Decrease of dielectric loss in giant dielectric constant CaCu3 Ti4 O12 ceramics by adding CaTiO3

CaCu₃ Ti₄ O₁₂–x CaTiO₃ ceramics (x=0,0.1,0.2,0.3,0.4 and 0.5) was studied by X-ray diffraction, scanning electron microscope and dielectric measurements. It was indicated that some CaTiO₃ entered the boundaries of CaCu₃ Ti₄ O₁₂ grains and/or subgrains. Dielectric measurement showed that the addition of CaTiO₃ lowered the dielectric loss remarkably, especially at low frequencies, while the giant dielectric constant still remained. At room temperature, the dissipation factor of the x=0.5 sample was decreased to 0.02 over the frequency range from 50 to 2000 Hz, and the dielectric constant was kept to be 4000. We explain this phenomenon in terms of internal barrier layer capacitance model by using the impedance spectroscopy analysis.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

Effect of phosphorus addition on the sintering and dielectric properties of Pb(Zr0.52Ti0.48)O3

It has been found that the sintering temperature of piezoelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) can be reduced by phosphorus addition without compromising the dielectric properties. A sintered density of 98.6% of the theoretical density was obtained for 2 wt.% P₂O₅ addition after sintering at 1050 °C for 4 h. The P₂O₅ addition, either above or below 2 wt.%, showed an inferior densification. Coincidentally, the P₂O₅ addition gave rise to a lower lead loss, and the dielectric constant showed a peak at 1 wt.% P₂O₅ addition.     

Phase transition characteristics and dielectric properties of rare-earth (La,Pr, Nd,Gd) doped Ba(Zr0.09Ti0.91)O3 ceramics

A-site deficient rare-earth doped barium zirconate titanate (BZT) ceramics (Ba_1−yLn_2y/3)Zr_0.09Ti_0.91O₃ (Ln = La, Pr, Nd, Gd) are obtained by a modified solid-state reaction method. Perovskite-like single-phase compounds were confirmed from X-ray diffraction data. Morphological analysis on sintered samples shows that the addition of rare-earth ions inhibits the growth of the grain and remarkably changes the grain morphology. The effect of rare-earth addition to BZT on phase transition and dielectric properties is analyzed. A dramatic fall in the transition temperature occurs when BZT ceramic is doped with rare-earths. Moreover, diffusivity degree of the phase transition increases and a relaxor-type behaviour is induced due to both the increment of the lanthanide content and the increase of the ionic radius of the dopant element. High values of dielectric tunability are obtained for lanthanum doped BZT. A direct relation between transition temperature and tunability is discussed. Conclusively, low permittivity and high tunability materials can be obtained by the adequate substitution of rare-earths into BZT ceramics.     

Crystallographic and dielectric properties of barium-substituted Pb(Mg1/3Ta2/3)O3 ceramics

Ceramic powders of (Ba,Pb)Pb(Mg_1/3Ta_2/3)O₃ were prepared via a B-site precursor route. Crystal symmetries and lattice parameters were determined. Monophasic perovskite was developed after the two-step reaction process, in which the lattice parameters showed linear changes in the entire composition range. Dielectric responses of the ceramics with compositional and frequency changes were investigated. The results were also compared with the (Ba,Pb)(Zn_1/3Ta_2/3)O₃ data.     

Effects of grain boundary on dielectric properties in fine-grained BaTiO3 ceramics

BaTiO₃ dielectric ceramics, which have no core–shell structure, were prepared. High-resolution transmission electron microscope (TEM) and the newly developed chemical etching analysis revealed the composition of the grain boundary. The grain boundary has an important role in stabilizing temperature dependence of a dielectric constant. The grain boundary causes a large stress against grains, resulting in a change of the domain structure. So, the stress from the grain boundary is considered to depress the dielectric abnormality at the Curie temperature.     

Comparative investigation of structure and dielectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) and 10% PbZrO3-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) ceramics prepared by a modified precursor method

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) and 10% PbZrO₃-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics were both prepared by a modified precursor method, which was based on the high-temperature synthesis of an oxide precursor that contained all the B-site cations for the consideration of B-site homogeneity. The dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramic was more of normal ferroelectric behavior, but the high dielectric constant (?_m = 34,200 at 1 kHz) and piezoelectric constant (d₃₃ = 709 pC/N) were observed for this composition close to the morphotropic phase boundary. Comparatively, introduction of 10% PbZrO₃ into Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics enhanced the diffuse phase transition as well as the rhombohedral to tetragonal phase transition temperature, while it also kept the high dielectric constant (?_m = 29,600 at 1 kHz) and piezoelectric constant (d₃₃ = 511 pC/N).     

Effect of temperature on nonlinear electrical behavior and dielectric properties of (Ca, Ta)-doped TiO2 ceramics

TiO₂ ceramics doped with 0.75 mol% Ca and 2.5 mol% Ta were sintered at different temperatures ranging from 1300 to 1450°C. The effects of sintering temperature on the microstructure, nonlinear electrical behavior, and dielectric properties of the ceramics were studied. The sample sintered at 1300°C exhibits the highest nonlinear coefficient (5.5) and a comparatively lower relative dielectric constant.     

Thickness effect on electrical properties of Pb(Zr0.52Ti0.48)O3 thick films embedded with ZnO nanowhiskers prepared by a hybrid sol-gel route

Silicon-based lead zirconate titanate thick films embedded with zinc oxide nanowhiskers (ZnO_w-PZT) were prepared by a hybrid sol-gel route. ZnO_w-PZT films with thickness from 1.5 μm to 4 μm are perovskite structure and have smooth surface without any cracks. As the thickness increases, the remanent polarization and dielectric constant increase, but the coercive field and tetragonality decrease. Compared with PZT films, the ZnO_w-PZT film has the close tetragonality and electrical properties which are different from those of bulk PZT-based ceramic doped with ZnO powder. The thickness dependences of the ferroelectric and dielectric properties are attributed to the relaxation of internal stress.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Synthesis, characterization, and dielectric properties of Ba(Ti1−xSnx)O3 nanopowders and ceramics

We prepared Ba(Ti_1−xSn_x)O₃ powders and ceramics by means of the sol-gel process, with dibutyltin dilaurate as the Sn precursor. The samples were characterized by means of Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy, and also determined the dielectric properties of the ceramics. The powders synthesized by means of the sol-gel process had a grain size on the nanometer scale, with the grains mainly composed of a cubic BaTiO₃ phase. Sn can disperse into BaTiO₃ more uniformly in the sol-gel technique using dibutyltin dilaurate as the Sn precursor. With increasing Sn concentration, the grain size of the Ba(Ti_1-xSn_x)O₃ ceramics increased and the maximum dielectric constant (?_max) first increased and then decreased. At a Sn concentration of 5 mol%, ?_max reached its maximum value (19,235).     

Enhanced dielectric,ferroelectric and optical properties of lead free (K0.17Na0.83)NbO3 ceramic with WO3 addition

Polycrystalline lead-free ceramics (K_0.17Na_0.83)NbO₃ + x wt.% WO₃; (x = 0, 1, 3 and 5) have been synthesized via solid state reaction method. X-ray diffraction pattern at room temperature indicates the formation of pure perovskite phase with monoclinic structure for all samples. Dielectric constant versus temperature measurements shows an increase in dielectric constant with a shift in Curie temperature (T_C) toward higher temperature side. Remnant polarization (P_r) is found to be enhanced and reached upto 24 μC/cm² for x = 5 wt.% WO₃ from 12.5 μC/cm² for pure (K_0.17Na_0.83)NbO₃ ceramic. The value of coercive field (E_c) decreases with increasing wt.% of WO₃. From optical band gap study, we found blue shift in the band gap of (K_0.17Na_0.83)NbO₃ with increasing concentration of WO₃.     

Effects of Mn doping on the structure and electrical properties of high-temperature BiScO3-PbTiO3-Pb(Zn1/3Nb2/3)O3 piezoelectric ceramics

The effects of Mn addition on the structure, ferroelectric, and piezoelectric properties of the 0.35BiScO₃-0.60PbTiO₃-0.05Pb(Zn_1/3Nb_2/3)O₃ ceramics were studied. The results demonstrate that the addition of small amounts of Mn did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure and ferro-piezoelctric properties. The addition of Mn can induce combinatory “hard” and “soft” piezoelectric characteristics due to aliovalent substitutions. The optimal electrical properties are obtained in the 0.25 mol% Mn-doped composition with a high Curie temperature, indicating that Mn doping contributes to the electrical properties of the ceramics. It can be expected that the improved piezoelectric material can be a promising candidate for high-temperature piezoelectric applications.     

Microwave dielectric properties of La1−xBix(Mg0.5Sn0.5)O3 ceramics

The La_1−xBi_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Bi_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. An apparent density of 6.50 g cm⁻³, a dielectric constant (?_r) of 20.2, a quality factor (Q × f) of 58,100 GHz and a temperature coefficient of resonant frequency (τ_f) of −84.2 ppm °C⁻¹ were obtained for La_0.97Bi_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Stoichiometric Pb(Mg1/3Nb2/3)O3 perovskite ceramics produced by reaction-sintering process

Stoichiometric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), perovskite ceramics produced by reaction-sintering process were investigated. Without calcination, a mixture of PbO, Nb₂O₅, and Mg(NO₃)₂ was pressed and sintered directly. Stoichiometric PMN ceramics of 100% perovskite phase were obtained for 1, 2, and 4 h sintering at 1250 and 1270 °C. PMN ceramics with density 8.09 g/cm³ (99.5% of theoretical density 8.13 g/cm³) and K_max 19,900 under 1 kHz were obtained.     

Electrical properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics modified with WO3

Ferroelectrics 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) + x mol% WO₃ (x=0.1, 0.5, 1, 2) were prepared by columbite precursor method. Electrical properties of WO₃-modified ferroelectrics were investigated. X-ray diffraction (XRD) was used to identify crystal structure, and pyrochlore phase were observed in 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃+2 mol% WO₃. Dielectric peak temperature decreased with WO₃ doping, indicating that W⁶⁺ incorporated into PMN-PT lattice. Lattice constant, pyrochlore phase and grain size contribute to the variation of K_max. Both piezoelectric constant (d₃₃) and electromechanical coupling factors (k_p) were enhanced by doping 0.1 mol% WO₃, which results from the introduction of “soft” characteristics into PMN-PT, while further WO₃ addition was detrimental. We consider that the two factors, introduction of “soft” characteristics and the formation of pyrochlore phase, appear to act together to cause the variation of piezoelectric properties of 0.67PMN-0.33PT ceramics doping with WO₃.     

Development of perovskite in Fe-substituted Pb(Zn1/3Ta2/3)O3 and dielectric characteristics

Pb(Zn_1/3Ta_2/3)O₃ ceramics, compositionally modified by the incorporation of Fe to the octahedral lattice sites, were prepared and characterized in terms of perovskite development, dielectric properties, as well as microstructure evolution. The powders of the B-site precursor compositions were synthesized separately and reacted with PbO to form Pb[(Zn_1/3Ta_2/3),(Fe_1/2Ta_1/2)]O₃. The perovskite contents increased continuously with the Fe concentration. The maximum dielectric constant values of the ceramics increased tremendously with the fraction of Fe, whereas the dielectric maximum temperatures were rather insensitive to the compositional change.     

Role of La0.5Sr0.5CoO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO₂/Si substrates. The films were initially grown at 300 °C using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 °C to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 °C. Films with highest perovskite content were found to form at 820-840 °C on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La_0.5Sr_0.5CoO₃ (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 °C. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan δ) of 0.035 at a frequency of 1 kHz at room temperature.     

Microstructures and dielectric properties of CaTiO3–LaSrAlO4 composite ceramics

The microstructures and dielectric properties of xCaTiO₃/(1−x)LaSrAlO₄ composite ceramics were investigated. CaTiO₃ and LaSrAlO₄ could co-exist when the content of CaTiO₃ was no more than 30 mol%, while LaAlO₃ and CaO phases were observed in the composite ceramics with higher CaTiO₃ content. The dielectric constant of the composite ceramics increased with increasing the additive content, and the dielectric loss generally increased with increasing the additive content because of the presence of phase boundary and the high dielectric loss of the minor phases. The temperature coefficient of dielectric constant decreased with increasing the additive content firstly, and then it increased abnormally when x equals to 40 mol%, finally it decreased with increasing the additive content further. The dielectric properties predicted from serial formula were most close to those obtained from experiment among the classical dielectric mixture rules.