The accommodation of Co in the oxygen-saturated solid-solution phase YBa2(Fe1-zCoz)3O8+w has been investigated by powder X-ray and neutron diffraction techniques, as well as by 57Fe Mössbauer spectroscopy. Of the nominal composition range 0.00≤z≤1.00 tested, the solid-solution limit under syntheses at 950°C in 1 barO2 is z=0.47(5). No symmetry change in the nuclear and magnetic structures is seen as a consequence of the Co substitution, and the Co atoms are distributed evenly over the two sites that are square-pyramidally and octahedrally coordinated for w=0. The oxygen-saturated samples maintain their oxygen content roughly constant throughout the homogeneity range, showing that Co3+ replaces Fe3+. Despite the nearly constant value of w, Mössbauer spectroscopy shows that the amount of tetravalent Fe slightly increases with increasing z, and this allows Co to adopt valence close to 3.00 to a good approximation. The magnitude of the antiferromagnetic moment (located in the a,b plane) decreases with z in accordance with the high-spin states of the majority Fe3+ and Co3+ ions. Bond-valence analyses are performed to illustrate how the structural network becomes increasingly frustrated as a result of the substitution of Fe3+ by the smaller Co3+ ion. A contrast is pointed out with the substitution of cobalt in YBa2Cu3O7 where it is a larger Co2+ ion that replaces smaller Cu2+.
- Fe Mössbauer spectra
- Solid-solution phase
- Triple-perovskite-type structure
- Yttrium-barium-iron-cobalt oxide