Photovoltaic-grade thin-film solar cell absorber layers composed of Cu 2 ZnSnS 4 are most often prepared under nonstoichiometric compositions, in particular Cu-poor and Zn-rich conditions. The effects of compositional deviations on chemical and electrical properties of this material are under investigation and are expected to have a strong influence on final device performance. Herein, a study of variation in the cationic ratios (Cu/Zn, Cu/Sn) across a broad range and their effect on the properties of thin films is presented. After etching to remove the ZnS phase, the ratio of Cu/Zn is nearly constant between all the films, while there are significant variations in the ratio of Cu/Sn. This is correlated with changes in the chemical and electrical properties of these films, as determined by variable temperature conductivity measurements. The postetching composition and absence of Sn-S secondary phases points to multivalency of Sn in this material, in addition to other potential factors such as differences in grain size and defect formation. The Cu/Sn ratio is shown to strongly affect the electrical properties of films, in particular of the conductivity, grain boundary barriers, and localization length.
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