Band-gap engineering of Cu2ZnSn1−xGexS4 single crystals and influence of the surface properties

Thin film solar cells based on Cu2ZnSn(S,Se)4 are very promising, because they contain earth-abundant elements and show high absorptivity. However, the performance of these solar cells needs to be improved in order to reach efficiencies as high as that reported for Cu(In,Ga)Se2-based devices. This study investigates the potential of band-gap engineering of Cu2ZnSn1−xGexS4 single crystals grown by chemical vapour transport as a function of the [Ge]/([Sn] + [Ge]) atomic ratio. The fundamental band gap E0 is found to change from 1.59 to 1.94 eV when the Ge content is increased from x = 0.1 to x = 0.5, as determined from spectroscopic ellipsometry measurements. This knowledge opens a route to enhancing the performance of kesterite-based photovoltaic devices by a Ge-graded absorber layer. Furthermore, the formation of GeO2 on the surface of the as-grown samples was detected by X-ray photoelectron spectroscopy, having an important impact on the effective optical response of the material. This should be also taken into account when designing photovoltaic solar cells.