Metallic, oxygen-deficient compounds in the Ba−La−Cu−O system, with the composition BaxLa5−xCu5O5(3−y) have been prepared in polycrystalline form. Samples withx=1 and 0.75,y>0, annealed below 900°C under reducing conditions, consist of three phases, one of them a perovskite-like mixed-valent copper compound. Upon cooling, the samples show a linear decrease in resistivity, then an approximately logarithmic increase, interpreted as a beginning of localization. Finally an abrupt decrease by up to three orders of magnitude occurs, reminiscent of the onset of percolative superconductivity. The highest onset temperature is observed in the 30 K range. It is markedly reduced by high current densities. Thus, it results partially from the percolative nature, bute possibly also from 2D superconducting fluctuations of double perovskite layers of one of the phases present.

Possible high Tc superconductivity in the Ba-La-Cu-O system

The oxide superconductors, particularly those recently discovered that are based on La2CuO4have a set of peculiarities that suggest a common, unique mechanism: they tend in every case to occur near a metal-insulator transition into an odd-electron insulator with peculiar magnetic properties. This insulating phase is proposed to be the long-sought “resonating-valence-bond” state or “quantum spin liquid” hypothesized in 1973. This insulating magnetic phase is favored by low spin, low dimensionality, and magnetic frustration. The preexisting magnetic singlet pairs of the insulating state become charged superconducting pairs when the insulator is doped sufficiently strongly. The mechanism for superconductivity is hence predominantly electronic and magnetic, although weak phonon interactions may favor the state. Many unusual properties are predicted, especially of the insulating state.

http://science.sciencemag.org/content/sci/235/4793/1196.full.pdf

The resonating valence bond state in La2CuO4 and superconductivity

Starting with the history of the fundamental science of the relation of structure to composition delineated completely by Goldschmidt, we use the perovskite structure to illustrate the enormous pow...

The perovskite structure—a review of its role in ceramic science and technology

Since the discovery of superconductivity above 30 K by Bednorz and M\"uller in the La copper oxide system, the critical temperature has been raised to 90 K in Y${\mathrm{Ba}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{7}$ and to 110 and 125 K in Bi-based and Tl-based copper oxides, respectively. In the two years since this Nobel-prize-winning discovery, a large number of electronic structure calculations have been carried out as a first step in understanding the electronic properties of these materials. In this paper these calculations (mostly of the density-functional type) are gathered and reviewed, and their results are compared with the relevant experimental data. The picture that emerges is one in which the important electronic states are dominated by the copper $d$ and oxygen $p$ orbitals, with strong hybridization between them. Photon, electron, and positron spectroscopies provide important information about the electronic states, and comparison with electronic structure calculations indicates that, while many features can be interpreted in terms of existing calculations, self-energy corrections ("correlations") are important for a more detailed understanding. The antiferromagnetism that occurs in some regions of the phase diagram poses a particularly challenging problem for any detailed theory. The study of structural stability, lattice dynamics, and electron-phonon coupling in the copper oxides is also discussed. Finally, a brief review is given of the attempts so far to identify interaction constants appropriate for a model Hamiltonian treatment of many-body interactions in these materials.

Electronic structure of the high-temperature oxide superconductors

It is well known that the breakthrough of Bednorz and Muller1 in discovering superconductivity in (La, Ba)2CuO4 was inspired in part by their knowledge of the superconducting properties of Ba(Pb, Bi)O3 (ref. 2). With a transition temperature, Tc, of ∼12 K, that compound was not generally considered anomalous despite the fact that its Tcis 3–5 times higher than that of traditional superconductors with comparable density of states3–5. The increases in Tc for copper-oxide-based materials continue to generate worldwide excitement, but from both a chemical and theoretical point of view it would also be exciting if high-Tcsuperconductivity were observed in another class of materials. Here we report the results of experiments leading us to the single-phase perovskite Ba0.6K0.4BiO3, which has a magnetically determined onset temperature of 29.8 K—a Tc considerably higher than that of conventional superconductors and surpassed only by copper-containing compounds. Superconductivity in this compound occurs within the framework of a three dimensionally connected bismuth-oxygen array. These results suggest that further research toward exploring the limiting Tcs for bismuth-oxide-based, high-temperature superconductors might be fruitful.

A.W. Sleight

Papers

High-temperature superconductivity in the BaPb/sub 1-x/Bi/sub x/O$sub 3$ system