Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ε _r ), high quality factor (Q × f), and small temperature coefficient of resonant frequency (TCF) are required for the application of chip passive components in wireless communication low temperature co-fired ceramics (LTCC). In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₅Nb₆O₂₈ ceramics were investigated as a function of B₂O₃-CuO content. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250^∘C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ε _r of 37, TCF of −12 ppm/^∘C. The addition of B₂O₃-CuO was revealed to lower the sintering temperature of Ba₃Ti₅Nb₆O₂₈, 900^∘C and to enhance the microwave dielectric properties: Q × f of 32,500 GHz, ε _r of 40, TCF of 9 ppm/^∘C. From the X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

Phase transformation and microwave dielectric properties of BiPO4 ceramics

Monazite-type compounds, BiPO₄ polymorphs were prepared by the solid-state reaction method. The phase transformation and microwave dielectric properties of sintered ceramics were investigated using the X-ray powder diffraction (XRD) and a network analyzer, respectively. The low-temperature phase of BiPO₄ has monoclinic structure, and was transformed into the high-temperature phase with a slight distortion of monoclinic when it is heated above 600^∘C. The effect of the transformation on the microwave dielectric properties was examined. It was found that the dielectric properties of each phase were significantly different. In particular, the high-temperature phase sintered at 950^∘C has good microwave dielectric properties; the relative dielectric constant (ε _r ) = 22, the quality factor (Q× f) = 32,500 GHz and the temperature coefficient of resonant frequency (τ _f ) = − 79 ppm/ ^∘C.     

Control of Microwave Dielectric Properties in the System BaO ⋅ Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>—BaO ⋅ Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>

BaO ⋅ Nd₂O₃ ⋅ 4TiO₂—based ceramics were prepared by the mixed oxide route. Specimens were sintered at temperatures in the range 1200–1450^∘C. Microstructures were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM); microwave dielectric properties were determined at 3 GHz by the Hakki and Coleman method. Product densities were at least 95% theoretical. The addition of up to 1 wt% Al₂O₃ to the starting mixtures reduced the sintering temperatures by at least 100^∘C. Incorporation of small levels of Al into the structure (initially Ti sites) led to an increase in Q × f values, from 6200 to 7000 GHz, a decrease in relative permittivity (ε_r) from 88 to 78, and moved the temperature coefficient of resonant frequency (τ_f) towards zero. The addition of 0.5 wt% Al₂O₃ with 8 wt% Bi₂O₃ improved densification, increased both ε_r (to 88) and Q× f (to 8000 GHz) and moved τ_f closer to zero. Ceramics in the system (1 − x)BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + xBaO ⋅ Al₂O₃ ⋅ 4TiO₂ exhibited very limited solid solubility. The end member BaO ⋅ Al₂O₃ ⋅ 4TiO₂ was tetragonal in structure with the following dielectric properties: ε_r = 35; Q× f = 5000 GHz; τ_f = −15ppm/^∘C. Microstructures of the mixed Nd-Al compositions contained two distinct phases, Nd-rich needle-like grains and large Al-rich, lath-shaped grains. Products with near zero τ_f were achieved at compositions of approximately 0.14BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + 0.86BaO ⋅ Al₂O₃ ⋅ 4TiO₂, where Q× f = 8200 GHz and ε_r = 71.     

Microwave dielectric properties of Ca[(Li1/3Nb2/3)1−x Tix]O3−δ ceramics with glass

The effect of the addition of glass on the densification, low temperature sintering, and microwave dielectric properties of the Ca[(Li_1/3Nb_2/3)_1−x Ti_x]O_3−δ(CLNT) was investigated. Addition of glass (B₂O₃-ZnO-SiO₂-PbO system) improved the densification and reduced the sintering temperature from 1150^∘C to 900^∘C of Ca[(Li_1/3Nb_2/3)_1−x -Ti_x]O_3−δ microwave dielectric ceramics. As increasing glass contents from 10 wt% to 15 wt%, the dielectric constants (ε_r) and bulk density were increased. The quality factor (Q⋅f₀), however, was decreased slightly. The temperature coefficients of the resonant frequency (τ_f) shifted positive value as increasing glass contents over Ti content is 0.2 mol. The dielectric properties of Ca[(Li_1/3Nb_2/3)_0.75Ti_0.25]O_3−δ with 10 wt% glass sintered at 900^∘C for 3 h were ε_r = 40 Q·f₀ = 11500 GHz, τ_f = 8, ppm/°C. The relationship between the microstructure and dielectric properties of ceramics was studied by X-ray diffraction (XRD), and scanning electron microscope (SEM).     

Sintering and compositional effects on the microwave dielectric characteristics of Mg(Ta1−x Nb x )2O6 ceramics with 0.25 ≦ x ≦ 0.35

1,500 °C−sintered MgTa₂O₆ ceramic exhibits microwave dielectric characteristics of ɛ _r = 30.5, Q × f = 56,900 GHz, and τ _f = 28.3 ppm/°C, whereas 1,400 °C-sintered MgNb₂O₆ ceramic exhibits microwave dielectric characteristics of ɛ _r = 21.7, Q × f = 89,900 GHz, and τ _f = −68.5 ppm/°C. In order to find the dielectric resonators with τ _f value close to 0 ppm/°C, the effects of sintering condition and composition on the microwave dielectric characteristics of Mg(Ta_1−x Nb _x )₂O₆ ceramics (0.25 ≦ x ≦ 0.35) prepared under sintering temperature of 1,300–1,450 °C are investigated. The results show that as the sintering temperature increases from 1,300 to 1,450 °C, the ɛ _r, Q × f and τ _f values of Mg(Ta_1−x Nb _x )₂O₆ ceramics all increase and saturate at 1,450 °C. On the other hand, as the Nb₂O₅ content decreases, the τ _f values of Mg(Ta_1−x Nb _x )₂O₆ ceramics will shift to near 0 ppm/°C. The optimized sintering conditions and composition to obtain the Mg(Ta_1−x Nb _x )₂O₆ dielectrics with τ _f close to 0 ppm/°C are sintering temperature of 1,450 °C, sintering duration of 4 h, and composition of x = 0.25, which exhibits the microwave dielectric characteristics of ɛ _r = 27.9, Q × f = 33,100 GHz, and τ _f = −0.7 ppm/°C.     

Piezoelectric and dielectric characteristics of low temperature sintering Pb(Ni1/3Nb2/3)O3-Pb(Mn1/3Nb2/3)O3-Pb(Zr1/2Ti1/2)O3 ceramics for multilayer piezoelectric actuator

In this study, in order to develop the composition ceramics for multilayer piezoelectric actuator, PNN substituted PMN-PZT ceramics were fabricated using Li₂CO₃ and Na₂CO₃ as sintering aids, and their piezoelectric and dielectric characteristics were investigated. With the increase of the amount of PNN substitution, dielectric constant (εr), electromechanical coupling factor (k _p), and piezoelectric constant (d ₃₃) of specimens showed the maximum value at each sintering temperature, and crystal structure changed from tetragonal to rhombohedral. At the sintering temperature of 950^∘C, the density, εr, k _p, d ₃₃, Q_m and Tc of 12 mol% PNN substituted PMN-PNN-PZT composition ceramics showed the optimal values of 7.79 g/cm³, 1160, 0.599, 419pC/N, 894 and 332^∘C, respectively, for low loss multilayer piezoelectric actuator application.     

Control of 0.2CaTiO3-0.8Li0.5Nd0.5TiO3 microwave dielectric ceramics by additions of Bi2Ti2O7

Ceramics of 0.2CaTiO₃-0.8Li_0.5Nd_0.5TiO₃) have been prepared by the mixed oxide route using additions of Bi₂O₃-2TiO₂ (up to 15 wt%). Powders were calcined 1100^∘C; cylindrical specimens were fired at temperatures in the range 1250–1325^∘C. Sintered products were typically 95% dense. The microstructures were dominated by angular grains 1–2 μm in size. With increasing levels of Bi₂O₃-2TiO₂ additions, needle and lath shaped second phases developed. For Bi₂Ti₂O₇ additions up to 5 wt%, the relative permittivity increased from 95 to 131, the product of dielectric Q value and measurement frequency increased from 2150 to 2450 GHz and the temperature coefficient of resonant frequency (τ _f ) increased from −28pp/^∘C to +22pp/^∘C. A product with temperature stable τ _f could be obtained at ∼2 wt% Bi₂Ti₂O₇ additions. For high levels of additives, there is minimal change in relative permittivity, the Qxf values degrade and τ _f becomes increasingly negative.     

High-ε Microwave Dielectrics in Pb0.6Ca0.4Zr0.6+x (Fe1/2Nb1/2)0.4−x O3 System

Modification of Pb_0.6Ca_0.4Zr_0.6(Fe_1/2Nb_1/2)_0.4O₃ dielectric ceramics was performed by Zr substitution for (Fe, Nb). The XRD patterns showed that the single phase with orthorhombic distortion unit cell was obtained in the present ceramics. The decreasing dielectric constant by Zr substitution was due to its smaller value of /r ³ _ion. The calculated polarizability was compared with the observed one, and the results showed a good fit, considering the polarizability of oxygen dependent on the V _ox. The Zr substitution on B-site reduced the temperature coefficient of dielectric constant effectively due to the reduced dielectric constant. The effects of tilting transition on the temperature coefficient of dielectric constant were also discussed. The modified microwave dielectric properties were obtained in Pb_0.6Ca_0.4Zr_0.6+x (Fe_1/2Nb_1/2)_0.4–x O₃ for x = 0.3: _r = 100, Q × f = 3,300 to 3,600 GHz, _f = 6–8 ppm/°C.     

Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C     

Sintering and dielectric properties of Al2O3 ceramics doped by TiO2 and CuO

The effects of CuO and TiO₂ additives on the microstructure and microwave dielectric properties of Al₂O₃ ceramics were investigated. Al₂O₃ ceramics with CuO and TiO₂ additions can be well sintered to achieve 93∼98% theoretical densities below 1,360 °C due to Ti₄Cu₂O liquid phase sintering effect. The Qf values decreased with increasing CuO and TiO₂ content, due to the formation of the second phase Ti₄Cu₂O. However, the varying behaviors of the dielectric constant (ɛ _r ) and temperature coefficients (τ _f ) were associated with phase constitutions, as a result of the change of CuO and TiO₂content. The τ _f can be shifted close to 0 ppm/°C by controlling the content of CuO and TiO₂. The specimens with 0.5 wt.% CuO and 7 wt.% TiO₂ sintered at 1,360 °C for 4 h showed ɛ _r of 11.8, Qf value of 30,000 GHz, and τ _f of −7 ppm/°C.     

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 relaxation and variable-range-hopping conduction in BaSn1−x Cr x O3 system

The possibility of formation of a solid solution in the system BaSn_1−x Cr _x O₃ has been explored upto x ≤ 0.20. It has been confirmed that single phase solid solution forms upto x ≤ 0.10. Dielectric and conduction behaviour of single phase samples have been studied in the temperature range 400–610 K and frequency range 10 Hz–2 MHz. Two dielectric relaxation processes in two different frequency ranges have been observed. The temperature dependence of both dc and ac resistivity obey relation ρ = ρ _o exp(B/T^1/4), indicative of variable range hopping conduction mechanism. The activation energy for dc conduction is higher than that for relaxation time (τ) of low frequency dielectric relaxation process. It has been observed that activation energy for dielectric relaxation matches with activation energy for ac conductivity (at 100 kHz) for both the dielectric relaxation processes. Seebeck coefficient ‘α’ of the samples have been measured in the temperature range 350–650 K. Negative value of ‘α’ in the entire range of temperature measurement shows that conduction species are negatively charged. On the basis of value of activation energy for dc conduction and sign of Seebeck coefficient, conduction in the low temperature region (below 500 K) is attributed to hopping of weakly bonded electrons among Sn²⁺ ⇔ Sn⁴⁺ or Sn³⁺ ⇔ Sn⁴⁺ and that in the high temperature region (above 500 K) to hopping of doubly ionized oxygen vacancies .     

Thermal and dielectric properties of ZnO-B2O3-MO3glasses (M = W, Mo)

Glasses in the ZnO-B₂O₃-MO₃(M = W, Mo) ternary were examined as potential replacements to PbO-B₂O₃-SiO₂-ZnO glass frits with the low firing temperature (500–600^∘C) for the dielectric layer of a plasma display panels (PDPs). Glasses were melted in air at 950–1150^∘C in a narrow region of the ternary using standard reagent grade materials. The glasses were evaluated for glass transition temperature (T _g ), softening temperature (T _d ), the coefficient of thermal expansion (CTE), dielectric constant (ε _r ), and optical property. The glass transition temperature of the glasses varied between 470 and 560^∘C. The coefficient of thermal expansion and the dielectric constant of the glasses were in the range of 5–8 × 10^{− 6}/^∘C and 8–10, respectively. The addition of MO₃to ZnO-B₂O₃binary could induce the expansion of glass forming region, the reduction of T _g and the increase in the CTE and the dielectric constant of the glasses. Also, the effect of the addition of MO₃to ZnO-B₂O₃binary on the transmittance in the visible-light region (350–700 nm) was investigated.     

Microwave Dielectric Properties of CuO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped ZnNb<Subscript>2</Subscript>O<Subscript>6</Subscript> Ceramics with Low Sintering Temperature

Microwave dielectric properties of low temperature sintering ZnNb₂O₆ ceramics doped with CuO-V₂O₅-Bi₂O₃ additions were investigated systematically. The co-doping of CuO, V₂O₅ and Bi₂O₃ can significantly lower the sintering temperature of ZnNb₂O₆ ceramics from 1150 to 870C. The secondary phase containing Cu, V, Bi and Zn was observed at grain boundary junctions, and the amount of secondary phase increased with increasing CuO-V₂O₅-Bi₂O₃ content. The dielectric properties at microwave frequencies (7–9 GHz) in this system exhibited a significant dependence on the relative density, content of additives and microstructure of the ceramics. The dielectric constant ( _r) of ZnNb₂O₆ ceramics increased from 21.95 to 24.18 with increasing CuO-V₂O₅-Bi₂O₃ additions from 1.5 to 4.0 wt%. The quality factors (Q× f) of this system decreased with increasing CuO-V₂O₅-Bi₂O₃ content and ranged from 36118 to 67100 GHz for sintered ceramics, furthermore, all Q× f values of samples with CuO-V₂O₅-Bi₂O₃ additions are lower than that of un-doped ZnNb₂O₆ ceramics sintered at 1150C for 2 h. The temperature coefficient of resonant frequency ( _f) changed from –33.16 to –25.96 ppm/C with increasing CuO-V₂O₅-Bi₂O₃ from 1.5 to 4.0 wt%     

Preparation and Characterization of PZT films Fabricated on Si Substrate

Lead zirconium titanate (PZT) films (Zr/Ti=45:55) with a high dielectric constant are prepared successfully on the low-resistance Si substrate in sol–gel dip-coating process with PT film used as the buffer layer. The dielectric and ferroelectric properties of the films as well as the relationship between crystallization and preparing condition are studied. It is shown that the PZT ferroelectric thin films with a (110) preferred orientation and a well-crystallized perovskite structure could be obtained after annealing at 800°C for 15 min. The particle size of the sample is about 14–25 nm. The P–E hysteresis loops are measured by means of the Sawyer-Tower test system with a compensation resistor at room temperature. The remanent polarization (P _r) and coercive electric field (E _c) of the measured PZT thin films are 47.7 μC/cm² and 18 kV/cm, respectively. The relative dielectric constant ε _r and the dissipation factor tgδ of the PZT thin films were measured with an LCR meter and were found to be 158 and 0.04–0.005, respectively. Translated from “Preparation and Characterization of PZT Films Fabricated on Si Substrates” published in Chinese Journal of Semiconductors, 2004, 25(4): 404–409 (in Chinese)     

Piezoelectric properties and dielectric behavior of Bi1/2Na1/2[Ti1−x (Sb1/2Nb1/2) x ]O3 lead-free piezoelectric ceramics

New lead-free piezoelectric ceramics of ABO₃ perovskite type, Bi_1/2Na_1/2[Ti_1−x (Sb_1/2Nb_1/2) _x ]O₃, were synthesized by conventional solid state reaction. The effect of the replacement of complex ions of (Sb_1/2Nb_1/2)⁴⁺ in the B cationic site on structural and electrical properties was investigated. The XRD analysis showed that all samples exhibited a single phase of perovskite structure. Piezoelectric and dielectric measurement revealed that the substitution of (Sb_1/2Nb_1/2)⁴⁺ ions lead to an increase in piezoelectric constant(d ₃₃), electromechanical coupling factor(k _t), relative dielectric constant(ɛ _r),and loss tangent (tanδ), while excess of (Nb_1/2Sb_1/2)⁴⁺ ions results in a decrease in d ₃₃, k _t, ɛ _r, but an increase in tanδ. Temperature dependence of dielectric constant ɛ _r measurement indicated these compounds were relaxor ferroelectric. At low frequency and high temperature, dielectric constant increased sharply attributed to the superparaelectric clusters after (Sb_1/2Nb_1/2)⁴⁺ ions substitution.     

Effects of complex doping on microstructural and electrical properties of PZT ceramics

The influence of complex dopants including donor and acceptor ions on microstructure and electrical properties of PZT (Zr/Ti = 53/47) ceramics was investigated. The prepared PZT ceramics modified with complex soft dopants, La⁺³ and Nb⁺⁵, showed that the piezoelectric properties were enhanced and stable with the compositional variations, which made it possible to establish the higher reliability and reproducibility of the piezoelectric performances. For 1.0 mol% La and 1.2 mol% Nb doped composition, the maximum value, k _P = 0.66, was obtained. Unlike single element doping, the complex doping of both the donor and acceptor ions caused various compensation effects for the piezoelectric properties of the PZT ceramics. The improved piezoelectric properties, i.e., enhanced Q _m with remaining higher k _p , were obtained in the PZT composition complexly doped with La⁺³ and Fe⁺³. For 1.0 mol% La and 2.0 mol% Fe doped PZT composition, relatively high Q _m and k _p values of 580 and 0.53, respectively, were obtained. It was also shown that the PZT composition had the rather lowered dielectric constant, ε _r = 800, and considerably low loss, tanδ = 0.003. By changing the dopants compositions, the properties can also be tailored over wider range.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Piezoelectric micromachined ultrasonic transducers with thick PZT sol gel films

The fabricated micro machined ultrasonic transducers (pMUT) was based on piezoelectric laminated plates operating at flexural modes. The fabricated bimorph pMUT transducers were composed of 5-layers. A 4 μm thick lead zirconate titanate (PZT) thin film deposited by a sol–gel method was used. The piezoelectric layer exhibited a capacitance corresponding to a permitivity of ɛ _r = 1,200. The electromechanical coupling coefficient (k ²) and quality factor (Q) were measured as k ² = 4.4% and Q = 145 in air for a low frequency transducer (240 kHz). The effect of DC bias voltage on frequency and k ² has been studied. The 16.9 MHz transducer yielded values of Q = 25 in air and k ² = 3%.     

Effects of ZnO on the piezoelectric properties of Pb (Mn1/3 Sb 2/3 )O 3 -Pb(Zr,Ti)O 3 Ceramics

Perovskite-types 0.05Pb(Mn_1/3Sb_2/3)O₂-0.95Pb- (Zr_0.5Ti_0.5)O₃ (PMS-PZT) was synthesized by conventional bulk ceramic processing technique. ZnO as a dopant up to 0.5 mol% was incorporated into the PMS-PZT system, and the effects on piezoelectric properties were investigated. Pyrochlore phase was not detected to form during the synthesis of the PMS-PZT system with 0–0.5 mol% ZnO addition. The highest density of 7.92 g/cm³ was obtained when sintered at 1200^∘C for 2 h. Piezoelectric properties as a function of ZnO content were evaluated using a gain phase analyzer. Piezoelectric charge constant (d ₃₁) and piezoelectric voltage output coefficient (g ₃₁) increased up to −130 pC/N and −24.9 × 10³Vm/N, respectively, with increasing ZnO content. Mechanical quality factor (Q _m) was shown to reduce considerably with increasing ZnO content. When 0.3 mol% of ZnO was added into the system, electromechanical coupling factor (k _p) and relative dielectric constant (ε₃₃ ^T /ε_o) reached to the maximum of 56% and 1727, respectively.