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Suresh Maniyarasu, J. Chun-Ren Ke, Ben F. Spencer, Alex S. Walton, Andrew G. Thomas and Wendy R. Flavell
ACS Appl. Mater. Interfaces 202

Perovskite solar cells (PSCs) based on organic–inorganic hybrid perovskites containing a small fraction of substituted alkali-metal cations have shown remarkable performance and stability. However, the role of these cations is unclear. The thermal- and moisture-induced degradation of FA1–xCsxPbI3 and (FA1–xCsx)1–yRbyPbI3 (where FA represents formamidinium, xy = 0.1, 0.05) is investigated using in situ photoelectron spectroscopy (PES). Both compositions exhibit superior moisture stability compared with methylammonium lead iodide under 9 mbar of water vapor. Ga Kα hard X-ray PES is used to investigate the composition of the perovskites at depths up to 45 nm into the surface. This allows more accurate quantification of the alkali-metal distribution than is possible using conventional X-ray PES. The addition of RbI results in a fairly homogeneous distribution of both Cs+ and Rb+ in the surface layers (in contrast to surface Cs depletion seen in its absence), together with a marked reduction in surface iodide vacancies. Overall, RbI is found to play a critical role in increasing the thermal stability of FA1–xCsxPbI3 by providing a source of I that fills iodine vacancy sites in the perovskite lattice, while Rb+ is not substantially incorporated into the perovskite. We suggest that the concomitant increase in ion migration barriers in the surface layers is key to improved PSC performance and long-lasting stability.