Magnetoelectric response and tunneling magnetoresistance behavior of flexible P(VDF-H FP)/Cobalt ferrite nanofiber composite films

Fabrication of magnetoelectric (ME) polymer composite films by embedding ferromagnetic cobalt ferrite (CoFe₂O₄) nanofibers into electroactive poly(vinylidene fluoride–hexafluoropropylene) (P(VDF-HFP)) matrix is reported. Single-phase CoFe₂O₄ nanofibers made of cubic spinel nano crystallites are synthesized by using electro-spinning method, whereas the solution-casting technique is adapted to prepare flexible polymer composite films. The influence of CoFe₂O₄ nanofiber on structural, functional, magnetic, ferroelectric, and magnetoresistance properties of the composite films is investigated. The cross-coupling between ferroelectric and ferromagnetic orderings is ensured, by the variations of ferroelectric response at different magnetic fields. These magnetoelectric films are found to exhibit a negative tunneling magnetoresistance (TMR) effect with maximum TMR% of 28 for the film with 20 wt% of CoFe₂O₄ loading. The dielectric constant and electrical energy storage density of the films are increased with the addition of CoFe₂O₄ nanofiber. The ME films exhibiting TMR and high energy density can be the potential candidates for multifunctional device applications such as memory and spintronics devices, magnetic sensor, and bio-sensor.     

Dielectric,ferroelectric and magnetoelectric properties of in-situ synthesized CoFe2O4/BaTiO3 composite ceramics

Magnetoelectric composite materials have attracted more and more attention because of their coupling of ferroelectricity and ferromagnetism. It is a hotspot to realize the combination of ferromagnetic phase and ferroelectric phase. In this work, we used a new strategy to prepare CoFe₂O₄/BaTiO₃ composite ceramics: firstly, porous ferromagnetic CoFe₂O₄ phase was prepared by annealing of MOFs (metal organic frameworks) precursor Fe₃[Co(CN)₆]₂. And then, the ferroelectric BaTiO₃ phase in-situ grew in the pores of CoFe₂O₄ by a hydrothermal method. In the end, the CoFe₂O₄/BaTiO₃ composite ceramics sintered at different temperatures have been synthesized. The effects of sintering temperature on the structure, dielectric and ferroelectric properties have also been studied. Because the crystallinity and density increase with the increase of sintering temperature, the composite ceramic sintered at 1200 °C shows the best dielectric properties. It is found that sintering temperature has little effect on the ferroelectric and magnetic properties of ceramics. Taking the CoFe₂O₄/BaTiO₃ composite ceramic sintered at 1200 °C as an example, derived from the interaction between the ferromagnetic CoFe₂O₄ phase and ferroelectric BaTiO₃ phase, the applied magnetic field lead to the reduction of P_r and E_c.     

Microstructural, electrical and magnetic properties of multiferroic CoFe2O4/0.68Pb(Mg1/3Nb2/3)O3-0.32PbTiO3 nanocomposite thin films

Bilayered CoFe₂O₄/0.68Pb(Mg_1/3Nb_2/3)O₃-0.32PbTiO₃ nanocomposite films are successfully prepared on Pt/Ti/SiO₂/Si substrate via simple sol-gel process. X-ray diffraction result reveals that there exists no chemical reaction or phase diffusion between the CoFe₂O₄ and 0.68Pb(Mg_1/3Nb_2/3)O₃-0.32PbTiO₃ phases. The microstructure is characterized by scanning/transmission electron microscopy (STEM). The composite thin films exhibit both strong ferroelectric and ferromagnetic responses at room temperature. The maximal magnetoelectric coupling coefficient of the nanocomposite films reaches up to 25 mV/cm Oe, occurs at a lower bias magnetic field (H_dc) of 550 Oe.     

Sonochemical synthesis of CoFe2O4 nanoparticles and their application in magnetic polystyrene nanocomposites

CoFe₂O₄ (CoFe) nanoparticles were synthesized via a facile surfactant-free sonochemical reaction. For preparation of magnetic polymeric films, CoFe₂O₄ nanoparticles were added to polystyrene (PS). Nanoparticles were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Magnetic properties of the samples were investigated using an alternating gradient force magnetometer (AGFM). CoFe₂O₄ nanoparticles exhibit a ferromagnetic behaviour with a saturation magnetization of 62 emu/g and a coercivity of 640 Oe at room temperature. By preparing magnetic films the coercivity is increased. The coercivity of PS/CoFe₂O₄ (10%) nanocomposites is higher than that obtained for PS/CoFe₂O₄ (30%).     

Crystallization Behavior and Multiferroic Properties of Bi3.15Nd0.85Ti3O12/CoFe2O4 Powders Synthesized by Sol–Gel Method

Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT)/CoFe₂O₄ (CFO) composite ceramic powders with embedded structures were successfully prepared by sol–gel processing. Their crystallization behavior was characterized by XRD, DTA, FT‐IR, and HRTEM. The magnetic and ferroelectric phases of these composite ceramic powders segregate during calcination. The CFO phase forms easily at ~300°C, thereafter the BNdT matrix phase nucleates with grain growth at the CFO grain boundaries at temperatures >500°C. The CFO phase acts as a heterogeneous nucleation point for formation of the ferroelectric BNdT phase. Furthermore, the 0.5BNdT–0.5CFO composite ceramic powders go through a ferroelectric–paraelectric phase transition at 259°C, and the magnetic CFO nanoparticles (50–100 nm, under calcination at 600°C) embedded in the ferroelectric matrix, show superior magnetic behavior (M_max = 16.50 emu/g), comparable to pure CFO nanoparticles.     

Magnetoelectricity in CoFe2O4 nanocrystal-P(VDF-HFP) thin films

Transition metal ferrites such as CoFe₂O₄, possessing a large magnetostriction coefficient and high Curie temperature (T_c > 600 K), are excellent candidates for creating magnetic order at the nanoscale and provide a pathway to the fabrication of uniform particle-matrix films with optimized potential for magnetoelectric coupling. Here, a series of 0–3 type nanocomposite thin films composed of ferrimagnetic cobalt ferrite nanocrystals (8 to 18 nm) and a ferroelectric/piezoelectric polymer poly(vinylidene fluoride-co-hexafluoropropene), P(VDF-HFP), were prepared by multiple spin coating and cast coating over a thickness range of 200 nm to 1.6 μm. We describe the synthesis and structural characterization of the nanocrystals and composite films by XRD, TEM, HRTEM, STEM, and SEM, as well as dielectric and magnetic properties, in order to identify evidence of cooperative interactions between the two phases. The CoFe₂O₄ polymer nanocomposite thin films exhibit composition-dependent effective permittivity, loss tangent, and specific saturation magnetization (M_s). An enhancement of the effective permittivity and saturation magnetization of the CoFe₂O₄-P(VDF-HFP) films was observed and directly compared with CoFe₂O₄-polyvinylpyrrolidone, a non-ferroelectric polymer-based nanocomposite prepared by the same method. The comparison provided evidence for the observation of a magnetoelectric effect in the case of CoFe₂O₄-P(VDF-HFP), attributed to a magnetostrictive/piezoelectric interaction. An enhancement of M_s up to +20.7% was observed at room temperature in the case of the 10 wt.% CoFe₂O₄-P(VDF-HFP) sample.     

Microstructure and multiferroic properties of BaTiO3/CoFe2O4 films on Al2O3/Pt substrates fabricated by electrophoretic deposition

BaTiO₃/CoFe₂O₄ bilayer films on high temperature resistant Al₂O₃/Pt substrates were fabricated using the electrophoretic deposition (EPD) method. Powder synthesis, suspension preparation and kinetics of deposition were investigated in detail. Two different sintering temperatures were tested and the resultant microstructure and properties of ceramic films were investigated. The composite films sintered at a temperature of 1200 °C/2 h yielded optimal microstructures and properties. The obtained bilayer films had a dense structure with no phase diffusion or passive layer. Besides to ferroelectric and magnetic properties, magnetoelectric (ME) coupling properties were also confirmed by the magnetic anisotropy and magnetic field induced polarization investigation. The composite films showed a increased P_s from 16.2 to 16.85 μC/cm² with variations ΔP_s of 4% when the magnetic field was applied in parallel direction and a decreased P_s from 16.2 to 14.9 μC/cm² with variations ΔP_s of ?8% when a normal direction field was applied.     

Lead-free BLTO/NMFO magnetoelectric composite films prepared by the sol-gel method

The lead-free ferroelectric films of Bi_4?xLa_xTi₃O₁₂(BLTO) and ferromagnetic films of Ni_1?xMn_xFe₂O₄(NMFO) were prepared on Pt/Ti/SiO₂/Si substrate by means of the sol-gel and spin-coating method. The lead-free magnetoelectric composite films with the structure of Bi_3.4La_0.6Ti₃O₁₂/Ni_0.7Mn_0.3Fe₂O₄/substrate (BN) and Ni_0.7Mn_0.3Fe₂O₄/Bi_3.4La_0.6Ti₃O₁₂/ substrate (NB) were also deposited on Pt/Ti/SiO₂/Si substrate. The X-ray diffraction results show that two composite films possess BLTO and NMFO phases without any intermediate phase. The SEM images show that two composite films exhibit layered structure, clear interface and no transition layer between BLTO and NMFO films. Two composite films exhibit both good ferromagnetic and ferroelectric properties, as well as magnetoelectric coupling effect. The deposition sequence of ferroelectric and ferromagnetic films in the composite films has significant influence on the ferroelectric, ferromagnetic and magnetoelectric coupling properties of the composite films. The values of magnetoelectric voltage coefficient of the BN composite films are higher than those of the NB composite films at any fixed H_bias.     

Magnetoelectric coupling effect of Ga0.8Fe1.2O3/Bi0.5(Na0.85K0.15)0.5TiO3 multiferroic composite films

Lead-free Ga_0.8Fe_1.2O₃/Bi_0.5(K_0.15Na_0.85)_0.5TiO₃ (GFO/BKNT) bilayer multiferroic composite films were fabricated on Pt(100)/Ti/SiO₂/Si substrates via sol-gel methods. The microstructure, domain structure, ferroelectric, piezoelectric, magnetic properties as well as magnetoelectric coupling effect were investigated for the composite films at room temperature. Well-defined interfaces between GFO and BKNT layers and clear electric domain structures are observed. A strong magentoelectric effect is obtained with magnetoelectric voltage coefficient of α_E=30.89 mV/cm Oe, which is attributed to excellent ferroelectric, piezoelectric, and magnetic properties, as well as the coupling interaction between ferromagnetic GFO and ferroelectric BKNT phases for lead-free bilayer composite films. Besides, GFO and BKNT demonstrate the similar perovskite structure with well lattice matching, which endows the outstanding coupling and fascinating magnetoelectric properties. The present work opens up the opportunity of lead-free magnetoelectric composite films for both further fundamental studies and practical device applications such as sensors, transducers and multistate memories.     

Magnetodielectric coupling in barium titanate–cobalt ferrite composites obtained via thermally-assisted high-energy ball milling

In this work, a magnetodielectric coupling observed in barium titanate–cobalt ferrite composites synthesized using high-energy ball milling assisted via a thermal treatment is discussed. Vibrating sample magnetometry and dielectric spectroscopy showed that multiferroic composites possess both ferromagnetic and dielectric behaviors inherited from the parent ferromagnetic cobalt ferrite and ferroelectric barium titanate phases. The magnetocapacitance (up to 35%) recorded for x = 0.3, (1-x)BaTiO₃–xCoFe₂O₄, can be attributed to the spin-dependent filtering mechanism. The composite with the aforementioned composition exhibited a homogeneous matrix–particle composite microstructure, which was achieved via high-energy ball milling during the mixing stage.     

Improved ferroelectric properties in KBiFe2O5-polymer composite film

Composite films of KBiFe₂O₅ and PVA were prepared with a varied weight percentage of PVA by spin coating method on platinised silicon wafer. The composite films were characterised for dielectric and ferroelectric properties in comparison to pure KBiFe₂O₅thick film. The frequency dependent permittivity measurement indicated a higher contribution of space charge/interfacial polarization in KBiFe₂O₅ thick film than that in the KBiFe₂O₅ -PVA composite films. The ferroelectric properties in composite films were enhanced due to the reduction in leakage current and they showed well saturated polarization hysteresis loops. The remanent polarization value in KBiFe₂O₅ -PVA composite film (Pr?=?3.7?μC/cm²) was found to be 2.5 times higher than that of the pure KBiFe₂O₅ film (Pr?=?1.45?μC/cm²) and with the increase in PVA percentage, the remanent polarization values also increased. The space charge dominated conduction in pure KBiFe₂O₅ became transformed to field assisted ionic conduction in the KBiFe₂O₅ composite films. The polymeric matrix in KBiFe₂O₅ composites helped in reducing the leakage current of pure KBiFe₂O₅ by four orders of magnitude and further reduced with the increase in the PVA content in the composite. The composite films showed fatigue free polarization even after 10⁸ switching cycles whereas the polarization degradation in KBiFe₂O₅ film was 30% around 10⁸switching cycles.     

Enhanced Room Temperature Multiferroic Properties of (Bi0.95La0.05)(Fe0.97Mn0.03)O3/CoFe2O4 and CoFe2O4/(Bi0.95La0.05)(Fe0.97Mn0.03)O3 Double‐Layered Thin Films

Multiferroic (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/CoFe₂O₄ and CoFe₂O₄/(Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃ double‐layered thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates via a chemical solution deposition method. In both the thin films, superior multiferroic properties were observed at room temperature. However, substantial enhancements in magnetic properties, such as saturated ferromagnetic hysteresis loop with large 2M_r (68.8 emu/cm³) and 2H_c (11.7 kOe), as well as moderate ferroelectric properties, such as 2P_r (58 μC/cm²) with low leakage current density (4 × 10^?9 A/cm² at 100 kV/cm), were observed in the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/CoFe₂O₄ at room temperature. Structural distortion, deformation of [(Fe, Mn)O₆] oxygen octahedra, and superexchange interaction in the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃ are attributed to the enhanced properties.     

Multiferroic and magnetoelectric properties of lead-free Ba0.8Sr0.2Ti0.9Zr0.1O3-Ni0.8Zn0.2Fe2O4 composite films with different deposition sequence

Ba_0.8Sr_0.2Ti_0.9Zr_0.1O₃/Ni_0.8Zn_0.2Fe₂O₄(BN) and Ni_0.8Zn_0.2Fe₂O₄/Ba_0.8Sr_0.2Ti_0.9Zr_0.1O₃ (NB) composite film were deposited on Pt/Ti/SiO₂/Si substrates by the sol-gel method and spin-coating method. The results show that the deposition sequences of the composite films have significant influence on the ferroelectric, ferromagnetic and magnetoelectric properties of the composite films. Two composite films possess not only good ferroelectric and ferromagnetic properties but good magnetoelectric properties as well. The NB composite film has clear interface between the ferroelectric film and ferromagnetic film and possesses greater magnetoelectric coupling effect than the BN composite film under the same H_bias. The maximum value of α_E is 70.14?mV?cm^?1 Oe^?1 was obtained in the NB composite film when H_bias is 638?Oe.     

Exchange-coupled of soft and hard magnetic phases on the interfaces of Fe3C/CoFe2O4 nanocomposites

It is extremely important and challenging to develop exchange-coupled nanomagnets with soft/hard magnetic phase to apply for energy-related devices. Herein, we presented a simple strategy to synthesize the Fe₃C/CoFe₂O₄ nanocomposites by a chemical coprecipitation method, in which effective exchange coupling at hard and soft magnetic interfaces was achieved. The as-synthesized Fe₃C/CoFe₂O₄ nanocomposites show exceptional exchange-coupled effect and enhanced magnetic properties. Moreover, this work provides a new soft magnetic phase and an entirely new attempt for nanomagnets based on soft/hard magnetic exchange coupling.     

Magnetic‐Field‐Induced Dielectric Anomaly and Electric Polarization in Co4Ta2O9

We report magnetic and electric properties of Co₄Ta₂O₉, which is a collinear antiferromagnet with trigonal structure. At zero magnetic fields, no dielectric anomaly and electric polarization are observed in this compound. While, finite dielectric peaks and electric polarization develop under applied magnetic field, and increase with increasing field, showing magnetodielectric and magnetoelectric performance. We ascribe the magnetic‐field‐induced dielectric anomaly and electric polarization in Co₄Ta₂O₉ to spin fluctuation and domain effect.     

Hybrid nanocomposites based on superparamagnetic and ferromagnetic particles: A comparison of their magnetic and dielectric properties

Nanocomposites of magnetic nanoparticles and polymer matrices combine the properties of their components, and as such are good examples of functional nanomaterials with excellent application potential. Against this background, experimental and theoretical studies of such composites are of great interest. In this study we aim to provide insight into the static and dynamic magnetic response, as well as the dielectric response, of magnetic nanocomposites subjected to external magnetic and electric fields. We directly compare the behavior of polyurethane films doped with superparamagnetic Fe₃O₄, and blocked ferromagnetic CoFe₂O₄ nanoparticles. While a reversible, Langevin magnetization curve is observed for Fe₃O₄@PU films, hysteretic magnetic behavior is found in case of CoFe₂O₄@PU films. The hysteresis observed for CoFe₂O₄ nanoparticles can be explained by interactions at the interface between particles and polymer matrix in conjunction with its ferromagnetic nature. The results of dielectric spectroscopy experiments revealed different effects of Fe₃O₄ and CoFe₂O₄ nanoparticles on polymer dynamics.     

Reduced leakage current and improved multiferroic properties of 0.5((1−x)BLPFO-xPZT)-0.5PVDF composite films

0.5((1−x)Bi_0.8La_0.1Pr_0.2FeO₃ (BLPFO)-xPb(Zr_0.52Ti_0.48)O₃ (PZT))-0.5Polyvinylidene difluoride (PVDF) composite films with x variations 0.25, 0.40 and 0.50 were synthesized using two step mixing, followed by hot pressing. The structural, microstructural, dielectric, magnetic, ferroelectric and magnetodielectric properties of composite films have been systematically investigated. The measurement of the dielectric properties at 1 kHz shows that the dielectric loss (tan δ) decreases with increasing the volume fraction of PZT. The value of maximum room temperature ε_r ~78 and low tan δ ~0.061 for 0.5((1−x)BLPFO-xPZT)-0.5PVDF composite film with x=0.50 suggests its usefulness for capacitor applications. For predictions of effective dielectric constant of composite films experimental data were fitted with Lichtenecker model. Among all the composite films, the film with x=0.50 was found to exhibit smallest leakage current density ~7×10⁻⁸ A/cm² and hence improved electrical resistivity. The variation of magnetization with temperature indicates the presence of spin glass behavior along with the ferromagnetic component at 5 K. The value of remnant polarization (2P_r) is found to increase with increase of PZT content in composite films. In the present composite films a significant dependence of dielectric constant on magnetic field has been observed, and highest value of magnetodielectric response of 2.85% is observed for composite film with x=0.50.     

Flexible magnetoelectric PVDF–CoFe2O4 fiber films for self-powered energy harvesters

Integrating the concept of magnetoelectric in the mechanical energy harvesters through the magneto-mechano-electrical (MME) nanogenerators has been explored to realize the self-powered devices. The magnetoelectric interaction enabled the output performance of the MME nanogenerator under magnetic stimulus of the active components of the energy harvesters. In this perspective, we fabricated a flexible biomechanical and MME nanogenerator using PVDF/CoFe₂O₄ fibers composite films. CoFe₂O₄ fibers were synthesized by the electrospinning technique and the process parameters were optimized to achieve uniform and bead-free fibers. The structural and morphological properties were investigated through scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The structural and morphology revealed the fibers calcined at 800 °C with a heating rate of 2 °C/min produced bead-free continuous fibers with a fiber diameter of 210 nm with cubic spinel crystalline structure with a crystallite size of 34 nm. These highly crystalline fibers were used to fabricate PVDF/CoFe₂O₄ fibers composite films. The magnetoelectric behaviour of the films verified through polarization vs. electric field (P-E) loops under magnetic field. The leakage current density and mechanism of the composite films were investigated, and it was discovered that the mechanism was due to Schottky emission. Further the energy harvesting performance of the composite films were estimated where the nanogenerator achieved an output voltage of 13 V under biomechanical tapping force while the MME nanogenerator produced 3.5 V under a low frequency stray magnetic field of 6 Oe with a power density of 28 μW/m².     

Effect of Substrate on Structure and Multiferrocity of (La,Mn) CoSubstituted BiFeO3 Thin Films

In this article, we report the substrate effect on ferroelectric and magnetic properties of epitaxial BiFeO₃‐based thin films at room temperature. (La, Mn) cosubstituted BiFeO₃ (BFOLM) thin films were deposited on differently lattice mismatched single‐crystal substrates to manipulate the strain states in the as‐deposited films. All the films with 30‐nm thick CaRuO₃ bottom electrodes exhibited highly epitaxial growth behavior with a slightly monoclinic distorted lattice structure while their strain states are drastically different as confirmed by X‐ray reciprocal space mapping. These films possessed significantly different macroscopic ferroelectric properties with giant remanent polarization of 101 ± 2, 65 ± 2, and 48 ± 2 μC/cm² for the films grown on SrTiO₃, (La, Sr)(Al, Ta)O₃, and LaAlO₃, respectively. It is found that the room‐temperature magnetic properties are also in accordance with their strain state, having a reciprocal relationship with polarization. For example, the enhanced magnetization is associated with the suppressed polarization and vice versa. The stain tunability of multiferroic properties in BFOLM thin films are presumably ascribed to the polarization rotation and oxygen octahedral tilts.     

Room temperature multiferroic properties of BiFeO3–MnFe2O4 nanocomposites

The novel functionalities of multiferroic magneto-electric nanocomposites have spawned substantial scope for fast-paced memory devices and sensor applications. Following this, herein we report the development of nanocomposites with soft ferromagnetic MnFe₂O₄ and ferroelectric BiFeO₃ to fabricate a system with engineered multiferroic properties. A modified sol-gel route called Pechini method is demonstrated for the preparation of the (1-x) BiFeO₃-x MnFe₂O₄ (x = 10%, 30%, 50%, 70%) nanocomposites. The crystallographic phase, structure, and morphology are characterized by XRD, FESEM, and HRTEM. The accurate crystallite size and lattice strain are determined by Williamson-Hall plot method and a comparative study with Scherer's equation is carried out. TEM image evidences the interface between BiFeO₃ and MnFe₂O₄ nanoparticles in the composite. The room temperature magnetic response reveals the strong dependence of magnetic saturation, remanent magnetization, and coercivity of the nanocomposites on MnFe₂O₄ addition. The dielectric response and impedance analysis of the prepared nanocomposites are observed. The electrical performance of the composite is affected by grain, grain boundaries, and oxygen vacancies. The unsaturated P-E loops exhibit the leaky ferroelectric behavior for the nanocomposite. The intrinsic magnetoelectric coupling between ferroelectric BiFeO₃ and ferromagnetic MnFe₂O₄ has been determined by varying H_dc/H_ac and its maximum coupling coefficient (α) is found to be 25.39 mV/cmOe for 70% BiFeO₃ -30% MnFe₂O₄ nanocomposite. These distinctive and achievable characteristics of the nanocomposite would enable the designing of magnetic field sensors, spintronic devices, and multiferroic memory devices.