Quantum-size-tuned heterostructures enable efficient and stable inverted perovskite solar cells

The energy landscape of reduced-dimensional perovskites (RDPs) can be tailored by adjusting their layer width (n). Recently, two/three-dimensional (2D/3D) heterostructures containing n = 1 and 2 RDPs have produced perovskite solar cells (PSCs) with >25% power conversion efficiency (PCE). Unfortunately, this method does not translate to inverted PSCs due to electron blocking at the 2D/3D interface. Here we report a method to increase the layer width of RDPs in 2D/3D heterostructures to address this problem. We discover that bulkier organics form 2D heterostructures more slowly, resulting in wider RDPs; and that small modifications to ligand design induce preferential growth of n ≥ 3 RDPs. Leveraging these insights, we developed efficient inverted PSCs (with a certified quasi-steady-state PCE of 23.91%). Unencapsulated devices operate at room temperature and around 50% relative humidity for over 1,000 h without loss of PCE; and, when subjected to ISOS-L3 accelerated ageing, encapsulated devices retain 92% of initial PCE after 500 h. A scheme to control the confinement within 2D/3D perovskite heterostructures results in stable, efficient inverted perovskite solar cells.