Effects of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> additive on sintering behavior and microwave dielectric properties of ZnTa<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics

ZnTa₂O₆ ceramics with various amount of Al₂O₃ additive were synthesized by a conventional mixed-oxide route. The grain growth of ZnTa₂O₆ ceramics was accelerated with Al₂O₃ additive. However, excessive addition (>1.0 wt%) of Al₂O₃ leaded to abnormal grain growth. With Al₂O₃ addition, the Al₂O₃ additive did not solubilized into ZnTa₂O₆ structure but resulted in forming the second phase. The Al₂O₃ addition resulted in the lower sintering temperature of ZnTa₂O₆ ceramics and improved microwave dielectric properties. The dielectric constant (ε_r) of the samples did not change much and ranged from 32.41 to 34.33 with different amount of Al₂O₃ addition. The optimized quality factor (Q × f) was higher than 70,000 GHz as a result of the denser ceramics. The temperature coefficient of resonant frequency (τ _f ) of the doped ZnTa₂O₆ ceramics could be optimized to near-zero.     

Tuning the temperature coefficient of resonant frequency for 8-layer twinned hexagonal perovskite Ba<Subscript>8</Subscript>ZnTa<Subscript>6</Subscript>O<Subscript>24</Subscript> ceramics

High-Q dielectric materials ilmenite MgTiO₃, columbite MgNb₂O₆ and cubic perovskite Ba₃NiTa₂O₉ with negative temperature coefficient of resonant frequency (τ _f ) were selected as candidates for compensating the τ _f of hexagonal perovskite Ba₈ZnTa₆O₂₄. X-ray diffraction data shows that Ba₈ZnTa₆O₂₄ coexists with Ba₃NiTa₂O₉ but is not compatible with MgTiO₃ and MgNb₂O₆ at high temperature. The τ _f for the mixed hexagonal/cubic perovskite Ba₈ZnTa₆O₂₄–Ba₃NiTa₂O₉ system is tunable via the temperature compensation effect and its quality factor may be improved via annealing the ceramics at high temperature to enhance the cation ordering in the cubic component. Permittivity ε _r  ~ 22–25, Q×f > 30,000 GHz and tunable τ _f within ±10 ppm/°C were achieved in the range of about 50–80 wt% Ba₃NiTa₂O₉ for the hexagonal/cubic perovskite composite Ba₈ZnTa₆O₂₄–Ba₃NiTa₂O₉ ceramics, which is suitable for the application as dielectric resonators and filters.     

Influence of Zr doping on the dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

Pure and Zr-substituted CaCu₃(Ti_1−x Zr _x )₄O₁₂ (x = 0, 0.01, 0.02, 0.03) ceramics were prepared by the Pechini method. X-ray powder diffraction analysis indicated the formation of single-phase compound, and all the diffraction peaks were completely indexed by the body-centered cubic perovskite-related structure. The effects of Zr⁴⁺ ion substituting partially Ti⁴⁺ ion on the dielectric properties were investigated in frequency range between 100 Hz and 1 GHz. The low frequency (f ≤ 10⁵ Hz) dielectric constant decreases with Zr substitution and the high frequency (f ≥ 10⁷ Hz) dielectric constant is unchanged. Interestingly, a low-frequency relaxation was observed at room temperature through Zr substitution. The observed dielectric properties in Zr-substituted samples were discussed using the internal barrier layer capacitor model. A corresponding equivalent circuit was adopted to explain the dielectric dispersion. The characteristic frequency of low-frequency relaxation rises due to the decrease of the resistivity of grain boundary with Zr substitution, which is likely responsible for the large low-frequency response at room temperature.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Optimized sintering properties and temperature stability of MgZrTa<Subscript>2</Subscript>O<Subscript>8</Subscript> ceramics with CuO addition for microwave application

Microwave dielectric ceramics CuO–modified MgZrTa₂O₈ were synthesized by the conventional solid-state reaction method. The effects of CuO additives on the sintering characteristics and microwave dielectric properties have been investigated. With CuO addition, the sintering temperature of MgZrTa₂O₈ ceramics can be effectively lowered from 1475 to 1375 °C without decreasing its dielectric properties obviously and the temperature coefficient of the resonant frequency of MgZrTa₂O₈ ceramics have been optimized to near-zero. The crystalline phase exhibited a wolframite crystal structure and no second phase was detected at low addition levels. The grain growth of CuO–modified MgZrTa₂O₈ ceramics was accelerated due to liquid phase effect. The relative dielectric constants (ε_r) were correlated with apparent density and were not significantly different for all levels of CuO concentration. The quality factors (Q?×??) and temperature coefficient of resonant frequency (τ_?), which were strongly dependent on the CuO concentration, were analyzed by the grain size and the dielectric constant respectively. A best Q?×?? value of 116400 GHz and τ_? value of ?6.19 ppm/℃ were obtained for specimen with 0.05 wt% CuO addition at 1375 °C.     

Structural investigation and giant dielectric response of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramic by Nd/Zr co-doping for energy storage applications

High performance dielectric materials are highly required for practical application for energy storage technologies. In this work, high-k pristine and modified calcium copper titanate having nominal formula Ca_0.95Nd_0.05Cu₃Ti_4?xZr_xO₁₂ (x?=?0.01, 0.03 & 0.10) were synthesized and characterized for structural and dielectric properties. Single phase formation of the synthesized compositions was confirmed by X-ray diffraction patterns and further analysed using Rietveld refinement technique. Phase purity of the synthesized ceramics was further confirmed by Energy-dispersive X-ray Spectroscopy (EDX) analysis. SEM images demonstrated that grain size of the modified CCTO ceramics was controlled by Zr⁴⁺ ions due to solute drag effect. Impedance spectroscopy was employed to understand the grain, grain boundaries and electrode contribution to the dielectric response. Nyquist plots were fitted with a 2R-CPE model which confirms the non-ideality of the system. Substitution of specific concentration of Nd and Zr improved the dielectric properties of high dielectric permittivity (ε′ ~?16,902) and minimal tanδ (≤?0.10) over a wide frequency range. The giant ε′ of the investigated system was attributed to internal barrier layer capacitance (IBLC) effect and reduced tanδ accredited to enhanced grain boundaries resistance due to substitution of Zr⁴⁺ ions at Ti⁴⁺ site.     

Effect of Ti-ion non-stoichiometry on microstructure and microwave dielectric characteristic of Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> ceramics

This paper studies the microwave dielectric properties, microstructure, vibration and densification of Li₂ZnTi_3+xO_8+2x (\(- 0.04 \le {\text{x}} \le +0.06\)) ceramics, manufactured via a conventional mixed oxide route. The X-ray diffraction and Raman spectroscopy revealed the unit cell parameter and cation ordering in LZT non-stoichiometry in their vibrational modes. The densification and phase composition were characterized by the EDX and SEM methods. It was found that a slight Ti vacancy can improve the relative density to the maximum value (96.2%). The XRD results showed that the second phase of TiO₂ in the Li₂ZnTi_3.06O_8.12 composition is formed. The sintered samples were detected in the microwave frequency range by using the resonance technique. The \({\text{~}}{\tau _f}\) values of the ceramics within Ti excess adjusted to near zero. The Li₂ZnTi_2.96O_7.92 ceramic showed the best relative density, single phase and best microwave dielectric \({\varepsilon _r}~={\text{ }}25.98\), Q?×?f?=?61,000 GHz, \({\tau _f}={\text{ }} - 17.4{\text{ ppm/}}^\circ {\text{C}}\) sintered at 1100 °C for 4 h.     

Microwave dielectric properties of Bi(Sc<Subscript>1/3</Subscript>Mo<Subscript>2/3</Subscript>)O<Subscript>4</Subscript> ceramics for LTCC applications

A novel microwave dielectric ceramics Bi(Sc_1/3Mo_2/3)O₄ with low firing temperature were prepared via the solid reaction method. The specimens have been characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy and DC conductivity. The Bi(Sc_1/3Mo_2/3)O₄ ceramics showed B-site ordered Scheelite-type structure with space group C2/c. Raman analysis indicated that prominent bands were attributed to the normal modes of vibration of MoO₄ ^2? tetrahedra. The dielectric loss of Bi(Sc_1/3Mo_2/3)O₄ ceramics can be depended strongly the bulk conductivity by DC measurement. The superior microwave dielectric properties are achieved in the Bi(Sc_1/3Mo_2/3)O₄ ceramic sintered at 875 °C/4 h, with dielectric constant?~?25, Q?×?f ~?51,716 GHz at 6.4522 GHz and temperature coefficient of resonance frequency ~???70.4 ppm/°C. It is a promising microwave dielectric material for low-temperature co-fired ceramics technology.     

Synthesis and microwave dielectric properties of Zn<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>Nb<Subscript>2</Subscript>O<Subscript>6+<Emphasis Type="Italic">x</Emphasis></Subscript>

We have studied the formation of zinc niobate, ZnNb₂O₆, with the columbite structure and the microstructure and microwave dielectric properties of Zn_1+x Nb₂O_6+x ceramics. The results demonstrate that, in the range 0.005 ≤ x ≤ 0.03, the excess zinc reduces the porosity of the material and increases its microwave quality factor Q. For x ≥ 0.03, the Q of the ceramics decreases because of the formation of an additional, zinc-enriched phase. Sintering in an oxygen atmosphere is shown to improve the dielectric properties of stoichiometric ZnNb₂O₆.     

Low-firing Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> microwave dielectric ceramics with BaCu(B<Subscript>2</Subscript>O<Subscript>5</Subscript>) additive

Phase purity, microstructure, sinterability and microwave dielectric properties of BaCu(B₂O₅)-added Li₂ZnTi₃O₈ ceramics and their cofireability with Ag electrode were investigated. A small amount of BaCu (B₂O₅) can effectively reduce the sintering temperature from 1075°C to 925°C, and it does not induce much degradation of the microwave dielectric properties. Microwave dielectric properties of ε _r = 23·1, Q × f = 22,732 GHz and τ _f = − 17·6 ppm/°C were obtained for Li₂ZnTi₃O₈ ceramic with 1·5 wt% BaCu(B₂O₅) sintered at 925°C for 4 h. The Li₂ZnTi₃O₈ +BCB ceramics can be compatible with Ag electrode, which makes it a promising microwave dielectric material for low-temperature co-fired ceramic technology application.     

Effects of LiF addition on the sintering behavior and microwave dielectric properties of Li<Subscript>2</Subscript>Mg<Subscript>3</Subscript>SnO<Subscript>6</Subscript> ceramics

Li₂Mg₃SnO₆ (abbreviation for LMS) ceramics doped with 1–4 wt% lithium fluoride (LiF) were prepared by the conventional solid-state reaction method. The effects of LiF addition on the phase compositions, sintering behaviors and microwave dielectric properties of LMS ceramics were investigated. A small amount of LiF addition could effectively decrease the sintering temperatures due to the liquid phase in the sintering process and induced no apparent degradation of the microwave dielectric properties. The optimized quality factor values for each composition firstly increased and then decreased with the increase of the LiF content. Whereas, the optimized dielectric permittivity increased with increasing of the LiF content. Distinguished microwave dielectric properties with a dielectric constant (ε _r) of 11.13, a quality factor (Q·f) of 104,750 GHz, and a temperature coefficient of resonant frequency (τ _f ) of ?10.83 ppm/°C were obtained for LMS ceramics sintered at 950?°C doped with 3 wt% LiF, which showed that the materials were suitable for the low temperature co-fired ceramics applications (LTCC).     

Microwave dielectric properties and its compatibility with silver electrode of LiNb<Subscript>0.6</Subscript>Ti<Subscript>0.5</Subscript>O<Subscript>3</Subscript> with B<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO additions

The influences of B₂O₃ and CuO (BCu, B₂O₃: CuO = 1:1) additions on the sintering behavior and microwave dielectric properties of LiNb_0.6Ti_0.5O₃ (LNT) ceramics were investigated. LNT ceramics were prepared with conventional solid-state method and sintered at temperatures about 1,100 °C. The sintering temperature of LNT ceramics with BCu addition could be effectively reduced to 900 °C due to the liquid phase effects resulting from the additives. The addition of BCu does not induce much degradation in the microwave dielectric properties. Typically, the excellent microwave dielectric properties of ε_r = 66, Q × f = 6,210 GHz, and τ _f  = 25 ppm/^oC were obtained for the 2 wt% BCu-doped sample sintered at 900 °C. Chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Effects of Gd doping on the sintering and microwave dielectric properties of BiNbO<Subscript>4</Subscript> ceramics

Gd³⁺ was chosen as a substitute for Bi³⁺ in BiNbO₄ ceramics, and the substitution effects on the sintering performance and microwave dielectric properties were studied in this paper. The high temperature triclinic phase was observed only in the Bi_0.98Gd_0.02NbO₄ ceramics when sintered at 920 °C. Both bulk densities and dielectric constant (ε_r) increased with the sintering temperature, while decreased with the Gd content. The quality factor (Q) exhibited a correlation to the Gd content and the microstructures of Bi_1−x Gd _x NbO₄ ceramics. At the sintering temperature of 900 °C, Bi_0.992Gd_0.008NbO₄ ceramics exhibited microwave dielectric properties of ε_r ∼ 43.87, Q × f ∼ 16,852 GHz (at 4.3 GHz), and its temperature coefficient of resonant frequency (τ_f) was found to be near-to-zero.     

Microstructure and microwave dielectric properties of MgNb2O6–ZnTa2O6 composite ceramics prepared by layered stacking method

ZnTa₂O₆/MgNb₂O₆/ZnTa₂O₆ layered ceramics with different volume fractions were designed and prepared to tailor the microwave dielectric properties of ZnTa₂O₆–MgNb₂O₆ composite ceramics. The crystal structure, microstructure and microwave dielectric properties of the composite ceramics were systematically investigated in this work. The formation of solid solutions at interface was confirmed by X-ray diffractometer. Scanning electron microscopy and energy dispersive spectroscopy were used to analysis the ionic diffusion behavior across the interface. The typical core–shell structure based on MgNb₂O₆ solid solution was clearly discerned in the composite ceramics. The ionic diffusion coefficients simulated by semi-infinite diffusion couple could give a reasonable explanation for the formation of the special structure. The tri-layered ZnTa₂O₆/MgNb₂O₆/ZnTa₂O₆ ceramic with the volume fraction of 6:1:6 had the optimum microwave dielectric properties of ε _r  = 31.98, Q × f = 82,778 GHz, and τ _f  = 0 ppm/°C, demonstrating a unique potential for low-loss microwave applications in resonators, filters and antenna substrates.     

Dielectric relaxation and polaronic hopping in the single-layered perovskite La<Subscript>1.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>4</Subscript> ceramics

Single tetragonal La_1.5Sr_0.5CoO₄ ceramics with the space group of I 4/mmm (139) were prepared by a solid-state reaction process, and dielectric characteristics were investigated on a broad frequency and temperature range. There was one obvious dielectric relaxation around room temperature plus a low temperature upturn on the curve of temperature dependence of dielectric properties for La_1.5Sr_0.5CoO₄ ceramics. This dielectric relaxation was a thermal-activated process. It should be attributed to the mixed-valence structure (Co²⁺/Co³⁺) since its activation energy was similar to that of small polaronic hopping process. After annealing the sample in O₂ atmosphere, dielectric constants and ac conductivities of La_1.5Sr_0.5CoO₄ ceramics increased and decreased after annealing the sample in N₂ atmosphere. This abnormal phenomenon should be attributed to the variation of concentration for holes (Co³⁺).     

Influence of CuO and B<Subscript>2</Subscript>O<Subscript>3</Subscript> on sintering and dielectric properties of tungsten bronze type microwave ceramics: a case study in Ba<Subscript>4</Subscript>Nd<Subscript>9.3</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript>

The effect of CuO and B₂O₃ co-doping on the sintering behavior, microstructure and microwave dielectric properties of tungsten bronze type Ba₄Nd_9.3Ti₁₈O₅₄ (BNT) ceramics has been investigated by means of a traditional solid-state mixed oxide route. On the one hand, it was indicated that the mixture of CuO and B₂O₃ is an effective sintering aid for BNT matrix compositions owing to the existence of a low-temperature eutectic reaction. On the other hand, it was found that the addition of CuO and B₂O₃ has an obvious effect on microwave dielectric properties of BNT ceramics, depending on the amount of sintering aids, the sample density and microstructure. The liquid phases from sintering aids can promote densification, but simultaneously induce grain growth which tends to decrease the sintering driving force. BNT ceramics doped with 3 wt% CuO–B₂O₃ mixture can be well sintered at 950°C for 4 h and still exhibit relatively good microwave dielectric properties.     

Frequency and temperature dependence of electrical properties of barium and gadolinium substituted SrBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

Barium strontium gadolinium bismuth niobate (Ba_0.1Sr_0.81Gd_0.06Bi₂Nb₂O₉, BSGBN) ceramics were prepared by using the conventional solid-state reaction method. The dielectric permittivity, modulus and impedance spectroscopy studies on BSGBN were investigated in the frequency range, 45 Hz–5 MHz and in the temperature range from room temperature (RT) to 570 °C. The dielectric anomaly with a broad peak was observed at 470 °C. Simultaneous substitution of Ba²⁺ and Gd³⁺ increases the transition temperature of SrBi₂Nb₂O₉ (SBN) from 392 to 470 °C. XRD studies in BSGBN revealed an orthorhombic structure with lattice parameters a = 5.4959 Å, b/a = 1.000, c = 25.0954 Å. Impedance and modulus plots were used as tools to analyse the sample behaviour as a function of frequency. Cole-Cole plots showed a non-Debye relaxation. Also, dc and ac conductivity measurements were performed on BSGBN. The electric impedance which describes the dielectric relaxation behaviour is fitted to the Kohlrausch exponential function. Near the phase transition temperature, a stretched exponential parameter β indicating the degree of distribution of the relaxation time has a small value.     

Low-temperature sintering and microwave dielectric properties of MgTiO<Subscript>3</Subscript> ceramics

The effects of CuO–Bi₂O₃–V₂O₅ additions on the sintering temperature and the microwave dielectric properties of MgTiO₃ ceramics were investigated systematically. The CuO–Bi₂O₃–V₂O₅ (CuBiV) addition significantly lowered the densification temperature of MgTiO₃ ceramics from 1400 °C to about 900 °C, which is due to the formation of the liquid-phase of BiVO₄ and Cu₃(VO₄)₂ during sintering. The saturated dielectric constant (ε_r) increased, the maximum quality factor (Qf) values decreased and the temperature coefficient of resonant frequency (τ_f) shifted to a negative value with the increasing CuBiV content, which is mainly attributed to the increase of the second phase BiVO₄. MgTiO₃ ceramics with 6 wt.% CuBiV addition sintered at 900 °C for 2 h have the excellent microwave dielectric properties: ε _r= 18.1, Qf = 20300 GHz and τ_f = −57 ppm/ °C.     

Microwave synthesis and sintering characteristics of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

CaCu₃Ti₄O₁₂ (CCTO) was synthesized and sintered by microwave processing at 2·45 GHz, 1·1 kW. The optimum calcination temperature using microwave heating was determined to be 950°C for 20 min to obtain cubic CCTO powders. The microwave processed powders were sintered to 94% density at 1000°C/60 min. The microstructural studies carried out on these ceramics revealed the grain size to be in the range 1–7 μm. The dielectric constants for the microwave sintered (1000°C/60 min) ceramics were found to vary from 11000–7700 in the 100 Hz–00 kHz frequency range. Interestingly the dielectric loss had lower values than those sintered by conventional sintering routes and decreases with increase in frequency.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>6</Subscript>Mg<Subscript>7</Subscript>Ti<Subscript>3</Subscript>O<Subscript>16</Subscript> ceramics with LiF additive for LTCC applications

Li₆Mg₇Ti₃O₁₆ ceramics were prepared by the conventional solid-state method with 1–5 wt% LiF as the sintering aid. Effects of LiF additions on the phase compositions, sintering characteristics, micro-structures and microwave dielectric properties of Li₆Mg₇Ti₃O₁₆ ceramics were investigated. The LiF addition could effectively lower the sintering temperature of Li₆Mg₇Ti₃O₁₆ ceramics from 1550 to 900 °C. For different LiF-doped compositions, the optimum dielectric permittivity (ε _r ) and quality factor (Q·f) values first increased and then decreased with the increase of LiF contents, whereas the temperature coefficient of resonant frequency (τ _f ) fluctuated between ??14.39 and ??8.21 ppm/°C. Typically, Li₆Mg₇Ti₃O₁₆ ceramics with 4 wt% LiF sintered at 900 °C exhibited excellent microwave dielectric properties of ε _r ?=?16.17, Q·f?=?80,921 GHz and τ _f ?=???8.21 ppm/°C, which are promising materials for the low temperature co-fired ceramics applications.