Electronic structure of nanograin barium titanate ceramics

The density of states and band structure of 20 nm barium titanate (BaTiO₃, BT) ceramics are investigated by first-principles calculation. The full potential linearized augmented plane wave (FLAPW) method is used and the exchange correlation effects are treated by the generalized gradient approximation (GGA). The results show that there is substantial hybridization between the Ti 3d and O 2p states in 20 nm BT ceramics and the interaction between barium and oxygen is typically ionic.     

Doped barium titanate nanoparticles

We have synthesized nickel (Ni) and iron (Fe) ion doped BaTiO₃ nanoparticles through a chemical route using polyvinyl alcohol (PVA). The concentration of dopant varies from 0 to 2 mole% in the specimens. The results from X-ray diffractograms and transmission electron micrographs show that the particle diameters in the specimen lie in the range 24–40 nm. It is seen that the dielectric permittivity in doped specimens is enhanced by an order of magnitude compared to undoped barium titanate ceramics. The dielectric permittivity shows maxima at 0.3 mole% doping of Fe ion and 0.6 mole% of Ni ion. The unusual dielectric behaviour of the specimens is explained in terms of the change in crystalline structure of the specimens.     

Microstructure and thermal properties of dysprosium and thulium co-doped barium titanate ceramics for high performance multilayer ceramic capacitors

The co-doping characteristics on microstructure and thermal properties of barium titanate (BaTiO₃) were investigated to elucidate formation of core-shell structure by dysprosium (Dy) and thulium (Tm) addition in the BaTiO₃-Dy₂O₃-Tm₂O₃ system. The dielectrics co-doped with 0.7 mol% Dy₂O₃ and 0.3 mol% Tm₂O₃ had the dielectric constant up to 2200 as a function of temperature, which was 30% higher than that of specimen containing only Tm₂O₃ at the room temperature. It could be explained by the fact that the increase of Dy₂O₃ addition contributed to the improvement of dielectric constant. On the other hand, the rapid diffusion rate of Dy³⁺ ions in BaTiO₃ showed an adverse effect on temperature stability caused by destruction of core-shell. As the compensation for shell expansion in BaTiO₃, the reinforcement of the core-shell structure through the addition of Tm₂O₃ was confirmed by TEM-EDS analysis and attributed the temperature coefficient of capacitance (TCC) in a reliability condition (−55 °C to 125 °C, △C = ±15% or less). The enhanced electrical properties and temperature stability could be deduced from the generation of electrons and the formation core-shell structure in co-doped BaTiO₃ system respectively.     

Study on the microstructure and dielectric properties of X9R ceramics based on BaTiO3

This paper investigated the microstructure and dielectric properties of BaTiO₃-Pb(Sn, Ti)O₃ system ceramics. The Curie point of BaTiO₃ is 130 °C. When the temperature is higher than 130 °C, the dielectric constant of BaTiO₃ drops severely according to Curie-Weiss law. Pb(Ti, Sn)O₃(PTS) was selected to compensate the dielectric constant doping of BaTiO₃ since it has high Curie temperature (Tc) point that is about 296 °C. The Curie temperature (Tc) point of BaTiO₃ was broadened and shifted to higher temperature because of the doping of PTS, so the temperature coefficient of capacitance (TCC) curves of the ceramics based on BaTiO₃ was flattened. When 2 wt% Pb(Ti_0.55Sn_0.45)O₃ was added, the sample showed super dielectric properties that the dielectric constant was >1750 at 25 °C, dielectric loss was lower than 2.0% and TCC was <±10% from −55 °C to 200 °C. Therefore the materials satisfied EIA X9R specifications.     

Influence of high temperature processing of sol-gel derived barium titanate thin films deposited on platinum and strontium ruthenate coated silicon wafers

Thin films of barium titanate (BTO) of 200 nm thickness, derived from an alkoxide-carboxylate sol-gel process, were deposited on Pt/Ti and SrRuO₃/ZrO₂-8%Y₂O₃ coated Si wafers. Films with a dense columnar microstructure were obtained by repeated deposition of thin amorphous layers from low-concentrated sols, and crystallization at 800 °C. This method added 10 nm thickness to the crystalline BTO film in each deposition step. The harsh processing conditions had a negative impact on the platinized silicon wafers, where Pt-Si silicides were formed. This led to diffusion of Si into BTO and interfacial silicate formation. The interfacial silicate layer was the cause of deteriorated dielectric and ferroelectric properties of the BTO layer. Use of SrRuO₃/ZrO₂-8%Y₂O₃/Si substrates solved the problem. No diffusion of Si was observed, and BTO films with good dielectric and ferroelectric properties were obtained.     

晶粒可控钛酸钡致密陶瓷的制备及表征

采用超重力反应沉淀法制备的纳米钛酸钡粉体和常规陶瓷工艺,通过控制烧结温度在 1200 ~1300℃,分别制备了晶粒尺寸 0.45~2.2μm的致密陶瓷。实验结果表明超重力反应沉淀法制备的粉体具有良好的烧结和介电性能。烧结温度为 1200℃时,相对密度即可达到95%,晶粒尺寸为 0.45μm,随烧结温度的升高,晶粒逐渐长大,未出现晶粒的异常长大现象,到1300℃相对密度和晶粒尺寸分别达到 97.7%和2.2μm。钛酸钡陶瓷介电性能有明显的粒度效应,晶粒在1.2μm左右时,室温介电常数达到最大(4143)。由于晶粒内部立方相成分的出现,包含更细晶粒的陶瓷(d=0.45μm)呈现低的介电常数。     

Influence of gamma irradiation on the refractive index of Fe-doped barium titanate thin films

Polycrystalline Fe-doped barium titanate (Fe-doped BaTiO₃) thin films were grown by thermal decomposition of the precursors deposited from a sol-gel system onto quartz substrates. The changes in the transmittance spectra induced by gamma irradiation on the Fe-doped BaTiO₃ thin films were quantified. The values for the optical energy band gap were in the range of 3.42-3.95 eV depending on the annealing time. The refractive index of the film, as measured in the 350-750 nm wavelength range was in the 2.17-1.88 range for the as prepared film, and this increased to 2.34-1.95 after gamma irradiation at 15 kGy. The extinction coefficient of the film was in the order of 10⁻² and increased after gamma irradiation. We obtained tuneable complex refractive index of the films by exposure to various gamma rays doses.     

(1-x)BiScO3-xPbTiO3铁电陶瓷的结构稳定性和电学性能研究

采用传统固相法制备了(1-x)BiScO3-xPbTiO3(BSPT)(x=0.58～0.66)铁电陶瓷.经XRD分析发现,BSPT体系三方相和四方相的准同型相界(MPB)在x=0.62附近.在准同型相界附近x=0.62处BSPT陶瓷的压电常数d33和平面机电耦合系数kp具有极大值,但机械品质因素Qm却最小.对BSPT体系及其它钙钛矿型ABO3化合物的结构稳定性进行了讨论,发现容差因子t和离子键百分比p可作为判定钙钛矿结构形成难易程度的基本参数,容差因子t越接近1且离子键百分比p越大的化合物,越容易合成稳定的钙钛矿结构.     

Dielectric and piezoelectric properties of alkaline-earth titanate doped (K0.5Na0.5)NbO3 ceramics

(K_0.5Na_0.5)NbO₃ (KNN) and 0.995(K_0.5Na_0.5)NbO₃-0.005AETiO₃ (AE = Mg, Ca, Sr, Ba) were successfully prepared by conventional ceramic processing and without the cold-isostatic-pressing (CIP) process. The effects of low AETiO₃ (AET) concentration on crystal structure, density, dielectric and piezoelectric properties of the KNN based ceramics were evaluated. The results show that adding MgTiO₃(MT) and BaTiO₃(BT) to KNN can lead to the appearance of a trace amount of second phase(s), reduced density and deteriorated electrical properties. Adding CaTiO₃(CT) and SrTiO₃(ST) to KNN can promote densification and optimize electrical properties. Two phase transitions at T_t-o ( the temperature at which the phase transition from orthorhombic to tetragonal occurs) and T_c (the Curie temperature) were observed in KNN and all KNN-AET ceramics, by using differential scanning calorimetry (DSC) analysis and dielectric characterization. Adding AET to KNN caused the variations of T_t-o and T_c.     

钙钛矿型低铅压电陶瓷的制备与性能研究

采用传统陶瓷工艺制备了钙钛矿型低铅压电陶瓷xPbTi0.4716Zr0.4834（Mn1/3Sb2/3）0.0450O3-（1-x）（K0.485Na0.485Li0.03）NbO3[xPMS-（1-x）KNLN],研究了该陶瓷体系的结构和介电、压电与铁电性能以及这些结构和性能与工艺条件的关系。XRD分析表明,随着烧结温度的升高,陶瓷晶相由焦绿石相与赝立方钙钛矿相共存转变为单一的四方钙钛矿相;SEM分析表明,在烧结过程中产生了以（K0.485Na0.485Li0.03）NbO3组分为主的液相,并在烧结温度提高的过程中产生孔洞出现-孔洞消失的现象;电学测试表明,xPMS-（1-x）KNLN陶瓷具有良好的性能,在x=0.75、烧结温度为1250℃时,陶瓷的性能参数为压电常数d33=182pC/N,机电耦合系数kp=34.5%,居里温度TC=165℃,剩余极化强度Pr=21.2μC/cm2,矫顽场强Ec=1.47kV/mm,介电常数εr=1879,介电损耗tanδ=0.92%。     

掺杂Y2O3对钛酸锶钡铁电陶瓷材料显微结构和介电性能的影响

钛酸锶钡(BSTO)铁电陶瓷材料的介电常数随外加直流电场的变化呈现非线性特性.纯BSTO材料由于较高的介电常数和较大的介电损耗不能满足移相器介质材料的要求.通过在BSTO中添加Y2O3来改善BSTO铁电陶瓷材料的介电性能.研究结果是:(1)在BSTO体系中微量掺杂Y2O3,Y3 以取代Ba2 的方式存在于钙钛矿的晶格中,形成均匀的固溶体Ba0.5-xYxSr0.5TiO3;(2)随Y3 添加量的增加,居里峰逐渐变宽,峰高逐渐降低,相变弥散效应增强;(3)Y3 的掺杂能促进BSTO陶瓷的致密化烧结,并显著降低BSTO陶瓷的介电常数.     

A位掺杂Bi4Ti3O12陶瓷的铁电性能研究

用传统固相烧结工艺,制备了纯相的Bi4Ti3O12 (BTO)陶瓷,A位掺杂的Bi3.25La0.75Ti3O12(BLT),Bi3.15Nd0.85Ti3O12(BNdT)铁电陶瓷.X射线衍射结果表明,所有样品均为单一的层状钙钛矿结构,La、Nd掺杂未改变BTO的晶体结构.铁电测试结果表明,BTO、BLT和BNdT陶瓷的剩余极化2Pr值分别为12.4、23.8和39.4μC/cm2.A位掺杂后,BLT、BNdT的2Pr值比未掺杂的BTO分别提高了1.92和3.18倍.漏电流测试表明,BLT、BNdT陶瓷的漏电流密度比BTO明显降低.A位掺杂显著提高了BTO陶瓷的铁电性能.     

Structural, electrical, luminescent, and magnetic properties of Ba0.77Ca0.23TiO3:Eu ceramics

The structural, electrical, luminescent, and magnetic properties of Eu³⁺-doped Ba_0.77Ca_0.23TiO₃ (BCT23:Eu) ceramics were investigated in this paper. Three different incorporation mechanisms of Eu³⁺ were realized in BCT23 by considering different charge compensation mechanisms: (i) Ca site substitution with Ca vacancy compensation; (ii) Ti site substitution with O vacancy compensation; (iii) simultaneous substitution at both Ca and Ti sites with self-compensation. Besides the evident ferroelectric properties, the BCT23:Eu ceramics showed the photoluminescence and paramagnetic properties, implying that they can be considered as the multifunctional materials. Both the electric and luminescent properties were sensitive to the Eu doping concentrations and positions, due to the variations of the microstructures and different charge compensation mechanisms.     

Effects of Bi2O3 and Cr2Ti3O9 Co-doping on dielectric properties in BaTiO3-based ceramics

A microwave ceramic with general composition (1-x-y) BaTiO₃ + x Cr₂Ti₃O₉ + y Bi₂O₃ has been prepared by solid state synthesis at 1300-1400 °C. The phase composition, perovskite structural parameters and dielectric properties have been obtained by X-ray diffraction and dielectric measurements as a function of chemical composition and temperature. At low doping levels the formation of BaTiO₃-based solid solution has been found. The precipitation of BaCrO₃ has been detected at x = y = 2.0 mol%. A model of the incorporation of Cr³⁺ and Bi³⁺ ions into BaTiO₃-based crystal lattice has been proposed. Diffused phase transition in the temperature range 100-140 °C have been revealed by dielectric measurements for different ceramic composition. As high dielectric constant as 7311 and as low dielectric loss as 0.02 have been found for the composition of 0.98BaTiO₃-0.01Cr₂Ti₃O₉-0.01Bi₂O₃.     

Effects of TiO2 doping on microstructure and properties of directed laser deposition alumina/aluminum titanate composites

ABSTRACT

Al₂O₃-based composite ceramics have excellent high temperature performance and are ideal materials for preparing hot end components. However, poor fracture toughness and thermal shock resistance limit its applications. Based on the excellent low thermal expansion characteristics and thermal shock resistance of Al₂TiO₅ ceramic, different composition ratios of Al₂O₃/Al₂TiO₅ composite ceramics were prepared by directed laser deposition (DLD) technology. Effects of TiO₂ doping amount on microstructure and properties of the composite ceramics were investigated. Results show that α-Al₂O₃ phase is discretely distributed in the continuous aluminum titanate matrix when TiO₂ doping amount between 2 and 30?mol%. With the increase of TiO₂ doping amount, content of Al₂O₃ gradually decreases and its morphology changes from cellular to dendritic. When TiO₂ doping amount reaches 43.9?mol%, the microstructure transforms into fine Al₂TiO₅/Al₆Ti₂O₁₃ eutectic structure. Property test results show that Al₂O₃/Al₂TiO₅ composite ceramics have good comprehensive mechanical properties when TiO₂ doping amount between 2 and 6?mol%.     

温度和电场对纳米晶钛酸钡陶瓷铁电性的影响

100nm是介于微米晶和纳米晶之间的重要临界尺寸,研究了平均晶粒尺寸为100nm的钛酸钡(BTO)陶瓷的微结构和铁电性能,分析了测试温度和外加电场对纳米晶钛酸钡陶瓷铁电性的影响。与超细纳米晶BTO陶瓷不同的是,100nm BTO陶瓷主要以四方相形式存在的;介电温谱显示,正交到四方相的相变具有典型的弥散特征,低温时介电损耗<0.02。此外,铁电性能测试表明,100nm BTO陶瓷具有良好的铁电滞后特征,随着电场的增加,能量损耗密度、剩余极化强度和矫顽场均增加;随着温度的升高,陶瓷的铁电性在逐渐减弱,高于居里温度时由铁电相转为顺电相,铁电性消失。实验结果表明,100nm BTO陶瓷的铁电性与测试温度和外加电场有着密切的关系。     

退火工艺对钛酸锶钡铁电多层膜结构与物性的影响

立足于无铅型钛酸锶钡(BST)铁电多层膜的制备及物性研究.采用溶胶-凝胶方法制备了Ba0.9Sr0.1TiO3铁电多层膜,并利用快速退火炉对多层膜进行热处理.重点分析两种不同热处理工艺对钛酸锶钡多层膜微观结构及相关物理性能的影响.通过X射线衍射(XRD),扫描隧道显微镜(SEM)及可见光范围反射谱测量等的表征方法,研究钛酸锶钡铁电多层膜微观结构的演化和形成机理,为制备性能优良的钛酸锶钡铁电多层膜提供基础数据.     

Microstructure and ferroelectric properties of epitaxial BaTiO3/SrRuO3/SrTiO3 (001) films grown by pulsed laser deposition under high oxygen pressure

BaTiO₃ films were epitaxially grown on SrTiO₃ (001) substrates buffered with SrRuO₃ films as bottom electrode by pulsed laser deposition under high oxygen pressure of 30 Pa. The quality of the BaTiO₃/SrRuO₃/SrTiO₃ multilayer films was analyzed by means of X-ray diffraction, atomic force microscopy and transmission electron microscopy. BaTiO₃ films were found to be highly c-axis-oriented tetragonal phase with c/a = 1.002. The dielectric constant first increased with increasing temperature, and showed a peak at the Curie temperature of about 356 K. The films had well-saturated hysteresis loops with a remnant polarization of 7.3 μC/cm² and a coercive field of 29.5 kV/cm at room temperature.     

Thermal expansion studies on ferroelectric materials

Thermal expansion data is reported over a wide temperature range (80–800 K) for BaTiO₃ (BT) and Pb(Fe_1/2 Nb_1/2)O₃ (PFN), belonging to different classes of the ferroelectric materials. The sharp structural phase transitions of BT result in lowering of the thermal expansion coefficient (α) at the transitions which is proportional to the change in polarization at the transitions. In PFN, a relaxor ferroelectric, lowering of α is spread over a wider temperature range across the dielectric maxima.