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The giant dielectric behavior of CaCu3Ti4O12 (CCTO) has been widely investigated owing to its potential applications in electronics; however, the loss tangent (tanδ) of this material is too large for many applications. A partial substitution of CCTO ceramics with either Al3+ or Ta5+ ions generally results in poorer nonlinear properties and an associated increase in tanδ (to ∼0.29–1.15). However, first-principles calculations showed that self-charge compensation occurs between these two dopant ions when co-doped into Ti4+ sites, which can improve the electrical properties of the grain boundary (GB). Surprisingly, in this study, a greatly enhanced breakdown electric field (∼200–6588 V/cm) and nonlinear coefficient (∼4.8–15.2) with a significantly reduced tanδ (∼0.010–0.036) were obtained by simultaneous partial substitution of CCTO with acceptor-donor (Al3+, Ta5+) dopants to produce (Al3+, Ta5+)-CCTO ceramics. The reduced tanδ and improved nonlinear properties were attributed to the synergistic effects of the co-dopants in the doped CCTO structure. The significant reduction in the mean grain size of the (Al3+, Ta5+)-CCTO ceramics compared to pure CCTO was mainly because of the Ta5+ ions. Accordingly, the increased GB density due to the reduced grain size and the larger Schottky barrier height (Φb) at the GBs of the co-doped CCTO ceramics were the main reasons for the greatly increased GB resistance, improved nonlinear properties, and reduced tanδ values compared to pure and single-doped CCTO. In addition, high dielectric constant values (ε′ ≈ (0.52–2.7) × 104) were obtained. A fine-grained microstructure with highly insulating GBs was obtained by Ta5+ doping, while co-doping with Ta5+ and Al3+ resulted in a high Φb. The obtained results are expected to provide useful guidelines for developing new giant dielectric ceramics with excellent dielectric properties.

The dielectric and non‐Ohmic properties of Na1/2Y1/2Cu3Ti4O12 ceramics sintered under various conditions to obtain different microstructures were investigated. Microstructure analysis confirmed the presence of Na, Y, Cu, Ti, and O and these elements were well dispersed in the microstructure. Na1/2Y1/2Cu3Ti4O12 ceramics exhibited non‐Ohmic characteristics with large nonlinear coefficients of about 5.7–6.6 irrespectively of sintering conditions. The breakdown electric field of fine‐grained ceramic with the mean grain size of ≈1.7 μm (≈5600 V/cm) was much larger than those of the course‐grained ceramics with grain sizes of ≈9.5–10.4 μm (≈1850–2180 V/cm). Through optimization of sintering conditions, a low loss tangent of about 0.03 and very high dielectric permittivities of 18 000–23 000 with good temperature stability were successfully accomplished. The electrical responses of the grains and grain boundaries can, respectively, be well described using admittance and impedance spectroscopy analyses based on the brickwork layer model. A possible mechanism for the origin of semiconducting grains is discussed. The colossal dielectric response was reasonably described as closely correlated with the electrically heterogeneous microstructure by means of strong interfacial polarization at the insulating grain‐boundary layers. The non‐Ohmic properties of Na1/2Y1/2Cu3Ti4O12 ceramics were primarily related to their microstructure, i.e., grain size and volume fraction of grain boundaries.

A solid–state reaction method was used to prepare (Sr2+, Ge4+) co-doped CaCu3Ti4O12 ceramics. A single-phase of CaCu3Ti4O12 was detected in all the ceramics. An enormous evolution of grain growth in (Sr2+, Ge4+) co-doped CaCu3Ti4O12 ceramics was observed, which was due to a liquid phase sintering mechanism. Theoretical calculations showed that Ge dopant ions are more likely substituted in Cu sites rather than Ti sites. High dielectric permittivity, ∼69,889, with a low dielectric loss tangent, ∼0.038, was achieved in a Ca0.95Sr0.05Cu3Ti3.95Ge0.05O12 ceramic. Furthermore, dielectric permittivity at 1 kHz of this ceramic is more temperature-stable than that of the CaCu3Ti4O12 and Ca0.95Sr0.05Cu3Ti4O12 ceramics. The enhanced dielectric permittivity with reduced loss tangent in the co-doped ceramics originated from a metastable insulating phase created by a liquid phase sintering mechanism. The local insulating phase along the grain boundary layers can increase the grain boundary resistance as well as the conduction activation energy of the grain boundaries, resulting in a decreased dielectric loss tangent. An internal barrier layer capacitor model supports the origin of the giant dielectric properties in CaCu3Ti4O12-based ceramics by all results in this work.