Eppur si Muove: Proton Diffusion in Halide Perovskite Single Crystals

Abstract Ion diffusion affects the optoelectronic properties of halide‐perovskites (HaPs). Until now, the fastest diffusion has been attributed to the movement of the halides, largely neglecting the contribution of protons, on the basis of computed density estimates. Here, the process of proton diffusion inside HaPs, following deuterium–hydrogen exchange and migration in MAPbI₃, MAPbBr₃, and FAPbBr₃ single crystals, is proven through D/H NMR quantification, Raman spectroscopy, and elastic recoil detection analysis, challenging the original assumption of halide‐dominated diffusion. The results are confirmed by impedance spectroscopy, where MAPbBr₃‐ and CsPbBr₃‐based solar cells respond at very different frequencies. Water plays a key role in allowing the migration of protons as deuteration is not detected in its absence. The water contribution is modeled to explain and forecast its effect as a function of its concentration in the perovskite structure. These findings are of great importance as they evidence how unexpected, water‐dependent proton diffusion can be at the basis of the ≈7 orders of magnitude spread of diffusion (attributed to I⁻ and Br⁻) coefficient values, reported in the literature. The reported enhancement of the optoelectronic properties of HaP when exposed to small amounts of water may be related to the finding.