Modulating the electronic and magnetic properties of the marcasite FeS₂ via transition metal atoms doping

First-principles calculations are used to investigate the electronic and magnetic properties of substitutional doping of transition metal (TM) atoms (V, Cr, Mn, Co, Ni, Cu and Zn) on marcasite FeS₂ (m-FeS₂). It is energetically favorable to combine TM atoms into m-FeS₂ under S-rich condition. The electronic properties of m-FeS₂ are changed significantly due to the introduced impurity states by TM atoms. Simultaneously, TM atoms doping can induce magnetism in m-FeS₂ except Cu and Zn. The magnetism stem from the localized unpaired 3d electrons of TM atoms, a small amount of magnetic moments are induced in the neighboring Fe and S atoms due to the p–d hybridization mechanism. V-, Mn- and Ni-doped m-FeS₂ compounds exhibit magnetic semiconducting character, Cr-doped compound display a half-metallic property, while Cu-doped compound shows non-magnetic metallic property, Zn-doped compound behavior as a non-magnetic semiconductor. More interestingly, a single Co-doped compound shows magnetic semiconducting but double Co-doped compound shows half metallic character. In addition, Co- and Cr-doped compounds prefer ferromagnetic state which is important for spintronics.