Tailoring the electrical properties of Cu2ZnSnS4 thin film by heterovalent Al3+ doping

Abstract

Kesterite Cu2ZnSnS4 (CZTS) thin film is an attractive photovoltaic material. Harmful vacancy and anti-site defects in CZTS can be reduced by equivalent doping. However, equivalent doping leads to a reduction in the carrier concentration that is essential to the built-in electric field and built-in potential of the device. In this work, we propose heterovalent Al doping to provide hole conduction in CZTS thin film. The chemical valence of doping cation Al3+ is different from that of the substituted cation Sn4+. Al-doped CZTS thin films were fabricated by magnetron sputtering and sulfurization. The Al content was controlled by the Al sputtering time of the precursor. The experimental results revealed the successful fabrication of heterovalent Al-doped CZTS with the preferred orientation of the (112) plane. The partial substitution of Sn by Al led to a right shift of the CZTS diffraction peaks. Al doping could improve the crystalline quality of CZTS, reduce the dislocation density and microstrain of CZTS, and enhance the compactness of the thin-film surface. With the increase in Al content, the distance decreased between the Fermi level and the valence band maximum of CZTS, and the hole concentration and conductivity of CZTS increased monotonously while the non-radiative recombination of carriers was suppressed. The conductivity of CZTS reached 1.47 × 102 S/cm. Therefore, heterovalent Al doping was found to be a useful method to regulate the electrical properties of CZTS thin film.