Cadmium‐Free Kesterite Thin‐Film Solar Cells with High Efficiency Approaching 12%

Cadmium sulfide (CdS) buffer layer is commonly used in Kesterite Cu(2)ZnSn(S,Se)(4) (CZTSSe) thin film solar cells. However, the toxicity of Cadmium (Cd) and perilous waste, which is generated during the deposition process (chemical bath deposition), and the narrow bandgap (≈2.4 eV) of CdS restrict its large‐scale future application. Herein, the atomic layer deposition (ALD) method is proposed to deposit zinc–tin‐oxide (ZTO) as a buffer layer in Ag‐doped CZTSSe solar cells. It is found that the ZTO buffer layer improves the band alignment at the Ag‐CZTSSe/ZTO heterojunction interface. The smaller contact potential difference of the ZTO facilitates the extraction of charge carriers and promotes carrier transport. The better p–n junction quality helps to improve the open‐circuit voltage (V (OC)) and fill factor (FF). Meanwhile, the wider bandgap of ZTO assists to transfer more photons to the CZTSSe absorber, and more photocarriers are generated thus improving short‐circuit current density (Jsc). Ultimately, Ag‐CZTSSe/ZTO device with 10 nm thick ZTO layer and 5:1 (Zn:Sn) ratio, Sn/(Sn + Zn): 0.28 deliver a superior power conversion efficiency (PCE) of 11.8%. As far as it is known that 11.8% is the highest efficiency among Cd‐free kesterite thin film solar cells.