Atomic scale chemistry of polycrystalline Cu(In,Ga)Se2 (CIGSe) thin film has been characterized at key points of the 3-stage process using atom probe tomography. 3D atom distributions have been reconstructed when the layer is Cu-poor ([Cu]/([Ga] + [In]) < 1), Cu-rich ([Cu]/([Ga] + [In]) > 1), and at the end of the process. Particular attention has been devoted to grain boundary composition and Na atomic distribution within the CIGSe layer. Significant variation of composition is highlighted during the growing process, providing fundamental information helping the understanding of high efficiency CIGSe formation.
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