Electrical Doping of Metal Halide Perovskites by Co‐Evaporation and Application in PN Junctions

Abstract Electrical doping of semiconductors is a revolutionary development that enabled many electronic and optoelectronic technologies. While doping of many inorganic and organic semiconductors is well‐established, controlled electrical doping of metal halide perovskites (MHPs) is yet to be demonstrated. In this work, efficient n‐ and p‐type electrical doping of MHPs by co‐evaporating the perovskite precursors alongside organic dopant molecules is achieved. It is demonstrated that the Fermi level can be shifted by up to 500 meV toward the conduction band and by up to 400 meV toward the valence band by n‐ and p‐doping, respectively, which increases the conductivity of the films. The doped layers are employed in PN and NP diodes, showing opposing trends in rectification. Demonstrating controlled electrical doping by a scalable, industrially relevant deposition method opens the route to developing perovskite devices beyond solar cells, such as thermoelectrics or complementary logic.