Dielectric Responses of (Zn0.33Nb0.67)xTi1−xO2 Ceramics Prepared by Chemical Combustion Process: DFT and Experimental Approaches

The (Zn, Nb)-codoped TiO₂ (called ZNTO) nanopowder was successfully synthesized by a simple combustion process and then the ceramic from it was sintered with a highly dense microstructure. The doped atoms were consistently distributed, and the existence of oxygen vacancies was verified by a Raman spectrum. It was found that the ZNTO ceramic was a result of thermally activated giant dielectric relaxation, and the outer surface layer had a slight effect on the dielectric properties. The theoretical calculation by using the density functional theory (DFT) revealed that the Zn atoms are energy preferable to place close to the oxygen vacancy (Vo) position to create a triangle shape (called the ZnVoTi defect). This defect cluster was also opposite to the diamond shape (called the 2Nb2Ti defect). However, these two types of defects were not correlated together. Therefore, it theoretically confirms that the electron-pinned defect-dipoles (EPDD) cannot be created in the ZNTO structure. Instead, the giant dielectric property of the (Zn_0.33Nb_0.67)_xTi_1−xO₂ ceramics could be caused by the interfacial polarization combined with electron hopping between the Zn²⁺/Zn³⁺ and Ti³⁺/Ti⁴⁺ ions, rather than due to the EPDD effect. Additionally, it was also proved that the surface barrier-layer capacitor (SBLC) had a slight influence on the giant dielectric properties of the ZNTO ceramics. The annealing process can cause improved dielectric properties, which are properties with a huge advantage to practical applications and devices.     

The Primary Origin of Excellent Dielectric Properties of (Co,Nb) Co-Doped TiO2 Ceramics: Electron-Pinned Defect Dipoles vs. Internal Barrier Layer Capacitor Effect

(Co, Nb) co-doped rutile TiO₂ (CoNTO) nanoparticles with low dopant concentrations were prepared using a wet chemistry method. A pure rutile TiO₂ phase with a dense microstructure and homogeneous dispersion of the dopants was obtained. By co-doping rutile TiO₂ with 0.5 at.% (Co, Nb), a very high dielectric permittivity of ε′ ≈ 36,105 and a low loss tangent of tanδ ≈ 0.04 were achieved. The sample–electrode contact and resistive outer-surface layer (surface barrier layer capacitor) have a significant impact on the dielectric response in the CoNTO ceramics. The density functional theory calculation shows that the 2Co atoms are located near the oxygen vacancy, creating a triangle-shaped 2CoV_oTi complex defect. On the other hand, the substitution of TiO₂ with Nb atoms can form a diamond-shaped 2Nb2Ti complex defect. These two types of complex defects are far away from each other. Therefore, the electron-pinned defect dipoles cannot be considered the primary origins of the dielectric response in the CoNTO ceramics. Impedance spectroscopy shows that the CoNTO ceramics are electrically heterogeneous, comprised of insulating and semiconducting regions. Thus, the dielectric properties of the CoNTO ceramics are attributed to the interfacial polarization at the internal insulating layers with very high resistivity, giving rise to a low loss tangent.