Effect of Gd doping on structural, electrical and magnetic properties of BiFeO3 electroceramic

Room temperature multiferroic electroceramics of Gd doped BiFeO₃ monophasic materials have been synthesized adopting a slow step sintering schedule. Incorporation of Gd nucleates the development of orthorhombic grain growth habit without the appearance of any significant impurity phases with respect to original rhombohedral (R3c) phase of un-doped BiFeO₃. It is observed that, the materials showed room temperature enhanced electric polarization as well as ferromagnetism when rare earth ions like Gd doping is critically optimized (x=0.15) in the composition formula of Bi_1+2xGd_2x/2Fe_1−2xO₃. We believe that magnetic moment of Gd⁺³ ions in Gd doped BiFeO₃ tends to align in the same direction with respect to ferromagnetic component associated with the iron sub lattice. The dielectric constant as well as loss factor shows strong dispersion at lower frequencies and the value of leakage current is greatly suppressed with the increase in concentration of x in the above composition. Addition of excess bismuth and Gd (x=0.1 and 0.15) caused structural transformation as well as compensated bismuth loss during high temperature sintering. Doping of Gd in BiFeO₃ also suppresses spiral spin modulation structure, which can change Fe-O-Fe bond angle or spin order resulting in enhanced ferromagnetic property.     

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.     

Improvement of multiferroic and leakage property in monophasic BiFeO3

This paper aims to report that impurity phase free single phase multiferroic BiFeO₃ ceramic can be prepared by critically optimizing the metal ion concentration using slow step sintering schedule at 850 °C for 24 h. Antiferromagnetic character of pure BiFeO₃ is completely changed and ferromagnetic behavior observed with increase of Bi as well as decrease of Fe concentration. It is found that Bi rich (Bi: 1.2) Fe deficient (Fe: 0.8) composition produces single phase rhombohedral structure with space group R3c along with enhanced ferroelectric and ferromagnetic properties. Incorporation of excess bismuth caused structural distortion and expected to compensate Bi loss during high temperature sintering. On the other hand, iron deficient helps the formation of Fe³⁺ state, which hinders the creation of oxygen vacancies and also favors the reduction of leakage current. Structural distortion in BiFeO₃ changes Fe-O-Fe bond angle or spin order, destructs the spin cycloid and releases a locked magnetization.     

Magnetic, electric, and optical functionalities of (PLZT)x(BiFeO3)1−x ferroelectric-ferromagnetic thin films

We have prepared a series of (PLZT)_x(BiFeO₃)_1−x transparent thin films with thickness of 300 nm by a thermal pyrolysis method. Only films with x≦0.10 formed a single phase of perovskite structure. The film where x=0.10 exhibited both ferromagnetic and ferroelectric properties at room temperature with spontaneous magnetization and coercive magnetic fields of 0.0027μ_B and 5500 G, respectively. The remanent electric polarization and coercive electric field for the film where x=0.10 were 3.0 μC/cm² and 24 kV/cm, respectively. Additionally, films with 0.02≦x≦0.10 showed both magneto-optical effects and the second harmonic generation of transmitted light.     

The effect of Er doping on the spin reorientation transition in Ho1−xErxAl2

The magnetothermal properties of pseudo binary Ho_1−xEr_xAl₂ alloys have been investigated by heat capacity measurements. Two anomalies are observed in the heat capacity of HoAl₂. A sharp peak at 20 K represents the first order spin reorientation transition, and a second order anomaly occurs in the vicinity of the ferromagnetic transition at 32 K. As Ho is partially replaced by Er in Ho_1−xEr_xAl₂ the sharpness of the first order heat capacity peak diminishes with increasing Er concentration, while the temperature of this transition remains practically unaffected. The second order ferromagnetic transition shifts to higher temperature region with increasing Er concentration. The observed behaviors are explained considering the geometry of 4f charge densities of Ho³⁺ and Er³⁺ and the easy magnetization directions of HoAl₂ and ErAl₂.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Magnetostriction of TbxHo0.75−xPr0.25(Fe0.9B0.1)2 (x=0–0.3) compounds

The Tb_xHo_0.75−xPr_0.25(Fe_0.9B_0.1)₂ (x=0, 0.1, 0.15, 0.2, 0.25, and 0.3) compounds are found to stabilize in a cubic Laves phase structure. The lattice parameter, magnetostriction (at 10 kOe), and Curie temperature are found to increase with increasing Tb content. The compound with x=0.15 exhibits a possible anisotropy compensation between the Tb and (Ho/Pr) sublattices. The easy magnetization direction rotates towards the 〈1 1 1〉 from the 〈1 0 0〉 direction, with increasing Tb content. The splitting of the (4 4 0) peak accompanied by the spontaneous magnetostriction-induced rhombohedral distortion is observed for compounds with x?0.15 and the spontaneous magnetostriction (λ_1 1 1) is found to increase with Tb content.     

Effect of K doping on the physical properties of La0.65Ca0.35−xKxMnO3 (0?x?0.2) perovskite manganites

The effects of K doping in the A-site on the structural, magnetic and magnetocaloric properties in La_0.65Ca_0.35−xK_xMnO₃ (0?x?0.2) powder samples have been investigated. Our samples have been synthesized using the solid-state reaction method at high temperature. The parent compound La_0.65Ca_0.35MnO₃ is an orthorhombic (Pbnm space group) ferromagnet with a Curie temperature T_C of 248 K. X-ray diffraction analysis using the Rietveld refinement show that all our synthesized samples are single phase and crystallize in the orthorhombic structure with Pbnm space group for x?0.1 and in the rhombohedral system with R3¯c space group for x=0.2 while La_0.65Ca_0.2K_0.15MnO₃ sample exhibits both phases with different proportions. Magnetization measurements versus temperature in a magnetic applied field of 50 mT indicate that all our investigated samples display a paramagnetic-ferromagnetic transition with decreasing temperature. Potassium doping leads to an enhancement in the strength of the ferromagnetic double-exchange interaction between Mn ions, and makes the system ferromagnetic at room temperature. Arrott plots show that all our samples exhibit a second-order magnetic-phase transition. The value of the critical exponent, associated with the spontaneous magnetization, decreases from 0.37 for x=0.05 to 0.3 for x=0.2. A large magnetocaloric effect (MCE) has been observed in all samples, the value of the maximum entropy change, |ΔS_m|_max, increases from 1.8 J/kg K for x=0.05 to 3.18 J/kg K for x=0.2 under a magnetic field change of 2 T. For x=0.15, the temperature dependence of |ΔS_m| presents two maxima which may arise from structural inhomogeneity.     

Effect of Ba and Ho co-doping on crystal structure,phase transformation,magnetic properties and dielectric properties of BiFeO3

Multiferroics having composition Bi_0.80-xBa_0.20Ho_xFeO₃ (BBFO, BBHFO5, BBHFO10, BBHFO15 and BBHFO20 for x?=?0.0, 0.05, 0.10, 0.15 and 0.20 respectively) were synthesized by method of solid state reaction. The crystal structure has been studied using X-ray diffraction technique. The X-ray patterns show enormous transform in crystal structure at concentration x?=?0.20. The Rietveld refinement of XRD patterns indicates that at concentration x?=?0.0 sample have rhombohedral structure with R3c space group while for the concentration x?=?0.05, 0.10, 0.15 and 0.20, the mixed phase including rhombohedral R3c and triclinic P1 space groups were obtained with best fitting. This phase transformation in crystal structure is observed due to mismatching of ionic radii of doped ions and parent ions. Magnetic properties of all samples were carried out by using vibrating sample magnetometry. M-H hysteresis loops shows that with doping of Ba and Ho antiferromagnetic BiFeO₃ (BFO) transforms into ferromagnetic. The dielectric and ferroelectric measurements were carried out which shows that dielectric constant, dielectric loss and ferroelectric properties are enhanced with co-doping of Ho in comparison of the pristine BFO due to structure deformation and decrease in oxygen vacancies with higher concentration of Ho. Significant improvement has been observed in dielectric constant and remnant magnetization values with increasing content of Ho and decrease in the dielectric loss.     

Low-temperature thermoelectric properties of Bi85Sb15−xNbx alloys prepared by high-press sintering

The nanocrystalline materials with the general formula Bi₈₅Sb_15−xNb_x (x=0, 0.5, 1, 2, 3) were prepared by mechanical alloying and subsequent high-pressure sintering. Their transport properties involving electrical conductivity, Seebeck coefficient and thermal conductivity have been investigated in the temperature range of 80-300 K. The absolute value of Seebeck coefficient of Bi₈₅Sb₁₃Nb₂ reaches a maximum of 161 μV/K at 105 K, which is 69% larger than that of Bi₈₅Sb₁₅ at the same temperature. The power factor and figure-of-merit are 4.45×10⁻³ WK⁻²m⁻¹ at 220 K and 1.79×10⁻³ K⁻¹ at 196 K, respectively. These results suggest that thermoelectric properties of Bi₈₅Sb₁₅ based material can be improved by Nb doping.     

Effect of Dy substitution on structural,magnetic and optical properties of BiFeO3 ceramics

Bi_1−xDy_xFeO₃ (x=0.0, 0.03, 0.05, 0.07, 0.10 and 0.12) ceramics were synthesized by solid state reaction method. Effects of Dy substitution on structural distortion, magnetic and optical properties of BiFeO₃ were examined by X-ray diffraction, Raman and UV–Visible spectroscopy. The samples were found to crystallize in rhombohedral structure of BiFeO₃ with R3c space group. The reduction in lattice parameters and unit cell volume indicate the distortion in FeO₆ octahedra of the rhombohedral structure without any signature of phase transformation up to x=0.12. The predictable weak ferromagnetic hysteresis loops can be observed in the Dy doped samples with maximum remnant magnetization of 0.2103 emu/g for x=0.12. The weak ferromagnetism is ascribed to the suppressed spiral spin structure and magnetically active characteristic of Dy³⁺ ions together with ferromagnetic coupling between Dy³⁺ and Fe³⁺ ions. With optical band gap in visible region, Dy doped BiFeO₃ ceramics are potential material for optoelectronic device and solar cell applications.     

Multiferroic studies on (BiFeO3)m(BaTiO3)n superlattice structures

BiFeO₃ has been studied extensively due to its room temperature multiferroic features and has been proven as a promising candidate for device applications. But BiFeO₃ possesses some drawbacks like high leakage current and complicated magnetic ordering, giving rise to a canted antiferromagnetic behavior. Hence, a superlattice approach of BiFeO₃ and BaTiO₃ with a good lattice matching was fabricated and the room temperature ferroelectric and ferromagnetic properties were studied. The macroscopic and local probe studies reveal a ferroelectric nature at room temperature, and most importantly a weak ferromagnetic like behavior was observed. The ferromagnetic behavior is expected to arise due to the variation introduced in the spin modulation of single BiFeO₃ layer due to the superstructure formation.     

Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Dielectric, ferroelectric, magnetic and magnetoelectric properties of PMN-PT based ME composites

A systematic study of magnetoelectric composite system (x) CoFe₂O₄+(1−x) Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x=0, 0.15, 0.30, 0.45 and 1 was carried out. The lattice strain was calculated using Williamson and Hall equation, which depends on the content of constituent phases in composites. The microstructure was studied using scanning electron microscopy. The ferroelectric transition temperature was independent of the content of individual phases, suggesting that the ferroelectric character is maintained in the composite. Observed P–E and M–H loops indicate that the multiferroic nature of magnetoelectric ceramics is dependent on the content of individual phases. The variation of magnetostriction with dc magnetic field was studied. The maximum magnetoelectric voltage coefficient of 7.2 mV/cm Oe is obtained for the synthesized composites. The magnetoelectric measurements are well explained with magnetostrictive behavior of the magnetic phase.     

Preparation of REFeAsO1−xFx (RE=Sm and Gd) superconductors at a relatively low temperature

A series of the SmFeAsO_1−xF_x and GdFeAsO_1−xF_x (x=0.05, 0.1, 0.15, 0.2, 0.25) samples have been prepared using nano-scaled ReF₃ as the fluorine resource at a relatively low temperature. The samples have been sintered at 1100 and 1120 °C for SmFeAsO_1−xF_x and GdFeAsO_1−xF_x, respectively. These temperatures are at least 50-60° lower than other previous reports. All of the so-prepared samples possess a tetragonal ZrCuSiAs-type structure. Dramatically supression of the lattice parameters and increase in T_c proved that this low temperature process was more effective to introduce fluorine into R_EFeAsO. Superconducting transition appeared at 39.5 K for SmFeAsO_1−xF_x with x=0.05 and at 22 K for GdFeAsO_1−xF_x with x=0.1. The highest T_c was detected to be 54 K in SmFeAsO_0.8F_0.2 and 40.2 K in GdFeAsO_0.75F_0.25. The use of the nano-scaled ReF₃ compounds has improved the efficiency of the present low temperature method in synthesizing the fluorine-doped iron-based superconductors.     

Magnetoelectric characterization of xNi0.75Co0.25Fe2O4-(1−x)BiFeO3 nanocomposites

Magnetoelectric (ME) nanocomposites containing Ni_0.75Co_0.25Fe₂O₄-BiFeO₃ phases were prepared by citrate sol-gel process. X-ray diffraction (XRD) analysis showed phase formation of xNi_0.75Co_0.25Fe₂O₄-(1−x)BiFeO₃ (x=0.1, 0.2, 0.3 and 0.4) composites on heating at 700 °C. Transmission electron microscopy revealed the formation of powders of nano order size and the crystal size was found to vary from 30 to 85 nm. Dispersion in dielectric constant (ε) and dielectric loss (tan δ) in the low-frequency range have been observed. It is seen that nanocomposites exhibit strong magnetic properties and a large ME effect. On increasing Ni_0.75Co_0.25Fe₂O₄ contents in the nanocomposites, the saturation magnetization (M_S) and coercivity (H_C) increased after annealing at 700 °C. The large ME output in the nanocomposites exhibits strong dependence on magnetic bias and magnetic field frequency. The large value of ME output can be attributed to small grain size of ferrite phase of nanocomposite being prepared by citrate precursor process.     

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.     

Enhanced thermoelectric properties of bismuth intercalated compounds BixTiS2

The thermoelectric properties of Bi intercalated compounds Bi_xTiS₂ have been investigated at the temperatures from 5 to 310 K. The results indicate that Bi intercalation into TiS₂ leads to substantial decrease of its electrical resistivity (one order low for x=0.05 and two orders low for x=0.15, 0.25 at 300 K) and lattice thermal conductivity (22, 115 and 158% low at 300 K for x=0.05, 0.15 and 0.25, respectively). Specially, the figure of merit, ZT, of lightly intercalated compound Bi_0.05TiS₂ has been improved at all temperatures investigated, and specifically reaches 0.03 at 300 K, which is about twice as large as that of TiS₂.     

A novel high-k ‘Y5V’ barium titanate ceramics co-doped with lanthanum and cerium

Structural, dielectric, and ferroelectric properties of a novel high-k ‘Y5V’ (Ba_1−xLa_x)(Ti_1−x/4−yCe_y)O₃ ceramics (where x=0.03 and y=0.05, denoted by BL3TC5) with the highest ‘Y5V’ dielectric response (ε′>10 000) among rare-earth-doped BaTiO₃ ceramics to date are investigated in detail using SEM, TEM, XRD, DSC, EPR, Raman spectroscopy (RS), temperature and frequency, electric field dependences of dielectric permittivity (ε′), and temperature and electric field dependences of ferroelectric hysteresis loops. The BL3TC5 diffusion of ferroelectric phase transition occurs around dielectric peak temperatures (T_m) near a room temperature characteristic of dielectric thermal relaxation. Powder XRD data and defect complex model were given. “Relaxor” behavior associated with an order/disorder model and formation of a solid solution were discussed. The EPR results provided the evidence of Ti vacancies as compensating for lattice defects. High-k relaxor nature of BL3TC5 is characterized by an average cubic structure with long-range lattice disordering and local polar ordering; a slow change of the ε′ (T) and P_r(T) curves around T_m; no phase transition observed by DSC; and a broad, red-shifted A₁ (TO₂) Raman phonon mode at 251 cm⁻¹ accompanying the disappearance of the “silent” mode at 305 cm⁻¹ and a clear anti-resonance effect at 126 cm⁻¹ at room temperature.     

Piezoresponse force microscopy and magnetic force microscopy characterization of γ-Fe2O3-BiFeO3 nanocomposite/Bi3.25La0.75Ti3O12 multiferroic bilayers

The multiferroic behavior of epitaxial γ-Fe₂O₃-BiFeO₃ (composite)/Bi_3.25La_0.75Ti₃O₁₂ bi-layered heterostructures grown on SrRuO₃/SrTiO₃ (1 1 1) substrates has been studied using piezoresponse force microscopy, magnetic force microscopy and magnetometry. The ferroelectric domain structure is ascribed to the BiFeO₃ phase while the magnetism originates in the γ-Fe₂O₃ phase of the composite layer. Our studies demonstrate the presence and switching of magnetic and ferroelectric domains within the same area of the sample. This confirms the presence of multiferroic behavior at the nanoscale in our γ-Fe₂O₃-BiFeO₃ nanocomposite thin films.