Understanding Differences in the Crystallization Kinetics between One-Step Slot-Die Coating and Spin Coating of MAPbI₃ Using Multimodal In Situ Optical Spectroscopy

To develop a detailed understanding about halide perovskite processing from solution, the crystallization processes are investigated during spin coating and slot-die coating of MAPbI₃ at different evaporation rates by simultaneous in situ photoluminescence, light scattering, and absorption measurements. Based on the time evolution of the optical parameters it is found that for both processing methods initially solvent-complex-structures form, followed by perovskite crystallization. The latter proceeds in two stages for spin coating, while for slot-die coating only one perovskite crystallization phase occurs. For both processing methods, it is found that with increasing evaporation rates, the crystallization kinetics of the solvent-complex structure and the perovskite crystallization remain constant on a relative time scale, whereas the duration of the second perovskite crystallization in spin coating increases. This second perovskite crystallization appears restricted due to differences in solvent-complex phase morphologies from which the perovskite forms. The work emphasizes the importance of the exact precursor state properties on the perovskite formation. It further demonstrates that detailed analyses of multimodal optical in situ spectroscopy allows gaining a fundamental understanding of the crystallization processes that take place during solution processing of halide perovskites, independent from the specific processing method.