Improved CZTSe solar cell efficiency via silver and germanium alloying

In this study, we report systematic investigation of the effects of Ag and Ge alloying on properties of CZTSe layers, as well as, on the performance of solar cells fabricated using these films. In this context, Ag-Ge doped CZTSe layers were produced by selenization of Cu/Sn/Zn/Cu/(Ag,Ge)/Se precursor stack structures using rapid thermal processing. All precursor stacks and the Ag-Ge doped CZTSe films obtained after selenization exhibited (Cu + Ag)-poor and Zn-rich chemical composition. XRD studies demonstrated pure kesterite phase for all reacted films. Raman spectra confirmed this finding. Cross-sectional SEMs showed large grain structure, which resulted from Ag-Se and Ge-Se liquid phase formation that assisted crystal growth during high temperature annealing. While a slight Ag-front-gradient was achieved in Ag-doped CZTSe film, the Ag gradient disappeared with incorporation of Ge into the lattice. Addition of Ge formed a gradient within the material such that near-contact region was more Ge-rich. Solar cells fabricated using films with various compositions demonstrated that double doping CZTSe with both Ag and Ge improved the device efficiency from about 5 % to over 8 %.