Partial charge ordering in the mixed-valent compound (Bi6O5)Rh83+Rh44+O24

Crystals of the mixed-valent compound (Bi6O5)Rh83+Rh44+O24 were grown from a flux. The room temperature conductivity of a crystal was 3 S/cm but decreased smoothly with decreasing temperature to 10−5 S/cm at 25 K. Magnetic susceptibility data indicate a localized moment for Rh4+. A Seebeck coefficient at 200 K of +280 μV/K further confirms that this compound is a semiconductor rather than a metal with a partially filled 4d t2g band. A structure refinement based on single crystal X-ray diffraction data obtained at 173 and 296 K provided Rh–O distances sufficiently accurate to indicate the nature of the charge ordering between Rh3+ and Rh4+. The large Seebeck coefficient coupled with the high electrical conductivity indicates that this may be a promising low-temperature thermoelectric material.

Graphical abstractCrystals of the mixed-valent compound (Bi6O5)Rh83+Rh44+O24 show semiconducting properties, and magnetic susceptibility data indicate a localized moment for Rh4+. Structure refinements at 173 and 296 K show partial charge ordering between Rh3+ and Rh4+.Figure optionsDownload full-size imageDownload as PowerPoint slide