Towards Better Perovskite Absorber Materials: Cu+ Doping Improves Photostability and Radiation Hardness of Complex Lead Halides
Marina I. Ustinova,
Maxim N. Sarychev,
Nikita A. Emelianov,
Yiqun Li,
Yuling Zhuo,
Tongjun Zheng,
Sergey D. Babenko,
Evgeniy D. Tarasov,
Pavel P. Kushch,
Nadezhda N. Dremova,
Galina A. Kichigina,
Alexandra V. Rasmetyeva,
Andrey I. Kukharenko,
Dmitry P. Kiryukhin,
Ernst Z. Kurmaev,
Xueqing Xu,
Pavel A. Troshin,
Lyubov A. Frolova,
Ivan S. Zhidkov
Affiliations
Marina I. Ustinova
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Maxim N. Sarychev
Institute of Physics and Technology Ural Federal University Yekaterinburg Russia
Nikita A. Emelianov
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Yiqun Li
Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of new and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion Chinese Academy of Sciences Guangzhou People's Republic of China
Yuling Zhuo
Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of new and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion Chinese Academy of Sciences Guangzhou People's Republic of China
Tongjun Zheng
Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of new and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion Chinese Academy of Sciences Guangzhou People's Republic of China
Sergey D. Babenko
V. L. Talrose Institute for Energy Problems of Chemical Physics, N. N. Semenov Federal Research Center for Chemical Physics Russian Academy of Sciences Moscow Russia
Evgeniy D. Tarasov
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Pavel P. Kushch
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Nadezhda N. Dremova
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Galina A. Kichigina
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Alexandra V. Rasmetyeva
Institute of Physics and Technology Ural Federal University Yekaterinburg Russia
Andrey I. Kukharenko
Institute of Physics and Technology Ural Federal University Yekaterinburg Russia
Dmitry P. Kiryukhin
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Ernst Z. Kurmaev
Institute of Physics and Technology Ural Federal University Yekaterinburg Russia
Xueqing Xu
Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of new and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion Chinese Academy of Sciences Guangzhou People's Republic of China
Pavel A. Troshin
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Lyubov A. Frolova
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences Chernogolovka Russia
Ivan S. Zhidkov
Institute of Physics and Technology Ural Federal University Yekaterinburg Russia
ABSTRACT The partial Pb2+ substitution with Cu+ ions has been thoroughly applied as an approach to produce new absorber materials with enhanced light and radiation hardness required for potential aerospace applications of perovskite solar cells. X‐ray photoelectron spectroscopy revealed that Cu+ ions are partially integrated into the crystal lattice of MAPbI3 on the surface of perovskite grains and induce p‐doping effect, which is crucial for a range of applications. Importantly, the presence of Cu+ enhances photostability of perovskite films and blocks the formation of metallic lead as a photolysis product. Furthermore, we have carried out one of the first studies on the radiation hardness of complex lead halides exposed to two different stressors: γ‐rays and 8.5 MeV electron beams. The obtained results demonstrate that Cu+ doping alters completely the radiation‐induced degradation pathways of the double cation perovskite. Indeed, while Cs0.12FA0.88PbI3 degrades mostly with segregation of δ‐phase of FAPbI3 forming a Cs‐rich perovskite phase, the Cs0.12FA0.88Pb0.99Cu0.01I2.99 films tend to expel δ‐CsPbI3 and produce FA‐rich perovskite phase, which shows impressive tolerance to both γ‐rays and high energy electrons. The beneficial effect of copper ion incorporation on the stability of lead halide perovskite solar cells under light soaking and γ‐ray irradiation conditions has been shown. The discovered possibility of controlling the electronic properties and major materials degradation pathways through minor modification of their chemical composition (e.g., replacing 1% of Pb2+ with Cu+) opens up tremendous opportunities for engineering new perovskite absorber compositions with significantly improved properties for both terrestrial and aerospace applications.