Unravelling Degradation Mechanisms and Atomic Structure of Organic-Inorganic Halide Perovskites by Cryo-EM

Despite rapid progress of hybrid organic-inorganic halide perovskite solar cells, using transmission electron microscopy to study their atomic structures has not been possible because of their extreme sensitivity to electron beam irradiation and environmental exposure. Here, we develop cryogenic-electron microscopy (cryo-EM) protocols to preserve an extremely sensitive perovskite, methylammonium lead iodide (MAPbI₃) under various operating conditions for atomic-resolution imaging. We discover the precipitation of lead iodide nanoparticles on MAPbI₃ nanowire's surface after short UV illumination and surface roughening after only 10 s exposure to air, while these effects remain undetected in conventional x-ray diffraction. We establish a definition for critical electron dose, and find this value for MAPbI₃ at cryogenic condition to be 12 e^-/Ų at 1.49 Å spatial resolution. Our results highlight the importance of cryo-EM since traditional techniques cannot capture important nanoscale changes in morphology and structure that have important implications for perovskite solar cell stability and performance.