Synthesis, structural and physical properties of new Terbium containing Tb-Hg-Sr-Ca-Cu-O superconducting system

Samples with various nominal compositions in the Tb-Hg-Sr-Ca-Cu-O system were prepared and studied by EDX, powder X-ray diffraction including the Rietveld refinement, electrical resistivity, magnetic susceptibility and thermoelectric power measurements. EDX and powder X-ray diffraction studies showed that Tb is required for the stabilization of the 1212, (Hg_1−yTb_y)Sr₂TbCu₂O_6+δ; y≈0.5 phase. Electrical resistivity and magnetic susceptibility measurements indicated that substitution of Tb by Ca is necessary to induce superconductivity in the 1212, (Hg_0.5Tb_0.5)Sr₂(Tb_1−xCa_x)Cu₂O_6+δ samples. The Rietveld refinements of the X-ray data of two samples with x=0.0 and 0.5 were carried out on the basis of tetragonal symmetry (space group P4/mmm) and the results indicated that the phase with x=0.5 has less puckered Cu-O planes than the Ca-free (Hg_0.5Tb_0.5)Sr₂TbCu₂O_6+δ phase. Syperconductivity is observed only for samples with x>0.2 and T_c increases with increasing Ca content, x. The results of thermoelectric power measurements suggest that the samples with x<0.8 are located in the underdoped region and the x=0.8 sample is optimally doped and exhibits the highest T_c of 88 K.     

Characterization of multiferroic LiTMxCu2−xO2 (TM=Ni and Zn) single crystals

We investigate a series of single crystalline samples of LiT_MxCu_2−xO₂ (T_M=Ni and Zn) grown by floating-zone technique. As-grown crystals showed a clear X-ray diffraction pattern of pure(single) phase. These crystals exhibit varied magnetic and electrical properties owing to successful incorporation of Ni and Zn dopants.     

Optical,physical and structural studies of vanadium doped P2O5–BaO–Li2O glasses

Glasses in the compositions (Li₂O)₂₅–(BaO)₂₅–(P₂O₅)_50−x–(V₂O₅)_x (with x=0.5,1.0,1.5,2.0,2.5, and 3.0 mol%) have been prepared by the conventional melt quenching technique. X-ray powder diffractrogram show broad peaks which conforms glassy nature of the sample. Differential scanning calorimetry (DSC) thermograms show characteristic glass transition temperature (T_g) and it increases with increasing substitution of V₂O₅ for P₂O₅. The measured physical parameters like density, refractive index, ionic concentration and electronic polarizability are found to vary linearly with increasing x. Infrared spectra exhibits few bands, which are attributed to (P=O)_AS, (P=O)_S, (V=O), (P–O–P)_AS,P–O–V, (P–O–P)_AS and O–P–O vibrations. The optical absorption spectra of VO²⁺ ions in these glasses show three bands and are assigned to the ²B₂→ ²E,²B₂→ ²B₁ and ²B₂→ ²A₁ transitions. Electron paramagnetic resonance spectra of all the glass samples exhibit resonance signals characteristic of VO²⁺ ions. The values of Spin-Hamiltonian parameters indicate that the VO²⁺ ions are present in octahedral sites with tetragonal compression and belong to C_4V symmetry.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

Characterization of Ni–Cu mixed spinel ferrite

Crystal structure, X-ray density, porosity, compressive strength of Ni_1−xCu_xFe₂O₄ have been investigated along with scanning electron microscopy (SEM) to study the effect of composition and microstructure on the magnetic and electrical properties. The formation of single-phase ferrite is confirmed by the X-ray diffraction. Tetragonal deformation is observed for the sample of composition x=1, i.e. for pure CuFe₂O₄ Crystal structure for samples of other compositions are face centered cubic (FCC). SEM micrographs exhibit increase in grain size with the increase of copper content. Compressive strength decreases with the increase of Cu. Initial magnetic permeability and saturation magnetization is maximum for the composition of x=0.2, i.e. for Ni_0.8Cu_0.2Fe₂O₄, which can be attributed to the maximum sintered density obtained for this composition. Resistivity decreases with the increase of Cu content.     

Magnetic and related properties of the solid solution CeCuxGa4−x

Physical properties of polycrystalline samples of CeCu_xGa_4−x (x = 0.2–1.4), crystallizing in the tetragonal BaAl₄-type structure (space group I 4/mmm), were studied by means of X-ray powder diffraction, magnetization, specific heat, electrical resistivity and magnetoresistivity measurements in wide temperature and magnetic fields ranges. The unit-cell volume of the system was found to decrease with increasing x (in total by about 4%) but the magnetic moments of Ce³⁺ ions remain localized in the whole x-range studied. The alloys exhibit ferromagnetic order at low temperatures, which manifests itself as distinct and relatively sharp anomalies in all the temperature characteristics measured. The ordering temperature decreases with increasing the Cu content from 5.5(1) K for x = 0.2 down to 1.35(5) K for x = 1.4, and the electrical transport properties of the system show some features characteristic of Kondo lattices.     

Structural and magnetic properties of Mg(In2−xMnx)O4 system

We synthesized the Mn-doped Mg(In_2−xMn_x)O₄ oxides with 0.03?x?0.55 using a solid-state reaction method. The X-ray diffraction patterns of the samples were in a good agreement with that of a distorted orthorhombic spinel phase. Their lattice parameters and unit-cell volumes decrease with x due to the substitution of the smaller Mn³⁺ ions to the larger In³⁺ ions. The undoped MgIn₂O₄ oxide presents diamagnetic signals for 5 K?T?300 K. The M(H) at T=300 K reveals a fairly negative-sloped linear relationship. Neither magnetic hysteresis nor saturation behavior was observed in this parent sample. For the Mn-doped samples, however, positive magnetization were observed between 5 and 300 K even if the x value is as low as 0.03. The mass susceptibility enhances with Mn content and it reaches the highest value of 1.4×10⁻³ emu/g Oe (at T=300 K) at x=0.45. Furthermore, the Mn-doped oxides with x=0.06 and 0.2, respectively, exhibit nonlinear magnetization curves and small hysteretic loops in low magnetic fields. Susceptibilities of the Mn-doped samples are much higher than those of MnO₂, Mn₂O₃ oxides, and Mn metals. These results show that the oxides have potential to be magnetic semiconductors.     

Magnetic interactions in Cu-substituted manganese ferrites

A series of Mn_1−xCu_xFe₂O₄, with x=0, 0.25, 0.50, 0.75 and 1.0, spinel ferrites were prepared by standard ceramic method, to study the effect of compositional variation on magnetic susceptibility, saturation magnetization (M_s), Curie temperature (T_c) and magnetic moments (μ_B). The Curie temperatures have been evaluated by measuring the ac susceptibility using the mutual inductance technique. On increasing Cu contents from 0.0 to 0.50, the saturation magnetization increases while the Curie temperature decreases. On further increase in Cu contents, x>0.50 a decreasing trend in M_s is exhibited while T_c continues to decrease. This effect can be partially related to the low magnetic moments of Cu⁺² ions. The dominant interaction in all ferrite samples is A-B interaction which is due to the negative values of the characteristic temperature θ(K) showing that the magnetic ordering is antiferromagnetic. The Y-K angle increases gradually with increasing copper contents and extrapolates to 90° for CuFe₂O₄. From the computation of Y-K angles for Mn_1−xCu_xFe₂O₄, it can be concluded that the mixed copper ferrites exhibit a non-collinearity of the Y-K type while MnFe₂O₄ shows a Neel type of ordering.     

Evidence of local structural transition during oxidation process of RBCO epitaxial films using time resolved reflexafs measurements

We report results of a time resolved X-ray Absorption Spectroscopy (XAS) experiment on the oxidation process of epitaxial Y₁(Nd_0.05Ba_1.95)Cu₃O_x superconducting thin films. For the first time Cu K-edge XAS technique has been used to explore local structural changes around the Cu ions during the oxidation process of a high critical temperature superconducting film. The results show that during the oxygenation of a tetragonal Y₁(Nd_0.05Ba_1.95)Cu₃O_x additional local transitions appear in the orthorhombic I phase, which are not linked to long range order transformations as shown by in situ X-ray diffraction experiment. New questions concerning the dynamic microscopic process leading to the oxygenation and eventually to superconductivity of the complex R_1+xBa_2-xCu₃O_x (R = Y or rare earth) compounds arose from these results. Received 21 December 2001 Published online 25 June 2002     

NMR investigations of ion distribution in real structure of manganese-zinc ferrites

Using the nuclear magnetic resonance, X-ray and electromagnetic methods we investigated structure and properties of the single- and polycrystalline manganous and manganese-zinc ferrites: MnFe₂O₄, Mn_0.8Zn_0.2Fe₂O₄, Mn_0.6−xCu_xZn_0.3Fe_2.1O₄ (0 ≤x ≤ 0.3). The real structure of the manganous and manganese-zinc ferrites is found to contain simultaneously vacancies in cationic and anionic sublattices. The analysis of the NMR spectra of⁵⁵Mn,⁵⁷Fe,^63,65Cu and⁶⁷Zn ions allowed us to find the magnetic and valence states of all ions and their distribution in the real spinel structure. It was shown that the Fe³⁺ paramagnetic ions, Zn²⁺ diamagnetic ions and cationic vacancies in tetrapositions are distributed statistically. The Mn³⁺ and Cu²⁺ Jahn-Teller ions and presumably Fe²⁺ in octahedral positions are distributed nonstatistically forming cluster-type mesoscopic inhomogeneities. The correlation between distribution of ions and vacancies in the real structure of manganese-zinc ferrites and their functional electromagnetic properties was found.     

μ+SR studies on superconducting YBa2(Cu1−xFex)3Oy system

Spin-glass like magnetic ordering of iron moments was observed in both orthorhombic and tetragonal YBa₂(Cu_1−xFe_x)₃O_y (x=0.08) by μ⁺SR measurements. In a “Tetra” sample, all the muons sense the superconducting transition at 60 K and magnetic ordering at around 15 K, while in an “Ortho” sample they reveal that two magnetically different parts exist in the sample: about 40% of the sample is superconducting withT _c ≈90K and the remaining part is magnetic withT _M≈33K. These phenomena can be explained in terms of clustering of the Fe atoms in the “Ortho” sample.     

Synthesis and superconductivity of a new 1222-type T1-based layered cuprate (T1, Nb) Sr2(Nd,Ce)2Cu2O z

Synthesis and superconductivity of a new 1222-type layered cuprate (Tl_1–x Nb _x ) Sr₂(Nd_1–y Ce _y )₂Cu₂O _z have been studied. The structure of this cuprate is directly related to that of Nb-1222 NbSr₂(Nd, Ce)₂Cu₂O _z with tetragonal body-center lattice. Partial substitution of Tl for Nb in Nb-1222 phase improves its superconductivity. (Tl_1–x Nb _x ) Sr₂(Nd_0.75Ce_0.25)₂Cu₂O _z samples prepared by the typical procedure exhibit superconductivity withT _c of 30–40 K. Effects of Tl and Nb on superconductivity of this cuprate are briefly discussed.     

Enhancement of microstructure and initial permeability due to Cu substitution in Ni0.50−xCuxZn0.50Fe2O4 ferrites

Structural and magnetic properties of Cu substituted Ni_0.50−xCu_xZn_0.50Fe₂O₄ ferrites (where x=0.0-0.25) prepared by an auto combustion method have been investigated. The X-ray diffraction patterns of these compositions confirmed the formation of the single phase spinel structure. The lattice parameter increases with the increase in Cu²⁺ content obeying Vegard's law. The particle size of the starting powder compositions varied from 22 to 72 nm. The theoretical density increases with increase in copper content whereas the Néel temperature decreases. The bulk density, grain size and permeability increases up to a certain level of Cu²⁺ substitution, beyond that all these properties decrease with increase in Cu²⁺ content. The bulk density increases with increase in sintering temperatures up to 1250 °C for the parent composition, while for substituted compositions it increases up to 1200 °C. Due to substitution of Cu²⁺, the real part of the initial permeability increases from 97 to ∼390 for the sample sintered at 1100 °C and from 450 to 920 for the sample sintered at 1300 °C. The ferrites with higher initial permeability have a relatively lower resonance frequency, which obey Snoek's law. The initial permeability strongly depends on average grain size and intragranular porosity. The saturation magnetization, M_s, and the number of Bohr magneton, n(μ_B)_, decreases up to x=0.15 due to the reduction of the A-B interaction in the AB₂O₄ spinel type ferrites. Beyond that value of x, the M_s and the n(μ_B) values are enhanced. The substitution of Cu²⁺ influences the magnetic parameters due to modification of the cation distribution.     

Effects of nickel doping on structural and optical properties of spinel lithium manganate thin films

Spinel LiNi_xMn_2−xO₄ (x≤0.9) thin films were synthesized by a sol-gel method employing spin-coating. The Ni-doped films were found to maintain cubic structure at low x but to exhibit a phase transition to tetragonal structure for x≥0.6. Such cubic-tetragonal phase transition can be explained in terms of Ni³⁺(d⁷) ions with low-spin (t_2g⁶,e_g¹) configuration occupying the octahedral sites of the compound, thus being subject to the Jahn-Teller effect. By X-ray photoelectron spectroscopy both Ni³⁺ and Ni²⁺ ions were detected where Ni²⁺ is more populated than Ni³⁺. Optical properties of the LiNi_xMn_2−xO₄ films were investigated by spectroscopic ellipsometry in the visible-ultraviolet range. The measured dielectric function spectra mainly consist of broad absorption structures attributed to charge-transfer transitions, O²⁻(2p)→Mn⁴⁺(3d) for 1.9 (t_2g) and 2.8-3.0 eV (e_g) structures and O²⁻(2p)→Mn³⁺(3d) for 2.3 (t_2g) and 3.4-3.6 eV (e_g) structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as being due to d-d crystal-field transitions within the octahedral Mn³⁺ ion. In terms of these transitions, the evolution of the optical absorption spectrum of LiMn₂O₄ by Ni doping could be explained and the related electronic structure parameters were obtained.     

Adsorption and photocatalytic degradation of methylene blue on Zn1−xCuxS nanoparticles prepared by a simple green method

Nanoparticles of Zn_1−xCu_xS with various dopant contents (0 ≤ x ≤ 0.15) were prepared in water by refluxing for 90 min at about 95 °C. Powder X-ray diffraction (XRD) patterns of the nanoparticles demonstrate that loading of Cu²⁺ ions does not change the crystal structure of ZnS. Scanning electron microscopy (SEM) images demonstrate that size of the nanoparticles decreases with increasing Cu²⁺ ions. UV-Vis diffuse reflectance spectra (DRS) of the nanoparticles show significant absorption in visible light region. Adsorption capacity of the nanoparticles for methylene blue (MB) increases with mole fraction of copper ions. Photocatalytic activity of the nanoparticles toward photodegradation of MB was evaluated under visible light irradiation. The results indicate that Zn_0.85Cu_0.15S nanoparticles exhibit highest photocatalytic activity among the prepared samples. Moreover, effects of refluxing time applied for preparation of the nanoparticles and calcination temperature were investigated.     

Structural, electrical and magnetic characterizations of Ni-Cu-Zn ferrite synthesized by citrate precursor method

Fine powders of NiCuZn ferrite with composition Ni_(0.7−x)Cu_xZn_0.3Fe₂O₄ (where x=0, 0.2, 0.4 and 0.6) were prepared by the citrate precursor method. X-ray diffraction measurements confirm the formation of single-phase cubic spinel structure. The grain size was estimated by SEM micrograph which increases with Cu content. Dielectric constant (?) and loss tangent (tan δ) were measured as a function of frequency. The ? and tan δ show a decreasing trend with increase of frequency for all the samples. The DC resistivity was measured as a function of temperature. The temperature-dependent DC resistivity measurements show that the room-temperature DC resistivity of NiCuZn ferrite with x=0.2 is of the order of 10⁹ Ω cm. The AC conductivity (σ_AC) was studied as a function of frequency. The hysteresis data indicate that the maximum saturation magnetization of 38.66 emu/g is obtained for the composition with x=0.2.     

Effects on structure and superconductivity for La and Ca codoping in YBa2Cu3Oy cuprates

The nominal composition of Y_0.8Ca_0.2Ba_2−xLa_xCu₃O_y (YBLCO) cuprates with x≤0.50 has been synthesized by the standard solid state reaction technique. X-ray diffraction and the resistivity measurements are used to characterize the structure and the superconductivity of YBLCO cuprates. There is no structural phase transition in the whole doping range. The dependencies of the lattice constants and some other structural parameters on the content of La for the samples YBLCO with x≤0.20 are different than those for the samples with x≥0.25. The zero resistance temperature T_c0 increases with the increase of the content of La in YBLCO as x≤0.20, and decreases as x≥0.25. We compared these results with those of Nd-doped Y_0.8Ca_0.2Ba_2−zNd_zCu₃O_y cuprates. It seems that T_c0 is related to the structural parameters due to Ca and La codoping in YBLCO.     

Structure and impedance spectroscopy of Pr1? x Sr x Fe0.8Co0.2O3? δ ( x =0.1, 0.2, 0.3) thin films grown by laser ablation

Polycrystalline samples of Pr_1−x Sr _x Fe_0.8Co_0.2 O_3−δ (x=0.1, 0.2, 0.3) (PSFC) were prepared by the combustion synthesis route at 1200°C. The structure of the polycrystalline powders was analysed with X-ray powder diffraction data. The X-ray diffraction (XRD) patterns were indexed as the orthoferrite similar to that of PrFeO₃ having a single-phase orthorhombic perovskite structure (Pbnm). Pr_1−x Sr _x Fe_0.8Co_0.2O_3−δ (x=0.1, 0.2, 0.3) films have been deposited on yttria-stabilized zirconia (YSZ) single-crystal substrates at 700°C by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell cathodes. The structure of the films was analysed by XRD, scanning electron microscopy (SEM) and atomic force microscopy (AFM). All films are polycrystalline with a marked texture and present pyramidal grains in the surface with different size distributions. Electrochemical impedance spectroscopy (EIS) measurements of PSFC/YSZ single crystal/PSFC test cells were conducted. The Pr_0.7Sr_0.3Fe_0.8Co_0.2O_3−δ film at 850°C presents a lower area specific resistance (ASR) value, 1.65 Ω cm², followed by the Pr_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (2.29 Ω cm² at 850°C) and the Pr_0.9Sr_0.1Fe_0.8Co_0.2O_3−δ films (5.45 Ω cm² at 850°C).     

Variations of ionic binding energies and the distribution of charge carriers in orthorhombic La2−x Sr x CuO4

The significance of heterovalent, substitutional disorder for the distribution of charge carriers in La_2−x Sr _x CuO₄ has been investigated. Disorder is shown to cause strong variations of binding energies of the ions ranging to some eV for Sr contentsx=0.1. Balancing the energy for a hole transport, Cu³⁺+O²⁻→Cu²⁺+O⁻, and taking binding energy variations into account, the process is realized to become possible without consuming energy for a subset Θ for allx Cu³⁺ in one formula unit of La_2−x Sr _x CuO₄. The functions Θ(x) are presented for hole transports to apex and in-plane oxygens, respectively. The delocalization of charge carriers is interpreted to be caused by valency disorder on metal lattice sites.     

Dielectric properties of lanthanum-doped CaCu3Ti4O12 synthesized by semi-wet route

Effect of La³⁺ doping at Ca²⁺ site in CaCu₃Ti₄O₁₂ has been examined. Compositions with x=0.10, 0.20 and 0.30 were synthesized in the system Ca_(1−3x/2)La_xCu₃Ti₄O₁₂ by semi-wet method. Powder X-ray diffraction confirmed the formation of monophasic compounds. The structure remains cubic similar to CaCu₃Ti₄O₁₂. Lattice parameter increases slightly with increasing La³⁺ concentration. Microstructure has been studied using scanning electron microscopy (SEM). Average grain size is in the range 2-4 μm for various compositions. Energy-dispersive spectrometer (EDS) studies confirm the stoichiometry of the synthesized materials. Dielectric constant, dielectric loss and conductivity of the samples decrease with increasing lanthanum concentrations.