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Title: New substitutions and novel derivatives of the Aurivillius phases, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}

Abstract

We investigated isomorphous substitution of several metal atoms in the Aurivillius structures, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}, in an effort to understand structure-property correlations. Our investigations have led to the synthesis of new derivatives, Bi{sub 4}LnTiMWO{sub 15} (Ln = La, Pr; M = Nb, Ta), as well as Bi{sub 4}PbNb{sub 2}WO{sub 15} and Bi{sub 3}LaPbNb{sub 2}WO{sub 15}, that largely retain the Aurivillius (n = 1) + (n = 2) intergrowth structure of the parent oxide Bi{sub 5}TiNbWO{sub 15}, but characteristically tend toward a centrosymmetric/tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2Ti{sup IV} {sup {yields}} M{sup V} + Fe{sup III} in Bi{sub 4}Ti{sub 3}O{sub 12}, yields new Aurivillius phases, Bi{sub 4}Ti{sub 3-2x}Nb {sub x}Fe {sub x}O{sub 12} (x = 0.25, 0.50) and Bi{sub 4}Ti{sub 3-2x}Ta {sub x}Fe {sub x}O{sub 12} (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi{sub 4}Ti{sub 3}O{sub 12}. Two new members of this family, Bi{sub 2}Sr{sub 2}Nb{sub 2}RuO{sub 12} and Bi{sub 2}SrNaNb{sub 2}RuO{sub 12} that are analogous to Bi{sub 2}Sr{sub 2}Nb{sub 2}TiO{sub 12}, possessing tetragonal (I4/mmm) Aurivillius structure have also been synthesized.

Authors:
 [1];  [1];  [2]
  1. Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India)
  2. Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India). E-mail: gopal@sscu.iisc.ernet.in
Publication Date:
OSTI Identifier:
21000641
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 42; Journal Issue: 5; Other Information: DOI: 10.1016/j.materresbull.2006.08.009; PII: S0025-5408(06)00329-1; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CHEMICAL PREPARATION; METALS; OPTICAL PROPERTIES; ORTHORHOMBIC LATTICES; OXIDES; TETRAGONAL LATTICES; X-RAY DIFFRACTION

Citation Formats

Tripathy, Mamata, Mani, Rohini, and Gopalakrishnan, J. New substitutions and novel derivatives of the Aurivillius phases, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}. United States: N. p., 2007. Web. doi:10.1016/j.materresbull.2006.08.009.
Tripathy, Mamata, Mani, Rohini, & Gopalakrishnan, J. New substitutions and novel derivatives of the Aurivillius phases, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}. United States. doi:10.1016/j.materresbull.2006.08.009.
Tripathy, Mamata, Mani, Rohini, and Gopalakrishnan, J. Thu . "New substitutions and novel derivatives of the Aurivillius phases, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}". United States. doi:10.1016/j.materresbull.2006.08.009.
@article{osti_21000641,
title = {New substitutions and novel derivatives of the Aurivillius phases, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}},
author = {Tripathy, Mamata and Mani, Rohini and Gopalakrishnan, J.},
abstractNote = {We investigated isomorphous substitution of several metal atoms in the Aurivillius structures, Bi{sub 5}TiNbWO{sub 15} and Bi{sub 4}Ti{sub 3}O{sub 12}, in an effort to understand structure-property correlations. Our investigations have led to the synthesis of new derivatives, Bi{sub 4}LnTiMWO{sub 15} (Ln = La, Pr; M = Nb, Ta), as well as Bi{sub 4}PbNb{sub 2}WO{sub 15} and Bi{sub 3}LaPbNb{sub 2}WO{sub 15}, that largely retain the Aurivillius (n = 1) + (n = 2) intergrowth structure of the parent oxide Bi{sub 5}TiNbWO{sub 15}, but characteristically tend toward a centrosymmetric/tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2Ti{sup IV} {sup {yields}} M{sup V} + Fe{sup III} in Bi{sub 4}Ti{sub 3}O{sub 12}, yields new Aurivillius phases, Bi{sub 4}Ti{sub 3-2x}Nb {sub x}Fe {sub x}O{sub 12} (x = 0.25, 0.50) and Bi{sub 4}Ti{sub 3-2x}Ta {sub x}Fe {sub x}O{sub 12} (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi{sub 4}Ti{sub 3}O{sub 12}. Two new members of this family, Bi{sub 2}Sr{sub 2}Nb{sub 2}RuO{sub 12} and Bi{sub 2}SrNaNb{sub 2}RuO{sub 12} that are analogous to Bi{sub 2}Sr{sub 2}Nb{sub 2}TiO{sub 12}, possessing tetragonal (I4/mmm) Aurivillius structure have also been synthesized.},
doi = {10.1016/j.materresbull.2006.08.009},
journal = {Materials Research Bulletin},
number = 5,
volume = 42,
place = {United States},
year = {Thu May 03 00:00:00 EDT 2007},
month = {Thu May 03 00:00:00 EDT 2007}
}
  • The ferroelectric layered Bi{sub 5}Ti{sub 3}FeO{sub 15} and LaBi{sub 4}Ti{sub 3}FeO{sub 15} Aurivillius phases were synthesized in high purity and textured microstructures in a molten Na{sub 2}SO{sub 4}/K{sub 2}SO{sub 4} (1:1 molar ratio) flux in much shortened reaction times, 1 h minimum compared to conventional techniques. The particle growth and microstructure of both phases were investigated as a function of temperature and reaction duration, and yielded plate-like particles that could be synthesized in sizes from <1 {mu}m to >20 {mu}m. The product crystallinity, purity and microstructures were characterized via powder X-ray diffraction and scanning electron microscopy. The UV-vis diffuse reflectancemore » of the products were measured and analyzed with respect to the resultant particle sizes.« less
  • We describe the synthesis and characterization of new intergrowth Aurivillius related phases, Bi{sub 4}LnNb{sub 3}O{sub 15} (Ln = La, Pr, Nd) and Bi{sub 4}LaTa{sub 3}O{sub 15}. Both powder X-ray diffraction and electron microscopy investigations show that the compounds adopt orthorhombic structures with the cell parameters a {approx} 5.5 A, b {approx} 5.5 A and c {approx} 20.9 A, suggesting an ordered intergrowth structure that consists of n = 1 [Bi{sub 2}NbO{sub 6}]{sup -} and n = 2 [Bi{sub 2}LnNb{sub 2}O{sub 9}]{sup +} Aurivillius fragments which are stacked alternately along the c-axis. The oxides do not show a second harmonic generationmore » (SHG) response toward 1064 nm laser radiation; they do not show a ferroelectric-paraelectric transition either between 30 and 900 deg. C in dielectric measurements, indicating a centrosymmetric structure. Optical absorption studies show that the intergrowth phases possess considerably smaller band gaps than the parent Nb{sub 2}O{sub 5} and Ta{sub 2}O{sub 5}.« less
  • The synthesis and structure of triple layered Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12} Aurivillius phases (Ln=La, Pr, Nd and Sm), prepared from K{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} Ruddlesden-Popper precursors, has been investigated. These materials adopt a body centred tetragonal structure (space group I4/mmm, with unit cell parameters a{approx}3.8 A and c{approx}33 A) comprising a regular intergrowth of [Bi{sub 2}O{sub 2}]{sup 2+} fluorite-type and [Ln{sub 2}Ti{sub 3}O{sub 10}]{sup 2-} perovskite-type layers. A significant degree of cation disorder is present in the Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12} system, involving the cross-substitution of Ln/Bi cations onto the Bi/Ln sites in the fluorite- and perovskite-typemore » layers, respectively. As the size of the lanthanide cation is reduced, Bi/Ln disorder is significantly suppressed due to the effect of bond length mismatch in the perovskite-type layer in the crystal structure of Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12}. This offers a potential strategy for the chemical control of cation disorder in the Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12} system.« less
  • Intergrowth BaBi{sub 2}Nb{sub 2}O{sub 9}-Bi{sub 4}Ti{sub 3}O{sub 12} (BaBi{sub 6}Ti{sub 3}Nb{sub 2}O{sub 21}) Aurivillius phase ceramic has been found to be a relaxor ferroelectric (RFE) with the highest reported temperature of the maximum of the dielectric permittivity (T{sub m}) of all of the known RFE systems. Dielectric characterization revealed that it has two dielectric anomalies. The first one is a frequency independent broad dielectric constant peak at {approx}280 deg. C, while the second anomaly shows relaxor behavior at 636 deg. C (100 kHz). There is obvious frequency dispersion of dielectric response at room temperature, which is in agreement with dielectricmore » properties of a typical relaxor. Ferroelectric hysteresis loops and a measurable value of piezoelectric constant d{sub 33} confirmed the ferroelectric nature of BaBi{sub 6}Ti{sub 3}Nb{sub 2}O{sub 21} ceramics. The piezoelectric response remained even after annealing at temperatures above 636 deg. C.« less
  • Aurivillius phase Bi{sub 5}Ti{sub 3}Fe{sub 0.7}Co{sub 0.3}O{sub 15} (BTF7C3O) thin films on {alpha}-quartz substrates were fabricated by a chemical solution deposition method and the room temperature ferroelectric and magnetic properties of this candidate multiferroic were compared with those of thin films of Mn{sup 3+} substituted, Bi{sub 5}Ti{sub 3}Fe{sub 0.7}Mn{sub 0.3}O{sub 15} (BTF7M3O). Vertical and lateral piezoresponse force microscopy (PFM) measurements of the films conclusively demonstrate that BTF7C3O and BTF7M3O thin films are piezoelectric and ferroelectric at room temperature, with the major polarization vector in the lateral plane of the films. No net magnetization was observed for the in-plane superconducting quantummore » interference device (SQUID) magnetometry measurements of BTF7M3O thin films. In contrast, SQUID measurements of the BTF7C3O films clearly demonstrated ferromagnetic behavior, with a remanent magnetization, B{sub r}, of 6.37 emu/cm{sup 3} (or 804 memu/g), remanent moment = 4.99 Multiplication-Sign 10{sup -5} emu. The BTF7C3O films were scrutinized by x-ray diffraction, high resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive x-ray analysis mapping to assess the prospect of the observed multiferroic properties being intrinsic to the main phase. The results of extensive micro-structural phase analysis demonstrated that the BTF7C3O films comprised of a 3.95% Fe/Co-rich spinel phase, likely CoFe{sub 2-x}Ti{sub x}O{sub 4}, which would account for the observed magnetic moment in the films. Additionally, x-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) imaging confirmed that the majority of magnetic response arises from the Fe sites of Fe/Co-rich spinel phase inclusions. While the magnetic contribution from the main phase could not be determined by the XMCD-PEEM images, these data however imply that the Bi{sub 5}Ti{sub 3}Fe{sub 0.7}Co{sub 0.3}O{sub 15} thin films are likely not single phase multiferroics at room temperature. The PFM results presented demonstrate that the naturally 2D nanostructured Bi{sub 5}Ti{sub 3}Fe{sub 0.7}Co{sub 0.3}O{sub 15} phase is a novel ferroelectric and has potential commercial applications in high temperature piezoelectric and ferroelectric memory technologies. The implications for the conclusive demonstration of ferroelectric and ferromagnetic properties in single-phase materials of this type are discussed.« less