferroelectric functional electronics. Ferroelectric polarization can be manipulated mechanically with a nano-tip through flexoelectricity. However, it usually occurs in a very localized area in ultrathin films, with possible permanent surface damage caused by a large tip-force. Here it is demonstrated that the deliberate engineering of transverse flexoelectricity offers a powerful tool for improving the mechanical domain switching. Sizable-area domain switching under an ultralow tip-force can be realized in suspended van der Waals ferroelectrics with the surface intact, due to the enhanced transverse flexoelectric field. The film thickness range for domain switching in suspended ferroelectrics is significantly improved by an order of magnitude to hundreds of nanometers, being far beyond the limited range of the substrate-supported ones. The experimental results and phase-field simulations further reveal the crucial role of the transverse flexoelectricity in the domain manipulation. This large-scale mechanical manipulation of ferroelectric domain provides opportunities for the flexoelectricity-based domain controls in emerging low-dimensional ferroelectrics and related devices.

Prominent Size Effects without a Depolarization Field Observed in Ultrathin Ferroelectric Oxide Membranes.

The increasing miniaturization of electronics requires a better understanding of material properties at the nanoscale. Many studies have shown that there is a ferroelectric size limit in oxides, below which the ferroelectricity will be strongly suppressed due to the depolarization field, and whether such a limit still exists in the absence of the depolarization field remains unclear. Here, by applying uniaxial strain, we obtain pure in-plane polarized ferroelectricity in ultrathin SrTiO_{3} membranes, providing a clean system with high tunability to explore ferroelectric size effects especially the thickness-dependent ferroelectric instability with no depolarization field. Surprisingly, the domain size, ferroelectric transition temperature, and critical strain for room-temperature ferroelectricity all exhibit significant thickness dependence. These results indicate that the stability of ferroelectricity is suppressed (enhanced) by increasing the surface or bulk ratio (strain), which can be explained by considering the thickness-dependent dipole-dipole interactions within the transverse Ising model. Our study provides new insights into ferroelectric size effects and sheds light on the applications of ferroelectric thin films in nanoelectronics.

Single-Crystalline BaZr0.2 Ti0.8 O3 Membranes Enabled High Energy Density in PEI-Based Composites for High-Temperature Electrostatic Capacitors.

Dielectric capacitors are promising for high power energy storage, but their breakdown strength (Eb ) and energy density (Ue ) usually degrade rapidly at high temperatures. Adding boron nitride (BN) nanosheets can improve the Eb and high-temperature endurance but with a limited Ue due to its low dielectric constant. Here, freestanding single-crystalline BaZr0.2 Ti0.8 O3 (BZT) membranes with high dielectric constant are fabricated, and introduced into BN doped polyetherimide (PEI) to obtain laminated PEI-BN/BZT/PEI-BN composites. At room temperature, the composite shows a maximum Ue of 17.94 J cm-3  at 730 MV m-1 , which is more than two times the pure PEI. Particularly, the composites exhibit excellent dielectric-temperature stability between 25 and 150 °C. An outstanding Ue  = 7.90 J cm-3  is obtained at a relatively large electric field of 650 MV m-1  under 150 °C, which is superior to the most high-temperature dielectric capacitors reported so far. Phase-field simulation reveals that the depolarization electric field generated at the BZT/PEI-BN interfaces can effectively reduce carrier mobility, leading to the remarkable enhancement of the Eb and Ue over a wide temperature range. This work provides a promising and scalable route to develop sandwich-structured composites with prominent energy storage performances for high-temperature capacitive applications.

Multiple Local Symmetries Result in a Common Average Polar Axis in High-Strain BiFeO_{3}-Based Ceramics.

For the first time, the origin of large electrostrain in pseudocubic BiFeO_{3}-based ceramics is verified with direct structural evidence backed by appropriate simulations. We employ advanced structural and microstructural characterizations of BiFeO_{3}-based ceramics that exhibit large electrostrain (>0.4%) to reveal the existence of multiple, nanoscale local symmetries, dominantly tetragonal or orthorhombic, which have a common, averaged direction of polarization over larger, meso- or microscale regions. Phase-field simulations confirm the existence of local nanoscale symmetries, thereby providing a new vision for designing high-performance lead-free ceramics for high-strain actuators.

Achieving giant electrostrain of above 1% in (Bi,Na)TiO3-based lead-free piezoelectrics via introducing oxygen-defect composition.

Piezoelectric ceramics have been extensively used in actuators, where the magnitude of electrostrain is key indicator for large-stroke actuation applications. Here, we propose an innovative strategy based on defect chemistry to form a defect-engineered morphotropic phase boundary and achieve a giant strain of 1.12% in lead-free Bi0.5Na0.5TiO3 (BNT)-based ceramics. The incorporation of the hypothetical perovskite BaAlO2.5 with nominal oxygen defect into BNT will form strongly polarized directional defect dipoles, leading to a strong pinning effect after aging. The large asymmetrical strain is mainly attributed to two factors: The defect dipoles along crystallographic [001] direction destroy the long-range ordering of the ferroelectric and activate a reversible phase transition while promoting polarization rotation when the dipoles are aligned along the applied electric field. Our results not only demonstrate the potential application of BNT-based materials in low-frequency, large-stroke actuators but also provide a general methodology to achieve large strain.

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.

Formation of Head/Tail-to-Body Charged Domain Walls by Mechanical Stress.

Domain walls (DWs) in ferroelectric materials are interfaces that separate domains with different polarizations. Charged domain walls (CDWs) and neutral domain walls are commonly classified depending on the charge state at the DWs. CDWs are particularly attractive as they are configurable elements, which can enhance field susceptibility and enable functionalities such as conductance control. However, it is difficult to achieve CDWs in practice. Here, we demonstrate that applying mechanical stress is a robust and reproducible approach to generate CDWs. By mechanical compression, CDWs with a head/tail-to-body configuration were introduced in ultrathin BaTiO3, which was revealed by in-situ transmission electron microscopy. Finite element analysis shows strong strain fluctuation in ultrathin BaTiO3 under compressive mechanical stress. Molecular dynamics simulations suggest that the strain fluctuation is a critical factor in forming CDWs. This study provides insight into ferroelectric DWs and opens a pathway to creating CDWs in ferroelectric materials.