Crystallization kinetics of rapid spray plasma processed multiple cation perovskites in open air

Rapid Spray Plasma Processing (RSPP) is a high throughput, scalable, and open-air route toward manufacturing perovskite solar modules. The plasma exposure is dosed such that the perovskite precursor solution is cured in milliseconds using a combination of rapid heating, reactive species, and UV photons. We implemented in situ wide angle X-ray scattering (WAXS) to characterize the crystal growth in multiple cation, mixed halide perovskite thin films - Cs_x(MA_zFA_1-z)_1-xPb(Br_0.17I_0.83)₃ for 0.05 ≤ x ≤ 0.25 - fabricated in open air. The use of synchrotron radiation and high detector speeds resolved the formation and dissolution of a transient intermediate crystalline phase during the tens of milliseconds when the perovskite crystallized. Increasing the mole fraction of cesium and methylammonium resulted in a decrease in the intermediate phase and an increase in the average grain diameter. Increasing the cesium fraction suppressed phase segregation, as observed in photoluminescence. Calculations showed the refractive index decreased and the extinction coefficient increased with cesium fraction. Based on the rapid crystallization kinetics, RSPP perovskite films exhibit residual stress values >5× lower than spin coated films. Understanding the kinetics of perovskite formation enables the design of perovskite films with improved thermomechanical and operational stability.