Solution-Processed Bismuth Halide Perovskite Thin Films: Influence of Deposition Conditions and A-Site Alloying on Morphology and Optical Properties

Bismuth-based halide perovskites have been proposed as a potential nontoxic alternative to lead halide perovskites; however, they have not realized suitable performance. Their poor performance has been attributed to substandard film morphologies and too wide of a band gap for many applications. Herein we used a two-step deposition procedure to convert BiI3 thin films into A3Bi2I9 (A = FA+, MA+, Cs+, or Rb+), which resulted in a substantial improvement in film morphology, a larger band gap, and greater compositional tunability compared toresults when using aconventional single-step deposition technique. Additionally, we attempted to reduce the undesirably wide band gap in Rb3Bi2I9 thin films by inducing chemical pressures through cation-size mismatch, with an underlying hypothesis that cation-size mismatch could induce compressive strain within the 2D Rb3Bi2I9 lattice. However, we found that all AxRb3–xBi2I9 compositions with x > 0 adopted the 0D structure, and no changes to the band gap were observed with alloy. These results imply that the band gap of AxRb3–xBi2I9 is insensitive to A-site alloying.