Cs‐Doped and Cs‐S Co‐Doped CuI p‐Type Transparent Semiconductors with Enhanced Conductivity

Abstract One hindrance in transparent electronics is the lack of high‐performance p‐type transparent conductors (TCs). The state‐of‐the‐art p‐type TC, CuI, has a conductivity two orders of magnitude lower than n‐type TCs like ITO. While doping strategies have shown promise in enhancing the hole carrier density in CuI, they often come at the expense of hole mobility. Therefore, understanding how extrinsic dopants affect the mobility of CuI is critical to further improve the performance of CuI‐based TCs. Here the structural and electronic properties of Cs‐doped CuI are investigated. It is demonstrated that ≈4 at.% Cs doping in CuI increases the carrier density from 2.1 × 10 19 to 3.8 × 10 20 cm −3 while preserving the film microstructure and local coordination of Cu, as confirmed by HRTEM and XAS analysis. Introducing S as a co‐dopant in Cs:CuI boosts the carrier density to 8.2 × 10 20 cm −3 , reaching a stable conductivity of ≈450 S cm −1 . In all cases, the enhanced carrier density negatively affects the hole mobility with ionized impurity scattering and increased Seebeck hole effective mass as mobility limiting mechanisms. Nonetheless, the new Cs, S co‐doped CuI exhibits high p‐type conductivity, Vis–NIR transparency, and stability, presenting an attractive candidate for future transparent electronic devices.