The Impacts and Origins of A-site Instability in Formamidinium-Cesium Lead Iodide Perovskite Solar Cells Under Extended Operation

Improved understanding of the origins of instability during photovoltaic operation of perovskite solar cell materials must be established to overcome barriers to commercialization. In this study, we analyze the microscopic mechanisms of degradation in high-performing methylammonium free (FA0.9Cs0.1PbI3) perovskite solar cells (PSC) over 600 hours of operation under stressors inherent to PV operation, including heat, illumination, and a load while excluding atmospheric effects by testing in a water-and oxygen-free atmosphere. While the PSCs exhibit reasonable thermal stability, they show considerable performance loss under constant illumination or stable power output. Synchrotron-based nanoprobe X-ray fluorescence and X-ray beam induced current (XRF/XBIC) measurements reveal segregation of current-blocking Cs-rich phases during stress testing. The decrease in performance correlates with the resulting number density of the Cs-rich clusters, which varies by stress condition. These findings unveil cation-dependent instability in FA0.9Cs0.1PbI3 perovskites and provide a framework for understanding the energy landscape in alloy perovskites to guide the engineering of long-lived halide perovskite devices.