LAUSR

ABSTRACT CaCu3Ti4O12 ceramics have been extensively studied for their potential applications as capacitors in recent years; however, these materials exhibit very large dielectric losses. A novel approach to reducing the dielectric loss tangent in two steps, while increasing the dielectric permittivity, is presented herein. Doping CaCu3Ti4O12 with a Zn dopant reduces the loss tangent of the ceramic material from 0.227 to 0.074, which is due to the increase in grain boundary (GB) resistance by an order of magnitude (from 6.3 × 103 to 3.93 × 104 Ω·cm). Zn-doping slightly changes the microstructure and dielectric permittivity of the CaCu3Ti4O12 ceramic, which reveals that the primary role of the Zn dopant is to tune the intrinsic properties of the GBs. Surprisingly, the addition of the Ge4+ dopant into the Zn2+-doped CaCu3Ti4O12 ceramic sample led to a further decrease in the loss tangent from 0.074 to 0.014, due to enhanced GB resistance (3.1 × 105 Ω·cm). The grain size increased remarkably from 2–3 μm to 85–90 μm, corresponding to a significant increase in the dielectric permittivity (∼1–4 × 104). The large increase in GB resistance is due to the intrinsic potential barrier height at the GBs and the segregation of the Cu-rich phase in the GB region. First-principles calculations revealed that Zn and Ge are preferentially located at the Cu sites in the CaCu3Ti4O12 structure. The substitution of the Ge dopant does not hinder the role of the Zn dopant in terms of improving the electrical properties at the GBs. These phenomena are effectively explained by the internal barrier layer capacitor model. This study provides a way of improving the dielectric properties of ceramics for their practical use as capacitors.