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.     

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.     

Broadband dielectric spectroscopy of PbMg1/3Nb2/3O3–PbSc1/2Nb1/2O3 ceramics

Broadband dielectric spectroscopy results of various ordered and disordered (1 ? x)Pb(Mg_1/3Nb_2/3)O₃–(x)Pb(Sc_1/2Nb_1/2)O₃ (PMN–PSN) ceramics are investigated in the temperature range from 80 K to 300 K and frequency range from 20 Hz to 2 THz. Dielectric dispersion is very broad and in the ferroelectrics case (x = 1, 0.95) consists of two parts: low-frequency part caused by ferroelectric domains and higher frequency part caused by soft mode. The relaxational soft mode exhibits pronounced softening close to phase transition temperature, as it is typical for order–disorder phase transitions. By substituting Sc³⁺ by Mg²⁺ in PMN–PSN ceramics relaxation slows down, and for relaxors (x = 0.2) the most probable relaxation frequency decreases on cooling according to Vogel–Fulcher law.     

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.     

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.     

Signature of lattice defects in far infrared reflectivity of Ba(Mg1/3Ta2/3)O3

Far infrared reflectivity spectra of Ba(Mg_1/3,Ta_2/3)O₃ prepared at several sintering temperatures were measured, and the eigenfrequencies and damping constants of the TO modes were determined. The reflectivity spectra were fitted with the four-parameter semi-quantum model. The variation in the E_u(O_II) at 222 cm⁻¹ and A_2u(O_II) at 238 cm⁻¹ modes in well ordered ceramics was attributed to the variation in the concentration of the B site defects. It was also found that the change in the oxygen partial pressure of the sintering atmosphere causes a change in the seventh (316 cm⁻¹) and eighth (352 cm⁻¹) modes. We attribute these changes to the oxygen site defect although we cannot evaluate the concentration of this defect at this moment. From the behavior of the damping constants it is suggested that the Ba(Mg_1/3Ta_2/3)O₃ (BMT) attains equilibrium defect density at the heat treatment temperature of more than 1630 °C (120 h).     

Tailoring the microwave dielectric properties of Ba(Mg1/3Ta2/3)O3 ceramics

Ba(Mg_1/3Ta_2/3)O₃ (BMT) is a very important microwave dielectric resonator material with a high dielectric constant of about 25, high quality factor and small temperature variation of resonant frequency. The preparation temperature of BMT ceramics is relatively high, about 1650 °C. The microwave quality factor of BMT depends on the ordering of Mg–Ta–Ta ions on the perovskite B-site. In the present paper we report how one can tailor the properties of BMT ceramics by glass addition, slight non-stoichiometry and by dopant addition. (a) It is found that addition of small amount of glasses such as B₂O₃, ZnO–B₂O₃, ZnO–2B₂O₃, ZnO–B₂O₃–SiO₂ reduces the sintering temperature, increases density, order parameter and quality factor. (b) Slight Mg or Ba deficiency improves densification, order parameter and quality factor whereas excess Mg or Ba deteriorated the properties (c) Small amounts of dopants such as Sb₂O₅, MnCO₃, ZrO₂, WO₃, SnO₂ and ZnO improve the microwave dielectric properties. It is found that the quality factor is maximum when the ionic radii of the dopant ions are close to the weighted average ionic radii of B site ions (i.e. Mg_1/3Ta_2/3), which is 0.653 Å.     

Ultra-high Q Ba(Mg1/3Ta0.675)O3 microwave dielectric ceramics realized by slowly cooling step process and the simulation design for hairpin dielectric filters

With the development of 5G technology, it would inevitably lead to the problem of energy consumption owing to the massive construction of 5G base stations and the increase in the number of antenna channels. Dielectric filters as the core component in the base station, the energy consumption was closely related to its insertion loss, which could be achieved by reducing the dielectric loss (tanδ = 1/Q) of microwave dielectric ceramics. In this work, in order to further enhance the Q × f value, the slowly cooling step process was innovatively introduced to the Ba(Mg_1/3Ta_0.675)O₃ ceramic. The optimal microwave dielectric properties were obtained in Ba(Mg_1/3Ta_0.675)O₃ ceramic with the step temperature of 1500 °C: ε_r = 24.767, Q × f = 298,051 GHz, τ_f = ?0.66 ppm/°C. Based on ultra-high Q Ba(Mg_1/3Ta_0.675)O₃ ceramic, the hairpin dielectric filter with high integration and low insertion loss was designed and simulated. Compared with traditional RT/duroid5870 dielectric substrate, the circuit area was reduced by more than 6 times and the passband insertion loss (|S₂₁| < 1 dB) was decreased by more than 50%. The current work could provide a solution for the low-power applications of microwave dielectric devices in 5G base stations.     

Effect of grain size and secondary phase on microwave dielectric properties of Ba(Mg1/3Ta2/3)O3 and Ba([Mg,Zn]1/3Ta2/3)O3 systems

Here we report the influence of the grain size of the Ba(Mg_1/3,Ta_2/3)O₃ (BMT) and secondary phase formed in Ba([Mg_0.8Zn_0.2]_1/3,Ta_2/3)O₃ (BMZT) ceramics on the microwave dielectric properties. BMT and BMZT ceramics were prepared by conventional mixed-oxide reaction method using high purity reagents. Samples with different grain size and secondary phase content were obtained by controlling the sintering time of the BMT and BMZT. The secondary phase comprised of BaTa₂O₆, which includes small amount of Zn, was formed due to the vaporization of ZnO from BMZT by the high temperature sintering. The Qf value of BMT increased up to 400 THz with increasing the grain size of ceramics, whereas the Qf value of BMZT decreased with increase of the BaTa₂O₆ content. This second phase also caused an increase in the temperature coefficient of the resonant frequency of BMZT.     

The effect of cation ordering and domain boundaries on low loss Ba(BI1/3BII2/3)O3 perovskite dielectrics revealed by high-angle annular dark-field scanning transmission electron microscopy (HAADF STEM)

High quality ceramics of Ba((Co_0.7Zn_0.3)_1/3Nb_2/3)O₃ (BCZN), Ba(Mg_1/3Nb_2/3)O₃ (BMN) and Ba(Mg_1/3Ta_2/3)O₃ (BMT) were prepared by the mixed oxide route using sintering temperatures up to 1620 °C. Products with a high degree of cation ordering exhibited dielectric Q × f values from 83,000 GHz (BCZN) to 360,000 GHz (BMT). High Resolution TEM and aberration-corrected scanning transmission electron microscopy (STEM) revealed ordering domains and type I, II and III boundary structures. High-Angle Angular Dark Field (HAADF) STEM images provided direct evidence of 1:2 ordering and stacking sequences, and the presence of disordered regions within domain boundaries. The exceptionally high Q × f values for BMT are associated with a high degree of B-site ordering and the removal of domain boundaries in large, single domain grains. The catastrophic degradation of Q × f values in BMN after prolonged sintering is associated with formation of a lossy ferroelectric secondary phase (Ba₃Nb₂O₈), and changes to composition and stoichiometry of BMN grains.     

Effects of Li doping on dielectric properties of Ag(Ta0.5Nb0.5)O3 thick films

Low loss ferroelectric materials have been extensively investigated for the high frequency device applications. Especially, weak frequency dispersion materials with high dielectric permittivity and low loss tangent have enormous potential for electronic components including filters, and embedded capacitors. Ag(Ta_0.5Nb_0.5)O₃ thick films have been prepared by low temperature sintering aid Li₂CO₃ (0, 1, 3 and 5 wt%). Ag(Ta_0.5Nb_0.5)O₃ thick films were characterized by X-ray diffraction analysis and scanning electron microscopy. The dielectric and ferroelectric properties were also investigated. We observed very weak frequency dispersion of dielectric permittivity at the microwave frequency range.     

Microwave dielectric properties of (Zn1/3B2/3)0.5(Ti0.8M0.2)0.5O2 (B = Nb5+, Ta5+, M = Sn4+, Ge4+) ceramics

Dielectric properties of (Zn_1/3Nb_(2?x)/3Ta_x/3)_0.5(Ti_0.8Sn_0.1Ge_0.1)_0.5O₂ (x = 0, 1, 2) and/or (Zn_1/3Nb_1/3Ta_l/3)_0.5(Ti_0.8Sn_0.2(l?y)Ge_0.2y)_0.5O₂ (y = 0, 0.5, 1) were investigated at the microwave frequencies. For the compositions with single phase of rutile structure, the dielectric constant (K) of specimens was not only dependent on the dielectric polarizabilities, but also on the bond length ratio of apical bond (d_apical) to equatorial bond (d_equatorial) of oxygen octahedron in the unit cell. Temperature coefficients of the resonant frequencies (TCF) of the specimens with B = Nb⁵⁺ and/or M = Sn⁴⁺ was larger than those with B = Ta⁵⁺ and/or M = Ge⁴⁺. These results could be attributed to the changes of the degree of oxygen octahedral distortion. Quality factors (Qf) of the specimens with B = Ta⁵⁺ and/or M = Sn⁴⁺ were larger than those with B = Nb⁵⁺ and/or M = Ge⁴⁺.     

Influence of sintering temperature on dielectric properties and crystal structure of corundum-structured Mg4Ta2O9 ceramics at microwave frequencies

Microwave dielectric properties of corundum-structured Mg₄Ta₂O₉ ceramics were investigated as a function of sintering temperatures by an aqueous sol–gel process. Crystal structure and microstructure were examined by X-ray diffraction (XRD) technique and field emission scanning electron microscopy (FE-SEM). Sintering characteristics and microwave dielectric properties of Mg₄Ta₂O₉ ceramics were studied as a function of sintering temperature from 1250 °C to 1450 °C. With increasing sintering temperature, the density, ε_r and Qf values increased, saturating at 1300 °C with excellent microwave properties of ε_r=11.9, Qf=195,000 GHz and τ_f=?47 ppm/°C. Evaluation of dielectric properties of Mg₄Ta₂O₉ ceramics were also analyzed by means of first principle calculation method and ionic polarizability theory.     

Microwave dielectric characteristics of Li2(Mg0.94M0.06)Ti3O8 (M=Zn,Co, and Mn) ceramics

Li₂(Mg_0.94M_0.06)Ti₃O₈ (M=Zn, Co, and Mn) ceramics were synthesized by the conventional solid-state reaction route. The effect of M (Zn, Co, and Mn) substitution on the structure, microstructure and microwave dielectric properties of Li₂(Mg_0.94M_0.06)Ti₃O₈ has been investigated. The XRD patterns of sintered samples revealed the single-phase formation with spinel structure. With the increase in ionic radius of M, the Qf value decrease is attributed to the decrease of packing fraction and grain size. The Li₂(Mg_0.94Zn_0.06)Ti₃O₈ ceramic sintered at 1075 °C for 4 h showed the best microwave dielectric properties with a dielectric constant of 27.1, a Qf value of 44 800 GHz, and a temperature coefficient of resonant frequency of (+)1.9 ppm/°C.     

Correlation of the phonon characteristics and microwave dielectric properties of the Ba(Mg1/3Ta2/3)O3 materials

The Ba(Mg_1/3Ta_2/3)O₃, BMT, materials possess the highest quality factor (Q × f) in microwave frequency regime among the microwave dielectric materials and can potentially be used for high frequency communication application. To understand the mechanism that determines microwave dielectric properties of the BMT materials, spectroscopic techniques including Raman and Fourier transform infrared (FTIR) analyses are used for investigating the phonon characteristics of the materials. The Raman-shift (Δω_0j) of the Raman peaks and the resonance frequency (ω_0j) of the FTIR peaks vary insignificantly among the samples, which correlate very well with the phenomenon that the K-values for these materials are similar with one another. In contrast, the full-width-at-half-maximum (FWHM) of the Raman peaks and the damping coefficient (γ_j) of the FTIR peaks vary markedly among the samples. The high-Q materials possess sharpest vibrational modes, viz., smallest FWHM value for Raman peaks and smallest γ_j value for FTIR peaks and vice versa. The intimate relationship between the phonon characteristics and the fine structure of the materials is confirmed.     

Effects of (Mg1/3Ta2/3)-substitution for Ti-site on the microwave dielectric properties of Li2MgTiO4 ceramics

Novel high quality factor microwave dielectric ceramics Li₂MgTi_1?x(Mg_1/3Ta_2/3)_xO₄ (0 ≤ x ≤ 0.5) were successfully prepared via a conventional solid-state ceramic route. The effects of isovalent substitutions (Mg_1/3Ta_2/3)⁴⁺ at the Ti-site on the sintering behaviors, microstructures, and microwave dielectric properties of Li₂MgTiO₄ ceramics were investigated in this paper. The sintered samples exhibited the single phase with cubic rock-salt structure belonging to Fm-3m space group in the whole composition range. Rietveld refinement which could be performed by the Fullprof program was taken to explain the effects of (Mg_1/3Ta_2/3)⁴⁺ ion substitution on the crystal structures of Li₂MgTiO₄ ceramics. With the (Mg_1/3Ta_2/3)⁴⁺ content increasing from 0 to 0.5, the quality factor Q·f firstly increased and decreased thereafter, while the dielectric constant ε_r almost linearly decreased. In addition, the τ_f values shifted to positive value with the amount of (Mg_1/3Ta_2/3)⁴⁺ increasing. The best composition appeared to be Li₂MgTi_0.6(Mg_1/3Ta_2/3)_0.4O₄, which showed excellent microwave dielectric properties of ε_r = 15.73, Q·f = 184,000 GHz and τ_f = ? 12.54 ppm/°C. This made the Li₂MgTi_0.6(Mg_1/3Ta_2/3)_0.4O₄ ceramic a very promising candidate for use as a low-loss microwave material.     

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.     

Microwave dielectric losses caused by lattice defects

Dielectric loss tangent at microwave frequency is mainly determined by the anharmonic terms in the crystal's potential energy. In addition, there is a kind of lattice defect that increases the dielectric loss tangent seriously. This paper presents the experimental results for two materials; the system Ba(Zn,Ta)O₃–BaZrO₃ and (Zr,Sn)TiO₄. The dielectric loss tangents of the system Ba(Zn,Ta)O₃–BaZrO₃ increases seriously when the B-site ions distribute disorderedly in the crystal. The doping of oxygen vacancies and acceptor ions in (Zr,Sn)TiO₄ increase tan δ by the way they increase the gradient and intercept of linear frequency dependency of tan δ. These experimental results are reasonably explained by Schlömann's theory. He predicted that the dielectric loss tangent increases when the ions are distributed disorderedly in a way that they break the periodic arrangement of charges in the crystal, and that the increase of tan δ is negligible if the disordered charge distribution maintains the charge neutrality within a short range of the lattice constant in the crystal.     

Dependence of dielectric properties on structural characteristics of (Zn1/3A2/3)0.5 (Ti1−xBx)0.5O2 (A = Nb5+, Ta5+, B = Ge4+, Sn4+) ceramics at microwave frequencies

The effects of structural characteristics on the dielectric properties of (Zn_1/3A_2/3)_0.5(Ti_1?xB_x)_0.5O₂ (A = Nb⁵⁺, Ta⁵⁺, B = Ge⁴⁺, Sn⁴⁺) (0.1 ≤ x ≤ 0.3) ceramics were investigated at microwave frequency. The sintered specimens showed solid solutions with a tetragonal rutile structure within the solid solution range of compositions. With an increase of BO₂, the temperature coefficient of resonant frequency (TCF) and dielectric constant (K) decreased with a decrease of oxygen octahedral distortion and dielectric polarizabilites, respectively. However, the quality factor (Qf) of the sintered specimens was increased with BO₂ due to the reduction of Ti⁴⁺ ions. The Qf value of the specimens with A = Ta was higher than that of the specimens with A = Nb.     

Abnormal variation of microwave dielectric properties in A/B site co-substituted (Ca1−0.3xLa0.2x)[(Mg1/3Ta2/3)1−xTix]O3 complex perovskite ceramics

A/B site co-substituted (Ca_1?0.3xLa_0.2x)[(Mg_1/3Ta_2/3)_1?xTi_x]O₃ ceramics (0.1 ≤ x ≤ 0.5) were prepared by solid state reaction and the structures, microstructures and dielectric properties were investigated. B site 1:2 cation ordering and oxygen octahedra tilting lead to monoclinic symmetry with space group P2₁/c for x = 0.1. For x above 0.1, the ordering was destroyed and the crystal structure became orthorhombic with space group Pbnm. The B site 1:2 cation ordering tended to be destroyed to form 1:1 ordering by the A site La³⁺ substitution. The dielectric constant increased linearly with increasing content of Ti⁴⁺ as the increasing second Jahn–Teller distortion enhanced the B site cation rattling. The temperature coefficient of resonant frequency and Qf values showed abnormal variations, which were refined to be caused by the increasing A site cation vacancy and diffused distribution of small size ordering domains respectively. Good combination of microwave dielectric properties was obtained at x = 0.5, where ?_r = 48, Qf = 21,000 GHz and τ_f = 2.2 ppm/°C.