Reversible Decomposition of Single-Crystal Methylammonium Lead Iodide Perovskite Nanorods

[Image: see text] Perovskite solar cells offer remarkable performance, but further advances will require deeper understanding and control of the materials and processing. Here, we fabricate the first single crystal nanorods of intermediate phase (MAI-PbI(2)-DMSO), allowing us to directly observe the phase evolution while annealing in situ in a high-vacuum transmission electron microscope, which lets up separate thermal effects from other environmental conditions such as oxygen and moisture. We attain the first full determination of the crystal structures and orientations of the intermediate phase, evolving perovskite, precipitating PbI(2), and e-beam induced PbI(2) during phase conversion and decomposition. Surprisingly, the perovskite decomposition to PbI(2) is reversible upon cooling, critical for long-term device endurance due to the formation of MAI-rich MAPbI(3) and PbI(2) upon heating. Quantitative measurements with a thermodynamic model suggest the decomposition is entropically driven. The single crystal MAPbI(3) nanorods obtained via thermal cycling exhibit excellent mobility and trap density, with full reversibility up to 100 °C (above the maximum temperature for solar cell operation) under high vacuum, offering unique potential for high-performance flexible solar cells.