Short Photoluminescence Lifetimes in Vacuum-Deposited CH₃NH₃PbI₃ Perovskite Thin Films as a Result of Fast Diffusion of Photogenerated Charge Carriers

It is widely accepted that a long photoluminescence (PL) lifetime in metal halide perovskite films is a crucial and favorable factor, as it ensures a large charge diffusion length leading to a high power conversion efficiency (PCE) in solar cells. It has been recently found that vacuum-evaporated CH₃NH₃PbI₃ (eMAPI) films show very short PL lifetimes of several nanoseconds. The corresponding solar cells, however, have high photovoltage (>1.1 V) and PCEs (up to 20%). We rationalize this apparent contradiction and show that eMAPI films are characterized by a very high diffusion coefficient D, estimated from modeling the PL kinetics to exceed 1 cm²/s. Such high D values are favorable for long diffusion length as well as fast transport of carriers to film surfaces, where they recombine nonradiatively with surface recombination velocity S ∼ 10⁴ cm/s. Possible physical origins leading to the high D values are also discussed.