Effect of vacancies and interstitials on the dynamic properties of the La2−x SrxCuO4 superconductor

The effect of vacancies and interstitials in the CuO₂ layer on the vibrational spectrum in the La_2−x Sr_xCuO₄ system has been calculated by molecular dynamics. It is shown that the excitation probability for local ∼0.4-eV high-frequency vibrations of nonphonon origin in the vicinity of Sr impurity atoms decreases if copper vacancies are introduced at a concentration x=0.17, which corresponds to the maximum superconducting transition temperature, this decrease being still more effective (by about ten times) if interstitial atoms are present. The appearance of interstitials makes a considerable region around them (five to six nearest neighbors) quasi-amorphous. A comparison with available experimental data is made. It is concluded that the behavior of the system under irradiation is accounted for primarily by interstitials, which bring about strong perturbation in the lattice (∼1 nm) up to making it completely amorphous. Fiz. Tverd. Tela (St. Petersburg) 40, 984–988 (June 1998)     

Influence of interatomic forces on the lattice dynamics of YBa2Cu3O7 (molecular dynamics method)

The method of molecular dynamics is used to study the dynamic properties of the high-temperature superconductor YBa₂Cu₃O₇. It is shown in the system La_2−x Sr_xCuO₄ that, due to the presence of strong anharmonism and a substantial difference in the interatomic forces, local “hot” regions arise around the Ba⁴⁺ charge defects in the CuO₂ and CuO planes, where the mean kinetic energy of the vibrations of the oxygen atoms reaches ∼0.5 eV. All other types of defects: oxygen and copper vacancies, substitutional atoms, and charge defects, do not lead to such effects. Fiz. Tverd. Tela (St. Petersburg) 41, 1729–1733 (October 1999)     

Relation between T c and the defect structure of neodymium cerium cuprite Nd2−x CexCuO4−y

Neutron powder diffraction has been used to study the defect structure of neodymium cerium cuprite Nd_2−x Ce_xCuO_4±y (x=0.15). It has been shown that in addition to oxygen vacancies, O2 sites in superconducting samples may also contain a small quantity of implanted oxygen atoms positioned between copper ions and neodymium/cerium, which control the electrical charge in the Cu-O planes. The oxygen distribution among crystal lattice sites in Nd_2−x Ce_xCuO_4±y (x=0.15) as determined, the average charge of the copper ions was calculated by the method of valence sums, and a correlation was established between the charge of the copper-oxygen plane and T _c. Fiz. Tverd. Tela (St. Petersburg) 40, 177–183 (February 1998)     

Specific heat of the electronic superconductor Pr1.85Ce0.15CuO4

We have investigated the specific heat of the ceramic Pr_1.85Ce_0.15CuO₄ in the temperature range 2–800K in magnetic fields up to 8 T. We have determined the magnitude of the specific-heat discontinuity at the superconducting transition ΔC/T _c and estimate the coefficient of the electronic specific heat. In the temperature interval 5–800K we have separated out the phonon contribution to the specific heat, determined the temperature dependence of the characteristic Debye temperature Θ, and calculated the mean frequencies (moments) of the phonon spectrum. We compare the parameter values obtained in this way with data for the compound La_1.85Sr_0.15CuO₄ having similar crystal structure, but hole conductivity. The magnitude of the specific-heat discontinuity and consequently the effective electron mass in the “electronic” superconductor Pr_1.85Ce_0.15CuO₄ is several times smaller than in the “hole” superconductor La_1.85Sr_0.15CuO₄. The phonon spectrum in Pr_1.85Ce_0.15CuO₄ in the low-energy region is somewhat “more rigid,” and in the high-energy region somewhat “softer” than in La_1.85Sr_0.15CuO₄. Fiz. Tverd. Tela (St. Petersburg) 41, 1154–1159 (July 1999)     

Anomalies of the low-temperature specific heat of the cuprates La2CuO4 and La2−x MxCuO4 (M = Sr, Ba)

The low-temperature specific heat of the cuprates La₂CuO₄, La_2−x M_xCuO₄ (M = Sr, Ba) in the temperature interval 2–45 K has been investigated by the technique of pulsed differential calorimetry. It is found that the coefficient of the residual linear term in the specific heat remains constant in the entire experimental temperature interval. It is shown that La atoms play a special role in the formation of the anomaly, associated with the specific nature of the interaction of these atoms with their environment, in the acoustic region of the phonon spectrum of these objects near 6 meV. Fiz. Tverd. Tela (St. Petersburg) 39, 1000–1004 (June 1997)     

Nonlinear magnetic susceptibility and microwave spin dynamics of R2CuO4 quasi-2D antiferromagnets (R=Eu, Pr, Gd)

An experimental study of nonlinear ac magnetic susceptibility and microwave spin dynamics of R₂CuO₄ quasi-2D Heisenberg antiferromagnets (R=Eu, Pr, Gd) has been carried out. The data obtained can be accounted for if one assumes the existence of a random-field (RF) state in the Eu₂CuO₄ and Pr₂CuO₄ tetragonal crystals within the 77⩽T⩽350 K range covered. If this is so, 3D antiferromagnetic order persists only within limited regions, while in CuO₂ layers there are 2D Heisenberg antiferromagnetic spin fluctuations with large correlation lengths. In the Gd₂CuO₄ crystal there exists, besides uniform 3D antiferromagnetic long-range order with weak ferromagnetism, an admixture of an RF-type state. Fiz. Tverd. Tela (St. Petersburg) 41, 1437–1444 (August 1999)     

On the La2CuO4-Nd2CuO4 system: Influence of oxygen pressure on the phase diagram,oxygen stoichiometry and transport properties of the T/O and T′ type solid solutions

Abstract

Two types of solid solutions exist in the La₂CuO₄-Nd₂CuO₄ system, with respectively the T/O and T′ type structure of La₂CuO₄ and Nd₂CuO₄. When synthesized in air at high temperature and normal pressure, both solid solutions exhibit semi-conducting properties. A treatment under oxygen pressure causes a slight change in the unit cell parameters of the T/O type solid solution, a significant shift of its upper limit towards higher neodynium contents and a small increase of the average oxidation state of copper. All these modifications result from the insertion of some oxygen species in the T/O type-structure and induce a superconducting behaviour.     

Structural phase transition and structural properties in oxygenated La2CuO4+y; y ∼0.02

The crystal structure of the oxygenated La₂CuO_4+y; y ～0.02 has been studied by X-ray diffraction. It is found that the structural phase transition from tetragonal to orthorhombic symmetry occurring at about 450 K (Tc) is of second order and shows diffuse scattering above Tc. The diffuse scattering is related to static and/or dynamic short-range order of cooperative tilts of rigid-like elongated CuO₆ octahedra, which make two-dimensional networks stacked along the [001] axis. The structures at room temperature and 210K are determined using a 4-circle X-ray diffractometer and have the orthorhombic space group ¹⁰D_2h-Pccn. The structure is mainly characterized by anisotropic cooperative tilts of the CuO₄ octahedra around the [100]_p and [010]_p primitive axes in two-dimensional octahedron-networks, where suffix “p” means pseudo K₂NiF₄-type structure. The anisotropy of the tilting-angles results from pushing by excess oxygen atoms to apical oxygen atoms of the CuO₆ octahedra. It is also found by refinement of the structure that the excess oxygen atoms are randomly sited at the atomic coordinates (1/4,1/4,0.244) and/or (1/4, 1/4,0.279).     

Photopyroelectric Surface Reflectance Spectra of Pr2−xCexCuO4 Single Crystals

Abstract

Surface reflectance spectra of Pr_2?xCe_xCuO₄ (x:0; 0.025; 0.075) single crystals in the photon energy range 0.5-3 eV were determined by the photopyroelectric (PPE) technique from direct measurements of absorptance. PPE reflectance spectroscopy allows a better resolution of the structural shape of the spectra. The main spectral features of the Pr₂CuO₄ reflectance are a peak around 1.45 eV and two shoulders (around 1.1 eV and 1.85 eV). The reflectivity peak is strongly reduced even for low level of Ce doping (x:0.025) although it can still be seen as a sharp peak with the maximum around 1.5 eV. The metallic Drude-like behavior, which appears already for x:0.025, becomes evident at x=0.075, with a clear reflectivity edge around 1.05 eV.     

Theory of the electronic structure and spin susceptibility of La2−x SrxCuO4

We solve the problem of the effect of strong electron correlations on the homogeneous spin susceptibility of current carriers in CuO₂ planes. We show that the dependence of the spin susceptibility χ(T) of high-T _c superconductors of the La_2−x Sr_xCuO₄ type on temperature and the doping index x can be explained fairly well by the two-band model suggested earlier (the singlet-correlated oxygen band plus the lower Hubbard band of copper). The model has features in common with the phenomenological t-J model but cannot be reduced to the latter completely. In contrast to the t-J model, the density of states of the oxygen holes has a peak near the bottom of the band. It is the presence of this peak together with the non-Fermi-liquid properties that explain the unusual behavior of the spin susceptibility of La_2−x Sr_xCuO₄. Zh. éksp. Teor. Fiz. 112, 1763–1777 (November 1997)     

Advances in single crystal growth and annealing treatment of electron-doped HTSC

High quality electron-doped HTSC single crystals of Pr_2−xCe_xCuO_4+δ and Nd_2−xCe_xCuO_4+δ have been successfully grown by the container-free traveling solvent floating zone technique. The optimally doped Pr_2−xCe_xCuO_4+δ and Nd_2−xCe_xCuO_4+δ crystals have transition temperatures T _c of 25 K and 23.5 K, respectively, with a transition width of less than 1 K. We found a strong dependence of the optimal growth parameters on the Ce content x. We discuss the optimization of the post-growth annealing treatment of the samples, the doping extension of the superconducting dome for both compounds as well as the role of excess oxygen. The absolute oxygen content of the as-grown crystals is determined from thermogravimetric experiments and is found to be ≥ 4.0. This oxygen surplus is nearly completely removed by a post-growth annealing treatment. The reduction process is reversible as demonstrated by magnetization measurements. In as-grown samples the excess oxygen resides on the apical site O(3). This apical oxygen has nearly no doping effect, but rather influences the evolution of superconductivity by inducing additional disorder in the CuO₂ layers. The very high crystal quality of Nd_2−xCe_xCuO_4+δ is particularly manifest in magnetic quantum oscillations observed on several samples at different doping levels. They provide a unique opportunity of studying the Fermi surface and its dependence on the carrier concentration in the bulk of the crystals.     

Pressure-and doping-induced interlayer charge transfer in mercury cuprates

An analysis of the variation of site parameters has permitted determination of the interlayer charge transfer in mercury cuprates induced by pressure and incorporation of superstoichiometric oxygen and fluorine anions into HgBa₂CuO₄. It is shown that the charge transfer is governed by charge balance between the mixed-valence cations, namely, the mercury in the charge reservoir and the copper in the conducting layers. Fiz. Tverd. Tela (St. Petersburg) 40, 1980–1983 (November 1998)     

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)     

Electronic structure of high-temperature superconductors II. La-Ba-Cu-O systems

Electronic structure of La_2–x Ba _x CuO₄ superconductors has been studied. Model systems La₁₀CuO ₂₂ ^–12 , La₁₀cuO ₁₄ ⁺⁴ and La_gBaCuO ₁₄ ⁺³ with various Ba positions have been investigated using the quasirelativistic INDO molecular orbital method. The oxidation state of copper atoms corresponds to Cu(II). The influence of Ba/La substitution on copper atoms is much lower than on their oxygen ligands sphere.     

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)     

Structural investigation of high-tc superconductors under high pressure

Abstract

The results of X-ray investigations of Tl₂Ba₂Ca₂Cu₃O₁₀ show a preferential c-axis decrease under high pressure, leading to a bulk modulus of B = 1370 kbar at 300 K. The results are compared to previous investigations of La₂CuO₄, La_1.8Sr_0.2CuO₄ and Pr₂CuO₄, that show a similar linear compressibility in a- and b- axis direction. The linear compressibility in c-axis direction is dominated by the degeneration of the Cu-O octohedra and by the compressibility of intercalated layers.     

Electronic superconductor Pr2CuO4−x Fx: Magnetic correlations at high temperatures (150<T<600 K) according to 19F NMR data

The longitudinal and transverse relaxation rates of ¹⁹F nuclei in Pr₂CuO_4−x F_x (x=0.20) samples are measured at high temperatures (150 K<T<600 K). A feature is found in the temperature dependence of the relaxation rates at temperature T′≅300 K. The magnetic properties of the electronic superconductor Pr₂CuO_4−x F_x as a possible system with a stripe ordering of carriers and spins are discussed. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 4, 328–332 (25 February 1997)     

Features of the spin fluctuations and superconductivity of Tl2Ba2CaCu2O8−δ according to 63Cu and 17O NMR data

Data on the NMR line shifts, the spin-lattice relaxation rate of ⁶³Cu and ¹⁷O nuclei, and the spin-spin relaxation rate of ⁶³Cu are obtained for Tl₂Ba₂CaCu₂O_8−δ (T _c =112 K) in the normal and superconducting states. The hyperfine constants at the copper and oxygen atoms in a CuO₂ plane are estimated from an analysis of the temperature dependence of the Knight shift. The temperature-dependent behavior of the long-and short-wavelength parts of the dynamic spin susceptibility is discussed by modeling an antiferromagnetic Fermi liquid. The possible relation between the characteristics of the spin-fluctuation spectrum and the superconducting transition temperature is analyzed for the oxide investigated. Zh. éksp. Teor. Fiz. 115, 991–1001 (March 1999)     

Oxygen deficiency and superconductivity in T-, T'- and T∗-Ln2CuO4

Abstract

Effect of oxygen deficiency on superconductivity is discussed for three well-known systems, T?, T'?, and T?-Ln₂CuO₄. Although their crystal structures are closely related to each other, the oxygen-deficiency effect on superconductivity is different from system to system. In T-(La, Sr)₂CuO₄ and T?-(Nd,Ce,Sr)₂-CuO₄, oxygen defects suppress T _c while they enhance T _c in T'-(Nd,Ce)₂CuO₄. In T-(La,Ba)₂CuO₄, oxygen defects have, for x ～ 0.065, a positive effect on superconductivity as well. This positive effect is discussed related to a low-temperature structural phase transition found in the Ba-system.