Observation of magnetoelectric behavior at room temperature in Pb(FexTi1−x)O3

The co-existence of ferroelectric and ferromagnetic properties at room temperature is very rarely observed. We have been successful in converting ferroelectric PbTiO₃ into a magnetoelectric material by partly substituting Fe at the Ti site. The Pb(Fe_xTi_1−x)O₃ system exhibits ferroelectric and ferromagnetic ordering at room temperature. Even more remarkably, our results demonstrate a coupling between the two order parameters. Hence it could be a futuristic material to provide cost effective and simple path for designing novel electromagnetic devices.     

Magnetic, electric, and optical functionalities of (PLZT)x(BiFeO3)1−x ferroelectric-ferromagnetic thin films

We have prepared a series of (PLZT)_x(BiFeO₃)_1−x transparent thin films with thickness of 300 nm by a thermal pyrolysis method. Only films with x≦0.10 formed a single phase of perovskite structure. The film where x=0.10 exhibited both ferromagnetic and ferroelectric properties at room temperature with spontaneous magnetization and coercive magnetic fields of 0.0027μ_B and 5500 G, respectively. The remanent electric polarization and coercive electric field for the film where x=0.10 were 3.0 μC/cm² and 24 kV/cm, respectively. Additionally, films with 0.02≦x≦0.10 showed both magneto-optical effects and the second harmonic generation of transmitted light.     

Effect of Gd doping on structural, electrical and magnetic properties of BiFeO3 electroceramic

Room temperature multiferroic electroceramics of Gd doped BiFeO₃ monophasic materials have been synthesized adopting a slow step sintering schedule. Incorporation of Gd nucleates the development of orthorhombic grain growth habit without the appearance of any significant impurity phases with respect to original rhombohedral (R3c) phase of un-doped BiFeO₃. It is observed that, the materials showed room temperature enhanced electric polarization as well as ferromagnetism when rare earth ions like Gd doping is critically optimized (x=0.15) in the composition formula of Bi_1+2xGd_2x/2Fe_1−2xO₃. We believe that magnetic moment of Gd⁺³ ions in Gd doped BiFeO₃ tends to align in the same direction with respect to ferromagnetic component associated with the iron sub lattice. The dielectric constant as well as loss factor shows strong dispersion at lower frequencies and the value of leakage current is greatly suppressed with the increase in concentration of x in the above composition. Addition of excess bismuth and Gd (x=0.1 and 0.15) caused structural transformation as well as compensated bismuth loss during high temperature sintering. Doping of Gd in BiFeO₃ also suppresses spiral spin modulation structure, which can change Fe-O-Fe bond angle or spin order resulting in enhanced ferromagnetic property.     

Evolution from relaxor-like dielectric to ferroelectric in Ba[(Fe0.5Nb0.5)1−xTix]O3 solid solutions

Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ (x=0.2,0.4,0.6,0.8,0.85,0.9 and 0.95) solid solutions were synthesized by a standard solid-state reaction technique. X-ray diffraction at room temperature and dielectric characteristics over a broad temperature and frequency range were evaluated systematically. The structure of Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ solid solutions changed from cubic to tetragonal with increasing x. A Debye-like dielectric relaxation following the Arrhenius law similar to that in Ba(Fe_0.5Nb_0.5)O₃ was observed at lower temperature in the composition range 0.2≤x≤0.8, while the relaxor ferroelectric, diffused ferroelectric and normal ferroelectric behavior were observed for x=0.85,0.9 and 0.95, respectively. The process of the evolution of relaxor-like dielectric to ferroelectric suggested the changing from dilute polar micro-domains to polar micro-domains, polar micro/macro-domains and then polar macro-domains in the present ceramics.     

Effect of holmium substitution for the improvement of multiferroic properties of BiFeO3

This paper reports on multiferroic properties of Ho substituted BiFeO₃ (Bi_1−xHo_xFeO₃) ceramics. It is observed that for x=0.15, a prominent ferroelectric loop is seen at 300 K even if the system remains in rhombohedral (R3c) phase without appearance of any observable impurity phases. A well shaped M-H loop is observed at 10 K for x=0.15. However it showed ferromagnetism, confirming the contribution of Ho³⁺ towards enhancement of ferromagnetic properties of BiFeO₃ at 300 K. Suppression of impurity phases of pure BiFeO₃ bulk ceramic favors the reduction of mobile oxygen vacancies and reduces leakage current, due to which ferroelectric properties of BiFeO₃ is enhanced. We argue that Ho substitution at Bi site is likely to suppress the spiral spin modulation and at the same time increase the canting angle, which favors enhanced multiferroic properties. XRD, SEM, magnetization, polarization and chemical bonding analysis measurements were carried out to explain the multiferroic behavior.     

Ferroelectric,magnetoelectric and photoelectric properties of BiFeO3 /LaNiO3 heterostructure

BiFeO₃/LaNiO₃ (BFO/LNO) heterostructure was fabricated on quartz substrate via RF sputtering method. The microstructure and surface morphology of the BFO/LNO heterostructure was demonstrated. BFO layer shows good ferroelectric and weak ferromagnetic characters at room temperature. The dielectric constants of the heterostructure under an applied magnetic field 1.2T and zero field are both decreased with increasing frequency at room temperature and the dielectric constant under the applied magnetic field is larger, which is attributed to the coupling between the electric and magnetic dipoles, and further demonstrated in the framework of the Ginzburg-Landau theory for second phase transition. Additionally, the photoconductivity of the heterostructure under blue-laser illumination was observed, and the photoconductivity increase with the enhanced power of the blue-laser.     

Effect of preferred orientation on magnetoelectric properties of multiferroic La0.7Sr0.3MnO3/BaTiO3 heterostructure

The epitaxial La_0.7Sr_0.3MnO₃/BaTiO₃ bilayer heterostructures were deposited on LaAlO₃ (001) and (110) substrates by pulsed laser deposition. The inherent ferromagnetic, ferroelectric properties and strong magnetoelectric (ME) effect at room temperature were approved, which correlated to the preferred orientation of the films. Both heterostructures showed similar frequency-dependent ME behavior in 0.1 kHz-100 kHz, the ME voltage coefficients were around 140 mV/cm Oe and 104.8 mV/cm Oe at 1 kHz for (001) and (110) oriented bilayers, respectively. This was at least one order of magnitude higher than previously reported results of the related heterostructures, which is mainly ascribed to the lower dielectric constant of BTO film.     

The multiferroic properties of Bi(Fe0.95Co0.05)O3 films

Bi(Fe_0.95Co_0.05)O₃ films were prepared on conductive indium tin oxide (ITO)/glass substrates by chemical solution deposition. Well saturated polarization hysteresis loop has been observed with a remnant polarization value of about 22 μC/cm² at room temperature. Weak ferromagnetism with saturation magnetization of about 3 emu/cm³ was observed at room temperature. The clear observation of both room temperature ferroelectric and ferromagnetic properties suggests the potential multiferroic applications of Bi(Fe_0.95Co_0.05)O₃.     

Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Effect of pore size on ferroelectric properties of multiferroic BiFeO3 films prepared on porous silicon

The ferroelectric properties of BiFeO₃ (BFO) films spray deposited on porous silicon have been studied. The analysis of XRD and FESEM investigations show that the crystalline strain in the BFO films increases with pore size. The BFO films on porous silicon substrate showed improvement in ferroelectric fatigue behavior, remanent polarization and ferroelectric switching time. A maximum memory window of 5.54 V at 1 MHz and a large remanent polarization (P_r) of 13.1 μC/cm² have been obtained at room temperature. The improvement in the ferroelectric properties of these films has been correlated to the crystalline strain.     

Effect of magnetic annealing on magnetization of BiFeO3 ceramics

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

Probing of local ferroelectricity in BiFeO3 thin films and (BiFeO3)m(SrTiO3)m superlattices

Ferroelectric BiFeO₃ thin films and artificial superlattices of (BiFeO₃)_m(SrTiO₃)_m (m∼1-10 unit cells) were fabricated on (0 0 1)-oriented SrTiO₃ substrates by pulsed laser ablation. The variation of leakage current and macroscopic polarization with periodicity was studied. Piezo force microscopy studies revealed the presence of large ferroelectric domains in the case of BiFeO₃ thin films while a size reduction in ferroelectric domains was observed in the case of superlattice structures. The results show that the modification of ferroelectric domains through superlattice could provide an additional control on engineering the domain wall mediated functional properties.     

Differential thermal analysis of phase transitions in (Bi1−xLax)FeO3 solid solution

(Bi_1?xLa_x)FeO₃ solid solution, a material exhibiting simultaneously electric and magnetic long range dipole order, is studied by the method of differential thermal analysis. The results confirm the data on ferroelectric phase transitions obtained from electric permittivity and dilatometric measurements above 500°C. The endothermal effect observed about 820°C is related to the ferroelectric phase transition of BiFeO₃.     

Study of the structural, dielectric and magnetic properties of Bi2O3 and PbO addition on BiFeO3 ceramic matrix

In this paper we studied the effects of Bi₂O₃ and PbO addition on BiFeO₃ (BFO) ceramic matrix. The structural, dielectric and magnetic properties of fifteen BFO samples were discussed in view of possible applications in RF and microwave devices. The present work also reports the preparation of the samples. Polyvinyl alcohol (PVA) and tetraethyl orthosilicate (TEOS) were also added as a binder in the fabrication procedure. The samples have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and magnetic hysteresis measurements. Further, a study based on impedance spectroscopy also has been done. Dielectric permittivity (ε′) and dielectric loss (tan δ) were measured at room temperature in the frequency range 100 Hz-10 MHz, as well as a.c. conductivity. The -Im[Z(f)] versus Re[Z(f)] plot has been obtained. The samples were investigated in view of possible applications like miniaturized filters, diplexers and dielectric resonator antennas (DRA). In the RF and MW frequency region, the application of magneto-dielectric and multiferroic perovskite composite materials is desirable for the miniaturization of components.     

Structural and electrical behavior of Pb(Mg1/4Cd1/4Mo1/2)O3 ceramics

Preliminary X-ray structural analysis of polycrystalline Pb(Mg_1/4Cd_1/4Mo_1/2)O₃ ceramics, prepared by a solid-state reaction technique, provides single-phase orthorhombic structure at room temperature. Detailed dielectric studies of the material as a function of temperature reveal a sharp phase transition at temperature T_c=49°C obeying Curie-Weiss behavior. Scanning electron microscope (SEM) studies of the sample show the uniform distribution of grains in the samples. A dielectric anomaly and ferroelectric phase transition observed at 49°C was supported by polarization studies. The activation energy of the sample was calculated from the dielectric data. The variation of dc resistivity with temperature suggests that the compound behaves as a negative temperature coefficient resistor (NTCR).     

Magnetic and transport property studies of nanocrystalline ZnxFe3−xO4

The magnetic and transport properties of nanocrystalline Zn_xFe_3−xO₄ with x=0.0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0, respectively, fabricated by the sol-gel method have been investigated. Large magnetoresistance (MR) was observed and found to be originated both from the tunneling of the spin-polarized electrons across the adjacent ferromagnetic grains and the scattering by the canted spins at the grain surface near the grain boundaries. It has been revealed that the MR for the Zn_xFe_3−xO₄ samples (x=0, 0.5 and 1.0) increases with the temperature decreasing from room temperature until a maximum is reached at around 55 K. Then a sharp drop occurs with the further decrease in temperature, regarded as a spin (cluster) glass transition. For the samples studied, a biggest low field (0.5 T) MR value of about 20% for x=0 at 55 K has been obtained. The mechanism of the MR behavior of the materials was discussed.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

Improvement of multiferroic and leakage property in monophasic BiFeO3

This paper aims to report that impurity phase free single phase multiferroic BiFeO₃ ceramic can be prepared by critically optimizing the metal ion concentration using slow step sintering schedule at 850 °C for 24 h. Antiferromagnetic character of pure BiFeO₃ is completely changed and ferromagnetic behavior observed with increase of Bi as well as decrease of Fe concentration. It is found that Bi rich (Bi: 1.2) Fe deficient (Fe: 0.8) composition produces single phase rhombohedral structure with space group R3c along with enhanced ferroelectric and ferromagnetic properties. Incorporation of excess bismuth caused structural distortion and expected to compensate Bi loss during high temperature sintering. On the other hand, iron deficient helps the formation of Fe³⁺ state, which hinders the creation of oxygen vacancies and also favors the reduction of leakage current. Structural distortion in BiFeO₃ changes Fe-O-Fe bond angle or spin order, destructs the spin cycloid and releases a locked magnetization.     

Doping strategies for increased performance in BiFeO3

Investigation of crystal structure, dielectric, magnetic and local ferroelectric properties of the diamagnetically substituted Bi_1−xA_xFeO_3−x/2 (A=Ca, Sr, Pb, Ba; x=0.2, 0.3) polycrystalline samples has been carried out. It has been shown that the heterovalent A²⁺ substitution result in the formation of oxygen vacancies in the host lattice. The solid solutions have been found to possess a rhombohedrally distorted perovskite structure described by the space group R3c. Piezoresponse force microscopy has revealed signs of existence of the ferroelectric polarization in the samples at room temperature. Magnetization measurements have shown that the magnetic state of these compounds is determined by the ionic radius of the substituting elements. A-site substitution with the biggest ionic radius ions has been found to suppress the spiral spin structure of BiFeO₃ giving rise to the appearance of room-temperature weak ferromagnetism.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.