Single-phase Multiferroics Research Articles

Improved Ferroelectric and Magnetic Properties of Bismuth Ferrite-Based Ceramics by Introduction of Non-Isovalent Ions and Grain Engineering

Single-phase multiferroics exhibiting ferroelectricity and ferromagnetism are considered pivotal for advancing next-generation multistate memories, spintronic devices, sensors, and logic devices. In this study, the magnetic and electric characteristics of bismuth ferrite (BiFeO3) ceramics were enhanced through compositional design and grain engineering. BiFeO3 ceramic was co-substituted by neodymium (Nd) and niobium (Nb), two non-isovalent elements, via the spark plasma sintering process using phase-pure powder prepared via sol-gel as the precursor. The symmetry of the sintered Nd–Nb co-doped samples changed from R3c to Pnma, accompanied by a decrease in the loss tangent, grain size, and leakage current density. The reduction in the leakage current density of the co-doped samples was ~three orders of magnitude. Moreover, ferroelectric, dielectric, and magnetic properties were substantially improved. The remanent polarization and magnetization values of the optimized Nd–Nb co-doped BiFeO3 sample were 3.12 μC cm−2 and 0.15 emu g−1, respectively. The multiferroic properties were enhanced based on multiple factors such as structural distortion caused by co-doping, grain size reduction, suppression of defect charges via donor doping, space-modulated spin structure disruption, and an increase in magnetic ions. The synergistic approach of composition design and grain engineering sets a paradigm for the advancement of multiferroic materials.

Direct magnetoelectric coupling in Pr doping Bi6Ti3Fe2O18 relaxor ferroics

Single-phase multiferroics are fractional and rarely meet at room temperature. Direct magnetoelectric coupling in relaxor ferroic phase was observed in Bi6−xPrxTi3Fe2O18 (x = 0.0, 0.3, 0.6, 0.9, and 1.2) films, where the chemical disorder doping-induced effective internal pressure played a key role. It is analytically formulated from the phase-structure shift, ferroelectric domain, and origin of the magnetic order. The strip magnetic domains are broken into a dotted domain structure following a quantitatively increase in lattice stress. A Monte Carlo simulation including stress energy items is used to unveil the hitherto unexplored coupling mechanism by tuning the symmetric exchange restriction of Fe3+–O–Fe3+. Moreover, the observation of coefficient 78.8 mV/cm·Oe at room temperature is intriguing for potential application.

A first-principles study on structural stability and magnetoelectric coupling of two-dimensional BaTiO3 ultrathin film with Cr and Cu substituting Ti site

A study on Jahn–Teller distortion reveals that the configuration with Ti-substitution is more stable than that in the case of Ba-replacement. However, magnetoelectric coupling is weak as no spontaneous polarization is formed in the doped unit cell. Taking the atomic radius, low price, and electronegativity into account, Cu was selected to replace Ti together with Cr. Formation energy and phonon spectrum show structural stability. The spontaneous polarization was calculated to be 0.110, 0.114, and 0.247 and 8.078, 0.288, and 0.255 μC/cm2, respectively, in the Cr- and Cu-doped unit cell, corresponding to the directions [100], [010], and [001]. With the application of electric fields, the total magnetic moment was generally enhanced, which resulted in a strong magnetoelectric coupling. In addition, the corresponding coefficient is more than 10 V/cmOe, indicating that the modified BaTiO3 may be a good candidate for single-phase multiferroics. Clearly, co-doping with nonferromagnetic and nonmagnetic elements increases the diversity of new multiferroics.

Enhanced multiferroic properties of NZCFO-BNFSO composites: Synthesis, characterization, and performance analysis

The structural and multiferroic properties of xNi0.24Zn0.58Cu0.18Fe2O4(NZCFO)-(1-x)Bi0.9Nd0.1Fe0.95 Sc0.05O3(BNFSO) are explored in this paper. Bi2O3 additives significantly lower the sintering temperature of the composites. The XRD analysis validates the coexistence of hexagonal perovskite BNFSO and spinel NZCFO phases. The FESEM images illustrate an almost homogeneous amalgamation of the BNFSO and NZCFO grains. The real part of initial permeability and the relative quality factor increases with NZCFO contents in the composites. The maximum permeability is observed for the composite with 80 % ferrite content. The ferroelectric BNFSO exhibits antiferromagnetic behavior and with the increase in NZCFO the saturation magnetization increases significantly. The dielectric constant confirms typical dielectric dispersion at low frequencies because of Maxwell–Wagner space charge polarization. The P-E hysteresis measurement reveals that the composite with 40 % ferrite content exhibits the highest loop area and hence a large energy storage capacity. Incorporating BNFSO and NZCFO into the composite boosts the multiferroic properties, which might be a suitable alternative to single-phase multiferroics.

Robust Ferrimagnetism and Ferroelectricity in 2D ɛ-Fe2O3 Semiconductor with Ultrahigh Ordering Temperature.

2D single-phase multiferroic materials with the coexistence of electric and spin polarization offer a tantalizing potential for high-density multilevel data storage. One of the current limitations for application is the scarcity of the materials, especially those combine ferromagnetism and ferroelectricity at high temperatures. Here, robust ferrimagnetism and ferroelectricity in 2D ɛ-Fe2O3 samples with both single-crystalline and polycrystalline form are demonstrated. Interestingly, the polycrystalline nanosheets also exhibit easily switchable ferroelectric polarizations comparable to that of single crystals. The existence of grain boundary does not hinder the switching and retention of ferroelectric polarization. Furthermore, the ɛ-Fe2O3 nanosheets show ferrimagnetic and ferroelectric Curie temperatures up to 800K, which reaches record highs in 2D single-phase multiferroic materials. This work provides important progress in the exploration of 2D high-temperature single-phase multiferroics for potentially compact high-temperature information nanodevices.

Optimization of noncollinear magnetic ordering temperature in Y-type hexaferrite by machine learning

Searching the optimal doping compositions of the Y-type hexaferrite Ba2Mg2Fe12O22 remains a long-standing challenge for enhanced non-collinear magnetic transition temperature (TNC). Instead of the conventional trial-and-error approach, the composition-property descriptor is established via a data driven machine learning method named sure independence screening and sparsifying operator. Based on the chosen efficient and physically interpretable descriptor, a series of Y-type hexaferrite compositions are predicted to hold high TNC, among which the BaSrMg0.28Co1.72Fe10Al2O22 is then experimentally validated. Test results indicate that, under appropriate external magnetic field conditions, the TNC of this composition reaches up to 568 K, and its magnetic transition temperature is also elevated to 735 K. This work offers a machine learning-based route to develop room temperature single phase multiferroics for device applications.

Room-temperature giant magnetotranstance effect in Y-type hexaferrite Ba0.8Sr1.2Co2Fe11.1−xAl0.9CrxO22 (x ≤ 0.4)

We have investigated the magnetoelectric effect of a series of Y-type hexaferrite Ba0.8Sr1.2Co2Fe11.1−xAl0.9CrxO22 (x ≤ 0.4) at room temperature. Although the magnetoelectric voltage coefficient αE of these multiferroic hexaferrites is not high, it changes rapidly with an applied DC magnetic field, a phenomenon known as the giant magnetotranstance (GMT) effect. It is found that the GMT effect is enhanced with increasing content of Cr and reaches the maximum for x = 0.2. Specifically, the magnetotranstance ratio in the x = 0.2 sample is as high as −96% at 2000 Oe and −84% at 500 Oe. Further addition of Cr content causes a decay of the GMT effect. This kind of room-temperature GMT effect in Y-type hexaferrites opens up a route toward practical applications for the single-phase multiferroics.

Rotational magnetoelectric switching in orthorhombic multiferroics

Controlling the direction of ferromagnetism and antiferromagnetism by an electric field in single-phase multiferroics will open the door to the next generation of devices for spintronics and electronics. The typical magnetoelectric coupling such as the linear magnetoelectric effect is very weak in type-I multiferroics and therefore the magnetoelectric switching is rarely achieved. Here, using first-principles simulations, we propose a magnetoelectric switching mechanism to achieve such highly desired control in orthorhombic multiferroics. One class of two-dimensional proper multiferroics (CrX2Se3 and MnX2Te3, X = Sn, Ge) and perovskite multiferroics (EuTiO3 and BiFeO3/LaFeO3 superlattice) are taken as examples to show the mechanism. In the ferroelectric switching process, the proper polarization rotates its direction by 180° and keeps its magnitude almost unchanged, the ferromagnetic or antiferromagnetic vector is rotationally switched by 180° following the rotation of ferroelectric polarization. This rotational magnetoelectric switching results from in-plane structural anisotropy and magnetic anisotropy, and the process of switching is governed by cosine functions from the phenomenological Landau-type models. This study addresses the challenge of magnetoelectric switching in type-I multiferroics by proposing a general magnetoelectric switching mechanism.

A new class of single-phase multiferroics: Bismuth-based layered supercell oxide thin films—Current progress and future perspectives

Multiferroic materials, where ferroelectric and magnetic orders coexist, have ignited substantial research interest due to the achievable manipulation of magnetic orders using external electric fields, a feature that has garnered serious interest for memory storage applications. Nonetheless, naturally occurring single-phase multiferroic materials are scarce, thus constraining options for practical use. Over the last decade, bismuth-based layered supercell (LSC) oxides have emerged as novel candidates for multiferroics, catalyzing extensive investigations in this domain. Additionally, these LSC systems are known for their anisotropic structures and optical properties, making them promising for application in optics such as polarizers, beam splitters, and modulators. This thorough review explores the development and current advancements in multiferroic bismuth-based LSC materials. It covers the diverse nature of LSCs, detailing their microstructure, properties, and the mechanics of self-assembly formation. It also highlights the remarkable multifunctional characteristics of LSC-based nanocomposites, with a particular focus on their applications in electronics and optics. Moreover, this review examines the significant potential of LSCs in practical applications, particularly through their integration onto silicon and flexible substrates via heteroepitaxy and film transfer techniques. Finally, it offers insights into potential future research avenues and the broader implications of these versatile LSC materials.

First-Principles Study on Evolution of Magnetic Domain in Two-Dimensional BaTiO3 Ultrathin Film Doped with Co under Electric Field.

The magnetization mechanism of Co-doped BaTiO3 ultrathin films is a subject of debate, which results in difficulties with the design of new multiferroics based on BaTiO3 matrixes. With the aid of a first-principles approach, it was observed that when the interstitial site and Ti vacancy were filled with Co, the configuration behaved in a nonmagnetic manner, indicating the significance of the Co content. Moreover, in the case of Co substituting two neighboring Ti atoms, when a direct current field was applied in the [100] direction, the magnetic domains excluding those in the [100], [010], and [001] directions were directed away. Further, the magnetoelectric constant was evaluated at ~449.3 mV/cmOe, showing strong magnetoelectric coupling at room temperature. Clearly, our study indicates that strict control of Ba, Ti, O, and Co stoichiometry can induce an electric and magnetic field conversion in two-dimensional BaTiO3 and may provide a new candidate for single-phase multiferroics for application in next-generation multifunctional devices.

Non-volatile voltage-controlled magnetization in single-phase multiferroic ceramics at room temperature

Single-phase multiferroics (MFs) exhibiting ferroelectricity and ferromagnetism and the strong magnetoelectric (ME) coupling effect at room temperature are seen as key to the development of the next-generation of spintronic devices, multi-state memories, logic devices and sensors. Herein, the single-tetragonal phase (1–x) (Sr0·3Bi0·35Na0·329Li0.021)TiO3-xBiFeO3 (x = 0.2 or 0.4) system was designed to study the intrinsic ME coupling effect at room temperature and high frequencies. The polarization arises from the cooperative displacement of both Fe3+ and Ti4+ relative to the oxygen sublattice in the tetragonally distorted perovskite structure, and the magnetization stems from indirect exchange magnetic interaction between adjacent iron ions. A switchable voltage-controlled magnetization was confirmed by a change of the coercive magnetic field, Hc, and remnant magnetization, Mr, in the x = 0.4 component subjected to an external electric field at room temperature and was possibly attributed to a strain-mediated ME coupling effect. In addition, resonance behaviours of the complex magnetic permeability and complex dielectric permittivity in the GHz band indicate that this ME effect is intrinsic in nature and could broaden the applications of multiferroics to devices operating at microwave frequencies.

Magnetoelectric behaviour of Pb-free Na0.5Bi0.5TiO3-Ni0.5Co0.5Fe2O4 particulate novel ceramic composites

Magnetoelectric (ME) multiferroic composites are more promising candidates for low-power consumption devices, next-generation spintronic devices, and multistate memory devices since they exhibit significantly higher Magnetoelectric interaction over single-phase multiferroics. In this regard magnetic behaviour, dielectric, and magnetoelectric characteristics of a novel Pb-free (1-x) Na0.5Bi0.5TiO3-(x) Ni0.5Co0.5Fe2O4, (x = 0, 0.2, 0.4, 0.6, 0.8 & 1) particulate composites were explored. Solid-state synthesis was adopted to prepare the single-phase Na0.5Bi0.5TiO3 (NBT), Ni0.5Co0.5Fe2O4 (NCFO), and their composites. The presence of rhombohedral NBT and cubic inverse spinel NCFO in the composites were confirmed with X-ray diffraction (XRD) patterns. Microstrain (ε) induced in the prepared samples was estimated by using the Williamson-Hall (W-H) method. The piezoelectric NBT phase shows the tensile strain and the ferromagnetic NCFO shows the comprehensive strain. Among all the composites 0.8NBT-0.2NCFO shows a higher strain value of 0.012%, and the decrement in the strain values was observed upon increases in ferrite concentration. Backscattered scanning electron microscope (BS-SEM) images revealed the existence of highly dense uniformly distributed elements and Energy dispersive spectroscopy (EDS) confirmed the existing elements in the composites. UV–vis absorbance spectra disclosed a rise in energy gap values from 1.14 eV to 3.0 eV with increasing NBT percentage. Variations of dielectric permittivity and dielectric loss with respect to AC frequency were studied at room temperature (RT), and the 0.2NBT-0.8NCFO sample shows a high dielectric permittivity of 8500 at ∼100Hz. M − H (Magnetization-Magnetic field) hysteresis loops demonstrate the pure ferrite phase has a coercive field (Hc) = 578 Oe, remnant magnetization (Mr) = 21.43 emu/g and saturation magnetization (Ms) = 71.29 emu/g. The Ms and Mr values in the composites are enhanced with increasing ferrite percentage. Studies on ME behaviour of (1-x) NBT-(x) NCFO, (x = 0.2,0.4,0.6 & 0.8) show the coupling effect between both the phases at room temperature and the highest coupling coefficient value 3.16mV/Cm. Oe was observed for the 0.8NBT-0.2NCFO further the reasons and mechanisms are discussed.

Structural analysis, ferroic properties with enhanced magnetoelectric coupling in novel (1-x)BiFeO3-(x)GdFeO3 nanocomposites

Multiferroic composites exhibit substantially greater magnetoelectric interaction among order variables as compared to single-phase multiferroics, making them particularly attractive for futuristic multi-state RAM and spintronic gadgets. The multiferroic nanocomposites (1-x)BiFeO3-xGdFeO3 (x = 0.05, 0.10, 0.15, & 0.20) are synthesized by using solid-state route. The crystallographic and profile parameters are extracted from the dual-phase refinement of the rhombohedral (R3c) and orthorhombic (Pbnm) crystal structures. The optimized density, crystallite size and homogenous microstructure may be responsible for the improved dielectric and ferroic properties. TEM images reveal a reduction in the particle size (67–59 nm) upon GdFeO3 (GFO) loading. The HRTEM images unravel the interplanar spacing and associated Bragg planes, while the SAED rings validate the polycrystalline features of the samples. The high Curie temperature (Tc ̴ 643 °C) with enhanced specific heat (Cp ̴ 29.5 J/g°C) in x= 0.10 sample ensures its stable operation, efficient heat dissipation, minimal overheating, and greater thermal stability for reliable performance in demanding conditions. The surface and finite-size effects enhanced the magnetization (MS=1.04emu/g) in nanostructured ferromagnetic nanocomposite, making it a promising candidate for high-density magnetic storage devices and sensors. The high polarization (Pmax=8.39µC/cm2) and ME-coupling coefficient (αE=0.16mVcm−1Oe−1) observed in the most dense nanocomposite make it a potential candidate for magnetoelectric applications.

Stabilization of room temperature spin driven ferroelectric phases in Ni2+ doped Y- type BaSrCo2-xNixFe11AlO22

Type II multiferroics possess the highest magnetoelectric coupling among single phase multiferroics due to the relation between the spin order and the ferroelectric polarization. However, these materials tend to exhibit magnetoelectric coupling at temperatures lower than room temperature which limits their applications. In recent years the Y-type hexaferrites have been studied due to the tunability of its magnetic structure which enables to stabilize its magnetoelectric phases up to room temperature. In the present work, the effects of Ni2+ doping in BaSrCo2-xNixFe11AlO22, with x varying from 0 to 1.5, Δx = 0.5, are studied. Temperature scan of the magnetic properties and hysteresis loops confirm that Ni2+ concentration reduces magnetization and, stabilizes the spin driven ferroelectric phases. Magnetic behavior and magnetodielectric measurements allow identifying that the samples with x of 1.0 and 1.5 mol of Ni2+ exhibit room temperature spin driven electric polarization. In addition, XRD Rietveld refinement shows a reduction of the a/b and c cell parameters while the T-S boundary through the Fe8–O9 bond is stretched, which may be attributed to the stability of the spin driven ferroelectric phases.

Unravelling the linear and biquadratic magnetoelectric coupling in Ba0.95Sn0.05Ti0.95 Ga0.05O3 – CoFe1.8Ga0.2O4 particulate multiferroic composites

Since multiferroic composites have substantially stronger magnetoelectric coupling between the order parameters than the single-phase multiferroics, they are more interesting prospects for next-generation multi-state memories and spintronic devices. In light of this, the current work outlines the fabrication of ferroelectric perovskite BaTiO3 and ferrimagnetic spinel CoFe2O4-based particulate multiferroic composites with general formulla (1-x) Ba0.95Sn0.05Ti0.95 Ga0.05O3 – x CoFe1.8Ga0.2O4 (x = 0.04, 0.08 & 0.12). At room temperature, the gallium and tin doping enhanced the dielectric properties of BaTiO3 (ε ´ =9200), and particulate composite (ε ´ =6000) with 12% of CoFe1.8Ga0.2O4 phase. In the same composite, the reduced leakage current density of 3.4 μA/cm2 and improved magnetoelectric properties, with linear and quardatic coupling coefficients of 3.41 mVcm−1Oe−1 and 3.4 × 10−4 mVcm−1Oe−2 were achieved. In composites with a larger magnetic phase, the decrease in cell volume and increased tetragonality produces the compressive strain, that in turn improves the ME coupling. Diffused ferroelectric transitions were ascertained by using the Curie- Weiss Law. Enhanced dielectric properties are linked to decrease in hopping and bond lengths, caused by the incorporation of non-magnetic Ga3+ ions in the CoFe2O4 lattice. A reduction in leakage current density was observed on Sn doping. The calculated square-ness ratios reveal an ordered multi-domain structure. Improved dielectric response along with linear and biquadratic coupling makes these Sn and Ga doped BaTiO3-CoFe2O4 particulate composites as potential candidates for magnetoelectric devices.

Great multiferroic properties in BiFeO3/BaTiO3 system with composite-like structure

Multiferroic materials have attracted significant research attention due to their technological potential for applications as multifunctional devices. The scarcity of single-phase multiferroics and their low inherent coupling between multiferroic order parameters above room temperature pose a challenge to their further applications. We propose a 3BiFeO3/7BaTiO3 perovskite–perovskite composite that combines ferroelectricity and ferromagnetism. We demonstrate that the sintering temperature can tailor the ferroelectricity and ferromagnetism of the composites. The multiferroicity can be achieved at a low sintering temperature in the composite-like structure ceramics, and its multiferroic properties, especially the ferromagnetism, are superior to those of solid solutions. We also investigate the dynamic evolution of multiferroicity with sintering temperature. We adopt a nano–micro strategy to construct a composite-like microstructure, which results in optimized ferroelectric (1.62 μC cm−2) and ferromagnetic (0.16 emu/g) characteristics at a sintering temperature of 750 °C. We also found experimental evidence of the competition between antiferromagnetic and ferromagnetic interactions in the transition metal cation sublattice. Multiferroic BiFeO3/BaTiO3 composites with combined ferroelectric and ferromagnetic properties have significant potential for various applications.

Grain size and piezoelectric effect on magnetoelectric coupling in BFO/PZT perovskite-perovskite composites

Magnetoelectric multiferroics are provoking much research activity for their potential applications in novel multifunctional devices. Compared with single-phase multiferroics, magnetoelectric composites have competitive advantages. The magnetoelectric coupling of composites is heavily influenced by composition and grain size. We prepared BFO/PZT composites with separate phases via the solid-state sintering method. We show that equal molar ratio composition has a better magnetoelectric coupling response than other compositions. The composites with nano bismuth ferrite have better magnetoelectric coupling performance, and these with both nano grain sizes present the highest magnetoelectric voltage coefficients (αE = 16.9 mV cm−1 Oe−1). The strain-mediated mechanism was confirmed via a comparison between strain response and polarization of nano/micro type composites with the composition of 3:7. We found that the magnetoelectric voltage coefficient αE positively correlates with strain response instead of polarization in BFO/PZT composites, which provides experimental evidence for the strain-mediated ME composite theory.

Magnetoelectric Coupling in Room Temperature Multiferroic Ba2EuFeNb4O15/BaFe12O19 Epitaxial Heterostructures Grown by Laser Ablation.

Multiferroic thin films are a promising class of multifunctional materials, since they allow the integration of multiple functionalities within a single device. In order to overcome the scarcity of single phase multiferroics, it is crucial to develop novel multiferroic heterostructures, combining good ferroelectric and ferromagnetic properties as well as a strong coupling between them. For this purpose, Ba2EuFeNb4O15/BaFe12O19 multiferroic magnetoelectric bilayers have been epitaxially grown on niobium doped SrTiO3 (100) single crystal substrates by pulsed laser deposition. The simultaneous presence of both ferroelectric and magnetic properties-due, respectively, to the Ba2EuFeNb4O15 and BaFe12O19 components-was demonstrated at room temperature, attesting the multiferroic nature of the heterostructure. More interestingly, a strong magnetoelectric coupling was demonstrated (i) by manipulating the ferroelectric properties via an external magnetic field, and conversely, (ii) by tuning the magnetic properties via an external electric field. This strong magnetoelectric coupling shows the high interdependence of both ferroic orders in the Ba2EuFeNb4O15/BaFe12O19 heterostructure, mediated by elastic (epitaxial) strain at the interfaces.

Gradient Strain-Induced Room-Temperature Ferroelectricity in Magnetic Double-Perovskite Superlattices.

Single-phase multiferroics suffer from a fundamental contradiction between polarity and magnetism in d0 electronic configuration, motivating studies of unconventional ferroelectricity in magnetic oxides. However, low critical temperature and polarization still need to be overcome. Here, it is reported that the switchable polarization behavior at room temperature in [(La2 NiMnO6 )/(La2 CoMnO6 )]n double-perovskite magnetic superlattice films is achieved by engineering a microstructure with gradient strains, and the ferromagnetic Curie temperature did not show a rapid decrease. The synergy of gradient strains and superlattice components plays a decisive role in inducing ferroelectricity via the tilting or rotation of various oxygen octahedra. Such distortion responses to gradient strains are accompanied by slight magnetic fluctuations, maximizing the preservation of the initial magnetic exchange interactions, which alleviates the contradiction of multiferroic coexistence to a certain extent. This work confirms the room-temperature ferroelectricity in double-perovskite superlattices and provides a preferred strategy for confronting the difficulty of multiferroic coexistence in single-phase materials.

Significantly Enhanced Room-Temperature Ferromagnetism in Multiferroic EuFeO3-δ Thin Films.

Regulating the magnetic properties of multiferroics lays the foundation for their prospective application in spintronic devices. Single-phase multiferroics, such as rare-earth ferrites, are promising candidates; however, they typically exhibit weak magnetism at room temperature (RT). Here, we significantly boosted the RT ferromagnetism of a representative ferrite, EuFeO3, by oxygen defect engineering. Polarized neutron reflectometry and magnetometry measurements reveal that saturation magnetization reaches 0.04 μB/Fe, which is approximately 5 times higher than its bulk phase. Combining the annular bright-field images with theoretical assessment, we unravel the underlying mechanism for magnetic enhancement, in which the decrease in Fe-O-Fe bond angles caused by oxygen vacancies (VO) strengthens magnetic interactions and tilts Fe spins. Furthermore, the internal relationship between magnetism and VO was established by illustrating how the magnetic structure and magnitude change with VO configuration and concentration. Our strategy for regulating magnetic properties can be applied to numerous functional oxide materials.