In Situ Formation of δ-FAPbI₃ at the Perovskite/Carbon Interface for Enhanced Photovoltage of Printable Mesoscopic Perovskite Solar Cells

Formamidinium lead triiodide (FAPbI3) perovskite has attracted intensive research attention due to its ideal band gap and low defect density for photovoltaic applications. Particularly, the existence of non-photoactive δ-phase FAPbI3 has been considered detrimental to regular-structured perovskite solar cells (PSCs). Here, in hole-conductor-free triple-mesoscopic PSCs, we observe that α-phase FAPbI3 transforms to δ-phase FAPbI3 at the perovskite/carbon interface and in situ forms an α/δ-phase junction when the as-fabricated cells are exposed to humid atmosphere. The α/δ-phase junction shows a favorable band alignment and significantly suppresses the charge recombination at the interface. By controlling the relative humidity of the atmosphere, we fabricate FAPbI3-based cells that deliver a champion efficiency of 17.11% with an enhanced open-circuit voltage (VOC) of 1020 mV. This work demonstrates the potential of δ-phase FAPbI3 for benefiting the device performance of PSCs and proposes the concept of constructing perovskite-based junctions at the interface between a perovskite-absorbing layer and charge-transporting layers for enhancing the VOC of PSCs.