Phase Behavior and Role of Organic Additives for Self-Doped CsPbI 3 Perovskite Semiconductor Thin Films.

The phase change of all-inorganic cesium lead halide (CsPbI 3 ) thin film from yellow δ-phase to black γ-/α-phase has been a topic of interest in the perovskite optoelectronics field. Here, the main focus is how to secure a black perovskite phase by avoiding a yellow one. In this work, we fabricated a self-doped CsPbI 3 thin film by incorporating an excess cesium iodide (CsI) into the perovskite precursor solution. Then, we studied the effect of organic additive such as 1,8-diiodooctane (DIO), 1-chloronaphthalene (CN), and 1,8-octanedithiol (ODT) on the optical, structural, and morphological properties. Specifically, for elucidating the binary additive-solvent solution thermodynamics, we employed the Flory-Huggins theory based on the oligomer level of additives' molar mass. Resultantly, we found that the miscibility of additive-solvent displaying an upper critical solution temperature (UCST) behavior is in the sequence CN:DMF > ODT:DMF > DIO:DMF, the trends of which could be similarly applied to DMSO. Finally, the self-doping strategy with additive engineering should help fabricate a black γ-phase perovskite although the mixed phases of δ-CsPbI 3 , γ-CsPbI 3 , and Cs 4 PbI 6 were observed under ambient conditions. However, the results may provide insight for the stability of metastable γ-phase CsPbI 3 at room temperature.