Gradient Doping in Sn–Pb Perovskites by Barium Ions for Efficient Single‐Junction and Tandem Solar Cells

Narrow-bandgap (NBG) tin (Sn)-lead (Pb) perovskites generally have a high density of unintentional p-type self-doping, which reduces the charge-carrier lifetimes, diffusion lengths, and device efficiencies. Here, a p-n homojunction across the Sn-Pb perovskite is demonstrated, which results from a gradient doping by barium ions (Ba2+ ). It is reported that 0.1 mol% Ba2+ can effectively compensate the p-doping of Sn-Pb perovskites or even turns it to n-type without changing its bandgap. Ba2+ cations are found to stay at the interstitial sites and work as shallow electron donor. In addition, Ba2+ cations show a unique heterogeneous distribution in perovskite film. Most of the barium ions stay in the top 600 nm region of the perovskite films and turn it into weakly n-type, while the bottom portion of the film remains as p-type. The gradient doping forms a homojunction from top to bottom of the perovskite films with a built-in field that facilitates extraction of photogenerated carriers, resulting in an increased carrier extraction length. This strategy enhances the efficiency of Sn-Pb perovskite single-junction solar cells to over 21.0% and boosts the efficiencies of monolithic perovskite-perovskite tandem solar cells to 25.3% and 24.1%, for active areas of 5.9 mm2 and 0.94 cm2 , respectively.