Abstract
Rietveld refinement of combined X-ray and neutron diffraction data has, within errors, confirmed the stoichiometries of two, cubic pyrochlore phases in the ZnO Bi 2O 3 Sb 2O 5 system. Neither phase has the ‘ideal’ stoichiometry, Zn 2Bi 3Sb 3O 14. One phase, P 1, is a Zn-rich, Bi-deficient solid solution Zn 2+ x Bi 2.96−( x− y) Sb 3.04− y O 14.04+ δ . The other, P 2, is a Bi-rich line phase, stoichiometry Zn 2Bi 3.08Sb 2.92O 14+ δ . Both structures have a mixture of Bi, Zn on the A-sites and Zn, Sb on the B-sites. However, Zn is displaced off-centre in the A-sites to achieve lower co-ordination number with realistic Zn O bond lengths. Additional structural complexities arise from: displacement of O(2) atoms; partial occupancies of O(1) and O(2) sites; partial occupancy of a third, interstitial oxygen site, O(3). Since the multiplicities of the off-centre sites are much higher than those of the ideal positions, there is considerable possibility for correlated short range order throughout the structures.
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