Superconductivity and crystallographic properties of La2 − xMxCuO4 − δ (M = Na, K)

Superconductivity and crystallographic properties of La_{2 − x}M_xCuO_{4 − δ} (M = Na, K) are studied. In the La_{2 − x}M_xCuO_{4 − δ} system, superconductivity is detected for x 0.2. Oxygen content analysis shows that the system has more oxygen vacancies than the La_{2 − x}Sr_xCuO_{4 − δ} system. These oxygen vacancies may reduce the hole concentration, and high Na-doping is needed to produce superconductivity. In the La_{2 − x}K_xCuO_{4 − δ} system, superconductivity is observed for the first time. Resistivity and magnetic susceptibility measurements show that T_c(onset) is 40 K and the Meissner volume fraction is about 4% for x = 0.7. The system changes from orthorhombic to a tetragonal K₂NiF₄ structure at x ≈ 0.3 and only tetragonal samples show superconductivity.     

Superconductivity due to charge transfer to the CuO2 sheet from the (Tl,Pb) O layer in Tl0.5Pb0.5Sr2−xNdxCuO5−δ

The superconductivity of Tl_0.5Pb_0.5Sr_2−xNd_xCuO_5−δ was observed for x ≥ 0.3, although the calculated Cu valence assuming Tl³⁺ and Pb⁴⁺ is slightly above or below 2.0. The binding energy of the Tl and Pb 4f core levels measured by XPS shifted to higher energy than those of Tl³⁺ and Pb⁴⁺ in the reference materials, showing that the Tl and Pb valences are lower than 3 + and 4 +, respectively. These observations strongly suggest that holes in the CuO₂ sheet are created by charge transfer from the (Tl,Pb)O layer, similar to the double-layered Tl---Ba cuprates.

In contrast, the temperature variation of electrical conductivity of Tl_0.5Pb_0.5Sr₂CuO_5−δ changed from metallic to semiconducting with increasing oxygen deficiency, δ, and no superconductivity was observed through any control of δ. Although XPS measurement also suggested that Tl and Pb valences lowered with increasing oxygen deficiency, δ, the reason why the system did not show superconductivity can be understood by the depletion of oxygen from the CuO₂ plane during deoxygenation.     

Electrons and holes in undoped Nd2CuO4

Nd₂CuO_4±δ is the non-superconducting prototype of the Re_2−xM_xCuO₄t−y family (Re=Pr, Nd, Sm and M=Ceor Th) of n-type oxide superconductors. Four-probe DC conductivity, EMF in P(O₂) gradient, and thermopower measurements have been used to characterise its electric transport and defect structure between 300 and 900°C and between 5×10⁻⁴ and 1 atm oxygen partial pressure.

The results show that Nd₂CuO_4±δ can be oxygen under-stoichiometric (with n-type conductivity), near-stoichiometric, and over-stoichiometric (with p-type conductivity) in different T, P(O₂) ranges.     

Tunneling studies on single crystals of superconducting Bi2Ca1−xYxSr2Cu2O8+δ

Tunneling studies have been carried out on single crystals of Bi₂Ca_1−xSr_xCu₂O_8+δ over a wide range of compositions wherein the hole concentration varies by a factor of 2.5. The 2Δ value varies between 25 meV and 75 meV over the composition range studied, but scales with 2Δ/k_BT_c≈9.5 throughout.     

Higher-order elastic constants of La1.84Sr0.16CuO4 high-temperature superconductor

Finite deformation theory is used to obtain the strain energy density of a tetragonal 2–1–4-type single crystal of the high-temperature superconductor La_2−xSr_xCuO₄. The complete set of second and third-order elastic constants of the high-temperature superconductor La_2−xSr_xCuO₄ (x = 0.16) is calculated by taking into account the interactions between nine nearest-neighbour atoms in the lattice and using Mie–Grüneisen interatomic potential. For the sake of comparison we have also computed the values of these constants for x = 0.13–0.20. The values of third-order elastic constants of La_2−xSr_xCuO₄ (x = 0.13–0.20) are negative and their absolute magnitudes are one order higher than those of the second-order elastic constants.     

Observation of superconductivity (Tc = 50 K) in a new tetragonal alkaline-earth cuprate Sr0.8Ba1.2CuO3+δ, synthesised at ambient pressure

The ambient-pressure synthesis of a new tetragonal alkaline-earth superconducting cuprate, Sr_0.8Ba_1.2CuO_3+δ, from a cupro-oxycarbonate is reported. Magnetic-susceptibility measurements show the presence of a superconducting transition 50 K in a post-annealed sample. The crystal structure, refined from time-of-flight powder neutron-diffraction data was found to have an oxygen-deficient La₂CuO₄-type tetragonal T structure (a = 3.8988(3) Å and C = 12.815(3) Å) with oxygen vacancies located within the CuO₂ planes. Ordering of these oxygen vacancies is responsible for the observation of a superlattice in both neutron- and electron-diffraction measurements. An interpretation of the electron-diffraction patterns suggests that the superlattice in Sr_0.8Ba_1.2CuO_3+δ and also in the isostructural superconductor Sr₂CuO_3+δ are of an identical nature.     

Origin of the metal-insulator transition in the superconducting series Bi2Sr2Ca1−xYxCu2O8+δ

The metal-insulator transition in the solid solution Bi₂Sr₂Ca_1−xY_xCu₂O_8+δ (0≤x≤1) has been investigated by TGA (oxygen content) and by X-ray absorption spectroscopy (Bi and Cu valence states). Resistivity and AC magnetic susceptibility measurements have shown that the superconducting properties and the metallic behavior vanish for x>0.55. The oxygen content δ is larger than x/2 for x≤0.3 and smaller than x/2 for x≥0.6. For x=0, the Cu K edge shows a shift towards high energy with respect to the Cu(II) oxide La₂CuO₄; this shift decreases with increasing x in agreement with the decrease of the doping hole density and the variations of the physical properties. For 0≤x≤0.3, the Bi L₃ edge shows a shift of 1 eV towards low energy with respect to the Bi(III) oxide Bi₂O₃ in agreement with the charge transfer between [CuO₂]_∞ and [BiO]_∞ planes. This shift also decreases with increasing x, but is still present for the x=0.6 composition for which δ is smaller than x/2. A model of the metal-insulator transition in this series is proposed based on the fact that the intercalation of excess oxygen raises the bottom of the Bi-O band with respect to the Fermi level and decreases the contribution of the Bi-O electron pocket to the hole density.     

Superconducting Nd1.85Ce0.15CuO4 films grown by the pulsed electron deposition technique

Nd_1.85Ce_0.15CuO_4−δ superconducting thin films were prepared on (1 0 0) SrTiO₃ substrates by pulsed electron deposition technique without reducing atmosphere. Oxygen content is finely controlled by high temperature vacuum annealing, and optimal superconductivity has been obtained. The deposition conditions of the film are discussed in details. Higher deposition temperature and lower gas pressure result in the loss of copper and the appearance of the foreign phase Ce_0.5Nd_0.5O_1.75. High quality Nd_1.85Ce_0.15CuO_4−δ epitaxial films are deposited at 840–870 °C in the mixed gas with a ratio of O₂:Ar = 1:3.     

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.     

Cu site substitution effect on the Hall coefficient of La2−xSrxCuO4

The Cu site substitution effects on the Hall coefficient R_H and the electrical resistivity have been studied for La_2−xSr_xCuO₄. In a small x region, R_H decreases largely with Zn doping and increases with Ni doping. In the Ni doped samples, shows the characteristic temperature dependence similar to those of the unsubstituted samples where the decrease of the slope of vs. T curve is observed for x<0.1 above 600K but in the Zn doped samples, the change of the slope of becomes smaller,i.e. the temperature dependence of below 600K becomes smaller. These results indicate that the origin of the change of the slope of around 600K for x<0.1 is magnetic and the spin correlation or the electronic state is rather different below and above 600K. The unusual Zn doping dependences of R_H and are naturally explained by considering that the electronic state at high temperatures above 600K which has a small Hall coefficient expected for the large Fermi surface comes down to lower temperatures by the Zn doping.     

Effect of Pr and Ca substitution on superconductivity in Y(1−x−yPrxCay)Ba2Cu3O7−δ

Pr substituted at constant Ca concentration for Y in (Y_1−x−yPr_xCa_y)Ba₂Cu₃O_7−δ superconductors have been prepared under identical conditions and the temperature dependence of the electrical resistivity of these samples are measured. The resistively determined values of T_c decrease linearly with increasing x (0 ≤ x ≤ 0.2) for constant y = 0.10 and 0.15 which provides convincing evidence that the suppression of superconductivity by Pr is mainly due to magnetic pair breaking. The suppression of superconductivity can also be correlated to the observed changes in oxygen content determined by iodometric analysis and to the average Cu-valences. However, it is found that the observed suppression of T_c cannot be compensated by appropriate hole doping with Ca.     

Structure and superconductivity of HgBa2CuO4+δ

We have used neutron powder diffraction to investigate the defect structure of HgBa₂CuO_4+δ. An interstitial oxygen defect in the Hg plane is the primary doping mechanism. A superconducting transition temperature, T_{c onset}, of 95 K is achieved when ≈0.06 oxygen atoms per formula unit are incorporated at this site by annealing the sample at 500°C in pure oxygen. Annealing in argon at 500°C lowers the oxygen content in this site to ≈0.01 and results in a T_c of 59 K. The neutron powder diffraction data give evidence for a second defect in the Hg plane which we conclude involves the substitution of copper for about 8% of the mercury and the incorporation of additional oxygen (≈0.1 atoms per formula unit), presumably bonded to the copper defects. In the present samples, the concentration of this defect does not vary with synthesis conditions and its contribution to doping is, therefore, unclear. The structure of the compound is the same at room temperature and superconducting temperatures.     

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.     

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.     

Properties of a large La1.92Sr0.08CuO4+δ single crystal grown by the travelling-solvent floating-zone method

A centimeter size single crystal of La_2−xSr_xCuO_4+δ (volume=1.32 cm³) with x_Sr=0.08 has been grown by the travelling-solvent floating-zone (TSFZ) method using a double ellipsoidal-type optical furnace as the heat source. The crystallised phase was checked solvent free by X-ray powder diffraction experiments, the crystal dimensions and quality being investigated by X-ray and neutron Laüe techniques. Several rocking curves of the Bragg peaks were performed by neutron diffraction giving a full width at half maximum (FWHM) of 0.200° for (006) reflection and clearly showing the presence of twin domains as expected for such an orthorhombic structure. The superconducting critical temperature of the as-grown crystal under 2 oxygen bar was determined by SQUID measurements with T_c=18–20 K. Thermal treatments at different oxygen pressures were carried out showing no significant improvement of the transition sharpness and the T_c value. Normal state susceptibility was also measured from 6 to 800 K for two different field orientations and can be interpreted as an antiferromagnetic insulating state behaviour. The resistivity measurements display an insulating behaviour perpendicular to the CuO₂ planes and a metallic behaviour in the planes, with a high anisotropy ratio R_c/R_b350 at room temperature and a zero resistivity achieved at 27 K in both directions. The specific heat measurements have revealed no anomalies in the temperature range 15–300 K.     

On the crystal field in REBa2Cu3O7 − x and Nd2CuO4-type superconductors

The superposition model calculation followed by the best-fit treatment of the available inelastic neutron scattering and susceptibility data were used to determine the CF parameters of the Nd³⁺ in Nd₂CuO₄, the parent compound of electron-doped superconductors. These parameters allow to account for the energy levels in Nd-compound and the anisotropy of susceptibility in RE₂CuO₄ (RE = Pr, Nd, Sm). Briefly discussed is the application of the superposition model of the crystal field of REBa₂Cu₃O_{7 − x} compounds.     

Preparation and superconductivity of the co-doped superconductor Nd2−x−yCayCexCuO4 with T′ structure

The preparation and superconductivity of the co-doped superconductor Nd_2−x−yCa_yCe_xCuO₄ with T′ structure were studied by XRD and superconductivity measurements. The results indicate that the effect of the co-doping of Ca²⁺ and Ce⁴⁺ on T_O and the carrier type is not significant, but the effect on the range of the superconducting compositions in this system is obvious. The study of co-doped superconductors could be important for an understanding of the effect of co-doping on the carrier concentration and to explore new superconductors.     

Nuclear magnetic resonance study of the electron-doped high-temperature superconducting cuprates

Nuclear magnetic resonance (NMR) measurements have been made on two of the electron-doped high-temperature superconducting cuprates (HTSCs), Pr_2−xCe_xCuO₄ and Sr_0.9La_0.1CuO₂ that represent the two known electron-doped structures. The results are compared with the more-studied hole-doped HTSCs. We show that the electron and hole-doped HTSCs probe a similar antiferromagnetic spin fluctuation spectrum in the normal state, which provides support for theories of superconductivity where the pairing is mediated by antiferromagnetic spin fluctuations and the superconducting order parameter has a d_x²−y² symmetry. Contrary to results from underdoped and hole-doped HTSCs, there is no evidence for a normal-state pseudogap in the NMR data from measurements on the electron-doped HTSCs. Therefore, the electron-doped HTSCs can be better compared with overdoped and hole-doped HTSCs where the normal-state pseudogap is absent. The antiferromagnetic spin fluctuation spectrum as probed by the Cu spin–lattice relaxation rate, is independent of the doped electrons per Cu. A similar effect is observed in the overdoped and hole-doped HTSC, Y_1−xCa_xBa₂Cu₃O_7−δ for a hole concentration range of 0.063. The anomalous Cu NMR linewidth anisotropy observed in the electron-doped HTSCs suggests a small and static spin variation for temperatures up to room temperature.     

Magnetic anisotropy and superconductivity in a model for high-Tc copper oxides

The phase diagram for the CuO₂-based superconductors is found to be consistent with an extended Hubbard Hamiltonian with competing positive-and negative-U interactions on a 2D lattice where sites are plaquettes formed by clusters of Cu and O atoms. The negative-U effective interactions are implied by the XY anisotropy in the Cu-Cu spin couplings and local hole pairing corresponds to vortex-antivortex spin configurations. The phase progression observed with the variation of dopant fraction x can be obtained via gradual implementation of canonical transformation that maps the properties of the positive-U Hubbard model at half-filling into those of the negative-U model away from half-filling. In the strong-coupling limit this process is described in terms of percolation-driven dilute magnetism for both spins (U>0) and pseudospins (U−1_x=ξ⁻¹_o+η⁻¹_x for x→O as seen in La_2-xSr_xCuO₄. (ii) An x-dependent reduction of spin fluctuations at low temperatures that conforms with NMR studies of La_2-xSr_xCuO₄. And, (iii) a reduced superconducting transition locus T_c(x)/T_cmax in agreement with the universal shape and location revealed by analysis of experimental data.