Halogen‐Bonded Hole‐Transport Material Suppresses Charge Recombination and Enhances Stability of Perovskite Solar Cells

Abstract Interfaces play a crucial role in determining perovskite solar cells, (PSCs) performance and stability. It is therefore of great importance to constantly work toward improving their design. This study shows the advantages of using a hole‐transport material (HTM) that can anchor to the perovskite surface through halogen bonding (XB). A halo‐functional HTM (PFI) is compared to a reference HTM (PF), identical in optoelectronic properties and chemical structure but lacking the ability to form XB. The interaction between PFI and perovskite is supported by simulations and experiments. XB allows the HTM to create an ordered and homogenous layer on the perovskite surface, thus improving the perovskite/HTM interface and its energy level alignment. Thanks to the compact and ordered interface, PFI displays increased resistance to solvent exposure compared to its not‐interacting counterpart. Moreover, PFI devices show suppressed nonradiative recombination and reduced hysteresis, with a V_oc enhancement of ≥20 mV and a remarkable stability, retaining more than 90% efficiency after 550 h of continuous maximum‐power‐point tracking. This work highlights the potential that XB can bring to the context of PSCs, paving the way for a new halo‐functional design strategy for charge‐transport layers, which tackles the challenges of charge transport and interface improvement simultaneously.