Zn0.85Mg0.15O buffer layers can replace both i-ZnO and CdS in n-ZnO/i-ZnO/CdS/Cu(InxGa1-x)(SySe1-y)(2)/Mo/glass (CIGSSe) solar cells without significant loss of efficiency. We found that the efficiency Of Zn0.85Mg0.15O buffered solar cells decreased with increasing sample temperature when we sputter-deposited Zn0.85Mg0.15O directly onto the CIGSSe absorber surface,e.g. frorn 9.5% without deliberate heating to 6.5% at 240 degrees C. To find an explanation for this behavior we sputter-coated bare, KCN-etched CIGSSe absorbers with about 420 nm of Zn0.85Mg0. 15O at different sample temperatures and subsequently removed the Zn0.85Mg0.15O layers by wet-chemical etching with dilute acetic acid. The exposed CIGSSe surfaces were examined by surface-sensitive X-ray photoelectron spectroscopy (XPS) and X-ray excited Auger electron spectroscopy (XAES). We found a strong increase in the [Cu]/([In] + [Cu]) ratio compared to a bare, Acetic-acid-etched CIGSSe reference. The surface of samples that had been sputter-coated at 150 degrees C changed from being initially Cu-poor to Cu-rich. The chemical shift of Cu Auger peaks from the same surface confirmed this finding. The increased Cu/In ratio and the chemical shift were reversed after KCN etch. These findings are discussed in the context of the model of a Cu-depleted, wide-band gap surface region in CIGSSe solar cells as a prerequisite for high efficiency. (C) 2007 Elsevier B.V. All rights reserved.