Search Results (14)

As the demand for miniaturization of electronic devices increases, ceramics with an ABO₃ structure require further improvement of the dielectric constant with high permittivity. In the present work, Ba_1−1.5xBi_xTiO₃ (BB100xT, x = 0.0025, 0.005, 0.0075, 0.01) ceramics were prepared via a solid-state reaction process. The effect of Bi doping on dielectric properties of lead-free relaxor ferroelectric BaTiO₃-based ceramics was studied. The results showed that both colossal permittivity (37,174) and a temperature stability of TCC ≤ ±15% (−27–141 °C) were achieved in BB100xT ceramics at x = 0.5%. The A-site donor doping produces A-site vacancies, a larger space for Ti⁴⁺, and fluctuation of the component, which is partially responsible for the high permittivity and responsible for the temperature stability. Meanwhile, the contribution of defect dipoles, and IBLC and SBLC effects to polarization leads to the colossal permittivity. The formation of a liquid phase during sintering promotes mass transfer when the doping content is higher than 0.5%. This work benefits the exploration of novel multilayer ceramic capacitors with colossal permittivity and temperature stability via defect engineering. Full article

This work explores the impact of the sintering temperature and co-dopant contents on the microstructure and dielectric properties of (Y_0.5Nb_0.5)_xTi_1−xO₂ (0.025 ≤ x ≤ 0.10) ceramics synthesized by the solid state reaction method. The physical mechanism underlying the colossal electric permittivity was systematically investigated with experimental methods and first principles calculations. All specimens exhibited the characteristic tetragonal structure of rutile, besides secondary phases. A niobium- and yttrium-rich secondary phase emerged at the grain boundaries after heating at 1500 °C, changing the main sintering mechanism. The highest value of the electric permittivity (13499 @ 60 °C and 10 kHz) was obtained for (Y_0.5Nb_0.5)_0.05Ti_0.95O₂ sintered at 1480 °C, and the lowest dissipation factor (0.21@ 60 °C and 10 kHz) for (Y_0.5Nb_0.5)_0.1Ti_0.90O₂ sintered at 1500 °C. The dielectric properties of Y³⁺ and Nb⁵⁺ co-doped TiO₂ are attributed to the internal barrier layer capacitance (IBLC) and electron-pinned dipole defect (EPDD) mechanisms. Full article

Commercially available LaFeO₃ powder was processed using the spark plasma sintering (SPS) technique. The results of the dielectric measurement showed high permittivity, but this was strongly frequency-dependent and was also accompanied by a high loss tangent. The chemical purity of the powder and changes induced by the SPS process influenced the stability of the dielectric parameters of the bulk compacts. A microstructure with a homogeneous grain size and a certain porosity was produced. The microhardness of the sintered LaFeO₃ was rather high, about 8.3 GPa. All the results are in reasonable agreement with the literature related to the production of LaFeO₃ using different techniques. At frequencies as low as 100 Hz, the material behaved like a colossal permittivity ceramic, but this character was lost with the increasing frequency. On the other hand, it exhibited persistent DC photoconductivity after illumination with a standard bulb. Full article

The effects of the sintering conditions on the phase compositions, microstructure, electrical properties, and dielectric responses of TiO₂-excessive Na_1/2Y_1/2Cu₃Ti_4.1O₁₂ ceramics prepared by a solid-state reaction method were investigated. A pure phase of the Na_1/2Y_1/2Cu₃Ti_4.1O₁₂ ceramic was achieved in all sintered ceramics. The mean grain size slightly increased with increasing sintering time (from 1 to 15 h after sintering at 1070 °C) and sintering temperature from 1070 to 1090 °C for 5 h. The primary elements were dispersed in the microstructure. Low dielectric loss tangents (tan δ~0.018–0.022) were obtained. Moreover, the dielectric constant increased from ε′~5396 to 25,565 upon changing the sintering conditions. The lowest tan δ of 0.009 at 1 kHz was obtained. The electrical responses of the semiconducting grain and insulating grain boundary were studied using impedance and admittance spectroscopies. The breakdown voltage and nonlinear coefficient decreased significantly as the sintering temperature and time increased. The presence of Cu⁺, Cu³⁺, and Ti³⁺ was examined using X-ray photoelectron spectroscopy, confirming the formation of semiconducting grains. The dielectric and electrical properties were described using Maxwell–Wagner relaxation, based on the internal barrier layer capacitor model. Full article

(Nb⁵⁺, Si⁴⁺) co-doped TiO₂ (NSTO) ceramics with the compositions (Nb_0.5Si_0.5)_xTi_1−xO₂, x = 0, 0.025, 0.050 and 0.1 were prepared with a solid-state reaction technique. X-ray diffraction (XRD) patterns and Raman spectra confirmed that the tetragonal rutile is the main phase in all the ceramics. Additionally, XRD revealed the presence of a secondary phase of SiO₂ in the co-doped ceramics. Impedance spectroscopy analysis showed two contributions, which correspond to the responses of grain and grain-boundary. All the (Nb, Si) co-doped TiO₂ showed improved dielectric performance in the high frequency range (>10³ Hz). The sample (Nb_0.5Si_0.5)_0.025Ti_0.975O₂ showed the best dielectric performance in terms of higher relative permittivity (5.5 × 10⁴) and lower dielectric loss (0.18), at 10 kHz and 300 K, compared to pure TiO₂ (1.1 × 10³, 0.34). The colossal permittivity of NSTO ceramics is attributed to an internal barrier layer capacitance (IBLC) effect, formed by insulating grain-boundaries and semiconductor grains in the ceramics. Full article

Giant dielectric (GD) oxides exhibiting extremely large dielectric permittivities (ε’ > 10⁴) have been extensively studied because of their potential for use in passive electronic devices. However, the unacceptable loss tangents (tanδ) and temperature instability with respect to ε’ continue to be a significant hindrance to their development. In this study, a novel GD oxide, exhibiting an extremely large ε’ value of approximately 7.55 × 10⁴ and an extremely low tanδ value of approximately 0.007 at 10³ Hz, has been reported. These remarkable properties were attributed to the synthesis of a Lu³⁺/Nb⁵⁺ co-doped TiO₂ (LuNTO) ceramic containing an appropriate co-dopant concentration. Furthermore, the variation in the ε’ values between the temperatures of −60 °C and 210 °C did not exceed ±15% of the reference value obtained at 25 °C. The effects of the grains, grain boundaries, and second phase particles on the dielectric properties were evaluated to determine the dielectric properties exhibited by LuNTO ceramics. A highly dense microstructure was obtained in the as-sintered ceramics. The existence of a LuNbTiO₆ microwave-dielectric phase was confirmed when the co-dopant concentration was increased to 1%, thereby affecting the dielectric behavior of the LuNTO ceramics. The excellent dielectric properties exhibited by the LuNTO ceramics were attributed to their inhomogeneous microstructure. The microstructure was composed of semiconducting grains, consisting of Ti³⁺ ions formed by Nb⁵⁺ dopant ions, alongside ultra-high-resistance grain boundaries. The effects of the semiconducting grains, insulating grain boundaries (GBs), and secondary microwave phase particles on the dielectric relaxations are explained based on their interfacial polarizations. The results suggest that a significant enhancement of the GB properties is the key toward improvement of the GD properties, while the presence of second phase particles may not always be effective. Full article

The Mg²⁺/Ta⁵⁺ codoped rutile TiO₂ ceramic with a nominal composition (Mg_1/3Ta_2/3)_0.01Ti_0.99O₂ was synthesized using a conventional solid-state reaction method and sintered at 1400 °C for 2 h. The pure phase of the rutile TiO₂ structure with a highly dense microstructure was obtained. A high dielectric permittivity (2.9 × 10⁴ at 10³ Hz) with a low loss tangent (<0.025) was achieved in the as-sintered ceramic. After removing the outer surface, the dielectric permittivity of the polished ceramic increased from 2.9 × 10⁴ to 6.0 × 10⁴, while the loss tangent also increased (~0.11). The dielectric permittivity and loss tangent could be recovered to the initial value of the as-sintered ceramic by annealing the polished ceramic in air. Notably, in the temperature range of −60–200 °C, the dielectric permittivity (10³ Hz) of the annealed ceramic was slightly dependent (<±4.4%), while the loss tangent was very low (0.015–0.036). The giant dielectric properties were likely contributed by the insulating grain boundaries and insulative surface layer effects. Full article

In this work, the colossal dielectric properties and Maxwell—Wagner relaxation of TiO₂–rich Na_1/2Y_1/2Cu₃Ti_4+xO₁₂ (x = 0–0.2) ceramics prepared by a solid-state reaction method are investigated. A single phase of Na_1/2Y_1/2Cu₃Ti₄O₁₂ is achieved without the detection of any impurity phase. The highly dense microstructure is obtained, and the mean grain size is significantly reduced by a factor of 10 by increasing Ti molar ratio, resulting in an increased grain boundary density and hence grain boundary resistance (R_gb). The colossal permittivities of ε′ ~ 0.7–1.4 × 10⁴ with slightly dependent on frequency in the frequency range of 10²–10⁶ Hz are obtained in the TiO₂–rich Na_1/2Y_1/2Cu₃Ti_4+xO₁₂ ceramics, while the dielectric loss tangent is reduced to tanδ ~ 0.016–0.020 at 1 kHz due to the increased R_gb. The semiconducting grain resistance (R_g) of the Na_1/2Y_1/2Cu₃Ti_4+xO₁₂ ceramics increases with increasing x, corresponding to the decrease in Cu⁺/Cu²⁺ ratio. The nonlinear electrical properties of the TiO₂–rich Na_1/2Y_1/2Cu₃Ti_4+xO₁₂ ceramics can also be improved. The colossal dielectric and nonlinear electrical properties of the TiO₂–rich Na_1/2Y_1/2Cu₃Ti_4+xO₁₂ ceramics are explained by the Maxwell–Wagner relaxation model based on the formation of the Schottky barrier at the grain boundary. Full article

NSCTO (Na_0.5Sm_0.5Cu₃Ti₄O₁₂) ceramics have been prepared by reactive sintering solid-state reaction where the powder was prepared from the elemental oxides by mechanochemical milling followed by conventional sintering in the temperature range 1000–1100 °C. The influence of sintering temperature on the structural and dielectric properties was thoroughly studied. X-ray diffraction analysis (XRD) revealed the formation of the cubic NSCTO phase. By using the Williamson–Hall approach, the crystallite size and lattice strain were calculated. Scanning electron microscope (SEM) observations revealed that the grain size of NSCTO ceramics is slightly dependent on the sintering temperature where the average grain size increased from 1.91 ± 0.36 μm to 2.58 ± 0.89 μm with increasing sintering temperature from 1000 °C to 1100 °C. The ceramic sample sintered at 1025 °C showed the best compromise between colossal relative permittivity (ε′ = 1.34 × 10³) and low dielectric loss (tanδ = 0.043) values at 1.1 kHz and 300 K. The calculated activation energy for relaxation and conduction of NSCTO highlighted the important role of single and double ionized oxygen vacancies in these processes. Full article

The effects of charge compensation on dielectric and electrical properties of CaCu₃Ti_4-x(Al_1/2Ta_1/4Nb_1/4)_xO₁₂ ceramics (x = 0−0.05) prepared by a solid-state reaction method were studied based on the configuration of defect dipoles. A single phase of CaCu₃Ti₄O₁₂ was observed in all ceramics with a slight change in lattice parameters. The mean grain size of CaCu₃Ti_4-x(Al_1/2Ta_1/4Nb_1/4)_xO₁₂ ceramics was slightly smaller than that of the undoped ceramic. The dielectric loss tangent can be reduced by a factor of 13 (tanδ ~0.017), while the dielectric permittivity was higher than 10⁴ over a wide frequency range. Impedance spectroscopy showed that the significant decrease in tanδ was attributed to the highly increased resistance of the grain boundary by two orders of magnitude. The DFT calculation showed that the preferential sites of Al and Nb/Ta were closed together in the Ti sites, forming self-charge compensation, and resulting in the enhanced potential barrier height at the grain boundary. Therefore, the improved dielectric properties of CaCu₃Ti_4-x(Al_1/2Ta_1/4Nb_1/4)_xO₁₂ ceramics associated with the enhanced electrical properties of grain boundaries. In addition, the non-Ohmic properties were also improved. Characterization of the grain boundaries under a DC bias showed the reduction of potential barrier height at the grain boundary. The overall results indicated that the origin of the colossal dielectric properties was caused by the internal barrier layer capacitor structure, in which the Schottky barriers at the grain boundaries were formed. Full article

The enhanced dielectric permittivity (ε′) while retaining a low loss tangent (tanδ) in silver nanoparticle−(In_1/2Nb_1/2)_0.1Ti_0.9O₂/poly(vinylidene fluoride) (Ag-INTO/PVDF) composites with different volume fractions of a filler (f_Ag-INTO) was investigated. The hybrid particles were fabricated by coating Ag nanoparticles onto the surface of INTO particles, as confirmed by X-ray diffraction. The ε′ of the Ag−INTO/PVDF composites could be significantly enhanced to ~86 at 1 kHz with a low tanδ of ~0.044. The enhanced ε′ value was approximately >8-fold higher than that of the pure PVDF polymer for the composite with f_Ag-INTO = 0.5. Furthermore, ε′ was nearly independent of frequency in the range of 10²–10⁶ Hz. Therefore, filling Ag−INTO hybrid particles into a PVDF matrix is an effective way to increase ε′ while retaining a low tanδ of polymer composites. The effective medium percolation theory model can be used to fit the experimental ε′ values with various f_Ag-INTO values. The greatly increased ε′ primarily originated from interfacial polarization at the conducting Ag nanoparticle–PVDF and Ag–INTO interfaces, and it was partially contributed by the high ε′ of INTO particles. A low tanδ was obtained because the formation of the conducting network in the polymer was inhibited by preventing the direct contact of Ag nanoparticles. Full article

(Co, Nb) co-doped rutile TiO₂ (CoNTO) nanoparticles with low dopant concentrations were prepared using a wet chemistry method. A pure rutile TiO₂ phase with a dense microstructure and homogeneous dispersion of the dopants was obtained. By co-doping rutile TiO₂ with 0.5 at.% (Co, Nb), a very high dielectric permittivity of ε′ ≈ 36,105 and a low loss tangent of tanδ ≈ 0.04 were achieved. The sample–electrode contact and resistive outer-surface layer (surface barrier layer capacitor) have a significant impact on the dielectric response in the CoNTO ceramics. The density functional theory calculation shows that the 2Co atoms are located near the oxygen vacancy, creating a triangle-shaped 2CoV_oTi complex defect. On the other hand, the substitution of TiO₂ with Nb atoms can form a diamond-shaped 2Nb2Ti complex defect. These two types of complex defects are far away from each other. Therefore, the electron-pinned defect dipoles cannot be considered the primary origins of the dielectric response in the CoNTO ceramics. Impedance spectroscopy shows that the CoNTO ceramics are electrically heterogeneous, comprised of insulating and semiconducting regions. Thus, the dielectric properties of the CoNTO ceramics are attributed to the interfacial polarization at the internal insulating layers with very high resistivity, giving rise to a low loss tangent. Full article

Single-phase Ce³⁺-doped BaTiO₃ powders described by the nominal formula Ba_1−xCe_xTi_1−x/4O₃ with x = 0.005 and 0.05 were synthesized by the acetate variant of the sol-gel method. The structural parameters, particle size, and morphology are strongly dependent on the Ce³⁺ content. From these powders, dense ceramics were prepared by conventional sintering at 1300 °C for 2 h, as well as by spark plasma sintering at 1050 °C for 2 min. For the conventionally sintered ceramics, the XRD data and the dielectric and hysteresis measurements reveal that at room temperature, the specimen with low cerium content (x = 0.005) was in the ferroelectric state, while the samples with significantly higher Ce³⁺ concentration (x = 0.05) were found to be in the proximity of the ferroelectric–paraelectric phase transition. The sample with low solute content after spark plasma sintering exhibited insulating behavior, with significantly higher values of relative permittivity and dielectric losses over the entire investigated temperature range relative to the conventionally sintered sample of similar composition. The spark-plasma-sintered Ce-BaTiO₃ specimen with high solute content (x = 0.05) showed a fine-grained microstructure and an almost temperature-independent colossal dielectric constant which originated from very high interfacial polarization. Full article

In this work, thin SiO₂ insulating layers were generated on the top and bottom surfaces of single-crystalline silicon plates (n type) by thermal oxidation to obtain an insulator/semiconductor/insulator (ISI) multilayer structure. X-ray diffraction (XRD) pattern and scanning electron microscope (SEM) pictures implied that all of the synthesized SiO₂ layers were amorphous. By controlling the thermal oxidation times, we obtained SiO₂ layers with various thicknesses. The dielectric properties of silicon plates with different thicknesses of SiO₂ layers (different thermal oxidation times) were measured. The dielectric properties of all of the single-crystalline silicon plates improved greatly after thermal oxidation. The dielectric constant of the silicon plates with SiO₂ layers was approximately 10⁴, which was approximately three orders more than that of the intrinsic single-crystalline silicon plate (11.9). Furthermore, both high permittivity and low dielectric loss (0.02) were simultaneously achieved in the single-crystalline silicon plates after thermal oxidation (ISI structure). Full article