Microwave properties of Ba(Mg1/3Ta2/3)O3, Ba(Mg1/3Nb2/3)O3 and Ba(Co1/3Nb2/3)O3 ceramics revealed by Raman scattering

Five Ba(Co_1/3Nb_2/3)O₃ samples sintered at different temperatures (form 1350 to 1550 °C), one Ba(Mg_1/3Ta_2/3)O₃ and a Ba(Mg_1/3Nb_2/3)O₃ sample were examined by Raman scattering to reveal the correlation of the 1:2 ordered perovskite structure with the microwave properties, such as dielectric constant and Q factors. The Ba(Co_1/3Nb_2/3)O₃ sample sintered at 1400 °C, which possesses the highest microwave Q value and the lowest dielectric constant among five Ba(Co_1/3Nb_2/3)O₃ samples, has the narrowest width and the highest frequency of the stretch mode of oxygen octahedron (i.e. A_1g(O) near 800 cm⁻¹). We found that the dielectric constant is strongly correlated with the Raman shift of A_1g(O) stretch modes, and the width of A_1g(O) stretch mode reflects the quality factor Q × f value in the 1:2 ordered perovskite materials. This concludes that the oxygen octahedron play an important role of the material's microwave performance. Based on the results of Q × f values and the lineshapes of A_1g(O) stretch mode, we found that the propagation of microwave energy in Ba(Mg_1/3Ta_2/3)O₃ and Ba(Mg_1/3Nb_2/3)O₃ shows weak damping behavior, however, Ba(Co_1/3Nb_2/3)O₃ samples sintered at different temperature exhibit heavily damped behavior.     

Effect of non-stoichiometry on the densification,phase purity,microstructure, crystal structure,and dielectric loss of Ba(Co1/3Nb2/3)O3 ceramics

The structural, vibrational, densification, and microwave properties of Ba(Co_1/3Nb_2/3)O₃ ceramics with small compositional variations along several tie lines in the ternary BaOCoONb₂O₅ diagram were studied. The results showed that very small deviation from stoichiometric Ba(Co_1/3Nb_2/3)O₃ composition has profound effect on Q × f, degree of ordering, densification, and phase assemblage. The 0.94 Ba(Co_1/3Nb_2/3)O₃–0.06 Ba₅Nb₄O₁₅ ceramic has the highest Q × f value (71 THz) – a value two times larger than that of stoichiometric Ba(Co_1/3Nb_2/3)O₃ (36 THz). Transformation from the (partial) disordered distribution of Co and Nb cations to 1:2 ordered arrangement in the octahedral sites was found to increase the Q factor of the high density and single phase ceramics. It was also observed that formation of very small amount of Ba₉CoNb₁₄O₄₅ second phase degraded Q × f value severely for the dense and highly ordered Nb-rich and Ba-deficient ceramics.     

Effect of nonstoichiometry on the structure and microwave dielectric properties of Ba(Co1/3Nb2/3)O3 ceramics

The effect of B-site cation deficiency on the structure and microwave dielectric properties of Ba(Co_1/3Nb_2/3)O₃ (BCN) was investigated. Stoichiometric and co-deficient compositions based on Ba(Co_1/3−xNb_2/3)O₃ [x = 0.0, 0.01, 0.02, 0.03 and 0.04] were prepared using the conventional mixed oxide route. Small amounts of V₂O₅ (0.1 wt%) were added to promote densification. The dielectric loss is very sensitive to the composition; it was found that co-deficiency degraded the microwave dielectric properties. The stoichiometric formulation (x = 0) exhibited the best microwave properties. The improvements in the microwave dielectric properties were achieved by increasing the degree of 1:2 cation ordering. The highly ordered, stoichiometric BCN ceramics showed a relative permittivity (ɛ_r) of 32, quality factor (Q × f) of 66,500 GHz and a negative temperature coefficient of resonant frequency (τ_f) of −10 ppm/°C at 4 GHz.     

Effect of CeO2 on the sintering behaviour,cation order and properties of Ba3Co0.7Zn0.3Nb2O9 ceramics

The effect of low-level CeO₂ addition and cooling rate on sintering, microstructures, phase formation, 1:2 ordering and microwave dielectric properties of Ba₃Co_0.7Zn_0.3Nb₉ (BCZN) was investigated. It was found that low levels doping of CeO₂ (up to 0.5 wt.%) could significantly improve densification of the specimens and their properties. Dielectric properties of CeO₂-doped samples were sensitive to 1:2 ordering in the B-site. Slow cooling after sintering improved the unloaded quality factor (Q × f values) significantly. The B-site ordering parameter (S) and lattice constant (c/a) values increased as the cooling rate decreased. Ba₅Nb₄O₁₅ (5/0/4) and Ba₈(Co,Zn)₁Nb₆O₂₄ (8/1/6) secondary phases were found on the surface of all the samples. At 0.4 wt.% CeO₂ the specimens showed maximum Q × f of 84,000 GHz attributed to high density and the degree of cation ordering.     

Microwave dielectric properties of Ca(Li1/4Nb3/4)O3–CaTiO3 ceramic systems

The microwave dielectric properties of Ca(Li_1/4Nb_3/4)O₃–CaTiO₃ ceramics have been investigated with regard to calcination temperature and the amount of CaTiO₃ additive. Ca(Li_1/4Nb_3/4)O₃ ceramics with an orthorhombic crystal structure can be synthesized by the conventional mixed oxide method by calcining at 750 °C and sintering at 1275 °C. The dielectric constant (ɛ_r), quality factor (Q × f₀) and temperature coefficient of resonant frequency (τ_f) for Ca(Li_1/4Nb_3/4)O₃ ceramics are 26, 13,000 GHz and −49 ± 2 ppm/°C, respectively. With increase in the CaTiO₃ content, ɛ_r and τ_f are increased and the quality factor decreased due to the solid-solution formation between Ca(Li_1/4Nb_3/4)O₃ and CaTiO₃. The 0.7Ca(Li_1/4Nb_3/4)O₃–0.3CaTiO₃ ceramic exhibits ɛ_r of 44, quality factor (Q × f₀) of 12,000 GHz and τ_f of −9 ± 1 ppm/°C.     

Structure and dielectric properties of perovskite ceramics in the system Ba(Ni1/3Nb2/3)O3–Ba(Zn1/3Nb2/3)O3

Ceramics in the system Ba(Ni_1/3Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ (BNN–BZN) were prepared by the mixed oxide route. Powders were mixed and milled, calcined at 1100–1200 °C then pressed and sintered at temperatures in the range 1400–1500 °C for 4 h. Selected samples were annealed or slowly cooled after sintering. Most products were in excess of 96% theoretical density. X-ray diffraction confirmed that all specimens were ordered to some degree and could be indexed to hexagonal geometry. Microstructural analysis confirmed the presence of phases related to Ba₅Nb₄O₁₅ and Ba₈Zn₁Nb₆O₂₄ at the surfaces of the samples. The end members BNN and BZN exhibited good dielectric properties with quality factor (Qf) values in excess of 25,000 and 50,000 GHz, respectively, after rapid cooling at 240 °C h⁻¹. In contrast, mid-range compositions had poor Qf values, less than 10,000 GHz. However, after sintering at 1450 °C for 4 h and annealing at 1300 °C for 72 h, specimens of 0.35(Ba(Ni_1/3Nb_2/3)O₃)–0.65(Ba(Zn_1/3Nb_2/3)O₃) exhibit good dielectric properties: τ_f of +0.6 ppm °C⁻¹, relative permittivity of 35 and quality factor in excess of 25,000 GHz. The improvement in properties after annealing is primarily due to an increase in homogeneity.     

Effect of small amount of cobalt substitution on structure and microwave dielectric properties of barium magnesium niobate ceramics

We investigated effects of substituting cobalt for magnesium on microstructures and microwave dielectric properties of BaMg_1/3Nb_2/3O₃ ceramics. Nucleation and growth of 1:2 ordered domains dominate microstructural variations for Ba(Mg_1?xCo_x)_1/3Nb_2/3O₃ ceramics. Microstructures such as grains sizes and domain sizes significantly dominate variations of Q × f value. Less ordered domains are nucleated when substituting small amount of cobalt (x < 0.1). Accordingly, domains and grains significantly grow with increased cobalt substitution. The 1:2 ordering degree is subsequently increased, and Q × f achieves a maximum value at x = 0.05. Nevertheless, while cobalt substitution exceeds x = 0.1, more ordered nuclei occur and consequently affect the domain growth and the grain growth. The Q × f value remarkably decreases at x = 0.1, and varies due to different ordering degrees and compositions. The Q × f value of specimens at x = 0.05 becomes as high as 43,000, and is similar to that of specimens at x = 0.5.     

Large Q factor variation within dense,highly ordered Ba(Zn1/3Ta2/3)O3 system

The large amount of Q factor variation within dense, highly ordered region of Ba(Zn_1/3Ta_2/3)O₃ (BZT) system were studied by means of crystal structure analysis, micro-structural analysis and electrical measurements using samples around stoichiometric BZT. Presence of small amount of secondary phase (e.g., less than 1%) affects Q factor decrements even in the dense (density = 7.15–7.78 g/cm³), highly ordered (estimated ordering ratio around 70–80%) samples. This suggests that the structural order and the presence of the secondary phase are playing an important role on Q factor in BZT system. Therefore, suppressions of small amount of secondary phase (e.g., less than 1%) by strict composition control can provide further Q factor improvements. Single phase ordered perovskite obtained in the vicinity of stoichiometric BZT showed an improvement in Q factor (Q × f = 133,000 GHz) by extended sintering up to 400 h at 1400 °C.     

Order–disorder behaviour in 0.9Ba([Zn0.60Co0.40]1/3Nb2/3)O3–0.1Ba(Ga0.5Ta0.5)O3 microwave dielectric resonators

0.9Ba([Zn_0.60Co_0.40]_1/3Nb_2/3)O₃–0.1Ba(Ga_0.5Ta_0.5)O₃ (BCZN–BGT) ceramic resonators (quality factor, Q=32,000 at the rate of 3.05 GHz, relative permittivity, ε_r=35 and temperature coefficient of the resonant, τ_f=0) have been fabricated which are suitable in terms of cost and performance for base stations supporting third generation architecture. The new compounds are perovskite structured (a=4.09 Å) but exhibit no superlattice reflections at any heat treatment temperature according to X-ray diffraction (XRD). However, annealing and quenching of samples followed by transmission electron microscopy and Raman spectroscopy revealed an order–disorder phase transition at ∼1200 °C. Annealing below this temperature (1100 °C) gave rise to discrete ±1/3{h k l}_p and diffuse 1/2{h k l}_p superlattice reflections in the same 〈1 1 0〉_p zone axis electron diffraction patterns and the presence of F_2g and A_1g modes in Raman spectra. It is proposed that ±1/3{h k l}_p reflections result from 1:2 long-range ordered domains of BCZN whereas the diffuse 1/2{h k l}_p reflections arise from short range fcc ordered BGT rich regions at the 1:2 domain boundaries. A short-range ordered fcc superlattice was observed in samples quenched from above the order–disorder phase transition (>1200 °C) which was accompanied by the presence of only the A_1g mode in Raman spectra.     

Effect of nonstoichiometry on the microstructure and microwave dielectric properties of Ba(Mg1/2W1/2)O3 ceramics

Effects of nonstoichiometry on crystal structure and the microstructure of double perovskite Ba(Mg_1/2W_1/2)O₃ ceramics have been investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and Raman spectrometry in this paper. The microwave dielectric properties of the ceramics were studied with a network analyzer at the frequency of about 8–11 GHz. The results show that small deviation from stoichiometric composition has little influence on the crystal structure such as B-site 1:1 ordering degree. Evaporation of BaO was confirmed during the sintering of BMW ceramics, which in turn produce more BaWO₄ phase. Ba-deficiency or W-excess in BMW could improve the sinterability and Q×f value, while Ba-excess or W-deficiency could suppress the formation of BaWO₄ at the expense of increase in sintering temperature and decrease in Q×f value. Mg nonstoichiometry has little effect on the variation of BaWO₄ content and Q×f value. Maximum Q×f value of about 140,000 GHz could be obtained for the Ba-deficient or W-excessive samples after sintering at 1500 °C/2 h or 1550 °C/2 h, respectively. All Mg-nonstoichiometric compositions exhibit high Q×f value of about 120,000 GHz after sintering at 1550 °C/2 h. All well-densified samples have dielectric permittivity of about 19–20 and τ_f value varied within the range of ?21～?28 ppm/°C.     

Extended X-ray absorption fine structure,X-ray diffraction and Raman analysis of nickel-doped Ba(Mg1/3Ta2/3)O3

Raman, X-ray diffraction and extended X-ray absorption fine structure (EXAFS) measurements of xBa(Ni_1/3Ta_2/3)O₃ + (1 − x)Ba(Mg_1/3Ta_2/3)O₃ samples with x = 0–0.03 were performed to reveal the nickel doping effect on the microwave properties. EXAFS result clearly shows that the nickel is located on the Mg lattice site. We also found that, as the nickel concentration increases, microwave dielectric constant decreases with the TaO and NiO bond distances. X-ray diffraction shows that the 1:2 ordered structure is degraded with the increasing of nickel concentration. The stretching phonon of the TaO₆ octahedra, that is A_1g(O) phonon near 800 cm⁻¹, are strongly correlated to the microwave properties of xBa(Ni_1/3Mg_2/3)O₃ + (1 − x)Ba(Mg_1/3Ta_2/3)O₃ samples. The large Raman shift and the large width of the A_1g(O) imply rigid but distorted oxygen octahedral structure, therefore, the effect of nickel doping lowers the dielectric constant and the Q × f value of Ba(Mg_1/3Ta_2/3)O₃ ceramic.     

Effect of B2O3 and CuO additives on the sintering temperature and microwave dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics

The B₂O₃ added Ba(Zn_1/3Nb_2/3)O₃ (BBZN) ceramic was sintered at 900 °C. BaB₄O₇, BaB₂O₄, and BaNb₂O₆ second phases were found in the BBZN ceramic. Since BaB₄O₇ and BaB₂O₄ second phases have an eutectic temperature around 900 °C, they might exist as the liquid phase during sintering at 900 °C and assist the densification of the BZN ceramics. Microwave dielectric properties of dielectric constant (ɛ_r) = 32, Q × f = 3500 GHz, and temperature coefficient of resonance frequency (τ_f) = 20 ppm/°C were obtained for the BZN with 5.0 mol% B₂O₃ sintered at 900 °C for 2 h. The BBZN ceramics were not sintered below 900 °C and the microwave dielectric properties of the BBZN ceramics sintered at 900 °C were very low. However, when CuO was added, BBZN ceramic was well sintered even at 875 °C. The liquid phase related to the BaCu(B₂O₅) second phase could be responsible for the decrease of sintering temperature. Good microwave dielectric properties of ɛ_r = 36, Q × f = 19,000 GHz and τ_f = 21 ppm/°C can be obtained for CuO doped BBZN ceramics sintered at 875 °C for 2 h.     

Temperature and frequency dependence of dielectric loss of Ba(Mg1/3Ta2/3)O3 microwave ceramics

Ba(Mg_1/3Ta_2/3)O₃ ceramic possessing extremely high Q × f value of more than 300 THz at microwave frequency was developed in our previous study. It is of great interest to understand the mechanism of microwave absorption in such a practical material. In the present study we report on the temperature dependence of the dielectric loss in the Ba(Mg_1/3Ta_2/3)O₃. The mechanism of the microwave absorption is discussed using two phonons difference process. The samples were prepared by conventional solid state reaction and sintered at 1893 K in oxygen atmosphere. Dielectric properties in the microwave range were measured by Hakki & Colemann and resonant cavity methods in the temperature range of 20–300 K. Whispering gallery mode technique was used for the measurement of the dielectric properties at the millimeter wave frequency. Dielectric loss of the Ba(Mg_1/3Ta_2/3)O₃ at the microwave frequency increases with temperature between 200 and 300 K in general agreement with the theory of intrinsic dielectric loss derived from the two phonon difference process. However below 200 K, the dielectric loss has shown a distinctive behavior with a loss peak at 40 K. It was inferred that the loss peak of the Ba(Mg_1/3Ta_2/3)O₃ was caused by the local orientation polarization having dispersion at the microwave frequency.     

Structural,chemical and dielectric properties of ceramic injection moulded Ba(Zn1/3Ta2/3)O3 microwave dielectric ceramics

We report the development of a ceramic injection moulding (CIM) process to produce complex-shaped structures using high-performance microwave ceramic materials. In particular, we describe the synthesis methods and the structural, chemical and dielectric properties of Ba(Zn_1/3Ta_2/3)O₃ (BZT) doped with Ni and Zr ceramics produced using ceramic injection moulding. Sintering the ceramic injection moulded Ba(Zn_1/3Ta_2/3)O₃ to a relative density of ∼94% was possible at a temperature of 1680 °C and a time of 48 h. The best samples to date exhibit a dielectric constant, ɛ_r, of ∼30, a Q value, of ∼31,250 (i.e. tan δ < 3.2 × 10⁻⁵) at 2 GHz, and a temperature coefficient of resonance frequency, τ_f, of 0.1 ppm/°C.     

Ordering structure of barium magnesium niobate ceramic with A-site substitution

The ordering behaviour of Ba(Mg_1/3Nb_2/3)O₃ ceramics (BMN) substituted by La³⁺, Na⁺, K⁺ was investigated using X-ray powder diffraction and transmission electron microscopy. The 1:2 ordered structure of BMN can be transformed to 1:1 ordered structure by substituting a small amount of La cation ion into the A-site. Moreover, the degree of ordering was increased with La content in the compound, and reached almost unity at [La] = 50 mol%. When the La ion in (Ba_1−xLa_x)(Mg_(1+x)/3Nb_(2−x)/3)O₃ (BLMN) was substituted by Na or K ions, the 1:1 ordered structure of BLMN was transformed into the 1:2 ordered structure. The degree of 1:2 ordering was influenced by the sintering temperature and the size difference between the A and B site ions.     

The effect of sintering temperature and time on microwave properties of Sm(Zn1/2Ti1/2)O3 ceramics for resonators

The microwave dielectric properties of Sm(Zn_1/2Ti_1/2)O₃ ceramics have been investigated. Sm(Zn_1/2Ti_1/2)O₃ ceramics were prepared by conventional solid-state route with various sintering temperatures and times. The prepared Sm(Zn_1/2Ti_1/2)O₃ exhibited a mixture of Zn and Ti showing 1:1 order in the B-site. Higher sintered density of 7.01 g/cm³ can be produced at 1310 °C for 2 h. The dielectric constant values (ɛ_r) of 22–31 and the Q × f values of 4700–37,000 (at 8 GHz) can be obtained when the sintering temperatures are in the range of 1250–1370 °C for 2 h. The temperature coefficient of resonant frequency τ_f was a function of sintering temperature. The ɛ_r value of 31, Q  ×  f value of 37,000 (at 8 GHz) and τ_f value of −19 ppm/°C were obtained for Sm(Zn_1/2Ti_1/2)O₃ ceramics sintered at 1310 °C for 2 h. For applications of high selective microwave ceramic resonator, filter and antenna, Sm(Zn_1/2Ti_1/2)O₃ is proposed as a suitable material candidate.     

Microwave dielectric properties and crystal structure of the tungstenbronze-type like (Ba1 − αSrα)6(Nd1 − βYβ)8Ti18O54 solid solutions

A study of the dielectric properties, especially the Q × f value, of the tungstenbronze-type like (Ba_1 − αSr_α)_6 − 3xNd_8 + 2xTi₁₈O₅₄ solid solutions in x = 0 system was carried out. These compositions near x = 0 have very low Q × f values. To improve the Q × f value of these materials, we tried two substitutional systems, which are (Ba_1 − αSr_α)₆Nd₈Ti₁₈O₅₄ and Ba₄Sr₂(Nd_1 − βY_β)₈Ti₁₈O₅₄. In the former composition, the Q × f value was increased from 206 to 5880 GHz in the range of 0 ≤ α ≤ 0.5. And we found that Sr ions substituted for Ba ions in A1 sites have good effect on increasing the Q × f value, but Sr ions substituted for Ba ions in A2 sites have poor effect on increasing it. The latter composition also has a small effect on increasing the Q × f value.     

Microwave dielectric properties and low-temperature sintering of Ba3Ti4Nb4O21 ceramics with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ɛ_r), high quality factor (Q × f) and small temperature coefficient of resonant frequency (τ_f) are required for the application of chip passive components in the wireless communication technologies. In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₄Nb₄O₂₁ ceramics were investigated as a function of B₂O₃–CuO content. Ba₃Ti₄Nb₄O₂₁ ceramics with B₂O₃ or CuO addition could be sintered above 1100 °C. However, the additions of both B₂O₃ and CuO successfully reduced the sintering temperature of Ba₃Ti₄Nb₄O₂₁ ceramics from 1350 to 900 °C without detriment to the microwave dielectric properties. From the X-ray diffraction (XRD) studies, the sintering behaviors and the microwave dielectric properties of low-fired Ba₃Ti₄Nb₄O₂₁ ceramics were examined and discussed in the formation of the secondary phases. The Ba₃Ti₄Nb₄O₂₁ sample with 1 wt% B₂O₃ and 3 wt% CuO addition, sintered at 900 °C for 2 h, had the good dielectric properties: ɛ_r = 65, Q × f = 16,000 GHz and τ_f = 101 ppm/°C.     

Structure and microwave dielectric properties of La(2−x)/3Nax(Mg1/2W1/2)O3

The structure evolution, sintering behavior and microwave dielectric properties of La_(2−x)/3Na_x(Mg_1/2W_1/2)O₃ (x = 0–0.5) were investigated in this paper. The X-ray diffraction (XRD) results show that all samples exhibit single phase, and the structure changed from orthorhombic when 0 ≤ x < 0.3 to monoclinic phase when 0.3 ≤ x ≤ 0.5. The size and ordering degree of A/B-site domains decrease with the increase in x value. The sintering temperature of the Na-doped samples increased compared to the pure La_2/3(Mg_1/2W_1/2)O₃ (LMW) due to the estimated decrease in the concentration of A-site vacancies. The addition of Na⁺ ion does not affect the dielectric permittivity greatly. The Q × f value decreases with the increase in x value, although the estimated concentration of A-site vacancies decreases with increasing x, which may be ascribed to the decrease of A/B-site ordering and domain size with the increase in x. The temperature coefficient of resonant frequency changed from negative values into positive values with the increase in x value.     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with ZnO–B2O3 glass additions for LTCC applications

The effects of ZnB₂O₄ glass additions on the sintering temperature and microwave dielectric properties of Ba₃Ti₅Nb₆O₂₈ have been investigated using dilatometer, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and a network analyzer. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250 °C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ɛ_r of 37.0, τ_f of −12 ppm/°C. It was found that the addition of ZnB₂O₄ glass to Ba₃Ti₅Nb₆O₂₈ lowered the sintering temperature from 1250 to 925 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases. Also the addition of ZnB₂O₄ glass enhanced the microwave dielectric properties: Q × f of 19,100 GHz, ɛ_r of 36.6, τ_f of 5 ppm/°C. From XPS and XRD studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.