Precisely Controlled Synthesis of High Quality Kesterite Cu2ZnSnS4 Thin Film via Co-Electrodeposited CuZnSn Alloy Film.

In this work, a facile co-electrodeposition method was used to fabricate CuZnSn alloy films where the content of copper, zinc and tin could be precisely controlled through manipulating the mass transfer process in the electrochemical deposition. By finely tuning the concentration of the cations of Cu2+, Zn2+ and Sn2+ in the electrochemical bath solution, uniform CuZnSn film with desired composition of copper poor and zinc rich was made. Sulphurisation of the CuZnSn alloy film led to the formation of compact and large grains Cu2ZnSnS4 thin film absorber with an optimum composition of Cu/(Zn+Sn) ≈ 0.8, Zn/Sn ≈ 1.2. Both SEM morphology and EDS mapping results confirmed the uniformity of the CuZnSn and Cu2ZnSnS4 films and the homogeneous distribution of Cu, Zn, Sn and S elements in the bulk films. The XRD and Raman measurements indicated that the synthesized Cu2ZnSnS4 film was kesterite phase without impurities detected. Photoelectrochemical tests were carried out to evaluate the CZTS film's photocurrent response under illumination of green light.