Effect of nominal copper concentration in YBa2Cu3±x O7−δ on the superconducting transition

Variation of the copper concentration in the nominal composition YBa₂Cu_3±x O_7−δ markedly influences the superconducting transition. The transition occurs at the highest temperature with lower width, whenx = +0·25. Communication No. 82 from Materials Research Laboratory.     

Relation between highT c superconductivity and structure: A study of Ba3+x Cu6O14+δ and YBa2Cu3O7−δ systems

Superconductivity is found in tetragonal La_3−x Ba_3+x Cu₆O_14+δ and La, Ba)_6−x Sr _x Cu₆O_14+δ even though they do not possess Cu-O chains or the K₂NiF₄ structure. Resistivity measurements confirm the occurrence of a transformation from chain-superconductivity to sheet-superconductivity in YBa₂Cu₃O_7−δ as δ is varied in the range 0.0–0.5. Contribution No. 481 from the Solid State and Structural Chemistry Unit     

Orthorhombic structure: a necessity in superconducting 1-2-3 compounds

X-ray and resistivity measurements on YBa₂Cu₃O_7−δ (1-2-3) samples show that for the same but low oxygen concentration,δ⋍0·55, no superconducting transition down to 4·2 K is observed for the tetragonal phase samples while the orthorhombic phase shows aT _c ∼ 31 K. The effect of oxygen concentration onT _c is isolated.T _c=91±1 K has, however, been observed continuously for the normal oxygen annealed samples,δ⋍0·07. The experimental results suggest strongly the necessity of the 1-2-3 compound to be in the orthorhombic phase for the superconducting mechanism to be operative.     

Effect of Zr,Ti substitutions onT c in superconducting YBa2Cu3O7−δ system

Zr and Ti have been substituted in the system Y_1−x M _x Ba₂Cu₃O_7−δ(M=Zr, Ti,x=0.05,0.1). We find that theT _c value is unchanged, ∼90K for Zr substitutions up to 10% and in the case of Ti substitutions theT _c drops significantly. These changes may arise from their site preference.     

Studies of synthesizing behaviors and superconductivity of sol-gel YBa2Cu3O7-x samples in flowing oxygen atmosphere

Systematic studies of synthesizing behaviors of sol-gel YBa₂Cu₃O_7−x samples in flowing oxygen atmosphere and their superconductivity have been performed. A set of high temperature ρ-T curves has been obtained for the whole synthesizing process. After four rounds of synthesizing, the resistivity of the sample was around ρ=1.00×10⁻³Ω · cm at room temperature. The ρ-T curve of the fourth round shows that the orthorhombic to tetragonal phase transformation of the sample occurs around 600 °C, which is lower than that of the YBa₂Cu₃O_7−x sample prepared by conventional solid-state reaction method. Other measurements, such as X-ray diffraction, SEM measurement and low temperature R-T and M-T measurement, were also performed. And the R-T and M-T measurement results suggest that during the synthesizing process, there exist some state at which the sample has better superconductivity than the other states. Moreover, we found screw dislocations presenting on the sample broken surface from the SEM images. This will change the concept that the screw dislocations can only grow on the surface of the YBCO thin films and single crystals.      

Effect of substrate temperature on electrical and magnetic properties of epitaxial La1−x Pb x MnO3 films

Epitaxial La_1−x Pb _x MnO₃ (LPMO) thin films, grown on (100) SrTiO₃ substrates by laser ablation technique at different temperatures between 600 and 850°C, have been characterized for electrical and magnetic properties. The temperature dependence of resistivity showed that the metal-insulator transition temperature (T _MI) decreases with increasing substrate temperature, which has been attributed to decrease in Pb content in the filsm. The YBa₂Cu₃O _x /La_1−x MnO₃ heterostructures, exhibiting both superconductivity and ferromagnetism, have been fabricated.     

Structural studies and T c dependence in La2−x Dy x Ca y Ba2Cu4+y O z type mixed oxide superconductors

A new series of mixed oxide superconductors with the stoichiometric composition La_2−x Dy _x Ca _y Ba₂Cu_4+y O _z (x=0.0 − 0.5, y=2x) has been studied for structural and superconductiong properties. Our earlier studies on La_2−x (Y/Er) _x Ca _y Ba₂Cu_4+y O _z series, show a strong dependence of T _c on hole concentration (p _sh). In the present work, the results of the analysis of the neutron diffraction measurements at room temprerature on x=0.3 and 0.5 samples are reported. It is interesting to know that Ca substitutes for both La and Ba site with concomitant displacement of La onto Ba site. Superconductivity studies show that maximum T _c is obtained for x=0.5, y=1.0 sample (T _c ∼ 75 K), for La_1.5Dy_0.5Ca₁Ba₂Cu₅O _z (La-2125).     

On the addition of silver to highT c (Y1Ba2Cu3O7−x ) superconductor

The superconducting transition temperature of the highT _c compound Y₁Ba₂Cu₃O_7−x does not show degradation consequent upon the addition of metallic silver up to a concentration of 60 wt per cent. The X-ray diffraction data confirm that the oxygen deficient distorted orthorhombic perovskite structure of the pure compound stays intact as if silver does not enter the crystal lattice. SEM studies do show the presence of silver at the grain boundaries only. Silver is found to restrict the grain growth.     

Physicochemical properties of LiAl x Mn2 − x O4 and LiAl0.05Mn1.95O4 − y F y cathode material by the citric acid-assisted sol–gel method

LiAl _x Mn_2 − x O₄ and LiAl_0.05Mn_1.95O_4 − y F _y spinel have been successfully synthesized by citric acid-assisted sol–gel method. The structure and physicochemical properties of this as-prepared powder were investigated by electronic conductivity test, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge test in detail. The electronic conductivity decreases with increasing of the content of doped Al. XRD patterns show that the diffraction of LiAl_0.05Mn_1.95O_4 − y F _y samples is similar, with all the peaks indexable in the Fd3m space group, and a little impurity appears in the LiAl_0.05Mn_1.95O_3.8F_0.2 sample. SEM reveals that all LiAl_0.05Mn_1.95O_4 − y F _y powders have the uniform, nearly cubic structure morphology with narrow size distribution which is less than 500 nm. Galvanostatic charge–discharge test indicates that LiAl_0.05Mn_1.95O₄ has the highest discharge capacity and electrochemical performance among all LiAl _x Mn_2 − x O₄ samples after 50 cycles, and the initial discharge capacity of LiAl_0.05Mn_1.95O_4 − y F _y (y = 0, 0.02, 0.05, 0.1) is 123.9, 124.6, 124.9, and 125.0 mAh g⁻¹, respectively, and their capacity retention ratios are 94.2%, 94.9%, 91.7%, and 89.9% after 50 cycles, respectively. EIS indicates that LiAl_0.05Mn_1.95O_3.98F_0.02 have smaller charge transfer resistance than that of LiAl_0.05Mn_1.95O₄ corresponding to the extraction of Li⁺ ions.     

Effect of substitution of Ce on superconducting properties of Bi1.7Pb0.3Sr2Ca2−x Ce x Cu3O10+δ system

We have investigated the superconducting properties of the Bi_1.7 Pb_0.3Sr₂Ca_2−xCe _x Cu₃O_10+δ system with x=0.00, 0.02, 0.04, 0.08 and 0.1 by X-ray diffraction and magnetic susceptibility. The substitution of Ce for Ca has been found to drastically change the superconducting properties of the system. X-ray diffraction studies on these compounds indicate decrease in the c-parameter with increased substitution of Ce at Ca site and volume fraction of high T _c (2 : 2 : 2 : 3) phase decreases and low T _c phase increases. The magnetic susceptibility of this compound shows that the diamagnetic on set superconducting transition temperature (onset) varies from 109 K to 51 K for x=0.00, 0.02, 0.04, 0.08 and 0.1. These results suggest the possible existence of Ce in a tetravalent state rather than a trivalent state in this system; that is, Ca²⁺ → Ce⁴⁺ replacement changes the hole carrier concentration. Hole filling is the cause of lowering T _c of the system.     

Colossal magnetoresistance in layered manganite Nd2−2x Sr1+2x Mn2O7 (0 ≤ x ≤ 0.5)

The layered manganite Nd_2−2x Sr_1+2x Mn₂O₇, with x varying between 0 and 0.5, has been synthesized using solid-state reaction method. We have found that Nd_2−2x Sr_1+2x Mn₂O₇ do not form the single-phase layered compound with A₃B₂O₇ structure. Instead, mixtures of various phases, such as, orthorhombic perovskite, i.e., Nd_1−z Sr _z MnO₃, layered manganite and unreacted starting compounds, have been obtained. Except for x=0.4, which is found to be an antiferromagnetic insulator, all other x values yielded metal-insulator transition and ferromagnetic ordering.     

Characterisation of Ba2In2 − x Sn x O5 + x/2 oxide ion conductors

The Ba₂In_2 − x Sn _x O_5 + x/2 solid solution was confirmed up to x = 1 by solid-state reaction. X-ray diffraction at room and at elevated temperatures, Raman scattering and impedance spectroscopy were used to characterise the samples. The structure refinement of the composition x = 0.1 from neutron diffraction data reveals that tin is preferentially located in the tetrahedral layers of the brownmillerite. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007     

Kinetics of oxygen desorption in Y Ba2Cu3O7-δ

In this paper the kinetics of oxygen desorption from Y Ba₂Cu₃O_7-δ has been investigated and measurements carried out in the temperature range 350–750 C. It is shown that the oxygen desorption is diffusion-controlled (and not surface-controlled), and characteristic of diffusion from small grains in a loosely coupled porous matrix. At every temperature a number of time constants with well-defined ratios appear and have been identified and measured. These time constants can be related to the average bulk diffusion constant which shows an Arrhenius behaviour with deviations around 750°C which are ascribed to the well-known orthorhombic to tetragonal transition. In this paper we establish the basic underlying physical mechanism of oxygen desorption in Y Ba₂Cu₃O_7-δ.     

μ− SR studies of oxide-superconductorsSR studies of oxide-superconductors

The negative muon spin rotation method (μ⁻ SR) has been applied to studies of electronic states at oxygen sites of oxide superconductors YBa₂Cu₃O₇, Nd_2−x Ce _x CuO_4−δ (x=0.15, oxygen reduced), LiTi₂O₄ and related oxide-insulators La₂CuO_4−δ, CuO, Cu₂O. The paramagnetic shifts of μ⁻ trapped at oxygen nuclei in these polycrystalline powder samples have been measured at 300 K. All the measured shifts are positive. In copper-oxides the paramagnetic shifts are of the order 10⁻³, while in LiTi₂O₄ is very small (8.4±3.34×10⁻⁵). In YBa₂Cu₃O₇, a fast μ⁻ spin relaxation timeT ₂ ^* (∼ 200 ns) has been observed; the reason for this is unknown and further studies are now in progress.     

Optical and electrical characteristics of (LiCl) x (P2O5)1 − x glass

Homogeneous (LiCl) _x (P₂O₅)_1 − x glasses were synthesised using a melt-quenching method for x = 0.1–0.6 in the interval of 0.05. The amorphous structure of the samples was evident by the X-ray diffraction spectrum. The short range structures of the binary phosphate samples were examined by Fourier transform infrared spectroscopy, whilst the density of the samples was measured as supportive data for the investigations. The results of refractive indices as measured using an ellipsometer reveal the homogeneity of samples and was found to depend on the glass composition. The electrical properties of the glasses were investigated by ac impedance spectroscopy from 10 mHz to 1 MHz for temperatures ranging from room temperature to 573 K. An estimation of the bulk resistivity was obtained by taking the intercepts on the real axis at low frequencies of the complex impedance plot. The dc conductivities derived from the reciprocal of resistivity values were found to obey the Arrhenius relationship, and its activation energy shows a decreasing trend with the increase in LiCl content in the glass. Lastly, an equivalent circuits consisting of real and complex capacitors is proposed to describe the dielectric response of the glass.     

Effect of Ca doping on the superconducting properties of GdBaSrCu3O7−δ bulk samples

Gd_1−xCa_xBaSrCu₃O_7−δ samples (0  x  0.1) were prepared via solid-state reaction. Four-point probes method was used for resistance versus temperature measurements. Results show decrease in T_c by increasing x content. This variation is assumed to be irrelevant to the different phases or impurity effects since X-ray patterns show all samples are tetragonal single-phase. Ca doping decreases the oxygen content and lattice parameters of the samples. It is suggested that Ca prevents the dislocation of oxygen, and then disrupts the hole concentration of the system and antiferromagnetic correlation at CuO₂ planes. Subsequently, destroys the superconductivity of the samples.     

Surface morphology of PrBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> single crystals after the long-lasting high-temperature reduction

The results of the detailed scanning electron microscopy study of PrBa₂Cu₃O_7-δ single crystals after the long-lasting high-temperature post-growth treatment are reported. The presence of the unstable decomposition products on the crystal surface indicates that the onset of superconductivity must be related to the structural transformations in the bulk (approximately 20% of the total volume of the examined crystals). The time-dependent character of the superconductivity in the Pr-123 crystals could be attributed to the migration of defects in the Pr−Ba sublattice from the bulk toward the surface.     

Metal-insulator transition in electron-doped Ba1−x La x MnO3 compounds

Electron-doped (Ba_1−x La _x )MnO₃ compounds were prepared for x=0−0.5. Measurements of X-ray diffraction (XRD) at room temperature and temperature variation of dc electrical resistivity down to 20 K were carried out. Samples with x=0.2–0.5 exhibit metal-insulator (M-I) transition. The maximum M-I transition temperature (T _c) of 289 K was observed for 30% of La doping (x=0.3). XRD patterns of these samples (x=0.2−0.5) were analyzed using Rietveld refinement. These samples are found to be mostly in single-phase form with orthorhombic symmetry (space group Pbnm). We have found strong correlation between Mn-O-Mn bond angles and T _c of M-I transition. The resistivity data below T _c could be fitted to the expression ρ=ρ ₁+ρ ₂ T ² and this shows that double exchange interaction plays a major role even in Mn⁴⁺-rich compound. Above T _c the resistivity data were fitted to variable range hopping and small polaron models.     

On the preparation and the characterization of superconducting thin films of YBa2Cu3O7−x

The results of our initial efforts to deposit thin films of YBa₂Cu₃O_7−x system on sapphire substrate are described. The deposited films are shiny black in appearance and are of quite uniform chemical composition. The annealed films exhibit zero resistance superconducting transition temperatureT _c(R=0) ranging between 23 K and 30 K.     

Specific heat anomaly in the 90 K superconductor HoBa2Cu3O7−y

We report here the results of our heat capacityC _p measurements on a monophasic material HoBa₂Cu₃O_7−y . ΔC _p/T_c, the jump inC _p at the superconducting transition temperature (=91 K) of the material is measured to be 31 mJ/mol-K².