Low-loss and ultra-low temperature sintering microwave dielectrics of pure and Ag-modified K2Mg2(MoO4)3 ceramics

Novel K_2–2xAg_2xMg₂(MoO₄)₃ (x = 0–0.09) ceramics were synthesized by conventional solid-state sintering method. Based on the X-ray diffraction (XRD) patterns, all samples were identified to belong to an orthorhombic structure with a space group of P212121(19). The pure phase K₂Mg₂(MoO₄)₃ specimen when sintered at 590 °C revealed the favorable microwave dielectric properties: ε_r of 6.91, Q×f of 21,900 GHz and τ_f of ?164 ppm/°C. The substitution of Ag⁺ for K⁺ in K_2–2xAg_2xMg₂(MoO₄)₃ (x = 0.01–0.09) ceramics led to the more stable structure and dramatically enhanced the Q×f to a value of 54,900 GHz at 500 °C. The microwave dielectric properties were related to the relative density, microstructure, ionic polarization, lattice energy, packing fraction, and bond valence of the ceramics. It was suggested that for ultra-low temperature co-fired ceramic (ULTCC) applications, K_1.86Ag_0.14Mg₂(MoO₄)₃ ceramic could be sintered at 500 °C, which revealed an excellent combination of microwave dielectric properties (ε_r =7.34, Q×f =54,900 GHz and τ_f =–156 ppm/°C) and good chemical compatibility with aluminum electrodes.     

Ultra-low temperature sintering and temperature stable microwave dielectrics of phase pure AgMgVO4 ceramics

The present study systematically invesitgates the formation and microwave dielectric properties of novel AgMgVO₄ ceramics fabricated via the solid-state reaction method. The crystal structure of the ceramics is confirmed to be orthorhombic with a space Group of Pnma (62). A high relative density of 96.2% and an excellent combination of microwave dielectric properties with ε_r of ~14.89, Q×f of ~19,400 GHz, and τ_f of ~ ? 2.71 ppm/°C can be achieved for the ceramic sintered at 630 °C. The dielectric constant is mainly influenced by the relative density (porosity) and dielectric polarizability. The Q×f is controlled by the microstructure, packing fraction, and lattice energy, which are also highly related to the unit-cell volume. A smaller unit-cell volume leads to a high Q×f. Variation of the τ_f is strongly correlated to the bond valence of the specimen. Furthermore, the ceramic exhibits good chemical compatibility with aluminum electrodes and is demonstrated as a potent substrate for a band-pass filter with a center frequency of 3.5 GHz. These findings show a great promise for ultra-low temperature co-fired ceramic applications at high frequencies.     

Enhanced Na+-substituted Li2Mg2Mo3O12 ceramic substrate based on ultra-low temperature co-fired ceramic technology for microwave and terahertz polarization-selective functions

A novel Li₂Mg_2-xNa_2xMo₃O₁₂ (x = 0.09) ceramic with ultra-low sintering temperature is prepared by the solid-state reaction method. This ceramic (625 °C) exhibits excellent microwave dielectric properties (ε_r = 7.9, Q×f = 43844 GHz, τ_f = ?48.3 ppm/°C), terahertz transmission properties (ε_r¹ = 7.4, tan σ¹ = 0.0158, T_coefficient = 0.598), and chemical compatibility with Ag. For the first time, two polarization selective devices are designed in the microwave and terahertz regions by using this ceramic substrate, respectively. The transmission amplitudes of the right- and left-handed circularly polarized waves of the microwave device at 9.7 GHz are 0.895 and 0.019, respectively. The transmission coefficients of the y- and x-polarized waves of the terahertz device at 0.45 THz are 0.598 and 0.075, respectively. Both functions are verified by the overall far-field radiation pattern. This work promotes the application of dielectric ceramics and ULTCC technology in the microwave and terahertz regions.     

Crystal structure and microwave dielectric properties of NaPb2B2V3O12(B=Mg,Zn) ceramics

Two low temperature sintered NaPb₂B₂V₃O₁₂ (B?=?Mg, Zn) ceramics with garnet structure were synthesized through conventional solid state reaction route and their crystal structure and microwave dielectric properties were investigated for the first time. Rietveld refinements of XRD patterns show both the compounds belong to cubic symmetry with space group Ia-3d. Observed number of Raman bands and group theoretical predictions also confirm cubic symmetry with space group Ia-3d for both NPMVO and NPZVO. At the optimum sintering temperature of 725?°C NPMVO has a relative permittivity of 20.6?±?0.2, unloaded quality factor (Q_uxf) of 22,800?±?1500?GHz (f?=?7.7?GHz) and temperature coefficient of resonant frequency +25.1?±?1?ppm/°C while NPZVO has relative permittivity of 22.4?±?0.2, Q_uxf of 7900?±?1500?GHz (f?=?7.4?GHz) and near zero temperature coefficient of resonant frequency of -6?±?1?ppm/°C at 650?°C. The relative permittivity of the compounds is inversely related to the corresponding Raman shifts.     

Effect of MgO/La2O3 additives on sintering behavior and microwave dielectric properties of (Sr,Ca)TiO3-(Sm,Nd)AlO3 ceramics

The effect of MgO/La₂O₃ additives on phase composition, microstructures, sintering behavior, and microwave dielectric properties of 0.7(Sr_0.01Ca_0.99)TiO₃−0.3(Sm_0.75Nd_0.25)AlO₃ (7SCT-3SNA) ceramics prepared via conventional solid-state route were systematically investigated. MgO/La₂O₃ as additives showed no obvious influence on the phase composition of the 7SCT-3SNA ceramics and all the samples exhibited pure perovskite structures. The presence of MgO/La₂O₃ additives effectively reduced the sintering temperature of 7SCT-3SNA ceramics due to the formation of a liquid phase at a relatively low temperature during sintering progress. The 0.5 wt% MgO doped 7SCT-3SNA sample with 0.5 wt% of La₂O₃, sintered at 1320 °C for 4 h, was measured to show superior microwave dielectric properties, with an ε_r of 45.57, a Q×f value of 46205 GHz (at 5.5 GHz), and τ_f value of −0.32 ppm/°C, which showed dense and uniform microstructure as well as well-developed grain growth.     

Effects of MnO2 and WO3 co-doping and sintering temperature on microstructure,microwave dielectric properties of Ba2Ti9O20 microwave ceramics

Ba₂Ti₉O₂₀ (short for B2T9) ceramics doped with 0.9 mol% MnO₂ and y mol% WO₃ were prepared by solid-state reaction. The influence of sintering temperature, content of WO₃ dopant and the molar ratio x of TiO₂: BaCO₃ on crystal structure, microstructures as well as microwave dielectric properties of B2T9 ceramics was systematically investigated. The major phase of all samples is B2T9, and the minor phase is BaWO₄, respectively. The content of impurity TiO₂ alternates with the variation of compositions and sintering temperature, which also leads to different microwave dielectric properties. With the continuous increase of the sintering temperature, the B2T9 phase grains gradually grow larger and transform from rod grains to plate-like grains. The enlargement and flattening of grains also result in the decrease of compactness and deterioration of microwave dielectric properties. It is found that B2T9 ceramics possess better performance when the sintering temperature is 1340°C, which is related to lower TiO₂ content, BaWO₄, B2T9 grain size, aspect ratio of B2T9 phase and high compactness. When x = 4 and y = 0.2, the relative dielectric constant, quality factor and the temperature coefficient of resonant frequency are 38, 23758 and 7 ppm/°C, respectively.     

Low-temperature firing and microwave dielectric properties of MgNb2-xVx/2O6-1.25x ceramics

MgNb_2-xV_x/2O_6-1.25x (0.1≤x≤0.6) ceramics with orthorhombic columbite structures were prepared at low-temperature by a solid-phase process. The phase component, microscopic morphology, low-temperature sintering mechanism and microwave dielectric performance of MgNb_2-xV_x/2O_6-1.25x ceramics were comprehensively investigated. Low-temperature sintering densification of dielectric ceramics was achieved via the nonstoichiometric substitution of vanadium (V) at the Nb-site. In contrast to pure MgNb₂O₆ ceramics, the sintering temperature of MgNb_2-xV_x/2O_6-1.25x (x = 0.2) ceramics was reduced by nearly 300 °C owing to the liquid-phase assisted sintering mechanism. The liquid phase arises from the autogenous low-melting-point phase. Meanwhile, MgNb_2-xV_x/2O_6-1.25x (x = 0.2) samples with nonstoichiometric substitution could achieve a more than 900% improvement in the Q × f value, compared with stoichiometrically MgNb_2-xV_xO₆ (x = 0.1, 0.2) ceramics. Finally, MgNb_2-xV_x/2O_6-1.25x dielectric ceramics possess outstanding microwave dielectric properties: ε_r = 20.5, Q × f = 91000, and τ_f = -65 ppm/°C when sintered at 1030 °C for x = 0.2, which provides an alternative material for LTCC technology and an effective approach for low-temperature sintering of Nb-based microwave dielectric ceramics.     

Influence of sintering temperature on dielectric properties and crystal structure of corundum-structured Mg4Ta2O9 ceramics at microwave frequencies

Microwave dielectric properties of corundum-structured Mg₄Ta₂O₉ ceramics were investigated as a function of sintering temperatures by an aqueous sol–gel process. Crystal structure and microstructure were examined by X-ray diffraction (XRD) technique and field emission scanning electron microscopy (FE-SEM). Sintering characteristics and microwave dielectric properties of Mg₄Ta₂O₉ ceramics were studied as a function of sintering temperature from 1250 °C to 1450 °C. With increasing sintering temperature, the density, ε_r and Qf values increased, saturating at 1300 °C with excellent microwave properties of ε_r=11.9, Qf=195,000 GHz and τ_f=?47 ppm/°C. Evaluation of dielectric properties of Mg₄Ta₂O₉ ceramics were also analyzed by means of first principle calculation method and ionic polarizability theory.     

Densification,microstructure evolution,and microwave dielectric properties of Mg1-xCaxZrTa2O8 ceramics

In this study, the effects of the Mg²⁺ ions replaced by Ca²⁺ ions on the microwave dielectric properties of newly developed MgZrTa₂O₈ were investigated. Mg_1-xCa_xZrTa₂O₈ (x = 0–1.0) ceramics were prepared via a solid-state reaction method. Calcination of the mixed powders was performed at 1200 °C and sintering of the powder compacts was accomplished at temperatures from 1200 to 1550 °C. The substitution of Ca²⁺ significantly inhibited the densification of Mg_1-xCa_xZrTa₂O₈, led to the expansion of the unit cells, and triggered the formation of a second phase, CaTa₂O₆. The porosity-corrected relative permittivity increased almost linearly with the x value because of the replacement of the less polarizable Mg²⁺ ions by the more polarizable Ca²⁺ ions. The variation in the Q × f values followed a similar trend as that of the sintered density, and the change trend in the τ_f values was in accordance with that of relative permittivity. The best composition appeared to be Mg_0.9Ca_0.1ZrTa₂O₈, which showed excellent microwave dielectric properties of ε_r = 22.5, Q × f = 231,951 GHz, and τ_f = −32.9 ppm/°C. The Q × f value obtained is the highest among the wolframite dielectric ceramics reported in literature.     

Low temperature fired CaF2-based microwave dielectric ceramics with enhanced microwave properties

Low-temperature-fired microwave ceramics are key to realizing the integration and miniaturization of microwave devices. In this study, a facile wet chemical method was applied to synthesize homogenous nano-sized CaF₂ powders for simultaneously achieving low-temperature sintering and superior microwave dielectric properties. Pure CaF₂ ceramics sintered at 950 °C for 6 h with good microwave dielectric properties (ε_r = 6.22, Q×f = 36,655 GHz, and τ_f = ?102 ppm/°C) was achieved. The microwave dielectric properties of the CaF₂ ceramics were further improved by introducing LiF as a sintering aid. The sintering temperature of CaF₂-based ceramics was effectively lowered from 950 °C to 750 °C with 10 wt% LiF doping, and excellent microwave dielectric properties (ε_r = 6.37, Q×f = 65,455 GHz, and τ_f = ?71 ppm/°C) were obtained.     

Study on structure,microstructure and microwave dielectric characteristics of CaV2O6 and (Ca0.95M0.05)V2O6 (M=Zn,Ba) ceramics

In this study, the (Ca_0.95M_0.05)V₂O₆ (M = Zn, Ba) and the CaV₂O₆ ceramics were synthesized through a solid-state reaction method, and the effects of Zn²⁺ and Ba²⁺ substitution on the structure, sintering temperature, densification, microstructure and microwave dielectric properties of CaV₂O₆ ceramic were analysed. The XRD patterns of the sintered samples indicated a single-phase of CaV₂O₆ in all temperatures. Substitution of Zn²⁺ caused a lower sintering temperature and improved the densification of the CaV₂O₆ ceramic. While the dielectric properties of the (Ca_0.95Ba0_.05)V₂O₆ compound were not desirable, the (Ca_0.95Zn_0.05)V₂O₆ sample sintered at 650°C for 4 hours showed significant dielectric properties, with ε_r = 10.29, Q × f ~  53 000 GHz (at 15.5 GHz) and τ_f = −72.37 ppm/°C. Moreover, the chemical compatibility of the CaV₂O₆ ceramic with Al electrode was examined.     

Improved sintering behavior and microwave dielectric properties of SnO2-based ceramics and their LTCC materials with ultrawide temperature stability

Microwave dielectric ceramics with simple composition, a low permittivity (ε_r), high quality factor (Q × f) and temperature stability, specifically in the ultrawide temperature range, are vital for millimetre-wave communication. Hence, in this study, the improvements in sintering behavior and microwave dielectric properties of the SnO₂ ceramic with a porous microstructure were investigated. The relative density of the Sn_1-xTi_xO₂ ceramic (65.1%) was improved to 98.8%, and the optimal sintering temperature of Sn_1-xTi_xO₂ ceramics reduced from 1525 °C to 1325 °C when Sn⁴⁺ was substituted with Ti⁴⁺. Furthermore, the ε_r of Sn_1-xTi_xO₂ (0 ≤ x ≤ 1.0) ceramics increased gradually with the rise in x, which can be ascribed to the increase in ionic polarisability and rattling effects of (Sn_1-xTi_x)⁴⁺. The intrinsic dielectric loss was mainly controlled by r_c (Sn/Ti–O), and the negative τ_f of the SnO₂ ceramic was optimised to near zero (x = 0.1) by the Ti⁴⁺ substitution for Sn⁴⁺. This study also explored the ideal microwave dielectric properties (ε_r = 13.7, Q × f = 40,700 GHz at 9.9 GHz, and τ_f = ?7.2 ppm/°C) of the Sn_0.9Ti_0.1O₂ ceramic. Its optimal sintering temperature was decreased to 950 °C when the sintering aids (ZnO–B₂O₃ glass and LiF) were introduced. The Sn_0.9Ti_0.1O₂-5 wt% LiF ceramic also exhibited excellent microwave dielectric properties (ε_r = 12.8, Q × f = 23,000 GHz at 10.5 GHz, and τ_f = ?17.1 ppm/°C). At the ultrawide temperature range (?150 °C to +125 °C), the τ_ε of the Sn_0.9Ti_0.1O₂-5 wt% LiF ceramic was +13.3 ppm/°C, indicating excellent temperature stability. The good chemical compatibility of the Sn_0.9Ti_0.1O₂-5 wt% LiF ceramic and the Ag electrode demonstrates their potential application for millimetre-wave communication.     

Low temperature sintering and microwave dielectric properties of TiO2 ceramics

The TiO₂ ceramics were prepared by a solid-state reaction in the temperature range of 920–1100 °C for 2 h and 5 h using TiO₂ nano-particles (Degussa-P25 TiO₂) as the starting materials. The sinterability and microwave properties of the TiO₂ ceramics as a function of the sintering temperature were studied. It was demonstrated that the rutile phase TiO₂ ceramics with good compactness could be readily synthesized from the Degussa-P25 TiO₂ powder in the temperature range of 920–1100 °C without the addition of any glasses. Moreover, the TiO₂ ceramics sintered at 1100 °C/2 h and 920 °C/5 h demonstrated excellent microwave dielectric properties, such as permittivity (Ɛ_r) value >100, Q × f  > 23,000 GHz and τ_f ≅ 200 ppm/°C.     

Effects of sintering parameters and Nd doping on the microwave dielectric properties of Y2O3 ceramics

Y₂O₃ ceramics with good dielectric properties were prepared via co-precipitation reaction and subsequent sintering in a muffle furnace. The effects of Nd doping and sintering temperature on microwave dielectric properties were studied. With the increase in sintering temperature, the density, quality factor (Q×f), and dielectric constant (ε_r) values of pure Y₂O₃ ceramics increased to the maximum and then gradually decreased. The Y₂O₃ ceramics sintered at 1500 °C for 4 h showed optimal dielectric properties: ε_r=10.76, Q×f=82, 188 GHz, and τ_f=−54.4 ppm/°C. With the addition of Nd dopant, the Q×f values, ε_r, and τ_f of the Nd: Y₂O₃ ceramics apparently increased, but excessive amount degraded the quality factor. The Y₂O₃ ceramics with 2 at% Nd₂O₃ sintered at 1460 °C displayed good microwave dielectric properties: ε_r=10.4, Q×f=94, 149 GHz and τ_f=−46.2 ppm/°C.     

Synthesis,lattice energy and microwave dielectric properties of BaCu2-xCoxSi2O7 ceramics

BaCu_2-xCo_xSi₂O₇ solid solutions with orthorhombic structure (Pnma) were prepared by solid-state reaction method. The phase synthesis process, structural evolution and microwave dielectric properties of BaCu_2-xCo_xSi₂O₇ ceramics were investigated. Single BaCu₂Si₂O₇ phase was obtained when calcined at 950 °C for 3 h and was decomposed into BaCuSi₂O₆ phase when calcined at 1075 °C for 3 h. The sintering process was effectively promoted when Cu²⁺ was replaced by Co²⁺ and the maximum solubility of BaCu_2-xCo_xSi₂O₇ was located between 0.15 and 0.20. P-V-L complex chemical bond theory and Raman spectra were used to explain the structure-property correlations of BaCu_2-xCo_xSi₂O₇ ceramics. The corrected dielectric constant (ε_r-corr) of BaCu_2-xCo_xSi₂O₇ ceramics decreased monotonously with the susceptibility (Σχ^μ) and ionic polarizability of primitive unit cell. The quality factor (Q × f) increased with bond strength and lattice energy (U_cal), especially the lattice energy of the Si-O bond. The temperature coefficient of resonant frequency (τ_f) was determined by the susceptibility and lattice energy of the Cu/Co-O bond. The following optimum microwave dielectric properties were obtained at x = 0.15 when sintered at 1000 °C for 3 h: ε_r = 8.45, Q×f =58958 GHz and τ_f = -34.4 ppm/°C.     

Microwave dielectric properties of Ca1-xBaxMgSi2O6 ceramics

Ca_1-xBa_xMgSi₂O₆(x = 0–0.4) ceramics were prepared through a traditional solid-state reaction sintering route with various sintering temperatures. The effects of substituting Ba²⁺ for Ca²⁺, the relative density, phase composition, crystal morphology, and microwave dielectric properties of Ca_1-xBa_xMgSi₂O₆ (x = 0–0.4) ceramics were thoroughly studied. X-ray diffraction patterns indicate a single phase was formed in the samples when x ≤ 0.2, and the second phase BaMg₂Si₂O₇ appeared at x = 0.4. As the amount of Ba²⁺ substitution increases, the Q×f value first increases and then decreases due to the combined effects of FWHM of peak v₁₁ and atomic packing density, and the ${\epsilon }_r$ value was increased continuously which was closely corrected with the relative density and molecular polarization. The ${\tau }_f$ value improved slightly with the substituting Ba²⁺ for Ca²⁺. Typically, the Ca_0.88Ba_0.12MgSi₂O₆ ceramic can be well sintered at 1275 °C for 4 h with a maximum relative density of 99.3%, and possesses optimal microwave dielectric properties: ${\epsilon }_r=7.49$, $Q\times f=64310$ GHz, ${\tau }_f=-44.02$ ppm/°C.     

Structural evolution and microwave dielectric properties in Sr2(Ti1-xSnx)O4 ceramics

The structure and microwave dielectric properties of Sr₂(Ti_1-xSn_x)O₄ ceramics were determined in the entire composition range of x?=?0–1.0. X-ray diffraction patterns and Raman spectra indicated a composition-induced onset of octahedral tilting at x?=?0.75, and the crystal structure transformed from tetragonal (I4/mmm) to orthorhombic (Pccn). An obvious change of grain morphology was observed in the phase transformation region as well. The variations of the microwave dielectric properties with composition were systematically investigated and the effect of octahedral tilting on the evolution of τ_f value was emphasized. Moreover, the relationship between τ_ε and tolerance factor of the present ceramics was revealed and compared with the empirical rule in perovskite structure. The role of tolerance factor in designing the materials with required performance was highlighted.     

Structure and microwave dielectric properties of NaSr4V5O17 ceramics for LTCC applications

A new microwave dielectric ceramic, NaSr₄V₅O₁₇ with low firing temperature was fabricated via the traditional mixed oxide method. Rietveld refinement of XRD profiles and Raman spectrum analysis ascertained that the NaSr₄V₅O₁₇ compounds crystallized into Sr₂V₂O₇-like triclinic structure with space group P-1 (2) and Z = 1.6. The variation of Q × f value was explained by the combined effects of mean grain size and cell volume rather than packing fraction and bond valence. The change regulation of ε_r was similar to that of density. The |τ_f| value is mainly related to the cations bond valence. The NaSr₄V₅O₁₇ ceramics sintered at 725 °C showed good compatibility with Ag electrode and superior dielectric properties: ε_r = 8.6, Q × f = 45 900 GHz, τ_f = ?57.0 ppm/K, making it a potential application for LTCC.     

A novel high-Q oxyfluoride Li4Mg2NbO6F microwave dielectric ceramic with low sintering temperature

Novel low-fired Li₄Mg₂NbO₆F ceramics were synthesised using a conventional solid-state reaction method. X-ray diffraction and Rietveld refinement confirmed that the Li₄Mg₂NbO₆F compound had a face-centred-cubic rock salt structure [Fm-3 m(225)] above 625 °C. Li₄Mg₂NbO₆F ceramics sintered between 875 °C and 950 °C displayed the optimised density (> 97.5 %). The theoretical ε_theo was calculated based on the refined crystal parameters, closing to the measured ε_r. The ceramic sintered at 900 °C exhibited excellent microwave dielectric properties with ε_r of 15.53 ± 0.03, Q × f value of 93,300 ± 1100 GHz (at 7.7 GHz) and τ_f value of ?39.8 ± 0.8 ppm/°C. The compatibility with Ag powders makes the oxyfluoride a potential candidate for LTCC applications.     

The microwave dielectric properties and crystal structure of low temperature sintering LiNiPO4 ceramics

The LiNiPO₄ ceramic for the LTCC technology was prepared via the traditional solid-state reaction route and its dielectric properties were investigated for the first time. The best dielectric properties of LiNiPO₄ ceramics with a ε_r of 7.18, Q×f value of 27,754?GHz and τ_f of ?67.7?ppm/°C were obtained in samples sintered at 825?°C for 2?h. Rietveld refinement was firstly employed to study the crystal structure and dielectric properties of LiNiPO₄ ceramics. Unfortunately, the relatively large negative τ_f was unfavorable to practical applications. Therefore, we introduced TiO₂, which possessed a considerable positive τ_f, to obtain a desired τ_f value. The prepared LiNiPO₄ ceramics with 15?wt% TiO₂ sintered at 900?°C for 2?h exhibited excellent dielectric properties of ε_r～11.49, Q×f～10,792?GHz, τ_f～?2.8?ppm/°C. The Ag co-fired experiments confirmed the excellent chemical compatibility with LiNiPO₄-TiO₂ ceramics which might be potential dielectric LTCCs for high frequency applications.