Journal of Electronic Materials

, Volume 38, Issue 1, pp 113–118

Phase Transitions in the BiVO4-nPbO (n = 1, 2) System: Structural–Electrical Properties Relationships

  • Jean-Pierre Wignacourt
  • Michel Drache
  • Olfa Labidi
  • Pascal Roussel
Article
  • 90 Downloads

Abstract

In a general survey of nPbO-BiVO4 compounds, interesting phases corresponding to n = 1: PbBiVO5, and n = 2: Pb2BiVO6 are described. A phase transition has been unambiguously characterized for PbBiVO5. The crystal structures were solved from twinned crystals at room temperature (α phase, triclinic, S.G. P-1) and at 530°C (β phase, monoclinic, C2/m). Powder neutron diffraction experiments confirmed these settings and both room-temperature (RT) and high-temperature (HT) refinements corroborated space group choices, clearing up a literature controversy about the centrosymmetry of the α phase, and identifying structural modifications occurring under the α → β transition. Cationic substitutions for V were tested and PbBi(V1−xMx)O5 (M = P) solid solutions identified. Pb2BiVO6 (n = 2) is a compound showing several successive structural transitions, i.e., α → β → δ. Structures of α and δ forms have been previously described from powder diffraction data (x-ray and neutron). In this work, we have refined these structures from single-crystal data, and the resolution of the intermediate β form, so far unsolved, was possible through a stabilization thermal cycle; its complete structural understanding required a 4D formalism. Two new polymorphic phases, α′ and δ′, were obtained by substituting Mn or P for V; their structures are closely related to, respectively, the α phase at room temperature, and the δ phase at 680°C. Electrical conductivities of all structurally characterized compositions were investigated, and correlations were drawn between their conduction properties and structural characteristics. Conductivity properties measured under variable O2 partial pressures for Pb2Bi(V0.75P0.25)O6 were interpreted as a mixed ionic–electronic (p-type) conduction mechanism.

Keywords

Phase transitions bismuth lead oxy-vanadates oxide ion and mixed conductivity 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    M. Drache, P. Roussel and J. P. Wignacourt, Chem. Rev. 107, 80 (2007). doi:10.1021/cr050977s.PubMedCrossRefGoogle Scholar
  2. 2.
    J.C. Boivin, G. Mairesse. Chem. Mater. 10, 2870 (1998). doi:10.1021/cm980236q.CrossRefGoogle Scholar
  3. 3.
    P. Conflant (Ph.D. thesis, University of Lille, France, 1985).Google Scholar
  4. 4.
    L.H. Brixner, C.M. Foris. Mater. Res. Bull. 9, 273 (1974). doi:10.1016/0025-5408(74)90076-2.CrossRefGoogle Scholar
  5. 5.
    P.L. Wang, Acta Phys. Sin-Ch. Ed. 2, 34 (1985).Google Scholar
  6. 6.
    S. Giraud, M. Mizrahi, M. Drache, P. Conflant, J.P. Wignacourt, H. Steinfink. Solid State Sci. 3, 593 (2001). doi:10.1016/S1293-2558(01)01166-9.CrossRefGoogle Scholar
  7. 7.
    R.N. Vannier (Ph.D. thesis, University of Lille, France, 1992).Google Scholar
  8. 8.
    O. Labidi, P. Roussel, F. Porcher, M. Drache, R.N. Vannier and J.P. Wignacourt, J. Solid State Chem. 181, 2260 (2008). doi:10.1016/j.jssc.2008.05.026.CrossRefADSGoogle Scholar
  9. 9.
    V. Petricek, M. Dusek, and L. Palatinus, JANA2006-β Version (Praha, Czech Republic: Institute of Physics, 2007).Google Scholar
  10. 10.
    O. Labidi, J.P. Wignacourt, P. Roussel, P. Conflant, M. Drache and H. Steinfink, Solid State Sci. 6, 783 (2004). doi:10.1016/j.solidstatesciences.2004.03.024.CrossRefGoogle Scholar
  11. 11.
    I. R. Evans, J.S.O. Evans and J.A.K. Howard, J. Mat. Chem. 12, 2648 (2002). doi:10.1039/b202648a.CrossRefGoogle Scholar
  12. 12.
    O. Labidi, P. Roussel, M. Huve, M. Drache, V. Petricek, and J.P. Wignacourt, Chem. Mater. (2008) (submitted).Google Scholar
  13. 13.
    O. Labidi, P. Roussel, M. Huve, P. Conflant, M. Drache, and J.P. Wignacourt, J. Solid State Chem., 178, 2247 (2005). doi:10.1016/j.jssc.2005.05.003.CrossRefADSGoogle Scholar
  14. 14.
    M. Drache, J.C. Schrotter and P. Conflant, Journal of Materials Chemistry. 3, 789 (1993). doi:10.1039/jm9930300789.CrossRefGoogle Scholar

Copyright information

© TMS 2008

Authors and Affiliations

  • Jean-Pierre Wignacourt
    • 1
  • Michel Drache
    • 1
  • Olfa Labidi
    • 1
  • Pascal Roussel
    • 1
  1. 1.UCCS, Equipe Chimie du Solide, CNRS UMR 8181, ENSC Lille-UST LilleVilleneuve d’Ascq cedexFrance

Personalised recommendations