Mo掺杂调控钛酸铋钠铁电陶瓷带隙的实验与第一性原理研究

为改善钛酸铋钠基无铅陶瓷的铁电光伏特性,通过传统固相法制备了B位Mo掺杂的Na0.5 Bi0.5(Ti1-x Mox)O3(BNT-Mox,x=0～0.02)无铅铁电陶瓷.通过XRD、拉曼光谱、吸收光谱等测试方法,结合基于密度泛函理论的第一性原理计算,研究了Mo掺杂对BNT陶瓷体系带隙的影响规律及机理.结果表明:随着M...     

Dielectric and Electromechanical Properties of Textured Niobium-Doped Bismuth Titanate Ceramics

Textured Nb-doped bismuth titanate ceramics (Bi₄Ti_{3− x /5}- Nb _{x /5}O₁₂, where x = 0.02) were fabricated by templated grain growth. It was found that the use of a fine precursor powder led to enhanced densification of the ceramic, while Nb doping reduced electrical conduction and dielectric loss, which enabled poling at high temperatures and high electric fields. Sintered tapes showed anisotropic dielectric and piezoelectric properties when measured parallel and perpendicular to the casting plane (e.g., the remanent polarization differed by more than a factor of 15 in the two directions). The piezoelectric constant parallel to the casting plane of the tape was ∼30 pC/N, or ∼77% of the single-crystal value. Thermal depoling studies demonstrated that high-temperature piezoelectric applications are possible up to ∼450°C in textured, doped bismuth titanate.     

Structural and dielectric properties of CuO nanoparticles

The DC conduction and dielectric behaviour of copper oxide nanoparticles prepared by sol-gel method and sintered at 950 °C were studied in the temperature range of 200–526 K. The formation of single phase monoclinic CuO was confirmed by x-ray diffraction. Chemical composition of the CuO ceramic was investigated with X-ray photoelectron spectroscopy (XPS) technique. Although XRD analysis shows the formation of single phase CuO, XPS spectra revealed the presence of Cu³⁺ and Cu²⁺. Deviation from linearity ln (σ_DC) vs. 1/T plot at ~390 K was observed, which indicates that DC conduction in the CuO pellet is dominated by two different conduction mechanisms. The results obtained on AC conductivity indicate that AC conduction mechanism could be well explained by the multihopping model at low frequencies, while high frequency AC conductivity data can be described by small polaron tunnelling model. The dielectric relaxation mechanism in the CuO pellet was studied by impedance spectroscopy. It was found that while dielectric constant is an increasing function of temperature, it decreases with increasing frequency. The obtained impedance spectra indicated that the grain boundary effects and intergranular activities play a crucial role on the dielectric relaxation processes.     

Structure,electrical and dielectric properties of Ca substituted BaTiO3 ceramics

BaTi_1-xCa_xO_3-x [BTC100x] ceramics were synthesized via solid-state reaction method. Effect of Ca substitution on the structure, electrical and dielectric properties of BTC100x ceramics was systematically investigated. Calcined BTC100x powders were in tetragonal phase when x?≤?0.01, whereas transformed to cubic at x?>?0.01. Additionally, the diffraction peak (200) shifted to lower angles with increasing x, indicating increased unit cell volume. Meanwhile, Ba_0.97Ca_0.03TiO₃ [BC3T] ceramic was prepared and studied, to compare with BaTi_0.97Ca_0.03O_2.97 (BTC3). It was found that pure BaTiO₃ [BT] and BC3T ceramics had the similar structural and dielectric properties, whereas BTC3 ceramic showed much difference,XRD patterns, Raman spectrum, impedance spectra and dielectric-temperature spectra provided strong evidence of Ca²⁺ substitution at Ti site in BT lattice. Finally, BTC100x ceramics were produced and dielectric properties were investigated. With increasing x, the Curie temperature decreased from 128?°C (BT) to 42?°C (BTC5).     

Sintering and dielectric properties of perovskite SrTaO2N ceramics

Single-phase perovskite oxynitride SrTaO₂N ceramics were prepared by pressureless sintering at 1400 °C under a nitrogen atmosphere, using 5 wt% of SrCO₃ or La₂O₃ as a sintering additive. In contrast, SrTaO₂N bulks without additives contained TaC and Ta₃N₅ impurities. Sintering in nitrogen led to oxygen/nitrogen deficiencies in the oxynitride, while post annealing in flowing ammonia was effective to eliminate the anion vacancies. The introduction of additives significantly improved the sinterability of SrTaO₂N ceramics. A relative density of >90% in the bulk was achieved with a highly dense microstructure with smaller grain sizes. The SrTaO₂N bulk with SrCO₃ additive exhibited superior dielectric performance with a high relative permittivity (?_r = 1.0 × 10⁴) and dissipation factor (tan δ = 0.039) at a frequency of 1 MHz.     

Effect of Potassium Concentration on the Grain Orientation in Bismuth Sodium Potassium Titanate

Bi_0.5(Na_{1- x} K _x )_0.5TiO₃ (BNKT) bulk ceramics with a preferred <100> orientation were prepared using the reactive templated grain-growth method with platelike Bi₄Ti₃O₁₂ particles as templates for BNKT. The potassium concentration ( x value) had a large effect on the degree of orientation, and highly oriented ceramics were obtained for the specimens with x = 0.10 and x = 0.15, whereas the specimen with x = 0.00 had a small degree of orientation. Increased potassium concentration from x = 0.00 to x = 0.15 decreased the grain-growth rate and changed the grain shape from irregular to cubic. These factors were responsible for the increased degree of orientation.     

Effect of yttrium (Y) substitution on the structure and dielectric properties of BaTiO3

As the rate of application of multilayer ceramic capacitors (MLCCs) in small electronic devices increases, the use of the raw material barium titanate (BaTiO₃) with a small particle size and excellent dielectric properties becomes needed. Due to the size effect, small-sized BaTiO₃ generally has a cubic phase structure with a low dielectric constant, which limits its use in MLCCs. We report the preparation of small cubic phase Y-doped BaTiO₃ (BYT) nanoparticles by a hydrothermal method and the preparation of highly dielectric tetragonal phase BYT ceramics based on this method. XRD and Raman analysis showed that the BYT nanoparticles are in substable cubic phases. The particle size of the BYT nanoparticles, measured by TEM, XRD, and BET, was approximately 35 nm. The dielectric properties of the BYT ceramics were tested by an impedance analyzer, and the dielectric constant of the BYT ceramics was 7547 when the Y³⁺ doping amount was 0.5 mol%. In addition, the substitution mechanism of Y³⁺ doping in BaTiO₃ crystals was proposed from XPS and EPR analysis. The results demonstrate for the first time that the 50 nm cubic phase BaTiO₃ powder can meet the needs of next-generation high-capacity MLCCs. This work provides a reference for small cubic phase BaTiO₃ as a dielectric material for high-capacity MLCCs.     

Synthesis,characterization, and dielectric properties of low loss LaBO3 ceramics

The preparation, sintering behaviour, and dielectric properties of low loss LaBO₃ ceramics have been investigated. Single-phase LaBO₃ powder was synthesized by the conventional solid-state ceramics route and dense ceramics (relative density >96%) with uniform microstructure (grain size ～30 μm) were obtained by sintering at 1300 °C in air. The electrical conductivity of LaBO₃ follows the Arrhenius law and the related activation energies for electrical conduction of bulk and grain boundary are 0.62 eV and 0.90 eV, respectively. The LaBO₃ ceramics sintered at 1300 °C exhibit excellent microwave dielectric properties with a relative permittivity, ?_r ～ 11.8, a quality factor, Q × f₀ value ～76,869 GHz (at ～15 GHz), and a negative temperature coefficient of resonant frequency τ_f ～ ?52 ppm/°C.     

Vanadium doping effects on microstructure and dielectric properties of barium titanate ceramics

V-doped barium titante ceramics were prepared by conventional solid state reaction method. XRD patterns show that V⁵⁺ ions have entered into the tetragonal perovskite structure of solid solution to substitute for Ti⁴⁺ ions on the B sites. Addition of vanadium accelerates grain growth of BTO ceramics and there is abnormal grain growth of barium titanate ceramics with higher vanadium concentration. Vanadium doping can increase the Curie temperature and decrease the dielectric loss of barium titanate ceramics. As vanadium concentration increases, the remnant polarization of V-doped BTO ceramics begins to increase and reaches the maximum and then decreases. The coercive electric field for V-doped barium titanate ceramics decreases with the increasing of vanadium concentration. As temperature rises, the remnant polarization and the coercive electric field of V-doped barium titanate ceramics decrease simultaneously.     

掺杂三氧化二锑的钛酸铋钠钾陶瓷的显微结构和电学性能

采用固相合成工艺制备了（1–x）[0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3]–xSb2O3（BNKT–xSb）压电陶瓷,研究了Sb2O3掺杂对BNKT陶瓷的显微结构和电学性能的影响规律。研究表明：Sb2O3掺杂量x小于0.020时,不改变基体的钙钛矿结构,且Sb具有可变化合价,能形成＂施主＂和＂受主＂2种掺杂而起到＂软化＂或＂硬化＂的作用。当Sb2O3掺杂量x≤0.005时,其压电系数d33随Sb2O3掺杂量的增加而增大,此时Sb2O3表现出了＂软化＂的特征;当Sb2O3掺杂量x〉0.005时,d33降低,从而又表现出了＂硬化＂的特性;当Sb2O3掺杂≥0.010时,诱使陶瓷室温下反铁电微畴的形成,导致铁电性和压电性的骤减。     

Effect of strontium substitution on the structure and dielectric properties of unfilled tungsten bronze Ba4-xSrxSmFe0.5Nb9.5O30 ceramics

The effects of Sr²⁺ substitution for Ba²⁺ on phase structure, microstructure, dielectric and electric properties for Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2, 3 and 4) ceramics were systematically researched. X-ray diffraction patterns show that Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2 and 3) ceramics are tetragonal tungsten bronze compound with a space group of P4bm, while the sample for x = 4 is an orthorhombic structure compound. The result can be corroborated by the analysis of Raman spectroscopy. As the Sr²⁺ contents increase from 0 to 3, the full width at half maximum of Raman lines of all samples increase gradually, indicating that the degree of lattice distortion increase. All tetragonal tungsten bronze ceramics exhibited a broad permittivity peaks, accompanied by frequency dispersion, indicating all samples are relaxor. The electrical properties of BSSFN ceramics were further studied by complex impedance spectroscopy. XPS spectrum shows that Fe²⁺ and Fe³⁺ coexist in Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ ceramics, and their proportion varies with the concentration of Sr²⁺.     

Formation mechanisms and electrical properties of perovskite mesocrystals

Mesocrystals are oriented polycrystals with superstructures consisting of crystallographically ordered nanocrystals. They usually show the electron diffraction behaviour of a single crystal owing to the high order of the nanoscale building units. Mesocrystals have potential applications in many processes such as catalysis, sensing, energy storage and conversion. Perovskite mesocrystals are a novel class of mesocrystalline dielectric nanomaterials that exhibit synergistic properties and anomalous electrical properties; so they have been extensively studied in various fields. This review investigates the chemical formation processes, formation mechanisms and mechanisms that affect performance of perovskite mesocrystals. Moreover, the formation mechanisms of perovskite mesocrystals, namely topochemical mesocrystal conversion mechanism is discussed. Understanding and application of these mechanisms are important for the design and preparation of advanced structural and functional materials. Most importantly, mesocrystal-derived functional materials can be designed by combining orientation, strain, and domain engineering. The potential applications of perovskite mesocrystals as structural and functional materials in piezoelectric, ferroelectric, dielectric, and catalytic devices as well as perovskite solar cells are discussed. This investigation not only develops the chemistry of mesocrystals and proposes new routes for the design of oriented film and ceramic materials, but also provides theoretical support for future applications of perovskite mesocrystals in material science.     

Effects of cerium doping on dielectric properties and defect mechanism of barium strontium titanate glass-ceramics

The effect of cerium content on phase evolution, dielectric properties and defect mechanism has been investigated in (Ba,Sr)TiO₃ glass-ceramics. Cerium mainly acts as an isovalent dopant in the B-site of ABO₃ perovskite structure at low content (1 mol%) and then cerium substitution gradually occurs in the A-site with increasing cerium content. A compensation mechanism related to variation in oxygen vacancy concentration has been identified. When cerium content increased to 2 mol%, the maximum values of dielectric constant and energy storage density were simultaneously achieved. The impedance spectra revealed the highest conductivity. It is due to the increase in the concentration of charge carriers accompanied by the decrease in the activation energy of oxygen vacancy migration. With a further addition of cerium to 3 mol%, the opposite trend was observed. The result is related to the presence of more cation vacancies, which, in turn, limits the diffusion rate of oxygen vacancy.     

Effect of hot-pressing sintering on thermal and electrical properties of AlN ceramics with impedance spectroscopy and dielectric relaxations analysis

The effects of hot-pressing sintering on the phase composition, microstructure, thermal and electrical properties of AlN ceramics with CeO₂–CeF₃ additives were studied. During hot-pressing sintering, high pressure reduced the grain boundary phase CeAlO₃ and decreased the concentration of oxygen in AlN ceramics. The hot-pressing sintered AlN samples had a much higher thermal conductivity of 191.9 W/m·K than pressureless sintered ones because of the great reduction of grain boundary phases and oxygen impurities in AlN ceramic. As the carbon content in hot-pressing sintered sample was very high, carbon contamination led to the decrease in electrical resistivity and changes in polarization mechanisms for AlN ceramics. The relaxation peak in the dielectric temperature spectrum with an activation energy of 0.64 eV for hot-pressing sintered samples was caused by electrons from free carbon at low temperature. Overall, hot-pressing sintering can effectively increase the thermal conductivity and change the electrical properties of AlN ceramics.     

Effect of neodymium ion on the structural,electrical and magnetic properties of nanocrystalline nickel ferrites

NiNd_xFe_2-xO₄ nanoferrites with different compositions of x?=?0.01, 0.03, 0.05, 0.07 and 0.09 were prepared using the sonochemical method. The structural, optical and morphological properties of the prepared nanoferrites were characterized by X-ray diffraction, ultra violet-diffuse reflectance spectroscopy, scanning electron microscopy and X-ray fluorescence techniques. The X-ray diffraction analysis of the prepared nanoferrites confirmed the presence of a cubic spinel structure. The average crystallite sizes of the prepared nanoferrites were 52, 49, 46, 44 and 40?nm for x?=?0.01, 0.03, 0.05, 0.07 and 0.09, respectively. The particle size of the prepared NiNd_xFe_2-xO₄ nanoferrites was in the range 60–40?nm. The dielectric parameters ranged from 2.9?GHz to 5.6?GHz. Decrease in the dielectric constant was observed with an increase in Nd³⁺ ions in the prepared NiNd_xFe_2-xO₄ nanoferrites. However, a reverse trend was observed in the dielectric loss. An impedance analysis of the prepared nanoferrites was carried out to explore the pseudo-capacitance behavior. The saturation magnetization and remnant magnetization values of the prepared nanoferrites decreased with an increase in the concentration of Nd³⁺ ions in NiNd_xFe_2-xO₄ nanoferrites.     

Effect of Fe2O3 content on the electrical resistivity of aluminous porcelain applied to electrical insulators

In general, the presence of Fe₂O₃ is claimed to reduce the insulating behavior of electrical porcelains, even if a rigorous proof has not yet been reported. The purpose of this study was to evaluate the real influence of Fe₂O₃ content on the electrical resistivity of a standard aluminous porcelain widely used in insulators. The electrical resistivity for the composition with 3 wt% Fe₂O₃ was higher than those found for standard aluminous porcelain, which was discussed in terms of the concentration of glassy and mullite phases. A reduction in the electrical resistivity was only observed in porcelain samples containing over 3 wt% Fe₂O₃. The presence of hematite phase was considered responsible for this reduction. These results suggest that low-cost raw materials with greater Fe₂O₃ content should not extensively affect the insulating properties and could therefore be used in manufacturing aluminous electrical porcelain.     

On the physico-mechanical,electrical and dielectric properties of mullite-glass composites

Mullite-glass composites were obtained by solid-state reactive sintering of kaolinite clay and kaolin waste mixtures with waste additions up to 100 wt%. The structural and microstructural analysis of starting powders and sintered samples were evaluated by X-ray diffractometry (XRD) and field-emission scanning electron microscopy (FESEM). The mechanical properties were evaluated by measuring the flexural strength of sintered bodies. Electrical properties of the composites were assessed by impedance spectroscopy (at 30 °C and from 400 to 700 °C) in air. A viscous flux mechanism resulting from the glassy phase filled up the open porosity and increased the mechanical strength. Electrical conductivity, dielectric constant and dielectric loss were strongly dependent on the microstructural features, namely glassy phase and porosity. The activation energies (0.89–0.99 eV) for electrical conduction were lower than typical literature values of mullite-based materials. The results indicated that the herein synthesized mullite-glass composites with up to 53.6 wt% mullite are promising low-cost materials for electronics-related applications.     

Effect of Mg doping on magnetic,and dielectric properties of NiCr2O4 nanoparticles

The structural, magnetic, and dielectric properties of spinel Magnesium (Mg) doped Nickel chromite (NiCr₂O₄) nanoparticles (NPs) have been studied in detail. The X-ray powder diffraction exhibited normal spinel phase formation of Mg_xNi_1-xCr₂O₄ (x = 0, 0.2, 0.4, 0.6, and 1) NPs with a maximum average crystallite size of about 44 nm for x = 0.2 composition. The FTIR spectra of these NPs revealed the characteristic Ni–O and Mg–O and Cr–O bands around 639 cm^?1 and 497 cm^?1, respectively which confirmed the spinel structure. Temperature-dependent zero field cooled and field cooled graphs of NiCr₂O₄ NPs showed phase changes from ferrimagnetic to paramagnetic state at 86 K, while MgCr₂O₄ NPs showed antiferromagnetic (AFM) transition at Neel temperature (T_N) at 15 K due to corner-sharing of Cr³⁺ ions at a tetrahedral lattice site resulting in a highly magnetic frustrated structure. The field dependent magnetization (M ? H) loops of Mg_xNi_1-xCr₂O₄ NPs confirmed the competing AFM interactions and ferrimagnetic interactions resulting in a sharp decreased saturation magnetization with Mg doping. Dielectric constant, dielectric loss, and ac conductivity of these NPs showed size-dependent variation and depicted maximum value at x = 0.2 Mg concentration. In summary, the magnetic and dielectric properties of Mg doped NiCr₂O₄ NPs were modified by variations in the average crystallite size and magnetic exchange interactions, which may be suitable for different technological applications.     

Influence of isovalent Cd doping concentration and temperature on electric and dielectric properties of ZnO films

In this study, pure zinc oxide and lightly cadmium doped zinc oxide (Zn_1-xCd_xO; x = 0.01, 0.03, 0.05 and 0.07) films were synthesized by chemical bath deposition to mainly investigate the possible impact of isovalent (in particular Cd) doping ratio and temperature on their electric and dielectric features. X-ray diffraction patterns revealed that all produced films have a dominance of ZnO hexagonal wurtzite structure with the emergence of a minor CdO cubic phase at x ≥ 0.03, and predicted the decrease in average crystallite sizes with Cd doping. Cd content in the films was verified by energy dispersive X-ray analysis. Images of scanning electron microscopy revealed the formation of nanorods and spheres on the surface of pure ZnO film which changed to porous/agglomerative spheres with Cd doping. Then a comprehensive electric and dielectric analysis was carried out as a function of frequency in a wide temperature range (300–700 K) using two separate experimental data sets, (Z, θ) and (C, G). The results demonstrated the critical effect of temperature and Cd doping ratio on the electrical and dielectric properties of ZnO films. Among the investigated films, Zn_0·97Cd_0·03O film recorded highest conductivity and enhanced dielectric properties which was attributed to the equal activation of grains and grain boundaries in the film structure verified by the estimation of activation energies from impedance spectrum. However, the effect of Cd doping on electric and dielectric properties was prominent only below 500 K, beyond which the doping effect became negligible which might be correlated with the effective dominance of grain boundaries at high temperatures as was witnessed by modulus spectrum.