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.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Influence of Sr doping on the free carrier absorption in high-T c superconductors La2−x SrxCuO4

The reflectance spectra of polycrystalline La_2–x Sr _x CuO₄ samples were investigated in the energy range between 50 meV and 4 eV in dependence of the Sr content. The spectra are attributed to free carrier absorption of the Drude type, superimposed by optical phonon excitations below 0.1 eV and intrinsic absorption above 1 eV. From the influence of Sr doping onto the plasma energy it is deduced that La_2–x Sr _x CuO₄ is ap-type conductor with a maximum carrier concentration of 2.0×10²¹ cm^–3 forx=0.15. The results are interpreted in terms of a Hubbard model with an empty upper and ap-doped lower Hubbard band with a width of 1.9 eV.     

A combined SIMS-ISS study of the high-Tc superconducting compound YBa2Cu3-yAlyOx

Secondary ion yields, secondary ion-energy spectra and ion-scattering spectra for high-T _c superconducting compound YBa₂Cu_3–y Al _y O _x have been studied as a function of Al content (y = 0–0.8). In accordance with data known from literature, it was shown by Secondary-Ion Mass Spectrometry (SIMS) that Al doping of YBaCuO results in the selective substitution of Cu1 atoms with Al atoms. The correlated non-monotonic variations of the secondary-ion yield, the most probable secondary ion energy and the scattered ion yield for Y and Ba were observed with a growth of Al concentration and were explained in terms of the modification of local composition and electronic structure in the vicinity of these atoms. The kinetics of secondary-ion emission during sputtering of the original surface layer degraded under air exposure has also been measured for the YBaCuAlO samples. It was found that the ion currents ratio Ba⁺/BaOH⁺ may characterize the level of degradation and the oxygen concentration in Cul-O layers     

CNDO studies of Y-Ba-Cu-O superconductors II. Simple models of YBa2Cu3Ox

The electronic structure of YBa₂Cu₃O_x (x=6 and 7) is investigated using the CNDO molecular orbital method. Electronic structures of model clusters [Cu₃O₁₀]^–15, [Ba₈Cu₃O₁₀]⁺¹, [Y₈Cu₃O₁₀]⁺⁹ of the non-superconducting (x=6) and [Cu₃O₁₂]^–17, [Ba₈Cu₃O₁₂]^–1, [Y₈Cu₃O₁₂]⁺⁷ of the superconducting (x=7) phases are compared. Y and Ba layers cause a considerable electron density transfer from the central Cu(1) region.     

μSR and NMR investigations on electronic and magnetic state aroundx=0.12 in La2−x Sr x CuO4 and La2−x Ba x ;CuO4

The muon spin rotation ( ⁺SR) and NMR measurements provides clear evidences of the antiferromagnetic order of Cu-moment 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 freezing of spin fluctuations of Cu-moment is relevant to the local suppression of SC under an change of the electronic state coupled with the lattice instability.     

Electrostatic lattice coefficients and binding energy of orthorhombic La2-x Sr x CuO4

Three valency models for orthorhombic La_2-x Sr _x CuO₄ were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu²⁺Cu³⁺, 2. apex O^2–O^– and 3. in-plane O^2–O^–. All calculations were done by using structural parameters valid for the temperature range from 10 to 22 K. We thereby calculated the electrostatic interaction energy which, next to ionization potentials and electron affinities, comprises a major of the binding energyE _B of crystals. Second-order effects were accounted for by calculating the strength of ionic dipole moments induced by crystal electric fields at relevant lattice sites. Their largest strengths are comparable to the dipole moment of the water molecule. Three out of five dipoles in La_2-x Sr _x CuO₄ vanish during the transition from the orthorhombic to the tetragonal phase. The binding energy differences between the different models suggest that the system is in a state of model 1. However, the differences are very small, being in the order of 0.3 to 0.76 eV atx=0.13.     

Influence of octahedral tilting and composition on electrical properties of the Li0.2 − xNaxLa0.6TiO3 (0 ≤ x ≤ 0.2) series

The Rietveld analysis of ND patterns of polycrystalline Li_0.2 − xNa_xLa_0.6TiO₃ (0 ≤ x < 0.2) samples, recorded between 300 and 1075 K, shows an orthorhombic–tetragonal transformation, in which the octahedral tilting along the b axis is eliminated at ~ 773 K, but the vacancy ordering along the c axis remains. In Li rich samples, conductivity (10^− 3 Ω^− 1 cm^− 1 at 300 K) departs from the Arrhenius behaviour, decreasing activation energies from 0.37 to 0.14 eV when octahedral tilting is eliminated. Successive Maxwell–Wagner blocking processes, detected in the real part of dielectric constant plots, have been ascribed to the Li blocking at interior domains, grain-boundary and electrode–electrolyte interfaces. The substitution of Li⁺ by Na⁺ decreases the amount of vacant A-sites, decreasing several orders of magnitude the conductivity when the amount of vacancies approaches the vacancy percolation threshold (n_p = 0.27). Below the percolation threshold, Li ions only display local mobility, remaining confined into small domains of perovskites.     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.     

Electronic structures of Fe in La1−x Ba x FeO3−y (0≤x≤0.70)

Mössbauer spectra of La_1–x Ba _x FeO_3–y recorded at room temperature for various values of x show a six-line and/or a single-line subspectrum. The six-line subspectrum with IS=0.41 mm/s and H=52 T results from an orthorhombic perovskite containing only Fe³⁺ ions. The single-line subspectrum at 0.17 mm/s from a cubic perovskite can be assigned to neither Fe³⁺ nor Fe⁴⁺ but to an intermediate valence state, which may be due to electron hopping between the Fe³⁺ and Fe⁴⁺ ions on the identical octahedral sites. The temperature dependence of electron hopping in the compound La_0.40Ba_0.60FeO_3–y is presented.     

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.     

Self-assembling of C and Sn in Ge

Self-assembling of isoelectronic C and Sn impurities in Ge is predicted. The formation of the 1C4Sn tetrahedral cells is thermodynamically profitable in Ge-rich C_xSn_yGe_1−x−y (4x<y) alloys in the ultra dilute C impurity limit with 1×10^-8x1×10^-3. The concentrations of Sn atoms when all C atoms are surrounded only by Sn atoms are estimated for the lower molecular beam epitaxy, intermediate annealing and higher bulk crystallization temperatures. The origin of this phenomenon is a considerable decrease of the strain energy after self-assembling. The same self-assembling in Si is thermodynamically non-profitable due to the large cohesive energy of Si–C chemical bonds.     

EPR Study of 5-Chlorosalicylate-Cu(II)-3-Pyridylmethanol Ternary Complex Systems in Frozen Water–Methanol Solutions

Two copper(II) ternary complex systems containing 5-chlorosalicylic acid (5-ClsalH) and different copper(II) salts with varying 3-pyridylmethanol (ron = ronicol) concentration, system I [CuSO₄ (aq) +2(5-ClsalH(solv)) + xron(l)] and system II [Cu(ac)₂(aq) + 2(5-ClsalH(solv)) + xron(l)], where x = 0, 2, 4, 6 and 8, were prepared and studied by electron paramagnetic resonance (EPR) spectroscopy in frozen water–methanol solutions to observe the effects of different copper(II) salts and varying neutral ligand concentration on the formation of resulting complexes in solution. The trend in g-values (g _|| > g _⊥ > 2.0023) indicates that the unpaired electron on the copper ion is localized in the d_{x² - y²} d_{{x}^{\rm{2}} - {y}^{\rm{2}}} orbital. The detailed analysis of the second-derivative Cu(II) EPR spectra has shown well-resolved ¹⁴N superhyperfine splitting in the perpendicular part of the axially symmetric spectra. The resolution of nitrogen superhyperfine multiplet patterns increased with increase in the ronicol concentration (ligand-to-metal ratio x). The number of superhyperfine lines was found to be constant (nonet) when x > 4 for system I and x ≥ 4 for system II. This fact indicates that for these x-values four equivalent nitrogen atoms could be coordinated to the central copper atom in the equatorial plane of both systems.     

Coexistence of superconductivity and magnetism in single crystalline highT c superconductor La2−x Sr x CuO4 revealed by the muon spin relaxation method

The positive muon (⁺) spin relaxation method under zero external field is applied to probe magnetic ordering in the superconducting phase of a high quality single crystal of La_2–x Sr _x CuO₄ (0.10<x<0.15). A series of well characterized crystals with nearly complete flux exclusion were found to exhibit a magnetic ordering with transition temperature depending onx with a peak atx=0.11. Possible explanations are given.     

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)     

Impurity distribution and electrical characteristics of boron-doped Si1−x Ge x /Si p +/N heterojunction diodes produced using pulsed UV-laser-induced epitaxy and Gas-immersion laser doping

A two-step pulsed UV-laser process which independently controls the metallurgical and electrical junction depth of a Si_1–x Ge _x /Si heterojunction diode has been implemented. Pulsed Laser-Induced Epitaxy (PLIE) combined with Gas-immersion Laser Doping (GILD) are used to fabricate boron-doped heteroepitaxial p ⁺/N Si_1–x Ge _x /Si layers and diodes. Borontrifluoride is used as the gaseous dopant source in the GILD process step. Boron incorporation and activation are investigated as a function of laser energy fluence and the number of laser pulses using SIMS and Halleffect measurements. The dose of incorporated dopant is on the order of 10¹³ cm^–2 per pulse. The B profiles obtained are flat except for a peak at the interface resulting from segregation effects. The B and Ge distributions are compared with shifts in the turn-on voltage of p ⁺/N Si_1–x /Si heterojunction diodes produced by the process. The GILD/PLIE process is spatially selective with the resulting diodes fabricated being quasiplanar. Hole mobilities in the heavily doped Si_1–x Ge _x films are found to be slightly lower than in comparable Si films.Presently at the Oregon Graduate Institute, Beaverton, OR 97006, USA     

Structural, thermal and conductive properties of Bi4−xMxV2O11 (M = La, Gd; 0 x 0.4) compounds

Bi_4−xM_xV₂O₁₁ (M = La, Gd) was prepared by solid state reactions. The amount of La and Gd in the (Bi_4−xM_xV₂O₁₁) was varied in the range of (0 x 0.4). The addition of La and Gd to Bi₄V₂O₁₁ electrolyte was found to stabilize the β crystalline phase for x 0.3. In addition, the phase transition corresponding β- to γ-phases are evident in the ionic conductivity plots as well as in XRD, DSC profiles of x 0.3 samples. The highest ionic conductivity was observed in Bi_3.9La_0.1V₂O₁₁ and Bi_3.8Gd_0.2V₂O₁₁ samples in the range of 10⁻³–10⁻⁴ S/cm for 700–500 °C. These results were supported by impedance spectroscopy, X-ray diffraction (XRD) and differential scanning calorimetry (DSC).     

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.     

Electric conductance and semi-empirical studies on two thiophene derivatives/metal cation complexation

The formation constants for 1:1 Stoichiometric complexes of 2,4-diamino-3,5-dicyano thiophene (DADCT) and 2-amino cyclohexane thiophene-3-carbonitrile (ACTC) with transition metal cations (Mn⁺² , Ni^+ 2 , Cu^+ 2 , Zn^+ 2 , Cd^+ 2 , UO₂^+ 2 , La^+ 3 and Zr^+ 4 ) in 50% (V./V.) ethanol–water and methanol–water solvents have been determined conductometrically at different temperatures. A semi-empirical PM3 calculations were also used to predict the structure of the metal complex by calculating the enthalpy of formation, the geometrical parameters and Mulliken charges of the free ligands and the suggested structures of the formed complexes. The values of the different thermodynamic parameters (ΔG, ΔH and ΔS) have been obtained. The results show that the complexation reactions are all exothermic except in the case of La^+ 3-DADCT, which is endothermic reaction. The formation constant for the transition metal cations-ACTC complexes were larger than that for the transition metal cations-DADCT complexes. Also, the formation constants for all studied complexes in ethanol–water solvent were higher than that in methanol–water solvent. Using the SPSS computer program, a second order relation was found between Log k and the ionic radius (r) of the cations under investigation. The semi-empirical PM3 calculations show that there are two suggested structures of the complexation of (DADCT) with the studied metal ions.     

Charge carriers and mobility of Cu-Ti ferrite

The concentration and drift mobility of charge carriers in Cu_1–x Ti _x Fe₂O₄ ferrite are calculated, over a wide range of temperatures (300–773 K), employing d.c. conductivity and thermoelectric power data. With increasing temperature the concentration of charge carriers decreases whilst the drift mobility exhibits an exponential increase. Over the above-mentioned temperature range, the obtained density of charge carriers varies between 10²¹ and 10²² cm^–3 whereas the drift mobility has values between 10^–8 and 10^–4 cm²/V s. The results are discussed on the basis of a small-polaron hopping conduction. The activation of the d.c. conductivity has been attributed to the thermal activation of the mobility.