Magnetoelectric and magnetoelastic interactions in NdFe3(BO3)4 multiferroics

Complex experimental and theoretical investigations of the magnetic, magnetoelectric, and magnetoelastic properties of neodymium iron borate NdFe₃(BO₃)₄ along various crystallographic directions have been carried out in strong pulsed magnetic fields up to 230 kOe in a temperature range of 4.2–50 K. It has been found that neodymium iron borate, as well as gadolinium iron borate, is a multiferroic. It has a much larger (above 300 μC/m²) electric polarization controlled by the magnetic field and giant quadratic magnetoelectric effect. The exchange field between the rare-earth and iron subsystems (～50 kOe) has been determined for the first time from experimental data. The theoretical analysis based on the magnetic symmetry and quantum properties of the Nd ion in the crystal provides an explanation of the unusual behavior of the magnetoelectric and magnetoelastic properties of neodymium iron borate in strong magnetic fields and correlation observed between them.     

单相ABO3型多铁材料的磁电耦合及磁电性质研究

实验发现多铁性钙钛矿物质YMnO₃和BiMnO₃在接近磁有序相变温度时,其介电常数和正切损失会出现异常,这些现象说明在物质的磁性和介电性质之间存在耦合.通过对系统磁性和铁电性之间可能磁电耦合方式的分析,考虑在系统哈密顿量中加入与自旋关联和极化相关的耦合项,对铁电子系统应用软模理论,对磁性运用基于海森伯模型的量子平均场近似,研究了外磁场诱导的极化、介电的变化和外电场诱导的磁化的变化等,并将以上结果与实验进行了比较和分析,较为合理地解释了一些多铁钙钛矿物质中的磁电现 关键词： 多铁 磁电耦合 铁电 铁磁     

Effect of magnetic annealing on magnetization of BiFeO3 ceramics

The effect of magnetic annealing treatment on the magnetization of multiferroic BiFeO₃ was studied systematically. A series of pelletized nano-sized BiFeO₃ powders were annealed at high temperature under different magnetic fields. Typical ferromagnetic hysteresis loops were obtained at room temperature of the ceramics which were derived from ferromagnetic BiFeO₃ precursors. On the other hand, antiferromagnetic behaviors were observed in other samples synthesized from nonmagnetic precursors. The enhanced magnetic properties were ascribed to the magnetic anisotropy which was induced by the strong magnetic fields. This work indicates that the strong magnetic annealing method is an alternative approach to tuning the magnetic properties of high performance multiferroic materials with canted antiferromagnetic ordering.     

Determination of the magnetoelectric coupling coefficient from temperature dependences of the dielectric permittivity for multiferroic ceramics Bi5Ti3FeO15

In the multiferroic materials, the dielectric and magnetic properties are closely correlated through the coupling interaction between the ferroelectric and magnetic order. We attempted to determine the magnetoelectric coupling coefficient from the temperature dependences of the dielectric permittivity for multiferroic Bi₅Ti₃FeO₁₅. Multiferroic ceramics Bi₅Ti₃FeO₁₅ belong to materials of the Aurivillius-type structure. Multiferroic ceramics Bi₅Ti₃FeO₁₅ was synthesized via sintering the Bi₂O₃ and Fe₂O₃ mixture and TiO₂ oxides. The precursor material was ground in a high-energy attritorial mill for 5 hours. This material was obtained by a solid-state reaction process at T = 1313 K. We investigated the temperature dependences of the dielectric permittivity for the different frequencies. From the dielectric measurements, we determined the temperature of phase transition of the ferroelectric-to-paraelectric type at about 1013 K. Based on dielectric measurements and theoretical considerations, the values of the magnetoelectric coupling coefficient were specified.     

Nature of unusual spontaneous and field-induced phase transitions in multiferroics RMn2O5

Complex magnetic, magnetoelectric and magnetoelastic studies of spontaneous and field-induced phase transitions in TmMn₂O₅ were carried out. In the vicinity of spontaneous phase transition temperatures (35 and 25 K) the magnetoelectric and magnetoelastic dependences demonstrated the jumps of polarization and magnetostriction induced by the field ∼150 kOe. These anomalies can be attributed to the influence of magnetic field on the conditions of incommensurate-commensurate phase transition at 35 K and the reverse one at 25 K. In b-axis dependences the magnetic field-induced spin-reorientation phase transition was also observed below 20 K. Finally the magnetoelectric anomaly associated with metamagnetic transition is observed below the temperature of rare-earth subsystem ordering at relatively small critical fields of 5 kOe. This variety of spontaneous and induced phase transitions in RMn₂O₅ stems from the interplay of three magnetic subsystems: Mn³⁺, Mn⁴⁺, R³⁺. The comparison with YMn₂O₅ highlights the role of rare earth in low-temperature region (metamagnetic and spin-reorientation phase transitions), while the phase transition at higher temperatures between incommensurate and commensurate phases should be ascribed to the different temperature dependences of Mn³⁺ and Mn⁴⁺ ions. The strong correlation of magnetoelastic and magnetoelectric properties observed in the whole class of RMn₂O₅ highlights their multiferroic nature.     

Magnetoelectric multiferroicity and quantum paraelectricity in hexaferrites

Multiferroic materials with coexisting ferroelectric and magnetic orders have attracted tremendous research interests because of their intriguing fundamental physics as well as potential applications in the next-generation multifunctional devices. Hexaferrites with conical magnetic structures are among the most promising single-phase multiferroics because strong magnetoelectric effects can be achieved in them from low temperatures up to room temperature in low magnetic fields. In this review, after briefly introducing the background on multiferroics and classification of hexaferrites, we summarize recent progress in multiferroic hexaferrites, including the mechanisms of spin-induced ferroelectricity, the magnetoelectric phase diagram, giant direct and converse magnetoelectric effects. Furthermore, we present a new mechanism of magnetic-ion-induced displacive polarization in hexaferrites, which leads to quantum paraelectricity and quantum electric-dipole liquid in M-type hexaferrites.     

Nucleation of electroactive β-phase poly(vinilidene fluoride) with CoFe2O4 and NiFe2O4 nanofillers: a new method for the preparation of multiferroic nanocomposites

Multiferroic and magnetoelectric materials show enormous potential for technological developments. Multiferroic composites are more attractive for applications due to their enhanced properties with respect to single-phase multiferroic materials. In this paper we report on the nucleation of the electroactive β-phase of poly(vinylidene fluoride), PVDF, by the addition of CoFe₂O₄ and NiFe₂O₄ nanoparticles in order to prepare poly(vinylidene fluoride)/ferrite nanocomposite for multiferroic and magnetoelectric applications,. The dispersed ferrite nanofiller particles strongly enhance the nucleation of the β-phase of the polymer matrix. In this way, magnetoelectric polymer nanocomposites can be processed avoiding the usual α- to β-phase transformation by stretching of the polymer matrix.     

Spin chirality and electric polarization in multiferroic compounds (, Er)

Polarized neutron diffraction experiments have been performed on multiferroic materials RMn₂O₅ (R=Ho, Er) under electric fields in the ferroelectric commensurate (CM) and the low-temperature incommensurate (LT-ICM) phases, where the former has the highest electric polarization and the latter has reduced polarization. It is found that, after cooling in electric fields down to the CM phase, the magnetic chirality is proportional to the electric polarization. Also we confirmed that the magnetic chirality can be switched by the polarity of the electric polarization in both the CM and LT-ICM phases. These facts suggest an intimate coupling between the magnetic chirality and the electric polarization. However, upon the transition from the CM to LT-ICM phase, the reduction of the electric polarization is not accompanied by any reduction of the magnetic chirality, implying that the CM and LT-ICM phases contain different mechanisms of the magnetoelectric coupling.     

Domain-based magnetoelectric studies for single crystals of chromium oxide

As is well known, the sign of parallel magnetoelectric susceptibility for chromium oxide can be positive or negative both depending on prehistory of the sample, but it is always opposite to the perpendicular susceptibility. In order to explain this behaviour, the concept of antiferromagnetic domains depending on the existence of two possibilities spin orientation in a magnetic unit cell was invoked both by Rado and Astrov. The authors have carried out detailed studies of domain-based magnetoelectric effect for Cr₂O₃ and the results are presented in this communication. Investigations were carried out both for static and dynamic effect. For static measurements the dielectric constant method developed earlier has been used. The domain pattern in the sample is altered by cooling in simultaneous presence of different electric (E) and magnetic (B) fields from paramagnetic state to the ordered state, and the magnetoelectric susceptibility evaluated. From the measurements it is concluded that the deciding parameter of magnetoelectric susceptibility if product of fields EB for low fields as reported by Martin and Anderson. For high fields, the electric field seems to play a more significant role, and magnetoelectric susceptibility is a function of E²B used for cooling. Static measurements are also extended to low temperatures for parallel susceptibility for the sample with largest magnetoelectric susceptibility. In the temperature range used (90 K to room temperature) the change in susceptibility observed is not very significant, a fact which is hard to explain. Data about the effect of variation of cooling rate and step function cooling is also presented, and it is concluded, though not in a definite manner, that rectangular step function cooling is as effective as continuous rate cooling in deciding magnetoelectric susceptibility of the sample.For dynamic studies, again the dielectric constant method is used, and measurements are reported at different frequencies for a sample with possibly a large number of domains. Two resonant peaks in the dielectric constant are observed and they are tentatively explained on the basis of domain wall resonance.     

Spatially modulated antiferromagnetic structures in an easy-plane multiferroic

Possible types of spatially modulated periodic antiferromagnetic structures in a uniaxial rhombohedral multiferroic with BiFeO₃ crystal symmetry have been studied depending on the ratio of the uniaxial anisotropy and magnetoelectric interaction parameters. It has been shown that, along with symmetric cycloid antiferromagnetic structures with zero transverse component of the antiferromagnetism vector, there are changes in the antiferromagnetism vector direction with both right and left nonzero components of the antiferromagnetic moment, which are branched from the high-symmetry spatially modulated distribution. These solutions degenerate into a homogeneous state at a critical value of the normalized easy-plane anisotropy parameter. The existence of the found spatially inhomogeneous antiferromagnetic states with an incommensurate period can lead to additional features in magnetoelectric properties in multiferroics of the type under consideration near magnetic phase transitions in electric and magnetic fields.     

A radical approach to promote multiferroic coupling in double perovskites

Double perovskites provide a unique opportunity to induce and control multiferroic behaviours in oxide systems. The appealing possibility to design materials with a strong coupling between the magnetization and the polarization fields may be achieved in this family since these magnetic insulators can present structural self-ordering in the appropriate growth conditions. We have studied the functional properties of La₂CoMnO₆ and Bi₂CoMnO₆ epitaxial thin films grown by pulsed laser deposition. Cation-ordered La₂CoMnO₆ films display a magnetic Curie temperature of 250 K while cation-disordered Bi₂CoMnO₆ films present ferromagnetism up to ∼800 K. Such high transition temperature for magnetic ordering can be further tuned by varying the strain in the films indicating an important contribution from the structural characteristics of the materials. Our approach might be generalized for other oxide systems. At this end, our results are compared with other multiferroic systems. The roles of various cations, their arrangements and structural effects are further discussed.     

Mn3TeO6 – a new multiferroic material with two magnetic substructures

From magnetic susceptibility, dielectric permittivity, electric polarization and specific heat measurements we discover spin‐induced ferroelectricity and magnetoelectric coupling in Mn₃TeO₆ and observe two successive magnetic transitions at low temperatures. A non‐ferroelectric intermediate magnetic state occurs below 23 K and a multiferroic ground state emerges below 21 K. Moreover, Mn₃TeO₆ is a candidate for a multiferroic material where two types of incommensurate spin structures, cycloidal and helical, coexist. Theoretically, both spin substructures may contribute to the macro electric polarization via different mechanisms. This could open new ways of manipulating the ferroelectric polarization in a multiferroic material. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Multiferroic and magnetoelectric properties of MnFe2O4/(Pb0.8Sr0.2)TiO3 composite films

Abstract

MnFe₂O₄/(Pb_0.8Sr_0.2)TiO₃ (MFO/PST20) heterostructured composite films with three different structures have been grown on Pt/TiO₂/SiO₂/Si substrates by metal–organic decomposition processing via spin coating technique. The structural analysis revealed that the crystal axes of the MnFe₂O₄ are aligned with those of the PST20 ferroelectric matrix with obvious interfaces and no diffusions exist in all the three composite films. These composite films exhibit simultaneously multiferroic and magnetoelectric responses at room temperature. The growth structure of MFO and PST20 layers has an effect on multiferroic and magnetoelectric coupling behaviours of the composite films. The bi- and four-layered MFO/PST20 composite films exhibit superior ferroelectric properties compared to the tri-layered film. The increasing MFO and PST20 layers in the composite films enhance ferromagnetic properties and are closely related to the strain release in MnFe₂O₄ phase. The MFO/PST20 bi-layered composite film shows a high magnetoelectric voltage co-efficient α_E ~ 194 mVcm^?1Oe^?1 at a dc magnetic field H_dc ~ 2.5 kOe. A significant decrease in α_E value has been observed for tri- and four- layered composite films. A close correlation between phase selective residual stress and magnetoelectric properties has been emerged. The results are reasonably encouraging for employing MnFe₂O₄ for growing multiferroic–magnetoelectric composite films.     

多铁异质结构中逆磁电耦合效应的研究进展

电场调控磁性能够有效降低功耗,在未来低功耗多功能器件等方面具有巨大的潜在应用前景.铁磁/铁电多铁异质结构是实现电场调控磁性的有效途径,其中室温、磁电耦合效应大的应变媒介磁电耦合是最为活跃的研究领域之一.本文简要介绍在以Pb(Mg_(1/3)Nb_(2/3))_(0.7)Ti_(0.3)O_3为铁电材料的多铁异质结构中通过应变媒介磁电耦合效应对磁性、磁化翻转及磁性隧道结调控的研究进展.首先讨论了多铁异质结构中电场对磁性的调控;之后介绍了电场调控磁化翻转的研究进展及理论上实现的途径;然后简述了电场对磁性隧道结调控的相关结果;最后在此基础上,对多铁异质结构中电场调控磁性及磁性器件进行了总结和展望.     

Effect of Gd-Mn exchange on phase transitions in GdMn<Subscript>2</Subscript>O<Subscript>5</Subscript> induced by a strong magnetic field

Complex studies of the magnetic, magnetoelectric, and magnetoelastic properties of GdMn₂O₅ single crystals in strong pulsed magnetic fields are carried out in order to obtain additional indirect information on the character of the rare-earth and manganese spin ordering. It is shown that magnetic ordering of Gd³⁺ spins affects the manganese sublattice spin orientation and initiates new magnetic phase transitions. The observed magnetoelectric properties of the GdMn₂O₅ system are interpreted in terms of the theory of phase transitions.     

Artificial multiferroic heterostructures for an electric control of magnetic properties

The control of magnetism by electric fields is an important goal for future low-power spintronics devices. This partly explains the intensified recent interest for magnetoelectric multiferroic materials and heterostructures. The lack of ferro- or ferrimagnetic–ferroelectric materials with large magnetoelectric coupling between the two orders has spurred intensive research on artificial multiferroics combining ferroelectric or piezoelectric materials and ferromagnets. In this paper we review synthetically the potential of thin-film-based heterostructures in which a magnetic film is in contact with a ferroelectric or piezoelectric one to obtain an electric control of magnetic properties. This electric control either results from a strain-induced magnetoelectric coupling, a charge-driven one, or from the modulation of an interfacial exchange-bias interaction.     

Anomalies of the phonon properties in multiferroic BiFeO3 thin films near the magnetic phase transition temperature

Size, substrate, doping and magnetic field effects on the phonon properties in multiferroic BiFeO₃ thin films are studied based on a microscopic model. We obtain an anomaly near the magnetic phase transition temperature TN which can be attributed to the magnetoelectric nature of BiFeO₃ and strong anharmonic spin-phonon interaction. It is shown that due to crystal lattice distortion for dopants with ionic radius smaller than that of the host ions the phonon energy decreases (for example Tb or Ti), whereas for the opposite case (larger radius of the doping ions, for example Co or Ni) it increases. The phonon damping is always enhanced compared to the undoped thin film.     

Electric field-induced magnetoresistance in spin-valve/piezoelectric multiferroic laminates for low-power spintronics

Electric field-induced magnetic anisotropy has been realized in the spin-valve-based {Ni₈₀Fe₂₀/Cu/Fe₅₀Co₅₀/IrMn}/piezoelectric multiferroic laminates. In this system, electric-field control of magnetization is accomplished by strain mediated magnetoelectric coupling. Practically, the magnetization in the magnetostrictive FeCo layer of the spin-valve structure rotates under an effective compressive stress caused by the inverse piezoelectric effect in external electrical fields. This phenomenon is evidenced by the magnetization and magnetoresistance changes under the electrical field applied across the piezoelectric layer. The result shows great potential for advanced low-power spintronic devices.     

Magnetoelectric effect and magnetostriction in the paramagnetic piezoelectric NiSO4 · 6H2O

The direct magnetoelectric effect, the magnetostriction, and the magnetic moment in piezoelectric paramagnetic NiSO₄ · 6H₂O single crystals is comprehensively studied over a wide temperature range in magnetic fields up to 14 T for several magnetic field directions with respect to crystallographic axes. At temperatures above 20 K, the magnetoelectric effect is rigorously quadratic in magnetic field over the entire magnetic field range. As the temperature decreases, the region of quadratic behavior shifts toward low fields. To explain the magnetoelectric effect, the contribution of the magnetostriction-induced piezoelectric effect is considered. It is shown that the piezoelectric effect may be neglected at the helium temperature, where the magnetoelectric effect is high, since its value does not exceed 1%. However, the relative contribution of the piezoelectric effect increases to 10% at T = 40 K, where the magnetoelectric polarization decreases strongly. In contrast to the earlier assumption that the magnetoelectric effect is rapidly and fully saturated in fields higher than 3 T, complete saturation is actually not detected even at 14 T.     

脉冲强磁场下的电极化测量系统

多铁性材料是当前物质科学研究的热点,具有重要的科学研究意义和应用前景.低温和强磁场实验环境为研究多铁性材料提供了一种有效途径.脉冲强磁场下的电极化测量系统能实现最高磁场强度60 T、最低温度0.5 K的铁电特性测量.该系统采用热释电方法,具有磁场强度高、控温范围广、转角测量等特点,可用于强磁场下的磁电特性研究.本文介绍了该系统的测量装置和实验原理,并展示了其在多铁性材料研究中的一系列应用,揭示了脉冲强磁场电极化测量系统在磁电特性探索中的重要作用.