A long photoluminescence decay lifetime has been regarded as a generic indication of long charge carrier recombination lifetime in semiconductors such as metal halide perovskites (MHPs), which have shown tremendous success in solar cells. Here, we report that MHP polycrystalline films with extrinsic metal ions have a very long charge recombination lifetime, but a much shorter photoluminescence decay lifetime, and this huge difference can be explained by a model of lateral homojunction within each individual grain. The lateral homojunction is formed due to the doping along grain boundaries by metal ions, and then verified by nanoscale potential mapping and transient photo-response mapping. The built-in electric field within each grain reduces the recombination of free charge carriers within the perovskite grain and along grain boundaries, while the free electrons and holes are collected to cathode and anode through the grain boundaries and grain interiors, respectively. Then, the efficiencies of MHP polycrystalline solar cells are increased.

The charge carrier lifetime in organic-inorganic perovskites is one of the most important parameters for modeling and design of solar cells and other types of devices. In this work, we use CH₃NH₃PbI₃ single crystal as a model system to study optical absorption, charge carrier generation, and recombination lifetimes. We show that commonly applied photoluminescence lifetime measurements may dramatically underestimate the intrinsic carrier lifetime in CH₃NH₃PbI₃, which could be due to severe charge recombination at the crystal surface and/or fast electron-hole recombination close to the surface. By using the time-resolved microwave conductivity technique, we investigated the lifetime of free mobile charges inside the crystals. Most importantly, we find that for homogeneous excitation throughout the crystal, the charge carrier lifetime exceeds 15 μs. This means that the diffusion length in CH₃NH₃PbI₃ can be as large as 50 μm if it is no longer limited by the dimensions of the crystallites.