Cation distribution and magnetic characterization of the multiferroic cobalt manganese Co2MnO4 spinel doped with bismuth

The structural and magnetic properties of the cubic spinel oxide Co2MnO4 (Fd3m space group) doped with different concentrations of bismuth, were investigated by X-ray diffraction and SQUID magnetometry. The Bi3+ ions entering into the CoIII octahedral sites do not alter the effective moment, μeff ∼8.2 μB, whereas both the magnetization M50kOe at the highest field (50 kOe) and the field-cooled MFC magnetizations increased when increasing the Bi content. The ferrimagnetic character of the parent compound, Co2MnO4, is maintained for all materials although the antiferromagnetic interactions Co2+–Co2+ are affected, resulting in higher values of the Curie–Weiss temperature. Due to the large ionic radius of Bi, octahedra distortions occur as well as valence fluctuations of the Mn ions, giving rise to Jahn-Teller effects and enhancing the exchange interactions. The off-center Bi3+ ion is responsible of non-centrosymmetric charge ordering and should lead to multiferroïsme conditions for the BixCo2−xMnO4 material. - Highlights: ► Bi-doped Co2MnO4 (BixCo2−xMnO4) synthesized by polymeric precursors method. ► Valence fluctuations and distribution of Co and Mn in tetrahedral and octahedral sites. ► Ferrimagnetism with TC, MS and field-cooled MFC magnetizations enhanced with Bi doping. ► Bi3+ substitution on octahedral CoIII sites enhance the ferromagnetic exchange.