High-Jc GdBa2Cu3O7−δ films fabricated by the metal–organic deposition process

We report a successful fabrication of high-J_c GdBa₂Cu₃O_7−δ (GdBCO) films by the metal–organic deposition process on the LaAlO₃ (LAO) (0 0 1) substrates. The coating solution was prepared by mixing Gd, Cu fluorine-free sources with Ba trifluoroacetate. Samples were dip-coated, pyrolized within 3 h at the temperature up to 400 °C in a humid oxygen atmosphere, and finally fired at various high temperatures in 100 ppm Ar/O₂ atmosphere. The GdBCO films fired at 775 and 800 °C exhibited J_c values of ∼2.1 MA/cm² at 77 K in a self-field, which are attributable to both high T_c,zero values of ∼89 K and high in-plane textures of 1.3–1.4°. Above 800 °C, however, the superconducting properties of GdBCO films are degraded due to the thermal decomposition of GdBCO film in 100 ppm Ar/O₂ atmosphere.     

Hall effect and sign reversal in Gd(Ba2−xNdx)Cu3O7+δ

We have investigated the Hall measurement of Gd(Ba_2−xNd_x)Cu₃O_7+δ with x=0, 0.05, 0.1, 0.15, and 0.2 in a magnetic field of 0–1 T. The nominal samples has been prepared by the conventional solid-state reaction technique. The iodometric titration experiment was carried out for samples. The Rietveld analysis of the X-ray diffraction patterns indicates that samples are mainly single phase. The normal state Hall coefficient behaves as 1/T in all samples. All samples with nominal compositions show single sign reversal with variation of magnetic field and temperature. The Hall resistivity of the samples with x=0 and 0.1 close to the superconducting transition temperature changes its sign with decreasing temperature and tends to a minimum −Δ_max, and then monotonically goes to zero. The absolute value of −Δ_max decreases with the increase of magnetic field. This can be qualitatively explained by a model calculation based on the time-dependent Ginsburg–Landau theory.     

Anomalous Hall effect in sputter-deposited CoxTi1−xO2–δ films

Hall effect measurements were performed on epitaxial Co_xTi_1−xO_2–δ thin films grown on (0 0 1) LaAlO₃ by reactive RF magnetron co-sputter deposition. Magnetization measurements reveal ferromagnetic behavior in M–H loop at room temperature for Co_xTi_1−xO_2–δ thin films for which x?0.02. An anomalous Hall effect was observed for Co_0.10Ti_0.90O_2−δ films grown with the partial pressure of water P(H₂O)=4×10⁻⁴ Torr or less. These films exhibit a positive ordinary Hall coefficient and a positive magnetoresistance. X-ray diffraction on films grown under these conditions shows evidence for Ti_nO_2n−1 phase due to the deficiency of oxygen. In contrast, Hall measurements taken for undoped and Co-doped TiO₂ thin films grown under more oxidizing conditions show only the ordinary Hall effect with a negative Hall coefficient consistent with n-type conduction. For these films, the magnetoresistance was positive and increased monotonically with increasing magnetic field. The results suggest that Co-doped Ti_nO_2n−1 may be a dilute magnetic semiconducting oxide for which the carriers couple to the spin polarization.     

Structural investigation of the BaSnO3–YBa2Cu3O7−x system

We report the microstructure change of BaSnO₃ (BSO)–YBa₂Cu₃O_7−x (YBCO) thin film system grown on SrTiO₃ single crystal substrates by pulsed laser deposition with using the “surface-modified-target” and “mixture-target” methods. Although it was confirmed that the thick BSO nanorods incorporated to YBCO films act as strong artificial pinning centers, the formation mechanism of the nanorods is still unclear. The purpose of this work is to extend the structural investigation to higher contents of BSO (up to 71 vol.%) in order to enlighten the relationship among interfacial energy, morphology and pinning performance in binary BSO–YBCO films.     

Fluorination of perovskite-related phases of composition La1−xSrxFe1−yCoyO3−δ

We report here on the fluorination of the perovskite-related phases La_1−xSr_xFe_1−yCo_yO_3−δ. The introduction of fluorine in place of oxygen is achieved through a low-temperature (400 °C) reaction with poly(vinylidene fluoride). X-ray powder diffraction data show that in all cases the fluorination leads to an expansion in the unit cell, which is consistent with partial replacement of oxygen by fluorine and consequent reduction in the oxidation state of iron and/or cobalt. This reduction in oxidation state is confirmed by X-ray absorption- and Mössbauer-spectroscopy. The Mössbauer spectra show complex magnetically split hyperfine patterns for the fluorinated samples, reflecting the interactions between Fe³⁺ ions, which are not possible in oxides containing Fe⁴⁺.     

La2−xSrxCuO4−δ superconducting samples prepared by the wet-chemical method

In this work, we report on the physical properties of good-quality polycrystalline superconducting samples of La_2−xSr_xCu_1−yZn_yO_4−δ (y=0, 0.02) prepared by a wet-chemical method, focusing on the temperature dependence of the critical current. Using the wet-chemical method, we were able to produce samples with improved homogeneity compared to the solid-state method. A complete set of samples with several carrier concentrations, ranging from the underdoped (strontium concentration x≈0.05) to the highly overdoped (x≈0.25) region, were prepared and investigated. The X-ray diffraction analysis, zero-field cooling magnetization and electrical resistivity measurements were reported on earlier. The structural parameters of the prepared samples seem to be slightly modified by the preparation method and their critical temperatures were lower than reported in the literature. The temperature dependence of the critical current was explained by a theoretical model which took the granular structure of the samples into account.     

Low-temperature synthesis of nanocrystalline Ca1−xHoxMnO3−δ (0?x?0.3) powders

Nanocrystalline Ca_1−xHo_xMnO_3−δ (0?x?0.3) manganites were synthesized as phase-pure by a simple and instantaneous solution autogel combustion method, which is a low temperature initiated synthetic route to obtain fine grain size. All the samples, heated at 800 °C for 18 h, can be produced as phase-pure; the polycrystalline powders are homogeneous and possess ultrafine particle size. The holmium-doped calcium manganites retain the orthorhombic phase of the undoped sample. The scanning electron microscope (SEM) images revealed that the combustion-derived compounds exhibit particle size that decreases with holmium content from 300 to 80 nm. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹. The high temperature dependence of resistivity was measured using a standard four-probe method in the range 25-600 °C. All the samples exhibit semiconductor behaviour and holmium induces a marked decrease in the electrical resistivity when compared with the parent CaMnO₃. The results can be well attributed to the Mn⁴⁺/Mn³⁺ ratio and to the particle grain size.     

High-temperature electronic transport properties of La1−xCaxMnO3+δ (0.0?x?1.0)

La_1−xCa_xMnO_3+δ (0.0?x?1.0) samples were prepared and their resistivity and Seebeck coefficients were measured in the high-temperature range. Ca doping changes the ratio of Mn³⁺/Mn⁴⁺ and influences the electronic transport behavior markedly. With the increase of Ca concentration, the samples change from a p-type semiconductor to an n-type one and Seebeck coefficient becomes increasingly negative. Low doping (x=0.2) and high doping (x=0.8) induces the drop of the resistivity compared with undoped LaMnO_3+δ and CaMnO_3+δ samples due to the rise of carrier concentration. However, the resistivity of moderate-doped samples (x=0.4, 0.6) is larger than low- and high-doped samples because dopant scattering decreases carrier mobility.     

Fluctuation conductivity along the c-axis and parallel to the ab-planes in melt-textured YBa2Cu3O7−δ samples doped with Y211 phase

We report measurements of in-plane and out-of-plane fluctuation conductivity under low applied magnetic fields up to 500 Oe in two melt-textured YBa₂Cu₃O_7−δ (YBCO) samples. 3D-Gaussian and genuine critical 3D-XY-E fluctuation regimes were identified in the conductivity parallel to the ab plane. In addition, a regime beyond 3D-XY was observed in the immediate vicinity of the superconducting transition of the in-plane fluctuation conductivity. The 3D-XY-E scaling was also identified in the fluctuation conductivity along the c-axis in the sample with smaller content of the Y₂BaCuO₅ (Y211) phase. This result indicates that the superconducting state in YBCO has a three-dimensional character, in contradiction to some studies suggesting that critical phenomenology is fundamentally distinct in orientations parallel or perpendicular to the Cu-O₂ planes of the high-temperature superconductors. However, the results suggests the presence of a sub-dominant order-parameter component in YBCO that has an appreciable projection along the c-axis.     

Structure, magnetic and superconducting properties of MoSr2HoCu2O8−δ

Samples with nominal composition MoSr₂HoCu₂O_8−δ were synthesized and their magnetic and superconducting (SC) properties were investigated. The obtained samples are Mo-deficient. It was established that the magnetic order is of a long-range type. The coincidence of the experimental value of the Curie constant and the theoretical one of MoSr₂HoCu₂O_8−δ shows that the observed magnetic properties of the samples are determined by the highly dominating phase Mo-1212. The two-step resistive SC transition, together with the absence of both diamagnetism and a peak in the specific heat between the two critical temperatures may be associated with the presence of a granular superconductivity. The effect of the Mo-deficiency on the magnetic and SC properties of MoSr₂HoCu₂O_8−δ was discussed.     

Superconductivity and critical fields in undoped and Sn-doped MoSr2YCu2O8−δ

Samples with nominal compositions MoSn_xSr₂YCu₂O_8−δ (0 ? x ? 0.075) were synthesized and their superconducting and magnetotransport properties were investigated. It was established that the optimum Sn-doping (x = 0.02 and 0.03) increases the T_c of the undoped MoSr₂YCu₂O_8−δ. The upper critical fields of the samples were determined using magnetization, susceptibility and resistivity measurements. It was established that the Sn-doping weakly affects the first and the intragrain second critical field of Mo-1212 but enhances the extrapolated to T = 0 (i.e. the intergrain) upper critical field. The observed phenomena were discussed on the basis of the Josephson-junction-arrays model. A phenomenological expression describing the temperature dependency of the susceptibility of Mo-1212 was found.     

Heterogeneous magnetic and electronic states in Ca1−xLaxMnO3−δ (x⩽0.12) single crystals with electron doping

The magnetic, transport, and optical properties of electron-doped Ca_1−xLa_xMnO_3−δ single crystals with x  ?0.12 were studied. The magnetic measurements show that in single crystals with x=0$x=0$ and 0.05 the G-type AFM phase with weak FM component is realized and in crystals with x=0.10$x=0.10$ and 0.12 the G- and C-type AFM phases coexist. The C-type magnetic structure arises at less concentration of La than in polycrystalline samples as a result of oxygen vacancies being additional source of electrons. Under magnetic transitions in the G- and C-type phases, resistivity and magnetoresistance of the doped single crystals have anomalies. Optical absorption in IR range indicates formation of a charge gap in crystals with x=0.10$x=0.10$ and 0.12 at appearance of the C-AFM and monoclinic phase with orbital/charge ordering. By comparing optical and transport properties, heterogeneous electronic state and its relation with heterogeneous magnetic state are shown.     

Pressure tuned crystal structure in NdBa2Cu3O6+δ superconductor

The high-pressure angle-dispersive X-ray diffraction experiments on the NdBa₂Cu₃O_6+δ superconductor were performed from ambient to above 30 GPa at room temperature. The structure analysis based on the Rietveld refinement methods shows the different pressure dependence for the bond length between the basal-plane copper of the pyramids to the apical oxygen (denoted Cu(2)–O(1)) and bond length between basal-plane copper to plane oxygen (denoted Cu(2)–O(2,3)). The ambient bulk modulus B₀ is derived as 127 GPa. A possible correlation between Cu(2)–O(1) and T_c was discussed.     

Critical RF losses in fine particles of La1−xAgyMnO3+δ: Prospects for temperature-controlled hyperthermia

Temperature and frequency dependencies of the real (χ′) and imaginary (χ″) parts of the dynamic magnetic susceptibility were studied experimentally in fine particles of La-Ag manganites prepared by various methods. The samples under study have the Curie points in the range T_C=42-48 °C, which is a medical hyperthermia range of interest. When approaching T_C from below, a critical peak of χ″ was revealed, followed by a steep drop while passing to the paramagnetic phase. The experiments on the magnetic radio-frequency (RF) heating of the manganite aqueous suspensions demonstrated good autostabilization of the temperature near T_C. Peculiar instability is found in the heating kinetics, caused by the observed critical behavior of the RF losses. The prospects of the La-Ag manganites as candidates for application in the temperature-controlled hyperthermia are discussed.     

Valence changes of manganese and praseodymium in Pr1−xSrxMn1−yInyO3−δ perovskites upon cation substitution as determined with XANES and ELNES

Systematic valence changes in Pr_1−xSr_xMn_1−yIn_yO_3−δ upon cation substitution with Sr²⁺ and In³⁺ have been found using Mn K-edge and Pr L-edge X-ray absorption, and Mn L_II,III and Pr M_IV,V electron energy-loss spectroscopy. The average valence of the praseodymium ions is close to +3.0 and virtually constant over the sample set when the samples also contained manganese ions. Pr_0.5Sr_0.5InO_3−δ showed a distinct increase in the praseodymium valence state. In contrast, the average valence of the manganese ions changed from the trivalent state to intermediate values between +3.0 and +4.0 and approached the tetravalent state depending on the level of substitution. The knowledge of the valence is required to understand the conduction mechanisms in the material due to the small polaron hopping (electronic conductivity) and motion of oxygen ions along the vacancies (ionic conductivity). Addition of strontium and indium led to the formation of oxygen vacancies. A previously assumed intermediate valence of praseodymium as causal factor for the higher oxygen catalytic activity cannot be confirmed with room temperature measurements.     

The epitaxial growth of BaSnO3 buffer layer on IBAD-MgO template and its effects on GdBa2Cu3O7−δ film: A preliminary study

We report a successful fabrication of c-axis oriented GdBa₂Cu₃O_7−δ (GdBCO) films on the BaSnO₃ (BSO) buffer layers on ion-beam assisted deposition (IBAD)-MgO template by pulsed-laser deposition (PLD). The (0 0 l) growth and in-plane textures of BSO buffer layers were found sensitive to the substrate temperature (T_s). With increasing the BSO layer thickness up to ∼165 nm, in-plane texture (Δ? ∼ 6.2°) of BSO layers was almost unaltered while completely c-axis oriented BSO layers were obtainable from samples with the thickness below ∼45 nm. On the BSO buffer layers showing in-plane texture of 6.2° and RMS surface roughness of ∼8.6 nm, GdBCO films were deposited at 780–800 °C. All GdBCO films exhibited Δ? values of 4.6–4.7°, T_c,zero of ∼91 K, and critical current density (J_c) over 1 MA/cm² at 77 K in a self-field. The highest J_c value of 1.82 MA/cm² (I_c of 51 A/cm-width) was achieved from the GdBCO film deposited at T_s of 790 °C. These results support that BSO can be a promising buffer layer on the IBAD-MgO template for obtaining high-J_c GdBCO coated conductors.     

Enhanced flux pinning in pulsed laser deposited Y Ba2Cu3O7−δ : BaTiO3 nanocomposite thin films

The effect of incorporation of BaTiO₃(BTO) nanoparticles on the flux pinning properties of pulsed laser deposited YBCO:BTO thin films was studied. Substantial increase in the critical current density (J_C) and the pinning force density (F_p) of the nanocomposite thin films was observed. At 77 K, and zero applied magnetic field, the value of J_C for YBCO and YBCO:BTO (2%) thin films were 2.93 MA/cm² and 6.43 MA/cm², respectively. At the same temperature and an applied magnetic field of 4 T, the value of J_C increases from 3.6×10⁴ A/cm² for YBCO thin film to 2.7×10⁵ A/cm² for YBCO:BTO (2%) nanocomposite thin film. The study of temperature and field dependence of of YBCO and YBCO:BTO thin films indicates similar type of pinning. The lattice mismatch between YBCO and BTO seems to introduce more defects resulting in the improvement of flux pinning properties.     

Dielectric properties of Cu0.5Tl0.5Ba2Ca3Cu4O12−δ bulk superconductor

The dielectric properties of Cu_0.5Tl_0.5Ba₂Ca₃Cu₄O_12−δ superconductor samples were studied at 79 and 290 K by means of capacitance (C) and conductance (G) measurements with the test frequency (f) in the range of 10 kHz to 10 MHz. A negative capacitance (NC) phenomenon has been observed, which is most likely arising due to higher Fermi level of ceramic superconductor samples than metal electrodes. Also the NC may be due to the space charge located at the multiple insulator–superconductor interfaces (grain boundaries) in the materials. The negative dielectric constant (ε′) and loss factor (tan δ) show strong dispersion at low frequencies. The lower thermal agitation at 79 K may enhance the polarizability and hence the dielectric constants (ε′ and ε″).     

Magnetic properties of low-doped bulk Sr(Ti, Co)O3−δ perovskites

Magnetic properties of bulk SrTi_1−xCo_xO_3−δ solid solutions (for x from 0 to 0.05), prepared in air as those partially reduced, were studied by following the influence of the dopant concentration and valence. A strong paramagnetic and/or diamagnetic contribution and an extremely weak ferromagnetic contribution maintained up to room temperature is observed for all the studied compositions, including the undoped samples. While the paramagnetic contribution shows a classical evolution with cobalt concentration and valence, the ferromagnetic part of the magnetization seems to be independent of the doping process. While some of the observations can support the assumption of an intrinsic property of the SrTiO₃ matrix, the hypothesis of a ferromagnetism associated to some contamination with external magnetic impurities cannot be completely discarded and will be retained here.