Effect of the addition of B2O3 and BaO-B2O3-SiO2 glasses on the microstructure and dielectric properties of giant dielectric constant material CaCu3Ti4O12

The effect of the addition of glassy phases on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics was investigated. Both single-component (B₂O₃) and multi-component (30 wt% BaO-60 wt% B₂O₃-10 wt% SiO₂ (BBS)) glass systems were chosen to study their effect on the density, microstructure and dielectric properties of CCTO. Addition of an optimum amount of B₂O₃ glass facilitated grain growth and an increase in dielectric constant. However, further increase in the B₂O₃ content resulted in its segregation at the grain boundaries associated with a reduction in the grain size. In contrast, BBS glass addition resulted in well-faceted grains and increase in the dielectric constant and decrease in the dielectric loss. An internal barrier layer capacitance (IBLC) model was invoked to correlate the dielectric constant with the grain size in these samples.     

A novel microwave dielectric ceramic Ca2Zn4Ti16O38: Preparation and dielectric properties

A novel microwave dielectric powder with composition of Ca₂Zn₄Ti₁₆O₃₈ was synthesized through a citrate sol-gel process. The development of crystalline phases with heat-treating temperature for the gel derived powders was evaluated by using thermo-gravimetric analysis and X-ray powder diffraction analysis techniques. The pure phase of Ca₂Zn₄Ti₁₆O₃₈ with crichtonite crystal structure was obtained at relatively low temperature of 1000 °C. The synthesized powder has high reactivity and the dense ceramics with single crystalline phase were obtained at low sintering temperature of 1100 °C. Impedance spectroscopy and microwave dielectric measurements on sintered samples showed the present compound to be a modest dielectric insulator with excellent dielectric properties of ε_r∼47-49, Qf value ∼27,800-31,600 GHz and τ_f∼+45 to +50 ppm/°C. It shows comparable microwave dielectric properties to other moderate-permittivity microwave dielectrics, but much lower sintering temperature of 1100 °C.     

Effect of La3+ content on the properties of ferroelectric Bi4?xLaxTi3O12 (BLT) thin films prepared by aqueous chemical solution deposition

Lanthanum substituted bismuth titanate thin films were deposited using an aqueous chemical solution deposition method. Varying the composition of Bi_4−x La _x Ti₃O₁₂, with x = 0.5, 0.65, 0.75 and 0.85, is shown to have a large influence on the microstructure and properties of the films. Increasing the amount of La³⁺, x, from 0.5 to 0.85 led to a decrease of the remanent polarization (P _r) from 6.2 to eventually 0 μC/cm². This decrease of P _r is explained by means of X-ray diffraction (XRD) study, which shows that there is an increased preference for c-axis orientation upon increasing the La³⁺ concentration. Furthermore, a strong decrease of the grain size upon increasing x is observed in a scanning electron microscopic (SEM) study. The concurrent increase of domain pinning on the grain boundaries is a second effect which may be responsible for the deterioration of the ferroelectric property at larger x.     

Ferroelectric and dielectric properties of bismuth-layered structural Sr2Bi4−xLnxTi5O18 (Ln=La, Nd, Sm and Dy) ceramics

La, Nd, Sm, and Dy-doped Sr₂Bi₄Ti₅O₁₈ (SBTi) ceramic samples have been prepared by the solid-state reaction method. The X-ray diffraction reveals that all of the ceramic samples are single phase compounds. Their remnant polarization (2P_r) increases at first, and then decreases with the increase of doping content. When doping content is 0.01, Sm and Dy-doped SBTi samples exhibit the maximum 2P_r of 18.2 and 20.1 μC/cm², respectively. While La and Nd-doped SBTi samples display the maximum 2P_r value of 18.4 and 19.1 μC/cm² with doping content of 0.05 and 0.10, respectively. The ferroelectric properties of Sr₂Bi_4−xLn_xTi₅O₁₈ are found to be dominated by the competition of the decrease of oxygen vacancy concentration and the relief of structural distortion.     

Insights on the origin of the structural phase transition in BaV10O15 from electronic structure calculations and the effect of Ti-doping on its structure and electrical transport properties

Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV₁₀O₁₅ and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV_10−xTi_xO₁₅, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi₁₀O₁₅”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti²⁺ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10⁻³ emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T^1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T^1/2 law, was seen, in sharp contrast to BaV₁₀O₁₅ where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.