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
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Geselbracht, M.J., Richardson, T.J., and Stacy, A.M., Superconductivity in the Layered Compound LixNbO2,Nature (London), 1990, vol. 345, pp. 324–326.
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.
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.
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.
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.
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.
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.
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.
Ridley, D. and Ward, R., The Preparation of a StrontiumNiobium Bronze with Perovskite Structure,J. Am. Chem. Soc., 1955, vol. 77, pp. 6132–6136.
Krylov, E.I. and Sharnin, A.A., Preparation and Properties of Niobium Bronzes,Zh. Obshch. Khim., 1955, vol. 25, pp. 1637–1640.
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.
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.
Kreiser, R.R. and Ward, R., The Preparation of a Barium Niobium Bronze,J. Solid State Chem., 1970, vol. 1, pp. 368–371.
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.
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.
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.
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.
Iyer, P.N. and Smith, A.J., Double Oxides Containing Niobium, Tantalum, or Protactinium, III,Acta Crystallogr., 1967, vol. 23, pp. 740–746.
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.
Galasso, F., Layden, G., and Ganung, G., ANb2O6 and ATa2O6 Phases,Mater. Res. Bull., 1968, vol. 3, pp. 397–408.
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.
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.
Trunov, V.K., Averina, I.M., and Velikodnyi, Yu.A., Refined Crystal Structure of SrNb2O6,Kristallografiya, 1981, vol. 26, pp. 390–391.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Subramanian, M., Aravamudan, G., and Subba Rao, G., Oxide Pyrochlores—A Review,Prog. Solid State Chem., 1981, vol. 15, pp. 55–143.
Sleight, A., New Ternary Oxides of Mercury with the Pyrochlore Structure,Inorg. Chem., 1968, vol. 7, pp. 1704–1708.
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.
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.
Chincholkar, V., New Compounds with Pyrochlore Structure,J. Inorg. Nucl. Chem., 1972, vol. 34, pp. 2973–2974.
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.
Bazuev, G.V. and Shveikin, G.P., Phase Relations in the Y-Nb-O System,Zh. Neorg. Khim., 1973, vol. 18, pp. 1930–1934.
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.
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.
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.
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.
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.
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.
Galasso, F., Layde, G., and Ganung, G., ANb2O6 and ATa2O6 Phases,Mater. Res. Bull., 1968, vol. 3, pp. 397–408.
Goodenough, J.B., Metallic Oxides,Prog. Solid State Chem., 1971, vol. 5, pp. 145–399.
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.
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.
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.
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.
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.
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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
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DOI: https://doi.org/10.1007/BF02757930