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.     

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.     

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 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.     

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 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.     

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.     

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.     

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.     

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.     

Probing the effects of oxygen-related defects on the optical and luminescence properties in CaCu3Ti4O12 ceramics

The formation of oxygen-related lattice defects and their influence on optical and electronic properties in CaCu₃Ti₄O₁₂ (CCTO) ceramics were studied by controlling the oxygen partial pressure during the sintering process at high temperatures. The samples were analyzed using complementary bulk spectroscopic techniques such as photoluminescence spectroscopy, ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, and electron paramagnetic resonance. Our comprehensive study shows that the oxygen content during sintering process exerts considerable control over the type and concentration of oxygen-related defects in the crystalline CCTO structure. Our results also suggest that the formation of different types of oxygen-related defects in the structure modifies electronic energy levels and thus directly affects the electronic and optical properties of the CCTO phase. These results provided further insight into the important role of oxygen in the crystalline defect arrangement in polycrystalline CCTO ceramics.     

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.     

Evolution of the intergranular phase during sintering of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ (CCTO) ceramics have been processed by solid state reaction and sintered at 1100 °C for different times. A clear increase of the dielectric constant of the material up to values of 6 × 10⁴ has been observed with the sintering time. This increase is accompanied by a limited grain growth and intergranular Cu-oxide phase thickness reduction. The disappearance of the Cu-oxide phase is caused by the incorporation of Cu cations into the grains, contributing to the increase of the dielectric constant. Raman spectroscopy shows the decrease of TiO₆ octahedral rotational modes with the sintering time due to the incorporation of Cu cations into the CCTO grains. XANES measurements show that the Cu main oxidation state is Cu²⁺ and does not change with the sintering time. The fitting of the experimental dielectric constant to the Internal Barrier Layer Capacitance (IBLC) model reveals the change of the intergranular phase dielectric constant, caused by a compositional change due to the incorporation of Cu into the CCTO grains.     

CaCu3Ti4O12 ceramics from co-precipitation method: Dielectric properties of pellets and thick films

Dielectric properties of CaCu₃Ti₄O₁₂ (CCTO)-based ceramics and thick films (e ～50 μm) prepared from powders synthesized by a soft chemistry method (co-precipitation) are presented and discussed. The characteristics of pellets and thick films are compared.The pellets exhibit high values of the dielectric permittivity (?_r ～1.4 × 10⁵) and relatively small dielectric losses (tan δ ～0.16) at 1 kHz and room temperature. These properties are independent of the nature of the metallization of the electrodes. In addition, the dielectric permittivity decreases when the diameter of the electrodes of the pellets increases, while the losses remain constant. This result, which is strongly related to the nature of the dielectric material in between the electrodes, constitutes a strong indication that the high dielectric permittivity values observed in this material are not related to an interfacial (electrode material) related mechanism but is an internal barrier layer capacitor (IBLC) type.Very high values of the dielectric permittivity of CCTO thick films are measured (?_r ～5 × 10⁴). The differences in dielectric permittivity between thick films and dense pellets may be attributed to the difference in grain size due to different CuO contents, and to the different reactivity of the materials.     

Microstructures and dielectric relaxation behaviors of pure and tellurium doped CaCu3Ti4O12 ceramics prepared via vibro-milling method

In this work, we have reported microstructures and the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics doped with different proportions of TeO₂ dopant (mol%, x=0, 0.5%, 1.0%, 2.0%). The pure and tellurium doping CCTO ceramics were prepared by a conventional solid-state reaction method and the effects of TeO₂ doping on the electrical properties and microstructures of these ceramics were investigated. XRD analysis confirmed the formation of single-phase material in samples. Scanning electron microscopy (SEM) is used in the micro structural studies of the specimens, which showed that TeO₂ doping can reduce the mean grain size and increasing size of an abnormal grain growth. Lattice parameter increases slightly with tellurium doping in CCTO, the dielectric constant reached a value as high as 18,000 (at 1 kHz) at a tellurium-doping concentration of 2.0 mol% and showed temperature stability at high frequency. The loss tangent of Te-doped CCTO ceramics was less than 0.05 at 1 kHz region below 105 °C. The loss tangent properties could be interpreted by the internal barrier layer capacitor model and the impedance measurement data.     

Nonlinear I–V electrical behaviour of doped CaCu3Ti4O12 ceramics

In this work a comparative study of undoped CaCu₃Ti₄O₁₂ (CCTO) and doped with Fe³⁺(CCTOF) and Nb⁵⁺(CCTON) ceramics, was aimed to modify the electronic transport. XRD patterns, FE-SEM microstructural analysis, impedance spectroscopy and I–V response curves were afforded to correlate the microstructure with the nonlinear I–V behaviour. The appearance of nonlinear behaviour in doped CCTO samples has been correlated with the ceramic microstructure that consists in n-type semiconductor grains, surrounded by a grain boundary phase based on CuO. The presence of this secondary grain boundary phase is the responsible of the assisted liquid phase sintering in CCTO ceramics. Doped samples showed cleaner grain boundaries than CCTO and nonlinearity in the I–V response.