Bismuth-Based Perovskite-Inspired Solar Cells: In Situ Diagnostics Reveal Similarities and Differences in the Film Formation of Bismuth- and Lead-Based Films

Organic-inorganic lead-based halide perovskite compounds currently yield thin film solar cells with a power conversion efficiency (PCE) of >23%. However, replacing the lead with less-toxic elements while maintaining a high PCE remains a challenge. For this reason, there has been significant effort to develop Pb-free compounds, including methylammonium bismuth iodide (MA(3)Bi(2)I(9)), but such systems severely underperform when compared with the prototypical Pb-based methylammonium lead iodide (MAPbI(3)). For the latter, it is known that lead complexes with polar solvents, such as dimethyl sulfoxide (DMSO) and dimethylformamide (DMF), to form iodoplumbates which can co-crystallize into solvated phases. Herein, the solidification and growth behaviors of Bi- and Pb-based films is investigated using multi-probe in situ characterization methods. It is shown that the Bi-based compound crystallizes directly and rapidly into a textured polycrystalline microstructure from a precursor solution without evolving through intermediate crystalline solvated phases, in contrast to MAPbI(3). This solidification process produces isolated crystals and challenges the growth of continuous and crystalline films required for solar cells. It is revealed that solvent engineering with antisolvent dripping is crucial to enable the formation of continuous polycrystalline films of MA(3)Bi(2)I(9) and functional solar cells thereof.