Neutron powder diffraction study on the crystal and magnetic structures of BiCoO3

The crystal and magnetic structures of polycrystalline BiCoO3 have been determined by the Rietveld method from neutron diffraction data measured at temperatures from 5 to 520 K. BiCoO3 (space group P4mm; Z = 1; a = 3.72937(7) (A) over circle and c = 4.72382(15) (A) over circle at room temperature; tetragonality c/a = 1.267) is isotypic with BaTiO3 and PbTiO3 in the whole temperature range. BiCoO3 is an insulator with a Neel temperature of 470 K. A possible model for antiferromagnetic order is proposed with a propagation vector of k = ((1)/(2), (1)/(2), 0). In this model, magnetic moments of Co3+ ions are parallel to the c direction and align antiferromagnetically in the ab plane. The antiferromagnetic ab layers stack ferromagnetically along the c axis, forming a C-type antiferromagnetic structure. Refined magnetic moments at 5 and 300 K are 3.24(2)mu(B) and 2.93(2)mu(B), respectively. The structure refinements revealed no deviation from stoichiometry in BiCoO3. BiCoO3 decomposed in air above 720 K to give Co3O4 and sillenite-like Bi25CoO39.