Cadmium sulfide (CdS) buffer layer is commonly used in Kesterite Cu₂ZnSn(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.

ZnSnN₂ has potential applications in photocatalysis and photovoltaics. However, the difficulty in preparing nondegenerate ZnSnN₂ hinders its device application. Here, the preparation of low-electron-density nanocrystalline ZnSnN₂ and its device application are demonstrated. Nanocrystalline ZnSnN₂ was prepared with reactive sputtering. Nanocrystalline ZnSnN₂ with an electron density of approximately 10¹⁷ cm⁻³ can be obtained after annealing at 300 °C. Nanocrystalline ZnSnN₂ is found to form Schottky contact with Ag. Both the current I vs. voltage V curves and the capacitance C vs. voltage V curves of these samples follow the related theories of crystalline semiconductors due to the limited long-range order provided by the crystallites with sizes of 2–10 nm. The I−V curves together with the nonlinear C⁻²−V curves imply that there are interface states at the Ag-nanocrystalline ZnSnN₂ interface. The application of nanocrystalline ZnSnN₂ to heterojunction solar cells is also demonstrated.