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Reversible Pb 2+ /Pb 0 and I − /I 3 − Redox Chemistry Drives the Light‐Induced Phase Segregation in All‐Inorganic Mixed Halide Perovskites
Author(s) -
Frolova Lyubov A.,
Luchkin Sergey Y.,
Lekina Yulia,
Gutsev Lavrenty G.,
Tsarev Sergey A.,
Zhidkov Ivan S.,
Kurmaev Ernst Z.,
Shen Ze Xiang,
Stevenson Keith J.,
Aldoshin Sergey M.,
Troshin Pavel A.
Publication year - 2021
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.202002934
Subject(s) - halide , perovskite (structure) , materials science , redox , phase (matter) , chemical physics , silver halide , inorganic chemistry , nanotechnology , crystallography , chemistry , organic chemistry , layer (electronics) , metallurgy
Tunability of optoelectronic properties of lead halide perovskites achieved through halide mixing can potentially enable their multiple applications, for example, in tandem solar cells and light‐emitting diodes. However, mixed halide perovskites are unstable under illumination due to their segregation to Br‐rich and I‐rich phases, which negatively affects the performance and the operational stability of devices. Research efforts over the past years provided a substantial understanding of the factors influencing light‐induced halide phase segregation. While several mechanisms have been proposed, none of them could account for all available experimental data; and hence the origin of the effect is still under active debate. Herein, the photodegradation of CsPbI 2 Br and Cs 1.2 PbI 2 Br 1.2 is thoroughly investigated using a set of complementary techniques. In situ atomic force microscopy provides a visualization of the real‐time halide phase segregation dynamics demonstrating that iodoplumbate is selectively expelled from the mixed halide perovskite grains and nucleates as a separate I‐rich phase at the grain boundaries. A mechanism based on the reversible Pb 2+ /Pb 0 and I − /I 3 − redox (photo)chemistry is proposed, which explains the experimental findings and other previously reported results. Furthermore, it sheds new insights on the underlying mechanisms of multiple phenomena related to light‐ or electric field‐induced degradation of various lead halide perovskites.