Electronic structure, magnetic and electrical properties of multiferroic PbFe1/2Ta1/2O3

Structural analysis of the synthesized lead iron tantalate, PbFe_1/2Ta_1/2O₃ (PFT) is performed by the refinement of the X-ray diffraction data at room temperature using the GSAS code. Energy dispersive X-ray spectrometry analysis is done to find out the chemical composition. The electronic structure of PFT is calculated by the first principles full potential linearized augmented plane wave method. The spin polarized density of states shows the insulating nature. The magnetic moment of 4.3 μB per Fe ion is obtained from the electronic structure calculation using the GGA+U method and compared with the available experimental data. The electronic structure of the PFT is verified by X-ray photoemission spectroscopy. The dielectric spectroscopy is applied to investigate the electrical properties of PFT in the frequency range from 100 Hz to 1 MHz and in the temperature range from 183 to 253 K. The frequency dependent electrical data are analyzed by conductivity formalism. The relaxation mechanism is explained using the Cole-Cole approach.     

Thermodynamic properties of LiCu2O2 multiferroic compound

A spin model of quasi-one-dimensional LiCu₂O₂ compound with ground state of ellipsoidal helical structure has been adopted. The helical axis is along the diagonal of CuO₄ squares. By taking into account the interchain coupling and exchange anisotropy, the exotic magnetic properties and ferroelectricity induced by spiral spin order have been studied by performing Monte Carlo simulation. The simulation results qualitatively reproduce the main characters of ferroelectric and magnetic behaviors of LiCu₂O₂ compound and confirm the low-temperature noncollinear spiral ordering. Furthermore, by performing the calculations of spin structure factor, we systematically investigate the effects of different exchange couplings on the lower-temperature magnetic transition, and find that the spiral spin order depends not only on the ratio of nearest and next-nearest neighbor inchain spin coupling but also strongly on the exchange anisotropy.     

Neutron polarization analysis on the multiferroic TbMn2O5

Polycrystalline TbMn₂O₅ was prepared by the standard solid-state reaction method and characterized by powder X-ray diffraction and magnetization to assure it is of single phase. Heat capacity measurements on the compound reveal an antiferromagnetic phase transition at 45 K. A broad peak below 6 K in the heat capacity measurements corresponds to the crossover transition of Tb³⁺ ordering. To confirm these magnetic orderings, neutron powder diffractions on TbMn₂O₅ with XYZ neutron polarization analysis were performed at the diffuse neutron scattering (DNS) spectrometer, FRJ-II, by using neutron wavelength of 4.8 Å in the temperature range of 1.8–250 K. Magnetic scattering was separated from nuclear coherent and spin incoherent scattering contributions. Long-range ordered magnetic peaks were observed below 39 K which is consistent with the heat capacity results. The drastic increasing intensities below 6 K indicate the ferromagnetic transition in Tb³⁺ orderings.     

Anisotropic dielectric properties of PbYb1/2Ta1/2O3 single crystals

PbYb_1/2Ta_1/2O₃ single crystals were obtained for the first time. They were grown by the flux method. The PbOPbF₂B₂O₃ system was used as a solvent. Dielectric investigations were carried out in 1 0 0_c, 1 1 0_c and 1 1 1_c pseudocubic directions. These studies pointed to anisotropy of dielectric properties. Frequency-independent ε′(T) and ε″(T) maxima related to the antiferroelectric–paraelectric (AFE—PE) phase transition are observed for all directions at 562 K. The frequency-dependent ε′(T) and ε″(T) maxima near 400 K related to the ferroelectric (FE)–AFE phase transition are observed only in 1 1 1_c direction. The hysteresis loops were observed in this direction only. These results point that ferroelectric relaxor properties appear only in 1 1 1_c direction. We propose to consider the ferroelectric phase as ferrielectric one.     

Physical properties of BaMg1/3Nb2/3O3-BaCo1/3Nb2/3O3 solid solutions

Structural, electric and magnetic properties of Ba₃Mg_1−xCo_xNb₂O₉ based dielectric ceramic compounds have been studied. The samples, prepared by a solid state reaction method, were characterised by X-ray powder diffraction (XRPD), electron microscopy (SEM), dielectric (ε(T)) and magnetic measurements (χ⁻¹(T)). The XRPD analyses showed that the crystal structure of these compounds does change by the increase of substitution degree, passing from a superstructure hexagonal-type, (no. 164), space group (SG) to a simple structure cubic-type, (no. 221), SG. However, the evolution of the elementary unit cell lattice parameter can be followed and it exhibit a linear increasing tendency with increase in the substitution, indicating the existence of a solid solution through out the investigated range of substitution (0-1). The microstructure analysis shows a variation in the grain size and also the porosity of the samples with the degree of substitution. The results are in good agreement with that of dielectric measurements, which also showed that the dielectric constant (ε) increases with the increase of cobalt content. The magnetic characterization of cobalt substituted samples showed an antiferromagnetic type super-exchange interaction between these magnetic ions. At the same time, the values of effective magnetic momentum (μ_eff) are close to the value that corresponds to Co²⁺ free ions. The study highlights the possibility of modelling these materials by substitutions, in order to improve properties of negative-positive-zero (NPO) type dielectric applications.     

Low-frequency dielectric dispersion and magnetic properties of La,Gd modified Pb(Fe1/2Ta1/2)O3 multiferroics

Pb(Fe_1/2Ta_1/2)O₃ (PFT) modified by rare-earth (La and Gd) ions has been synthesized in a single phase using a double-stage synthesis (i.e., Columbite) technique. Scanning electron micrographs (SEM) of the pellet samples have shown a significant change in their grain size and uniform distribution of Gd/La at the Fe-sites. The room temperature X-ray structural analysis shows that the reported cubic (or tetragonal) structure of PFT has been distorted to a monoclinic system on substitution of La/Gd at the Fe-site. Detailed studies of dielectric properties of the above compound on La/Gd substitution have shown strong dielectric dispersion at low frequency (i.e. relaxor behavior) with drastic change in transition temperature. Magnetic characterization shows that though the PFT sample displays an antiferromagnetic transition at ∼150 K, the rare-earth ions-substituted samples do not. Furthermore, temperature dependence of magnetization measurements shows that spin glass transition observed in PFT at low temperatures (5–20 K) does not exist in the La and Gd substituted PFT. Doping of Gd in PFT increases the sample magnetization, especially at low temperature.     

Terahertz spectroscopy of multiferroic EuFe3(BO3)4

The terahertz spectra of a rare-earth iron borate with the huntite structure are obtained for the first time. We study the low-temperature (4.0–90 K) α-polarized transmittance spectra of the EuFe₃(BO₃)₄ single crystal in the region 0.9–6.0 THz. Pronounced shifts of phonon frequencies and appearance of new phonon modes at the temperature _TS=58 K$T_S=58\text{K}$ of the R32→P₃₁21$R32\to P{3}_{1}21$ structural phase transition are observed. Additional shifts of phonon frequencies occur at the temperature _TN=34 K$T_N=34\text{K}$ of the magnetic ordering of the Fe subsystem, thus evidencing the spin–phonon coupling in this multiferroic material.     

Improved multiferroic properties and a novel magnetic behavior of Bi0.8La0.2Fe1−xCoxO3 nanoparticles

Bi_0.8La_0.2Fe_1−xCo_xO₃ nanoparticles of single phase (BLFCO_x, x=0, 0.005, 0.01, 0.02) were prepared by a sol-gel method using polyvinyl alcohol as a surfactant. Co substitution at Fe site improved further dielectric properties of Bi_0.8La_0.2FeO₃ nanoparticles in the frequency range below 25 MHz at room temperature. Magnetization at 10 kOe, coercivities, and remanence of BLFCO_x nanoparticles increased with increasing Co content. It is interesting that the hysteresis loop of all the BLFCO_x nanoparticles presented a wasp-waisted shape. The property can open an important way to design new multiferroic applications of low hysteresis loss in low magnetic fields.     

Structural and magnetic studies of Fe2O3/SiO2 granular nanocomposites

Fe₂O₃/SiO₂ nanocomposites were synthesized by mechanical alloying, using Fe and SiO₂ powders as precursors. After 340 h milling, the sample essentially consists of hematite and amorphous silica. TEM images show hematite particles embedded in and surrounded by an amorphous silica matrix. A broad size distribution—5–50 nm—of hematite particles is found, and other group of very small—2–3 nm—unidentified particles are observed. Room temperature Mössbauer spectra show a paramagnetic doublet, which may correspond to a non-crystalline phase in the sample (probably the small unidentified particles), and a sextet corresponding to hematite. Magnetic properties were investigated by measuring hysteresis curves at different temperatures (5–300 K) and by zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves (10 mT). The hysteresis loops were well fitted by a ferromagnetic contribution. No evidence of Morin transition is found down to 5 K.     

Improvement of the remanence properties and the weakening of interparticle interactions in BaFe12O19 particles by B2O3 addition

In the present study, the effects of B₂O₃ addition on the remanence properties of barium ferrite magnets are examined. The relationship between isothermal magnetization remanence M_R(H) and demagnetization remanence M_D(H) for non-interacting single domain particles, M_D(H)=M_R(H_max)−2M_R(H), was used in order to investigate the interactions between particles. We have found that remanence magnetization M_R increased by 40% in magnitude with B₂O₃ addition in addition to the weakened couplings between particles. The B₂O₃ addition seems to supply the required conditions for usage of these materials in the magnetic recording media.     

Magnetic properties of a cermet on the base of Al2O3

The zero-field-cooled and field-cooled magnetizations, magnetization versus field, and remanent magnetization were measured for a cermet on the base of Al₂O₃ using a SQUID magnetometer in the temperature range of 2–360 K. It was shown that magnetic properties of the cermet are determined by independent ferromagnetic, paramagnetic and spin-glass contributions. The spin-glass behavior was studied.     

Effect of Fe/Pb molar ratio on the structure,magnetic and dielectric properties of PbFe12O19 nanoparticles

In this paper, lead hexaferrite (PbFe₁₂O₁₉) nanoparticles were synthesized by sol-gel method. In order to prepare PbFe₁₂O₁₉ nanoparticles, the metal nitrates with Fe/Pb?=?8, 10, 11, 12, 14 ratios and citric acid were used. The structure, morphology, magnetic, and dielectric properties of PbFe₁₂O₁₉ nanoparticles were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), vibrating sample magnetometer (VSM) and LCR meter. XRD results revealed that the samples with Fe/Pb?≤?10 and Fe/Pb?>?10 have single-phase hexaferrite and hematite (α- Fe₂O₃) structures, respectively. As a result, the sample with Fe/Pb?=?10 is single-phase and shows the highest values of the saturation magnetization and remanence magnetization. We found that the values of dielectric constant (ε′) and dielectric loss (ε″) increase with an increase in the Fe/Pb molar ratio from 8 to 12 and then decreases with an increase of Fe/Pb molar ratio to 14. The variation of ac conductivity (σ_ac) with frequency ranging from 1?kHz to 200?kHz showed that electrical conductivity in these ferrites is mainly due to the electron hopping mechanism.     

Electrical properties of SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. Scanning electron microscopy was applied to investigate the grain structure. The XRD studies revealed an orthorhombic structure in the SBNT 50/50 with lattice parameters a=5.522 Å, b=5.511 Å and c=25.114 Å. The dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material. Its occurrence was ascribed to the presence of ionized space charge carriers such as oxygen vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. The temperature dependence of various electrical properties was determined and discussed. The thermal activation energy for the grain electric conductivity was lower in the high temperature region (T>303.6 °C, E_a−ht=0.47 eV) and higher in the low temperature region (T<303.6 °C, E_a−lt=1.18 eV).     

Structural, microstructural and magnetic properties of NiFe2O4, CoFe2O4 and MnFe2O4 nanoferrite thin films

The structural, microstructural and magnetic properties of nanoferrite NiFe₂O₄ (NF), CoFe₂O₄ (CF) and MnFe₂O₄ (MF) thin films have been studied. The coating solution of these ferrite films was prepared by a chemical synthesis route called sol-gel combined metallo-organic decomposition method. The solution was coated on Si substrate by spin coating and annealed at 700 °C for 3 h. X-ray diffraction pattern has been used to analyze the phase structure and lattice parameters. The scanning electron microscopy (SEM) and atomic force microscopy (AFM) have been used to show the nanostructural behavior of these ferrites. The values of average grain's size from SEM are 44, 60 and 74 nm, and from AFM are 46, 61 and 75 nm, respectively, measured for NF, CF and MF ferrites. At room temperature, the values of saturation magnetization, M_s∼50.60, 33.52 and 5.40 emu/cc, and remanent magnetization, M_r∼14.33, 15.50 and 1.10 emu/cc, respectively, are observed for NF, CF and MF. At low temperature measurements of 10 K, the anisotropy of ferromagnetism is observed in these ferrite films. The superparamagnetic/paramagnetic behavior is also confirmed by χ′(T) curves of AC susceptibility by applying DC magnetizing field of 3 Oe. The temperature dependent magnetization measurements show the magnetic phase transition temperature.     

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.     

Electric field effects on the dielectric and acoustic anomalies of Pb[(Mg1/3Nb2/3)0.83Ti0.17]O3 single crystals studied by dielectric and Brillouin spectroscopies

The effect of the electric field on the dielectric and acoustic properties of Pb[(Mg_1/3Nb_2/3)_0.83Ti_0.17]O₃ single crystals was investigated as functions of temperature and the electric field strength. The dielectric constant and the acoustic mode behaviors exhibited typical relaxor behaviors when there was no bias field. The longitudinal acoustic mode showed splitting under a moderate electric field of 1 kV/cm applied along the [001] direction, indicating coexistence of macroscopic/mesoscopic ferroelectric states and relaxor states. Further increase in the electric field up to 2 kV/cm induced a clear ferroelectric phase transition, which became smeared out due to the proximity of the electric field to the critical point. The electric field-temperature phase diagram of Pb[(Mg_1/3Nb_2/3)_0.83Ti_0.17]O₃ was suggested based on the observed field-induced changes in the dielectric and the acoustic properties.     

Dielectric relaxation and ac conduction in multiferroic TbMnO3 ceramics: Impedance spectroscopy analysis

Polycrystalline samples of Tb_1−xAl_xMnO₃ (x = 0, 0.1, 0.2) have been synthesized by means of standard high-temperature solid-state reaction technique. Detailed studies on the effect of compositional variation of aluminum (Al) on the electrical behavior (complex impedance Z*, complex modulus M*, and relaxation mechanisms) of the parent TbMnO₃ have been performed by using the nondestructive complex impedance spectroscopy technique at temperatures above room temperature. In the temperature range covered, the impedance plots signalize that the grains are the unique responsible for the conduction mechanism of the concerned material. The impedance spectra are well modeled in terms of electrical equivalent circuit with a grain resistance (R_g) and constant phase element impedance (Z_CPE). The conductivity data of the undoped and Al-doped samples are well fitted by the universal Jonscher's power law. The resulting fitting parameters indicate that for the studied samples, the hopping process occurs between neighboring sites. Activation energy values for dc conductivity are calculated for undoped and Al-doped samples and found to decrease when Al is incorporated. In turn, the emergence of single arc in the complex modulus spectrum for all the compositions of Al suggests that for the studied samples only one type of relaxation behavior is present at the selected temperatures. A non-Debye-type relaxation is clearly verified. The relaxation process in the present samples seems to be composition and temperature dependent, particularly at higher frequencies.     

Piezoelectric, dielectric and magnetic properties of (1-x)Pb[Zr, Ti, (Mg1/2W1/2), (Ni1/3Nb2/3)]O3+x(Ni, Co, Cu)FeO4 composites

The phase structure, microstructure, piezoelectric properties, dielectric characteristic and the ME effect of magnetoelectric Pb[Zr_0.23Ti_0.36+0.02(Mg_1/2W_1/2)+0.39(Ni_1/3Nb_2/3)]O₃ (PZT)+xNi_0.8Co_0.1Cu_0.1Fe₂O₄ (NCCF) composite ceramics were prepared by the conventional solid state reaction method. The structural analysis of both the constituent phases and their composites was carried out by X-ray diffraction, energy dispersive spectrometry and scanning electron microscopy. The results showed cubic spinel structure for ferrite phase and tetragonal perovskite structure for ferroelectric phase. The piezoelectric constant, dielectric constant, Curie temperature, remanent polarization and coercive electric field decreased with increase of ferrite content. The coercive field strength, saturation magnetization and remanent magnetization increased with increasing ferrite content.     

Bi1-xYbxFeO3的结构相变与磁性

用溶胶-凝胶法制备了Bi_1-xYb_xFeO₃(0≤x≤0.2)粉晶样品,并用X射线衍射光谱和拉曼光谱对其结构进行了研究. 结果表明, 在x=0.1～0.125, 发生了结构相变, 由菱形R3c结构变为正交Pnma结构,对应的应该是从铁电相到顺电相的转变. 在结构相变边界,磁化强度达到最大值. 其原因是在低浓度掺杂区域,随着Yb³⁺的掺杂浓度的增大,BiFeO₃的自旋螺旋结构受到抑制,部分未被抵消的磁矩被释放出来,到了相变边界,自旋螺旋结构受到的抑制达到最大,磁矩被完全释放出来. 随着x的继续增大,磁化强度开始逐渐减小,这是由于逐渐形成了良好的反铁磁序排列.     

Magnetic and rheological properties of monodisperse Fe3O4 nanoparticle/organic hybrid

Fe₃O₄ nanoparticle/organic hybrids were synthesized via hydrolysis using iron (III) acetylacetonate at ∼80 °C. The synthesis of Fe₃O₄ was confirmed by X-ray diffraction, selected-area diffraction, and X-ray photoelectron spectroscopy. Fe₃O₄ nanoparticles in the organic matrix had diameters ranging from 7 to 13 nm depending on the conditions of hydrolysis. The saturation magnetization of the hybrid increased with an increase in the particle size. When the hybrid contained Fe₃O₄ particles with a size of less than 10 nm, it exhibited superparamagnetic behavior. The blocking temperature of the hybrid containing Fe₃O₄ particles with a size of 7.3 nm was 200 K, and it increased to 310 K as the particle size increased to 9.1 nm. A hybrid containing Fe₃O₄ particles of size greater than 10 nm was ferrimagnetic, and underwent Verwey transition at 130 K. Under a magnetic field, a suspension of the hybrid in silicone oil revealed the magnetorheological effect. The yield stress of the fluid was dependent on the saturation magnetization of Fe₃O₄ nanoparticles in the hybrid, the strength of the magnetic field, and the amount of the hybrid.