Probing structural changes in Ca(1−x)Nd2x/3TiO3 ceramics by Raman spectroscopy

Ceramics in the system Ca(1−x)Nd2x/3TiO3, intended for mobile communication applications, exhibit grossly non-linear variations in microwave dielectric properties with composition. There is evidence of a structural transition and the formation of vacancies on the A-site of the perovskite structure. High density, single phase perovskite Ca(1−x)Nd2x/3TiO3 ceramics have been prepared by the mixed oxide route. Raman spectroscopy was used to investigate the structural variations, which impact on dielectric properties. The Raman spectra show that with increasing Nd content, there is a transition from an ordered structure, to a disordered arrangement of cations and vacancies, and back to an ordered arrangement in Ca0.1Nd0.6TiO3. A structural phase transition from orthorhombic Pbnm to monoclinic C2/m coincides with the order-disorder transition at Ca0.1Nd0.6TiO3. Polarized Raman spectroscopy facilitated the assignment of the Raman modes and investigation of the role of importance of domain structures. Large variation in the plane angles was attributed to differences in domain structures. Differences in the angular dependence of the Raman modes with Nd content reflect changes in the preferred orientation of the domains from lamellar twins, to wedge shaped and back to lamellar twins.