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Crystal Structure Of Fluorite-related Ln3sbo7 (ln = La-dy) Ceramics Studied By Synchrotron X-ray Diffraction And Raman Scattering
Ln3SbO7 (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) ceramics were synthesized by solid-state reaction in optimized conditions of temperature and time to yield single-phase ceramics. The crystal structures of the obtained ceramics were investigated by synchrotron X-ray diffraction, second harmonic generation (SHG) and Raman scattering. All samples exhibited fluorite-type orthorhombic structures with different oxygen arrangements as a function of the ionic radius of the lanthanide metal. For ceramics with the largest ionic radii (La-Nd), the ceramics crystallized into the Cmcm space group, while the ceramics with intermediate and smallest ionic radii (Sm-Dy) exhibited a different crystal structure belonging to the same space group, described under the Ccmm setting. The results from SHG and Raman scattering confirmed these settings and ruled out any possibility for the non-centrosymmetric C2221 space group describing the structure of the small ionic radii ceramics, solving a recent controversy in the literature. Besides, the Raman modes for all samples are reported for the first time, showing characteristic features for each group of samples. © 2013 Elsevier Inc. All rights reserved.203326332Abe, R., Higashi, M., Zou, Z.G., Sayama, K., Abe, Y., Arakawa, H., (2004) J. Phys. Chem. B, 108, pp. 811-814Cai, L., Nino, J.C., (2007) J. Eur. Ceram. Soc., 27, pp. 3971-3976Cai, L., Nino, J.C., (2010) J. Eur. Ceram. Soc., 30, pp. 307-313Doi, Y., Harada, Y., Hinatsu, Y., (2009) J. Solid State Chem., 182, pp. 709-715Wakeshima, M., Nishimine, H., Hinatsu, Y., (2004) J. Phys. Condens. Matter, 16, pp. 4103-4120Wakeshima, M., Hinatsu, Y., (2010) J. Solid State Chem., 183, pp. 2681-2688Hinatsu, Y., Ebisawa, H., Doi, Y., (2009) J. Solid State Chem., 182, pp. 1694-1699Cai, L., Denev, S., Gopalan, V., Nino, J.C., (2010) J. Am. Ceram. Soc., 93, pp. 875-880Hinatsu, Y., Doi, Y., Nishimine, H., Wakeshima, M., Sato, M., (2009) J. Alloys Compd., 488, pp. 541-545Rossell, H.J., (1979) J. Solid State Chem., 27, pp. 115-122Kahn-Harari, A., Mazerolles, L., Michel, D., Robert, F., (1995) J. Solid State Chem., 116, pp. 103-106Khalifah, P., Huang, Q., Lynn, J.W., Erwin, R.W., Cava, R.J., (2000) Mater. Res. Bull., 35, pp. 1-7Wiss, F., Raju, N.P., Wills, A.S., Greedan, J.E., (2000) Int. J. Inorg. Mater., 2, pp. 53-59Harada, D., Hinatsu, Y., Ishii, Y., (2001) J. Phys. Condens. Matter, 13, pp. 10825-10836Harada, D., Hinatsu, Y., (2001) J. Solid State Chem., 158, pp. 245-253Lam, R., Langet, T., Greedan, J.E., (2002) J. Solid State Chem., 171, pp. 317-323Hinatsu, Y., Wakeshima, M., Kawabuchi, N., Taira, N., (2004) J. Alloys Compd., 374, pp. 79-83Plaisier, J.R., Drost, R.J., Ijdo, D.J.W., (2002) J. Solid State Chem., 169, pp. 189-198Gemmill, W.R., Smith, M.D., Mozharivsky, Y.A., Miller, G.J., Zur Loye, H.-C., (2005) Inorg. Chem., 44, pp. 7047-7055Lam, R., Wiss, F., Greedan, J.E., (2002) J. Solid State Chem., 167, pp. 182-187Vente, J.F., Helmholdt, R.B., Ijdo, D.J.W., (1994) J. Solid State Chem., 108, pp. 18-23Vente, J.F., Ijdo, D.J.W., (1991) Mater. Res. Bull., 26, pp. 1255-1262Nishimine, H., Wakeshima, M., Hinatsu, Y., (2004) J. Solid State Chem., 177, pp. 739-744Greedan, J.E., Raju, N.P., Wegner, A., Gougeon, P., Padiou, J., (1997) J. Solid State Chem., 129, pp. 320-327Nishimine, H., Wakeshima, M., Hinatsu, Y., (2005) J. Solid State Chem., 178, pp. 1221-1229Nath, D.K., (1970) Inorg. Chem., 9, pp. 2714-2718Fennell, T., Bramwell, S.T., Green, M.A., (2001) Can. J. Phys., 79, pp. 1415-1419Fu, W.T., Ijdo, D.J.W., (2009) J. Solid State Chem., 182, pp. 2451-2455Gemmill, W.R., Smith, M.D., Zur Loye, H.-C., (2004) Inorg. Chem., 43, pp. 4254-4261Moreira, R.L., Lobo, R.P.S.M., Subodh, G., Sebastian, M.T., Matinaga, F.M., Dias, A., (2007) Chem. Mater., 19, pp. 6548-6554Dias, A., Sá, R.G., Moreira, R.L., (2008) J. Raman Spectrosc., 39, pp. 1805-1810Dias, A., Siqueira, K.P.F., (2010) J. Raman Spectrosc., 41, pp. 93-97Dias, A., Subodh, G., Sebastian, M.T., Moreira, R.L., (2010) J. Raman Spectrosc., 41, pp. 702-706Larson, A.C., Von Dreele, R.B., (2000) Los Alamos National Laboratory Report LAUR 86-748Toby, B.H., (2001) J. Appl. Crystallogr., 34, pp. 210-213Boyd, R.W., (2008) Non Linear Optics, , third ed., Academic Press, Burlington, MAHayes, W., Loudon, R., (1978) Scattering of Light by Crystals, , Wiley, New YorkRousseau, D.L., Bauman, R.P., Porto, S.P.S., (1981) J. Raman Spectrosc., 10, pp. 253-290Shannon, R.D., (1976) Acta Crystallogr. Sect. A: Found. Crystallogr., 32, pp. 751-767Siqueira, K.F.P., Moreira, R.L., Dias, A., (2010) Chem. Mater., 22, pp. 2668-267