The structural and multiferroic properties of (Bi1−xLax)(Fe0.95Co0.05)O3 ceramics

La and Co co-doped BiFeO₃ ((Bi_1−xLa_x)(Fe_0.95Co_0.05)O₃ (x=0, 0.10, 0.20, 0.30)) ceramics were prepared by tartaric acid modified sol–gel method. The X-ray diffraction patterns indicate a transition from rhombohedral structure to tetragonal structure at x=0.20, which has been confirmed by the Raman measurements. The band gap increases with increasing x to 0.20, and then decreases with further increasing x to 0.30. The structural transition has significant effects on the multiferroic properties. The remnant magnetization and saturate ferromagnetic magnetization decrease abruptly with increasing x to 0.10, and then gradually increase with further increasing x up to 0.30. The coercivity is significantly reduced with increasing La doping concentration. The ferroelectricity has been improved by La doping, and the polarization increases with increasing x to 0.10, then decreases with further increasing x up to 0.30. The simultaneous coexistence of soft ferromagnetism and ferroelectricity at room temperature in tetragonal Bi_0.70La_0.30Fe_0.95Co_0.05O₃ indicates the potential multiferroic applications.     

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.     

Microstructures and multiferroic properties of textured Bi0.8La0.2FeO3 thin films

La-substituted BiFeO₃, Bi_0.8La_0.2FeO₃, thin films were fabricated on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscope were used to analyze the structures of the films. The results show the films fabricated under optimized growth condition are (0 1 2) textured. X-ray photoemission spectroscopy results indicate that the oxidation state of Fe ion is Fe³⁺ in the films without detectable Fe²⁺. The films show low leakage current and excellent dielectric characters. Multiferroic properties with a remnant ferroelectric polarization of 5.2 μC/cm² and a remanent magnetization of 0.02 μ_B/Fe were established. These results have some implications for further research.     

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.     

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.     

Synthesis and magnetic properties of hexagonal Y(Mn,Cu)O3 multiferroic materials

Single-phase hexagonal-type solid solutions based on the multiferroic YMnO₃ material were synthesized by a modified Pechini process. Copper doping at the B-site (YMn_1−xCu_xO₃; x<0.15) and self-doping at the A-site (Y_1+yMnO₃; y<0.10) successfully maintained the hexagonal structure. Self-doping was limited to y(Y)=2 at% and confirmed that excess yttrium avoids formation of ferromagnetic manganese oxide impurities but creates vacancies at the Mn site. Chemical substitution at the B-site inhibits the geometrical frustration of the Mn³⁺ two-dimensional lattice. The magnetic transition at T_N decreases from 70 K down to 49 K, when x(Cu) goes from 0 to 15 at%. Weak ferromagnetic Mn³⁺-Mn⁴⁺ interactions created by the substitution of Mn³⁺ by Cu²⁺, are visible through the coercive field and spontaneous magnetization but do not modify the overall magnetic frustration. Presence of Mn³⁺-Mn⁴⁺ pairs leads to an increase of the electrical conductivity due to thermally-activated small-polaron hopping mechanisms. Results show that local ferromagnetic interactions can coexist within the frustrated state in the hexagonal polar structure.     

Effect of different annealing methods on ferroelectric properties of 0.95Pb(Sc0.5Ta0.5)O3-0.05PbTiO3 thin films

0.95Pb(Sc_0.5Ta_0.5)O₃-0.05PbTiO₃ thin films were prepared on LaNiO₃/SiO₂/Si substrate by radio frequency magnetron sputtering, and the films were annealed subsequently with repeated many times by two approaches: normal one-step rapid thermal annealing and innovative two-steps rapid thermal annealing. X-ray diffraction demonstrates that all the films were preferred (1 0 0) oriented and an appropriate repeat of annealing process can enhance perovskite phase of the films. Scanning electron microscopy suggests that the films treated by two-steps rapid thermal annealing show crack-free, uniform size grains and dense microstructure. Measurement of remnant polarization and leakage current dependence of electric field confirms that the films treated by two-steps rapid thermal annealing exhibit better ferroelectric properties than the films treated by one-steps rapid thermal annealing. The results reveal that microstructure plays an important role in enhanced ferroelectric properties of the 0.95Pb(Sc_0.5Ta_0.5)O₃-0.05PbTiO₃ thin films.     

多铁性BiFeO3纳米颗粒的尺寸依赖磁性能研究

采用乙二胺四乙酸杂化溶胶法制备了不同晶粒尺寸的纯相BiFeO₃纳米颗粒,并利用X射线衍射仪、扫描电镜、超导量子干涉仪和Mossbauer 谱系统研究了其结构、形貌以及磁性能.结果表明: BiFeO₃纳米颗粒具有明显的弱铁磁性,并呈现强烈的尺寸依赖特性; 这种弱铁磁性主要源于纳米材料的尺寸限制效应,而非杂质相或Fe²⁺ 的存在所致.     

Effect of Cr substitution on the multiferroic properties of BiFe1 − xCrxO3 compounds

Single-phase BiFe_1 − xCr_xO₃ (x=0, 0.05 and 0.1) compounds are synthesized by a sol-gel process. The lattice parameters decrease and the magnetizations increase with the Cr content. Moreover, the magnetoelectric coupling between magnetic order and ferroelectric order at room temperature was enhanced.     

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.     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

Resistive switching in ceramic multiferroic Bi0.9Ca0.1FeO3

We report resistive switching effects in polycrystalline samples of the multiferroic Bi_0.9Ca_0.1FeO₃ with silver electrodes. Mössbauer spectroscopy shows that upon Ca-doping the Fe remains in a 3+ valence state, suggesting charge compensation through the creation of large amounts of oxygen vacancies. Electrical characterization shows that the oxide/metal resistance can be switched between high and low resistance states by applying voltage pulses. This process was shown to be forming free and a strong relaxation after switching was found. We rationalize our results by considering oxygen vacancies migration to and from the metal–oxide interface, resulting in variations of the Schottky potential barrier height that modulate the interface resistance.     

(Ba, Ca)(Ti, Zr)O3-BiFeO3 lead-free piezoelectric ceramics

Effects of BiFeO₃ (BFO) content on the microstructure and electrical properties of Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ (BCTZ) ceramics prepared by normal sintering in air were investigated. A stable solid solution is formed between BCTZ and BFO. The grain size gradually becomes smaller, and the ceramics become denser with increasing the BFO content. The Curie temperature, dielectric constant, and dielectric loss of BCTZ ceramics decrease simultaneously with the introduction of BFO. Moreover, the remanent polarization reaches a maximum at x = 0.2 mol%, and the coercive field continuously increases with increasing the BFO content due to the introduction of BFO with a higher coercive field. Improved piezoelectric properties (d₃₃ ∼ 405 pC/N and k_p ∼ 0.44) are demonstrated for the BCTZ ceramic with x = 0.2 mol%.     

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.     

Effect of La doping in the multiferroic compound BiFeO3

We have performed magnetization and magnetocapacitance measurements on ceramic samples of the multiferroic series Bi_1−xLa_xFeO₃ for 0≤x≤.0.25. We show that doping with La reduces the transition magnetic field from the spatially modulated state to a homogenous one and increases the magnetocapacitance, these effects being the strongest for x=0.15, which is the highest concentration for maintaining the non-centrosymmetric rhomboedral structure (R3c) of BiFeO₃. For highest La content (x≥0.17), analysis of the XRD patterns shows that the lattice symmetry gradually changes to orthorhombic (C222), giving rise to an enhancement of the latent magnetization and to a drop of the magnetodielectric constant.     

Mn:BiFeO3/Zn:BiFeO3 bilayered thin films of (1 1 1) orientation

Ferroelectric and fatigue behavior of bilayered thin films consisting of Mn⁴⁺-modified BiFeO₃ and Zn²⁺-modified BiFeO₃, which were deposited on SrRuO₃-buffered Pt coated silicon substrates, were systematically investigated. The (1 1 1) orientation is induced for the BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer, due to the introduction of the bottom BiFe_0.95Zn_0.05O₃ layer. With increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer, their leakage current decreases, and the fatigue endurance is greatly improved owing to the introduction of the BiFe_0.95Mn_0.05O₃ layer with a lower fatigue rate. The BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer with the thickness ratio of 3:1 exhibits a larger remanent polarization of 2P_r ∼ 161.0 μC/cm² than those of bilayers with different thickness ratios, while their coercive field slightly increases with increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer.     

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

Influence of heating rate on the crystalline properties of 0.7BiFeO3-0.3PbTiO3 thin films prepared by sol-gel process

0.7BiFeO₃-0.3PbTiO₃ (BFPT7030) thin films were deposited on SiO₂/Si substrates by sol-gel process. The influence of heating rate on the crystalline properties of BFPT7030 thin films were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). XRD patterns of the films showed that a pure perovskite phase exists in BFPT7030 films annealed by rapid thermal annealing (RTA) technique. SEM and AFM observations demonstrated that the BFPT7030 films annealed by RTA at 700 °C for 90 s with the heating rate of 1 °C s⁻¹ could show a dense, crack-free surface morphology, and the films’ grains grow better than those of the films annealed by RTA at the same temperature with other heating rates. XPS results of the films indicated that the ratio of Fe³⁺:Fe²⁺ is about 21:10 and 9:5 for the films annealed by RTA at 700 °C for 90 s with the heating rate of 1 and 20 °C s⁻¹, respectively. That means the higher the heating rate, the higher the concentration of Fe²⁺ in the BFPT7030 thin films.     

Ferromagnetism in epitaxial orthorhombic YMnO3 thin films

Epitaxial orthorhombic YMnO₃ thin films, (0 0 1) oriented, have been grown by pulsed laser deposition on (0 0 1)SrTiO₃ substrates. Their crystal structure and magnetic response have been studied in detail. Although bulk o-YMnO₃ is antiferromagnetic, our magnetic measurements reveal intriguing thermal hysteresis between the zero-field-cooled and field-cooled curves below the onset of the antiferromagnetic ordering temperature, thus signaling a more complex magnetic structure with net ferromagnetic moments. We discuss on the possible origin of this net magnetization and we have found a correlation of the magnetic response with the strain state of the films. We propose that substrate-induced strain modifies the subtle competition of magnetic interactions and leads to a non-collinear magnetic state that can thus be tuned by strain engineering.