Impact of the stack order in Cu-Zn-Sn metal precursors on the properties of Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ (CZTS) thin films were grown by the annealing of metallic precursors with different stack orders in sulfur atmosphere. The sequential deposition of the metal layers from single Cu, Zn, and Sn targets on Mo-coated soda-lime glass substrates was carried out using radio-frequency magnetron sputtering. In this work, we investigated the effect of the sequence of metal layers on the chemical, structural, and morphological properties of the final CZTS films using X-ray fluorescence (XRF), X-ray diffraction (XRD), Raman scattering spectroscopy, scanning electron microscopy, and energy-dispersive spectroscopy. The realized stack sequences were Mo/Sn/Zn/Cu, Mo/Sn/Cu/Zn, Mo/Cu/Zn/Sn, Mo/Cu/Sn/Zn, and Mo/Zn/Cu/Sn. XRF measurements revealed notable impact of the metal layers´ stacking order in the precursor on the chemical composition. It also showed Sn loss and high Zn concentration in all sulfurized films; however, having Cu on the Sn or Zn/Sn layer showed some minimization of the Sn loss. XRD showed CZTS films with good crystallinity and no evidence of the presence of secondary phases. Changing the precursor stack order did not show any influence on the films´ crystallinity or texture. Raman spectroscopy, in contrast, indicated the presence of ZnS phase beside the main CZTS phase. The morphology study showed significant effect on the structure of the final CZTS films depending on the used stack order. Generally, the films that originated from precursors having a Zn layer deposited directly on Mo or as the second layer exhibited better adhesion to the Mo layer and showed fewer or even no voids compared to the other films.