Revealing the Role of Hydrogen in Highly Efficient Ag-Substituted CZTSSe Photovoltaic Devices:Photoelectric Properties Modulation and Defect Passivation

The presence of SnZn-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 SnZn-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 SnZn 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 SnZn-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.