Abstract

AbstractAll‐inorganic lead‐free Cs2AgBiBr6 double perovskites have gained significant attention due to their potential as stable and nontoxic photoactive semiconductors. Currently, it remains challenging to synthesize homogeneous microcrystals (MCs) exhibiting excellent properties, which are necessary for large‐area device integration. This work proposes a two‐step synthesis approach involving the introduction of a foreign silver cation to transform the 0D layered Cs3Bi2Br9 to 3D Cs2AgBiBr6 perovskite structure. This work has studied the cation exchange (CE) transformation mechanism by isolating intermediates to be able to follow the evolution of the crystal lattice as well as the structural and optical properties over time. Moreover, complete CE results in phase‐pure, highly crystalline Cs2AgBiBr6 MCs exhibiting excellent photonic properties, superior to their counterparts synthesized by anti‐solvent precipitation. These findings highlight the potential of CE‐induced transformation as a means of synthesizing novel, stable perovskites.

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