Preparation of Strontium Titanate Thin Film on Titanium Metal Substrate by Hydrothermal-Electrochemical Method

Polycrystalline SrTiO₃ thin films have been prepared on Timetal substrates by the hydrothermal-electrochemical method. The films were prepared at temperatures ranging from 100° to 200°C and under saturated vapor pressures in electrolytic solutions of 1 N to 5 N Sr(OH)₂. A galvanostat was used to apply a direct current of 5 to 25 mA/cm². The films had smooth and homogeneous surfaces without any visible pores or defects. The dielectric constant of the films was approximately 129 assuming 25 nm for film thickness.     

Hydrothermal Synthesis of Thin Films of Barium Titanate Ceramic Nano-Tubes at 200°C

A novel, low-temperature synthesis method for producing BaTiO₃ thin films patterned in the form of nano-tubes ("honeycomb") on Ti substrates is reported. In this two-step method, the Ti substrate is first anodized to produce a surface layer (∼200–300-nm thickness) of amorphous titanium oxide nano-tube (∼100-nm diameter) arrays. In the second step, the anodized substrate is subjected to hydrothermal treatment in aqueous Ba(OH)₂, where the nano-tube arrays serve as templates for their hydrothermal conversion to polycrystalline BaTiO₃ nano-tubes. This opens the possibility of tailoring the nano-tube arrays and of using various precursor solutions and their combinations in the hydrothermal bath, to produce ordered, patterned thin-film structures of various Ti-containing ceramics. These could find use not only in a variety of electronic device applications but also in biomedical applications, where patterned thin films are also desirable.     

Hydrothermal Synthesis of Tetragonal Barium Titanate from Barium Chloride and Titanium Tetrachloride under Moderate Conditions

Tetragonal BaTiO₃powders were prepared hydrothermally at 240°C, in only 12 h, using BaCl₂·2H₂O and TiCl₄, which are rather easy to manipulate. Characterization via X-ray diffractometry, scanning electron microscopy, Brunauer–Emmett–Teller analysis, and differential scanning calorimetry confirmed that increasing the NaOH excess concentration (from 0.5 M to 2.0 M ) and decreasing the initial TiCl₄concentration (from 0.625 M to 0.15 M ) promotes the formation of tetragonal BaTiO₃powders. After reaction, the powders were proved to be phase-pure BaTiO₃, with no impurities, such as Cl⁻ and CO₃²⁻.     

Preparation of a Monodispersed Suspension of Barium Titanate Nanoparticles and Electrophoretic Deposition of Thin Films

A transparent and stable monodispersed suspension of nanocrystalline barium titanate was prepared by dispersing a piece of BaTiO₃ gel into a mixed solvent of 2-methoxyethanol and acethylacetone. The results of high-resolution transmission electron microscopy (HR-TEM) and size analyzer confirmed that the BaTiO₃ nanoparticles in the suspension had an average size of ∼10 nm with a narrow size distribution. Crystal structure characterization via TEM and X-ray diffraction indicated BaTiO₃ nanocrystallites to be a perovskite cubic phase. BaTiO₃ thin films of controlled thickness from 100 nm to several micrometers were electrophoretic deposited compactly on Pt/Ti/SiO₂/Si substrates. The deposited thin film had uniform nanostructure with a very smooth surface.     

Ruddlesden–Popper Planar Faults and Nanotwins in Heteroepitaxial Nonstoichiometric Barium Titanate Thin Films

Nonstoichiometric 10-mol%-excess-BaO–BaTiO₃ (Ba_1.1TiO_3.1) thin film grown on a (100) SrTiO₃ substrate consisted of heteroepitaxial c -axis-oriented BaTiO₃ perovskite crystals including Ruddlesden–Popper planar faults and nanometer-scale multiple (111) twin lamellae. High-resolution electron microscopy and electron energy-loss spectroscopy revealed that nanotwins with coherent (111) Σ3 coincident site lattice boundaries were terminated in the BaTiO₃ matrix to form incoherent (211) Σ3 boundaries accommodating excess barium ions. Both Ruddlesden–Popper planar fault and incoherent (211) boundary formation were proposed as possible accommodation mechanisms of excess barium ions in the perovskite film.     

Self-Mending of Microcracks in Barium Titanate Glass-Ceramic Thin Films with High Dielectric Constant

BaTiO₃ glass-ceramic thin films were deposited on silicon substrates by the sol–gel method. The films exhibited a mixed structure of glass phase and BaTiO₃ grains tens of nanometers in diameter, and had a high dielectric constant, low leakage current, and dielectric loss. An interesting self-mending phenomenon for microcracks due to the fluidity of the glass phase during the annealing process was observed in the films. The effects of the existence of the self-mended microcracks on electrical properties were evaluated. Our experimental results indicate the potential value of BaTiO₃ glass-ceramic thin films for integrated high-dielectric-constant media.     

Effect of Precursor Pyrolysis on the Dielectric Properties of Hydrothermally Derived Barium Titanate Thin Films

BaTiO₃ thin films were processed hydrothermally on Ag-coated quartz substrates at 90°C by reacting films of titanium dimethoxy dineodecanoate (TDD) in aqueous solutions of Ba(OH)₂. Two reaction sequences were used: either the TDD was reacted directly in aqueous Ba(OH)₂, or the TDD was first pyrolyzed in air at temperatures ranging from 200° to 500°C before hydrothermal reaction. Depending on the processing conditions, the dielectric constant of the thin films ranged from 5 to 170, the dielectric constant increasing with increasing pyrolysis temperature. Thin film porosimetry data suggest that the improvement in film dielectric performance is related to decreases in thin film residual porosity after hydrothermal reaction.     

BaTiO3粉体的水热法合成

本文阐述了水热合成粉体的一般原理及其与其它方法相比的特点。讨论了水热合成BaTiO3粉体的基本机理（包括原位转变机理和溶解－沉淀机理）、影响因素和存在的一些问题。     

水热法制备钕掺杂BaTiO3粉体及其介电性能研究

以BaCl2·2H2O、TiCl4和NdCl3为原料,采用水热法制备了掺钕的BaTiO3纳米粉体,并经高温烧结后得到瓷体。利用DTA、XRD、SEM等测试手段,分析了钕掺杂对钛酸钡粉体及其陶瓷电性能的影响。研究表明,掺杂后,钕固溶到了钛酸钡的晶格中并取代钡位或钛位。钕的掺杂有助于获得细晶高致密的陶瓷,当W(NdCl3)%为0.6时,致密度最高,常温下相对介电常数高达5650,击穿场强达到3.5kV/mm。     

微波水热法合成Mn掺杂BaTiO_3纳米粉体

以Ti(OC_4H_9)_4 、Ba(NO_3)_2 和C_4H_6MnO_4·4H_2O为原料,采用微波水热法合成了Mn掺杂的BaTiO_3纳米粉体.通过X射线衍射(XRD)和扫描电子显微镜(SEM)对产物进行了表征.并研究了影响Mn掺杂BaTiO_3晶体生长和形貌的主要影响因素.实验结果表明:掺杂量为1.0%,反应时间为30 min,烘箱干燥温度为82 ℃,能制备出单一的粒径均匀的掺Mn的BaTiO_3纳米粉体,且粉体的粒径尺寸约为100 nm.     

钛酸锶钡结构与制备工艺研究进展

钛酸锶钡[(Ba,Sr)TiO3,SBT]是1种重要的电子陶瓷材料,具有高介电常数、低漏电流、高热释电系数,高的介电可调等特性,广泛用于动态随机存储器、热释电探测器、介质移相器等电子元件的制备。综述了钛酸锶钡[(Ba,Sr)TiO3,SBT]的结构和制备工艺研究进展,评述了制备工艺和掺杂等对钛酸锶钡的结构和性能的影响,并指出了钛酸锶钡尚待解决的问题。     

Tetragonal Nanocrystalline Barium Titanate Powder: Preparation, Characterization, and Dielectric Properties

Nanocrystalline tetragonal-BaTiO₃ powder was prepared using a hydrothermal method, under moderate conditions, and with a high precursor concentration. Characterization via X-ray diffractometry and differential scanning calorimetry confirmed that the average particle size and tetragonal content of the prepared powder were 70 nm and 80%, respectively. The sintered sample made from the prepared powder had a room-temperature dielectric constant of 6900, which was high for BaTiO₃.     

一步水热法制备钛酸锂材料

采用一步水热法制备钛酸锂材料,并对制备的钛酸锂的性能进行研究。该方法与传统的水热合成法相比,具有制备工艺周期缩短,无其它试剂使用,减少环境污染等优点。结果表明,该方法制备的钛酸锂材料,在0.1 C倍率下的首次放电比容量为163 mAh·g^-1,首次效率为100%;XRD分析表明,其晶型结构与标准的钛酸锂图谱一致;SEM表征显示其颗粒形貌规则、分布均匀;循环伏安法测试表明,其具有良好的充放电可逆性能。     

Defect Chemistry and Microstructure of Hydrothermal Barium Titanate

Hydrothermal powders of BaTiO₃ and (Ba,Ca)(Ti,Zr)O₃ contain large amounts of protons in the oxygen sublattice. The proton defects are compensated by vacancies on metal sites. When the powder is annealed, water is released and the point defects disappear in the temperature range of 100°–600°C. Metal and oxygen vacancies combine to small nanometer-sized intragranular pores. At temperatures of >800°C, the intragranular pores migrate to the grain boundaries and disappear. In multilayer ceramic capacitors that have been prepared from hydrothermal powders, the intragranular pores are preferentially collected at the inner electrodes, which results in bloating, cracks, and delamination.     

微波辅助草酸盐沉淀法合成钛酸钡纳米粉体的分散性研究

本文采用微波辅助草酸盐沉淀法在微波条件为80℃,30 min和煅烧条件为700℃,1h的工艺参数下制备了四方相钛酸钡纳米粉体.用X射线衍射仪和透射电子显微镜研究了分散剂种类及用量对钛酸钡纳米粉体的相组成与微观形貌的影响,探讨了其分散机理.结果表明,有着不同分散机理的阳离子分散剂三乙醇胺和非离子分散剂OP-10都能使纳米粉体具有良好的分散效果.当分散剂添加量为3％ ～5％时,分散效果最明显.     

Preparation of Lead Zirconate Titanate Thin Films Derived by Hybrid Processing: Sol-Gel Method and Laser Ablation

Thin films of Pb(Zr_0.52Ti_0.48)O₃ (PZT) were prepared by hybrid processing (sol-gel and excimer laser ablation) on Pt/Ti/SiO₂/Si substrates. Crystalline phases and microstructures of the PZT films were investigated by X-ray diffraction analysis and scanning electron microscopy, respectively. Electrical properties of the films were evaluated by measuring their P - E hysteresis loops and dielectric constants. The temperature of postdeposition annealing in hybrid processing was lower than that in the case of direct film deposition by laser ablation on a Pt/Ti/SiO₂/Si substrate. The preferred orientation of the films derived by hybrid processing could be controlled using the seeding layer deposited by the sol-gel process. The films fabricated by hybrid processing consisted of the perovskite phase with a (111) preferred orientation and had good ferroelectric properties.     

Preparation and Characterization of Barium Titanate Suspensions for Stereolithography

Ferroelectric photoactive suspensions for stereolithography have been developed by dispersing a high volume fraction of barium titanate powder in hexanediol diacrylate (HDDA) with the aid of effective photoinitiators and dispersants. Rheological properties showed a shear thinning behavior and a low viscosity at a shear rate adequate for the recoating process. The barium titanate–HDDA suspension showed poor curing behavior due to the large refractive index difference between the ceramic and the resin. The coarse barium titanate–HDDA suspension showed a smaller surface reflectance and a larger cure depth than the fine barium titanate–HDDA suspension.     

Preparation of Highly Dispersed Ultrafine Barium Titanate Powder by Using Microbial-Derived Surfactant

To uniformly disperse ultrafine BaTiO₃ particles with a stoichiometric composition and several tens of nanometers in diameter to primary particles during the sol–gel synthesis process, a new aqueous surfactant with a high hydrophilic group density and special cis-structure was prepared from a microbial product and added to solution before the sol–gel synthesis reaction. Because of the rapid formation of large and porous aggregates which were 30–50 μm in diameter in suspension without addition of this unique structural surfactant, the prepared ultrafine BaTiO₃ particles caused rapid sedimentation in suspension. The addition of the surfactant in the range of 7.1 wt% for the synthesized BaTiO₃ particles made it possible to decrease the size of the aggregates in suspension as well as the sedimentation velocity while maintaining the stoichiometric composition. The optimum additive content to obtain the minimum aggregate size of about 100–200 nm in diameter and the highest dispersion stability in suspension while maintaining the stoichiometric composition of prepared ultrafine BaTiO₃ particles without other phases was determined at about 7.1 wt%. Because the excess addition of this surfactant at more than 8.5 wt% inhibited the uniform synthesis of BaTiO₃ particles, an amorphous phase with a highly specific surface area and a BaCO₃ phase formed in the synthesized particles.     

Preparation of a Barium Titanate Thin Film on a Porous Titanium Body by the Hydrothermal-Electrochemical Method

The electrolysis profile of the hydrothermal-electrochemical method that was used to grow BaTiO₃ thin films uniformly on porous titanium bodies 5.0 mm in diameter and 1.0-2.5 mm thick, with 32.7 vol% porosity, in an aqueous solution of Ba(OH)₂ at 150°C, was investigated. The thin films could be grown only in a surface region that was limited to a depth of lessthan equal to0.25 mm into the porous titanium body via a "single-step" electrolysis, in which an anodic potential was applied continuously to the porous titanium body. In contrast, the thin films could be grown uniformly on the entire surface of the porous titanium body using a "cyclic" electrolysis, in which an anodic potential and a rest potential were applied alternately. The BaTiO₃ film growth inside the porous titanium body is considered to be dominated by the local solution pH.     

Effects of Excess Barium Ions on Aqueous Barium Titanate Tape Properties

The effects of excess free barium ions in aqueous barium titanate slip on the resulting BaTiO₃ tape properties were investigated in terms of the slip behavior, green/sintered tape density and morphology, and dielectric properties. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. Increase in the slip viscosity, green porosity, and agglomeration along with a decrease in mechanical properties and green/sintered density were found with the increase in the Ba/Ti ratio. However, dielectric permittivity was increased with increase in the Ba/Ti ratio. An effort was made to correlate these phenomena with Ba²⁺ leaching in water for realistic multilayer ceramic capacitor applications.