Despite tremendous progress in efficiency and stability, perovskite solar cells are still facing the challenge of upscaling. Here we present unique advantages of reactive polyiodide melts for solvent- and adduct-free reactionary fabrication of perovskite films exhibiting excellent quality over large areas. Our method employs a nanoscale layer of metallic Pb coated with stoichiometric amounts of CH3NH3I (MAI) or mixed CsI/MAI/NH2CHNH2I (FAI), subsequently exposed to iodine vapour. The instantly formed MAI3(L) or Cs(MA,FA)I3(L) polyiodide liquid converts the Pb layer into a pure perovskite film without byproducts or unreacted components at nearly room temperature. We demonstrate highly uniform and relatively large area MAPbI3 perovskite films, such as 100 cm2 on glass/fluorine-doped tin oxide (FTO) and 600 cm2 on flexible polyethylene terephthalate (PET)/indium tin oxide (ITO) substrates. As a proof-of-concept, we demonstrate solar cells with reverse scan power conversion efficiencies of 16.12% (planar MAPbI3), 17.18% (mesoscopic MAPbI3) and 16.89% (planar Cs0.05MA0.2FA0.75PbI3) in the standard FTO/c(m)-TiO2/perovskite/spiro-OMeTAD/Au architecture.

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