Skip to main content
Log in

Synthesis, structure, and properties of mixed niobium(IV,V) oxides

  • Devoted to the 100th Anniversary of Academician A. V. Novoselova
  • Published:
Inorganic Materials Aims and scope

Abstract

This review paper summarizes data on mixed oxides containing niobium in an intermediate valence state, between 4+ and 5+. The major preparation procedures are considered, and the effects of different process parameters—composition of the starting reagents, temperature, pressure, duration, and environment—are analyzed from the viewpoint of the preparation of bulk, single-phase materials with niobium in a controlled formal oxidation state. The optimal synthesis conditions are established for reduced niobates with different structures. The oxidation behavior of the niobates(IV,V) is examined as a function of the structure type. The structural and electrical properties of the reduced niobates are shown to correlate with the carrier concentration (formal oxidation state of niobium). The major factors determining the carrier concentration in the niobates are identified. The results are used to establish the conditions under which a semiconductor—metal transition is possible in reduced niobates

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Geselbracht, M.J., Richardson, T.J., and Stacy, A.M., Superconductivity in the Layered Compound LixNbO2,Nature (London), 1990, vol. 345, pp. 324–326.

    Article  CAS  Google Scholar 

  2. Kellerman, D.G., Gorshkov, V.S., Tyutyunnik, A.P.,et al., Synthesis, Superconducting Properties, and Electronic Structure of LixNbO2,Sverkhprovodimost: Fiz., Khim., Tekh., 1992, vol. 2, no. 11, pp. 2146–2153.

    Google Scholar 

  3. Kellerman, D.G., Zubkov, V.G., Tyutyunnik, A.P.,et al., Superconductivity in NaxNbO2,Sverkhprovodimost: Fiz., Khim., Tekh., 1992, vol. 5, no. 5, pp. 961–963.

    CAS  Google Scholar 

  4. Akimitsu, J., Amano, J., Sawa, H.,et al., A New NonCu-Oxide Superconductor: (Sr1 xLnx)Nb2O6-y (Ln: La, Nd, Pr, and Ce),Jpn. J. Appl. Phys., 1991, vol. 30, pp. L1155-L1156.

    Article  CAS  Google Scholar 

  5. Akimitsu, J., Amano, J., Tomimoto, K.,et al., Superconductivity in Sr(Ln)-Nb-O System (Ln: La, Pr, Nd, Ce, Gd, and Ho,Physica C (Amsterdam), 1991, vols. 185–189, pp. 723–724.

  6. Nakamura, A., A2Nb1 + xOy (A = Ca, Sr) (0 ≤x ≤0.5): New Reduced Niobate Superconductors with the Distorted Defect-Perovskite Structure,Jpn. J. Appl. Phys., 1994, vol. 33, part 2, pp. 583–586.

    Article  Google Scholar 

  7. Solodovnikov, S.F., Yudanova, L.I., Gurov, V.V.,et al., Search for Superconductors with the Tetragonal Tungsten Bronze Structure in the Sr-La-Nb-O System,Zh. Neorg. Khim., 1995, vol. 40, pp. 179–183.

    CAS  Google Scholar 

  8. Gasparov, V.A., Strukova, G.K., and Khasanov, S.S., Superconductivity above 20 K in Barium-NiobiumOxide Compounds,Pis’ma Zh. Eksp. Teor. Fiz., 1994, vol. 60, no. 6, pp. 425–428.

    CAS  Google Scholar 

  9. Ridley, D. and Ward, R., The Preparation of a StrontiumNiobium Bronze with Perovskite Structure,J. Am. Chem. Soc., 1955, vol. 77, pp. 6132–6136.

    Article  Google Scholar 

  10. Krylov, E.I. and Sharnin, A.A., Preparation and Properties of Niobium Bronzes,Zh. Obshch. Khim., 1955, vol. 25, pp. 1637–1640.

    CAS  Google Scholar 

  11. Hessen, B., Sunshine, S.A., Siegrist, T., and Jimenez, R., Crystallization of Reduced Strontium and Barium Niobate Perovskites from Borate Fluxes,Mater. Res. Bull., 1991, vol. 26, pp. 85–90.

    Article  CAS  Google Scholar 

  12. Isawa, K., Sugiyama, J., Matsuura, K.,et al., Synthesis and Transport Properties of Sri1-xNbO3 (0.75 ≤x ≤ 0.90),Phys. Rev. B: Condens. Matter, 1993, vol. 47, pp. 2849–2853.

    CAS  Google Scholar 

  13. Kreiser, R.R. and Ward, R., The Preparation of a Barium Niobium Bronze,J. Solid State Chem., 1970, vol. 1, pp. 368–371.

    Article  Google Scholar 

  14. Casais, M.T., Alonso, J.A., Rasines, I., and Hidalgo, M.A., Preparation, Neutron Structural Study, and Characterization of BaNbO3: A Pauli-like Metallic Perovskite,Mater. Res. Bull., 1995, vol. 30, pp. 201–208.

    Article  CAS  Google Scholar 

  15. Svensson, G. and Werner, P.-E., Determination of the Composition of BaNbO3 Using Profile Refinement and Phase Analysis,Mater. Res. Bull., 1990, vol. 25, pp. 9–14.

    Article  CAS  Google Scholar 

  16. Lamure, J. and Colas, J.-L., Formation de l’oxyde double CaNbO3 du niobium(IV) et d’une variété du niobate Ca2Nb2O7, C.R. Acad. Sci., 1970, vol. 270, pp. 700–701.

    CAS  Google Scholar 

  17. Trunov, V.K., Averina, I.M., Evdokimov, A.A., and Frolov, A.M., Crystal Structure of La0.33NbO3,Kristallografiya, 1981, vol. 26, pp. 189–191.

    CAS  Google Scholar 

  18. Iyer, P.N. and Smith, A.J., Double Oxides Containing Niobium, Tantalum, or Protactinium, III,Acta Crystallogr., 1967, vol. 23, pp. 740–746.

    Article  CAS  Google Scholar 

  19. Abakumov, A.M., Shpanchenko, R.V., and Antipov, E.V., Synthesis and Properties of Niobium Bronzes R1 + xNb3O9 (R = La, Ce, Nd),Mater. Res. Bull., 1995, vol. 30, no. 1, pp. 97–103.

    Article  CAS  Google Scholar 

  20. Galasso, F., Layden, G., and Ganung, G., ANb2O6 and ATa2O6 Phases,Mater. Res. Bull., 1968, vol. 3, pp. 397–408.

    Article  CAS  Google Scholar 

  21. Brasset, H., Giller-Pandraud, and Volitis, S.D., Étude du polymorphisme du métaniobate de strontium SrNb2O6,Mater. Res. Bull., 1971, vol. 6, pp. 5–14.

    Article  Google Scholar 

  22. Marinder, B.-O., Wang, P.-L., and Werner, P.-E., Powder Diffraction Studies of SrNb2O6 and SrNb6O16,Acta Chem. Scand. A, 1986, vol. 40, pp. 467–475.

    Article  Google Scholar 

  23. Trunov, V.K., Averina, I.M., and Velikodnyi, Yu.A., Refined Crystal Structure of SrNb2O6,Kristallografiya, 1981, vol. 26, pp. 390–391.

    CAS  Google Scholar 

  24. Whiston, C. and Smith, A., Double Oxides Containing Niobium or Tantalum: II. Systems Involving Strontium or Barium,Acta Crystallogr., 1967, vol. 23, pp. 82–84.

    Article  CAS  Google Scholar 

  25. Sirotinkin, S.P., Sirotinkin, V.P., and Trunov, V.K., Structure of the Low-Temperature Form of BaNb2O6,Zh. Neorg. Khim. 1990, vol. 35, pp. 1609–1611.

    CAS  Google Scholar 

  26. Fayolle, J.-P., Studer, F., Desgardin, G., and Raveau, B., Étude de nouveaux oxydes ternaires d’europium divalent, de type bronze oxygène de tungstène quadratique et de type pérovskite,J. Solid State Chem., 1975, vol. 13, pp. 57–64.

    Article  CAS  Google Scholar 

  27. Istomin, S.Ya., D’yachenko, O.G., Antipov, E.V.,et al., Synthesis and Characterization of Reduced Niobates [Sr1 - xLnxNb2O6, Ln = La, Nd],Mater. Res. Bull., 1994, vol. 29, no. 7, pp. 743–749.

    Article  CAS  Google Scholar 

  28. Nguyen, N., Choisnet, J., and Raveau, B., Sur de nouveaux bronzes oxygènes de niobium quadratiques,C. R. Seances Acad. Sci., Ser. C, 1976, vol. 282, pp. 303–306.

    Google Scholar 

  29. Studer, F., Allais, G., and Raveau, B., Niobates et tantalates d’europium de type “bronze de tungstène quadratique”-I,J. Phys. Chem. Solids, 1980, vol. 41, pp. 1187–1197.

    Article  CAS  Google Scholar 

  30. Hessen, B., Sunshine, S., Siegrist, T.,et al., Structure and Properties of Reduced Barium Niobium Oxide Single Crystals Obtained from Borate Fluxes,Chem. Mater., 1991, vol. 3, pp. 528–534.

    Article  CAS  Google Scholar 

  31. Feltz, A. and Langbein, H., Über die Verbindungen Ba6Nb IV2 Nb V8 O30 und Ba9CuIINb V14 O45 und Untersuchungen zur Mischkristallbildung mit Ba6Ti IV2 Nb V8 O30,Z. Anorg. Allg. Chem., 1976, vol. 425, pp. 47–56.

    Article  CAS  Google Scholar 

  32. D’yachenko, O.G., Istomin, S.Ya., Fedotov, M.M.,et al., Structure and Properties of Ba6-xLnxNb10O30, Ln = La, Ce, and Nd Compounds,Mater. Res. Bull., 1997, vol. 32, no. 4, pp. 409–419.

    Article  CAS  Google Scholar 

  33. Bazuev, G.V. and Shveikin, G.P.,Slozhnye oksidy elementov s dostraivayushchimisya di f-obolochkami (Mixed Oxides of Transition and Rare-Earth Metals), Moscow: Nauka, 1985.

    Google Scholar 

  34. Subramanian, M., Aravamudan, G., and Subba Rao, G., Oxide Pyrochlores—A Review,Prog. Solid State Chem., 1981, vol. 15, pp. 55–143.

    Article  Google Scholar 

  35. Sleight, A., New Ternary Oxides of Mercury with the Pyrochlore Structure,Inorg. Chem., 1968, vol. 7, pp. 1704–1708.

    Article  CAS  Google Scholar 

  36. Brisse, F., Stewart, D., Seidl, V., and Knop, O., Pyrochlores: VII. Studies of Some 2–5 Pyrochlores and Related Compounds and Minerals,Can. J. Chem., 1972, vol. 50, pp. 3648–3666.

    Article  CAS  Google Scholar 

  37. Beech, F., Jordan, W.M., Catlow, C.R.,et al., Neutron Powder Diffraction Structure and Electrical Properties of the Defect Pyrochlores Pb1.5M2O6.5 (M = Nb, Ta),J. Solid State Chem., 1988, vol. 77, pp. 322–335.

    Article  CAS  Google Scholar 

  38. Chincholkar, V., New Compounds with Pyrochlore Structure,J. Inorg. Nucl. Chem., 1972, vol. 34, pp. 2973–2974.

    Article  CAS  Google Scholar 

  39. Lewandowski, J., Pickering, I., and Jacobson, A., Hydrothermal Synthesis of Calcium-Niobium and Tantalum Oxides with the Pyrochlore Structure,Mater. Res. Bull., 1992, vol. 27, pp. 981–988.

    Article  CAS  Google Scholar 

  40. Bazuev, G.V. and Shveikin, G.P., Phase Relations in the Y-Nb-O System,Zh. Neorg. Khim., 1973, vol. 18, pp. 1930–1934.

    CAS  Google Scholar 

  41. Safronenko, M.G., Bogatov, Yu.E., and Molodkin, A.K., Reaction of Lanthanum Oxide with Niobium(II) and (IV) Oxides,Zh. Neorg. Khim., 1988, vol. 33, pp. 2650–2653.

    CAS  Google Scholar 

  42. Istomin, S.Ya., D’yachenko, O.G., Antipov, E.V., and Svensson, G., Synthesis and Characterization of Reduced Niobates CaLnNb2O7, Ln=Y, Nd with a Pyrochlore Structure,Mater. Res. Bull., 1997, vol. 32, no. 4, pp. 421–430.

    Article  CAS  Google Scholar 

  43. Istomin, S.Ya., D’yachenko, O.G., Antipov, E.V.,et al., Synthesis and Chracterization of Reduced Niobates CaLnNb2O7, Ln = La-Pr, Sm, Gd-Lu, with the Pyrochlore-Type Structure,Mater. Res. Bull., 1998, vol. 33, no. 8, pp. 1251–1256.

    Article  CAS  Google Scholar 

  44. Bacon, P.E., Hou, J.G., Sleight, A.W., and Nielsen, R.L., Nitride Formation by Air Ignition,J. Solid State Chem., 1995, vol. 119, pp. 207–209.

    Article  CAS  Google Scholar 

  45. Istomin, S.Ya., Svensson, G., D’yachenko, O.G.,et al., Perovskite-Type Ca1-xSrxNbO3 (0 ≤x ≤1) Phases: A Synthesis, Structure, and Electron Microscopy Study,J. Solid State Chem., 1998, vol. 141, pp. 514–521.

    Article  CAS  Google Scholar 

  46. Kopnin, E.M., Istomin, S.Ya., D’yachenko, O.G.,et al., Synthesis, Structure, and Resistivity Properties of K1-xBaxNbO3 (0.2 ≤x ≤ 0.5) and K0.5Sr0.5NbO3,Mater. Res. Bull., 1995, vol. 30, no. 11, pp. 1379–1386.

    Article  CAS  Google Scholar 

  47. Galasso, F., Layde, G., and Ganung, G., ANb2O6 and ATa2O6 Phases,Mater. Res. Bull., 1968, vol. 3, pp. 397–408.

    Article  CAS  Google Scholar 

  48. Goodenough, J.B., Metallic Oxides,Prog. Solid State Chem., 1971, vol. 5, pp. 145–399.

    Article  CAS  Google Scholar 

  49. Isawa, K., Itti, R., Sugiyama, J.,et al., Photoelectron Spectroscopic Study of Sr1-xNbO3,Phys. Rev. B: Condens. Matter, 1994, vol. 49, pp. 3534–3538.

    CAS  Google Scholar 

  50. Rao, C.N.R. and Gopalakrishnan, J.,New Directions in Solid State Chemistry: Structure, Synthesis, Properties, Reactivity, and Materials Design, Cambridge: Cambridge Univ. Press, 1986. Translated under the titleNovye napravleniya v khimii tverdogo tela, Novosibirsk: Nauka, 1990.

    Google Scholar 

  51. Shannon, R.D. and Prewitt, C.T., Effective Ionic Radii in Oxides and Fluorides,Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem., 1969, vol. 25, no. 5, pp. 925–946.

    Article  CAS  Google Scholar 

  52. Ellis, B., Doumerc, J.-R, Dordor, P.,et al., Conduction Mechanism in Polycrystalline Na1-xSrxNbO3 Niobium Bronzes,Solid State Commun., 1984, vol. 51, pp. 913–917.

    Article  CAS  Google Scholar 

  53. Abakumov, A.M., Lin’kova, E.B., Shpanchenko, R.V.,et al., Synthesis and Properties of Potassium Niobium Oxyfluorides KNbO3-xFx with Cubic Perovskite Structure,Zh. Neorg. Khim., 1996, vol. 41, no. 6, pp. 985–988.

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

D’yachenko, O.G., Istomin, S.Y., Abakumov, A.M. et al. Synthesis, structure, and properties of mixed niobium(IV,V) oxides. Inorg Mater 36, 247–259 (2000). https://doi.org/10.1007/BF02757930

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02757930

Keywords

Navigation