Building Blocks of Hybrid Perovskites: A Photoluminescence Study of Lead-Iodide Solution Species.

In this work, we present a detailed investigation of the optical properties of hybrid perovskite building blocks, [PbI2+n ]n- , that form in solutions of CH3 NH3 PbI3 and PbI2 . The absorbance, photoluminescence (PL) and photoluminescence excitation (PLE) spectra of CH3 NH3 PbI3 and PbI2 solutions were measured in various solvents and a broad concentration range. Both CH3 NH3 PbI3 and PbI2 solutions exhibit absorption features attributed to [PbI3 ]1- and [PbI4 ]2- complexes. Therefore, we propose a new mechanism for the formation of polymeric polyiodide plumbates in solutions of pristine PbI2 . For the first time, we show that the [PbI2+n ]n- species in both solutions of CH3 NH3 PbI3 and PbI2 exhibit a photoluminescence peak at about 760 nm. Our findings prove that the spectroscopic properties of both CH3 NH3 PbI3 and PbI2 solutions are dominated by coordination complexes between Pb2+ and I- . Finally, the impact of these complexes on the properties of solid-state perovskite semiconductors is discussed in terms of defect formation and defect tolerance.