Temperature dependence of the resistivity and its anisotropy in n-type Nd1.85Ce0.15CuO4 single crystal

Measurements of the in-plane and c-axis normal-state resistivity in a superconducting Nd_1.85Ce_0.15CuO_4−δ single crystal are reported. The resistivity anisotropy of this n-type material is ≤250, much smaller than BiSCCO and comparable to YBaCuO. Both, _ab(T) and _c(T) displays a metallic-like positive temperature coefficient of resistivity with a basic T² dependence. We discuss some possible origins of this peculiar temperature dependence.     

A comparison of the zero bias differential resistance of Ag:Nb and Ag:Nd1.85Ce0.15CuO4−δ point contacts as a function of temperature below Tc

Point contact spectra for contacts between Ag and two different superconductors, Nb and Nd_1.85Ce_0.15CuO_4−δ, were measured as a function of temperature using a crossed wire-wedge technique (R.C. Reinertson et al., Physica B 165&166 (1990) 1615). The temperature dependence of the zero bias resistance quantitatively agrees with predictions of the theory by Blonder, Tinkham and Klapwijk (Phys. Rev. B 25 (1982) 4515) for normal:superconductor point contacts for all interface scattering barrier strengths observed in this study (Z = 0.3 to Z = 1.0). The zero bias temperature dependence of Ag:Nd_1.85Ce_0.15CuO_4−δ contacts indicates a systematically higher range of barrier strengths and contact resistances than typical Ag:Nb contacts.     

Picosecond nonlinear optical response of Ba0.5Sr0.5TiO3 thin films fabricated by pulsed laser deposition

Well-crystallized Ba_0.5Sr_0.5TiO₃ thin films with good surface morphology were prepared on MgO(1 0 0) substrates by pulsed laser deposition technique at a deposition temperature of 800 °C under the oxygen pressure of 2 × 10⁻³ Pa. X-ray diffraction and atomic force microscopy were used to characterize the films. The full width at half maximum of the (0 0 2) Ba_0.5Sr_0.5TiO₃ rocking curve and the root-mean-square surface roughness within the 5 μm × 5 μm area were 0.542° and 0.555 nm, respectively. The nonlinear optical properties of the films were determined by a single beam Z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that Ba_0.5Sr_0.5TiO₃ thin films exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 5.04 × 10⁻⁶ cm²/kW and β = 3.59 × 10⁻⁶ (m/W), respectively.     

Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Ferromagnetic Zr1−xMnxCo2 laves phase compounds

Structure and magnetic properties of the Zr_1−xMn_xCo_2+δ alloys were studied for 0 x <0.7, δ=0, 0.45. The cubic C15 Laves phase structure shows Mn solubility up to x≈0.4. The other Laves phase with the hexagonal C36 structure found for x0.5 apparently has a small region of Mn solubility in the vicinity of Zr_0.4Mn_0.6Co₂. Though the parent Mn-free compounds are known to be paramagnetic, the Mn-substituted alloys show ferromagnetic behavior with the Curie temperatures up to 625 K and the room-temperature saturation magnetization of about 100 emu/g. The onset of ferromagnetism with the Mn substitution for Zr may be caused by polarization of itinerant 3d electrons, like it was earlier supposed for the off-stoichiometric ZrCo_2+δ. The universal composition dependencies of the intrinsic magnetic properties for different δ can be obtained, if plotted against the amount of zirconium atoms missing in its sublattice. The room-temperature anisotropy with the noticeable anisotropy field of 24 kOe and the 1 1 0 easy magnetization direction laying in a basal plane was found in the hexagonal Zr_0.5Mn_0.5Co₂.     

A study on the structural–microstructural characterisation and defect structure of Ru based magnetosuperconductor, RuSr2Eu1.6Ce0.4Cu2O10−δ

The structural–microstructural characterization and defect structure of Ru based magnetosuperconductor RuSr₂Eu_1.6Ce_0.4Cu₂O_10−δ has been investigated by selected area electron diffraction pattern and high resolution electron microscopy. Under the present investigations, RuSr₂Eu_1.6Ce_0.4Cu₂O_10−δ magnetosuperconductor shows the presence of both Ru-1222 and Ru-1212 phases. Analysis of the selected area electron diffraction pattern indicates superstructure in Ru-1212 while Ru-1222 phase does not show the presence of superlattice structure. A careful and detailed investigations of the HRTEM image shows the presence of defects like 90° domains, intergrowths, and dislocations.     

Observation of unrecoverable domains in two-dimensional-arrayed Pr0.5Ca0.5MnO3−y junctions

Two-dimensional-arrayed 14×14 sandwich-type junctions of Au–Pr_1−xCa_xMnO_3−y (PCMO, x=0.5)–SrRuO₃ were fabricated on SrTiO₃ (0 0 1) substrates. The resistivity–voltage (ρ–V) characteristics of each junction was measured by a two-probe method. The junctions that return to the insulating state after removing the voltage (recoverable) and the ones that remain metallic (unrecoverable) were found to co-exist in one PCMO film. The variation in the lattice constant of the PCMO film, rather than the variation of the composition, is thought to be related to the separation of recoverable–unrecoverable domains. Among several samples with a PCMO layer fabricated under various conditions, the junctions with thin PCMO layers deposited at low temperature showed a pronounced hysteresis in their ρ–V characteristics. The clear hysteresis and good crystallinity of PCMO films were correlated.     

Transport properties of SrCe0.95Y0.05O3−δ and its application for hydrogen separation

Transport properties of SrCe_0.95Y_0.05O_3−δ were studied by impedance spectroscopy and by measuring open-cell voltage (OCV) and gas permeation. Ionic transference numbers were determined by measuring the OCV of concentration cells and water vapor evolution of an O₂/H₂ fuel cell. We observed interfacial polarization on the basis of the I–V curves obtained by discharging a hydrogen concentration cell or an O₂/H₂ fuel cell. The observed high protonic conductivity (high proton and low oxide ion transference numbers) makes SrCe_0.95Y_0.05O_3−δ a potential material for hydrogen separation. From proton conductivity measurements, under a given hydrogen partial pressure difference of 4%/0.488%, the hydrogen permeation rate (of a dense membrane with 0.11 cm in thickness) was calculated to be ≈0.072 cm³ (STP) cm⁻² min⁻¹ at 800°C, whereas the permeation rate calculated from short-circuit current measurements was ≈0.023 cm³ (STP) cm⁻² min⁻¹ at 800°C. The difference between calculated and observed permeation rates is probably due to interfacial polarization.     

Microstructural analysis of Nd1.85Ce0.15CuO4−y superconductor sintered under high pressure and ambient pressure

The microstructure of Nd_1.85Ce_0.15CuO_4−y superconductor sintered under high pressure and ambient pressure has been characterized by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HREM). It has been observed that the conventional sample is porous, while the high-pressure sample is almost pore-free. It is confirmed that the thermal treatment under high pressure recovers fairly well connections between grains which were partly crushed during the compression process; hence the weak links at grain boundary are improved. Furthermore, a high density of defects induced by pressure is observed in the high-pressure sample. In contrast, the conventional sample is nearly perfect. For comparison, the microstructure of a sample pressed at high pressure at room temperature is also examined. The influence of pressure on the microstructure and the superconductivity is discussed.     

The effect of oxygen vacancy on the oxide ion mobility in LaAlO3-based oxides

The electrical property of (La_1−xSr_x)_1−z(Al_1−yMg_y)O_3−δ (LSAM; x≤0.3, y≤0.15 and z≤0.1) was measured using the DC four-probe method as a function of temperature (500–1000°C) and oxygen partial pressure (1–10⁻²² atm). Among LSAMs, (La_0.9Sr_0.1)AlO_3−δ showed the highest ionic conductivity, σ_i=1.3×10⁻² S cm⁻¹ at 900°C. A simultaneous substitution at A and B sites or A site deficiency is expected to create larger oxygen vacancy and higher ionic conductivity. However, it showed a negative effect. The effect of the vacancy increase did not effect monotonously the ionic conductivity. It was found that the concentration of oxygen vacancy, [V_O], influences not only the oxide ion conductivity, σ_i, but also the mobility, μ_v, of [V_O]. These properties exhibit a maximum at around [V_O]=0.05. With the increase in [V_O], the activation energy, E_a, of the ionic conduction dropped from 1.8 to ca. 1.0 eV at [V_O]=0.05 and became almost constant at [V_O]>0.05. The dependency of the pre-exponential term, μ⁰_v, and E_a on [V_O] was analyzed and their effect on μ_v and σ_i was discussed with respect to crystal structure and defect association. It was estimated that the crystal structure mainly governs these properties. The effect of defect association could not be ignored but is considered to be a complicated correlation.     

Germanium and iron co-substituted SrCoO2.5+δ as oxygen permeable membrane

Germanium and iron co-doped SrCoO_2.5+δ was investigated in terms of phase stability, oxygen permeability and electrical conductivity. The favorable high-temperature cubic structure of SrCoO_2.5+δ was stabilized to lower temperatures by co-doping Ge (10 mol%) and Fe (10 mol%) that substituted for Co, which however could not be achieved by doping Ge (20 mol%) alone. In contrast to SrCo_0.8Ge_0.2O_2.5+δ sample which showed a sharp decrease in oxygen permeability at temperature of 875 °C upon cooling, SrGe_0.1Co_0.8Fe_0.1O_3−δ sample remained well-permeable to oxygen at lower temperatures down to at least 820 °C; an abrupt change in electrical conductivity in SrCo_0.8Ge_0.2O_2.5+δ also occurred accompanying the phase transition. The oxygen permeation flux for SrGe_0.1Co_0.8Fe_0.1O_3−δ increased significantly with the decrease of the membrane thickness, indicating the transport of oxygen ions in the bulk of the membrane as the rate-limiting step.     

Oxygen permeability of La2Cu(Co)O4+δ solid solutions

Formation of the La₂Cu_1−xCo_xO_4+δ solid solutions with orthorhombic K₂NiF₄-type structure was found to be in the range of 0≤x≤0.30 at temperatures above 1270 K. Incorporating cobalt into the copper sublattice of lanthanum cuprate leads to increasing oxygen hyperstoichiometry and decreasing electrical conductivity. Thermal expansion coefficients of the La₂Cu_1−xCo_xO_4+δ (x=0.02–0.30) ceramics at 470–1100 K were calculated from the dilatometric data to vary in the range (12.2–13.2)×10⁻⁶ K⁻¹. Studying the dependence of oxygen permeation fluxes through La₂Cu(Co)O_4+δ on the membrane thickness demonstrated that the oxygen transport at the thickness values below 1 mm is limited by both surface exchange rate and bulk ionic conductivity. Oxygen permeability of the La₂Cu_1−xCo_xO_4+δ solid solutions was ascertained to increase with cobalt concentration at x=0.02–0.10 and to decrease with further dopant additions, indicating a participation of interstitial oxygen in the ionic transport.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

Structural study and magnetoresistance effect of epitaxial La0.67Sr0.33MnO3–δ and Pr0.7Ca0.3MnO3−δ multilayer films

La_0.67Sr_0.33MnO_3−δ (LSMO) and Pr_0.7Ca_0.3MnO_3−δ (PCMO) multilayer epitaxial films, which were fabricated with different LSMO and PCMO layer thickness on LaAlO₃ single crystal substrates of (0 0 1) orientation by a direct current magnetron sputtering technique, were studied further, after the structure, magnetoresistance effect and magnetic properties of LSMO/PCMO/LSMO (LPL) trilayer epitaxial films were systemically studied. The superlattice structures of multilayer films were observed according to the diffraction peaks of X-ray diffraction patterns at small angles. The metal–insulator transition temperature (T_P) and peak resistivity (ρ_max) obviously changed when we altered the thickness of PCMO middle layer and the intra-field related with the thickness of those layers and their interaction. Considering the effect of the distribution of electrical field and current, and the interaction among the layers of LSMO and PCMO, an effective fact n* was introduced to replace n (the number of layer). All the calculated values of ρ (the resistivity of multilayer films) accorded with the experimental values.     

Trapping mechanism of superconductivity suppression induced by Pr substitution in the Ho1−xPrxBa2Cu3O7−δ system

Pr concentration dependence of the superconducting transition temperature T_c in the Ho_1−xPr_xBa₂Cu₃O_7−δ system is determined from measurements of DC electrical resistance. This dependence coincides with that for the parallely studied Y_1−xPr_xBa₂Cu₃O_7−δ reference system. Both systems have the same value of the critical concentration x_c=0.58, in accordance with nearly equal ionic radii of Ho³⁺ and Y³⁺ ions. It has been shown that the T_c(x) curve can be described with a single mechanism based on a decreasing number of sheet holes trapped by Pr^IV-ions, if one takes also into account that the number of these ions changes with x.     

Characterization of nonstoichiometric nickel manganite spinels NixMn3−x□3δ/4O4+δ by temperature programmed reduction

Cation deficient spinels Ni_xMn_3−x□_3δ/4O_4+δ (0≤x≤1) have been prepared by thermal decomposition of mixed oxalates Ni_x/3Mn_(3−x)/3(C₂O₄)·nH₂O in air at 623 K. They have been characterised by temperature programmed reduction (TPR) under H₂, the reaction being followed by gravimetric and powder X-ray diffraction measurements. It has been shown that TPR proceeds in several steps. The first steps correspond to the loss of nonstoichiometric oxygen leading to the formation of a stoichiometric oxide. During the following stages the manganese cations are reduced, causing the spinel structure to be destroyed, and the formation of solid solution of NiO in a cubic MnO. Subsequently, Ni²⁺ cations undergo a reduction to metallic nickel, and, finally, a mixture of nonstoichiometric MnO_1−δ and metallic nickel is formed. These oxides contain a high level of vacancies which vary with the nickel content with a maximum of δ≈1 near x=0.6. This nonstoichiometry is ascribed both to the presence of Ni³⁺ and excess of Mn⁴⁺.     

Deuterium conductivity, diffusion and implantation in Sr-doped LaYO3

A study of deuterium conductivity and diffusion in the oxide perovskite La_0.9Sr_0.1YO_3−δ is presented in this work. Deuterium ions were implanted into La_0.9Sr_0.1YO_3−δ (50 keV, 1×10¹⁶ atoms/cm²) and the corresponding deuterium depth profile was determined by SIMS and compared with a Monte Carlo simulation (TRIM96). This implant was used as a standard for the determination of deuterium concentration in a La_0.9Sr_0.1YO_3−δ sample pre-treated in D₂O atmosphere. In this way, it was fully confirmed that La_0.9Sr_0.1YO_3−δ incorporates water at high temperatures. The conductivity of La_0.9Sr_0.1YO_3−δ was measured in D₂O atmosphere and compared with other proton (deuteron) conductors. Concentration and conductivity data were used in conjunction to estimate the deuterium diffusivity and the constant of reaction of (heavy) water incorporation into LaYO₃. Some comments on the catalytic activity of this oxide are made.     

Evidence for pinning by (Sr,Ca)2CuOy particles in partial-melting processed bulk Bi2Sr2CaCu2O8+δ ceramics

Flux distributions of partial-melting processed Bi₂Sr₂CaCu₂O_8+δ ceramics are obtained using magneto-optic imaging. In remanent states (μ₀H_a=0 T), large amounts of trapped flux are observed along (Sr,Ca)₂CuO_y particles embedded in the Bi₂Sr₂CaCu₂O_8+δ matrix. Despite the relatively large size of these particles (up to 30 μm), the pinning effect is similar to that of Y₂BaCuO₅ particles in melt-processed YBa₂Cu₃O_7−δ. Furthermore, we discuss how the pinning capability of non-superconducting particles of different sizes and densities will show up in magneto-optic images.     

Phase formation and magnetic properties of Nd2Fe14B-type Nd16Co76B8−xCx alloys and their hydrides

An attempt is made to synthesize Nd₂Co₁₄C compound by mechanical alloying Nd₁₆Co₇₆B_8−xC_x (0x8) alloys and subsequent annealing. Phase formation and magnetic properties of Nd₂Fe₁₄B-type Nd₁₆Co₇₆B_8−xC_x alloys and their hydrides are investigated. The Nd₂Co₁₄(B,C) phase with Nd₂Fe₁₄B-type structure is formed for Nd₁₆Co₇₆B_8−xC_x (0x7) alloys, while NdCo₇C_δ phase with TbCu₇-type structure is observed in Nd₁₆Co₇₆C₈ alloy. The lattice parameter c of the Nd₂Co₁₄(B,C) phase decreases with increasing the carbon content. A limit volume of the unit cell to form the Nd₂Fe₁₄B-type structure is estimated to be 0.870 nm³. The spin-reorientation temperature T_SR increases with increasing the carbon content, due to an enhancement of magnetocrystalline anisotropy caused by carbon substitution for boron. After hydrogenation, the lattice expansion is observed for Nd₁₆Co₇₆B_8−xC_x (0x7) alloys. The spin-reorientation temperature of Nd₁₆Co₇₆B_8−xC_xH_y (0x7) is much lower than that of the host alloys. Some structural and magnetic properties of hypothetic Nd₂Co₁₄C and Nd₂Co₁₄CH_y compounds are estimated by extrapolation.     

X-ray diffraction characterization of MBE grown Pr1−xSrxMnO3 thin films on NGO(1 1 0)

Oxygen plasma-assisted molecular beam epitaxial (MBE) growth of Pr_1−xSr_xMnO₃ (PSMO) thin films has been carried out on NdGaO₃(1 1 0) (NGO) substrates. The growth parameters have been optimized to realize 2D layer-by-layer growth. XRD results of the epilayers show that the PSMO/NGO(1 1 0) thin films are of high crystal quality, as clear diffraction peaks can be observed belonging to the film and the substrate, respectively. Based on analysis of the peaks, it was concluded that epitaxial relation is PSMO(1 1 0)//NGO(1 1 0), i.e., the c-axis being parallel to the surface. Both single scans (ω scan, 2θ/ω scan) and 2-axis reciprocal space mapping (RSM) were performed in an effort to assess the crystal structure, crystalline quality, surface and interface properties of the epitaxial layers. High temperature annealing effects on lattice structure and crystal quality have been studied and discussed. Transport property measurement of the PSMO thin film samples has been carried out and main features discussed.