Tracking the dimensionality transition from a three dimensional single crystal to a two dimensional perovskite

This work carefully studied the transition from 3D perovskite to 2D perovskite. Our system includes single crystals (SCs) of MAPbBr3, which were dipped in a solution of barrier molecules. Three monoammonium cations and one di‐ammonium cation were studied. Absorbance and cathodoluminescence were used to follow the formation of low‐dimensional perovskite on the SC surface. Quantitative nuclear magnetic resonance and scanning electron microscopy assist in quantitatively tracking the exchange process. We followed the barrier molecules' concentration during the exchange process and their penetration depth into the 3D single crystal. The short aliphatic chain penetrates much farther into the crystal (ca. 450 mm) than the long aliphatic chain barrier molecule. In contrast, the process time is the opposite: the long aliphatic chain requires 5 days to achieve an equilibrium state compared with 15 days for the short aliphatic chain. Ab initio calculations indicate that the exchange process initiates due to the methylammonium vacancies on the surface, and the process is inhibited by the interactions between the ‐NH3 group and the PbBr2 planes. This work sheds light on the kinetics and thermodynamics of the transition from 3D to 2D perovskites, which is important for stabilizing the hybrid perovskites.