Electron microscopy study of CVT grown Fe-sulphides

Abstract

Recent studies of {110} twin boundaries in natural pyrite (FeS2) indicated that twinning is triggered by the presence of Cu during crystal growth. Here we investigated the formation sequence of Fe-sulphides produced by the chemical vapor transport (CVT) method at 600°C in an evacuated quartz tube using Fe- and Cu-halides and elementary S as the reaction precursors. Depending on the mobility of elements different Fe-sulphides crystallized through gradually decreasing temperature zones. At the higher temperature zones, where metal ions are present in abundance, the main reaction product is FeS in form of pyrrhotite-3T. The main characteristic of this pyrrhotite is the presence of {111} layers cubic FeS coherently intergrown with the {0001} layers of the hosting hexagonal FeS. While the hosting structure corresponds to distorted troilite (nickeline-type structure) with octahedrally coordinated Fe2+ ions, iron in cubic FeS either remains in octahedral coordination (rocksalt-type structure) or is translated to tetrahedral interstices (sphalerite-type structure). HRTEM analysis suggests that Fe2+ ions in the cubic sequences remain in the octahedral sites, suggesting a new, cubic close-packed, rocksalt-type structure of FeS. Cubic FeS shows a high density of twins and SFs in the {111} planes. Pyrite crystallized in the temperature zone between 500 and 450°C, where the concentration of metal ions is depleted. With a decreasing temperature its morphology changes from {111}→{210}→{100}. Doping with copper did not result in twinning of pyrite, suggesting that different thermodynamic conditions are present in the natural environment. Using the natural seed crystal we showed that the twin boundaries are continued across the interface into the CVT grown epitaxial pyrite, whereas the marcasite-type SFs terminate at the interface.