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The effects of Eu substituting for Ba on structural and superconducting properties were investigated for a series of superconductors Eu 1+ x Ba 2− x Cu 3 O 7− δ ( x =0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12, 0.14, 0.16, 0.18, and 0.2). With Eu content increasing, the random substitution of excessive Eu for Ba ion forms a Eu–Ba non-stoichiometric distribution on Ba site, which deviates from the ideal 123 phase stoichiometry. The analysis of crystallographic structure shows that the solid solubility x of Eu on Ba site is over 0.2. Eu 1+ x Ba 2− x Cu 3 O 7− δ take on an orthorhombic–tetragonal (O–T) phase transition from x =0.06, and end in x =0.18. Corresponding to the O–T phase transition, superconducting critical temperature T c rapidly decreases with Eu content increasing, which is attributed to the decline of carrier density and the proximity effects of non-superconducting clusters. The positron annihilation measurements show anomalous changes for lifetime spectra and Doppler-broadened radiation spectra when the O–T phase transition occurs. By the model of excessive oxygen defects in Cu–O chain regions, we discuss effects of Eu–Ba non-stoichiometric distribution on structural and superconducting properties.

A series of single crystals with starting composition Y1−xEuxBa2Cu3O7−δ (x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 1.0) were prepared in Al2O3 crucibles in the self-flux method. A home-made setup for crystal growth and a new flux separation method are introduced. Eu-doped Y-123 single crystals were characterized by means of X-ray diffraction, energy dispersive X-ray spectrometry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and AC susceptibility. All single crystal samples maintain the crystallographical structure of the 123-phase. The SEM and AFM measurements indicate a growth anisotropy. The growth of the (0 0 1) surface is related to different growth mechanisms, and the spiral growth mechanism is the predominant one. For the first time, we observed a regular array of groove on (0 0 1) surface. A drastic suppression of the superconducting transition temperature with Eu concentration was observed. Al contamination from crucible corrosion and Eu substitution for the Ba site result in a heavy reduction of Tc in single crystals.

The effect of Sn-doping on (La 1− x Sr x ) 2 Cu 1− x Sn x O 4 ( x =0.075, 0.090 and 0.110) has been studied. Lattice parameters monotonically decrease with Sn dopant increasing. Sn atoms dominantly occupy Cu sites and form Sn–O clusters as point-like defects. Flux pinning properties of ceramic samples of (La 1− x Sr x ) 2 Cu 1− x Sn x O 4 have been investigated by magnetic measurements from 6 to 30 K up to 5 T. The current carrying scale-length analysis has been determined from the reverse leg of the magnetization hysteresis loops and compared to the actual dimensions of the sample. Magnetization hysteresis loops of the more richly Sn-doped sample exhibit stronger pinning behavior, especially in the higher temperature range. The intra-granular critical current J c in the rich Sn-doping sample has a significant increase. We discuss the experimental results within a pinning model of point-like defects. From our data we infer that the Sn–O cluster near Cu–O layers provides an effective pinning center.

The magnetic properties of ceramic samples of Bi 2−2 x (PbSn) x Sr 2 CaCu 2 O y ( x =0,0.1,0.2,0.3 and 0.4) superconductors have been investigated using a vibrating sample magnetometer from 20 to 50 K and up to 8 T. Phase analysis shows that most of the (Pb,Sn) dopant enters the Bi-2212 lattice and occupies Bi sites. The current-carrying scale-length analysis has been determined from the reverse leg of the magnetization hysteresis loops and compared to the actual dimensions of the sample. Magnetization hysteresis loops of the (PbSn)-doped sample exhibit strong pinning behaviour in the higher temperature range. The effect of (Pb,Sn) doping on intragranular critical current J c was found to be enhanced by one order of magnitude at 50 K. We discuss the experimental results within a model of (PbSn) cluster pinning in blocking layers. Doping by (PbSn) clusters into the Bi–O layers provides effective pinning centres, as well as a large reduction of the resistivity anisotropy.

The Fe-doping effects on superconductivity, transport and microstructure are investigated by means of Hall coefficient measurements, thermogravimetric analysis, Mossbauer spectroscopy and the calculation of the point-charge-effective-valence model (PCEV model) in Fe-doped Tl 0.5 Pb 0.5 (Sr 0.8 Ba 0.2 ) 2 Ca 2 (Cu 1− x Fe x ) 3 O y (Tl-1223) superconductors. In the doping level of Fe ( x =0–0.05), both zero-resistance temperature T co and carrier concentration n H decrease linearly with Fe dopants increasing. The striking linear behavior of T co and n H suggests the potential effects of charge localization on the transport properties and also shows that Fe dopants occupy different Cu sites in a stable manner with Fe content increasing. The thermogravimetric analysis shows the Fe 3+ ions substituting for Cu 2+ ions can bring excess oxygen atoms into lattice and form some Fe–O defect clusters. Mossbauer measurements are performed to investigate the microstructure of Fe–O defects. In addition, the atomic position of Fe dopant and the electric field gradient (EFG) on Fe sites are investigated under the PCEV model. We found that the signs of the EFG on Fe sites are positive. According to quadrupole splittings deduced from Mossbauer spectroscopies and results of model calculation, it is further confirmed that there is a small shift of Fe ion relative to the original center of the CuO 2 network, and in some different kinds of Fe–O defect clusters, Fe dopants can lead to excess oxygen atoms entering lattice. These results provide a further support for the interpretation about the displacement of Fe dopant and the assignment of Fe site. Our discussion suggests that the microstructural distortion and the excess oxygen defect induced by Fe doping encourage in the localization of cruising carrier on CuO 2 planes, which is one of the reasons to explain the decrease of T c and carrier concentration.

The simultaneous measurements of Doppler-broadened radiation spectra and lifetime spectra have been performed on (Y 1− x Eu x )Ba 2 Cu 3 O 7− y ( x =0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1) superconductors. The mean lifetime and S -parameter, respectively show a characteristic significantly symmetric to Eu-doping concentration. Since lifetime and Doppler broadening spectroscopies are rather sensitive to the variation of the lattice distortion and defects induced by the stress-field of lattice mismatch, such symmetric behaviors of the S -parameter and the mean lifetime suggest a striking characteristic of stress in Y 1− x Eu x -123 superconductor. When the doping concentration x reaches 30%, the density of defects corresponding to stress-field appears the maximum, and there is an optimum distribution of the stress-field so as to increase critical current J c in Eu-doped Y-123 superconductors. Our results of the critical current density obtained by means of measurements of susceptibility χ ′( T , H AC ) and χ ″( T , H AC ) also suggest that the enhancement of the critical current density to reach an optimum when Eu doping x is 30%. We also qualitatively discuss experimental results in the framework of the model of stress-field pinning. The model calculating results also show the stress-field induced by lattice mismatch is an effective pinning center, and further conform that the stress pinning mechanism is dominant in RE-doped Y-123 superconductors.

A significant drop of the resistance around 235 K was observed in our experiment of mercury-based samples synthesized under high pressure and high temperature. The drop of the resistance alwaysappeared in samples containing tiny mercury droplets or HgAu alloys; it was sometimes also observed in samples with grains of Hg-1223 and grain boundaries containing an excess of Hg compared with the composition ratio of the superconducting phase of Hg-12(n-1)n. The measurements of DC magnetic susceptibility by a SQUID magnetometer did not demonstrate any diamagnetic behavior around 235 K although a very small drop in the AC magnetic susceptibility was observed at this temperature with a Lakeshore magnetometer. The paper will discuss if the drop in the resistance for the mercury-based compounds at 235 K is due to superconductivity; we rather believe that it is due to the presence of liquid mercury of its alloys in the sample.

High-temperature superconductors of the mercury-based system were synthesized under high temperature and high pressure. The measurements of resistance and DC magnetic susceptibility for the samples prepared at 20-35 kbar and 850-degrees-C for 1-3.5 h show that the as-synthesized sample (1) prepared at 20 kbar, 850-degrees-C for 1.5 h was a multiphase of Hg-1212 and Hg-1223 phases and showed superconducting transitions of both 132 and 120 K. The sample (2) prepared at 30 kbar, 850-degrees-C for 3.5 h has Hg-1212 as the major phase with only a small amount of impurity phase. The intergrowth of Hg-1212/Hg-1223 was found in the sample (1). The dependence of pressure on T(c) for the Hg-1212 and Hg-1223 phases, measured under hydrostatic pressure, shows that dT(c)/dp is 0.17 and 0.23 K/kbar, respectively, in the pressure range below 10 kbar.

57 Fe Mossbauer measurements have been performed on Fe-doped samples of Bi 1.6 Pb 0.4 Sr 2 Ca 3 Cu 4- x Fe x O y ( x =0.06 and 0.08) at room temperature. The Mossbauer spectra show three quadrupole doublets that can be related to different Cu sites. Two doublets (B and C) with larger quadrupole splitting (QS) are assigned with a 57 Fe probe atom on the Cu-O square planar sites of the compound with different local charge environments. Another doublet A with smallest quadrupole splitting is associated with a Fe atom in a planar pyramid site. the doublet with smallest QS possesses relatively the smaller area indicating that the Fe atom preferentially occupies a square planar site rather than a pyramid site. To assure our assignment, we calculated the EFG (electric field gradient) on different Cu sites with the use of the point charge model and of the calculation of an effective ions valence.

Samples with different fractions of structural modulation were synthesized in order to study the effect of a defective modulated structure on the critical temperature T c of Hg-1234. Electron microscopy revealed the existence of modulated and unmodulated Hg-1234 structures in these samples. Measurements of critical temperature T c on these samples revealed that the structural modulation significantly suppresses the T c . For the Hg-1234 sample without the structural modulation, the T c was found to be close to the highest T c for the Hg-1223 phase.

The magnetic properties of (Eu 1-x Y x )Ba 2 Cu 3 O 7−y (x=0 and 0.3) superconductors have been investigated by vibrating sample magnetometry (VSM) from 20 to 90 K and up to 8 T. Hysteresis loops of the Y-doped sample exhibit a strongly developed second peak at higher temperatures. The critical current densities derived from these data were nonmalised to the values at the peak position, J Cp , and analysed as a function of applied field normalised to the peak field. We discuss the experimental results in terms of a stress-field pinning model: The stress-field induced by lattice mismatch provides an effective pinning centre, in addition to the 211 phase precipitates and oxygen vacancies. We further suggest that in the Eu 0.7 Y 0.3 -123 sample, the oxygen-deficient region induced by the stress-field also adds to the pinning, and accounts for the enhancement of the peak effect in the J C -H curves of the Eu 0.7 Y 0.3 -123 superconductor.

The dynamic studies of the hyperfine interactions and the lattice vibrational behavior are performed by means of temperature-dependent Mossbauer spectroscopy on the Bi-, Tl-, and Y-based superconductors, respectively. The temperature-dependent Mossbauer recoil-free factor f show that, above, but relatively close to, the transition temperature, there is an anomalous lattice effect which is related to the softening of phonon vibrational modes for Bi-2223, Tl-1223, and Y-123 superconductors. Moreover, for such three systems, the anomalous decrease of the Mossbauer isomer shift above Tc reveal the delocalization effect of d-electrons. Since the lattice effect is accompanied by d-electron delocalization effect at the almost same temperature region, it is believed that the structural instability involved in phonon softening is strongly interrelated to the change of the electronic states, and the phase separation behavior.

The phonon softening near T c on iron-doped Tl - 1223 phase samples were observed by 57 Fe Mo¨ssbauer measurements at temperatures ranging from 77K to 250K. Simultaneously, the temperature dependence of positron annihilation parameters on an iron-free sample show the anomaly of the electronic behavior in the temperature range from T c to T c +30K.

The variety of intergrowth in the Hg Ba Ca Cu O oxide system was found by the high resolution electron microscope(HREM). A new phase of Hg-2435 was synthesized under high pressure for long time. Another longer period structure of -2223- was also found in such prepared sample. However, these complex intergrowth structures only contain the Hg-1212 and Hg-1223 phases.

The photoemission spectrum was measured on YNi2B2C and was found to be well coincident with calculation except in the vacinity of EF. The DOS peak at EF predicted by band theory has not been detected. The author suggests that the low energy excitation which is responsible for the suppression of DOS at EF, is responsible for the pairing of superconductivity as well.

A excess oxygen model that explains the Fe-doping mechanism in 1223 Tl Ba Ca Cu O superconducting phase is presented. So far the details of the coordination of Fe dopant is not understood completely yet, for Fe dopant substitution in Tl-system cuprate oxide. The similarity in the ionic radii and electronegativity of Cu and Fe lead to the Fe occupying Cu lattice site. However, the difference between the oxidation states of Fe and Cu means that Fe will bring the excess oxygen into lattice to keep the charge balance. We show that, for the evidence of the excess oxygen., the bonding energy of Fe-cluster in Cu O layer reach its minimum when Fe make a shift from the center of Cu O square network. Moreover, under the scheme of effective valence, the calculated value of Fe effective valence is relatively close to that of Mossbauer measurement.

The temperature-dependent Mossbauer study was performed in Fe-doped Bi-2223 phase. The anomalous behaviors of hyperfine interactions have been observed to take place above, but relatively close to, the transition temperature. The anomalous drop of isomer shift and quadrupole splitting show the delocalization effect of d-electron.