Influence of Ge Incorporation from GeSe2 Vapor on the Properties of Cu2ZnSn(S,Se)4 Material and Solar Cells

Cu2ZnSn(S,Se)4 (CZTSSe) and Cu2Zn(Sn,Ge)(S,Se)4 (CZTGSSe) thin films were prepared based on a non-vacuum solution method. The CZTSSe films were obtained by annealing the solution-deposited precursor films with Se, while the CZTGSSe films were obtained by annealing the similar precursor films with Se and GeSe2. We found that Ge could be incorporated into the annealed films when GeSe2 was present during the annealing process. The Ge incorporation obviously enlarged the sizes of the crystalline grains in the annealed films. However, the energy dispersive spectrometry (EDS) measurements revealed that the element distribution was not uniform in the CZTGSSe films. We fabricated solar cells based on the CZTSSe and CZTGSSe films. It was found the Ge incorporation decreases the Eu energy of the absorber material. The solar cell efficiency was increased from 5.61% (CZTSSe solar cell) to 7.14% (CZTGSSe solar cell) by the Ge incorporation. Compared to CZTSSe solar cells, the CZTGSSe solar cells exhibited a lower diode ideality factor and lower reverse saturation current density.