A ZnInxSey buffer layer and a ZnO buffer layer have been applied as an attractive alternative to the CdS buffer layer in the development of polycrystalline Cu(InGa)Se2 (CIGS) thin-film solar cells and thus proposed the entire elimination of cadmium. For ZnInxSey/CIGS structure, we have already achieved an efficiency of 15.1% (Y. Ohtake, T. Okamoto, A. Yamada, M. Konagai, K. Saito, Sol. Energy Mater. Sol. Cell, 49 (1997) 269). In addition to ZnInxSey/CIGS, we proposed a ZnO (low resistivity)/ZnO (high resistivity)/CIGS structure, where a high resistive ZnO layer was deposited by the atomic layer deposition (ALD) method. In ALD, we alternatively supplied source gases, DEZn and H2O. When the H2O flow rate was kept at 24.2 μmol/min and the DEZn flow rate was ranged between 40 and 53 μmol/min, we obtained ALD growth of ZnO. The increase of growth rate was observed by the decrease of DEZn flow rate down to 15 μmol/min and we obtained high resistive ZnO (1 KΩ cm) at these growth conditions. Up to now, we have achieved an efficiency of 13.2% (0.189 cm2) with a high resistive ZnO buffer layer.