High temperature study of yttrium--barium--copper oxides near the YBa2Cu3Ox composition by 111In/Cd time differential \gamma--\gamma perturbed angular correlation spectroscopy

The local atomic order around very dilute indium impurities in c-axis-oriented YBa₂Cu₃O₇ and YBa₂Cu₃O_6.25 films at room temperature and in YBa₂Cu₃O_x bulk powders held in air or oxygen over a wide temperature range were investigated using ¹¹¹In/Cd \gamma--\gamma perturbed angular correlation (PAC) spectroscopy. The probe atoms occupy a single substitutional lattice position in YBa₂Cu₃O_x, and evidence reported here strongly supports previous claims that this is the yttrium position. In YBa₂Cu₃O_x powders, the local atomic order changes continuously with temperature. At room temperature the electric field gradient measured by PAC in bulk YBa₂Cu₃O_x powder is indistinguishable from that in the fully oxygenated YBa₂Cu₃O₇ film. Near the decomposition temperature, the bulk YBa₂Cu₃O_x powder data are semiquantitatively similar to data in the room temperature YBa₂Cu₃O_6.25 film, with quantitative differences that we attribute to temperature averaging in the former. Other sites usually found in PAC spectra of YBa₂Cu₃O_x bulk samples arise from ¹¹¹In dissolved in Y₂BaCuO₅ and Y₂Cu₂O₅ impurity phases. The latter phase apparently arises because of significant barium loss during processing; the barium deficiency is clearly demonstrated by comparison of PAC data with the alloy phase diagram above the decomposition temperature. PAC data on pure Y₂Cu₂O₅ are reported here also. This revised version was published online in July 2006 with corrections to the Cover Date.     

Antiferromagnetic order in PrBa2Cu3O x (x≈6, 7)

Zero and weak transverse fieldμ ⁺ SR measurements on PrBa₂Cu₃O _x samples withx≈6 andx≈7 show ordered magnetism in both oxygen concentration limits. As expected for equivalent doping (nominally PrBa₂Cu₃O _x ∼YBa₂Cu₃O _x −0.5), neither sample is superconducting. Two muon signals are observed in thex≈6 sample, as in YBa₂Cu₃O₆, but only one (the weaker) has the same local magnetic field as in YBa₂Cu₃O₆. In thex≈7 sample, only one site is observed; its local field is reduced with respect to that of the primary site in YBa₂Cu₃O₆ by a factor roughly consistent with the carrier-density dependence of the Cu ion moment in antiferromagnetic YBa₂Cu₃O _x .     

Measurements of the electric field gradient at cadmium in the high Tc superconductor YBa2Cu3O6+x

The electric field gradient (EFG) at¹¹¹Cd probe atoms in YBa₂Cu₃O_6+x has been studied by the perturbed angular correlation (PAC) spectroscopy. After annealing at temperatures below 1000 K the probe atoms are located at the Cu(1) site; above 1100 K they preferentially occupy the Y site, whereas in the intermediate temperature range they also reside on the Ba site. A reduction of the oxygen content from x=1.0 to 0.2 resulted in a decrease of the asymmetry parameter measured at the Ba site, but in an increase of it at the Y site, indicating there a local distortion of the YBa₂Cu₃O_6+x lattice by the Cd impurity. Two different surroundings for the Cd atoms at the Cu(1) site were observed.     

Positive muon sites and possibility of anyons in the YBa2Cu3O x system

Possible positive muon sites in YBa₂Cu₃O _x were determined from the observedμ ⁺ hyperfine fields in antiferromagnetically ordered YBa₂Cu₃O _x and GdBa₂Cu₃O₇. After determining theμ ⁺ sites, the possibility of anyons or chiral spin ordering in the superconducting YBa₂Cu₃O₇ is discussed. Positive muon implanted in YBa₂Cu₃O₇ feel static magnetic fields of average 1.4G, which are explicable in terms of nuclear magnetic dipolar fields. Non observation of static local magnetic fields of electronic origin (the upper limit is the order of 0.1 G) means that anyons or chiral spin ordering might not exist in superconducting YBa₂Cu₃O₇.     

X-ray photoelectron spectroscopy of the high-temperature superconductor YBa2Cu3O7−x and the copper oxides

The X-ray photoelectron (XPS) core-level spectra of Cu-metal, Cu₂O, CuO, NaCuO₂ and YBa₂Cu₃O_7–x have been determined. It has been shown, that the Cu³⁺ ions in NaCuO₂ are reduced to lower valence states by X-rays in ultrahigh vacuum (UHV). The determination of the electron binding energy of the Cu 2 _{p 3/2} level in NaCuO₂ yields a value of 934.1 eV. The shape of the Cu 2 _{p 3/2} peak as well as the appearence of a shake-up satellite in YBa₂Cu₃O_7–x which is smaller than in CuO show that YBa₂Cu₃O_7–x contains Cu³⁺ ions. The behaviour of YBa₂Cu₃O_7–x also was studied during X-ray irradiation and a reduction was noticeable.     

YBa2Cu3O7-x涂层导体的外延生长和性能对CeO2缓冲层的依赖性

利用倾斜衬底沉积法在无织构的金属衬底上生长了MgO双轴织构的模板层,在这一模板层上实现了YBa₂Cu₃O_7-x薄膜的外延生长.在外延YBa₂Cu₃O_7-x薄膜前,依次沉积了钇稳定的立方氧化锆和CeO₂作为缓冲层.利用X射线衍射2θ扫描、扫描、Ω扫描和极图分析测定了这些膜的结构和双轴织 关键词： 2Cu₃O_7-x镀膜导体')" href="#">YBa₂Cu₃O_7-x镀膜导体 2缓冲层')" href="#">CeO₂缓冲层 厚度依赖性 外延生长     

CNDO studies of Y-Ba-Cu-O superconductors II. Simple models of YBa2Cu3Ox

The electronic structure of YBa₂Cu₃O_x (x=6 and 7) is investigated using the CNDO molecular orbital method. Electronic structures of model clusters [Cu₃O₁₀]^–15, [Ba₈Cu₃O₁₀]⁺¹, [Y₈Cu₃O₁₀]⁺⁹ of the non-superconducting (x=6) and [Cu₃O₁₂]^–17, [Ba₈Cu₃O₁₂]^–1, [Y₈Cu₃O₁₂]⁺⁷ of the superconducting (x=7) phases are compared. Y and Ba layers cause a considerable electron density transfer from the central Cu(1) region.     

Interface and grain boundary structures in YBa2Cu3O7-x and YBa2Cu4O8 materials

Y₂BaCuO₅YBa₂Cu₃O_7-x (Y211/Y123) interfaces in melt-processed YBa₂Cu₃O_7-x were studied by high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Yttrium enrichment and barium depletion were observed locally at the Y211/Y123 interfaces where Y123 (001) facets were present. This effect may be interpreted as the result of lattice substitution of Ba by Y near these interfaces. Cation nonstoichiometry was found near Y211/Y123 interfaces where liquid phases (Cu-Ba-O) were present. This chemical disorder introduces numerous point defects in the Y123, and these defects may act as additional pinning sites alongwith stacking faults. A comparison of grain boundary (GB) chemical composition in polycrystalline YBa₂Cu₃O_7-x and YBa₂Cu₄O₈(Y124), studied using nanoprobe parallel-detection electron energy-loss spectroscopy (EELS), is presented. The studies of Y124 show that stoichiometric grain boundaries can also form weak links between superconducting grains. It is suggested that weak-link behavior is determined largely by misorientation at grain boundaries.     

Comparative analysis of the effect of La and Co on the superconductivity and energyband spectrum of YBa2Cu3Oy for different oxygen contents

Temperature dependences of the resistivity and Seebeck coefficient of Y(Ba_1−x La_x)₂Cu₃O_y and YBa₂Cu_3−x Co_xO_y samples (x=0–0.25) have been measured under maximum sample saturation with oxygen, as well as following their anneal in an oxygen-deficient atmosphere. The T _c (x) dependences for as-prepared samples were found to pass through a maximum at x=0.05, which persists after annealing for Y(Ba_1−xLa_x)₂Cu₃O_y and disappears for YBa₂Cu_3−x Co_xO_y. A phenomenological model of the band spectrum in normal phase has been used to determine the parameters of the conduction band and of the carrier system, and to analyze their variation with the dopant type and content, as well as with annealing. Despite the differences observed in the T _c (x) dependence, the critical temperatures for all the sample series studied were found to correlate with the conduction-band effective width. The mechanism of the effect of impurities on the band-structure parameters and the reasons for the different influence of annealing on the properties of Y(Ba_1−x La_x)₂Cu₃O_y and YBa₂Cu_3−x Co_xO_y are discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 389–394 (March 1997)     

Magnetic phase present in YBa2(Cu1−x Fe x )3O6+δ oxides

The Mössbauer study of⁵⁷Fe: YBa₂Cu₃O_6+δ oxides was very important to establish the preferential occupation of Cu(1) site by Fe at very low concentrations. Recent determination of antiferromagnetic ordering for Cu moments in Cu(2) sites (T≈450 K) and our early observation of a small proportion of a magnetic phase at room temperature for Fe:YBa₂Cu₃O₆ lead us to perform systematic studies of YBa₂(Cu_1?x Fe _x )₃O₆ withx=0.005, 0.03, 0.05, 0.10 and 0.15 in order to obtain information about the iron occupation of Cu(2) sites.     

Photoemission study of the Ba core levels in YBa2Cu3O7-x

Angle dependent X-ray photoemission spectra of epitaxial thin YBa₂Cu₃O_7-x films show characteristic differences after various heat and oxygen pretreatments. The component with the lowest binding energy in Ba 3d _5/2 and 4d _5/2 peaks results from bulk Ba in YBa₂Cu₃O_7-x . A component with 2 eV higher binding energy results from Ba in the surface unit cell with different bonding if compared with the bulk superconductor. This surface structure is observed for all YBa₂Cu₃O_7-x surfaces which have been exposed to oxygen. It is not observed for UHV prepared surfaces after mechanical scraping or fracturing.     

μ− SR studies of oxide-superconductorsSR studies of oxide-superconductors

The negative muon spin rotation method (μ⁻ SR) has been applied to studies of electronic states at oxygen sites of oxide superconductors YBa₂Cu₃O₇, Nd_2−x Ce _x CuO_4−δ (x=0.15, oxygen reduced), LiTi₂O₄ and related oxide-insulators La₂CuO_4−δ, CuO, Cu₂O. The paramagnetic shifts of μ⁻ trapped at oxygen nuclei in these polycrystalline powder samples have been measured at 300 K. All the measured shifts are positive. In copper-oxides the paramagnetic shifts are of the order 10⁻³, while in LiTi₂O₄ is very small (8.4±3.34×10⁻⁵). In YBa₂Cu₃O₇, a fast μ⁻ spin relaxation timeT ₂ ^* (∼ 200 ns) has been observed; the reason for this is unknown and further studies are now in progress.     

Magnetic-field-induced damage in a superconducting YBa2Cu3O7−x film

During investigations of the magnetic flux dynamics in thin superconducting YBa₂Cu₃O_7?x films we have observed the spontaneous formation of a damage in the film, apparently induced by the applied magnetic field of 0.1 T. The damage developed within less than 40 ms (the time resolution of the experiment) and showed up in the magnetiooptically recorded image of the flux above the sample as a path for massive flux penetration. A subsequent analysis revealed a 1 μm wide gap in the YBa₂Cu₃O_7?x film which had developed over a major portion of the 1 · 1 cm² sample. It is suggested that the film locally melted as a result of an instability of the superconductor in the critical state.     

TDPAC and emission Mössbauer spectroscopy of99Ru in YBa2Cu3O7−x

The hyperfine interactions of⁹⁹Ru(⁹⁹Rh) in YBa₂Cu₃O_7–x withx<0.2 andx1 were studied by means of TDPAC and emission Mössbauer spectroscopy. The superconductor YBa₂Cu₃O_7–x withx<0.2 was prepared by conventional heat treatment in oxygen, the semiconductor withx1 by heating the superconductor under a reduced pressure. The TDPAC and Mössbauer measurements show that Ru ions exclusively occupy the Cu-1 site, which forms one-dimensional Cu-O chains in the orthorhombic phase.     

Controllable generation of harmonics by means of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7 − <Emphasis Type="Italic">x</Emphasis></Subscript> superconductors

The nonlinear magnetic properties of YBa₂Cu₃O_{7 − x} high-temperature superconducting polycrystals are investigated. Using the results of investigations as a basis, a method for controlling the amplitudes of generated magnetization harmonics is worked out and a controllable harmonic generator is devised. The amplitudes of the harmonics are controlled by means of a permanent magnetic field or current. The use of YBa₂Cu₃O_{7 − x} polycrystals makes it possible to produce a spectrum with offering a large number of higher harmonics. An YBa₂Cu₃O_{7 − x} -based device has a wide dynamic range; its design is simple and reliable in a wide interval of the amplitudes of an input signal.     

Andreev states and the Josephson effect in superconducting heterojunctions on thin YBa2Cu3Ox films

Conductance anomalies at low bias voltages and superconducting currents in Au/YBa₂Cu₃O_x and Nb/Au/YBa₂Cu₃O_x heterojunctions in which the c axis of the YBa₂Cu₃O_x (YBCO) epitaxial film is rotated in the (110) YBCO plane through 11° with respect to the normal to the substrate plane were studied experimentally. The films were prepared by laser deposition onto (7 2 10)-oriented NdGaO₃ substrates. The current-voltage characteristics of the heterojunctions exhibit conductance anomalies at low voltages. The behavior of these anomalies is studied at various temperatures and in various magnetic fields. The critical current and Shapiro steps observed in the current-voltage characteristics of Nb/Au/YBa₂Cu₃O_x were evidence of the Josephson effect in these heterojunctions. The experimental results are analyzed in terms of the model of the arising of bound states caused by Andreev reflection in superconductors with d-type symmetry of the superconducting order parameter.     

Study of YBa2Cu3O7−x films at various stages of their growth by medium-energy ion scattering

The initial stages in the formation and growth of yttrium-barium cuprate films have been studied in the course of magnetron sputtering of a ceramic target by combining medium-energy-ion scattering (MEIS) and scanning-electron microscopy. The growth mechanisms of YBa₂Cu₃O_7−x films on MgO and substrates having the perovskite structure, SrTiO₃ and LaAlO₃, at deposition temperatures of 700–780 °C and (Ar+O₂) pressure of ∼70 Pa were found to be essentially different. Simulation of MEIS spectra (H⁺ or He⁺ ions with initial energies of 150–250 keV) and comparison of these results with experimental data revealed that in the first case a film forms from pyramid-shaped islands and, in the second, it grows by a two-dimensional layer-by-layer process starting practically with the first monolayer. For the island mechanism, MEIS permitted determination of the substrate surface coverage and showed the growth of the YBa₂Cu₃O_7−x phase to be paralleled by formation of epitaxial nuclei of a Cu₂O phase. After the first, initial stage in the film formation, the second stage, regular growth within reduced thicknesses of 7–15 nm, sets in. This stage is characterized by a practically complete coverage of the substrate and a stable composition. The third stage, regular growth, of an apparently helical nature, was observed to set in at thicknesses above 100 nm. In this stage, the quality of film structure in the bulk and on the surface was found to be somewhat inferior to that of YBa₂Cu₃O_7−x single crystals and did not depend on substrate type. Fiz. Tverd. Tela (St. Petersburg) 41, 588–595 (April 1999)     

Hole doping by Li substitution and antiferromagnetism in YBa Cu O studied by neutron powder diffraction measurements

The magnetic structure of tetragonal insulating YBa₂Cu_3-xLi_xO_y has been studied as a function of x and y. The Néel temperature and the mean ordered magnetic moment on the Cu2 sites were determined by neutron powder diffraction measurements. The decrease of these two parameters as compared to YBa₂Cu₃O₆ is much stronger for lithium than for zinc substitution. The difference is quantitatively explained by the presence of holes created in the CuO₂ planes. These holes arise from the substitution of plane Cu²⁺ by Li⁺. We suggest an explanation why such holes are not seen for the same substitution of plane Cu²⁺ by Li⁺ in orthorhombic superconducting YBa₂Cu_3-xLi_xO _{7 - δ} . Received 31 October 2001 and Received in final form 6 March 2002 Published online 25 June 2002     

Spectroscopic studies of the high-Tc superconducting cuprate perovskites

We present XRD, ESR, IR, DR(UV, VIS) as well as resistivity and magnetic susceptibility data of single phase superconducting perovskites YBa₂Cu₃O_x and EuBa₂Cu₃O_x. A rich phonon structure for both oxide compounds has been observed with a peak at: 72, 108, 135, 148, 172, 570 and 620 cm^-1. The edge of the low energy side was observed at 55 cm^-1. The estimated carrier density for YBa₂Cu₃O_x is (1–2) × 10²¹ cm^-3. A weak ESR signal has also been observed for superconducting phases which is associated with the lattice defects.We also report ESR and optical measurements of constitutent materials as well as not superconducting phases Y₂Cu₂O₅ and BaCuO₂.     

Mössbauer measurements on170Yb3+ substituted into YBa2Cu3O7

We present some results obtained by Mössbauer spectroscopy on Yb³⁺ when substituted into YBa₂Cu₃O _x -like compounds. For the fully substituted compound YbBa₂Cu₃O₇, we describe the properties of the rare earth sublattice magnetic ordering which coexists with superconductivity. From measurements at the dilute substitution level, we study the Yb³⁺ crystal field properties and the thermal dependence of the Yb³⁺ paramagnetic relaxation rate. By making use of the molecular field produced on the Yb³⁺ probe by the magnetically correlated Cu(2), we examine the evolution of the Cu(2)-based magnetism as a function of carrier density and study the phase separation which occurs in the superconducting samples with intermediate oxygen levels. We also examine how the properties of the Yb³⁺ probe are influenced by the substitution of Pr³⁺ or Zn²⁺ (these substitutions are known to considerably influence the superconducting properties).