Effects of A-site substitution on the structure and magnetic properties of Bi(0.15)Sr(0.85-y)Ae(y)Co(1-x)Fe(x)O(3-delta) perovskites

Journal article, 2009

The effects of partial substitution of Sr2+ by Ca2+ and Ba2+ on the A-site of oxygen-deficient perovskites, Bi(0.15)Sr(0.85-y)Ae(y)Co(1-x)FeO(3-delta), where y = 0.28 for Ae = Ba and y = 0.17 for Ae = Ca, and 0.0 <= x <= 1.0, have been investigated. The differing ionic size of the Ca2+ and Ba2+ cations influences both the crystal structure and the properties of the materials. The smaller Ca2+ cation favoured formation of an oxygen vacancy ordered perovskite superstructure (14/mmm, a = 2ap, c = 4a(p)), meanwhile the presence of the larger Ba2+ cation promoted a disordered simple cubic structure (Pm (3) over barm, a = ap) that was also found for all Fe containing samples, i.e. x >= 0.25. The samples were studied with PXRD, NPD, TGA, electron microscopy and magnetic susceptibility measurements. All as-prepared samples exhibited long range G-type antiferromagnetic ordering. The effect of oxygen annealing was dramatic for the Bi0.15Sr0.68Ca0.17Co1-xFexO3-delta series, with a disappearance of magnetic order for x >= 0.25 linked to increasing spin-glass properties. The oxygen content of the Bi0.15Sr0.57Ba0.28Co1-xFexO3-delta as-prepared materials was generally higher than their Ca substituted counterparts, and the long range antiferromagnetic order was more resistant to oxygen annealing. (C) 2009 Elsevier Masson SAS. All rights reserved.