Synthesis, Sintering, and Microwave Dielectric Properties of KTaO3 Ceramics

Studies of a synthesis of KTaO₃ displayed a two-step reaction path with the intermediate formation of K₂Ta₄O₁₁. Thermal and X-ray diffraction analysis showed that the synthesis is completed at 900°C. Sintering studies showed that KTaO₃ powder can produce single phase ceramics with 85% of relative density with the addition of 5% of potassium excess when sintered at 1330°C for 1 h. Longer sintering times or higher temperatures result in enhanced potassium loss and consequent formation of K₆Ta_10.8O₃₀ secondary phase with tetragonal tungsten bronze structure. Room- and low-temperature microwave dielectric properties of KTaO₃ ceramics compare well with measurements performed on single crystals. We evaluated the influence of microstructural features (porosity, structural defects, secondary phases) on the dielectric properties of the ceramic samples.     

Defect Structure and Electrical Properties of KTaO3

The electrical conductivity and thermoelectric power of KTaO₃ were measured from 900° to 1300°C over a range of oxygen partial pressures. The isothermal electrical conductivity showed a minimum at an oxygen partial pressure corresponding to the transition between p-type and n-type behavior. A point defect model was developed which involved fully ionized potassium and tantalum vacancies, singly and doubly ionized oxygen vacancies, holes, and electrons. The values of all pertinent equilibrium constants were calculated from the experimental data and the nonsimplified neutrality condition was solved to give each of the defect concentrations as a function of temperature and oxygen partial pressure. The calculated conductivity agreed extremely well with the experimental data over the full temperature and oxygen partial pressure range, and the band gap derived from these calculations (3.43 eV) was in excellent agreement with the reported value (3.5 eV).     

Growth of KTaO3-KNbO3 Mixed Crystals

Crystals of potassium tantalum niobate (KTN) were grown by two techniques: (1) pulling in the 〈100〉 direction with a continuously increasing crystal diameter, and (2) growing {100} platelets while floating on the surface of the melt. The amount of tantalum in the crystals increased rapidly with increasing potassium in the melt. The rate of potassium oxide evaporation from the melt was significant.     

Low-Temperature Sintering and Dielectric Properties of Ag(Nb,Ta)O3 Composite Ceramics

The sintering behavior and dielectric properties of perovskite Ag(Nb_{1− x} Ta _x )O₃ (0 < x < 1) solid solutions and two-phase composite assemblages were explored. A small amount of CuO (1 wt%) was used for liquid-phase sintering and led to high densification at temperatures <950°C. The temperature coefficient of capacitance, TCC, was adjusted by varying the Nb:Ta ratio within the solid-solution series and by creating composite microstructures. Two-phase assemblages consisting of Ag(Nb_3/4Ta_1/4)O₃ and Ag(Nb_1/4Ta_3/4)O₃ were synthesized to achieve a temperature-stable dielectric material for high-frequency applications. The composite dielectric with CuO addition had an average dielectric constant of 390 and a Q × f factor of 410 GHz at 2 GHz, with a stable TCC (0 to −180 ppm/°C) in the temperature range from −20° to +60°C. In addition, process compatibility with a silver conductor was confirmed by high-frequency ring-resonator measurements and microstructural characterization. The Ag(Nb_{1− x} Ta _x )O₃ solid solutions and composites are promising candidates as embedded capacitors for radio-frequency/microwave applications.     

Microwave Dielectric Properties and Low-Temperature Sintering of Ba0.60Sr0.40TiO3 Ceramics

In the present work, the sintering behaviors and dielectric properties of Ba_0.60Sr_0.40TiO₃ (BST) ceramics with the addition of BaCu(B₂O₅) were investigated in detail. The results indicated that the addition reduced the sintering temperature of BST by about 500°C. It was suggested that a liquid phase BaCu(B₂O₅) assisted the densification of BST ceramics at lower temperatures. For a low-level BaCu(B₂O₅) addition (2.0 mol%), the BST sample sintered at 950°C for 5 h displayed good dielectric properties, with a moderate dielectric constant (ɛ=2553) and a low dielectric loss (tan δ=0.00305) at room temperature and at 10 kHz. The sample showed 45.9% tunability at 10 kHz under a dc electric field of 30 kV/cm. At the frequency of 0.984 GHz, BST-added 2.0 mol% BaCu(B₂O₅) possessed a dielectric constant of 2204 and a Q value of 146.7.     

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.     

Low-Temperature Sintering and Microwave Dielectric Properties of Li2MgSiO4 Ceramics

Development of a low-temperature sintered dielectric material derived from Li₂MgSiO₄ (LMS) for low-temperature cofired ceramic (LTCC) application is discussed in this paper. The LMS ceramics were prepared by the solid-state ceramic route. The calcination and sintering temperatures of LMS were optimized at 850°C/4 h and 1250°C/2 h, respectively, for the best density and dielectric properties. The crystal structure and microstructure of the ceramic were studied by the X-ray diffraction and scanning electron microscopic methods. The microwave dielectric properties of the ceramic were measured by the cavity perturbation method. The LMS sintered at 1250°C/2 h had ɛ_r=5.1 and tan δ=5.2 × 10⁻⁴ at 8 GHz. The sintering temperature of LMS is lowered from 1250°C/2 h to 850°C/2 h by the addition of both lithium borosilicate (LBS) and lithium magnesium zinc borosilicate (LMZBS) glasses. LMS mixed with 1 wt% LBS sintered at 925°C/2 h had ɛ_r=5.5 and tan δ=7 × 10⁻⁵ at 8 GHz. Two weight percent LMZBS mixed with LMS sintered at 875°C/2 h had ɛ_r=5.9 and tan δ=6.7 × 10⁻⁵ at 8 GHz.     

Low-Temperature Sintering of (Ba0.6Sr0.4)TiO3

An addition of just 0.4 wt% Li₂O to (Ba_0.6Sr_0.4)TiO₃ powder was able to reduce the sintering temperature to ≤900°C and produce ceramics with a relative density of 97%. Small amounts of two secondary phases were formed during this process: Li₂TiO₃ and Ba₂TiO₄. The addition of Li₂O depresses the ferroelectric character of the (Ba_0.6Sr_0.4)TiO₃ and, as a result, reduces the permittivity, improves the temperature coefficient of permittivity, and reduces the dielectric losses. The tunability shows no significant variation with Li₂O concentration and remains between 16.5% and 13.5%. A low-temperature sintering mechanism was proposed. The mechanism involves the intermediate formation of BaCO₃, its melting and the incorporation of Li⁺ into the BST. The sintering mechanism can be characterized as reactive liquid-phase sintering.     

Low-Temperature Sintering and Microwave Dielectric Properties of the Zn2SiO4 Ceramics

B₂O₃ was added to nominal composition Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature for application to low-temperature cofired ceramic (LTCC) devices. B₂O₃ reacted with SiO₂ to form a liquid phase containing SiO₂ and B₂O₃. The composition and melting temperature of the liquid phase depended on the sintering temperature and the B₂O₃ content. The specimen containing 20.0 mol% of B₂O₃ sintered at 900°C exhibited high microwave dielectric properties of Q × f =53 000 GHz, ɛ _r=5.7, and τ_f=−16 ppm/°C, confirming the promising potential of the B₂O₃-added ZS ceramics as candidate materials for the LTCC devices.     

Low-Temperature Sintering and Piezoelectric Properties of (Na0.5K0.5)NbO3 Lead-Free Piezoelectric Ceramics

(Na_0.5K_0.5)NbO₃ (NKN) ceramic with 1.5 mol% CuO added (NKNC) was well sintered even at a low temperature of 900°C with the addition of ZnO. Most of the ZnO reacted with the CuO and formed the liquid phase that assisted the densification of the specimens at 900°C. A few Zn²⁺ ions entered the matrix of the specimens and increased the coercive field ( E _c) and Q _m values of the specimens. High-piezoelectric properties of k _p=0.37, Q _m=755, and ɛ₃ ^T /ɛ₀=327 were obtained from the NKNC ceramics containing 1.0 mol% ZnO sintered at 900°C for 2 h.     

Dielectric Properties of Ceramics in Ba (Co1/3 Nb2/3)O3–Ba(Zn1/3Nb2/3)O3 Solid Solution

The dielectric properties of the Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ system were determined. Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ has a complex perovskite structure, a high dielectric constant, a low dielectric loss, and a low temperature coefficient of the resonant frequency. A solid-solution ceramic with 0.7Ba (Co_1/3 Nb_2/3)O₃·0.3 Ba(Zn_1/3Nb_2/3)O₃ has a dielectric constant of K=33.5, Q=11000 at 6.5 GHz, and a temperature coefficient of the resonant frequency of τ_f=0 ppm/°C. The temperature coefficient of resonant frequency can be varied by changing the composition. The Q values of the ceramics can be increased by annealing in a nitrogen atmosphere. These ceramics can be used for resonant elements and stabilized oscillators.     

Spray Pyrolysis Synthesis and Dielectric Properties of Pb(Mg1/3Nb2/3)O3

Spray pyrolysis was used to synthesize lead magnesium niobate (PMN) by atomizing a mixture of nitrate aqueous solutions into a high-temperature furnace. This approach allows for instant removal of solvents and decomposition of metal–salts, thereby limiting phase segregation on a nanometer scale, and lowering the transformation temperature for pyrochlore-to-perovskite phase transition. As-synthesized particles were nanocrystalline pyrochlores, with an average crystallite size ∼22 nm. More than 96% perovskite phase was obtained when as-sprayed powders were subsequently calcined at 750°C for 4 h. Sintered PMN ceramics exhibited the typical frequency-dependent dielectric properties, with a peak value of dielectric constant of 18 000, and a transition temperature at −9.6°C at 100 Hz. A series of ceramics were prepared with varied grain sizes. Increasing the grain size increased the dielectric constant, probably due to the smaller fraction of the less-polarizable grain-boundary phases.     

Effects of Silver and Palladium Doping on the Dielectric Properties of 0.9Pb(Mg1/3Nb2/3)O3–0.1 PbTiO3 Ceramic

The doping of silver and palladium into a 0.9Pb-(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃ (PMN–PT) ceramic has been investigated. It was found that Ag could be incorporated into the PMN–PT lattice, though this was almost impossible with Pd. Doping at up to 0.2 mol% of Ag and Pd reduced the maximum dielectric constant ( K _max) from 21000 to 14000 without any conspicuous change in physical properties. Order–disorder transitions in the perovskite structure contributed to the decrease in K _max, since the diffuseness parameter, δ, which represents the degree of the order-disorder relationship, increased with Ag doping. However, addition of more than 0.2 mol% increased K _max. Increases in grain size and in the perovskite ratio contributed to this increase. The dielectric properties of Ag/Pd-doped samples were intermediate between the Ag- and Pd-doped samples.     

Ordered Structure and Dielectric Properties of Lanthanum-Substituted Ba(Mg1/3Ta2/3)O3

Both 1:2 and 1:1 ordered structures form in the perovskite solid solutions of La-substituted BMT Ba_{1− x} La _x (Mg_{(1+ x )/3}Ta_{(2− x )/3})O₃, sintered at 1600°C. The 1:2 ordered structure exists in the composition range 0.0 ≤ x ≤ 0.12, while that of 1:1 ordered structure exists in a wider composition range 0.04 ≤ x ≤ 1.0. Two ordered phases coexist in 0.04 ≤ x ≤ 0.12. High-resolution micrographs indicate that 1:2 and 1:1 ordered domains coexist in one grain. The ordering parameter of 1:2 phase decreases with x , yet that of 1:1 phase increases with x . Both increase with soak time. Variations in ordering are discussed in terms of cation occupancy and crystal chemistry. The quality factor increases with x , reaches a maximum, then decreases with x . The dielectric constant increases with x first, and levels off.     

Dielectric Properties of Pb(Fe2/3W1/3)O3–PbTiO3 Solid-Solution Ceramics

The dielectric properties of (1− x )Pb(Fe_2/3W_1/3)O₃· x PbTiO₃ solid solutions were investigated from 10² to 10⁶ Hz in the temperature range 150–600 K. The phase transition of Pb(Fe_2/3W_1/3)O₃ (PFW) was shifted by PbTiO₃ (PT) additions to higher temperatures at a rate of 6.3 K/mol% of PT. The temperature dependence of dielectric permittivity showed a sharper transition as the PT content increased. Dielectric measurements in a wide temperature range showed the presence of a second set of dielectric peaks at higher temperatures (350–600 K), besides the ferroelectric–paraelectric phase transition. This second set of peaks vanished when the samples were annealed in nitrogen. The activation energy values for the second relaxation varied between 0.50 and 0.63 eV, in agreement with the conduction activation energy determined for each sample. This relaxation is apparently related to electron holes.     

Dielectric Properties of Explosively Compacted BaTiO3

Polycrystalline BaTiO₃ was explosively compacted to nearly theoretical density, and its dielectric and piezoelectric properties were investigated. The compacted bodies did not exhibit dielectric hysteresis, a Curie point, or piezoelectric properties; their dielectric constant and dissipation factor increased linearly with temperature. The dielectric constant was much lower than those of similar dense bodies obtained by conventional sintering. These results may be interpreted in terms of weak intergranular bonding and increased numbers of defects generated in the shocked material. When explosively compacted bodies were sintered, normal ferroelectric and piezoelectric properties and improved microstructures were obtained.     

Effect of BaWO4 on the Microwave Dielectric Properties of Ba(Mg1/3Ta2/3)O3 Ceramics

Physical and microwave dielectric properties of complex perovskite Ba(Mg_1/3Ta_2/3)O₃ ceramics have been investigated as a function of the amount of BaWO₄ in the temperature range from 20° to 80°C at 10.5 GHz. Up to 0.05 mol BaWO₄ addition, the lattice constant ratio ( c/a ), ordering parameter, apparent density, and unloaded Q all increase, due to the increase in the substitution of Ta⁵⁺ ions of Ba(Mg_1/3Ta_2/3)O₃ by W⁶⁺ ions from the melted BaWO₄ at above 1430°C. With further addition of BaWO_4, the unloaded Q decreases, due to an increase of the BaWO₄ phase. The temperature coefficient of resonant frequency (TCF) can be controlled by the volume mixture rule of Ba(Mg_1/3Ta_2/3)O₃ and BaWO₄. When 0.09 mol BaWO₄ is added, TCF becomes 0 ppm/°C.     

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.