Abstract
Hybrid halide perovskite has established its credibility as high performance thin film photovoltaic technology. Perovskite based on formamidinium cation is at the core composition to top performances and stability. Herein, a depth study based on temperature‐controlled in situ X‐ray diffraction focusing on the photo‐active formamidinium lead iodide ( α ‐FAPbI 3 ) is reported. In particular, the thermal stability of the latter and the degradation pathways under different experimental conditions are clarified. Based on this in situ technique, the lattice thermal expansion coefficient is reported that provides relevant information on possible mechanical stress created upon temperature cycling or damp heat test. The results support that α ‐FAPbI 3 degradation is substantially accelerated when temperature is combined to illumination and when it is interfaced with the extraction layers. In addition, by contrast to in darkness for which α ‐FAPbI 3 degrades directly into PbI 2 , the existence of a temperature gap under illumination involving an intermediate step with a non‐crystalline phase resulting from the perovskite degradation and contributing to the formation of PbI 2 by‐product is revealed.