Dielectric Properties of Colossal-Dielectric-Constant Na1/2La1/2Cu3Ti4O12 Ceramics Prepared by Spark Plasma Sintering

In the current study, we report on the dielectric behavior of colossal-dielectric-constant Na_1/2La_1/2Cu₃Ti₄O₁₂ (NLCTO) ceramics prepared by mechanochemical synthesis and spark plasma sintering (SPS) at 850 °C, 900 °C, and 925 °C for 10 min. X-ray powder diffraction analysis showed that all the ceramics have a cubic phase. Scanning electron microscope observations revealed an increase in the average grain size from 175 to 300 nm with an increase in the sintering temperature. SPS NLCTO ceramics showed a room-temperature colossal dielectric constant (>10³) and a comparatively high dielectric loss (>0.1) over most of the studied frequency range (1 Hz–40 MHz). Two relaxation peaks were observed in the spectra of the electrical modulus and attributed to the response of grain and grain boundary. According to the Nyquist plots of complex impedance, the SPS NLCTO ceramics have semiconductor grains surrounded by electrically resistive grain boundaries. The colossal dielectric constant of SPS NLCTO ceramics was attributed to the internal barrier layer capacitance (IBLC) effect. The high dielectric loss is thought to be due to the low resistivity of the grain boundary of SPS NLCTO.     

Capacitance scaling of grain boundaries with colossal permittivity of CaCu3Ti4O12-based materials

Samples of copper-deficient CaCu₃Ti₄O₁₂ (CCTO) compared to the nominal composition, all synthesized via organic gel-assisted citrate process, show huge change of grain boundaries capacitance as deduced from a fit of an RC element model to the impedance spectroscopic data. The grain boundary capacitance is found to scale with the permittivity measured at 1 kHz weighted by the size of the grains. This result is found consistent with the internal barrier layer capacitance (IBLC) model.     

Decrease in dielectric loss of CaCu3Ti4O12 by the addition of TeO2

CaCu₃Ti₄O₁₂ (CCTO) has challenged for the last few years the scientific community due to its large dielectric constant, which is almost temperature and frequency independent, from 100 K to 400 K and from 1 kHz to 1 MHz, respectively. This makes the material desirable for many electronic applications. However, the dissipation factor is very large, with tan δ values, at room temperature and 1 kHz, higher than 0.1.In our work we report how the addition of TeO₂ lowers the dielectric loss and, although there is a decrease of dielectric constant of doped samples relatively to the undoped one, high dielectric constant values are still being reached. The sample of doped CCTO with 1.5% of TeO₂ by weight, presents, at room temperature and 60 kHz, a large dielectric constant, over 3000, and a dissipation factor around 0.09, which represents a decrease on tan δ over 30% relatively to the CCTO undoped sample. Two relaxation processes were identified for all the samples, one at MHz region and the other one at low frequency region (< 1 kHz). DC bias voltage was applied up to 40 V and a strong dc bias influence on the low frequency region was observed both at dielectric and impedance responses of the undoped sample, which was much weaker than the dc bias effects on the 4% Te doped sample.Dielectric measurements will be discussed and correlated with the samples' microstructure, supported on internal barrier layer capacitance (IBLC) and surface barrier layer capacitance (SBLC) models.     

Schottky-type grain boundaries in CCTO ceramics

In this work we studied electrical barriers existing at CaCu₃Ti₄O₁₂ (CCTO) ceramics using dc electrical measurements. CCTO pellets were produced by solid state reaction method and X-ray diffractograms showed which single phase polycrystalline samples were obtained. The samples were electrically characterized by dc and ac measurements as a function of temperature, and semiconductor theory was applied to analyze the barrier at grain boundaries. The ac results showed the sample’s permittivity is almost constant (10⁴) as function of temperature at low frequencies and it changes from 100 to 10⁴ as the temperature increases at high frequencies. Using dc measurements as a function of temperature, the behavior of barriers was studied in detail. Comparison between Schottky and Poole-Frenkel models was performed, and results prove that CCTO barriers are more influenced by temperature than by electric field (Schottky barriers). Besides, the behavior of barrier width as function of temperature was also studied and experimental results confirm the theoretical assumptions.     

Synthesis, structure and electrical properties of Cu3.21Ti1.16Nb2.63O12 and the CuOx-TiO2-Nb2O5 pseudoternary phase diagram

Subsolidus phase relations in the CuO_x-TiO₂-Nb₂O₅ system were determined at 935 °C. The phase diagram contains one new phase, Cu_3.21Ti_1.16Nb_2.63O₁₂ (CTNO) and one rutile-structured solid solution series, Ti_1−3xCu_xNb_2xO₂: 0<x<0.2335 (35). The crystal structure of CTNO is similar to that of CaCu₃Ti₄O₁₂ (CCTO) with square planar Cu²⁺ but with A site vacancies and a disordered mixture of Cu⁺, Ti⁴⁺ and Nb⁵⁺ on the octahedral sites. It is a modest semiconductor with relative permittivity ∼63 and displays non-Arrhenius conductivity behavior that is essentially temperature-independent at the lowest temperatures.     

Fabrications and dielectric performances of novel composites: Calcium copper titanate / Polyvinylidene fluoride

CCTO (Calcium copper titanate) powder as inorganic filler was synthesized by the Sol-gel method firstly. CCTO/PVDF (Polyvinylidene fluoride) composite was fabricated by solution mixing based on high temperature resistance of PVDF and insulated property of CCTO. The composite of CCTO/PVDF were characterized by X-ray diffraction, Fourier Transform infrared spectroscopy, Scanning Electron Microscope and impedance analysis. The results showed that the addition of CCTO and increasing in its content did not affect the phase- and micro-structure of the composites,but the increase of CCTO content can induce the generation of C–F new bonds. PVDF/CCTO composites were enhanced in performance of thermal and frequency-depended stability with increasing in the fraction of CCTO. The dielectric constant of CCTO/PVDF composite materials with 50% CCTO achieved to a maximum value of 50 almost, which is 5 times higher the pure PVDF. The conductivity felled into 10⁻⁸ to 10⁻¹ S m⁻¹ during the frequency of 10²–10⁸ Hz. The composite material would be expected to be applied in the field of integrated circuit.     

Central role of TiO2 anatase grain boundaries on resistivity of CaCu3Ti4O12-based materials probed by Raman spectroscopy

This study focuses on characterization and control of grain boundaries to enhance the properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics capacitors for industrial applications. A novel factor deals with TiO₂ anatase revealed by Raman scattering in grain boundaries, found as a dominant parameter of largest sample resistivity, consistent with higher grain boundary resistivity and higher breakdown voltage. Four selected samples of CCTO-based compositions showing very different properties in terms of permittivity ranging from 1000 to 684 000 measured at 1 kHz, capacitance of grain boundaries ranging from 8 10⁻¹⁰ to 4.5 10⁻⁷ F cm⁻¹, grain boundary resistivity ranging from 193 to 30,000,000 Ω cm and sample resistivity extending from 450 to 10¹¹ Ω cm. The relationship between permittivity weighted by grain size and capacitance of grain boundaries confirms the internal barrier layer capacitance model over 5 orders of magnitude.