Bond characteristics,vibrational spectrum and optimized microwave dielectric properties of chemically substituted NdNbO4

Coordination chemistry, bond state and vibrational spectrum of co-substituted microwave dielectric NdNb_1-x(Zr_0.5W_0.5)_xO₄ ceramics (x = 0.01∼0.05) were investigated. Raman spectra and XRD refinement showed a solid solution was formed. The compressed and elongated chemical bonds are responsible for the variations of crystal parameters and cell volume. Calculated chemical bond parameters indicated bond covalency, lattice energy and Nb-site bond energy act on the fluctuations of the permittivity, quality factor and temperature coefficient, respectively. Meanwhile, the infrared vibrational spectrum is fitted to quantify the contributions of observed IR mode to the intrinsic loss. Compact ceramic possesses excellent properties: ε_r ∼ 19.2, Q × f ∼ 55282 GHz and τ_f ∼ -11.36 ppm/°C with x = 0.04, at 1250°C.     

A new BaB2O4 microwave dielectric ceramic for LTCC application

To satisfy the requirements of miniaturization and integration of microwave devices, microwave dielectric ceramics with low sintering temperatures and good microwave dielectric properties are particularly important for LTCC materials. In this study, low-cost BaB₂O₄ ceramics were prepared with different Ba/B ratios using a solid-phase method. Combined with the Raman spectra, the effects of the Raman shift and FWHM of the vibration peaks on the microwave dielectric properties were determined. As a novel microwave dielectric ceramic, BaB₂O₄ consists of a highly dense structure with optimal microwave dielectric properties (ε_r = 4.06, Q×f = 23845 GHz, and τ_f = −7.2 ppm/℃) at a low sintering temperature (840 ℃). In addition, BaB₂O₄ ceramic is chemically compatible with Ag, making it a promising candidate substrate for microwave communications.     

Tunable microwave dielectric properties in SrO-V2O5 system through compositional modulation

Adjustment on resonance frequency stability against the sintering temperature of Sr₃V₂O₈ was realized by adjusting the Sr:V mole ratio. Effects of Sr:V ratio on sintering behavior and dielectric properties of Sr₃V₂O₈ were studied. The sintering temperature was sucessfully reduced to 950°C from 1150°C. With increasing vanadium content, both relative permittivity and quality factor decreased, while the temperature coefficient of resonance frequency shifted from positive to negative values. Especially, a near-zero τ_f of −1.1 ppm/°C along with a low permittivity (ε_r) of 9.8 and a quality factor Q × f of 24 120 GHz was successfully achieved in Sr_3-yV₂O_8-y ceramic (y = 0.6, sintered at 950°C). The wide compositional and processing adjustment window, favorable dielectric performances, and good chemical compatibility with silver render Sr_3-yV₂O_8-y ceramics potential candidates in multilayer electronic devices.     

Bond characteristics and microwave dielectric ceramic of rare-earth tantalite NdTaO4 ceramic

A type of rare-earth tantalite ceramic NdTaO₄ was synthesized by the solid-state reaction method and investigated for the relationship between the structure and microwave dielectric properties for the first time. X-ray diffraction and Rietveld refinement confirmed that an M-fergusonite phase was formed. The dense micromorphology and uniform grain distribution obtained at 1500 °C are advantageous for the microwave dielectric properties. Based on the different bonding properties in the crystal, we investigated the dependence between the crystal structure and the dielectric properties of NdTaO₄, where the ionicity of Nd–O bond in the crystal structure mainly determines the dielectric constant compared with Ta–O bond, and the lattice energy of Ta–O contributes significantly to the quality factor, the TaO₄ and NdO₈ polyhedron contributes collectively to the thermal stability. The optimum microwave dielectric properties were obtained for 1500 °C - sintered samples: ε_r = 18, Q × f = 13,000 GHz (at 8.9 GHz), τ_f = ?21 ppm/^°C.     

Ti4+ modified MgZrNb2O8 microwave dielectric ceramics with an ultra-high quality factor

Ti⁴⁺-modified MgZrNb₂O₈ (MgZr_1-xTi_xNb₂O₈, x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were synthesized using the traditional solid-state reaction method. Pure MgZr_1–xTi_xNb₂O₈ was detected without any secondary phase via the X-ray diffraction patterns. According to the sintering behavior and the surface morphology results, the introduction of Ti⁴⁺ reduced the sintering temperature and promoted the grain growth. The correlations between the dielectric properties and the crystal structure were analyzed through the Rietveld refinement and Raman spectroscopy. The slight shifts of the Raman peaks, corresponding to different vibration modes, were induced by the substitution of Ti⁴⁺ for Zr⁴⁺ and related to the improved quality factor. In general, the sample of MgZr_0.9Ti_0.1Nb₂O₈ sintered at 1320°C for 4 h exhibited promising microwave dielectric properties with an ultra-high Q × f value of 130 123 GHz (at 7.308 GHz, 20°C), which is potential for 5G communication applications.     

Structure,microwave dielectric performance,and infrared reflectivity spectrum of olivine-type Mg2Ge0.98O4 ceramic

An ultra-low dielectric loss ceramics Mg₂Ge_0.98O₄ with olivine structure was fabricated by conventional solid-state route. The phase composition, crystal structure, and microwave dielectric properties were investigated. The phase of Mg₂Ge_0.98O₄ is formed to the orthorhombic forsterite structure with a space group Pmnb (62). The dense microstructure and excellent microwave dielectric properties of Mg₂Ge_0.98O₄ ceramic were obtained at 1360°C for 4 hours, with relative density ~96.4%, ε_r ~ 7.3, Q × f = 112 400 GHz, and τ_f ~ −64.6 ppm/°C. The conductive mechanism of Mg₂Ge_0.98O₄ in the low frequency (<1 MHz) was studied by the dielectric spectroscopy and the result with E_dc = 0.93 eV demonstrates that the defect was contributed to the double ionized oxygen vacancies. The intrinsic dielectric properties of Mg₂Ge_0.98O₄ in the microwave region were obtained by infrared reflectivity spectra with ε_r ~ 7.13, Q × f = 120 400 GHz. And, acceptable τ_f (~+2.6 ppm/°C) of 0.92Mg₂Ge_0.98O₄–0.08CaTiO₃ composite ceramic was obtained by adding the CaTiO3.     

A novel temperature-stable Ba2-xCaxMgTi5O13 microwave dielectric ceramic

The Ba_2-xCa_xMgTi₅O₁₃ (0 ≤ x ≤ 0.3) microwave dielectric ceramics were for the first time prepared via a conventional solid-state reaction method. A small amount of Ca²⁺ can dissolve into the lattice by forming solid solutions with a monoclinic structure (C2/m) and further influence the sintering behavior, grain growth and microwave dielectric properties of Ba_2-xCa_xMgTi₅O₁₃ ceramics. Both increase of ε_r and decrease of Qxf with x should be associated with increased lattice distortion and uneven grain growth although the sample density and the ratio of the ionic polarizability to the molar volume show little variation. Moreover, the A-site bond valence and τ_f indicate a close relation in current study, such that the Ca²⁺substitution can induce an increase of τ_f values. The optimum microwave dielectric properties of ε_r ∼ 29.3, Qxf ∼ 30,870 GHz (6.5 GHz), and a near-zero τ_f ∼ +2.1 ppm/°C can be contained in the x = 0.15 ceramic sintered at 1160 °C.     

Cold sintering and microwave dielectric properties of dense HBO2-II ceramics

HBO₂-II ceramics were prepared by cold sintering with 10wt% dehydrated ethanol as the transient liquid phase. When the processing temperature is 30°C, the relative density of the mechanically robust HBO₂-II ceramics increases from 77.5% to 84.5% with increasing the uniaxial pressure from 200 to 500 MPa. It changes less than 0.2% for higher pressure up to 700 MPa. Under a constant uniaxial pressure of 500 MPa, the relative density further increases to 94.7% for the processing temperature of 120°C. HBO₂-I is observed as the secondary phase when the processing temperature is 150°C. In comparison, the compacts prepared in the absence of ethanol are fragile, and the relative densities are 78.5%-84.5% for the processing temperatures of 30-120°C and uniaxial pressure of 500 MPa. It is indicated that ethanol promotes the densification significantly through the dissolution-precipitation mechanism. The permittivity increases with increasing the processing temperature, while the Qf value decreases. The optimal properties with the relative density of 94.7%, ε_r = 4.21, Qf = 47 500 GHz, and τ_f = −70.0 ppm/°C were obtained in the single-phase HBO₂-II ceramics cold sintered at 120°C under 500 MPa for 10 minutes. The relative density and Qf value are significantly higher than those of the HBO₂-II ceramic prepared by sintering the H₃BO₃ compact at 180°C for 2 hours (70.3% and 32 700 GHz, respectively). The results indicate that the nonaqueous solvent can also be used as the transient liquid phase for cold sintering, so that more materials that are unstable or insoluble in water can be densified by this method.     

Phase evolution and microwave dielectric properties of BaTi4O9 ceramics prepared by reaction sintering method

BaTi₄O₉ microwave dielectric ceramics were prepared by reaction sintering method using BaCO₃ and TiO₂ as raw materials. The phase evolution and the chemical reactions were proposed based on the X-ray diffraction results with sintering temperature. The microstructure characteristics were observed using scanning electron microscopy and energy dispersive spectrometer. The compact ceramics with a single phase of BaTi₄O₉ could be prepared successfully by reaction sintering method, exhibiting optimum microwave dielectric properties: a dielectric constant of 36.9, a high quality factor of 52 735 (at 7.5GHz), and a near zero temperature coefficient of resonant frequency of 5.8 ppm/°C, after sintering at 1200°C for 6 hours.     

MSO4 (M = Ca,Sr, Ba) microwave dielectric ceramics with low dielectric constant

MSO₄ (M = Ca, Sr, Ba) ceramics with relative densities exceeding 96% were prepared by solid-state sintering at low sintering temperatures of 625–875°C, and their structures and microwave dielectric properties at 10–19 GHz were characterized. MSO₄ ceramics crystallized in orthorhombic symmetry with the space groups of Amma for CaSO₄ and Pnma for SrSO₄ and BaSO₄. The optimal microwave dielectric properties were obtained with ε_r = 5.85, Qf = 57 000 GHz, τ_f,W = −98.8 ppm/°C for CaSO₄, ε_r = 10.95, Qf = 15 500 GHz, τ_f,W = 101.6 ppm/°C for SrSO₄, and ε_r = 9.42, Qf = 38 200 GHz, τ_f,W = −4.7 ppm/°C for BaSO₄. The increased ε_r and τ_f,W while decreased Qf value in the order of CaSO₄, BaSO₄, and SrSO₄ were attributed to the enhanced rattling effect of M²⁺. Besides, the temperature dependence of τ_f was weak for CaSO₄ and BaSO₄, whereas much stronger for SrSO₄. As most low-ε_r microwave dielectric ceramics are of large negative τ_f, the near-zero τ_f of BaSO₄ and positive τ_f of SrSO₄ are rare, indicating they are potential candidates for millimeter-wave communication as a temperature-stable dielectric ceramic and a compensator for tuning negative τ_f to near-zero, respectively.     

Sm掺杂对Ba_4La_(19.33)Ti_(18)O_(54)陶瓷结构和介电性能的影响分析

主要研究了不同Sm掺杂浓度对Ba4La19.33Ti18O54陶瓷的微波介电性能和微观结构的影响。首先利用常规固相反应技术制备了Sm含量y分别为0.0,0.1,0.3,0.5和0.7的五种Ba4(La1-ySmy)9.33Ti18O54陶瓷样品;室温下在0.3～3.0GHz频率范围内,利用网格分析仪测量了这些样品的介电常数和介电损耗因子;结果表明随着Sm掺杂含量的增大,样品介电损耗明显减小,而介电常数只有微小减少。当Sm掺杂含量y=0.5时,样品的介电性能最好。此外,还利用X射线衍射仪和扫描电子显微镜研究了样品的微观结构及随微波介电性能的变化。     

Structure and microwave dielectric characteristics of Hf1-xTixO2 ceramics

Hf_1-xTi_xO₂ dense ceramics were prepared by a standard solid-state reaction process, and the microwave dielectric properties in a wide frequency range were determined together with structure evolution. With increasing x, the structure gradually changed from HfO₂-based solid solution (monoclinic in space group P2₁/c, x ≤ 0.05) to HfTiO₄ (orthorhombic in space group Pbcn, x = 0.5), and the two phase regions were determined for 0.1 ≤x < 0.5 and x = 0.55. The microwave dielectric properties of HfO₂ ceramics at 10 GHz were determined as ε_r = 14, Qf = 24 500 GHz, τ_f = –50 ppm/℃. With Ti-substitution, the microwave dielectric characteristics, especially the Qf value, could be significantly improved, and the best combination of microwave dielectric characteristics was achieved at x = 0.05: ε_r = 17, Qf = 84 020 GHz (at 7.8 GHz) and 151 260 GHz (at 27.9 GHz), and τ_f = –47 ppm/℃. The smallest temperature coefficient of resonance frequency (τ_f = –4.8 ppm/℃) was obtained for x = 0.55 together with a Qf value of 52 370 GHz at 5.0 GHz and 60 390 GHz at 17.9 GHz, where the dielectric constant was 40. Moreover, Hf_1-xTi_xO₂ microwave dielectric ceramics might be very competitive in the future of mobile communication technology due to their excellent compatibility with Si.     

A low-permittivity microwave dielectric ceramic BaZnP2O7 and its performance modification

Complex pyrophosphates compounds have attracted much attention as promising candidates for substrate applications. In the work, a low-permittivity BaZnP₂O₇ ceramic was synthesized through solid-state reaction. The pure phase BaZnP₂O₇ was crystallized in the triclinic P−1 space group. Excellent microwave dielectric properties of the BaZnP₂O₇ ceramic with ε_r = 8.23, Qf = 56170 GHz, and τ_f = −28.7 ppm/°C were obtained at 870°C for 4 h. The substitution of Mg²⁺ for Zn²⁺ was found to have positive effects on grain morphology and dielectric properties. Optimized performance of ε_r = 8.21, Qf = 84760 GHz, and τ_f = −21.9 ppm/°C was yielded at 900°C for the BaZn₀.₉₈Mg_0.02P₂O₇ ceramic. Intrinsic dielectric properties of BaZn_1-xMg_xP₂O₇ ceramics were studied via Clausius–Mossotti equation and complex chemical bond theory.     

Optimized crystal structure and microwave dielectric properties of BaZnSi3O8-based ceramics

In this study, we synthesized BaZnSi₃O₈-based compounds with monoclinic structures (P21/a) using a solid-state method. The crystal structure, phase composition, and microwave dielectric properties of BaZnSi₃O₈-based ceramics were systematically investigated systematically. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images proved that the maximum solubility of BaZn_1-xMg_xSi₃O₈ ranged between 0.3 and 0.4. Rietveld refinement and Phillips–Van Vechten–Levine complex chemical bond theory were used to illustrate the relationship between the microwave dielectric performance and lattice parameters. To further improve the properties, we substituted Ba²⁺ with Sr²⁺ in BaZn_0.8Mg_0.2Si₃O₈. Ba_1-ySr_yZn_0.8Mg_0.2Si₃O₈ remained in a single-phase as y increased from 0 to 1.0. We achieved thermal stability of the resonance frequency of the BaZnSi₃O₈-based ceramics by adjusting TiO₂ to form composite ceramics. After sintering at 1020°C for 5 h, excellent microwave dielectric properties with ε_r = 7.44, Q×f = 57,400 GHz, and τ_f = − 0.2 ppm/°C were realized in the SrZn_0.8Mg_0.2Si₃O₈+8 wt %TiO₂ system.     

Mg3B2O6 microwave dielectric ceramics fabricated by combining cold sintering with post-annealing process

It is difficult to get pure-phase Mg₃B₂O₆ (abbreviated as MBO) ceramics by the traditional high-temperature solid-state reaction method. In this paper, pure-phase MBO ceramics were successfully densified and obtained by combining the cold sintering and post-annealing process. The relative density of MBO ceramics was ∼80% cold sintered at 150°C/90 min/800 MPa, which was further improved to ∼91% by post-annealing at 900°C, 400°C lower than that of the traditional high-temperature sintering process (∼1300°C). X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and Raman results demonstrated that the secondary phase of MgO was effectively eliminated, and dense microstructure was observed by the cold-sintering process plus post-annealing treatment. Finally, the microwave dielectric properties of MBO were evaluated with ε_r: 5.15–6.37, Q×f: 5942–16 686 GHz, τ_f: −48.45–69.72 ppm/°C.     

A synergistic effect of Li-B-Si glass and La-B on low-temperature sintering of BaO-0.15ZnO-4TiO2 dielectric ceramic

In the present work, the synergistic effect of Li₂O-B₂O₃-SiO₂ glass (LBS) and La₂O₃-B₂O₃ (LaB) addition on the wetting behavior, activation energy, phase composition, microstructure and microwave dielectric properties of the BaO-0.15ZnO-4TiO₂ ceramic (Ba-Zn-Ti) has been investigated to understand the low temperature mechanism of the sintering kinetic. The results show that co-doping with LBS and LaB decreases the activation energy and therefore accelerates the sintering process of the Ba-Zn-Ti due to the liquid phase formed at a low sintering temperature. Moreover, the co-doping of LBS and LaB restrains the appearance of BaTi(BO₃)₂ caused by the reaction of Ba-Zn-Ti and LBS, which has a deleterious effect on the densification and microwave dielectric properties of Ba-Zn-Ti. With LBS and LaB co-doped, the sintering temperature of Ba-Zn-Ti significantly dropped from 1150 °C to 850–900 °C and remained excellent microwave dielectric properties.     

Synthesis and microwave dielectric properties of new high quality Mg2NdNbO6 ceramics

New high‐quality microwave dielectric ceramics Mg₂NdNbO₆ were prepared by conventional solid‐state sintering method. The phases, micro‐structures and microwave dielectric properties of Mg₂NdNbO₆ ceramics were investigated at sintering temperature in the range of 1275°C‐1400°C. The X‐ray diffraction patterns showed that the peaks of the compounds were attributed to two phases, including the main crystalline phase of NdNbO₄ that was indexed as the monoclinic phase and MgO as the second phase. Well‐developed microstructures of Mg₂NdNbO₆ ceramics can be achieved, and the grain size reached the maximum value (1.63 μm) at 1375°C. As the sintering temperature increased, the dielectric constant, temperature coefficient of resonant frequency and apparent density remained almost unchanged, however, the significant change in the quality factor was observed. At 1375°C, Mg₂NdNbO₆ ceramics possessed excellent microwave dielectric properties: ε_r = 16.22, Q × f = 116 000 GHz and τ_f = ?30.96 ppm/°C.     

Complex impedance spectroscopy of perovskite microwave dielectric ceramics with high dielectric constant

The AC impedance of SrTiO₃, Ca_0.9Sr_0.1TiO₃, Ca_0.7Sm_0.2TiO₃, and Ca_0.7Sm_0.3Ti_0.7Al_0.3O₃ microwave dielectric ceramics with perovskite structures has been analyzed. The impedance spectroscopy results reveal the electrical properties of this series of samples vary significantly with the ceramic microstructure and electrical homogeneity. The ε_r values of grains for SrTiO₃ and Ca_0.9Sr_0.1TiO₃ ceramics are 193.8 and 138.1, respectively, confirming that dielectric response of the high-ε_r microwave ceramics is contributed to the grains, at microwave frequencies. Impedance spectroscopy of Ca_0.7Sm_0.2TiO₃ ceramic illustrates that electrical heterogeneous microstructures include interior grains and grain shells. The secondary phase existing in Ca_0.7Sm_0.2TiO₃ ceramic causes deviation in bulk permittivity, resulting in a higher ε_r ~ 148 of grains than ε_r ~ 112 of bulk permittivity, measured at microwave frequencies. Grain and grain-boundary impedance of Ca_0.7Sm_0.3Ti_0.7Al_0.3O₃ ceramic cannot be separated completely. The permittivities of grains and grain boundaries in Ca_0.7Sm_0.3Ti_0.7Al_0.3O₃ ceramic are ε_g ~ 17.8 and ε_gb ~ 20.8, and the combination of them is close to ε_r ~ 40 at microwave frequencies. The LogI−LogU curves of the ceramic system indicate that the conducting mechanism of grains and grain boundaries follows ohmic behavior.     

Phase evolution,crystal structure,and microwave dielectric properties of gillespite-type ceramics

A gillespite-structured MCuSi₄O₁₀ (M = Ba_1-xSr_x, Sr_1-xCa_x) ceramics with tetrahedral structure (P4/ncc) were prepared by solid-state reaction method. X-ray diffraction and thermogravimetry with differential scanning calorimetry (TG-DSC) were employed to study the phase synthesis process of BaCuSi₄O₁₀. Pure BaCuSi₄O₁₀ phase was obtained at 1075°C and decomposed into BaSiO₃, BaCuSi₂O₆, and SiO₂ when calcined at 1200°C. The relationships between the crystal structure and microwave dielectric properties of MCuSi₄O₁₀ ceramics were revealed based on the Rietveld refinement and P-V-L complex chemical bond theory. The dielectric constant (ε_r) decreased linearly with decreasing total bond susceptibility and ionic polarizability. Quality factor (Q × f) was closely dependent on bond strength and lattice energy. The temperature coefficient of resonant frequency (τ_f) was controlled by the stability of [CuO₄]⁶⁻ plane in MCuSi₄O₁₀. Optimum microwave dielectric properties were obtained for SrCuSi₄O₁₀ when sintered at 1100°C for 3 hours with a ε_r of 5.59, a Q × f value of 82 252 GHz, and a τ_f of −41.34 ppm/°C. Thus, SrCuSi₄O₁₀ is a good candidate for millimeter-wave devices.