Structure and microwave dielectric properties of Bi- and Ge-doped calcium molybdate

Abstract

The powders of Ca1–2xBi2xMo1–xGexO4 solid solutions were synthesized by the conventional solid state method and investigated by X–ray powder diffraction and Raman spectroscopy. The Ca1–2xBi2xMo1–xGexO4 compositions crystallize in scheelite structure (sp. gr. I41/a) at 0 ≤x ≤ 0.4, but traces of bismuth germanates are detected by scanning electron microscopy. The x = 0.5 composition contains several phases with BiVO4- type structures. Raman spectroscopy detected the deformation of [BO4]2– polyhedra and changes in B–O bond length (B = Mo, Ge). The energy gaps were calculated from the diffuse scattering spectra by the Kubelka-Munk method. Energy gap (Eg) values decrease with x from 3.29 eV to 2.91 eV, probably due to 6s2 electrons of bismuth in the valence band and changes of the conductivity band by electrons of germanium. Such values of Eg can provide photocatalytical activity of powders under UV and visible light. The electrodynamic parameters of the ceramic sample of Ca1–2xBi2xMo1–xGexO4 were measured by the transmission line method. The average permittivity increases with x from ~10 to ~18 which correlates with theoretical ε, Vmol and total polarizability of samples. An increase in the concentration of bismuth and germanium leads to the additional resonant peaks in the spectra of ε, S11 and S21. These resonant peaks can be probably caused by the appearance of irregular structural domains of Bi atoms or induced by the increased size of grains in the ceramic samples.