Influence of V2O5 Additions to 5Li2O–1Nb2O5–5TiO2 Ceramics on Sintering Temperature and Microwave Dielectric Properties

The effects of the addition of V₂O₅ on the sintering behavior, microstructure, and microwave dielectric properties of 5Li₂O–1Nb₂O₅–5TiO₂ (LNT) ceramics have been investigated. With low-level doping of V₂O₅ (≤3 wt%), the microstructure of the LNT ceramic changed from a special two-level intergrowth structure into a two-phase composite structure with separate grains. And the sintering temperature of the LNT ceramics could be lowered to around 900°C by adding a small amount of V₂O₅ without much degradation in microwave dielectric properties. Typically, better microwave dielectric properties of ɛ_r=41.7, Q × f =7820 GHz, and τ _f =45 ppm/°C could be obtained for the 1 wt% V₂O₅-doped ceramics sintered at 900°C.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Sintering and Electrical Properties of Lead-Free Na0.5K0.5NbO3 Piezoelectric Ceramics

Lead-free Na_0.5K_0.5NbO₃ (NKN) piezoelectric ceramics were fairly well densified at a relatively low temperature under atmospheric conditions. A relative density of 96%–99% can be achieved by either using high-energy attrition milling or adding 1 mol% oxide additives. It is suggested that ultra-fine starting powders by active milling or oxygen vacancies and even liquid phases from B-site oxide additives mainly lead to improved sintering. Not only were dielectric properties influenced by oxide additives, such as the Curie temperature ( T _c) and dielectric loss ( D ), but also the ferroelectricity was modified. A relatively large remanent polarization was produced, ranging from 16 μC/cm² for pure NKN to 23 μC/cm² for ZnO-added NKN samples. The following dielectric and piezoelectric properties were obtained: relative permittivity ɛ ^T ₃₃/ɛ ₀ =570–650, planar mode electromechanical coupling factor, k _p=32%–44%, and piezoelectric strain constant, d ₃₃=92–117 pC/N.     

Reduced Dielectric Loss of Modified ZnNb2O6 Ceramics by Substituting Nb5+ with Ta5+

The effects of substituting Nb⁵⁺ with Ta⁵⁺ on the microwave dielectric properties of the ZnNb₂O₆ ceramics were investigated in this study. The forming of Zn(Nb_{1− x} Ta _x )₂O₆ ( x =0–0.09) solid solution was confirmed by the measured lattice parameters and the EDX analysis. By increasing x , not only could the Q × f of the Zn(Nb_{1− x} Ta _x )₂O₆ ( x =0–0.09) solid solution be tremendously boosted from 83 600 GHz at x =0 to a maximum 152 000 GHz at x =0.05, the highest ɛ_r∼24.6 could also be achieved simultaneously. It was mainly due to the uniform grain morphology and the highest relative density of the specimen. A fine combination of microwave dielectric properties (ɛ_r∼24.6, Q × f ∼152 000 GHz at 8.83 GHz, τ_f∼–71.1 ppm/°C) was achieved for Zn(Nb_0.95Ta_0.05)₂O₆ solid solution sintered at 1175°C for 2 h.     

Spectroscopic Properties of Er3+-Doped Na2O–La2O3–Al2O3–SiO2 Glasses

Er³⁺-doped sodium lanthanum aluminosilicate glasses with compositions of (90− x )(0.7SiO₂·0.3Al₂O₃)· x Na₂O·8.2La₂O₃· 0.6Er₂O₃·0.2Yb₂O₃·1Sb₂O₃ (in mol%) ( x = 12, 20, 24, 40, 60 mol%) were prepared and their spectroscopic properties were investigated. Judd–Ofelt analysis was used to calculate spectroscopic properties of all glasses. The Judd–Ofelt intensity parameter Ω _t ( t = 2, 4, 6) decreases with increasing Na₂O. Ω₂ decreases rapidly with increasing Na₂O while Ω₄ and Ω₆ decrease slowly. Both the fluorescent lifetime and the radiative transition rate increase with increasing Na₂O. Fluorescence spectra of the ⁴ I _13/2 to ⁴ I _15/2 transition have been measured and the change with Na₂O content is discussed. It is found that the full width at half-maximum decreases with increasing Na₂O.     

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.     

(Bi1/2Na1/2)TiO3–Ba(Cu1/2W1/2)O3 Lead-Free Piezoelectric Ceramics

(Bi_1/2Na_1/2)TiO₃ with 0–6 mol% Ba(Cu_1/2W_1/2)O₃ (BNT-BCW), a new member of the BNT-based group, has been prepared following the conventional mixed oxide route. The compacted bodies were sintered at 1130°C for 2 h to get dense ceramics. The addition of BCW into BNT ceramics facilitated the poling process because of a reduction in leakage current. 0.995BNT·0.005BCW ceramics exhibit a relatively high piezoelectric constant ( d ₃₃= 80 × 10⁻¹² C/N) and a relatively low dielectric loss (tan δ= 1.5%). Increased amount of BCW was found to increase the dielectric constant and loss of BNT-BCW ceramics and to suppress the grain growth. During sintering, some BCW diffuses into the lattice of BNT to form a solid solution and some remains on the grain boundaries.     

Synthesis of BaCu(B2O5) Ceramics and their Effect on the Sintering Temperature and Microwave Dielectric Properties of Ba(Zn1/3Nb2/3)O3 Ceramics

BaCu(B₂O₅) ceramics were synthesized and their microwave dielectric properties were investigated. BaCu(B₂O₅) phase was formed at 700°C and melted above 850°C. The BaCu(B₂O₅) ceramic sintered at 810°C had a dielectric constant (ɛ_r) of 7.4, a quality factor ( Q × f ) of 50 000 GHz and a temperature coefficient of resonance frequency (τ_f) of −32 ppm/°C. As the BaCu(B₂O₅) ceramic had a low melting temperature and good microwave dielectric properties, it can be used as a low-temperature sintering aid for microwave dielectric materials for low temperature co-fired ceramic application. When BaCu(B₂O₅) was added to the Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramic, BZN ceramics were well sintered even at 850°C. BaCu(B₂O₅) existed as a liquid phase during the sintering and assisted the densification of the BZN ceramic. Good microwave dielectric properties of Q × f =16 000 GHz, ɛ_r=35, and τ_f=22.1 ppm/°C were obtained for the BZN+6.0 mol% BaCu(B₂O₅) ceramic sintered at 875°C for 2 h.     

Adhesive-Bonded Ca(Mg1/3Nb2/3)O3/Ba(Zn1/3Nb2/3)O3 Layered Dielectric Resonators with Tunable Temperature Coefficient of Resonant Frequency

Ca(Mg_1/3Nb_2/3)O₃ and Ba(Zn_1/3Nb_2/3)O₃ ceramic cylinders with the same diameter were bonded by adhesive with low dielectric loss to yield the layered dielectric resonators, and the microwave dielectric characteristics were evaluated with TE_01δ mode. With increasing the Ba(Zn_1/3Nb_2/3)O₃ thickness fraction, the resonant frequency ( f ₀) decreased, while the effective dielectric constant (ɛ _{r ,eff}) and temperature coefficient of resonant frequency (τ _f ) increased. Good microwave dielectric characteristics were attained for the samples with the Ba(Zn_1/3Nb_2/3)O₃ thickness fraction of 0.5: ɛ _{r ,eff}=34.33, Q × f =57 930 GHz and τ _f =2.6 ppm/°C. Finite-element method was used to predict the microwave dielectric characteristics of the layered resonators and good agreements were attained between the experimental results and predicted ones. Also, both experiment and finite-element analysis indicated that the effects of the adhesive on f ₀, ɛ _{r ,eff}, and τ _f were slight, while that on Q × f value was significant.     

Microwave Dielectric Properties of Li2TiO3 Ceramics Doped with ZnO–B2O3 Frit

A type of new low sintering temperature ceramic, Li₂TiO₃ ceramic, has been found. Although it is difficult for the Li₂TiO₃ compound to be sintered compactly at temperatures above 1000°C for the volatilization of Li₂O, dense Li₂TiO₃ ceramics were obtained by conventional solid-state reaction method at the sintering temperature of 900°C with the addition of ZnO–B₂O₃ frit. The sintering behavior and microwave dielectric properties of Li₂TiO₃ ceramics with less ZnO–B₂O₃ frit (≤3.0 wt%) doping were investigated. The addition of ZnO–B₂O₃ frit can lower the sintering temperature of the Li₂TiO₃ ceramics, but it does not apparently degrade the microwave dielectric properties of the Li₂TiO₃ ceramics. Typically, the good microwave dielectric properties of ɛ_r=23.06, Q × f =32 275 GHz, τ_f = 35.79 ppm/°C were obtained for 2.5 wt% ZnO–B₂O₃ frit-doped Li₂TiO₃ ceramics sintered at 900°C for 2 h. The porosity was 0.08%. The Li₂TiO₃ ceramic system may be a promising candidate for low-temperature cofired ceramics applications.     

Electrical Properties of Sr0.7Ba0.3TiO3 Ceramics Doped with Nb2O5, 3Li2O · 2SiO2, and Bi2O3

The electrical properties of Sr_0.5Ba_0.3TiO₃ in the presence of Nb₂O₅ as a donor, 3Li₂O · 2SiO₂ as a sintering agent, and Bi₂O₃ as a dopant have been studied. When the compositions of the ceramics were 1 mol Sr_0.7Ba_0.3TiO₃+ 0.5 mol% Nb₂O₅+ 2 mol% 3Li₂O · 2SiO₂+ 0.2 mol% Bi₂O₃, the ceramics were sintered at 1100°C and exhibited the following characteristics: apparent dielectric constant ɛ, 25000; loss factor tan δ, 2%; insulating resistivity ρ_j, 10¹⁰Ω· cm; variation of dielectric constant with temperature Δɛ/ɛ (−25° to +85°C), +10%, −14%. ɛ and tan δ show only small changes with frequency. The study shows this ceramic can be used in multilayer technology.     

Sr3LaNb3O12: A New Low Loss and Temperature Stable A4B3O12-Type Microwave Dielectric Ceramic

The microwave dielectric properties of dense ceramics of a new A₄B₃O₁₂ type cation-deficient hexagonal perovskite Sr₃LaNb₃O₁₂ are reported. Single-phase powders can be obtained from the mixed-oxide route at 1320°C and dense ceramics (>96% of the theoretical X-ray density) with uniform microstructures (5–12 um) can be obtained by sintering in air at 1430°C. The ceramic exhibits a moderate dielectric constant ɛ_r∼36, a high quality factor Q × f ∼45 327 GHz, and a low temperature coefficient of resonant frequency τ _f of −9 ppm/°C.     

BiNbO4-Based Glass–Ceramic Composites for Microwave Applications

The effect of a bespoke glass sintering aid, 0.3Bi₂O₃–0.3Nb₂O₅–0.3B₂O₃–0.1SiO₂ (BN1), developed from the base ceramic composition, BiNbO₄ (BN), on the sinterability, microstructure, and microwave (MW) dielectric properties of BN ceramics has been investigated. Densities >97% theoretical could be achieved at 1020°C for samples with up to 15% BN1 additions. The resulting microstructure was composed of BN laths surrounded by a residual glass phase that contained small fibrous crystals. Some evidence of dissolution of BN crystals was observed. Optimum properties were exhibited for samples with 15 wt% of glass addition sintered for 4 h at 1020°C with a relative permittivity ɛ_r=38, a MW quality factor Q × f ₀=17 353 at 5.6 GHz, and a temperature coefficient of resonant frequency τ_f=−10 ppm/°C. The high Q × f ₀, ɛ_r, and low τ_f, coupled with a relatively low sintering temperature, suggest that the use of bespoke glass sintering aids of this type may have great potential for the fabrication of MW ceramics.     

Low-Temperature Firing and Microwave Dielectric Properties of Ca[(Li1/3Nb2/3)0.84Ti0.16]O3−δ Ceramics for LTCC Applications

The effects of LiF and ZnO–B₂O₃–SiO₂ (ZBS) glass combined additives on phase composition, microstructures, and microwave dielectric properties of Ca[(Li_1/3Nb_2/3)_0.84Ti_0.16]O_3−δ (CLNT) ceramics were investigated. The LiF and ZBS glass combined additives lowered the sintering temperature of CLNT ceramics effectively from 1150° to 880°C. The main diffraction peaks of all the specimens split due to the coexistence of the non-stoichiometric phase (A) and stoichiometric phase (B), which all possess CaTiO₃-type perovskite structures. The transformation from A into B became accelerated with the increase of LiF or ZBS content. ZBS glass restrained the volatilization of lithium salt, which greatly affected the microstructures and microwave dielectric properties. CLNT ceramics with 2 wt% LiF and 3 wt% ZBS sintered at 900°C for 2 h show excellent dielectric properties: ɛ_r=34.3, Q × f =17 400 GHz, and τ_f=−4.6 ppm/°C. It is compatible with Ag electrodes, which makes it a promising ceramic for low-temperature cofired ceramics technology application.     

Effects of La on Dielectric and Piezoelectric Properties of Pb1−xLa2x/3(Nb0.95Ti0.0625)2 O6 Ceramics

Ceramics with the chemical compositions of Pb_{1− x} La_{2 x /3}(Nb_0.95Ti_0.0625)₂O₆ (0≤ x ≤0.060) (PLTN) were prepared by the conventional solid-state reaction method. X-ray diffraction analysis indicated that Ti and La doping not only decreased the rhombohedral–tetragonal phase transformation temperature, but also stabilized the orthorhombic phase of PLTN ceramics. All ceramics sintered at 1190°–1250°C had shown the pure orthorhombic ferroelectric phase. La doping suppresses grain growth and inhibits the formation of pores and cracks, resulting in an increase in relative density up to 97%. The amount of La doping to PLTN ceramics obviously affect ceramics' piezoelectric constant ( d ₃₃) and dielectric loss (tanδ). The sample with x =0.015 possesses high Curie temperature ( T _c=560°C), low dielectric loss (tanδ=0.0054), and excellent piezoelectric constant ( d ₃₃=92 pC/N), presenting a high potential to be used in high-temperature applications as piezoelectric transducers.     

Effect of MnO2 Addition on the Structure and Electrical Properties of Pb(Zn1/3Nb2/3)0.20(Zr0.50Ti0.50)0.80O3 Ceramics

Pb(Zn_1/3Nb_2/3)_0.20(Zr_0.50Ti_0.50)_0.80O₃ ceramics of pure perovskite structure were prepared by the two-stage method with the addition of 0–3.0 wt% MnO₂ and their piezoelectric properties were investigated systematically. The MnO₂ addition influences in a pronounced way both the crystal structure and the microstructure of the materials. The materials are transformed from the tetragonal to the rhombohedral structure, and the grain size is enhanced when manganese cations are added. The distortion of crystal structure for samples with MnO₂ addition can be explained by the Jahn–Teller effect. The values of electromechanical coupling factor ( k _p) and dielectric loss (tan δ) are optimized for 0.5-wt%-MnO₂-doped samples ( k _p= 0.60, tan δ= 0.2%) and the mechanical quality factor ( Q _m) is maximized for 1.0-wt%-MnO₂-doped samples ( Q _m= 1041), which suggests that oxygen vacancies formed by substituting Mn³⁺ and Mn²⁺ ions for B-site ions (e.g., Ti⁴⁺ and Zr⁴⁺ ions) in the perovskite structure partially inhibited polarization reversal in the ferroelectrics. The ceramics with 0.50–1.0 wt% MnO₂ addition show great promise as practical materials for piezoelectric applications.     

Sintering and Microwave Dielectric Properties of the LiNb0.63Ti0.4625O3 Ceramics with the B2O3–SiO2 Liquid-Phase Additives

The effect of B₂O₃–SiO₂ liquid-phase additives on the sintering, microstructure, and microwave dielectric properties of LiNb_0.63Ti_0.4625O₃ ceramics was investigated. It was found that the sintering temperature could be lowered easily, and the densification and dielectric properties of LiNb_0.63Ti_0.4625O₃ ceramics could be greatly improved by adding a small amount of B₂O₃–SiO₂ solution additives. No secondary phase was observed for the ceramics with B₂O₃–SiO₂ additives. With the addition of 0.10 wt% B₂O₃–SiO₂, the ceramics sintered at 900°C showed favorable microwave dielectric properties with ɛ_r=71.7, Q × f =4950 GHz, and τ_f=−2.1 ppm/°C. The energy dispersive spectra analysis showed an excellent co-firing interfacial behavior between the LiNb_0.63Ti_0.4625O₃ ceramic and the Ag electrode. It indicated that LiNb_0.63Ti_0.4625O₃ ceramics with B₂O₃–SiO₂ solution additives have a number of potential applications on passive integrated devices based on the low-temperature co-fired ceramics technology.     

Microwave Dielectric Properties of 5Li2O–0.583Nb2O5–3.248TiO2 Ceramics with V2O5

The effects of V₂O₅ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O–0.583Nb₂O₅–3.248TiO₂ (LNT) ceramics have been investigated. With addition of low-level doping of V₂O₅ (≤2 wt%), the sintering temperature of the LNT ceramics could be lowered down to around 920°C due to the liquid phase effect. A secondary phase was observed at the level of 2 wt% V₂O₅ addition. The addition of V₂O₅ does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the excellent microwave dielectric properties of ɛ_r=21.5, Q × f =32 938 GHz, and τ_f=6.1 ppm/°C could be obtained for the 1 wt% V₂O₅-doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as an internal electrode.     

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.     

Microstructure, Piezoelectric, and Ferroelectric Properties of Bi2O3-Added (K0.5Na0.5)NbO3 Lead-Free Ceramics

Lead-free piezoelectric (K_0.5Na_0.5)NbO₃– x wt% Bi₂O₃ ceramics have been synthesized by an ordinary sintering technique. The addition of Bi₂O₃ increases the melting point of the system and improves the sintering temperature of (K_0.5Na_0.5)NbO₃ ceramics. All samples show a pure perovskite phase with a typical orthorhombic symmetry when the Bi₂O₃ content <0.7 wt%. The phase transition temperature of orthorhombic–tetragonal ( T _{O − T} ) and tetragonal–cubic ( T _C) slightly decreased when a small amount of Bi₂O₃ was added. The remnant polarization P _r increased and the coercive field E _c decreased with increasing addition of Bi₂O₃. The piezoelectric properties of (K_0.5Na_0.5)NbO₃ ceramics increased when a small amount of Bi₂O₃ was added. The optimum piezoelectric properties are d ₃₃=140 pC/N, k _p=0.46, Q _m=167, and T _C=410°C for (K_0.5Na_0.5)NbO₃–0.5 wt% Bi₂O₃ ceramics.