Abstract
The changes of the chemical structure of and of the superconducting transition temperature associated with Ca doping have been investigated by means of neutron and x-ray powder diffraction, oxygen content determination and magnetic susceptibility measurements. In this work, we were able to show that the depression of superconductivity in Ca-substituted orthorhombic is related to essential structural changes. Using the cation - oxygen distances obtained by neutron diffraction at 1.5 K we calculated the bond valence sums of the cations. This allows us to estimate the charge distribution within the structure and yields a direct correlation between structural changes induced by Ca doping and . Our results show clearly that Ca doping leads to an overdoping of which cannot be reached by oxygen non-stoichiometry alone.
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