The operational stability of perovskite solar cells (PSCs) remains a limiting factor in their commercial implementation. We studied the long-term outdoor stability of ITO/SnO2/Cs0.05((CH3NH3)0.15(CH-(NH2)2)0.85)0.95PbI2.55Br0.45/spiro-OMeTAD/Au cells, as well as the dynamics of their degradation, under simulated sunlight indoors and their recovery in the dark. The extent of overall degradation was found to depend on processes occurring both under illumination and in the dark, i.e., during the daytime and nighttime, with the dynamics varying with cell aging. Full recovery of efficiency in the dark was observed for cells at early degradation stages. Further cell degradation resulted in recovery times much longer than one night, appearing as irreversible degradation under real operational conditions. At later degradation stages, very different dynamics were observed: short-circuit current density and fill factor exhibited a pronounced drop upon light turn-off but strong improvement under subsequent illumination. The interplay of reversible and irreversible degradation processes with different recovery dynamics was demonstrated to result in changes in the cell’s diurnal PCE dependence during its operational lifespan under real sunlight conditions.

In this work, we employ vacuum deposited Au nanoparticles (similar to 4 nm) to control the defect density on the surface of hydrothermally synthesized ZnO nanorod arrays (ZnO-NR), which are of interest for electron-transport layers in perovskite solar cells. Using a combination of photoluminescence spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy, we show that the Au particles reduce the presence of defects in the ZnO-NR We discuss this in terms of trap filling due to band bending at the ZnO-NR surface. As a proof-of-concept, we apply the Au-decorated ZnO-NR as electron-transport layers in mixed-cation and mixed-halide lead perovskite solar cells (Cs(0.15)FA(0.85)PbI(2.75)Br(0.25)). Devices prepared with the Au-decorated ZnO-NR electron-transport layers demonstrate higher open-circuit voltages and fill factors compared to solar cells prepared with pristine ZnO-NR, resulting in an increase in the power-conversion efficiency from 11.7 to 13.7%. However, the operational stability of the solar cells is not improved by the Au nanoparticles, indicating that bulk properties of the perovskite may limit device lifetime.