This work presents a two-step procedure to obtain thin films with a combination of CuSbS2 and Cu12Sb4S13 phases for study in thermoelectric applications. The procedure consisted of the physical evaporation of sulfides layers (Sb2S3 and CuS) on glass substrates and the subsequent annealing of the samples in a N2 atmosphere. The characterizations by Raman spectroscopy and XRD revealed that the samples presented a varied percentage of Cu12Sb4S13 and CuSbS2. The results indicated that the percentage of phases depended on the initial thickness of the sulfide layers and the annealing temperature. The lower initial ratio between sulfide thicknesses and annealing temperature above 300 °C favored the formation of Cu12Sb4S13. However, the thermoelectric properties were improved when the phases coexisted in the thin film compared to samples with high percentages of Cu12Sb4S13. In this way, a sample with a power factor of 2.30 μW /cm∙ K2 at 60 ºC was identified.

Abstract Bismuth (III) sulfide thin films are prepared on glass substrates by physical vapor deposition technique. Then, the films are annealed at different temperatures from 150 to 350°C with nitrogen and nitrogen-sulfur atmospheres, respectively. The effect of annealing temperature on the optoelectronic properties is investigated. The layers were characterized using ultraviolet-visible spectroscopy, XRD, Raman spectroscopy, EDS analysis and Hall effect. The film annealed at 250°C in a nitrogen-sulfur atmosphere exhibited the best condition with an initial thickness of 106 nm and band gap of 1.37 eV. Also, Bismuthinite phase was obtained, close to the stoichiometry with 59.95 and 40.05 at % for bismuth and sulfur, respectively. The charge carrier concentration of 6.9x1019 cm-3 with a n-type conductivity, the resistivity of 0.19 Ω-cm, and mobility of 0.44 cm2V-1s-1 are obtained.