Surface atomic imaging of La2CuO4 and superconducting Tl2Ba2Ca2Cu3O10

Surface structures of the high T_c oxide superconductors Tl₂Ba₂Ca₂Cu₃O₁₀ and La₂CuO₄ have been studied by high resolution electron microscopy. In addition to the single atomic layer of La on the (113) surface observed previously, several atomic layers of the C-form of La₂O₃ were found to coat the (001) surfaces of La₂CuO₄. Surface reconstruction with the incorporation of excess Ba on the (110) surface of Tl₂Ba₂Ca₂Cu₃O₁₀ has been observed together with a stepped (11l) surface produced by a combination of the (110) and (001) planes. The (001) surface of Tl₂Ba₂Ca₂Cu₃O₁₀ was also found to terminate with a Ba-O layer. Possible mechanisms for the formation of these surface structures are discussed.     

Planar oxygen-centered lattice instabilities in Tl-based high- temperature superconductors

Analysis of the copper K-edge X-ray absorption finestructure on Tl₂Ba₂CuO₆, Tl₂Ba₂CaCu₂O₈, and Tl₂Ba_1.2Sr_0.8 CuO₆ indicates that the copper-equatorial oxygen local structure changes in the vicinity of the superconducting transition. These data also show that the radial distribution function for these bonds is complex with several oxygen positions relative to the copper, indicating that the local structure of the CuO₂ planes differs significantly from the average crystal structure. These results suggest the presence of polarons in these planes, whose structure changes across the superconducting transition, and are thus coupled to the hole pairing states.     

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.     

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.     

Phase decomposition in nominal LaxCuO4 (x≤2.00) determined by extended x-ray absorption fine structure

Cu K-edge and La L₃-edge X-ray absorption spectra have been measured on a series of nominal La_xxCuO₄ samples with x≤2.00. The extended X-ray absorption fine structure (EXAFS) results show that the x<2.0 samples always consist of stoichiometric (La/Cu=2/1) La₂CuO₄ and CuO. The number of La vacancies in the La₂CuO₄ structure, if any, should be very small. The sensitivity of the EXAFS technique to impurity phases under favorable conditions is demonstrated.     

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.     

Inhomogeneous Tl NMR line broadening in Tl2Ba2CuOx single crystals

Temperature and angular dependences of ²⁰⁵Tl line width, Δ , and transverse relaxation time, τ, have been measured in two crystals of Tl₂Ba₂CuO_x with T_c = 32 and 115 K, respectively. In the normal state both Δ and τ have been found to be temperature-independent and not to vary with varying T_c, implying that the size of inhomogeneous broadening is also invariable. Analysis of the line width angular dependence shows that the inhomogeneous broadening originates, most probably, from local distortions associated with Cu substitution for Tl. A conclusion is that variations in T_c are not related to this substitution.     

The effects of substrate temperature on the superconducting properties of Tl2Ca2Ba2Cu3O10 films sputter-deposited from stoichiometric oxide targets

The annealing characteristics and the superconducting properties of Tl₂Ca₂Ba₂Cu₃O₁₀ thin films sputter-deposited onto yttrium- stabilized ZrO₂ substrate at up to 500°C from two stoichiometric oxide targets are reported. The films deposited at 400–500°C were found to require a lower post-annealing temperature than the films deposited at lower temperatures to attain the highest T_c superconducting state, due to a more pronounced Ba diffusion toward the substrate as indicated by their secondary ion mass spectrometry depth profiles. The highest T_c achieved tends to degrade with increasing substrate temperatures, a zero resistance T_c of 121 and ≈90 K, respectively, being observed for the films deposited at -ambient temperature and at 500°C. The formation of the highest T_c phase (Tl₂Ca₂Ba₂Cu₃O₁₀) generally is associated with a sheet type of crystal growth morphology with smooth and aligned surfaces which can be obtained only from the films capable of sustaining prolonged annealing at 900°C. Annealing at lower temperatures (≈860°C) results in the formation of rod or sphere type of morphologies with rough and randomly oriented crystals and the lower T_c phases such as Tl₂Ca₁Ba₂Cu₂O₈.     

X-ray diffraction studies of epitaxy in orthorhombic- DyMnO3/Er1Ba2Cu3O7-δ thin film heterostructures on LaAlO3 (100) substrates

The heteroepitaxy in DyMnO₃/Er₁Ba₂Cu₃O_7-δ bilayer thin films on LaAlO₃ (100) substates was characterized by four-circle X-ray diffractometry. The Er₁Ba₂Cu₃O_7-δ thin films on LaAlO₃ (100) substrates were prepared by molecular-beam deposition (MBD) and post-growth annealing in wet and dry O₂ at 880°C, whereas the DyMnO₃ thin films on the Er₁Ba₂Cu₃O_7-δ/LaAlO₃ (100) heterostructure were deposited by MBD and post-growth annealing in dry O₂ at 750°C. The conventional X-ray diffraction (XRD) patterns as well as pole figures (φ-scans) for specific (hkl) reflections were acquired. The Er₁Ba₂Cu₃O_7-δ thin film in the DyMnO₃/Er₁Ba₂Cu₃O_7-δ/LaAlO₃ (100) heterostructure showed [001] oriented epitaxial growth, as expected. The DyMnO₃ thin film on the Er₁Ba₂Cu₃O_7-δ epilayer in the heterostructure grew with (110) epitaxy in its metastable orthorhombic phase (lattice constants: a_o=5.272 Å, b_o=5.795 Å and c_o=7.38 Å). The heteroepitaxial relationships at the orthorhombic-DyMnO O₃ (110) /Er₁Ba₂Cu₃O_7-δ (001) interface was determined as the following: DyMnO₃ (110) Er₁Ba₂Cu₃O_7-δ (001), DyMnO₃ [1 0] ¶r; Er₁Ba₂Cu₃O_7-δ[100] or Er₁Ba₂Cu₃O_7-δ[010], and DyMnO₃ [001] ¶r; Er₁Ba₂Cu₃O _7-δ[010] or Er₁Ba₂Cu₃O_7-δ [100].     

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.     

(Tl, Pb, Cu)Sr2(Tl, Pb, Cu)2Cu2O8−δ: a nonsuperconducting Tl-1222 cuprate with both heavy atom single and oxygen depleted double layer motifs

An account is given of the synthesis and structural investigation of a newly discovered tetragonal (Tl, Pb, Cu)Sr₂(Tl, Pb, Cu)₂Cu₂O_8−δ compound (Tl-1222^* phase) with both (Tl, Pb, Cu)O single and oxygen depleted (Tl, Pb, Cu)₂O_x double layer motifs, space group I4/mmm, lattice parameters a=3.8405(2), c=29.2536(5) Å, and D_x=7.46 g cm⁻³. Micaceous and highly reflecting black single crystals of 1 mm×1 mm×3–5 μm size were obtained from a Tl₂O₃- and CuO-rich partial melt. The as-grown compound is nonsuperconducting. The very thin crystals are extremely liable to bend out of shape. Deterioration could not be observed within the period of a year under ambient conditions. The complex crystal structure has been solved using single crystals. We take note of the similarity of the unit cell dimensions to superconducting (Tl, Cu)₂Ba₂(Ca, Tl)Cu₂O₈ (Tl-2212 phase) with TlO double rocksalt layers, and compare crystal-chemical details of similar compounds. Apart from the possibility of obtaining superconducting properties by suitable doping, the mechanical properties of the new material are very attractive from the point of view of its use as highly scattering composite layers of an X-ray monochromator.     

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.     

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.     

O KVV Auger emission versus resonant photoemission at the O K edge of high-Tc superconductors

Photoelectron spectroscopy results on single crystals of the superconductors Bi₂Sr₂CaCu₂O₈,Bi₂Sr₂CuO₆, Ba_0.6K_0.4BiO₃ and the semiconductor Ba_0.9K_0.1BiO₃ are reported for the photon energy region around the O K absorption threshold. The development of the O-KVV Auger structure has been carefully monitored as a function of photon energy. A non-monotonic behavior displaying a feature at a constant binding energy of about 14 eV was found for Bi₂Sr₂CaCu₂O₈ and Bi₂Sr₂CuO₆ in a narrow photon energy region of 1 eV at the main edge of the O K absorption spectrum around 530 eV. The corresponding enhancement, connected with the autoionization of O 2p states, is absent in Ba_1−xK_xBiO ₃ in contrast to Bi₂Sr₂CaCu₂O₈ and Bi₂Sr₂CuO₆. The resonant enhancement is more pronounced for Bi₂Sr₂CuO₆ as compared to Bi₂Sr₂CaCu₂O₈, which can be explained by a lower charge carrier concentration in the former case, leading to a more localized nature of intermediate O 2p states. The model parameters Cu d–d and O p–p Coulomb interactions and the charge transfer energy Δ are estimated from the experiments.     

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.     

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.     

Synthesis and properties of Hg0.7Pb0.3(BaSr)2Ca2Cu3Oz superconductors

We have synthesized Hg(Pb)-1223 with substitutions of Sr for Ba, i.e. Hg_0.7Pb_0.3Ba_2−xSr_xCa₂Cu₃O_z (x = 0.0–2.0) by the ampoule method. The spray-drying method and thermal decomposition under vacuum were applied for the preparation of homogeneous precursors. Samples with T_c = 110–128 K were obtained without oxygen annealing. We found that substitution of Ba by Sr remarkably relaxed the requirements on the precursors preparation and allowed their handling under ambient conditions.     

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.     

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.