Thermodynamic Constraints for the In Situ MOCVD Growth of Superconducting Tl-Ba-Ca-Cu-O Thin Films

In spite of several attempts, superconducting Tl-Ba-Ca-Cu-O thin films have not been successfully prepared in situ by metal organic chemical vapor deposition (MOCVD). Preparation of a phase by MOCVD requires that it be thermodynamically stable with respect to its decomposition into volatile species and other condensed phases. For MOCVD growth of Tl-Ba- Ca-Cu-O compounds in the presence of oxygen from reagents containing only C-H or C-H-O ligands, Tl2O(g) and TIOH(g) exhibit appreciable volatility. If reagents with ligands containing fluorine are used, the formation of volatile TIF(g) must also be considered. Thermodynamic data for these materials are compiled, and thermodynamic relationships between these gases, H2O(g) and HF(g) are established. The thermodynamic stability of TIOH(g) and TIF(g) makes the in situ growth of Tl-Ba-Ca-Cu-O compounds by MOCVD more difficult than their in situ growth by physical vapor deposition processes, for which Tl2O(g) is the only volatile TI-containing species present.