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The application of Zn compounds as buffer layers was recently extended to wide-gap CuInS2 (CIS) based thin film solar cells. Using an alternative chemical deposition route for the buffer preparation aiming at the deposition of a single-layer, nominal ZnS buffer without the need for any toxic reactants such as hydrazine has helped us to achieve a similar efficiency as respective CdS-buffered reference devices. In order to shed light on the differences of other Zn-compound buffers deposited in conventional chemical baths [chemical bath deposition (CBD)] compared to the buffer layers deposited by this alternative CBD process, the composition of the deposited buffers was investigated by x-ray excited Auger electron and x-ray photoelectron spectroscopy to potentially clarify their superiority in terms of device performance. We have found that in the early stages of this alternative CBD process a thin ZnS layer is formed on the CIS, whereas in the second half of the CBD the growth rate is greatly increased and Zn(S,O) with a ZnS/(ZnS+ZnO) ratio of ∼80% is deposited. Thus, a ZnS/Zn(S,O) bilayer buffer is deposited on the CIS thin film solar cell absorbers by the alternative chemical deposition route used in this investigation. No major changes of these findings after a postannealing of the buffer/CIS sample series and recharacterization could be identified. [ABSTRACT FROM AUTHOR]