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Cu2ZnSnS4 (CZTS) thin films were synthesized in a two-step procedure. Sulfurization of stacked thin films SLG/ZnS/Sn/Cu (S1) and SLG/Cu/Sn/ZnS (S2) after sequential deposition of Cu, ZnS, and Sn precursors was carried out. At 550 °C, two sulfurization periods were applied to both stack orders. Sample S1 sulfurized for 30 min (S1-T30) had a better crystallite size of roughly 50 nm, lower lattice strain, and lower dislocation density than other samples. The Cu/Zn cation ordering in the CZTS crystal system was significantly affected by stack sequence and sulfurization time, according to Q-factor calculation. The stack order of the S1 series allowed for homogenous and distinct particle development. From the elemental analysis, it is observed that the stack sequence and sulfurization used for sample S1-T30 permitted a near stoichiometric composition. The sample S1-T30 exhibited an optimal band gap value of 1.47 eV. To propose feasible alterations in the structural ordering, band gap calculations were used. In comparison to the stack order of the S2 series, the stack order SLG/ZnS/Sn/Cu with a sulfurization time of 30 min created a single-phase CZTS, implying less synthesis time to obtain an absorber quality CZTS layer for solar photovoltaic application.