Effect of Oxygen-Deficiency of CuO2 Plane on the Structure, Magnetism, and Transport Properties

Polycrystalline samples La_{2 – x} Sr _x CuO_{4 –} (0.06 x 1.0) and the corresponding vacuum annealed samples were investigated systematically by means of XRD, infrared (IR) spectra, ESR, and resistivity. It is found that the doping of Sr and the oxygen vacancies in CuO₂ planes show different effects on the lattice parameters a and c, and the changes of a and c of La_{2 – x} Sr _x CuO_{4 –} samples (x 0.2) rest with the cooperation of the two factors. The two high frequency IR vibration modes at 500 and 689 cm^–1, which are referred to the vibrations of apical oxygen and planar oxygen, are analyzed in detail. The disappearance of the mode at 689 cm^–1 is interpreted in terms of the screened effect of charge carriers in CuO₂ planes. ESR results indicate that oxygen deficiency of CuO₂ layers not only decreases carrier concentration, but also destroys the antiferromagnetic spin correlation or spin fluctuation and results in localized Cu²⁺ spins. The effect of localized Cu²⁺ spins (or spin scattering) on the superconductivity and transport properties is discussed in the text.     

Structural instabilities and superconductivity in La-214 compounds

In La_2–x Ba _x CuO₄ (LBCO) the transition to a low-temperature tetragonal phase and the suppression of superconductivity occur at the carrier concentration p 1/8 per copper. We will discuss the roles of various material parameters that control this instability. An unusual lattice softening has been found by ultrasonic measurement on La_2–x Sr _x CuO₄ (LSCO). This softening is present only in an in-plane shearing mode and is ascribed to the growth of structural fluctuations in the normal state.These phenomena are closely related because both the structural change in LBCO and the applied strain in LSCO lift the degeneracy of in-plane oxygen sites. They clarify the importance of strong coupling between the normal-state electronic system and the lattice by a Peierls-type mechanism.     

Point contact spectroscopy in oriented La2?xSrxCuO4 superconductors; energy gap and Fermi velocity

Point contact measurements in oriented La_2–xSr_xCuO₄ samples were performed using metal tips. The current-voltage curves measured along the CuO plane direction (ab) are characteristic of the Andreev reflection phenomenon. The superconducting energy gap in theab plane is determined, _ab = 6± 1 meV, with a possibility for the existence of a lower subgap in the plane. A lower limit for the Fermi velocity in the CuO planes is also set by the measurements;V _F6×10⁷ cm/sec, which is significantly higher than the average velocity obtained by band calculations. The results are discussed in the context of different models for superconductivity in the layered oxides. In particular, we raise the possibility of an anisotropic gap parameter which may indicate a nonstandards-wave pairing in La_2–xSr_xCuO₄. A comparison with previous results obtained on YBa₂Cu₂O_7– is made.     

Magnetic order and evolution of the electronic state aroundx=0.12 in La2?xBaxCuO4 and La2?xSrxCuO4

Muon spin rotation ( ⁺SR) measurement provides clear evidence of the antiferromagnetic order of Cu moments below 35 K for La_2–x Ba _x CuO₄ and below 15 K for La_2–x Sr _x CuO₄ in the narrow range ofx where the high-T _c superconductivity (SC) is suppressed remarkably. The results suggest that the change of the electronic state coupled with the lattice instability is relevant to the local suppression of SC and freezing of spin fluctuations of the Cu moment.     

Superconductivity in the tetragonal phase of La1.9Bi0.1CuO4+δ annealed under high oxygen pressure

We have investigated the relation between the crystal structure and superconductivity in La_1.9Bi_0.1CuO₄₊ , in which the phase separation observed in La₂CuO₄₊ is suppressed. A phase diagram in theT– plane is given for La_1.9Bi_0.1CuO₄₊ with excess oxygen. For very small values, the crystal structure is orthorhombic, and an orthorhombic-tetragonal phase transition occurs markedly at 0.03 in the measured temperature range between 13 and 293 K. Superconductivity is observed in the range of 0.04<<0.11. This is clear evidence thathigh-T _c superconductivity also appears in the tetragonal phase.     

Stability of the low-temperature tetragonal phase in La2?xBaxCuO4 and related compounds

In La_2–x Ba _x CuO₄ (LBCO), the structural transition to a low-temperature tetragonal phase below 60 K and suppression of superconductivity are observed when the carrier density isp 1 /8 per copper. The replacement by divalent ions smaller than Ba²⁺ suppresses the static deformation of the lattice. We have found that the variationsT _d2 and superconducting transition temperatureT _c are quantitatively characterized by the averaged ionic radius at the La site or lattice parameters. This aspect of substitution could be regarded as the effect of chemical pressure, since similar variations have been reported on applying hydrostatic pressure. In La_2–x–y Nd _y (Ba, Sr) _x CuO₄,T _d2 increases with increasingy in a wide range ofp whileT _c is suppressed only at p l /8. The structural transition atT _d2 here should be ascribed mainly to the crystallochemical origin.     

High-temperature ceramic oxide superconductors

High-temperature superconductivity in oxides of the type La_2−x Ba _x (Sr _x )CuO₄, YBa₂Cu₃O_7−δ , La_3−x Ba_3+x Cu₆O₁₄ and Bi(Tl)-Ca-Sr(Ba)-Cu-O systems is discussed, with special emphasis on the experimental findings from the author’s laboratory. The importance of holes on oxygen and of the Cu¹⁺ (d ¹⁰) state is examined. A transition is shown to occur from chain- to sheet-superconductivity in YBa₂Cu₃O_7−δ accompanying a change in oxygen stoichiometry. Some of the important material parameters and technological applications are briefly presented. There is every hope that materials withT _c close to room temperature will be discovered in the near future. All the highT _c oxides found hitherto have perovskite-related structures with two-dimensional Cu-O sheets. Contribution No. 485 from the Solid State and Structural Chemistry Unit.     

Structural commonalities of high-temperature superconductors

It is shown that all of the presently known high-temperature superconductors belong to one structural type with a basic cell of approximate 4/mmm,D _4h symmetry in tetragonal compounds andmmm,D _2h symmetry in orthorhombic compounds. In the Ba(Pb1–xBi _x )O₃ and YBa₂Cu₃O_7– compounds the basic cell is the unit cell and in the (La_1–x Sr _x )₂CuO₄, BiSrCaCuO and TIBaCaCuO compounds it is half the unit cell. The features of more than one copper oxide layer per basic cell, oxygen-free cation layers (e.g., Ca, Y) between CuO₂ layers, and slightly puckered CuO₂ planes seem to favor higher transition temperatures. The feasibility of several proposed or potentially superconducting structures are analyzed by this scheme.     

Correlation Between Superconducting Transition Temperature and Bond Length Ba–O in High-Tc Cuprate Superconductors

A well-known correlation of the maximum superconducting transition temperature (T _c,max) with ionic radius of rare earths and Y (R) in the series RBa₂Cu₃O_{7 –} is converted to the intrinsic correlation of T _c,max with bond length between Ba and oxygen in CuO₂ plane, being valid not only for RBa₂Cu₃O_{7 –} but also for other cuprate superconductors containing BaO plane such as HgBa₂CaCu₂O_{6 +} . It is pointed out that this correlation places a constraint on possible mechanisms inducing the high-T _c superconductivity.     

On the oxygen isotope shift in La2?xSrxCuO4

The anomalous oxygen isotope shift observed in the high-temperature superconductors La_2–xSr_xCuO₄ and La_2–xBa_xCuO₄ is discussed within the model of superconductivity in which the apex oxygen vibrations play the major role in the pairing mechanism. We show that the dependence of both the critical temperature and its isotope shifts on the doping level is consistently described within this model. The anomaly occurring in the isotope shift between x = 0.11 andx=0.15 is traced back to the oxygen mass exponent associated with the apex oxygen frequency.     

Anisotropic uniaxial pressure effects in YBa2Cu3O7?δ

We present measurements of the uniaxial pressure dependence ofT _c of untwinned YBa₂Cu₃O_7– crystals with various oxygen stoichiometries. For all samples investigated,T _c decreases for pressure alonga, increases for pressure alongb, and, in oxygen deficient samples, increases strongly for pressure alongc. These results are compared to the behavior found in the La_2–x Sr _x CuO₄ and YBa₂Cu₄O₈ systems. Neither the model of pressure-induced charge transfer nor coupling to orthorhombic distortions can explain all the data. However, the presence of singularities in the electronic density of states close to the Fermi energy is a possible origin of the observed behavior. Our preliminary data on the pressure dependence of thec-axis and in-plane resistivities in twinned crystals are consistent with this view.     

On the high-temperature superconductivity of SrxLa2?xCuO4?δ

The superconducting properties of Sr_xLa_2–xCuO_4– are analyzed by employing the model of interaction between charge carriers and the oxygen-displacive modes of the lattice. The role played by the hole concentration, as related to the Sr content x and oxygen deficiency, is thoroughly emphasized. The critical temperature, the ratio of twice the superconducting gap to the critical temperature, and the isotope shift are estimated as functions of the hole concentration and compared with the experimental data.     

1/8 Anomaly in the Excess-Oxygen-Doped La2−x A x CuO4+δ (A = Nd, Bi, Pr)

We have investigated in detail dependence on p (the hole concentration per Cu) of the transport properties and T _c in the excess-oxygen-doped La_2–x A _x CuO₄₊ (A=Nd, Bi, Pr), where the phase separation of the excess oxygen is suppressed. The so-called 1/8 anomaly has been found in La_1.8Nd_0.2CuO₄₊. The 1/8 anomaly has become marked through the 1% substitution of Zn for Cu. The SR measurements have revealed that the magnetic correlation develops at low temperatures below about 40 K in both Zn-free and 1% Zn-substituted samples with p=1/8 and that a long-range magnetic order is formed below 1 K in the 1% Zn-substituted sample with p=1/8. These results support the stripe-pinning model. Neither La_2–x Bi _x CuO₄₊ nor La_2–x Pr _x CuO₄₊ has exhibited the clear 1/8 anomaly.     

Cooper pair breaking and isotope effect coefficient variation in high-Tc superconductors

The effect of pair breaking on the isotope effect coefficient=–d lnT _c/d lnM in La_2–x Sr _x CuO₄ and Pr-, Ca-, and Zn-doped YBa₂Cu₃O_7–x and EuBa₂Cu₃O_7–x is studied using the generalized Abrikosov-Gorkov theory recently employed by Singh and Kishore for superconductivity. It is argued that the isotope effect coefficient can be further enhanced, in agreement with experimental observations, by considering the dependence of the characteristic scattering time _s for Cooper pairs on the concentrationn of impurities (both magnetic and nonmagnetic) and the disorder ignored by them (J. Supercond. 8, 9 (1995).     

Dynamic Inhomogeneities in the La2CuO4-Based Superconductors

Polarization-dependent X-ray-absorption fine-structure (XAFS) measurements on the local structure of the La₂CuO₄-based high-T _c superconductors La_2–x Sr _x CuO₄, La_2–x Ba _x CuO₄, and La_1.6–x Sr _x Nd_0.4CuO₄ find, among others, orientation disorder induced in the Cu–O₂ planes by doping Sr, Ba, and alloying Nd atoms, all such atoms residing in La-sites. The orientation disorder is of two types: mostly static-buckling disorder, and dynamic disordering of the tilt angles of the Cu–O₆ octahedra correlated in nanoscale regions, with respect to neighboring nanoscale regions. Buckling disorder in the Cu–O₂ planes has the greatest detrimental effect on T _c and conductivity for such foreign atoms.     

Microstructure and Physical Properties of Bi1.9+xSr1.7?xLa0.4CuO6 System

The crystal microstructure, superconductivity, and normal state transport properties of Bi_1.9+x Sr_1.7–x La_0.4CuO₆₊(0 x 0.4) system were investigated by means of electron diffraction (ED), resistivity, and TEP. Analyses of the experimental results indicate that with the increase of Bi content, the incommensurate modulation wavelength decreases and the distortion of CuO₆ octahedron enhances. Increasing Bi content decreases the carrier concentration rapidly, and induces an MI transition. The destruction of superconductivity mainly derives from two aspects: the enhancement of structural distortion due to the introduction of more Bi and the variation of the carrier concentration of the system.     

Microscopic Charge Inhomogeneities in Underdoped La2?xSrxCuO4: Local Structural Evidence

We present local structural evidence for the existence of charge inhomogeneities at low temperature in underdoped and optimally doped La_2–x Sr _x CuO₄. The inhomogeneities disappear for x 0.2. The evidence for the charge inhomogeneities comes from an anomalous increase in the inplane Cu–O bond length distribution in the underdoped samples as well as evidence for CuO₆ octahedral tilt inhomogeneities in the intermediate range structure. Preliminary analysis of the temperature dependence of this phenomenon indicates that the inhomogeneities set in at temperatures in the range 60 K < T _co < 130 K, which depends on doping.