Structural and microstructural features of pyrite FeS_2−x thin films obtained by thermal sulfuration of iron

Structural and microstructural properties of synthetic thin films of pyrite (FeS_2−x), prepared by thermal sulfuration of iron layers, were investigated from Rietveld refinements of x-ray diffraction data, collected by step/scan mode. From this refinement lattice constant, a, and sulfur position parameter, u, nearest neighbor Fe–S and S–S bond distances and tetrahedral and octahedral bond angles have been determined. Moreover, sulfur deficit in the samples, surface and volume-weighted crystallite size and microstrains were also obtained. From these data, the influence of temperature and time of sulfuration and sulfur pressure on their structural and microstructural properties has been established. Stoichiometric pyrite thin films are obtained by sulfurating the iron films at low temperatures (T_s ∼ 600–700 K) during short times (t_s ∼ 0.5–2 h). These experimental conditions yield films with the highest a, u, Fe–S bond distance, and microstrains, as well as S/Fe ratios about 2.00, i.e., null sulfur vacancies, the smallest S–S bond distances, and crystallite size. Finally, the possible influence of these structural and microstructural characteristics on some physical properties (optical absorption, electrical resistivity …) of the films is discussed.