Sintering Process and Microwave Dielectric Properties of Bi8TiO14 Ceramics

The formation of a homogeneous Bi₈TiO₁₄ phase was successfully achieved in a specimen calcined at 600°C. However, a Bi₄Ti₃O₁₂ secondary phase also developed in specimens calcined at temperatures higher than 600°C, probably because of Bi₂O₃ evaporation. For specimens sintered above 800°C, a small amount of the Bi₈TiO₁₄ phase melted during sintering, with the liquid phase contributing to the densification of the specimens; however, Bi₄Ti₃O₁₂ and Bi₁₂TiO₂₀ secondary phases were still formed in these specimens. The microwave dielectric properties of the Bi₈TiO₁₄ phase were considerably affected by variations in the microstructure of the specimens. When the sintering temperature exceeded 825°C, the amount of secondary phases increased, and this decreased the density and Q×f values of the specimens. Bi₈TiO₁₄ ceramics sintered at 825°C exhibited promising microwave dielectric properties, with ε_r = 47.4, Q×f = 5370 GHz, and τ_f = ?16.01 ppm/°C.     

Sintering Mechanism and Microwave Dielectric Properties of Bi12TiO20 Ceramics

A homogeneous Bi₁₂TiO₂₀ phase was developed in a specimen that was calcined at 700°C without the formation of a secondary phase. A small amount of the Bi₁₂TiO₂₀ phase melted during sintering and assisted the densification of the specimen. The Bi₂O₃ and Bi₈TiO₁₄ secondary phases were found in all specimens. All the specimens that were sintered at temperatures ≥775°C exhibited high relative densities above 98% of the theoretical density. The Q × f value of the Bi₁₂TiO₂₀ ceramics was influenced by the grain size. The Bi₁₂TiO₂₀ ceramics sintered at 800°C for 5 h showed promising microwave dielectric properties of ε_r = 41, Q × f = 10 400 GHz, and τ_f = ?10.8 ppm/°C.     

Effects of Nb2O5 Doping on the Microwave Dielectric Properties and Microstructures of Bi2Mo2O9 Ceramics

This study investigated the effects of the addition of Nb₂O₅ and sintering temperature on the properties of Bi₂Mo₂O₉ ceramics. The ceramics were sintered in air at temperatures ranging from 620°C to 680°C. The addition of small amounts of Nb₂O₅ as a dopant significantly affected the crystalline phase and the microwave dielectric properties of the Bi₂Mo₂O₉ ceramics. The secondary phase, γ‐Bi₂MoO₆, was observed when Nb₂O₅ was added. However, unlike the Bi₂Mo₂O₉ ceramic without Nb₂O₅ sintered above 645°C, the ceramics with 3 mol% Nb₂O₅ contained no γ‐Bi₂MoO₆ when sintered at 660°C. The Q × f value and τ_f of the Bi₂Mo₂O₉ ceramics were improved by Nb₂O₅ doping. The Bi₂Mo₂O₉ ceramics doped with 2 mol% Nb₂O₅ exhibited the best microwave dielectric properties, with a permittivity of 36.5, a Q × f value (f = resonant frequency, Q = 1/dielectric loss at f) of 14100 GHz and τ_f of +5.5 ppm/°C after sintering at 620°C.     

Crystal structure,Raman spectra,and modified dielectric properties of pure-phase ZnZrNb2O8 ceramics at low temperature

Low-temperature co-fired ceramics technology (LTCC) exhibits enormous superiorities in packaging, integration, and interconnection. However, the complex compositions of low-melting point sintering aids may react with ceramic matrix, which increases the difficulties of phase control and tape casting. In this work, the Li₂CO₃–B₂O₃–Bi₂O₃–SiO₂ (LBBS) sintering aid was adopted to sinter ZnZrNb₂O₈ ceramics with single phase at low temperatures. The LBBS glass could be used to fabricate pure-phase ZnZrNb₂O₈ ceramics at a low sintering temperature, promote the grain growth, and increase the densification of ZnZrNb₂O₈ ceramics. Furthermore, the unit cell volume, NbO₆ octahedral distortion, Raman shift, and FWHM changed along with LBBS addition, thereby affecting the microwave dielectric properties. Remarkably, ZnZrNb₂O₈ ceramics doped with 0.75 wt.% LBBS at 950°C were chemically compatible with the silver electrode and exhibited excellent microwave dielectric characteristics: ε_r = 27.1, Q × f = 54 500 GHz, and τ_f = −48.7 ppm/°C, providing candidates for LTCC applications.     

Phase transitions and microwave dielectric properties of Bi3NbO7 ceramics with Bi4B2O9 addition

The effects of Bi₄B₂O₉ on the phase transitions, sinterability and microwave dielectric properties of Bi₃NbO₇ ceramics were investigated. Densities around 96% theoretical could be achieved at 900 °C for samples with up to 20 wt% Bi₄B₂O₉ addition. Phase transitions of cubic→tetragonal→cubic with the increase of sintering temperature were observed for the samples with Bi₄B₂O₉ addition. Moreover, the Bi₄B₂O₉ addition effectively accelerated the phase transition from cubic Bi₃NbO₇ to tetragonal Bi₃NbO₇. Bi₄B₂O₉ addition and the sintering temperature significantly affected the microwave dielectric properties mainly due to the phase transitions. When 20 wt% Bi₄B₂O₉ was added, a dense ceramic could be sintered at 900 °C with relative permittivity ε_r=79, microwave quality factor Qf₀=1010 GHz, and temperature coefficient of resonance frequency τ_f=+8 ppm/°C, which makes it a promising candidate for LTCC applications.     

Novel Temperature Stable Li2MnO3 Dielectric Ceramics with High Q for LTCC Applications

Novel microwave dielectric ceramics in the Li₂MnO₃ system with high Q prepared through a conventional solid‐state route had been investigated. All the specimens exhibited single phase ceramics sintered in the temperature range 1140°C–1230°C. The microwave dielectric properties of Li₂MnO₃ ceramics were strongly correlated with sintering temperature and density. The best microwave dielectric properties of ε_r = 13.6, Q × f = 97 000 (GHz), and τ_f = ?5.2 ppm/°C could be obtained as sintered at 1200°C for 4 h. BaCu(B₂O₅) (BCB) could effectively lower the sintering temperature from 1200°C to 930°C and slightly induced degradation of the microwave dielectric properties. The Li₂MnO₃ ceramics doped with 2 wt% BaCu(B₂O₅) had excellent dielectric properties of ε_r = 11.9, Q × f = 80 600 (GHz), and τ_f = 0 ppm/°C. With low sintering temperature and good dielectric properties, the BCB added Li₂MnO₃ ceramics are suitable candidates for LTCC applications in wireless communication system.     

Microstructural and Microwave Dielectric Properties of Bi12GeO20 and Bi2O3‐Deficient Bi12GeO20 Ceramics

Bi₁₂GeO₂₀ ceramics sintered at 800°C had dense microstructures, with an average grain size of 1.5 μm, a relative permittivity (ε_r) of 36.97, temperature coefficient of resonance frequency (τ_f) of ?32.803 ppm/°C, and quality factor (Q × f) of 3137 GHz. The Bi_12‐xGeO_20‐1.5x ceramics were well sintered at both 800°C and 825°C, with average grain sizes exceeding 100 μm for x ≤ 1.0. However, the grain size decreased for x > 1.0 because of the Bi₄Ge₃O₁₂ secondary phase that formed at the grain boundaries. Bi_12‐xGeO_20‐1.5x (x ≤ 1.0) ceramics showed increased Q × f values of >10 000 GHz, although the ε_r and τ_f values were similar to those of Bi₁₂GeO₂₀ ceramics. The increased Q × f value resulted from the increased grain size. In particular, the Bi_11.6GeO_19.4 ceramic sintered at 825°C for 3 h showed good microwave dielectric properties of ε_r = 37.81, τ_f = ?33.839 ppm/°C, and Q × f = 14 455 GHz.     

Structure and Microwave Dielectric Properties of Low Firing Bi2Te2W3O16 Ceramics

Dense Bi₂Te₂W₃O₁₆ ceramics were prepared by the conventional solid‐state reaction route. X‐ray diffraction data show the room‐temperature (RT) crystal symmetry of Bi₂Te₂W₃O₁₆ to be well described by the centrosymmetric monoclinic C2/c space group [a = 21.280(5) Å, b = 5.5663(16) Å, c = 12.831(3) Å and β = 124.014(19)° and Z = 4]. Raman spectroscopy analyses are in broad agreement with space group assignment, but also revealed the presence of Bi₂W₂O₉ as a secondary phase. This phase is present as plate‐like grains embedded on a fine‐grained equiaxed matrix, as revealed by scanning electron microscopy. From the fitting of infrared reflectivity data the relative permittivity, ε_r, was estimated as 34.2, and the intrinsic quality factor, Q_u × f as 57 500 GHz. At RT and microwave frequencies, Bi₂Te₂W₃O₁₆ ceramics sintered at 720°C for 6 h exhibit ε_r ~ 34.5, Q_u × f = 3173 GHz (at 7.5 GHz), and temperature coefficient of resonant frequency, τ_f = ?92 ppm/°C. This shows a good agreement between the estimated and measured ε_r values, but also shows that, in principle, the dielectric losses of the ceramics are of extrinsic origin.     

Dielectric Properties of Sol–Gel‐Derived Bi12SiO20 Thin Films

In this paper the dielectric properties of crack‐free, Bi₁₂SiO₂₀ thin films were investigated. The films were prepared on Pt/TiO₂/SiO₂/Si and corundum substrates using the sol–gel method. The formation of a pure Bi₁₂SiO₂₀ phase was observed at a temperature of 700°C. The Bi₁₂SiO₂₀ thin films, heat treated at 700°C for 1 h, had a dense microstructure with an average roughness (R_a) of 50 nm. The dielectric properties of the film were characterized by using both low‐ and microwave‐frequency measurement techniques. The low‐frequency measurements were conducted with a parallel capacitor configuration. The dielectric constant and dielectric losses were 44 and 7.5 × 10^?3, respectively. The thin‐film dielectric properties at the microwave frequency were measured using the split‐post, dielectric resonator method (15 GHz) and the planar capacitor configuration (1–5 GHz). The dielectric constant and the dielectric losses measured at 15 GHz were 40 and 17 × 10^?3, respectively, while the dielectric constant and the dielectric losses measured with the planar capacitor configuration were 39 and 65 × 10^?3, respectively.     

Structure and dielectric properties of novel low temperature co-fired Bi2O3-RE2O3-MoO3 (RE=Pr,Nd, Sm,and Yb) based microwave ceramics

Novel monoclinic Bi₂O₃-xRE₂O₃-yMoO₃ (RE=Pr, Nd, Sm, and Yb) based low temperature co-fired ceramics (LTCC) systems with high sintering density and low microwave dielectric loss are synthesized by conventional solid state reaction technique. The structure and dielectric properties of Bi₂O₃-xRE₂O₃-yMoO₃ ceramics are investigated. Dense BiNdMoO₆ ceramics sintered at 900 °C for 8 h in air have a low dielectric constant ε_r=~7.5, a high quality factor Q×f=~ 24, 800 GHz at 7.0 GHz, and τ_f=~−16 ppm/̊C. Especially, good chemical compatibility of BiNdMoO₆ with Ag electrodes is represented as well. In contrast, BiSmMoO₆ ceramics sintered at 1000 °C for 8 h show enhanced Q×f=~43, 700 GHz at 7.8 GHz with ε_r=~8.5 and τ_f=~−27 ppm/°C. Bi₂O₃-xRE₂O₃-yMoO₃ (RE=Pr, Nd, Sm, and Yb) based ceramics could be considered as promising microwave ceramics for LTCC applications.     

Grain boundary segregation and microwave dielectric properties of low loss Mg1·5Zn0·5SiO4 ceramics containing Bi2O3

Abstract

Abstract

Uncommon low loss Mg_1·5Zn_0·5SiO₄ ceramics containing Bi₂O₃ were investigated by focusing on the roles of Bi₂O₃ on phase evolution and resultant microwave dielectric properties. While the primary goal of lowering sintering temperature can be easily assumed, some unexpected behaviours of the Bi₂O₃ containing materials are highlighted with experimental evidences concerning selective dissolution of Zn₂SiO₄ and grain boundary segregation of gradual Bi richer phases. These evidences are strongly dependent on the content of Bi₂O₃ and sintering temperature. As an optimal composition, Mg_1·5Zn_0·5SiO₄ with 0·5?mol.-%Bi₂O₃ exhibited promising dielectric properties of a k value ～6·8 and a Q×f value ～23?300 at a sintering temperature of 1150°C, which is much lower than typical sintering temperature of 1450°C.     

Phase evolution and microwave dielectric properties of SrTiO3 added ZnAl2O4–Zn2SiO4–SiO2 ceramics

Phase evolution and microwave dielectric properties of SrTiO₃ added ZnAl₂O₄–3Zn₂SiO₄–2SiO₂ ceramics system were investigated. With the addition of SrTiO₃, the sintering temperature for dense ceramic is reduced from 1320 °C to 1180–1200 °C. According to the nominal composition ZnAl₂O₄–3Zn₂SiO₄–2SiO₂-ySrTiO₃, phase evolution is revealed by XRD patterns and Back Scattering Electron images: Zn₂SiO₄, ZnAl₂O₄ and SiO₂ phases coexist at y = 0; SrTiO₃ reacts with ZnAl₂O₄ and SiO₂ to form SrAl₂Si₂O₈, TiO₂ and Zn₂SiO₄ at y = 0.2 to 0.8, and SiO₂ phase disappears at y = 0.8; new phase of Zn₂TiO₄ is obtained at y = 1. The existence of TiO₂ has important effect on the dielectric properties. The optimized microwave dielectric properties are obtained at y = 0.6 and the ceramics show low dielectric constant (7.16), high-quality factor (57, 837 GHz), and low temperature coefficient of resonant frequency (−30 ppm °C⁻¹).     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.     

Low‐Temperature Sintering and Microwave Dielectric Properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4–(Ca0.8Sr0.2)TiO3 Composite Ceramics

0.9(Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄–0.1(Ca_0.8Sr_0.2)TiO₃ (MZTS–CST) ceramics were prepared by a conventional solid‐state route. The MZTS–CST ceramics sintered at 1325°C exhibited ε_r = 18.2, Q × f = 49 120 GHz (at 8.1 GHz), and τ_f = 15 ppm/°C. The effects of LiF–Fe₂O₃–V₂O₅ (LFV) addition on the sinterability, phase composition, microstructure, and microwave dielectric properties of MZTS–CST were investigated. Eutectic liquid phases 0.12CaF₂/0.28MgF₂/0.6LiF and MgV₂O₆ were developed, which lowered the sintering temperature of MZTS–CST ceramics from 1325°C to 950°C. X‐ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS) analysis revealed that MZTS and CST coexisted in the sintered ceramics. Secondary phase Ca₅Mg₄(VO₄)₆ as well as residual liquid phase affected the microwave dielectric properties of MZTS–CST composite ceramics. Typically, the MZTS–CST–5.3LFV composite ceramics sintered at 950°C showed excellent microwave dielectric properties: ε_r = 16.3, Q × f = 30 790 GHz (at 8.3 GHz), and τ_f = ?10 ppm/°C.     

Microwave dielectric properties and microstructures of Nb2O5-Zn0.95Mg0.05TiO3 + 0.25TiO2 ceramics with Bi2O3 addition

The effects of Bi₂O₃ addition on the microwave dielectric properties and the microstructures of Nb₂O₅-Zn_0.95Mg_0.05TiO₃ + 0.25TiO₂ (Nb-ZMT′) ceramics prepared by conventional solid-state routes have been investigated. The results of X-ray diffraction (XRD) indicate the presence of four crystalline phases, ZnTiO₃, TiO₂, Bi₂Ti₂O₇, and (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ in the sintered ceramics, depending upon the amount of Bi₂O₃ addition. In addition, in order to confirm the existence of (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ phase in the samples, the microstructure of Nb-ZMT′ ceramic with 5 wt.% B₂O₃ addition was analyzed by using a transmission electron micrograph. The dielectric constant of Nb-ZMT′ samples was higher than ZMT′ ceramics. The Nb-ZMT′ ceramic with 5 wt.% Bi₂O₃ addition exhibits the optimum dielectric properties: Q × f = 12,000 GHz, ?_r = 30, and τ_f = ?12 ppm/°C. Unlike the ZMT′ ceramic sintered at 900 °C, the Nb-ZMT′ ceramics show higher Q value and dielectric constant. Moreover, there is no Zn₂TiO₄ existence at 960 °C sintering. To understand the co-sinterability between silver electrodes and the Nb-ZMT′ dielectrics, the multilayer samples are prepared by multilayer thick film processing. The co-sinterability (900 °C) between silver electrode and Nb-ZMT′ dielectric are well compatible, because there are no cracks, delaminations, and deformations in multilayer specimens.     

The Influence of the Precursor on the Formation of Bi2O3 Polymorphs in CSD‐Derived Thin Films

This work examines the synthesis and characterization of crack‐free, β‐Bi₂O₃ thin films prepared on Pt/TiO₂/SiO₂/Si or corundum substrates using the sol‐gel method. We observed that the Bi‐based precursor has a pronounced influence on the β‐Bi₂O₃ phase formation. Well‐crystallized, single β‐Bi₂O₃ thin films were obtained from Bi‐2ethylhexanoate at a temperature of 400°C. In contrast, thin films deposited from Bi‐nitrate and Bi‐acetate resulted in non‐single Bi₂O₃ phase formation. TEOS was used for the stabilization of the β‐Bi₂O₃ phase. The phase composition of the thin films was characterized by means of X‐ray diffraction (XRD), whereas the morphology and thickness of the thin films were studied using scanning electron microscopy (SEM). The β‐Bi₂O₃ films' dielectric properties were characterized utilizing microwave‐frequency measurement techniques: (1) the split‐post dielectric resonator method (15 GHz) and (2) the planar capacitor configuration (1–5 GHz). The dielectric constant and dielectric loss measured at 15 GHz were 257 and 7.5 × 10^?3, respectively.     

Effects of ZnO and B2O3 on the Microstructure and Microwave Dielectric Properties of 5Li2O‐1Nb2O5‐5TiO2 Ceramics

The effects of ZnO and B₂O₃ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O‐1Nb₂O₅‐5TiO₂ (LNT) ceramics have been investigated. With addition of low‐level doping of ZnO and B₂O₃, the sintering temperature of the LNT ceramics can be lowered down to near 920°C due to the liquid phase effect. The Li₂TiO₃ss and the “M‐phase” are the two main phases, whereas other phase could be observed when co‐doping with ZnO and B₂O₃ in the ceramics. And the amount of the other phase increases with the ZnO content increasing. The addition of ZnO does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the good microwave dielectric properties of ε_r = 36.4, Q × f = 8835 GHz, τ_f = 4.4 ppm/°C could be obtained for the 1 wt% B₂O₃ and 4 wt% ZnO co‐doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as internal electrode.     

Microwave dielectric properties of (0.75ZnAl2O4–0.25TiO2)–MgTiO3 ceramics prepared using digital light processing technology

ZTM ceramics comprising of 0.75ZnAl₂O₄–0.25TiO₂ and MgTiO₃ at a ratio of 90:10 wt.% are widely used in the field of communication as filters and resonators owing to their excellent microwave dielectric properties. However, the development of such dielectrics with complex structures, as required by microwave devices, is difficult using traditional fabrication methods. In this study, ZTM microwave dielectric ceramics were prepared using the digital light processing (DLP) technology. The influence of the sintering temperature on the phase composition, microstructure, and microwave dielectric properties of ZTM ceramics was investigated. Results showed that with an increase in the sintering temperature, the dielectric constant (ε_r) and quality factor (Q × f) of ZTM ceramics initially increased owing to the increase in the density and diffusion of ions. However, when the sintering temperature was excessively high, the abnormal growth of crystal grains and micropores led to a decrease in ε_r and Q × f. The ZTM ceramics sintered at 1450°C exhibited the optimum microwave dielectric properties (ε_r = 12.99, Q × f = 69 245 GHz, τ_f = −9.50 ppm/°C) owing to the uniform microstructure and a high relative density of 95.02%. These results indicate that DLP is a promising method for preparing high-performance microwave dielectric ceramics with complex structures.     

Srn+1TinO3n+1 (n=1, 2) microwave dielectric ceramics with medium dielectric constant and ultra‐low dielectric loss

Sr_n+1Ti_nO_3n+1 (n=1, 2) ceramics with tetragonal Ruddlesden–Popper structure were prepared via a standard solid‐state reaction process, and their microstructures and microwave dielectric properties were investigated systematically. The phase composition, grain morphology, and densification behavior were explored using X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Outstanding microwave dielectric properties were achieved in the present ceramics: ε_r=42, Q × f=145 200 GHz, τ_f=130 ppm/°C for Sr₂TiO₄, and ε_r=63, Q × f=84 000 GHz, τ_f=293 ppm/°C for Sr₃Ti₂O₇, respectively. The present ceramics might be expected as excellent candidates for next‐generation medium‐permittivity microwave dielectric ceramics after the further optimization of τ_f value.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.