Ferroelectric Characteristics of Bi 4−x La x Ti 3 O 12 Thin Films Crystallized at Low Temperetures

Recently, Bi 4 m x La x Ti 3 O 12 (BLT) has received much attention because it enables low crystallization temperature with a large remanent polarization. BLT films were prepared using a metal organic decomposition technique followed by a rapid thermal annealing (RTA) and a furnace annealing. The annealing of BLT was performed in the temperature range from 550 to 700C. In particular, BLT film annealed at 600C using the RTA tool and the furnace shows good ferroelectric characteristics. The BLT film annealed at 600C exhibits a large value of remanent polarization (22 w C/cm 2 at 250kV/cm), and a low leakage current density (7 2 10 m 7 A/cm 2 at 250kV/cm), a good endurance characteristics for up to 3.2 2 10 11 cycles at 250kV/cm at 85C. From an accelerated imprint test, the lifetime of hysteresis integrity is estimated to be over 10 years at 85C. In conclusion, BLT is the one of the promising material to achieve the high density FeRAMs.     

Dielectric Properties of Bi4−x La x Ti3O12 (0 ≤ x ≤ 2) Ceramics

The dielectric properties of the Bi_4–x La _x Ti₃O₁₂ (0 x 2) ceramics were characterized and discussed together with the P-E relation (polarization vs. electric field). With increasing x, the P-E relation changed from normal ferroelectric hysteresis loops to pure linear relation, which indicated that La³⁺ substitution for Bi³⁺ in Bi₄Ti₃O₁₂ induced a phase transition from ferroelectric to paraelectric state at ambient temperature. Low loss dielectric ceramics with temperature stable dielectric constant were obtained for x > 1.2 in Bi_4–x La _x Ti₃O₁₂ at 1 MHz. And the loss increased in all the compositions when the ceramics were measured at microwave frequencies.     

Preparation and Properties of Bi4 − x Nd x Ti3O12 Thin Films by Chemical Solution Deposition

Neodymium-modified Bi₄Ti₃O₁₂, (Bi, Nd)₄Ti₃O₁₂ (BNT) ferroelectric thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates using metal-organic precursor solutions by the chemical solution deposition method. The BNT precursor films crystallized into the Bi layered perovskite Bi₄Ti₃O₁₂ (BIT) as a single-phase above 600C. The synthesized BNT films revealed a random orientation having a strong 117 reflection, whereas non-substituted BIT thin films exhibited a random orientation with strong 00l diffractions. Among Bi_{4 – x}Nd_xTi₃O₁₂ [x = 0.0, 0.5, 0.75, 1.0] thin films, Bi_3.25Nd_0.75Ti₃O₁₂ thin films showed a well-saturated P-E hysteresis loop with the highest P_r (22 C/cm²) and a low E_c (69 kV/cm) at an applied voltage of 5 V. The Nd-substitution with the optimum amount for the Bi site in the BIT structure was effective not only for promoting the 117 preferred orientation but also for improving the microstructure and ferroelectric properties of the resultant films.     

Chemical Vapor Deposition of Ru Bottom Electrode for Ferroelectric Bi4 − x La x Ti3O12 Capacitors

Ruthenium films formed by metalorganic chemical vapor deposition were investigated, taking account of the application to the bottom electrode of ferroelectric capacitors. Ruthenium films were deposited using a liquid-type source of Ru[EtCp]₂ in a cold-wall type reactor with infrared lamps. A smooth and flat Ru film was successfully formed on a SiO₂-covered Si substrate without a seed layer. As the deposition temperature increased to 400°C, the crystallinity of the Ru film improved and the film exhibited high c-axis orientation. After forming a Bi_{4 ? x} La _x Ti₃O₁₂ (BLT) film by a sol-gel technique, a Pt/BLT/Ru capacitor was fabricated on the Ru film. Good hysteresis loops with 2P _r = 20 μC/cm² and 2V _c = 3.4 V were successfully obtained and the ferroelectric property did not depend on the deposition temperature of Ru in the temperature range from 325°C to 400°C. On the contrary, the leakage current density was significantly suppressed down to 1/100 as the deposition temperature of Ru increased from 325°C to 400°C.     

Bi4Ti3O12铁电薄膜的制备及研究进展

铁电薄膜具有良好的铁电、介电性能,在非挥发存储器件方面有很好的应用前景.本文介绍了钛酸铋(Bi4Ti3O12)铁电薄膜的研究现状,对目前Bi4Ti3O12铁电薄膜最常用的几种主要制备方法及其掺杂改性进行了评述,指出了Bi4Ti3O12铁电薄膜研究中亟待解决的几个问题.     

Temperature-Stable High-ε Dielectrics Ceramics Based on (1 − x) Ba5NdTi3Ta7O30/xBi4Ti3O12

Modification of Ba₅NdTi₃Ta₇O₃₀ dielectric ceramics was investigated through introducing Bi₄Ti₃O₁₂. With increasing of Bi₄Ti₃O₁₂ content, the dielectric constant increased, and the temperature coefficient of the dielectric constant changed from negative to positive. The small temperature coefficient ( < 50 ppm/°C) combined with high dielectric constant ( = 178) and low dielectric loss (tan = 0.007 at 1 MHz) was achieved in the composition x = 0.6.     

电极材料Li4Ti5O12的研究进展

分析了尖晶石型钛酸锂(Li4Ti5O12)的晶体结构;介绍了提高Li4Ti5O12的电子电导率及改善其工作电压所进行的研究,如Li4Ti5O12掺杂后的特性、电化学应用及材料的制备;总结了Li4Ti5O12在锂离子电池和不对称超级电容器中的应用情况.     

Structure and dielectric properties of Bi5−x La x Nb3O15 ceramics

Bi_5?x La _x Nb₃O₁₅ (x?=?0–?1.25) ceramics prepared by conventional solid-state reaction were studied using X-ray diffraction (XRD), electron probe microanalysis (EPMA) and dielectric spectroscopy techniques. The XRD analysis indicated single phase solid solution of Bi_5?x La _x Nb₃O₁₅ is formed for x?≤?1.25. EPMA showed good densification and homogeneous microstructures for the ceramics. With increasing x, the dielectric constant decreases monotonously and can vary from 258 to 158 at 300 kHz. The frequency dependence of dielectric constants indicated these ceramics are promising candidates for high frequency applications.     

Effect of B2O3 Nano-Coating on the Sintering Behaviors and Electrical Microwave Properties of Ba(Nd2 − x Sm x )Ti4O12 Ceramics

Ba(Nd_0.8Sm_0.2)₂Ti₄O₁₂ ceramics prepared by conventional solid-state sintering have a dielectric constant of about 80 and a nearly zero temperature coefficient of resonant frequency; however, the sintering temperature is above 1350_C. Doping with B₂O₃ (up to 5 wt%) promotes the densification and dielectric properties of BNST ceramics. It is found that coating BNST powder with thin B₂O₃ layer of about 180 nm reduces the sintering temperature to below 1020_C. The effects of B₂O₃ nano-coating on the dielectric microwave properties and the microstructures of BNST ceramics are investigated. Ninety-six percent of theoretical densities is obtained for specimens coated with 2 wt% B₂O₃ sintered at 960_C and the samples exhibit significant (002) preferred orientation and columnar structure.     

Sb2O3对锂离子负极材料Li4Ti5O12电化学性能的影响

采用喷雾干燥法制备尖晶石Li_4Ti_5O_(12)。将所得Li_4Ti_5O_(12)与纳米Sb_2O_3混合后高能球磨得到Sb_2O_3掺杂的Li_4Ti_5O_(12)。经X射线衍射(XRD)测试,结果表明Sb_2O_3未进入Li_4Ti_5O_(12)尖晶石结构。经扫描电子显微镜(SEM)测试,结果表明高能球磨法使颗粒更小、更分散。采用充放电测试、循环伏安法和交流阻抗测试研究了Sb_2O_3对Li_4Ti_5O_(12)电化学性能的影响。研究结果表明,Sb_2O_3的掺杂能提高Li_4Ti_5O_(12)的电化学性能。在15 C的高电流密度下,循环10次后其放电比容量仍保持在113.7 mAh/g,远高于未掺杂的Li_4Ti_5O_(12)电极放电比容量(62.7 mAh/g)。交流阻抗测试结果表明,Sb_2O_3/Li_4Ti_5O_(12)电极的电化学性能改善的主要原因是其R_(CT)值较小。     

Li4Ti5O12的合成及其性能研究

用固相法制备了尖晶石Li4Ti5O12,用X射线衍射(XRD)对样品进行了表征.采用恒电流充放电、循环伏安法(CV)、电化学交流阻抗频谱(EIS)技术对Li4Ti5O12体系进行电化学性能测试.首次放电比容量达到163.1 mAh/g,库仑效率达97.5%.经过60次充放电循环之后,容量衰减仅为4.4%.结果表明,Li4Ti5O12是一种循环性能优良的锂离子蓄电池负极材料,可改善锂离子蓄电池的安全和循环性能.     

Li4Ti5O12负极材料合成研究进展

综述了近年来锂离子电池用Li4Ti5O12负极材料的合成方法的研究现状,重点对高温固相法和溶胶-凝胶法进行了总结和探讨,并对Li4Ti5O12负极材料的发展前景进行了展望.     

C改性Li4Ti5O12的性能研究

采用固相法制备了C改性的Li4Ti5O12.用X射线衍射法(XRD)、扫描电子显微镜(SEM)表征了材料的结构和形貌特征.用循环伏安、电化学阻抗和恒流充放电研究了材料的电化学性能.结果显示,C的加入抑制了颗粒的增大,材料晶胞产生了收缩,首次放电比容量为107.93 mAh·g-1,循环100次后容量衰减仅为3.01%.电化学阻抗表明,C的加入减小了Warburg扩散阻抗.     

Li4Ti5O12的合成及性能研究

采用固相反应合成出锂离子电池负极材料Li_4Ti_5O_(12)。考察了两种原料混合方法以及掺杂石墨对产品性能的影响。对产品进行了XRD(X射线衍射)、SEM(扫描电子显微镜)及电化学性能测试研究。结果表明,球磨混合原料的方法制备出的Li4Ti5O12颗粒更均匀,具有更好的电化学性能;掺杂石墨后,产品的大电流充放电性能得到改善。     

负极复合材料Li4Ti5O12-Li3VO4/C的制备及性能

采用高温固相法制备Li4 Ti5 O12-Li3 VO4/C复合材料,利用XRD、SEM和电化学性能测试,分析样品的结构、形貌和性能.复合5％的Li3 VO4和引入少量的碳,均未改变Li4 Ti5 O12的尖晶石结构,但柠檬酸高温分解产生的CO2会造成复合材料中TiO2的残留.有机碳源柠檬酸热解产生部分还原性气体,造成复合材料含有氧空位,导致晶胞参数减小.碳的引入加剧了Li4 Ti5 O12与Li3 VO4的复合,降低了复合材料的扩散阻抗,提高了导电性,使Li3 VO4在小电流充放电时提供的容量较多.在1.0～2.2 V循环,Li4 Ti5 O12-Li3 VO4/C的0.2 C、10.0 C放电比容量分别为205.1 mAh/g、105.2 mAh/g.     

Low-temperature sintering and dielectric properties of the Bi(Nb1−x Ta x )O4 system

Low-temperature sintering and dielectric properties of the Bi(Nb_1?x Ta _x )O₄ (x?=?0.1, 0.3, and 0.5) system was investigated as a function of the zinc borosilicate (ZBS) glass content with a view to applying this system to LTCC technology. The addition of 7 wt% ZBS glass ensured a successful sintering below 900°C. The complete solid solution of Bi(Nb, Ta)O₄ with an orthorhombic structure was formed and the high temperature form of Bi(Nb, Ta)O₄ with a triclinic structure was not observed. The second phase of Bi₂SiO₅ was observed for all compositions. The non-relative liquid phase sintering (NLPS) occurred and the one-stage sintering was conducted. The Q?×?f values were improved by the addition of Ta. Bi(Nb_0.7Ta_0.3)O₄ with 7 wt% ZBS glass sintered at 900°C demonstrated 35.8 in the dielectric constant (? _r), 2,200 GHz in the quality factor (Q?×?f ₀), and ?48 ppm/°C in the temperature coefficient of resonant frequency (τ _f).     

Raman Scattering Study of the Pb(Hf x Ti1−x )O3 Ceramics

Raman spectroscopy was used to study the long wavelength vibrations of tetragonal perovskite (space group P4mm) Pb(Hf_xTi_1–x)O₃ (PHT) (0.10 x 0.50) samples at room temperature and at 20 K. For x 0.40, Raman spectra collected from the PHT samples were very similar to the previous spectra collected from the PZT samples with the same value of x, except the mode at around 190 cm^–1, whose frequency was decreasing with increasing x in PHT ceramics. Correspondingly, the latter feature was taken as a sign of the mass effect (Hf versus Zr) while the similarity of the remaining parts of the Raman spectra was assumed to be due to the almost identical ionic radii difference between Ti⁴⁺ and Zr⁴⁺ and between Ti⁴⁺ and Hf⁴⁺ ionic radii. The behaviour of the mode at around 280 cm^–1 revealed that a phase transition occurred once x was changing from 0.40 to 0.50.     

纳米Li4Ti5O12的合成及其电化学性能

采用溶胶-凝胶法合成了Li4Ti5O12纳米材料,研究了不同Li/Ti摩尔比、煅烧温度以及保温时间对材料结构及性能的影响.采用XRD、SEM以及恒流充放电测试对材料的结晶度、表面形貌以及电化学性能进行了表征.研究表明,锂钛摩尔比为1 800℃下保温10h后制备的产物具有单一的尖晶石结构,颗粒大小均一且电化学性能优良.在...     

改善Li4Ti5O12倍率性能的研究进展

综述了提高Li4Ti5O12倍率性能的主要途径以及研究进展,并对今后的发展方向进行了展望.改性的有效途径主要有:溶胶-凝胶法合成纳米Li4Ti5O12提高离子导电能力;对Li4Ti5O12进行离子掺杂,提高电子导电能力;向Li4Ti5O12中引入高电子导电相(如金属,碳等),提高表面电子导电能力.