Electrical behavior of high resistivity Ce-doped BiFeO3 multiferroic

Bi_1+xCe_xFeO₃ (Ce–BFO) for x=0, 0.05, 0.1, and 0.15 monophasic ceramic samples were successfully synthesized by conventional solid-state reaction routes. The influences of Ce doping on structural, dielectric, ferroelectric, leakage current and capacitive properties of BiFeO₃ ceramics were investigated intensively. At higher concentrations of x (x=0.1 and 0.15) the samples showed good crystallinity with almost impurity free phases. No structural phase transformation took place after partial doping of Ce ions and all ceramic bulk samples remain in their rhombohedral structure with space group R3c. The dielectric behavior of the samples improved significantly and the ferroelectric hysteresis loops changed their shape from rounded to a strongly nonlinear typical ferroelectric feature mainly originating from the domain switching and became enhanced with increase in doping concentration of cerium (Ce). Experimental results also suggested that partial doping of higher valence, smaller ionic radius Ce ions in BiFeO₃ forces the reduction of oxygen vacancies, resulting in a great suppression of leakage current. It is found that the sharp capacitance peak/discontinuity present in the C–V characteristics of Ce–BFO for different Ce doping concentrations is directly associated with the polarization reversal. Incorporation of excess bismuth in the presence of Ce in BiFeO₃ is expected to compensate Bi loss during high temperature sintering and caused structural distortion which also favors enhancement of ferroelectric properties in Ce-doped BFO.     

Electrophoretic deposition of BaTiO3/CoFe2O4 multiferroic composite films

Electrophoretic deposition was utilized for preparation of BaTiO₃/CoFe₂O₄ multiferroic composite thick films on indium-tin oxide substrates. The suspensions for electrophoretic experiments were prepared by dispersing BaTiO₃ and CoFe₂O₄ nanoparticles with different molar ratios into solvents composed of ethanol and acetylacetone. Polyvinyl butyral was added to the suspensions in order to enhance the adhesion and strength of deposit and prevent cracking. The zeta potential values of BaTiO₃/CoFe₂O₄ suspensions were measured to be 26.4-36.9 mV. The experiment results showed that deposited films were obtained only when the applied electric field was larger than a certain critical value. XRD and SEM analysis depicted the presence of constituent phases in composite films. The percolation threshold of composite films was improved through dispersing ferromagnetic phase into ferroelectric phase. Therefore, the ferroelectric properties of composite thick films were maintained when the ferromagnetic properties were enhanced significantly with increasing CFO content.     

Magnetic structure and physical properties of the multiferroic compound PrMn2O5

RMn₂O₅ (R=lanthanide, Bi, Y) multiferroic compounds are intensively studied for their potential application in the spintronic field. In these systems, the key issue is to understand the origin of the strong coupling between the ferroelectric and magnetic orders and to investigate the influence of the nature of the R ions in this coupling. While the phase diagram of RMn₂O₅ compounds with small R size is well established, this of large R size compounds is missing due to the lack of samples originating with difficulties of synthesis. We present in this paper the first investigation of the thermodynamic, structural and magnetic properties of high quality polycrystalline PrMn₂O₅ samples. Our work shows that PrMn₂O₅ presents two magnetic transitions corresponding to commensurate magnetic orderings. We also evidence a weak lattice effect coupled to the magnetic order. Our results point out that the physical properties of PrMn₂O₅ differ from those of the parent compounds with magnetic R ions.     

Soft-mode driven tetragonal-to-monoclinic phase transition in multiferroic BiFeO3

The phase transition of BiFeO₃ (BFO) from tetragonal to monoclinic induced by pressure was investigated by first-principles method. The sequential monoclinic phase, _Ma$M_{\mathrm{a}}$, which is favorable during low compression with respect to the tetragonal phase, was characterized. The order parameters were calculated in the vicinity of the phase transition, showing that phase transition has a second-order character. The results demonstrated that the pressure-induced tetragonal-to-monoclinic phase transition in BFO is related to the softening behavior of the E mode, which are very helpful in further investigations of the morphotropic phase boundary (MPB) in lead-free materials.     

Effect of non-magnetic doping on leakage and magnetic properties of BiFeO3 thin films

In this paper, we show that the leakage current properties of BiFeO₃ (BFO) thin films have been greatly improved by Zr-doping. In contrast, the magnetic properties of Zr-doped BFO films are affected as a weak ferromagnetism. Beyond the double-exchange interactions arising from the creation of Fe²⁺, we propose another simple model considering the replacement of the magnetically active Fe³⁺, time to time, by a non-active Zr⁴⁺, which is expected to induce a local ferromagnetic coupling rather than an antiferromagnetic one.     

Bi(Fe1-xMnx)O3的结构与磁性

使用快速烧结和溶胶-凝胶方法制备了Bi(Fe_1-xMnx)O₃的块材陶瓷,其x能够达到0.3,因而可以得到较细的粉末. 经X射线衍射谱和拉曼光谱研究发现其结构转变取决于锰的掺杂浓度. 当x=0.05和0.1时,Bi(Fe_1-xMnx)O₃的结构保持斜方六面体结构;当x=0.3时,Bi(Fe_1-xMnx)O₃的结构变化到正方六面体结构.在x=0.05和0.1时观测到弱铁磁性,但在x=0.3时观测到强顺磁性. 这显示了Bi(Fe_1-xMnx)O₃从反铁磁性到顺磁性的磁相变,同时也表明其结构从R3C变化到C222. 在30和140 K, x=0.05和0.1时,观察到Bi(Fe_1-xMnx)O₃的两个反常现象. 在30 K时,直流磁记忆和缓慢测量Bi(Fe_1-xMnx)O₃团族的反常现象与冷冻的旋转玻璃系统有关.     

Magnetic characterization of Bi(Fe1 − xMnx)O3

Bi(Fe_1 − xMn_x)O₃ ceramics (x up to 0.3) were prepared by rapid sintering. Weak ferromagnetism with two magnetic anomalies at low temperatures was observed for Bi(Fe_0.95Mn_0.05)O₃ and Bi(Fe_0.9Mn_0.1)O₃. From temperature-dependent magnetic relaxation measurements, the anomalies at 20 K and 100 K are related to the freezing of cluster spin glass.     

Effects of magnetic annealing on structure and multiferroic properties of pure and dysprosium substituted BiFeO3

In this work, the effects of magnetic annealing on crystal structure and multiferroic properties of BiFeO₃ and Bi_0.85Dy_0.15FeO₃ have been investigated. It is found that the X-ray diffraction patterns of pure BiFeO₃ samples are obviously broadened after magnetic annealing, whereas those of Bi_0.85Dy_0.15FeO₃ samples are almost unchanged. Magnetic field annealing did not affect the magnetic properties of these two kinds of samples much. However, ferroelectric properties of the two materials exhibited different behaviors after magnetic field annealing. For pure BiFeO₃ samples, the remnant polarizations (P_r) are suppressed; in contrast, for Bi_0.85Dy_0.15FeO₃ samples, P_r is greatly enhanced. Possible mechanisms for the effects of magnetic field annealing have been discussed.     

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.     

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.     

Magnetic properties of Ni-substituted BiFeO3

BiFe_1−xNi_xO₃ ceramic powders with x up to 0.10 have been prepared by the sol-gel technique. The band gap of BiFeO₃ is 2.23 eV, and decreases to 2.09 eV for BiFe_0.95Ni_0.05O₃ and BiFe_0.90Ni_0.10O₃. The Mössbauer spectra show sextet at room temperature, indicating the magnetic ordering and the presence of only Fe³⁺ ions. Superparamagnetism with blocking temperature of 31 K for BiFe_0.95Ni_0.05O₃ and 100 K for BiFe_0.90Ni_0.10O₃ was observed. Enhanced magnetization at room temperature have been observed (1.0 emu/g for BiFe_0.95Ni_0.05O₃ and 2.9 emu/g for BiFe_0.90Ni_0.10O₃ under magnetic field of 10,000 Oe), which is one order larger than that of BiFeO₃ (0.1 emu/g under magnetic field of 10,000 Oe). The enhanced magnetization was attributed to the suppression of the cycloidal spin structure by Ni³⁺ substitution and the ferrimagnetic interaction between Fe³⁺ and Ni³⁺ ions.     

Local leakage current behaviours of BiFeO3 films

The leakage current behaviours of polycrystalline BiFeO₃ thin films are investigated by using both conductive atomic force microscopy and current-voltage characteristic measurements. The local charge transport pathways are found to be located mainly at the grain boundaries of the films. The leakage current density can be tuned by changing the post-annealing temperature, the annealing time, the bias voltage and the light illumination, which can be used to improve the performances of the ferroelectric devices based on the BiFeO₃ films. A possible leakage mechanism is proposed to interpret the charge transports in the polycrystalline BiFeO₃ films.     

Exchange bias effect in multiferroic Eu0.75Y0.25MnO3

The exchange bias phenomenon has been investigated in multiferroic Eu_0.75Y_0.25MnO₃. The material shows a weak ferromagnetism with cone spin configuration induced by external magnetic field below 30 K. Consequently, the electric polarization coming from the cycloid spin order below 30 K can be suppressed by external magnetic fields. The magnetic hysteresis loops after cooling in a magnetic field exhibit characteristics of exchange bias below the spin glassy freezing temperature (T_g)∼16 K. The exchange bias field, coercivity field, and remanent magnetization increase with increasing cooling magnetic field. The exchange bias effect is ascribed to the frozen uncompensated spins at the antiferromagnetism/weak ferromagnetism interfaces in the spin-glass like phase.     

Synthesis and characterization of MnFe2O4-BiFeO3 multiferroic composites

The mixed spinel-perovskite composites of xMnFe₂O₄-(1-x)BiFeO₃ with x=0, 0.1, 0.2, 0.3 and 0.4 were prepared by solid state reaction method. The structure and grain size were examined by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM), respectively. The XRD results showed that the composites consisted of spinel MnFe₂O₄ and perovskite BiFeO₃ phases after being calcined at the temperature 950 °C for 2 h. The grain size ranged from 0.8 to 1 μm. Magnetization was found to increase with increasing concentration of ferrite content. The variation of dielectric constant and dielectric loss with frequency showed dispersion in the low frequency range. Magnetocapacitance was also observed in the prepared composites, which may be the sign of magnetoelectric coupling in the synthesized composites at room temperature.     

Phase transition in multiferroic YMnO3 and its solid solution YMn(0.93)Fe(0.07)O3

Ceramics of YMnO₃ and its Fe substituted YMn_(0.93)Fe_(0.07)O₃ solid solution were synthesized by solid state reaction of the oxides at 1200 °C. Hexagonal phase was identified in both cases by X-ray powder diffraction. Rietveld refinement of cell parameters showed an increase of the parameter values for the solid solution. Dielectric permittivity measurements versus temperature showed a phase transition at 655 °C for yttrium manganite, however, for the solid solution no phase transition was detected on heating up to 700 °C. Dielectric loss measurements showed higher slope changes and better defined local maxima for the solid solution than for the pure phase.     

Magnetic,ferroelectric and magnetoelectric properties of Ba-doped BiFeO3

Bi_1–xBa_xFeO₃ (0.0≤x≤0.25) ceramics are prepared by chemical synthesis route. At room temperature, antiferromagnetic BiFeO₃ is converted to ferromagnetic on doping Ba. A large change in the magnetization is observed around 370 °C which is close to the Neel temperature (T_N) of parent compound. Another magnetic transition is also observed near 600 °C. Spin canting or impurity phase could be a probable reason for the origin of ferromagnetism in both cases. Ferroelectric and magnetic transitions of the compounds shift towards higher temperature with Ba-doping concentration. Anomaly in the dielectric constant is also observed near the T_N of BiFeO₃. The composition x=0.15 shows the maximum magnetic moment at room temperature while better fatigue resistance and maximum magnetoelectric coupling are observed for x=0.20 composition.     

Magnetoelectric properties of Mn-substituted BiFeO3 thin films with a TiO2 barrier

Multiferroic thin films with the general formula TiO₂/BiFe_1−xMn_xO₃ (x=0.00, 0.05, 0.10 and 0.15) (TiO₂/BFMO) were synthesized on Au/Ti/SiO₂/Si substrates using a chemical solution deposition (CSD) method assisted with magnetron sputtering. X-ray diffraction analysis shows the thin films contained perovskite structures with random orientations. Compared with BFMO films, the leakage current density of the TiO₂/BFMO thin films was found to be lower by nearly two orders of magnitude, and the remnant polarizations were increased by nearly ten times. The enhanced ferroelectric properties may be attributed to the lower leakage current caused by the introduction of the TiO₂ layer. The J-E characteristics indicated that the main conduction mechanism for the TiO₂/BFMO thin film was trap-free Ohmic conduction over a wide range of electric fields (0-500 kV/cm). In addition, ferromagnetism was observed in the Mn doped BFO thin films at room temperature. The origin of ferromagnetism is related to the competition between distortion of structure and decrease of grain size and decreasing net magnetic moment in films due to Mn doping.     

Magnetic properties of Mn-substituted GdCoxMn1−xO3 and LaCoxMn1−xO3

Partial substitution of manganese by cobalt in rare-earth perovskites REMnO₃ leads to unusual magnetic phenomena because of the simultaneous presence of Mn³⁺, Mn⁴⁺, Co²⁺ and Co³⁺ species. The magnetic nature of the RE cation plays a fundamental role in the magnetic properties. We present herein two specific families: for RE=La the magnetic behavior of the |Co+Mn| network is observed, while for Gd its strong magnetic moment interacts with the transition metals, leading to a spin reversal state. Magnetic interactions are maximized at x=0.50, as if two regimes exist: for x<0.5 Co substitutes Mn in the REMnO₃ manganite, and for x>0.5 Mn substitutes Co in the RECoO₃ cobaltite.     

Ab-initio study of competing magnetic configurations in cubic BiFeO3 alloys

Using ab-initio calculations, we study the properties of the multiferroic BiFeO₃ compounds in the perfect cubic perovskite lattice structure. We show that the appearance of magnetism is energetically favorable. Except the ferromagnetic structure, there are three possible antiferromagnetic arrangements, which are close in energy, and for large values of the lattice constant a G-type antiferromagnetism is the most stable magnetic order. Fe atoms are responsible for the spin magnetic moments while the values of the induced spin moments at the other sites depend strongly on the local environment of the atoms. There is a significant charge transfer from the Fe and Bi atoms towards the p-states of O atoms.     

Enhanced multiferroic properties in La and Ce co-doped BiFeO3 nanoparticles

Room temperature multiferroic properties of BiFeO₃ (BFO), Bi_0.9La_0.1FeO₃ ((La)BFO) and Bi_0.9La_0.075Ce_0.025FeO₃ ((La,Ce)BFO) nanoparticles have been reported in this paper. XRD (X-ray diffraction) analyses of the nanoparticles show a decrease in the lattice constants and cell volume with the substitution of La and Ce. It is evident from the SEM (scanning electron microscope) micrographs that the (La,Ce) co-doped sample possesses dense microstructure made of smaller particles. Raman study accounts for the weakening of the strong hybridization between Bi-O by the substitution of La and Ce ions. This is also accompanied by an increase in the remanent magnetization, dielectric constant, and ferroelectric polarization. BFO nanoparticles show exchange bias effect under an applied magnetic field while the (La)BFO and (La,Ce)BFO samples show no trace of such effect. Ac-conductivity of (La,Ce) co-doped sample is observed to be several orders lesser in magnitude than bulk BFO ceramics. These results are interpreted by means of the subtle change in the structure, suppression of the spin cycloid and reduction of oxygen vacancies in the doped samples.