铋层状共生化合物Bi7Ti4NbO21亚结构层Bi4Ti3O12中Nb的固溶

doi:10.3724/SP.J.1077.2013.12716

无机材料学报 ›› 2013, Vol. 28 ›› Issue (5): 561-565.DOI: 10.3724/SP.J.1077.2013.12716

铋层状共生化合物Bi₇Ti₄NbO₂₁亚结构层Bi₄Ti₃O₁₂中Nb的固溶

高翔^1,3, 王贤浩¹, 邢娟娟¹, 顾辉¹, 张发强^2,3, 李永祥²

(1.中国科学院上海硅酸盐研究所, 高性能陶瓷与超微结构国家重点实验室, 上海200050; 2. 中国科学院上海硅酸盐研究所, 信息功能材料与器件研究中心, 上海200050; 3. 中国科学院大学, 北京100039)

收稿日期:2012-11-29 出版日期:2013-05-10 网络出版日期:2013-04-22
作者简介:高翔. E-mail: g.xiang@yahoo.cn

Nb Solution within Bi₄Ti₃O₁₂ Sub-structure in the Intergrowth Bismuth-layered Compound Bi₇Ti₄NbO₂₁

GAO Xiang^1,3, WANG Xian-Hao¹, XING Juan-Juan¹, GU Hui¹, ZHANG Fa-Qiang^2,3, LI Yong-Xiang²

(1. State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; 2. The Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; 3. University of Chinese Academy of Sciences, Beijing 100039, China)

Received:2012-11-29 Published:2013-05-10 Online:2013-04-22
About author:GAO Xiang (1982–), male, candidate of PhD. E-mail: g.xiang@yahoo.cn
Supported by:
Foundation item: National Natural Science Foundation of China (50932007);National Basic Research Program of China (973 Program) (2009CB613305);Since the discovery of bismuth-layer structured ferroelectrics (BLSF) in 1949^[2], their natural superlattice structures and unique ferroelectric behaviors have attracted attentions in both fundamental researches and device applications. The BLSF compounds are generally formulated as [Bi₂O₂][Bi_m_-1B_mO₃_m₊₁], where m is the number of corner-sharing [BO₆] octahedra sheets^[3-4]. Intergrowth BLSF compounds are formed by alternative stacking of two successive layered constituents or sub-structures (m and m+1) along the common c-axis, which enable further tailoring of the ferroelectric properties^[5-10]. Intergrowth Bi₇Ti₄NbO₂₁ (iBTN, m=2+3) is one such compound derived from Bi₃TiNbO₉ (BTN, m=2) and Bi₄Ti₃O₁₂ (BiT, m=3) sub-structures^[11-13]. In general, it is taken as granted that different types of cations occupy the B-sites in the constituent sub-structures by inheriting directly from their parent phases.

摘要/Abstract

摘要：

采用常规高分辨透射电镜(HRTEM)在层状共生化合物Bi₇Ti₄NbO₂₁中可经常观察到大量生长缺陷:比如插入额外的Bi₃TiNbO₉或Bi₄Ti₃O₁₂层而产生的无序共生结构, 以及由共生相Bi₇Ti₄NbO₂₁和母相Bi₄Ti₃O₁₂在同一晶粒内形成的共相体^[1]。为了给先前提出的共生结构重组生长模型提供更充分的依据, 采用低/中分辨率下的高角环暗场像(HAADF)配合X射线能谱(EDXS)定量分析来研究共生缺陷的产生原因。观察到一种共生缺陷可以从共生相到Bi₄Ti₃O₁₂母相发生结构渐变。用空间分辨的能谱测量可以排除相邻Bi₃TiNbO₉层所带来的干扰, 其结果表明Bi₄Ti₃O₁₂层中固溶了相当含量的Nb。一定量Nb的固溶进一步表明, 在形成共生结构的过程中两种亚结构层之间发生了普遍的阳离子互换过程, 而这一过程应该通过重组模型中的部分溶解液相来实现^[1]。

关键词: 层状铁电体, 固溶, HAADF, 烧结机制

Abstract:

In intergrowth bismuth-layered compound Bi₇Ti₄NbO₂₁, growth defects, such as disordered intergrowth with extra layers of Bi₄Ti₃O₁₂ or Bi₃NbTiO₉ constituent sub-structures, or as the co-growth of Bi₇Ti₄NbO₂₁ onto Bi₄Ti₃O₁₂ grains, were frequently observed using high-resolution transmission electron microscope (HRTEM)^[1]. In order to further find evidence to support the re-ordering picture that was proposed to explain formation of the intergrowth and associated defects, we employ the low- and medium-resolution high-angle annular-dark-field (HAADF) imaging combined with the quantitative energy dispersive X-ray spectroscope (EDXS) analysis to probe into a heavily defected intergrowth structure. A gradual transformation from the ordered intergrowth of both sub-structures to the dominance of Bi₄Ti₃O₁₂ sub-structure was observed. A substantial level of Nb solution could be detected in n-layered (n≥2) Bi₄Ti₃O₁₂ sub-structure by spatially-resolved compositional quantification to differentiate the contribution from the adjacent single Bi₃NbTiO₉ layer. The presence of a finite Nb concentration in the Bi₄Ti₃O₁₂ sub-structure indicates a substantial and uniform cations inter-change occurred between the two sub-structures, which is inherited most likely from the parent phases via the partially dissolved sintering melts^[1].

Key words: layered-ferroelectrics, solubility, HAADF, sintering mechanism

中图分类号:

TQ174

高翔, 王贤浩, 邢娟娟, 顾辉, 张发强, 李永祥. 铋层状共生化合物Bi₇Ti₄NbO₂₁亚结构层Bi₄Ti₃O₁₂中Nb的固溶[J]. 无机材料学报, 2013, 28(5): 561-565.

GAO Xiang, WANG Xian-Hao, XING Juan-Juan, GU Hui, ZHANG Fa-Qiang, LI Yong-Xiang. Nb Solution within Bi₄Ti₃O₁₂ Sub-structure in the Intergrowth Bismuth-layered Compound Bi₇Ti₄NbO₂₁[J]. Journal of Inorganic Materials, 2013, 28(5): 561-565.

图/表 4

<![CDATA[Fig. 1 XRD patterns of the pre-calcined powders (bottom) and the ceramic sample of iBTN-1100 (top). Inset shows the enlarged details around the]]><![CDATA[peak of iBTN phase]]>

Fig. 2 Low-magnification HAADF image taken along the [110] zone-axis showing the distribution of constituent BTN and BiT layers in the target grain

Fig. 3 Medium-magnification HAADF images showing the stacking of BTN between different numbers of BiT layers (n) along the common [001] direction, from the standard intergrowth (n=1) in (a) to the pure BiT phase (n>10) in (d), corresponding respectively to the marked regions A, B, C and D in Fig. 2

Fig. 4 EDXS measurements for Nb solution within BiT sub-structure: (a) Spectra of typical intergrowth iBTN (n=1) and BiT (n=14) regions respectively; (b) The measured Nb:Ti ratios plotted against the number (n) of continuous (BiT)n layers

参考文献 15

[1]	Gao X, Gu H, Li Y X, et al. Structural evolution of the intergrowth bismuth-layered Bi7Ti4NbO21. Journal of Material Sciences, 2011, 46(16): 5423-5431.
[2]	Aurivillius B. Mixed bismuth oxides with layer lattices. Arkiv for Kemi, 1949, 1(1): 499-512.
[3]	Frit B, Mercurio J P. The crystal chemistry and dielectric properties of the Aurivillius family of complex bismuth oxides with perovskite-like layered structures. Journal of Alloys Compounds, 1992, 188(19): 27-35.
[4]	Park B H, Kang B S, Bu S D, et al. Lanthanum-substituted bismuth titanate for use in non-volatile memories. Nature, 1999, 401(14): 682-684.
[5]	Noguchi Y, Miyayama M, Kudo T. Ferroelectric properties of intergrowth Bi4Ti3O12-SrBi4Ti4O15 ceramics. Applied Physics Letters, 2000, 77(22): 3639-3641.
[6]	Goshima Y, Noguchi Y, Miyayama M. Dielectric and ferroelectric anisotropy of intergrowth Bi4Ti3O12-PbBi4Ti4O15 single crystals. Applied Physics Letters, 2002, 81(12): 2226-2228.
[7]	Shibuya A, Noda M, Okuyama M, et al. Natural-superlattice- structured Bi4Ti3O12-SrBi4Ti4O15 ferroelectric thin films. Applied Physics Letters, 2003, 82(5): 784-786.
[8]	Kobayashi T, Noguchi Y, Miyayama M. Polarization properties of superlattice-structured Bi4Ti3O12-BaBi4Ti4O15 single crystals and ceramics: compositions with Bi4Ti3O12 and BaBi4Ti4O15. Japan Journal of Applied Physics, 2004, 43(9B): 6653-6657.
[9]	Yi Z G, Wang Y, Li Y X, et al. Ferroelectricity in intergrowth Bi3TiNbO9-Bi4Ti3O12 ceramics. Journal of Applied Physics, 2006, 99(11): 114101-1-4.
[10]	Ikezaki M, Noguchi Y, Miyayama M. Electrical properties of superlattice-structured Bi4Ti3O12-PbBi4Ti4O15 single crystals. Journal of the American Ceramic Society, 2007, 90(9): 2814-2818.
[11]	Kikuchi T. Synthesis of new, layered bismuth titanates, Bi7Ti4NbO21 and Bi6Ti3WO18. Journal of the Less-Common Metals, 1976, 48(2): 319-323.
[12]	Horiuchi S, Kikuchi T, Goto M. Structure determination of a mixed-layer bismuth titanate, Bi7Ti4NbO21, by super-high-resolution electron microscopy. Acta Crystallographica, 1977, A33(5): 701-703.
[13]	Mercurio D, Trolliard G, Hansen T, et al. Crystal structure of the ferroelectric mixed aurivillius phase Bi7Ti4NbO21. International Journal of Inorganic Materials, 2000, 2(5): 397-406.
[14]	Chu F, Damjanovic D, Steiner O, et al. Piezoelectricity and phase transitions of the mixed-layer bismuth titanate niobate Bi7Ti4NbO21. Journal of the American Ceramic Society, 1995, 78(11): 3142-3144.
[15]	Cliff G, Lorimer G W. The quantitative analysis of thin specimens. Journal of Microscopy, 1975, 103(2): 203-207.

铋层状共生化合物Bi₇Ti₄NbO₂₁亚结构层Bi₄Ti₃O₁₂中Nb的固溶

Nb Solution within Bi₄Ti₃O₁₂ Sub-structure in the Intergrowth Bismuth-layered Compound Bi₇Ti₄NbO₂₁

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 4

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价

[1]	肖鹏, 祝玉林, 王松, 余艺平, 李浩. 超高熔点Ta_xHf_1-_xC固溶陶瓷的制备工艺与性能研究进展[J]. 无机材料学报, 2021, 36(7): 685-694.
[2]	孙娅楠, 叶丽, 赵文英, 陈凤华, 邱文丰, 韩伟健, 刘伟, 赵彤. 液相聚合物前驱体法制备高熵碳化物纳米粉体[J]. 无机材料学报, 2021, 36(4): 393-398.
[3]	张霄, 李友兵, 陈科, 丁浩明, 陈露, 李勉, 史蓉蓉, 柴之芳, 黄庆. M位与A位双固溶MAX相的磁学性能研究[J]. 无机材料学报, 2021, 36(12): 1247-1255.
[4]	周星圆, 柳伟, 张程, 华富强, 张敏, 苏贤礼, 唐新峰. Nb掺杂Mo_1-_xW_xSeTe固溶体的热-电输运性能优化[J]. 无机材料学报, 2020, 35(12): 1373-1379.
[5]	邹灿辉, 龙莹, 郑鑫, 张锦阳, 林华泰. 三元过渡金属硼化物Os_1-_xRu_xB₂的制备及其结构和性能研究[J]. 无机材料学报, 2018, 33(7): 787-792.
[6]	聂文波, 肖其昌, 王京亮, 雷钢铁, 肖启振, 李朝晖. Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅核壳复合材料的制备及其电化学性能[J]. 无机材料学报, 2014, 29(3): 257-263.
[7]	张国芳, 张羊换, 刘卓承, 许剑轶, 张胤. CeO₂基固溶体对Mg₂Ni合金储氢动力学性能的影响研究[J]. 无机材料学报, 2014, 29(12): 1241-1245.
[8]	宋继梅, 胡海琴, 王秀芝, 赵绍娟, 师亚利, 任明松. Bi₂Mo_xW_1-xO₆固溶体的水热合成、表征及光催化性能[J]. 无机材料学报, 2013, 28(12): 1275-1280.
[9]	张茜, 刘伟伟, 方国清, 夏丙波, 孙洪丹, 金子信悟, 杨裕生, 郑军伟, 李德成. 喷雾干燥法制备Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂的结构与电化学性能[J]. 无机材料学报, 2013, 28(06): 616-622.
[10]	石维, 冷森林, 龙禹, 朱建国, 肖定全. BiYbO₃固溶极限对BSPT压电陶瓷结构和电学性能的影响[J]. 无机材料学报, 2013, 28(06): 623-628.
[11]	王艳芝, 赵敏寿. Ti-V基固溶体/AB₅型镧镁基合金复合储氢材料的结构与电化学性能[J]. 无机材料学报, 2012, 27(5): 463-468.
[12]	陈云霞, 胡琪, 曹春娥, 卢希龙, 洪琛, 沈华荣. Zn²⁺、Cr³⁺掺杂对水热合成纳米CoAl₂O₄尖晶石色料的影响[J]. 无机材料学报, 2012, 27(12): 1317-1320.
[13]	姚春发, 李财富, 刘志权, 尚建库. (1-x)Pb(Fe_2/3W_1/3)O₃-xPb(Mg_1/2W_1/2)O₃多铁性材料的有序结构及磁性能[J]. 无机材料学报, 2011, 26(6): 649-654.
[14]	那文菊, 丁士华, 宋天秀, 王久石, 王岩. (Ba_1-xCa_x)(Ti_0.82Zr_0.18)O₃陶瓷结构与介电性能研究[J]. 无机材料学报, 2011, 26(6): 655-658.
[15]	杨修春,卢振光,康晓春,韦亚南. ZrO₂对NiO/CeO₂/γ-Al₂O₃复合催化剂结构的影响[J]. 无机材料学报, 2009, 24(1): 187-191.