Understanding the Role of Lithium Doping in Reducing Nonradiative Loss in Lead Halide Perovskites

Adding alkali metal into lead halide perovskites has recently been demonstrated as an effective strategy for reducing nonradiative loss. However, the suggested role of the alkali metal is usually limited to surface passivation, and the semiconductor doping effect is rarely discussed. Here, the mechanism of lithium doping in the photocarrier recombination in solution‐processed methylammonium lead halide films is investigated by photoluminescence and photoelectron spectroscopies. It is demonstrated that lithium doping weakens the electron–phonon coupling and acts as donor in perovskites, which provide solid evidence that lithium enters the lattice rather than just in the surface region. The n‐type doping creates free electrons to fill the trap states in both the bulk and surface regions, leading to suppressed trapping of photocarriers and reduces nonradiative recombination.