Critical Influence of Organic A′-Site Ligand Structure on 2D Perovskite Crystallization

Organic A′-site ligand structure plays a crucial role in the crystal growth of 2D perovskites, but the underlying mechanism has not been adequately understood. This problem is tackled by studying the influence of two isomeric A′-site ligands, linear-shaped n-butylammonium (n-BA⁺) and branched iso-butylammonium (iso-BA⁺), on 2D perovskites from precursor to device, with a combination of in situ grazing-incidence wide-angle X-ray scattering and density functional theory. It is found that branched iso-BA⁺, due to the lower aggregation enthalpies, tends to form large-size clusters in the precursor solution, which can act as pre-nucleation sites to expedite the crystallization of vertically oriented 2D perovskites. Furthermore, iso-BA⁺ is less likely to be incorporated into the MAPbI₃ lattice than n-BA⁺, suppressing the formation of unwanted multi-oriented perovskites. These findings well explain the better device performance of 2D perovskite solar cells based on iso-BA⁺ and elucidate the fundamental mechanism of ligand structural impact on 2D perovskite crystallization.