Microstructure-dependent giant dielectric response in CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ ceramics were prepared at the sintering temperatures ranged from 1025 to 1125 °C, and the dielectric characteristics were evaluated together with the microstructures. The giant dielectric constant with the maximum of 53,120 was obtained in CaCu₃Ti₄O₁₂ ceramics at room temperature and 10 kHz, and strong processing and microstructure dependence of dielectric characteristics of the present ceramics was determined. The precipitation of the dispersed Cu-rich secondary phases of CuO and/or Cu₂O and their network structure provided the extrinsic origins of the enhanced giant dielectric response, and the present findings would offer the greater potential for enhancing the giant dielectric constant and controlling the dielectric loss in CaCu₃Ti₄O₁₂ ceramics by optimizing the microstructures.     

Synthesis and dielectric characteristics of La0.5Bi0.5MnO3 ceramics

La_0.5Bi_0.5MnO₃ ceramics with a single phase were prepared by a solid-state reaction method, and their dielectric properties were characterized. Two dielectric relaxations with a giant dielectric constant were identified in the temperature range from 125 to 350 K. The electron hopping between Mn³⁺ and Mn⁴⁺ was found to be the origin of the dielectric relaxation at low temperatures (125–200 K) with an activation energy of 0.18 eV. The high temperature (200–350 K) dielectric relaxation can be attributed to the conduction.     

Nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route

A method of preparing the nanoparticles of CaCu₃Ti₄O₁₂ (CCTO) with the crystallite size varying from 30 to 200 nm is optimized at a temperature as low as 680 °C from the exothermic thermal decomposition of an oxalate precursor, CaCu₃(TiO)₄(C₂O₄)₈·9H₂O. The phase singularity of the complex oxalate precursor is confirmed by the wet chemical analyses, X-ray diffraction, FT-IR and TGA/DTA analyses. The UV-vis reflectance and ESR spectra of CCTO powders indicate that the Cu(II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square-planar geometry with increasing annealing temperature. The HRTEM images have revealed that the evolution of the microstructure in nanoscale is related to the change in Cu(II) coordination around the surface regions for the chemically prepared powder specimens. The nearly flattened tetrahedral geometry prevails for CuO₄ in the near surface regions of the particles, whereas square-planar CuO₄ groups are dominant in the interior regions of the nanoparticles. The powders derived from the oxalate precursor have excellent sinterability, resulting in high-density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25 °C, accompanied by low dielectric loss <0.07.     

Reduced dielectric loss and leakage current in CaCu3Ti4O12/SiO2/CaCu3Ti4O12 multilayered films

The CaCu₃Ti₄O₁₂/SiO₂/CaCu₃Ti₄O₁₂ (CCTO/SiO₂/CCTO) multilayered films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition method. It has been demonstrated that the dielectric loss and the leakage current density were significantly reduced with the increase of the SiO₂ layer thickness, accompanied with a decrease of the dielectric constant. The CCTO film with a 20 nm SiO₂ layer showed a dielectric loss of 0.065 at 100 kHz and the leakage current density of 6×10⁻⁷ A/cm² at 100 kV/cm, which were much lower than those of the single layer CCTO films. The improvement of the electric properties is ascribed to two reasons: one is the improved crystallinity; the other is the reduced free carriers in the multilayered films.     

Oxygen-defects-related dielectric response in CaCu3Ti4O12 ceramics

A 10 mm thickness columned CaCu₃Ti₄O₁₂ ceramic was fabricated by the conventional solid-state reaction method and the dielectric properties of different parts in ceramic had been investigated. For the sample close to the surface, only one Debye-type relaxation around 10⁷ Hz was observed at room temperature. However, for the sample close to the core, another relaxation peak was observed at about 10⁴ Hz. The results were explained in terms of the equivalent circuit model by showing in the impedance spectroscopy. Moreover, it was introduced that the low-frequency dielectric relaxation is associated with the electrode-sample contact effect based on varying sample thickness and an annealing treatment in the nitrogen atmospheres.     

Experimental and numerical investigation of a ceramic dielectric resonator (DRA): CaCu3Ti4O12 (CCTO)

In this study, the CaCu₃Ti₄O₁₂ (CCTO) ceramic phase was synthesized by microwave heating in a much shorter time compared to the conventional heating methods. The results indicate that microwave processing is a promising method for preparing CCTO ceramics. CCTO was prepared using a domestic microwave oven operated at 2.45 GHz with 800 W. After a few minutes of microwave irradiation the formation of CCTO was confirmed by X-ray powder diffraction. The CCTO ceramic was studied in the medium-frequency (MF) range (100 Hz-1 MHz) and in the microwave range of frequencies. The experimental and theoretical characteristics of the dielectric resonator antenna are investigated.     

Observation of giant dielectric constant in CdCu3Ti4O12 ceramics

Although CdCu₃Ti₄O₁₂ is isostructural to CaCu₃Ti₄O₁₂, the room temperature low-frequency dielectric constant of the former compound was reported to be ∼400, only 1/25 of that of the latter material [M.A. Subramanian, et al., J. Solid State Chem. 151 (2000) 323]. In this communication, we report that the dielectric constant of CdCu₃Ti₄O₁₂ can be remarkably increased by elevating the sintering temperature. The room temperature dielectric constant at 100 kHz achieves 9000, almost as much as that of CaCu₃Ti₄O₁₂, for the sample sintered at 1283 K. The appearance of giant dielectric constant in CdCu₃Ti₄O₁₂ is explained in terms of internal barrier layer capacitance (IBLC) effect with the subgrain boundary as the barrier. Our result supplies an approach in searching for new giant-dielectric-constant materials in the CaCu₃Ti₄O₁₂ family.     

Dielectric property of CaCu3Ti4O12 thin film grown on Nb-doped SrTiO3(100) single crystal

Thin film of CaCu₃Ti₄O₁₂ (CCTO) has been deposited on Nb-doped SrTiO₃(100) single crystal using pulsed laser deposition. The dielectric constant and AC conductivity of CCTO film in the metal–insulator–metal capacitor configuration over a wide temperature (80 to 500 K) and frequency (100 Hz to 1 MHz) range have been measured. The small dielectric dispersion with frequency observed in the lower temperature region (<300 K) indicates the presence of small defects in the deposited CCTO thin film. The frequency-dependent AC conductivity at lower temperature indicates the hopping conduction. The dielectric dispersion data has been analyzed in the light of both conductivity relaxation and Debye type relaxation with a distribution of relaxation times. Origin of dielectric dispersion is attributed to the distribution of barrier heights such that some charge carriers are confined between long-range potential wells associated with defects and give rise to dipolar polarization, while those carriers which do not encounter long-range potential well give rise to DC conductivity.     

Evidence for internal resistive barriers in a crystal of the giant dielectric constant material: CaCu3Ti4O12

Complex impedance spectra were obtained on a crystal of CaCu₃Ti₄O₁₂ (CCTO) from 289 to 456 K. As in the case of ceramic CCTO, these spectra can be interpreted as arising from a conducting material containing insulating barriers. This is then further evidence for the existence of planar defects within crystals of CCTO that act as insulating barriers and produce the large dielectric constant through a space charge mechanism.     

Low-temperature sintering and microwave dielectric properties of Ca2Zn4Ti15O36 ceramics

The sintering behavior, microstructures, and microwave dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics with B₂O₃ addition were investigated. The crystalline phases and microstructures of Ca₂Zn₄Ti₁₅O₃₆ ceramics with 0-10 wt% B₂O₃ addition were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The sintering temperature of Ca₂Zn₄Ti₁₅O₃₆ ceramic was lowered from 1170 to 930 °C by 10 wt% B₂O₃ addition. Ca₂Zn₄Ti₁₅O₃₆ ceramics with 8 wt% B₂O₃ addition sintered at 990 °C for 2 h exhibited good microwave dielectric properties, i.e., a quality factor (Qf) 11,400 GHz, a relative dielectric constant (ε_r) 41.5, and a temperature coefficient of resonant frequency (τ_f) 94.4 ppm/°C.     

Dielectric characteristics of CaCu3Ti4O12/P(VDF-TrFE) nanocomposites

Composite thin film is highly desirable for the dielectric applications. In order to develop composite thin film, a nanocomposite, in which nanosized CaCu₃Ti₄O₁₂ (CCTO) particles are used as filler and P(VDF?CTrFE) 55/45 mol% copolymer is used as polymer matrix, is investigated. The contents of CCTO in the nanocomposites range from 0% to 50?vol%. The dielectric property of these nanocomposites was characterized at frequencies ranging from 100 Hz to 1 MHz and at temperatures ranging from 200 K to 370 K. A dielectric constant of 62 with a loss of 0.05 was obtained in nanocomposite with 50?vol% CCTO at room temperature at 1 kHz. At the phase transition temperature (??340?K) of the copolymer, a dielectric constant of 150 with a loss less than 0.1 was obtained in this nanocomposite. It is found that the dielectric loss of the nanocomposites is dominated by the polymer which has a relaxation process. Comparing to composites made using microsized CCTO, the nanocomposites exhibit a much lower dielectric loss and a lower dielectric constant. This indicates that the nanosized CCTO particles have a lower dielectric constant than the microsized CCTO particles.     

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

In this work, the influence of Lu₂O₃ doped on the dielectric and electrical properties of CaCu₃Ti₄O₁₂ was reported. Lu₂O₃-doped CCTO was prepared by a conventional solid state technique using CuO, TiO₂, and CaCO₃ as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 10² Hz–10⁷ Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu₂O₃ resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu₂O₃ resulted in decreasing nonlinear coefficients.     

Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

Effect of sintering temperature on structure and nonlinear dielectric properties of Ba0.6Sr0.4TiO3 ceramics prepared by the citrate method

Ba_0.6Sr_0.4TiO₃ ceramics were prepared by a citrate precursor method. The structure and nonlinear dielectric properties of the resulting ceramics were investigated within the sintering temperature range 1200-1300 °C. Adopting fine Ba_0.6Sr_0.4TiO₃ powder derived from the citrate method was confirmed to be effective in reducing the sintering temperatures required for densification. The ceramic specimens sintered at 1230-1280 °C presented relative densities of around 95%. A significant influence of sintering temperature on the microstructure and nonlinear dielectric properties was detected. The discrepancy in nonlinear dielectric behavior among the specimens sintered at different temperatures was qualitatively interpreted in terms of the dielectric response of polar micro-regions under bias electric field. The specimens sintered at 1230 and 1250 °C attained superior nonlinear dielectric properties, showing relatively low dielectric losses (tan δ) of 0.24% and 0.22% at 10 kHz together with comparatively large figure of merits (FOM) of 121 and 142 at 10 kHz and 20 kV/cm, respectively.     

Electrical and magnetic behavior of La0.7Ca0.3MnO3/La0.7Sr0.2Ca0.1MnO3 composites

The electrical transport properties and the magnetoresistance of La_0.7Ca_0.3MnO₃/La_0.7Sr_0.2Ca_0.1MnO₃ composites are investigated as a function of sintering temperature. On the basis of an analysis by X-ray powder diffraction and scanning electron microscopy we suggest that raising the sintering temperature enhanced the interfacial reaction and creates interfacial phases at the boundaries of the La_0.7Ca_0.3MnO₃ and La_0.7Sr_0.2Ca_0.1MnO₃. Results also show that in 3 kOe, and at the Curie temperature, the magnetoresistance value of 14% was observed for the composite sintered at 1300 °C. Based on the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the experimental resistivity—temperature data from 50-300 K and find that the activation barrier decreases as temperature is increased.     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

La substitution in four-layers Aurivillius phase SrBi4Ti4O15

Ceramics with the nominal composition of SrBi_4−xLa_xTi₄O₁₅ have been prepared within the range of 0≤x≤1.8, and the dielectric properties are investigated. Single phase SrBi_4−xLa_xTi₄O₁₅ solid solution exists until the secondary phase of La_2/3TiO₃ appears at x=1.6. The Curie temperature is 520 °C for pure SrBi₄Ti₄O₁₅, and it shifts to low temperature with increasing x, which is due to the smaller structural distortion caused by La³⁺ substitution. In addition, the dielectric constant anomaly is suppressed with the substitution. No dielectric relaxation behavior is observed. When x≥1.2, the paraelectric state is attained in the present ceramics. La³⁺ substitution effects on the SrBi₄Ti₄O₁₅ ceramics are also compared with the previous work on Bi_4−xLa_xTi₃O₁₂.     

Dielectric relaxations in Tb0.91Yb1.38Bi0.71Fe5O12 ceramics

Dielectric relaxations of Tb_0.91Yb_1.38Bi_0.71Fe₅O₁₂ ceramics were investigated. A Debye-type relaxation was observed in the temperature range of 125-620 K with an activation energy of 0.29 eV. This activation energy agreed well with that of carriers hopping between Fe²⁺ and Fe³⁺, indicating that this relaxation might be a dipolar-type relaxation associated with the hopping carries. A high relaxorlike dielectric peak with a very strong frequency dispersion in the high temperature range of 400-620 K might be originate from the oxygen vacancies related dielectric relaxation.     

巨介电常数氧化物CaCu3Ti4O12的介电和阻抗特性

采用固相烧结法合成了单相巨介电常数氧化物CaCu₃Ti₄O₁₂（CCTO）.用阻抗分析仪分析了10—420 K温度范围内的介电频谱和阻抗谱特性,并结合ZVIEW软件进行了模拟.结果表明：温度高于室温时,频谱出现两个明显的弛豫台阶,低频弛豫介电常数随温度升高而显著增大,表现出热离子极化特点;温度低于室温时,频谱表现出类德拜弛豫,且高、低平台介电常数值基本不随温度变化,表现出界面极化特点和较好的温度稳定性.频谱中依次出现的介电弛豫对应于阻抗谱中 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 介电频谱 阻抗谱 Cole-Cole半圆弧     

Temperature-dependent ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films

To investigate temperature-dependent ferroelectric and dielectric properties of ferroelectric films, Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were prepared on Pt-coated silicon substrates by pulsed laser deposition. The ferroelectric and dielectric behaviors have been studied in a wide temperature range from 80 K to room temperature. The saturated polarization (P_sat) decreases with decreasing temperature and decreasing electric field, whereas remnant polarization (P_r) shows a more complex temperature dependence. These results, which can be well explained based on a temperature-dependent charged defects-domain wall interaction model, might be helpful for further understanding the domain switching behavior. Based on these results, an alternative way to investigate temperature-dependent ferroelectric fatigue is proposed and experimentally carried out. The measured fatigue rate is found to be linearly dependent on temperature, consistent with the report on Pb(Zr,Ti)O₃ films. Temperature-dependent dielectric measurements of the films further confirm the above explanation.