Catalytic and photoelectrochemical performances of Cu-Zn-Sn-Se thin films prepared using selenization of electrodeposited Cu-Zn-Sn metal precursors

Abstract In this study, Cu₂ZnSnSe₄ (CZTSe) films are deposited onto the fluorine-doped-tin-oxide-coated glass substrate via the selenization of electrodeposited Cu-Zn-Sn metal precursors in an acidic solution with the applied potential of -0.9 V vs. an Ag/AgCl electrode. X-ray diffraction patterns reveal that the samples are the quaternary tetragonal CZTSe phase. The thicknesses and direct band gaps of the samples are in the ranges of 2.3 to 2.7 μm and 0.95 to 1.02 eV, respectively. All samples are p-type semiconductors with carrier density, mobility and flat-band potential in the ranges of 3.88 × 10¹⁷ to 1.37 × 10¹⁸ cm^-3, 10.31 to 12.6 cm² V^-1 s^-1 and -0.01 V to -0.08 V vs. Ag/AgCl reference electrode, respectively. The sample with [Cu]/[Zn + Sn] and [Zn]/[Sn] molar ratios of 0.87 and 0.66, respectively, has a maximum photo-enhanced current density of 0.41 mA cm^-2 at an applied bias of -0.5 V vs. an Ag/AgCl electrode in 0.5 M H₂SO₄ solution under illumination. The best photo-conversion efficiency of dye-sensitized solar cells using CZTSe with [Cu]/[Zn + Sn] and [Zn]/[Sn] molar ratios of 0.87 and 0.66, respectively, as the counter electrode was 7.98%. The results show the high quality CZTSe films have potentials in applications of photoelectrochemical water splitting and dye-sensitized solar cells. Crown