A Novel Thiazole‐Core Spacer Based Dion–Jacobson Perovskite with Type II Quantum Well Structure for Efficient Photovoltaics

2D Dion–Jacobson (DJ) perovskites show structural stability and tunability and are regarded as promising photovoltaic materials. The spacer cations play an important impact on exciton separation and charge transport of 2D perovskites. Herein, a novel spacer with thiazole as core, 2‐thiazolemethanammonium (AMT), owning characters of small molecular size, delocalized π‐electrons, and strong electron‐withdrawing ability, is introduced to construct 2D DJ perovskites. Owing to the strong orbital coupling between AMT spacer and inorganic layers, the AMT‐based perovskite exhibits type II quantum well structure, which is favorable for exciton separation. On contrary, such interaction does not appear in the DJ perovskite when aliphatic propyldiammonium (PDA), with a similar length, is used as spacer. The AMT spacer can also induce better crystallinity, resulting in reduced defect density and improved charge transport ability. The optimized device based on (AMT)MA3Pb4I13 exhibits a power conversion efficiency (PCE) of 19.69%, which is a record for 2D DJ perovskite solar cells (PSCs) (n ≤ 4). This work provides deep understanding of the impact of aromatic spacer on the electronic structure of 2D DJ perovskites and the corresponding photovoltaic performance and provides a new opportunity toward highly efficient and stable PSCs. Introducing 2‐thiazolemethanammonium (AMT) as a new spacer, the (AMT)MA3Pb4I13 device reaches a record PCE of 19.69% for n ≤ 4 2D perovskites. Due to the strong orbital coupling between AMT spacer and inorganic layers, the AMT‐based 2D perovskite features a type II quantum well, enhancing exciton separation, and charge transport.