Compound Defects in Halide Perovskites: A First-Principles Study of CsPbI$_3$

TL;DR

This study uses first-principles calculations to identify and analyze the most prominent compound defects in CsPbI3 perovskites, revealing their impact on stability and electronic properties under various conditions.

Contribution

It provides a detailed first-principles analysis of compound defects in CsPbI3, highlighting their formation, prevalence, and electronic effects under different conditions.

Findings

Pb substituting Cs antisite forms at significant concentrations.

Compound defects generally cause shallow or inactive traps.

Deeper traps may develop under operating conditions with specific Fermi levels.

Abstract

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 CsPbI$_3$, 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 PbI$_2$ or CsPbI$_3$ 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.