Sprayed films of stannite Cu2ZnSnS4

A stoichiometric Cu2ZnSnS4 film with the stannite structure and resistivity of 2 × 102 Ω · cm has been prepared by annealing polycrystalline quaternary films at 550°C, which are spray-deposited on glass substrates, in an argon gas flow containing H2S. Non-stoichiometric films consisting mostly of the stannite phase exhibit p-type conduction. Their resistivity decreases steeply as the ratio of copper to another metal increases. A copper-rich film tends to contain an impurity phase of chalcocite while a zinc-lean film that of copper tin sulfide Cu2SnS3.