Effect of the Precursor Chemistry on the Crystallization of Triple Cation Mixed Halide Perovskites

作者：Mriganka Singh, Maged Abdelsamie, Qihua Li, Tim Kodalle, Do Kyung Lee, Simon Arnold, Davide Raffaele Ceratti, Jonathan Slack, Craig P. Schwartz, Christoph J. Brabec, Shuxia Tao, Carolin M. Sutter‐Fella · 发表于：Chemistry of Materials · 年份：2023 · DOI：10.1021/acs.chemmater.3c00799 · 被引用次数：24 · 研究领域：Perovskite Materials and Applications、Solid-state spectroscopy and crystallography、Crystal Structures and Properties

Triple cation, mixed halide perovskite compositions have been reported to be more thermally stable, exhibit fewer phase impurities, and show higher power conversion efficiency and better reproducibility than single cation perovskites. In this work, we explain the formation of Cs 0.05 FA 0.81 MA 0.14 Pb(I 0.85 Br 0.15 ) 3 via a multimodal in situ study combining structural information from synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and optical properties from photoluminescence (PL) spectroscopy with density functional theory calculations (DFT). The focus here is on the effects of the solvent and antisolvent during crystallization. The predominantly used solvents N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the antisolvent chlorobenzene (CB) as well as the solvent–antisolvent–precursor interactions are investigated. Given the high elemental complexity and mutual interdependencies between solvent, antisolvent, and perovskite precursors, we found significant differences in the crystallization pathways. DMF-pure precursors show the formation of the DMF-containing intermediate phase and the nucleation of compositionally distinct perovskite phases, while when DMSO is added, only crystalline α- and δ-phases were found. In addition, the presence of DMSO helps the formation of α-perovskite. Coordination energy and bond order (BO) calculations support our experimental findings. Dripping of CB induces nucleation at room temperature, slows the α-phas...