Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO₂, Y₂Cu₂O₅ and Y₂BaCuO₅ from component oxides have been measured using solid state galvanic cells incorporating CaF₂ as the solid electrolyte under pure oxygen at a pressure of 1.01×10⁵ Pa BaO + CuO BaCuO₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=–63.4–0.0525T(K) Y₂O₃ + 2CuO Y₂Cu₂O₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=18.47–0.0219T(K) Y₂O₃ + BaO + CuO Y₂BaCuO₅ G _f,ox ^o (± 0.7) (kJ mol^–1)=–72.5–0.0793T(K) Because the superconducting compound YBa₂Cu₃O_7– coexists with any two of the phases CuO, BaCuO₂ and Y₂BaCuO₅, the data on BaCuO₂ and Y₂BaCuO₅ obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.     

Photoinduced Changes of the Electrical Anisotropy in Oxygen-Depleted YBa2Cu3O x

Long-term photoexcitation experiments were performed on Y Ba ₂ Cu ₃ O _x (x6.6) thin films, prepared by pulsed-laser deposition on tilted SrTiO₃ substrates. From the anisotropic resistance of the samples, the in-plane and the out-of-plane resistivities were calculated. Photoexcitation was carried out with a He-Ne laser at various temperatures from 70 K to 305 K. We observed that the electrical anisotropy _c/_ab increased at low temperatures, but decreased at high temperatures. This unusual behavior resembles that of the in-plane Hall mobility in a previous study. Possible interpretations according to the models for the photodoping effect in YBa ₂ Cu ₃ O _x are discussed.     

EPR study of polycrystalline superconductors with YBa2Cu3O7 structure

Electron paramagnetic resonance (EPR) of Gd³⁺, Eu²⁺, and copper ions has been investigated in the high-T_c superconductor with YBa₂Cu₃O_7– structure. It has been established that the system is heterogeneous at 0.150.5 and consists of metallic and dielectric regions. The former arises due to oxygen enrichment while the later due to oxygen deficiency. The integral of exchange interaction between Gd³⁺ localized moments and conduction electrons J_sf=0.016 eV has been determined from the normal state temperature dependence of Gd³⁺ EPR linewidth for metallic regions. T_c depression by gadolinium-localized moments for GdBa₂Cu₃O_7– was estimated to be T_c–2K. Anomalies in linewidth temperature dependence upon transition from the normal to the superconducting state have given information about the value and temperature behavior of the superconductor's energy gap. The model, which gives the opportunity to understand some peculiarities of the EPR signal for YBa₂Cu₃O_7– samples, is proposed in terms of several bottlenecked spinsubsystems: spin-liquid in CuO planes and Cu²⁺-O^– and Cu²⁺-O^2– fragments in CuO chains.     

Investigation of the dominant point defects in tetragonal YBa2Cu3Ox at elevated temperatures

The manner in which oxygen is incorporated into YBa₂Cu₃O _x (YBCO) at 800°C for values ofx close to 6 is shown to be in the form of neutral oxygen interstitials, O _i ^x . The experimental data on which this conclusion is based are obtained from measurements of oxygen partial pressure,P(O₂), as a function of compositionx and temperatureT (5.99x 6.35, 825T1120 K). The data are obtained by a solid-state electrochemical method. Other conclusions of this study include: (a) O _i ^x are noninteracting forx 6. (b) The stoichiometric composition of YBCO isx 6.0. (c) The reaction enthalpy of oxidation is 179 kJ/mol O₂. (d) The Fermi level changes by –0.2 eV asx increases from 6.05 to 6.35.     

Comparison of Superconductivity and Structure for Lanthanum Replacing for Barium and Copper in YBa2Cu3Od

X-ray diffraction studies and the resistivity measurements are used to characterize the structure and the superconductivity of the nominal composition of YBa₂Cu_{3 – x} La _x O _d (YBCLO) cuprates with x 0.30. There was a BaCuO₂ impurity phase detected with x 0.10. The structure of the main phase (123) has the orthorhombic form with Pmmm symmetry in the whole doping range. With increasing content of lanthanum, x, the lattice constants increase for x < 0.04, and decrease for x 0.04. Rietveld refinements for X-ray diffraction show that the dopant of lanthanum substitutes for copper in the lower doping level, and replaces for both barium and copper in the high doping level. The zero-resistance temperature T _c0 first increases with the increase of the content of lanthanum in YBCLO as x 0.04 and then decreases with x as x 0.04. We compared the results with those of La-doped YBa_{2 – z} La _z Cu₃O _y cuprates. The different relationship in superconductivity dependence of lanthanum content may result from the strains due to the different occupancy of lanthanum in the unit cell of YBa₂Cu₃O _d .     

Glassy behavior of low-temperature energy relaxation in YBa2Cu3O7 and YBa2Cu3O6

Measuring the power release after rapid cooling a YBa₂Cu₃O₇ sample (m=42.85 g, T_c=91 K) from the equilibrium temperature T₁ (2.35 KT₁15.1 K) to T₀=1.5 K, we observed a time dependence typical of a glass: is proportional to t^–1. The results allow us to determine the linear term of the heat capacity (0.8 mJ/mole · K²) due to the two-level systems. While the low-temperature heat capacity anomaly noticeably decreases, the power release is essentially unchanged after oxygen reduction of the sample.     

Temperature-dependent change of Cu-O bond in La2CuO4 and YBa2Cu3O7

Valence-band spectra of La₂CuO₄ and YBa₂Cu₃O₇ were obtained by using X-ray photoemission varying the temperature of the measurement (35, 260, 300, and 500 C). In La₂CuO₄ the broad band centred around 4eV splits into two peaks at 260 C. At both 35 and 500 C the spectra show almost similar shape. In YBa₂Cu₃O₇ the broad peak centred around 4eV splits into two peaks at 500 C. Below 300 C the spectra show almost similar shape. These splittings of the valence-band spectra may be due to the rearrangement of the crystal structure accompanying the phase transition from the orthorhombic to tetragonal symmetry.     

Evidence for vortex lattice melting and softening in untwinned YBa2Cu3O7 single crystal

Real part of the ac susceptibility X₁ of an untwinned YBa₂ Cu₃O₇ single crystal jumps at the onset temperature in the narrow width (0.1 K in 0.7 T), suggesting the first-order melting transition. A sharp X₁ dip and a sharp X peak can be interpreted as synchronous trapping of vortices due to lattice softening prior to melting. At lower temperatures, the X₁-X₁ chart shows a single-parameter behavior while the melting occurs as a strong deviation from this.     

Nonmonotonic Temperature Dependence of the Thermal Hall Angle of a YBa2Cu3O6.95 Single Crystal

We have performed high-resolution measurements of the magnetic field (0 TB9 T) and temperature (10 KT<140 K) dependence of the longitudinal and transverse Hall thermal conductivity of a twinned YBa₂Cu₃O_6.95 single crystal. We have used and compared two recently published methods to extract the thermal Hall angle _H(T, B). Our results indicate that cot(_H) varies quite accurately as T⁴ in the intermediate temperature range 0.3c. It shows a well defined minimum at T_m20 K which resembles that observed in the c-axis microwave conductivity. The electronic part of the longitudinal and the transverse thermal conductivity show the scaling behavior for transport properties predicted for d-wave superconductors in the temperature range 18 KT30 K.     

Ionic conductivity and crystal structure relationships in Ti/Cu substituted Bi4V2O11

Crystal structure and oxide ion conductivity of a series of Ti and Ti-Cu double substituted Bi₄V₂O₁₁ compounds, Bi₂V_(1–x)Ti _x O_(11–x)/2 (0.085 x 0.15), and Bi₂V_0.9Cu_(0.1–x)TixO_5.35+x (0 x 0.1), were investigated using X-ray powder diffraction and ac impedance spectroscopy in the temperature and frequency range of 100–700°C and 10^–2–10⁷ Hz, respectively.Structural phase transitions, and , occur as a function of composition in Ti substituted compounds for which the is evidenced to be stable at room temperature when x exceeds 0.125. For all Ti-Cu double substituted compounds studied, the room temperature phase was identified to be phase.The required amount of Ti for phase stabilization at room temperature was significantly reduced and the conductivity improved when Cu substituted a part of Ti. Therefore, for the Bi₂V_0.9Cu_(0.1–x)Ti _x O_5.35+x (0 x 0.075) compounds the ionic conductivity increased and activation energy decreased with decreasing x. At low temperature, the highest ion conductivity was obtained for Bi₂V_0.9Cu_0.1O_5.35. At high temperature (T>500°C), a different behavior was observed. The total conductivity increased at first with decreasing x values down to x = 0.05 and then decreased. The maximum conductivity was obtained for Bi₂V_0.9Cu_0.05Ti_0.05O_5.4, and the activation energy decreased with decreasing x values, such as what happened at low temperature.     

Photoinduced Changes of the In-Plane and Out-Of-Plane Electronic Properties in YBa2Cu3Ox

We report on the photoinduced changes of the electronic properties of YBa₂Cu₃O_x (x 6.6) thin films, focussing on the electrical anisotropy in the normal and the superconducting state. The latter was determined from magnetoconductivity measurements, performed before and after light excitation, and fitting the experimental results to the Aslamazov–Larkin theory of superconducting order-parameter fluctuations. The normal-state anisotropy _ab/_c was calculated from resistance measurements carried out on samples grown on vicinal substrates. We observed that the photodoping process enhanced superconducting coherence lengths _c(0) and _ab(0), but reduced the superconducting anisotropy _ab(0)/_c(0) at all studied temperatures. In contrast, _ab/_c was enhanced by photodoping at low temperatures, but reduced at high temperature. Our results strongly suggest that two different mechanisms contribute to the photodoping process, with one affecting only the normal-state properties.     

Energy Scales in the Local Magnetic Excitation Spectrum of YBa2Cu3O6+y

The wave-vector integrated dynamical spin susceptibility _2D() of YBa ₂ Cu ₃ O _6+y cuprates is considered. _2D is calculated in the superconducting state from a renormalized mean-field theory of the t–t–J-model, based on the slave-boson formulation. Besides the well-known 41 meV resonance a second, much broader peak ('hump') appears in Im _2D. It is caused by particle-hole excitations across the maximum gap ⁰ . In contrast to the resonance, which moves to lower energies when the hole filling is reduced from optimal doping, the position of this 'hump' at 2 ⁰ stays almost unchanged. The results are in reasonable agreement with inelastic neutronscattering experiments.     

Equation of State and Thermodynamic Properties of Pure D2O and D2O + H2O Mixtures in and Beyond the Critical Region

A parametric crossover model is adapted to represent the thermodynamic properties of pure D₂O in the extended critical region. The crossover equation of state for D₂O incorporates scaling laws asymptotically close to the critical point and is transformed into a regular classical expansion far from the critical point. An isomorphic generalization of the law of corresponding states is applied to the prediction of thermodynamic properties and the phase behavior of D₂O + H₂O mixtures over a wide region around the locus of vapor-liquid critical points. A comparison is made with experimental data for pure D₂O and for the D₂O + H₂O mixture. The equation of state yields a good representation of thermodynamic property data in the range of temperatures 0.8T _c(x)T1.5T _c(x) and densities 0.35_c(x)1.65_c(x).     

Vortex Phase Diagram in Zn-Doped YBa2Cu3O y Crystals

Effects of Zn impurities on the vortex phase diagram of YBa₂(Cu_1–x Zn _x )₃O _y single crystals with 0x0.064 have been investigated in magnetic field up to 18 T. The first-order vortex lattice melting transition and the field-driven disordering transition are extremely suppressed by small amount of Zn impurities. As for Zn-doped YBCO with x>0.001, the resistive transition shows a broad temperature dependence due to the second-order vortex glass melting transition, while the field-driven disordering transition survives up to 0.003. These behaviors suggest that disorderes induced by Zn impurities strongly affect the vortex system in comparison with the oxygen deficiency in YBCO.     

Normal-State Gap, Supercarrier Mass Anisotropy and Isotope Effects in La2?xSrxCuO4

Magnetization measurements have been performed on the oxygen-isotopeexchanged samples (¹⁶O and ¹⁸O) of the one-layer cuprate superconductorsLa_2–x Sr _x CuO₄ (0.06x0.20). We find that there is an oxygen-isotopeeffect on the effective supercarrier mass m**, which is huge for x=0.06,and reduced to a smaller value for x=0.15. We also find that there coexistsmall (bi)polarons and free carriers for x0.09, but only small (bi)polaronsare present for x0.09. The normal-state gap is related to the bipolaronbinding energy which is inversely proportional to x for 0.05x0.15. Theobserved isotope effects, supercarrier mass anisotropy, normal-state gap,and mid-infrared spectra for x0.09 can be quantitatively explained by the small(bi)polaron theory of superconductivity proposed by Alexandrov, Kabanov, andMott (AKM).     

Disappearance of Bose-Glass Behavior in Transport Properties of YBa2Cu3O y Films with Columnar Defects

The glass transitions of the vortex system in Au-ion irradiated YBa₂Cu₃O _y films have been studied by the measurements of transport properties as a function of magnetic field B and angle of B to the direction of columnar defects. At =0°, we find an anomalous upturn behavior of the glass transition line B _g(T) at BB /3, where B is the matching field. In B>B /3, the dependence of glass transition temperature T _g reveals cusplike behavior with a peak at =0°, which is consistent with the Bose glass theory. In B<B /3, on the other hand, T _g is almost independent of , suggesting the system undergoes the vortex glass transition induced by the inherent point-like defects.     

Electron Paramagnetic Resonance of Tb3+ Ions in YBa2Cu3O6

The first observation of electron paramagnetic resonance (EPR) of Tb³⁺ doped into YBa₂Cu₃O₆ is reported. EPR is used to determine the local symmetry of the rare-earth ion and to study the effect of suppression of high-T _c superconductivity by doping. The distance between the lowest singlets of Tb³⁺ ion 7.1 GHz 0.24 cm^–1 and g-factor g 17.9 have been estimated from measurements. Both these parameters are in a good agreement with the corresponding calculated values. No evidence of Tb⁴⁺ ions was found.     

The Interplay of Electronic and Nuclear Magnetism in PtFe x at Milli-, Micro-, and Nanokelvin Temperatures

We have measured ac susceptibility, nuclear magnetic resonance, and nuclear heat capacity of two PtFe _x samples with concentrations of magnetic impurities x = 11 ppm and 41 ppm at magnetic fields (0 ± 0.05) mTB248 mT. The susceptibility data have been measured at temperatures of 0.3 KT100 mK, no hint for nuclear magnetic ordering could be detected to a temperature of 0.3 K. The nuclear heat capacity data taken at 1.4 KT10 mK show enhanced values which scale with x at low polarization. This effect is described by a model assuming an internal magnetic field caused by the impurities. No indication for nuclear magnetic ordering could be detected to 1.4 K. The nuclear magnetic resonance experiments have been performed on these samples at 0.8 KT0.5 mK and 2.5 mTB22.8 mT as well as on three other samples with x = 5, 10, 31 ppm in a different setup at 40 KT0.5 mK and at 5.4 mTB200 mT. Spin-lattice and effective spin-spin relaxation times ₁and ₂ ^* of ¹⁹⁵ Pt strongly depend on x and on the external magnetic field. No temperature dependence of ₁and ₂ ^* could be detected and the NMR data, too, give no hint for nuclear magnetic ordering to 0.8 K.     

Magnetic scattering of conduction carriers in 3d transition-metal intercalates of M x TiS2 (M=Mn,Fe, Co,and Ni)

Galvanomagnetic measurements on layer-structured 3d transition-metal intercalates of M_xTiS₂ (M = Mn, Fe, Co, and Ni;x0.33) have been made over the temperature range 0.34–20 K. Resistivity minima and negative magneto-resistances are observed for paramagnetic Mn, Fe, and Ni intercalates with low guest concentrations (x0.1), as found in well-known dilute alloys. However, in the case of the weak-ferromagnetic phase of Co_xTiS₂ (0.10x0.33) with the Curie temperatureT _c =120–140 K, such anomalous behaviors are also observed, which is not commonly found in the magnetically ordered phases of various magnetic materials. With these data we have given qualitative discussions on the magnetic scattering process of conduction carriers. Further, some of the experimental results are discussed in connection with the band calculations for M_1/3TiS₂.     

Structure and Diamagnetic Properties of (Pb0.6SnyCu0.4 ? y)Sr2(Y1 ? xCax)Cu2Oz

The effect of Sn doping in (Pb_0.6Sn _y Cu_{0.4 – y} )Sr₂(Y_{1 – x} Ca _x )Cu₂O _z with 0 y 0.3 and 0 x 0.7 was investigated. It was established that a nearly pure 1212 phase can be obtained at 0 y 0.1 and 0 x 0.3. The obtained XRD patterns as well as the results of the EDX and ICP-AES analyses showed that Sn substitution is possible in the (Pb,Cu)-1212 phase. Superconductivity was observed at 0.4 x 0.7. The onset of the diamagnetic transitions varied from 10 to 30 K. The influence of the strong Pb deficiency on the superconducting properties of the samples was discussed.