Gold-Nanoparticle-Deposited TiO2 Nanorod/Poly(Vinylidene Fluoride) Composites with Enhanced Dielectric Performance.

Flexible dielectric polymer composites have been of great interest as embedded capacitor materials in the electronic industry. However, a polymer composite has a low relative dielectric permittivity (ε' < 100), while its dielectric loss tangent is generally large (tanδ > 0.1). In this study, we fabricate a novel, high-permittivity polymer nanocomposite system with a low tanδ. The nanocomposite system comprises poly(vinylidene fluoride) (PVDF) co-filled with Au nanoparticles and semiconducting TiO2 nanorods (TNRs) that contain Ti3+ ions. To homogeneously disperse the conductive Au phase, the TNR surface was decorated with Au-NPs ~10-20 nm in size (Au-TNRs) using a modified Turkevich method. The polar ß-PVDF phase was enhanced by the incorporation of the Au nanoparticles, partially contributing to the enhanced ε' value. The introduction of the Au-TNRs in the PVDF matrix provided three-phase Au-TNR/PVDF nanocomposites with excellent dielectric properties (i.e., high ε' ≈ 157 and low tanδ ≈ 0.05 at 1.8 vol% of Au and 47.4 vol% of TNRs). The ε' of the three-phase Au-TNR/PVDF composite is ~2.4-times higher than that of the two-phase TNR/PVDF composite, clearly highlighting the primary contribution of the Au nanoparticles at similar filler loadings. The volume fraction dependence of ε' is in close agreement with the effective medium percolation theory model. The significant enhancement in ε' was primarily caused by interfacial polarization at the PVDF-conducting Au nanoparticle and PVDF-semiconducting TNR interfaces, as well as by the induced ß-PVDF phase. A low tanδ was achieved due to the inhibited conducting pathway formed by direct Au nanoparticle contact.

Effects of Charge Compensation on Colossal Permittivity and Electrical Properties of Grain Boundary of CaCu3Ti4O12 Ceramics Substituted by Al3+ and Ta5+/Nb5.

The effects of charge compensation on dielectric and electrical properties of CaCu3Ti4-x(Al1/2Ta1/4Nb1/4)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 CaCu3Ti4-x(Al1/2Ta1/4Nb1/4)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 CaCu3Ti4-x(Al1/2Ta1/4Nb1/4)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.

Significantly Enhanced Dielectric Properties of Ag-Deposited (In1/2Nb1/2)0.1Ti0.9O2/PVDF Polymer Composites.

The enhanced dielectric permittivity (ε') while retaining a low loss tangent (tanδ) in silver nanoparticle-(In1/2Nb1/2)0.1Ti0.9O2/poly(vinylidene fluoride) (Ag-INTO/PVDF) composites with different volume fractions of a filler (fAg-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 fAg-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 fAg-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.

Colossal dielectric permittivity, reduced loss tangent and the microstructure of Ca1-x Cd x Cu3Ti4O12-2y F2y ceramics.

Ca1-x Cd x Cu3Ti4O12-2y F2y (x = y = 0, 0.10, and 0.15) ceramics were successfully prepared via a conventional solid-state reaction (SSR) method. A single-phase CaCu3Ti4O12 with a unit cell ∼7.393 Šwas detected in all of the studied ceramic samples. The grain sizes of sintered Ca1-x Cd x Cu3Ti4O12-2y F2y ceramics were significantly enlarged with increasing dopant levels. Liquid-phase sintering mechanisms could be well matched to explain the enlarged grain size in the doped ceramics. Interestingly, preserved high dielectric permittivities, ∼36 279-38 947, and significantly reduced loss tangents, ∼0.024-0.033, were achieved in CdF2 codoped CCTO ceramics. Density functional theory results disclosed that the Cu site is the most preferable location for the Cd dopant. Moreover, F atoms preferentially remained close to the Cd atoms in this structure. An enhanced grain boundary response might be a primary cause of the improved dielectric properties in Ca1-x Cd x Cu3Ti4O12-2y F2y ceramics. The internal barrier layer capacitor model could well describe the colossal dielectric response of all studied sintered ceramics.

Enhanced dielectric properties with a significantly reduced loss tangent in (Mg2+, Al3+) co-doped CaCu3Ti4O12 ceramics: DFT and experimental investigations.

CaCu3Ti4O12 and CaCu2.95Mg0.05Ti3.95Al0.05O12 ceramics were fabricated via a solid-state reaction method. A single-phase of CaCu3Ti4O12 was found in these two ceramics. Very great grain size expansion was produced by co-doping with Mg2+ and Al3+. DFT results indicate that both Mg and Al atoms preferentially occupy Cu sites, creating liquid-phase sintering decomposition at grain boundary layers. Very high dielectric permittivity of ∼58 397 and low loss tangent of about 0.047 were achieved in a CaCu2.95Mg0.05Ti3.95Al0.05O12 ceramic. Additionally, the temperature stability of the dielectric response was improved. Better dielectric properties in the co-doped ceramic have possible origins from enhanced grain boundary responses, especially from the influences of metastable phases and oxygen enrichment at the grain boundaries. Experimental and computational results indicate that the colossal dielectric properties in CaCu3Ti4O12 ceramics might be correlated with an internal barrier layer capacitor structure.