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Preparation, structural characterization, and luminescence properties of Eu3+-doped nanocrystalline ZrO2

  • A. Speghini (a1), M. Bettinelli (a1), P. Riello (a2), S. Bucella (a2) and A. Benedetti (a2)...


Eu3+-doped zirconia nanopowders were prepared by the sol-gel technique using two different methods, based on the hydrolysis of zirconium n-propoxide, producing tetragonal and monoclinic zirconia under different preparation conditions. A detailed microstructure characterization was performed through wide angle x-ray scattering, small angle x-ray scattering, trasmission electron microscopy, and nitrogen physisorption measurements. The possible influence of the zirconia crystalline phases and particle sizes on the luminescence properties of the lanthanide ion was investigated. A detailed analysis of the emission spectra of the samples suggested that the dopant Eu3+ ions replace the Zr4+ ions in the zirconia crystal lattice. Moreover, samples prepared by the two different methods were characterized by different decay times of the Eu3+ ion luminescence.


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1Blasse, G. and Grabmaier, B.C.: Luminescent Materials (Springer-Verlag, Berlin, Heidelberg, Germany, 1994).
2Ishizaka, T., Nozaki, R. and Kurokawa, Y.: Diffuse phase transition in Ba5NdTi3−xZrxNb7O30 ferroelectric ceramics. J. Phys. Chem. Solids 63, 613 (2002).
3Bihari, B., Eilers, H. and Tissue, B.M.: Spectra and dynamics of monoclinic Eu2O3 and Eu3+:Y2O3 nanocrystals. J. Lumin. 75, 1 (1997).
4Wang, Y., Cheng, H., Zhang, L., Hao, Y., Ma, J., Xu, B. and Li, W.: The preparation, characterization, photoelectrochemical and photocatalytic properties of lanthanide metal-ion-doped TiO2 nanoparticles. J. Molecular Cat. A: Chem. 151, 205 (2000).
5Reisfeld, R., Zelner, M. and Patra, A.: Fluorescence study of zirconia films doped by Eu3+, Tb3+ and Sm3+ and their comparison with silica films. J. Alloys Compd. 300–301, 147 (2000).
6Bekiari, V., Pistolis, G. and Lianos, P.: Improvement of the emission properties of sol–gel silica matrices containing Eu3+ in the presence of poly(ethylene glycol)-200. J. Non-Cryst. Solids 226, 200 (1998).
7Jin, T., Inoue, S., Tsutsumi, S., Machida, K. and Adachi, G.: Luminescence properties of lanthanide complexes incorporated into sol-gel derived inorganic-organic composite materials. J. Non-Cryst. Solids 223, 123 (1998).
8van der Voort, D. and Blasse, G.: Luminescence of the europium(3+) ion in zirconium(4+) compounds. Chem. Mater. 3, 1041 (1991).
9Patra, A.: Effect of crystal structure and concentration on luminescence in Er3+:ZrO2 nanocrystals. Chem. Phys. Lett. 387, 35 (2004).
10Patra, A., Friend, C.S., Kapoor, R. and Prasad, P.N.: Upconversion in Er3+:ZrO2 Nanocrystals. J. Phys. Chem. B 106, 1909 (2002).
11Gutzov, S. and Lerch, M.: Optical properties of europium containing zirconium oxynitrides. Opt. Mater. 24, 547 (2003).
12Tissue, B.M.: Synthesis and luminescence of lanthanide ions in nanoscale insulating hosts. Chem. Mater. 10, 2837 (1998).
13Alivisatos, A.P.: Nanocrystals: Building blocks for modern materials design. Endeavour 21, 56 (1997).
14Vetrone, F., Boyer, J.C., Capobianco, J.A., Speghini, A. and Bettinelli, M.: Effect of Yb3+ codoping on the upconversion emission in nanocrystalline Y2O3:Er3+. J. Phys. Chem. B. 107, 1107 (2003).
15Zych, E., Hreniak, D. and Strek, W.: Spectroscopic properties of Lu2O3/Eu3+ nanocrystalline powders and sintered ceramics. J. Phys. Chem. B 106, 3805 (2002).
16Gutzov, S., Bredol, M. and Wasgestian, F.: Cathodoluminescence study of europium-doped zirconia and cassiterite powders. J. Phys. Chem. Solids 59, 69 (1998).
17Gedanken, A., Reisfeld, R., Sominski, E., Palchik, O., Koltypin, Yu., Panczer, G., Gaft, M. and Minti, H.: Sonochemical preparation and characterization of europium oxide doped in and coated on ZrO2 and yttrium-stabilized zirconium (YSZ). J. Phys. Chem. B 104, 7057 (2000).
18Garcia-Hipolito, M., Martinez, E., Alvarez-Fregoso, O., Falcony, C. and Aguilar-Frutis, M.A.: Preparation and characterization of Eu doped zirconia luminescent films synthesized by the pyrosol technique. J. Mater. Sci. Lett. 20, 1799 (2001).
19Reisfeld, R., Saraidarov, T., Pietraszkiewicz, M. and Lis, S.: Luminescence of europium(III) compounds in zirconia xerogels. Chem. Phys. Lett. 349, 266 (2001).
20Goncalves, R.R., Messaddeq, Y., Atik, M. and Ribeiro, S.J.L.: Optical properties of ZrO2, SiO2 and TiO2–SiO2 xerogels and coatings doped with Eu3+ and Eu2+. Mater. Res. 2, 11 (1999).
21Dexpert-Ghys, J., Faucher, M. and Caro, P.: Fluorescence spectra of Eu3+ in monoclinic zirconia (baddeleyite). C. R. Acad. Sc. Paris. 298, 621 (1984).
22Gutzof, S., Kynev, K. and Peneva, S.K.: Structure and luminescence of Eu-activated zirconium hydroxide and dioxide at relatively low temperatures. Cryst. Res. Techol. 28, 3 (1993).
23de Rosa-Cruz, E. la, Díaz-Torres, L.A., Rodríguez-Rojas, R.A., Menedes-Nava, M.A. and Barbosa-Garcia, O.: Luminescence and visible upconversion in nanocrystalline ZrO2:Er3+. Appl. Phys. Lett. 83, 4903 (2003).
24Opalińska, A., Hreniak, D., Łojkowski, W., Strek, W., Presz, A. and Grzanka, E.: Structure, morphology and luminescence properties of Pr-doped nanocrystalline ZrO2 obtained by hydrothermal method. Solid State Phenom. 94, 141 (2003).
25Gu, F., Wang, F., , M.K., Zhou, G.J., Liu, S.W., Xu, D. and Yuan, D.R.: Effect of Dy3+ doping and calcination on the luminescence of ZrO2 nanoparticles. Chem. Phys. Lett. 380, 185 (2003).
26Chen, L., Liu, Y. and Li, Y.: Preparation and characterization of ZrO2:Eu3+ phosphors. J. Alloys Compd. 381, 266 (2004).
27Quan, Z.W., Wang, L.S. and Lin, J.: Synthesis and characterization of spherical ZrO2:Eu3+ phosphors by spray pyrolysis process. Mater. Res. Bull. 40, 810 (2005).
28Boulc’h, F. and Djurado, E.: Preparation and characterisation of nanostructured spherical powders for thermoelectric applications. Solid State Ionics 157, 335 (2003).
29Chuah, G.K., Liu, S.H., Jaenicke, S. and Li, J.: High surface area zirconia by digestion of zirconium propoxide at different pH. Micropor. Mesopor. Mater. 39, 381 (2000).
30Riello, P., Canton, P. and Fagherazzi, G.: Quantitative phase analysis in semicrystalline materials using the rietveld method. J. Appl. Crystallogr. 31, 78 (1998).
31Maczka, M., Lutz, E.T.G., Verbeek, H.J., Oskam, K., Meijerink, A., Hanuza, J. and Stuivinga, M.: Spectroscopic studies of dynamically compacted monoclinic ZrO2. J. Phys. Chem. Solids 60, 1909 (1999).
32Zhang, H., Liu, Y., Zhu, K., Siu, G., Xiong, Y. and Xiong, C.: Infrared spectra of nanometre granular zirconia. J. Phys. Condens. Matter 11, 2035 (1999).
33Lopez, E.F., Escribano, V. Sanchez, Panizza, M., Carnasciali, M.M. and Busca, G.: Vibrational and electronic spectroscopic properties of zirconia powders. J. Mater. Chem. 11, 1891 (2001).
34Vetrone, F., Boyer, J.C., Capobianco, J.A., Speghini, A. and Bettinelli, M.: Luminescence spectroscopy and near-infrared to visible upconversion of nanocrystalline Gd3Ga5O12:Er3+. J. Phys. Chem. B 107, 10747 (2003).
35Blasse, G.: Structure and Bonding, Vol. 26 (Springer Verlag, Berlin, Germany, 1976), p. 43.
36Hoefdraad, H.E.: The charge-transfer absorption band of Eu3+ in oxides. J. Solid State Chem. 15, 175 (1975).
37Kaminskii, A.A.: Laser Crystals, 2nd ed. (Springer Verlag, Berlin, Germany, 1990), p. 120.
38Oomen, E.W.J.L. and van Dongen, A.M.A.: Europium (III) in oxide glasses: Dependence of the emission spectrum upon glass composition. J. Non-Cryst. Solids 111, 205 (1989).
39Reisfeld, R., Zigansky, E. and Gaft, M.: Europium probe for estimation of site symmetry in glass films, glasses and crystals. Mol. Phys. 102, 1319 (2004).
40Polizzi, S., Fagherazzi, G., Battagliarin, M., Bettinelli., M. and Speghini, A.: Investigation on lanthanide-doped Y2O3 nanopowders obtained by wet chemical synthesis. J. Mater. Chem. 12, 742 (2002).
41Nakazawa, E. Fundamentals of luminescence, in Phosphor Handbook, edited by Shionoya, S. and Yen, W.M., (CRC Press, Boca Raton, FL, 1999), p. 104.
42Brecher, C. and Riseberg, R.A.: Laser-induced fluorescence line narrowing in Eu glass: A spectroscopic analysis of coordination structure. Phys. Rev. B 13, 81 (1976).
43Gutzov, S., Kohls, M. and Lerch, M.: The luminescence of Zr–Eu– O–N materials. J. Phys. Chem. Solids 61, 1301 (2000).
44Meltzer, S., Feofilov, S.P., Tissue, B. and Yuan, H.B.: Dependence of fluorescence lifetimes of Y2O3:Eu3+ nanoparticles on the surrounding medium. Phys. Rev. B 60, R14012 (1999).
45Cannas, C., Casu, M., Mainas, M., Musinu, A., Piccaluga, G., Polizzi, S., Speghini, A. and Bettinelli, M.: Synthesis, characterisation and optical properties of nanocrystalline Y2O3–Eu3+ dispersed in a silica matrix by a deposition–precipitation method. J. Mater. Chem. 13, 3079 (2003).


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Preparation, structural characterization, and luminescence properties of Eu3+-doped nanocrystalline ZrO2

  • A. Speghini (a1), M. Bettinelli (a1), P. Riello (a2), S. Bucella (a2) and A. Benedetti (a2)...


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