In this work, a multilayer structure was obtained using ZnO and Cu 2 ZnSnS 4 (CZTS) inks on a molybdenum substrate by spraying. The obtained samples were annealed in Argon for 10 and 60 min at temperatures of 250°C, 450°C and 550°C. Structural and substructural characteristics were studied by X-ray diffraction. Due to this, the influence of temperature and annealing time on the sizes of coherent scattering regions (CSR), the level of microdeformations and the lattice parameters of the obtained samples were investigated. Based on the study, the optimal annealing conditions in Argon were determined to obtain multilayer structures using ZnO and Cu 2 ZnSnS 4 materials for use in solar energy.