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.

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.

Antiferroelectricity-Induced Negative Thermal Expansion in Double Perovskite Pb2 CoMoO6.

Materials with negative thermal expansion (NTE) attract significant research attention owing to their unique physical properties and promising applications. Although ferroelectric phase transitions leading to NTE are widely investigated, information on antiferroelectricity-induced NTE remains limited. In this study, single-crystal and polycrystalline Pb2 CoMoO6 samples are prepared at high pressure and temperature conditions. The compound crystallizes into an antiferroelectric Pnma orthorhombic double perovskite structure at room temperature owing to the opposite displacements dominated by Pb2+ ions. With increasing temperature to 400 K, a structural phase transition to cubic Fm-3m paraelectric phase occurs, accompanied by a sharp volume contraction of 0.41%. This is the first report of an antiferroelectric-to-paraelectric transition-induced NTE in Pb2 CoMoO6 . Moreover, the compound also exhibits remarkable NTE with an average volumetric coefficient of thermal expansion αV = -1.33 × 10-5 K-1 in a wide temperature range of 30-420 K. The as-prepared Pb2 CoMoO6 thus serves as a prototype material system for studying antiferroelectricity-induced NTE.

Self-Recovery of a Buckling BaTiO3 Ferroelectric Membrane.

The characteristic of self-recovery holds significant implications for upholding performance stability within flexible electronic devices following the release of mechanical deformation. Herein, the dynamics of self-recovery in a buckling inorganic membrane is studied via in situ scanning probe microscopy technology. The experimental results demonstrate that the ultimate deformation ratio of the buckling BaTiO3 ferroelectric membrane is up to 88%, which is much higher than that of the buckling SrTiO3 dielectric membrane (49%). Combined with piezoresponse force microscopy and phase-field simulations, we find that ferroelectric domain transformation accompanies the whole process of buckling and self-recovery of the ferroelectric membrane, i.e., the presence of the nano-c domain not only releases part of the elastic energy of the membrane but also reduces the interface mismatch of the a/c domain, which encourages the buckling ferroelectric membrane to have excellent self-recovery properties. It is conceivable that the evolution of ferroelectric domains will play a greater role in the regulation of the mechanical properties of ferroelectric membranes and flexible devices.

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.

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.

Tuning Piezoelectricity via Thermal Annealing at a Freestanding Ferroelectric Membrane.

Tuning the ferroelectric domain structure by a combination of elastic and electrostatic engineering provides an effective route for enhanced piezoelectricity. However, for epitaxial thin films, the clamping effect imposed by the substrate does not allow aftergrowth tuning and also limits the electromechanical response. In contrast, freestanding membranes, which are free of substrate constraints, enable the tuning of a subtle balance between elastic and electrostatic energies, giving new platforms for enhanced and tunable functionalities. Here, highly tunable piezoelectricity is demonstrated in freestanding PbTiO3 membranes, by varying the ferroelectric domain structures from c-dominated to c/a and a domains via aftergrowth thermal treatment. Significantly, the piezoelectric coefficient of the c/a domain structure is enhanced by a factor of 2.5 compared with typical c domain PbTiO3. This work presents a new strategy to manipulate the piezoelectricity in ferroelectric membranes, highlighting their great potential for nano actuators, transducers, sensors and other NEMS device applications.

Well-defined double hysteresis loop in NaNbO3 antiferroelectrics.

Antiferroelectrics (AFEs) are promising candidates in energy-storage capacitors, electrocaloric solid-cooling, and displacement transducers. As an actively studied lead-free antiferroelectric (AFE) material, NaNbO3 has long suffered from its ferroelectric (FE)-like polarization-electric field (P-E) hysteresis loops with high remnant polarization and large hysteresis. Guided by theoretical calculations, a new strategy of reducing the oxygen octahedral tilting angle is proposed to stabilize the AFE P phase (Space group Pbma) of NaNbO3. To validate this, we judiciously introduced CaHfO3 with a low Goldschmidt tolerance factor and AgNbO3 with a low electronegativity difference into NaNbO3, the decreased cation displacements and [BO6] octahedral tilting angles were confirmed by Synchrotron X-ray powder diffraction and aberration-corrected scanning transmission electron microscopy. Of particular importance is that the 0.75NaNbO3-0.20AgNbO3-0.05CaHfO3 ceramic exhibits highly reversible phase transition between the AFE and FE states, showing well-defined double P-E loops and sprout-shaped strain-electric field curves with reduced hysteresis, low remnant polarization, high AFE-FE phase transition field, and zero negative strain. Our work provides a new strategy for designing NaNbO3-based AFE material with well-defined double P-E loops, which can also be extended to discover a variety of new lead-free AFEs.

Electrical and magnetic anisotropies in van der Waals multiferroic CuCrP2S6.

Multiferroic materials have great potential in non-volatile devices for low-power and ultra-high density information storage, owing to their unique characteristic of coexisting ferroelectric and ferromagnetic orders. The effective manipulation of their intrinsic anisotropy makes it promising to control multiple degrees of the storage "medium". Here, we have discovered intriguing in-plane electrical and magnetic anisotropies in van der Waals (vdW) multiferroic CuCrP2S6. The uniaxial anisotropies of current rectifications, magnetic properties and magnon modes are demonstrated and manipulated by electric direction/polarity, temperature variation and magnetic field. More important, we have discovered the spin-flop transition corresponding to specific resonance modes, and determined the anisotropy parameters by consistent model fittings and theoretical calculations. Our work provides in-depth investigation and quantitative analysis of electrical and magnetic anisotropies with the same easy axis in vdW multiferroics, which will stimulate potential device applications of artificial bionic synapses, multi-terminal spintronic chips and magnetoelectric devices.

Unravelling the electromechanical coupling in a graphene/bulk h-BN heterostructure.

The stacking heterostructure of graphene on bulk h-BN produces a moiré pattern with topographic corrugation. The corrugation of the moiré pattern expectantly induces a considerable curvature and a flexoelectric response, which calls for a detailed study. In this work, we used lateral force microscopy, a scanning technique to locally observe the moiré pattern and topographic corrugation. The curvature and flexoelectric potentials are derived from the measured topographic corrugation, revealing a huge curvature of ∼107 m-1 and a flexoelectric potential of ∼10 mV in the hexagonal domain wall region (∼3-4 nm) of the moiré pattern. In addition, the domain walls of the moiré pattern also generate a clear electromechanical and frictional response, arising from the corrugation-induced flexoelectric response. In summary, the results of this work provide insights into the understanding of the flexoelectricity in the graphene/bulk h-BN and its associated electromechanical coupling behavior in the moiré pattern of a van der Waals stacking heterostructure.

Giant ferroelectric polarization in a bilayer graphene heterostructure.

At the interface of van der Waals heterostructures, the crystal symmetry and the electronic structure can be reconstructed, giving rise to physical properties superior to or absent in parent materials. Here by studying a Bernal bilayer graphene moiré superlattice encapsulated by 30°-twisted boron nitride flakes, we report an unprecedented ferroelectric polarization with the areal charge density up to 1013 cm-2, which is far beyond the capacity of a moiré band. The translated polarization ~5 pC m-1 is among the highest interfacial ferroelectrics engineered by artificially stacking van der Waals crystals. The gate-specific ferroelectricity and co-occurring anomalous screening are further visualized via Landau levels, and remain robust for Fermi surfaces outside moiré bands, confirming their independence on correlated electrons. We also find that the gate-specific resistance hysteresis loops could be turned off by the other gate, providing an additional control knob. Furthermore, the ferroelectric switching can be applied to intrinsic properties such as topological valley current. Overall, the gate-specific ferroelectricity with strongly enhanced charge polarization may encourage more explorations to optimize and enrich this novel class of ferroelectricity, and promote device applications for ferroelectric switching of various quantum phenomena.

Two-dimensional electronic structure for high thermoelectric performance in halide perovskite Cs2Au(I)Au(III)I6.

Pb- or Sn-based halide perovskites usually exhibit poor thermoelectric performance, arising from their low electrical conductivity or oxidation state instability. It is highly desired to search for new halide perovskites with good thermoelectric properties. In this work, the thermally stable mixed-valence halide perovskite Cs2Au(I)Au(III)I6 is revealed to be a highly promising thermoelectric material with high in-plane power factor and ultralow lattice thermal conductivity using first-principles calculations. The high in-plane power factor is achieved due to the novel two-dimensional electronic structure near the Fermi level driven by the weak interaction between AuI-5d and I-p orbitals. In addition, the small group velocities and short phonon lifetimes give rise to ultralow lattice thermal conductivity in Cs2Au(I)Au(III)I6. These excellent electronic and thermal properties lead to a high ZT value, which is close to 1 at 300 K and ∼4 at 800 K. Our results suggest that the 2D electronic structure from the weak interaction between d and p crystal orbitals is a promising route to design high-efficiency halide double perovskite thermoelectric materials.

Enhanced polarization and abnormal flexural deformation in bent freestanding perovskite oxides.

Recent realizations of ultrathin freestanding perovskite oxides offer a unique platform to probe novel properties in two-dimensional oxides. Here, we observe a giant flexoelectric response in freestanding BiFeO3 and SrTiO3 in their bent state arising from strain gradients up to 3.5 × 107 m-1, suggesting a promising approach for realizing ultra-large polarizations. Additionally, a substantial change in membrane thickness is discovered in bent freestanding BiFeO3, which implies an unusual bending-expansion/shrinkage effect in the ferroelectric membrane that has never been seen before in crystalline materials. Our theoretical model reveals that this unprecedented flexural deformation within the membrane is attributable to a flexoelectricity-piezoelectricity interplay. The finding unveils intriguing nanoscale electromechanical properties and provides guidance for their practical applications in flexible nanoelectromechanical systems.

Response to Comment on "Improper molecular ferroelectrics with simultaneous ultrahigh pyroelectricity and figures of merit".

Szafranski and Katrusiak stated that [Hdabco]ClO4 and [Hdabco]BF4 are proper ferroelectrics and exhibit much smaller pyroelectric coefficients than our results. We disagree with the arguments and provide a detailed answer highlighting misunderstandings in their interpretation.

Emergent multiferroism with magnetodielectric coupling in EuTiO3 created by a negative pressure control of strong spin-phonon coupling.

Negative pressure has emerged as a powerful tool to tailor the physical properties of functional materials. However, a negative pressure control of spin-phonon coupling for engineering magnetism and multiferroicity has not been explored to date. Here, using uniform three-dimensional strain-induced negative pressure in nanocomposite films of (EuTiO3)0.5:(MgO)0.5, we demonstrate an emergent multiferroicity with magnetodielectric coupling in EuTiO3, matching exactly with density functional theory calculations. Density functional theory calculations are further used to explore the underlying physics of antiferromagnetic-paraelectric to ferromagnetic-ferroelectric phase transitions, the spin-phonon coupling, and its correlation with negative pressures. The observation of magnetodielectric coupling in the EuTiO3 reveals that an enhanced spin-phonon coupling originates from a negative pressure induced by uniform three-dimensional strain. Our work provides a route to creating multiferroicity and magnetoelectric coupling in single-phase oxides using a negative pressure approach.

Strain Modulation for Light-Stable n-i-p Perovskite/Silicon Tandem Solar Cells.

Perovskite/silicon tandem solar cells are promising to penetrate photovoltaic market. However, the wide-bandgap perovskite absorbers used in top-cell often suffer severe phase segregation under illumination, which restricts the operation lifetime of tandem solar cells. Here, a strain modulation strategy to fabricate light-stable perovskite/silicon tandem solar cells is reported. By employing adenosine triphosphate, the residual tensile strain in the wide-bandgap perovskite absorber is successfully converted to compressive strain, which mitigates light-induced ion migration and phase segregation. Based on the wide-bandgap perovskite with compressive strain, single-junction solar cells with the n-i-p layout yield a power conversion efficiency (PCE) of 20.53% with the smallest voltage deficits of 440 mV. These cells also maintain 83.60% of initial PCE after 2500 h operation at the maximum power point. Finally, these top cells are integrated with silicon bottom cells in a monolithic tandem device, which achieves a PCE of 26.95% and improved light stability at open-circuit.

Atomic reconfiguration among tri-state transition at ferroelectric/antiferroelectric phase boundaries in Pb(Zr,Ti)O3.

Phase boundary provides a fertile ground for exploring emergent phenomena and understanding order parameters couplings in condensed-matter physics. In Pb(Zr1-xTix)O3, there are two types of composition-dependent phase boundary with both technological and scientific importance, i.e. morphotropic phase boundary (MPB) separating polar regimes into different symmetry and ferroelectric/antiferroelectric (FE/AFE) phase boundary dividing polar and antipolar dipole configurations. In contrast with extensive studies on MPB, FE/AFE phase boundary is far less explored. Here, we apply atomic-scale imaging and Rietveld refinement to directly demonstrate the intermediate phase at FE/AFE phase boundary exhibits a rare multipolar Pb-cations ordering, i.e. coexistence of antipolar or polar displacement, which manifests itself in both periodically gradient lattice spacing and anomalous initial hysteresis loop. In-situ electron/neutron diffraction reveals that the same parent intermediate phase can transform into either FE or AFE state depending on suppression of antipolar or polar displacement, coupling with the evolution of long-/short-range oxygen octahedra tilts. First-principle calculations further show that the transition between AFE and FE phase can occur in a low-energy pathway via the intermediate phase. These findings enrich the structural understanding of FE/AFE phase boundary in perovskite oxides.

Manipulation of current rectification in van der Waals ferroionic CuInP2S6.

Developing a single-phase self-rectifying memristor with the continuously tunable feature is structurally desirable and functionally adaptive to dynamic environmental stimuli variations, which is the pursuit of further smart memristors and neuromorphic computing. Herein, we report a van der Waals ferroelectric CuInP2S6 as a single memristor with superior continuous modulation of current and self-rectifying to different bias stimuli (sweeping speed, direction, amplitude, etc.) and external mechanical load. The synergetic contribution of controllable Cu+ ions migration and interfacial Schottky barrier is proposed to dynamically control the current flow and device performance. These outstanding sensitive features make this material possible for being superior candidate for future smart memristors with bidirectional operation mode and strong recognition to input faults and variations.

Self-Assembled Epitaxial Ferroelectric Oxide Nanospring with Super-Scalability.

Oxide nanosprings have attracted many research interests because of their anticorrosion, high-temperature tolerance, oxidation resistance, and enhanced-mechanic-response from unique helix structures, enabling various applications like nanomanipulators, nanomotors, nanoswitches, sensors, and energy harvesters. However, preparing oxide nanosprings is a challenge for their intrinsic lack of elasticity. Here, an approach for preparing self-assembled, epitaxial, ferroelectric nanosprings with built-in strain due to the lattice mismatch in freestanding La0.7 Sr0.3 MnO3 /BaTiO3 (LSMO/BTO) bilayer heterostructures is developed. It is found that these LSMO/BTO nanosprings can be extensively pulled or pushed up to their geometrical limits back and forth without breaking, exhibiting super-scalability with full recovery capability. The phase-field simulations reveal that the excellent scalability originates from the continuous ferroelastic domain structures, resulting from twisting under co-existing axial and shear strains. In addition, the oxide heterostructural springs exhibit strong resilience due to the limited plastic deformation nature and the built-in strain between the bilayers. This discovery provides an alternative way for preparing and operating functional oxide nanosprings that can be applied to various technologies.