Surface Cu depletion of Cu(In,Ga)Se2 films: An investigation by hard X-ray photoelectron spectroscopy Original Research Article

The origin of surface Cu depletion of polycrystalline chalcopyrite thin films and its consequences for the physics of related solar cells have been discussed for the past 15 years. In order to shed light on the composition and thickness of this Cu-depleted surface layer, depth-dependent compositional analysis by hard X-ray photoelectron spectroscopy was performed. The data from Cu-poor grown Cu(In,Ga)Se2 samples point to a surface layer in the sub-nanometer regime, which is completely depleted of Cu. This result supports the surface reconstruction model proposed by first-principles calculations by other authors. Analysis of the surface morphology of the investigated samples confirms the conjunction of Cu depletion and faceting of the surface. Theoretical considerations show that the apparent surface concentration ratio of [Cu]/([In] + [Ga]) = 1/3 found by conventional photoelectron spectroscopy studies can be explained by the surface reconstruction model.