Unraveling the Compositional Heterogeneity and Carrier Dynamics of Alkali Cation Doped 3D/2D Perovskites with Improved Stability

Preventing the degradation of hybrid perovskite by humid air remains a challenge for their future commercial utilization. 3D/2D perovskites with hierarchical architecture have attracted significant attention due to their promising power conversion efficiency (PCE) and device stability. Here, we report novel 3D/2D planar bi-layer perovskite obtained by growing 2D Ruddlesden–Popper layer on top of 3D rubidium (Rb)-doped triple-cation perovskite. Rb cation incorporation decreases the work function, and 3D/2D films show smaller work function values compared to classic 3D perovskites. X-ray photoemission spectroscopy (XPS) confirms the presence of 2D perovskite capping layer and observes halide migration. Time-resolved terahertz spectroscopy (TRTS) shows average DC carrier mobility for 3D/2D hierarchical structures and their 3D counterparts are one order of magnitude higher than 2D perovskite. The resulting 3D/2D Rb-incorporated perovskite solar cells show a peak PCE of >20%, which is slightly higher than their 3D counterpart (19.5%). Benefited from moisture resistivity, the 3D/2D perovskite photovoltaics show significantly improved long-term stability by retaining 81% of the initial PCE after 60 days of exposure in ambient air (50 ± 10% relative humidity) without encapsulation, highlighting the potential of engineered stable 3D/2D perovskite solar cells for their commercial utilization.