This work reports the Raman scattering surface and in-depth resolved analysis of Cu-poor Cu(In,Ga)Se-2 (CIGS) grown on polyimide substrates. In order to study the effect of Na on the formation and microstructure of the CIGS and the corresponding Cu-poor ordered vacancy compound (OVC) phases, a NaF precursor layer with different thicknesses was deposited on the Mo-coated substrates before growing of the samples. The Raman spectroscopy data are correlated with the analysis of the samples by Auger electron spectroscopy and scanning electron microscopy. These data corroborate the significant role of Na on the inhibition of Ga-In interdiffusion and on the formation of the MoSe2 interfacial phase at the back region of the layers. Presence of Na also leads to an enhancement in the formation of the chalcopyrite CIGS phase and a decrease in the occurrence of the dominant OVC phase at the surface region. This study confirms the strong dependence of the microstructure and phase distribution in CIGS absorber layers on the Na available during their growth. (C) 2010 Elsevier B.V. All rights reserved.