Effects of Ti and Mn Co-substitution on P4mm BiFeO3: An Ab Initio Calculation

Tetragonal BiFeO3 (BFO), which has a giant spontaneous polarization, has attracted a great deal of attention recently. In this paper, we systematically study the structural, magnetic, electronic and optic properties of BFO, BiFe0.75Mn0.25 O 3 (BFMM), and BiFe0.75Ti0.125Mn0.125 O 3 (BFMT). Results show that doping Ti and Mn into the Fe sites increases the c/a ratio and enhances the magnetization of BiFeO3 from 0 to 5 μB. The crystal symmetry changes from orthogonality to tetragonality with half of the Mn atoms being replaced by Ti in BiFe0.75Mn0.25 O 3, which suppresses the energy splitting of the Mn 3d orbitals and thus enlarge the band gap to 1.21 eV for BiFe0.75Ti0.125Mn0.125 O 3. Our calculated Bader charge and charge density difference show that the smallest volume of BiFe0.75Mn0.25 O 3 arises from the strong Mn–O bonds in BiFe0.75Mn0.25 O 3. Further investigations indicate similar optical behaviors for BiFeO3 and BiFe0.75Ti0.125Mn0.125 O 3. However, BiFe0.75Mn0.25 O 3 exhibits strong absorption in the infrared region for the transition from O 2p to Mn \({e_{g}^{2}}\) and \(t_{2g}^{3}\).