Impact of the Solvation State of Lead Iodide on Its Two-Step Conversion to MAPbI₃: An In Situ Investigation

Producing high efficiency solar cells without high-temperature processing or use of additives still remains a challenge with the two-step process. Here, the solution processing of MAPbI₃ from PbI₂ films in N,N-dimethylformamide (DMF) is investigated. In-situ grazing incidence wide-angle X-ray scattering (GIWAXS) measurements reveal a sol–gel process involving three PbI₂-DMF solvate complexes—disordered (P₀) and ordered (P₁, P₂)—prior to PbI₂ formation. When the appropriate solvated state of PbI₂ is exposed to MAI (methylammonium Iodide), it can lead to rapid and complete room temperature conversion into MAPbI₃ with higher quality films and improved solar cell performance. Complementary in-situ optical reflectance, absorbance, and quartz crystal microbalance with dissipation (QCM-D) measurements show that dry PbI₂ can take up only one third of the MAI taken up by the solvated-crystalline P₂ phase of PbI₂, requiring additional annealing and yet still underperforming. The perovskite solar cells fabricated from the ordered P₂ precursor show higher power conversion efficiency (PCE) and reproducibility than devices fabricated from other cases. The average PCE of the solar cells is greatly improved from 13.2(±0.53)% (from annealed PbI₂) to 15.7(±0.35)% (from P₂) reaching up to 16.2%. This work demonstrates the importance of controlling the solvation of PbI₂ as an effective strategy for the growth of high-quality perovskite films and their application in high efficiency and reproducible solar cells.