Grain Boundary Engineering with Self-Assembled Porphyrin Supramolecules for Highly Efficient Large-Area Perovskite Photovoltaics

Grain boundary management is critical to the performance and stability of polycrystalline perovskite solar cells (PSCs), especially large-area devices. However, typical passivators are insulating in nature and limit carrier transport. Here, we design a supramolecular binder for grain boundaries to simultaneously passivate defects and promote hole transport across perovskite grain boundaries. By doping the monoamine porphyrins (MPs, M = Co, Ni, Cu, Zn, or H) into perovskite films, MPs self-assemble into supramolecules at grain boundaries. Organic cations in perovskites protonate MPs in supramolecules to form ammonium porphyrins bound on the perovskite grain surface, to passivate defects and extract holes from the perovskite lattice. Periodic polarons in supramolecules (especially NiP-supramolecule) promote the transport of extracted holes across boundaries, reducing nonradiative carrier recombination. The NiP-doped PSCs reveal a certified efficiency of 22.1% for an active area of 1.0 cm2 with the remarkably improved open-circuit voltage and fill factor. The unencapsulated device retained over 80% initial performance under AM 1.5G solar light continuous illumination or heating at 85 °C over 3000 h.