Chalcopyrites are important contenders among solar-cell materials due to direct band gap and very high-absorption coefficients. Copper-indium-gallium disulfide (CIGS2) is a chalcopyrite material with a near-optimum band gap of 1.5 eV for terrestrial as well as space applications. At FSEC PV Materials Laboratory, record efficiency of 11.99% has been achieved on a 2.7 mu m CIGS2 thin film prepared by sulfurization. There are reports of influence of sodium on copper-indium-gallium selenide (CIGS) as well as copper-indium disulfide (CIS2) solar cells. However, this is the first of its kind approach to study the effect of sodium on CIGS2 solar cells and resulting in encouraging efficiencies. Copper-deficient CIGS2 thin films were prepared with and without the addition of sodium fluoride (NaF). Effects of addition of NaF on the microstructure and device electrical properties are presented in this work. (C) 2008 Elsevier B.V. All rights reserved.