The crystallisation of Cu2ZnSnS4 thin film solar cell absorbers from co-electroplated Cu–Zn–Sn precursors

Abstract The best CZTS solar cell so far was produced by co-sputtering continued with vapour phase sulfurization method. Efficiencies of up to 5.74% were reached by Katagiri et al. The one step electrochemical deposition of copper, zinc, tin and subsequent sulfurization is an alternative fabrication technique for the production of Cu 2 ZnSnS 4 based thin film solar cells. A kesterite based solar cell (size 0.5 cm 2 ) with a conversion efficiency of 3.4% (AM1.5) was produced by vapour phase sulfurization of co-electroplated Cu–Zn–Sn films. We report on results of in-situ X-ray diffraction (XRD) experiments during crystallisation of kesterite thin films from electrochemically co-deposited metal films. The kesterite crystallisation is completed by the solid state reaction of Cu 2 SnS 3 and ZnS. The measurements show two different reaction paths depending on the metal ratios in the as deposited films. In copper-rich metal films Cu 3 Sn and CuZn were found after electrodeposition. In copper-poor or near stoichiometric precursors additional Cu 6 Sn 5 and Sn phases were detected. The formation mechanism of Cu 2 SnS 3 involves the binary sulphides Cu 2 − x S and SnS 2 in the absence of the binary precursor phase Cu 6 Sn 5 . The presence of Cu 6 Sn 5 leads to a preferred formation of Cu 2 SnS 3 via the reaction educts Cu 2 − x S and SnS 2 in the presence of a SnS 2 (Cu 4 SnS 6 ) melt. The melt phase may be advantageous in crystallising the kesterite, leading to enhanced grain growth in the presence of a liquid phase.