Dynamical anisotropic magnetoelectric effects at ferroelectric/ferromagnetic insulator interfaces

The interfacial magnetoelectric interaction originating from multi-orbital hopping processes with ferroelectricassociated vector potential is theoretically investigated for complex-oxide composite structures.Large mismatch in the electrical permittivity of the ferroelectric and ferromagnetic materials gives rise to giant anisotropic magnetoelectric effects at their interface.Our study reveals a strong linear dynamic magnetoelectric coupling which genuinely results in electric control of magnetic susceptibility.The constitutive conditions for negative refractive index of multiferroic composites are determined by the analysis of light propagation.     

Studies on multiferroic materials in high magnetic fields

In this article, studies on the magnetoelectric effects of multiferroic materials in high magnetic fields, particularly pulsed magnetic fields, are discussed and results for some representative materials are presented. In the discussions on representative materials, the relationship between the crystallographic symmetry and the linear magnetoelectric effect in Cr₂O₃ is introduced. Then drastic changes in polarization caused by magnetic transitions are discussed through a case study of manganites with a perovskite-type structure. In addition, high field studies on the magnetoelectric effects in BiFeO₃, which is an exceptional multiferroic material, are presented and discussed in the framework of the Landau-Ginzburg theory.     

Features of the direct magnetoelectric effect in two-layer Tb0.12Dy0.2Fe0.68-PbZr0.53Ti0.47O3 composites

The transverse magnetoelectric effect in two-layer Tb_0.12Dy_0.2Fe_0.68-PbZr_0.53Ti_0.47O₃ composites with Tb_0.12Dy_0.2Fe_0.68 ferromagnetic layers of various thicknesses are studied over the temperature range of 77 to 423 K at resonant frequencies of the bending oscillations. It is established that for all of the studied composites, the transverse magnetoelectric voltage constant passes at 253 K through a peak whose nature is associated with features of the magnetic constituent of the composites.     

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.     

Magnetoelectric properties of particulate and bi-layer PMN-PT/CoFe2O4 composites

Our studies comprise electrical dielectric and magnetoelectric properties of CoFe₂O₄ (CFO) and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ [PMN-PT] magnetoelectric composites. The individual phases were prepared by conventional ceramic method. The particulate composites of ferrite and ferroelectric phases were prepared in ferroelectric rich region. Presence of both the phases in the composites was confirmed using X-ray diffraction techniques. The scanning electron microscopic images recorded in backscattered mode were used to study the microstructure of composites. Lattice constant, dielectric constant, electrical resistivity, ferroelectric, and magnetic properties of individual as well as particulate composites were studied. Further the bi-layer composites were made using the discs obtained from the powders of individual phases where hot press technique was employed to obtain disc of individual phases. CFO phase used in bi-layer composites was obtained using chemical co-precipitation technique. Magnetoelectric (ME) measurements were carried out on both, particulate and layered magnetoelectric composites. Comparison of ME signal obtained from particulate and layered composites revealed that the layered composites gives superior magnetoelectric signal. ME data obtained for layered composites show good agreement with the theoretical model.     

Molecular dynamics simulations of interfaces between NiO and cubic ZrO2

The structures of eight heterophase interfaces between cubic ZrO₂ and NiO simulated by molecular dynamics (MD) are compared with those of the corresponding isolated surfaces to better understand the factors influencing interface formation and coherency in ceramic oxides. The near coincident site lattice (NCSL) theory used to construct initial configurations with small lattice mismatch between low index crystal planes is extended to describe interface planes with rectangular symmetry. Interface energies, works of adhesion, expansion volumes, lattice strains and planar structure factors are reported for several bicrystals. Most interfaces are found to consist of disordered, open structures with correspondingly high energies as a consequence of the strong repulsive forces between like-charged ions brought into close proximity. The exception is the (111) NiO//(100) c-ZrO₂ interface, which exhibits good coherency across the interphase boundary and consists of a shared oxygen plane. The relatively high crystallinity of the interface explains its low energies and small excess volume. The results are discussed in the context of developing a simulation-based method for identifying interface configurations with high lattice coherency and strong cohesiveness for optimizing the properties of composites of technologically important materials.     

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.     

Role of electrodes materials in determining the interfacial and magnetoelectric properties in BaTiO<Subscript>3</Subscript>-based multiferroic tunnel junctions

Using the first-principles calculations based on density functional theory, the important role of electrode materials in determining the interfacial, ferroelectric stability and magnetoelectric properties in BaTiO₃-based multiferroic tunnel junctions (MFTJs) have been investigated comparatively. It is found that the SrO–TiO₂ interface of MFTJs with oxide electrode SrRuO₃ is the most favorable interfacial structure. The average ferroelectric polarizations of MFTJs with electrode Co, FeCo and SrRuO₃ are 25, 36 and 0 μC/cm², respectively. The using of alloy electrode FeCo is more contributed to ferroelectric stability and the enhancement of magnetoelectric coupling of BaTiO₃-based MFTJs. We expect our findings can provide an essential evaluation for the selection of electrode materials in spintronic storage devices.     

Studies on lead-free multiferroic magnetoelectric composites

Lead-free multiferroic magnetoelectric composites consisting of ferrimagnetic Ni_0.93Co_0.02Mn_0.05Fe_1.95O₄ (NMF) and ferroelectric Na_0.5Bi_0.5TiO₃ (NBT) phases were synthesized by the solid-state sintering method. The presence of constituent phases in composites was confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). A systematic study of dc conductivity as a function of temperature (RT −450 °C) revealed that the conduction is due to small polarons. The effect of constituent phase variation on the dielectric constant and piezoelectric strength (d₃₃) was examined. The composites exhibited typical magnetic hysteresis (M–H) loops at room temperature. Furthermore, magnetoelectric (ME) output was evaluated as a function of applied magnetic field, which is a product property of the constituent phases. The compound 50% NMF–50%NBT is a new lead-free magnetoelectric composite with 155 μV/cm ME output, which may have potential applications.     

Interfacial electronic structure and magnetoelectric effect in M/BaTiO3 (M=Ni,Fe) superlattices

Using first-principles density functional theory, we investigate the interfacial electronic structure and magnetoelectric effect in M/BaTiO₃ (M=Ni, Fe) superlattices, and find a novel type of interfacial magnetoelectric coupling mechanism in the Ni/BaTiO₃ interface. This magnetoelectric effect is determined by the change of magnetic moments on Ni atoms near the interface, instead of the induced moments on interfacial Ti atoms in Fe/BaTiO₃ system, which is also distinguished from the spin-polarized carriers screening mechanism. The underlying physics is the strong interface bonding and the pdσ-type magnetic interactions between Ni 3d and O 2p spins. Furthermore, there exists an extraordinary intralayer oscillation of magnetic moments within the Ni layers, which may be observed in experiments.     

Dielectric, ferroelectric, magnetic and magnetoelectric properties of PMN-PT based ME composites

A systematic study of magnetoelectric composite system (x) CoFe₂O₄+(1−x) Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x=0, 0.15, 0.30, 0.45 and 1 was carried out. The lattice strain was calculated using Williamson and Hall equation, which depends on the content of constituent phases in composites. The microstructure was studied using scanning electron microscopy. The ferroelectric transition temperature was independent of the content of individual phases, suggesting that the ferroelectric character is maintained in the composite. Observed P–E and M–H loops indicate that the multiferroic nature of magnetoelectric ceramics is dependent on the content of individual phases. The variation of magnetostriction with dc magnetic field was studied. The maximum magnetoelectric voltage coefficient of 7.2 mV/cm Oe is obtained for the synthesized composites. The magnetoelectric measurements are well explained with magnetostrictive behavior of the magnetic phase.     

The pyroelectric effect in magnetoelectric 0.8 PZT-0.2 MZF and 0.8 PZT-0.2 NZF composites

The pyroelectric response is measured using the dynamic method in preliminarily polarized magnetoelectric 0.8PbZr_0.53Ti_0.47O₃-0.2Mn_0.4Zn_0.6Fe₂O₄(0.8 PZT-0.2 MZF) and 0.8PbZr_0.53Ti_0.47O₃-Ni_0.4Zn_0.6Fe₂O₄ (0.8 PZT-0.2 NZF) composites, where PZT is a ferroelectric, and MZF and NZF are manganese-zinc and nickel-zinc ferrites, respectively. Values of the pyroelectric coefficient Γ for the materials under study vary over the range of 1.5–4 × 10⁻⁸ C cm⁻² K⁻¹. It is shown that the polarized samples of the composites have a heterogeneous distribution of polarization across the sample thickness. The heterogeneity is more pronounced in the near-surface layers of the investigated materials.     

Internal friction and magnetoelectric response in two-layer composites Tb<Subscript>0.12</Subscript>Dy<Subscript>0.2</Subscript>Fe<Subscript>0.68</Subscript>–PbZr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>O<Subscript>3</Subscript>

The inverse magnetoelectric effect and internal friction in two-layer composites based on ferromagnetic Tb_0.12Dy_0.2Fe_0.68 and piezoelectric PbZr_0.53Ti_0.47O₃ are studied in an ac electrical field in the frequency range of 52–213 kHz at temperatures of 293 to 400 K. A correlation is found between the internal friction and the efficiency of the inverse magnetoelectric transformation at resonant frequencies.     

Mn的价态对La0.8Ba0.2MnO3电磁性能的影响

在2—390K温度之间研究了La_0.8Ba_0.2MnO₃的 磁矩、磁电阻与温度的关系.发 现以不同价态的Mn元素引入得到的La_0.8Ba_0．2MnO₃ ，性能虽然都存在金属 —绝缘体转变，以及在磁场作用下居里温度附近电阻率变化非常显著的特点，但是价态对磁 性转变温度T_C，金属—绝缘体转变温度T_mi，以及磁电阻极大 值温度T_MR的影 响都非常显著.三种价态相比较，使用二价Mn的电阻率最低以及磁性转变温度更接近室温.认 为影响材料性能的主要因素是材料制备时引进的Mn元素的价态，由于原料价态的不同而形成 的氧空位浓度变化，进而影响了Mn⁴⁺/Mn³⁺的比. 关键词： 价态 磁电阻 居里温度 金属—绝缘体转变     

Ni/Pb(Zr,Ti)O3/TbFe2层状复合材料的谐振磁电特性研究

采用化学镀和黏接法制备层状磁电复合材料Ni/PZT/TbFe₂,研究其磁电性能及谐振频率随Ni层厚度的变化情况. 结果表明:Ni/PZT/TbFe₂层状磁电复合材料与其他结构的磁电性能不同,其一阶弯曲谐振峰值和纵向谐振峰值都很大. 随着Ni层厚度的增加,Ni/PZT/TbFe₂层状磁电复合材料的一阶纵向谐振峰值逐渐增大. 结合实验数据和理论计算值得出了材料的一阶弯曲谐振频率fr1和一阶纵向谐振频率f 关键词： 磁电效应 正磁致伸缩 负磁致伸缩 谐振频率     

Magnetic,magnetoelectric and dielectric behavior of CoFe2O4–Pb(Fe1/2Nb1/2)O3 particulate and layered composites

Magnetic, magnetoelectric and dielectric properties of multiferroic CoFe₂O₄–Pb(Fe_1/2Nb_1/2)O₃ composites prepared as bulk ceramics were compared with those of tape cast and cofired laminates consisting of alternate ferrite and relaxor layers. X-ray diffraction analysis and Scanning Electron Microscope observations of ceramic samples revealed two-phase composition and fine grained microstructure with uniformly distributed ferrite and relaxor phases. High and broad maxima of dielectric permittivity attributed to dielectric relaxation were found for ceramic samples measured in a temperature range from −55 to 500 °C at frequencies 10 Hz–2 MHz. Magnetic hysteresis, zero-field cooled (ZFC) and field cooled (FC) curves, and dependencies of magnetization on temperature for both magnetoelectric composites were measured with a vibrating sample magnetometer in an applied magnetic field up to 80 kOe at 4–400 K. The hysteresis loops obtained for composites are typical of a mixture of the hard magnetic material with a significant amount of the paramagnet. The bifurcation of ZFC–FC magnetizations observed for both composites implies spin-glass behavior. Magnetoelectric properties at room temperature were investigated as a function of dc magnetic field (0.3–7.2 kOe) and frequency (10 Hz–10 kHz) of ac magnetic field. Both types of composites exhibit a distinct magnetoelectric effect. Maximum values of magnetoelectric coefficient attained for the layered composites exceed 200 mV/(cm Oe) and are almost three times higher than those for particulate composites.     

铁电/铁磁1-3型结构复合材料磁电性能分析

磁致伸缩和压电复合材料通过机械力作用可获得较大的磁电效应，由Terfenol-D粉末与树脂黏接剂构成压磁相，和压电陶瓷PZT黏结在一起，形成1-3型柱状阵列结构，可获得很大的磁电转换系数.采用有限元方法，对此结构的复合材料进行静态分析.复合材料的介电常数和磁电系数的计算结果和实验数值一致，得到样品中应力、应变和电极化分布情况及其关系，并给出进一步提高磁电转换系数的途径，该种复合方式有望成为一种新型高性能的磁电结构. 关键词： 复合材料 磁电效应 有限元     

Dielectric properties and magnetoelectric effect of (x)NiFe2O4+(1−x)Ba0.8Sr0.2TiO3 composites

Magnetoelectric composites of NiFe₂O₄ and Ba_0.8Sr_0.2TiO₃ were prepared using conventional double-sintering ceramic method. The phase formation of magnetoelectric composites was confirmed by XRD technique. Variation of dielectric constant and loss tangent at room temperature with frequency in the range 100 Hz-1 MHz has been studied. Also the variation of dielectric constant and loss tangent with temperature and composition at fixed frequencies of 1 kHz, 10 kHz, 100 kHz and 1 MHz is reported. The static value of the magnetoelectric conversion factor was measured as a function of intensity of the magnetic field. The ME voltage coefficient of about 430 μV/cm Oe was observed for 15% NiFe₂O₄+85% Ba_0.8Sr_0.2TiO₃ composite. All the samples show linear variation of magnetoelectric conversion in the presence of static magnetic field.     

Semiconducting large bandgap oxides as potential thermoelectric materials for high-temperature power generation?

Semiconducting large bandgap oxides are considered as interesting candidates for high-temperature thermoelectric power generation (700–1,200 °C) due to their stability, lack of toxicity and low cost, but so far they have not reached sufficient performance for extended application. In this review, we summarize recent progress on thermoelectric oxides, analyze concepts for tuning semiconductor thermoelectric properties with view of their applicability to oxides and determine key drivers and limitations for electrical and thermal transport properties in oxides based on our own experimental work and literature results. For our experimental assessment, we have selected representative multicomponent oxides that range from materials with highly symmetric crystal structure (SrTiO₃ perovskite) over oxides with large densities of planar crystallographic defects (Ti _n O_2n?1 Magnéli phases with a single type of shear plane, NbO _x block structures with intersecting shear planes and WO_3?x with more defective block and channel structures) to layered superstructures (Ca₃Co₄O₉ and double perovskites) and also include a wide range of their composites with a variety of second phases. Crystallographic or microstructural features of these oxides are in 0.3–2 nm size range, so that oxide phonons can efficiently interact with them. We explore in our experiments the effects of doping, grain size, crystallographic defects, superstructures, second phases, texturing and (to a limited extend) processing on electric conductivity, Seebeck coefficient, thermal conductivity and figure of merit. Jonker and lattice-versus-electrical conductivity plots are used to compare specific materials and material families and extract levers for future improvement of oxide thermoelectrics. We show in our work that oxygen vacancy doping (reduction) is a more powerful driver for improving the power factor for SrTiO₃, TiO₂ and NbO _x than heterovalent doping. Based on our Seebeck-conductivity plots, we derived a set of highest achievable power factors. We met these best values in our own experiments for our titanium oxide- and niobium oxide-based materials. For strontium titanate-based materials, the estimated highest power factor was not reached; further material improvement is possible and can be reached for materials with higher carrier densities. Our results show that periodic crystallographic defects and superstructures are most efficient in reducing the lattice thermal conductivity in oxides, followed by hetero- and homovalent doping. Due to the small phonon mean free path in oxides, grain boundary scattering in nanoceramics or materials with nanodispersions is much less efficient. We investigated the impact of texturing in Ca₃Co₄O₉ ceramics on thermoelectric performance; we did not find any improvement in the overall in-plane performance of a textured ceramic compared to the corresponding random ceramic.     

有限输入阻抗下压电/磁伸层叠材料磁电效应理论及实验

将磁致伸缩材料及压电材料本构方程与运动方程结合,考虑压电材料具有的高输出阻抗的特点及测试设备的有限输入阻抗和传输信号引线电容对磁电效应输出电压的影响,推出了Terfenol-D巨磁伸材料与横向极化Pb(Zr_1-xTi_x)O₃压电材料的磁电效应理论,研制了由一维磁伸材料构成的三明治结构元件并对其性能进行了测试,采用考虑了测试系统有限输入阻抗后建立的磁电效应理论结果与实验结果更符合.理论结果表明磁电元件在有限输入阻抗 关键词： 磁电效应 有限输入阻抗 压电/磁伸复合 一维磁伸材料