Abstract
Effectively incorporating alkali metals or alternative isovalent cations into Cu2ZnSnS4 (CZTS) is considered one of the most promising strategies for realizing a step-change improvement in the photovoltaic device performance. Herein, the local distribution of Na and Cd by a moisture-assisted postdeposition annealing (MAPDA) treatment combined with a subsequent heterojunction heat treatment is manipulated. The MAPDA treatment facilitates the controllable reduction of the Na concentration, thus promoting the spontaneous diffusion of Cd into the heterojunction region. A subsequent 150 degrees C low-temperature heterojunction heat treatment after MAPDA treatment enables further modification of Cd and Na distributions, leading to significantly enhanced optoelectronic properties at the CZTS/CdS heterojunction and greatly improved device performance with a peak conversion efficiency of 9.40%. The modified heterojunction significantly improves quasi-Fermi-level splitting under low-photon injection, making CZTS solar cells more feasible in low-light applications. This work provides an effective approach to simultaneously manipulate the distribution of Na and Cd, enabling pronounced modification of the heterojunction quality of CZTS solar cells and boost of conversion efficiencies. Insights gleaned herein may also be applicable to manipulating other critical trace elements in chalcogenide materials in general.