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The performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cell is known to be severely limited by the nonradiative recombination near the heterojunction interface and within the bulk of the CZTSSe absorber resulting from abundant recombination centers and limited carrier collection efficiency. Herein, nonradiative recombination is simultaneously reduced by incorporating small amounts of Ge and Cd into the CZTSSe absorber. Incorporation of Ge effectively increases the p‐type doping, thus successfully improving the bulk conductance and reducing the recombination in the CZTSSe bulk via enhanced quasi‐Fermi level splitting, while the incorporation of Cd greatly reduces defects near the junction region, enabling larger depletion region width and better carrier collection efficiency. The combined effects of Cd and Ge incorporation give rise to systematic improvement in open‐circuit voltage (VOC), short‐circuit current density (JSC), and fill factor (FF), enabling a high conversion efficiency of 11.6%. This study highlights the multiple cation incorporation strategy for systematically manipulating the opto‐electronic properties of kesterite materials, which may also be applicable to other semiconductors. [ABSTRACT FROM AUTHOR]

Antimony sulfide (Sb2S3) as a wide‐bandgap, nontoxic, and stable photovoltaic material reveals great potential for the uppermost cells in Si‐based tandem cell stacks. Sb2S3 solar cells with a compatible process, acceptable cost, and high efficiency therefore become the mandatory prerequisites to match silicon bottom cells. The performance of vacuum processed Sb2S3 device is pinned by bulk and interfacial recombination. Herein, a thermally treated TiO2 buffer layer induces quasiepitaxial growth of vertical orientation Sb2S3 absorber overcoming interface defects and absorber transport loss. Such novel growth could pronouncedly improve the open‐circuit voltage (Voc) due to the superior interface quality and intraribbon transport. The epitaxial rough Sb2S3 surface shows a texturized‐like morphology. It is optimized by tuning the grain sizes to form strong light trapping effect, which further enhances the short‐circuit current density (Jsc) with a 16% improvement. The final optimal device with high stability obtains a power conversion efficiency of 5.4%, which is the best efficiency for full‐inorganic Sb2S3 solar cells. The present developed quasiepitaxy strategy supports a superior interface, vertical orientation, and surface light trapping effect, which provides a new perspective for efficient noncubic material thin film solar cells. [ABSTRACT FROM AUTHOR]