Identification of lead vacancy defects in lead halide perovskites

Perovskite photovoltaics advance rapidly, but questions remain regarding point defects: while experiments have detected the presence of electrically active defects no experimentally confirmed microscopic identifications have been reported. Here we identify lead monovacancy (V(Pb)) defects in MAPbI(3) (MA = CH(3)NH(3)(+)) using positron annihilation lifetime spectroscopy with the aid of density functional theory. Experiments on thin film and single crystal samples all exhibited dominant positron trapping to lead vacancy defects, and a minimum defect density of ~3 × 10(15) cm(−3) was determined. There was also evidence of trapping at the vacancy complex [Formula: see text] in a minority of samples, but no trapping to MA-ion vacancies was observed. Our experimental results support the predictions of other first-principles studies that deep level, hole trapping, [Formula: see text] , point defects are one of the most stable defects in MAPbI(3). This direct detection and identification of a deep level native defect in a halide perovskite, at technologically relevant concentrations, will enable further investigation of defect driven mechanisms.