Retarding solid-state reactions enable efficient and stable all-inorganic perovskite solar cells and modules.

All-inorganic CsPbI 3 perovskite solar cells (PSCs) with efficiencies exceeding 20% are ideal candidates for application in large-scale tandem solar cells. However, there are still two major obstacles hindering their scale-up: (i) the inhomogeneous solid-state synthesis process and (ii) the inferior stability of the photoactive CsPbI 3 black phase. Here, we have used a thermally stable ionic liquid, bis (triphenylphosphine)iminium bis (trifluoromethylsulfonyl)imide ([PPN][TFSI]), to retard the high-temperature solid-state reaction between Cs 4 PbI 6 and DMAPbI 3 [dimethylammonium (DMA)], which enables the preparation of high-quality and large-area CsPbI 3 films in the air. Because of the strong Pb-O contacts, [PPN][TFSI] increases the formation energy of superficial vacancies and prevents the undesired phase degradation of CsPbI 3 . The resulting PSCs attained a power conversion efficiency (PCE) of 20.64% (certified 19.69%) with long-term operational stability over 1000 hours. A record efficiency of 16.89% for an all-inorganic perovskite solar module was achieved, with an active area of 28.17 cm 2 .