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.     

Structure and Dielectric Properties of Re0.02Sr0.97TiO3 (Re = La,Sm, Gd,Er) Ceramics for High‐Voltage Capacitor Applications

Rare–earth‐doped strontium titanate ceramics yielding the formula Re_0.02Sr_0.97TiO₃ (Re–ST, Re = La, Sm, Gd, Er) were prepared by solid‐state reaction route. All Re–ST ceramics had single cubic perovskite structure similar to pure SrTiO₃ (ST). The grain size of Re–ST ceramics dramatically decreased to 1–10 μm, depending on different rare‐earth elements, as compared to ~30 μm of pure ST. The relative dielectric constant of Re–ST ceramics (ε_r = 2750–4530 at 1 kHz) showed about 10–15 times higher than that of pure ST (ε_r = 300 at 1 kHz), whereas the dielectric loss of Re–ST ceramics still remained lower than 0.03 (at 1 kHz) at room temperature. Under 0–1.63 × 10⁶ V/m bias electric field testing conditions, the ε_r of Re–ST ceramics at room temperature changed within 14%. The P–E results indicated that the Re–ST ceramics were linear dielectrics. Together with their relatively high breakdown strength (E_b > 1.4 × 10⁷ V/m), the Re–ST ceramics could be very promising for high‐voltage capacitor applications. Meanwhile, the temperature stability of the ε_r of Re–ST ceramics was evaluated in a temperature range of ?60°C–200°C.     

Three Layer Perovskite‐Like Structured Pr3Ti2TaO11 Ferroelectrics with Super‐High Curie Point

Pr₃Ti₂TaO₁₁ was prepared by co‐precipitation and subsequent solid‐state reaction at 1300°C. The compound has a perovskite‐like layered structure belonging to space group Pmc2₁ with unit cell parameters a = 3.8689(3) Å, b = 20.389(2) Å, c = 5.5046(5) Å. Second harmonic generation results confirm the structure of Pr₃Ti₂TaO₁₁ as being noncentrosymmetric. Dense and textured ceramics were prepared by spark plasma sintering. Analysis of the X‐ray diffraction and transmission electron microscopy results showed that Pr₃Ti₂TaO₁₁ ceramics have an n = 3 (type II) heteroblock structure consisting of alternating n = 2 and 4 octahedral oxide layers. High‐resolution electron microscopy revealed the layered structure to be highly disordered, with faulting of the heteroblock structure and the coexistence of a n = 4 phase on a fine scale (nm), which was evident as a broadening of the X‐ray diffraction peaks of the ceramics. Pr₃Ti₂TaO₁₁ ceramic exhibits a super‐high Curie point (1415 ± 5°C). A small, but measurable piezoelectric constant d₃₃ between 0.1 and 0.2 pC/N was detected for the samples poled above 900°C under an electric field of 100–200 V/cm.     

Crystal structure and temperature dependence of permittivity in barium aluminate based solid solutions

This study systematically investigated the structural, dielectric, and ferroelectric properties of BaAl_(2−2x)(Mg_0.5Ti_0.5)_2xO₄ ceramics in the 0 ≤ x ≤ 0.04 range. Single-phase solid solutions in the P6₃ space group with hexagonal crystal symmetry were confirmed in the composition range of 0 ≤ x ≤ 0.03. The bond lengths of Al1/(Mg,Ti)–O, Al₂/(Mg,Ti)–O, and Al₃/(Mg,Ti)–O increased with the increase in x, as confirmed through the Rietveld refinement and evolutions of corresponding modes in Raman spectra. The temperature stability of dielectric properties improved at a composition around x = 0.03, and the dielectric constant ε_r ascended with the increase in x. Ultrabroad temperature stability (−100°C to 700°C) was obtained, and an optimal combination (ε_r = 18.5, tan δ < 10⁻³, −22 ppm/°C ≤ TCC ≤ +20 ppm/°C, resistivity ~4.5 × 1014 Ω·cm) was achieved for the x = 0.03 ceramic sintered at 1260°C in air for 6 hours. The increase in stability was ascribed to the variations in axial bonds, and lattice distortions were determined through high-resolution transmission electron microscopy. The x = 0.03 ceramic could be a promising candidate for C0G or NP0 multilayer ceramic capacitors because of its low loss, high reliability, superior insulating properties and comparatively low-cost raw materials.     

Facile Synthesis of “Quench‐Free Glass” and Ceramic‐Glass Composite for LTCC Applications

The 10 mol% ZnO–2 mol% B₂O₃–8 mol% P₂O₅–80 mol% TeO₂ (ZBPT) glass was prepared by quenching as well as slowly cooling the melt. The ZBPT glass prepared by both methods show similar microwave dielectric properties. ZBPT glass has an ε_r of 22.5 (at 7 GHz), Q_u × f of 1500 GHz, and τ_f of ?100 ppm/°C. The ceramic‐glass composites of Sr₂ZnTeO₆ (SZT) and ZBPT is prepared through two convenient methods: (a) conventional way of co‐firing the ceramic with ZBPT glass powder and (b) a nonconventional facile route by co‐firing the ceramic with precursor oxide mixture of ZBPT glass at 950°C. In the former route, SZT + 5 wt% ZBPT composite sintered at 950°C showed moderately good microwave dielectric properties (ε_r = 13.4, Q_u × f = 4500 GHz and τ_f = ?52 ppm/°C). Although the SZT + 5 wt% ZBPT composite prepared through the nonconventional method also showed similar microwave dielectric properties (ε_r = 13.8, Q_u × f = 5300 GHz and τ_f = ?50 ppm/°C), the synthesis procedure is much simplified in the latter case. The composites are found to be chemically compatible with Ag. The composite containing 5 wt% ZBPT prepared through conventional and nonconventional ways shows linear coefficients of thermal expansion of 7.0 ppm/°C and 7.1 ppm/°C, respectively. Both the composites have a room‐temperature thermal conductivity of 2.1 Wm^?1 K^?1.     

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.     

Enhanced Multiferroic and Magnetocapacitive Properties of (1 − x)Ba0.7Ca0.3TiO3–xBiFeO3 Ceramics

The structures, Curie temperature, dielectric relaxor behaviors, ferroelectricity, ferromagnetism, and magnetocapacitance of the (1?x)Ba_0.70Ca_0.30TiO₃–xBiFeO₃ [(1?x)BCT–xBF, x = 0–0.90] solid solutions have been systematically investigated. The ceramics have coexisted tetragonal (T) and orthorhombic (O) phases when x ≤ 0.06, coexisted pseudocubic (PC) and O phases when x = 0.065, coexisted cubic and O phases when 0.07 ≤ x ≤ 0.12, PC phase when 0.21 ≤ x ≤ 0.42, coexisted T and rhombohedral (R) phases when 0.52 ≤ x ≤ 0.70, and R phase when x ≥ 0.75. Significantly, composition‐dependent microstructures and Curie temperature are observed, the average grain size increases from 1.9 μm for x = 0, reaches 12.0 μm for x = 0.67, and then decreases to 1.3 μm for x = 0.90. At room temperature, the ceramics with x = 0.42–0.70 show piezoelectric properties and multiferroic behaviors, characterized by the polarization‐electric field, polarization current intensity–electric field, and magnetization–magnetic field curves, the composition with x = 0.67 has maximum polarization, remnant polarization, maximum magnetization, and remnant magnetization of 15.0 μC/cm², 9.1 μC/cm², 0.33 emu/g, and 0.14 emu/g, respectively. In addition, the magnetocapacitance is evidenced by the increased relative dielectric constant with increasing the applied magnetic field (H). With ΔH = 8 kOe, the composition with x = 0.67 shows the largest values of (ε_r(H) ? ε_r(0))/ε_r(0) = 2.96% at room temperature. The structure–property relationship is discussed intensively.     

Effect of TiO2 Doping on the Structure and Microwave Dielectric Properties of Cordierite Ceramics

The (1?x)Mg₂Al₄Si₅O₁₈–xTiO₂ |(1?x)MAS‐xT| (0 ≤ x ≤ 0.35) cordierite ceramics are fabricated by solid‐state reaction method for obtaining near‐zero temperature coefficient of resonant frequency (τ_f). The XRD and SEM results show that (1?x)MAS‐xT (0 ≤ x ≤ 0.10) ceramics exhibit single cordierite solid solution, whereas as 0.15 ≤ x ≤ 0.35, present composite phases of Mg₂Al₄Si₅O₁₈ solution and TiO₂. Rietveld refinements of XRD data suggest that the [(Si₄Al₂)O₁₈] hexagonal shape in cordierite structure happens to alternate change from nonsymmetrical hexagonal rings to almost centrosymmetrical equilateral rings as x increases to 0.10 comparing to that of x = 0. As Ti⁴⁺ ions squeeze into the [(Si₄Al₂)O₁₈] rings structure, the orientation and shapes of the rings begin to rotate and expand from initial state of [1–20] (x = 0) to near [210] direction (x = 0.10), and then continue to expand toward close to [110] direction (x = 0.25). Due to centrosymmetry adjustment of [(Si₄Al₂)O₁₈] hexagonal rings and of other microstructure factors improvement, the (1?x)MAS‐xT (x = 0.10) cordierite solution achieves optimum quality factor Q_f: ε_r = 6.3, Q_f = 55 400 GHz (17.6 GHz), τ_f = ?21 ppm/°C. The (1?x)MAS‐xT (x = 0.25) composites obtain a near‐zero temperature coefficient of resonance frequency: ε_r = 6.8, Q_f = 37 800 GHz (18.4 GHz), τ_f = ?0.2 ppm/°C.     

Microwave Dielectric Properties of Ultralow‐Temperature Cofirable Ba3V4O13 Ceramics

Ultralow‐temperature sinterable Ba₃V₄O₁₃ ceramics have been prepared through solid‐state ceramic route. Structural properties of the ceramic material are studied using powder X‐ray diffraction. Ba₃V₄O₁₃ ceramic has monoclinic structure and the existence of [V₄O₁₃]^6? polyhedra is confirmed through Laser Raman studies. The sample sintered at 600°C for 1 h shows dense microstructure with microwave dielectric properties of ε_r = 9.6, Q × f = 56 100 GHz, and τ_f = ?42 ppm/°C. The ceramics under study show good chemical compatibility with aluminum during cofiring.     

Low‐Temperature‐Fired ReVO4 (Re = La,Ce) Microwave Dielectric Ceramics

We report a series of ReVO₄ (Re = La, Ce) microwave dielectric ceramics fabricated by a standard solid‐state reaction method. X‐ray diffraction and scanning electron microscopy measurements were performed to explore the phase purity, sintering behavior, and microstructure. The analysis revealed that pure and dense monoclinic LaVO₄ ceramics with a monazite structure and tetragonal CeVO₄ ceramics with a zircon structure could be obtained in their respective sintering temperature range. Furthermore, LaVO₄ and CeVO₄ ceramics sintered at 850°C and 950°C for 4 h possessed out‐bound microwave dielectric properties: ε_r = 14.2, Q × f = 48197 GHz, τ_f = ?37.9 ppm/°C, and ε_r = 12.3, Q × f = 41 460 GHz, τ_f = ?34.4 ppm/°C, respectively. The overall results suggest that the ReVO₄ ceramics could be promising materials for low‐temperature‐cofired ceramic technology.     

Novel Series of Low‐Firing Microwave Dielectric Ceramics: Ca5A4(VO4)6 (A2+ = Mg,Zn)

Using a conventional solid‐state reaction Ca₅A₄(VO₄)₆ (A²⁺ = Mg, Zn) ceramics were prepared and their microwave dielectric properties were investigated for the first time. X‐ray diffraction revealed the formation of pure‐phase ceramics with a cubic garnet structure for both samples. Two promising ceramics Ca₅Zn₄(VO₄)₆ and Ca₅Mg₄(VO₄)₆ sintered at 725°C and 800°C were found to possess good microwave dielectric properties: ε_r = 11.7 and 9.2, Q × f = 49 400 GHz (at 9.7 GHz) and 53 300 GHz (at 10.6 GHz), and τ_f = ?83 and ?50 ppm/°C, respectively.     

Crystal structure,phase compositions,and microwave dielectric properties of malayaite-type Ca1−xSrxSnSiO5 ceramics

Low-permittivity Ca_1−xSr_xSnSiO₅ (0 ≤ x ≤ 0.45) microwave dielectric ceramics were prepared via traditional state-reaction at 1400°C-1450°C for 5 hours. Moreover the microwave dielectric properties of SnO₂ ceramic were obtained for the first time. SnO₂ ceramic was difficult to densify, and SnO₂ ceramic (ρ_rel = 65.1%) that was sintered at 1525°C exhibited the optimal microwave dielectric properties of ε_r = 5.27, Q × f = 89 300 GHz (at 14.5 GHz), and τ_f = −26.7 ppm/°C. For Ca_1−xSr_xSnSiO₅ (0 ≤ x ≤ 0.15) ceramics, Sr²⁺ could be dissolved in the Ca²⁺ site of Ca_1−xSr_xSnSiO₅ to form a single phase, and the partial substitution of Ca²⁺ by Sr²⁺ could improve the microwave dielectric properties of CaSnSiO₅ ceramic. Secondary phases (SnO₂ and SrSiO₃) appeared at 0.2 ≤ x ≤ 0.45 and could adjust the abnormally positive τ_f value of CaSnSiO₅ ceramic. The highest Q × f value (60 100 GHz at 10.4 GHz) and optimal microwave dielectric properties (ε_r = 9.42, Q × f = 47 500 GHz at 12.4 GHz, and τ_f = −1.2 ppm/°C) of Ca_1−xSr_xSnSiO₅ ceramics were obtained at x = 0.05 and 0.45, respectively.     

Novel thermally stable,high quality factor Ba4(Pr0.4Sm0.6)28/3Ti18−yGa4y/3O54 microwave dielectric ceramics

High dielectric constant Ba₄(Pr_0.4Sm_0.6)_28/3Ti_18−yGa_4y/3O₅₄ (BPSTG) (0 ≤ y ≤ 1) microwave ceramics with enhanced dielectric properties were synthesized via the traditional solid-state processing for the first time. The crystal structure, microstructure, and microwave dielectric characteristics were investigated in details. X-ray diffraction results showed that all well-sintered samples belonged to a single tungsten bronze type phase. Results showed that partial substitution of Ga³⁺ for Ti⁴⁺ is an effective way in adjusting the temperature coefficient of resonant frequency (TCF) value of the Ba₄(Pr_0.4Sm_0.6)_28/3Ti₁₈O₅₄ ceramics and increased the quality factor (Qf) values. The variation tendency of dielectric constant was in accordance with the ionic polarizability. The Qf values highly depend on the grain size from the scanning electron microscopy results. A near zero TCF value can be obtained by carefully adjusting the substitution of Ga³⁺ content. Infrared reflectivity (FIR) spectra were employed to reveal the relationship between the phonons and microwave dielectric properties. At last, excellent combinations dielectric properties of ε_r = 78.5, Qf = 12,400 GHz, TCF = +2.1 ppm/°C were achieved in BPSTG ceramics when y = 0.75.     

Improved sinterability and microwave dielectric properties of [Zn0.5Ti0.5]3+-doped ZnAl2O4 spinel solid solution

Low-permittivity ZnAl_2-x(Zn_0.5Ti_0.5)_xO₄ ceramics were synthesized via conventional solid-state reaction method. A pure ZnAl₂O₄ solid-state solution with an Fd-3m space group was achieved at x ≤ 0.1. Results showed that partial substitution of [Zn_0.5Ti_0.5]³⁺ for Al³⁺ effectively lowered the sintering temperature of the ZnAl₂O₄ ceramics and remarkably increased the quality factor (Q × f) values. Optimum microwave dielectric properties (ε_r = 9.1, Q × f = 115,800 GHz and τ_f = −78 ppm/°C) were obtained in the sample with x = 0.1 sintered at 1400°C in oxygen atmosphere for 10 h. The temperature used for the sample was approximately 250°C lower than the sintering temperature of conventional ZnAl₂O₄ ceramics.     

Low‐Temperature Sintering and Electric Properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 Ferroelectric Ceramics with CuO Additive

The low‐temperature sintering and electric properties of Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ (PZTN 95/5) ferroelectric ceramics with CuO addition was investigated. The CuO addition significantly promoted the densification and reduced the sintering temperature of PZTN 95/5 ceramics by more than 200°C. The 0.2 wt% CuO‐added sample sintered at 1150°C exhibited the optimum relative density of 96.7% and excellent electric properties with values of P_r = 37.80 μC/cm², T_C = 223°C, ε_r = 329, and tan δ = 0.016, which were superior to that of PZTN 95/5 ceramics sintered at 1350°C.     

Microstructure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of Sc‐Modified BiFeO3–BaTiO3 Multiferroic Ceramics with MnO2 Addition

0.725BiFe_1?xSc_xO₃–0.275BaTiO₃ + y mol% MnO₂ multiferroic ceramics were fabricated by a conventional ceramic technique and the effects of Sc doping and sintering temperature on microstructure, multiferroic, and piezoelectric properties of the ceramics were studied. The ceramics can be well sintered at the wide low sintering temperature range 930°C–990°C and possess a pure perovskite structure. The ceramics with x/y = 0.01–0.02/1.0 sintered at 960°C possess high resistivity (~2 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 19.1–20.4 μm/cm²), good piezoelectric properties (d₃₃ = 127–128 pC/N, k_p = 36.6%–36.9%), and very high Curie temperature (618°C–636°C). The increase in sintering temperature improves the densification, electric insulation, ferroelectric, and piezoelectric properties of the ceramics. A small amount of Sc doping (x ≤ 0.04) and the increase in the sintering temperature significantly enhance the ferromagnetic properties of the ceramics. Improved ferromagnetism with remnant magnetization M_r of 0.059 and 0.10 emu/g and coercive field H_c of 2.51 and 2.76 kOe are obtained in the ceramics with x/y = 0.04/1.0 (sintered at 960°C) and 0.02/1.0 (sintered at 1050°C), respectively. Because of the high T_C (636°C), the ceramic with x/y = 0.02/1.0 shows good temperature stability of piezoelectric properties. Our results also show that the addition of MnO₂ is essential to obtain the ceramics with good electrical properties and electric insulation.     

Low‐firing and temperature stable microwave dielectric ceramics: Ba2LnV3O11 (Ln = Nd,Sm)

Low‐firing and temperature stable microwave dielectric ceramics of Ba₂LnV₃O₁₁ (Ln = Nd, Sm) were prepared by solid‐state reaction. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate the phase purity, crystal structure, sintering behavior, and microstructure. The XRD patterns indicated that Ba₂LnV₃O₁₁ (Ln = Nd, Sm) ceramics belong to monoclinic crystal system with P2₁/c space group in the whole sintering temperature range (800°C ‐900°C). Both ceramics could be well densified at 880°C for 4 hours with relative densities higher than 96%. The Ba₂LnV₃O₁₁ (Ln = Nd, Sm) samples sintered at 880°C for 4 hours exhibited excellent microwave dielectric properties: ε_r = 12.05, Q × f = 23 010 GHz, τ_f = ?7.7 ppm/°C, and ε_r = 12.19, Q × f = 27 120 GHz, τ_f = ?16.2 ppm/°C, respectively. Besides, Ba₂LnV₃O₁₁ (Ln = Nd, Sm) ceramics could be well co‐fired with the silver electrode at 880°C.     

Ultra-low permittivity MgF2 ceramics with high Qf values and their role as microstrip patch antenna substrates

MgF₂ ceramics have been prepared via the standard solid-state reaction method, and their microwave dielectric properties are reported for the first time. The permittivity (ε_r) and quality factor (Qf) of MgF₂ ceramics are closely related to porosity and lattice energy, respectively. The optimum microwave dielectric properties (ε_r = 4.67, Qf = 92,233 GHz, and τ_f = ?67.1 ppm/°C) are obtained when sintered at 1100 °C. The ultra-low permittivity and high Qf value distinguish MgF₂ ceramic as a perfect substitute for the commonly used polymer-based FR4 epoxy in the coming 5G/6G era. The feasibility of using MgF₂ ceramics as antenna substrates is demonstrated by fabricating an X-band microstrip patch antenna. The MgF₂-based antenna resonating at 8.25 GHz exhibits excellent antenna performance with a return loss (S₁₁) of ?23.39 dB and impedance bandwidth of 318 MHz.     

Temperature‐Stable Relative Permittivity from −70°C to 500°C in (Ba0.8Ca0.2)TiO3–Bi(Mg0.5Ti0.5)O3–NaNbO3 Ceramics

Temperature‐stable relaxor dielectrics have been developed in the solid solution system: 0.45Ba_0.8Ca_0.2TiO₃–(0.55 ? x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃. Ceramics of composition x = 0 have a relative permittivity ?_r = 950 ± 15% over a wide temperature range from +70°C to 600°C. Modification with NaNbO₃ at x = 0.2 decreases the lower limiting temperature to ?70°C, but also decreases relative permittivity such that ?_r ~ 600 ± 15% over the temperature range ?70°C to 500°C. For composition x = 0.3, the low‐temperature dispersion in loss tangent, tan δ, (at 1 kHz) shifts to lower temperature, giving tan δ values ≤0.02 across the temperature range ?60°C to 300°C in combination with ?_r ~ 550 ± 15%. Values of dc resistivity for all samples are of the order of 10¹⁰ Ω m at 250°C and 10⁷ Ω m at 400°C.     

Relationship between bond characteristics and microwave dielectric properties of REVO4 (RE = Yb,Ho) ceramics

Two novel low-ε_r REVO₄ (RE = Yb, Ho) microwave dielectric ceramics with the symmetry of the zircon structure, space group I4₁/amd, were prepared using the solid-state method. Dense REVO₄ (RE = Yb, Ho) ceramics sintered at 1200 °C and 1160 °C performed ε_r ～ 12.3 ± 0.1 and 13.3 ± 0.1, Q × f ～ 28,200 ± 300 GHz and 24,100 ± 300 GHz, τ_f ～ ?18.8 ± 0.5 ppm/°C and ?17.4 ± 0.5 ppm/°C, along with thermal expansion coefficient (α_L) of 9.0 ppm/°C and 8.1 ppm/°C, respectively. Bond valence results indicated that the slightly rattling RE³⁺ cations at the A-site and compressed V⁵⁺ at the B-site occurred in both ceramics. The positive deviations (Δε_r) of porosity corrected ε_r(Corr) from those calculated by the Clausius-Mosotti equation ε_r(C-M), 8.1% for YbVO₄ and 17.7% for HoVO₄, were observed, implying that the rattling effect of RE³⁺ in dodecahedral A-site were greater than those of compressed V⁵⁺ in tetrahedral B-site. Rattling effect also led REVO₄ (RE = Yb, Ho) to develop higher ε_r, and smaller τ_ε and τ_αm, then closer to zero τ_f values than other zircon-structured REVO₄ (RE = Ce, Nd, Sm, Eu) ceramics with large negative τ_f. The differences in sintering temperature and microwave dielectric performance of both ceramics were discussed using the packing fraction, full width at half maximum (FWHM) of Raman modes and Phillips-Van Vechten-Levine (P–V-L) theory.