First-principles calculation of temperature-dependent electronic transitions mechanism in V or Nb substituted BiFeO3

Here, we present a simulation study of temperature-dependent electronic transitions in BiVO₃ (BVO) and BiNbO₃ (BNO) using density functional theory (DFT) together with generalized gradient approximation (GGA) and two-dimensional correlation analysis (2D-CA). The results indicate that heat accumulation can accelerate the degeneracy of V-3d orbital in BVO and the splitting of Nb-4d orbital in BNO at 750 K. We found changes in the type of d–p hybrid orbital as follows, for BVO: V-d_x²_+y² + d_Z²-O-2p_z → V-d_x²_+y²-O-2p_z; and for BNO: Nb-d_x²_+y²-O-2p_z → Nb-d_x²_+y² + d_Z²-O-2p_z. Furthermore, we found changes in the type of hybrid orbital leading to the following electron–electron interactions, for BVO: t_2g (V-d_Z²-O-2p_z) + e_g (V-d_x²_+y²-O-2p_z) → t_2g (V-d_x²_+y²-O-2p_z); and for BNO: t_2g + e_g (Nb-d_x²_+y² + d_Z²-O-2p_z) → t_2g (Nb-d_x²_+y²-O-2p_z) + e_g (Nb-d_z²-O-2p_z). The electronic transitions are determined by a charge-transfer from the occupied O-2p⁴ orbitals to the unoccupied V-3d³ (or Nb-4d³) and Bi-6p³ orbitals. Due to the temperature-dependent electronic structure closely related to these electronic transitions, this study provides a new perspective for the design and improvement of BFO-based temperature-sensitive devices.