Improved dielectric properties in A′‐site nickel‐doped CaCu3Ti4O12 ceramics

The improved dielectric properties and voltage‐current nonlinearity of nickel‐doped CaCu₃Ti₄O₁₂ (CCNTO) ceramics prepared by solid‐state reaction were investigated. The approach of A′‐site Ni doping resulted in improved dielectric properties in the CaCu₃Ti₄O₁₂ (CCTO) system, with a dielectric constant ε′≈1.51×10⁵ and dielectric loss tanδ≈0.051 found for the sample with a Ni doping of 20% (CCNTO20) at room temperature and 1 kHz. The X‐ray photoelectron spectroscopy (XPS) analysis of the CCTO and the specimen with a Ni doping of 25% (CCNTO25) verified the co‐existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺. A steady increase in ε′(f) and a slight increase in α observed upon initial Ni doping were ascribed to a more Cu‐rich phase in the intergranular phase caused by the Ni substitution in the grains. The low‐frequency relaxation leading to a distinct enhancement in ε′(f) beginning with CCNTO25 was confirmed to be a Maxwell‐Wagner‐type relaxation strongly affected by the Ni‐related phase with the formation of a core‐shell structure. The decrease of the dielectric loss was associated with the promoted densification of CCNTO and the increase of Cu vacancies, due to Ni doping on the Cu sites. In addition, the Ni dopant had a certain effect on tuning the current‐voltage characteristics of the CCTO ceramics. The present A′‐site Ni doping experiments demonstrate the extrinsic effect underlying the giant dielectric constant and provides a promising approach for developing practical applications.     

Non‐Ohmic Properties and Electrical Responses of Grains and Grain Boundaries of Na1/2Y1/2Cu3Ti4O12 Ceramics

The dielectric and non‐Ohmic properties of Na_1/2Y_1/2Cu₃Ti₄O₁₂ 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. Na_1/2Y_1/2Cu₃Ti₄O₁₂ 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 Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramics were primarily related to their microstructure, i.e., grain size and volume fraction of grain boundaries.     

Liquid‐phase sintering,microstructural evolution,and microwave dielectric properties of Li2Mg3SnO6–LiF ceramics

The liquid‐phase sintering behavior and microstructural evolution of x wt% LiF aided Li₂Mg₃SnO₆ ceramics (x = 1‐7) were investigated for the purpose to prepare dense phase‐pure ceramic samples. The grain and pore morphology, density variation, and phase structures were especially correlated with the subsequent microwave dielectric properties. The experimental results demonstrate a typical liquid‐phase sintering in LiF–Li₂Mg₃SnO₆ ceramics, in which LiF proves to be an effective sintering aid for the Li₂Mg₃SnO₆ ceramic and obviously reduces its optimum sintering temperature from ~1200°C to ~850°C. The actual sample density and microstructure (grain and pores) strongly depended on both the amount of LiF additive and the sintering temperature. Higher sintering temperature tended to cause the formation of closed pores in Li₂Mg₃SnO₆‐x wt% LiF ceramics owing to the increase in the migration ability of grain boundary. An obvious transition of fracture modes from transgranular to intergranular ones was observed approximately at x = 4. A single‐phase dense Li₂Mg₃SnO₆ ceramic could be obtained in the temperature range of 875°C‐1100°C, beyond which the secondary phase Li₄MgSn₂O₇ (<850°C) and Mg₂SnO₄ (>1100°C) appeared. Excellent microwave dielectric properties of Q × f = 230 000‐330 000 GHz, ε_r = ~10.5 and τ_f = ~?40 ppm/°C were obtained for Li₂Mg₃SnO₆ ceramics with x = 2‐5 as sintered at ~1150°C. For LTCC applications, a desirable Q × f value of ~133 000 GHz could be achieved in samples with x = 3‐4 as sintered at 875°C.     

Deficient or excessive CuO-TiO2 phase influence on dielectric properties of CaCu3Ti4O12 ceramics

The influence of the CuO–TiO₂ phase (CT) on dielectric properties of the CCTO ceramic was investigated. CaCu_XTi_YO₁₂ (CC_XT_YO) powders were prepared based on the coprecipitated method, where 2.70 ≤ x ≤ 3.30 and 3.25 ≤ y ≤ 4.75. XRD patterns confirmed the presence of CCTO and also the secondary phases as CuO, TiO₂, and CaTiO₃ for each sample and aided in its quantification. Scanning Electron Microscopy (SEM) shows secondary phases evolution in the grain boundaries, and its influence on size and morphology of the grains. Impedance spectroscopy measurements showed that the ceramics with lower amount of CuO and TiO₂ phases (CT/deficient ceramics) exhibited the highest ε′ values (2.1 × 10⁴ at 1 kHz for CC_2.9T_3.75O ceramic). Also, CT/deficient ceramics showed lower tanδ values (0.090 at 1 kHz for CC_2.9T_3.75O ceramic) than ceramics prepared with excessive CuO–TiO₂ phase (0.241 at 1 kHz for CC_3.1T_4.25O ceramics). The deficiency of CuO and TiO₂ phases associated with high percentage of CCTO and CaTiO₃ phases resulted in ceramics with the higher ε′ values.     

Wideband frequency tunability of CaCu3Ti4O12-based dielectric resonator antennas via the addition of glass

In this study, DRAs produced using CaCu₃Ti₄O₁₂ (CCTO) as a high dielectric material (ε_r) was added with BaO–SrO–Nb₂O₅–B₂O₃–SiO₂ (BSNBS) glass for possible tunability in a wideband frequency range. BSNBS glass (0.01-1 wt%) was mixed with CCTO powders (calcined) and compacted at 250 MPa into mixed-powder pellets. All the green body samples were then sintered at 1040°C for 10 hours. The wideband frequency tunability, measured using a network analyzer, showed that the addition of ≤0.05 wt% BSNBS glass decreased the resonance frequency from 9.51 to 9.33 GHz; later, the values increased to 9.89 GHz when BSNBS content was > 0.05 wt%. The ε_r of each sample was around 11-36 when measured at 9.5-11.8 GHz. The radiation pattern of CCTO for each sample that had been set up as a DRA radiated the signal equally or nearly identical to each other. Furthermore, the addition of BSNBS glass produced micrographs with finer grains, improved the density and reduced the porosity of the composite. Therefore, the addition of the BSNBS glass is a successful aid in the wideband frequency tunability of pure CCTO-based ceramics when used as DRAs.     

Giant dielectric constant,dielectric relaxations,and tunable properties of Sm2/3Cu3Ti4O12 ceramics

The polycrystalline Sm_2/3Cu₃Ti₄O₁₂ (SCTO) ceramics have been prepared by solid-state reaction. The crystallinity of the compound has been investigated by Rietveld refinement which has revealed a cubic structure with space group Im3. It is observed that at low frequencies, SCTO ceramic exhibits tremendously high values of dielectric permittivity ε′, larger than 32,000, at room temperature. Two distinct, thermally triggered, dielectric relaxations have been noted. This mechanism has been confirmed through impedance analysis of the ceramics. The complex impedance plane shows three semicircles, which confirm the existence of two dielectric relaxations in SCTO ceramics. In general, the electrical as well as dielectric behavior of SCTO ceramics are seen to be reasonably analogous to those of CaCu₃Ti₄O₁₂ (CCTO) ceramics. The emergence of the enormous dielectric constant in SCTO ceramic is accredited to the combined effect of polarization both at the sample-electrode interface as well as at the insulating grain boundary interface. The SCTO ceramics are identical to the CCTO ceramics in their structure and composition and hence, as the above results indicate, the IBLC effect mechanism, originally put forward for CCTO ceramics, is furthermore plausible to account for the mammoth values of dielectric constant in SCTO ceramics.     

Microstructural evolution and dielectric properties of SiO2-doped CaCu3Ti4O12 ceramics

The abnormal grain growth (AGG) behavior of undoped and SiO₂-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. With the addition of 2 wt.% SiO₂, the AGG-triggering temperature decreased from 1100 to 1060 °C, and the temperature for obtaining a uniform and coarse microstructure decreased from 1140 to 1100 °C. The lowering of the AGG temperature by SiO₂ addition was attributed to the formation of a CuO-SiO₂-rich intergranular phase at lower temperature. The apparent dielectric permittivity of coarse SiO₂-doped CCTO ceramics was ∼10 times higher than that of fine SiO₂-doped CCTO ceramics at the frequency of 10³–10⁵ Hz. The doping of SiO₂ to CCTO ceramics provides an efficient route of improving the dielectric properties via grain coarsening. The correlation between the microstructure and apparent permittivity suggests the presence of a barrier layer near the grain boundary.     

Enhanced magnetic and dielectric properties of Ti‐doped YFeO3 ceramics

Polycrystalline YFeO₃ (YFO) and YFe_1?(4/3)xTi_xO₃(YFTO) ceramics were prepared using the powder synthesized from the sol‐gel route. X‐ray diffraction analyses of the polycrystalline ceramics revealed the crystallization of the phase in orthorhombic crystal structure associated with the space group Pnma. The magnetization versus magnetic field hysteresis loops were obtained at room temperature for YFO and YFTO ceramics. The magnetic property changes from weak ferromagnetic in YFO to ferromagnetic in YFTO ceramics. The dielectric constant recorded at room temperature for YFTO ceramics was six times higher than that of YFO, whereas the dielectric loss gets reduced to 0.06 from 0.3 for YFO at 1 kHz. Impedance spectroscopy study carried out on YFO and YFTO ceramics confirmed the existence of non‐Debye‐type relaxation. Observed single semicircle in Z′ vs ?Z′′ plot established the incidence of intrinsic (bulk) effect and ruled out any grain boundary or electrode effects. The mechanism for the dielectric relaxation and electrical conduction process observed in YFO and YFTO ceramics was discussed by invoking electric modulus formalisms. Activation energy obtained by ac conductivity study suggested that the conduction process in YFO was linked up with the existence of the polaron and oxygen vacancies, whereas only oxygen vacancies contribute to the conduction process in YFTO ceramics.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Defect mechanisms in BaTiO3‐BiMO3 ceramics

Often, addition of BiMO₃ to BaTiO₃ (BT) leads to improvement in resistivity with a simultaneous shift to n‐type conduction from p‐type for BT. In considering one specific BiMO₃ composition, that is, Bi(Zn_1/2Ti_1/2)O₃ (BZT), several prospective candidates for the origin of this n‐type behavior in BT‐BZT were studied—loss of volatile cations, oxygen vacancies, bismuth present in multiple valence states and precipitation of secondary phases. Combined x‐ray and neutron diffraction, prompt gamma neutron activation analysis and electron energy loss spectroscopy suggested much higher oxygen vacancy concentration in BT‐BZT ceramics (>4%) as compared to BT alone. X‐ray photoelectron spectroscopy and x‐ray absorption spectroscopy did not suggest the presence of bismuth in multiple valence states. At the same time, using transmission electron microscopy, some minor secondary phases were observed, whose compositions were such that they could result in effective donor doping in BT‐BZT ceramics. Using experimentally determined thermodynamic parameters for BT and slopes of Kröger‐Vink plots, it has been suggested that an ionic compensation mechanism is prevalent in these ceramics instead of electronic compensation. These ionic defects have an effect of shifting the conductivity minimum in the Kröger‐Vink plots to higher oxygen partial pressure values in BT‐BZT ceramics as compared to BT, resulting in a significantly higher resistivity values in air atmosphere and n‐type behavior. This provides an important tool to tailor transport properties and defects in BT‐BiMO₃ ceramics, to make them better suited for dielectric or other applications.     

Dielectric relaxation and electrical conduction in (BixNa1−x)0.94Ba0.06TiO3 ceramics

The dielectric relaxation and electrical conduction were investigated in (Bi_xNa_1?x)_0.94Ba_0.06TiO₃ (Abb. xBNBT6, x = 0.5, 0.495, 0.485, and 0.475) ceramics prepared by solid state reaction. With a decrease in x, the dielectric properties of the ceramics decreased, whereas the electrical conduction increased, resulting in a transition from insulator to oxide‐ions conductor. When x = 0.475, the ceramics exhibited large conductivity (~10^?3 S cm^?1 at 575°C) and low activation energy (~0.45 eV), indicating their potential application in solid oxide fuel cells. A mixed conduction mechanism with oxide‐ions, electrons, and holes was proposed. With a decrease in x from 0.495 to 0.475, it was found that the p‐type conduction was switched to n‐type conduction. The dielectric relaxation of the x = 0.495 sample was associated with short‐range hopping of oxygen vacancies. However, the dielectric properties of the x = 0.485 and 0.475 samples can be explained by Maxwell‐Wagner interface relaxation.     

Remarkable piezoelectricity and stable high‐temperature dielectric properties of quenched BiFeO3–BaTiO3 ceramics

Effects of quenching process on dielectric, ferroelectric, and piezoelectric properties of 0.71BiFeO₃?0.29BaTiO₃ ceramics with Mn modification (BF–BT?xmol%Mn) were investigated. The dielectric, ferroelectric, and piezoelectric properties of BF–BT?xmol%Mn were improved by quenching, especially to the BF–BT?0.3 mol%Mn ceramics. The dielectric loss tanδ of quenched BF–BT?0.3 mol%Mn ceramics was only 0.28 at 500°C, which was half of the slow cooling one. Meanwhile, the remnant polarization P_r of quenched BF–BT?0.3 mol%Mn ceramics increased to 21 μC/cm². It was notable that the piezoelectric constant d₃₃ of quenched BF–BT?0.3 mol%Mn ceramics reached up to 191 pC/N, while the T_C was 530°C, showing excellent compatible properties. The BF–BT?xmol%Mn system ceramics showed to obey the Rayleigh law within suitable field regions. The Rayleigh law results indicated that the extrinsic contributions to the dielectric and piezoelectric responses of quenched BF–BT?xmol%Mn ceramics were larger than the unquenched ceramics. These results presented that the quenched BF–BT?xmol%Mn ceramics were promising candidates for high‐temperature piezoelectric devices.     

Defect structure‐electrical property relationship in Mn‐doped calcium strontium titanate dielectric ceramics

Ca_0.6Sr_0.4TiO₃ (CST) ceramics with different amounts of Mn dopant (0‐2.0 mol%) were prepared by solid‐state reaction method. The electric field and temperature stability of energy storage performance was found to be greatly enhanced with moderate doped level of 0.5 mol%. The dielectric loss‐frequency spectra revealed the existence and evolution of defect dipoles at elevated temperature, which was confirmed directly by electron paramagnetic resonance (EPR) spectra. The response of defect dipoles was characterized by thermally stimulated depolarization current (TSDC), where the activation energy and the concentration evolution of defect dipoles were calculated, with the highest values observed for 0.5% doped samples. The dissociation of defect dipoles and the movement of free were analyzed by high‐temperature impedance spectra analysis, with the activation energy of 1.04‐1.60 eV, and 0.5% doped samples also demonstrated the highest E_a. The relationship between microscopic defect structure and macroscopic electrical behavior was established in this work.     

Grain boundary engineering that induces ultrahigh permittivity and decreased dielectric loss in CdCu3Ti4O12 ceramics

Dielectric materials with ultrahigh permittivity are attracting attention due to the increasing demand for these types of materials for microelectronics and energy storage applications. In this work, we successfully synthesized Zn-doped CdCu₃Ti₄O₁₂ (CdCTO) ceramics with low dielectric loss and large permittivity via an ordinary mixed-oxide technique. Remarkably, at a Zn doping level of 0.10, a CdCu_2.9Zn_0.1Ti₄O₁₂ ceramic exhibited both decreased dielectric loss tangent of ~0.058 and large dielectric permittivity > 4.0 × 10⁴, as well as a good frequency stability over a wide frequency range from 40 Hz to 10⁶ Hz. The high dielectric performance was attributed to the enhanced grain boundary resistance and internal barrier layer capacitor (IBLC) effect due to the fine and uniform grains that formed upon Zn doping. The findings reported in this work provide valuable insights into how to simultaneously realize a low dielectric loss and high permittivity in CdCTO and other related dielectric ceramics.     

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.     

Crystal structure,defect relaxation,and microwave dielectric properties of Ba[(Mg1/3Nb2/3)1−xHfx]O3 solid solutions

Ba[(Mg_1/3Nb_2/3)_1?xHf_x]O₃ (BMNH, x = 0.05, 0.1, 0.15, 0.2) solid solutions were prepared via the solid‐state reaction method. The effect of BaHfO₃ on the crystal structure, microwave dielectric performance, and defect relaxation behavior of Ba(Mg_1/3Nb_2/3)O₃ (BMN) were studied. BaHfO₃ additions degraded the sintering activity of BMN powder, requiring a high sintering temperature (T_s) ~ 1650°C; but it could be effectively improved by a prolonged sintering process at a lower T_s of 1600°C. The well‐sintered BMNH ceramics (1600°C for 30 h) possessed a high densification >96%, and exhibited cubic perovskite structures without 1:2 cation ordering. Once doped with Hf, the low‐temperature relaxation in dielectric spectroscopy and thermally stimulated depolarization current (TSDC) for pure BMN disappeared, further indicating such relaxation is related to cation‐ordered structure. Oxygen vacancies, namely showing in‐grain and across‐grain‐boundary relaxation of ‐related defects, were the main defect types in BMNH. The concentrations of in‐grain decreased as x increased, which is beneficial to BMNH to maintain high Q × f values of 69 400‐73 000 GHz. Accompanied by a high ε_r of 33.27‐33.59 and a low τ_f of +13.6 to +20.7 ppm/°C, these materials have a good potential for applications in microwave components and devices.     

Ionic occupation,structures, and microwave dielectric properties of Y3MgAl3SiO12 garnet‐type ceramics

The Y₃MgAl₃SiO₁₂ ceramics with pure phase were successfully synthesized by solid‐state sintering reaction method for the first time. Their microwave dielectric properties were investigated as a function of sintering temperature. Their microstructure characteristics and ionic occupation sites of tetrahedral and octahedral units were characterized and analyzed by SEM& energy dispersive spectrometer (EDS) and Rietveld refinement of X‐ray powder diffraction data. Crystal structure of Y₃MgAl₃SiO₁₂ is isostructural to Y₃Al₅O₁₂ with a cubic garnet structure and space group of Ia‐3d, which contains YO₈ dodecahedra, (Mg/Al_oct)O₆ octahedral, and (Si/Al_tet)O₄ tetrahedral units. The Qf and ε_r values of different samples are strongly dependent on the distribution of grain sizes, grain sizes, and porosity. The samples sintered at 1550°C exhibit optimized microwave dielectric properties with relative permittivity (?_r) of 10.1, Qf values of 57 340GHz (at 9.5 GHz), and τ_f values of ?32 ppm/°C. Such properties indicate potential application of Y₃MgAl₃SiO₁₂ as microwave substrates.     

Decisive role of mixed‐valence structure in colossal dielectric constant of LaFeO3

The role of mixed‐valence structure in colossal dielectric constant (CDC) behavior has been investigated in LaFeO₃ ceramics by tuning the ratio of Fe²⁺/Fe³⁺ through substituting Al for Fe. The ratio of Fe²⁺/Fe³⁺ is decreased gradually from 1.0 to 0.0 by increasing the concentration of Al³⁺. Two clear‐cut correlations have been found: (i) the relationship between the CDC behavior and the ratio of Fe²⁺/Fe³⁺ follows an exponential function and (ii) the activation energy of the polaron relaxation is proportional to , where is the intrinsic dielectric constant. These findings underscore the role of the mixed‐valence structure in CDC behavior and suggest that adjusting the mixed‐valence structure through doping/alloying can be a promising strategy to achieve superior CDC behavior in transition‐metal oxides.     

Enhancing giant dielectric properties of Ta5+-doped Na1/2Y1/2Cu3Ti4O12 ceramics by engineering grain and grain boundary

Various strategies to improve the dielectric properties of ACu₃Ti₄O₁₂ (A = Sr, Ca, Ba, Cd, and Na_1/2Bi_1/2) ceramics have widely been investigated. However, the reduction in the loss tangent (tanδ) is usually accompanied by the decreased dielectric permittivity (ε′), or vice versa. Herein, we report a route to considerably increase ε′ with a simultaneous reduction in tanδ in Ta⁵⁺–doped Na_1/2Y_1/2Cu₃Ti₄O₁₂ (NYCTO) ceramics. Dense microstructures with segregation of Cu– and Ta–rich phases along the grain boundaries (GBs) and slightly increased mean grain size were observed. The samples prepared via solid-state reaction displayed an increase in ε′ by more than a factor of 3, whereas tanδ was significantly reduced by an order of magnitude. The GB–conduction activation energy and resistance raised due to the segregation of Cu/Ta–rich phases along the GBs, resulting in a decreased tanδ. Concurrently, the grain–conduction activation energy and grain resistance of the NYCTO ceramics were reduced by Ta⁵⁺ doping ions owing to the increased Cu⁺/Cu²⁺, Cu³⁺/Cu²⁺, and Ti³⁺/Ti⁴⁺ ratios, resulting in enhanced interfacial polarization and ε′. The effects of Ta⁵⁺ dopant on the giant dielectric response and electrical properties of the grain and GBs were described based on the Maxwell–Wagner polarization at the insulating GB interface, following the internal barrier layer capacitor model.     

Microstructural and Microwave Dielectric Properties of Bi12GeO20 and Bi2O3‐Deficient Bi12GeO20 Ceramics

Bi₁₂GeO₂₀ ceramics sintered at 800°C had dense microstructures, with an average grain size of 1.5 μm, a relative permittivity (ε_r) of 36.97, temperature coefficient of resonance frequency (τ_f) of ?32.803 ppm/°C, and quality factor (Q × f) of 3137 GHz. The Bi_12‐xGeO_20‐1.5x ceramics were well sintered at both 800°C and 825°C, with average grain sizes exceeding 100 μm for x ≤ 1.0. However, the grain size decreased for x > 1.0 because of the Bi₄Ge₃O₁₂ secondary phase that formed at the grain boundaries. Bi_12‐xGeO_20‐1.5x (x ≤ 1.0) ceramics showed increased Q × f values of >10 000 GHz, although the ε_r and τ_f values were similar to those of Bi₁₂GeO₂₀ ceramics. The increased Q × f value resulted from the increased grain size. In particular, the Bi_11.6GeO_19.4 ceramic sintered at 825°C for 3 h showed good microwave dielectric properties of ε_r = 37.81, τ_f = ?33.839 ppm/°C, and Q × f = 14 455 GHz.