Structure and interstitial iodide migration in hybrid perovskite methylammonium lead iodide

Hybrid perovskites form an emerging family of exceptional light harvesting compounds. However, the mechanism underpinning their photovoltaic effect is still far from understood, which is impeded by a lack of clarity on their structures. Here we show that iodide ions in the methylammonium lead iodide migrate via interstitial sites at temperatures above 280 K. This coincides with temperature dependent static distortions resulting in pseudocubic local symmetry. Based on bond distance analysis, the migrating and distorted iodines are at lengths consistent with the formation of I 2 molecules, suggesting a 2I − →I 2 +2 e − redox couple. The actual formula of this compound is thus (CH 3 NH 3 )PbI 3−2 x (I 2 ) x where x ∼0.007 at room temperature. A crucial feature of the tetragonal structure is that the methylammonium ions do not sit centrally in the A-site cavity, but disordered around two off-centre orientations that facilitate the interstitial ion migration via a gate opening mechanism. The mechanism underpinning the photovoltaic effect in hybrid perovskite solar cells has remained unclear. Here, Green and co-workers suggest that iodide ions in methylammonium lead iodide perovskite migrate via interstitial sites and undergo a redox reaction to form molecular iodine and free electrons.