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.     

Crystal structure of the superconducting infinite-chain cuprate Ba2Cu2.89O6−y

The orthorhombic structure of Ba₂Cu_2.89O_6−y (sp. gr. Pccm, a=13.065(15), b=20.654(21) and c=11.431(8) Å) contains two nonintersecting symmetrically equivalent sets of parallel CuO₂-chains running along [110] and [1̄10] directions. Along the c-axis the Cu–O sheets are separated by identical layers of Ba-atoms. The Cu–O chains are distorted within the xy plane producing zigzag. Three of 14 positions of copper atoms were found to be partly vacant that caused the significant shifts of the neighbouring Ba atoms in the plane. The determined structure of Ba₂Cu_2.89O_6−y is compared to that of the monoclinic Ba₂Cu₃O₆ modification, of another infinite-chain compound Sr_0.73CuO₂, and to one of the substructures of ladder compounds (Sr,Ca)₁₄Cu₂₄O_41+y. The superconductivity in Ba₂Cu_2.89O_6−y is associated with the CuO₂-chains consisting of CuO₄-squares sharing edges. The attention is paid to the coincidence of the temperatures of the superconducting transitions in Ba₂Cu_2.89O_6−y and in ladder compound with the temperature of the sharp magnetic transition in another infinite-chain compound Sr_0.73CuO₂.     

ELECTRONIC STRUCTURE OF THE T*-TYPE SUPERCONDUCTORS (Bi0.5Sr1.5)(Y, Ce)2Cu2Oy STUDIED BY PHOTOELECTRON SPECTROSCOPY

The electronic structure of T^*-type compounds (Bi_0.5Sr_1.5)(Y_2-xCe_x)Cu₂O_y has been studied by X-ray photoelectron spectroscopy. From analysis of the results, it was found that cation deficiency in Ce⁴⁺ introduced holes to conduction planes in the T^* phase as in the p-type infinite layer compounds. Some Cu ions in the sample without cation-deficiency contained two-oxygen coordination, which resulted in the incompleteness of the CuO₂ sheets. Bi ions in the T^* phase cuprates take exact valence of 3_{+, Pb ions cannot replace them due to the too large an ionic radius of Pb²⁺/Pb⁴⁺.}     

Superconductivity at 40 K in La1.8Sr0.2CuO4

High-T _c superconductivity withT _c onsets up to 42 K (midpoint: 37 K, zero resistance: 34 K) is observed in X-rays homogeneous single phase La_1.8Sr_0.2CuO₄. The quarternary compounds La_2–x Ba _x CuO₄ and La_2–x Sr _x CuO₄ (0x0.3 for Ba and 0x<1 for Sr, depending on the heating conditions) are mixed-valence oxygen defect oxides, characterized by the presence of Cu²⁺ and Cu³⁺ simultaneously. These oxides have a tetragonal symmetry (space group:I 4/mmm) similar to that of K₂NiF₄. We report the synthesis, characterization, and superconducting properties of various high-temperature superconducting La–Ba–Cu–O and La–Sr–Cu–O compounds. Through the substitution of Sr for Ba in these oxygen defect compounds an increasing superconducting transition temperature onset from 28 K to 35 K for La_1.8Sr_0.1Ba_0.1CuO₄ was observed. A positive initial pressure coefficient ofdTc/dp=290 (mK/kbar) has been found for La_1.8Sr_0.2CuO₄ with a magnetic susceptibility change consistent with the 100% diamagnetic expectation value.     

Two-dimensional quantum interference contributions to the magnetoresistance of Nd2−x CexCuO4−δ single crystals

Two-dimensional (2D) weak localization effects at low temperatures T=0.2–4.2 K are investigated in a nonsuperconducting sample Nd_1.88Ce_0.12CuO_4−δ and in the normal state of a superconducting sample Nd_1.82Ce_0.18CuO_4−δ for B>B _c2≃3 T. The phase coherence time τφ (≃5×10⁻¹¹ s at 1.9 K) and the effective thickness d of a conducting CuO₂ layer (≃1.5 Å) are estimated by fitting the expressions from the 2D weak localization theory to the magnetoresistivity data for the normal-to-plane and in-plane magnetic fields. The estimated value of the parameter d ensures the condition of strong carrier confinement and justifies a model of almost decoupled 2D metallic sheets for the Nd_2−x Ce_xCuO_4−δ single crystals. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 2, 93–99 (25 July 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Electrical resistivity of some La-Sr-Nb oxides to 77 K

The electrical resistivity of compounds having compositions LaSr₂Nb _x ,O _y LaSrNb _x O _y , and La₂SrNb _x O _y , prepared by arc melting under argon atmosphere, is determined from 77 to 300 K. Low resistivity compositions are found in these systems for x > 2 and niobium in divalent state. None of the compounds investigated showed large resistance drop reported by Oguchi et al. (1987) in La-Sr-Cu-O compounds prepared by sputtering La₂CuO₄ on niobium substrate and attributed to possible superconductivity about 250 K.     

Synthesis and electrical properties of Ln<Subscript>2</Subscript>CuO<Subscript>4+</Subscript><Subscript><Emphasis Type="Italic">δ</Emphasis></Subscript> (Ln: Nd or La) mixed conductor sputter deposited coatings

Nd₂CuO₄ and La₂CuO₄ are potential candidates as cathode material for intermediate temperature-solid oxide fuel cells. Nd–Cu and La–Cu oxides were co-sputtered on rotating substrates from metallic La, Nd and Cu targets in the presence of a reactive argon–oxygen gas mixture. Structural and chemical features of these films have been determined by X-ray diffraction and energy-dispersive spectroscopy. Their electrical resistivity was measured using the four-point probe method. As-deposited Nd–Cu based coatings are amorphous and, after annealing, crystallise in K₂NiF_{4+ δ} -type structure for Nd/Cu atomic ratio of 2, with more or less Nd₂O₃ or CuO, depending on whether Nd or Cu is in excess, respectively. As-deposited La–Cu based coatings are also amorphous and crystallise in La₂CuO₄ for La/Cu >2 or in LaCuO_3±δ perovskite-type structure when Cu is in excess. The electrical measurements show a clear relation between resistivity and structure of the coatings. After annealing, crystallised neodymium-based coatings show higher resistivity than lanthanum-based ones. Finally, LaCuO_3±δ exhibit higher resistivity than La₂CuO₄. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Microphase separation and magnetic Jahn-Teller polarons in LaSrAl1−xCuxO4−δ

An EPR study of the solid solutions LaSrAl_1−x Cu_xO₄, which are isostructural to La₂CuO₄, shows that microphase separation of the structure occurs already at small copper concentrations (x≈0.01). A phase enriched with Cu appears along with a phase of La₂AlO₄, which contains isolated CuO₆ centers. It is established that the nature of the states and the deformations of the CuO₆ centers is determined by internal Jahn-Teller factors. When x⩽0.1, EPR signals are detected for new dynamic centers, which are identified as CuO₆ Jahn-Teller centers with a hole delocalized among the four in-plane oxygen ions (the total spin S=1). When 0.1⩽x<1, local CuO ₆ ⁻ hole centers transform into magnetic Jahn-Teller polarons, which include five or more CuO₆ fragments, in the copper phase of the structure. Their transformations and the conditions for observing them are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 622–628 (April 1998)     

La2-xNdxCuO4+δ(0.1≤x≤1.2)体系中滞弹性弛豫与相变内耗研究

通过对La_2-xNd_xCuO_4+δ(0.1≤x≤1.2)体系中滞弹性弛豫与相变内耗性能的研究发现,当0.1≤x≤1.0时,在250K左右存在一个与间隙氧有关的弛豫内耗峰,并且当0.1≤x≤0.4时,弛豫内耗峰峰高随着x值的增大而升高,此时体系为正交结构;当0.5≤x≤1.0时,体系在宏观上呈现四方结构,此时内耗峰峰高随着x< 关键词： 2-xNd_<i>xCuO_4+δ')" href="#">La_2-xNd_<i>xCuO_4+δ 间隙氧 弛豫内耗峰 相变内耗峰     

Copper NQR study of the La 214 system from an aspect of microscopic environment of copper

The nuclear quadrupole resonance (NQR) has been investigated for Cu in La_2–x A _x CuO _y (A=Sr and Ba). Three Cu NQR lines, A, B and C, have been observed, which correspond to three different Cu sites. From the analysis of these NQR intensities, site assignments are possibly as follows. These lines A, B and C are attributed to CuO₆ octahedral, CuO₅ pyramidal and CuO₄ planar sites, respectively. The apical oxygen O(2) is induced to transfer to the interstitial O(3) site between LaO planes when two or more Sr²⁺ ions are located in its neighboring La sites. The excess holes doped into the CuO₂ plane are provided mainly by O(3) as well as the unpaired Sr²⁺ ion.     

Alternate structure for Ba2YCu3O7

Based of known structural frameworks of oxygen-deficient perovskites, an alternate structure for Ba₂YCu₃O₇ is proposed. It is compatible with the X-ray data of that phase. The lattice is made up of perovskite layers of corner-sharing CuO₆ octahedra interlinked with corner-sharing square-planar CuO₄ units. The proposed structure makes the class of high-T _c superconductors with perovskite-related structures more consistent.     

New phases in the most basic zone of the system Ba−Cu−O

Summary In the most basic part of the binary system BaO−CuO two new compounds were identified corresponding to the Ba₂CuO₃ and Ba₃CuO₄ formulae. Another more oxidized phase of composition Ba₂CuO_3+δ was also obtained, which can exist in two crystalline modifications. For all these new substances the structural type and the lattice parameters are reported.     

Magnetism in electron-doped copper oxides

We report muon spin relaxation/rotation measurements on sintered powder samples of Nd_2−x Ce _x CuO_4−y and a large single crystal of Nd₂CuO_4−y . We find an electronic phase diagram which is quite similar to that of hole-doped superconductors such as La_2−x Sr _x CuO_4−y , although the doping of electrons into the system is less efficient in destroying the static moments on the copper spins. Static magnetic order in Nd₂CuO_4−y appears below about 250 K, and two spin reorientations are seen atT=75 K andT=35 K. Measurements of the magnetic field penetration depth have been unsuccessful due to the rare-earth paramagnetism of these materials.     

Workshop on fast structural changes

Copper-oxide (cuprate) high-temperature superconductors are doped Mott insulators. The undoped parent compounds are antiferromagnetic insulators, and superconductivity occurs only when an appropriate number of charge carriers (electrons or holes) are introduced by doping. All cuprate materials contain CuO₂ planes (Figure 1a) in their crystal structure; the doped carriers are believed to go into these CuO₂ planes, which are responsible for high-temperature superconductivity. High-temperature superconductors are characterized by their unusual physical properties, both in the superconducting state (below the superconducting transition temperature T_c) and in the normal state (above T_c). Since the discovery of high-temperature superconductivity in 1986 [1], these unusual physical properties and the mechanism of superconductivity have been prominent issues in condensed matter physics [2].     

Photoemission investigation of the high temperature superconductors La2−x Sr x CuO4

Photoemission spectra of the La_2–x Sr _x CuO₄ system which recently has been demonstrated of being capable to produce high temperature (T _c >35 K) superconducting compounds are reported. The photoemission spectra of the basic system (La₂CuO₄) and of samples which contain up to 20% Sr are not significantly different. The density of states at the Fermi energy is small (smaller than that of metallic Cu) and the samples show a possible small shift of the Cu 2p lines towards the trivalent position with increasing tendency to superconductivity. From the Sr 3d spectra a considerable amount of oxygen defects coordinated to the Sr ions is estimated.     

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)     

Electronic phase separation in a low-temperature tetragonal phase of lanthanum-strontium cuprates according to 139La NQR data

A nonuniform electron density distribution is observed in La_{1−x− y} Nd_ySr_xCuO₄ and La_1−x−y Eu_ySr_xCuO₄, and long-lived magnetic fluctuations in these compounds are studied. The dynamics of the magnetic fluctuations depends strongly on the magnetic properties of the rare-earth ions, which stabilize the low-temperature tetragonal phase. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 5, 344–349 (10 March 1998)     

Competition of magnetic order and superconductivity investigated by positive muon spin rotation in La2−x M x CuO4 (M = Ba,Sr) aroundx=0.12

Muon spin rotation (SR) is applied to La_2–x Ba _x CuO₄ aroundx=0.12 where the superconductivity (SC) is suppressed remarkably. The magnetic ordering of Cu-moments appears below 35 K in the narrow range ofx where a lattice instability from the low temperature orthorhombic (LTO) to the low-temperature tetragonal (LTT) structure exists. The present study suggests strongly that the magnetic ordering of Cu-moments is an important factor in the suppression of high-T _c superconductivity aroundx=0.12 in La_2–x Ba _x CuO₄. Similar results are obtained for the La_2–x Sr _x CuO₄ and La_2–x–y Sr _x Nd _y CuO₄ systems.     

Charge Carrier Dynamics in Zn-Doped Cuprates

We have measured the static magnetic susceptibility, the resistivity and muon spin relaxation (⁺SR) spectra of Zn and Sr doped La₂CuO₂. Our data show that non-magnetic Zn impurities lead to an increase of the Néel temperature T _N in weakly hole doped compounds. This increase of T _N correlates with an increase of the resistivity. The analysis of our data strongly suggests that the hole mobility is the most important source for the strong suppression of long range antiferromagnetic order in La_2–x Sr _x CuO₄.