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.     

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.     

Controlling Phase Assemblage in a Complex Multi‐Cation System: Phase‐Pure Room Temperature Multiferroic (1−x)BiTi(1−y)/2FeyMg(1−y)/2O3–xCaTiO3

A room temperature magnetoelectric multiferroic is of interest as, e.g., magnetoelectric random access memory. Bulk samples of the perovskite (1?x)BiTi_(1?y)/2Fe_yMg_(1?y)/2O₃–xCaTiO₃ (BTFM–CTO) are simultaneously ferroelectric, weakly ferromagnetic, and magnetoelectric at room temperature. In BTFM–CTO, the volatility of bismuth oxide, and the complex subsolidus reaction kinetics, cause the formation of a microscopic amount of ferrimagnetic spinel impurity, which complicates the quantitative characterization of their intrinsic magnetic and magnetoelectric properties. Here, a controlled synthesis route to single‐phase bulk samples of BTFM–CTO is devised and their intrinsic properties are determined. For example, the composition x = 0.15, y = 0.75 shows a saturated magnetization of 0.0097μ_B per Fe, a linear magnetoelectric susceptibility of 0.19(1) ps m^?1, and a polarization of 66 μC cm^?2 at room temperature. The onset of weak ferromagnetism and linear magnetoelectric coupling are shown to coincide with the onset of bulk long‐range magnetic order by neutron diffraction. The synthesis strategy developed here will be invaluable as the phase diagram of BTFM–CTO is explored further, and as an example for the synthesis of other compositionally complex BiFeO₃‐related materials.     

Long‐Range Nonvolatile Electric Field Effect in Epitaxial Fe/Pb(Mg1/3Nb2/3)0.7Ti0.3O3 Heterostructures

One of the ideal candidates of using electric field to manipulate magnetism is the recently developed multiferroics with emergent coupling of magnetism and electricity, particularly in synthesizing artificial nanoscale ferroelectric and ferromagnetic materials. Here, a long‐range nonvolatile electric field effect is investigated in Fe/Pb(Mg_1/3Nb_2/3)_0.7Ti_0.3O₃ heterostructure using the dependence of the magnon‐driven magnetoelectric coupling on the epitaxial Fe thin film (4–30 nm) thickness at room temperature using measurements based on the ferromagnetic resonance. The magnon‐driven magnetoelectric coupling tuning of the ferromagnetic resonance field shows a linear response to the electric field, with a resonance field shift that occurs under both positive and negative remanent polarizations, and demonstrates nonvolatile behavior. Moreover, the spin diffusion length of the epitaxial Fe thin film of ≈9 nm is obtained from the results that the change of the cubic magnetocrystalline anisotropy field under different electric fields varies with Fe thickness. These results are promising for the design of future multiferroic devices.     

Spatially modulated antiferromagnetic structures in a multiferroic with biaxial anisotropy

Possible types of spatially modulated periodic antiferromagnetic structures in a uniaxial rhombohedral multiferroic with BiFeO₃ crystal symmetry are studied depending on the ratio of the parameters of uniaxial and basal anisotropy and on magnetoelectric coupling.     

Deterministic Manipulation of Multi-State Polarization Switching in Multiferroic Thin Films

Deterministically controllable multi-state polarizations in ferroelectric materials are promising for the application of next-generation non-volatile multi-state memory devices. However, the achievement of multi-state polarizations has been inhibited by the challenge of selective control of switching pathways. Herein, an approach to selectively control 71° ferroelastic and 180° ferroelectric switching paths by combining the out-of-plane electric field and in-plane trailing field in multiferroic BiFeO₃ thin films with periodically ordered 71° domain wall is reported. Four-state polarization states can be deterministically achieved and reversibly controlled through precisely selecting different switching paths. These studies reveal the ability to obtain multiple polarization states for the realization of multi-state memories and magnetoelectric coupling-based devices.     

Observation of Magnetic‐Switching and Multiferroic‐Like Behavior of Co Nanoparticles in a C60 Matrix

A novel magnetoelectric effect is found to appear in a C₆₀‐Co nanocomposite. Although Co is well‐known as a ferromagnet, its nanoparticles embedded in a C₆₀ matrix can exhibit multiferroic‐like behavior, i.e., an electric field controls magnetic alignment of the nanoparticles and a magnetic field controls their charged states. This novel effect enables a strong magnetic switching effect for which the on/off ratio is ca. 10⁴. Such an effect has been expected to exist and these findings show this magnetoelectric coupling for the first time.     

Mechanical Switching of Nanoscale Multiferroic Phase Boundaries

Tuning the lattice degree of freedom in nanoscale functional crystals is critical to exploit the emerging functionalities such as piezoelectricity, shape‐memory effect, or piezomagnetism, which are attributed to the intrinsic lattice‐polar or lattice‐spin coupling. Here it is reported that a mechanical probe can be a dynamic tool to switch the ferroic orders at the nanoscale multiferroic phase boundaries in BiFeO₃ with a phase mixture, where the material can be reversibly transformed between the “soft” tetragonal‐like and the “hard” rhombohedral‐like structures. The microscopic origin of the nonvolatile mechanical switching of the multiferroic phase boundaries, coupled with a reversible 180° rotation of the in‐plane ferroelectric polarization, is the nanoscale pressure‐induced elastic deformation and reconstruction of the spontaneous strain gradient across the multiferroic phase boundaries. The reversible control of the room‐temperature multiple ferroic orders using a pure mechanical stimulus may bring us a new pathway to achieve the potential energy conversion and sensing applications.     

The Polar/Antipolar Phase Boundary of BiMnO3–BiFeO3–PbTiO3: Interplay among Crystal Structure,Point Defects,and Multiferroism

The ferromagnetic perovskite oxide BiMnO₃ is a highly topical material, and the solid solutions it forms with antiferromagnetic/ferroelectric BiFeO₃ and with ferroelectric PbTiO₃ result in distinctive polar/nonpolar morphotropic phase boundaries (MPBs). The exploitation of such a type of MPBs could be a novel approach to engineer novel multiferroics with phase‐change magnetoelectric responses, in addition to ferroelectrics with enhanced electromechanical performance. Here, the interplay among crystal structure, point defects, and multiferroic properties of the BiMnO₃–BiFeO₃–PbTiO₃ ternary system at its line of MPBs between polymorphs of tetragonal P4mm (polar) and orthorhombic Pnma (antipolar) symmetries is reported. A strong dependence of the phase coexistence on thermal history is found: phase percentage significantly changes whether the material is quenched or slowly cooled from high temperature. The origin of this phenomenon is investigated with temperature‐dependent structural and physical property characterizations. A major role of the complex defect chemistry, where a Bi/Pb‐deficiency allows Mn and Fe ions to have a mixed‐valence state, in the delicate balance between polymorphs is proposed, and its influence in the magnetic and electric ferroic orders is defined.     

Ferroelectric Self‐Poling,Switching, and Monoclinic Domain Configuration in BiFeO3 Thin Films

Self‐poling of ferroelectric films, i.e., a preferred, uniform direction of the ferroelectric polarization in as‐grown samples is often observed yet poorly understood despite its importance for device applications. The multiferroic perovskite BiFeO₃, which crystallizes in two distinct structural polymorphs depending on applied epitaxial strain, is well known to exhibit self‐poling. This study investigates the effect of self‐poling on the monoclinic domain configuration and the switching properties of the two polymorphs of BiFeO₃ (R′ and T′) in thin films grown on LaAlO₃ substrates with slightly different La_0.3Sr_0.7MnO₃ buffer layers. This study shows that the polarization state formed during the growth acts as “imprint” on the polarization and that switching the polarization away from this self‐poled direction can only be done at the expense of the sample's monoclinic domain configuration. The observed reduction of the monoclinic domain size is largely reversible; hence, the domain size is restored when the polarization is switched back to its original orientation. This is a direct consequence of the growth taking place in the polar phase (below T_c). Switching the polarization away from the preferred configuration, in which defects and domain patterns synergistically minimize the system's energy, leads to a domain state with smaller (and more highly strained and distorted) monoclinic domains.     

Room Temperature Electric‐Field Control of Magnetism in Layered Oxides with Cation Order

Searching for materials with room‐temperature electric‐field control of magnetism has interested researchers for many years with three‐dimensional perovskite BiFeO₃‐based compounds as the main focus. Here we choose the layered hybrid improper ferroelectric Ruddlesden‐Popper oxides as a platform from which to realize electric field controllable magnetism, leveraging a recently identified strain tunable polar‐to‐nonpolar (P‐NP) transition. We first propose a design principle for selecting the required A and B cation chemistries that will ensure (001) A₃B₂O₇ films exhibit P‐NP transitions, which we substantiate with density functional calculations. By extending the guideline to B‐site ordered A₃BB′O₇ oxides, we identify more compounds exhibiting P‐NP transitions marked by the disappearance of an in‐plane polarization that can be functionalized. We then demonstrate that weak ferromagnetism can be tuned by an electric field at the boundary of the P‐NP transition in B‐site ordered (001) A₃BB′O₇ magnetic films, based on which we predict that cation ordered Ca₃TcTiO₇ may be a viable candidate for room‐temperature electric‐field control of magnetism.     

Low‐Symmetry Monoclinic Phases and Polarization Rotation Path Mediated by Epitaxial Strain in Multiferroic BiFeO3 Thin Films

A morphotropic phase boundary driven by epitaxial strain has been observed in lead‐free multiferroic BiFeO₃ thin films and the strain‐driven phase transitions have been widely reported as iso‐symmetric Cc‐Cc by recent works. In this paper, it is suggested that the tetragonal‐like BiFeO₃ phase identified in epitaxial films on (001) LaAlO₃ single crystal substrates is monoclinic M_C. This M_C phase is different from the M_A type monoclinic phase reported in BiFeO₃ films grown on low mismatch substrates, such as SrTiO₃. This is confirmed not only by synchrotron X‐ray studies but also by piezoresponse force microscopy measurements. The polarization vectors of the tetragonal‐like phase lie in the (100) plane, not the (11 0) plane as previously reported. A phenomenological analysis is proposed to explain the formation of M_C Phase. Such a low‐symmetry M_C phase, with its linkage to M_A phase and the multiphase coexistence open an avenue for large piezoelectric response in BiFeO₃ films and shed light on a complete understanding of possible polarization rotation paths and enhanced multiferroicity in BiFeO₃ films mediated by epitaxial strain. This work may also aid the understanding of developing new lead‐free strain‐driven morphotropic phase boundary in other ferroic systems.     

Hybrid Improper Ferroelectricity in Multiferroic Superlattices: Finite‐Temperature Properties and Electric‐Field‐Driven Switching of Polarization and Magnetization

The so‐called hybrid improper ferroelectricity (HIF) mechanism allows to create an electrical polarization by assembling two nonpolar materials within a superlattice. It may also lead to the control of the magnetization by an electric field when these two nonpolar materials are magnetic in nature, which is promising for the design of novel magneto‐electric devices. However, several issues of fundamental and technological importance are presently unknown in these hybrid improper ferroelectrics. Examples include the behaviors of its polarization and dielectric response with temperature, and the paths to switch both the polarization and magnetization under electric fields. Here, an effective Hamiltonian scheme is used to study the multiferroic properties of the model superlattice (BiFeO₃)₁/(NdFeO₃)₁. Along with the development of a novel Landau‐type potential, this approach allows to answer and understand all the aforementioned issues at both microscopic and macroscopic levels. In particular, the polarization and dielectric response are both found to adopt temperature dependences, close to the phase transition, that agree with the behavior expected for first‐order improper ferroelectrics. And most importantly, a five‐state path resulting in the switching of polarization and magnetization under an electric field, via the reversal of antiphase octahedral tiltings, is also identified.     

Modulation of Spin Dynamics via Voltage Control of Spin‐Lattice Coupling in Multiferroics

Motivated by the most recent progresses in both magnonics (spin dynamics) and multiferroics fields, this work aims at magnonics manipulation by the magnetoelectric coupling effect. Here, voltage control of magnonics, particularly the surface spin waves, is achieved in La_0.7Sr_0.3MnO₃/0.7Pb(Mg_1/3Nb_2/3)O₃‐0.3PbTiO₃ multiferroic heterostructures. With the electron spin resonance method, a large 135 Oe shift of surface spin wave resonance (≈7 times greater than conventional voltage‐induced ferromagnetic resonance shift of 20 Oe) is determined. A model of the spin‐lattice coupling effect, i.e., varying exchange stiffness due to voltage‐induced anisotropic lattice changes, has been established to explain experiment results with good agreement. Additionally, an “on” and “off” spin wave state switch near the critical angle upon applying a voltage is created. The modulation of spin dynamics by spin‐lattice coupling effect provides a platform for realizing energy‐efficient, tunable magnonics devices.     

Toward On‐and‐Off Magnetism: Reversible Electrochemistry to Control Magnetic Phase Transitions in Spinel Ferrites

The magnetoelectric effect, i.e., electric‐field control of magnetism in artificial heterostructures is usually limited to surface/interface atoms of the magnetic materials. In order to attain electrical control of magnetism in bulk ferromagnets, this study proposes to extend the definition of magnetoelectric phenomena to include reversible, chemistry‐controlled magnetization switching. A large and reversible change in the room temperature magnetization in strong ferromagnets is reported, with electrochemistry‐driven Li‐ion exchange; carefully chosen spinel ferrites demonstrate a reversible magnetization variation up to 50% for CuFe₂O₄ and 70% for ZnFe₂O₄. In case of CuFe₂O₄, the magnetization variation is predominantly associated with the preferential reduction of Cu²⁺ to Cu⁺ ions, and, hence, abides a nearly one‐to‐one relationship with the amount of injected Li‐ions. In addition, the reduction of Cu²⁺ also annihilates the Fe³⁺? O? Cu²⁺ magnetic interaction, resulting in a marked decrease in the Neél temperature of CuFe₂O₄. In contrast, the electrical tuning of superexchange interactions is found to play the decisive role in ZnFe₂O₄, where the simple electrochemical reduction model of magnetic cations can only explain a nominal fraction of the total magnetization variation, and indeed an electrochemically controlled reversible change in transition temperature is found necessary to account for the large magnetization variation observed.     

Atomic‐Scale Visualization of Polarization Pinning and Relaxation at Coherent BiFeO3/LaAlO3 Interfaces

Complex oxide heterointerfaces, which play host to an incredible variety of interface physical phenomena, are of great current interest in introducing new functionalities to systems. Here, coherent super‐tetragonal BiFeO₃/LaAlO₃ and rhombohedral BiFeO₃/LaAlO₃ heterointerfaces are investigated by using a combination of high‐angle annular dark‐field (HAADF) imaging and annular bright‐field (ABF) imaging in a spherical aberration (Cs) corrected scanning transmission electron microscope (STEM), and first‐principles calculations. The complicated ferroelectric polarization pinning and relaxation that occurs at both interfaces is revealed with atomic resolution, with a dramatic change in structure of BiFeO₃, from cubic to super‐tetragonal‐like. The results enable a detailed explanation to be given of how non‐bulk phase structures are stabilized in thin films of this material.     

The Effect of Heat Treatment on Structural and Multiferroic Properties of Phase-Pure BiFeO3

Phase-pure multiferroic BiFeO₃ (BFO) was prepared by the coprecipitation technique using diverse precursors bismuth oxide at temperature as low as 400°C. The dependence of structural, microstructural, thermal, electrical (AC and DC), and magnetic properties on sintering temperature was systematically investigated. Uniaxially pressed samples (Ø8 mm) were sintered in air at 500°C to 800°C for 4 h. X-ray diffraction analysis was used to determine the amorphous and perovskite nature of as-synthesized and calcined/sintered samples, respectively. The crystallite size of sintered powders increased from 47 nm to 67 nm. Scanning electron microscopy showed grain growth during sintering, which improved intergranular connectivity and decreased porosity in the samples. The ferroelectric to paraelectric Curie transition temperature (T _C) of pure BFO powder was detected by differential scanning calorimetry analysis and found to be 820°C ± 1°C. The samples exhibited high AC resistivity and dielectric constant, and low loss tangent values. The samples exhibited weak ferromagnetic behavior with an unsaturated magnetization versus magnetic field hysteresis loop at room temperature. Ferroelectric behavior and variation in remnant polarization and coercivity were observed from polarization versus electric field loops. Enhanced capacitance in the magnetic field revealed the magnetoelectric effect in the samples.     

Ferroelectric,Ferromagnetic, and Magnetoelectric Properties of Multiferroic Ni0.5Zn0.5Fe2O4–BaTiO3 Composite Ceramics

Lead-free multiferroic composite ceramics xNi_0.5Zn_0.5Fe₂O₄–(1 ? x)BaTiO₃ (x = 0.2, 0.5, 0.8) with a 0–3-type connection structure have been prepared by a traditional ceramic process. The cubic spinel Ni_0.5Zn_0.5Fe₂O₄ phase and the tetragonal perovskite BaTiO₃ phase were confirmed by x-ray diffraction. The effect of Ni_0.5Zn_0.5Fe₂O₄ ferrite content on ferroelectric and ferromagnetic behavior, and the magnetoelectric coupling effect of the composite ceramics is discussed. With increasing Ni_0.5Zn_0.5Fe₂O₄ ferrite content, the saturation magnetization of the composite ceramic increased and the saturation polarization decreased. The magnetoelectric coupling response voltage was observed to decrease rapidly for samples with x = 0.2, then 0.5, then 0.8. The highest magnetoelectric coupling response voltage, measured for 0.2Ni_0.5Zn_0.5Fe₂O₄–0.8BaTiO₃, was 150 μV, which corresponds to a maximum magnetoelectric coupling voltage coefficient of 109 μV/cm Oe. When x = 0.5, the maximum magnetoelectric response voltage is only 8 μV, and when x = 0.8, no magnetoelectric response voltage is detected because of very large leakage current of the 0.8Ni_0.5Zn_0.5Fe₂O₄–0.2BaTiO₃ composite ceramic.     

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.     

E‐Field Control of Exchange Bias and Deterministic Magnetization Switching in AFM/FM/FE Multiferroic Heterostructures

The coexistence of electrical polarization and magnetization in multiferroic materials provides great opportunities for novel information storage systems. In particular, magnetoelectric (ME) effect can be realized in multi­ferroic composites consisting of both ferromagnetic and ferroelectric phases through a strain mediated interaction, which offers the possibility of electric field (E‐field) manipulation of magnetic properties or vice versa, and enables novel multiferroic devices such as magnetoelectric random access memories (MERAMs). These MERAMs combine the advantages of FeRAMs (ferroelectric random access memories) and MRAMs (magnetic random access memories), which are non‐volatile magnetic bits switchable by electric field (E‐field). However, it has been challenging to realize 180° deterministic switching of magnetization by E‐field, on which most magnetic memories are based. Here we show E‐field modulating exchange bias and for the first time realization of near 180° dynamic magnetization switching at room temperature in novel AFM (antiferromagnetic)/FM (ferromagnetic)/FE (ferroelectric) multiferroic heterostructures of FeMn/Ni₈₀Fe₂₀/FeGaB/PZN‐PT (lead zinc niobate–lead titanate). Through competition between the E‐field induced uniaxial anisotropy and unidirectional anisotropy, large E‐field‐induced exchange bias field‐shift up to $ {{{\Delta H_{ex}}}\over{{H_{ex}}}} = 218\%$ and near 180° deterministic magnetization switching were demonstrated in the exchange‐coupled multiferroic system of FeMn/Ni₈₀Fe₂₀/FeGaB/PZN‐PT. This E‐field tunable exchange bias and near 180° deterministic magnetization switching at room temperature in AFM/FM/FE multiferroic heterostructures paves a new way for MERAMs and other memory technologies.