In Situ Observation of Crystallization of Methylammonium Lead Iodide Perovskite from Microdroplets

It is of great importance to investigate the crystallization of organometallic perovskite from solution for enhancing performance of perovskite solar cells. Here, this study develops a facile method for in situ observation of crystallization and growth of the methylammonium lead iodide (MAPbI3) perovskite from microdroplets ejected by an alternating viscous and inertial force jetting method. It is found that there are two crystallization modes when MAPbI3 grows from the CH3NH3I (MAI)/PbI2/N,N‐dimethylformamide (DMF) solution: needle precursors and granular perovskites. Generally, needle Lewis adduct of MAPbI3·DMF tends to nucleate and grow from the solution due to low solubility of PbI2. The growth of MAPbI3·DMF depends on both the concentration of MAI and temperature. It tends to form large perovskite domains on substrates at high temperature. The MAPbI3·DMF coverts to nanocrystalline perovskite due to lattice shrinkage when DMF molecules escape from the Lewis adduct. Granular perovskite can also directly nucleate from the solution at high concentration of MAI due to compositional segregation. Crystallization of perovskite related materials are in situ investigated from microdroplets of CH3NH3I/PbI2/N,N‐dimethylformamide (DMF). Two crystallization modes are observed. Similar to PbI2·DMF, it inclines to form a Lewis adduct of CH3NH3 PbI3·DMF with needle shapes from the solution without compositional segregation. Perovskite grains can also precipitate from the droplet where there is enrichment of CH3NH3I.