Detecting and identifying reversible changes in perovskite solar cells by electrochemical impedance spectroscopy

The current status of electrochemical impedance spectroscopy (EIS) and related analysis on perovskite solar cells (PSC) is still unsatisfactory. The provided models are still vague and not really helpful for guiding the efforts to develop more efficient and stable devices. Due to the slow and complex dynamics of these devices, the obtained spectra need to be validated, which is hardly ever done. This study may be the first to provide fully validated impedance spectra and presents reproducible EIS time series at open circuit voltage (V-OC) for more than 20 hours, with a total of 140 analysed spectra. We conclude that the observed changes stem from a temporary reduction of the electronically active area of the devices, as can be deduced from the inverse behaviour of resistance and capacitance. The changes in these values are almost 100% reversible if the devices are kept in the dark for only one day, while the time constant of the high-frequency process remains unchanged throughout the whole characterization procedure. The tested devices are full PSC devices that have proven to be stable over more than 500 hours, and the non-steady impedance measurements shine a critical light on previously published EIS data. With the results of this study, it can be rationalized that the high-frequency semicircle can serve as a good indicator for ionic migration by monitoring its consequences. The results presented here are helpful to quantify ionic migration on the device level in order to derive new stability criteria and countermeasures against degradation.