Optical properties and mechanisms of current flow in Cu2ZnSnS4 films prepared by spray pyrolysis

Thin films Cu₂ZnSnS₄ (up to 0.9 μm thick) with p-type conductivity and band gap E_g = 1.54 eV have been prepared by the spray pyrolysis of 0.1 M aqueous solutions of the salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, SnCl₄ · 5H₂O, and (NH₂)₂CS at a temperature T_S = 290°C. The electrophysical properties of the films have been analyzed using the model for polycrystalline materials with electrically active grain boundaries. The energy and geometric parameters of the grain boundaries have been determined as follows: the height of the barriers is E_b ≈ 0.045–0.048 eV, and the thickness of the depletion region is δ ≈ 3.25 nm. The effective concentrations of charge carriers p₀ = 3.16 × 10¹⁸ cm^–3 and their mobilities in crystallites μ_p = 85 cm²/(V s) have been found using the technique for determining the kinetic parameters from the absorption spectra of thin films at a photon energy hν ≈ E_g. The density of states at grain boundaries N_t = 9.57 × 10¹¹ cm^–2 has been estimated.