Crystal and electronic band structures of homologous compounds ZnkIn2Ok+3 by Rietveld analysis and first-principle calculation

Crystal structure of homologous compounds, Zn3In2O6, Zn4In2O7, Zn5In2O8, Zn7In2O10, and In2O3 were refined by X-ray Rietveld analysis. Band structures of the homologous compounds were evaluated by first-principle calculation (Cambridge Serial Total Energy Package, CASTEP), using the structural data obtained from the Rietveld analysis. According to the results of CASTEP calculations, a sharp cut-off at the Fermi level could be observed when In3+ preferentially occupies the tetrahedral site (Zn3In2O6(4)) or the trigonal bipyramid site (Zn3In2O6(5)) in the (InZnk)Ok+1+ layers. The cut-off at the Fermi level could not be observed when In3+ and Zn2+ are totally disordered at these sites. Electronic structure calculation suggested that Zn3In2O6(4) is a good conductor and that Zn3In2O6(5) is a poor conductor. Results of geometry optimization indicate that the formation enthalpy of Zn3In2O6(4) was lower than that of Zn3In2O6(5). Considering the electronic structure and the formation enthalpy, Zn3In2O6(4) in which In3+ in the (InZnk)Ok+1+ layer occupies the tetrahedral site preferentially, is likely to be the favored structure.