Colossal Dielectric Permittivity in (Nb+Al) Codoped Rutile TiO2 Ceramics: Compositional Gradient and Local Structure

(Nb+Al) codoped rutile TiO 2 ceramics with nominal composition Ti 4+ 0.995 Nb 5+ 0.005y Al 3+ 0.005z O 2, z = (4–5 y )/3 and y = 0.4, 0.5, 0.6, 0.7, and Ti 4+ 0.90 Nb 5+ 0.05 Al 3+ 0.05 O 2 have been synthesized. The resultant samples in ceramic pellet form exhibit a colossal dielectric permittivity (>∼10 4 ) with an acceptably low dielectric loss (∼10 –1 ) after optimization of the processing conditions. It is found that a conventional surface barrier layer capacitor (SBLC) effect, while it contributes significantly to the observed colossal permittivity, is not the dominant effect. Rather, there exists a subtle chemical compositional gradient inward from the pellet surface, involving the concentration of Ti 3+ cations gradually increasing from zero at the surface without the introduction of any charge compensating oxygen vacancies. Instead, well-defined G r ± 1 / 3 [011]* satellite reflections with the modulation wave-vector q = 1 / 3 [011] r * and sharp diffuse streaking running along the G r ± ε[011]* direction from electron diffraction suggest that the induced additional metal ions appear to be digested by a locally intergrown, intermediate, metal ion rich structure. This gradient in local chemical composition exists on a scale up to ∼ submillimeters, significantly affecting the overall dielectric properties. This work suggests that such a controllable surface compositional gradient is an alternative method to tailor the desired dielectric performance.