Room‐Temperature Nonvolatile Memory Based on a Single‐Phase Multiferroic Hexaferrite

The cross‐coupling between electric polarization and magnetization in multiferroic materials provides a great potential for creating next‐generation memory devices. Current studies on magnetoelectric (ME) applications mainly focus on ferromagnetic/ferroelectric heterostructures because single‐phase multiferroics with strong magnetoelectric coupling at room temperature are still very rare. Here a type of nonvolatile memory device is presented solely based on a single‐phase multiferroic hexaferrite Sr₃Co₂Fe₂₄O₄₁ which exhibits nonlinear magnetoelectric effects at room temperature. The principle is to store binary information by employing the states (magnitude and sign) of the first‐order and the second‐order magnetoelectric coefficients (α and β), instead of using magnetization, electric polarization, and resistance. The experiments demonstrate repeatable nonvolatile switch of α and β by applying pulsed electric fields at room temperature, respectively. Such kind of memory device using single‐phase multiferroics paves a pathway toward practical applications of spin‐driven multiferroics.     

Readdressing of Magnetoelectric Effect in Bulk BiFeO3

After decades of study, BiFeO₃ is still the most promising single‐phase multiferroic material due to its large polarization and high operating temperature, drawing much attention. As a typical type‐I multiferroic material, the magnetoelectric coupling in BiFeO₃ is deemed to be weak due to the different origins of its ferroelectricity and magnetism. Here, the magnetoelectric effect in bulk BiFeO₃ is readdressed both theoretically and experimentally. Based on the Dzyaloshinsky–Moriya interaction scenario, the magnetoelectric effect in BiFeO₃ is actually strong, with a coupling energy of about 1.25 meV and a magnetism‐coupled parasitic polarization comparable to that of the type‐II multiferroics. However, such strong magnetoelectric coupling also causes the cycloidal spin structure, which inhibits the observation of linear magnetoelectric coupling in bulk BiFeO₃. To resolve this contradiction, Sm‐substitution is utilized to suppress the magnetoelectric effect and unlocks the weak ferromagnetism. At an optimized composition, such a weak ferromagnetic state can be switched back to the cycloidal state by an electric field, thus realizing electrical control of the magnetism. It has been argued that field‐controlled phase transition is a promising path to colossal magnetoelectric effect. It is of pioneering significance for further investigations down this road.     

Ionic Modulation of Interfacial Magnetism in Light Metal/Ferromagnetic Insulator Layered Nanostructures

Ferromagnetic insulator thin film nanostructures are becoming the key component of the state‐of‐the‐art spintronic devices, for instance, yttrium iron garnet (YIG) with low damping, high Curie temperature, and high resistivity is explored into many spin–orbit interactions related spintronic devices. Voltage modulation of YIG, with great practical/theoretical significance, thus can be widely applied in various YIG‐based spintronics effects. Nevertheless, to manipulate ferromagnetism of YIG through electric field (E‐field), instead of current, in an energy efficient manner is essentially challenging. Here, a YIG/Cu/Pt layered nanostructure with a weak spin–orbit coupling interaction is fabricated, and then the interfacial magnetism of the Cu and YIG is modified via ionic liquid gating method significantly. A record‐high E‐field‐induced ferromagnetic resonance field shift of 1400 Oe is achieved in YIG (17 nm)/Cu (5 nm)/Pt (3 nm)/ionic liquid/Au capacitor layered nanostructures with a small voltage bias of 4.5 V. The giant magnetoelectric tunability comes from voltage‐induced extra ferromagnetic ordering in Cu layer, confirmed by the first‐principle calculation. This E‐field modulation of interfacial magnetism between light metal and magnetic isolator may open a door toward compact, high‐performance, and energy‐efficient spintronic devices.     

Low-Voltage Magnetoelectric Coupling in Fe0.5Rh0.5/0.68PbMg1/3Nb2/3O3-0.32PbTiO3 Thin-Film Heterostructures

The rapid development of computing applications demands novel low-energy consumption devices for information processing. Among various candidates, magnetoelectric heterostructures hold promise for meeting the required voltage and power goals. Here, a route to low-voltage control of magnetism in 30 nm Fe_0.5Rh_0.5/100 nm 0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) heterostructures is demonstrated wherein the magnetoelectric coupling is achieved via strain-induced changes in the Fe_0.5Rh_0.5 mediated by voltages applied to the PMN-PT. We describe approaches to achieve high-quality, epitaxial growth of Fe_0.5Rh_0.5 on the PMN-PT films and, a methodology to probe and quantify magnetoelectric coupling in small thin-film devices via studies of the anomalous Hall effect. By comparing the spin-flop field change induced by temperature and external voltage, the magnetoelectric coupling coefficient is estimated to reach ≈7 × 10⁻⁸ s m⁻¹ at 325 K while applying a −0.75 V bias.     

Symmetry Modulation and Enhanced Multiferroic Characteristics in Bi1‐xNdxFeO3 Ceramics

BiFeO₃ is recognized as the most important room temperature single phase multiferroic material. However, the weak magnetoelectric (ME) coupling remains as a key issue, which obstructs its applications. Since the magnetoelectric coupling in BiFeO₃ is essentially hindered by the cycloidal spin structure, here efforts to improve the magnetoelectric coupling by destroying the cycloidal state and switching to the weak ferromagnetic state through symmetry modulation are reported. The structure is tuned from polar R3c to polar Pna2₁, and finally to nonpolar Pbnm by forming Bi_1‐xNd_xFeO₃ solid solutions, where two morphotropic phase boundaries (MPBs) are detected. Greatly enhanced ferroelectric polarization is obtained together with the desired weak ferromagnetic characteristics in Bi_1‐xNd_xFeO₃ ceramics at the compositions near MPBs. The change of magnetic state from antiferromagnetic (cycloidal state) to ferromagnetic (canted antiferromagnetic) is confirmed by the observation of magnetic domains using magnetic force microscopy. More interestingly, combining experiments and first‐principles‐based simulations, an electric field‐induced structural and magnetic transition from Pna2₁ back to R3c is demonstrated, providing a great opportunity for electric field‐controlled magnetism, and this transition is shown to be reversible with additional thermal treatment.     

Electric Field‐Induced Oxidation of Ferromagnetic/Ferroelectric Interfaces

Composite multiferroics are a new class of material where magneto‐electric coupling is achieved by creating an interface between a ferromagnetic and a ferroelectric compound. The challenge of understanding the chemical and magnetic properties of such interface is a key to achieve good magneto‐electric coupling. The unique possibilities offered by isotope sensitive techniques are used to selectively investigate the interface's chemistry and magnetism in Fe/BaTiO₃ and Fe/LiNbO₃ systems during the application of an electric field. With a large enough electric field, a strong oxidation of Fe is triggered, which creates a magnetically dead interface. This leads to an irreversible decrease of the magneto‐electric coupling properties. Material parameters are identified that determine under which electric field the interface may be modified. The results are confirmed on the two systems and are expected to be widespread in this new class of hybrid material.     

Mechanical Strain‐Tunable Microwave Magnetism in Flexible CuFe2O4 Epitaxial Thin Film for Wearable Sensors

Purely mechanical strain‐tunable microwave magnetism device with lightweight, flexible, and wearable is crucial for passive sensing systems and spintronic devices (noncontact), such as flexible microwave detectors, flexible microwave signal processing devices, and wearable mechanics‐magnetic sensors. Here, a flexible microwave magnetic CuFe₂O₄ (CuFO) epitaxial thin film with tunable ferromagnetic resonance (FMR) spectra is demonstrated by purely mechanical strains, including tensile and compressive strains, on flexible fluorophlogopite (Mica) substrates. Tensile and compressive strains show remarkable tuning effects of up‐regulation and down‐regulation on in‐plane FMR resonance field (H_r), which can be used for flexible tunable resonators and filters. The out‐of‐plane FMR spectra can also be tuned by mechanical bending, including H_r and absorption peak. The change of out‐of‐plane FMR spectra has great potential for flexible mechanics‐magnetic deformation sensors. Furthermore, a superior microwave magnetic stability and mechanical antifatigue character are obtained in the CuFO/Mica thin films. These flexible epitaxial CuFO thin films with tunable microwave magnetism and excellent mechanical durability are promising for the applications in flexible spintronics, microwave detectors, and oscillators.     

Local Writing of Exchange Biased Domains in a Heterostructure of Co/Pd Pinned by Magnetoelectric Chromia

The writing of micrometer‐scaled exchange bias domains by local, laser heating of a thin‐film heterostructure consisting of a perpendicular anisotropic ferromagnetic Co/Pd multilayer and a (0001) oriented film of the magnetoelectric antiferromagnet Cr₂O₃ (chromia) is reported. Exchange coupling between chromia's boundary magnetization and the ferromagnet leads to perpendicular exchange bias. Focused scanning magneto‐optical Kerr measurements are used to measure local hysteresis loops and create a map of the exchange bias distribution as a function of the local boundary magnetization imprinted in the antiferromagnetic pinning layer on field cooling. The robust boundary magnetization of the Cr₂O₃ fundamentally alters the exchange bias mechanism, enabling the writing of micrometer‐scaled regions of oppositely directed exchange bias using a focused laser beam.     

Nitrogen Tuned Charge Redistribution and Orbital Reconfiguration in Fe/MgO Interface for Significant Interfacial Magnetism Tunability

Modulating the orbital configuration of ferromagnetic metal (FM)/metal‐oxide (MO) interfaces is crucial for obtaining a controllable interfacial magnetism for constructing energy‐efficient magnetic memory and logic devices. The traditional works of orbital regulation depend on external fields, such as electric field, temperature field, and stress field. This work proposes a novel orbital modulation strategy by modifying the coordination environment of FM/MO interface with nitrogen (N) incorporation. By preparing a Fe/MgO bilayer at a N₂ atmosphere, N atoms occupy the interstitial sites of the Fe lattice, which induces a charge redistribution at the Fe/MgO interface and toggles a prominent orbital reconstruction of Fe with an increment of out‐of‐plane orbital occupancy. Therefore, the orbital magnetism is tuned effectively, which remarkably strengthens the interfacial magnetic anisotropy energy by 0.6 erg cm^?2 and enables a broad magnetic anisotropy tunability from in‐plane to perpendicular direction. Besides, the Fe thickness for maintaining perpendicular magnetic anisotropy extends from less than 1 to 3 nm, which is favorable for improving the signal‐to‐noise ratio and stability of devices in nanoscale. These findings provide an external‐field‐independent strategy of orbital engineering for tailoring obit‐controlled performance at FM/MO heterointerfaces, which practically advances the magnetic storage and logic devices.     

Giant Electric Field Tuning of Magnetic Properties in Multiferroic Ferrite/Ferroelectric Heterostructures

Multiferroic heterostructures of Fe₃O₄/PZT (lead zirconium titanate), Fe₃O₄/PMN‐PT (lead magnesium niobate‐lead titanate) and Fe₃O₄/PZN‐PT (lead zinc niobate‐lead titanate) are prepared by spin‐spray depositing Fe₃O₄ ferrite film on ferroelectric PZT, PMN‐PT and PZN‐PT substrates at a low temperature of 90 °C. Strong magnetoelectric coupling (ME) and giant microwave tunability are demonstrated by a electrostatic field induced magnetic anisotropic field change in these heterostructures. A high electrostatically tunable ferromagnetic resonance (FMR) field shift up to 600 Oe, corresponding to a large microwave ME coefficient of 67 Oe cm kV^?1, is observed in Fe₃O₄/PMN‐PT heterostructures. A record‐high electrostatically tunable FMR field range of 860 Oe with a linewidth of 330–380 Oe is demonstrated in Fe₃O₄/PZN‐PT heterostructure, corresponding to a ME coefficient of 108 Oe cm kV^?1. Static ME interaction is also investigated and a maximum electric field induced squareness ratio change of 40% is observed in Fe₃O₄/PZN‐PT. In addition, a new concept that the external magnetic orientation and the electric field cooperate to determine microwave magnetic tunability is brought forth to significantly enhance the microwave tunable range up to 1000 Oe. These low temperature synthesized multiferroic heterostructures exhibiting giant electrostatically induced tunable magnetic resonance field at microwave frequencies provide great opportunities for electrostatically tunable microwave multiferroic devices.     

The Effects of Multiphase Formation on Strain Relaxation and Magnetization in Multiferroic BiFeO3 Thin Films

Multiferroic epitaxial Bi‐Fe‐O thin films of different thicknesses (15–500 nm) were grown on SrTiO₃ (001) substrates by pulsed laser deposition under various oxygen partial pressures to investigate the microstructural evolution in the Bi‐Fe‐O system and its effect on misfit strain relaxation and on the magnetic properties of the films. Films grown at low oxygen partial pressure show the canted antiferromagnetic phase α‐Fe₂O₃ embedded in a matrix of BiFeO₃. The ferromagnetic phase, γ‐Fe₂O₃ is found to precipitate inside the α‐Fe₂O₃ grains. The formation of these phases changes the magnetic properties of the films and the misfit strain relaxation mechanism. The multiphase films exhibit both highly strained and fully relaxed BiFeO₃ regions in the same film. The magnetization in the multiphase Bi‐Fe‐O films is controlled by the presence of the γ‐Fe₂O₃ phase rather than heteroepitaxial strain as it is the case in pure single phase BiFeO₃. Also, our results show that this unique accommodation of misfit strain by the formation of α‐Fe₂O₃ gives rise to significant enhancement of the piezo electric properties of BiFeO_3.     

Nonvolatile Magnetoelectric Switching of Magnetic Tunnel Junctions with Dipole Interaction

The magnetoelectric effect is technologically appealing because of its ability to manipulate magnetism using an electric field rather than magnetic field or current, thus providing a promising solution for the development of energy-efficient spintronics. Although 180° magnetization switching is vital to spintronic devices, the achievement of 180° magnetization switching via magnetoelectric coupling is still a fundamental challenge. Herein, voltage-driven full resistance switching of a magnetic tunnel junction (MTJ) with dipole interaction on a ferroelectric substrate through switchable parallel/antiparallel magnetization alignment is demonstrated. Parallel magnetization alignment along the y direction is obtained under a bias magnetic field. By rotating the magnetic easy axis via strain-mediated magnetoelectric coupling, the parallel magnetizations in the MTJ reorient to the x axis with opposite paths because of dipole interaction, thus resulting in antiparallel alignment. Moreover, this voltage switching of MTJs is nonvolatile owing to variations in dipole interaction and can be well understood via phase field simulations. The results provide an avenue to realize electrical switching of MTJs and are significant for exploring energy-efficient spintronic devices.     

A Three Component Self‐Assembled Epitaxial Nanocomposite Thin Film

A self‐assembled three phase epitaxial nanocomposite film is grown consisting of ≈3 nm diameter fcc metallic Cu nanorods within square prismatic SrO rocksalt nanopillars in a Sr(Ti,Cu)O_3‐δ perovskite matrix. Each phase has an epitaxial relation to the others. The core–shell‐matrix structures are grown on SrTiO₃ substrates and can also be integrated onto Si using a thin SrTiO₃ buffer. The structure is made by pulsed laser deposition in vacuum from a SrTi_0.75Cu_0.25O₃ target, and formed as a result of the limited solubility of Cu in the perovskite matrix. Wet etching removes the 3 nm diameter Cu nanowires leaving porous SrO pillars. The three‐phase nanocomposite film is used as a substrate for growing a second epitaxial nanocomposite consisting of CoFe₂O₄ spinel pillars in a BiFeO₃ perovskite matrix, producing dramatic effects on the structure and magnetic properties of the CoFe₂O₄. This three‐phase vertical nanocomposite provides a complement to the well‐known two‐phase nanocomposites, and may offer a combination of properties of three different materials as well as additional avenues for strain‐mediated coupling within a single film.     

Single‐Crystalline Films of the Homologous Series InGaO3(ZnO)m Grown by Reactive Solid‐Phase Epitaxy

Single‐crystalline thin films of the homologous series InGaO₃(ZnO)_m (where m is an integer) are fabricated by the reactive solid‐phase epitaxy (R‐SPE) method. Specifically, the role of ZnO as epitaxial initiator layer for the growth mechanism is clarified. High‐temperature annealing of bilayer films consisting of an amorphous InGaO₃(ZnO)₅ layer deposited at room temperature and an epitaxial ZnO layer on yttria‐stabilized zirconia (YSZ) substrate allows for the growth of single‐crystalline film with controlled chemical composition. The epitaxial ZnO thin layer plays an essential role in determining the crystallographic orientation, while the ratio of the thickness of both layers controls the film composition.     

The Biaxial Strain Dependence of Magnetic Order in Spin Frustrated Mn3NiN Thin Films

Multicomponent magnetic phase diagrams are a key property of functional materials for a variety of uses, such as manipulation of magnetization for energy efficient memory, data storage, and cooling applications. Strong spin‐lattice coupling extends this functionality further by allowing electric‐field‐control of magnetization via strain coupling with a piezoelectric. Here this work explores the magnetic phase diagram of piezomagnetic Mn₃NiN thin films, with a frustrated noncollinear antiferromagnetic (AFM) structure, as a function of the growth induced biaxial strain. Under compressive strain, the films support a canted AFM state with large coercivity of the transverse anomalous Hall resistivity, ρ_xy, at low temperature, that transforms at a well‐defined Néel transition temperature (T_N) into a soft ferrimagnetic‐like (FIM) state at high temperatures. In stark contrast, under tensile strain, the low temperature canted AFM phase transitions to a state where ρ_xy is an order of magnitude smaller and therefore consistent with a low magnetization phase. Neutron scattering confirms that the high temperature FIM‐like phase of compressively strained films is magnetically ordered and the transition at T_N is first‐order. The results open the field toward future exploration of electric‐field‐driven piezospintronic and thin film caloric cooling applications in both Mn₃NiN itself and the broader Mn₃AN family.     

Thickness‐Dependent Structure–Property Relationships in Strained (110) SrRuO3 Thin Films

Thickness‐dependent structure–property relationships in strained SrRuO₃ thin films on GdScO₃ (GSO) substrates are reported. The film is found to have epitaxially stabilized crystal structures that vary with the film thickness. Below 16 nm, the √2a_pc × √2a_pc × 2a_pc monoclinic structure is stabilized while above 16 nm the film has the a_pc × 2a_pc × a_pc tetragonal structure. The thickness‐dependent structural changes are ascribed to the substrate‐induced modification in the RuO₆ octahedral rotation pattern, which highlights the significance of the octahedral rotations for the epitaxial strain accommodation in the coherently‐grown films. Close relationships between the structural and physical properties of the films are also found. The monoclinic film has the uniaxial magnetic easy axis 45° away from the [110]_GSO direction while the tetragonal film has the one that lies along the in‐plane [1–10]_GSO direction. The results demonstrate that the octahedral rotations in the strained perovskite oxide thin films are a key factor for determining their structure phases and physical properties.     

Interfacial Strain Gradients Control Nanoscale Domain Morphology in Epitaxial BiFeO3 Multiferroic Films

Domain switching pathways fundamentally control performance in ferroelectric thin film devices. In epitaxial bismuth ferrite (BiFeO₃) films, the domain morphology is known to influence the multiferroic orders. While both striped and mosaic domains have been observed, the origins of the latter have remained unclear. Here, it is shown that domain morphology is defined by the strain profile across the film–substrate interface. In samples with mosaic domains, X‐ray diffraction analysis reveals strong strain gradients, while geometric phase analysis using scanning transmission electron microscopy finds that within 5 nm of the film–substrate interface, the out‐of‐plane strain shows an anomalous dip while the in‐plane strain is constant. Conversely, if uniform strain is maintained across the interface with zero strain gradient, striped domains are formed. Critically, an ex situ thermal treatment, which eliminates the interfacial strain gradient, converts the domains from mosaic to striped. The antiferromagnetic state of the BiFeO₃ is also influenced by the domain structure, whereby the mosaic domains disrupt the long‐range spin cycloid. This work demonstrates that atomic scale tuning of interfacial strain gradients is a powerful route to manipulate the global multiferroic orders in epitaxial films.     

Ultraflexible and Malleable Fe/BaTiO3 Multiferroic Heterostructures for Functional Devices

The high demand for flexible spintronics based on multiferroic heterostructures makes growing high-quality flexible, functional oxides urgently, in which needs to be deposited on lattice-matched substrates. In this paper, ultraflexible and malleable iron (Fe)/BaTiO₃ (BTO) multiferroic heterostructures are demonstrated, showing a perfect crystallinity and hetero-epitaxial growth. In terms of performance, they indicate good multiferroic properties and excellent bending tunability, as well as obvious magnetoelectric (ME) coupling effect. During the phase transformation from the rhombohedral phase to the orthorhombic phase of BTO layers in the heating process, a large ME coupling coefficient of 120 Oe  ° C⁻¹ along the out-of-plane direction is obtained. This value keeps consistent in the phase-field simulation of magnetic domain evolution, in which the biaxial compressive strain induced-magnetoelastic anisotropy facilitates the magnetic easy axis of Fe layers to the [110] or [–1–10] direction. Besides, ultraflexible Fe/BTO heterostructures are found to have a 690 Oe ferromagnetic resonance (FMR) field shift along the out-of-plane direction under the flexible tuning (R  = 5 mm). This work should pave a way toward flexible spintronic and functional devices with fast speed, portability, and low energy consumption.     

High‐Performance,Transparent Thin Film Hydrogen Gas Sensor Using 2D Electron Gas at Interface of Oxide Thin Film Heterostructure Grown by Atomic Layer Deposition

A high‐performance, transparent, and extremely thin (<15 nm) hydrogen (H₂) gas sensor is developed using 2D electron gas (2DEG) at the interface of an Al₂O₃/TiO₂ thin film heterostructure grown by atomic layer deposition (ALD), without using an epitaxial layer or a single crystalline substrate. Palladium nanoparticles (≈2 nm in thickness) are used on the surface of the Al₂O₃/TiO₂ thin film heterostructure to detect H₂. This extremely thin gas sensor can be fabricated on general substrates such as a quartz, enabling its practical application. Interestingly, the electron density of the Al₂O₃/TiO₂ thin film heterostructure can be tailored using ALD process temperature in contrast to 2DEG at the epitaxial interfaces of the oxide heterostructures such as LaAlO₃/SrTiO₃. This tunability provides the optimal electron density for H₂ detection. The Pd/Al₂O₃/TiO₂ sensor detects H₂ gas quickly with a short response time of <30 s at 300 K which outperforms conventional H₂ gas sensors, indicating that heating modules are not required for the rapid detection of H₂. A wide bandgap (>3.2 eV) with the extremely thin film thickness allows for a transparent sensor (transmittance of 83% in the visible spectrum) and this fabrication scheme enables the development of flexible gas sensors.     

Colossal X‐Ray‐Induced Persistent Photoconductivity in Current‐Perpendicular‐to‐Plane Ferroelectric/Semiconductor Junctions

Persistent photoconductivity (PPC) is an intriguing physical phenomenon, where electric conduction is retained after the termination of electromagnetic radiation, which makes it appealing for applications in a wide range of optoelectronic devices. So far, PPC has been observed in bulk materials and thin‐film structures, where the current flows in the plane, limiting the magnitude of the effect. Here using epitaxial Nb:SrTiO₃/Sm_0.1Bi_0.9FeO₃/Pt junctions with a current‐perpendicular‐to‐plane geometry, a colossal X‐ray‐induced PPC (XPPC) is achieved with a magnitude of six orders. This PPC persists for days with negligible decay. Furthermore, the pristine insulating state could be fully recovered by thermal annealing for a few minutes. Based on the electric transport and microstructure analysis, this colossal XPPC effect is attributed to the X‐ray‐induced formation and ionization of oxygen vacancies, which drives nonvolatile modification of atomic configurations and results in the reduction of interfacial Schottky barriers. This mechanism differs from the conventional mechanism of photon‐enhanced carrier density/mobility in the current‐in‐plane structures. With their persistent nature, such ferroelectric/semiconductor heterojunctions open a new route toward X‐ray sensing and imaging applications.