Abstract
The presence of Sn(Zn)-related defects in Cu(2)ZnSn(S,Se)(4) (CZTSSe) absorber results in large irreversible energy loss and extra irreversible electron-hole non-radiative recombination, thus hindering the efficiency enhancement of CZTSSe devices. Although the incorporation of Ag in CZTSSe can effectively suppress the Sn(Zn)-related defects and significantly improve the resulting cell performance, an excellent efficiency has not been achieved to date primarily owing to the poor electrical-conductivity and the low carrier density of the CZTSSe film induced by Ag substitution. Herein, this study exquisitely devises an Ag/H co-doping strategy in CZTSSe absorber via Ag substitution programs followed by hydrogen-plasma treatment procedure to suppress Sn(Zn) defects for achieving efficient CZTSSe devices. In-depth investigation results demonstrate that the incorporation of H in Ag-based CZTSSe absorber is expected to improve the poor electrical-conductivity and the low carrier density caused by Ag substitution. Importantly, the C=O and O-H functional groups induced by hydrogen incorporation, serving as an electron donor, can interact with under-coordinated cations in CZTSSe material, effectively passivating the Sn(Zn)-related defects. Consequently, the incorporation of an appropriate amount of Ag/H in CZTSSe mitigates carrier non-radiative recombination, prolongs minority carrier lifetime, and thus yields a champion efficiency of 14.74%, showing its promising application in kesterite-based CZTSSe devices.