Li2ZnTi3O8 based High κ LTCC tapes for improved thermal management in hybrid circuit applications

A low temperature co-fired ceramic based on Li₂ZnTi₃O₈ (LZT), that possess auspicious thermal and dielectric properties is reported. In order to achieve the low sintering temperature suitable for LTCC applications (875 °C), 1 wt% of 20:Li₂O-20: MgO-20: ZnO-20:B₂O₃-20: SiO₂ (LMZBS) glass was added to LZT ceramics. The post-milled powder had an average particle size of 450 nm with an effective surface area of 0.812 m²g⁻¹. A well dispersed tape casting slurry was prepared using xylene/ethanol mixture as solvent and fish oil as dispersant. The crystal structure and microstructure of the tapes were analyzed through XRD and scanning electron microscopy (SEM). The microwave dielectric properties of the green as well as sintered tapes were measured at different frequencies (5, 10 and 15 GHz). The Li₂ZnTi₃O₈+1 wt% LMZBS has shown excellent thermal conductivity of 5.8 W/mK, thermal expansivity (11.97 ppm/°C) closer to silver electrode, low temperature coefficient of dielectric constant (−29 ppm/°C) and ultralow dielectric losses (tanδ~10⁻⁴).     

Temperature–stable dielectrics based on Cu–doped Bi2Mg2/3Nb4/3O7 pyrochlore ceramics for LTCC

Temperature–stable dielectrics based on Cu–doped Bi₂Mg_2/3Nb_4/3O₇ pyrochlore ceramics were prepared by conventional solid–state reaction. Microstructure analysis indicates that all of the specimen maintain the cubic pyrochlore phase, a fluorite–like phase of Bi₃NbO₇ and a Bi₅Nb₃O₁₅ formed for Cu doping. The dielectric constant is dominated by densification of samples and secondary phases, while the dielectric loss is related by the secondary phases, grain boundaries, and leakage current characteristics. The (1-x)BMN - xCuO(x = 0.1 mol%) ceramic sintered at 925 °C shows excellent dielectric properties with dielectric constant of ~184.06, dielectric loss of ~0.0017 and near zero τ_ε (?20 ppm/°C) is obtained at sintering temperature of 925 °C, which could be a promising candidate for LTCC.     

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.     

Low-temperature sintering of Ti1−xCux/3Nb2x/3O2 (x = 0.23) microwave dielectric ceramics with CuO and B2O3 addition

The influence of CuO and B₂O₃ addition on the sintering behavior, microstructure and microwave dielectric properties of Ti_1?xCu_x/3Nb_2x/3O₂ (TCN, x = 0.23) ceramic have been investigated. It was found that the addition of CuO and B₂O₃ successfully reduced the sintering temperature of TCN ceramics from 950 to 875 °C. X-ray diffraction studies showed that addition of CuO-B₂O₃ has no effect on the phase composition. The TCN ceramics with 0.5 wt% CuO-B₂O₃ addition showed a high dielectric constant of 95.63, τ_f value of + 329 ppm/°C and a good Q × f value of 8700 GHz after sintered at 875 °C for 5 h, cofirable with silver electrode.     

Low-temperature-sintered Bi0.5Na0.5TiO3-based lead-free ferroelectric ceramics with good piezoelectric properties

Li₂CO₃ has been used as a sintering aid for fabricating lead-free ferroelectric ceramic 0.93(Bi_0.5Na_0.5TiO₃)-0.07BaTiO₃. A small amount (0.5 wt%) of it can effectively lower the sintering temperature of the ceramic from 1200 °C to 980 °C. Unlike other low temperature-sintered ferroelectric ceramics, the ceramic retains its good dielectric and piezoelectric properties, giving a high dielectric constant (1570), low dielectric loss (4.8%) and large piezoelectric coefficient (180 pC/N). The “depolarization” temperature is also increased to 100 °C and the thermal stability of piezoelectricity is improved. Our results reveal that oxygen vacancies generated from the diffusion of the sintering aid into the lattices are crucial for realizing the low temperature sintering. Owing to the low sintering temperature and good dielectric and piezoelectric properties, the ceramics, especially of multilayered structure, should have great potential for practical applications.     

Co2O3 substitution effects on the structure and microwave dielectric properties of low-firing (Zn0.9Mg0.1)TiO3 ceramics

Low-firing (Zn_0.9Mg_0.1)_1?xCo_xTiO₃ (x = 0.02–0.10) (ZMC_xT) microwave dielectric ceramics with high temperature stability were synthesized via conventional solid-state reaction. The influences of Co₂O₃ substitution on the phase composition, microstructure and microwave dielectric properties of ZMC_xT ceramics were discussed. Rietveld refinement results show the coexistence of ZnTiO₃ and ZnB₂O₄ phases at x = 0.02–0.10. (Zn_0.9Mg_0.1)_1?xCo_xTiO₃ ceramic with x = 0.06 (ZMC_0.06T) obtains the best combination microwave dielectric properties of: ε_r = 21.58, Q × f = 53,948 GHz, τ_f = ? 54.38 ppm/°C. For expanding its application in LTCC field, 3 wt% ZnO-B₂O₃-SiO₂ (ZBS) and 9 wt% TiO₂ was added into ZMC_0.06T ceramic, great microwave dielectric properties were achieved at 900 °C for 4 h: ε_r = 26.03, Q × f = 34,830 GHz, τ_f = ? 4 ppm/°C, making the composite ceramic a promising candidate for LTCC industry.     

Role of Nano‐ and Micron‐Sized Particles of TiO2 Additive on Microwave Dielectric Properties of Li2ZnTi3O8 – 4 wt% TiO2 Ceramics

Microwave dielectric ceramics with the composition of Li₂ZnTi₃O₈ – 4 wt% TiO₂ were synthesized by the conventional solid‐state reaction. 4 wt% TiO₂ powders with different particles size were added to the Li₂ZnTi₃O₈ ceramic. Then the ceramic samples were sintered at temperatures 1075°C, 1050°C, 1000°C, and 950°C for 4 h. The effect of the particles size of TiO₂ additive on the microwave dielectric properties of the ceramics has been investigated. In the study two categories of particles size of TiO₂ additive have been used; (i) Nanoparticle (50 nm), (ii) Micron sized (40, 5, 1 μm) powder. X‐ray showed that the TiO₂ additive has not solved in the LZT structure and has not almost undergone chemical reaction with the LZT ceramic. The results showed that the addition of TiO₂ nanoparticles to the LZT ceramics significantly improved the density and a dense and uniform microstructure and also abnormal grain growth were observed by SEM. The use of TiO₂ nanoparticle reduces porosity and leads to an increase in green density. The maximum density was found to be 98.5% of the theoretical density and the best relative permittivity of 28, quality factor of 68000 GHz and τ_f value of ?2 ppm/°C were obtained for the samples added with 4 wt% of the TiO₂ nanoparticles, sintered at 1050°C for 4 h.     

Fabrication and performance of dielectric tape based on CaO-B2O3-SiO2 glass/Al2O3 for LTCC applications

A non-aqueous tape-casting process for fabricating CaO-B₂O₃-SiO₂ glass/Al₂O₃ dielectric tape for LTCC applications was investigated. An isopropanol/ethanol/xylene ternary solvent-based slurry was developed by using castor oil, poly(vinyl butyral), and dibutyl phthalate as dispersant, binder, and plasticizer, respectively. The effects of dispersant concentration, binder content, plasticizer/binder ratio, and solid loading, on the properties of the casting slurry and resultant tape were systematically investigated. The results showed that the optimal values for the dispersant and binder contents, plasticizer/binder ratio, and solid loading were 2.0 wt%, 7.5 wt%, 0.6, and 62 wt%, respectively. The resultant flexible and uniform, 120-μm-thick CaO-B₂O₃-SiO₂ glass/Al₂O₃ tape had a density of 1.90 g/cm^?3, tensile strength of 1.66 MPa, and average surface roughness of 310 nm. Laminated tapes sintered at 875 °C for 15 min exhibited excellent properties: relative density of 97.3%, ε_r of 7.98, tan δ of 1.3 × 10^?3 (10 MHz), flexural strength of 205 MPa, and thermal expansion coefficient of 5.47 ppm/°C. The material demonstrated good chemical compatibility with Ag electrodes, indicating a significant potential in LTCC applications.     

Microstructure and microwave dielectric properties of Al2O3 added Li2ZnTi3O8 ceramics

Recently, the rapid development of advanced communication systems increasingly strongly demands high-performance microwave dielectric ceramics in microwave circuits. Among them, Li₂ZnTi₃O₈ ceramics have been one of the most widely investigated species, due to its high quality factor, moderate firing conditions and low cost. However, the dielectric constants of the already reported Li₂ZnTi₃O₈ ceramics are fixed in a narrow range, limiting their wider applications. To adjust the dielectric constant of the Li₂ZnTi₃O₈ based ceramics, in this work Li₂ZnTi₃O₈ ceramics added with different amounts of Al₂O₃ (0–8?wt%) were prepared by conventional solid-state reaction. The microstructure and microwave dielectric properties of the samples were investigated. Due to the addition of Al₂O₃, the sintering temperature of the ceramics would be increased somewhat. Some Al³⁺ ions could substitute for Ti⁴⁺ ions in Li₂ZnTi₃O₈, and the added Al₂O₃ would react with ZnO to produce a ZnAl₂O₄ phase accompanying with the formation of TiO₂ phase, which would inhibit the growth of Li₂ZnTi₃O₈ grains. The dielectric constant of the finally obtained ceramics would be reduced from 26.2 to 17.9, although the quality factors of the obtained ceramics would decrease somewhat and the temperature coefficient of resonant frequency would deviate further from zero.     

Sintering behavior and microwave dielectric properties of 0.67CaTiO3–0.33LaAlO3 ceramics modified by B2O3–Li2O–Al2O3 and CeO2

A low temperature sintering method was used to avoid the relatively high sintering temperatures typically required to prepare 0.67CaTiO₃–0.33LaAlO₃ (CTLA) ceramics. Additionally, CeO₂ was introduced into the CTLA ceramics as an oxygen-storage material to improve their microwave dielectric properties. 0.67CaTiO₃–0.33LaAlO₃ ceramics co-doped with B₂O₃–Li₂O–Al₂O₃ and CeO₂ were prepared by a conventional two-step solid-state reaction process. The sintering behavior, crystal structure, surface morphology, and microwave dielectric proprieties of the prepared ceramic samples were studied, and the reaction mechanism of CeO₂ was elucidated. CTLA+0.05 wt% BLA+3 wt% CeO₂ ceramics sintered at 1360 °C for 4 h exhibited the optimal microwave dielectric properties: dielectric constant (ε_r)=45.02, quality factor (Q×f)=43102 GHz, and temperature coefficient of resonant frequency (τ_f)=2.1 ppm/°C. The successful preparation of high-performance microwave dielectric ceramics provides a direction for the future development and commercialization of CTLA ceramics.     

Low-dielectric-constant LiAlO2 ceramics combined with LBSCA glass for LTCC applications

This study used Li₂O–B₂O₃–SiO₂–CaO–Al₂O₃ (LBSCA) glass to reduce the sintering temperature of LiAlO₂ ceramics and to realise the low dielectric constants (ɛ_r<5) of low-temperature co-fired ceramic (LTCC) materials. LBSCA glass remarkably enhanced the densification of LiAlO₂ ceramics. X-ray diffraction patterns indicated that only the γ-LiAlO₂ phase occurred within the doping range of 1 wt% to 3.5 wt%. Scanning electron microscopy images showed dense and uniform grains in samples with 3.0 wt% LBSCA glass. These samples also exhibited low dielectric constants and low dielectric loss when sintered at 900 °C and 950 °C (i.e., ɛ_r=4.48, Qf=35,540 GHz and τ_f=−53 ppm/°C at 900 °C; ɛ_r=4.50, Qf=38,979 GHz and τ_f=−55 ppm/°C at 950 °C, respectively). The material prepared was chemically compatible with silver and showed potential in applications of high-frequency LTCC microwave substrates.     

Temperature stability and high-Qf of low temperature firing Mg2SiO4–Li2TiO3 microwave dielectric ceramics

In this work, a series of low-temperature-firing (1−x)Mg₂SiO₄–xLi₂TiO₃–8 wt% LiF (x = 35–85 wt%) microwave dielectric ceramics was prepared through conventional solid state reaction. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that the Li₂TiO₃ phase was transformed into cubic phase LiTiO₂ phase and secondary phase Li₂TiSiO₅. Partial substitution of Mg²⁺ ions for Ti³⁺ ions or Li⁺Ti³⁺ ions increased the cell volume of the LiTiO₂ phase. The dense microstructures were obtained in low Li₂TiO₃ content (x ≤ 65 wt%) samples sintered at 900 °C, whereas the small quantity of pores presented in high Li₂TiO₃ content (x ≥ 75 wt%) samples sintered at 900 °C and low Li₂TiO₃ content (x = 45 wt%) sintered at 850 and 950 °C. Samples at x = 45 wt% under sintering at 900 °C for 4 h showed excellent microwave dielectric properties of ε_r = 10.7, high Q × f = 237,400 GHz and near-zero τ_f = − 3.0 ppm/°C. The ceramic also exhibited excellent chemical compatibility with Ag. Thus, the fabricated material could be a possible candidate for low temperature co-fired ceramic (LTCC) applications.     

Enhanced dielectric and energy-storage properties in ZnO-doped 0.9(0.94Na0.5Bi0.5TiO3−0.06BaTiO3)−0.1NaNbO3 ceramics

[0.9(0.94Na_0.5Bi_0.5TiO₃?0.06BaTiO₃)?0.1NaNbO₃]-xZnO (NBT-BT-NN-xZnO, x=0, 0.5 wt%, 1.0 wt%, 1.5 wt%, and 2.0 wt%) ferroelectric ceramics were fabricated using a conventional solid-state reaction method. The effects of ZnO content on dielectric, energy-storage and discharge properties were systematically investigated. Dielectric constant and difference between maximum and remanent polarization were significantly improved by ZnO doping. Dielectric constant of NBT-BT-NN-1.0-wt% ZnO was 3218 at 1 kHz and room temperature, i.e. one time bigger than that of pure NBT-BT-NN ceramic. As a consequence, a maximum energy-storage density of 1.27 J/cm³ with a corresponding efficiency of 67% was obtained in NBT-BT-NN-1.0-wt% ZnO ceramic. Moreover, its pulsed discharge energy density was 1.17 J/cm³, and 90% of which could be released in less than 300 ns. Therefore, ZnO doped NBT-BT-NN ceramic with a large energy-storage density and short release time could be a potential candidate for applications in high energy-storage capacitors.     

Tetragonal Er3+-doped (K0.48Na0.48Li0.04)(Nb0.96Bi0.04)O3: Lead-free ferroelectric transparent ceramics with electrical and optical multifunctional performances

The lead-free Er³⁺-doped (K_0.48Na_0.48Li_0.04)(Nb_0.96Bi_0.04)O₃ (KNLNB-Er-x) ceramics were fabricated by conventional pressureless sintering. They possess a tetragonal perovskite phase with dense microstructure. High transmittances of the ceramics are obtained both in the visible and infrared regions. The optical band gap energies of them are 3.07–3.11 eV, close to other KNN-based materials. The relaxor-like characteristics, good dielectric, ferroelectric and piezoelectric properties of the ceramics have been obtained. The up-conversion photoluminescence spectra have been studied and obvious color-tunable emissions have been observed by modulating temperature. The fluorescence intensity ratio (FIR) value based on green emissions at 533 and 555 nm in the temperature ranging from 300 to 750 K have been investigated, giving the maximum sensitivity of ~ 0.0038 K^?1. Furthermore, the FIR technique opens up a method to detect the Curie temperature of the ceramics. Owing to both optical and electrical properties, the KNLNB-Er-x transparent ceramics could be a promising candidate in the application of color-tunable solid-state lightings, optical temperature sensors, and electrical-optical coupling devices.     

Effects of TiO2 addition on dielectric and energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics

In this work, 25.6BaO-6.4K₂O-32Nb₂O₅-36SiO₂-xTiO₂ (0 ≤ x ≤10 mol%) (BKNST) glass ceramics were synthesized by conventional melts and controllable crystallization method. The effects of different TiO₂ addition on the phase composition, dielectric and energy storage properties of BKNS glass ceramics were systematically evaluated. With the TiO₂ concentration increasing, a growing content of Ba₂TiO₄ phase was observed in the glass ceramics. The microstructures appeared to be homogenous and uniform with very low porosity through the addition of TiO₂, for which the maximal breakdown strength of 2112 kV/cm and the corresponding energy storage density of 9.48 J/cm³ were obtained with x = 7.5. The extremely low dielectric loss of less than 1‰ (25 °C, 100 kHz) and the obviously improved microstructure contributed to the increased breakdown strength. In addition, the discharge power density of the glass-ceramic capacitor (x = 7.5) was investigated using the RLC charge-discharge circuit and a relatively high value of 16 MW/cm³ at 300 kV/cm was obtained.     

Low temperature sintering and microwave dielectric properties of Li2ZnTi3O8 ceramics doped with ZnO–La2O3–B2O3 glass

Li₂ZnTi₃O₈ ceramics doped with ZnO–La₂O₃–B₂O₃ glass were prepared by the conventional solid-state ceramic route. The effects of the ZnO–La₂O₃–B₂O₃ glass on the sintering temperature, phase composition, microstructure and microwave dielectric properties of Li₂ZnTi₃O₈ ceramics were investigated. The addition of ZLB glass can reduce the sintering temperature of Li₂ZnTi₃O₈ ceramic from 1075 °C to 925 °C without obvious degradation of the microwave dielectric properties. Only a single phase Li₂ZnTi₃O₈ with cubic spinel structure is formed in Li₂ZnTi₃O₈ ceramic with ZLB addition sintered at 925 °C. Typically, 1.0 wt% ZLB-doped Li₂ZnTi₃O₈ ceramic sintered at 925 °C can reach a maximum relative density of 95.8% and exhibits good microwave dielectric properties of ε_r=24.34, Q×f=41,360 GHz and τ_f=−13.4 ppm/°C. Moreover, this material is compatible with Ag electrode, which makes it a promising candidate for LTCC application.     

Effect of Li2O–V2O5 on the low temperature sintering and microwave dielectric properties of Li1.0Nb0.6Ti0.5O3 ceramics

Li₂O–Nb₂O₅–TiO₂ based ceramic systems have been the candidate materials for LTCC application, due to their high dielectric constant and Q × f value and controllable temperature coefficient in the microwave region. However, the sintering temperature was relatively higher (above 1100 °C) for practical application. In this study, dielectric properties of Li_(1+x−y)Nb_(1−x−3y)Ti_(x+4y)O₃ solid solution were studied with different x and y contents and among them, the Li_1.0Nb_0.6Ti_0.5O₃ composition (x = 0.1, y = 0.1) was selected, due to its reasonable dielectric properties to determine the possibility of low temperature sintering. The effects of 0.17Li₂O–0.83V₂O₅, as a sintering agent, on sinterability and microwave dielectric properties of Li_1.0Nb_0.6Ti_0.5O₃ ceramics were investigated as a function of the sintering agent content and sintering temperature. With addition of 0.17Li₂O–0.83V₂O₅ above 0.5 wt%, the specimens were well densified at a relatively lower temperature of 850 °C. Only slight decrease in apparent density was observed with increasing 0.17Li₂O–0.83V₂O₅ content above 0.75 wt%. In the case of 0.5 wt% 0.17Li₂O–0.83V₂O₅ addition, the values of dielectric constant and Q × f reached maximum. Further addition caused inferior microstructure, resulting in degraded dielectric properties. For the specimens with 0.5 wt% 0.17Li₂O–0.83V₂O₅ sintered at 850 °C, dielectric constant, Q × f and TCF values were 64.7, 5933 GHz and 9.4 ppm per °C, respectively.     

Microwave dielectric properties of CaWO4–Li2TiO3 ceramics added with LBSCA glass for LTCC applications

In this work, 0.86CaWO₄–0.14Li₂TiO₃ ceramics were prepared via a traditional solid-state process. The effects of Li₂O–B₂O₃–SiO₂–CaO–Al₂O₃ (LBSCA) addition on the phase formation, sintering character, microstructure and microwave dielectric properties of the ceramics were investigated. A small amount of LBSCA addition could effectively lower the sintering temperature of the ceramics. X-ray diffraction analysis revealed that CaWO₄ and Li₂TiO₃ phases coexisted without producing any other crystal phases in the sintered ceramics. The dielectric constant and Qf values were related to the amount of LBSCA addition and sintering temperatures. All specimens could obtain near-zero temperature coefficient (τ_f) values through the compensation of the positive τ_f of Li₂TiO₃ and the negative τ_f of CaWO₄. The 0.86CaWO₄–0.14Li₂TiO₃ ceramic with 0.5 wt% LBSCA addition and sintered at 900 °C for 3 h exhibited excellent microwave dielectric properties of ε_r=12.43, Qf=76,000 GHz and τ_f=−2.9 ppm/°C.     

Effects of lanthanides on structural and dielectric properties of NdNbO4-LnNbO4 ceramics

Recently, lanthanide niobates have attracted significant attentions in multi-functional materials. Herein a series of fergusonite structure-related (1-x)NdNbO₄-xLnNbO₄ (Ln = Yb, Er, Ho, Dy, Gd and Ce; 0.02 ≤ x ≤ 0.08) ceramics were prepared via conventional solid-state reaction method and the microwave dielectric properties were systematically discussed. The X-ray diffraction, Raman spectra were employed to investigate the crystal structure. Obtained results indicate that the ceramic samples present single monoclinic phase belong to the space group of I2/a. Microwave dielectric behaviors shown that the permittivity (ε_r) and the quality factor (Q × f) were influenced by the relative density, and the temperature coefficients of resonant frequency (τ_?) value kept the same variation tendency with the Nb-site bond valence. Furthermore, Far-IR and bond energy study evidenced the Ln-O oscillations dominated the main dielectric polarization and system stability. Good microwave dielectric properties, with ε_r ~ 20.88, Q × f ~ 66,510 GHz (at 8.60 GHz) and τ_f ~ ? 36.59 ppm/°C, were obtained in 0.94NdNbO₄–0.06YbNbO₄ ceramics when sintered at 1250 °C for 4 h. The (Nd_0.94Yb_0.06)NbO₄ might be potential candidate for the applications of modern microwave devices.     

A novel Li2TiO3–Li2CeO3 ceramic composite with excellent microwave dielectric properties for low-temperature cofired ceramic applications

A novel low-temperature sinterable (1 ? x)Li₂TiO₃-xLi₂CeO₃ (x = 0.08 ? 0.16 in molar) microwave dielectric ceramic was successfully prepared by a conventional solid-state reaction method. The X-ray diffraction and scanning electron microscopy analysis revealed the coexistence of two phases with different structures owing to their good chemical stability. Their relative content was easily adjusted to achieve near-zero temperature coefficient of the resonant frequency (τ_f) according to the mixing rule of dielectrics. The low-temperature sintering and desirable microwave dielectric properties can be simultaneously achieved by adding Li₂CeO₃ to the Li₂TiO₃ matrix owing to its low-firing characteristic and opposite-sign τ_f. The composite ceramics with x = 0.14 could be well sintered at 850 °C and exhibited excellent microwave dielectric properties of ε_r ～ 21.2, Qxf～ 59,039 GHz and τ_f ～?7.4 ppm/°C. In addition, no chemical reaction was identified between the matrix phase and Ag, suggesting that the Li₂TiO₃-Li₂CeO₃ ceramics might be promising candidates for low-temperature co-fired ceramic applications.