Voltage Control of Multiple Electrochemical Processes during Lithium Ion Migration in NiFe2O4 Ferrite.

Li-ion-based electric field control has been attracting significant attention, since it is able to penetrate deep into materials to exhibit diverse and controllable electrochemical processes, which offer more degrees of freedom to design multifunctional devices with low power consumption. As opposed to previous studies that mainly focused on single lithiation/delithiation mechanisms, we reveal three Li-ion modulation mechanisms in the same NiFe2O4 spinel ferrite by in situ magnetometry, i.e., intercalation, conversion, and space charge, which are respectively demonstrated in high, medium, and low voltage range. During the intercalation stage, the spinel structure is preserved, and a reversible modulation of magnetization arises from the charge transfer-induced variation of Fe valence states (Fe2+/Fe3+). Conversion-driven change in magnetization is the largest up to 89 emu g-1, due to the structural and magnetic phase transitions. Although both intercalation and conversion exhibit sluggish kinetics and long response times, the space charge manifests a faster switching speed and superior durability due to its interface electrostatic effect. These results not only provide a clear and comprehensive understanding on Li-based modulation mechanisms but also facilitate multifunctional and multiscenario applications, such as multistate memory, micromagnetic actuation, artificial synapse, and energy storage.

Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane.

The engineering of ferroic orders, which involves the evolution of atomic structure and local ferroic configuration in the development of next-generation electronic devices. Until now, diverse polarization structures and topological domains are obtained in ferroelectric thin films or heterostructures, and the polarization switching and subsequent domain nucleation are found to be more conducive to building energy-efficient and multifunctional polarization structures. In this work, a continuous and periodic strain in a flexible freestanding BaTiO3 membrane to achieve a zigzag morphology is introduced. The polar head/tail boundaries and vortex/anti-vortex domains are constructed by a compressive strain as low as ≈0.5%, which is extremely lower than that used in epitaxial rigid ferroelectrics. Overall, this study c efficient polarization structures, which is of both theoretical value and practical significance for the development of next-generation flexible multifunctional devices.

Current-Induced Magnetization Switching in Light-Metal-Oxide/Ferromagnetic-Metal Bilayers via Orbital Rashba Effect.

The orbital angular momentum (OAM) generation as well as its associated orbital torque is currently a matter of great interest in spin-orbitronics and is receiving increasing attention. In particular, recent theoretical work predicts that the oxidized light metal Cu can serve as an efficient OAM generator through its surface orbital Rashba effect. Here, for the first time, the crucial current-induced magnetic-field-free in-plane magnetization reversal is experimentally demonstrated in CoFeB/CuOx bilayers without any heavy elements. We show that the critical current density can be comparable to that of strong spin-orbit coupling systems with heavy metals (Pt and Ta) and that the magnetization reversal mechanism is governed by coherent rotation in the grains through the second-harmonic and magneto-optical Kerr effect measurements. Our results indicate that light metal oxides can play an equally important role as heavy metals in magnetization reversal, broadening the choice of materials for engineering spintronic devices.

Quantum anomalous Hall effect with a high and tunable Chern number in monolayer NdN2.

Due to the presence of dissipationless edge states, the quantum anomalous Hall (QAH) insulator has garnered significant attention for both fundamental research and practical application. However, the majority of QAH insulators suffer from a low Chern number (C = 1), and the Chern number is basically unadjustable, which constrains their potential application in spintronic devices. Here, based on a tight-binding model and first-principles calculations, we propose that two-dimensional (2D) ferromagnetic monolayer NdN2 exhibits a high-Chern-number QAH effect with C = ±3, accompanied by a nontrivial band gap of 97.4 meV. More importantly, by manipulating the magnetization orientation in the xz plane, the Chern number of 2D NdN2 can be further tuned between C = ±3 and C = ±1. When the magnetization vector is confined to the xy plane, the monolayer NdN2 would exhibit either a Dirac half-semimetal or in-plane QAH phase. Moreover, the QAH effect with a higher Chern number C = 9 can be achieved by constructing a multilayer van der Waals heterostructure composed of monolayers NdN2 and BN with alternative stacking order. These findings provide a reliable platform for exploring the novel QAH effect and developing high-performance topological devices.

Duplex Interpenetrating-Phase FeNiZn and FeNi3 Heterostructure with Low-Gibbs Free Energy Interface Coupling for Highly Efficient Overall Water Splitting.

The sluggish kinetics of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) generate the large overpotential in water electrolysis and thus high-cost hydrogen production. Here, multidimensional nanoporous interpenetrating-phase FeNiZn alloy and FeNi3 intermetallic heterostructure is in situ constructed on NiFe foam (FeNiZn/FeNi3@NiFe) by dealloying protocol. Coupling with the eminent synergism among specific constituents and the highly efficient mass transport from integrated porous backbone, FeNiZn/FeNi3@NiFe depicts exceptional bifunctional activities for water splitting with extremely low overpotentials toward OER and HER (η1000 = 367/245 mV) as well as the robust durability during the 400 h testing in alkaline solution. The as-built water electrolyzer with FeNiZn/FeNi3@NiFe as both anode and cathode exhibits record-high performances for sustainable hydrogen output in terms of much lower cell voltage of 1.759 and 1.919 V to deliver the current density of 500 and 1000 mA cm-2 as well long working lives. Density functional theory calculations disclose that the interface interaction between FeNiZn alloy and FeNi3 intermetallic generates the modulated electron structure state and optimized intermediate chemisorption, thus diminishing the energy barriers for hydrogen production in water splitting. With the merits of fine performances, scalable fabrication, and low cost, FeNiZn/FeNi3@NiFe holds prospective application potential as the bifunctional electrocatalyst for water splitting.

Extreme Enhanced Curie Temperature and Perpendicular Exchange Bias in Freestanding Ferromagnetic Superlattices.

Most recently, the freestanding of an epitaxial single-crystal oxide has been greatly developed to its fundamental concerns and the possibility of integration with metal, two-dimensional, and organic materials for more promising functionalities. In an artificial ferromagnetic oxide heterostructure and superlattice, the release of the substrate constraint can induce a reasonable transformation of the magnetic structure because the change of the lattice field occurs. In this study, we have comprehensively investigated the evolution of magnetic properties of (La0.7Ca0.3MnO3/SrRuO3)n [(LCMO/SRO)n] ferromagnetic superlattices while they are epitaxially on SrTiO3 and freestanding. It is found that the Curie temperature and the perpendicular exchange bias of the freestanding superlattices exhibit extreme sensitivity to the interface number and the thickness of LCMO and SRO, which can maximumly reach ∼293 K and ∼1150 Oe. These enhanced and bulk-beyond magnetic behaviors originate from the interfacial magnetic transition from ferromagnetic to antiferromagnetic via the charge reconstruction with the assistance of strain. Our study provides not only a reference for designing a high-performance flexible ferromagnetic architectural superlattice but also a deep understanding of the interfacial effect in freestanding ferromagnetic heterostructures benefiting flexible spintronics.

Engineering Spin Configurations of Synthetic Antiferromagnet by Controlling Long-Range Oscillatory Interlayer Coupling and Neighboring Ferrimagnetic Coupling.

Controllable manipulation of specific spin configurations of magnetic materials is the key to constructing functional spintronic devices. Here, it is demonstrated by integrating the merits of ferromagnetic, ferrimagnetic, and antiferromagnetic spin configurations into one synthetic antiferromagnetic (SAF) heterostructure by controlling both long-range oscillatory interlayer coupling and neighboring ferrimagnetic coupling. A controllable manipulation of four types of spin configurations of the Pt/[Co/Pt/Co]/Ru/CoTb SAF heterostructures composed of ferromagnetic Co/Pt/Co and ferrimagnetic CoTb layers is successfully achieved. In particular, the compensated magnetization, enhanced anomalous Hall resistance in the remanence state, wide-temperature spin-orbit torque switching of magnetization, and high immunity to the external magnetic field are simultaneously obtained in one of the SAF heterojunctions with macroscopic interlayer antiferromagnetic coupling. This design concept of engineering spin configurations may enable efficient spin manipulation for customized memory and logic applications.

Space-Charge Control of Magnetism in Ferromagnetic Metals: Coupling Giant Magnitude and Robust Endurance.

Ferromagnetic metals show great prospects in ultralow-power-consumption spintronic devices, due to their high Curie temperature and robust magnetization. However, there is still a lack of reliable solutions for giant and reversible voltage control of magnetism in ferromagnetic metal films. Here, a novel space-charge approach is proposed which allows for achieving a modulation of 30.3 emu/g under 1.3 V in Co/TiO2 multilayer granular films. The robust endurance with more than 5000 cycles is demonstrated. Similar phenomena exist in Ni/TiO2 and Fe/TiO2 multilayer granular films, which shows its universality. The magnetic change of 107% in Ni/TiO2 underlines its potential in a voltage-driven ON-OFF magnetism. Such giant and reversible voltage control of magnetism can be ascribed to space-charge effect at the ferromagnetic metals/TiO2 interfaces, in which spin-polarized electrons are injected into the ferromagnetic metal layer with the adsorption of lithium-ions on the TiO2 surface. These results open the door for a promising method to modulate the magnetization in ferromagnetic metals, paving the way toward the development of ionic-magnetic-electric coupled applications.

Revealing interfacial space charge storage of Li+/Na+/K+ by operando magnetometry.

Interfacial space charge storage between ionic and electronic conductor is a promising scheme to further improve energy and power density of alkali metal ion batteries (AMIBs). However, the general behavior of space charge storage in AMIBs has been less investigated experimentally, mostly due to the complicated electrochemical behavior and lack of proper characterization techniques. Here, we use operando magnetometry to verify that in FeSe2 AMIBs, abundant Li+/Na+/K+ (M+) can be stored at M2Se phase while electrons accumulate at Fe nanoparticles, forming interfacial space charge layers. Magnetic and dynamics tests further demonstrate that with increasing ionic radius from Li+, Na+ to K+, the reaction kinetics can be hindered, resulting in limited Fe formation and reduced space charge storage capacity. This work lays solid foundation for studying the complex interfacial effect in electrochemical processes and designing advanced energy storage devices with substantial capacity and considerable power density.

Field-Free Magnetization Switching in a Ferromagnetic Single Layer through Multiple Inversion Asymmetry Engineering.

A simple, reliable, and self-switchable spin-orbit torque (SOT)-induced magnetization switching in a ferromagnetic single layer is needed for the development of next generation fully electrical controllable spintronic devices. In this work, field-free SOT-induced magnetization switching in a CoPt single layer is realized by broken multiple inversion symmetry through simultaneously introducing both oblique sputtering and a vertical composition gradient. A quantitative analysis indicates that multiple inversion asymmetries can produce dynamical bias fields along both z- and x-axes, leading to the observed field-free deterministic magnetization switching. Our study provides a method to accomplish fully electrical manipulation of magnetization in a ferromagnetic single layer without the external magnetic field and auxiliary heavy metal layer, enabling flexible design for future spin-orbit torque-based memory and logic devices.

Flexible Self-Powered Weak Light Detectors Based on ZnO/CsPbBr3/γ-CuI Heterojunctions.

Halide perovskites (HPs) with marvelous optical and electrical properties are regarded as one of the competitive candidates for building next-generation photodetectors (PDs). However, combining their excellent properties with satisfactory long-term robustness is still challenging, ultimately limiting the practical applications of HP-based PDs. Herein, a high vacuum deposition system is employed to fabricate flexible self-powered PDs with a ZnO/CsPbBr3/γ-CuI structure, which shows excellent stability and outstanding performance in weak light detection. Benefiting from the improved crystallinity and optimized device structure, a high detectivity of 8.1 × 1013 Jones and a rapid response speed (rise/decay time of 3.9/1.8 µs) are obtained in this self-powered device. Furthermore, the unencapsulated device exhibits intriguing environmental stability and mechanical flexibility. The photocurrent remains unchanged after 7000 s of continuous operation or 100 bending cycles. Furthermore, a 15 × 15 PD array is fabricated as an image sensor. A high contrast image of the target object can be obtained owing to the high sensitivity and uniformity of the self-powered PDs. These results demonstrate the feasibility and practicality of the ZnO/CsPbBr3/γ-CuI heterojunction for applications in weak light detection and image formation.

Sign Change of Spin-Orbit Torque in Pt/NiO/CoFeB Structures.

Antiferromagnetic insulators have recently been proved to support spin current efficiently. Here, we report the dampinglike spin-orbit torque (SOT) in Pt/NiO/CoFeB has a strong temperature dependence and reverses the sign below certain temperatures, which is different from the slight variation with temperature in the Pt/CoFeB bilayer. The negative dampinglike SOT at low temperatures is proposed to be mediated by the magnetic interactions that tie with the "exchange bias" in Pt/NiO/CoFeB, in contrast to the thermal-magnon-mediated scenario at high temperatures. Our results highlight the promise to control the SOT through tuning the magnetic structure in multilayers.

Quasi-two-dimensional α-molybdenum oxide thin film prepared by magnetron sputtering for neuromorphic computing.

Two-dimensional (2D) layered materials have attracted intensive attention in recent years due to their rich physical properties, and shown great promise due to their low power consumption and high integration density in integrated electronics. However, mostly limited to mechanical exfoliation, large scale preparation of the 2D materials for application is still challenging. Herein, quasi-2D α-molybdenum oxide (α-MoO3) thin film with an area larger than 100 cm2 was fabricated by magnetron sputtering, which is compatible with modern semiconductor industry. An all-solid-state synaptic transistor based on this α-MoO3 thin film is designed and fabricated. Interestingly, by proton intercalation/deintercalation, the α-MoO3 channel shows a reversible conductance modulation of about four orders. Several indispensable synaptic behaviors, such as potentiation/depression and short-term/long-term plasticity, are successfully demonstrated in this synaptic device. In addition, multilevel data storage has been achieved. Supervised pattern recognition with high recognition accuracy is demonstrated in a three-layer artificial neural network constructed on this α-MoO3 based synaptic transistor. This work can pave the way for large scale production of the α-MoO3 thin film for practical application in intelligent devices.

Programmable Spin-Orbit Torque Multistate Memory and Spin Logic Cell.

Controllable spin-orbit torque based nonvolatile memory is highly desired for constructing energy efficient reconfigurable logic-in-memory computing suitable for emerging data-intensive applications. Here, we report our exploration of the IrMn/Co/Ru/CoPt/CoO heterojunction as a potential candidate for applications in both multistate memory and programmable spin logic. The studied heterojunction can be programmed into four different magnetic configurations at will by tuning both the in-plane exchange bias at the interface of IrMn and Co layers and the out-of-plane exchange bias at the interface of CoPt and CoO layers. Moreover, on the basis of the controllable exchange bias effect, 10 states of nonvolatile memory and multiple logic-in-memory functions have been demonstrated. Our findings indicate that IrMn/Co/Ru/CoPt/CoO multilayered structures can be used as a building block for next-generation logic-in-memory and multifunctional multidimensional spintronic devices.

Reacquainting the Electrochemical Conversion Mechanism of FeS2 Sodium-Ion Batteries by Operando Magnetometry.

In spite of the excellent electrochemical performance in lithium-ion batteries (LIBs), transition-metal compounds usually show inferior capacity and cyclability in sodium-ion batteries (SIBs), implying different reaction schemes between these two types of systems. Herein, coupling operando magnetometry with electrochemical measurement, we peformed a comprehensive investigation on the intrinsic relationship between the ion-embedding mechanisms and the electrochemical properties of the typical FeS2/Na (Li) cells. Operando magnetometry together with ex-situ transmission electron microscopy (TEM) measurement reveal that only part of FeS2 is involved in the conversion reaction process, while the unreactive parts form "inactive cores" that lead to the low capacity. Through quantification with Langevin fitting, we further show that the size of the iron grains produced by the conversion reaction are much smaller in SIBs than that in LIBs, which may lead to more serious pulverization, thereby resulting in worse cycle performance. The underlying reason for the above two above phenomena in SIBs is the sluggish kinetics caused by the larger Na-ion radius. Our work paves a new way for the investigation of novel SIB materials with high capacity and long durability.

Controllable field-free switching of perpendicular magnetization through bulk spin-orbit torque in symmetry-broken ferromagnetic films.

Programmable magnetic field-free manipulation of perpendicular magnetization switching is essential for the development of ultralow-power spintronic devices. However, the magnetization in a centrosymmetric single-layer ferromagnetic film cannot be switched directly by passing an electrical current in itself. Here, we demonstrate a repeatable bulk spin-orbit torque (SOT) switching of the perpendicularly magnetized CoPt alloy single-layer films by introducing a composition gradient in the thickness direction to break the inversion symmetry. Experimental results reveal that the bulk SOT-induced effective field on the domain walls leads to the domain walls motion and magnetization switching. Moreover, magnetic field-free perpendicular magnetization switching caused by SOT and its switching polarity (clockwise or counterclockwise) can be reversibly controlled in the IrMn/Co/Ru/CoPt heterojunctions based on the exchange bias and interlayer exchange coupling. This unique composition gradient approach accompanied with electrically controllable SOT magnetization switching provides a promising strategy to access energy-efficient control of memory and logic devices.

Operando Magnetometry Probing the Charge Storage Mechanism of CoO Lithium-Ion Batteries.

Cobalt oxide (CoO) is a promising electrode for high-energy-density Li-ion batteries (LIBs), where the charge storage is believed to take place solely during the electrochemical oxidation/reduction processes. However, this simple picture has been increasingly challenged by reported anomalously large storage capacities, indicating the existence of undiscovered extra charge reservoirs inside the system. Here, an advanced operando magnetometry technology is employed to monitor the magnetization variation of the CoO LIBs in real time and, in this particular system, it is clearly demonstrated that the anomalous capacity is associated with both the reversible formation of a spin capacitor and the growth of a polymeric film at low voltages. Furthermore, operando magnetometry provides direct evidence of the catalytic role of metallic Co in assisting the polymeric film formation. These critical findings help pave the way for better understanding of the charge storage mechanisms of transition-metal oxides and further utilizing them to design novel electrode materials.

Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry.

In lithium-ion batteries (LIBs), many promising electrodes that are based on transition metal oxides exhibit anomalously high storage capacities beyond their theoretical values. Although this phenomenon has been widely reported, the underlying physicochemical mechanism in such materials remains elusive and is still a matter of debate. In this work, we use in situ magnetometry to demonstrate the existence of strong surface capacitance on metal nanoparticles, and to show that a large number of spin-polarized electrons can be stored in the already-reduced metallic nanoparticles (that are formed during discharge at low potentials in transition metal oxide LIBs), which is consistent with a space charge mechanism. Through quantification of the surface capacitance by the variation in magnetism, we further show that this charge capacity of the surface is the dominant source of the extra capacity in the Fe3O4/Li model system, and that it also exists in CoO, NiO, FeF2 and Fe2N systems. The space charge mechanism revealed by in situ magnetometry can therefore be generalized to a broad range of transition metal compounds for which a large electron density of states is accessible, and provides pivotal guidance for creating advanced energy storage systems.

Nonvolatile Multistates Memories for High-Density Data Storage.

In the current information age, the realization of memory devices with energy efficient design, high storage density, nonvolatility, fast access, and low cost is still a great challenge. As a promising technology to meet these stringent requirements, nonvolatile multistates memory (NMSM) has attracted lots of attention over the past years. Owing to the capability to store data in more than a single bit (0 or 1), the storage density is dramatically enhanced without scaling down the memory cell, making memory devices more efficient and less expensive. Multistates in a single cell also provide an unconventional in-memory computing platform beyond the Von Neumann architecture and enable neuromorphic computing with low power consumption. In this review, an in-depth perspective is presented on the recent progress and challenges on the device architectures, material innovation, working mechanisms of various types of NMSMs, including flash, magnetic random-access memory (MRAM), resistive random-access memory (RRAM), ferroelectric random-access memory (FeRAM), and phase-change memory (PCM). The intriguing properties and performance of these NMSMs, which are the key to realizing highly integrated memory hierarchy, are discussed and compared.

Interfacial properties in energy storage systems studied by soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering.

Interfacial behaviors and properties play critical roles in determining key practical parameters of electrochemical energy storage systems, such as lithium-ion and sodium-ion batteries. Soft x-ray spectroscopy features shallow penetration depth and demonstrates inherent surface sensitivity to characterize the interfacial behavior with elemental and chemical sensitivities. In this review, we present a brief survey of modern synchrotron-based soft x-ray spectroscopy of the interface in electrochemical energy storage systems. The technical focus includes core-level spectroscopy of conventional x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS). We show that while conventional techniques remain powerful for probing the chemical species on the surface, today's material research studies have triggered much more demanding chemical sensitivity that could only be offered by advanced techniques such as RIXS. Another direction in the field is the rapid development of various in situ/operando characterizations of complex electrochemical systems. Notably, the solid-state battery systems provide unique advantages for future studies of both the surface/interface and the bulk properties under operando conditions. We conclude with perspectives on the bright future of studying electrochemical systems through these advanced soft x-ray spectroscopic techniques.