C. Strom et al., THE EFFECT OF THALLIUM AND OXYGEN STOICHIOMETRY ON STRUCTURE AND TC IN TL-2201 AND TL-2212, Journal of solid state chemistry, 109(2), 1994, pp. 321-332
By a novel method we have prepared the high-T(c) superconductors Tl2-x
BaCuO6-d Tl-2201) and Tl2-xBa2CaCu2O8-d (Tl-2212) in a reproducible wa
y with respect to purity, thallium and oxygen content, crystal structu
re, and superconducting properties. The changes in structure induced b
y changes in thallium or oxygen content were studied by X-ray and neut
ron powder diffraction techniques. Tl-2201 crystallizes in either the
tetragonal or orthorhombic system, and both forms can be made supercon
ducting. The detailed atomic order in the Tl2O4 layers seems to be det
ermined by the thallium as well as by the oxygen content. A high thall
ium and oxygen content stabilizes the orthorhombic form. Tl-2212 has t
etragonal symmetry irrespective of thallium or oxygen content. In samp
les low in thallium content no single layer thallium compounds are for
med, the thallium deficiency being accommodated as statistically distr
ibuted vacancies in the Tl2O4 layers. The oxygen content is the main f
actor in determining T(c) in Tl-2201 and Tl-2212. Low thallium content
promotes higher T(c)'s, whereas addition of oxygen to the as prepared
samples decreases T(c). The c-axis length of Tl-2201 decreases by abo
ut 0.06 angstrom when annealed in oxygen at 300-degrees-C. In Tl-2212
the shortening of the c-axis length is about 0.08 angstrom for the sam
e annealing treatment. The change in c-axis length and the atom displa
cements, in particular in the Tl-2212 system, can be explained in term
s of a charge redistribution as for the Y-123 system. An increase in o
xygen content leads to a shift of Ba2+ toward the Tl2O4 layers, and to
an increase in the CuO2 plane puckering as expected from an increase
in hole concentration in the CuO2 planes. (C) 1994 Academic Press, Inc
.