Abstract

Abstract Each component layer in a perovskite solar cell plays an important role in the cell performance. Here, a few types of polymers including representative p‐type and n‐type semiconductors, and a classical insulator, are chosen to dope into a perovskite film. The long‐chain polymer helps to form a network among the perovskite crystalline grains, as witnessed by the improved film morphology and device stability. The dewetting process is greatly suppressed by the cross‐linking effect of the polymer chains, thereby resulting in uniform perovskite films with large grain sizes. Moreover, it is found that the polymer‐doped perovskite shows a reduced trap‐state density, likely due to the polymer effectively passivating the perovskite grain surface. Meanwhile the doped polymer formed a bridge between grains for efficient charge transport. Using this approach, the solar cell efficiency is improved from 17.43% to as high as 19.19%, with a much improved stability. As it is not required for the polymer to have a strict energy level matching with the perovskite, in principle, one may use a variety of polymers for this type of device design.