Crystal Structure and Microwave dielectric Properties of Ba(Zn1/3Ta2/3)O3–(Sr,Ba)(Ga1/2Ta1/2)O3 Ceramics

The microwave dielectric properties and crystal structure of Ba(Zn_1/3Ta_2/3)O₃– (Sr,Ba)(Ga_1/2Ta_1/2)O₃ ceramics were investigated in the present study. The Q value of Ba(Zn_1/3Ta_2/3)O₃ was improved by adding 5 mol% Sr(Ga_1/2Ta_1/2)O₃. The maximum Q value of Q × f = 162000 GHz was obtained at 0.95Ba(Zn_1/3Ta_2/3)O₃. 0.05Sr(Ga_1/2Ta_1/2)O₃. For this composition, a lattice super structure caused by hexagonal ordering was observed. A further improvement in the Q value was attained when some Sr was replaced with Ba, and 0.95Ba(Zn_1/3Ta_2/3)O₃· 0.05(Sr_0.25Ba_0.75)(Ga_1/2Ta_1/2)O₃ exhibited a maximum Q value such that Q × f = 210000 GHz. Despite the increased Q value with the replacement of Sr by Ba, the c/a value, which indicates the degree of lattice distortion, remained constant near 3/2. The Q value thus improved without lattice distortion in the system Ba(Zn_1/3Ta_2/3)O₃-(Sr,Ba)(Ga_1/2Ta_1/2)O₃, whereas the improvement of Q value increased with lattice distortion in the solid solution system with Ba(Zn_1/3Ta_2/3)O₃ as an end member.     

Far Infrared Reflection Spectra of Ba(Zn,Ta)O3-BaZrO3 Dielectric Resonator Material

The dielectric ceramic materiala Ba(Zn_1/3Ta_2/3)O₃–BaZrO₃ has extremely low dielectric loss at microwave frequencies. To investigate the lattice vibrations of Ba(Zn,Ta)O₃ and Ba(Zr, Zn, Ta)O₃ solid solutions, far infrared reflection spectra were measured from 50 to 4000 cm⁻¹ using a Fourier transform infrared spectrometer. These data were analyzed according to the classical dispersion theory. The spectra of Ba(Zn,Ta)O₃ are well fitted by using the 14 resonant modes, and the spectra of Ba(Zr, Zn, Ta)O₃ solid solution are fitted by assuming the normal distribution on resonant frequencies. The damping constant of these materials is discussed, and the values of tan δ calculated from the dispersion parameters agree with the measured values.     

Ba8ZnTa6O24: A New High Q Dielectric Perovskite

The hexagonal perovskite, Ba₈ZnTa₆O₂₄, was prepared in single-phase form and was found to be a stable secondary phase, formed as a result of the loss of ZnO from Ba(Zn_1/3Ta_2/3)O₃ microwave dielectrics. The experimental and calculated X-ray patterns of Ba₈ZnTa₆O₂₄ indicate it is isostructural with Ba₈Ta₆NiO₂₄ with an 8H (cchc)₂ close-packed BaO₃ stacking sequence and the lattice parameters, a =10.0825(14), c =19.0587(38)Å. High-density ceramics of Ba₈ZnTa₆O₂₄ could be prepared at temperatures considerably lower (1400°C) than those used to sinter pure Ba(Zn_1/3Ta_2/3)O₃, and exhibit very good microwave dielectric properties with ɛ=30.5, Q _f=62 300, and τ_f=+36 ppm/°C at 8.9 GHz.     

Ba(Zn1/3Ta2/3)O3 Ceramics with Low Dielectric Loss at Microwave Frequencies

The dielectric properties at microwave frequencies of Ba(Zn_1/3Ta_2/3)O₃ ceramics prepared by sintering were investigated. These ceramics had lower density but higher loss quality than ceramics hot-pressed at 1400°C. Loss quality was greatly improved by prolonged sintering. The Q of the ceramics measured by the dielectric resonator method was 14 000 at 12 GHz. The ceramics were investigated by X-ray diffraction analysis. It was found that Q improvement corresponds with increased Zn and Ta ordered structures in the ceramics.     

Formation and Structural Characterization of 1:1 Ordered Perovskites in the Ba(Zn1/3Ta2/3)O3–BaZrO3 System

The phase stabilities in the(1−x)Ba(Zn_1/3Ta_2/3)O₃ (BZT)-xBaZrO₃(BZ)system have been investigated using samples prepared by the mixed oxide method. The substitution of Zr⁴⁺destabilizes the 1:2 cation ordering in BZT and pro-motes the formation of a cubic, 1:1 ordered structure with a doubled perovskite repeat. The homogeneity range of the 1:1 phase extends from x = 0.04 to approximately x = 0.25; substitutions beyond this range stabilize a disordered perovskite. The limits of stability of the 1:1 ordering coin-cide with compositions previously found to exhibit anoma-lies in their dielectric loss. The range of homogeneity is consistent with a "random layer" model for the 1:1 ordered "Ba{β';_1/2β^1/2}O₃" structure. In this model the B× positions are assumed to be occupied exclusively by Ta⁵⁺, and the b× sites by a random distribution of Zn₂₊, Zr₄₊, and the remaining Ta 5+ cations. The validity of the model, where the ordered solid solutions can be represented by Ba{[Zn_{2− y /3}Ta_{(1−2 y )/3}Zr y ]_1/2[Ta]_1/2}O₃(y =2x)was con-firmed by Rietveld refinements conducted using data col-lected with a synchrotron X-ray source.     

Atomic Resolution Transmission Electron Microscopy of the Microstructure of Ordered Ba(Cd1/3Ta2/3)O3 Perovskite Ceramics

Microstructures of ordered Ba(Cd_1/3Ta_2/3)O₃ perovskite dielectric ceramics with and without a boron additive have been observed by atomic resolution transmission electron microscopy (TEM). The selected area electron diffraction and lattice image show a well-ordered structure with hexagonal symmetry (lattice constants of a ∼5.8 Å and c ∼7.1 Å) in the ordered Ba(Cd_1/3Ta_2/3)O₃ with a boron additive, which is similar to those in ordered Ba(Zn_1/3Ta_2/3)O₃ and Ba(Mg_1/3Ta_2/3)O₃ ceramics. Ordered domains with a twin crystallographic relationship and high-density domain interfaces induced by ordering were observed in the ordered Ba(Cd_1/3Ta_2/3)O₃ without a boron additive sintered at a relatively high temperature. Atomic resolution TEM further revealed the conservative twin boundaries along (001) and (110) planes and non-conservative antiphase boundaries with a projected displacement vector of the type [001] in the ordered Ba(Cd_1/3Ta_2/3)O₃ without a boron additive. Finally, the energetics of different domain interfaces are discussed with the interfacial structures in ordered Ba(Cd_1/3Ta_2/3)O₃ ceramics revealed by an electron microscope.     

Microwave Loss Quality of BaZn13Ta2/3O3 Ceramics

Loss of ZnO explains the improved microwave loss quality (Q) for Ba(Zn_1/3Ta_2/3)O₃ ceramics which have been sintered at high temperatures or longer times. Ordering of Zn and Ta is complete in 60 h at 1400°C, but crystallographic distortion and Q continue to increase up to 120 h. As ZnO volatilizes from the sample, Ba replaces Zn on the B sites and permits additional crystallographic distortion; meanwhile, barium tantalate phases also appear. Crystallographic compositional data are presented to confirm this interpretation.     

Dielectric Properties of Ceramics in Ba (Co1/3 Nb2/3)O3–Ba(Zn1/3Nb2/3)O3 Solid Solution

The dielectric properties of the Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ system were determined. Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ has a complex perovskite structure, a high dielectric constant, a low dielectric loss, and a low temperature coefficient of the resonant frequency. A solid-solution ceramic with 0.7Ba (Co_1/3 Nb_2/3)O₃·0.3 Ba(Zn_1/3Nb_2/3)O₃ has a dielectric constant of K=33.5, Q=11000 at 6.5 GHz, and a temperature coefficient of the resonant frequency of τ_f=0 ppm/°C. The temperature coefficient of resonant frequency can be varied by changing the composition. The Q values of the ceramics can be increased by annealing in a nitrogen atmosphere. These ceramics can be used for resonant elements and stabilized oscillators.     

Perovskite Formation and Dielectric Characteristics of Pb(Zn1/3Ta2/3)O3 with PbTiO3 Substitution

Perovskite developments in the Pb(Zn_1/3Ta_2/3)O₃–PbTiO₃ system were explored. Formation yields and lattice parameters of the perovskite were determined from X-ray diffractometry results. Weak-field low-frequency dielectric properties of the system ceramics were investigated, followed by microstructure examination. Perovskite started to develop in Pb(Zn_1/3Ta_2/3)O₃ after the introduction of 30 mol% PbTiO₃, whereas complete stabilization was accomplished at 60% substitution. Dielectric relaxation behavior was not substantial across the entire composition range, whereas phase transition modes changed from diffuse to sharp with increased PbTiO₃ fraction.     

Adhesive-Bonded Ca(Mg1/3Nb2/3)O3/Ba(Zn1/3Nb2/3)O3 Layered Dielectric Resonators with Tunable Temperature Coefficient of Resonant Frequency

Ca(Mg_1/3Nb_2/3)O₃ and Ba(Zn_1/3Nb_2/3)O₃ ceramic cylinders with the same diameter were bonded by adhesive with low dielectric loss to yield the layered dielectric resonators, and the microwave dielectric characteristics were evaluated with TE_01δ mode. With increasing the Ba(Zn_1/3Nb_2/3)O₃ thickness fraction, the resonant frequency ( f ₀) decreased, while the effective dielectric constant (ɛ _{r ,eff}) and temperature coefficient of resonant frequency (τ _f ) increased. Good microwave dielectric characteristics were attained for the samples with the Ba(Zn_1/3Nb_2/3)O₃ thickness fraction of 0.5: ɛ _{r ,eff}=34.33, Q × f =57 930 GHz and τ _f =2.6 ppm/°C. Finite-element method was used to predict the microwave dielectric characteristics of the layered resonators and good agreements were attained between the experimental results and predicted ones. Also, both experiment and finite-element analysis indicated that the effects of the adhesive on f ₀, ɛ _{r ,eff}, and τ _f were slight, while that on Q × f value was significant.     

Effect of BaWO4 on the Microwave Dielectric Properties of Ba(Mg1/3Ta2/3)O3 Ceramics

Physical and microwave dielectric properties of complex perovskite Ba(Mg_1/3Ta_2/3)O₃ ceramics have been investigated as a function of the amount of BaWO₄ in the temperature range from 20° to 80°C at 10.5 GHz. Up to 0.05 mol BaWO₄ addition, the lattice constant ratio ( c/a ), ordering parameter, apparent density, and unloaded Q all increase, due to the increase in the substitution of Ta⁵⁺ ions of Ba(Mg_1/3Ta_2/3)O₃ by W⁶⁺ ions from the melted BaWO₄ at above 1430°C. With further addition of BaWO_4, the unloaded Q decreases, due to an increase of the BaWO₄ phase. The temperature coefficient of resonant frequency (TCF) can be controlled by the volume mixture rule of Ba(Mg_1/3Ta_2/3)O₃ and BaWO₄. When 0.09 mol BaWO₄ is added, TCF becomes 0 ppm/°C.     

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.     

Pb(Zn1/3Ta2/3)O3–PbTiO3 Derived from Mechanical Activation

Nanocrystalline Pb(Zn_1/3Ta_2/3)O₃ (PZTa) of perovskite structure, which cannot be synthesized by either the conventional solid-state reaction of mixed oxides or wet chemistry routes, has been successfully synthesized via a mechanical activation route. The effects of PbTiO₃ (PT) doping in PZTa on the phase formation, thermal stability of the nanocrystalline perovskite phase, and dielectric properties of the resulting PZTa–PT are studied. PZTa doped with a low PT content exhibited a diffuse phase transition, while those with high PT contents demonstrated an expected sharp phase transition at the Curie temperature.     

Effects of Stacking Scheme on Microwave Dielectric Characteristics of Ca(Mg1/3Nb2/3)O3–Ba(Zn1/3Nb2/3)O3 Layered Dielectric Resonators

Ca(Mg_1/3Nb_2/3)O₃ (CMN) and Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramic disks were stacked with three stacking schemes, designated as CMN/BZN, CMN/BZN/CMN, and BZN/CMN/BZN, to yield layered dielectric resonators, and the microwave dielectric characteristics were evaluated with the TE_01δ mode. Both experiments and finite element analysis showed that the microwave dielectric characteristics of the layered resonator were determined not only by the volume fraction of BZN but also by the stacking scheme. For each stacking scheme, a good combination of microwave dielectric characteristics with an effective dielectric constant of 34.33–34.52, a Q × f value of 58 800–62 080 GHz, and a near-zero temperature coefficient of resonant frequency could be achieved by adjusting the volume fraction of BZN. The effects of the stacking scheme on the microwave dielectric characteristics of the temperature-stable layered resonator were discussed by combining finite element analysis and dielectric composite models.     

Sol–Gel Processing and Microwave Characteristics of Ba(Mg⅓Ta⅔)O3 Dielectrics

The sol–gel method has been developed for the preparation of pure Ba(Mg_1/3Ta_2/3)O₃ ceramics. This involves the reaction of the heterometallic alkoxide Ta₂Mg(OEt)₁₂ with hydrated barium hydroxide Ba(OH)₂·8H₂O. Complete crystallization of the sol–gel-derived powder is achieved at 600°C, leading to a cubic perovskite type phase. After sintering at 1400°C (2–5 h), a trigonal cell arises from Mg–Ta ordering (the degree of order is greater than 0.9), and about 98.5% of the theoretical density is obtained. Preliminary microwave dielectric measurements show that the dielectric constant and the unloaded Q _u of the ceramics are 24.2 and 6750, respectively, at 7.7 GHz.     

Influence of Non-Stoichiometry on the Structure and Properties of Ba(Zn1/3Nb2/3)O3 Microwave Dielectrics: I. Substitution of Ba3W2O9

A narrow region of Zn-vacancy-containing cubic perovskites was formed in the (1− x )Ba₃(ZnNb₂)O₉−( x )Ba₃W₂O₉ system up to 2 mol% substitution ( x =0.02). The introduction of cation vacancies enhanced the stability of the 1:2 B-site ordered form of the structure, Ba(Zn_{1− x} □ _x )_1/3(Nb_{1− x} W _x )_2/3O₃, which underwent an order–disorder transition at 1410°C, ∼35° higher than pure Ba(Zn_1/3Nb_2/3)O₃. The Zn vacancies also accelerated the kinetics of the ordering reaction, and samples with x =0.006 comprised large ordered domains with a high lattice distortion ( c/a =1.226) after a 12 h anneal at 1300°C. The tungstate-containing solid solutions can be sintered to a high density at 1390°C, and the resultant ordered ceramics exhibit some of the highest microwave dielectric Q factors ( Q × f =1 18 000 at 8 GHz) reported for a niobate-based perovskite.     

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.     

Effect of La/K A-site Substitutions on the Ordering of Ba(Zn1/3Ta2/3)O3

The 1/3 <111>-type ordering of Ba(Zn_1/3Ta_2/3)O₃ (BZT) can be transformed to 1/2 <111>–type ordering by substituting the La³⁺ cation into the A site. The 1/3 <111> ordering in BZT is shown to be reduced, discontinued, and then replaced by 1/2 <111> ordering, using X–ray diffraction, electron microscopy, and Raman spectroscopy. On the other hand, potassium–substituted BZT only displays a reduction in the degree of ordering.     

Microstructure and Microwave Dielectric Properties of Ba(Zn1/3Ta2/3)O3 Ceramics with ZrO2 Addition

The effect of ZrO₂ on crystallographic order, microstructure, and microwave dielectric properties of Ba(Zn_1/3Ta_2/3)O₃ (BZT) ceramics was investigated. A small amount of ZrO₂ disturbed the 1:2 cation ordering. The average grain size of the BZT significantly increased with the addition of ZrO₂, which was attributed to liquid-phase formation. The relative density increased with the addition of a small amount of ZrO₂, but it decreased when the ZrO₂ content was increased. Variation of the dielectric constant with ZrO₂ addition ranged between 27 and 30, and the temperature coefficient of resonant frequency increased abruptly as the ZrO₂ amount exceeded 2.0 mol%. The Q value of the BZT significantly improved with the addition of ZrO₂, which could be explained by the increased relative density and grain size. The maximum Q × f value achieved in this investigation was ∼164 000 GHz for the BZT with 2.0 mol% ZrO₂ sintered at 1550°C for 10 h.     

Cation Ordering Transformations in the Ba(Zn1/3Nb2/3)O3-La(Zn2/3Nb1/3)O3 System

Single-phase perovskites were formed in the (1−_x)Ba(Zn_1/3Nb_2/3)O₃-( _x )La(Zn_2/3Nb_1/3)O₃ system for compositions with 0.0≤ x ≤0.6. Although the stability of the trigonal "1:2" ordered structure of the Ba(Zn_1/3Nb_2/3)O₃ end member is very limited (0.0≤ x ≤0.05), low levels of lanthanum induce a transformation to a cubic, "1:1" ordered structure that has a broad range of homogeneity (0.05≤ x ≤0.6). Samples with x > 0.6 were comprised of La₃NbO₇, ZnO, and a perovskite with x = 0.6. The cubic 1:1 phases were fully ordered and no evidence was found for a compositionally segregated microstructure. These observations could not be reconciled in terms of a "space-charge" model; rather, they supported a charge-balanced, "random-site" structure for the 1:1 cation-ordered Ba(β_1/2'β_1/2")O₃ phases.