Superconducting Properties of Zn-Doped Cu0.5Tl0.5Ba2Ca2Cu3?yZnyO10?δ Superconductors

A reproducible synthesis and characterization of Zn-doped Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−y Zn _y O_12−δ (y=0, 0.5, 1.0, 1.5) superconductors at a relatively lower synthesis temperature of 840°C are studied by using X-ray diffraction, resistivity, ac-susceptibility and FTIR absorption measurements. The X-ray diffraction (XRD) studies of these samples have shown a tetragonal structure in which the c-axis length has been found to decrease with increased Zn doping. The critical temperature and magnitude of diamagnetism have not been significantly affected with the doping of Zn at this synthesis temperature. The magnitude of diamagnetism in the as-prepared undoped samples is decreased, whereas it remains stable (unchanged) in oxygen post-annealed samples. The apical oxygen phonon’s modes of type Tl–O_A–M(2) and Cu(1)–O_A–M(2) {where M=Cu/Zn} and the planar oxygen phonon modes of type M(2)–O_P–M(2) are also softened with the increase of Zn doping. We interpreted the softening of these oxygen related phonon modes linked with the decreased c-axis length, reduced John–Teller distortions and increased mass of Zn (65.38 amu) as compared to that of Cu (63.54 amu) (Kaplan et al., Phys. Rev. B 65, 214509, 2002).     

Cd-Doped Cu0.5Tl0.5Ba2Ca2Cu3?yCdyO10?δ (y=0,0.5,1.0,1.5,2.0) Superconductors

Superconducting properties of cadmium doped Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−y Cd _y O_10−δ (y=0,0.5,1.0,1.5,2.0) samples have been studied using X-ray diffraction, resistivity, ac-susceptibility and FTIR absorption measurements. In X-ray diffraction studies these samples have shown to have tetragonal structure. The zero resistivity critical temperature and magnitude of diamagnetism are suppressed with the increased incorporation of Cd in the final compound. A change in the shape of FTIR absorption spectra, after doping, has shown the incorporation of Cd in the unit cell. A systematic hardening of the apical oxygen modes and softening of the CuO₂ planar modes of vibration with increased Cd doping have shown that it is incorporated in the unit cell of Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−y Cd _y O_10−δ (y=0,0.5,1.0,1.5,2.0) superconductors. The FTIR absorption measurements of these samples have shown that hardening of the apical oxygen modes of types Cu(1)–O(2)–Tl and Cu(1)–O(2)–Cu(2)/Cd _y (y=0,0.5,1.0,1.5,2.0) increases with the increase of Cd doping in the samples. A softening of the CuO₂ planar oxygen mode Cu(2)–O–Cu(2) is also observed with the increased Cd doping in the final compound. It is most likely that hardening of the apical oxygen modes and the softening of the planar modes of vibration are associated damped harmonic oscillations produced by heavier Cd atoms in the CuO₂ planes, which suppress the phonon population from a desired level, reducing the magnitude of superconductivity in the final compound.     

Suppression of Anti-ferromagnetism by K Doping in?(Cu0.5Tl0.5?xKx)Ba2Ca2Cu3O10?δ Superconductors

In the inner CuO₂ planes (IP) of (Cu_0.5Tl_0.5)Ba₂ Ca₂Cu₃O_10−δ superconductors the density of the carriers is in the under-doped state which promotes enhancement in the anti-ferromagnetism. Consequently, the critical temperature of the final compound is suppressed. In the present studies, we have enhanced the density of mobile carriers in the inner CuO₂ planes by doping K at the charge reservoir layer by preparing (Cu_0.5Tl_0.5−x K _x )Ba₂Ca₂Cu₃O_10−δ superconductors. The higher density of mobile carriers increases the Fermi velocity V _F, and hence enhances the superconductivity parameters such as T _c, H _c, and J _c. The main objective of these experiments was to suppress the anti-ferromagnetism in the final compound. We have enhanced the inter-plane coupling by partially substituting Be and Mg at the Ca sites. The melting point of the final compounds is significantly reduced with the incorporation of Be and Mg. The incorporation of these elements has been found to facilitate the formation superconductors with higher numbers of CuO₂ planes, i.e., (Cu_0.5Tl_0.5−x K _x )Ba₂Ca_3−y M _y Cu₄O_12−δ .     

AC Response of Cu0.5Tl0.5Ba2Ca2Cu3?xSnxO10?δ Superconductor

We have studied the ac response of Sn doped Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−x Sn _x O_10−δ superconductor samples from their ac-susceptibility measurements under different magnitudes of ac magnetic fields; H _ac=0.4, 4, 16 A/m. The samples with x=0.5 and 1.0 have shown strong flux pinning and intergrain coupling. However, the sample with Sn doping of x=1.5 has shown very poor flux pinning characteristics.     

Enhanced Superconductivity in?(Cu0.5Tl0.25M0.25)Ba2Ca2Cu3O10?δ Samples

The elements (M = Li, Na, K) of group I-A of the periodic table having lower electronegativity as compared to that of Tl have been partially doped at Tl sites in the (Cu_0.5Tl_0.25M_0.25)Ba₂O_4−δ charge reservoir layer of (Cu_0.5Tl_0.25M_0.25)Ba₂Ca₂Cu₃O_10−δ superconductor. The objective was to investigate the role of electron–phonon interactions and mobile charge carriers in the oxide high temperature superconductors. It has been observed from these studies that the superconductivity parameters were improved after the doping of lower electronegative elements in the charge reservoir layer. The substitution of lower electronegative elements retains smaller amount of oxygen in (Cu_0.5Tl_0.25M_0.25)Ba₂O_4−δ charge reservoir layer, which in turn facilitates the transfer of mobile charge carriers to the conducting CuO₂ planes.     

Be-Doped Cu0.5Tl0.5Ba2Ca1(Cu0.5Zn1.5)O8?δ Superconductors

We have enhanced the superconducting properties of newly discovered Cu_0.5Tl_0.5Ba₂Ca₁(Cu_0.5Zn_1.5)O_8−δ superconductor by doping Be at Ca sites. The superconducting properties, such as critical current density, in-field magnetic properties and quantity of diamagnetism, are enhanced by Be doping at the Ca sites. The decreased c-axis length and the volume of the unit cell have shown that the inter-ZnO₂-plane coupling is enhanced. We have not observed any localization of the carriers in the neighborhood of Zn atoms in Cu_0.5Tl_0.5Ba₂Ca_1−y Be _y (Cu_0.5Zn_1.5)O_8−δ (y=0, 0.15, 0.30, 0.45, 0.6) superconductors, as proposed in the previous studies. One must expect such effects if present, through the decreased c-axis length by Be doping. The decreased c-axis length results in enhancement of coherence length and Fermi velocity of the carriers, which in turn result in enhanced superconductivity parameters. The presence of Be at the termination ends of the crystals results in enhanced inter-grain coupling and substantially improved their weak link behavior. The optimization of the carriers in CuO₂/ZnO₂-planes have been found to enhance the T _c (R=0) and the magnitude of diamagnetism in Be-doped samples. Also the softening of phonon modes with the increased Zn doping evidenced the incorporation of Zn at the CuO₂ planar sites.     

Effect of Pb Doping on the Superconducting Properties of?(Cu0.5?xPbxTl0.5)Ba2Ca2Cu3O10?δ

The effect of Pb doping on the superconducting properties of (Cu_0.5−x Pb _x Tl_0.5)Ba₂Ca₂Cu₃O_10−δ (x=0.0, 0.15, 0.25, 0.35) samples has been investigated. Lead is doped in Cu_0.5Tl_0.5Ba₂O_4−δ charge reservoir layer and at the CuO₂ planar sites. A multiphase material is achieved with the doping of Pb at the CuO₂ planar sites; however, a predominant single-phase (Cu_0.5−x Pb _x Tl_0.5)Ba₂Ca₂Cu₃O_10−δ (x=0.0, 0.15, 0.25, 0.35) material is synthesized with the doping of Pb at the charge reservoir layers. Formation of multiphase material with the doping of lead at the planar sites showed that its substitution at the planar site is not possible and the formation of PbO₂ planes is less likely. In the samples doped at the charge reservoir layer, the zero critical temperature [T _c (R=0)] is systematically depressed with the increased concentration of lead. The T _c (R=0) and magnitude of the diamagnetism are enhanced after post-annealing the samples in oxygen atmosphere. An apical oxygen mode is observed around 438 cm⁻¹ in undoped samples, which is shifted to 457–461 cm⁻¹ in the Pb-doped samples. This shift in the peak position is most likely associated with the connectivity of apical oxygen atoms with Pb atoms of (Cu_0.5−x Pb _x Tl_0.5)Ba₂O_4−δ (x=0.0, 0.15, 0.25, 0.35) charge reservoir layers. The presence of Pb in the charge reservoir layer and its increased concentration, somehow, stops the flow of mobile carriers to the conducting CuO₂ planes. The decreased density of mobile carriers diminishes the critical temperature and magnitude of diamagnetism in the final compound. The increased oxygen diffusion in the unit cell achieved by post-annealing in oxygen replenishes the concentration of carriers in conducting CuO₂ planes, which increases the T _c (R=0) and the magnitude of diamagnetism. These experiments have shown that the density of mobile carriers plays a vital role in the mechanism of superconductivity and their depressed density suppresses the superconductivity parameters.     

Improvement of Superconductivity with the Modification of Charge Reservoir Layer in (Cu0.5Tl0.5?xMx)Ba2Ca2Cu3O10?δ

The relatively higher electronegative elements (M = Pd, Nb, Bi, Hg) have been partially doped at Tl sites in Cu_0.5Tl_0.5−x M _x Ba₂O_4−δ (x=0,0.25) charge reservoir layer of Cu_0.5Tl_0.5−x M _x Ba₂Ca₂Cu₃O_10−δ superconductor. These elements may retain more oxygen in the charge reservoir layer due to their higher electronegativity as compared to Tl, and the higher population of oxygen in the charge reservoir layer can optimize the charge carriers’ density in the conducting CuO₂ planes. The optimum density of mobile charge carriers in the conducting CuO₂ increases Fermi wave-vector K _F and Fermi velocity v _F of the carriers, which results in the improvement of superconducting properties of the material.     

AC-field Frequency Response of?Cu0.5Tl0.5Ba2(Ca2?qMgq)Cu3O10?δ Bulk Superconductor

The dielectric properties of Cu_0.5Tl_0.5Ba₂Ca_2−q Mg _q Cu₃O_10−δ (q=0, 0.5, 1.0 1.5) superconductor samples were studied at two temperatures of 80 and 290 K by capacitance (C) and conductance (G) measurements with the test frequency (f) in the range of 10 KHz to 10 MHz. We have presented the measurements of the dielectric constants (ε′ and ε″), dielectric loss factor (tan δ) and ac-conductivity (σ _ac) as a function of frequency and temperature. A negative capacitance (NC) experience has been observed, which is most likely due to different contact electrodes and superconductor samples’ Fermi levels. Since metals have their Fermi levels higher than ceramics, there is a flow of the carriers from the ceramic samples towards the metal electrodes. The dielectric polarization phenomenon is observed, which is due to dislodgment of mobile charges from their equilibrium position relative to fixed charges of the reservoir layer. The improved inter plane coupling promoted by Mg substitution at Ca site would change the dielectric response of Cu_0.5Tl_0.5Ba₂Ca_2−q Mg _q Cu₃O_10−δ superconductors. To observe such effects in Mg doped Cu_0.5Tl_0.5Ba₂Ca_2−q Mg _q Cu₃O_10−δ superconductors, di- electric measurements were carried out both at room temperature (290 K) and in the superconducting state closer to the boiling point of liquid nitrogen (80 K). The excess conductivity arising due to superconducting state of material has been determined, and its role in the mechanism of superconductivity is suggested. The negative dielectric constant (ε′) and dielectric loss factor (tan δ) show strong dispersion at low frequencies. The lower thermal agitation at 80 K may enhance the polarizability and hence the dielectric constants (ε′ and ε″).     

Superconductivity and Electron–Phonon Interaction in?Cu0.5Tl0.5Ba2Ca2Cu3?yMyO10?δ (M=0, Si, Ge, Sn, and?y=0,?1)

Superconducting properties of Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−y M _y O_10−δ (M=0, Si, Ge, Sn and y=0, 1) samples have been studied by using x-ray diffraction (XRD), resistivity, ac-susceptibility and Fourier Transform Infrared (FTIR) absorption measurements. We have tried to explore the role of the electron-phonon interaction in bringing about superconductivity in the Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−y M _y O_10−δ material. A change in the cell parameters from XRD and the change in the shape of FTIR absorption spectra have shown the incorporation of doped elements (M=Si, Ge, Sn) in the unit cell of the final compound. It is most likely that the change in oxygen phonon modes is associated with the oscillations of heavier and lighter atoms in MO₂/CuO₂ planes. These oscillations of heavier and lighter atoms suppress the density of the phonon population from the desired level for optimum superconductivity in the final compound.     

Effect on Diamagnetism and Phonon Modes due to Mg and Be Doping at Ca Sites in Cu0.5Tl0.5Ba2Ca3?yMyCu4O12?δ (y=0 and 1.5 for M=Mg, Be) High Temperature Superconductors

We synthesized as prepared and oxygen annealed Cu_0.5Tl_0.5Ba₂Ca_3−y M _y Cu₄O_12−δ (y=0 and 1.5 for M=Mg, Be) High Temperature Superconductors (HTSCs) by using the solid state reaction method. It is observed that superconducting properties and the magnitude of the diamagnetism are enhanced by the doping of Mg and Be at the Ca site; this is due to smaller ionic sizes and higher electronegativities of Mg and Be as compared to Ca. Furthermore, interplanar coupling is also improved and shrinking of the axis length is the direct evidence of it. The carrier’s concentration in conducting planes is improved by carrying out post-annealing experiments in the oxygen atmosphere. Moreover, FTIR absorption measurements are also incorporated.     

Effect of Nano-Sized ZnO on the Physical Properties of (Cu0.5Tl0.25Pb0.25)Ba2Ca2Cu3O10?δ

High-temperature superconductor phase of (Cu_0.5Tl_0.25Pb_0.25)-1223 was synthesized by solid-state reaction technique and characterized using X-ray powder diffraction (XRD). XRD analysis revealed that the prepared sample was nearly monophase and exhibited tetragonal structure with space group P4/mmm. Nano-zinc-oxide, prepared by Co-precipitation method, was added to the sample. ZnO-concentrations y varied from 0.0 to 2.0 wt.% of the sample’s mass. The prepared samples were investigated through XRD, scanning electron microscope (SEM), energy dispersive X-ray (EDX), particle size analyzer (PSA), differential scanning calorimeter (DSC), electrical resistivity and transport critical current density measurement. X-ray data analysis showed that the nano-Zn addition does not affect the tetragonal structure of (Cu_0.5Tl_0.25Pb_0.25)-1223 phase, whereas the lattice parameters showed an insignificant variation. The results of the superconducting transition temperature, the transport critical current density and melting point of the prepared samples were found to depend on nano-ZnO concentrations.     

Neutron structural investigations of Y1?xCaxBa2Cu3?yCoyO7±δ

The results of a systematic powder neutron study on Y_1–x CaxBa₂Cu_3–y Co _y O_7± for A (x=y=0), B (x=0;y=0.2), C (x= 0;y=0.4), D (x=y=0.2), and E (x=y=0.4) are investigated with a view to understanding the relation between the structural parameters and superconductivity. Rietveld refinements of the structures show that: (a) Co substitutes at the chain Cu(1) sites only, except for sample E, where the presence of a minor amount of Co at the planar Cu(2) site cannot be ruled out; (b) Co substitution reduced thec-parameter, which is reduced even further upon substitution of Ca at the Y-sites; (c) the occupancy factors of the chain O(1) site indicate an average coordination of 4.8 and 5.1 for Co for samples B and C, but only 4 for D and E; (d) Cu/Co(1) atoms for B and C display large thermal parameters, suggesting a displacement from their ideal centrosymmetric location; (e) the apical Cu(1)-O(4) bond lengthens upon substitution of Co in samples B and C but undergoes shortening upon substitution of Ca in the case of samples D and E. The apical Cu(2)-O(4) bond, on the other hand, shows just the opposite trend; (f) samples D and E show a reduction in the separation of CuO₂ layers and their oxygen content; and (e) the bond valence of the Cu(2) ion shows the lowest value of 2.127 for the nonsuperconducting sample C.     

Role of Mobile Charge Carriers and Fluctuation Induced Conductivity in (Cu0.5Tl0.5?xKx)Ba2Ca3Cu1Zn3O12?δ Superconductor

The main role played by mobile carriers and fluctuation induced conductivity (FIC) in (Cu_0.5Tl_0.5−x K _x )Ba₂Ca₃Cu₁Zn₃O_12−δ (x=0, 0.25) superconductor samples are analyzed in the light of the Aslamazov–Larken (AL) theory. The enhancement of three-dimensional (3D) conductivity and grain size is achieved with K-doping at Tl sites in the (Cu_0.5Tl_0.5−x K _x )Ba₂O_4−δ charge reservoir layer, which are further improved by post-annealing the samples in oxygen. The improvement of these factors causes the increase in cross-over temperature (T _o), zero resistivity critical temperature {T _c(R=0)} and T _c(onset) of diamagnetism to their higher values. We have also evaluated the exponents (λ _2D and λ _3D), zero temperature coherence lengths ξ _c(0), and interlayer coupling (J) for these samples and tried to correlate them to the superconductivity order parameters.     

Fluctuation Conductivity and Phase Separation in Polycrystalline Y1?xCexBa2Cu3O7?δ Superconductors

Fluctuations on the electrical conductivity of polycrystalline Y_1−x Ce _x Ba₂Cu₃O_7−δ superconductors were investigated with Ce contents from x=0.01 up to 0.10. The results showed that the resistive transition proceeded in two stages, intragranular and intergranular, as indicated by the temperature derivative of the resistivity and verified by critical exponent analysis. Also, from the critical exponent analysis, we have observed a splitting of the pairing transition in all investigated samples. Our results strongly suggest that this pairing transition splitting is related to the occurrence of a phase separation associated with Ce doping. In the regime of near-zero resistance state, the temperature dependence of our data is consistent with a power-law behavior which is indicative of a phase transition from a paracoherent to a coherent state of the granular array.     

Optimum Synthesis Temperature of (Cu1?xTlx)Ba2Ca3Cu4O12?δ Superconductor

The effect of synthesis temperature on the superconducting properties of (Cu_1−x Tl _x )Ba₂Ca₃Cu₄O_12−δ (CuTl-1234) samples has been explored. Almost all the superconducting parameters studied in this research work are observed to be suppressed with the increase of synthesis temperature beyond 880 °C, which may be due to impurities caused by the volatility of some constituents such as thallium and oxygen deficiencies as well in the final compound. The Fluctuation Induced Conductivity (FIC) analysis has shown a decrease in the cross-over temperature (T ₀) and the shift of three-dimensional (3D) Aslamasov–Larkin (AL) regions to the lower temperature with the increase of synthesis temperature beyond 880 °C. A direct correlation between the cross-over temperature (T ₀), the zero temperature coherence length {ξ _c (0)}, the zero resistivity critical temperature {T _c (R=0)} as well as carrier concentration has also been observed.     

Extraordinary behaviour of the Y1?xPrxBa2Cu3O7?δ system

Investigations of Y_1–x M _x Ba₂Cu₃O_7– (M=Ce, Th)c-axis oriented thin film specimens show that the rate of depression ofT _c withx is larger for M=Th, than for M=Ce and Pr, and suggest that Ce, like Th, is tetravalent in this compound. Hall effect measurements on Y_1–x Pr _x Ba₂Cu₃O_7– single crystals reveal aT ² dependence of the cotangent of the Hall angle in the normal state and a negative Hall anomaly belowT _c in the superconducting state, in agreement with recent reports. Our research shows that the depth, , of the negative Hall signal scales withT/T _c and that the maximum value of decreases linearly withx and vanishes atx0.24. Magnetoresistance measurements on Y_1–x Pr _x Ba₂Cu₃O_7– single crystals indicate that the irreversibility lineH(T ^*) obeys a universal scaling relation characterized by anm=3/2 power law nearT _c, with a crossover to a more rapid temperature dependence of belowT/T _c 0.6, similar to that observed for polycrystalline specimens.     

Anisotropic Ultrafast Dynamics of Quasiparticles on CuO2 Planes of Y0.7Ca0.3Ba2Cu3O7?δ

The orientation-resolved femtosecond spectroscopy, combined with the well-textured (110)- and (001)-Y_0.7Ca_0.3Ba₂Cu₃O_7−δ thin films, serves as an effective probe to quasiparticle relaxation dynamics on the ab planes and along the diagonal orientations. The significant divergences in the temperature-dependent relaxation time (τ) associated with the opening of superconducting gap were observed along the nodal directions and on the CuO₂ planes which are dominated by the a axis and b axis in the overdoped region. Moreover, the divergence in the temperature-dependent τ along the nodal direction disappears around optimal doped region. This implies that the superconducting gap evolves from the dominant s-wave symmetry in overdoped region into the dominant d-wave symmetry in optimal doped region.     

Critical and Gaussian Conductivity Fluctuations in Granular Ho1?xPrxBa2Cu3O7?δ Superconductor

Fluctuations in the electrical conductivity of polycrystalline Ho_1−x Pr _x Ba₂Cu₃O_7−δ superconductors were investigated with Ho contents from x=0.01 up to 0.10. Samples were prepared by the standard solid-state reaction technique. The method of analysis is based on the determination of the quantity c_s^-1=-\fracddTlnDs\chi_{\sigma}^{-1}=-\frac{d}{dT}\ln\Delta\sigma, where Δσ=σ−σ _R is the fluctuation conductivity. The results show that the resistive transition proceeds in two stages as seen by the temperature derivative of the resistivity near T _C . In the normal phase, Gaussian and critical fluctuation conductivity regimes were identified. The pairing transition splitting, associated with Pr doping and related to the occurrence of a phase separation, as observed in studies with other rare earth elements, was not clearly observed. On approaching the zero-resistance state, our results show a power-law behavior that corresponds to a phase transition from a paracoherent to a coherent state of the granular array. This behavior was not affected by Pr doping.     

Anisotropic uniaxial pressure effects in YBa2Cu3O7?δ

We present measurements of the uniaxial pressure dependence ofT _c of untwinned YBa₂Cu₃O_7– crystals with various oxygen stoichiometries. For all samples investigated,T _c decreases for pressure alonga, increases for pressure alongb, and, in oxygen deficient samples, increases strongly for pressure alongc. These results are compared to the behavior found in the La_2–x Sr _x CuO₄ and YBa₂Cu₄O₈ systems. Neither the model of pressure-induced charge transfer nor coupling to orthorhombic distortions can explain all the data. However, the presence of singularities in the electronic density of states close to the Fermi energy is a possible origin of the observed behavior. Our preliminary data on the pressure dependence of thec-axis and in-plane resistivities in twinned crystals are consistent with this view.