Dielectric properties of CaCu3Ti4O12 ceramics with Zn substitution for Cu

Abstract

CaCu_3–xZn_xTi₄O₁₂ (x is from 0 to 1·0) polycrystalline samples were fabricated via a two-step solid state reaction process. The lattice parameter of the monophasic CaCu₃Ti₄O₁₂ phase increased as Zn content increased. Scanning electron microscopy (SEM) images of the CCTO ceramic show bimodal grain size distribution and the grain size decrease largely with the appearance of Zn₂TiO₄ second phase. The dielectric permittivity of pure CCTO ceramic is ～1·5×10⁴ at f?=?100 Hz. The dielectric constant of the sample largely increased with Zn substitution in the frequency range f<10⁴ Hz. The highest dielectric constant was 6·2×10⁴ at f?=?100 Hz with Zn substitution of x?=?0·8. The improved dielectric properties are believed to be related to the presence of a thin grain boundary barrier layer. The resistivity of the grain boundary decreased largely with Zn substitution as evidenced from the impedance plots.     

Effect of calcium stoichiometry on the dielectric response of CaCu3Ti4O12 ceramics

Ca_xCu₃Ti₄O₁₂ (x = 0.90, 0.97, 1.0, 1.1 and 1.15) polycrystalline powders with variation in calcium content were prepared via the oxalate precursor route. The structural, morphological and dielectric properties of the ceramics fabricated using these powders were studied using X-ray diffraction, scanning electron microscope along with energy dispersive X-ray analysis, transmission electron microscopy, electron spin resonance (ESR) spectroscopy and impedance analyzer. The X-ray diffraction patterns obtained for the x = 0.97, 1.0 and 1.1 powdered ceramics could be indexed to a body-centered cubic perovskite related structure associated with the space group Im3. The ESR studies confirmed the absence of oxygen vacancies in the ceramics that were prepared using the oxalate precursor route. The dielectric properties of these suggest that the calcium deficient sample (x = 0.97) has a reduced dielectric loss while retaining the high dielectric constant which is of significant industrial relevance.     

Improved dielectric,nonlinear and magnetic properties of cobalt-doped CaCu3Ti4O12 ceramics

The dielectric properties and voltage–current nonlinearity of the pure and various cobalt-doped CaCu₃Ti₄O₁₂ (Co-doped CCTO) prepared by solid-state reactions were investigated. The improved dielectric properties in the Co-doped CCTO, with a dielectric constant $\text{ε'}$ ≈7.4?×?10⁴ and dielectric loss $\text{tan}\text{δ}$?≈?0.034, were observed in the sample with a Co doping of 5% (CCTO05) at room temperature and 1?kHz. The related multi-relaxations, RII (?20 to 40?°C) and RIII (100–150?°C), were demonstrated to be a Debye-like relaxation and a Maxwell–Wagner relaxation related to oxygen vacancies. The low dielectric loss of CCTO05 was associated with the high grain boundary resistance and the increase in cation vacancies. The improved nonlinear electrical properties (CCTO05, with nonlinear coefficients $\text{α}$?≈?5.22 and breakdown electric field ${\text{E}}_{\text{b}}$?≈?300.46?V/cm) and the ferromagnetism in Co-doped CCTO were also discussed.     

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.     

Dielectric properties of Sm-doped CaCu3Ti4O12 ceramics

The effects of Sm substitution on structure, dielectric properties and conductivity of CaCu₃Ti₄O₁₂ ceramics were investigated. Ca_1?xSm_xCu₃Ti₄O₁₂ (x=0.0%, 0.5%, 1.0%) ceramics were synthesized by the solid-state reaction method. Single phase crystal of the ceramics with space group Im3 was obtained. With increasing Sm content, the dielectric loss of Ca_1?xSm_xCu₃Ti₄O₁₂ ceramics improved but the dielectric constant also decreased significantly, with both the low- and high-temperature dielectric relaxations suppressed.     

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.     

Dielectric properties of CaCu3Ti4O12 based multiphased ceramics

A “soft chemistry” method, the coprecipitation, has been used to synthesize the perovskite CaCu₃Ti₄O₁₂ (CCT). Three main types of materials were obtained for both powders and sintered ceramics: a monophased consisting of the pure CCT phase, a biphased (CCT + CaTiO₃), and a three-phased (CCT + CaTiO₃ + copper oxide (CuO or Cu₂O)). These ceramics, sintered at low temperature, 1050 °C, present original dielectric properties. The relative permittivity determined in the temperature range (−150 < T < 250 °C) is significantly higher than the one reported in the literature. Internal barrier layer capacitor is the probable mechanism to explain the particular behaviour. Moreover, the presence of a copper oxide phase beside the perovksite CCT plays an important role for enhancing the dielectric properties.     

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.     

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.     

Optimize the dielectric properties of CaCu3Ti4O12 ceramics by adjusting the conductivities of grains and grain boundaries

Reduction of dielectric loss for CCTO ceramics is a prerequisite for their applications. Considering internal barrier layer capacitance effect, improving the capacitance and grain boundary resistance is an effective way to reduce dielectric loss. Therefore, more conductive Ti³⁺ and Cu⁺ ions were introduced to grains by adding carbon to ceramic bodies, improving the permittivity of CCTO ceramics. Annealing was performed to increase the grain boundary resistance. The dielectric loss of the CCTO ceramics thus prepared, which maintain a giant permittivity, is significantly reduced. Specifically, the CCTO ceramic with carbon addition, which was sintered at 1080 °C for 8 h and air annealed at 950 °C for 2 h, exhibits a giant permittivity of about 2.50(5)×10⁴ and a low dielectric loss of less than 0.050(2) from below 20 Hz to 50 kHz at room temperature. Meanwhile, its dielectric loss at 1–10 kHz is less than 0.050(2) from below room temperature to about 100 °C.     

Improved dielectric and nonlinear properties of CaCu3Ti4O12 ceramics with Cu-rich phase at grain boundary layers

The formation and compositions of grain boundary layers are very important factors to improve the electrical properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics. In present work, the dielectric and nonlinear properties of the CCTO ceramics are enhanced by controlling the Cu-rich phase degree at grain boundary layers. The dense CCTO ceramics were prepared successfully through mixing the nanometer and micrometer powders and using the cold isostatic pressing process. The average grain size of these CCTO ceramics is about 30.71(±11.76) ∼ 62.01(±32.16) μm, and their grain microstructures show the Cu-rich phases at grain boundary layers. The CCTO ceramics with the mass ratios of nanometer and micrometer powders 7:3 display a giant dielectric constant of 5.4 × 10⁴, low dielectric loss of 0.048 at 10³ Hz, enhanced nonlinear coefficients of 11.12, as well as the noteworthy breakdown field of 4466.17 V/cm. The complex impedance spectroscopy results indicate that the giant dielectric behavior is due to the electrically heterogeneous grain/grain boundary characteristics from internal barrier layer capacitance (IBLC) model. The lower dielectric loss and the higher breakdown field are attributed to the high resistance grain boundary layers with the Cu-rich phase. The improved nonlinear properties are related to the increased Schottky barrier height at grain boundary. This work may provide a potential way to design the CCTO ceramics with excellent electrical properties from the viewpoint of controlling the response of the Cu-rich phase grain boundary.     

Electrical properties of Co-doped CaCu3Ti4O12

Co-doped CaCu₃Ti₄O₁₂ samples were synthesized by solid-phase reaction. Electrical properties were studied by impedance spectroscopy in wide temperature (25–450 °C) and frequency (10 Hz–10 MHz) intervals. It was shown that the presence of the copper oxide interlayer significantly reduces the value of the dielectric constant. The amount of impurity copper in the CaCu₃Ti_4-хCo_хO_12-δ samples (x = 0.06; 0.12; 0.24) rise with an increase in the cobalt content. The samples are characterized by a granular microstructure, with an average grain size ranging from 2 to 10 μm. The impedance of the samples was simulated at a temperature of 25 °C and in the range of 100–450 °C. It was found that the samples are characterized by low- and high-frequency polarization. The conductivity activation energy varied from 0.94 to 0.87 eV depending on the cobalt content. The CaCu₃Ti_3.94Co_0.06O_12-δ sample are characterized by the best values of the dielectric permittivity and the dielectric loss tangent, ε = 400 and tanδ = 0.2 (at 1 MHz and room temperature), respectively.     

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.     

Co-doping effects of A-site Y3+ and B-site Al3+ on the microstructures and dielectric properties of CaCu3Ti4O12 ceramics

Different doping elements have been used to reduce the dielectric losses of CaCu₃Ti₄O₁₂ ceramics, but their dielectric constants usually are undesirably decreased. This work intends to reduce their dielectric losses and simultaneously enhance their dielectric constants by co-doping Y³⁺ as a donor at A site and Al³⁺ as an acceptor at B site for substituting Ca²⁺ and Ti⁴⁺, respectively. Samples with different doping concentrations x = 0, 0.01, 0.02, 0.03, 0.05 and 0.07 have been prepared. It has been shown that their dielectric losses are generally reduced and their dielectric constants are simultaneously enhanced across the frequency range up to 1 MHz. The doped sample with x = 0.05 exhibits the highest dielectric constant, which is well over 10⁴ for frequency up to 1 MHz and is about 20% higher than the undoped sample. Impedance spectra indicate that the doped samples have much higher grain boundary resistance than the undoped one.     

Effects of multiwall carbon nanotubes on dielectric and mechanical properties of CaCu3Ti4O12 composite

This work reports the synthesis of calcium copper titanate (CaCu₃Ti₄O₁₂)/multiwall carbon nanotubes (MWCNT) composites using ultrasonic technique followed by sintering in a high vacuum furnace. The effect of MWCNT content (0.05, 0.1, 0.15, and 0.2 wt%) on the structural, dielectric, and mechanical properties of CaCu₃Ti₄O₁₂ (abbreviated as CCTO) were investigated by TEM, XRD, FTIR, FESEM-EDAX, dielectric measurement, as well as tensile strength and flexural strength tests. XRD patterns revealed that the MWCNT loading did not affect the phase structure; however, the average crystallite size (D) was reduced from 60.88 nm to 40.79 nm. The samples had porous structures and the porosity reduced from 45.57% to 40.73% with MWCNT loading. The dielectric and mechanical properties of CCTO were enhanced with an increase in MWCNT loading. An important observation was that the CCTO mixed with 0.2 wt% MWCNT exhibited the highest dielectric permittivity (ε_r = 27,768) and the lowest dielectric loss (tan δ = 0.52) at 1 kHz. With the addition of 0.2 wt% MWCNT, the values of load, tensile, and flexural strength increased to 10.38 kN, 101.88 MPa, and 275.07 MPa, respectively, due to improvement in densification. These outcomes have values for the fabrication of CCTO and the optimization of its performance for electronic devices such as capacitors and antennas.     

Influence of micro- and nanoparticles of zirconium oxides on the dielectric properties of CaCu3Ti4O12

This work presents the results of Zr oxide doping of a CaCu₃Ti₄O₁₂ (CCTO) ceramic prepared by a solid-state reaction. Different stoichiometries (ZrO and ZrO₂) and grain sizes (micro- and nanoparticles) were added as dopants at concentrations of 0.5 and 1.0 wt%. Zr-doping controls the grain size growth, leading to a reduction of the grain size as observed by scanning electron microscopy. For both dopant concentrations, all of the samples exhibited lower dielectric loss and a smaller dielectric constant than those of undoped CCTO. The sample doped with 0.5% of the non-stoichiometric ZrO exhibits a dielectric constant over 3200 and a dissipation factor of 0.02 at 1 kHz. The impedance spectroscopy analysis confirms that the decrease of dielectric loss is mainly due to an increase in resistivity at grain boundaries, which is attributed to the suppression of oxygen-loss promoted by dopants.     

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.     

Study of structural,dielectric and electrical conduction behaviour of Gd substituted CaCu3Ti4O12 ceramics

Effect of Gd on microstructural, dielectric and electrical properties has been studied over wide temperature (300–500 K) and frequency range (100 Hz–1 MHz). Gd substitution in CCTO system results in decrease in the grain size and increase of Schottky potential barrier which causes lower value of dielectric constant. The dielectric constant remains nearly constant in temperature range 300–350 K. Doped samples show lower dielectric loss in middle frequency range (～10 kHz–1 MHz) at room temperature. The AC conductivity (σ_ac) obeys a power law, σ_ac = Afⁿ, where n is temperature dependent frequency exponent. The AC conductivity behaviour can be divided into three regions depending on conduction processes and the relevant charge transport mechanisms have been discussed.     

Synthesis and dielectric anomalies of CdCu3Ti4O12 ceramics

CdCu₃Ti₄O₁₂ ceramics were successfully synthetized by the conventional solid-state reaction method. The influences of sintering parameters on phase structure, microstructure and dielectric properties were investigated systematically. CdCu₃Ti₄O₁₂ ceramics sintered at 1020 °C for 15 h exhibited high temperature stability and outstanding dielectric properties, evidenced by the △C_T/C_25 °C ranges from −14.8% to 12.1% measured from −55 to 125 °C at 1 kHz, and the giant dielectric constant ε′=2.4×10⁴ as well as dielectric loss tanδ=0.072. Four dielectric anomalies were evidenced in dielectric temperature spectra and the related physical mechanisms were discussed in detail. The oxygen vacancies play an important role in dielectric anomalies in the high temperature range.     

Enhanced dielectric properties and grain boundary potentials in sulfur-doped CaCu3Ti4O12 thin films

CaCu₃Ti₄O₁₂ (CCTO) has been reported to possess a colossal dielectric constant owing to the intrinsic interfacial polarization via charge accumulations across the grain boundary. Herein, we explore the effects of unusual anion-doping on the dielectric properties of sputter-deposited CCTO thin films using an example of sulfur-doping. A post-annealing process of the films was utilized in a flowing H₂S atmosphere for the sulfur-doping. The incorporation of sulfur into the perovskite structure was evidenced with the changes in chemical states, such as the reduced cations of Cu⁺ and Ti³⁺, the increased concentration of oxygen vacancies, and the formation of S-O bonds. The sulfurized CCTO thin films demonstrated an enhanced relative permittivity of ∼620 at 100 Hz, which is substantially better than that of the unsulfurized film. Direct measurement of the grain-boundary potential using Kelvin probe force microscopy suggests that the enhanced relative permittivity is associated with an increased Schottky barrier height.