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Here, the deliberate introduction of K and Na into Cu(In, Ga)Se₂ (CIGS) absorbers was investigated by varying a combination of an SiO₂ diffusion barrier, coevaporation of KF with the CIGS absorber, and a KF postdeposition treatment (PDT). Devices made with no diffusion barrier and KF coevaporation treatment exhibited the highest photovoltaic conversion efficiency with the smallest overall distribution in key current density-voltage (J-V) performance metrics. Out-diffusion of Na and K from the substrate, KF coevaporation, and KF PDT all increased carrier concentration, open-circuit voltage, fill factor, and power conversion efficiency. Quantum-efficiency analysis of devices highlighted the greatest loss in themore » short-circuit current density due to incomplete absorption and collection. Secondary ion mass spectrometry illustrated the efficacy of the SiO₂ film as a sodium and potassium diffusion barrier, as well as their relative concentration in the absorber. Introduction of KF appeared to enhance diffusion of Na from the substrate, in agreement with previous studies.« less