Bismuth-tungsten oxide bronzes: a study of intergrowth phases and related aspects

Ramanan, A. ; Gopalakrishnan, J. ; Uppal, M. K. ; Jefferson, D. A. ; Rao, C. N. R. (1984) Bismuth-tungsten oxide bronzes: a study of intergrowth phases and related aspects Proceedings of the Royal Society A: Mathematical, Physical & Engineering Sciences, 395 (1808). pp. 127-139. ISSN 1364-5021

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Reaction of bismuth metal with WO3 in the absence of oxygen yields interesting bronze-like phases. From analytical electron microscopy and X-ray photoelectron spectroscopy, the product phases are found to have the general composition BixWO3 with bismuth in the 3+ state. Structural investigations made with high resolution electron micrscopy and cognate techniques reveal that when x<0.02, a perovskite bronze is formed. When x≥0.02, however, intergrowth tungsten bronzes (i.t.b.) containing varying widths of the WO3 slab are formed, the lattice periodicity being in the range 2.3-5.1 nm in a direction perpendicular to the WO3 slabs. Image-matching studies indicate that the bismuth atoms are in the tunnels of the hexagonal tungsten bronze (h.t.b.) strips and the h.t.b. strips always remain one-tunnel wide. Annealed samples show a satellite structure around the superlattice spots in the electron diffraction patterns, possibly owing to ordering of the bismuth atoms in the tunnels. The i.t.b. phases show recurrent intergrowths extending up to 100 nm in several crystals. The periodicity varies considerably within the same crystal wherever there is disordered intergrowth, but unit cell dimensions can be assigned from X-ray and electron diffraction patterns. The maximum value of x in the i.t.b. phases is ca. 0.07 and there is no evidence for the i.t.b. phase progressively giving way to the h.t.b. phase with increase in x. Hexagonal tungsten bronzes that contain bismuth with x up to 0.02 can be formed by starting from hexagonal WO3, but the h.t.b. phase seems to be metastable. Optical, magnetic and electron transport properties of the i.t.b. phases have been measured and it appears that the electrons become itinerant when x<0.05.

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