Bismuth and antimony were reacted in sulfur/iodine flux mixtures at various temperatures and iodine concentrations to explore their effects on the synthesis and properties of M13S18I2 (M = Bi/Sb), MSI, and M2S3 products. The ternary phase “Bi19I3S27” grows as well formed needles from the flux, enabling crystallographic studies by single crystal XRD and powder synchrotron XRD. These data have enabled a reinterpretation of the disordered sites in the structure to indicate the presence of subvalent Bi-Bi dimers, yielding a modified stoichiometry of Bi13S18I2. Raman spectroscopy and thermal decomposition studies support this structural model. Substitution of antimony into the structure was explored and its effect on band gap measured.

Synthesis and substitution chemistry of complex bismuth sulfide iodides in sulfur/iodine melts

253rd National Meeting (2017)

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