Dielectric and Structural Characteristics in Barium Lanthanum Magnesium Niobate

The dielectric properties and their related microstructural characteristics in solid solutions of (1 — x )Ba(Mg_1/3Nb_2/3)O₃ (BMN)— x La(Mg_2/3Nb_1/3)O₃ (LMN) (BLMN) were investigated by measuring the relative permittivity (ɛ_r), Q value, and temperature coefficient of resonator frequency (τ_f), and by observing the microstructure using transmission electron microscopy. The trend of variation of the temperature coefficient of the dielectric permittivity (τ_ɛ) was the same for our solid solutions as that reported by Reaney et al . When the tolerance factor ( t ) was >1.01 in BLMN with composition x = 0 to 1.0, where the tilting of oxygen octahedra was not involved, the components of the microstructure included a disordered and transition phase as well 1:1 and 1:2 ordered phases. In the region where 1.01 < t < 0.96 with x = 0.2 to 0.7, the 1:1 order, the disorder, and the phase due to the antiphase tilting of oxygen octahedra were present. Finally, in the region where t < 0.96 with x = 0.7 to 1.0, the microstructure of BLMN was the same as that of the pure LMN, including the 1:1 order and the antiphase, inphase tilting of oxygen octahedra, and the antiparallel shift of A-site cations.     

Structural and Dielectric Characteristics in a Ca(Mg1/3Nb2/3)O3–CaZrO3 System

This study investigates the effect of CaZrO₃ (CZ) substitution on the evolution of an ordered structure in a Ca(Mg_1/3Nb_2/3)O₃ (CMN) system using Raman spectroscopy, X-ray diffractometry, and transmission electron microscopy. It indicates that a (1− x ) CMN−( x )CZ solid solution has the 1:2 and 1:1 ordered structure distorted by the antiphase, the inphase tilting of oxygen octahedra, and the antiparallel shift of A-site cation. A distinct correlation is noted between the transition of the ordered structure and microwave dielectric properties. The differences in ɛ_r and τ_f are attributed exclusively to the differences in the type of cation arrangement. The structure with the 1:2 ordering exhibits a lower relative permittivity and a more negative τ_f than the structure with the 1:1 ordering. The increased fraction of compressed Nb–O bond in the 1:2 ordered structure associated with a large NbO₆ octahedral distortion is correlated with a decrease in relative permittivity and change of τ_f toward more negative values. Simultaneously, the substitution of the Zr⁴⁺ ion causes a linear increase in polarizability, and it also results in an increase in the relative permittivity.     

Microstructure and Dielectric Properties of Barium Strontium Magnesium Niobate

Dielectric properties and their related microstructural characteristics in solid solutions of (1 – x )Ba(Mg_1/3Nb_2/3)O₃– x Sr(Mg_1/3Nb_2/3)O₃ (BMN–SMN, or BSMN) were investigated by measuring the relative permittivity (ɛ_r), Q values, and temperature coefficient of resonator frequency (τ_f), and by observing microstructure using transmission electron microscopy. When the tolerance factor ( t ) was >0.99 in BSMN with composition 0 < x < 0.5, where the tilting of oxygen octahedra was not involved, the microstructure included only 1:2 ordered phase. In the region where 0.99 > t > 0.97 with 0.7 < x < 1.0, the phase due to the antiphase tilting of oxygen octahedral, the disordered phase, and the 1:2 ordered phase were also present. In a few of the grains, core–shell-type structures, whose main components were dislocations and stacking faults, were found in the solid solution of BSMN.     

Structure–Property Relations in xBaTiO3–(1−x)La(Mg1/2Ti1/2)O3 Solid Solutions

The microwave dielectric properties and microstructures of compounds in the solid solution series x BaTiO₃–(1− x )La(Mg_1/2Ti_1/2)O₃ (BTLMT) have been investigated. The structural phase transitions that occur as a function of x have been studied and are related to changes in the dielectric properties. For compounds where x ≤ 0.1, X-ray diffraction (XRD) showed evidence of 1:1 ordering between Mg and Ti cations. For x ≤ 0.3, XRD and electron diffraction revealed that compounds were tilted in both antiphase and in-phase. However, for 0.3 < x < 0.7, only antiphase tilting was present. The temperature coefficient of resonant frequency (τ_f) vs the relative permittivity (ɛ_r) was linear until x = 0.5 at which point in the solid solution the transition to a nontilted structure resulted in nonlinear behavior. τ_f values close to zero (−2 ppm/°C) were achieved at x = 0.5 (ɛ_r∼ 60), which had a quality factor ( Q · f _o) of 9600 GHz.     

Contribution of Structure to Temperature Dependence of Resonant Frequency in the (1 −x)La(Zn1/2Ti1/2)O3·xATiO3 (A = Ca, Sr) System

The crystal structure and microwave dielectric properties of the (1 − x ) La(Zn_1/2Ti_1/2)O₃· x SrTiO₃ and (1 − x )La(Zn_1/2Ti_1/2)O₃· x CaTiO₃ system were investigated. X-ray powder diffraction showed that cation ordering disappeared at x > 0.3 for both systems. However, infrared spectra demonstrated that short-range cation ordering could exist at x = 0.4. Permittivity and the temperature coefficient of the resonant frequency (τ_f) of both systems exhibited nonmonotonic variations with composition. Both systems exhibited a τ_f of zero at the same composition of x = 0.5 although the τ_f of SrTiO₃ was about two times larger than that of CaTiO₃. The behavior of the permittivity and τ_f were described by the tilting of oxygen octahedra and cation ordering. The relation between τ_f and cation ordering of La(Zn_1/2Ti_1/2)O₃ was discussed in conjunction with the experimental results on metal halides. It is suggested that cation ordering induced a negative τ_f and suppressed the increase of permittivity for compositions between x = 0 to x = 0.5 for (1 − x )La(Zn_1/2Ti_1/2)O₃· x SrTiO₃ and (1 − x )La(Zn_1/2Ti_1/2)O₃· x CaTiO₃ systems.     

A- and B Site Cosubstituted Ba6−3xSm8+2xTi18O54Microwave Dielectric Ceramics

Tin (Sn) substitution into the B-site and Nd/Sn cosubstitution into the A- and B-sites were investigated in a Ba _{6−3 x} Sm_{8+2 x} Ti₁₈O₅₄solid solution ( x = 2/3). A small amount of tin substitution for titanium improved the temperature coefficient of resonant frequency (τ_f) but led to a decrease of the relative dielectric constant (ɛ) and the quality factor ( Qf ). The Ba_{6−3 x} Sm_{8+2 x} (Ti_{1− z} Sn_z)₁₈O₅₄-based tungsten-bronze phase became unstable for compositions with a tin content of ≥10 mol%, where BaSm₂O₄and Sm₂(Sn,Ti)₂O₇appeared, and finally, these phases became the major phases. On the other hand, Nd/Sn cosubstitution led to a good combination of high ɛ, high Qf , and near-zero τ_f. Excellent microwave dielectric properties were achieved in Ba_{6−3 x} (Sm_{1− y} Nd _y )_{8+2 x} (Ti_{1− z} Sn _z )₁₈O₅₄ceramics with y = 0.8 and z = 0.05 sintered at 1360°C for 3 h: ɛ= 82, Qf = 10 000 GHz, and calculated τ_f=+17 ppm/°C. The tolerance factor and electronegativity difference exhibited important effects on the microwave dielectric properties, especially the Qf value. A large tolerance factor and high electronegativity difference generally led to a higher Qf value.     

Microstructure and Microwave Dielectric Properties of (1−x)Ca(Mg1/3Ta2/3)O3/xCaTiO3 Ceramics

Dense (1− x )Ca(Mg_1/3Ta_2/3)O₃/ x CaTiO₃ ceramics (0.1≤ x ≤0.9) were prepared by a solid-state reaction process. The crystal structures and microstructures were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Single-phase solid solutions were obtained in the entire composition range. Long-range 1:2 ordering of B-site cations and oxygen octahedra tilting lead to the monoclinic symmetry with space group P 2₁/ c for x =0.1. For x above 0.1, the long-range ordering was destroyed and the crystal structure became the orthorhombic with space group Pbnm . The microwave dielectric properties showed a strong dependence on the composition and microstructure. The dielectric constant and temperature coefficient of resonant frequency increased nonlinearly as the CaTiO₃ content increased while the Qf values decreased approximately linearly. Good combination of microwave dielectric properties was obtained at x =0.45, where ɛ_r=45.1, Qf =34 800 GHz, and τ_f=17.4 ppm/°C.     

Microstructure Characterization of the (1−x)La2/3TiO3·xLaAlO3 System

Microstructural characterizations on the (1− x )La_2/3TiO₃· x LaAlO₃ (LTLA) system were conducted using transmission electron microscopy. The presence of La₂Ti₂O₇ and La₄Ti₉O₂₄ phases in pure La_2/3TiO₃ is confirmed by the electron diffraction pattern. When x = 0.1, the ordering due to the A-site vacancies could be confirmed by the presence of antiphase boundaries (APBs) and return ½(100) superlattice reflection. As x increases, the ordering decreases and finally disappears when x = 0.6. The tilting of oxygen octahedra could be demonstrated by the presence of the ferroelastic domains in the matrix and return ½(111) and return ½(110) superlattice reflections in selected area electron diffraction patterns. In pure LaAlO₃, only the antiphase tilting of oxygen octahedra is present due to the presence of return ½(111) superlattice reflection. In the LTLA system of x = 0.1, both the antiphase and in-phase tiltings of the oxygen octahedra are involved; however, in the range of x from 0.3 to 0.9, the antiphase tilting of oxygen octahedra has appeared. The growth of the ferroelastic domains is influenced by the APBs in the matrix.     

Structure and Microwave Dielectric Characteristics of Ca1+xNd1−xAl1−xTixO4 Ceramics

CaNdAlO₄ microwave dielectric ceramics were modified by Ca/Ti co-substitution, and their dielectric characteristics were evaluated along with their structure and microstructures. Ca_{1+ x} Nd_{1− x} Al_{1− x} Ti _x O₄ ( x =0, 0.025, 0.05, 0.10, 0.15, 0.20) ceramics with the relative density of over 95% theoretical density were obtained by sintering at 1400°–1450°C in air for 3 h, where the K₂NiF₄-type solid solution single phase was determined from the compositions of x <0.20, while a small amount of CaTiO₃ secondary phase was detected for x =0.20. With Ca/Ti co-substitution in CaNdAlO₄ ceramics, the dielectric constant (ɛ_r) increased with increasing x , and the temperature coefficient of resonant frequency (τ_f) was adjusted from negative to positive, while the Q × f ₀ value increased significantly at first and reached an extreme value at x =0.025 and the maximum at x =0.15. The best combination of microwave dielectric characteristics were achieved at x =0.15 (ɛ_r=19.5, Q × f ₀=93 400 GHz, τ_f=−2 ppm/°C). The improvement of the Q × f ₀ value primarily originated from the reduced interlayer polarization with Ca/Ti co-substitution, while the decreased tolerance factor, the subsequent increased interlayer stress, and the appearance of CaTiO₃ secondary phase brought negative effects upon the Q × f ₀ value.     

Improved Microwave Dielectric Properties of Ba6Ti1−xSnxNb4O18 Ceramics

Single-phase polycrystalline microwave dielectric ceramics Ba₆Ti_{1− x} Sn _x Nb₄O₁₈, with x changing from 0 to 1, were synthesized by the solid-state reaction method. All the solid solutions fitted well with A₆B₅O₁₈ cation-deficient hexagonal perovskite structure. The substitution of Sn for Ti effectively enhanced the quality factor and controlled τ_f. With increasing Sn content, the dielectric constant decreased from ∼47 to ∼32, and the Q × f value increased significantly from 11 530 to 28 496 GHz, with τ_f varying from 64 to 0 ppm/°C. A zero τ_f was realized when Sn was fully replaced by Ti with the composition Ba₆SnNb₄O₁₈.     

The Effect of Dopants on the Dielectric Properties of Ba(B'1/2Ta1/2)O3 (B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb, and In) Microwave Ceramics

Low-loss dielectric ceramics based on Ba(B'_1/2Ta_1/2)O₃ (B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb, and In) complex perovskites have been prepared by the solid-state ceramic route. The dielectric properties (ɛ_r, Q _u, and τ_f) of the ceramics have been measured in the frequency range 4–6 GHz by the resonance method. The resonators have a relatively high dielectric constant and high quality factor. Most of the compounds have a low coefficient of temperature variation of the resonant frequencies. The microwave dielectric properties have been improved by the addition of dopants and by solid solution formation. The solid solution Ba[(Y_{1− x} Pr _x )_1/2Ta_1/2]O₃ has x =0.15, with ɛ_r=33.2, Q _u× f =51,500 GHz, and τ_f≈0. The microwave dielectric properties of Ba(B'_1/2Ta_1/2)O₃ ceramics are found to depend on the tolerance factor ( t ), ionic radius, and ionization energy.     

Dielectric Properties of (1−x)CaTiO3–xCa(Zn1/3Nb2/3)O3 Ceramic System at Microwave Frequency

The microwave dielectric properties of the (1− x )CaTiO₃– x Ca(Zn_1/3Nb_2/3)O₃ ceramic system have been investigated. The ceramic samples sintered at 1300°–1450°C for 4 h in air exhibit orthorhombic pervoskite and form a complete solid solution for different x value. When the x value increased from 0.2 to 0.8, the permittivity ɛ_r decreased from 115 to 42, the unloaded quality factor Q × f increased from 5030 to 13 030 GHz, and the temperature coefficient τ_f decreased from 336 to −28 ppm/°C. When x =0.7, the best combination of dielectric properties, a near zero temperature coefficient of resonant frequency of τ_f∼−6 ppm/°C, Q × f ∼10 860 GHz and ɛ_r∼51 is obtained.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Thermodynamic Regularities in Perovskite and K2NiF4 Compounds

It has been found that the enthalpy of formation of perovskite compounds, Δ_fH° (ABO₃, B = transition metais), from binary oxides can be well characterized in terms the tolerance factor, t≡(r_A+ r_o)√2 (r_B+ r_o), where r_A and r_B are the radii of A-site ions with 12-coordination and B-site ions with 6-coordination, respectively, and Δ_fH°=−168 + 270(1 − t) kJ·mol⁻¹ for A^IB^VO₃, Δ_fH°=−125 + 1000(1 − t) kJ·mol⁻¹ for A^IIB^IVO₃, and Δ_fH°=− 90 + 720(1 − t) kJ·mol⁻¹ for A^IIIB^IIIO₃. Although the thermodynamic data of K₂NiF₄ compounds are not extensive, a similar regularity can be found when use is made of the radii of A-site ions with 9-coordination for the K₂NiF₄ compounds. These correlations will be quite useful in predicting.     

Bismuth/Samarium Cosubstituted Ba6−3xNd8+2xTi18O54 Microwave Dielectric Ceramics

Modification of the microwave dielectric properties in Ba_{6−3 x} Nd_{8+2 x} Ti₁₈O₅₄ ( x = 0.5) solid solutions by Bi/Sm cosubstitution for Nd was investigated. A large increase in the dielectric constant and near-zero temperature coefficient combined with high Qf values were obtained in modified Ba_{6−3 x} Nd_{8+2 x} Ti₁₈O₅₄ solid solutions where an enlarged solid solution limit of Bi in Ba_{6−3 x} Nd_{8+2 x} Ti₁₈O₅₄ was observed. Excellent microwave dielectric characteristics (ɛ= 105, Qf = 4110 GHz, and very low τ_f) were achieved in the composition Ba_{6−3 x} (Nd_0.7Bi_0.18Sm_0.12)_{8+2 x} Ti₁₈O₅₄.     

Microstructures and Microwave Dielectric Characteristics of CaRAlO4 (R = Nd, Sm, Y) Ceramics with Tetragonal K2NiF4 Structure

CaRAlO₄ (R = Nd, Sm, Y) ceramics with a K₂NiF₄ structure were prepared by a solid-state reaction approach, and their microwave dielectric characteristics were evaluated, along with their microstructures. Dense CaNdAlO₄, CaSmAlO₄, and CaYAlO₄ ceramics were obtained by sintering at 1425°–1500°C in air for 3 h, and good microwave dielectric characteristics were achieved: (1) ɛ= 18.2, Qf = 17 980 GHz, τ_f=−52 ppm/°C for CaNdAlO₄; (2) ɛ= 18.2, Qf = 51 060 GHz, τ_f=−3 ppm/°C for CaSmAlO₄; and (3) ɛ= 18.9, Qf = 39 960 GHz, τ_f= 6 ppm/°C for CaYAlO₄.     

Effect of Cation Substitution and Non-Stoichiometry on the Microwave Dielectric Properties of Sr(B'0.5Ta0.5)O3 [B'=Lanthanides] Perovskites

The Sr(B'_0.5Ta_0.5)O₃ ceramics where B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, and Yb have been prepared by the conventional solid-state ceramic route and their microwave dielectric properties have been investigated. The structure and microstructure of the ceramics have been characterized by X-ray diffraction and scanning electron microscope techniques. The relative permittiviy (ɛ_r) varies linearly with B'-site ionic radii, except for La, and the temperature coefficient of resonant frequency (τ_f) varies linearly with the tolerance factor. The Sr(B'_0.5Ta_0.5)O₃ ceramics have ɛ_r in the range 25.9–32, Q _u× f =4500–54 300 GHz, and τ_f=−79 to −42 ppm/°C. A slight deviation from stoichiometry affects the dielectric properties of these double perovskites. Partial substitution of Ba for Sr could tune the dielectric properties. Addition of rutile (TiO₂) lowered the sintering temperature and improved the dielectric properties of Sr(B'_0.5Ta_0.5)O₃ ceramics.     

Synthesis and Microwave Dielectric Properties of Re3Ga5O12 (Re: Nd, Sm, Eu, Dy, Yb, and Y) Ceramics

Re₃Ga₅O₁₂ (Re: Nd, Sm, Eu, Dy, Yb, and Y) garnet ceramics were synthesized and their microwave dielectric properties were investigated for advanced substrate materials in microwave integrated circuits. The Re₃Ga₅O₁₂ ceramics sintered at 1350°–1500°C had a high-quality factor ( Q × f ) ranging from 40 000 to 192 173 GHz and a low-dielectric constant (ɛ_r) of between 11.5 and 12.5. They also exhibited a relatively stable temperature coefficient of resonant frequency (τ_f) in the range of −33.7 to −12.4 ppm/°C. In particular, the Sm₃Ga₅O₁₂ ceramics sintered at 1450°C exhibited good microwave dielectric properties of ɛ_r=12.4, Q × f =192 173 GHz, and τ_f=−19.2 ppm/°C.     

A Novel Temperature-Compensated Microwave Dielectric (1−x)(Mg0.95Ni0.05)TiO3−xCa0.6La0.8/3TiO3 Ceramics System

The microstructure and microwave dielectric properties of a (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics system have been investigated. The system was prepared using a conventional solid-state ceramic route. In order to produce a temperature-stable material, Ca_0.6La_0.8/3TiO₃ was added for a near-zero temperature coefficient (τ_f). With partial replacement of Mg²⁺ by Ni²⁺, the dielectric properties of the (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature and the composition. An excellent Q × f value of 118,000 GHz can be obtained for the system with x =0.9 at 1325°C. For practical application, a dielectric constant (ɛ_r) of 24.61, a Q × f value of 102,000 GHz, and a temperature coefficient of resonant frequency (τ_f) of −3.6 ppm/°C for 0.85(Mg_0.95Ni_0.05)TiO₃−0.15Ca_0.6La_0.8/3TiO₃ at 1325°C are proposed. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

The Li2O–Nb2O5–TiO2 Composite Microwave Dielectric Ceramics with Adjustable Permittivities

A group of new y M-phase/(1− y ) Li_{2+ x} Ti_{1−4 x} Nb_{3 x} O₃ composite ceramics with adjustable permittivities for low-temperature co-fired ceramic applications was initially investigated in the study. The 0.5 M-phase/0.5 Li_{2+ x} Ti_{1−4 x} Nb_{3 x} O₃ ( x =0.01, 0.02, 0.04, 0.06, 0.081) composite ceramics were first investigated to find the appropriate "Li₂TiO₃ss" composition ( x value). The best dielectric properties of ɛ_r=40.1, Q × f values up to 9318 GHz, τ_f=25 ppm/°C, were obtained for the ceramics composites at x =0.02. Based on the good dielectric properties, the suitable "Li₂TiO₃ss" composition with x =0.02 was mixed with the Li_1.0Nb_0.6Ti_0.5O₃ powder as the ratio of y "M-phase"/(1− y ) "Li₂TiO₃ss" ( y =0.2, 0.4, 0.5, 0.6, 0.8). By adjusting the y values, the group of composite ceramics could exhibit largely are adjustable permittivities varying from ∼20 to ∼60, while Q × f and τ_f values relatively good. Nevertheless, in this study, because there are interactions between the M-phase and Li₂TiO₃ss during sintering process, their microwave dielectric properties could not be predicted precisely by the empirical model.