Designing new n=2 Sillen–Aurivillius phases by lattice-matched substitutions in the halide and [Bi{sub 2}O{sub 2}]{sup 2+} layers

Journal Article · Sun Sep 15 00:00:00 EDT 2013 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2013.07.004· OSTI ID:22274086

Liu, Samuel ^[1]; Blanchard, Peter E.R. ^[1]; Avdeev, Maxim ^[2]; Kennedy, Brendan J.; Ling, Chris D. ^[1]

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1. School of Chemistry, University of Sydney, Sydney 2006 (Australia)
2. The Bragg Institute, ANSTO, PMB 1, Menai 2234 (Australia)

A new n=2 Sillen–Aurivillius compound Bi{sub 3}Sr{sub 2}Nb{sub 2}O{sub 11}Br has been synthesised based on Bi{sub 3}Pb{sub 2}Nb{sub 2}O{sub 11}Cl by simultaneously replacing Pb{sup 2+} with Sr{sup 2+} and Cl{sup −} with Br{sup −}. Rietveld refinements against X-ray and neutron powder diffraction data revealed a significant relative compression in the stacking axis (c-axis) of the new compound. Sr{sup 2+} doping reduces the impact of the stereochemically active 6s{sup 2} lone pair found on Pb{sup 2+} and Bi{sup 3+}, resulting in a contraction of the c-axis by 1.22% and an expansion of the ab plane by 0.25%. This improves the inter-layer compatibility with the larger halide Br{sup −}. Analysis of X-ray absorption near-edge spectroscopy data show that the ferroelectric distortion of the B-site cation is less apparent in Bi{sub 3}Sr{sub 2}Nb{sub 2}O{sub 11}Br compared to Bi{sub 3}Pb{sub 2}Nb{sub 2}O{sub 11}Cl, and variable-temperature neutron diffraction data show no evidence for a ferroelectric distortion. - Graphical abstract: The structural expansion and contractions in the stacking axis of co-doped Sillen–Aurivillius phases. Display Omitted - Highlights: • A new Sillen–Aurivillius phase Bi{sub 3}Sr{sub 2}Nb{sub 2}O{sub 11}Br is synthesised based on Bi{sub 3}Pb{sub 2}Nb{sub 2}O{sub 11}Cl. • The stacking axis contracts although local expansion accommodates the larger halide Br. • Majority of the contraction is observed in the [Bi{sub 2}O{sub 2}]{sup 2+} layers where we replaced Pb{sup 2+} for Sr{sup 2+}. • Removing the Pb{sup 2+} lowers the lone pair effect and improves inter-layer compatibility. • XANES and NPD suggest that the ferroelectric properties are minimised or suppressed.

• OSTI ID: 22274086
• Journal Information: Journal of Solid State Chemistry, Vol. 205; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
ABSORPTION
ABSORPTION SPECTROSCOPY
BISMUTH IONS
CATIONS
COMPRESSION
CONTRACTION
DESIGN
DOPED MATERIALS
EXPANSION
FERROELECTRIC MATERIALS
HALIDES
LAYERS
LEAD IONS
NEUTRON DIFFRACTION
NEUTRON TEMPERATURE
OXYBROMIDES
STRONTIUM IONS
SYNTHESIS
X RADIATION
X-RAY SPECTROSCOPY