Rb Diffusion and Oxide Removal at the RbF-Treated Ga₂O₃/Cu(In,Ga)Se₂ Interface in Thin-Film Solar Cells

We report on the chemical structure of Cu(In,Ga)Se₂ (CIGSe) thin-film solar cell absorber surfaces and their interface with a sputter-deposited Ga₂O₃ buffer. The CIGSe samples were exposed to a RbF postdeposition treatment and an ammonia-based rinsing step, as used in corresponding thin-film solar cells. For a detailed chemical analysis of the impact of these treatments, we employed laboratory-based X-ray photoelectron spectroscopy, X-ray-excited Auger electron spectroscopy, and synchrotron-based hard X-ray photoelectron spectroscopy. On the RbF-treated surface, we find both Rb and F, which are then partly (Rb) and completely (F) removed by the rinse. The rinse also removes Ga-F, Ga-O, and In-O surface bonds and reduces the Ga/(Ga + In) ratio at the CIGSe absorber surface. After Ga₂O₃ deposition, we identify the formation of In oxides and the diffusion of Rb and small amounts of F into/onto the Ga₂O₃ buffer layer but no indication of the formation of hydroxides.