| Summary: | Despite the remarkable progress in perovskite solar cells (PSCs), their instability and rapid degradation over time still restrict their commercialization. A 2D capping layer has been proved to overcome the stability issues; however, an in-depth understanding of the complex degradation processes over a prolonged time at PSC interfaces is crucial for improving their stability. In the current work, we investigated the stability of a triple cation 3D ([(FA<sub>0.83</sub>MA<sub>0.17</sub>)Cs<sub>0.05</sub>]Pb(I<sub>0.83</sub>Br<sub>0.17</sub>)<sub>3</sub>) and 2D/3D PSC fabricated by a layer-by-layer deposition technique (PEAI-based 2D layer over triple cation 3D perovskite) using a state-of-art characterization technique: electrochemical impedance spectroscopy (EIS). A long-term stability test over 24 months was performed on the 3D and 2D/3D PSCs with an initial PCE of 18.87% and 20.21%, respectively, to suggest a more practical scenario. The current-voltage (J-V) and EIS results showed degradation in both the solar cell types; however, a slower degradation rate was observed in 2D/3D PSCs. Finally, the quantitative analysis of the key EIS parameters affected by the degradation in 3D and 2D/3D PSCs were discussed.
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