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

doi:10.3724/SP.J.1077.2013.12716

Journal of Inorganic Materials ›› 2013, Vol. 28 ›› Issue (5): 561-565.DOI: 10.3724/SP.J.1077.2013.12716

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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.

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 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

References 15

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

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