Structure,spectral analysis and microwave dielectric properties of novel x(NaBi)0.5MoO4-(1-x)Bi2/3MoO4 (x = 0.2 ∼ 0.8) ceramics with low sintering temperatures

Herein, the x(NaBi)_0.5MoO₄-(1-x)Bi_2/3MoO₄ (xNBM-(1-x)BMO, x = 0.2 ∼ 0.8) microwave dielectric ceramics with low sintering temperatures were prepared via the traditional solid-state method to adjust the τ_f value and dielectric constant. The crystal structure was determined using X-Ray diffraction and Raman spectroscopy, the microstructure was investigated using scanning electron micrograph and energy disperse spectroscopy, and the dielectric properties were studied using a network analyser and infrared spectroscopy. For the xNBM-(1-x)BMO composite ceramics, the (NaBi)_0.5MoO₄ tetragonal phase coexisted with the Bi_2/3MoO₄ monoclinic phase. With the rise of x value, the permittivity increased from 23.7–29.8, and the τ_f value shifited from -53.3 ppm/°C to -13.7 ppm/°C. The 0.8NBM-0.2BMO ceramic sintered at 680 °C possessed excellent microwave dielectric properties with a ε_r = 29.8 (6.7 GHz), a Qf = 11,800 GHz, and a τ_f = -13.7 ppm/°C. These results made the xNBM-(1-x)BMO composite ceramics great candidates in low temperature co-fired ceramics technology.     

Structure,Infrared Reflectivity and Microwave Dielectric Properties of (Na0.5La0.5)MoO4–(Na0.5Bi0.5)MoO4 Ceramics

A series of temperature‐stable microwave dielectric ceramics, (1?x)(Na_0.5La_0.5)MoO₄–x(Na_0.5Bi_0.5)MoO₄ (0.0 ≤ x ≤ 1.0) were prepared by using solid‐state reaction. All specimens can be well sintered at temperature of 580°C–680°C. Sintering behavior, phase composition, microstructures, and microwave dielectric properties of the ceramics were investigated. X‐ray diffraction results indicated that tetragonal scheelite solid solution was formed. Microwave dielectric properties showed that permittivity (ε_r) and temperature coefficient of resonant frequency (τ_f) were increased gradually, while quality factor (Q × f) values were decreased, at the x value was increased. The 0.45(Na_0.5La_0.5)MoO₄–0.55(Na_0.5Bi_0.5)MoO₄ ceramic sintered at 640°C with a relative permittivity of 23.1, a Q × f values of 17 500 GHz (at 9 GHz) and a near zero τ_f value of 0.28 ppm/°C. Far‐infrared spectra (50–1000 cm^?1) study showed that complex dielectric spectra were in good agreement with the measured microwave permittivity and dielectric losses.     

Polarization-dependent multichannel transmission of 5G signals based on Zn0.91(Li0.5Bi0.5)0.09MoO4 low-temperature co-fired ceramics

Microwave communication for 5 G signals is the preferred solution in modern communication networks where fiber optic cables are difficult to deploy or base stations operate incorrectly. Here, a novel Zn_1-x(Li_0.5Bi_0.5)_xMoO₄ (ZLBMO∼xLB, x = 0.09) ceramic with excellent microwave dielectric properties (ε_r = 10.5, Q×f = 43,001 GHz, τ_f = −21.5 ppm/°C) is developed using solid-state reaction method. The sintering temperature is successfully reduced from 850 °C to 725 °C. For the first time, an all-ceramic device for multichannel transmission of 5 G signals is designed using this ceramic material. This device exhibits transverse dual-channel, longitudinal dual-channel, and four-channel transmission under x-, y- and 45°-polarized waves incidence, respectively. The number of channels can be changed by switching the polarization state of the incident wave. This functionality is verified by simulation results of the electric field and phase. This work provides new ideas for the combination of dielectric ceramics and communication devices.     

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.     

Nonstoichiometric microwave dielectric ceramics [(Na0.5-xBi0.5+x/3)0.5Ca0.5]MoO4 with low sintering temperatures

In this work, [(Na_0.5-xBi_0.5+x/3)_0.5Ca_0.5]MoO₄ (x = ±0.03, ±0.06, ±0.09, ±0.12) microwave dielectric ceramics prepared by the solid-state reaction method are investigated. All the samples can be sintered well below 800℃. The sintered ceramics show a scheelite structure without any secondary phase, indicating that a solid solution is formed in nonstoichiometric [(Na_0.5-xBi_0.5+x/3)_0.5Ca_0.5]MoO₄. While x value increases from -0.12 to 0.12, the relative permittivity rises from 16.7 to 21.0, TCF value is improved from -21 ppm/℃ to +1 ppm/℃, and Q × f value varies in the range of 17,000 GHz and 34,000 GHz. The Raman analysis reveals that one of the external modes is attributed to be the main factor affecting the performances. When x = 0.09 and 0.12, high performance microwave dielectric ceramics can be well densified at low sintering temperatures (750−775℃) with relative permittivities of 20.9–21.0, improved Q × f values of 31,400−33,000 GHz, and near-zero temperature coefficients of resonate frequency (|TCF| ≈ ±2 ppm/℃).     

The spectra analysis and microwave dielectric properties of [Ca0.55(Sm1-xBix)0.3]MoO4 ceramics

A series of low-temperature firing ceramics with scheelite structure, [Ca_0.55(Sm_1-xBi_x)_0.3]MoO₄ (x = 0.2–0.95), were prepared via solid-state reaction. The sintering temperature ranges from 660 to 760°C. A standard tetragonal scheelite phase was formed without secondary phase. When the x value was 0.95, the temperature coefficient of resonant frequency (τ_f) moved to a near zero value (−2.1 ppm/°C) with a dielectric constant 13.7 and the quality factor (Qf) of 33 200 GHz. The Raman spectra shows that the more vibration modes appeared with x value, which is due to the increasing of Bi concentration and results in increase in permittivities and decrease in Qf values. The classical harmonic oscillator model is used in the infrared spectra and extrapolate to the microwave range. The [Ca_0.55(Sm_1-xBi_x)_0.3]MoO₄ ceramics show high-performance microwave dielectric properties at low-sintering temperature.     

Ultra-low temperature sintering and microwave dielectric properties of a novel temperature stable Na2Mo2O7-Na0.5Bi0.5MoO4 ceramic

The novel ultra-low temperature sintering (1-x)Na₂Mo₂O₇-xNa_0.5Bi_0.5MoO₄ ceramics have been obtained via solid-state reaction method for passive integration use. The Na₂Mo₂O₇ and Na_0.5Bi_0.5MoO₄ crystal phases are found to be compatible with each other from the results of XRD and SEM-EDS. With the x value changing from 0.36 to 1.00, the ε_r increases from 16.0 to 32.0 and the τ_f value varies from ?58 to 47 ppm/°C. At x = 0.75, the 0.25Na₂Mo₂O₇-0.75Na_0.5Bi_0.5MoO₄ ceramic sintered at an ultra-low sintering temperature of 580 °C can be densified (>96%) and possesses good microwave dielectric properties of an ε_r of 24.0, a Q × f value of 13,000 GHz (at 6.2 GHz), and a τ_f value of 3 ppm/°C. The theoretical ε_r and τ_f of the (1-x)Na₂Mo₂O₇-xNa_0.5Bi_0.5MoO₄ composites were calculated using the mixing law and in accordance with the measured values.     

Large field-induced strain with enhanced temperature-stable dielectric properties of AgNbO3-modified (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(1-x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-xAgNbO₃ lead-free piezoelectric ceramics (abbreviated as BNBT-100xAN) were prepared using the conventional solid-state sintering method. The effects of the introduction of AgNbO₃ (AN) dopants for the dielectric and piezoelectric performances of BNBT-100xAN ceramics were systematically studied. The XRD patterns and Raman spectra demonstrated that AN as a modifier was successfully diffused into the BNBT-100xAN lattice and revealed a pseudo-cubic symmetry structure. All samples exhibited a dense surface morphology accompanied by the uniform distribution of elements. A large bipolar strain of ~0.501% and unipolar strain of ~0.481% corresponding to the normalized strain d₃₃* of ~740 p.m./V were achieved for BNBT-1AN ceramic at 65 kV/cm field. The BNBT-4AN ceramic exhibited an excellent temperature-stable permittivity with the range from 59 to 380 °C and its dielectric loss was less than 0.02 between 97 °C and 329 °C. These results revealed that BNBT-100xAN ceramics were more hopeful candidates for actuators, strain sensors, and high-temperature capacitors.     

Effects of (Cr0.5Ta0.5)4+ on the microstructure,chemical bond characteristics,and dielectric properties of molybdate-based ceramics at microwave and terahertz frequency

In this study, Ce₂ [Zr_1−x (Cr_0.5Ta_0.5)_x]₃(MoO₄)₉ (x = 0.02–0.10) ceramics were synthesized using the solid-state reaction technique, and the crystalline parameters, sintering behaviors, chemical bond characteristics, infrared reflection spectrum, and dielectric response at microwave and terahertz frequency were examined. X-ray diffraction results demonstrated the crystallization of all ceramics in the trigonal structure (R-3c space group), and additional peaks were not detected. The densification point of ceramic was 875 °C. The addition of (Cr_0.5Ta_0.5)⁴⁺ significantly reduced the dielectric loss in the host ceramic. For Ce₂ [Zr_0.96(Cr_0.5Ta_0.5)_0.04]₃(MoO₄)₉, outstanding microwave properties of ε_r = 10.66, Qf = 79,436 GHz, and τ_f = −19.07 ppm/°C were obtained at 875 °C. The chemical bond characteristics were also parameterized to explore the relationship between Zr(CrTa)–O and microwave properties. Infrared spectral results further indicate that phonon vibrations lower than 400 cm⁻¹ contribute to 80% of the polarization. In our comparison between the infrared spectrum and terahertz time-domain spectrum, we found that the permittivity extracted by the latter is closer to the observed value.     

Sintering Behavior and Dielectric Properties of Ultra‐Low Temperature Fired Silver Molybdate Ceramics

Ag₂MoO₄ ceramic was prepared by using the solid‐state reaction method, which could be sintered at 450°C for 2 h, having a relative permittivity of 8.08, a Qf value of 17 000 GHz, and a temperature coefficient of resonance frequency about ?133 ppm/°C. Ag₂MoO₄ ceramic was chemically compatible with silver but reacted seriously with aluminum to form (Ag_0.5Al_0.5)MoO₄ during the sintering. The fitting of infrared spectra and the Shannon's additive rule were employed to study intrinsic dielectric behaviors of the ceramics at microwave region. Ionic displacive polarization and the electronic polarization contributed almost equally to the dielectric permittivity of the ceramic at microwave region. The Ag₂MoO₄ ceramics could be a good candidate for ultra‐low temperature co‐fired microwave devices.     

Ultra-high quality factor and low dielectric constant of (Zn0.5Ti0.5)3+ co-substituted MgAl2O4 ceramic

In this study, MgAl₂O₄-based ceramics with high quality factor (Qf) and low dielectric constant (ε_r ≤ 10) were obtained by fabricating MgAl_2-x(Zn_0.5Ti_0.5)_xO₄ (x = 0–0.5) ceramics via conventional solid-state reaction method. Excellent microwave dielectric properties were achieved for samples at x = 0.5 and sintered at 1550 °C, i.e., ε_r = 9.86, Qf = 263 900 GHz (five times better than that for x = 0 sample) and τ_f = ?92 ppm/°C. The X-ray diffraction (XRD) patterns displayed characteristic peaks of MgAl₂O₄ with spinel structure. MgTi₂O₅ and MgTiO₃ were considered as secondary phases. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and relative density analysis indicated that ultra-high Qf values were dominated by dense microstructure, secondary phase and cation vacancies; whereas ε_r values were mainly affected by secondary phase and ionic polarizability. MgAl_2-x(Zn_0.5Ti_0.5)_xO₄ ceramics with excellent microwave dielectric properties have potential application in millimeter-wave communication, dielectric filters, dielectric antennas and resonators.     

Phase transitions and microwave dielectric behaviors of the (Bi1−xLi0.5xY0.5x)(V1−xMox)O4 ceramics

Microwave dielectric ceramics with intrinsic low sintering temperatures are potential candidates for low temperature co-fired ceramics technology. In the present work, the (Li_0.5Y_0.5)MoO₄ ceramic with tetragonal scheelite structures was selected to improve microwave dielectric properties of BiVO₄ ceramics. As proved by X-ray diffraction (XRD) results, scheelite structured solid-solution ceramics were formed with x value ≤0.1 in the (Bi_1−xLi_0.5xY_0.5x)(V_1−xMo_x)O₄. In situ XRD results further confirmed that the addition of (Li_0.5Y_0.5)MoO₄ also lowered transition temperature from distorted monoclinic to tetragonal scheelite structure. When x value increased further, zircon phase was detected by XRD. Room and high-temperature Raman spectra also supported the XRD results. Differences of thermal expansion coefficients of both monoclinic and tetragonal scheelite phases lead to an abnormality at phase transition temperature. Good microwave dielectric properties with permittivity above 70 and Qf (Q = quality factor = 1/dielectric loss and f = frequency) value above 8000 GHz were obtained in the (Bi_1−xLi_0.5xY_0.5x)(V_1−xMo_x)O₄ solid-solution ceramics with x value ≤0.1 sintered below 800°C. However, permittivity peak values at phase transition temperatures lead to large positive or negative temperature coefficient of resonant frequency, and this needs to be modified via composite technologies in the future.     

Microwave dielectric properties and thermal conductivities of low-temperature sintered (Na1-xKx)2MoO4 (x ≤ 0.2) ceramics

The Mo-based glass-free spinel-type structure of the (Na_1-xK_x)₂MoO₄ (x = 0.0, 0.1, and 0.2) ceramic series was prepared using the traditional solid-state method at the low sintering temperature (<650 °C). The microwave dielectric properties of the (Na_1-xK_x)₂MoO₄ series were determined in terms of phase compositions, crystal structure (via XRD), and microstructure analysis (via FE-SEM and EDS). The results revealed that the double-phase (cubic and orthorhombic) formation plays a significant role in the entire (Na_1-xK_x)₂MoO₄ series. It exhibits excellent dielectric properties: dielectric constant ε_r = 4 (1 GHz)/3.77 (15 GHz), tangent loss tan δ = 8.3 × 10^?2 (1 GHz)/7 × 10^?3 (15 GHz; Q × f = 2143 GHz), temperature coefficient of frequency (TCF) τ_f = ?6.45 ppm/°C, and room temperature thermal conductivity (κ) = 1.76 W/(m.K) for x = 0.1 at a sintering temperature of 575 °C. These make the (Na_1-xK_x)₂MoO₄ ceramic series a potential candidate for low-temperature co-fired ceramic (LTCC) substrate applications (as used in antennas) for high-speed data communications.     

Crystal structure,infrared-reflectivity spectra,and microwave dielectric properties of novel Ce2(MoO4)2(Mo2O7) ceramics

Novel Ce₂(MoO₄)₂(Mo₂O₇) (CMO) ceramics were prepared by a conventional solid-state method, and the microwave dielectric properties were investigated. X-ray diffraction results illustrated that pure Ce₂(MoO₄)₂(Mo₂O₇) structure formed upon sintering at 600 °C-725 °C. [CeO₇], [CeO₈], [MoO₄], and [MoO₆] polyhedra were connected to form a three-dimensional structure of CMO ceramics. Analysis based on chemical bond theory indicated that the Mo–O bond critically affected the ceramics’ performance. Furthermore, infrared-reflectivity spectra analysis revealed that the primary polarisation contribution was from ionic polarisation. Notably, the optimum microwave dielectric properties of ε_r = 10.69, Q·f = 49,440 GHz (@ 9.29 GHz), and τ_f = −30.4 ppm/°C were obtained in CMO ceramics sintered at 700 °C.     

Cold sintered temperature stable xLi2MoO4-(1-x)(LiBi)0.5MoO4 microwave dielectric ceramics

Temperature stable xLi₂MoO₄-(1-x)(LiBi)_0.5MoO₄ (x = 0, 40, 50, 60, 70, 100 vol%) microwave dielectric ceramics obtained by cold sintering process (CSP) under a mild sintering condition (120 ℃/30 min/200 MPa) are introduced in this work. The XRD, SEM, and Raman analysis indicate the coexistence of Li₂MoO₄ and (LiBi)_0.5MoO₄ phases. Li₂MoO₄-(LiBi)_0.5MoO₄ ceramics are compatible with Ag and Al electrode materials under cold sintering condition. The specimens exhibit high relative densities and good microwave dielectric properties (relative permittivities: 31.5–5.5; Q×f values: 1900 - 18,500 GHz; TCF values: from +144 ppm/℃ to ?106 ppm/℃), in particular, TCF = +0.7 ppm/℃ can be obtained in the case of x = 50 vol%. The extrapolated microwave dielectric properties obtained by the fitted infrared reflectivity spectrum are close to the measured data, revealing that the dielectric responses of cold sintered Li₂MoO₄-(LiBi)_0.5MoO₄ ceramics in the microwave range are dominated by the polar optical phonons.     

Low temperature firing microwave dielectric ceramics (K0.5Ln0.5)MoO4 (Ln = Nd and Sm) with low dielectric loss

In the present work, novel low temperature firing microwave dielectric ceramics (K_0.5Ln_0.5)MoO₄ (Ln = Nd and Sm) were prepared via the traditional solid state reaction method. A pure monoclinic phase can be formed at a low sintering temperature around 680 °C for both (K_0.5Nd_0.5)MoO₄ and (K_0.5Sm_0.5)MoO₄ ceramics. The densification temperature for the (K_0.5Nd_0.5)MoO₄ and (K_0.5Sm_0.5)MoO₄ ceramics are 700 °C and 800 °C for 2 h, respectively. The best microwave dielectric properties for (K_0.5Nd_0.5)MoO₄ was obtained in ceramic sample sintered at 760 °C for 2 h, with a dielectric permittivity of 9.8, a Qf about 69,000 GHz and a temperature coefficient of frequency about −62 ppm/°C. The best microwave dielectric properties for (K_0.5Sm_0.5)MoO₄ was obtained in ceramic sample sintered at 800 °C for 2 h, with a dielectric permittivity of 9.7, a Qf about 20,000 GHz and a temperature coefficient of frequency about −65 ppm/°C.     

Effects of (Cr0.5Ta0.5)4+ on structure and microwave dielectric properties of Ca0.61Nd0.26TiO3 ceramics

The Ca_0.61Nd_0.26Ti_1-x(Cr_0.5Ta_0.5)_xO₃ (CNT-CTx) ceramics with orthorhombic perovskite structure were prepared using the conventional solid-state method. The X-ray diffraction (XRD), Raman spectra and X-ray photoelectron spectra (XPS) were employed to investigate the correlations between crystal structure and microwave dielectric properties of CNT-CTx ceramics. The XRD results showed that all CNT-CTx samples were crystallized into the orthorhombic perovskite structure. The SEM micrographs indicated that the average grain size of samples depended on the sintering temperature. As (Cr_0.5Ta_0.5)⁴⁺ concentration increased, there was a significant decrease in the average grain size of samples. The short range order (SRO) structure and structural distortion of oxygen octahedra proved to exist in CNT-CTx crystals according to the analysis of Raman spectra results. The microwave dielectric properties highly depended on the full width at half maximum (FWHM) of Raman spectra, oxygen octahedra distortion, reduction of Ti⁴⁺ to Ti³⁺ and bond valence. At last, the CNT-CT0.05 ceramic sintered at 1420?°C for 4?h exhibited the good and stable comprehensive microwave dielectric properties: relative permittivity of 96.5, quality factor of 14,360?GHz, and temperature coefficient of resonant frequency of +153.3?ppm/°C.     

Microwave dielectric properties of low firing temperature stable scheelite structured (Ca,Bi)(Mo,V)O4 solid solution ceramics for LTCC applications

In the present work, a systematic study on microwave properties of Ca_1-xBi_xMo_1-xV_xO₄ (0.2 ≤ x ≤ 0.5) solid solution ceramics synthesized by using the traditional solid-state reaction method was conducted. A scheelite structured solid solution was formed in the composition range 0.2 ≤ x ≤ 0.5. We successfully prepared a microwave dielectric ceramic Ca_0.66Bi_0.34Mo_0.66V_0.34O₄ with a temperature coefficient of resonant frequency (TCF) near to zero and a low sintering temperature by using (Bi, V) substituted (Ca, Mo) in CaMoO₄ to form a solid solution. The Ca_0.66Bi_0.34Mo_0.66V_0.34O₄ ceramic can be well sintered at only 870 °C and exhibits good microwave dielectric properties with a permittivity (ε_r) ?21.9, a Qf ?18,150 GHz (at 7.2 GHz) (Q = quality factor = 1/dielectric loss; f = resonant frequency), a TCF ? + 0.1 ppm/°C. The chemical compatibility with silver indicated that the Ca_0.66Bi_0.34Mo_0.66V_0.34O₄ ceramic might be a good candidate for the LTCC applications.     

Temperature stable K0.5(Nd1−xBix)0.5MoO4 microwave dielectrics ceramics with ultra‐low sintering temperature

K_0.5(Nd_1?xBi_x)_0.5MoO₄ (0.2 ≤ x ≤ 0.7) ceramics were prepared via the solid‐state reaction method. All ceramics densified below 720°C with a uniform microstructure. As x increased from 0.2 to 0.7, relative permittivity (?_r) increased from 13.6 to 26.2 commensurate with an increase in temperature coefficient of resonant frequency (TCF) from – 31 ppm/°C to + 60 ppm/°C and a decrease in Qf value (Q = quality factor; f = resonant frequency) from 23 400 to 8620 GHz. Optimum TCF was obtained for x = 0.3 (?15 ppm/°C) and 0.4 (+4 ppm/°C) sintered at 660 and 620°C with ?_r ~15.4, Q_f ~19 650 GHz, and ?_r ~17.3, Q_f ~13 050 GHz, respectively. Ceramics in this novel solid solution are a candidate for ultra low temperature co‐fired ceramic (ULTCC) technology.