To realize high-performance thin film solar cells, we prepared CIGS by the co-evaporation technique on both sodalime and Corning glass substrates. The structural and efficient properties were investigated by varying the thickness of the Mo:Na layer, where the total thickness of the back contact was fixed at 1 μm. As a result, when the Mo:Na thickness was 300 nm on soda-lime glass, the measured Na content was 0.28 %, the surface morphology was a plate-like compact structure, and the crystallinity by XRD showed a strong peak of (112) preferential orientation together with relatively intense (220) and (204) peaks as the secondary phases influenced crystal formation. In addition, the substrates on soda-lime glass effected the lowest surface roughness of 2.76 nm and the highest carrier density and short circuit current. Through the optimization of the Mo:Na layer, a solar conversion efficiency of 11.34% was achieved. When using the Corning glass, a rather low conversion efficiency of 9.59% was obtained. To determine the effects of the concentration of sodium and in order to develop a highefficiency solar cells, a very small amount of sodium was added to the soda lime glass substrate.