Sr doping effects on the transport and magnetic properties of GdBaCo2O5+δ

Studies on some new members of the cobalt perovskite Gd_1−xSr_xBaCo₂O_5+δ with low strontium concentrations (0<x<0.1) have been carried out with the aim of investigating possible metallization of the GdBaCo₂O_5+δ system by hole doping. Low temperature electrical resistivity, magnetic susceptibility and thermopower of the above system have been studied. The pristine compound with x=0 and δ∼0.5 exhibits a semiconductor-like behavior and two magnetic transitions below room temperature. Upon Sr²⁺ substitution, there is a fall in resistivity by 2-3 orders of magnitude at low temperature and also a dramatic reduction in the ferromagnetic to antiferromagnetic transition temperature. These changes can be explained on the basis of hole doping (and increase in the Co⁴⁺content). Evidence for an increase in Co⁴⁺ with Sr²⁺ substitution is provided by iodometric analysis.     

The effect of Fe substitution on the electrical and thermal conductivity and thermopower of Ca3(FexCo1−x)4O9 synthesised by a sol–gel process

The effect of Fe substitution for Co on direct current (DC) electrical and thermal conductivity and thermopower of Ca₃(Co_1−xFe_x)₄O₉ (x = 0, 0.05, 0.08), prepared by a sol–gel process, was investigated in the temperature range from 380 down to 5K. The results indicate that the substitution of Fe for Co results in an increase in thermopower and DC electrical resistivity and substantial (14.9–20.4% at 300K) decrease in lattice thermal conductivity. Experiments also indicated that the temperature dependence of electrical resistivity ρ for heavily substituted compounds Ca₃(Co_1−xFe_x)₄O₉ (x = 0.08) obeyed the relation lnρ ∝ T^−1/3 at low temperatures, T < ~55K, in agreement with Mott’s two-dimensional (2D) variable range hopping model. The enhancement of thermopower and electrical resistivity was mainly ascribed to a decrease in hole carrier concentration caused by Fe substitution, while the decrease of thermal conductivity can be explained as phonon scattering caused by the impurity. The thermoelectric performance of Ca₃Co₄O₉ was not improved in the temperature range investigated by Fe substitution largely due to great increase in electrical resistivity after Fe substitution.     

High-temperature thermoelectric properties of Ca3Co4O9+δ with Eu substitution

We have prepared polycrystalline Ca_3−xEu_xCo₄O_9+δ (x=0, 0.15, 0.3 and 0.45) samples using a sol-gel process followed by SPS sintering and investigated the Eu substitution effects on their high-temperature thermoelectric properties. With the Eu substitution, both the electrical resistivity and thermopower increase monotonously. This could be attributed to the decrease of hole concentrations by substitution of trivalent Eu³⁺ for divalent Ca²⁺. The Eu substituted samples (x=0.15, x=0.3) have lower thermal conductivity than Ca₃Co₄O_9+δ due to their lower electronic and lattice thermal conductivity. The dimensionless figure of merit ZT reaches 0.3 at 1000 K for the sample of Ca_2.7Eu_0.3Co₄O_9+δ.     

Photoluminescence in MgxSr1−xAl2O4:Eu, Ndand electron-vibrational interaction in the Eu 5d states

Green phosphor compositions Mg_xSr_1−xAl₂O₄:Eu, Nd (with x=0.05-0.25) were prepared by solid state reaction method. The effect of Mg substitution on photoluminescence characteristics was investigated. The photoluminescence show intense green emission for MgSrAl₂O₄:Eu²⁺, Nd³⁺ with long persistence. This green emission corresponds to transitions from 4f⁶5d¹ to 4f⁷ of Eu²⁺ ion. Comparative analysis of the excitation and emission spectra were used to evaluate the crystal field splitting of the 5d states of Eu²⁺ and the parameters of electron-vibrational interaction, such as Huang-Rhys factor, effective phonon energy, and zero-phonon line position.     

Could Mg content control the conduction mechanism of Ba Co Zn-W-type hexagonal ferrites?

Electrical properties as a function of composition, frequency and temperature for a series of W-type hexagonal ferrites with the general formula BaCoZn_1−xMg_xFe₁₆O₂₇; 0≤x≤0.6 prepared using the conventional ceramic method were studied. These samples are semiconductor-like materials, where the ac conductivity increases with increasing temperature. The results show that the conduction mechanism depends on the Mg²⁺ substitution. The transition temperature (T_σ) increases with increasing Mg content and gives a hump at x=0.5; after that T_σ decreases again. Both the ac conductivity and dielectric constant vary with Mg content and reach the highest value at x=0.5, due to the highest value of the ratio of Fe²⁺/Fe³⁺ at x=0.5. The peak value of the dielectric constant depends on the Mg content x.     

Substitutional effect of Cr ions on the properties of Mg–Zn ferrite nanoparticles

The effect of Cr³⁺ substitution in Mg–Zn ferrite, with a chemical formula Mg_0.5Zn_0.5Cr_xFe_2−xO₄ (x=0.0–1.0), synthesized by a sol–gel auto-combustion reaction is presented in this paper. The resultant powders were investigated by various techniques, including X-ray diffractometry (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR), vibrating sample magnetometry (VSM), and DC resistivity. The XRD pattern revealed that the cubic spinel structure is maintained for the all the compositions. The particle sizes measured from XRD and TEM are in good agreement with each other. The cation distribution suggests that Mg²⁺, Cr³⁺ and Fe³⁺ have strong preference towards octahedral B-site. The theoretical lattice constant and experimental lattice constant match each other very well. The IR analysis supports the presently accepted cation distribution. The saturation magnetization decreases linearly with increasing Cr³⁺ content. Curie temperatures are obtained by the Laoria and AC susceptibility techniques. The dc resistivity has been investigated as a function of temperature and composition.     

Cation distribution in NixMg1−xFe2O4 studied by XPS and Mössbauer spectroscopy

Ni–Mg ferrites, synthesized by solid-state route, were analyzed by X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy to find the distribution of Mg²⁺ in tetrahedral (A) and octahedral (B) sites of the spinel. In Ni_xMg_1−xFe₂O₄, Ni²⁺ enters in B site resulting in a reduction in the availability of B sites for the distribution of Mg²⁺ and Fe³⁺ and thereby influences the distribution of Mg²⁺. It was observed through both techniques that higher percentage of Mg²⁺ occupied the tetrahedral sites of Ni rich spinel systems. Thermodynamic considerations showed that entropy played significant role in the distribution of Mg²⁺ in Ni_xMg_1−xFe₂O₄, in addition the difference in site preference energy between Fe³⁺ and Mg²⁺ was too small to cause any influence.     

Spin-glass and spin-fluctuation in Mo-doped Ca3Co4O9 system

Structural, magnetic, resistivity and thermal transport measurements have been performed to study the Mo-doping effect on a layered cobaltite Ca₃Co_4−xMo_xO₉(0≤x≤0.4) system. The results indicate that the low-temperature magnetic behavior of the system changes from a ferrimagnetic state to a spin-glass-like state upon Mo doping, which is due to the decrease in the average valence of Co ions. Moreover, all the Mo-doped samples have a higher resistivity and larger thermopower S compared with the Mo-free sample. The variation in the resistivity and thermopower between the Mo-doped and the Mo-free samples is dominated by the change in the carrier concentration of the samples. In the Mo-doped samples with x≥0.1, both the resistivity and thermopower decrease gradually with increasing Mo-doping level, which is suggested to mainly originate from the variation in the carrier mobility of the samples. In addition, an obvious thermopower upturn is observed in the S(T) curve of all the Mo-doped samples, which can be explained by the enhancement of spin-fluctuation induced by Mo-doping.     

Power factors of late rare earth-doped Ca3Co2O6 oxides

Polycrystalline samples of (Ca_1−xR_x)₃Co₂O₆ with R = Gd, Tb, Dy and Ho at x=0-0.1 were synthesized and the effects of rare earth substitution on their thermoelectric properties were investigated. In the high-temperature region, the rare earth substitution resulted in an increase in the Seebeck coefficients (S), and the S values increased with decreasing ionic radius of rare earth elements in the order Gd³⁺>Tb³⁺>Dy³⁺>Ho³⁺. In contrast, the influence of rare earth substitution on the electrical resistivity was small. The high-temperature power factor was thereby improved by the late rare earth substitutions, particularly those with Ho³⁺ for Ca²⁺. For the Ho-doped samples (x≤0.05), the power factor was significantly improved by increasing Ho concentration.     

Suppression of charge ordering and thermal hysteresis of electronic transport and magnetisation in La0.5Ca0.5Mn1−xNixO3

A series of polycrystalline La_0.5Ca_0.5Mn_1?xNi_xO₃ (x = 0.00, 0.025, 0.050, 0.075, 0.100 and 0.125) was synthesised using solid state reaction. Measurements in a cooling and warming cycle between 300 and 80 K were carried out to study the Ni-doping effects on the electrical resistivity, thermopower and magnetisation of single-phase La_0.5Ca_0.5Mn_1?xNi_xO₃. Partial substitution of Ni for Mn leads to the suppression of charge ordering state, the evidence of which is shown by the dramatic decrease in electrical resistivity and thermal hysteresis width in electrical resistivity, thermopower and magnetisation. However, the magnitude of both electrical resistivity and thermopower increases with increasing Ni content. This can be attributed to an increase in the Mn⁴⁺ concentration, which favours the antiferromagnetic state and leads to a gradual disappearance of ferromagnetic double exchange interaction. Besides, the metal–nonmetal transition temperature decreases with increasing Ni content until x = 0.075, which might arise from increased electron–phonon coupling due to less ordered spins at temperatures above ferromagnetic transition. For samples with x greater than 0.075, no metal–nonmetal transition is observed due to the suppression of double exchange mechanism.     

Kinetic effects in manganites La1 − x Ag y MnO3 (y ≤ x)

We have measured the resistivity, magnetoresistance, and thermopower of ceramic manganite samples La_{1 ? x} Ag _y MnO₃ (y ≤ x) doped with silver as functions of temperature (4.2–350 K) and magnetic field (up to 26 kOe). A metal-insulator phase transition is observed in all investigated samples at temperatures close to room temperature. The behavior of the resistivity and thermopower in the high-temperature paramagnetic region is interpreted using the concept of small radius polaron; the activation energy decreases with increasing doping level. The resistivity in the low-temperature ferromagnetic region is approximated by the expression ρ_FM(T) = ρ₀ + AT ² + BT ^4.5 presuming the existence of electron-electron and electron-magnon interactions. A resistivity minimum and a strong magnetoresistive effect are observed at low temperatures. The latter effect is associated with scattering of charge carriers at grain boundaries, which are antiferromagnetically ordered relative to one another. The temperature dependence of thermopower in the magnetically ordered phase is described in the framework of a model taking into account the drag of charge carriers by magnons.     

Structural,electrical and magnetic properties of Zr–Mg cobalt ferrite

Spinel cobalt ferrite, CoFe_2−xM_xO₄ has been synthesized by substitution of the combination of metallic elements M=Zr–Mg by the microemulsion method using polyethylene glycol as a surfactant. Powder X-ray diffraction analysis reveals that the substitution results in shrinkage of the unit cell of cobalt ferrite due to higher binding energy of the synthesized samples. The energy-dispersive X-ray fluorescence analysis confirms the stoichiometric ratios of the elements present. The thermogravimetric analysis shows that the minimum temperature required for the synthesis of these substituted compounds is 700 °C. A two-point probe method was employed for the measurement of the electrical resistivity in a temperature range of 293±5 to 673±5 K. It appears that there is a decrease in the number of Fe²⁺/Fe³⁺ pairs at the octahedral sites due to the substitution and corresponding migration of some of the Fe³⁺ ions to tetrahedral sites, consequently increasing the resistivity and the activation energy of hopping of electron at the octahedral sites. The susceptibility data also suggest migration of Fe³⁺ to tetrahedral site in the initial stage, which results in an increase in A–B interactions leading to large increase in the blocking temperature (T_B) as observed in samples having dopant content x=0.1.     

Magnetic ordering and magnetoresistive effect in La1−x Srx(Mn1−y Mey)O3 perovskites (Me = Nb, Mg)

Perovskites of composition La_1?x Sr_x(Mn_1?x/2Nb _x/2)O₃ and La_0.49Sr_0.51(Mn_1?y Nb_y)O₃ have been synthesized and investigated. The substitution of nonmagnetic niobium ions for manganese was shown to lead to a transition from the metallic into the insulating state due to a decrease in the number of dissimilar (different-valence) manganese atoms in the lattice. In spite of the high resistivity, the niobium-containing perovskites exhibit a large magnetoresistive effect and ferromagnetic ordering. Small additions of Nb⁵⁺ to La_0.49Sr_0.51MnO₃ stimulate the transition from the antiferromagnetic into the ferromagnetic state, whereas the substitution of Mg²⁺ for Mn stabilizes the antiferromagnetic state. It is supposed that the ferromagnetism in the insulating perovskites at hand is due to the positive superexchange of the Mn³⁺-O-Mn³⁺ type, and the magnetoresistive effect owes to the intergranular transfer of spin-polarized charge carriers and the suppression of magnetic nonuniformities by an applied magnetic field near T _C.     

Critical current density and flux pinning in La2−xPrxCa2x Ba2Cu4+2xOz (x=0.1-0.5) superconductors

Polycrystalline La_2−xPr_xCa_2xBa₂Cu_4+2xO_z (LPCaBCO) compounds with x=0.1-0.5 were synthesized by solid-state reaction method and studied by room temperature X-ray diffraction, dc resistivity, dc magnetization and iodometry. The superconducting transition temperatures in these tetragonal triple perovskite compounds increases from 32 to 62 K (T_c^onset values) with increasing dopant concentration. The mixing of rare earth La³⁺ and Pr^3+/4+ ions at rare earth site (La³⁺) along with substitution of divalent Ca²⁺ results in the shrinkage of unit cell volume. The contraction of unit cell volume due to larger ion being substituted by smaller ions, gives rise to creation of pinning centres in the unit cell leading to increase in critical current density and flux pinning.     

Research on La–Co-substituted strontium ferrite magnets for high intrinsic coercive force

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, and a little amount of Fe³⁺ by Co²⁺ according to the formula Sr_1−xLa_xFe_12−xCo_xO₁₉, are prepared by the ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and B–H hysteresis curve measurements. In our results, the suitable amount of La³⁺–Co²⁺ substitution may remarkably increase saturation magnetization. Intrinsic coercive force (H_cj) of Sr ferrite magnets is evidently increased without significant decrease in residual flux density (B_r) by La³⁺–Co²⁺ substitution.     

Enhancement of the crystal size and magnetic properties of Mg-substituted Co ferrite

Standard ceramic technique was used to prepare the ferrite Co_1−xMg_xFe₂O₄ 0.0?x?1. FTIR and X-ray diffraction were performed to assure the formation of the sample in the proper form. The obtained lattice parameter was interpreted on the basis of cation distribution. The replacement of Co²⁺ instead of Mg²⁺ on B sites expands slightly the size of the lattice. The sample MgFe₂O₄ does not exhibit high thermal stability. The general trend of χ_M with Mg content is the decrease in its values by decreasing x from 1 to ≈0.6. The obtained data was interpreted also on the basis of redistribution of iron ions between the two sublattices.     

Screening effect of Ti ions on the electrical conductivity and thermoelectric power of Mg ferrite

The samples Mg_1+xTi_xFe_2−2xO₄ were prepared in a single phase spinel structure as indicated from X-ray analysis. The preference of Mg²⁺ ions to the octahedral site decreases the ratio of the normal spinel in the investigated ferrite where the Mg²⁺ increases on the expense of the Fe³⁺ ions on the same site. The increase in the conductivity was found to be due to thermally activated mobility of charge carriers. The mobility data enhances the use of Verway model of conductivity which depends on the electron exchange between iron ions of different valences located on the same crystallographic sites. The existence of Ti⁴⁺ ions on the octahedral site screens the polarization and decreases the conductivity of the samples. Peculiar behavior was obtained for Ti content of 0.7 and 0.8 due to the presence of secondary phases.     

Electrochemical luminescence of Mg1−xCaxIn2O4:Er electrodes

Improvement for electrochemical luminescence (ECL) property of MgIn₂O₄ is attempted by partial exchange of Mg²⁺ ion in MgIn₂O₄ to Ca²⁺ ion. Mg_1−xCa_xIn₂O₄ solid solution was obtained in the region 0<x<0.4. Efficiency for ECL per unit current for Mg_1−xCa_xIn₂O₄:Er³⁺ increased with the increase in the ratio of Ca²⁺ ion, and showed a peak at x=0.25 and then decreased steeply. ECL efficiency for other rare-earth ion-(RE:Sm, Eu, Ho) doped Mg_1−xCa_xIn₂O₄ also increased comparing with those for MgIn₂O₄:RE. This Ca²⁺ addition effect on the ECL efficiency seems to be caused by the improvement of the efficiency for the impact activation.     

Effect of substitution of K ions on the structural and electrical properties of nanocrystalline MgAl2O4 spinel oxide

Potassium substituted nanosized magnesium aluminates having a nominal composition Mg_1−xK_xAl₂O₄ where x=0.0, 0.25, 0.5, 0.75, 1.0 have been synthesized by the chemical co-precipitation method. The samples have been characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), and dc electrical resistivity measurements. The XRD results reveal that the samples are spinel single phase cubic close packed crystalline materials. The calculated crystallite size ranges between 6 and 8 nm. The behaviour of the lattice constant seems to deviate from the Vegard's law. While X-ray density clearly increases, the bulk density and consequently, the percentage porosity do not exhibit a significant change on increasing the K⁺ content. The SEM micrographs suggest homogeneous distribution of the nanocrystallites in the samples. The dc electrical resistivity exhibits a typical semiconducting behaviour. Substitution of a Mg²⁺ ion by a K⁺ ion provides an extra hole to the system, which forms small polaron. Thermally activated hopping of these small polarons is believed to be the conduction mechanism in the Mg_1−xK_xAl₂O₄. The activation energy of hopping of small polarons has been calculated and found K⁺ ions content dependent.