Structural study of modified Bi{sub 4}V{sub 2}O{sub 10+{delta}} phases ({delta} = 0, 0.5, 1): Influence of antimony contribution

Journal Article · Sat May 01 04:00:00 EDT 1999 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1006/jssc.1999.8169· OSTI ID:351518

Sorokina, S; Enjalbert, R; Baules, P; Galy, J ^[1]; Castro, A ^[2]

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1. CNRS, Toulouse (France). Centre d`Elaboration de Materiaux et d`Etudes Structurales
2. CSIC, Cantoblanco, Madrid (Spain). Inst. de Ciencia de Materiales

Three solid solutions of general composition Bi{sub 4{minus}x}Sb{sub x}V{sub 2}O{sub 10}, Bi{sub 4}V{sub 2{minus}y}{sup 4+}V{sub y}{sup 5+}O{sub 10+y/2}, and Bi{sub 4}V{sub 2{minus}z}Sb{sub z}O{sub 11} have been investigated in the fivefold Bi{sub 2}O{sub 3}-V{sub 2}O{sub 5}-V{sub 2}O{sub 4}-Sb{sub 2}O{sub 3}-Sb{sub 2}O{sub 5} system. These oxides have been characterized by X-ray diffraction and electron microscopy techniques. Single phases have been isolated for values ranging from 0 to x, z = 0.8 and y = 2. Single crystals of Bi{sub 3.2}Sb{sub 0.8}V{sub 2}O{sub 10}, Bi{sub 4}V{sub 2}O{sub 10.5}, and Bi{sub 4}V{sub 1.2}Sb{sub 0.8}O{sub 11} have been grown and their structures determined by X-ray diffraction methods. The three oxides crystallize in the orthorhombic system, space groups F222, Amam, and Fmmm, respectively. Their structures keep the classical two-dimensional array of Aurivillius-like oxides with (Bi, Sb)-O layers interleaved with (V, Sb)-O sheets. It has been found that Sb{sup 3+} is introduced into the bismuth layer, due to its similar sterical behavior, by the presence of a 5s{sup 2} lone pair associated with Sb{sup 3+} and 6s{sup 2} associated with Bi{sup 3+}, whereas Sb{sup 5+} substitutes for the V{sup 5+} cation. All of the substitutions carried out mainly act on the vanadium layer, which can accommodate different coordination polyhedra for cations: tetrahedra for V{sup 5+}, square pyramids and distorted trigonal bipyramids or octahedra for V{sup 4+} and V{sup 5+}, and octahedra for Sb{sup 5+}. This fact can be related to the electrical properties, such as high ionic conduction and ferroelectricity, shown by these types of materials.

• OSTI ID: 351518
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 2 Vol. 144; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ANTIMONY OXIDES
BISMUTH OXIDES
CRYSTAL STRUCTURE
ELECTRON MICROSCOPY
EXPERIMENTAL DATA
LATTICE PARAMETERS
PHASE STUDIES
SOLID SOLUTIONS
VANADIUM OXIDES
X-RAY DIFFRACTION