Efficiency Improvement of Near‐Stoichiometric CuInSe2 Solar Cells for Application in Tandem Devices

State‐of‐the‐art Cu(In,Ga)Se2 (CIGS) solar cells are grown with considerably substoichiometric Cu concentrations. The resulting defects, as well as potential improvements through increasing the Cu concentration, have been known in the field for many years. However, so far, cells with high Cu concentrations show decreased photovoltaic parameters. In this work, it is shown that RbF postdeposition treatment of CuInSe2 solar cells allows for capturing the benefits from the improved absorber quality with increasing Cu content. A reduced defect density and an increased doping level for cells with high Cu concentrations close to stoichiometry are demonstrated. Implementing a high mobility front transparent conductive oxide (TCO), the improved absorbers with 1.00 eV bandgap yield a solar cell efficiency of 19.2%, and combined with a perovskite top cell a 4‐terminal tandem efficiency of 25.0% are demonstrated, surpassing the record efficiency of both subcell technologies. CuInSe2 thin film solar cells are grown with almost stoichiometric absorber compositions. The performance degradation commonly observed for high copper contents is prevented by implementation of an RbF postdeposition treatment. Improvements in carrier concentration and defect density result in cell performance up to 19.2% at a bandgap of 1.00 eV and 24.1% in 4‐terminal tandem configuration with a perovskite top cell.