Growth mechanism of Ge-doped CZTSSe thin film by sputtering method and solar cells.

Ge-doped CZTSSe thin films were obtained by covering a thin Ge layer on CZTS precursors, followed by a selenization process. The effect of the Ge layer thickness on the morphologies and structural properties of Ge-doped CZTSSe thin films were studied. It was found that Ge doping could promote grain growth to form a compact thin film. The lattice shrank in the top-half of the film due to the smaller atomic radius of Ge, leading to the formation of tensile stress. According to thermodynamic analysis, Sn was easier to be selenized than Ge. Thus, Ge preferred to remain on the surface and increased the surface roughness when the Ge layer was thin. CZTSe was easier to form than Ge-doped CZTSe, which caused difficulty in Ge doping. These results offered a theoretical and experimental guide for preparing Ge-doped CZTSSe thin films for the potential applications in low-cost solar cells. With a 10 nm Ge layer on the top of the precursor, the conversion efficiency of the solar cell improved to 5.38% with an open-circuit voltage of 403 mV, a short-circuit current density of 28.51 mA cm-2 and a fill factor of 46.83% after Ge doping.