Thickness dependent magnetic and ferroelectric properties of LaNiO3 buffered BiFeO3 thin films

BiFeO₃ (BFO) thin films with thickness increasing from 40 to 480 nm were successfully grown on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si(100) substrate and the effects of thickness evolution on magnetic and ferroelectric properties are investigated. The LNO buffer layer promotes the growth and crystallization of BFO thin films. Highly (100) orientation is induced for all BFO films regardless of the film thickness together with the dense microstructure. All BFO films exhibited weak ferromagnetic response at room temperature and saturation magnetization is found to decrease with increase in film thickness. Well saturated ferroelectric hysteresis loops were obtained for thicker films; however, the leakage current dominated the ferroelectric properties in thinner films. The leakage current density decreased by three orders of magnitude for 335 nm film compared to 40 nm film, giving rise to enhanced ferroelectric properties for thicker films. The mechanisms for the evolution of ferromagnetic and ferroelectric characteristics are discussed.     

Effects of BaTiO<Subscript>3</Subscript> and SrTiO<Subscript>3</Subscript> as the buffer layers of epitaxial BiFeO<Subscript>3</Subscript> thin films

BiFeO₃ (BFO) thin films with BaTiO₃ (BTO) or SrTiO₃ (STO) as buffer layer were epitaxially grown on SrRuO₃-covered SrTiO₃ substrates. X-ray diffraction measurements show that the BTO buffer causes tensile strain in the BFO films, whereas the STO buffer causes compressive strain. Different ferroelectric domain structures caused by these two strain statuses are revealed by piezoelectric force microscopy. Electrical and magnetical measurements show that the tensile-strained BFO/BTO samples have reduced leakage current and large ferroelectric polarization and magnetization, compared with compressively strained BFO/STO. These results demonstrate that the electrical and magnetical properties of BFO thin films can be artificially modified by using a buffer layer.     

Simultaneous reduction in leakage current and enhancement in magnetic moment in BiFeO3 nanofibers via optimized Sn doping

Sn⁴⁺‐doped BiFeO₃ (BFO) nanofibers have been fabricated by sol–gel based electrospinning method with nanofiber diameter in the range of 30–100 nm in the annealed state. The leakage current density dropped by two orders of magnitude in 3% Sn‐doped BFO nanofibers compared to undoped BFO samples. Our density functional theory (DFT) simulation results indicate that Sn⁴⁺ prefers to occupy the Fe³⁺ site in BFO with a formation energy of 1.89 eV. The impurity Sn acts as a shallow donor with a low transition energy level of 41 meV. Furthermore, an enhancement in the saturation magnetization was simultaneously observed for 3% Sn‐doped nanofibers, which correlated well with our theoretical calculations. In other words, by carefully tailoring the degree of Sn doping in BFO nanofibers, we can reduce the leakage current and concurrently enhance the magnetic moment. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic field annealing effects on self-oriented BiFeO3 thin films prepared by chemical solution deposition

Self-oriented BiFeO₃ (BFO) thin films are prepared via chemical solution deposition method with magnetic field in-situ annealing process. The effects of magnetic annealing on the microstructure, magnetic and dielectric properties as well as magnetoelectric coupling effect of the BFO thin films are investigated. With increasing the annealing magnetic field, the crystallization quality, texture, grain boundary connectivity and densification of the films are enhanced, which is attributed to the improvement of connection and diffusion of components. The magnetization of the field-annealing films and dielectric constant as well as remanent polarization increases with increasing the strength of annealing magnetic field. In addition, it is observed that magnetocapacitance value of the magnetic-field-annealing BFO thin film is higher than the non-field-annealing one. Moreover the BFO thin films annealed at 3 kOe magnetic field show the magnetoelectric effect with 4% under 2 kOe at room temperature.     

Off-stoichiometry effects on BiFeO3 thin films

The effects of Bi and Fe-excess on the structure, ferroelectric, leakage current and magnetic properties of BiFeO₃ (BFO) thin films are reported. BFO with 5% excess exhibits no change in the structure with an improvement in leakage current properties in comparison to stoichiometric BFO. Raman spectroscopy of 10% Bi excess suggests a structural change from monoclinic to rhombohedral accompanied with an improvement of resistivity and ferroelectric polarization switching. A higher Fe-excess leads to the formation of pyrochlore Bi₂Fe₄O₉ and gamma-Fe₂O₃ that cause an increase in conductivity at the macroscopic scale. The results are discussed in terms of Fe and Bi-excess effects on the defect structure of BFO.     

(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%.     

Effects of ion-doping at different sites on multiferroic properties of BiFeO3 thin films

A-site Ce and B-site Zr codoped Bi_1−x Ce _x Fe_1−y Zr _y O₃ (BCFZ) thin films with different compositions were successfully prepared on the Pt/Ti/SiO₂/Si substrates by chemical solution deposition. The influence of the A-site Ce and B-site Zr codoping on the structure, surface morphology, electrical and magnetic properties of BFO films were investigated, respectively. The comparative study suggested that the A-site Ce doping with various contents have notable influences on the electrical properties of the BFO films, while the B-site Zr doping with different contents affect mainly the magnetic properties of the BFO films. Compared with the other BCFZ films studied here, the Bi_0.97Ce_0.03Fe_0.97Zr_0.03O₃ film showed the lowest dielectric loss and leakage current density, a well-squared P–E loop and fatigue-free characteristics as well as the strong magnetization.     

Enhancement in multiferroic properties of Bi0.7−xLaxDy0.3FeO3 system with removal of La

La doping at Bi Site in multiferroic BiFeO₃ (BFO) is known to stabilize the ferroelectric perovskite phase and reduce the leakage current. It has been observed that in Dy modified BFO sample, La is not required for the said reason. In fact, the removal of La from Dy modified BFO system leads to the reduction in leakage current. Moreover, the magnetic properties are enhanced by order of magnitude in the absence of La in the system. Remarkably, a similar trend in properties has been also observed in thin films grown on Pt/TiO₂/SiO₂/Si substrate by using the pulsed laser deposition technique. This significant variation in the properties after removal of La from the system could be attributed to the change in lattice parameters, bond lengths and Fe–O–Fe bond angle as determined by powder x-ray and neutron diffraction study.     

Modulation of ultrafast laser-induced magnetization precession in BiFeO<Subscript>3</Subscript>-coated La<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> thin films

The ultrafast laser-excited magnetization dynamics of ferromagnetic (FM) La_0.67Sr_0.33MnO₃ (LSMO) thin films with BiFeO₃ (BFO) coating layers grown by laser molecular beam epitaxy are investigated using the optical pump-probe technique. Uniform magnetization precessions are observed in the films under an applied external magnetic field by measuring the time-resolved magneto-optical Kerr effect. The magnetization precession frequencies of the LSMO thin films with the BFO coating layers are lower than those of uncoated LSMO films, which is attributed to the suppression of the anisotropy field induced by the exchange interaction at the interface between the antiferromagnetic order of BFO and the FM order of LSMO.     

复合薄膜NiFe2 O4-BiFeO3 中的磁电耦合

采用化学溶液沉积法(CSD)在Au/Ti/SiO₂/Si衬底上通过自组装生长制备了BiFeO₃-NiFe₂O₄ (BFO-NFO)多铁性复合薄膜.X射线衍射图谱(XRD)显示形成了分离的钙钛矿结构的铁电相BFO和尖晶石结构的铁磁相NFO. NFO的引入导致复合薄膜的泄漏电流减小,剩余极化强度增加.相比于纯BFO薄膜,0.25NFO-0.75BFO样品泄漏电流下降了约两个数量级,剩余极化强度( M _{关键词： 多铁性复合薄膜 磁电耦合 铁电性 铁磁性}     

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.     

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.     

Effect of Sc substitution on the structure,electrical, and magnetic properties of multiferroic BiFeO3 thin films grown by a sol–gel process

Multiferroic BiFeO₃ (BFO), Bi_1−xSc_xFeO₃ (BSF), and BiFe_1−xSc_xO₃ (BFS) (x=0.3 mol%) thin films are prepared on Pt/Ti/SiO₂/Si substrates using a sol–gel technique. The effect of Sc substitution along with the annealing ambient (N₂ and O₂) on the structure, electrical, and magnetic properties of the films are reported. X-ray diffraction (XRD) analysis reveals that the films can be prepared with the single-phase perovskite structure by annealing at 700 °C for 10 min either in O₂ or N₂ ambient. The unit cell volume increases on the substitution of Sc, which are 61.39, 62.50, and 62.57 (Å)³ for BFO, BSF, and BFS, respectively. X-ray photoelectron spectroscopy (XPS) study reveals that the chemical environments of Bi and Fe are different in BFO, BSF, BFS films. Similarly, XPS spectra for Sc2p lines in BSF and BFS also have different peak positions; this indicates Sc doping has certain chemical impact on BSF and BFS films. Systematic studies of Sc substitution along with the effect of annealing ambient on the dielectric constant (ε) and dielectric loss (tan δ), leakage current, remnant polarization (P_r), coercive field (E_c), and magnetic properties of the films are carried out. The room temperature values of ε and tan δ at 1 kHz for BFO and BFS films annealed in N₂ ambient are (∼208; 0.035) and (∼235; 0.023), respectively. The comparative value of leakage current for the BFO and BFS films at an applied field strength of 50 kV/cm are 2.997×10⁻⁴ and 1.87×10⁻⁵ A/cm², respectively. Room temperature value of coercive magnetization for BFS films has one order small compared to that of the BFO films; this indicates BFS films are magnetically soft and more suitable for potential device applications. Finally, among the studied compositions, the BFS films annealed in N₂ ambient show the best property.     

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.     

Effects of co-substitution on the electrical properties of BiFeO3 thin films prepared by chemical solution deposition

Ferroelectric BiFeO₃ thin films with Nd-Cr (or Sm-Cr) co-substitution (denoted by BNdFCr and BSmFCr, respectively) were deposited on the Pt(2 0 0)/TiO₂/SiO₂/Si(1 0 0) substrates by a chemical solution deposition method. X-ray diffraction patterns revealed the formation of BNdFCr and BSmFCr thin films without any secondary phases. The co-substituted BNdFCr (or BSmFCr) thin films, which were annealed at 550 °C for 30 min in N₂ atmosphere, exhibited enhanced electrical properties compared to BFO thin films with the remanent polarization (2P_r) and coercive electric field (2E_c) of 196, 188 μC/cm² and 600, 570 kV/cm with the electric field of 800 kV/cm, respectively. The leakage current densities of BNdFCr and BSmFCr thin films measured at room temperature were approximately three orders of magnitude lower than that of BFO thin film, and the leakage current at room temperature of the thin films exhibited three distinctive conduction behaviors. Furthermore, the values of pulse polarizations [i.e., +(P*-P^{^}) or −(P*-P^{^})] of BNdFCr and BSmFCr thin films were reasonably unchanged up to 1.4 × 10¹⁰ switching cycles.     

Bi0.5Ba0.5Fe0.5Ti0.49Nb0.01O3热敏陶瓷的微结构和电学性能研究

采用固相合成工艺,制备了Bi_05Ba_05Fe_05Ti_049Nb_001O₃（BBFTN）热敏陶瓷,借助X射线衍射仪、扫描电子显微镜、阻温测试仪和交流阻抗谱考察其微结构、直流电阻、介电特性、阻抗和电学模量方面的电学性能. 结果表明：BBFTN材料依然为立方钙钛矿结构,平均晶粒尺寸约为10 μm,晶格常数相对于BaTiO₃的晶格常数有所变大;室温电 关键词： 05Ba_05Fe_05Ti_049Nb_001O₃')" href="#">Bi_05Ba_05Fe_05Ti_049Nb_001O₃ 微结构 电学性能     

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.     

Centimeter-size BiFeO3 single crystals grown by flux method

A narrow part of Fe₂O₃–Bi₂O₃ phase diagram was re-investigated in order to elaborate single crystals of the multiferroic BiFeO₃ (BFO). Centimeter-size single crystals were successfully obtained by flux method, and present a preferred growth direction. X-ray diffraction studied have highlighted that the growth direction is along the polar axis [111] _r of the structure. The stability of BFO versus temperature (reversible ferroelectric transition followed by multiple irreversible decompositions) is discussed in the light of Differential Scanning Calorimetry (DSC) analysis performed between 25 and 1400°C.     

Effect of low-temperature high-pressure sintering on BiFeO3 density,electrical magnetic and structural properties

Single-phase multiferroic BiFeO₃ (BFO) powders were prepared by hydrothermal microwave synthesis and dense BiFeO₃ ceramics were fabricated for the first time by the low-temperature high-pressure (LTHP) sintering technique. Effect of sintering temperature ranging from 400 to 800 °C (3 min and 10 min) and pressure of 3–8 GPa on structural, microstructural, electric and magnetic properties were investigated through X-ray diffraction, scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), density and magnetic measurements. The results highlighted that LTHP sintering method, thanks to the high pressure involved, requires lower temperature and shorter time than other techniques, avoiding BiFeO₃ phase degradation. SEM images show that for short experimental time (t = 3 min) the average grain size of the sintered samples was approximately the same size of raw powder. Extending the sintering time up to 10 min the grain growth phenomena occurred. Moreover the results indicate that the best obtained density value was around 98% of theoretical density. The dielectric behavior of BiFeO₃ ceramics was not significantly influenced by the LTHP sintering conditions. Magnetic measurements showed that ceramic BiFeO₃ is weakly ferromagnetic at room temperature.     

Modification in structure of La and Nd co‐doped epitaxial BiFeO3 thin films probed by micro Raman spectroscopy

The influence of La and Nd co‐substitution on structure, electric and magnetic properties of epitaxial thin films of BiFeO₃ (BFO) was examined. We demonstrate structural phase transition in co‐doped La and Nd BFO thin films using Raman spectroscopy. Based on group theoretical analysis of the number and symmetry of Raman lines, we provide strong experimental evidence that the structure has been changed from rhombohedral to monoclinic due to co‐doping in BFO. The change in structure was also reflected in morphology of these films. Room temperature magnetic hysteresis curves showed that doped films exhibit enhanced ferromagnetic properties with remnant magnetization of ~10 emu/cm³ and coercive field of 1.2 kOe. The enhanced magnetic properties highlight the potential applications of doped BLNFO thin film for smart devices. Copyright © 2015 John Wiley & Sons, Ltd.