Ag Alloying in Cu_2−yAg_yBa(Ge,Sn)Se₄Films and Photovoltaic Devices

Trigonal Cu₂BaGe_1−xSn_xSe₄(CBGTSe) has recently gained interest as a potential photovoltaic absorber to target mitigation of antisite defect formation in Cu₂ZnSn(S,Se)₄. This study examines partial substitution of Cu by Ag as a potential approach to tune the properties of Ag‐incorporated CBGTSe in the following aspects: 1) phase stability and crystal structure as a function of Ag content; 2) film morphology and grain structure; 3) charge carrier properties; 4) band positions; and 5) charge carrier kinetics and recombination. Up to 20% of Cu can be substituted by Ag in CBGTSe, while above 20% a phase mixture appears. Increasing Ag content induces larger average grain size and reduced hole carrier densities. In contrast, photoelectron spectroscopy and photoluminescence measurements reveal negligible impact of Ag substitution on ionization potential (≈5.4 eV) and electron affinity (≈3.7 eV). Also, Ag content offers negligible impact on carrier lifetimes (few ns). Consistent with these fundamental properties, solar cells based on two different Ag/(Ag + Cu) ratios (≈0% and ≈20%) show comparable power conversion efficiencies (≈2.7–2.8%). These results indicate that CBGTSe films and solar cells may be less sensitive to Ag substitution compared to Cu₂ZnSn(S,Se)₄, at least at the current level of absorber and device optimization.