Structure of a Novel Spinel Li 0 . 5 Zn 5 / 3 Sb 2 . 5 / 3 O 4 by Neutron and Synchrotron Diffraction Analysis

Zn7/3Sb2/3O4 is a secondary phase in ZnO-based varistors. Acceptor impurities, such as Li+, increase the resistivity. This effect is produced by a modification of the grain boundary barriers. The role of the cationic distribution in the mentioned events is worth clarifying. The Li0.5Zn5/3Sb2.5/3O4 room-temperature structure was determined by means of a neutron diffraction and synchrotron X-ray diffraction investigation. The title compound was prepared by conventional ceramic process. The elemental composition of the investigated sample was verified by means of electron microscopy—energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The neutron experiment was performed at the high-intensity neutron diffractometer with position-sensitive detector at the D1B beamline of the Laue-Langevin Institute, Grenoble. The high resolution synchrotron measurement was carried out at MCX beamline of Elettra Sincrotrone Trieste. Rietveld analysis was performed with the FullProf program. Li0.5Zn5/3Sb2.5/3O4 belongs to the spinel family, space group Fd3m (227). The measured lattice parameter is a = 8.5567(1) Å. The Li+1 and Zn+2 ions are randomly distributed among the tetrahedral and octahedral sites as opposed to Sb+5 ions which have preference for octahedral sites. Fractional coordinate of oxygen, u = 0.2596(1), indicates a slight deformation of the tetrahedral and octahedral sites. The data given in this paper provide structural support for further studies on measurements and microscopic explanations of the interesting properties of this family of compounds.