Abstract
AbstractThe natural semiconductor cylindrite FeSn4Pb3Sb2S14 was synthesised by chemical vapour transport (CVT). Crystals with lamellar shape and cylindrical morphology could be deposited on substrates. The endothermic reactions responsible for material transport were simulated by means of thermodynamic modelling. Cylindrite belongs to the class of misfit layered compounds, where its modulated incommensurate crystal structure is based on the regular alternation of two types of layers. The so called T‐ and H‐slab are incommensurately linked. Determined from single crystal XRD measurements, the modulation of atom positions as well as modulation of metal site occupancy of both subsystems are presented. The origin of super structure reflections found in scattering experiments can be clearly explained by a structure model. Based on experimentally determined single crystal XRD data and HRTEM inspections a model is derived to explain the formation of cylindrical architecture of crystals. The specific electrical conductivity of cylindrite improves from 10−2 to 101 Ω−1/m when increasing the atomic ratio Pb/Sb from 1.35 to 1.75. In the same way the Seebeck coefficient S can reach negative values of −730 µV/K indicating n‐type conduction. The band gap energy Eg rises from 0.65 to 1.15 eV with decreasing (Pb + Fe)/(Sn + Sb) from 0.71 to 0.53. magnified image TEM bright field image of high magnification demonstrating the continuous bending of (100) layers in a cylindrite cylinder.
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