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Tl-Ba-Cu-Cu-O superconducting thin films were prepared by magnetron sputtering with postannealing in a reduced oxygen atmosphere. Single-phase Tl2Ba2Ca2Cu3Oχ can form on the MgO substrate at 800°C under P(O2)≈0.1 atm. However, the phase formation temperature can be affected by the starting composition of the film. Tl1Ba2 Ca2Cu2Oχ phase can be formed by simply lowering the Tl2O pressure. The thermal stability of Tl1Ba2Ca2Cu3Oχ phase was studied by resistivity measurements at high temperatures.