Perovskite solar cells (PSCs) based on lead halide perovskite have attracted much attention owing to the fast development of their power conversion efficiency (PCE) from 3.8% to 25%. Various factors play important roles in affecting the conversion efficiency of PSCs, such as charge carrier generation, transport, recombination, and collection. In addition, the presence of interfacial defects has also a crucial effect in charge carrier transfer and recombination processes. However, the origin and mechanism of interfacial charge recombinations in PSCs are still not comprehensively investigated. For that purpose, we have performed intensity-modulated photovoltage spectroscopy (IMVS) and transient photovoltage (TPV) measurements of PSCs, which were fabricated with FTO/c-TiO2/mp-TiO2/Perovskite/PTAA/Au cell structure. The solar cell (J-V) characteristics of the PSCs on the day-1, day-2, day-3, and day-6 after the cell fabrication, indicating a significant degradation of the cell with time. The Nyquist plots of IMVS measurement on the same day as the J-V measurement seem to be composed of two semicircles at a lower frequency range and a higher frequency range. The semicircle at the lower frequency range enlarged on the day-6 measurement, but the semicircle at higher frequency decreased. The change of this Nyquist plot is in agreement with a significant decrease in the J-V curves. The semicircle at lower frequency may be assigned to the ion diffusion or migration. Therefore, cell degradation may be caused by the liberation of ions (including iodide) from the surface of the perovskite crystal structure. It then increases recombination loss due to back charge transfer from TiO2 to perovskite as indicated by the changing of the semicircle at high frequency into a smaller semicircle. Therefore, the present results reemphasize that the improvement of PSC stability needs the prevention of ions liberations from the surface by introducing passivation substances. In addition, the results also show the practical usefulness of IMVS for inspecting PSC degradation due to such an ion liberation process.
Modeling of Intensity-Modulated Photocurrent/Photovoltage Spectroscopy: Effect of Mobile Ions on the Dynamic Response of Perovskite Solar Cells