Oxygen nonstoichiometry and valence of copper in the Cu-1222 superconductor

Essentially single-phase Cu(Ba0.67Eu0.33)2(Ce0.33Eu0.67)2Cu2O9±δ samples of the Cu-1222 phase with a fluorite-structured (Ce,Eu)–O2–(Ce,Eu) block between the superconductive CuO2 planes were synthesized in O2 atmosphere to exhibit superconductivity with Tc around 25 K. Wide-range tuning of oxygen content and thereby the overall hole-doping level of the phase was found possible through (i) temperature-controlled oxygen-depletion (TCOD) annealing carried out in a thermobalance in N2 at various temperatures (for reduction), and (ii) high-pressure oxygenation (HPO) treatments carried out in a cubic-anvil-type high-pressure apparatus in the presence of various amounts of Ag2O2 as an excess oxygen source (for oxidation). For the HPO samples a record-high Tc value of 62 K was achieved. On the other hand, deoxygenation to the oxygen content less than image was found to kill superconductivity. The degree of hole doping (both in overall and for the CuO2 plane and CuO1±δ charge reservoir separately) in the samples is discussed on the bases of Cu L-edge and O K-edge XANES data.