Mixed-valent antimony-induced disorder in substituted antiferromagnetic Mn₂SnS₄

Among MII2AIVQ4 (M = transition metal; A = Si, Ge, and Sn; Q = S, Se, and Te)-type compounds, most of which crystallize in an olivine or spinel structure, Mn2SnS4 is a unique compound that crystallizes in the orthorhombic space group Cmmm and exhibits complex magnetic properties. In this article, we report synthesis and study of the effect of Sb substitution (up to 20%) on the magnetic properties of Mn2SnS4. All the compounds were found to be in a single phase and indexed with the orthorhombic parent structure. Rietveld refinement of the room-temperature neutron diffraction data of Mn2Sn0.85Sb0.15S4 sample shows that Sb occupies the Mn site by replacing an equivalent amount of Mn. Subsequently, the replaced Mn occupies the Sn site causing disorder at both the Mn and the Sn sites, and the refined composition (Mn1.85(1)Sb0.15(1))(Sn0.85(1)Mn0.15(1))S4 is obtained. Although the purpose of incorporation of Sb(iii) was to create a mixed valence state at the Mn site, XPS study shows contrasting results. Sb exists in a mixed valence state, Sb(iii) and Sb(v), which balances the charge at the Sn(iv) site. Magnetic study of the compounds shows a very interesting trend. Pure Mn2SnS4 shows two magnetic transitions: one at 152 K that corresponds to antiferromagnetic ordering and other at 53 K corresponding to weak ferromagnetic ordering possibly due to spin canting. With antimony substitution, the temperature (152 K) of antiferromagnetic ordering remains unchanged, whereas the temperature of weak ferromagnetic ordering gradually increases with an increase in the Sb content from 53 K for the undoped compound to 88 K for 20% Sb-doped Mn2SnS4. The increase in the temperature of weak ferromagnetic ordering could be attributed to the incorporation of Sb, which induces more disorder at the Mn site, thereby making the magnetic lattice dilute with reduced frustration.