Bismuth-based cuprates

One of main thrusts in organic-perovskite hybrids has been in the preparation of stable delaminated perovskite sols as the building blocks of nanocomposite materials. A well-known process for exfoliation is to weaken the attractive interaction of the layers through intercalation of bulky organic components. A representative example is exfoliation of bismuth-based cuprate superconductors (Figure 14.12). °3... 

Since the discovery of high temperature superconductivity (T > 30 K) in the La-Ba-Cu-O system hundreds of high temperature superconducting oxides have been found, with the record Tc of 164 K in Hg-1223 under high pressure. According to their major chemical difference, these superconductors can be classified into six major categories K2Nip4-type cuprates, rare-earth-based cuprates, bismuth-based cuprates, thallium-based cuprates, mercury-based cuprates, and other cuprates. Details of every superconductor are not presented, but at least one typical composition of each major type will be discussed in detail. Interested readers can read the relevant literature to get specific information on other systems. 

Preparation of Superconductive Ceramics 17.3.10.2. High Temperature Superconductors 17.3.10.2.3. Bismuth-Based Cuprates. 

Preparation of Bismuth- and Thallium-Based Cuprate Superconductors... 

The layer-type structures and chemical nature of the constituents of the bismuth and thallium-based cuprate superconductors - notably the lone-pair stereochemistry of Bis+, variable valence of copper, and considerable exchange among some of the cation sites - combine to make structural non-ideality, nonstoichiometry, and phase intergrowth the rule rather that the exception in these families of materials. These features, as well as the probable metastability of the phases (and possibly all high-temperature oxide superconductors), also contribute to the difficulties typically encountered in preparing single-phase samples with reproducible properties and compositions. 

The volatility of the reactants is a concern in some solid state syntheses. This may be a slight problem in bismuth cuprates synthesized at high temperatures because Bi2Os has an appreciable vapor pressure at these temperatures (i.e. 900-950°C) however, chemical analyses of samples of bismuth-based superconductors before and after reactions at temperatures up to 900°C indicate no detectable loss of bismuth. This problem is much more severe in the case of thallium chemistry. 

The following sections will outline specific methods for the synthesis of Bi- and Tl-based cuprate superconductors. Because the synthetic methods and historical evolution of the compounds are different, the bismuth and thallium families are described separately. 

This chapter presents an overview of our understanding of phase relationships and a summary of synthetic techniques for the synthesis of phase-pure superconducting samples in the bismuth-and thallium-based families of high Tc cuprate superconductors. 

Thallium, bismuth, and lead based HTSCs are relatively degradation-resistant and are therefore convenient systems for conducting electrochemical changes in the oxygen stoichiometry. At the same time, physical properties of these materials are less exactly related to 6 because of the more complicated phase compositions of the corresponding systems. The electrochemical treatment of Bi-Pb cuprates in nitrate melts [297] makes it possible to vary 8 within the region of 0.1. 

Although the bismuthate Bai cKxBi03 and fullerene-based materials have been discovered with f above 3OK, the HTS cuprates remain the only materials where Tc is above 40 K, and reaching as high as 135 K. Moreover, there are dozens of examples of such... 

---