Resumen de Preparation of high efficiency Cu2ZnSn(S,Se)4solar cells based on a single-step sulfo-selenization process
Cu2ZnSn(S,Se)4 (CZTSSe) kesterite semiconductors have been proposed as a potential medium to long term replacement of Cu(In,Ga)(S,Se)2 (CIGS) chalcopyrites for sustainable cost-efficient thin film technologies compatible with mass deployment at Terawatt level, being only constituted by elements abundant in the earth crust in contrast with the scarce Indium in CIGS. In this thesis, high efficiency CZTSSe solar cells were fabricated based on a single-step sulfo-selenization process. CZTSSe absorbers with optimal S/(S+Se) ratio, minimized Zn(S,Se) secondary phases in the interfaces, and good crystal quality were achieved through systematically fine tuning of various processing parameters during thermal treatments. The thermodynamic equilibrium of the single-step sulfo-selenization process was also analysed to elucidate the impact of different parameters on the thin films S/(S+Se) ratio. Besides, to address the big challenge of secondary phases in CZTSSe solar cells, an innovative (NH4)2S etching was developed for the selective and effective removal of Sn-(S,Se) secondary phases. This (NH4)2S etching can also passivate the absorber surface and a passivation mechanism was proposed to explain this behaviour. To further improve the efficiency of the CZTSSe solar cells, the CZTSSe/CdS interface was focused and engineered. Na spatial distribution in the CZTSSe/CdS interface region was optimized by a post low temperature treatment process (PLTT), leading to considerable enhancement of the performance of CZTSSe solar cells. An innovative Na dynamics model was established to illustrate the Na in-depth profiles. In addition, Cu doped CdS was investigated to reduce the thickness of CdS while keeping the comparable performance of the kesterite devices, which provides new possibilities to address the Cd concern. Finally, to suppress the CZTSSe/CdS interface recombination and reduce the Voc deficit of the CZTSSe solar cells, a facile wet chemical route based on AlCl3/GaCl3 + thioacetamide solutions were developed. The Voc and efficiency improvement after the chemical treatments can be mainly ascribed to the decrease of interface recombination and shunt paths. A champion CZTSSe solar cell with 9.1% efficiency and FF over 69% was achieved after all these processing optimizations (no ARC). This demonstrates that the single-step sulfo-selenization methodology is promising and feasible for obtaining high efficiency CZTSSe solar cells.
