Effect of Al Doping on the Electric and Dielectric Properties of CaCu3Ti4O12

Al-doped CaCu₃Ti_{4− x} Al _x O_{12− x /2} (CCTO, x =0–0.1) ceramics were prepared by the solid-state reaction, and their electric and dielectric properties were investigated. Al doping has been shown to reduce the dielectric loss remarkably while maintaining a high dielectric constant. At x =0.06, the loss tangent (tan δ) was below 0.06 over the frequency range of 10²–10⁴ Hz, and the dielectric constant was 41 000 at 10 kHz. Impedance spectra indicated that Al doping increased the resistivity of the grain boundary by an order of magnitude. The improvement of the dielectric loss in Al-doped CCTO was attributed to the enhanced grain boundary resistivity.     

Structural and Dielectric Properties of Ag(Nb0.8Ta0.2)1−xSbxO3 (x≤0.08) Ceramics

Sb₂O₅ were selected to substitute (Nb_0.8Ta_0.2)₂O₅ and the effects of Sb substitution on the dielectric properties of Ag(Nb_0.8Ta_0.2)O₃ ceramics were studied. The perovskite Ag(Nb_0.8Ta_0.2)_{1− x} Sb _x O₃ ceramics showed no obvious change with x value being no more than 0.08, and the pseudoperovskite unit cell parameters a = c , b and monoclinic angle β decrease with Sb concentration increasing. The dielectric properties of Ag(Nb_0.8Ta_0.2)_{1− x} Sb _x O₃ ceramics were found to be affected greatly by the substitution of Sb for Nb/Ta. The ɛ value of Ag(Nb_0.8Ta_0.2)_{1− x} Sb _x O₃ ceramics sintered at their densified temperature increased from 480 to 825 with x from 0 to 0.08, the tan δ value decreased sharply from 0.0065 to 0.0023 (at 1 MHz) with x increasing from 0 to 0.04, and then kept a stable lower tan δ value ∼0.0024 with x to 0.08. The temperature coefficient of capacitance values continuously decreased from a positive value of 1450 ppm/°C for x =0 to a negative value of −38.52 ppm/°C for x =0.08.     

Effects of V Substitution on Dielectric and Polarization Properties for Sr0.5Bi2.25Na1.25(Nb3−xVx)O12 Ceramics

The effects of V substitution for Nb on the dielectric and polarization properties of Sr_0.5Bi_2.25Na_1.25(Nb_{3− x} V _x )O₁₂ ceramics were investigated in this study. From the X-ray powder diffraction results, no secondary phase was detected in the composition range of 0–0.075. The remanent polarizations ( P _r) of the samples in the composition range of 0–0.03 were improved by the V substitution for Nb and the highest P _r value of approximately 15 μC/cm² was obtained at x =0.03; it was noted that the V substitution for Nb was effective in improving the P _r values in this ceramics. On the other hand, the coercive fields ( E _c) of the samples were on the order of approximately 40 kV/cm in such a composition range. Moreover, the anomalous variations in the dielectric constant were observed in the composition range of 0–0.075. Also, it was observed that the dielectric loss increased drastically at the temperature of approximately 500°C.     

Effects of Sm3+ Substitution on Dielectric Properties of Ca1−xSm2x/3TiO3 Ceramics at Microwave Frequencies

Microwave dielectric properties of Ca_{1- x} Sm_{2 x /3}TiO₃ ceramics were investigated as a function of the amount of Sm³⁺ substitution (0.0 ≤ x ≤ 0.8). The structure was changed from orthorhombic perovskite at x = 0.0 to tetragonal at x = 0.6. As the calcium vacancy concentration increased with increased Sm³⁺ substitution, the unloaded Q value (similar/congruent 1/tan delta) increased up to the solid-solution limit at x = 0.6 and then decreased because of formation of the secondary phase Sm₂Ti₂O₇. The dielectric constant decreased with increased Sm³⁺ substitution. The effects of Sm³⁺ substitution on dielectric loss and dielectric constant of the specimens were analyzed by the infrared reflectivity spectra in the range 50–4000 cm⁻¹, which were evaluated using the Kramers-Kronig analysis and classical oscillator model. The correlations among dielectric constant, dielectric loss, and dispersion parameters were studied.     

Microstructure, Density, and Dielectric Properties of Lead-Free (K0.44Na0.52Li0.04)(Nb0.96−xTaxSb0.04)O3 Piezoelectric Ceramics

Lead-free (K_0.44Na_0.52Li_0.04) (Nb_0.96−xTa_xSb_0.04)O₃ piezoelectric ceramics were prepared by the conventional solid-state sintering method. The grain growth of the ceramics was inhibited and the relative density was improved with Ta substituting for Nb. Increasing x led to different variations of dielectric properties before and after poling, and prevented the occurrence of orthorhombic–tetragonal phase transition (at T _{o − t} ). All the ceramics show an intermediate relaxor-like behavior between normal and ideal relaxor ferroelectrics. Significantly enhanced dielectric and piezoelectric properties were obtained in the ceramics with x =0.20. The ceramics are very promising lead-free materials for electromechanical device applications.     

Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

Enhancement of Giant Dielectric Response in CaCu3Ti4O12 Ceramics by Zn Substitution

Zn-substituted CaCu₃Ti₄O₁₂ ceramics were synthesized by solid-state sintering. Their microstructures and dielectric properties were investigated. Ca(Cu_{1− x} Zn _x )₃Ti₄O₁₂ single-phase structures were obtained up to x =0.1, and the Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ mixed-valent structure was enhanced with increasing Zn substitution. The giant dielectric response was significantly enhanced by Zn substitution. The dielectric constant increased with increasing x , and a giant dielectric constant plateau as high as ∼9 × 10⁴ was achieved for x =0.1 at 10 kHz, while that for x =0 was ∼3 × 10⁴. The enhanced giant dielectric response was profoundly concerned with the modified mixed-valent structure.     

Grain-Boundary Migration and Dielectric Properties of Semiconducting SrTiO3 in the SrTiO3-BaTiO3-CaTiO3 System

Chemically induced grain-boundary migration and its effects on the interface and dielectric properties of semiconducting SrTiO₃ have been investigated. Strontium titanate specimens that had been doped with 0.2 mol% of Nb₂O₅ were sintered in 5H₂/95N₂. The sintered specimens were diffusion annealed at 1400°C in 5H₂/95N₂ with BaTiO₃ or 0.5BaTiO₃-0.5CaTiO₃ (mole fraction) packing powder. The grain boundaries of the annealed specimens were oxidized in air. In the case of BaTiO₃ packing, grain-boundary migration occurred with the diffusion of BaTiO₃ along the grain boundary. The effective dielectric constant of the specimen decreased gradually as the temperature increased but showed two peaks, possibly because of barium enrichment at the grain boundary and an oxidized Sr(Ba)TiO₃ layer. In the case of 0.5BaTiO₃-0.5CaTiO₃ packing, although barium and calcium were present at the grain boundary of the specimen, no boundary migration occurred, as in a previous investigation. With the diffusion of barium and calcium, the resistivity of the specimen increased and the variation of the effective dielectric constant with temperature was much reduced, in comparison to those without solute diffusion. These enhanced properties were attributed to the solute enrichment and the formation of a thin diffusional Sr(Ba,Ca)TiO₃ layer at the grain boundary.     

Lanthanum-Modified (1 – x)(Bi0.8La0.2)(Ga0.05Fe0.95)O3·xPbTiO3 Crystalline Solutions: Novel Morphotropic Phase-Boundary Lead-Reduced Piezoelectrics

(1 – x )(Bi_0.8La_0.2)(Ga_0.05Fe_0.95)O₃· x PbTiO₃ (BLGF-PT) crystalline solutions have been fabricated by solid-state reactions. BLGF-PT has single perovskite phase structure with a rhombohedral–tetragonal (FE_r-FE_t) morphotropic phase boundary (MPB) at a PT content of x = 0.43. Lanthanum substitution has been found to increase the insulation resistance and decrease the coercive field down to 20 kV/cm, which results in significant improvements in dielectric and piezoelectric properties of BLGF-PT. The dielectric constant, loss tangent, Curie temperature, remnant polarization, piezoelectric d ₃₃ constant, and planar coupling factor of 1760, 0.05, 264°C, 33 μC/cm², 295 pC/N, and 0.36, respectively, have been achieved for BLFG-PT in the vicinity of the MPB. Compared with conventional Pb(Zr,Ti)O₃ (PZT) piezoelectric ceramics, the BLGF-PT is a competitive alternative piezoelectric material with decreased lead content.     

Mechanical Properties of La1-xSrxCo0.2Fe0.8O3 Mixed-Conducting Perovskites Made by the Combustion Synthesis Technique

This paper examined the room-temperature mechanical properties of a mixed-conducting perovskite La_{1– x} Sr _x Co_0.2Fe_0.8O₃ ( x = 0.2–0.8). Powders were made by the combustion synthesis technique and sintered at 1250°C in air. Sintered density, crystal phase, and grain size were characterized. Young's and shear moduli, microhardness, indentation fracture toughness, and biaxial flexure strength were determined. The Young's and shear moduli slightly increased with increasing strontium content. Young's modulus of 151–188 GPa and shear modulus of 57–75 GPa were measured. Biaxial flexure strength of ∼160 MPa was measured for lower strontium content batches. Strength greatly decreased to ∼40 MPa at higher strontium concentrations ( x = 0.6–0.8) because of the formation of extensive cracking. Indentation toughness showed a higher value (∼1.5 MPa·m^1/2) for low strontium ( x = 0.2) content and a lower value (∼1.1 MPa·m^1/2) for the other batches ( x = 0.4–0.8). Materials with fine and coarse grain size were also tested at various indent loads and showed no dependence of toughness on crack size. In addition, fractography was used to characterize the critical flaw and fracture mode.     

Grain Growth-Controlled Giant Permittivity in Soft Chemistry CaCu3Ti4O12 Ceramics

We report a dielectric constant of up to 5.4 × 10⁵ at room temperature and 1 kHz for CaCu₃Ti₄O₁₂ (CCTO) ceramics, derived from multiphase powders (coprecipitation products), made by a "chimie douce" (coprecipitation) method, and then sintered in air. The sintered products are pure-phase CCTO ceramics. The high dielectric constant is achieved by tuning the size of grains and the thickness of grain boundaries. The grain growth is controlled by varying the concentration of excess CuO in the initial powder (calcined coprecipitation products) between 1 and 3.1 wt%. The dielectric constant of pure CCTO ceramics increases with the initial CuO concentration, reaching its maximum at 2.4 wt% of CuO. A further increase of excess CuO in powders results in a permittivity decrease, accompanied by the formation of CuO as a separate phase in the sintered products. The unusual grain growth behavior is attributed to a eutectic reaction between CuO and TiO₂ present in the initial powder.     

Microwave Dielectric Properties and Far-Infrared Reflectivity Characteristics of the CaTiO3–Li(1/2)−3xSm(1/2)+xTiO3Ceramics

Microwave dielectric properties and far-infrared reflectivity spectra of the 0.3CaTiO₃–0.7Li_{(1/2)−3 x} Sm_{(1/2)+ x} TiO₃ ceramics were investigated as a function of Sm³⁺ substitution (0.0 ≤ x ≤ 0.12). The dielectric constant decreased as the Sm³⁺ substitution increased. The Q × f value increased, up to a solid-solution limit at x = 0.11, because of the change of vibration modes between the A-site cation and the TiO₆ octahedron, and then decreased because of the formation of a secondary phase (Sm₂Ti₂O₇). On the analysis of the far-infrared reflectivity spectra, in the 50–4000 cm⁻¹ range, the change of the dielectric loss and dielectric constant could be explained by the intrinsic factor.     

Microstructure and Piezoelectric Properties of (1−x)(Na0.5K0.5)NbO3–xLiNbO3 Ceramics

(1− x )(Na_0.5K_0.5)NbO₃– x LiNbO₃ [(1− x )NKN– x LN] ceramics were produced by the conventional solid-state sintering method, and their microstructure and piezoelectric properties were investigated. The formation of the liquid phase and K₆Li₄Nb₁₀O₃₀ second phase that were observed in the (1− x )NKN– x LN ceramics was explained by the evaporation of Na₂O during the sintering. A morphotropic phase boundary (MPB) was observed in the specimens with 0.05< x <0.08. Promising piezoelectric properties were obtained for the specimens with x =0.07. Therefore, the piezoelectric properties of this 0.93NKN–0.07LN ceramic were further investigated and were found to be influenced by their relative density and grain size. In particular, grain size considerably affected the d ₃₃ value. Two-step sintering was conducted at different temperatures to increase the grain size. Piezoelectric properties of d ₃₃=240 (pC/N) and k _p=0.35 were obtained for the 0.93NKN–0.07LN ceramics sintered at 1030°C and subsequently annealed at 1050°C.     

Dielectric and Piezoelectric Properties of the Morphotropic Phase Boundary Composition in the (0.8−x) Pb(Mg1/3Ta2/3)O3−0.2PbZrO3−xPbTiO3 Ternary System

Morphotropic phase boundary (MPB) compositions separating rhombohedral and tetragonal phases in the (1− x − y )Pb(Mg_1/3Ta_2/3)O₃– y PbZrO₃– x PbTiO₃ (PMT–PZ–PT100 x ) ternary solid solution system were characterized using X-ray diffraction and dielectric, piezoelectric properties. This work focused on compositions with a PZ content fixed at y =0.2, with an MPB composition found to be located at x =0.4. Piezoelectric coefficients and dielectric permittivity were found to be on the order of d ₃₃=580 pC/N and 4100, respectively. Acceptor modification using manganese was found to induce a "hardening" effect in 0.4PMT–0.2PZ–0.4PT, with decreased piezoelectric coefficients d ₃₃ and dielectric loss and increased mechanical quality factor Q . Piezoelectric coefficients d ₃₃, Q values, and dielectric loss were found to be 500 pC/N, 2000, and 0.4%, respectively, for 0.4PMT–0.2PZ–0.4PT with MnO₂ dopant levels around 0.5 wt%. The figure of merit (product of Q and d ₃₃) was found to be on the order of 1 × 10⁶, significantly higher when compared with other hard piezoelectric PZT materials. Specifically, the PMT–PZ–PT materials may be attractive candidates for high-power ultrasonic applications, particularly fine-scale components that require relating high permittivities.     

Dielectric Properties of Pb0.97La0.02(Zr0.87−xSnxTi0.13)O3 Thin Films with Compositions near the Morphotropic Phase Boundary

Pb_0.97La_0.02(Zr_{0.87− x} Sn _x Ti_0.13)O₃ (PLZST, x =0.27, 0.17, 0.07)) thin films with the compositions in ferroelectric rhombohedral (FE_R) region, near the morphotropic phase boundary (MPB), were deposited on the Pt-electroded silicon (PtSi) substrates by the sol–gel process. The phase structure and surface morphology of PLZST thin films were analyzed by XRD and SEM, respectively. The dc electric field and temperature-dependent dielectric properties of the PLZST thin films were investigated in detail. The results indicated that the dielectric constant, remnant polarization, and the Curie temperature ( T _c) of PLZST films were elevated with the decrease of Sn content. Hence, the larger dielectric tunability (τ) was obtained for PLZST thin films with x =0.07, and the maximum τ value was 78.1%.     

Dielectric Properties of (1−x)CaTiO3–xCa(Zn1/3Nb2/3)O3 Ceramic System at Microwave Frequency

The microwave dielectric properties of the (1− x )CaTiO₃– x Ca(Zn_1/3Nb_2/3)O₃ ceramic system have been investigated. The ceramic samples sintered at 1300°–1450°C for 4 h in air exhibit orthorhombic pervoskite and form a complete solid solution for different x value. When the x value increased from 0.2 to 0.8, the permittivity ɛ_r decreased from 115 to 42, the unloaded quality factor Q × f increased from 5030 to 13 030 GHz, and the temperature coefficient τ_f decreased from 336 to −28 ppm/°C. When x =0.7, the best combination of dielectric properties, a near zero temperature coefficient of resonant frequency of τ_f∼−6 ppm/°C, Q × f ∼10 860 GHz and ɛ_r∼51 is obtained.     

Structure, Properties, and Impedance Spectroscopy of CaCu3Ti4O12 Ceramics Prepared by Sol–Gel Process

CaCu₃Ti₄O₁₂ (CCTO) ceramics with high dielectric constant (2–4 × 10⁴) and low loss (0.04) were prepared by the sol–gel process and sintered at 1050°C for different times. The sintering time has a sensitive influence on the values of the dielectric constant and nonlinear coefficient. Tailored dielectric constant and nonlinear coefficient can be obtained by selecting a suitable sintering time according to different desired device application. The result of current–voltage characteristics and Cole–Cole plots in a broad temperature range (60–400 K) provide more effective evidence of the high dielectric constant supported by the grain boundary barrier layer (GBBL) capacitors model. Below 150 K, the GBBL capacitors effect weakens and gradually disappears with further decrease of temperature, thus leading the dielectric constant to decrease rapidly. Two values of grain activation energy acting at different temperature for each sample were obtained.     

Effects of Calcium Substitution on the Structural and Microwave Dielectric Characteristics of [(Pb1−xCax)1/2La1/2](Mg1/2Nb1/2)O3 Ceramics

The effects of calcium substitution on the structural and microwave dielectric characteristics of [(Pb_{1− x} Ca _x )_1/2La_1/2](Mg_1/2Nb_1/2)O₃ ceramics (with x = 0.01–0.5) were investigated. All the materials were observed to have an ordered A(B_1/2^'B_1/2^")O₃-type perovskite structure; however, the space group of the structure changed from Fm 3 m to Pa 3 as the calcium content increased to x = 0.1, and then from Pa 3 to R 3¯ at the x = 0.5 composition. During the structural evolution, the lattice parameter of the perovskite cell decreased linearly, and the dielectric constant ( k ) also decreased, from k = 80 to k = 38. However, the product of the quality factor and the resonant frequency ( Q × f ) increased from 50 000 GHz to 90 000 GHz as the calcium content increased. Also, the temperature coefficient of resonant frequency (τ_ƒ) gradually changed from 120 ppm/°C to −40 ppm/°C as the calcium content increased. At the x = 0.3 composition, a combination of properties— k ∼ 50, Q × f ∼ 86 000 GHz, and τ_ƒ∼ 0 ppm/°C—can be obtained.     

Piezoelectric Properties and Phase Relations of Pb(Mg1/3Nb2/3)O3-PbTiO3−PbZrO3 Ceramics with Barium or Strontium Substitutions

When a small amount of Ba or Sr is substituted for Pb in Pb(Mg_1/3 Nb_2/3)O₃-PbTiO₃-Pb2rO 3 , the morphotropic boundary and the compositions which show the highest planar coupling coefficient and dielectric constant shift slightly toward the decreasing PbTiO₃ content. The tetragonality of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ and Pb(Mg_1/2 Nb_2/3)-O₃-PbTiO₃-PbZrO₃ ceramics decreased with increasing Ba or Sr content. The lattice parameter (α axis) in the rhombohedral or pseudocubic phase increased with the increase of Ba but decreased with the increase of Sr substitution. Although the Curie temperature was lowered with the increase of Ba or Sr, the dielectric constants of the ceramics were increased. The dielectric and piezoelectric properties of the ternary compositions near the morphotropic boundary were improved through selection of sub-stituent and base composition. A planar coupling coefficient of 0.66 and a low Young's modulus were obtained with substitution of 5 mole % Ba. A dielectric constant greater than 3500 and a planar coupling of 0.63 can be obtained by substituting 5 mole % Sr.     

Microstructure and Microwave Dielectric Properties of (1−x)Ca(Mg1/3Ta2/3)O3/xCaTiO3 Ceramics

Dense (1− x )Ca(Mg_1/3Ta_2/3)O₃/ x CaTiO₃ ceramics (0.1≤ x ≤0.9) were prepared by a solid-state reaction process. The crystal structures and microstructures were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Single-phase solid solutions were obtained in the entire composition range. Long-range 1:2 ordering of B-site cations and oxygen octahedra tilting lead to the monoclinic symmetry with space group P 2₁/ c for x =0.1. For x above 0.1, the long-range ordering was destroyed and the crystal structure became the orthorhombic with space group Pbnm . The microwave dielectric properties showed a strong dependence on the composition and microstructure. The dielectric constant and temperature coefficient of resonant frequency increased nonlinearly as the CaTiO₃ content increased while the Qf values decreased approximately linearly. Good combination of microwave dielectric properties was obtained at x =0.45, where ɛ_r=45.1, Qf =34 800 GHz, and τ_f=17.4 ppm/°C.