Structural dependence of microwave dielectric properties in ilmenite-type Mg(Ti1-xNbx)O3 solid solutions by Rietveld refinement and Raman spectra

Abstract

Mg(Ti1-xNbx)O3 (x = 0–0.09) ceramics were prepared by the conventional solid-state reaction method. The phase composition, sintering characteristics, microstructure and dielectric properties of Ti4+ replacement by Nb5+ in the formed solid solution Mg(Ti1-xNbx)O3 (x = 0–0.09) ceramics were systematically studied. The structural variations and influence of Nb5+ doping in Mg(Ti1-xNbx)O3 were also systematically investigated by X-ray diffraction and Raman spectroscopy, respectively. X-ray diffraction and its Rietveld refinement results confirmed that Mg(Ti1-xNbx)O3 (x = 0–0.09) ceramics crystallised into an ilmenite-type with R-3 (148) space group. The replacement of the low valence Ti4+ by the high valence Nb5+ can improve the dielectric properties of Mg(Ti1-xNbx)O3 (x = 0–0.09). This paper also studied the different sintering temperatures for Mg(Ti1-xNbx)O3 (x = 0–0.09) ceramics. The obtained results proved that 1350 °C is the best sintering temperature. The permittivity and Q × f initially increased and then decreased mainly due to the effects of porosity caused by the sintering temperature and the doping amount of Nb2O5, respectively. Furthermore, the increased Q × f is correlated to the increase in Ti–O bond strength as confirmed by Raman spectroscopy, and the electrons generated by the oxygen vacancies will be compensated by Nb5+ to a certain extent to suppress Ti4+ to Ti3+, which was confirmed by XPS. The increase in τf from −47 ppm/°C to −40.1 ppm/°C is due to the increment in cell polarisability. Another reason for the increased τf is the reduction in the distortion degree of the [TiO6] octahedral, which was also confirmed by Raman spectroscopy. Mg(Ti0.95Nb0.05)O3 ceramics sintered at 1350 °C for 2 h possessed excellent microwave dielectric properties of εr = 18.12, Q × f = 163618 GHz and τf = −40.1 ppm/°C.