Multiferroic Effect Research Articles

Multiferroic Microstructure Created from Invariant Line Constraint

AbstractFerroic materials enable a multitude of emerging applications, and optimum functional properties are achieved when ferromagnetic and ferroelectric properties are coupled to a first‐order ferroelastic transition. In bulk materials, this first‐order transition involves an invariant habit plane, connecting coexisting phases: austenite and martensite. Theory predicts that this plane should converge to a line in thin films, but experimental evidence is missing. Here, the martensitic and magnetic microstructure of a freestanding epitaxial magnetic shape memory film is analyzed. It is shown that the martensite microstructure is determined by an invariant line constraint using lattice parameters of both phases as the only input. This line constraint explains most of the observable features, which differ fundamentally from bulk and constrained films. Furthermore, this finite‐size effect creates a remarkable checkerboard magnetic domain pattern through multiferroic coupling. The findings highlight the decisive role of finite‐size effects in multiferroics.

A study on BaTiO3 – NiFe2O4 composite; microstructure, multiferroic and magnetodielectric properties

The lead-free x NiFe2O4 – (1-x) BaTiO3 (x = 0, 0.05, 0.1, 0.15) multiferroic composites were prepared via the solid-state sintering technique. Microstructure, multiferroic, and magnetodielectric properties of composites were investigated. According to the XRD data (from x = 5 to 15 wt%), the tetragonality factor (cT/aT) and unit cell volume of the BaTiO3 (BTO) crystal system diminished. Based on SEM images, ferromagnetic NiFe2O4 (NFO) grains are uniformly dispersed in the ferroelectric BTO matrix without additional reaction in the interfaces of two phases. The highest values of dielectric (dielectric constant (εr) ∼ 1905 and dielectric loss factor (tan δ) ∼ 0.049) and ferroelectric properties (saturation polarization (PS) ∼ 13 μC/cm2 and remnant polarization (Pr) ∼ 10 μC/cm2) are attained for x = 5 wt% due to the lowest NFO (non-ferroelectric) concentration. Also, with increasing ferrite concentration (up to 15 wt%), the ferroelectric properties of the composites show a gradual decrease. The saturation magnetization (MS) values rise due to increasing ferrite concentration (from 2 to 5 emu/g for x = 5 to 15 wt%). Moreover, coercivity (HC) drops from 150 to 110 Oe. The simultaneous observation of the ferroelectric and ferromagnetic characteristic hysteresis loops confirmed the multiferroic effect for x = 5, 10, and 15 wt%. The highest magnetodielectric constant (3 %) is obtained for x = 15 wt% multiferroic composite at the applied magnetic field of 6 kOe.

Enhanced structural, magnetodielectric, and multiferroic response in Fe and Co Co-doped Barium strontium titanate ceramics

In this paper, the ambient temperature multiferroic effect resulting from the incorporation of transition metal ions (Fe3+ and Co2+) in lead-free BST [ Ba0.7Sr0.3(Fex/2Cox/2)Ti1−xO3;x=0,0.01,0.03,0.05,0.07 ] ceramics synthesized via the solid-state reaction (SSR) procedure has been thoroughly analyzed. The investigation consistently scrutinized the effects of augmenting transition metal co-doping on the structural, ferroelectric, dielectric, magnetic, and magnetodielectric characteristics. The x-ray diffraction (XRD) patterns for all ceramic compositions demonstrated the formation of a monophasic (P4mm) crystalline structure. The Raman analysis evidenced the presence of various modes, which are associated with the occurrence of the single-phase and provide strong corroboration for the x-ray diffraction observations. Scanning electron micrographs reveals that the inclusion of transition metal ions results in the diminution of grain size. The frequency-dependent dielectric characteristics were represented over the frequency range of 1 kHz to 1 MHz. The P-E hysteresis curves demonstrate a consistent reduction in the values of Ps and Pr, whereas, the M-H curve reveals the enhancement in magnetic properties with increased doping. The magnetodielectric analysis confirmed the interplay between the ferroelectric and ferromagnetic ordering. The BST-1CF sample exhibited the highest MC % value of 5.30% along with the magnetoelectric coupling coefficient ‘γ’ of −6.01×10−1(memu/g)−2, making it a favorable entrant for the advancement of innovative non-volatile multiferroic memory gadgets.

Direct observation of intrinsic room-temperature ferroelectricity in 2D layered CuCrP2S6

Multiferroic materials have ignited enormous interest owing to their co-existence of ferroelectricity and ferromagnetism, which hold substantial promise for advanced device applications. However, the size effect, dangling bonds, and interface effect in traditional multiferroics severely hinder their potential in nanoscale device applications. Recent theoretical and experimental studies have evidenced the possibility of realizing two-dimensional (2D) multiferroicity in van der Waals (vdW) layered CuCrP2S6. However, the incorporation of magnetic Cr ions in the ferroelectric framework leads to antiferroelectric and antiferromagnetic orderings, while macroscopic spontaneous polarization is always absent. Herein, we report the direct observation of robust out-of-plane ferroelectricity in 2D vdW CuCrP2S6 at room temperature with a comprehensive investigation. Modification of the ferroelectric polarization states in 2D CuCrP2S6 nanoflakes is experimentally demonstrated. Moreover, external electric field-induced polarization switching and hysteresis loops are obtained in CuCrP2S6 down to ~2.6 nm (4 layers). By using atomically resolved scanning transmission electron microscopy, we unveil the origin of the emerged room-temperature ferroelectricity in 2D CuCrP2S6. Our work can facilitate the development of multifunctional nanodevices and provide important insights into the nature of ferroelectric ordering of this 2D vdW material.

Intrinsic multiferroicity and magnetoelectric coupling in VSI2 monolayer

Two dimensional (2D) multiferroic materials have great potential for miniaturized electronic and high-density multi-states data storage devices due to the coexistence of electric and spin polarization. Because the origins of magnetism and ferroelectricity are mutually exclusive and difficult to coexist, there are still rare to date 2D multiferroic semiconductors with good performance. Here, we propose a 2D multiferroic material, VSI2 monolayer, which has both ferromagnetic and ferroelectric properties by first principles calculation. It shows robust ferroelectricity with an appropriate switching barrier (∼140 meV), and the in-plane ferroelectric polarization is 1.44 × 10−10 C/m. At the same time, the VSI2 monolayer magnetic easy axis is along the b-axis direction and owns a large magnetic anisotropy energy (MAE) (512 μeV/V-ion). Based on Monte Carlo simulations of the Heisenberg model, the Curie temperature (TC) is calculated to be approximately 92 K. In addition, biaxial strain can significantly change the MAE, and the in-plane magnetic easy axis can be switched to the out-of-plane direction by 5% biaxial tensile strain. In particular, we can change the magnetic moment at the two ends of VSI2 nanoribbons by switching the direction of electric polarization, providing an opportunity for the application of magnetic-electric control and memory devices. Our theoretical prediction provides a good platform for studying the 2D multiferroic effects and spintronic properties.

Evidence of magnetoelectronic electromagnon-mediated transport in flexoelectronic heterostructures

The superposition of atomic vibrations and flexoelectronic effect gives rise to a cross correlation between free charge carriers and temporal magnetic moment of phonons in conducting heterostructures under an applied strain gradient. The resulting dynamical coupling is expected to give rise to quasiparticle excitations called magnetoelectronic electromagnons that carry electronic charge and temporal magnetic moment. Here, we report experimental evidence of magnetoelectronic electromagnons in the freestanding degenerately doped $p$-Si based heterostructure thin film samples. These quasiparticle excitations give rise to long-distance ($>100 \ensuremath{\mu}\mathrm{m}$) spin transport, demonstrated using spatially modulated transverse magnetothermoelectric and nonlocal resistance measurements. The magnetoelectronic electromagnons are nonreciprocal and give rise to large magnetochiral anisotropy $(0.352\phantom{\rule{0.16em}{0ex}}{\mathrm{A}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{T}}^{\ensuremath{-}1})$ that diminishes at lower temperatures. The superposition of nonreciprocal magnetoelectronic electromagnons gives rise to longitudinal and transverse modulations in charge carrier density, spin density, and magnetic moment, demonstrated using the Hall effect and edge dependent magnetoresistance measurements, which can also be called inhomogeneous magnetoelectronic multiferroic effect. These quasiparticle excitations are analogous to photons where time dependent polarization and temporal magnetic moment replace electric and magnetic field, respectively, and most likely topological because they manifest topological Nernst effect. Hence, the magnetoelectronic electromagnon can potentially give rise to quantum interference and entanglement effects in conducting solid state systems at room temperature in addition to efficient spin transport.

Perspective on computational design of two-dimensional materials with robust multiferroic coupling

Two-dimensional (2D) multiferroic materials with robust magnetoelectric coupling and controllable topological solitons (such as skyrmions) are promising candidates for advanced information storage and processing. Due to the limitations of experimental techniques, first-principles investigations stand out in answering fundamental questions of 2D multiferroic couplings, thus providing guidance for experimental validation. Herein, we will give a review of recent theoretical progress in the exploration of 2D multiferroic coupling via structural design and molecular engineering approach. Particularly, we will focus on (i) how to design the multiferroic structure in the 2D form; (ii) how to achieve robust magnetoelectric coupling; and (iii) how to electrically control the magnetic skyrmion via multiferroic effects. Finally, we give some perspectives on the remaining challenges and opportunities for predicting 2D multiferroic materials.

Two-Dimensional Multiferroics with Intrinsic Magnetoelectric Coupling in A-Site Ordered Perovskite Monolayers

The magnetoelectric coupling effect in multiferroics provides a route to realize the control of magnetism by electric field. Here, we demonstrate the coexistence and coupling of ferroelectricity and ferromagnetism in designed A-site ordered perovskite oxide monolayers by combining symmetry analysis and first-principles calculation. These monolayers all exhibit a layered ordering and tilt distortion, and some of them exhibit rotation or Jahn-Teller distortion simultaneously, leading to the emergence of in-plane ferroelectricity. The Mn-based monolayers exhibit robust ferromagnetism, while some monolayers tend to form E-type spin order due to the splitting of the nearest-neighbor exchange interactions. Whether polarization reversal can lead to magnetization reversal depends on the mode of ferroelectric switching, that is, only the ferroelectric switching that reversing the tilt distortion can lead to magnetization reversal. This work demonstrates the feasibility of controlling the direction of magnetization by electric field in the monolayer limit of perovskites.

Simultaneously improving Rashba-type and Zeeman effects in two-dimensional multiferroics

First-principles calculations are performed to investigate Rashba-type and Zeeman effects in two-dimensional three-atom-layer structures $X\mathrm{Te}$/MnTe/$X\mathrm{Te}$ ($XMX, X=\text{Sn}$, Ge). It is found that the Rashba-type and Zeeman effects that typically compete against each other rather cooperatively work together and are improved in $XMX$, as compared to $X\mathrm{Te}/X\mathrm{Te}/X\mathrm{Te}$ ($XXX$). This cooperation and improvement are highly required in Majorana qubits for topological quantum computing, Josephson junction of topological superconductivity, and other phenomena. The Rashba-type effect is improved because replacing $X\mathrm{Te}$ by MnTe leads to a reduction of the thickness of $XMX$ and increases the interaction between the surface state of the lowest conduction bands and its neighboring states. The improved Zeeman effect in the $XMX$ structure arises from s-d and p-d exchange interactions between Te and Mn ions. The present strategy of simultaneously largely improving Rashba-type and Zeeman effects therefore provides a route to realize stable Majorana fermions, topological superconductivity, and other phenomena that require both large Rashba-type and Zeeman effects.

Enhanced multiferroic effect in multi-phased Eu substituted Bi–Fe–Mn perovskite oxides

Eu substituted Bi–Fe–Mn multiferroics with a chemical formula Bi1-xEux(Fe0.8Mn0.2)O3 (x = 0.0, 0.01, 0.02, 0.03 and 0.04) were synthesized by the sol-gel auto-combustion method. Crystal structure phases of all the prepared samples were investigated by X-ray diffraction (XRD) patterns. Three different phases triclinic/anorthic (space group: P1), cubic (space group: I 2 3) and orhtorhombic (space group: Pbam) ware observed in the samples. The grain size obtained from scanning electron micrographs was found in the range of few micro-meter dimensions. The X-ray electron diffraction analysis spectrum indicates that the percentage of Bi, Eu, Fe and Mn elements are presented in approximately stoichiometric proportion. Substitution of Eu enhaces the ferromagnetic properties obtained by using vibrating sample magnetometer. The dielectric constant (ε′) and dielectric loss tangent (tanδ) measured as a function of applied frequency by using two-probe technique attains saturation state in the higher frequency regime. Impedence spectroscopy reveals the Eu-substitution dependency of the bulk relaxation in the investigated frequency range. The ferroelectric polarization electric field (P–E) curves of Bi1-xEux(Fe0.8Mn0.2)O3 measured under the electric field and at a constant frequency. The variation of magneto-electric (ME) coupling coefficient with the application of DC magnetic field were measured for all the samples.

Reversibly Controlled Ternary Polar States and Ferroelectric Bias Promoted by Boosting Square-Tensile-Strain.

Interaction between dipoles often emerges intriguing physical phenomena, such as exchange bias in the magnetic heterostructures and magnetoelectric effect in multiferroics, which lead to advances in multifunctional heterostructures. However, the defect-dipole tends to be considered the undesired to deteriorate the electronic functionality. Here, deterministic switching between the ferroelectric and the pinched states by exploiting a new substrate of cubic perovskite, BaZrO3 is reported, which boosts the square-tensile-strain to BaTiO3 and promotes four-variants in-plane spontaneous polarization with oxygen vacancy creation. First-principles calculations propose a complex of an oxygen vacancy and two Ti3+ ions coins a charge-neutral defect-dipole. Cooperative control of the defect-dipole and the spontaneous polarization reveals ternary in-plane polar states characterized by biased/pinched hysteresis loops. Furthermore, it is experimentally demonstrated that three electrically controlled polar-ordering states lead to switchable and nonvolatile dielectric states for application of nondestructive electro-dielectric memory. This discovery opens a new route to develop functional materials via manipulating defect-dipoles and offers a novel platform to advance heteroepitaxy beyond the prevalent perovskite substrates.

Intrinsic multiferroic MnOF monolayer with room-temperature ferromagnetism

Two-dimensional (2D) multiferroic materials have generated substantial interest owing to the interplay between various ferroic states and the potential applications in miniaturized electronic devices. Using first-principles calculations, we report a ferromagnetic, ferroelectric, and ferroelastic MnOF monolayer, which is an indirect semiconductor with a band gap of 1.8 eV. The Cuire temperature is predicted to be 420 K based on the Monte Carlo simulation of Heisenberg model. The magnetic easy-axis prefers to align along c-axis. Moreover, it shows excellent ferroelectricity with a switchable spontaneous polarization of 7.5 μC/cm2. Meanwhile, MnOF monolayer also habors ferroealsticity with a large reversible strain of 21.4% and a moderate switching energy barrier, which can effectively switchferroelectric polarization direction. MnOF monolayer thus offers a perfect platform for studying the 2D multiferroic coupling effects.

Mechanisms of Magnetoelectric Effects in Oxide Multiferroics with a Perovskite Praphase

Mechanisms of Magnetoelectric Effects in Oxide Multiferroics with a Perovskite Praphase

Mechanisms of magnetoelectric effects in oxide multiferroics with a perovskite praphase

Magnetoelectric effects are discussed in multiferroics with the perovskite structure: bismuth ferrite, rare-earth orthochromites, and Ruddlesden--Popper structures belonging to the trigonal, orthorhombic, and tetragonal syngonies. The influence of structural distortions on magnetic and ferroelectric properties is studied, possible magnetoelectric effects (linear, quadratic, inhomogeneous) in these materials are determined, and expressions for the linear magnetoelectric effect tensor are given. Macroscopic manifestations of the inhomogeneous magnetoelectric effect in multiferroic nanoelements are considered. Keywords: multiferroics, magnetoelectric effect, perovskites, symmetry.

New trends in the nanophysics of ferroics, relaxors and multiferroics

The review covers the theoretical and experimental results obtained in the recent years by the scientists with the help of comprehensive investigation of nanoferroics and multiferroics. The main attention will be paid to spontaneous flexoeffects and reentrant phase in nanoferroics as well as to a recently discovered giant magnetoelectric effect in multiferroics.

Multiferroic Coupling of Ferromagnetic and Ferroelectric Particles through Elastic Polymers.

Multiferroics are materials that electrically polarize when subjected to a magnetic field and magnetize under the action of an electric field. In composites, the multiferroic effect is achieved by mixing of ferromagnetic (FM) and ferroelectric (FE) particles. The FM particles are prone to magnetostriction (field-induced deformation), whereas the FE particles display piezoelectricity (electrically polarize under mechanical stress). In solid composites, where the FM and FE grains are in tight contact, the combination of these effects directly leads to multiferroic behavior. In the present work, we considered the FM/FE composites with soft polymer bases, where the particles of alternative kinds are remote from one another. In these systems, the multiferroic coupling is different and more complicated in comparison with the solid ones as it is essentially mediated by an electromagnetically neutral matrix. When either of the fields, magnetic or electric, acts on the ‘akin’ particles (FM or FE) it causes their displacement and by that perturbs the particle elastic environments. The induced mechanical stresses spread over the matrix and inevitably affect the particles of an alternative kind. Therefore, magnetization causes an electric response (due to the piezoeffect in FE) whereas electric polarization might entail a magnetic response (due to the magnetostriction effect in FM). A numerical model accounting for the multiferroic behavior of a polymer composite of the above-described type is proposed and confirmed experimentally on a polymer-based dispersion of iron and lead zirconate micron-size particles.

Solid-State Heating Using the Multicaloric Effect in Multiferroics

The multicaloric effect is defined as the adiabatic reversible temperature change in multiferroic materials induced by the application of an external electric or magnetic field, and it was first theoretically proposed in 2012. The multicaloric effects in multiferroics, as well as other similar caloric effects in single ferroics, such as magnetocaloric, elastocaloric, barocaloric, and electrocaloric, have been the focus of much research due to their potential commercialization in solid-state refrigeration. In this short communication article, we examine the thermodynamics of the multicaloric effect for solid-state heating applications. A possible thermodynamic multicaloric heating cycle is proposed and then implemented to estimate the solid-state heating effect for a known electrocaloric system. This work offers a path to implementing caloric and multicaloric effects to efficient heating systems, and we offer a theoretical estimate of the upper limit of the temperature change achievable in a multicaloric cooling or heating effect.

Quadratic magnetoelectric effect during field cooling in sputter grown Cr2O3 films

${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$ is the archetypal magnetoelectric (ME) material, which has a linear coupling between electric and magnetic polarizations. Quadratic ME effects are forbidden for the magnetic point group of ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$, due to space-time inversion symmetry. In ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$ films grown by sputtering, we find a signature of a quadratic ME effect that is not found in bulk single crystals. We use Raman spectroscopy and magnetization measurements to deduce the removal of space-time symmetry and corroborate the emergence of the quadratic ME effect. We propose that metastable site-selective trace dopants remove the space, time, and space-time inversion symmetries from the original magnetic point group of bulk ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$. We include the quadratic ME effect in a model describing the switching process during ME field cooling and estimate the effective quadratic susceptibility value. The quadratic magnetoelectric effect in a uniaxial antiferromagnet is promising for multifunctional antiferromagnetic and magnetoelectric devices that can incorporate optical, strain-induced, and multiferroic effects.

МАГНИТОЭЛЕКТРИЧЕСКИЕ ЭФФЕКТЫ В МУЛЬТИФЕРРОИКАХ

Research of magnetoelectric effects and multiferroic materials, in which these effects are manifested, is among key areas in modern magnetism. This is associated with promising aspects of applying the results to spintronics, orbitronics, and new generation systems for information storage and processing. Despite a great many of already known materials which, in varying degrees, have magnetoelectric properties, the question regarding physical mechanisms and nature of magnetoelectric effects still remains open. Single-phase multiferroics with their magnetic and segnetoelectric properties implemented in a single crystalline phase are of especially great interest for studying. The most known "traditional multiferroics", such as bismuth ferrite, manganites, rare earthearth orthoferrites and orthochromites, fall into the class of perovskite multiferroics, i.e. the crystalline structure of ABO3 perovskites serve as their pre-phase. However, the difference between crystallographic distortions that results in the formation of various crystalline structures, for example, bismuth ferrite and rare-earth orthoferrites/orthochromites, leads to an essential difference in their physical properties, including magnetoelectric ones. Whereas bismuth ferrite characterized by the R3c symmetry space group is a segnetoelectric (i.e. it has spontaneous segnetoelectric polarization), the presence of segnetoelectric polarization in orthoferrites/orthochromites with the Pbnm symmetry space group is impossible from the symmetry standpoint. However, recent experimental and theoretical research works show that under certain conditions magnetoelectric properties are found in both classes of the said multiferroics. This paper is an overview by its nature and discusses magnetoelectric effects in various classes of single-phase multiferroics with the distorted perovskite structure: proper multiferroics exemplified by bismuth ferrite and improper multiferroics exemplified by rare-earth orthoferrites/orthochromites. Consideration is given to basic principles of the symmetry approach used to study magnetoelectric effects in multiferroics; calculations and analysis of magnetoelectric effects in rare-earth orthoferrites/orthochromites are performed through the methods of group-theoretical analysis.

Electrocaloric effects in multiferroics

An atomistic effective Hamiltonian is used to compute electrocaloric (EC) effects in rare-earth substituted BiFeO$_{3}$ multiferroics. A phenomenological model is then developed to interpret these computations, with this model indicating that the EC coefficient is the sum of two terms, that involve electric quantities (polarization, dielectric response), the antiferromagnetic order parameter, and the coupling between polarization and antiferromagnetic order. The first one depends on the polarization and dielectric susceptibility, has the analytical form previously demonstrated for ferroelectrics, and is thus enhanced at the ferroelectric Curie temperature. The second one explicitly involves the dielectric response, the magnetic order parameter and a specific magnetoelectric coupling, and generates a peak of the EC response at the N\'eel temperature. These atomistic results and phenomenological model may be put in use to optimize EC coefficients.