Tl-2212 superconducting thin films were fabricated on LaAlO3 (00l) substrates by sol-gel method. In the process, the precursor films were annealed in various gas atmospheres. XRD and EDX testing results showed that the precursors annealed in O2 converted into pure Tl-2212 superconducting phase, and the nominally stoichiometric cation ratio of TlBaCaCu was close to 2:2:1:2. The Tl-2212 film had a layered morphology and medium-quality superconductive parameters, which included the critical temperature T c of 105.5 K, and the critical current density J c of 0.8 MA/cm2 (self-field, 77K).
Owing to high critical temperature (125 K) and high upper critical field, TlBa2Ca2Cu3O9 (Tl-1223) superconductor is a kind of superconducting power transmission material working at liquefied natural gas temperature, and it has a great potential application value in the strong and weak electric field. In this work, the Tl-1223 superconducting films are fabricated by rapidly heating-up sintering technology (RHST) on (00l) lanthanum aluminate substrates. The Tl-Ba-Ca-Cu-O target is used as a sputtering source to deposit the precursor films by the radio-frequency magnetron sputtering technique. The Tl-contained pellets, named annealing targets, are fabricated by the solid-state reaction of stoichiometric quantities of Tl2O3, BaO2, CaO and CuO powders with an initial cation ratio of m Tl:Ba:Ca:Cu=0.4-1.8:2:2:3. The amorphous precursors together with the annealing target providing Tl source are sealed in a silver foil and annealed at 820℃ for 5 min in argon atmosphere, then converted into Tl-1223 superconducting phase. The heating rates are set at 2.5℃/s from room temperature to 350℃, 5℃/s from 350℃ to 650℃, and 35℃/s from 650℃ to 820℃, respectively. The prepared films are characterized by X-ray diffraction and scanning electron microscope. In the conventional low heating rate process, all of the precursor films sintered together with the annealing targets containing different Tl content are first converted into Tl-2212 superconducting phase. That is because the sample residence time in the phase transition temperature range of Tl-2212 is longer, while the phase-formed temperature of Tl-2212 is lower than that of Tl-1223. In the RHST, when the metal ion molar ratio of Tl to Ba in the annealing target is 1.8:2, the main phase of the film is (00l)-oriented Tl-2212. In addition, the film also contains a small number of Tl-2223 grains. On reducing the ratio to 1:2, the film is composed of Tl-1212, Tl-2212, Tl-1223 and Tl-2223 grains. As the ratio decreases to 0.8:2, the film contains the (00l)-oriented Tl-1223 grains and traces of Tl-2223 grains. With the ratio decreasing to 0.4:2, purely c-axis oriented Tl-1223 film is obtained. The critical transition temperature Tc onset of the as-grown film is only 103 K. The film annealed again in oxygen gas has a dense crystal structure and excellent electrical properties. The Tc onset of the sample is about 116 K, and the critical current density Jc is about 1.5 MA/cm2 (77 K, 0 T). The experimental results show that the new sintering process to grow Tl-based films has several advantages such as the short processing cycles, less raw-material consumption, and low production cost.
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