Lessons Learnt from Spatially Resolved Electro‐ and Photoluminescence Imaging: Interfacial Delamination in CH3NH3PbI3 Planar Perovskite Solar Cells upon Illumination

The influence of illumination on the long‐term performance of planar structured perovskite solar cells (PSCs) is investigated using fast and spatially resolved luminescence imaging. The authors analyze the effect of illuminated current density–voltage (J–V) and light‐soaking measurements on pristine PSCs by providing visual evidence for the spatial inhomogeneous evolution of device performance. Regions that are exposed to light initially produce stronger electroluminescence signals than surrounding unilluminated regions, mainly due to a lower contact resistance and, possibly, higher charge collection efficiency. Over a period of several days, however, these initially illuminated regions appear to degrade more quickly despite the device being stored in a dark, moisture‐ and oxygen‐free environment. Using transmission electron microscopy, this accelerated degradation is attributed to delamination between the perovskite and the titanium dioxide (TiO₂) layer. An ion migration mechanism is proposed for this delamination process, which is in accordance with previous current–voltage hysteresis observations. These results provide evidence for the intrinsic instability of CH₃NH₃PbI₃‐based devices under illumination and have major implications for the design of PSCs from the standpoint of long‐term performance and stability.