Microwave dielectric properties of temperature stable Ca5A2Ti1−x Hf x O12 (A = Nb, Ta) ceramics

Ca₅A₂Ti_1−xHf_xO₁₂ (A = Nb, Ta) ceramics have been prepared as single-phase materials by conventional solid-state ceramic route. Their structure and microstructure were studied by X-ray diffraction and scanning electron microscopic methods and dielectric properties were characterised in the 4–6 GHz microwave frequency range. We observed an increase in cell volume and theoretical density with compositional variations. In Ca₅Nb₂Ti_1−xHf_xO₁₂ ceramics the dielectric constant varied from 48 to 22 and quality factor from 26000 to 16000 GHz whereas in Ca₅Ta₂Ti_1−xHf_xO₁₂ the variation in dielectric constant was from 38 to 17 and quality factor from 33000 to 18000 GHz with increase in x. In both the ceramic systems the temperature coefficient of resonant frequency shifted from positive to negative values with Hf ⁴⁺ substitution for Ti⁴⁺.     

Effect of La3+ substitution on microwave dielectric properties of (Pb0.5Ca0.5)(Fe0.5Nb0.5)O3 ceramics

Microwave dielectric properties of the [(Pb_0.5Ca_0.5)_1?x La_2x/3](Fe_0.5Nb_0.5)O₃ and [(Pb_0.5Ca_0.5)_1?x La _x ](Fe_0.5Nb_0.5)O₃ ceramics were investigated as a function of La³⁺ content $ {\left( {0.0 \leqslant \times \leqslant 0.2} \right)} $ . A single perovskite phase was detected in [(Pb_0.5Ca_0.5)_1?x La_2x/3](Fe_0.5Nb_0.5)O₃, while Pb₃Nb₄O₁₃ were detected as a secondary phase in [(Pb_0.5Ca_0.5)_1?x La _x ](Fe_0.5Nb_0.5)O₃ beyond x?=?0.05 due to the excess of unbalanced charge. The amount of Pb₃Nb₄O₁₃ was proportional to the unbalanced charge. Qf value of [(Pb_0.5Ca_0.5)_1?x La_2x/3](Fe_0.5Nb_0.5)O₃ decreased remarkably with La³⁺ substitution due to the increase of oxygen vacancy. For [(Pb_0.5Ca_0.5)_1?x La _x ](Fe_0.5Nb_0.5)O₃ ceramics, dielectric constant and Qf value increased with La³⁺ content up to x?=?0.03 due to an increase of density and grain size. Temperature coefficient of resonant frequency (TCF) was depended on B-site bond valence in single perovskite phase.     

Effect of Temperature on the Elastic and Anelastic Behaviour of Magneto-Ferroelectric Composites Ba0.8Pb0.2TiO3 + Ni0.93Co0.02Mn0.05Fe1.95O4-δ in the Ferroelectric Rich Region

Composites with composition xBa_0.8Pb_0.2TiO₃+ (1 –x) Ni_0.93Co_0.02Mn_0.05Fe_1.95O_4- in which x varies as 1.0, 0.9, 0.7 and 0.5 in molar percent have been prepared by the conventional ceramic double sintering process. The presence of the two phases has been confirmed by X-ray diffraction. These composites were prepared for their use as magnetoferrolectric devices. Variation of longitudinal modulus (L) and internal friction loss (Q ^–1) of these samples with temperature at 142 kHz has been studied in the wide temperature range 300 to 630 K. The elastic behaviour (L) showed a break at the ferroelectric Curie temperature (498 K) in the case of pure ferroelectric material (Ba_0.8Pb_0.2TiO₃). This break shifted to lower temperature side as the ferrite component increases in the composite. The temperature variation of internal friction loss (Q ^–1) showed a corresponding stress induced relaxation peak at the ferroelectric-non-ferroelectric phase transition. This behaviour is explained in the light of structural phase transition.     

Ferroelectric properties of heterolayered lead zirconate titanate thin films

Heterolayered Pb(Zr_{1 − x} Ti _x )O₃ thin films consisting of alternating PbZr_0.7Ti_0.3O₃ and PbZr_0.3Ti_0.7O₃ layers were successfully deposited via a multistep sol-gel route assisted by spin-coating. These heterolayered PZT films, when annealed at a temperature in the range of 600–700^∘C show (001)/(100) preferred orientation, demonstrate desired ferroelectric and dielectric properties. The most interesting ferroelectric and dielectric properties were obtained from the six-layered PZT thin film annealed at 650^∘C, which exhibits a remanent polarization of 47.7 μC/cm² and a dielectric permittivity of 1002 at 100 Hz. Reversible polarization constituents a considerably high contribution towards the ferroelectric hysteresis of the heterolayered PZT films, as shown by studies obtained from C-V and AC measurement.     

Substrate effect on in-plane ferroelectric and dielectric properties of Ba0.7Sr0.3TiO3 thin films

Heteroepitaxial Ba_0.7Sr_0.3TiO₃ thin films were grown on (LaAlO₃)_0.3(Sr₂AlTaO₆)_0.35 (001) (LSAT) and SrTiO₃ (001) (STO) single crystal substrates using pulsed laser deposition (PLD). X-ray diffraction characterization revealed a good crystallinity and a pure perovskite structure for films grown on both LSAT and STO substrates. The in-plane ferroelectric and dielectric properties of the films were studied using interdigital electrodes (IDE). The film grown on LSAT substrate exhibited an enhanced in-plane ferroelectricity, including a well-defined P-E hysteresis loop with the remnant polarization P _r = 10.5 μC/cm² and a butterfly-shaped C-V curve. Nevertheless, only a slim hysteresis loop was observed in the film grown on STO substrate. Curie temperature T _c of the film grown on LSAT substrate was found to be ∼105^∘C, which is nearly 70^∘C higher than that of the bulk Ba_0.7Sr_0.3TiO₃ ceramics. T _c of the film grown on STO substrate has almost no change compared to the bulk Ba_0.7Sr_0.3TiO₃ ceramics. The dielectric tunabilities were found to be 64% and 52% at 1 MHz for the films grown on LSAT and STO substrates, respectively.     

Ferroelectric and Pyroelectric Properties of Sol-Gel Derived PbCaTiO3 Thin Films Using Low-Temperature Annealing

PCT7030 (Pb_0.7Ca_0.3TiO₃, PCT7030) films have been prepared by a sol-gel method on platinum-coated Si substrate. PCT7030 films were treated at different radiation densities using CO₂ laser annealing to obtain good ferroelectric properties without causing thermal deterioration of the underlying layer. In addition, metallic oxide LaSrMnO₃ buffer layer was employed to improve the electrical properties of PCT7030 films. From XRD measurements, we found that fully perovskite phase of PCT7030 films could be obtained at a radiation density below 572 W/cm². On the other hand, perovskite phase of PCT7030 films with co-existing TiO_x were observed for specimens treated at a higher radiation density. The correspondent P-E curves of PCT7030 films with entirely perovskite phase exhibited saturated hysteresis loops and the specimens possessing perovskite PCT7030 and co-existing TiO_x phase showed serious leakage. Microstructural investigations imply that grain size increases with increasing radiation density, and voids may evolve on the grain boundaries when high radiation density was employed, indicating that atomic species evaporation of PCT7030 films or coarsening-induced voids may be produced at an over-annealing condition and therefore electrical properties were deteriorated. In the pyroelectric measurement, pyroelectric coefficient of CO₂ laser-annealed PCT7030 films varied as a function of calcium content and a pyroelectric coefficient maximum were obtained at a composition near PCT7030, indicating that low temperature laser-annealing process can be employed in ferroelectric and pyroelectric thin film preparation.     

Conductivity and expansion at high temperature in Sr0.7La0.3TiO3−α prepared under reducing atmosphere

Sr_0.7La_0.3TiO_3−α specimens were prepared in reducing atmosphere, and the structural and electrical properties were studied. The lattice parameter of Sr_0.7La_0.3TiO_3−α at room temperature was larger than that expected from Vegard’s law between SrTiO₃ and LaTiO₃ due to the reductive expansion. The conductivity of this specimen was 100 S cm⁻¹ at 1000°C, p_O2 = 10⁻¹³ Pa. However, the conductivity was not preserved after an oxidation-reduction cycle. Over p_O2 = 10² Pa, the conductivity drastically dropped with increasing p_O2. The thermal expansion coefficient of Sr_0.7La_0.3TiO_3−α was 11.8 × 10⁻⁶ K⁻¹ in 9% H₂/N₂ (room temperature – 1000°C). In this Sr_0.7La_0.3TiO_3−α, the chemical expansion on oxidation reached Δl/l_o = 0.51%, when changing p_O2 from 10⁻¹¹ Pa to 2 × 10⁴ Pa (air) at 1000°C.     

Acoustic properties of PLZT ceramics studied by Brillouin scattering

Brillouin spectra of lanthanum lead zirconate titanate (Pb_1−x La_x)(Zr_yTi_1−y )O₃ (PLZT-100(x/y/1−y)) relaxor ferroelectric ceramics with the famous composition of PLZT-10/65/35 have been investigated using a high-resolution Brillouin spectroscopy. The central peak of PLZT-10/65/35 appeared below ∼600 K, which is similar to the Burns temperature. The integrated intensity of the central peak grew on cooling and reached its maximum value at around 370 K, which is higher than the dielectric maximum temperatures. The overall shape and width of central peaks did not change in the electric field range of 0–7 kV/cm at room temperature. These observations were discussed in relation with the dynamics of nano-sized polar clusters, which have been suggested as the origin of the complex dynamical behaviors of ferroelectric relaxors.     

Synthesis and sintering properties of (La0.8Ca0.2−x Sr x )CrO3 perovskite materials for SOFC interconnect

Synthesis and sintering properties of the (La_0.8Ca_0.2−x Sr _x )CrO₃ samples doped by two alkaline earth metals in comparison to the doped only by one alkaline earth metal were evaluated by phase analysis, sintering properties, thermal expansion behaviors, and electrical conductivity. The sintered (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, and 0.1) and (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0.2) were found to have orthorhombic and rhombohedral symmetries, respectively. Relative density of the (La_0.8Sr_0.2)CrO₃ sample sintered at 1500^∘C for 5 h was lower than that of the (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, and 0.1) sample. TECs of the (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, 0.1, and 0.2) in air were 11 × 10⁻⁶/^∘C, 11.2 × 10⁻⁶/^∘C, 11.2 × 10⁻⁶/^∘C, and 11.3 × 10⁻⁶/^∘C, respectively. The electric conductivity of the (La_0.8Ca_0.2−x Sr _x )CrO₃ sample was determined.     

Preparation of sol-gel-derived Ca1−x Sr x ZrO3 perovskite dielectric thin films

The sol-gel wet chemical synthesis of dielectric thin films of perovskite Ca_1−x Sr _x ZrO₃ has been studied in detail using different techniques. To the best of our knowledge, it is the first time in the literature to systemically study the properties of Ca_1−x Sr _x ZrO₃ dielectric thin films in the whole solid solution composition range. Based on X-ray diffraction (XRD), Flourier transform infrared (FT-IR) reflectivity spectroscopy and atomic force microscope (AFM) data, the mechanisms of Ca_1−x Sr _x ZrO₃ phase transformation and crystallinity have been investigated. The results show that the film annealed at 550 °C is amorphous with existing of carbonates, while the carbonates and other organics are decomposed at 600 °C and above, and the film is crystallized into the perovskite phase with increasing annealing temperature. The values of dielectric constant in a range of 16–30 for Ca_1−x Sr _x ZrO₃ thin films have been obtained. Measured dielectric properties show that those films exhibit stable dielectric properties nearly independent on the applied electrical field and frequency at room temperature. Based on above data, it can be concluded that Ca_1−x Sr _x ZrO₃ thin films are a promising candidate system for the high-k microelectronic devices application.     

Origin of giant dielectric response in ferroelectric thin film multilayers

Abstract

A thermodynamic theory of dielectric response in ferroelectric thin film multilayers is developed. The solution of Lame equation for static dielectric susceptibility has shown that susceptibility diverges at the transition temperature of the thickness induced ferroelectric phase. This divergence is shown to be the origin of the giant dielectric response observed in some multilayers. The theory gives an excellent fit to the temperature dependence of the giant susceptibility observed recently in multilayers of PbTiO₃-Pb_1-xLa_xTiO₃ (x = 0.28).     

Ionic Doping Effects in SrBi2Nb2O9 Ferroelectric Ceramics

Ionic doping effects of various ions in Bi-layered ferroelectric SrBi₂Nb₂O₉ (SBN) ceramics were studied. Un-doped and doped SBN ceramics with Ba²⁺, Pb²⁺, Ca²⁺, Bi³⁺, La³⁺, Ti⁴⁺, Mo⁶⁺, and W⁶⁺ ions were made with solid state reactions. Temperature dependent dielectric constants were measured. Ferroelectric transition temperature (T_C) decreased with Ba²⁺ and Pb²⁺ ions but increased with Ca²⁺ ion which substitutes the 12-coordinated Sr²⁺ site. T_C increased with Ti⁴⁺, Mo⁶⁺, and W⁶⁺ ions which substitute the 6-coordinated Nb⁵⁺ sites. With trivalent Bi³⁺ and La³⁺ ions, T_C increased with Bi³⁺ ion but much decreased with La³⁺ ion. These results showed that the ion size plays an important role in ferroelectricity of SBN ceramics.     

Phase transition and electrical studies of wolframium doped SrBi2Ta2O9 ferroelectric ceramics

In this study, crystalline structure, dielectric and impedance properties of SrBi₂Ta₂O₉ (SBT) - based ferroelectric ceramics have been investigated with the substitution of wolframium/tungsten (W) onto the tantalum site. Wolframium doped SrBi₂(W _x Ta_{1 − x} )₂O₉ (0.0 ≤ x ≤ 0.20) ceramics were synthesized by solid state reaction method. The X-ray diffractogram analysis revealed that the substitution formed a single phase layered perovskite structure for the doping content up to x ≤ 0.05. The dielectric measurements as a function of temperature show an increase in Curie temperature (T _c ) over the composition range of x = 0.05 to 0.20. The W^{6 +} substitution in perovskite-like units results in a sharp dielectric anomaly at the ferroelectric phase transition. Furthermore, the dielectric constant at their respective Curie temperature increases with wolframium doping. Both enhanced Curie temperatures and dielectric constants at the Curie points indicate an increase in polarizability, which could be attributed to the increased “rattling space” due to the incorporation of the smaller tungsten cations. The dielectric loss reduces significantly with tungsten addition. AC impedance properties vis-à-vis wolframium content has also been studied.     

Dielectric Properties of Bi4−x La x Ti3O12 (0 ≤ x ≤ 2) Ceramics

The dielectric properties of the Bi_4–x La _x Ti₃O₁₂ (0 x 2) ceramics were characterized and discussed together with the P-E relation (polarization vs. electric field). With increasing x, the P-E relation changed from normal ferroelectric hysteresis loops to pure linear relation, which indicated that La³⁺ substitution for Bi³⁺ in Bi₄Ti₃O₁₂ induced a phase transition from ferroelectric to paraelectric state at ambient temperature. Low loss dielectric ceramics with temperature stable dielectric constant were obtained for x > 1.2 in Bi_4–x La _x Ti₃O₁₂ at 1 MHz. And the loss increased in all the compositions when the ceramics were measured at microwave frequencies.     

Diffuse Dielectric Anomaly in Ferroelectric Materials

It has not been clear whether the diffuse dielectric anomaly by Debye-type dielectric relaxation is extrinsic or intrinsic in origin although it has been frequently found in ferroelectric materials regardless of their structures and ferroelectric properties. We experimentally investigated the extrinsic nature of the diffuse dielectric anomaly in ferroelectric oxides and sulfide such as BaTiO₃, Pb_0.9La_0.1TiO₃, and SnP₂S₆. The advanced fitting method using the modified Debye relaxation equation was introduced in order to explain the temperature dependent behavior of the diffuse dielectric anomaly. It was confirmed that the diffuse dielectric anomaly was a competitive phenomenon between the dielectric relaxation and the electrical conduction of the relaxing species. It was also proved that the activation energy of the dielectric relaxation should be always higher than the conductivity activation energy of the relaxing species in the diffuse dielectric anomaly.     

Dielectric and Mechanical Losses in (Ba,Sr)TiO3 Systems

In the application of tuneable microwave devices of ferroelectric (BaSr)TiO₃ systems the two critical parameters needed for optimal device performance are high tunability and low dielectric loss. The dielectric loss of the materials is strongly dependent on microstructure. This paper is concerned with an investigation of the variation in the dielectric and mechanical losses in Ba _x Sr_{1 – x} TiO₃ systems (x = 0.5, 0.6, 0.7 and 1.0) with microstructure (grain sizes from 1 m to 50 m). The magnitude of the loss peak and sharpness of the anomaly in the dielectric constant/elastic modulus observed for the phase transitions in Ba _x Sr_{1 – x} TiO₃, depend not only on the composition and but also on the grain size. A relaxation peak has been observed in large grain material, which is indication of interactions between different configurations of domain walls and the diffusion of oxygen vacancies in the domains.     

Morphotropic phase boundary and electrical properties of lead-free bismuth sodium lanthanum titanate—barium titanate ceramics

The important properties of lead-free piezoelectric ceramics have been investigated from Bismuth Sodium Lanthanum Titanate and Barium Titanate system: (1 − y)(Bi_0.5Na_0.5)_{(1 − 1.5x)}La _x TiO₃(BNLT)—yBaTiO₃(BT) where x = 0.017 and y = 0 − 0.2, respectively. The morphotropic phase boundary (MPB) was found to be around y = 0.1 by the x-ray diffraction and dielectric measurement at various amount of BT. The temperature dependence of dielectric constant (ε _r ) at various value of y showed the diffuse phase transition exhibiting the relaxor type ferroelectrics. The degree of diffuseness increased at a high doping content of about y = 0.15 where the second phase transition (T₂) of the ferroelectric to antiferroelectric phase disappeared. Moreover, this sample had the maximum piezoelectric coefficient (d ₃₃) of about 112 pC/N with relatively low dielectric constant. The optimum sintering temperatures and the microstructures of the dense BNLT-BT ceramics were also examined.     

Dielectric properties and morphotropic phase boundaries in the xPb(Zn1/3Nb2/3)O3−(1−x)Pb(Zr0.5Ti0.5O3 pseudo-binary system

Ceramics in the xPb(Zn_1/3Nb_2/3)O₃−(1−x)Pb(Zr_0.5Ti_0.5)O₃ [xPZN–(1−x)PZT] solid solution system are expected to display excellent dielectric, piezoelectric, and ferroelectric properties in compositions close to the morphotropic phase boundary (MPB). The dielectric behavior of ceramics with x = 0.1−0.6 has been characterized in order to identify the MPB compositions in this system. Combined with X-ray diffraction results, ferroelectric hysteresis measurements, and Raman reflectivity analysis, it was consistently shown that an MPB exists between x = 0.2 and x = 0.3 in this binary system. When x ≤ 0.2, the tetragonal phase dominates at ambient temperatures. In the range of x ≥ 0.3, the rhombohedral phase dominates. For this rhombohedral phase, electrical measurements reveal a profound frequency dispersion in the dielectric response when x ≥ 0.6, suggesting a transition from normal ferroelectric to relaxor ferroelectric between 0.5 ≤ x ≤ 0.6. Excellent piezoelectric properties were found in 0.3PZN–0.7PZT, the composition closest to the MPB with a rhombohedral structure. The results are summarized in a PZN–PZT binary phase diagram.     

Photoluminescence and ESR identification of γ-ray irradiation induced defects responsible for thermoluminescence in Tb<Superscript>3+</Superscript> activated hibonite (CaAl<Subscript>12</Subscript>O<Subscript>19</Subscript>) powder material

In this paper, we report the effect of Pb doping on the magnetic and magnetocaloric properties of La_0.7Ca_0.3-x Pb _x MnO₃ (0.15?≤?x?≤?0.3) polycrystalline samples. The samples were prepared by solid state synthesis method. X-ray diffraction patterns indicate that these samples have monoclinic structure with the Pc/2 space group. The magnetization measurements indicated that all samples exhibited a paramagnetic–ferromagnetic transition and the transition temperature increased with increasing of Pb concentration. Using phenomenological model, the magnetocaloric behavior of all the samples has been calculated based on the experimental magnetization data. Our results on the magnetocaloric properties suggest that the compound La_0.7Ca_0.15Pb_0.15MnO₃ is attractive as a possible material for magnetic refrigeration.     

Dielectric properties of (Ba1-2x Sr x Ca x )TiO3 ferroelectric ceramics

Ferroelectric ceramics of (Ba_1?2x Sr _x Ca _x )TiO₃ (0?≤?x?≤?0.30) were prepared by a routine solid-state reaction technique. Co-substitution of Sr²⁺ and Ca²⁺ for Ba²⁺ with equal mole in BaTiO₃ restrain the maximal dielectric constant K _m strongly when 0.2?≥?x?>?0. However, composition (Ba_0.4Sr_0.3Ca_0.3)TiO₃ shows the higher maximal dielectric constant. With increasing Sr and Ca content x, temperature T _m of the maximal dielectric constant K _m shifts to low temperature and all selected compositions for study exhibit a broad phase transition temperature range. The composition (Ba_0.4Sr_0.3Ca_0.3)TiO₃ presents characteristics of ferroelectric relaxor, value of K _m decreases and temperature T _m increases with increasing frequency.