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.     

Study of superstructure II in multiferroic BiMnO3

The crystal structure of the minor phase, named superstructure II, existing in multiferroic compound BiMnO3 has been studied by electron diffraction and high-resolution transmission electron microscopy. Domains of major and minor phases coexisting in BiMnO3 were observed in high-resolution electron microscope images. The unit cell of minor phase was determined to be triclinic with the size 4×4×4 times as large as the distorted perovskite subcell. The [111] and [101] projected structure maps of the minor phase have been derived from the corresponding images by means of the image processing. A possible rough three-dimensional （3D） structure model was proposed based on the 3D structural information extracted from the two projected structure maps. Since there is no inversion centre in the proposed model, the minor phase may contribute to the ferroelectric property of BiMnO3.     

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.     

Piezoelectric measurements on BiFeO3 single crystal by Raman scattering

The piezoelectric response of BiFeO₃ at low temperature has been investigated by Raman scattering measurements. The application of an external electric field at T=10 K induces frequency shifts of the lowest frequency mode related to the Bi-O bonds and corresponding to the soft mode of the ferroelectric transition. The piezoelectric effect is responsible for the softening of this mode via the tensile stress leading to the expansion of the crystal. The phonon deformation potential associated with the soft mode has been estimated around −200 cm⁻¹/strain units using the linear piezoelectric coefficient d₃₃=16 pm/V. It found in the range of the ones obtained for typical piezoelectrics.     

On the Mossbauer parameters in BiFeO3

The Mössbauerspectrum of BiFeO₃ is shown to consist of two super-imposed six-line spectra. The main distinction between the two iron sites is made up by the different ΔE_Q values, even having opposite sign. A qualitative explanation is proposed.     

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.     

Magnetic and dielectric properties of alkaline earth Ca and Ba ions co-doped BiFeO3 nanoparticles

Ca²⁺ and Ba²⁺ ions co-doped BiFeO₃ nanoparticles, Bi_0.8Ca_0.2−xBa_xFeO₃ (x=0-0.20), were prepared by a sol-gel method. The phase structure, grain size, dielectric and magnetic properties of the prepared samples were investigated. The results showed that the lattice structure of the nanoparticles transformed from rhombohedral (x=0) to orthorhombic (x=0.07-0.19) and then to tetragonal (x=0.20) with x increased. The dielectric properties of the nanoparticles were affected by the properties of the substitutional ions as well as the crystalline structure of the samples. The magnetic properties of the nanoparticles were greatly improved and the T_N of the nanoparticles was obviously increased. All the Ca²⁺ and Ba²⁺ ions co-doped BiFeO₃ nanoparticles presented the high ratio of M_r/M from 0.527 to 0.571 and large coercivity from 4.335 to 5.163 KOe.     

Swift heavy ion irradiation induced modification of BiFeO3 thin films prepared by sol-gel method

We report the preparation of multiferroic BiFeO₃ thin films on ITO coated glass substrates through sol-gel spin coating method followed by thermal annealing and their modification by swift heavy ion (SHI) irradiation. X-ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 550°C. Both XRD and Raman studies indicated that SHI irradiation by 200 MeV Au ions result in fragmentation of particles and progressive amorphization with increasing irradiation fluence. The average crystallite size estimated from the XRD line width decreased from 38 nm in pristine sample annealed at 550°C to 29 nm on irradiating these films by 200 MeV Au ions at 1 × 10¹¹ ions cm⁻². Complete amorphization of the rhombohedral BiFeO₃ phase occurs at a fluence of 1 × 10¹² ions.cm⁻². Irradiation by another ion (200 MeV Ag) had the similar effect. For both the ions, the electronic energy loss exceeds the threshold electronic energy loss for creation of amorphized latent tracks in BiFeO₃.     

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.     

Study on up-conversion emissions of Yb/Tm co-doped GdF3 and NaGdF4

The Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were synthesized through a combination method of a co-precipitation and an argon atmosphere annealing procedures. X-ray diffraction analysis indicated that the Yb³⁺/Tm³⁺ co-doped GdF₃ sample crystallized well and was orthorhombic phase, and the Yb³⁺/Tm³⁺ co-doped NaGdF₄ sample was hexagonal phase. With a 980-nm semiconductor continuous wave laser diode as the excitation source, the up-conversion emission spectra of the two samples in the wavelength range of 240-510 nm were recorded. In the up-conversion emissions of the samples, Yb³⁺ transferred energies to Tm³⁺ resulting in their ultraviolet, violet, and blue up-conversion emissions. And, Tm³⁺ simultaneously transferred energies to Gd³⁺, which finally resulted in ultraviolet up-conversion emissions of Gd³⁺. The study on the excitation power dependence of up-conversion fluorescence intensity indicated that there were multi-photon (three-, four-, five-, and six-) processes in the up-conversion emissions of the samples. And the up-conversion emissions of Gd³⁺ and Tm³⁺ in the Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were compared studied, too.     

Spin Hall Magnetoresistance in Pt/BiFeO3 Bilayer

Multiferroic materials are general antiferromagnets with negligibly small net magnetization, which strongly limits their magnetoelectric applications in spintronics. Spin Hall magnetoresistance(SMR) is sensitive to the orientation of the Néel vector, which can be applied for the detection of antiferromagnetic states. Here, we apply SMR on the unique room-temperature antiferromagnetic multiferroic material BiFeO₃(BFO). The angular dependence of SMR in a bilayer of epitaxial BFO(001) an...     

Enhanced room temperature ferromagnetism in porous BiFeO3 prepared using cotton templates

Porous BiFeO₃ has been prepared using cotton templates. Strongly enhanced ferromagnetism with saturate magnetization of 3 emu/g at 300 K has been observed. An energy band gap of 2.21 eV was determined from the UV-visible diffuse reflectance spectrum. The Raman and X-ray photoelectron spectroscopy measurements indicate the existence of Fe²⁺ and the suppression of the oxygen octahedral tilts. The enhanced ferromagnetism has been attributed to the enhanced double exchange interaction with increased angle of Fe^{2 +}-O-Fe^{3 +}.     

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.     

Ferroelectric polarization reversal tuned by magnetic field in a ferroelectric BiFeO3/Nb-doped SrTiO3 heterojunction

Interfacial resistive switching of a ferroelectric semiconductor heterojunction is highly advantageous for the newly developed ferroelectric memristors. Moreover, the interfacial state in the ferroelectric semiconductor heterojunction can be gradually modified by polarization reversal, which may give rise to continuously tunable resistive switching behavior. In this work, the interfacial state of a ferroelectric BiFeO₃/Nb-doped SrTiO₃ junction was modulated by ferroelectric polarization reversal. The dynamics of surface screening charges on the BiFeO₃ layer was also investigated by surface potential measurements, and the decay of the surface potential could be speeded up by the magnetic field. Moreover, ferroelectric polarization reversal of the BiFeO₃ layer was tuned by the magnetic field. This finding could provide a method to enhance the ferroelectric and electrical properties of ferroelectric BiFeO₃ films by tuning the magnetic field.     

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.     

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.     

Weak ferromagnetism in BiFeO3 doped with titanium

The Bi_1−xA_xFe_1−xTi_xO₃ (A—Ca, Sr, Pb, Ba) and BiFe_1−xTi_xO_3+δ systems have been studied using X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that all Bi_1−xA_xFe_1−xTi_xO₃ solid solutions are rhombohedral up to x=0.3. In the case of BiFe_1−xTi_xO_3+δ the rhombohedral distortion preserved up to x=0.11. A homogeneous weakly ferromagnetic state was found for Bi_1−xCa_xFe_1−xTi_xO₃ (0.15≤x≤0.25) and BiFe_1−xTi_xO_3+δ (0.06≤x≤0.11), probably due to magnetoelectric interactions, whereas Bi_1−xA_xFe_1−xTi_xO₃ (A—Sr, Pb, Ba) compounds above doping level x>0.1 seem to be collinear antiferromagnets.     

Magnetic properties of hydrothermally synthesized BiFeO3 nanoparticles

BiFeO₃ nanoparticles with diameters in the range 65–90 nm were prepared using a hydrothermal technique. Low-temperature magnetic measurements showed ferromagnetic behavior of the samples below a certain temperature. The magnetization values were drastically reduced in the case of samples having larger diameters. This was explained as arising due to a reduction of the number of uncompensated spins associated with Fe³⁺ ions as particle diameter was increased. A surface spin disorder is believed to be responsible for this property.     

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.