Deterministic synthesis of phase pure 2D perovskites via progressive transformation of layer thickness

Two-dimensional (2D) halide perovskites have emerged as semiconductor platforms for realizing efficient and durable optoelectronic devices. However, the reproducible synthesis of 2D perovskite crystals with desired layer thickness (or n value) greater than 2, has been an enduring challenge due to the lack of kinetic control (temperature, time, stoichiometry) for each layer thickness. Here, we demonstrate a novel method term as the kinetically controlled space confinement (KCSC) for the deterministic growth of phase pure Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) 2D perovskites. The phase-pure growth was achieved by progressively increasing the temperature (fixed time) or the crystallization time (fixed temperature), which allowed for an acute control of the crystallization kinetics. We also observe a systematic transformation from a lower n-value to n=3, 4, 5, 6 in 2D perovskites. In-situ photoluminescence spectroscopy and imaging suggest that the progressive transformation from lower to higher n-value occurs via intercalation of excess precursor ions. These experiments enabled the development of a machine learning assisted multi-parameter phase diagram, which predicts the growth of 2D phase with a specific n-value.