Real-Time Observation of Iodide Ion Migration in Methylammonium Lead Halide Perovskites

Abstract

Organic-inorganic metal-halide perovskites (e.g. CH3NH3PbI3-xClx) emerged as a promising opto-electronic material. However, the Shockley–Queisser Limit for the power conversion efficiency (PCE) of perovskite-based photovoltaic devices has still not been reached, which was attributed to non-radiative recombination pathways, as suggested by photoluminescence (PL) inactive (or dark) areas on perovskite films. Although these observations have been related to the presence of ions/defects, the underlying fundamental physics and detailed microscopic processes, concerning trap/defect status, ion migration, etc., still remain poorly understood. Here we utilize correlated wide-field PL microscopy and impedance spectroscopy (IS) on perovskite films to in-situ investigate both the spatial and temporal evolution of these PL inactive areas under external electrical fields. We attribute the formation of PL inactive domains to the migration and accumulation of iodine ions under external fields. Hence we are able to characterize the kinetic processes and determine the drift velocities of these ions. In addition, we show that I2 vapor directly affects the PL quenching of a perovskite film, which provides evidence that the migration/segregation of iodide ions plays an important role in the PL quenching and consequently limits the PCE of organometal halide based perovskite photovoltaic devices.