On the interpretation of the phase diagram of La<Subscript>2−x</Subscript>M<Subscript>x</Subscript>CuO<Subscript>4</Subscript>

The difference between the phase diagrams of La_2?x(Ba,Sr)_xCuO₄ and Nd_2?xCe_xCuO₄ is discussed. It is proposed that the discrepancy of x-values corresponding to the transition from antiferromagnetic dielectric state to conducting one (respectively, x≈0.06 in La_2?x(Ba,Sr)_xCuO₄ and x≈0.125 in Nd_2?xCe_xCuO₄) results from non-homogeneous doping of La_2?x(Ba,Sr)_xCuO₄ over the range 0.06<x<0.125, when localized holes are added to each second CuO₂ layer. Therefore the actual phase diagram of the “holedoped” superconductor La_2?x(Ba,Sr)_xCuO₄ coincides with one for the “electron-doped” superconductor Nd_2?xCe_xCuO₄. It is shown that all features observed in La_2?x(Ba,Sr)_xCuO₄ around x=0.125 are clarified on this basis.     

New class of T′-structure cuprate superconductors

High-temperature superconductivity has been discovered in La_2−xBa_xCuO₄ [J.G. Bednorz, K.A. Müller, Z. Phys. B 64 (1986) 189. [1]], a compound that derives from the undoped La₂CuO₄ crystallizing in the perovskite T-structure. In this structure oxygen octahedra surround the copper ions. It is common knowledge that charge carriers induced by doping in such an undoped antiferromagnetic Mott-insulator lead to high-temperature superconductivity [V.J. Emery, Phys. Rev. Lett. 58 (1987) 2794; C.M. Varma, S. Schmitt-Rink, E. Abrahams, Solid State Commun. 62 (1987) 681; E. Dagotto, Rev. Mod. Phys. 66 (1994) 763. [2], [3] and [4]]. The undoped material La₂CuO₄ is also the basis of the electron-doped cuprate superconductors [Y. Tokura, H. Takagi, S. Uchida, Nature (London) 337 (1989) 345. [5]] of the form La_2−xCe_xCuO_4+y [M. Naito, M. Hepp, Jpn. J. Appl. Phys. 39 (2000) L485; A. Sawa, M. Kawasaki, H. Takagi, Y. Tokura, Phys. Rev. B 66 (2002) 014531. [6] and [7]] which, however, crystallize in the so-called T′-structure, i.e. without apical oxygen above or below the copper ions of the CuO₂-plane. It is well known that for La_2−xCe_xCuO_4+y the undoped T′-structure parent compound cannot be prepared due to the structural phase transition back into the T-structure occurring around x∼0.05. Here, we report that if La is substituted by RE=Y, Lu, Sm, Eu, Gd, or Tb, which have smaller ionic radii but have the same valence as La, nominally undoped La_2−xRE_xCuO₄ can be synthesized by molecular beam epitaxy in the T′-structure. The second important result is that all these new T′-compounds are superconductors with fairly high critical temperatures up to 21 K. For this new class of cuprates La_2−xRE_xCuO₄, which forms the T′-parent compounds of the La-based electron doped cuprates, we have not been able to obtain the Mott-insulating ground state for small x before the structural phase transition into the T-structure takes place.     

Muon and other studies of magnetic ordering in cuprate layer-compounds

Muon spin rotation studies of magnetic ordering in the planar cuprates are reviewed. Particular attention is given to doped La₂CuO₄ and oxygen-depleted YBa₂Cu₃O_7-δ and to related experimental investigations. Studies of transition element substituted compounds are also reviewed.     

Structural phase transition in substituted La2CuO4 and Pr2CuO4−y

The structural phase transition from orthorhombic (T) phase to tetragonal (T′) phase in substituted La_2−x R _x CuO₄ (R = Pr, Nd, Sm, Eu and Gd) and T′ to T-phase in Pr_2−x M _x CuO_4−y (M = Sr, Ca) has been studied by X-ray diffraction technique. The T-phase of La₂CuO₄ is transferred to T′ phase abruptly atx=0.8, 0.4, 0.4, 0.3 and 0.4 respectively for substitution of Pr, Nd, Sm, Eu and Gd for La in La₂CuO₄ without evidence of the T* phase. The T′ structure of Pr₂CuO₄ (x = 0.0) gets transformed to the T* structure at 30% Ca doping (x=0.6) and then to the T structure at 50% Ca doping (x=1.0), while for Sr-contentx=0.0, 0.4 and 1.0 it shows T′, T* and T structure respectively.     

119Sn and57Fe Mössbauer study of La2−x Sr x CuO4

Mössbauer absorption measurements were carried out for¹¹⁹Sn and⁵⁷Fe impurities in La₂CuO₄, La_1.85Sr_0.15CuO₄ and La_1.6Sr_0.4CuO₄. For all cases,⁵⁷Fe spectra at 4.2 K show magnetic hyperfine splittings. On the other hand, a magnetic hyperfine field at Sn nucleus is observed only in the case of La_1.85Sr_0.15CuO₄. The results indicate that the Cu magnetic spins are collectively fluctuating in the superconducting sample.     

μSR study of internal magnetic fields in superconducting La1.9Sr0.1CuO4 in the mK region

Muon-spin-rotation (μSR) experiments were performed on superconducting La_1.90Sr_0.10CuO₄ in zero external field. Below 2 K, a fast depolarization of the muon signal is observed, indicating that internal magnetic fields are present at the muon site. The average magnitude of the magnetic field in La_1.90Sr_0.10CuO₄ is in the order of 3 mT and thus approximately 14 times smaller than the corresponding field in antiferromagnetic La₂CuO₄. The present data support theoretical models of superconductivity in which magnetic correlations are responsible for pairing.     

X-ray Fluorescence Spectroscopic Studies of High TeSuperconductors

The Cu-Lβ/Cu-Lα x-ray emission intensity ratio of the following compounds have been found to show an interesting consistency: Cu, Cu₂O, CuO, La_1.85Ba_.15CuO₄ (vacuum annealed), La_1.85Ba_.15CuO₄ (air annealed, T_C = 26K), La_1.85Sr_.15CuO₄ (T_C = 35K), YBa₂Cu₃O_7-Δ (T_C = 91K), ErBa₂Cu₃O_7-Δ (T_C = 81K), and La₂CuO₄. The interesting consistency is that all of the last six compounds, all superconductors or superconductor related, have the same Lβ/Lα intensity ratio, namely, 0.33±0.01. The Cu-Lα,β spectra of CuO, air and vacuum annealed La_1.85 Ba_.15CuO₄ and YBa₂Cu₃O_7-Δ are presented. Also presented are O-K x-ray fluorescence spectra of air and vacuum annealed La_1.85 Ba_.15CuO₄, and of “new” and “old” YBa₂Cu₃O_7-Δwhich seem to show a correspondence between spectral sharpness and high T_C behavior.     

Location of superconductivity in La2-βSrβCuO4

Evidence is presented that the superconductivity of La_{2 ?β} Sr_β CuO₄ and La₂CuO4_+δ occurs via holes in the LaO planes, rather than in the CuO₂ planes.     

Intercalation and staging behavior in super-oxygenated La2CuO4 + δ

A high temperature electrochemical oxidation process has been used to produce large single crystals of La₂CuO_{4 + δ} suitable for neutron scattering experiments. Below room temperature the oxygen-rich phases have structural superlattice scattering peaks which indicate new periodicities ranging from 2 to 6.6 layers perpendicular to the copper oxide planes. A model structure originally proposed for La₂NiO_{4 + δ} can account for the superlattice peaks as a result of anti-phase domain boundaries between different tilt directions of the CuO₆ octahedra. Within this model, the changes in CuO₆ tilt directions are induced by segregated layers of interstitial oxygen which order in a manner similar to intercalants in graphite. This structural model thus clarifies previous work and establishes La₂CuO_{4 + δ} as a unique lamellar superconducting system with annealed disorder.     

Approaches to the synthesis of High-TC superconducting oxides in La–Ba–Cu–O and Y–Ba–Cu–O systems

Abstract

High-T_C superconducting oxides of nominal La_1.85Ba_0.15 CuO₄ and YBa₂ Cu₃ O₇ have been prepared by using nitrate, carbonate, oxalate/malonate and citrate precursors. While the samples in the Y-system are generally monophasic YBa₂Cu₃O_7?δ with T_C around 90K, the preparations in the La-system are biphasic containing K₂NiF₄-like La_1.85Ba_0.15 CuO₄ (T_C = 30K) and a perovskite-like phase with' a much higher T_C (200–300K). Effect of Ca, Zr, Ce as well as S substitution in YBa₂Cu₃O_7?δ has also been investigated     

Low-temperature synthesis of T′-La2CuO4 using CaH2 as reductant

We have successfully synthesized polycrystalline bulk samples of La₂CuO₄ with the Nd₂CuO₄-type (T′) structure at low temperatures. First of all, La₂CuO₄ with the K₂NiF₄-type (T) structure was prepared by the conventional solid-state reaction. Secondly, La₂CuO_3.5+δ with the Sr₂CuO₃-type structure was obtained by heating mixed powder of T-La₂CuO₄ and CaH₂ at 175 °C in an evacuated Pyrex tube. Thirdly, T′-La₂CuO_4+δ was prepared by heating La₂CuO_3.5+δ at 250 °C in air. Finally, T′-La₂CuO_4+δ was reduced using CaH₂ to remove excess oxygen. The powder X-ray diffraction pattern has revealed that the product is of the single phase of T′-La₂CuO₄, but no superconductivity has been observed at T > 2 K in the magnetic susceptibility measurement. The residual excess oxygen may suppress the appearance of superconductivity.     

Magnetic order in La2-x Bax CuO4 and La1.6-x Nd0.4 Srx CuO4 for x=0.125

We present μSR experiments on La_2-x Ba_x CuO₄ and La_1.6-x Nd_0.4 Sr_x CuO₄ for x=0.125. Both of these materials order magnetically with T_N\approx30\ K, while a superconducting sample of La_1.4 Nd_0.4 Sr_0.2 CuO₄ showed no evidence for static copper moments. Our results support the conclusion that the so‐called “1/8” anomaly in La_2-x Ba_x CuO₄ is a result of static (pinned) charge segregation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Magnetic order in LaEuSrCuO studied [2pt] by Fe Mössbauer spectroscopy

⁵⁷Fe M?ssbauer effect studies of La_1.65Eu_0.20Sr_0.15CuO₄ doped with 0.5 at% ⁵⁷Fe performed in the temperature region 300 K > T > 4.2 K give an onset temperature for magnetic ordering of K. This temperature practically is the same as that found in Nd doped La_2-xSr_xCuO₄. It indicates that the magnetic ordering temperature in the LTT phase of rare earth (RE) doped La_2-xSr_xCuO₄ is independent of the RE moment. The direction of the ⁵⁷Fe magnetic moment in the magnetically ordered state is within the CuO₂ plane, while it has been found to be parallel to the c-axis in Nd doped La_2-xSr_xCuO₄. Received: 23 June 1998 / Accepted: 14 July 1998     

The high-T c superconductor Sr0.2Lai1.8CuO4: A direct and inverse-photoemission study

We have measured ultraviolet and inverse-photoemission spectra of the novel superconductor Sr₀₂La_1.8CuO₄. Our results compare favorably with recent band-structure calculations for La₂CuO₄.A full account of this work will be published elsewhere [1]     

Domain-wall mechanism of nucleation in a magnetic structural phase transition in La<Subscript>2</Subscript>CuO<Subscript>4</Subscript>

The structure of domain walls and new-phase nucleation are investigated in a four-sublattice antiferromagnet (AFM) of the La₂CuO₄ type placed in a magnetic field which initiates an AFM-weak-ferromagnet (WFM) magnetic structural phase transition. The critical fields for nucleus growth are found in the case of two types of domain walls present. The magnetization curve is calculated and a two-step mechanism is proposed for the AFM-WFM phase transition observed in La₂CuO₄.     

Modeling of a structural phase transition in La2−x SrxCuO4

The structural, vibrational, and elastic properties of La₂CuO₄ are calculated using a model for calculating the energy of the crystal based on interionic potentials with the multiparticle Jahn-Teller contribution included explicitly. The microscopic reasons for the structural instability of the La₂CuO₄ lattice relative to rotations of the oxygen octahedra are investigated. A structural phase transition from the orthorhombic phase (space group D _2h ¹⁸ ) into the tetragonal phase (space group D _4h ¹⁷ ) under hydrostatic compression of an La_2−x Sr_xCuO₄ crystal is modeled. The (P,x) structural phase diagram for La_2−x Sr_xCuO₄ is constructed. Fiz. Tverd. Tela (St. Petersburg) 41, 1096–1102 (June 1999)     

Microhardness of the compounds La2CuO4 and La1.85Sr0.15CuO4 at temperatures from 81 to 292 K

The microhardness of La₂CuO₄ and La_1.85Sr_0.15CuO₄ crystals is measured in the temperature range 81–292 K, and the influence of various factors on it is investigated. The thermal activation parameters of the plastic deformation process in the vicinity of the indenter impression are estimated. The change of the phase state of the compound La_1.85Sr_0.15CuO₄ at the temperature T ₀=180 K and the appearance of domain (twin) boundaries formed in the ferroelastic tetraortho transition are not seen in the temperature dependence of the microhardness. The results of the study are compared with previously published results for YBa₂CuO_7−x crystals. Fiz. Tverd. Tela (St. Petersburg) 40, 493–497 (March 1998)     

Are the high temperature superconductors real metals?

A comparison of the experimental band structure of oxygen on Cu(110) and the theoretical band structure of the prototype material for the high temperature superconductors La₂CuO₄ is performed. This comparison suggests, that the theoretical band structure describes the occupied electronic states of La₂CuO₄ adequately.     

Jahn-Teller effect and the orbital ground state of Cu2+ ions in Eu2CuO4 and La2CuO4 crystals

Local ion displacements and their anharmonicity in Eu₂CuO₄ and La₂CuO₄ crystals are studied by high-precision x-ray diffractometry. A symmetry analysis and the temperature behavior of the probability density function of Cu²⁺ ions reveal a degenerate ground orbital state in the Eu₂CuO₄ crystal (tetragonal doublet d _xz, d _yz). The pattern and anharmonicity of the local displacements are found to be determined not only by lattice vibrations but by 2D antiferromagnetic spin fluctuations in the CuO₂ sheet as well. By contrast, in the La₂CuO₄ crystal the orbital ground state of the Cu²⁺ ion is a singlet (d _z 2). The pattern of Eu³⁺ local displacements and their effect on the properties of the Cu subsystem in the Eu₂CuO₄ crystal are also studied. Fiz. Tverd. Tela (St. Petersburg) 39, 1600–1608 (September 1997)     

Valence fluctuations in La2−xSrxCuO4

Ab-initio electronic band structure calculations are presented for the perovskite La₂CuO₄ and for this material doped with Sr for a supercell of composition La₃SrCu₂O₈. This material is close to the high Tc superconductor La_2−xSr_xCuO₄ discovered recently. The Sr doping gives rise to strong valence fluctuations. We discuss the effect of the valence fluctuations on the stability of the lattice, indicating a small value of U and enhancing the electron-phonon coupling λ, mainly by a mechanism of incipient peroxide formation.