Fluoride Chemistry in Tin Halide Perovskites

Tin is the frontrunner for substituting toxic lead in perovskite solar cells. However, tin suffers the detrimental oxidation of Sn(II) to Sn(IV). Most of reported strategies employ SnF(2) in the perovskite precursor solution to prevent Sn(IV) formation. Nevertheless, the working mechanism of this additive remains debated. To further elucidate it, we investigate the fluoride chemistry in tin halide perovskites by complementary analytical tools. NMR analysis of the precursor solution discloses a strong preferential affinity of fluoride anions for Sn(IV) over Sn(II), selectively complexing it as SnF(4). Hard X‐ray photoelectron spectroscopy on films shows the lower tendency of SnF(4) than SnI(4) to get included in the perovskite structure, hence preventing the inclusion of Sn(IV) in the film. Finally, small‐angle X‐ray scattering reveals the strong influence of fluoride on the colloidal chemistry of precursor dispersions, directly affecting perovskite crystallization.