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.     

Influence of Nd substitution on the superconducting properties of ceramics in the 2212 system Bi2−wPbwSr2−xCa1−yNdx+yCu2O8+z

In the system Bi_2−wPb_wSr_2−xCa_1−yNd_x+yCu₂O_8+z different fractions of Nd are substituted on either Sr of Ca sites in order to introduce intrinsic insulating pinning centres. It is shown that a Nd concentration around x or y = 0.2 is likewise favourable with an average Nd---Nd distance in the range of the coherence length in the a, b-plane. However, clear evidence of flux pinning is only present for charge compensation with Pb²⁺. A simultaneous substitution of the Bi-based 2212 superconductor with moderate amounts of Nd³⁺ and Pb²⁺ improves the superconducting properties by strengthening the flux pinning forces.     

The incommensurate modulation in the Bi2Sr2−xCaxCuO6 superconductor, and its relation to the modulation in Bi2Sr2−xCaxCu2O8

The modulation of the (221) superconducting Bi₂Sr_2−xCa_xCuO₆ phase has been analyzed by X-ray diffraction, using four-dimensional symmetry theory. The pseudo-orthorhombic diffraction pattern is a superposition of two twin related components, such that the main reflections with hkl and hk m superimpose, but the satellite hklm and hk m do not. The latter feature allows separation of the twin intensities. The modulation analysis in superspace group P:Aa:1 shows displacements similar to those observed in the 2212 compound [Y. Gao et al., Science 241 (1988) 954] but with generally larger displacements. In particular, the c-axis displacement amplitude of the Cu atoms is increased to almost 0.5 Å. This and the obliqueness of the q vector (q=0.214a^*+0.61c^*) indicate the absence of a restraining influence exerted by the CuO₂/Sr(Ca)/CuO₂ double layers in the multi-Cu layer phases.     

Physical characterization and vibrational spectroscopy of Bi(Pb) cuprate 2212 ceramics prepared by sol-gel

Samples of bismuth cuprate with and without lead substitution were prepared by the sol-gel method. The general formula was Bi_2−xPb_xSr₂CaCu₂O_8+δ, where 0≤x≤0.6. The samples were characterized by X-ray diffraction (XRD), electron probe microanalysis (EPMA), magnetic susceptibility, Raman spectroscopy and IR reflectance. Regarding homogeneity, density, purity and superconductivity, optimal behavior was found x = 0.2-0.4. An increase of hole concentration in the CuO₂-planes with Pb²⁺/Bi³⁺ ratio was observed from the optical data. The Raman spectra modifications with lead substitution are discussed. Evidence of the interaction between CuO₂-plane hole continuum and 150 cm⁻¹ IR active modes was found.     

Ramans study of Y1−xPrxBa2Cu3O7−δ and YB2Cu3−xZnxO7−δ single crystals

Single crystals with known T_c values of Y_1−xPr_xBa₂Cu₃O_7−δ (Y---Pr1:2:3) and YBa₂Cu_3−xZn_3−xZn_xO_7−δ (Y---Zn1:2:3) systems are studied by Raman measurements. The Raman spectra for (Y---Pr1:2:3) single crystals show that the frequencies of Ba and O_z modes increase as the Pr content increases. The results are consistent with the hole-localization scheme proposed for the suppression of superconductivity in the polycrystalline Y---Pr1:2:3 systems. On the other hand, in the Y---Zn1:2:3 system, all the Raman modes do not change in frequencies. However, the FWHM of the Cu(2) mode increases with the decrease of T_c, indicating strong scattering of charge carriers by the substituted Zn ions in the CuO₂ planes. The induced disorder in the CuO₂ planes may be related with suppression of T_c in the Y---Zn1:2:3 system. Thus, the suppression mechanism in the Y---Zn1:2:3 systems seems to be different from that in the Y---Pr1:2:3 systems.     

The crystal structure of (Pb0.5Cd0.5)Sr2 (Y1−xCax)Cu2O7

The crystal structures of (Pb_0.5Cd_0.5)Sr₂YCu₂O₇, (Pb_0.5Cd_0.5)Sr₂(Y_0.6Ca_0.4)Cu₂O₇ and (Pb_0.5Cd _0.5)Sr₂(Y_0.5Ca_0.5)Cu₂O₇ have been refined by the Rietveld method for the X-ray diffraction data. The refinement results indicate that both Pb and Cd atoms in the (Pb, Cd)O layers and O(3) atoms are displaced from their ideal sites, and that there is a complicated occupation in the (Pb, Cd)O layers, i.e., other cations, such as Sr²⁺, Cu²⁺ and Ca²⁺, can occupy the (Pb, Cd) site for these samples. This may be the reason why the lattice constants do not vary monotanically with the calcium content, and why there exist broad superconducting transitions in the system (Pb_0.5Cd_0.5)Sr₂(Y_1−xCa_x)Cu₂O₇. The refinement results also indicate that, as the calcium content increases, the O(2) atoms move close to the CuO₂ planes and far from the (Pb, Cd)O layers. Thus, the increase of calcium content results in charge transfer from the charge reservoir layer (Pb, Cd)O to the CuO₂ planes. This result is consistent with the bond valence sums of the Cu ions in the CuO₂ planes.     

Synthesis and characterization of the Aurivillius phases Bi2 − xPbxSr1 − xNdxNb2O9

The n = 2 Aurivillius phase Bi_{2 − x}Pb_xSr_{1 − x}Nd₂O₉ was successfully synthesized as a ceramic material over the whole range of simultaneous, charge compensated substitution x = 0–1.0. Structural investigations were performed by Rietveld refinement applying different space groups Fmmm and A2₁am, and additionally by X-ray absorption spectroscopy (EXAFS) on the Nd L_III-edge, confirming the accommodation of Nd on the atomic sites of Sr, which implies the substitution of Bi³⁺ by the isoelectronic Pb²⁺. The ferroelectric transition temperature T_c = 270 °C of the substituted powders with x = 0.4 and 1.0 is distinctly reduced compared to the unsubstituted sample with T_c = 450 °C. In temperature resolved powder X-ray diffraction patterns no structural phase transition could be detected.     

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.     

Over-doping of Tl2Ba2CuO6 due to charge transfer Tl-(Cu-O)

Superconductivity was observed in La substituted Tl₂Ba₂CuO₆. Both T_c and unit cell dimension, a, increase with increasing La concentration, indicating that an over-doping state in Tl₂Ba₂CuO₆, which was due to charge transfer Tl^3−t-(Cu-O)^p as supported from XPS measurements, was relieved by La substitution for Ba.     

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.     

Crystal structure of Tl0.5Pb0.5Sr2Ca2Cu3O9 at 300 K and around Tc (118 K)

The crystal structure including the cation distribution, of a polycrystalline sample of nominal composition Tl_0.5Pb_0.5Sr₂Ca₂Cu₃O₉ with T_c = 118.2 K has been determined using resonant synchrotron X-ray diffraction data collected at the Cu K, Tl L_III and Sr K edges and time-of-flight powder neutron diffraction data. No oxygen deficiency was observed, but cation disorder at all the non copper sites according to the formula (Tl_0.60Pb_0.40)(Sr_1.60Ca_0.40)(Ca_1.93Tl_0.07) Cu₃O₉ gives a mean hole concentration of 0.18(1) per Cu atom for the three CuO₂ planes, consistent with the high T_c for this material. Analysis of five time-of-flight powder neutron diffraction data between 80 and 150 K have revealed a possible discontinuity in the variation of the c lattice parameter at T_c, due to an anomaly in the position of the apical oxygen atoms.     

Synthesis and superconducting properties of the infinite-layer compounds Sr1−xLnxCuO2(Ln=La, Nd, Sm, Gd)

Infinite-layer-type superconductors Sr_1−xLn_xCuO₂ are synthesized under high pressure of 3 GPa for Ln=Sm, Gd as well as for Ln=La, Nd. Their chemical and superconducting properties are systematically studied as functions of doping concentration and the kind of lanthanide ion. As a result, it is demonstrated that the variation of these properties with doping concentration is similar for all the examined Ln³⁺ ions. The solubility limit lies at x ≈ 0.10. CuO₂ sheets are expanded with increasing x, while their spacing decreases. The T_c onset determined by magnetic measurements remains constant for any doping concentration; only the Meissner fraction increases with increasing x.     

A 62 K superconductor with an original structure: Sr4−xBaxTlCu2CO3O7

A new superconductor with an original structure, Sr_4−xBa_xTlCu₂CO₃O₇ has been isolated for 1≤x≤2. It crystallizes in a A-type space group with a=3.84 Å≈a_p, b≈8 × a_p, c≈17.0 Å. The HREM study of this new curprate shows that it derives from the Tl_0.5Pb_0.5Sr₄Cu₂CO₃O₇ structure by a shearing mechanism. Indeed, it can be described as ribbons of the latter structure, four octahedra thick, shifted c/2 with respect to each other. It results in infinite single perovskite layers waving along the (001) plane and connected through flat mixed layers [(TIO)₄(CO)₄]∞. This oxycarbonate can also be described as a 1201-type structure in which the [TIO]∞ layers are replaced by mixed [(TIO)₄(CO)₄]∞ layers. The susceptibility measurements show that this cuprate exhibits a significantly higher critical temperature than the 1201-cuprates. The T_{c onset} of the synthesized phase is 56 K and it can be increased up to 62 K by hydrogen annealing; in the same way, one observes a large Meissner volume fraction of 35% at 4.2 K.     

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.     

Synthesis and investigation of the complex copper oxides Bi2Sr2R2−xCexCu2O10+δ (R=rare earth)

Bi-2222 phases were prepared by solid state reactions and were studied using X-ray diffraction, chemical and EDS-analysis. Compounds with composition Bi₂Sr₂R_1.33Ce_0.67Cu₂O_10+δ were obtained for R=Pr, Nd, Sm-Er. The phases Bi₂Sr₂Cu₂O_10+δ with similar structure but without Ce were prepared for R = Pr, Sm-Dy. For Bi₂Sr₂Eu_2−xCe_xCu₂O_10+δ the solubility limit was determined and the effect of treatment under different oxygen pressures was investigated. Weak diamagnetic signals (<3%) were detected for some of these samples.     

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.     

Systematic thermopower measurements of the thallium cuprates Tl(Ba,Sr)2Cam−1CumO2m+3−δ and Tl2Ba2Cam−1CumO2m+4+δ

The thermoelectric power (TEP) S versus temperature has been systematically investigated for several series of the superconducting cuprates Tl(Ba,Sr)₂Ca_m−1Cu_mO_2m+3−δ (m = 2, 3) and Tl₂Ba₂Ca_m−1Cu_mO_2m+4+δ (m = 1, 2, 3). The consideration of the S(T_c) curves allows two important points to be found evidence for. The first one deals with the fact that all these superconducting thallium cuprates are systematically overdoped whatever T_c, and whatever the number of Cu or Tl layers; no underdoped superconducting cuprate could be obtained. The second point shows that there exist two classes of Tl cuprates: the weakly overdoped cuprates that exhibit a T_{c max} ≥ 100 K (all the triple copper layer cuprates and the 2212 cuprates) and those which can be heavily doped that exhibit a T_{c max} ≤ 90 K (the 2201 and the 1212 cuprates). The different behavior of thallium cuprates compared to YBa₂Cu₃O_7−δ and to bismuth cuprates is discussed.     

Oxygen tracer diffusion in La1 − xSrxCoO3

Tracer diffusion of ¹⁸O in dense, polycrystalline La_1−xSr_xCoO₃ for x = 0.1 has been measured in the temperature range 400 to 600 °C and at 500 °C for x = 0.2 at an oxygen partial pressure of 1 × 10⁵ Pa. Depth profiles were obtained by secondary ion mass spectrometry. The diffusion coefficient for La_0.9Sr_0.1CoO₃ is given by D = (17–247) exp[(−232 ± 8 kJ/mole)/RT] cm²/s. This value is several orders of magnitude lower than D extrapolated from the results for x = 0.2 measured in the 700–900 °C temperature range. One possible explanation for the discrepancy is that the two measurements reflect different diffusion paths. As expected, La_0.8Sr_0.2CoO₃ exhibits a higher diffusivity at 500 °C than does La_0.9Sr_0.1CoO₃.     

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.     

Superconductivity in Ba2−xSrxYCu3Oz prepared at GPa

The compounds Ba_1.4Sr_0.6YCu₃O_z (7.0≤z<7.4) were synthesized at 2 GPa to clarify the effect of high temperature and pressure on the superconducting properties. The structure as observed by powder X-ray diffraction was tetragonal for z≥7.2, and orthorhombic or tetragonal for z<7.1. It has been revealed that high-pressure syntheses suppress the superconductivity in the compounds with z<7.1. Recovery of the superconducting properties occurs above z≥7.2. The effect of Sr substitution on the superconducting properties was also studied. The magnitude of diamagnetism at 5–30 K decreases monotonically from −0.003 to −0.0002 emu/g Oe with increasing x in Ba_2−xSr_xYCu₃O_z (x≥1.2).