Oxygen Content and Valence of Ru in RuSr2(Gd0.75Ce0.25)2Cu2O10−δ (Ru-1222) Magnetosuperconductor

The valence of Ru was analyzed for two RuSr2(Gd0.75Ce0.25)2Cu2O10−δ samples with different oxygen contents by Ru LIII-edge x-ray absorption near-edge structure (XANES) spectroscopy. For the sample as-synthesized in 1 atm O2 the DC magnetization data measured in an applied field of 5 Oe showed a clear branching of the zero-field-cooled (ZFC) and field-cooled (FC) curves around 140 K, an up-turn for both around 100 K and a cusp at 85 K and a diamagnetic transition around 20 K in the ZFC part. A further confirmation for the superconductivity at 28 K was obtained from a resistance vs. temperature measurement. Annealing the as-synthesized sample in 100-atm O2 atmosphere at 420°C increased the diamagnetic transition temperature from 20 K to 40 K. According to a thermogravimetric analysis, the oxygen content increased accordingly by ca. 0.1 oxygen atoms per formula unit. Quantitative analysis of the XANES spectra using Sr2RuO4 (RuIV) and Sr2GdRuO6 (RuV) as reference materials revealed a valence value of +4.74 and +4.81 for Ru in the as-synthesized and the 100-atm O2-annealed sample, respectively. The obtained result suggests that the valence of Ru in Ru-1222 is affected by the change in oxygen content.