Modeling and Fundamental Dynamics of Vacuum, Gas, and Antisolvent Quenching for Scalable Perovskite Processes.

Hybrid perovskite photovoltaics (PVs) promise cost-effective fabrication with large-scale solution-based manufacturing processes as well as high power conversion efficiencies. Almost all of today's high-performance solution-processed perovskite absorber films rely on so-called quenching techniques that rapidly increase supersaturation to induce a prompt crystallization. However, to date, there are no metrics for comparing results obtained with different quenching methods. In response, the first quantitative modeling framework for gas quenching, anti-solvent quenching, and vacuum quenching is developed herein. Based on dynamic thickness measurements in a vacuum chamber, previous works on drying dynamics, and commonly known material properties, a detailed analysis of mass transfer dynamics is performed for each quenching technique. The derived models are delivered along with an open-source software framework that is modular and extensible. Thereby, a deep understanding of the impact of each process parameter on mass transfer dynamics is provided. Moreover, the supersaturation rate at critical concentration is proposed as a decisive benchmark of quenching effectiveness, yielding ≈ 10 -3 - 10 -1 s -1 for vacuum quenching, ≈ 10 -5 - 10 -3 s -1 for static gas quenching, ≈ 10 -2 - 10 0 s -1 for dynamic gas quenching and ≈ 10 2 s -1 for antisolvent quenching. This benchmark fosters transferability and scalability of hybrid perovskite fabrication, transforming the "art of device making" to well-defined process engineering.