Methylammonium fragmentation in amines as source of localized trap levels and the healing role of Cl in hybrid lead-iodide perovskites

The resilience to deep traps and localized defect formation is one of the important aspects that qualify a material as a suited photoabsorber in solar cell devices. Here we investigate by ab initio calculations the fundamental physics and chemistry of a number of possible localized defects in hybrid methylammonium lead-iodide perovskites. Our analysis encompasses a number of possible molecular fragments deriving from the dissociation of methylammonium. In particular, we found that in stoichiometric conditions both ammonia and methylamine molecules present lone-pair localized levels well within the perovskite band gap, while the radical cation CH<inf>2</inf>NH<inf>3</inf>⁺ observed by EPR after irradiation injects partially-occupied levels into the band gap but only in p-type conditions. These defects are thus potentially capable of significantly altering absorption and recombination properties. Amazingly, we found that additional interstitial Cl is capable of removing these localized states from the band gap. These results are consistent with the observed improvement of photoabsorption properties due to the Cl inclusion in the solution processing.