© 2021 International Solar Energy SocietyIn this work, we report the incorporation of sodium (Na) alkaline element into copper-zinc-tin-sulphide (Cu-Zn-Sn-S) precursor films by adding radio frequency (RF)-sputtered sodium fluoride (NaF) intermediate layers bringing a new approach to the bifacial sodium-incorporated treatment (BIST) and its effect on the properties of Cu2ZnSnS4 (CZTS) absorber films. Due to the absence of alkaline diffusion barrier layers on soda lime glass (SLG) substrates, Na additions from both NaF intermediate layers and SLG substrate were evaluated together. With additional NaF intermediate layers among the elemental metal stacks, the films exhibited better crystalline properties and a more compact structure. However, the amount of the Cu2-xS secondary phases formed on the surfaces increased by the additional NaF layers. Raman spectra confirmed the formation of the kesterite phase and showed the peaks corresponding to Cu3SnS4 and Cu2-xS secondary phases. Na diffusion originating from NaF layers deposited on molybdenum (Mo) films occurred in both directions of the CZTS film and the SLG substrate. The photoluminescence (PL) bands located at around 1.40 eV were attributed to the band to band (BB) transitions. The film with additional NaF intermediate layers exhibited higher carrier concentrations and lower resistivity than the other film due to the presence of the higher amount of Cu2-xS secondary phases on its surface.