In an effort to synthesize the high-T c superconducting phase in the thallium system, two nominal compositions, Tl 2 Ca 2 Ba 2 Cu 3 O 10 and Tl 1 Ca 3 Ba 1 Cu 3 O 8.5, have been investigated for superconductivity as a function of the sintering temperature, time, atmosphere, and quench rate. Samples have been characterized by electrical resistivity measurements, X-ray diffraction, and scanning electron microscopy. Samples of starting composition Tl 2 Ca 2 Ba 2 Cu 3 O 10 fired in air at 860–900°C and rapidly quenched showed T c (R = 0) of 96–107 K. In contrast, specimens of starting composition Tl 1 Ca 0 Ba 1 Cu 3 O 8.5 when baked at 900°C and slow cooled in oxygen were superconducting at ≥ 116 K and consisted of Tl 2 Ca 2 Ba 2 Cu 3 O 10+x as the dominant phase. Our results also show that, in contrast to the case of YBa 2 Cu 3 O 7−x, doping with a small concentration of fluorine sharpens the resistive transition and produces large T c increase in thallium-based superconductors.
