Black-phase formamidinium lead iodide (FAPbI), with a narrow bandgap and high thermal stability, has emerged as an in-demand material for highly efficient perovskite solar cells (PSCs). In a two-step sequential deposition, the PbI film plays an important role in the formation of a perovskite film with desirable qualities. This paper explores using N-methyl-2-pyrrolidone (NMP), a strong Lewis base, and N,N-dimethylformamide (DMF) as a mixed precursor solvent (DMF/NMP) of PbI and reports on preparing PbI films with a porous morphology by thermal treatment. Porous PbI films ensure the diffusion and sufficient reaction of the formamidinium iodide solution to form a smooth perovskite film. In addition, a dynamic spin coating method is also introduced to improve the uniformity of the perovskite film. Both methods yield a pure α-phase FAPbI film immediately in the unannealed state, which is necessary for the perovskite film to maintain phase stability. Finally, PSCs with a power conversion efficiency of 21.20% (0.13 cm) are fabricated and optimized. The unencapsulated PSCs retain 90% of the initial efficiency for 1000 hours in dry air and exhibit a good thermal stability when heated to 85 °C.
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