The deviation from stoichiometry and the understanding of its consequences are key factors for the application of kesterites as solar cell absorbers. Therefore, this study investigates the local atomic structure of off-stoichiometric Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe) and Cu2ZnGeSe4 (CZGSe) by means of Extended X-ray Absorption Fine Structure Spectroscopy. Temperature dependent measurements yield the bond stretching force constants of all cation-anion bonds in stoichiometric CZTS and CZTSe and nearly stoichiometric CZGSe. Low temperature measurements allow high precision analysis of the influence of off-stoichiometry on the element specific average bond lengths and their variances. The overall comparison between the materials is in excellent agreement with measures like ionic/atomic radii and bond ionicities. Furthermore, the small uncertainties allow the identification of systematic trends in the Cu–Se and Zn–Se bond lengths of CZTSe and CZGSe. These trends are discussed in context of the types and concentrations of certain point defects, which gives insight into the possible local configurations and their influence on the average structural parameters. The findings complement the understanding of the effect of off-stoichiometry on the local structure of kesterites, which affects their electronic properties and thus their application for solar cells.
