Abstract
The thermodynamic properties of Hg 1201 have been studied by thermogravimetry in terms of point defects, related to the departure from stoichiometry δ. The oxygen intercalation/disintercalation process is shown to be not completely reversible in the temperature range of 150–450°C. The reversible fraction δ ∗ depends on the oxygen pressure according to a law in (p O 2) 1 6 which corresponds to the insertion of interstitial oxygen and the formation of two holes per oxygen. The formation enthalpy of these defects, 0.5 eV, is rather small. A model based on temperature dependent barrier heights is introduced to account for the non-reversible fraction. The barrier mechanism may be related to exchange interactions between interstitial oxygens mediated by the mercury sublattice. The thermogravimetric analysis has allowed to derive the T c versus δ curve without resorting in particular in the overdoped regime to high oxygen pressures.
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