Room-temperature oxidation of La2?xSrxCuO4

A series of oxidized La_2–x Sr _x CuO_4+y compounds has been prepared by treating the starting materials with a solution of Br₂ in NaOH at room temperature. The structural modifications due to the oxidation of the materials have been studied by X-ray diffraction. Some of the observed changes are: (i) a large increase in the long parameter of the unit cell for samples with Sr content and (ii) a slight decrease in a along the whole range ofx. Interesting features have been observed regarding the critical temperatures of these materials: transition temperatures are higher for those containing lower Sr amounts (some of them were even nonsuperconducting before the oxidation treatment) in contrast to materials with x0.15, whoseT _c's do not change very much. The influence of both oxygen and strontium contents on the structural modifications and the superconducting properties of the oxidized materials will be discussed.     

Experimental determination of the spatial distribution of electron defects in La2 ? xSrxCuO4 and Nd2 ? xCexCuO4 crystal lattices

The data of M?ssbauer emission spectroscopy on ⁶⁷Cu(⁶⁷Zn) and ⁶⁷Ga(⁶⁷Zn) isotopes show that holes appearing as a result of the Sr²⁺ substitution for La³⁺ in the La_{2 − x} Sr _x CuO₄ crystal lattice are localized predominantly at oxygen atoms occurring in the same atomic plane as the copper atoms. In contrast, electrons appearing as a result of the Ce⁴⁺ substitution for Nd³⁺ in the Nd_{2 − x} Ce _x CuO₄ crystal lattice are localized in the copper sublattice. These results are consistent with the model assuming that a mechanism responsible for the high-temperature superconductivity in La_{2 − x} Sr _x CuO₄ and Nd_{2 − x} Ce _x CuO₄ crystal lattices is based on the interaction of electrons with two-site two-electron centers possessing negative correlation energies (negative-U centers).     

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.     

Microscopic Scenario for x = 1/8 Anomaly in La2 ? xSrxCuO4

We adopt a t ₁-t ₂-t ₃-J-G model for explanation of x = 1/8 anomaly in La_{2 – x} Sr _x CuO₄ family compound. The calculated charge susceptibility shows a maximum near Q = (, ) at intermediate temperatures and near (, /2) as temperature approaches zero, in agreement with neutron scattering experiments. Coulomb repulsion G between the first neighbors turns out to be the source of Charge Density Waves (CDW) in narrow band t ^eff ₁, t ^eff ₂, t ^eff ₃ < G. For physically realistic hopping values we obtain the CDW amplitude e _Q = x. The in-phase domain structure as a candidate for stripe picture is proposed.     

The spin susceptibility of singlet correlated oxygen band in La2?xSrxCuO4

We have shown that the unconventional temperature dependence of the static susceptibility(T) of the perovskite high-T _c superconductors above the superconducting transition temperatureT _c can be explained in terms of two relevant band models containing the singlet-correlated oxygen band and the copper character band. The usual copper-oxygen Hamiltonian containing hopping and Coulomb repulsion terms has been reduced to an effective Hubbard-liket-t-t-U _eff model to describe the low-energy properties. The unusual behaviour of the susceptibility is due to thermally activated oxygen holes coming into the hybridization singularity peak in the density of states. A possible physical origin ofT _max in the temperature dependence of the susceptibility is discussed.     

Electronic Properties and Superconductivity of Electron-Doped La1?x/2Pr1?x/2CexCuO4

La_1−x/2Pr_1−x/2Ce _x CuO _y (LPCCO) samples with doping level up to 20% have been synthesized and their electronic and superconductive properties are studied. X-ray diffraction revealed that the LPCCO system is a pure phase system with a T’214 structure. Magnetic and resistive measurements show that the system is superconducting at 0.08≤x<0.20 with T _cmax=25 K at x=0.12. An anti-ferromagnetism transition was also observed in under-doped PLCCO (x=0.05) with the window width of the anti-ferromagnetism phase being significantly narrower than that NCCO and PCCO systems. The behavior of the Ce doping is compared with Sr doping in this system, and the mechanism is discussed.     

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.     

Growth and Accurate Characterization of Bi2Sr2?xLaxCuO6+δ Single Crystals

High-quality and various doped Bi₂Sr_2−x La _x CuO_6+δ (x=0–0.90) single crystals were obtained by floating-zone method. Analysis of the thermal behavior indicated an incongruent melt for all the doped compounds. The segregation coefficient of La related to Sr was estimated to be ∼1.02. Chemical compositions including the La doping in the crystals were accurately determined to study the effect of doping on the structural, chemical and superconducting property of the compounds. Raman spectra were performed to show the high-frequency modes 627 cm⁻¹ softened with increasing the doping level of La. Implications of the doping effect on crystals for understanding the superconductivity are discussed.     

Preparation and Magnetic Properties of?(La1?xSr1+x)(Mn0.5Co0.5)O4

A series of single phase (La_1−x Sr_1+x ) (Mn_0.5Co_0.5)O₄ (0≤x≤0.40) materials with a tetragonal K₂NiF₄ structure was prepared by a solid state reaction method at 1400 or 1450 °C with a short period of heating time. Powder X-ray diffraction (XRD) and the Rietveld refinement method were employed for the structural analysis. Unit cell a- and c-axes decrease with increasing amount of Sr substitution. A discrepancy between the zero-field-cooled and the field-cooled magnetization is observed in all samples investigated below a characteristic temperature, T ^*, which likely arises from the canted nature of spins or the random freezing of spins. It appears that T ^* decreases with increasing amount of Sr substitution, which is possibly due to the enhancement of chemical pressure induced by Sr and a corresponding increases of the valence of Mn and/or Co.     

Preparation, characterization and conductivity studies of Li3?2xAl2?xSbx(PO4)3

New NASICON type materials of composition, Li_3−2x Al_2−x Sb _x (PO₄)₃ (x = 0·6 to 1·4), have been prepared and characterized by powder XRD and IR. D.C. conductivities were measured in the temperature range 300–573 K by a two-probe method. Impedance studies were carried out in the frequency region 10²−10⁶ Hz as a function of temperature (300–573 K). An Arrhenius behaviour is observed for all compositions by d.c. conductivity and the Cole-Cole plots obtained from impedance data do not show any spikes on the lower frequency side indicating negligible electrode effects. A maximum conductivity of 4·5 × 10⁻⁶ S cm⁻¹ at 573 K was obtained for x = 0·8 of the Li_3−2x Al_2−x Sb _x (PO₄)₃ system.     

Magnetic and dielectric properties of Mg1+x Mnx, Fe2?2x, O4 ferrite system

Ferrites with the general formula Mg_1+xMn_xFe_2–2xO₄(where x = 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared by the standard ceramic technique and studied by means of X-ray diffraction, magnetization, a.c. susceptibility and dielectric constant measurements. The X-ray analysis confirmed the single-phase formation of the samples. The lattice parameter is found to increase up to x = 0.3 and thereafter it decreases as x increases. The cation distribution has been studied by X-ray analysis and magnetization. Magnetization results exhibit collinear ferrimagnetic structure for x 0.3 and thereafter structure changes into non-collinear for x > 0.3. Curie temperature (T_C) obtained from a.c. susceptibility data decreases with increasing x. The dielectric constant (), loss tangent (tan ) show strong frequency dependence.     

Phase Separation in La2CuO4+δ by electrical transport measurements

The dc conductivity and the high-frequency capacitance of a La₂CuO₄₊ single crystal are determined by impedance spectroscopy in the frequency range 20 Hz to 1 MHz at liquid helium temperature. Using isochronal annealing, the effect of the phase separation on these quantitites is studied for E parallel and perpendicular to the CuO₂ planes as well as for different oxygen doping levels,, of the sample. The results are consistent with the model of a diffusion-controlled formation of a metallic—and belowT _c superconducting—percolation network in an insulating background.     

X-ray diffraction study of multicomponent oxides in the Zn2 ? x(TiaZrb)1 ? xFe2xO4 system

The multicomponent refractory oxide system Zn_{2 − x} (Ti _a Zr _b )_{1 − x} Fe_2x O₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 4: 1; x = 0–1.0; Δx = 0.05) has been studied by X-ray diffraction, using samples prepared by melting appropriate metal oxide mixtures in a low-temperature hydrogen-oxygen plasma. Two phases, both with wide homogeneity ranges, have been identified: α-phase, with a cubic inverse spinel structure, and β-phase, with a tetragonal inverse spinel structure. The phase boundaries in the system have been determined. Structural data are presented for about 100 solid solutions.     

Griffiths Phase and Disorder in Perovskite Manganite Oxides La1?xCaxMnO3 and La0.7Sr0.3MnO3

Polycrystalline samples La_1−x Ca _x MnO₃ (x=0.17, 0.15, 0.10) and La_0.7Sr_0.3MnO₃ were prepared in order to investigate the Griffiths-like features induced by disorder compared with their counterpart single crystals. The magnetization data exhibit the traditional transition from ferromagnetic phase to paramagnetic phase. From the temperature dependence of inverse susceptibility, it can be testified that the Griffiths-like features still exist in as-prepared Ca doped samples, while non-Griffiths-like features exist in La_0.7Sr_0.3MnO₃. All these samples, however, exhibit the large effective spins resulting from formation of the short-order ferromagnetic clusters. The O K-edge X-ray absorption spectra indicate the Jahn–Teller (J-T) distortions are definitely present due to the J-T ion Mn³⁺, which indicate that static J-T distortion is not a sufficient condition for the existence of Griffiths phase in Sr-doped system. And, the size of J-T distortion is a little larger in polycrystalline La_0.7Sr_0.3MnO₃ than that in polycrystalline samples La_1−x Ca _x MnO₃ (x=0.17, 0.15, 0.10), revealed by X-ray diffraction parameters and extended X-ray fine structure absorption data of Mn K-edge. It also testifies that the disorder in La_0.7Sr_0.3MnO₃ caused by both chemical doping and J-T distortions is lower than that in polycrystalline samples La_1−x Ca _x MnO₃, which may be the reason of non-Griffiths-like phase existing in La_0.7Sr_0.3MnO₃ samples.     

Investigation of the quasi-ternary system LaMnO3–LaCoO3–“LaCuO3”. II: The series LaMn0.25?xCo0.75?xCu2xO3?δ and LaMn0.75?xCo0.25?xCu2xO3?δ

This paper investigates the crystal structure, thermal expansion, and electrical conductivity of two series of perovskites (LaMn_0.25−x Co_0.75−x Cu_2x O_3−δ and LaMn_0.75−x Co_0.25−x Cu_2x O_3−δ with x = 0, 0.025, 0.05, 0.1, 0.15, 0.2, and 0.25) in the quasi-ternary system LaMnO₃–LaCoO₃–“LaCuO₃”. The Mn/Co ratio was found to have a stronger influence on these properties than the Cu content. In comparison to the Co-rich series (LaMn_0.25−x Co_0.75−x Cu_2x O_3−δ), the Mn-rich series (LaMn_0.75−x Co_0.25−x Cu_2x O_3−δ) showed a much higher Cu solubility. All compositions in this series were single-phase materials after calcination at 1100 °C. The Co-rich series showed higher thermal expansion coefficients (α_max = 19.6 × 10⁻⁶ K⁻¹) and electrical conductivity (σ_max = 730 S/cm at 800 °C) than the Mn-rich series (α_max = 10.6 × 10⁻⁶ K⁻¹, σ_max = 94 S/cm at 800 °C). Irregularities in the thermal expansion curves indicated phase transitions at 150–350 °C for the Mn-rich series, while partial melting occurred at 980–1000 °C for the Co-rich series with x > 0.15. I. Arul Raj—on leave from Central Electrochemical Research Institute, Karaikudi, 630006 India.     

Superconducting Properties of Carbon and Zn Double-doped Mg1?xZnx(B1?xCx)2

A series of polycrystalline samples of Mg_1−x Zn _x (B_1−x C _x )₂ (x=0.00, 0.02, 0.04, 0.06, 0.08, and 0.10) were synthesized by a conventional solid-state reaction method under a background pressure about 10⁻³ Pa. Phase identification, crystal structure and superconducting transition temperature (T _c) were studied by means of X-ray diffraction (XRD) and resistivity measurements. The results indicated that the lattice parameters a and c show no clear trend in their changes with increasing doping level, and it turned out that the dopants had a marked effect on the crystal-lattice parameters and changed the crystal structure of the samples. The T _c for Mg_1−x Zn _x (B_1−x C _x )₂ decreased with C and Zn doping, but the rate of decrease was slower than single C-doped. We propose that the suppression of T _c by doping originates largely from the structural change.     

Cation mobility in Li1 + xTi2 ? xCrx(PO4)3 NASICON-type phosphates

Li_{1 + x} Ti_{2 − x} Cr _x (PO₄)₃ NASICON-type materials have been prepared and characterized by X-ray diffraction, scanning electron microscopy, and impedance spectroscopy. The results demonstrate that Cr³⁺ doping increases the ionic conductivity of LiTi₂(PO₄)₃ within the single-phase region of the doped material, which extends to x = 0.7. From temperature-dependent ionic conductivity data, the activation energy for lithium transport through interstitial sites and the enthalpy of defect formation in LiTi₂(PO₄)₃ are estimated at 30.0 ± 0.5 and 56 ± 1 kJ/mol, respectively.     

Electrical and magnetic properties of the diluted magnetic semiconductors Cd1 ? xMnxGeP2 and Cd1 ? xMnxGeAs2 at high pressures

The structural and magnetic phase transitions and magnetoresistance of the diluted magnetic semiconductors Cd_{1 − x} Mn _x GeAs₂ and Cd_{1 − x} Mn _x GeP₂ have been studied at high hydrostatic pressures, up to 7 GPa. The normal and anomalous Hall coefficients of the samples have been determined graphically from experimental data.     

The Anomalous Optical Conductivity of Metallic La2?xSrxCuO4

The in-plane optical conductivity of three metallic La_2–x Sr _x CuO₄ single crystals with 0.10 x 0.15 has been studied between 30 and 295 K. Strong peaks in the far-infrared are observed, which cannot be explained by Drude-like models. Their similarity with peaks reported in Cu–O ladders with one-dimensional charge-ordering, their extremely low frequency, and their behavior with temperature allows us to conclude that those anomalous features are excitations of charge stripes in the Cu–O planes.