Synergistic modification of properties in Ba[(Zn0.8Mg0.2)1/3Nb2/3]O3 ceramics through ordered domain engineering

The ordered domain engineering was investigated for Ba[(Zn_0.8Mg_0.2)_1/3Nb_2/3]O₃ microwave dielectric ceramics to synergistically modify the physical properties especially the temperature coefficient of resonant frequency τ_f and quality factor Q value together with the thermal conductivity. The ordered domain structure could be tailored and controlled by the post-densification annealing, and the fine ordered domain structures with high ordering degree and low-energy domain boundary were obtained in the present ceramics annealed around 1400°C for 24 h, where the Qf value was improved from 51 000 to 118 000 GHz, τ_f was suppressed from 30 to 25.5 ppm/°C. Moreover, the thermal conductivity at room temperature was increased from 3.79 to 4.30 W m⁻¹ K⁻¹, and the Young's modulus was improved from 98 to 214 GPa. The present work provided a promising approach for synergistic modification of physical properties in Ba-based complex perovskite microwave dielectric ceramics.     

Origin of dielectric loss in Ba(Co1/3Nb2/3)O3 microwave ceramics

The microwave dielectric loss of stoichiometric and non‐stoichiometric Ba(Co_1/3Nb_2/3)O₃ ceramics have been measured from 2 to 300 K in magnetic fields ranging from 0 to 5 T using a dielectric resonator (DR) technique. The microwave absorption from spin excitations of unpaired d‐electrons in exchange coupled Co²⁺ ions dominate the loss of the Ba(Co_1/3Nb_2/3)O₃ ceramics at cryogenic temperatures. Two peaks in the loss tangent (tan δ) vs temperature relation from a distinctly different origin occur at 25‐30 K and 90 K, which increase in magnitude with increasing Co content in the bulk dielectric samples. Evidence that these peaks result from polaron conduction from hopping between Co²⁺ and Co³⁺ ions includes (i) the peak's observed temperature range; (ii) the decrease in peak intensity of approximately a factor of two in a large applied magnetic fields (5 T); and (iii) a strong correlation between the peak's magnitude and both the fraction of the minority Co³⁺ in the dominant Co²⁺ matrix and D.C. conductivity at elevated temperatures. A magnetic‐field independent high temperature peak with a maximum at 250 K dominates the room temperature microwave loss whose magnitude correlates with those of the low temperature peaks. This suggests that the defects responsible for carrier conduction play an important role in establishing the loss tangent at room temperature.     

复合钙钛矿型Ba（Mg1／3Ta2／3）O3中B位有序结构的研究

本文讨论了复合钙钛矿型Ｂａ（Ｍｇ１／３Ｔａ２／３）Ｏ３中Ｂ位离子的有序程序同材料的介电损耗之间的关系。用Ｘ射线谱和Ｒａｍａｎ光谱研究了陶瓷烧结温度对Ｂａ（Ｍｇ１／３Ｔａ２／３）Ｏ３中Ｂ位离子的有序程度的影响，当适当提高烧结温度可增大有序程度。     

Ba-based complex perovskite ceramics with superior energy storage characteristics

Linear dielectrics are widely used to create high power capacitors, where it is a big challenge to achieve high energy storage density in such dielectrics. Here, Ba-based complex perovskite ceramics with high dielectric strength, medium dielectric constant, and ultra-low dielectric loss are proposed as the candidates for high energy storage density dielectric materials, and the significant effects of 1:2 B-site ordering and ordering domain structure are systematically investigated. In Ba(Mg_1/3Nb_2/3)O₃ ceramics, high dielectric strength of 1452 kV cm⁻¹ combined with high energy storage density of 3.31 J cm⁻³ are achieved in the samples after post-densification annealing, and they are 28% and 57%, respectively, higher than those in the as-sintered samples. The significant enhancement of energy storage performance could be attributed to the increased B-site ordering degree, and the uniform ordering domain structure. Furthermore, amorphous alumina thin films are introduced as the charge blocking layers, which significantly enhance the energy storage density to 5.09 J cm⁻³. The present work provides a new approach to develop the dielectric ceramics with high energy storage density.     

Relationship between distortion of crystal structure and dielectric properties of complex perovskite oxide Ba(Co,Zn)1/3Nb2/3O3 thin films

The oxygen octahedral can be distorted by epitaxial strain due to the lattice mismatch. The epitaxial strain (ε_yy) linearly decreases from ? 0.244% to ? 0.445% with the growth temperature. Thin films grow along c axis on the SrTiO₃ substrate and exhibit the epitaxial relationship of Ba(Co,Zn)_1/3Nb_2/3O₃ (001) // SrTiO₃ (001). The superlattice reflections arising from in-phase tilting of the oxygen octahedra are clearly visible along [010] and [111] zone axis. The IR modes at 330 cm^?1 and 390 cm^?1 related to in-phase tilting are observed in far-infrared reflectivity spectroscopy. The calculated Q×f values from far-infrared reflectivity spectra of films grown at 550 °C to 700 °C increases from 51,000 GHz to 91,000 GHz mainly due to the enhancement of crystalline quality. The intrinsic quality factor (Q) is mainly contributed by O-(Co, Nb)-O and O-(Zn, Nb)-O bonding modes, while in-phase tilting in BCZN films may result in enhanced dielectric constants.     

Fabrication and microstructure of preferential orientated 1:1 ordered Ba(Mg1/3Nb2/3)O3 complex perovskite microwave dielectric ceramics by laser floating zone technique

Dense Ba(Mg_1/3Nb_2/3)O₃ complex perovskite ceramics have been successfully fabricated by directional solidification using a laser floating zone (LFZ) technique with various pulling rates. The crystal structure, microstructure, and especially ordering structure are thoroughly investigated by transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). The LFZ solidified rods are all of the fcc lattice structure with Fm$\bar{3}$m space group resulting from B-site 1:1 cation ordering in comparison to the hexagonal structure associated with 1:2 ordering prepared by conventional sintering. The 1:1 ordering domains are formed based on the space charge model and separated by anti-phase domain boundaries related to reducing pure translational symmetry upon phase transition. Preferential orientations that <110> directions in the fcc unit cell align along the growth direction (//ND) exist in all the LFZ solidified rods. The slightest deviation is obtained with 75 μm/s pulling rate. The preferential orientated 1:1 ordered ceramics are expected to adopt properties superior to the conventional sintered polycrystalline counterparts.     

Structure and microwave dielectric properties of 1:1 ordered Nd[(Mg1-xZnx)1/2Ti1/2]O3 complex perovskite ceramics

Nd[(Mg_1-xZn_x)_1/2Ti_1/2]O₃ perovskite ceramics (x = 0, 0.2, 0.4, 0.6, 0.8) are prepared by the solid-state reaction method. The effects of Zn²⁺ substitution on the structure, microstructure, especially the B-site 1:1 cation ordering and microwave dielectric properties have been investigated. Sintered Nd[(Mg_1-xZn_x)_1/2Ti_1/2]O₃ ceramics all adopt dense microstructure, along with increased dimensional uniformity as Zn²⁺ substitution. All the ceramics are confirmed to have B-site 1:1 ordered monoclinic perovskite structure with P2₁/n space group. Atomic mass difference of B-site elements might be an important factor affecting the B-site 1:1 cation ordering. HRSTEM observation suggest that the doped Zn²⁺ cations have roughly entered the Mg²⁺ sites to promote 1:1 cation ordering. The degree of the 1:1 cation ordering can be negatively reflected by the full width at half maximum (FWHM) of F_2g(B) mode at 372 cm^?1 in Raman spectra. With Zn²⁺ doping, the degree of the 1:1 cation ordering first increases then decreases, and reaches its maximum at x = 0.6. Meanwhile the best combination of microwave dielectric properties is obtained, as ε_r = 31.4, Q × f = 74,000 GHz, τ_f = ?44 ppm/°C. It is found that the long-range ordering not only decreases the dielectric loss but also affects the dielectric constant, providing a theoretical foundation to understand further the correlation between ionic configuration and microwave dielectric properties.     

Structural ordering and dielectric properties of Ba3CaNb2O9-based microwave ceramics

Ba₃CaNb₂O₉ is a 1:2 ordered perovskite which presents a trigonal cell within the D_3d³ space group. Dense ceramics of Ba₃CaNb₂O₉ were prepared by the solid-state reaction route, and their microwave dielectric features were evaluated as a function of the sintering time. From Raman spectroscopy, by using group-theory calculations, we were able to recognize the coexistence of the 1:1 and 1:2 ordering types in all samples, in which increasing the sintering time tends to reduce the 1:1 domain, leading to an enhancement of the unloaded quality factor. We concluded that this domain acts as a lattice vibration damping, consequently raising the dielectric loss at microwave frequencies. The best microwave dielectric parameters were determined in ceramics sintered at 1500 °C for 32h: ε′ ~ 43; Q_u×f_r = 15,752 GHz; τ_f ~ 278 ppm °C⁻¹.     

Co-optimization of microwave dielectric properties in Ba(Mg1/3Ta2/3)O3 complex perovskite ceramics through ordered domain engineering

It is an important subject to improve the temperature coefficient of resonant frequency (τ_f) and thermal conductivity (κ) of microwave dielectric ceramics without reducing the Qf value. Ordered domain engineering was applied to realize the previous objectives in Ba(Mg_1/3Ta_2/3)O₃ ceramics. With the increasing ordering degree from 0.835 to 0.897, the optimized Qf value was obtained. Meanwhile, near zero τ_f from 11.9 to 5.6 ppm °C⁻¹ was achieved, together with increased κ from 5.5 to 7.6 W m⁻¹ K⁻¹, and enhanced dielectric strength from 801 to 921 kV cm⁻¹. The noticeable ordered domain structure with large ordered domains (∼100 nm) and low-energy domain boundaries was revealed in Ba(Mg_1/3Ta_2/3)O₃. The consequent weakened phonon scattering rises the thermal conductivity. The increased bond covalency and oxygen distortion in ceramics with higher ordering degree were suggested as a cause of enlarged bandgap, which enhanced the dielectric strength. The reduced τ_f is dominated by the less “rattling” space of the cations in the ordered state by inducing more positive τ_ε. The reduced τ_f, optimized thermal conductivity, and Qf value in the present work indicate that the ordered domain engineering could open up a new direction for the optimization of microwave dielectric ceramics.     

Improvement of microwave dielectric properties for Ba(Ni1/3Nb2/3)O3 ceramics by Zr-substitution

Effects of Zr-substitution on the structure, microstructure and microwave dielectric properties of Ba(Ni_1/3Nb_2/3)O₃ ceramics have been investigated. A small amount of Zr-substitution facilitates the densification of Ba(Ni_1/3Nb_2/3)O₃ ceramics. Within x≤0.05, the densification temperature decreases with increasing x in Ba[(Ni_1/3Nb_2/3)_1−xZr_x]O₃, while it turns to increase for x>0.05. With increasing x, the grains become more homogeneous and closely contacted, and significantly increase in size for x=0.15–0.20. The B-site cations 1:2 ordering is destroyed by Zr-substitution, and only stabilizes for x≤0.04. B-site cations 1:1 ordering starts to form in x=0.04, and the 1:1 ordering degree first increases and then decreases with increasing x. Qf value decreases slightly in x=0.01 and then increases monotonously with x increasing from 0.02 to 0.20. The destroyed 1:2 ordering structure is responsible for the decreased Qf value in x=0.01, while the improved grain configuration dominates the increase of Qf value for x=0.02–0.20. The dielectric constant ε_r increases monotonously with increasing x, due to the higher polarizability of Zr ion than the average value of Ni/Nb ions. The temperature coefficient of resonant frequency τ_f shifts from negative to positive through zero with increasing x, which is ascribed to the highly positive τ_f value of the end member BaZrO₃. The significant improvement of microwave dielectric properties has been achieved for x=0.10, higher ε_r, higher Qf as well as near zero τ_f value have been obtained: ε_r=31.8, Qf=36,100 GHz, τ_f=7.8 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.     

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.     

Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 ternary ceramics with temperature-insensitive and superior piezoelectric property

The development of ferroelectric ceramics with both large piezoelectric responses and broad service temperature range is still a key challenge for practical applications due to the so-called d₃₃-T_C trade-off. Here we report the strategy to utilize the synergistic contribution of morphotropic phase boundary and enhanced local structural heterogeneity, in which an excellent piezoelectric coefficient d₃₃ of 680 pC/N and a high Curie temperature of 330 ℃ are simultaneously achieved in Sm modified 0.25PIN-0.325PZ-0.425PT ceramics. The underlying mechanism responsible for the high dielectric and piezoelectric properties is studied based on cryogenic dielectric measurement and Rayleigh analysis. Of particular interest is that, a high field-induced strain of 0.19% is achieved in 0.25PIN-0.32PZ-0.43PT at electric field of 20 kV/cm, corresponding to a piezoelectric d₃₃ * of 945 pm/V, showing an excellent temperature stability with minimal variation of 7% up to 310 °C. This work demonstrates the introduction of high temperature end members and rare earth doping are conducive to ferroelectric solid solutions with desired broad usage temperature range and superior piezoelectric properties, which will greatly benefit high temperature actuator applications.     

High frequency dielectric properties of Ba(Mg1/3Ta2/3)O3 complex perovskite ceramics

The dielectric properties of Ba(Mg_1/3Ta_2/3)O₃ and Ba(Mg_1/3Nb_2/3)O₃ ceramics were investigated using Fourier transformed infrared and Raman spectroscopies. The real part of dielectric constant of these materials decreases when the heavier Ta atoms replaced the lighter Nb atoms, which is closely related to the shift of mode-frequency. The Q-factor of the materials depends weakly on the composition. The decrease in Q-factor with the frequency is due to the presence of a resonance mode at around 3 THz. Larger width of the breathing Raman mode, A_1g[O], correlates very well with the lower Q-value of the BMN materials, as compared with the BMT materials.     

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.     

Preparation and characterization of indium based complex perovskites-Pb(In1/2Nb1/2)O3 (PIN), Ba Ba(In1/2Nb1/2)O3 (BIN), and Ba(In1/2Nb1/2)O3 (BIT)

The processing of order-disorder perovskites Ba(In_1/2Nb_1/2)O₃ (BIN), Ba(In_l/2Ta_1/2)O₃ (BIT), and the lead analogue Pb(In_1/2Nb_1/2)O₃ (PIN) was investigated with an emphasis on improving and expanding our knowledge of microwave dielectric materials. Both BIN and BIT were shown to be paraelectric perovskites. The processing and annealing of PIN were related to the perovskite and its transformation to pyrochlore. Dielectric and physical characteristics were examined by X-ray diffraction profiles (XRD), scanning electron microscopy (SEM), and dielectric behavior. Attempts to enhance B-site cation order in PIN by thermal annealing were unsuccessful due to a pyrochlore formation.     

(1-x)Pb(Ni1/3 Nb2/3)O3-xPbTiO3陶瓷的合成及其电滞回线

采用两步法在850℃合成了(1-x)Pb(Ni1／3Nb2／3)O3-xPbTiO3(x=0．28～0．42)陶瓷,粉末均为单一钙钛矿相。扫描电子显微镜观察和介电性能检测表明：所研究的陶瓷的最佳烧结温度为1200℃。对1200C烧结的0．64Pb(Ni1/3Nb2/3)O3-0．36PbTiO3陶瓷的铁电性能进行了详细地研究,发现组成在准同型相界的陶瓷铁电性得到增强．而这种铁电性增强正是由组分及结构和准同型相界的本质共同决定的。     

(1-y)Ca1-xLa2x/3TiO3-yCa(Mg1/3Nb2/3)O3复合微波介质陶瓷的研究

采用固相合成法制备了 ( 1-y)Ca1 -xLa2x/ 3 TiO3 -yCa(Mg1 / 3 Nb2 / 3 )O3 系列微波介质陶瓷材料 ,研究了复合系统的微波介电性能、烧结性能和微观结构。研究结果表明 :在y =0 .4～ 0 .6范围内 ,体系形成了单一的钙钛矿结构 ;当复合体系组成 0 .5Ca0 .6La0 .2 67TiO3 -0 .5Ca(Mg1 / 3 Nb2 / 3 )O3 时 ,在 14 0 0℃下烧结保温 4小时所得到材料的微波介电性能最佳 ;εf=5 5 ,Q×f =45 0 0 0GHz( 7.6GHz下 ) ,τf=0 .0 4ppm/℃。     

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.