Electrical conductivity and structural stability of SrCo1−xFexO3−δ

Perovskite compounds in the system of SrCo_1−xFe_xO_3−δ (x=0.2, 0.4 and 0.6) were synthesized by solid state reaction. SrCo_1−xFe_xO_3−δ shows the p-type small polaron conduction behavior. Electrical conductivity and oxygen vacancy content decrease with increase in Fe content. The incorporation of Fe increases the structural stability of SrCo_1−xFe_xO_3−δ at low temperatures, while decreasing the structural stability at high temperatures. Oxygen partial pressure has a strong influence on electrical conductivity. At low oxygen partial pressure, SrCo_0.8Fe_0.2O_3−δ will transform from cubic to orthorhombic structure. This structure can remain in 5%H₂/Ar only for a short time and then dissociates into Sr₃Fe₂O_6.64 and Co due to the reduction of B-site elements.     

Effect of granularity and inhomogeneity in excess conductivity of YBa2Cu3O7−δ+xBaTiO3 superconductor

Synthesis of polycrystalline YBCO+xBaTiO₃ (x=1.0, 2.5, 5.0) superconductor has been done and the effects of granularity and inhomogeneities due to inclusions of nano-BaTiO₃ in excess conductivity are reported in this work. The phase formation, texture and grain alignments were analyzed through XRD and SEM techniques. SEM results reveal that the grain size is reduced and morphology is improved with the incorporation of nano-BaTiO₃ particles. Superconducting order parameter fluctuation (SCOPF) studies on the electrical conductivity were investigated from the resistivity vs. temperature data in the experimental domain relatively above T_c. Log(Δσ) vs. log(ε) plots show that the 2D to 3D crossover temperature (T_LD) that demarcates dimensional nature of fluctuation inside the grains is influenced by BaTiO₃ incorporation in YBCO matrix. An upward shift of T_LD in the mean field region has been observed as a consequent dominance of 3D region with increase in 1 wt% BaTiO₃ in the composites as compared to higher inclusions. It has been analyzed that microscopic inhomogeneities produced as a result of diffusion of a fraction of Ti ions into the grains affect fluctuations in the excess conductive region. The interplay of microscopic inhomogeneities produced inside the grains and mesoscopic inhomogeneities in the grain boundaries on the excess conductivity has been explained in terms of thermal fluctuations for the composites.     

Co-L3 X-ray absorption near-edge structure analysis of Pr1−xCaxCoO3−δ and Pr1−xSrxCoO3−δ

The valence state of Co ions in Pr_1−xCa_xCoO_3−δ and Pr_1−xSr_xCoO_3−δ has been investigated by an analysis of the Co-L₃ X-ray absorption near-edge structure (XANES) profile. The observed intensity distributions of Co-L₃ XANES change continuously with increasing concentration of alkaline-earth ions. To investigate the origin of this change in the XANES profile, charge transfer multiplet calculations were carried out, which could successfully explain the change in the spectral profile; they also suggest that the valence state of Co ions in Pr_1−xCa_xCoO_3−δ and Pr_1−xSr_xCoO_3−δ is between 3+ and 4+ and increases gradually with the concentration of alkaline-earth ions.     

Fabrication, sintering and electrical properties of cobalt oxide doped Gd0.1Ce0.9O2 − δ

Ceria-based electrolytes have been widely researched in intermediate-temperature solid oxide fuel cell (SOFC), which might be operated at 500~600 °C. Gd0.1Ce0.9O1.95(GDC10) powders were prepared by a modified chemical co-precipitation process with Gd(NO3)3 and Ce(NO3)3 as precursors, and ammonia and hydrogen peroxide as precipitants. The precursors of GDC10 were fired at 350 °C for 2 h, then the fluorite structure cerias were identified by X-ray diffraction. The powders are well crystallized, with the size about 5 nm and surface area of 148.3 m2/g. Loading 1mol% cobalt oxide as additive, the GDC10 were succeeded to densify at 950 °C by liquid phase sintering mechanism. The grain size of 1CoGDC10 is small, about 100 nm. The electrical conductivity of samples sintered at 950 °C is about 0.01S/cm at 600 °C. The existence of cobalt oxide and smaller grain size of 1CoGDC10 don't affect the electrical conductivity.     

Transport properties and in-situ Raman spectroscopy study of BaCe0.9Y0.1O3 − δ as a function of water partial pressures

The total conductivity of BaCe_0.9Y_0.1O_3 − δ material was measured under air, in a large p(H₂O) range up to 0.30 bar. The defect concentrations (OH_O^·, V_O^· · and h^·) and electrical conductivities were calculated on the basis of chemical constants (diffusion coefficients and equilibrium constants reported in the past literature) and compared to the experimental data. Protonic transport number as high as 0.8 was found at 700 °C, under air containing 0.30 bar of water, which allows a possible extension of the protonic temperature range of this material using water rich atmosphere. In-situ Raman spectroscopy under wet and dry air was performed from room temperature up to 700 °C in two wavenumber ranges. At low wavenumber, characteristic of lattice vibrations, this study clearly shows that no significant changes occur upon water insertion while at high wavenumbers, characteristic of OH vibrations, two contributions to the OH vibrations were found. This is discussed in terms of proton environment and transient hydrogen bonds. Moreover, this in situ study confirms that, at moderate p(H₂O), water insertion becomes significant at temperature below 650 °C.     

Studies on sintering of solid state synthesized Ba1−xKxBiO3−δ superconducting phase

Superconducting Ba_1−xK_xBiO_3−δ pellets were synthesized by solid state reaction followed by sintering. Thermo-gravimetric and differential thermo-gravimetric analysis (TG-DTA) of the mixture of nitrates was carried out to study the reactions during the phase formation. The effect of different sintering temperatures on the phase formation was studied. The X-ray diffraction data confirms the formation of superconducting Ba_0.6K_0.4BiO_2.23 phase at 700 °C. The surface morphological studies as a function of sintering temperature were studied by SEM. It is observed that the pellets prepared by solid state reaction followed its sintering at 700°C shows the superconducting transition at 26.8 K.     

High temperature transport and thermoelectric properties of Ca3−xErxCo4O9+δ

Ca_3−xEr_xCo₄O_9+δ (x=0, 0.05, 0.15, 0.3 and 0.5) samples were prepared using a sol-gel method followed by hot-pressing sintering technique. Powder X-ray diffraction analysis showed the single-phases of Ca_3−xEr_xCo₄O_9+δ were obtained up to x=0.3 and the crystallinity of the samples decreased with increasing Er-doping amount. The high-temperature (323-1073 K) thermoelectric properties of the samples were investigated. The substitution of Er³⁺ for Ca²⁺ resulted in the decrease of electrical conductivity, thermal conductivity and the increase of Seebeck coefficient for all the samples except the x=0.05 one. The dimensionless figure of merit ZT reached 0.28 at 1073 K for Ca_2.7Er_0.3Co₄O_9+δ, indicating the thermoelectric properties of CaCo₄O_9+δ can be enhanced by doping Er in the system.     

Structure and magnetism in Ho1−xSrxCoO3−δ

We have magnetically and structurally characterized the Ho_1−xSr_xCoO_3−δ family of materials where 0.67≤x≤0.95. The solid solution range and evolution of the structure as a function of x is established and correlated with the broad range of magnetic behavior observed. The structure is shown to be tetragonal I4/mmm although is possibly cubic when x=0.95. For 0.67≤x≤0.9 the material shows antiferromagnetic long range order and ferromagnetic clusters. At x=0.95 the magnetic transition is at 120 K and the imaginary susceptibility becomes non-zero and the temperature of the cusp in the ac susceptibility shows a frequency dependence indicative of glassiness.     

Influence of the substrate material on the properties of pulsed laser deposited thin Li1+xMn2O4−δ films

Thin Li_1+xMn₂O_4−δ films were deposited on several substrate materials (stainless steel, p-doped silicon and glassy carbon) by pulsed laser deposition. To obtain the correct thin film stoichiometries, targets with a different amount of excess lithium were required (Li_1.03Mn₂O₄ + xLi₂O; x = 2.5 and 7.5 mol%). The resulting polycrystalline thin films were characterized with respect to their morphology and electrochemical activity. It was found that only thin Li_1+xMn₂O_4−δ films deposited on stainless steel and glassy carbon showed the typical insertion and deinsertion peaks of Li⁺ during cycling.     

Role of growth temperature and oxygen partial pressure on the structural and electrical properties of pulsed laser deposited La1−xSrxnO3−δ thin films

The paper presents the fabrication and characterization of La_0.65Sr_0.35MnO_3−δ (LSMO) polycrystalline thin films deposited directly on Si (1 0 0) substrates using pulsed laser deposition technique. Various deposition parameters like substrate temperature and oxygen partial pressure have been varied systematically to obtain stoichiometric, crack-free films with smooth surface morphology having nearly monodisperse grain size distribution. The substrate temperature variation from 600 to 800 °C had profound effects on the microstructure and topography of the deposited film, with optimum result being obtained at 700 °C. The variation of partial pressure of oxygen controls the deposition kinetics as well as the stoichiometry of the film in terms of oxygen vacancy, which influences the magnetic and electrical transport properties of the manganate films. The microstructure and crystallinity of the deposited films have been studied using X-ray diffraction, scanning electron microscopy and atomic force microscopy. A correlation between the oxygen stoichiometry and micro-structural and transport properties of the deposited films has been obtained.     

Low-field magnetic properties of LaMnO3+δ with 0.065≤δ≤0.154

In a weak magnetic field LaMnO_3+δ exhibits at δ=0.065 below the paramagnetic-to-ferromagnetic (FM) Curie temperature, T_C, a mixed (spin-glass and FM) phase followed by a frustrated FM phase at δ between 0.100 and 0.154. The same behavior is observed in La_1−xCa_xMnO₃ with x between 0 and 0.3. This can be understood by the similar variation of the Mn⁴⁺ concentration, c between ≈0.13 and 0.34, in both materials when x or δ is increased. On the other hand, considerable differences are found between these compounds in the values of the magnetic irreversibility, in the dependencies of T_C(c) and the magnetic susceptibility, χ(c), as well as in the critical behavior of χ(T) near T_C. These differences can be explained by distortions of the cubic perovskite structure, by the reduced lattice disorder and by the more homogeneous hole distribution in LaMnO_3+δ than in La_1−xCa_xMnO₃.     

Oxygen nonstoichiometry, defect structure and electrical properties of LaFe0.7Ni0.3O3 − δ

Oxygen nonstoichiometry (δ), total conductivity (σ) and thermoelectric power (S) of the LaFe_0.7Ni_0.3O_3 − δ sample have been studied as functions of temperature and oxygen partial pressure. Based on the results of the direct reduction of the sample in hydrogen flow at 1100 °C the absolute oxygen content (3 − δ) has been found to vary from 2.999 to 2.974 in the range of 1273-1373 K and 10^− 3-0.21 atm. The point defect equilibrium models have been proposed and fitted to the set of experimental data in the form of log p(O₂) = f(δ)_T dependences. The values of standard thermodynamic quantities of defect formation reactions have been assessed. The joint analysis of oxygen nonstoichiometry, total conductivity and thermoelectric power has been performed using a small-polaron approach. The values of partial conductivity, partial thermopower and mobilities of electronic charge carriers have been calculated. The p-type semiconducting behavior of LaFe_0.7Ni_0.3O_3 − δ has been explained by the higher mobility values of electron holes than those of electrons in the whole range of thermodynamic parameters studied.     

Effect of high pressure on the fluctuation paraconductivity in Y0.95Pr0.05Ba2Cu3O7−δ single crystals

The effect of high hydrostatic pressure up to 17 kbar on the fluctuation conductivity of lightly Pr-doped Y_1−xPr_xBa₂Cu₃O_7−δ (x ≈ 0.05) single crystals is investigated. We show that in contrast to non-doped YBa₂Cu₃O_7−δ samples, application of a high pressure leads to a substantial increase of the pressure derivative of the coherence length dξ_c/dP and a temperature shift of the 2D-3D crossover point. Possible mechanisms of the influence of high pressure on the critical temperature and the coherence length are discussed within the framework of a model assuming the presence of singularities in the charge carriers electron spectrum typical for lattices with strong coupling.     

The effect of La-substitution on magnetic properties of nanosized Sr1−xLaxTi0.05Zn0.2(Fe)11.75−δ(Fe)δO19 powders

A series of La-substituted M-type Sr hexaferrite powders Sr_1−xLa_xTi_0.05Zn_0.2Fe³⁺_11.75O₁₉, wherein x ranges from 0.1 to 0.5 with a step of 0.1, have been prepared by the conventional ceramic method and were then milled in a high energy mill to prepare nanosized powders. XRD investigation of the calcined and the milled powders shows that single phase hexaferrite structure has been formed after calcining and has not changed after milling. The lattice parameters and the mean crystallite sizes of the samples have been determined from the XRD data and Scherrer's formula. The results show that the lattice parameters (“а” and “c”) decrease with increase in La-substitution and the mean crystallite size of the milled powders is about 17 nm. Coercivities and magnetizations of the samples in a magnetic field of 16 kOe have been determined from the room temperature hysteresis loops. It was found that both parameters increase with La substitutions up to 0.3 and then decrease for higher substitutions. These variations were attributed to the enhancement of hyperfine field and spin-canting magnetic structure when La content increases. In addition, the magnetizations were smaller for the nanosized samples in comparison with those of bulk ones, which were discussed according to the core-shell model. Also the results show that annealing of the nanosized samples up to 500 °C can enhance coercivity and magnetization of the samples, which is discussed based on crystallite size growth.     

Manifestation of vortex depinning transition in nonlinear current-voltage characteristics of polycrystalline superconductor Y1−xPrxBa2Cu3O7−δ

We present our recent results on the temperature dependence of current-voltage characteristics for polycrystalline Y_1−xPr_xBa₂Cu₃O_7−δ superconductors with x=0.0, 0.1 and 0.3. The experimental results are found to be reasonably well fitted for all samples by a power like law of the form V=R(I−Ic)^a(T). Here, we assume that a(T)=1+Φ₀IC(T)/2πkBT and IC(T)=IC(0)(1−T/TC)^3/2 for the temperature dependences of the power exponent and critical current, respectively. According to the theoretical interpretation of the obtained results, nonlinear deviation of our current-voltage characteristics curves from Ohmic behavior (with a(TC)=1) below TC is attributed to the manifestation of dissipation processes. They have a characteristic temperature Tp defined via the power exponent as a(Tp)=2 and are related to the current induced depinning of Abrikosov vortices. Both TC(x) and Tp(x) are found to decrease with an increase of Pr concentration x reflecting deterioration of the superconducting properties of the doped samples.     

Ferromagnetism in diluted magnetic Zn-Co-doped CeO2−δ

Several oxides doped with transition metals can be used in spintronics devices due to their conductive and magnetic properties at room temperature. In this work, samples of Ce_1−2xZn_xCo_xO_2−δ were obtained by an alternative sol–gel proteic process for x=0.01, 0.05 and 0.1. The structural properties of samples were analyzed by XRD and Raman spectroscopy. Magnetization measurements revealed a ferromagnetic behavior at room temperature probably induced by oxygen vacancies.     

The effects of Cr-doping on the room temperature ferromagnetism of chemically synthesized CeO2−δ nanoparticles

We report an investigation of the nature of room-temperature ferromagnetism enhancement in Ce_1−xCr_xO_2−δ nanoparticles (0.00≤x≤0.05), synthesized by a sol–gel-based method. Energy-dispersed X-ray spectrometry (EDS) analysis was used to estimate the dopant concentrations. The average crystallite sizes and particle size were estimated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. Both studies showed a gradual decrease in the size of the crystallites and particles for x>0.01. Cr can substitute for Ce in the crystal lattice, and the Raman measurements indicated that structural defects in the samples increased as a function of the Cr content in the CeO₂ crystal lattice. The surface topography, examined by scanning electron microscopy (SEM), showed that the undoped sample has a porous and loosely organized structure, whereas the Cr-doped samples exhibited a dense and compact structure. Magnetic measurements of the Ce_1−xCr_xO_2−δ samples at 27 ^oC showed a maximum remanent magnetization value of 0.01 emu/g for x=0.05. The nature and enhancement of room-temperature ferromagnetism was interpreted by taking into account the exchange interaction between Cr³⁺ ions and oxygen vacancies in CeO₂.     

Investigation on cation distribution and magnetic properties in self-doped manganites La0.6−xSr0.4MnO3−δ

Self-doped manganites with nominal composition La_0.6−xSr_0.4MnO_3−δ (0≤x≤0.175) have been prepared by the sol–gel method. The X-ray diffraction (XRD) patterns and magnetic measurements indicate that the samples have two phases with the ABO₃ perovskite structure being the dominant phase and Mn₃O₄ being the minor phase when the doping level x≥0.05. On the basis of the thermal equilibrium theory of crystal defects, the contents of various ions in the perovskite phases were estimated, in which there are Mn²⁺ ions and no vacancies at A sites. The ion contents have been corrected by Rietveld fitting of the powder samples' X-ray diffraction data. The change tendency of the Curie temperature T_C vs. the Mn⁴⁺ ion content ratio at the B sites of ABO₃ perovskite phase is in accord with the experimental result of the samples La_1−xSr_xMnO₃.     

Non-universal dielectric relaxation in SrFeO3 − δ

SrFeO_3 − δ compound is prepared by the thermal decomposition method followed by ball milling. Analysis of Mössbauer spectrum and X-ray diffraction study proves the presence of multi-phase nature, i.e., Sr₈Fe₈O₂₃ and Sr₄Fe₄O₁₁ phases at room temperature. Furthermore, the Mössbauer spectrum at room temperature evidenced the presence of major Fe^3.5+ which is the resultant of equal contributions of Fe⁴⁺ and Fe³⁺. The Nyquist plot at all measured temperatures (80–230 K) suggests that the dielectric response is well associated with single relaxation time (exponential parameter, n∼1$n\sim 1$) i.e., the Debye-type. Modulus analysis exhibits the non-universal dielectric behaviour (stretched exponential parameter, β>1$\beta >1$) below 230 K and the Debye-type responds (β∼1$\beta \sim 1$) at and above 230 K. The Debye-type behaviour exhibited by SrFeO_2.81 at around room temperature in its defect state offers a new opening for this material for multifunctional applications.