TY - JOUR
T1 - First-principles calculations of defects in metal halide perovskites
T2 - A performance comparison of density functional
AU - Xue, Haibo
AU - Brocks, Geert
AU - Tao, Shuxia
PY - 2021/12/27
Y1 - 2021/12/27
N2 - Metal halide perovskite semiconductors have outstanding optoelectronic properties. Although these perovskites are defect-tolerant electronically, defects hamper their long-term stability and cause degradation. Density functional theory (DFT) calculations are an important tool to unravel the microscopic structures of defects, but results suffer from the different approximations used in the DFT functionals. In the case of metal halide perovskites, qualitatively different results have been reported with different functionals, either predicting vacancy or interstitial point defects to be most dominant. Here, we conduct a comprehensive comparison of a wide range of functionals for calculating the equilibrium defect formation energies and concentrations of point defects in the archetype metal halide perovskite, MAPbI3. We find that it is essential to include long-range van der Waals interactions in the functional, and that it is vital to self-consistently optimize structure and volume of all compounds involved in the defect formation. For calculating equilibrium formation energies of point defects in MAPbI3 and similar metal halide perovskites, we argue that the exact values of the chemical potentials of the species involved, or of the intrinsic Fermi level, are not important. In contrast to the simple Schottky or Frenkel pictures, we find that the dominant defects are MA and I interstitials, and Pb vacancies.
AB - Metal halide perovskite semiconductors have outstanding optoelectronic properties. Although these perovskites are defect-tolerant electronically, defects hamper their long-term stability and cause degradation. Density functional theory (DFT) calculations are an important tool to unravel the microscopic structures of defects, but results suffer from the different approximations used in the DFT functionals. In the case of metal halide perovskites, qualitatively different results have been reported with different functionals, either predicting vacancy or interstitial point defects to be most dominant. Here, we conduct a comprehensive comparison of a wide range of functionals for calculating the equilibrium defect formation energies and concentrations of point defects in the archetype metal halide perovskite, MAPbI3. We find that it is essential to include long-range van der Waals interactions in the functional, and that it is vital to self-consistently optimize structure and volume of all compounds involved in the defect formation. For calculating equilibrium formation energies of point defects in MAPbI3 and similar metal halide perovskites, we argue that the exact values of the chemical potentials of the species involved, or of the intrinsic Fermi level, are not important. In contrast to the simple Schottky or Frenkel pictures, we find that the dominant defects are MA and I interstitials, and Pb vacancies.
KW - 2023 OA procedure
U2 - 10.1103/PhysRevMaterials.5.125408
DO - 10.1103/PhysRevMaterials.5.125408
M3 - Article
SN - 2475-9953
VL - 5
JO - Physical Review Materials
JF - Physical Review Materials
IS - 12
M1 - 125408
ER -