Compound Defects in Halide Perovskites: A First-Principles Study of CsPbI3

Lattice defects affect the long-term stability of halide perovskite solar cells. Whereas simple point defects, i.e., atomic interstitials and vacancies, have been studied in great detail, here we focus on compound defects that are more likely to form under crystal growth conditions, such as compound vacancies or interstitials, and antisites. We identify the most prominent defects in the archetype inorganic perovskite CsPbI3, through first-principles density functional theory (DFT) calculations. We find that under equilibrium conditions at room temperature, the antisite of Pb substituting Cs forms in a concentration comparable to those of the most prominent point defects, whereas the other compound defects are negligible. However, under nonequilibrium thermal and operating conditions, other complexes also become as important as the point defects. Those are the Cs substituting Pb antisite, and, to a lesser extent, the compound vacancies of PbI2 or CsPbI3 units, and the I substituting Cs antisite. These compound defects only lead to shallow or inactive charge carrier traps, which testifies to the electronic stability of the halide perovskites. Under operating conditions with a quasi-Fermi level very close to the valence band, deeper traps can develop.