Enhanced room-temperature magnetoelectric coupling effects in c-axis oriented polycrystalline BaSrCo2-xMgxFe11AlO22

The influence of applied magnetic field during annealing process as well as of Mg doping on the room-temperature magnetoelectric coupling effects in BaSrCo_2-xMg_xFe₁₁AlO₂₂ are experimentally studied through the magnetization, magnetodielectric, and magnetoelectric current measurements. Hexaferrite samples of Co₂Y were found to be highly oriented by an applied magnetic field (H_o) during the annealing process, leading to an enhancement of the room-temperature magnetoelectric coupling effects. Although the substitution of nonmagnetic Mg ions in Co sites tends to reduce the ferromagnetism at macroscopic scale, a proper amount of Mg doping content facilitates the superexchange interaction between the adjacent magnetic blocks; meanwhile modulates the magnetic anisotropy in the samples. An appropriate adjustment of the competition between the anisotropy and the superexchange could enhance the magnetoelectric coupling at room temperature, which can be confirmed by the magnetic-field-induced dielectric constant and current density study.     

Modulation of magnetoelectric coupling through systematically engineered spin canting in nickel–zinc ferrite

A nickel–zinc ferrite system, which is one of the well-known versatile soft-ferromagnetic oxides, was investigated in terms of magnetoelectric (ME) coupling at room temperature. Herein, we demonstrated that spin canting is manipulated through a composition-induced structural transition from an inverse to a normal spinel structure, leading to modulation in the ME coupling. The ME coefficient was maximized at 60 at.% Zn substitution with a value of 0.1 mV/(Oe·cm), denoting ∼70% enhancement compared to that of the pure nickel ferrite. It was revealed that the interspin angle is enhanced along the octahedral site at up to ∼60 at.% Zn substitution, consistent with the composition level at the culmination of the ME coupling, evidenced by X-ray diffraction profiles and magnetic hysteresis loops combined with density functional theory calculations. Given that this approach is based on a tractable fabrication method, this study is expected to be widely used in modulation of the ME coupling in spinel-structured oxides.     

Can the ferroelectric soft mode trigger an antiferromagnetic phase transition?

Type-II multiferroics, where spin interactions induce a ferroelectric polarization, are interesting for new device functionalities due to large magnetoelectric coupling. We report on a new type of multiferroicity in the quadruple-perovskite BiMn₃Cr₄O₁₂, where an antiferromagnetic phase is induced by the structural change at the ferroelectric phase transition. The displacive nature of the ferroelectric phase transition at 125 K, with a crossover to an order-disorder mechanism, is evidenced by a polar soft phonon in the THz range and a central mode. Dielectric and pyroelectric studies show that the ferroelectric critical temperature corresponds to the previously reported Néel temperature of the Cr³⁺ spins. An increase in ferroelectric polarization is observed below 48 K, coinciding with the Néel temperature of the Mn³⁺ spins. This increase in polarization is attributed to an enhanced magnetoelectric coupling, as no change in the crystal symmetry below 48 K is detected from infrared and Raman spectra.     

Ferroic ordering and charge‐spin‐lattice order coupling in Gd‐doped Fe3O4 nanoparticles relaxor multiferroic system

We investigated the effect of gadolinium doping (1‐5 at.%) on the magnetic and dielectric properties of Fe₃O₄ nanoparticles, synthesized by the chemical co‐precipitation technique, primarily to understand the onset of multifunctional properties such as ferroelectricity and magnetodielectric coupling. The substitution of larger Gd³⁺ ions at smaller Fe³⁺ octahedral sites in inverse spinel Fe₃O₄ has significantly influenced the morphology, average crystallite size, and more importantly, the magneto‐crystalline anisotropy and saturation magnetization. The magneto‐crystalline anisotropy and the saturation magnetization decreases substantially, however, significant increase in the average crystallite size is observed upon Gd doping. Furthermore, temperature‐dependent dielectric studies suggest that these nanoparticle systems exhibit relaxor ferroelectric behavior, with much pronounced ferroelectric polarization moment recorded for 5 at.% Gd doped Fe₃O₄ as compared to its undoped counterpart.     

Enhancement in electrical and magnetodielectric properties of Ca‐ and Ba‐doped BiFeO3 polycrystalline ceramics

We carried out a comparative study on the electrical and magnetodielectric properties of polycrystalline BiFeO₃, Bi_0.9Ca_0.1FeO_2.95, Bi_0.9Ba_0.05Ca_0.05FeO_2.95, and Bi_0.9Ba_0.1FeO_2.95 ceramics. The two dielectric anomalies, near 25 K and 281 K, are observed for BiFeO₃. Interestingly, the anomaly near 25 K shifts towards a higher temperature above 60 K with Ca and/or Ba doping, attributed to the doping induced chemical pressure. In addition, the room temperature switchable magnetodielectric effect is witnessed for the doped BiFeO₃ compounds, due to the quadratic magnetoelectric coupling. This indicates the improved magnetoelectric coupling in BiFeO₃ with the Ca and Ba doping. This is essentially due to the enhanced magnetic ordering and reduced leakage current in BiFeO₃ after the doping.     

Tailoring the multiferroic properties of BiFeO3 by co-doping Er at Bi site with aliovalent Nb,Mn and Mo at Fe site

Single phase multiferroic undoped BiFeO₃ notoriously suffers due to the poor spin–charge coupling resulting in limitations to device applications. The present work focuses on the tailoring of its multiferroic and magnetoelectric coupling properties by synthesizing multiferroic Bi_0.95Er_0.05Fe_0.98TM_0.02O₃ (TM = Nb, Mn and Mo) ceramics. The ferroelectric, magnetic, current leakage measurements and magnetoelectric effect were investigated. XRD along with the Reitveld refinement results confirms that all the samples possess perovskite based rhombohedral structure and reveals that doping of (Er, Nb), (Er, Mn) and (Er, Mo) induced the crystallographic distortion in the BFO lattice and hence induced a variation in the bond lengths and bond angle. Dual doping significantly enhanced the electrical, magnetic properties and magnetoelectric coupling as compared to BiFeO₃. Doping has lowered the leakage current by three to four orders compared to BFO. The lattice distortion, reduced leakage current and destruction of spin–cycloidal structure could be the origin for these improved features. The (Er, Nb) doped BiFeO₃ yields enhanced ferroelectric character with the maximum polarization value of 0.46 µC/cm², maximum ME coupling of 0.22 mV/cm at a magnetic field of 130 G, an improved magnetization with a remanance value of 0.0903 emu/g and the lowest leakage current density.     

Ferroelectric and magnetoelectric origins of multiferroic SmCrO3

We investigated the magnetic and ferroelectric properties of orthochromite SmCrO₃ by using density functional theory simulations. The atom coordinates of both Pbnm and Pna2₁ were calculated, and Pna2₁ was found to be the ground state structure. The spontaneous polarization in Pna2₁ structure is sensitive to delicate structure change which is induced by different antiferromagnetic order, and its direction is along the c axis. The spin structure of Pbnm was analyzed and it was found to not support ferroelectricity. The results revealed the origin of ferroelectricity of multiferroic SmCrO₃ and explained the magnetoelectric effect.     

On the Photomagnetic Properties of the Binuclear Spin Crossover Complexes {[Fe(bt)(NCSe)<Subscript>2</Subscript>]<Subscript>2</Subscript>(bpym)} and {[Fe(bpym)(NCSe)<Subscript>2</Subscript>]<Subscript>2</Subscript>(bpym)}

Infrared and visible light irradiation effects on the spin state of iron(II) ions have been investigated in the binuclear molecules {[Fe(bt)(NCSe)₂]₂(bpym)} (4) and {[Fe(bpym)(NCSe)₂]₂(bpym)} (2). For compound 2 we could observe LIESST and partial reverse-LIESST effects under visible and infrared light irradiation, respectively. Compound 4 exhibits a wavelength-selective photoconversion at 10 K from the low spin (LS–LS) ground state of the binuclear molecule to the metastable high spin (HS–HS) state under visible (785 or 532 nm) light irradiation or to the metastable HS–LS state under infrared (1,342 nm) light irradiation. In addition we also observed the reverse (HS–HS → HS–LS) and the cascade (LS–LS → HS–LS → HS–HS) photoconversions as well. These phenomena lead to complex and original photomagnetic behaviour due to the intramolecular magnetic coupling. This article is dedicated to Professor Didier Astruc in honor of his scientific achievements, with friendship and sincere respect.     

Direct visualization of magnetic‐field‐induced magnetoelectric switching in multiferroic aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi₆Ti_2.8Fe_1.52Mn_0.68O₁₈, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi₆Ti_2.99Fe_1.46Mn_0.55O₁₈, via the liquid injection chemical vapor deposition technique. High‐resolution magnetic measurements reveal a considerably higher in‐plane ferromagnetic signature than CSD grown films (M_S=24.25 emu/g (215 emu/cm³), M_R=9.916 emu/g (81.5 emu/cm³), H_C=170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in‐plane magnetic field cycle, where increased volumes (8.6% to 14% compared with 4% to 7% for the CSD‐grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.     

Size and Lone Pair Effects on the Multiferroic Properties of Bi0.75A0.25FeO3−δ (A = Sr,Pb, and Ba) Ceramics

The work presents a comparative study of the effects of divalent Ba, Sr, and Pb substituents on the multiferroic properties of BiFeO₃. The multiferroic properties of Bi_0.75A_0.25FeO₃ (A = Sr, Pb, Ba) solid solution have been explained taking into account the effects of size differences and electronic configuration differences between the host element (Bi) and the substituent. X‐ray diffraction studies revealed that Sr and Pb substitution at Bi‐site transforms the rhombohedral phase (R3c) to cubic phase (Pm3m), whereas the Ba‐substituted sample exhibited the presence of both rhombohedral and cubic phases (R3c + Pm3m). Electronic structure studies through XPS revealed that charge imbalance induced by divalent substitution was being compensated by the formation of oxygen vacancies, while the Fe ions exist in Fe²⁺ and Fe³⁺ states. Replacement of volatile Bi by Sr, Pb, and Ba reduces the concentration of oxygen vacancies (V_O²⁺) and helps to improve the dielectric properties. Strong magnetization enhancement was observed in the substituted compositions and was seen to be consistent with the suppression of cycloid spin structure due to structural transformation as well as possible changes in Fe–O local environment leading to local lattice distortion effects. Furthermore, the observed decrease in the values of magnetic coercivity at low temperature in all the substituted samples is explained in terms of reduced effective single ion anisotropy, originating in the magnetoelectric coupling and being a particularly stronger effect in the case of the lone pair dopant Pb, consistent with theoretical predictions. The lone pair substituent Pb leads to the largest dielectric constant, enhanced magnetization, and large effects on the low‐temperature hysteresis.     

Oxygen octahedra distortion-induced multiferroic properties of Er and Zr co-doped BiFeO3 nanoparticles

The present work unveiled the distortion of oxygen octahedra influencing magnetic and magnetoelectric properties of novel Bi_1−xEr_xFe_1−yZr_yO₃ (x = 0, .05, .1, y = .02, .05) polycrystalline nanoparticles by sol–gel route. X-ray diffraction patterns analysis reveals that pristine BiFeO₃ and doped BiFeO₃ are crystalized in the rhombohedral structure (R3c). The Fe–O–Fe bond angle of Bi_1−xEr_xFe_1−yZr_yO₃ (x = 0, .05, .1, y = .02, .05) varies between 141° and 159.62° as the concentration of Er (via Bi site) and Zr (via Fe site) ions increases in BiFeO₃. As a result, the tilt angle of oxygen octahedra and the canting angle of spiral spin arrangement increase. Hence, the maximum magnetization varies between .03144 and .37558 emu/g in Er and Zr co-doped BiFeO₃ system. The number of electrons per unit cell of Bi_1−xEr_xFe_1−yZr_yO₃ (x = 0, .05, .1, y = .02, .05) lies between 733.38 and 831, respectively. Further, the number of coherently diffracting domains increases from 3.07 to 5.21, and then it decreases when Er and Zr are increased in BiFeO₃. Consequently, the magnetoelectric coupling coefficient varies between .0265 and .2511 mV/cm Oe, respectively. Particularly, Bi_0.95Er_0.05Fe_0.98Zr_0.02O₃ shows enhanced magnetic and magnetoelectric behaviors compared to other samples.     

The Effect of Different Active Sites on the Catalytic Activity of Fe-ZSM-5 Zeolite for N2O Direct Decomposition

Fe-modified ZSM-5 zeolites (Si/Al = 25) were prepared by adopting the liquid ion-exchange method with nitrate and oxalate of iron as Fe precursors and their catalytic performance was studied in the N₂O decomposition reaction. The results of FT-IR and H₂-TPR investigations indicated that (i) part of the iron ions could replace Brönsted acid protons at the straight channel wall (α sites), intersection of straight and sinusoidal channels (β sites), and sinusoidal channel wall (γ sites) within the ZSM-5 zeolite; and (ii) different Fe precursors gave rise to various distributions of α, β, and γ sites. We observed that the Fe-ZSM-5 catalyst prepared with iron oxalate as Fe precursor outperformed the ones prepared with iron nitrate as Fe precursor in the direct decomposition of N₂O. Furthermore, the catalytic activity of iron ions located at the α sites was higher than those of iron ions located at the β and γ sites.     

A review of the structure,magnetic and electrical properties of bismuth ferrite (Bi2Fe4O9)

Nowadays, investigations on the materials with multiferroic properties are in progress. These materials compromise simultaneous electric and magnetic properties. Ferrite Bismuth (FB) is one of the ceramic materials that enjoy this property and possesses three different crystalline structures (perovskite BiFeO₃, selenite Bi₂₅FeO₄₀ and mullite Bi₂Fe₄O₉). In this review, first, the crystalline structure and the electric and magnetic properties of Bi₂Fe₄O₉ are studied, and then, the effects of adding dopants to the ferrite are discussed. Mullite-type bismuth ferrite (Bi₂Fe₄O₉) as a spin frustrated multiferroic has potential for magnetoelectric coupling, and it might be an appropriate alternative for some of the multiferroics that suffer from a weak magnetoelectric coupling.     

Thermally activated giant piezoelectricity and enhanced interface elastic strain-mediated magnetoelectric coupling

Perovskite materials with compositions in the vicinity of the steep morphotropic phase boundary (MPB) exhibit various intriguing properties including giant piezoelectricity and large dielectric constant. Aside from composition, the phase configuration of the perovskites is also strongly related to the ambient temperature. Here, we report a giant piezoelectricity of 10 980 pm/V at 93°C in the 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) single crystals which is more than five times larger than that at room temperature. The enhanced piezoelectricity can be attributed to the instability of the thermally induced tetragonal phase which can be converted to the orthorhombic phase by the external electric field in the <011> oriented single crystal. The transverse piezoelectricity has been investigated by measuring the electric-field-dependent ferromagnetic resonance (FMR) field in the CoFeB/PMN-PT magnetoelectric (ME) heterostructures. The ME coupling coefficient has been increased from 49.3 to 476 Oe cm/kV as temperature increased from 25 to 90°C. The findings reveal that both longitudinal and transverse piezoelectricity in the PMN-PT single crystals can be greatly enhanced by proper setting of ambient temperature, indicating an effective route for the design of strain-mediated tunable devices with ultralow driving voltage.     

Influence of Zn2+ doping on the microstructure and magnetic properties of CuFeO2

The mineral delafossite CuFeO₂ exhibits triangular spin frustration with strong magnetoelectric coupling and unique magnetic properties. In this work, the crystal structure, microstructure, oxidation states, and magnetic properties of synthetic CuFe_1-xZn_xO₂ samples have been systematically studied with a view to understanding the effect of small amounts of the diamagnetic Zn²⁺ ion on the magnetoelectric properties of CuFeO₂. Samples were confirmed by XRD as having a single-phase delafossite structure, although the introduction of Zn²⁺ resulted in distortion of the crystal lattice. Addition of Zn²⁺ also increased the particle size and the number of pores, but did not change the oxidation states of either the Cu or Fe. Magnetic susceptibility measurements show that Zn²⁺ disrupted the antiferromagnetic structure of the samples, and resulted in generation of significant ferromagnetism. Overall, the magnetic properties of CuFeO₂ are closely related to ionic substitution, lattice distortion and microscopic defects.     

Field‐Dependent Magnetoelectric Effects in Polycrystalline Co2Y‐Type Ba0.5Sr1.5Co2(Fe1−xAlx)12O22 Hexaferrites

Polycrystalline Ba_0.5Sr_1.5Co₂(Fe_1?xAl_x)₁₂O₂₂ (x = 0, 0.04, 0.08, and 0.12) hexaferrites were prepared by conventional solid‐state reaction method and the magnetic field dependences of magnetic and magnetoelectric properties were investigated. With Al doping (x = 0.04, 0.08), much enhanced ferroelectric polarization and abnormal magnetodielectric properties can be observed at a low applied magnetic field and be maintained down to zero field at 200 K, which may result from the occurrence of field‐induced spin transverse cone structure. The magnetoelectric coefficient increases from 500 ps/m to 1481 ps/m with increasing x value from 0.04 to 0.08. These results suggest that Al ions play an effective role in modifying the magnetoelectricity of hexaferrites.     

Magnetoelectric properties of 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectrics are materials that join magnetic and electric orderings in the same phase. They exhibit magnetoelectric coupling which is important from the fundamental and practical point of view. The subject of the paper is a presentation of magnetic, electric and magnetoelectric properties of 0.5BiFeO₃–0.5Pb(Fe_0.5Nb_0.5)O₃ solid solution. The obtained material belongs to oxide perovskite magnetoelectrics of relatively high magnetic and electric ordering temperatures. Both temperatures are considerably above room what suggests potential application possibilities of the material. The magnetic properties were investigated using Mössbauer spectroscopy and magnetization measurements. The solid solution is an antiferromagnet with incomplete compensated magnetic moments. The electrical properties were determined using impedance spectroscopy analysis. There is an observed change of the electrical properties at the magnetic ordering temperature what indicates magnetoelectric coupling in the system. The electrical conductivity mechanism is also proposed. Magnetoelectric voltage coefficient was determined and possible explanation of its changes was proposed.     

Insight into the Growth Reaction Mechanism of Ceramic Co3TeO6: Synchrotron Structural and Thermal Analysis

A two‐step solid‐state reaction is proposed to synthesize monophasic cobalt tellurate Co₃TeO₆ (CTO), a type II multiferroic, using Co₃O₄ and TeO₂ as the starting reagents. First step of the reaction results in the secondary monoclinic (P2₁/c) CoTeO₄ compound, which on further calcination (second step) leads to the primary monoclinic (C2/c) Co₃TeO₆ phase. High‐resolution synchrotron X‐ray diffraction and the subsequent Rietveld analysis are used to probe different phases present in the synthesized CTO and to achieve its single phase. X‐ray absorption near‐edge structure studies at Co K and Te L edges reveal mixed oxidation states (Co^2+/3+) of Co and hexavalent Te, respectively. Charge imbalance due to mixed valence Co ions has been attributed to cations vacancies. Enhanced multiferroic properties, such as effective magnetic moment, spin phonon coupling, etc., have been attributed to the aforementioned observations in grown ceramic CTO via proposed synthesis route.     

Spin canting in a novel (3,4)-connected mixed-valence cobalt coordination polymer based on oxalates and [Co(Hbiim)3] (H2biim = 2,2′-biimidazole) building blocks

Hydrothermal treatment of cobalt chloride, 2,2′-biimidazole (H₂biim), oxalate acid and NaOH at 160 °C for five days produced a three-dimensional mixed-valence metal-organic framework [Co^III(Hbiim)₃]₂[Co^II₃(ox)₃]·4H₂O (1). Compound 1 exhibits a 3D network with tri-nodal (3-c)₂(4-c)₃ topology, in which [Co^III(Hbiim)₃] building blocks as 3-connected nodes, and Co^II ions as 4-connected nodes. The magnetic measurements reveal that compound 1 exhibits a spin canting antiferromagnetic coupling between adjacent Co^II ions.     

Mechanosynthesis of the multiferroic cubic spinel Co2MnO4: Influence of the calcination temperature

Multiferroic materials showing magnetoelectric coupling are required in various technological applications. Many synthetical approaches can be used to improve the magnetic and/or electrical properties, in particular when the materials exhibit cationic valence fluctuations, as in the Co₂MnO₄ cubic spinel. In this compound, Co and Mn ions are in competition at the tetrahedral and octahedral positions, depending on their various oxidation states. The Co₂MnO₄ was prepared following two techniques: by a soft chemical route based on a modified polymer precursor method, and by a mechanoactivation route. Both approaches yield polycrystalline powders, but their crystallites sizes and particles morphologies differ as a function of the calcination conditions. The magnetic characterization (ZFC/FC cycles, ordering temperatures, ferromagnetic coercive fields and saturation magnetizations) showed that the synthesis procedure influenced the physical properties of Co₂MnO₄ mainly through the size of the magnetic domains, which play an important role on the magnetic interactions between the Co/Mn cations.