Engineering Oxide Epitaxy beyond Substrate Constraint.

Orientation engineering is a crucial aspect of thin film growth, and it is rather challenging to engineer film epitaxy beyond the substrate constraint. Guided by density functional theory calculations, we use SrRuO3 (SRO) as a buffer layer and successfully deposit [111]-oriented CoFe2O4 (CFO) on [001]-, [110]-, and [111]-oriented SrTiO3 (STO) substrates. This enables subsequent growth of [111]-oriented functional oxides, such as PbTiO3 (PTO), overcoming the constraint of the substrate. This strategy is quite general and applicable to lanthanum aluminate and yttria-stabilized zirconia substrates as well. X-ray Φ scans and atomic resolution aberration-corrected scanning transmission electron microscopy (AC-STEM) reveal detailed epitaxial relations in each of the cases, with four variants of [111]-CFO found on [001]-STO and two variants found on [110]-STO, formed to mitigate the large lattice misfit strain between the film and substrate. Our strategy thus provides a general pathway for orientation engineering of oxide epitaxy beyond substrate constraint.

Revealing Fast Negative Capacitance in PbZr0.2Ti0.8O3 Thin Film with Acicular Ferroelastic Domains.

Negative capacitance effects with fast response times hold great potential for reducing the power consumption in high-frequency nanoelectronics. Nevertheless, the negative capacitance effect faces considerable complexity arising from the dynamic interplay among electrostatic, nucleation energies, and domain evolution. This intricate balance poses a formidable challenge to achieving fast negative capacitance. Herein, we have achieved a fast negative capacitance time of ∼16.23 ns in PbZr0.2Ti0.8O3 (PZT) thin film, and our investigation confirms the presence of acicular ferroelastic domains within the PZT thin film. Under reversal electric fields, these acicular ferroelastic domains undergo a unique flipping process, transitioning through domain expansion and contraction. This distinct domain flipping manner accelerates the nucleation and growth of ferroelectric domains, thereby facilitating the observed fast negative capacitance. The realization of fast negative capacitance holds substantial promise for reducing operational time and power consumption, offering prospects for the design of nanoelectronics with significantly lower power requirements.

Strong mechanical anisotropy and an anisotropic Dirac state in 2D C5N3.

Two-dimensional (2D) carbon nitride materials have emerged as a versatile platform for the design of high-performance nanoelectronics, but strong anisotropy in 2D carbon nitrides has rarely been reported. In this work, a 2D carbon nitride with strong anisotropy composed of tetra-, penta-, and hexa-rings (named as TPH-C5N3) is proposed. This TPH-C5N3 exhibits both dynamical and mechanical stability. Furthermore, it also showcases remarkable thermal stability, reaching up to 2300 K, as evidenced by AIMD simulations conducted in an NVT environment utilizing the Nosé-Hoover thermostat. Significantly, TPH-C5N3 demonstrates high anisotropic ratios in its mechanical properties, positioning it as the frontrunner in the current carbon nitride systems. In addition, a Dirac cone with an anisotropic ratio of 55.8% and Fermi velocity of 7.26 × 105 m s-1 is revealed in TPH-C5N3. The nontrivial topological properties of TPH-C5N3 are demonstrated by a non-zero Z2 invariant and topologically protected edge states. Our study offers theoretical insights into an anisotropic 2D carbon nitride material, laying the groundwork for its design and synthesis.

Highly Flexible Freestanding BaTiO3 -CoFe2 O4 Heteroepitaxial Nanostructure Self-Assembled with Room-Temperature Multiferroicity.

Multiferroics with simultaneous electric and magnetic orderings are highly desirable for sensing, actuation, data storage, and bio-inspired systems, yet developing flexible materials with robust multiferroic properties at room temperature is a long-term challenge. Utilizing water-soluble Sr3 Al2 O6 as a sacrificial layer, the authors have successfully self-assembled a freestanding BaTiO3 -CoFe2 O4 heteroepitaxial nanostructure via pulse laser deposition, and confirmed its epitaxial growth in both out-of-plane and in-plane directions, with highly ordered CoFe2 O4 nanopillars embedded in a single crystalline BaTiO3 matrix free of substrate constraint. The freestanding nanostructure enjoys super flexibility and mechanical integrity, not only capable of spontaneously curving into a roll, but can also be bent with a radius as small as 4.23 µm. Moreover, piezoelectricity and ferromagnetism are demonstrated at both microscopic and macroscopic scales, confirming its robust multiferroicity at room temperature. This work establishes an effective route for flexible multiferroic materials, which have the potential for various practical applications.

Ion Leakage Current Control for Polycrystalline Metal Halide Perovskite Direct X-ray Detectors.

Metal halide perovskites have emerged as promising materials for X-ray detection due to their high X-ray attenuation coefficients, defect tolerance, and suitability for large-area, low-temperature fabrication. However, the intrinsic high ion conductivity of these materials presents challenges, such as high dark current density and current drift, which impair the stability and sensitivity of perovskite X-ray detectors. This study introduces an approach to mitigating these issues by incorporating 2,2,3,3,3-pentafluoropropylamine hydrochloride (PFH) into polycrystalline MAPbI3-xClx films using a one-step blade-coating method. PFH aggregates at grain boundaries, raising local vacuum energy levels and passivating surface defects, thereby reducing ion conductivity without affecting electron conductivity. As a result, this approach significantly reduces the dark current and enhances sensitivity, achieving a low detection limit of 14.7 nGyair/s. Additionally, it improves signal stability, consistency, and response speed of the detector. These findings suggest that PFH is a promising additive for advancing the performance and practical application of polycrystalline metal halide perovskite-based X-ray detectors.

High-entropy superparaelectrics with locally diverse ferroic distortion for high-capacitive energy storage.

Superparaelectrics are considered promising candidate materials for achieving superior energy storage capabilities. However, due to the complicated local structural design, simultaneously achieving high recoverable energy density (Wrec) and energy storage efficiency (η) under high electric fields remains a challenge in bulk superparaelectrics. Here, we propose utilizing entropy engineering to disrupt long-range ferroic orders into local polymorphic distortion disorder with multiple BO6 tilt types and diverse heterogeneous polarization configurations. This strategy reduces the switching barriers, thereby facilitating the emergence of superparaelectric behaviors with ideal polarization forms. Furthermore, it enables high polarization response, negligible remnant polarization, delayed polarization saturation, and enhanced breakdown electric fields (Eb) in high-entropy superparaelectrics. Consequently, an extraordinary Wrec of 15.48 J cm-3 and an ultrahigh η of 90.02% are achieved at a high Eb of 710 kV cm-1, surpassing the comprehensive energy storage performance of previously reported bulk superparaelectrics. This work demonstrates that entropy engineering is a viable strategy for designing high-performance superparaelectrics.

An inorganic liquid crystalline dispersion with 2D ferroelectric moieties.

Electro-optical effect-based liquid crystal devices have been extensively used in optical modulation techniques, in which the Kerr coefficient reflects the sensitivity of the liquid crystals and determines the strength of the device's operational electric field. The Peterlin-Stuart theory and the O'Konski model jointly indicate that a giant Kerr coefficient could be obtained in a material with both a large geometrical anisotropy and an intrinsic polarization, but such a material is not yet reported. Here we reveal a ferroelectric effect in a monolayer two-dimensional mineral vermiculite. A large geometrical anisotropy factor and a large inherent electric dipole together raise the record value of Kerr coefficient by an order of magnitude, till 3.0 × 10-4 m V-2. This finding enables an ultra-low operational electric field of 102-104 V m-1 and the fabrication of electro-optical devices with an inch-level electrode separation, which has not previously been practical. Because of its high ultraviolet stability (decay <1% under ultraviolet exposure for 1000 hours), large-scale production, and energy efficiency, prototypical displayable billboards have been fabricated for outdoor interactive scenes. This work provides new insights for both liquid crystal optics and two-dimensional ferroelectrics.

An adjustable multistage resistance switching behavior of a photoelectric artificial synaptic device with a ferroelectric diode effect for neuromorphic computing.

Neuromorphic computing, which mimics biological neural networks, is widely regarded as the optimal solution for addressing the limitations of traditional von Neumann computing architecture. In this work, an adjustable multistage resistance switching ferroelectric Bi2FeCrO6 diode artificial synaptic device was fabricated using a sol-gel method with a simple process. The device exhibits nonlinearity in its electrical characteristics, demonstrating tunable multistage resistance switching behavior and a strong ferroelectric diode effect through the manipulation of ferroelectric polarization. One of its salient advantages resides in its capacity to dynamically regulate its polarization state in response to an external electric field, thereby facilitating the fine-tuning of synaptic connection strength while maintaining synaptic stability. The device is capable of accurately simulating the fundamental properties of biological synapses, including long/short-term plasticity, paired-pulse facilitation, and spike-timing-dependent plasticity. Additionally, the device exhibits a distinctive photoelectric response and is capable of inducing synaptic plasticity by light signal activation. The utilization of a femtosecond laser for the scrutiny of carrier transport mechanisms imparts profound insights into the intricate dynamics governing the optical memory effect. Furthermore, utilizing a convolutional neural network (CNN) architecture, the recognition accuracy of the MNIST and fashion MNIST datasets was improved to 95.6% and 78%, respectively, through the implementation of improved random adaptive algorithms. These findings present a new opportunity for utilizing Bi2FeCrO6 materials in the development of artificial synapses for neuromorphic computation.

High-Throughput Scanning Second-Harmonic-Generation Microscopy for Polar Materials.

The Materials Genome Initiative aims to discover, develop, manufacture, and deploy advanced materials at twice the speed of conventional approaches. To achieve this, high-throughput characterization is essential for the rapid screening of candidate materials. In this study, a high-throughput scanning second-harmonic-generation microscope with automatic partitioning, accurate positioning, and fast scanning is developed that can rapidly probe and screen polar materials. Using this technique, typical ferroelectrics, including periodically poled lithium niobate crystals and PbZr0.2 Ti0.8 O3 (PZT) thin films are first investigated, whereby the microscopic domain structures are clearly revealed. This technique is then applied to a compositional-gradient (100-x)%BaTiO3 -x%SrTiO3 film and a thickness-gradient PZT film to demonstrate its high-throughput capabilities. Since the second-harmonic-generation signal is correlated with the macroscopic remnant polarization over the probed region determined by the laser spot, it is free of artifacts arising from leakage current and electrostatic interference, while materials' symmetries and domain structures must be carefully considered in the data analysis. It is believed that this work can help promote the high-throughput development of polar materials and contribute to the Materials Genome Initiative.

A multifunctional optoelectronic device based on 2D material with wide bandgap.

Low-dimensional materials exhibit unique quantum confinement effects and morphologies as a result of their nanoscale size in one or more dimensions, making them exhibit distinctive physical properties compared to bulk counterparts. Among all low-dimensional materials, due to their atomic level thickness, two-dimensional materials possess extremely large shape anisotropy and consequently are speculated to have large optically anisotropic absorption. In this work, we demonstrate an optoelectronic device based on the combination of two-dimensional material and carbon dot with wide bandgap. High-efficient luminescence of carbon dot and extremely large shape anisotropy (>1500) of two-dimensional material with the wide bandgap of >4 eV cooperatively endow the optoelectronic device with multi-functions of optically anisotropic blue-light emission, visible light modulation, wavelength-dependent ultraviolet-light detection as well as blue fluorescent film assemble. This research opens new avenues for constructing multi-function-integrated optoelectronic devices via the combination of nanomaterials with different dimensions.

Adhesive, multifunctional, and wearable electronics based on MXene-coated textile for personal heating systems, electromagnetic interference shielding, and pressure sensing.

Adhesion between flexible devices and skin surface facilitates portability of devices and reliable signal acquisition from human body, which is essential for medical therapy devices or monitoring systems. Here, we utilize a simple, cost-effective, and scalable layer-by-layer dip-coating method to fabricate a skin-adhesive multifunctional textile-based device, consisting of three parts: low-cost and easily available airlaid paper (AP) substrate, conductive MXene sensitive layer, and adhesive polydimethylsiloxane (PDMS). The adhesive layer of lightly cross-linked PDMS enables the device to form conformal contact with skin even during human joint bending. The smart textile device exhibits excellent electro-thermal and photo-thermal conversion performance with good cycling stability and tunability. Furthermore, the textile electronics show good electromagnetic interference (EMI) shielding properties due to the good electrical conductivity, as well as sensitive and stable pressure sensing properties for human motion detection. Consequently, this efficient strategy provides a possible way to design multifunctional and wearable electronic textiles for medical applications.

Probing Ultrafast Dynamics of Ferroelectrics by Time-Resolved Pump-Probe Spectroscopy.

Ferroelectric materials have been a key research topic owing to their wide variety of modern electronic and photonic applications. For the quick exploration of higher operating speed, smaller size, and superior efficiencies of novel ferroelectric devices, the ultrafast dynamics of ferroelectrics that directly reflect their respond time and lifetimes have drawn considerable attention. Driven by time-resolved pump-probe spectroscopy that allows for probing, controlling, and modulating dynamic processes of ferroelectrics in real-time, much research efforts have been made to understand and exploit the ultrafast dynamics of ferroelectric. Herein, the current state of ultrafast dynamic features of ferroelectrics tracked by time-resolved pump-probe spectroscopy is reviewed, which includes ferroelectrics order parameters of polarization, lattice, spin, electronic excitation, and their coupling. Several potential perspectives and possible further applications combining ultrafast pump-probe spectroscopy and ferroelectrics are also presented. This review offers a clear guidance of ultrafast dynamics of ferroelectric orders, which may promote the rapid development of next-generation devices.

Highly Ordered SnO2 Nanopillar Array as Binder-Free Anodes for Long-Life and High-Rate Li-Ion Batteries.

SnO2, a typical transition metal oxide, is a promising conversion-type electrode material with an ultrahigh theoretical specific capacity of 1494 mAh g-1. Nevertheless, the electrochemical performance of SnO2 electrode is limited by large volumetric changes (~300%) during the charge/discharge process, leading to rapid capacity decay, poor cyclic performance, and inferior rate capability. In order to overcome these bottlenecks, we develop highly ordered SnO2 nanopillar array as binder-free anodes for LIBs, which are realized by anodic aluminum oxide-assisted pulsed laser deposition. The as-synthesized SnO2 nanopillar exhibit an ultrahigh initial specific capacity of 1082 mAh g-1 and maintain a high specific capacity of 524/313 mAh g-1 after 1100/6500 cycles, outperforming SnO2 thin film-based anodes and other reported binder-free SnO2 anodes. Moreover, SnO2 nanopillar demonstrate excellent rate performance under high current density of 64 C (1 C = 782 mA g-1), delivering a specific capacity of 278 mAh g-1, which can be restored to 670 mAh g-1 after high-rate cycling. The superior electrochemical performance of SnO2 nanoarray can be attributed to the unique architecture of SnO2, where highly ordered SnO2 nanopillar array provided adequate room for volumetric expansion and ensured structural integrity during the lithiation/delithiation process. The current study presents an effective approach to mitigate the inferior cyclic performance of SnO2-based electrodes, offering a realistic prospect for its applications as next-generation energy storage devices.

Super-Flexible Freestanding BiMnO3 Membranes with Stable Ferroelectricity and Ferromagnetism.

Multiferroic materials with flexibility are expected to make great contributions to flexible electronic applications, such as sensors, memories, and wearable devices. In this work, super-flexible freestanding BiMnO3 membranes with simultaneous ferroelectricity and ferromagnetism are synthesized using water-soluble Sr3 Al2 O6 as the sacrificial buffer layer. The super-flexibility of BiMnO3 membranes is demonstrated by undergoing an ≈180° folding during an in situ bending test, which is consistent with the results of first-principles calculations. The piezoelectric signal under a bending radius of ≈500 µm confirms the stable existence of electric polarization in freestanding BiMnO3 membranes. Moreover, the stable ferromagnetism of freestanding BiMnO3 membranes is demonstrated after 100 times bending cycles with a bending radius of ≈2 mm. 5.1% uniaxial tensile strain is achieved in freestanding BiMnO3 membranes, and the piezoresponse force microscopy (PFM) phase retention behaviors confirm that the ferroelectricity of membranes can survive stably up to the strain of 1.7%. These super-flexible membranes with stable ferroelectricity and ferromagnetism pave ways to the realizations of multifunctional flexible electronics.

Large-scale multiferroic complex oxide epitaxy with magnetically switched polarization enabled by solution processing.

Complex oxides with tunable structures have many fascinating properties, though high-quality complex oxide epitaxy with precisely controlled composition is still out of reach. Here we have successfully developed solution-based single-crystalline epitaxy for multiferroic (1-x)BiTi(1-y)/2Fe y Mg(1-y)/2O3-(x)CaTiO3 (BTFM-CTO) solid solution in large area, confirming its ferroelectricity at the atomic scale with strong spontaneous polarization. Careful compositional tuning leads to a bulk magnetization of 0.07 ± 0.035 µB/Fe at room temperature, enabling magnetically induced polarization switching exhibiting a large magnetoelectric coefficient of 2.7-3.0 × 10-7 s/m. This work demonstrates the great potential of solution processing in large-scale complex oxide epitaxy and establishes novel room-temperature magnetoelectric coupling in epitaxial BTFM-CTO film, making it possible to explore a much wider space of composition, phase, and structure that can be easily scaled up for industrial applications.

Self-Assembled Ferroelectric Nanoarray.

Self-assembled heteroepitaxial nanostructures have played an important role for miniaturization of electronic devices, e.g., the ultrahigh density ferroelectric memories, and cause for great concern. Our first principle calculations predict that the materials with low formation energy of the interface ( Ef) tend to form matrix structure in self-assembled heteroepitaxial nanostructures, whereas those with high Ef form nanopillars. Under the guidance of the theoretical modeling, perovskite BiFeO3 (BFO) nanopillars are swimmingly grown into CeO2 matrix on single-crystal (001)-SrTiO3 (STO) substrates by pulsed laser deposition, where CeO2 has a lower formation energy of the interface ( Ef) than BFO. This work provides a good paradigm for controlling self-assembled nanostructures as well as the application of self-assembled ferroelectric nanoscale memory.

Deterministic, Reversible, and Nonvolatile Low-Voltage Writing of Magnetic Domains in Epitaxial BaTiO3/Fe3O4 Heterostructure.

The ability to electrically write magnetic bits is highly desirable for future magnetic memories and spintronic devices, though fully deterministic, reversible, and nonvolatile switching of magnetic moments by electric field remains elusive despite extensive research. In this work, we develop a concept to electrically switch magnetization via polarization modulated oxygen vacancies, and we demonstrate the idea in a multiferroic epitaxial heterostructure of BaTiO3/Fe3O4 fabricated by pulsed laser deposition. The piezoelectricity and ferroelectricity of BaTiO3 have been confirmed by macro- and microscale measurements, for which Fe3O4 serves as the top electrode for switching the polarization. X-ray absorption spectroscopy and X-ray magnetic circular dichroism spectra indicate a mixture of Fe2+ and Fe3+ at O h sites and Fe3+ at T d sites in Fe3O4, while the room-temperature magnetic domains of Fe3O4 are revealed by microscopic magnetic force microscopy measurements. It is demonstrated that the magnetic domains of Fe3O4 can be switched by not only magnetic fields but also electric fields in a deterministic, reversible, and nonvolatile manner, wherein polarization reversal by electric field modulates the oxygen vacancy distribution in Fe3O4, and thus its magnetic state, making it attractive for electrically written magnetic memories.