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.     

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.     

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.     

Effect of Cu-stoichiometry on the dielectric and electric properties in CaCu3Ti4O12 ceramics

CaCu_3+yTi₄O₁₂ (y=0, ±0.025, ±0.05, ±0.1 and −0.15) ceramics are prepared by the conventional solid-state reaction technique under sintering condition of 1050 ^°C, 10 h. X-ray diffraction shows that they all have the good crystalline structure. Cu-deficient ceramics exhibit the microstructures of uniform grain size distribution, whereas both Cu-stoichiometric and Cu-rich ceramics display microstructures of bimodal grain size distribution. The largeness of low-frequency dielectric permittivity at room temperature is found to be very sensitive to the Cu-stoichiometry. Upon raising the measuring temperature, all of the ceramics present commonly three semicircles in the complex impedance plane. It indicates that there exist three distinct contributions, which are ascribed to arising from domains, grain boundaries and domain boundaries. In addition, the influence of CuO segregation on the dielectric and electrical properties is also discussed.     

Bismuth zinc niobate (Bi1.5ZnNb1.5O7) ceramics derived from metallo-organic decomposition precursor solution

The preparation, microstructure development and dielectric properties of Bi_1.5ZnNb_1.5O₇ pyrochlore ceramics by metallo-organic decomposition (MOD) route are reported. Homogeneous precalcined ceramic powders of 13-36 nm crystallite size were obtained at temperatures ranging from 500 to 700 °C. The thermal decomposition/oxidation of the gelled precursor solution was chemically analyzed, TG/DTA, XRD, and SEM, led to the formation of a pure cubic pyrochlore phase with a stoichiometry close to Bi_1.5ZnNb_1.5O₇ which begins to form at 500 °C. The metallo-organic precursor synthesis method, where Bi, Zn and Nb ions are chelated to form metal complexes, allows the control of Bi/Zn/Nb stoichiometric ratio on a molecular scale leading to the rapid formation of bismuth zinc niobate (Bi_1.5ZnNb_1.5O₇) ceramic fine powders with pure pyrochlore structure. The powders were pressed into pellets and can be sintered at temperatures as low as 800-1000 °C. Fine crystalline ceramics with the grain size in the range of 200-500 nm have been obtained at the sintering temperature of 800 °C. The dielectric properties in high frequency to microwave range were measured and discussed.     

Dielectric-spectroscopic and a.c. conductivity investigations on copper doped layered Na1.8K0.2Ti3O7 ceramics

Dielectric studies on copper doped derivatives of polycrystalline layered mixed alkali trititanate Na_1.8K_0.2Ti₃O₇ ceramics indicate that the losses are of mixed type and decrease on copper doping. However, the temperature dependent permittivity plots are characteristic of the diffuse nature of a possible ferroelectric phase transition and hence give indication of relaxor ferroelectric behaviour. From the EPR spectra, recorded at room temperature, it can be seen that the substitution of copper occurs at Ti⁴⁺ as preferred site with a divalent oxidation state (Cu²⁺) for all compositions. Also, copper doping enhances the transition temperature, which is indicative of the stabilization of the existing ferroelectric phase up higher temperatures. Besides bolstering electron hopping conduction, acceptor doping restrains the interlayer ionic conduction. Moreover, electron hopping (polaron) conduction is dominant over the lower temperature region, while interlayer ionic conduction prevails in the higher temperature region.     

The effect of potential of impedance in the pulsed-laser-deposited SrBi2Ta2O9 thin film

Ferroelectrics SrBi₂Ta₂O₉ (SBTO) thin films were grown on a highly oriented Pt/Ti/SiO₂/Si substrates using the pulsed laser ablation. The ac impedance of SBTO thin films have been measured at room temperature both in the frequency range from 10⁻¹ to 10⁶ Hz and bias voltage range from −6 to 6 V. The ac impedance dispersion was observed at low frequency with increasing bias voltage, which was interpreted based on a blocked charge. We can explain that the blocking interface gives rise to constant phase element (CPE) response, and we give an impedance model function that can fit data along the low frequency range when such a CPE is found. The low frequency dispersion phenomena of SBTO thin film are related to a charge diffusion process at the surface of thin film.     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

Ferroelectric properties of Pr and Nb co-substituted Sr0.8Bi2.2Ta2O9 thin films

Thin film of both A- and B-site co-substituted Sr_0.8Bi_2.2Ta₂O₉ (SBT) by Pr³⁺ and Nb⁵⁺, i.e. Sr_0.8Pr_0.1Bi_2.1Ta_1.5Nb_0.5O₉ (SPBTN) was fabricated on Pt/Ti/SiO₂/Si substrates by metalorganic decomposition method. The Nb⁵⁺ substitution at B-site and Pr³⁺ substitution at A-site enhanced the remanent polarization and reduced the coercive field of the films, respectively. The remanent polarization (2P_r) value of the SPBTN film was 22 μC/cm². The coercive field (2E_c) value of the SPBTN film was 102 kV/cm, which was much lower than that of SBTN (165 kV/cm). The effects of substitution on structural and ferroelectric properties of SBT were discussed in detail. As a result, the A- and B-sites co-substitution may be one of the promising ways to improve ferroelectric properties of SBT.     

Electric-field dependence of dielectric properties of sol-gel derived Ba(Zr0.2Ti0.8)O3 ceramics

The effect of a dc bias field on the diffuse phase transition and nonlinear dielectric properties of sol-gel derived Ba(Zr_0.2Ti_0.8)O₃ (BZT) ceramics are investigated. Diffuse phase transitions were observed in BZT ceramics and the Curie–Weiss exponent (CWE) was γ∼2.0. The dielectric constant versus temperature characteristics and the γ in the modified Curie–Weiss law, ε ⁻¹=ε _m ⁻¹[1+(T−T _m ) ^γ /C₁](1≤γ≤2), as a function of the dc bias field was obtained for BZT ceramics. The results indicated that γ is a function of dc bias field, and the γ value decreased from 2.04 to 1.73 with dc bias field increasing from 0 to 20 kV/cm. The dielectric constant decreases with increasing dc bias field, indicating a field-induced phase transition. The dc bias field has a strong effect on the position of the dielectric peak and affects the magnitude of the dielectric properties over a rather wide temperature range. The peak temperature of the dielectric loss does not coincide with the dielectric peak and an obvious minimum value for the dielectric loss at the temperature of the dielectric peaks is observed. At room temperature, 300 K, the high tunability (K=80%), the low loss tangent (≈0.01) and the large FOM (74), clearly imply that these ceramics are promising materials for tunable capacitor-device applications.     

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.     

Electrical properties of pulsed laser-deposited SrxBiyTa2O9 thin films on Bi/Sr ratios

The dependence of the electrical properties of Sr_xBi_yTa₂O₉ thin films on the (Bi/Sr ratio 1.6, 2.3, 2.8, 3.4) has been investigated. The Sr_xBi_yTa₂O₉ ferroelectric thin films were synthesized on Pt/Ti/SiO₂/Si substrates using the pulsed laser deposition method. Saturation polarization (P_st) and coercive field (2E_c) depend on the Bi/Sr ratio. P_st increases while E_c decreases with an increase in Bi/Sr ratio. Atomic Force Microscopy images show that the grain size grows with increasing Bi/Sr ratio. It is observed that the impedance behavior in Sr_xBi_yTa₂O₉ thin film, conforms to the Constant Phase Element (CPE) model. It is believed that the diffuse charges at the grain boundary build up a surface polarization because the impedance behavior close to pure capacitor with grain size increased.     

Maxwell-Wagner characterization of dielectric relaxation in Ni0.8Zn0.2Fe2O4/Sr0.5Ba0.5Nb2O6 composite

Dense composites were prepared through incorporating the dispersed Ni_0.8Zn_0.2Fe₂O₄ ferromagnetic particles into Sr_0.5Ba_0.5Nb₂O₆ ferroelectric matrix. Extrinsic dielectric relaxation and associated high permittivities of the materials are reported in the composites. We used an ideal equivalent circuit to explain electrical responses in impedance formalism. A Debye-like relaxation in the permittivity formalism was also found. Interestingly, real permittivity (ε′) of the sample containing 30% Ni_0.8Zn_0.2Fe₂O₄ shows obvious independence of the temperature at 100 kHz. Dielectric relaxation and high-ε′ properties of the composites are explained in terms of the Maxwell-Wagner (MW) polarization model.     

Investigation of microwave dielectric relaxation process in the antiferroelectric phase of NaNbO3 ceramics

This letter reports microwave dielectric measurements performed in the antiferroelectric phase of NaNbO₃ ceramics from 100 to 450 K. Remarkable dielectric relaxation was found within the antiferroelectric phase and in the vicinity of the ferroelectric-antiferroelectric phase transition. Such dielectric relaxation process was associated with relaxations of polar nanoregions with strong relaxor-like characteristic. In addition, the microwave dielectric measurements also revealed an unexpected and unusual anomaly in the relaxation strength, which was related to a disruption of the antiferroelectric order induced by a possible AFE-AFE phase transition.     

Relaxor Behaviour and Ferroelectric Properties of （Li0.12Na0.88） （Nb0.9-xWa0.10Sbx）O3 Lead-Free Ceramics

New lead-free ceramics （Lio.12Na0.88） （Nbo.9-x Ta0.10 Sbx） 03 （0.01 × 0.06） are synthesized by solid-state reaction method. The dielectric, piezoelectric and ferroelectric properties of the ceramics are studied. The dielectric constant dependence with temperature and frequency of the ceramic specimen with x = 0.04 shows typical characteristics of relaxor ferroelectrics, and the Vogel-Fulcher relationship is fulfilled. The dielectric behaviour and its relation to the phase transition phenomena are discussed. The polarization hysteresis loops at room temperature are also measured.     

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.     

Enhanced spontaneous polarization in Sr and Ca co-doped BaTiO3 ceramics

The dielectric and ferroelectric properties of (Ba_xSr_1−x)_0.77Ca_0.23TiO₃ ceramics with x=1 to 0.7 were studied and compared with those of Ba_xSr_1−xTiO₃ and Ba_0.77Ca_0.23TiO₃ ceramics. It has been found that Sr doping of the Ba_0.77Ca_0.23TiO₃ ceramics causes a drastic decrease of the Curie temperature, just like Sr doping of pure BaTiO₃ ceramics, demonstrating a cell volume effect. However, the (Ba_xSr_1−x)_0.77Ca_0.23TiO₃ ceramics with x=0.9 and 0.8 have larger spontaneous polarization than those of the corresponding Ba_xSr_1−xTiO₃ and Ba_0.77Ca_0.23TiO₃ ceramics, along with sufficient insulating properties. The enhancement of their polarization was explained by the increase of the lattice parameter c/a ratio due to the lattice distortion and strain developed in the ceramics.     

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.     

Ferroelectric properties of Pr6O11-doped Bi4Ti3O12

Praseodymium doped Bi₄Ti₃O₁₂ (BIT) ceramics with composition Bi_2.9Pr_0.9Ti₃O₁₂ (BPT) were prepared by solid state reaction. These samples have polycrystalline Bi-layered perovskite structure without preferred orientation, and consist of well-developed plate-like grains with random orientation. Pr doping into BIT causes a large shift of the Curie temperature (T_C) of the BIT from 675 to 398 °C. At an electric field of 87 kV/cm, the remanent polarization and the coercive field of the BPT ceramics are 30 μC/cm² and 52 kV/cm, respectively. Furthermore, the dielectric permittivity and the dissipation factor of the BPT ceramics are 300 and 0.003 at 1 MHz, 1 V, and room temperature. Ferroelectric properties of the BPT ceramics are superior to V-doped Bi₄Ti₃O₁₂ (∼20 μC/cm² and 80 kV/cm) and (Sr, Ta)-doped Bi₄Ti₃O₁₂ (∼12 μC/cm² and 71 kV/cm) ceramics. In addition, the dense ceramics of praseodymium-doped B₄Ti₃O₁₂ were obtained by sintering at 1100 °C, about 100-200 °C lower than those of the SrBi₂Ta₂O₉ system.     

Relaxor behavior of K0.5La0.5Bi2Ta2O9 ceramics

Potassium lanthanum bismuth tantalate (K_0.5La_0.5Bi₂Ta₂O₉), a new relaxor ferroelectric was synthesized via the solid-state reaction route. X-ray structural studies along with Rietveld refinement confirmed it to be an n=2 member of the Aurivillius family of oxides and the refined lattice parameters are , and . The appearance of 1/2{h00} and 1/2{hk0} type superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak associated with frequency dependent dielectric maximum temperature was observed. The value of the diffuseness parameter γ=1.93, obtained from the fit of a modified Curie-Weiss law established the relaxor nature of the title compound. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein and . The relaxor behavior was attributed to the local polar ordering on A-sites.