Structure and superconductivity in FexCu1−xBa2YCu2O7+y superconductors synthesized by high pressure

Comprehensive studies of X-ray diffraction, oxygen content, superconductivity and Mössbauer effect have been made on Fe_xCu_1−xBa₂YCu₂O_7+y superconductors (0.00≤x≤0.70) synthesized by ambient (AM) and high pressure (HP). Results indicate that all the HP-samples have tetragonal structure, smaller lattice parameter c and unit-cell volume than the AM-samples. The studies of oxygen content, and Mössbauer spectroscopy indicate that the HP-samples have higher oxygen content, carrier concentration and average valence of Fe than the AM-samples. Moreover, for the HP-samples more Fe atoms located in CuO_x chains have fivefold-oxygen coordination. These are important reasons for the enhancement of T_c in the HP-samples.     

Temperature-dependent Fe Mössbauer spectroscopy and local structure of the mullite-type Bi2(FexGa1−x)4O9 (0.1≤x≤1) solid solution

The Bi₂(Fe_xGa_1−x)₄O₉ oxide solid solution possessing a mullite-type structure has been investigated by ⁵⁷Fe Mössbauer spectroscopy in dependence of composition (0.1≤x≤1) and temperature (293≤T/K≤1073). The spectra have been fitted with two doublets for tetrahedrally and octahedrally coordinated high-spin Fe³⁺ ions, respectively. The experimental areas of the subspectra were used to determine the distribution of iron on the two inequivalent structural sites. The fraction of iron cations occupying the octahedral site is found to increase with decreasing Fe content and the cation distribution is almost independent of temperature. The unusual temperature dependence of the quadrupolar splitting, QS, observed for the octahedral site with dQS/dT>0 is discussed in connexion with structural data for Bi₂Fe₄O₉. The temperature dependence of Mössbauer isomer shifts and signal intensities is examined in the context of local vibrational properties of iron on the two inequivalent sites of the mullite-type lattice structure.     

Critical behaviour and magnetic properties of A-B spinel ZnxCu1−xFe2O4

Polycrystalline Zn_0.6Cu_0.4Fe₂O₄ ferrites have been prepared using a solid-state reaction technique. Their structural and magnetic properties have been studied, using X-ray diffraction and Mössbauer and magnetic measurements. These results have been compared to a more general theoretical study, on Zn_xCu_1−xFe₂O₄, based on mean field theory and high-temperature series expansions (HTSE), and extrapolated with the Padé approximant method. The nearest neighbour super-exchange interactions for the intra-site and the inter-site of Zn_xCu_1−xFe₂O₄ spinel ferrites, in the range 0≤x≤1, have been computed using the probability approach, based on Mössbauer data. The Curie temperature T_C is calculated as a function of Zn concentration. The theoretical results obtained are in good agreement with the experimental results obtained by magnetic measurements.     

Properties of Fe–Ga based powders prepared by mechanical alloying

Alloys of Fe–Ga with starting compositions of 17, 19, 21, 23, and 25 at% Ga and Fe₈₁Ga₁₇Z₂ (Z=Si, Sn) have been prepared by mechanical alloying. Samples were milled in a SPEX Model 8000 mill with a ball to sample weight ratio of about 4:1. Phase formation as a function of milling time has been investigated for the 19 at% Ga sample and suggests that milling times of 12 h produce fully alloyed samples. Alloys have been studied by electron microprobe, X-ray diffraction, vibrating sample magnetometery and ⁵⁷Fe Mössbauer effect spectroscopy. Fully milled powders have measured compositions of Fe_100−xGa_x with x=15.7, 17.0, 19.0, 22.4, and 24.0 and Fe_83.1Ga_15.2Z_1.7 (for both Z=Si and Sn). X-ray diffraction showed the presence of a disordered bcc phase with no indication of an ordered D0₃ phase. However, the latter is difficult to observe with X-ray diffraction because of the low intensity of the fcc superlattice peaks. A bimodal Fe hyperfine field distribution as obtained from Mössbauer effect spectra indicated the presence of two discrete Fe environments. The results suggested a lower degree of Ga clustering than has been previously observed in Fe–Ga alloys, of similar composition, prepared by melt spinning. The microstructure is similar to that of Fe–Ga thin films prepared by combinatorial sputtering. Some samples have also been studied after annealing at 800 °C for 8 h. No changes were observed in X-ray diffraction patterns after annealing. However, Mössbauer effect studies show the formation of D0₃ and L1₂ order in annealed samples analogous to the phases observed in melt spun ribbons of similar composition.     

Structural and Magnetic Properties of NiFe2−2xSnxCuxO4

The substituted nickel ferrite (NiFe_2−2xSn_xCu_xO₄, x=0, 0.1, 0.2, 0.3) was prepared by the conventional ceramic method. The effect of substitution of Fe³⁺ ions by Sn⁴⁺ and Cu²⁺ cations on the structural and magnetic properties of the ferrite was studied by means of ⁵⁷Fe Mössbauer spectroscopy, alternating gradient force magnetometry (AGFM) and Faraday balance. Whereas undoped NiFe₂O₄ adopts a fully inverse spinel structure of the type (Fe)[NiFe]O₄, Sn⁴⁺ and Cu²⁺ cations tend to occupy octahedral positions in the structure of the substituted ferrite. Based on the results of Mössbauer spectroscopic measurements, the crystal-chemical formula of the substituted ferrite may be written as (Fe)[NiFe_1−2xSn_xCu_x]O₄, where parentheses and square brackets enclose cations in tetrahedral (A) and octahedral [B] coordination, respectively. The Néel temperature and the saturation magnetization values of the NiFe_2−2xSn_xCu_xO₄ samples were found to decrease with increasing degree of substitution (x). The variation of the saturation magnetization with x measured using the AGFM method and that calculated on the basis of the Mössbauer spectroscopic measurements are in qualitative agreement.     

Superconductivity in CoSr2(Y1−xCax)Cu2O7+δ

The roles of aliovalent Ca^II-for-Y^III substitution and high-pressure-oxygen annealing in the process of ‘superconducterizing’ the Co-based layered copper oxide, CoSr₂(Y_1−xCa_x)Cu₂O_7+δ (Co-1212), were investigated. The as-air-synthesized samples up to x=0.4 were found essentially oxygen stoichiometric (−0.03≤δ≤0.00). These samples, however, were not superconducting, suggesting that the holes created by the divalent-for-trivalent cation substitution are trapped on Co in the charge reservoir. Ultra-high-pressure heat treatment carried out at 5 GPa and 500 °C for 30 min in the presence of Ag₂O₂ as an excess oxygen source induced bulk superconductivity in these samples. The highest T_c was obtained for the high-oxygen-pressure treated x=0.3 sample at ∼40 K.     

Synthesis and magnetic properties of ferrites spinels MgxCu1−xFe2O4

Polycrystalline Mg_0.6Cu_0.4Fe₂O₄ ferrites have been prepared using solid-state reaction technique. Their structural and magnetic properties have been studied, using X-ray diffraction and magnetic measurements.Using mean field theory and high-temperature series expansions (HTSE), extrapolated with the padé approximants method, the magnetic properties of Mg_1−xCu_xFe₂O₄ have been studied. The nearest neighbor super-exchange interactions for intra-site and inter-site of the Mg_1−xCu_xFe₂O₄ ferrites spinels, in the range 0≤x≤1, have been computed using the probability approach, based on Mössbauer data. The Curie temperature T_c is calculated as a function of Mg concentration. The obtained theoretical results are in good agreement with experimental ones obtained by magnetic measurements.     

Mössbauer study of Fe0.92−xCoxP0.08 nanowire arrays

Arrays of Fe_0.92−xCo_xP_0.08 (0.22≤x≤0.78) ternary alloy nanowires were fabricated in anodic aluminium oxide templates by electrochemical deposition. The broadened peaks in transmission Mössbauer spectra and the halo in selected area electron diffraction patterns indicate that the structure of Fe_0.92−xCo_xP_0.08 nanowires is amorphous. However, the short-range order of Fe_0.92−xCo_xP_0.08 nanowires has a bcc structure with a [110]-preferred orientation that is parallel to the nanowires. The magnetic texture results in the magnetic moment direction of the Fe atoms being along the nanowires. The short-range order around the Fe atoms reaches a minimum at x=0.45. With increasing Co content, the average hyperfine field decreases, while the isomer shift and quadrupole splitting remain almost constant, which result from the variation of 3d and 4s electron volume density at the Fe sites.     

Mössbauer spectroscopy and magnetic properties in thin films of FexNi100−x electroplated on silicon (1 0 0)

Fe_xNi_100−x thin films were produced by galvanostatic electrodeposition on Si (1 0 0), nominal thickness 2800 nm, and x ranging 7-20. The crystalline structure of the sample was determined by X-ray diffraction (XRD). The magnetic properties were investigated by vibration sample magnetometry (VSM) and room temperature ⁵⁷Fe Mössbauer spectroscopy. Conversion Electron Mössbauer spectroscopy (CEMS) in both film surfaces for the thick self-supported films showed that the magnetic moment direction is in the plane and conventional transmission (MS) that the directions are out of the plane films. The results were interpreted assuming a three-layer model where the external layer has in-plane magnetization and the internal one, out of plane magnetization.     

Defect formation and transport in mixed-conducting La0.90Sr0.10Al0.85−xFexMg0.15O3−δ

The redox behavior of perovskite-type La_0.90Sr_0.10Al_0.85−xFe_xMg_0.15O_3−δ (x=0.20-0.40) mixed conductors was analyzed by the Mössbauer spectroscopy and measurements of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10⁻²⁰ to 0.5 atm at 1023-1223 K. The results combined with oxygen-ion transference numbers determined by the faradaic efficiency technique in air, were used to calculate defect concentrations, mobilities, and partial ionic and p- and n-type electronic conductivities as a function of oxygen pressure. The redox and transport processes can be adequately described in terms of oxygen intercalation and iron disproportionation reactions, with the thermodynamic functions independent of defect concentrations. No essential delocalization of the electronic charge carriers was found. The oxygen non-stoichiometry values estimated from the conductivity vs. p(O₂) dependencies, coincide with those evaluated from the Mössbauer spectra.     

Mössbauer study of cobalt ferrite nanocrystals substituted with rare-earth Y ions

Mössbauer spectroscopy is used to characterize the crystallite size and structure of CoFe_2−xY_xO₄ (x=0, 0.1, 0.3, 0.5) ferrite nanocrystallites synthesized by the sol-gel auto-combustion method. The effect of the substitution of Fe³⁺ ions by Y³⁺ ions on the structure of cobalt ferrite nanocrystallites is investigated. The Mössbauer spectra showed two sets of six-line hyperfine patterns for all the samples, indicating the presence of Fe in both A and B-sites. On increasing the concentration of doped Y, the hyperfine field strength and the isomer shift first increase and then decrease, whereas the quadrupole splitting continuously increases. The superparamagnetism was observed for all the samples and the change of ratio of the superparamagnetism component reflects the size of crystal grain.     

Studies on Structural, Magnetic and Thermal Properties of xFe2TiO4-(1−x)Fe3O4 (0≤x≤1) Pseudo-binary System

The xFe₂TiO₄-(1−x)Fe₃O₄ pseudo-binary systems (0≤x≤1) of ulvöspinel component were synthesized by solid-state reaction between ulvöspinel Fe₂TiO₄ precursors and commercial Fe₃O₄ powders in stochiometric proportions. Crystalline structures were determined by X-ray powder diffraction (XRD) and it was found that the as-obtained titanomagnetites maintain an inverse spinel structure. The lattice parameter a of synthesized titanomagnetite increases linearly with the increase in the ulvöspinel component. ⁵⁷Fe room temperature Mössbauer spectra were employed to evaluate the magnetic properties and cation distribution. The hyperfine magnetic field is observed to decrease with increasing Fe₂TiO₄ component. The fraction of Fe²⁺ in both tetrahedral and octahedral sites increases with the increase in Ti⁴⁺ content, due to the substitution and reduction of Fe³⁺ by Ti⁴⁺ that maintains the charge balance in the spinel structure. For x in the range of 0 ≤x≤0.4, the solid solution is ferrimagnetic at room temperature. However, it shows weak ferrimagnetic and paramagnetic behavior for x in the range of 0.4<x≤0.7. When x>0.70, it only shows paramagnetic behavior, with the appearance of quadrupole doublets in the Mössbauer spectra. Simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC-TGA) studies showed that magnetite is not stable, and thermal decomposition of magnetite occurs with weight losses accompanying with exothermic processes under heat treatment in inert atmosphere.     

Magnetic properties and phase diagram of ZnxNi1−xFe2O4: High-temperature series expansions

Using mean field theory and high-temperature series expansions (HTSEs), extrapolated with the Padé approximants method, the effect of Zn doping on magnetic properties of NiFe₂O₄ ferrite spinel has been studied. The nearest neighbour super-exchange interactions for intra-site (J_AA, J_BB) and inter-site (J_AB) of the Zn_xNi_1−xFe₂O₄ ferrites spinels, in the range 0≤x≤1, have been computed using the probability approach, based on Mössbauer data. The paramagnetic Curie-Weiss temperature θ and the Curie temperature T_C are calculated as a function of Zn concentration. The critical exponent γ associated with magnetic susceptibility is calculated. The spin correlation functions intra-plane and inter-plane have been also computed and compared with exchange couplings. The obtained theoretical results are in good agreement with experimental ones obtained by magnetic measurements and Mössbauer spectroscopy.     

Mössbauer spectroscopy as a probe of magnetic states in La0.5Ca0.5FeO3−δ perovskite

Charge disproportionation in La_0.5Ca_0.5FeO_3−δ perovskite has been detected by zero-field Mössbauer spectra from 20 K to room temperature. On the basis of the parameters of center shifts and hyperfine fields, Mössbauer spectra identified that the iron ionic states are Fe³⁺ and Fe⁵⁺ below 150 K, Fe³⁺, Fe⁴⁺ and Fe⁵⁺ in the intermediate temperature region, as well as Fe³⁺ and Fe⁴⁺ above 220 K. At low temperatures, the system exhibits a cluster-glass-like state resulting from competition between antiferromagnetic interaction of Fe³⁺–Fe³⁺ and ferromagnetic interaction of Fe³⁺–Fe⁵⁺.     

Phonon dynamics of hexagonal Y Mn1−xFexO3

Phonon dynamics was investigated on Y Mn_1−xFe_xO₃(0≤x≤0.20) hexagonal manganite polycrystals. Phonon modes were properly assigned using results obtained on Y MnO₃ single crystal, by mixing the ab plane and the c axis optical responses. Upon increasing the Fe content, most of the phonon mode frequencies do not vary drastically. However, some modes involving Y and O atom displacements along the c axis are affected by doping. Indeed, a redshift of their transverse optical frequency was interpreted as an elongation of Y-O distance along the c-axis, resulting in a change in yttrium coordination.     

Coexistence of superconductivity and magnetism in the La0.87−xLnxSr0.13FeAsO (Ln=Sm, Gd, Dy) system

The interplay between the superconducting phase and spin density wave order phase was studied. We report the magnetic and superconducting properties of the hole-doped FeAs-based superconducting compound La_0.87−xLn_xSr_0.13FeAsO (Ln=Sm, Gd, Dy; 0≤x≤0.06). Both resistivity and magnetic susceptibility measurements show that the superconducting transition temperature decreases with increase in composition of magnetic ions. The hysteresis loop of the La_0.87−xLn_xSr_0.13FeAsO sample shows a superconducting hysteresis in addition to a paramagnetic background. The experiment demonstrates that the magnetism and superconductivity coexist in hole-doped FeAs-based superconducting compounds. Among these three magnetic rare-earth elements, the influence of Dy³⁺ doping on superconductivity is more evident than that of Gd³⁺ doping, while the influence of Sm³⁺ doping is the weakest. The trend is consistent with the variation of the lattice parameter along c-axis.     

Antiferromagnetism and spin-glass transition in the FeInxCr2−xSe4 series of selenides

The magnetic behavior of the FeIn_xCr_2−xSe₄ system (with x=0.0, 0.2 and 0.4) has been investigated by magnetic and Mössbauer spectroscopy. Hyperfine parameters indicate that iron is in the Fe²⁺ oxidation state, with a minor (∼9%) Fe³⁺ fraction, located at different layers in the structure. Low-field magnetization curves as a function of temperature showed that the antiferromagnetic (AFM) order temperature is T_N=208(2) K for FeCr₂Se₄ and decreases to 174(3) K for FeIn_0.4Cr_1.6Se₄. The effective magnetic moment μ_eff decreases with increasing In contents, and shows agreement with the expected values from the contribution of Fe²⁺ (⁵D) and Cr³⁺ (⁴F) electronic states. A second, low-temperature transition is observed at T_G∼13 K, which has been assigned to the onset of a glassy state.     

Crystallinity and morphology dependent luminescence of Li-doped Y2−xGdxO3:Eu thin film phosphors

The influence of lithium doping on the crystallization, the surface morphology, and the luminescent properties of pulsed laser deposited Y_2−xGd_xO₃:Eu³⁺ thin film phosphors was investigated. The crystallinity, the surface morphology, and the photoluminescence (PL) of films depended highly on the Li-doping and the Gd content. The relationship between the crystalline and morphological structures and the luminescent properties was studied, and Li⁺ doping was found to effectively enhance not only the crystallinity but also the luminescent brightness of Y_2−xGd_xO₃:Eu³⁺ thin films. In particular, the incorporation of Li and Gd into the Y₂O₃ lattice could induce remarkable increase in the PL. The highest emission intensity was observed Li-doped Y_1.35Gd_0.6O₃:Eu³⁺ thin films whose brightness was increased by a factor of 4.6 in comparison with that of Li-doped Y₂O₃:Eu³⁺ thin films.     

Spectral studies of Co substituted Ni-Zn ferrites

The spinel ferrites Zn_0.35Ni_0.65−xCo_xFe₂O₄, 0≤x≤1, have been prepared using the standard ceramic technique. Room temperature Mössbauer, X-ray and infrared IR spectra were used for carrying out this study. X-ray patterns reveal that all the samples have single-phase cubic spinel structure. The Mössbauer spectra of the samples show a paramagnetic phase for x=0 and a six-line magnetic pattern and a central paramagnetic phase for x≥0.1. They are analyzed and attributed to two magnetic subpatterns and two quadrupole doublets due to Fe³⁺ ions at the tetrahedral A-sites and octahedral B-sites. Four absorption bands are observed in IR spectra. They confirm the spinel structure of the samples and existence of Fe³⁺ ions in the sample sublattices. The deduced hyperfine interactions, lattice parameters, absorption band positions and intensities and force constant are found to be dependent on the substitution factor x, where the cation distribution is estimated. The hyperfine magnetic fields, magnetization and lattice resonant frequency are found to be dependent on the interionic distance.