In-situ ellipsometry measurements on the phase segregation of mixed halide lead perovskites

Mixed halide lead perovskite such as methylammonium lead iodide bromides MAPb(BrxI1-x)3 have emerged as one of the most promising materials of future solar cells, offering high power conversion efficiencies and bandgap tunability. Among other factors, the reversible phase segregation under even low light intensities is still limiting their potential use. During this process, the material segregates locally into iodide-rich and bromide-rich phases, lowering the effective bandgap energy. While several studies have been done to illuminate the mechanism and suppression of phase segregation, fundamental aspects remain unclear. Phase compositions after segregation vary extensively between different studies and the exact amounts of phases often remain unmentioned. For iodide-rich phases, the end-point compositions at around x=0.2 are widely accepted but the proportion of the phase is difficult to measure. In this report, we observe the phase segregation using spectroscopic ellipsometry, a powerful, nondestructive technique that has been employed in the study of film degradation before. We obtained dynamic ellipsometric measurements from x=0.5 mixed halide lead perovskite thin films protected by a polystyrene layer under green laser light with a power density of ~11 W/cm2. Changes in the bandgap region can be correlated to the changes in composition caused by phase segregation, allowing for the kinetics to be observed. Time constants between 1.7(± 0.7)×10-3 s-1 for the segregation and 1.5(± 0.6)×10-4 s-1 for recovery were calculated. We expect ellipsometry to serve as a complementary technique to other spectroscopies in studying mixed-halide lead perovskites phase segregation in the future.