Spontaneous Supercrystal Formation During a Strain-Engineered Metal-Insulator Transition.

Mott metal-insulator transitions possess electronic, magnetic, and structural degrees of freedom promising next-generation energy-efficient electronics. A previously unknown, hierarchically ordered, and anisotropic supercrystal state is reported and its intrinsic formation characterized in-situ during a Mott transition in a Ca2RuO4 thin film. Machine learning-assisted X-ray nanodiffraction together with cryogenic electron microscopy reveal multi-scale periodic domain formation at and below the film transition temperature (TFilm ≈ 200-250 K) and a separate anisotropic spatial structure at and above TFilm. Local resistivity measurements imply an intrinsic coupling of the supercrystal orientation to the material's anisotropic conductivity. These findings add a new degree of complexity to the physical understanding of Mott transitions, opening opportunities for designing materials with tunable electronic properties.

Generative learning facilitated discovery of high-entropy ceramic dielectrics for capacitive energy storage.

Dielectric capacitors offer great potential for advanced electronics due to their high power densities, but their energy density still needs to be further improved. High-entropy strategy has emerged as an effective method for improving energy storage performance, however, discovering new high-entropy systems within a high-dimensional composition space is a daunting challenge for traditional trial-and-error experiments. Here, based on phase-field simulations and limited experimental data, we propose a generative learning approach to accelerate the discovery of high-entropy dielectrics in a practically infinite exploration space of over 1011 combinations. By encoding-decoding latent space regularities to facilitate data sampling and forward inference, we employ inverse design to screen out the most promising combinations via a ranking strategy. Through only 5 sets of targeted experiments, we successfully obtain a Bi(Mg0.5Ti0.5)O3-based high-entropy dielectric film with a significantly improved energy density of 156 J cm-3 at an electric field of 5104 kV cm-1, surpassing the pristine film by more than eight-fold. This work introduces an effective and innovative avenue for designing high-entropy dielectrics with drastically reduced experimental cycles, which could be also extended to expedite the design of other multicomponent material systems with desired properties.

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.

Harnessing the duality of bases toward controlled color and fluorescence.

Bases can promote keto-enol tautomerism, a prevalent form of prototropic tautomerism, and facilitate the ring opening of anhydride ring structures. The intrinsic chemical distinctions between these processes provide an opportunity to modulate these seemingly parallel reactions. However, this potential remains largely unexplored. In this work, we report homophthalic anhydride, the first molecule exhibiting simultaneous halochromism, turn-on fluorescence (halofluorochromism), and subsequent self-destruction. Through comprehensive spectroscopic analysis and theoretical calculations, we unravel the mechanisms underlying these phenomena, revealing that the pivotal roles of the base's basicity and nucleophilicity specifically allow us to achieve controlled durations of color change and turn-on fluorescence. Capitalizing on these intriguing properties, we develop a highly dynamic CMY (cyan-magenta-yellow) palette ideal for entity encryption and anti-counterfeiting applications. Our work reshapes the understanding of the relationship between the basicity and nucleophilicity of bases, enriching the comprehension of keto-enol tautomerism and homophthalic anhydride chemistry, and unveils a spectrum of potential applications.

In-Operando Spatiotemporal Imaging of Coupled Film-Substrate Elastodynamics During an Insulator-to-Metal Transition.

The drive toward non-von Neumann device architectures has led to an intense focus on insulator-to-metal (IMT) and the converse metal-to-insulator (MIT) transitions. Studies of electric field-driven IMT in the prototypical VO2 thin-film channel devices are largely focused on the electrical and elastic responses of the films, but the response of the corresponding TiO2 substrate is often overlooked, since it is nominally expected to be electrically passive and elastically rigid. Here, in-operando spatiotemporal imaging of the coupled elastodynamics using X-ray diffraction microscopy of a VO2 film channel device on TiO2 substrate reveals two new surprises. First, the film channel bulges during the IMT, the opposite of the expected shrinking in the film undergoing IMT. Second, a microns thick proximal layer in the substrate also coherently bulges accompanying the IMT in the film, which is completely unexpected. Phase-field simulations of coupled IMT, oxygen vacancy electronic dynamics, and electronic carrier diffusion incorporating thermal and strain effects suggest that the observed elastodynamics can be explained by the known naturally occurring oxygen vacancies that rapidly ionize (and deionize) in concert with the IMT (MIT). Fast electrical-triggering of the IMT via ionizing defects and an active "IMT-like" substrate layer are critical aspects to consider in device applications.

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.

Programming Polarity Heterogeneity of Energy Storage Dielectrics by Bidirectional Intelligent Design.

Dielectric capacitors, characterized by ultra-high power densities, are considered as fundamental energy storage components in electronic and electrical systems. However, synergistically improving energy densities and efficiencies remains a daunting challenge. Understanding the role of polarity heterogeneity at the nanoscale in determining polarization response is crucial to the domain engineering of high-performance dielectrics. Here, a bidirectional design with phase-field simulation and machine learning is performed to forward reveal the structure-property relationship and reversely optimize polarity heterogeneity to improve energy storage performance. Taking BiFeO3-based dielectrics as typical systems, this work establishes the mapping diagrams of energy density and efficiency dependence on the volume fraction, size and configuration of polar regions. Assisted by CatBoost and Wolf Pack algorithms, this work analyzes the contributions of geometric factors and intrinsic features and find that nanopillar-like polar regions show great potential in achieving both high polarization intensity and fast dipole switching. Finally, a maximal energy density of 188 J cm-3 with efficiency above 95% at 8 MV cm-1 is obtained in BiFeO3-Al2O3 systems. This work provides a general method to study the influence of local polar heterogeneity on polarization behaviors and proposes effective strategies to enhance energy storage performance by tuning polarity heterogeneity.

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.

Strong electron-phonon coupling driven pseudogap modulation and density-wave fluctuations in a correlated polar metal.

There is tremendous interest in employing collective excitations of the lattice, spin, charge, and orbitals to tune strongly correlated electronic phenomena. We report such an effect in a ruthenate, Ca3Ru2O7, where two phonons with strong electron-phonon coupling modulate the electronic pseudogap as well as mediate charge and spin density wave fluctuations. Combining temperature-dependent Raman spectroscopy with density functional theory reveals two phonons, B2P and B2M, that are strongly coupled to electrons and whose scattering intensities respectively dominate in the pseudogap versus the metallic phases. The B2P squeezes the octahedra along the out of plane c-axis, while the B2M elongates it, thus modulating the Ru 4d orbital splitting and the bandwidth of the in-plane electron hopping; Thus, B2P opens the pseudogap, while B2M closes it. Moreover, the B2 phonons mediate incoherent charge and spin density wave fluctuations, as evidenced by changes in the background electronic Raman scattering that exhibit unique symmetry signatures. The polar order breaks inversion symmetry, enabling infrared activity of these phonons, paving the way for coherent light-driven control of electronic transport.

Sub-Nanosecond Reconfiguration of Ferroelectric Domains in Bismuth Ferrite.

Domain switching is crucial for achieving desired functions in ferroic materials that are used in various applications. Fast control of domains at sub-nanosecond timescales remains a challenge despite its potential for high-speed operation in random-access memories, photonic, and nanoelectronic devices. Here, ultrafast laser excitation is shown to transiently melt and reconfigure ferroelectric stripe domains in multiferroic bismuth ferrite on a timescale faster than 100 picoseconds. This dynamic behavior is visualized by picosecond- and nanometer-resolved X-ray diffraction and time-resolved X-ray diffuse scattering. The disordering of stripe domains is attributed to the screening of depolarization fields by photogenerated carriers resulting in the formation of charged domain walls, as supported by phase-field simulations. Furthermore, the recovery of disordered domains exhibits subdiffusive growth on nanosecond timescales, with a non-equilibrium domain velocity reaching up to 10 m s-1 . These findings present a new approach to image and manipulate ferroelectric domains on sub-nanosecond timescales, which can be further extended into other complex photoferroic systems to modulate their electronic, optical, and magnetic properties beyond gigahertz frequencies. This approach could pave the way for high-speed ferroelectric data storage and computing, and, more broadly, defines new approaches for visualizing the non-equilibrium dynamics of heterogeneous and disordered materials.

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.

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.

Giant Energy Density via Mechanically Tailored Relaxor Ferroelectric Behavior of PZT Thick Film.

Relaxor ferroelectrics (RFEs) are being actively investigated for energy-storage applications due to their large electric-field-induced polarization with slim hysteresis and fast energy charging-discharging capability. Here, a novel nanograin engineering approach based upon high kinetic energy deposition is reported, for mechanically inducing the RFE behavior in a normal ferroelectric Pb(Zr0.52 Ti0.48 )O3 (PZT), which results in simultaneous enhancement in the dielectric breakdown strength (EDBS ) and polarization. Mechanically transformed relaxor thick films with 4 µm thickness exhibit an exceptional EDBS of 540 MV m-1 and reduced hysteresis with large unsaturated polarization (103.6 µC cm-2 ), resulting in a record high energy-storage density of 124.1 J cm-3 and a power density of 64.5 MW cm-3 . This fundamental advancement is correlated with the generalized nanostructure design that comprises nanocrystalline phases embedded within the amorphous matrix. Microstructure-tailored ferroelectric behavior overcomes the limitations imposed by traditional compositional design methods and provides a feasible pathway for realization of high-performance energy-storage materials.

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.

Exchange-Interaction-Like Behavior in Ferroelectric Bilayers.

Interlayer coupling in materials, such as exchange interactions at the interface between an antiferromagnet and a ferromagnet, can produce exotic phenomena not present in the parent materials. While such interfacial coupling in magnetic systems is widely studied, there is considerably less work on analogous electric counterparts (i.e., akin to electric "exchange-bias-like" or "exchange-spring-like" interactions between two polar materials) despite the likelihood that such effects can also engender new features associated with anisotropic electric dipole alignment. Here, electric analogs of such exchange interactions are reported, and their physical origins are explained for bilayers of in-plane polarized Pb1-x Srx TiO3 ferroelectrics. Variation of the strontium content and thickness of the layers provides for deterministic control over the switching properties of the bilayer system resulting in phenomena analogous to an exchange-spring interaction and, leveraging added control of these interactions with an electric field, the ability to realize multistate-memory function. Such observations not only hold technological promise for ferroelectrics and multiferroics but also extend the similarities between ferromagnetic and ferroelectric materials to include the manifestation of exchange-interaction-like phenomena.

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.

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.