Sodium incorporation into Cu2ZnSnSe4 (CZTSe) substantially improves the device efficiency by enhancing the open-circuit voltage (VOC) and fill factor. Sodium increases hole density, makes the acceptor shallower, shifts the Fermi level lower, and leads to higher built-in voltage and, consequently, higher VOC. Sodium reduces the concentration of certain deep recombination centers, which further benefits VOC. The increase of hole density and mobility enhances the CZTSe conductivity leading to higher fill factor. Sodium causes smaller depletion width, hence, lower short-circuit current. The minority-carrier lifetime decreases slightly after sodium is incorporated via the Mo-coated soda-lime glass, although adding NaF provides some amelioration.
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