Memory Seeds Enable High Structural Phase Purity in 2D Perovskite Films for High‐Efficiency Devices

2D perovskites are a class of halide perovskites offering a pathway for realizing efficient and durable optoelectronic devices. However, the broad chemical phase space and lack of understanding of film formation have led to quasi‐2D perovskite films with polydispersity in perovskite layer thicknesses, which have hindered device performance and stability. Here, a simple and scalable approach is reported, termed as the “phase‐selective method”, to fabricate 2D perovskite thin films with homogenous layer thickness (phase purity). The phase‐selective method involves the dissolution of single‐crystalline powders with a homogeneous perovskite layer thickness in desired solvents to fabricate thin films. In situ characterizations reveal the presence of sub‐micrometer‐sized seeds in solution that preserve the memory of the dissolved single crystals and dictate the nucleation and growth of grains with an identical thickness of the perovskite layers in thin films. Photovoltaic devices with a p–i–n architecture are fabricated with such films, which yield an efficiency of 17.1% enabled by an open‐circuit voltage of 1.20 V, while preserving 97.5% of their peak performance after 800 h under illumination without any external thermal management. Fabrication of phase‐pure films of 2D perovskites using a novel, simple, and scalable method, referred to as the phase‐selective method, is demonstrated. Phase‐purity is enabled by the presence of sub‐micrometer‐sized seeds in the precursor‐solution that preserves the memory of the dissolved single‐crystals. A photovoltaic efficiency of 17.1% with a VOC of 1.20 V and stability T97.5 = 800 h at MPP is reported.