Degree of inversion of A/B lattice sites and microwave/millimeter wave/terahertz dielectric properties of MgAl2-x(Zn0.5Mn0.5)xO4 ceramics

In this work, spinel-structured MgAl_2-x(Zn_0.5Mn_0.5)_xO₄ (0 ≤ x ≤ 0.08) single-phase ceramics were prepared through a solid-state reaction route. The substitution of (Zn_0.5Mn_0.5)³⁺ for Al³⁺ at the octahedral site affected the degree of inversion of A/B lattice sites, bond length/strength/valence, and covalency of metal-oxygen bond in the tetrahedron and hence microwave dielectric properties of MgAl₂O₄. The variation in ε_r and tanδ of ceramics is investigated in the millimeter wave-terahertz frequency band by combining infrared reflection spectrum and terahertz time-domain spectroscopy. A high Q×f value of 111,010 GHz @ 12.01 GHz, low ε_r = 8.3, and slightly lower τ_f = −60 ppm/°C is obtained for MgAl_1.98Zn_0.01Mn_0.01O₄ ceramics, which is tuned by adding a small amount of SrTiO₃. The composite ceramics exhibited a near-zero τ_f (2.8 ppm/°C), high Q×f (55,400 GHz @ 11.15 GHz), and low ε_r (= 8.5), showing a great potential application prospect for 5G/6G wireless communication.     

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-loss and temperature stable (1-x)Ba3P2O8-xMg2B2O5 composite ceramics with low sintering temperature

In this study, the Ba₃P₂O₈ and Mg₂B₂O₅ were fabricated by the solid-state reaction method separately, and the (1-x)Ba₃P₂O₈-xMg₂B₂O₅ (x = 0.2–0.4) low-temperature co-fired ceramic (LTCC) materials were obtained in the sintering temperature range of 880–960 °C. The phase compositions, microstructures, elemental compositions, and microwave dielectric properties of the (1-x)Ba₃P₂O₈-xMg₂B₂O₅ composite ceramics were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and TE_01δ mode dielectric resonator method, respectively. The results revealed that the Mg₂B₂O₅ phase and Ba₃P₂O₈ phase could coexist well in the (1-x)Ba₃P₂O₈-xMg₂B₂O₅ composite ceramics without formation of any new phases. The abnormal grain growth of Ba₃P₂O₈ grains was inhibited by the addition of Mg₂B₂O₅. In addition, through composition of Ba₃P₂O₈ and Mg₂B₂O₅, the temperature coefficient of resonant frequency (τ_f) and quality factor (Q×f) were effectively optimized, and the sintering temperature was reduced to 880–960 °C. The optimal performance of 0.8Ba₃P₂O₈-0.2Mg₂B₂O₅ composite ceramic was achieved at a sintering temperature of 920 °C, τ_{f =} ?1.9 ppm/°C, Q×f = 61,250 GHz, and a low permittivity ε_r = 10.7. The chemical compatibility test demonstrated that the composite ceramic could coexist well with silver, which indicated that the 0.8Ba₃P₂O₈-0.2Mg₂B₂O₅ composite ceramic is a candidate LTCC material with wide application prospects.     

Novel temperature stable NiSnTa2O8 microwave dielectric ceramics with trirutile structure

A novel low-loss and temperature stable NiSnTa₂O₈ ceramic with trirutile structure was prepared using traditional solid-state method. The structure-performance relationships were investigated by Rietveld refinement, chemical bond theory and far-infrared spectrum. The results show that the relative densities play a dominant role in the change of dielectric constant. Theoretical dielectric constant calculated via bond theory, Clausius-Mossotti equation and fitted result of far-infrared spectrum are close to experimental value. Ta–O bonds with greatest bond ionicity and bond energy have the primary contributions to dielectric polarizabilities and dielectric loss. The optimal microwave dielectric performances of NiSnTa₂O₈ ceramics were obtained: ε_r ∼21.04, Q×f ∼31328 GHz and τ_f = −2.63 ppm/^°C at 1425 °C.     

Correlation between the structure and modified microwave dielectric characteristics of Zr4+ substituted Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics

Microwave ceramics are an important classes of materials that are used in microwave communication systems, especially in the area of 5G wireless communication and the internet of things. In this work, to improve the Q×f values and enhance the temperature stability of Ni_0.4Zn_0.6TiNb₂O₈ ceramics, the influence of the substitution of Zr⁴⁺ ions at the Ti site in Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics was investigated. The Q×f value increases from 32114 GHz to 45733 GHz and the τ_f value changes from 38.1 ppm/°C to 3 ppm/°C with a slight Zr⁴⁺ ion substitution (x = 0.1). Meanwhile, the sample with the Zr⁴⁺ ion substitution (x = 0.3) that was sintered at 1120 °C shows a very high Q×f value of 92078 GHz. Furthermore, the XRD results reveal that the phase and structure of the Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics change with the different Zr⁴⁺ ion contents. The substitution of the Zr⁴⁺ ion can promote the sintering process for the Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics and restrain the Ni_0.5Ti_0.5NbO₄ phase formation. The results obtained from Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics can offer useful information for the study and application of high-frequency microwaves.     

Dielectric resonator antenna with Y3Al5O12 transparent dielectric ceramics for 5G millimeter-wave applications

Microwave dielectric ceramics are considered to be one of the key materials for dielectric resonators (DR) and have very broad application prospects in the fifth generation (5G) mobile communication system. Here we have prepared high-quality factor Y₃Al₅O₁₂ (YAG) transparent dielectric ceramics using high-purity α-Al₂O₃ and Y₂O₃ powders by cold isostatic pressing of the vacuum sintered with tungsten meshes as the heating elements. Optimum relative permittivity () ~10.53, quality factor Q × f (Q = 1/dielectric loss, f = resonant frequency) ~95, 270 GHz (at =7.37 GHz), and temperature coefficient of resonant frequency (TCF) ~ −51.7 ppm °C⁻¹ were obtained at a sintering temperature of 1780°C for 12 h. For the first time, YAG transparent ceramic dielectric resonator antenna (DRA) is designed as a dominant mode and a higher-order mode using the aperture coupling feeding configuration excitation. The proposed transparent dielectric ceramic DRA can provide a broad impedance bandwidth of 4.193 GHz (ranging from 21.90 to 26.09 GHz) for S₁₁ < −10 dB, radiation efficiency of 92.1%, and compact DR unit. The proposed DRA can be used potentially as a 5G millimeter (mm)-wave multiple-input-multiple-output (MIMO) antenna unit.     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.     

Cold sintering optimized SrF2 microwave dielectric ceramics for the development of dielectric resonator antenna at 5G millimeter-wave band

SrF₂ is a promising low-ε_r fluoride with outstanding microwave dielectric properties, while densification of SrF₂ ceramics is challenging via traditional thermal sintering (TTS). In this work, dense SrF₂ ceramics with 93.4%–97.2% relative density have been obtained via cold sintering (300 MPa–900 MPa, 150 °C, 1 h) and subsequent post-annealing at 950 °C/3 h. The pretreated cold sintering process is beneficial for microstructure optimization, where the maximum Qf value (62,037 GHz) is obtained at 750 MPa, nearly three times higher than the TTS sample (21,080 GHz). An ultra-low dielectric constant (ε_r) of 5.94 is simultaneously obtained, together with a temperature coefficient of resonant frequency τ_f = ?78.26 ppm/°C. Good chemical compatibility between SrF₂ ceramics and silver is verified, indicating great promise for their use in LTCC technology. Moreover, the low-ε_r and high Qf values of the cold sintering optimized SrF₂ ceramics suggest great potential in the 5G millimeter-wave antenna systems. A SrF₂-based dielectric resonator antenna is designed and fabricated, which resonates at the desired 24.5 GHz and exhibits an outstanding S₁₁ of ?43.95 dB and a broad bandwidth of 4.51 GHz.     

Structure,far-infrared reflectance spectra,and microwave dielectric properties of Ba2MGa11O20 (M = Bi,La) ceramics

Ba₂MGa₁₁O₂₀ (M = Bi, La; called BBG and BLG, respectively) ceramics with monoclinic space group I2/m were prepared through a solid-state reaction method. BBG ceramic sintered at 1150 °C for 6 h has the best microwave dielectric properties with low ε_r = 10.68, Q × f = 41,756 GHz, and negative τ_f = ?61.3 ppm/°C. BLG ceramic sintered at 1440 °C for 6 h exhibits ε_r = 13.94, Q × f = 45,592 GHz, and near-zero τ_f = ?16.3 ppm/°C. The large deviation between ε_r and ε_th was ascribed to the “rattling” effect of the cations and the existence of lone pair ions of Bi³⁺. The difference in Q × f of the two ceramics was discussed in terms of packing fraction, and the τ_f of BLG was closer to zero than that of BBG due to the smaller τ_ε value. Their intrinsic dielectric properties were analyzed through far-infrared reflectivity spectroscopy.     

(Cu1/3Nb2/3)4+ ionic substituting effects,low-temperature sintering behaviors,and improved temperature stability of Ba3Nb4Ti4O21 microwave dielectric ceramics

In this study, (Cu_1/3Nb_2/3)⁴⁺ complex cation and BaO–ZnO–B₂O₃ glass frit were adopted to solve the high sintering temperature and poor temperature stability of Ba₃Nb₄Ti₄O₂₁ ceramics. It is shown that pure Ba₃Nb₄Ti₄O₂₁ phase was formed when Ti site was partially replaced by (Cu_1/3Nb_2/3)⁴⁺ cation. The increasing number of dopants decreases the dielectric polarizability, correspondingly, the dielectric constant and temperature coefficient of the resonance frequency values are reduced consistently. The variation of the Q × f value is determined by internal ionic packing fraction and external sintering densification. The (Cu_1/3Nb_2/3)⁴⁺ cation effectively decreases the suitable sintering temperature from 1200 to 1050 °C while greatly improving the temperature stability. BaO–ZnO–B₂O₃ glass was used to further improve the low-temperature sintering characteristics of Ba₃Nb₄Ti₄O₂₁ ceramics. It is proven that the addition of glass frits effectively decreases the temperature to 925 °C with combinational excellent microwave dielectric properties: ε_r ～55.6, Q × f ～5700 GHz, τ_f ～3 ppm/^°C, making the Ba₃Nb₄Ti₄O₂₁ ceramics promising in the applications of low-temperature cofired ceramic technology.     

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 dependence of microwave dielectric properties in Zn2-xSiO4-x-xCuO ceramics

In this work, the Zn_2-xSiO_4-x-xCuO (x = 0, 0.04, 0.08, 0.12, 0.16 and 0.20) ceramics were synthesized through solid state reaction. The dependence of microwave dielectric properties on the structure was investigated through X-ray diffraction (XRD) with Rietveld refinements, Scanning electron microscope (SEM) and Raman spectra. The melting of CuO can reduce the densification temperature of Zn_2-xSiO_4-x ceramics. In comparison with x = 0, the x = 0.08 ceramics were densified at 1150℃ and the excellent microwave dielectric properties with low dielectric constant (ε_r = 6.01), high quality factor (Qf = 105 500 GHz) and τ_f = ?28 ppm/°C, were obtained. The ε_r, Qf and τ_f value are dominated by covalency of Si-O bond and secondary phase, crystallinity and lattice energy, respectively. This provides a theoretical basis to further adjust the microwave dielectric property (especially τ_f value) from the structural point of view.     

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.     

A/B-site cosubstituted Ba4Pr28/3Ti18O54 microwave dielectric ceramics with temperature stable and high Q in a wide range

High permittivity Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄(0.4≤x ≤ 0.7, 0≤y ≤ 1.5) ceramics were synthesized using a standard solid-state method. The effects of Sm³⁺ substitution into the A-site and Sm³⁺/Al³⁺ cosubstitution into the A/B-sites on the microstructure, crystal structure, Raman spectra, infrared reflectivity (IR) spectra and dielectric characteristics were investigated in a Ba₄Pr_28/3Ti₁₈O₅₄ solid solution. In the ceramic samples of Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄(0.4≤x ≤ 0.7), Sm³⁺ partial substitution for Pr³⁺ could improve the quality factor (Qf) value and reduce the TCF value. Nevertheless, the quality factor (Qf~10,000GHz) needed further improvement and the TCF values (+12.3~+35.4 ppm/°C) were still too large. Therefore, Al³⁺ was introduced for further optimization of the TCF values and Qf values of the Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄ ceramics. Sm/Al cosubstitution led to a good combination of high ε_r (ε_r ≥ 70), high Qf (Qf ≥ 12,000 GHz), and near-zero TCF (−10 < TCF < +10 ppm/°C) in a wide range (0.4≤x ≤ 0.7). Infrared reflectivity (IR) spectra indicated that A-TiO₆ vibration modes gave the primary contribution rather than Ti–O bending and stretching modes. The decrease in the degree of B-site cations order could be confirmed by Raman spectra. XPS results demonstrated that the improvement of quality factor (Qf) value was strongly related to the suppression of Ti³⁺. Excellent dielectric properties were achieved in Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄ microwave ceramics with x = 0.5 and y = 1.25: ε_r = 72.5, Qf = 13,900GHz, TCF = +1.3 ppm/°C.     

Effect of Li nonstoichiometry and TiO2 addition on the microwave dielectric properties of Li3PO4 ceramics

Li₃PO₄ ceramic is a promising microwave ceramic material with low dielectric constant. The effect of Li nonstoichiometry on phase compositions, microstructures, and microwave dielectric characteristics of Li₃PO₄ ceramics, on the other hand, has been examined infrequently. Therefore, in the first part of this study, the stoichiometry and Li nonstoichiometry compositions based on Li_3+xPO₄(x = 0, 0.03, 0.06, 0.09, 0.12 and 0.15) were prepared by conventional solid-phase method. The results show that a few nonstoichiometric lithium ions enter the lattice of Li_3+xPO₄. Compared with the chemical content of Li₃PO₄, the sintering characteristics, relative dielectric constants and quality factors of Li_3+xPO₄ ceramics can be improved by slightly excessive Li ions, while the properties of Li₃PO₄ ceramics can be deteriorated by excessive Li ions. Li_3.12PO₄ ceramics sintered at 975 °C for 2 h have good dielectric properties (ε_r = 5.89, Q×f = 44,000 GHz, τ_f = ?206 ppm/^°C). In order to improve its large negative temperature coefficient of resonant frequency, in the following study, rutile nano TiO₂ particles were added as τ_f compensator. Adding TiO₂ powders not only effectively improve the temperature stabilities of the multiphase ceramics, but also make the grain growth more uniform. With the increase of TiO₂ content from 0.40 to 0.60, τ_f increases from ?73.5 ppm/^°C to +42.3 ppm/^°C. The best dielectric property of 0.45Li_3.12PO₄-0.55TiO₂ composite ceramic is ε_r = 13.29, Q×f = 40,700 GHz, τ_f = +8.8 ppm/^°C.     

Microstructure and broadband dielectric properties of Zn2SiO4 ceramics with nano-sized TiO2 addition

Zn₂SiO₄ ceramics with nano-sized TiO₂ addition (ZST) were synthesized by conventional solid state method. The association between the new composite's microstructures and dielectric properties reveals that reduced pores, increased density and average grain sizes with increasing sintering temperatures, have contributed to the increased permittivities at kHz and microwave bands; the decrease of the permittivities at 1275 °C is due to the form of twin planes. At the terahertz band, the competition of generating oxygen vacancies and forming them into twin crystallographic shear planes dominates the change of permittivities: the crystallographic shear planes decrease the permittivity at the sintering temperature 1225 °C and 1250 °C, and the high-rate generation of oxygen vacancies at 1275 °C increases the permittivities. The ZST ceramics demonstrate stable permittivity and low dielectric losses (<10^–3 from 10 kHz to microwave band; and <10^–2 at THz range); and the temperature coefficient of resonant frequency is optimized to close zero. These advanced dielectric properties and low sintering temperature (<1300 °C) provide the ZST ceramics great potential in designing microwave and THz devices.     

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.     

Crystal structure,chemical bonding and infrared reflectivity of microwave dielectric SrIn2O4 ceramics

In this work, the orthorhombic structured SrIn₂O₄ ceramics with a space group Pnam were synthesized by a solid-state reaction method. A high relative density (96.5%) coupled with excellent microwave dielectric properties (ε_r ∼ 12.3, Q × f = 96,900 GHz, τ_f ∼ −61.6 ppm/°C) were obtained as sintered 1300 °C for 4 h. The bond valence analysis demonstrates that the large sized cation Sr²⁺ exhibits a compressed state, while the In³⁺ exhibits a weaken rattling effect. The P-V-L chemical bond theory analysis indicates that the In-O bonds play a key role in affecting the dielectric loss. The thermally conductivity activation energy E_dc (0.94 eV) of SrIn₂O₄ was obtained by the dielectric spectroscopy, indicating that the E_dc was contributed to the double ionized oxygen vacancies. Furthermore, the intrinsic dielectric properties (ε_r ∼ 11.2, Q × f = 148,900 GHz) of SrIn₂O₄ were obtained by infrared reflectivity spectroscopy.     

Enhancement of structural and microwave properties of Zn2+ ion-substituted Li2MgSiO4 ceramics for LTCC applications

In this study, Zn²⁺-substituted Li₂MgSiO₄ ceramics (Li₂(Mg_1-xZn_x)SiO₄, x = 0.00, 0.05, 0.10, 0.15, and 0.20) were synthesized using a traditional solid-state method. A fixed amount of LiF sintering aid (1.5 wt%) was added to the ceramics for decreasing the sintering temperature and adjusting their microwave dielectric properties. X-ray diffraction (XRD) results revealed no secondary phases, and scanning electron microscopy (SEM) data suggest that the Zn²⁺ ion substitution increased the size and uniformity of the grains, thereby affecting the densification of the prepared ceramics. The maximum bulk density (2.94 g/cm³) was found in a Zn²⁺ ion-substituted ceramic with x = 0.10 at a relative density of 94.2% (compared with the XRD theoretical density). Excellent microwave dielectric properties (ε_r = 6.28, Q × f = 50400 GHz, and τ_f = ?145 ppm/°C) can also be obtained at this zirconium content. We believe that the developed ceramics are promising for use as antenna substrates or transmit/receive modules in low-temperature co-firing ceramic applications.