Homogeneously Large Polarons in Aromatic Passivators Improves Charge Transport between Perovskite Grains for >24 % Efficiency in Photovoltaics.

Aromatic passivators, such as porphyrin, with large π-backbones have attracted considerable attention to boost the charge carrier in polycrystalline perovskite films, thus enabling the fabrication of efficient and stable perovskite solar cells (PSCs). However, they often self-assemble into supramolecules that probably influence the charge-transfer process in the perovskite grain boundary. Here, by doping a monoamine Cu porphyrin into perovskite films, two porphyrin-based self-assembled supramolecules were successfully prepared between perovskite grains. Crystal structures and theoretical analyses reveal the presence of a stronger interaction between the amine units and the central Cu ions of neighbouring porphyrins in one of the supramolecules. This has a modified effect on the dipole direction of the porphyrins to be quantized as homogeneously large polarons (HLPs) in a periodic lattice. The porphyrin supramolecules can stabilize perovskite grain boundaries to greatly improve the stability of PSCs, while the HLPs-featured supramolecule facilitates hole transport across perovskite grains to remarkably increase the cell performance to as high as 24.2 %. This work proves that the modulation of the intermolecular interaction of aromatic passivators to yield HLPs is crucial for the cascaded acceleration of charge transport between perovskite grains.