We report a systematic study of a series of single-phased LaiBa2Cu307-& samples where the oxygen content was determined by thermogravimetric analysis. The highest zero-resistance T, was 72 K, corresponding to 8 0.25. An increase in 8 reduced T, to 44 K, similar to the behavior reported for Y&Ba2Cu307-&. This is consistent with the idea that, as oxygen is taken away from the planes where Cu-0 chains exist, T, is reduced. For samples where the oxygen content was increased until 8 became negative, T, decreased to a value as low as 23 K, presumably due to increased La-Ba disorder. These samples with low T, and high oxygen content have apparent tetragonal x-ray spectra, suggesting that Cu-0 chain ordering has been further disrupted and that the oxygen occupancy on these planes has increased. Extensive experimental studies have been focused on the high-T, superconductor Y|BazCu307-s. Detailed neutron studies on this'2 compound as well as several structural studies on 1:2:3compounds with Y replaced by rare-earth elements,~~have associated the orthorhombic sequential structure with high zero-resistance T, 's near 90 K. The orthorhombicity is attributed to the ordering of oxygen vacancies in the copper planes between the Ba layers such that ordered Cu-0 chains remain. While the exact role of these Cu-0 chains is unclear, they are thought to be important to the high superconducting transition temperature either directly or through their interaction with the inner Cu-0 sheets. Recently, considerable attention has been focused on the compound LaiBa2Cu307s and its variations where different levels of lanthanum are doped into the barium sites. s '7 X-ray spectra on samples of the La|Ba2Cu307-s compound with low T, 's have been reported to appear tetragonal, although orthorhombic shoulderin~has been observed in samples with T, 's above 60 K. Further x-ray studies on samples of La|BazCu307-s with zero resistances as high as 80 K concluded that the samples with high T, 's were indeed orthorhombic. s7 This strengthens the idea that ordered Cu-0 chains play a very important role in these so-called 1:2:3 superconducting RiBa2Cu307-s (R is Y, La, and other rare-earth elements) materials, and that for these samples with T, 's approaching the 90-K plateau, an orthorhombic structure is required.The importance of the Cu-0 chains has been questioned by the observation that there exist certain LalBa2Cu3-07s samples that possess an apparent tetragonal structure but still become superconductors below 40 K. While several quenching studies on the Y|Ba2Cu307s compound have suggested an empirical relation between the orthorhombic distortion and T, (with the tetragonal phase being nonsuperconducting), a similar relationship has yet to be established in La|Ba2Cu307 s In thispa.per, we report a systematic study of the dependence of T, on the oxygen content (x) in La|Ba2Cu30q-s samples as measured by thermogravimetric analysis (TGA). The samples are predominantly single-phased with T, 's ranging from 23 to 72 K. Our highest zero-resistance transitio...
The synthesis and superconducting properties of Pb-and Sb-substituted Bi-2 : 2 : 2 : 3 materials have been investigated. The preparation conditions for t h e formation of the pure 2 : 2 : 2 : 3 phase have been optimized. Actual Sb-substitution into the Bi-system 2 : 2: 2 : 3 phase was successful as indicated by t h e XRO study. The transport measurements revealed no significant enhancement of t h e critical temperature such as was reported previously for the Sb-substituted phase. However, an enhanced melt-sintering orientation effect was observed in samples containing unreacted Sb,O,
We report resistivity, structural, and magnetic susceptibility IZ'~(T)] measurements for the compounds Priaa2Cu307-g and Ndiaa2Cu307-g. The Nd compound is superconducting with an onset transition temperature of 90 K, while the Pr compound is semiconducting above 4 K. The lattice parameters for these two materials have been determined using x-ray diN'raction techniques, and both appear to be tetragonal, although the NdiBa2Cu307-~compound may exhibit some orthorhombic splitting. The high-temperature effective moments in the two systems are within a few percent of the free-ion moments. In each case the presence of signincant curvature in the inverse susceptibility versus T behavior on the scale of 100 K suggests the presence of crystalline electric Seld splittings on the same energy scale. For the Pr compound this is further confirmed by a finite value for Xn (0) and a residual large constant term at high temperatures.The possible origin of semiconducting behavior as compared with superconducting behavior in the Nd and other rarewarth compounds is discussed in terms of differences in charge-carrier density and possible role of valence fluctuations among Pr rare-earth ions. I. INTRODUCj IONIt is now well known that high-temperature superconductivity near 90 K in compounds of the generic form RBa2Cu307-s is almost independent of which trivalent R ion is used from among yttrium and the rare earths. ' 3 Exceptions to this rule are lanathanum, 4 cerium, ' terbium (for which, as far as we are aware, no 1:2:3compound has been prepared), and prasadynium (which forms a semiconductor). 5 7 It has been noted that Tb, Ce, and Pr all have a tendency towards valence instabilities (partial tetravalence) which may be related to the difficulties in making superconductors out of these compounds. It should be noted that diSculties with the light lanthanides may arise in part from the larger ionic radius.These "exceptions" to the independence of the trivalent substitution may play an important role in probing the physics of high-temperature superconductivity.It is therefore prudent to characterize the properties of these materials as thoroughly as for the 90-K superconductors. In this work we will examine the details of resistivity, magnetic susceptibility, and structural measurement on single-phase polycrystalline samples of NdtBa2Cu307-s and PrtBa2Cu307 s. To our knowledge these are the first reported detailed magnetic measurements on these materials which differ only by one atomic number. A comparison of the properties of the Nd and Pr compounds enables insight into the origins of high-temperature superconductivity present only in the Nd compound. It is suggested that this results from differences in the chargecarrier density and possible role of valence fiuctuations.Our resistivity measurements reveal the Nd-based sample to be superconducting with an onset temperature of 90 K and zero resistance at 75 K. The resistivity curves are shown in Fig. l. X-ray diffraction measurements reveal I l I Nd, B&,Cu, O~s 0 I) 00 0 0 0 0 0 0 0 0 0 ...
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