Structural and dielectric properties,and nonlinear electrical response of the CaCu3-xZnxTi4O12 ceramics: Experimental and computational studies

CaCu_3-xZn_xTi₄O₁₂ ceramics (x = 0, 0.05, 0.10) were successfully prepared by a conventional solid-state reaction method. Their structural and dielectric properties, and nonlinear electrical response were systematically inspected. The X-ray diffraction results indicated that single-phase CaCu₃Ti₄O₁₂ (JCPDS no. 75–2188) was obtained in all sintered ceramics. Changes in the lattice parameter are well-matched with the computational result, indicating an occupation of Zn²⁺ doping ions at Cu²⁺ sites. The overall tendency shows that the average grain size decreases when x increases. Due to a decrease in overall grain size, the dielectric permittivity of CaCu_3-xZn_xTi₄O₁₂ decreases expressively. Despite a decrease in the dielectric permittivity, it remains at a high level in the doped ceramics (~3,406–11,441). Besides retention in high dielectric permittivity, the dielectric loss tangent of x = 0.05 and 0.10 (~0.074–0.076) is lower than that of x = 0 (~0.227). A reduction in the dielectric loss tangent in the CaCu_3-xZn_xTi₄O₁₂ ceramics is closely associated with the enhanced grain boundary response. Increases in grain boundary resistance, breakdown electric field, and conduction activation energy of grain boundary as a result of Zn²⁺ substitution are shown to play a crucial role in improved grain boundary response. Furthermore, the XPS analysis shows the existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺, indicating charge compensation due to the loss of oxygen lattice. Based on all results of this work, enhanced dielectric properties of the Zn-doped CCTO can be explained using the internal barrier layer capacitor model.     

Effect of oxygen sintering atmosphere on the electrical behavior of CCTO ceramics

The CaCu₃Ti₄O₁₂ ceramics were sintered in air and pure O₂ atmosphere, respectively, and the effect of pure O₂ atmosphere on the electrical behavior of the CaCu₃Ti₄O₁₂ ceramics was investigated. It was found that the dielectric properties of the CaCu₃Ti₄O₁₂ ceramics displayed a Debye-like relaxation between 20 Hz and 1 MHz, but the permittivity of the sample sintered in pure O₂ atmosphere was decreased drastically. Moreover, the I-V behavior of the ceramic sintered in pure O₂ atmosphere presented a linear feature. With XPS analysis, it was illustrated that the valence of Cu and Ti elements in the CaCu₃Ti₄O₁₂ ceramics had obviously been influenced by the O₂ concentration. Based on the experimental comparison of CaCu₃Ti₄O₁₂ ceramics sintered in air and pure O₂ atmosphere, it was suggested that the valence of metallic elements and defects played key role for the origin of the giant permittivity and I-V nonlinear feature in the CaCu₃Ti₄O₁₂ ceramics.     

Microstructural evolution,non‐Ohmic properties,and giant dielectric response in CaCu3Ti4−xGexO12 ceramics

The microstructural evolution, non‐Ohmic properties, and giant dielectric properties of CaCu₃Ti_4?xGe_xO₁₂ ceramics (x=0‐0.10) are systematically investigated. The Rietveld refinement confirms the existence of a pure CaCu₃Ti₄O₁₂ phase in all samples. Significantly enlarged grain sizes of CaCu₃Ti_4?xGe_xO₁₂ ceramics are associated with the liquid phase sintering mechanism. Enhanced dielectric permittivity from 6.90×10⁴ to 1.08×10⁵ can be achieved by increasing Ge⁴⁺ dopant from x=0‐0.10, whereas the loss tangent is remarkably reduced by a factor of ≈10. Non‐Ohmic properties are enhanced by Ge⁴⁺ doping ions. Using impedance and admittance spectroscopies, the underlying mechanisms for the dielectric and nonlinear properties are well described. The improved nonlinear properties and reduced loss tangent are attributed to the enhanced resistance and conduction activation energy of the grain boundaries. The largely enhanced permittivity is closely associated with the enlarged grain sizes and the increase in the Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ ratios, which are calculated from the X‐ray absorption near‐edge structure.     

Enhancement of giant dielectric response in Ga-doped CaCu3Ti4O12 ceramics

The influences of Ga³⁺ doping ions on the microstructure, dielectric and electrical properties of CaCu₃Ti₄O₁₂ ceramics were investigated systematically. Addition of Ga³⁺ ions can cause a great increase in the mean grain size of CaCu₃Ti₄O₁₂ ceramics. This is ascribed to the ability of Ga³⁺ doping to enhance grain boundary mobility. Doping CaCu₃Ti₄O₁₂ with 0.25 mol% of Ga³⁺ caused a large increase in its dielectric constant from 5439 to 31,331. The loss tangent decreased from 0.153 to 0.044. The giant dielectric response and dielectric relaxation behavior can be well described by the internal barrier layer capacitor model based on Maxwell?Wagner polarization at grain boundaries. The nonlinear coefficient, breakdown field, and electrostatic potential barrier at grain boundaries decreased with increasing Ga³⁺ content. Our results demonstrated the importance of ceramic microstructure and electrical responses of grain and grain boundaries in controlling the giant dielectric response and dielectric relaxation behavior of CaCu₃Ti₄O₁₂ ceramics.     

Dramatically enhanced non-Ohmic properties and maximum stored energy density in ceramic-metal nanocomposites: CaCu3Ti4O12/Au nanoparticles

Non-Ohmic and dielectric properties of a novel CaCu₃Ti₄O₁₂/Au nanocomposite were investigated. Introduction of 2.5 vol.% Au nanoparticles in CaCu₃Ti₄O₁₂ ceramics significantly reduced the loss tangent while its dielectric permittivity remained unchanged. The non-Ohmic properties of CaCu₃Ti₄O₁₂/Au (2.5 vol.%) were dramatically improved. A nonlinear coefficient of ≈ 17.7 and breakdown electric field strength of 1.25 × 10⁴ V/m were observed. The maximum stored energy density was found to be 25.8 kJ/m³, which is higher than that of pure CaCu₃Ti₄O₁₂ by a factor of 8. Au addition at higher concentrations resulted in degradation of dielectric and non-Ohmic properties, which is described well by percolation theory.     

Effects of Ta5+ doping on microstructure evolution,dielectric properties and electrical response in CaCu3Ti4O12 ceramics

The effects of Ta⁵⁺ substitution on the microstructure, electrical response of grain boundary, and dielectric properties of CaCu₃Ti₄O₁₂ ceramics were investigated. The mean grain size decreased with increasing Ta⁵⁺ concentration, which was ascribed to the ability of Ta⁵⁺ doping to inhibit grain boundary mobility. This can decrease dielectric constant values. Grain boundary resistance and potential barrier height of CaCu₃Ti₄O₁₂ ceramics were reduced by doping with Ta⁵⁺. This results in enhancement of dc conductivity and the related loss tangent. Influence of charge compensations on microstructure and intrinsic electrical properties of grain boundaries resulting from the effects of replacing Ti⁴⁺ with Ta⁵⁺ are discussed. The experimental data and variation caused by the substitution of Ta⁵⁺ can be described well by the internal barrier layer capacitor model based on space charge polarization at the grain boundaries.     

A novel strategy to enhance dielectric performance and non-Ohmic properties in Ca2Cu2−xMgxTi4O12

A novel strategy to improve the dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ ceramics that deliberately created a binary-phase system of CaCu_3−xMg_xTi₄O₁₂/CaTiO₃ was proposed and can be performed with a starting nominal formula of Ca₂Cu_2−xMg_xTi₄O₁₂. Mg²⁺ doping ions were preferentially incorporated only into the CaCu₃Ti₄O₁₂ phase. Substitution of Mg²⁺ into CaCu₃Ti₄O₁₂/CaTiO₃ can cause a significant increase in dielectric permittivity and a large reduction of the loss tangent to <0.015 at 1 kHz; while, retaining excellent temperature dielectric-stability. Sintering time had a slight influence on the dielectric properties, but remarkable effects upon the nonlinear electrical properties of CaCu_3−xMg_xTi₄O₁₂/CaTiO₃ ceramics. Degradation of nonlinear properties with increased sintering time is suggested to be the result of the dominant effect of oxygen vacancies. Impedance spectroscopy analysis demonstrated that improved dielectric and nonlinear properties could be attributed to the enhanced electrical responses of CaCu₃Ti₄O₁₂–CaTiO₃ and CaCu₃Ti₄O₁₂–CaCu₃Ti₄O₁₂ interfaces resulting from Mg²⁺ doping ions.     

Effects of LiF addition on microstructure and dielectric properties of CaCu3Ti4O12 ceramics

The effects of small amounts of lithium fluoride sintering aid on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. CCTO polycrystalline ceramics with 0.5 and 1.0 mol% LiF, and without additive were prepared by solid state synthesis. Good densification (>90% of the theoretical density) was obtained for all prepared materials. Specimens without the sintering aid and sintered at 1090 °C exhibit secondary phases as an outcome of the decomposition reaction. The mean grain size is controlled by the amount of LiF in specimens containing the additive. Impedance spectroscopy measurements on CaCu₃Ti₄O₁₂ ceramics evidence the electrically heterogeneous nature of this material consisting of semiconductor grains along with insulating grain boundaries. The activation energy for grain boundary conduction is lower for specimens prepared with the additive, and the electric permittivity reached 53,000 for 0.5 mol% LiF containing CCTO.     

Low temperature preparation of CaCu3Ti4O12 ceramics with high permittivity and low dielectric loss

Low temperature preparation of CaCu₃Ti₄O₁₂ ceramics with large permittivity is of practical interest for cofired multilayer ceramic capacitors. Although CaCu₃Ti₄O₁₂ ceramics have been prepared at low temperatures as previously reported, they have rather low permittivity. This work demonstrates that CaCu₃Ti₄O₁₂ ceramics can not only be prepared at low temperatures, but they also have large permittivity. Herein, CaCu₃Ti₄O₁₂ ceramics were prepared by the solid state reaction method using B₂O₃ as the doping substance. It has been shown that B₂O₃ dopant can considerably lower the calcination and sintering temperatures to 870 °C and 920 °C, respectively. The relative permittivity of the low temperature prepared CaCu₃Ti_4−xB_xO₁₂ ceramics is about 5 times larger than the previously reported results in the literature. Furthermore, the dielectric loss of the CaCu₃Ti_4−xB_xO₁₂ ceramics is found to be as low as 0.03. This work provides a beneficial base for the future commercial applications of CaCu₃Ti₄O₁₂ ceramics with large permittivity for the cofired multilayer ceramic capacitors.     

Origin of the temperature stability of dielectric constant in CaCu3Ti4O12

The temperature and dc bias stability of the dielectric constant and loss tangent of CaCu₃Ti₄O₁₂ samples sintered under different oxygen atmospheres are discussed. The results suggest that the metal-oxygen vacancy related defects not only provide the charge carriers for the conduction (defect doping) but also contribute to the huge permittivity in the way of defect dipoles repositioning under charge carrier hopping. The charge localization in a specific copper-oxygen vacancy defect complex is the reason of the huge and stable permittivity and low dielectric loss in the middle temperature range, 90 K-200 K (20 Hz), while the implementation of the large barrier layer height needs a contribution by the titanium oxygen vacancy related trap charges in the grain boundaries, which also lead to a second permittivity stable range in a higher temperature range 200 K–300 K.     

Improved non-ohmic and dielectric properties of Cr3+ doped CaCu3Ti4O12 ceramics prepared by a polymer pyrolysis solution route

CaCu_3-xCr_xTi₄O₁₂ (x?=?0.00–0.20) ceramics were prepared via a polymer pyrolysis solution route. Their dielectric properties were improved by Cr³⁺ doping resulting in an optimal dielectric constant value of 7156 and a low tanδ?value of 0.092 in a sample with x?=?0.08. This might have resulted from a decrease in oxygen vacancies at grain boundaries. XANES spectra confirmed the presence of Cu⁺ ions in all ceramic samples with a decreasing Cu⁺/Cu²⁺ ratio due to an increased content of Cr³⁺ ions. All CaCu_3-xCr_xTi₄O₁₂ ceramics showed nonlinear characteristic with improvement in both the breakdown field (E_b) and its nonlinear coefficient (α). Interestingly, the highest values of α, ～ 114.4, and that of E_b, ～8455.0?±?123.6?V?cm^?1, were obtained in a CaCu_3-xCr_xTi₄O₁₂ sample with x?=?0.08. The improvement of dielectric and nonlinear properties suggests that they originate from a reduction of oxygen vacancies at grain boundaries.     

Enhanced electrical and photoluminescence properties of BiSbO4-doped CaCu3Ti4O12 ceramics by modifying grain boundary response

CaCu₃Ti₄O₁₂-xwt%BiSbO₄ ceramics (CCTO-xwt%BSO, x = 0, 1, 2, 3) were prepared by solid-state reaction method. The microstructure, dielectric properties, varistor properties, photoluminescence properties of CCTO-xwt%BSO ceramics were studied in this work. Results showed that all samples formed CaCu₃Ti₄O₁₂ (CCTO) single phase. Doping BiSbO₄ (BSO) restrained the abnormal grain growth and increased the grain boundary density of ceramics. The introduction of BSO led to the increase of the grain boundary resistance, reducing the dielectric loss and enhancing the temperature stability of dielectric properties. The nonlinear electrical characteristics are enhanced with proper concentration of BSO. And the improved varistor performance with breakdown electric field of ～3.98–34.6 and nonlinear coefficient of ～1.49–2.96 are obtained for CCTO-xwt%BSO samples. In addition, the photoluminescent emission of the samples is enhanced with the addition of appropriate equivalent BSO, showing the potential applications in novel devices with photoluminescent/electrical multifunctional properties.     

Influence of Zn doping on microstructures and dielectric properties in CaCu3Ti4O12 ceramic synthesised by semiwet route

Abstract

A single phase of calcium copper titanate [CaCu₃Ti₄O₁₂ (CCTO)] was produced at lower temperature and shorter calcination time via a novel semiwet route. Undoped CCTO and zinc doped CaCu_3?xZn_xTi₄O₁₂ samples with x?=?0·10, 0·20 and 0·30 were prepared by this method for the first time using solid TiO₂ powder in metal nitrate solutions. The CaCu_3?xZn_xTi₄O₁₂ ceramics were characterised by thermogravimetric/differential thermal analysis, X-ray diffraction, SEM and EDX techniques. The SEM images of the sintered CaCu_3?xZn_xTi₄O₁₂ ceramics showed average grain size in the ranges of 2–6, 8–13, 12–16 and 14–20 μm for x?=?0·00, 0·10, 0·20 and 0·30 respectively. Energy dispersive X-ray spectroscopy studies confirm the purity of parent and Zn doped CCTO ceramics. At room temperature, the dielectric constants of Zn doped CCTO are always higher than pure CCTO. CaCu_3?xZn_xTi₄O₁₂ (x?=?0·20) ceramic has the maximum value of ?_r≈4347 along with the minimum value of tan?δ≈0·14 at 1 kHz.     

Thermal stability improvement of dielectric properties and non-ohmic characteristic of CaCu3+xTi4O12 ceramics via a Cu-nonstoichiometric approach

In this work, the effects of Cu composition on the thermal stability of the dielectric and nonlinear properties of CaCu_3+xTi₄O₁₂ (?0.2 ≤ x ≤ 0.2) ceramics obtained via a polymer-pyrolysis chemical process were studied. The mean grain sizes of Cu-stoichiometric (x = 0), Cu-deficient (x < 0) and Cu-excess (x > 0) CaCu_3+xTi₄O₁₂ ceramics were found to be ~3.2, ~3.4 and ~3.7 μm, respectively. Interestingly, very good dielectric properties (0.020 ≤ tanδ ≤ 0.038 and 4000 ≤ ε′ ≤ 7065) were attained in CaCu_3+xTi₄O₁₂ (?0.2 ≤ x ≤ 0.1, excluding x = 0.2) ceramics. Moreover, the variation of dielectric constant (ε′) within a limit of ±15% (Δε′_{± 15%}) over a wide temperature range (T_R) of ?70 – 220 °C with low tanδ < 0.05 (tanδ_<0.05) over a T_R of ?70 to 80 °C were achieved in a CaCu_2.8Ti₄O₁₂ ceramic. These results suggest that this ceramic could be applicable for X9R capacitors and energy storage devices that require high thermal stability. Additionally, the nonlinear properties of Cu-nonstoichiometric ceramics could be improved when compared with those of the Cu-stoichiometric material. The incremental changes of dielectric and nonlinear properties of CaCu_3+xTi₄O₁₂ (?0.2 ≤ x ≤ 0.2) ceramics revealed the significant role of Cu composition on grain boundary resistance (R_gb), which was confirmed by impedance spectroscopy analysis. In addition, XANES results revealed the proper ratios of Cu⁺:Cu²⁺ and Ti³⁺:Ti⁴⁺ found in these ceramics, indicating the semiconducting behavior of these grains.     

Improved dielectric properties and grain boundary response of SrTiO3 doped Y2/3Cu3Ti4O12 ceramics fabricated by Sol-gel process for high-energy-density storage applications

A chemical solution processing method based on sol-gel chemistry (SG) was used to synthesize (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.25) ceramics successfully. The 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics sintered at 1050 °C for 20 h showed fine-grained microstructure and high dielectric constant (ε′ ≈ 1.7 × 10⁵) at 1 kHz. Furthermore, the 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics appeared distinct pseudo-relaxor behavior. Two electrical responses were observed in the combined modulus and impedance plots, indicating the presence of Maxwell-Wagner relaxation. Sr vacancies and additional oxygen vacancies had substantial contribution to the sintering behavior, an increase in grain growth, and relaxation behaviors in grain boundaries. The contributions of semiconducting grains with the nanodomain and insulating grain boundaries (corresponding to high-frequency and low-frequency electrical response, respectively) played important roles in the dielectric properties of (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ ceramics. The occurrence of the polarization mechanism transition from the grain boundary response to the electrode one with temperature change was clearly evidenced in the low frequency range.     

Experimental study and DFT calculations of improved giant dielectric properties of Ni2+/Ta5+ co-doped TiO2 by engineering defects and internal interfaces

High-performance ceramics with chemical formula (Ni_1/3Ta_2/3)_xTi_1?xO₂ with excellent dielectric properties are demonstrated. The dopants of Ni²⁺ and Ta⁵⁺ in TiO₂ caused the formation of oxygen vacancies and free electrons. The (Ni_1/3Ta_2/3)_xTi_1?xO₂ exhibited low loss tangent of 0.046 and a high dielectric permittivity of 3.5–4.5 × 10⁴ with a very weak dependence on temperature (?60 to 200 °C). Broadband dielectric spectroscopy shows at least four dominant sources in the dielectric relaxation response in the temperature range of ? 253–210 °C. DFT calculations indicate the formation of defect clusters, which are the largest contributors to the dielectric response, and these are found to be dominant even at temperatures down to ? 253 °C. Both grain boundary and surface layer mechanisms in the ceramics contribute to the dielectric response at the relatively high temperatures. The sample–electrode contact effect associated with oxygen vacancy diffusion is dominant at high temperatures above 150 °C.     

High dielectric permittivity and dielectric relaxation behavior in a Y2/3Cu3Ti4O12 ceramic prepared by a modified Sol−Gel route

In this work, Y_2/3Cu₃Ti₄O₁₂ ceramics were fabricated via a modified sol?gel route. Structural, dielectric, and electrical parameters were systematically investigated. The XRD results indicate that a CaCu₃Ti₄O₁₂ phase (JCPDS No. 75–2188) is present in every sintered sample. SEM images of Y_2/3Cu₃Ti₄O₁₂ ceramics disclose a fine-grained ceramic microstructure. Interestingly, high dielectric permittivity, ～6600–7600, with loss tangents of ～0.918–1.086 were achieved in the sintered Y_2/3Cu₃Ti₄O₁₂ samples. Density functional theory (DFT) calculations were used to investigate the most stable structure of the Y_2/3Cu₃Ti₄O₁₂ ceramics. Our DFT results reveal that two calcium vacancies (V_Ca) are isolated from each other. We also determined the lowest energy configuration of an oxygen vacancy (V_O) in the Y_2/3Cu₃Ti₄O₁₂ ceramics occurred during the sintering process. We found that the V_O is trapped close to the Y atom in this structure. Both computational and experimental studies specify that the oxygen vacancy is located close to the Y atom in the Y_2/3Cu₃Ti₄O₁₂ lattice and it might be a bivalent oxygen vacancy. As a result, due to charge balance, charge compensation of the transition ions, i.e., Cu and Ti ions, might take place. The charge compensation mechanisms in the Y_2/3Cu₃Ti₄O₁₂ lattice were verified using an XPS technique. Impedance spectroscopy confirms the presence of an inhomogeneous microstructure consisting of semiconducting grains and insulating grain boundaries in the sintered Y_2/3Cu₃Ti₄O₁₂ ceramics. This electrical result is consistent with the computational analysis, showing that a charge compensation mechanism might be involved in generation of the grains' semiconductive region due to the presence of a V_O. Consequently, high dielectric permittivity in Y_2/3Cu₃Ti₄O₁₂ may have originated from an internal barrier layer capacitor (IBLC) effect.     

Effect of La-doping on the properties of CaCu3Ti4O12 dielectric ceramics

Nano-size Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ (χ = 0.00, 0.05, 0.10, 0.15 and 0.20) precursor powders were prepared via the sol–gel method and the citrate auto-ignition route and then processed into micro-crystal Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics under heat treatment. Characterization of the as-obtained ceramics with XRD and SEM showed an average grain sizes of ∼1–2 μm, indicating La³⁺ amount to have little impact on grain size. The room-temperature dielectric constant of the Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics sintered at 1000 °C was of the order of 10³–10⁴ despite the variation of χ values. Compared with CaCu₃Ti₄O₁₂, La³⁺-doped CaCu₃Ti₄O₁₂ showed a flatter dielectric constant curve related to frequency. It was found that the loss tangent of the Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics was less than 0.20 in ∼600–10⁵ Hz region, which rapidly decreased to a minimum value of 0.03 by La³⁺doping with χ = 0.05. Our measurement of the ceramics conductivities (σ) also indicated that the appropriate introduction of La³⁺ into CaCu₃Ti₄O₁₂ would distinctly result in its dielectric properties.     

Giant dielectric behavior of monovalent cation/anion (Li+, F−) co-doped CaCu3Ti4O12 ceramics

Giant dielectric behavior and electrical properties of monovalent cation/anion (Li⁺, F⁻) co-doped CaCu₃Ti₄O₁₂ ceramics prepared by a solid-state reaction route were systematically investigated. Substitution of Li⁺ and F⁻ led to a significantly enlarged mean grain size. A reduced loss tangent (tanδ ~0.06) with the retainment of an ultra-high dielectric permittivity (ε′ ~7.7-8.8 × 10⁴) was achieved in the co-doped ceramics, while the breakdown electric field and nonlinear coefficient of CaCu₃Ti₄O₁₂ ceramics were increased by co-doping with (Li⁺, F⁻). The variations in nonlinear electrical properties and giant dielectric response, as well as the dielectric relaxation, were well explained by the Maxwell-Wagner polarization model for an electrically heterogeneous microstructure, in which a Schottky barrier height at the grain boundaries (GBs) was formed. ε′ was closely correlated to the GB capacitance. Significantly decreased tanδ value and enhanced nonlinear properties were related to a significant increase in the GB resistance, which was attributed to the significantly increased potential barrier height and conduction activation energy at the GBs. The semiconducting nature of the grains was also studied using X-ray photoelectron spectroscopy and found to originate from the presence of Cu⁺ and Ti³⁺ ions.     

First-principles calculations and experimental study of enhanced nonlinear and dielectric properties of Sn4+-doped CaCu2.95Mg0.05Ti4O12 ceramics

High dielectric permittivity (ε′ ≈ 2000―6900) was accomplished in Sn⁴⁺-doped CaCu_2.95Mg_0.05Ti₄O₁₂ ceramics while retaining a low loss tangent (tanδ ≈ 0.027―0.075). Further, significant improvements in the nonlinear electrical properties, such as high values of the breakdown electric field (E_b ≈ 1.2―1.3 × 10⁴ V cm^?1) and nonlinear coefficient (α ≈ 31), were achieved. In addition, the nonlinear electrical parameters significantly improved, which is consistent with the increase in the electrical resistivities of the grains and grain boundaries due to the decrease in the Cu⁺/Cu²⁺ ratio. According to our first-principles calculations, the Sn atom at the Ti site prefers to be close to the Mg atom at the Cu site, while the oxygen vacancy prefers to be located at large distances from the Sn and Mg co-dopants. This confirms that the dielectric behavior and the nonlinear electrical properties originate from the interface between the grain and grain boundary.