A range of slow dynamic processes occurring in perovskite solar cells have been linked to ionic migration, including J-V hysteresis and long photovoltage rise and decay times. This work demonstrates the remarkably slow response time of triple mesoporous carbon-based cells, containing the additive 5-aminovaleric acid iodide (AVA). The photovoltage rise under illumination is 1-2 orders of magnitude longer than has previously been observed for planar and mesoporous TiO2 based devices. Transient photovoltage measurements during this slow rise in voltage show a strong negative transient feature which demonstrates the presence of fast recombination. By analysing the rate of Voc rise and the decay of this negative transient, we show a clear link between this recombination process and the limiting of the Voc. The reduction of recombination over time, and resultant rise in Voc, is influenced by the movement of ions in the perovskite. From temperature dependent measurements an activation energy consistent with previous literature values for iodide ion migration is obtained, although the attempt frequency is found to be many orders of magnitude lower than in pure MAPI perovskite devices. We attribute this to the presence of the AVA molecule inhibiting the movement of ions. The importance of the TiO2/ZrO2 interface in leading to this slow behaviour is revealed by studying devices with different architectures with and without the AVA additive. A significant increase in response time can only be recreated in a device with both of the mesoporous metal oxide layers and the AVA additive present in the perovskite.

The authors would like to thank the EPSRC (EP/N020863/1, EP/R032750/1, EP/M015254/2, EP/P032591/1), the Welsh European Funding Office (SPARC II) and the Welsh Government's Sêr Solar programme for funding.