Preparation, characterization and DFT+U study of the polar Fe3+-based phase Ba5Fe2ZnIn4S15 containing S = 5/2 zigzag chains

Abstract

The polar magnetic chalcogenide phase Ba₅Fe₂ZnIn₄S₁₅ was synthesized and its structure was solved by single crystal XRD. It is the first member with a 3d magnetic metal (Fe³⁺) in the Pb₅ZnGa₆S₁₅-type structure family of wide bandgap materials with non-linear optical properties. The three-dimensional framework possesses a low dimensional magnetic character through the presence of weakly interacting zig-zag chains made of corner-sharing FeS₄ tetrahedra forming chain 1, [FeS₂]⁻_∞. The latter chains are separated by InS₄ tetrahedra providing weak magnetic super-super exchanges between them. The framework is also constituted by chain 2, [In₃Zn₁S₉]⁷⁻_∞ (chain of T2-supertetrahedra) extended similarly to chain 1 along the direction c and connected through InS₄ tetrahedra. Symmetry analysis shows that the intrinsic polarization observed in this class of materials is mostly due to the anionic framework. Preliminary magnetic measurements and density functional theory calculations suggest dominating antiferromagnetic interactions with strong super-exchange coupling within the Fe-chains.