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

Singh M, Abdelsamie M, Li Q, Kodalle T, Lee DK, Arnold S, Ceratti DR, Slack JL, Schwartz CP, Brabec C, Tao S, Sutter-Fella CM (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Chemistry of Materials American Chemical Society

DOI: 10.1021/acs.chemmater.3c00799

Abstract

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 Cs0.05FA0.81MA0.14Pb(I0.85Br0.15)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-phase formation rate, and appears to reduce the nucleation radius. These findings provide novel insights into solvent, antisolvent, and perovskite precursor interactions and their formation pathways. The complexity of interactions between solvents and reagents highlights the importance of understanding these effects to further improve the reproducibility and optimize processing conditions.

Authors with CRIS profile

Simon Arnold Lehrstuhl für Elektronische Bauelemente Christoph Brabec Institute Materials for Electronics and Energy Technology (i-MEET)

Involved external institutions

Lawrence Berkeley National Laboratory (LBNL) US United States (USA) (US) King Fahd University of Petroleum and Minerals (KFUPM) SA Saudi Arabia (SA) Eindhoven University of Technology / Technische Universiteit Eindhoven (TU/e) NL Netherlands (NL) Sorbonne Université FR France (FR) University of Nevada Las Vegas US United States (USA) (US)

How to cite

APA:

Singh, M., Abdelsamie, M., Li, Q., Kodalle, T., Lee, D.K., Arnold, S.,... Sutter-Fella, C.M. (2023). Effect of the Precursor Chemistry on the Crystallization of Triple Cation Mixed Halide Perovskites. Chemistry of Materials. https://doi.org/10.1021/acs.chemmater.3c00799

MLA:

Singh, Mriganka, et al. "Effect of the Precursor Chemistry on the Crystallization of Triple Cation Mixed Halide Perovskites." Chemistry of Materials (2023).

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