High-entropy polymer produces a giant electrocaloric effect at low fields.

More than a decade of research on the electrocaloric (EC) effect has resulted in EC materials and EC multilayer chips that satisfy a minimum EC temperature change of 5 K required for caloric heat pumps1-3. However, these EC temperature changes are generated through the application of high electric fields4-8 (close to their dielectric breakdown strengths), which result in rapid degradation and fatigue of EC performance. Here we report a class of EC polymer that exhibits an EC entropy change of 37.5 J kg-1 K-1 and a temperature change of 7.5 K under 50 MV m-1, a 275% enhancement over the state-of-the-art EC polymers under the same field strength. We show that converting a small number of the chlorofluoroethylene groups in poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer into covalent double bonds markedly increases the number of the polar entities and enhances the polar-nonpolar interfacial areas of the polymer. The polar phases in the polymer adopt a loosely correlated, high-entropy state with a low energy barrier for electric-field-induced switching. The polymer maintains performance for more than one million cycles at the low fields necessary for practical EC cooling applications, suggesting that this strategy may yield materials suitable for use in caloric heat pumps.

Subterahertz collective dynamics of polar vortices.

The collective dynamics of topological structures1-6 are of interest from both fundamental and applied perspectives. For example, studies of dynamical properties of magnetic vortices and skyrmions3,4 have not only deepened our understanding of many-body physics but also offered potential applications in data processing and storage7. Topological structures constructed from electrical polarization, rather than electron spin, have recently been realized in ferroelectric superlattices5,6, and these are promising for ultrafast electric-field control of topological orders. However, little is known about the dynamics underlying the functionality of such complex extended nanostructures. Here, using terahertz-field excitation and femtosecond X-ray diffraction measurements, we observe ultrafast collective polarization dynamics that are unique to polar vortices, with orders-of-magnitude higher frequencies and smaller lateral size than those of experimentally realized magnetic vortices3. A previously unseen tunable mode, hereafter referred to as a vortexon, emerges in the form of transient arrays of nanoscale circular patterns of atomic displacements, which reverse their vorticity on picosecond timescales. Its frequency is considerably reduced (softened) at a critical strain, indicating a condensation (freezing) of structural dynamics. We use first-principles-based atomistic calculations and phase-field modelling to reveal the microscopic atomic arrangements and corroborate the frequencies of the vortex modes. The discovery of subterahertz collective dynamics in polar vortices opens opportunities for electric-field-driven data processing in topological structures with ultrahigh speed and density.

Transparent ferroelectric crystals with ultrahigh piezoelectricity.

Transparent piezoelectrics are highly desirable for numerous hybrid ultrasound-optical devices ranging from photoacoustic imaging transducers to transparent actuators for haptic applications1-7. However, it is challenging to achieve high piezoelectricity and perfect transparency simultaneously because most high-performance piezoelectrics are ferroelectrics that contain high-density light-scattering domain walls. Here, through a combination of phase-field simulations and experiments, we demonstrate a relatively simple method of using an alternating-current electric field to engineer the domain structures of originally opaque rhombohedral Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) crystals to simultaneously generate near-perfect transparency, an ultrahigh piezoelectric coefficient d33 (greater than 2,100 picocoulombs per newton), an excellent electromechanical coupling factor k33 (about 94 per cent) and a large electro-optical coefficient γ33 (approximately 220 picometres per volt), which is far beyond the performance of the commonly used transparent ferroelectric crystal LiNbO3. We find that increasing the domain size leads to a higher d33 value for the [001]-oriented rhombohedral PMN-PT crystals, challenging the conventional wisdom that decreasing the domain size always results in higher piezoelectricity8-10. This work presents a paradigm for achieving high transparency and piezoelectricity by ferroelectric domain engineering, and we expect the transparent ferroelectric crystals reported here to provide a route to a wide range of hybrid device applications, such as medical imaging, self-energy-harvesting touch screens and invisible robotic devices.

Real-space imaging of periodic nanotextures in thin films via phasing of diffraction data.

New properties and exotic quantum phenomena can form due to periodic nanotextures, including Moire patterns, ferroic domains, and topologically protected magnetization and polarization textures. Despite the availability of powerful tools to characterize the atomic crystal structure, the visualization of nanoscale strain-modulated structural motifs remains challenging. Here, we develop nondestructive real-space imaging of periodic lattice distortions in thin epitaxial films and report an emergent periodic nanotexture in a Mott insulator. Specifically, we combine iterative phase retrieval with unsupervised machine learning to invert the diffuse scattering pattern from conventional X-ray reciprocal-space maps into real-space images of crystalline displacements. Our imaging in PbTiO3/SrTiO3 superlattices exhibiting checkerboard strain modulation substantiates published phase-field model calculations. Furthermore, the imaging of biaxially strained Mott insulator Ca2RuO4 reveals a strain-induced nanotexture comprised of nanometer-thin metallic-structure wires separated by nanometer-thin Mott-insulating-structure walls, as confirmed by cryogenic scanning transmission electron microscopy (cryo-STEM). The nanotexture in Ca2RuO4 film is induced by the metal-to-insulator transition and has not been reported in bulk crystals. We expect the phasing of diffuse X-ray scattering from thin crystalline films in combination with cryo-STEM to open a powerful avenue for discovering, visualizing, and quantifying the periodic strain-modulated structures in quantum materials.

Spatially resolved steady-state negative capacitance.

Negative capacitance is a newly discovered state of ferroelectric materials that holds promise for electronics applications by exploiting a region of thermodynamic space that is normally not accessible1-14. Although existing reports of negative capacitance substantiate the importance of this phenomenon, they have focused on its macroscale manifestation. These manifestations demonstrate possible uses of steady-state negative capacitance-for example, enhancing the capacitance of a ferroelectric-dielectric heterostructure4,7,14 or improving the subthreshold swing of a transistor8-12. Yet they constitute only indirect measurements of the local state of negative capacitance in which the ferroelectric resides. Spatial mapping of this phenomenon would help its understanding at a microscopic scale and also help to achieve optimal design of devices with potential technological applications. Here we demonstrate a direct measurement of steady-state negative capacitance in a ferroelectric-dielectric heterostructure. We use electron microscopy complemented by phase-field and first-principles-based (second-principles) simulations in SrTiO3/PbTiO3 superlattices to directly determine, with atomic resolution, the local regions in the ferroelectric material where a state of negative capacitance is stabilized. Simultaneous vector mapping of atomic displacements (related to a complex pattern in the polarization field), in conjunction with reconstruction of the local electric field, identify the negative capacitance regions as those with higher energy density and larger polarizability: the domain walls where the polarization is suppressed.

Author Correction: Spatially resolved steady-state negative capacitance.

In this Letter, the first name of author Bhagwati Prasad was misspelled Bhagawati. This error has been corrected online.

Tuning Topology Phases by Controlling Effective Screening and Depolarization in Oxide Superlattices.

Polar topological phases in oxide superlattices attracted significant attention due to their unique properties. Previous work revealed that a polar vortex and polar skyrmions exist in (PTO)/(STO) superlattices under different elastic constraints, i.e., on different substrates. Here, our phase-field simulation demonstrates that manipulating the PTO and STO layers' thickness can control the effective screening provided by STO and the depolarization degree in PTO, thus switching the system among the polar skyrmions, vortex labyrinth, or paraelectric phase without changing elastic constraints. Additionally, reducing the STO thickness creates interlayer coupling among PTO layers, generating the long-range order of topological phases within superlattices. Furthermore, we construct a PTO-STO thickness topological phase diagram. These findings offer insights into the polar topological phases' formation in oxide superlattices, elucidating the roles of ferroelectric and paraelectric layers in their formation.

Interlayer Coupling Controlled Ordering and Phases in Polar Vortex Superlattices.

The recent discovery of polar topological structures has opened the door for exciting physics and emergent properties. There is, however, little methodology to engineer stability and ordering in these systems, properties of interest for engineering emergent functionalities. Notably, when the surface area is extended to arbitrary thicknesses, the topological polar texture becomes unstable. Here we show that this instability of the phase is due to electrical coupling between successive layers. We demonstrate that this electrical coupling is indicative of an effective screening length in the dielectric, similar to the conductor-ferroelectric interface. Controlling the electrostatics of the superlattice interfaces, the system can be tuned between a pure topological vortex state and a mixed classical-topological phase. This coupling also enables engineering coherency among the vortices, not only tuning the bulk phase diagram but also enabling the emergence of a 3D lattice of polar textures.

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.

Electro-thermal actuation in percolative ferroelectric polymer nanocomposites.

The interconversion between electrical and mechanical energies is pivotal to ferroelectrics to enable their applications in transducers, actuators and sensors. Ferroelectric polymers exhibit a giant electric-field-induced strain (>4.0%), markedly exceeding the actuation strain (≤1.7%) of piezoelectric ceramics and crystals. However, their normalized elastic energy densities remain orders of magnitude smaller than those of piezoelectric ceramics and crystals, severely limiting their practical applications in soft actuators. Here we report the use of electro-thermally induced ferroelectric phase transition in percolative ferroelectric polymer nanocomposites to achieve high strain performance in electric-field-driven actuation materials. We demonstrate a strain of over 8% and an output mechanical energy density of 11.3 J cm-3 at an electric field of 40 MV m-1 in the composite, outperforming the benchmark relaxor single-crystal ferroelectrics. This approach overcomes the trade-off between mechanical modulus and electro-strains in conventional piezoelectric polymer composites and opens up an avenue for high-performance ferroelectric actuators.

Non-volatile electric-field control of inversion symmetry.

Competition between ground states at phase boundaries can lead to significant changes in properties under stimuli, particularly when these ground states have different crystal symmetries. A key challenge is to stabilize and control the coexistence of symmetry-distinct phases. Using BiFeO3 layers confined between layers of dielectric TbScO3 as a model system, we stabilize the mixed-phase coexistence of centrosymmetric and non-centrosymmetric BiFeO3 phases at room temperature with antipolar, insulating and polar semiconducting behaviour, respectively. Application of orthogonal in-plane electric (polar) fields results in reversible non-volatile interconversion between the two phases, hence removing and introducing centrosymmetry. Counterintuitively, we find that an electric field 'erases' polarization, resulting from the anisotropy in octahedral tilts introduced by the interweaving TbScO3 layers. Consequently, this interconversion between centrosymmetric and non-centrosymmetric phases generates changes in the non-linear optical response of over three orders of magnitude, resistivity of over five orders of magnitude and control of microscopic polar order. Our work establishes a platform for cross-functional devices that take advantage of changes in optical, electrical and ferroic responses, and demonstrates octahedral tilts as an important order parameter in materials interface design.

Phase-Field Model of Electronic Antidoping.

Charge carrier doping usually reduces the resistance of a semiconductor or insulator, but was recently found to dramatically enhance the resistance in certain series of materials. This remarkable antidoping effect has been leveraged to realize synaptic memory trees in nanoscale hydrogenated perovskite nickelates, opening a new direction for neuromorphic computing. To understand these phenomena, we formulate a physical phase-field model of the antidoping effect based on its microscopic mechanism and simulate the voltage-driven resistance change in the prototypical system of hydrogenated perovskite nickelates. Remarkably, the simulations using this model, containing only one adjustable parameter whose magnitude is justified by first-principles calculations, quantitatively reproduce the experimentally observed treelike resistance states, which are shown unambiguously to arise from proton redistribution-induced local band gap enhancement and carrier blockage. Our work lays the foundation for modeling the antidoping phenomenon in strongly correlated materials at the mesoscale, which can provide guidance to the design of novel antidoping-physics-based devices.

Inherent stochasticity during insulator-metal transition in VO2.

Vanadium dioxide (VO2), which exhibits a near-room-temperature insulator-metal transition, has great potential in applications of neuromorphic computing devices. Although its volatile switching property, which could emulate neuron spiking, has been studied widely, nanoscale studies of the structural stochasticity across the phase transition are still lacking. In this study, using in situ transmission electron microscopy and ex situ resistive switching measurement, we successfully characterized the structural phase transition between monoclinic and rutile VO2 at local areas in planar VO2/TiO2 device configuration under external biasing. After each resistive switching, different VO2 monoclinic crystal orientations are observed, forming different equilibrium states. We have evaluated a statistical cycle-to-cycle variation, demonstrated a stochastic nature of the volatile resistive switching, and presented an approach to study in-plane structural anisotropy. Our microscopic studies move a big step forward toward understanding the volatile switching mechanisms and the related applications of VO2 as the key material of neuromorphic computing.

Reversible Phase Transition between Vortex Lattice and Hexagonal Polar Skyrmion Crystals.

Polar skyrmions in oxide heterostructures have recently attracted extensive interest due to their unique physical properties and potential applications. Here, we report the formation of the vortex lattice and the nanoscale polar skyrmion crystals with two-dimensional hexagonal symmetry in PbTiO3/SrTrO3 (PTO/STO) superlattices. Under an increasing external field, the system transitions from a vortex lattice phase to hexagonal polar skyrmion crystals (PSkC). The formation and annihilation process of the polar skyrmion crystals resemble the structural phase transition observed in atomic crystals. A temperature-electric field topological phase diagram is constructed, demonstrating stabilization of the vortex lattice and polar skyrmion crystals in a wide temperature and electric-field range. This study demonstrates the potential of manipulating the topological phase transition and its long-range order through an external field.

Thermodynamics of Light-Induced Nanoscale Polar Structures in Ferroelectric Superlattices.

We study the thermodynamics of nanoscale polar structures in PbTiO3/SrTiO3 ferroelectric superlattices induced by above-bandgap optical excitation using a phase-field model explicitly considering both structural and electronic processes. We demonstrate that the light-excited carriers provide the charge compensation of polarization bound charges and the lattice thermal energy, both of which are key to the thermodynamic stabilization of a previously observed supercrystal, a three-dimensionally periodic nanostructure, within a window of substrate strains, while different mechanical and electrical boundary conditions can stabilize a number of other nanoscale polar structures by balancing the competing short-range exchange interactions responsible for the domain wall energy and long-range electrostatic and elastic interactions. The insights into the light-induced formation and richness of nanoscale structures from this work offer theoretical guidance for exploring and manipulating the thermodynamic stability of nanoscale polar structures employing a combination of thermal, mechanical, and electrical stimuli as well as light.

Atomic-scale observation of non-classical nucleation-mediated phase transformation in a titanium alloy.

Two-phase titanium-based alloys are widely used in aerospace and biomedical applications, and they are obtained through phase transformations between a low-temperature hexagonal closed-packed α-phase and a high-temperature body-centred cubic ß-phase. Understanding how a new phase evolves from its parent phase is critical to controlling the transforming microstructures and thus material properties. Here, we report time-resolved experimental evidence, at sub-ångström resolution, of a non-classically nucleated metastable phase that bridges the α-phase and the ß-phase, in a technologically important titanium-molybdenum alloy. We observed a nanosized and chemically ordered superstructure in the α-phase matrix; its composition, chemical order and crystal structure are all found to be different from both the parent and the product phases, but instigating a vanishingly low energy barrier for the transformation into the ß-phase. This latter phase transition can proceed instantly via vibrational switching when the molybdenum concentration in the superstructure exceeds a critical value. We expect that such a non-classical phase evolution mechanism is much more common than previously believed for solid-state transformations.

High-entropy enhanced capacitive energy storage.

Electrostatic dielectric capacitors are essential components in advanced electronic and electrical power systems due to their ultrafast charging/discharging speed and high power density. A major challenge, however, is how to improve their energy densities to effectuate the next-generation applications that demand miniaturization and integration. Here, we report a high-entropy stabilized Bi2Ti2O7-based dielectric film that exhibits an energy density as high as 182 J cm-3 with an efficiency of 78% at an electric field of 6.35 MV cm-1. Our results reveal that regulating the atomic configurational entropy introduces favourable and stable microstructural features, including lattice distorted nano-crystalline grains and a disordered amorphous-like phase, which enhances the breakdown strength and reduces the polarization switching hysteresis, thus synergistically contributing to the energy storage performance. This high-entropy approach is expected to be widely applicable for the development of high-performance dielectrics.

Sublattice-Dependent Antiferromagnetic Transitions in Rare Earth Nickelates.

Perovskite rare earth nickelates exhibit remarkably rich physics in their metal-insulator and antiferromagnetic transitions, and there has been a long-standing debate on whether their magnetic structures are collinear or noncollinear. Through symmetry consideration based on the Landau theory, we discover that the antiferromagnetic transitions on the two nonequivalent Ni sublattices occur separately at different Néel temperatures induced by the O breathing mode. It is manifested by two kinks on the temperature-dependent magnetic susceptibilities with the secondary kink being continuous in the collinear magnetic structure but discontinuous in the noncollinear one. The prediction on the secondary discontinuous kink is corroborated by an existing magnetic susceptibility measurement on bulk single-crystalline nickelates, thus strongly supporting the noncollinear nature of the magnetic structure in bulk nickelates, thereby shedding new light on the long-standing debate.

Light-Driven Ultrafast Polarization Manipulation in a Relaxor Ferroelectric.

Relaxor ferroelectrics have been intensely studied for decades based on their unique electromechanical responses which arise from local structural heterogeneity involving polar nanoregions or domains. Here, we report first studies of the ultrafast dynamics and reconfigurability of the polarization in freestanding films of the prototypical relaxor 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 (PMN-0.32PT) by probing its atomic-scale response via femtosecond-resolution, electron-scattering approaches. By combining these structural measurements with dynamic phase-field simulations, we show that femtosecond light pulses drive a change in both the magnitude and direction of the polarization vector within polar nanodomains on few-picosecond time scales. This study defines new opportunities for dynamic reconfigurable control of the polarization in nanoscale relaxor ferroelectrics.

Flexoelectric Domain Walls Originated from Structural Phase Transition in Epitaxial BiVO4 Films.

Polar domain walls in centrosymmetric ferroelastics induce inhomogeneity that is the origin of advantageous multifunctionality. In particular, polar domain walls promote charge-carrier separation and hence are promising for energy conversion applications that overcome the hurdles of the rate-limiting step in the traditional photoelectrochemical water splitting processes. Yet, while macroscopic studies investigate the materials at the device scale, the origin of this phenomenon in general and the emergence of polar domain walls during the structural phase transition in particular has remained elusive, encumbering the development of this attractive system. Here, it is demonstrated that twin domain walls arise in centrosymmetric BiVO4 films and they exhibit localized piezoelectricity. It is also shown that during the structural phase transition from the tetragonal to monoclinic, the symmetry reduction is accompanied by an emergence of strain gradient, giving rise to flexoelectric effect and the polar domain walls. These results not only expose the emergence of polar domain walls at centrosymmetric systems by means of direct observation, but they also expand the realm of potential application of ferroelastics, especially in photoelectrochemistry and local piezoelectricity.