Effect of Na doping on the performance and the band alignment of CZTS/CdS thin film solar cell

•Fabrication of CZTS:Na/CdS with Na doping on the surface using spin coating method.•The typical cliff-like CBO were obtained to 0.25 eV for CZTS/CdS heterojunction and 0.1 eV for CZTS:Na/CdS.•Sodium doping improves the performance of CZTS solar cells. Alkali doping can suppress deleterious antisite defects in kesterite Cu2ZnSnS4 (CZTS) and improve the open-circuit voltage. In this study, the effects of light Na-doping on the performance and the band alignment of CZTS/CdS thin-film solar cells were investigated. CZTS:Na thin films were fabricated by the spin coating with 10% Na doping on the surface of CZTS. The Na-doping led to the narrower FWHM and larger grain size. The hole concentration and the conductivity were improved due to the NaZn shallow acceptor defects. In addition, Na-doping can improve the band alignment of absorber/buffer interface and inhibit SRH recombination by the Na passivation effect and the suppression of SnZn defects. The typical cliff-like conduction band offset (CBO) was reduced from 0.25 eV in CZTS:Na/CdS to 0.1 eV in CZTS/CdS heterojunction. CZTS:Na device exhibited a higher Voc of 653 mV than that of CZTS/CdS device. The maximum conversion efficiency reached 7.46%, increased by 44% after Na-doping. These results clarify the effect of Na-doping on the band structure of the heterojunction in CZTS solar cells and support a new aspect that synthesis of a surface-doping CZTS:Na absorber has great potential for future research.