In Situ Ellipsometry Measurements on the Halide Phase Segregation of Mixed Halide Lead Perovskites

Annik Bernhardt; Tharushi D Ambagaspitiya; Martin E Kordesch; Katherine Leslee A Cimatu; Jixin Chen

doi:10.1002/cphc.202200022

In Situ Ellipsometry Measurements on the Halide Phase Segregation of Mixed Halide Lead Perovskites

Chemphyschem. 2022 Aug 3;23(15):e202200022. doi: 10.1002/cphc.202200022. Epub 2022 Jun 7.

Authors

Annik Bernhardt^{1

2

3}, Tharushi D Ambagaspitiya^{1

3}, Martin E Kordesch^{3

4}, Katherine Leslee A Cimatu^{1

3}, Jixin Chen^{1

3}

Affiliations

¹ Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701, United States.
² Department of Chemistry, University of Leipzig, 04103, Leipzig, Germany.
³ Nanoscale and Quantum Phenomena Institute, Ohio University, Athens, OH 45701, United States.
⁴ Department of Physics and Astronomy, Ohio University, Athens, OH 45701, United States.

Abstract

Methylammonium lead iodide bromides MAPb(Br_x I_1-x )₃ are a class of mixed halide lead perovskites, materials that offer high-power conversion efficiencies and bandgap tunability. For these reasons, they are a promising absorber material for future solar cells, although their use is still limited due to several factors. The reversible phase segregation under even low light intensities is one of them, lowering the effective bandgap due to local segregation into iodide-rich and bromide-rich phases. While several studies have been done to illuminate the mechanism and suppression of phase segregation, challenges remain to understand its kinetics. 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 . 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. The phase segregation rate constants are surprisingly two orders of magnitude slower than and the recovery rate is consistent with those measured using photoluminescence methods under similar conditions. These results confirm a concern in the literature about the complexity in the phase separation kinetics measured from photoluminescence. We expect ellipsometry to serve as a complementary technique to other spectroscopies in studying mixed-halide lead perovskites phase segregation in the future.

Keywords: ellipsometry; kinetic measurements; mixed-halide lead perovskites; phase separation; solar cells.