Ferroelectricity and Crystal Phases in Mixed‐Cation Lead Iodide Perovskite Solar Cells

After the discovery of ferroelectricity in archetypal methylammonium lead iodide (MAPbI$_3$), the discussion arose, if more advanced derivatives thereof are also ferroelectric and to what extent the polar domains mitigate detrimental charge carrier recombination in perovskite solar cells. Herein, the A-site cation methylammonium is gradually substituted with formamidinium and cesium. The domain contrast measured by piezoresponse force microscopy is correlated with the distortion of the crystal structure measured by X-ray diffraction. By Rietveld analysis, a detailed structural model together with texture information is determinded, which reveals an intriguing interplay between lead iodide and the perovskite phases. Finally, the bearing of ferroelectric domains in mixed-cation perovskites on the solar cell performance is discussed.