Development of sputtered CuSbS2 thin films grown by sequential deposition of binary sulfides

In this work, CuSbS2 thin films were developed by annealing binary precursors deposited sequentially by rf magnetron sputtering. The recrystallization process was optimized and the films were extensively characterized using a number of tools such as XRD, Raman, SEM, energy dispersive x-ray spectroscopy, atomic force microscopy, Hall, UV–vis spectroscopy, Ellipsometry, Seebeck, and photoresponse. The influence of annealing temperature on the structure, morphology, elemental composition, optical and electrical properties are reported. Annealing below 350 °C resulted in famatinite (Cu3SbS4) and chalcostibite (CuSbS2) ternaries as well as binary phases. Phase-pure chalcostibite was obtained in the range of 350 °C–375 °C. At 400 °C, although CuSbS2 was predominant, tetrahedrite phase (Cu12Sb4S13) appeared as an additional phase. The elemental composition of the films was slightly sulfur deficient, and the atomic percentages of Cu, Sb and S showed a dependence on annealing temperature. The material properties of the phase-pure CuSbS2 thin films are: optical band gap in the range of 1.5–1.62 eV, absorption coefficient close to 105 cm−1, atomic ratios of Cu/Sb ~1 and (Cu + Sb)/S ~1.2, crystal size 18.3–24.5 nm and grain size 50–300 nm. The films were photo-sensitive, showed p-type semiconductor behavior. Electrical resistivity, carrier density and hole mobility were 94–459 Ω cm, 1.6–7.0 × 1015 cm−3 and 8.4–9.5 cm2 V−1 s respectively.