Electrodeposition of CuGaSe2 and CuGaS2 thin films for photovoltaic applications

CuGaSe2 and CuGaS2 polycrystalline thin film absorbers were prepared by one-step electrodeposition from an aqueous electrolyte containing CuCl2, GaCl3 and H2SeO3. The pH of the solution was adjusted to 2.3 by adding HCl and KOH. Annealing improved crystallinity of CuGaSe2 and further annealing in sulphur atmosphere was required to obtain CuGaS2 layers. The morphology, topography, chemical composition and crystal structure of the deposited thin films were analysed by scanning electron microscopy, atomic force microscopy, energy dispersive spectroscopy and X-ray diffraction, respectively. X-Ray diffraction showed that the as-deposited CuGaSe2 film exhibited poor crystallinity, but which improved dramatically when the layers were annealed in forming gas atmosphere for 40 min. Subsequent sulphurization of CuGaSe2 films was performed at 400 °C for 10 min in presence of molecular sulphur and under forming gas atmosphere. The effect of sulphurization was the conversion of CuGaSe2 into CuGaS2. The formation of CuGaS2 thin films was evidenced by the shift observed in the X-ray diffraction pattern and by the blue shift of the optical bandgap. The bandgap of CuGaSe2 was found to be 1.66 eV, while for CuGaS2 it raised up to 2.2 eV. A broad intermediate absorption band associated to Cr and centred at 1.63 eV was observed in Cr-doped CuGaS2 films.