Chemical pressure effects on the spectroscopic properties of Nd3+-doped gallium nano-garnets

[EN] Nd3+-doped RE3Ga5O12 (RE = Gd, Y, and Lu) nano-crystalline garnets of 40-45 nm in size have been synthesized by a sol-gel method. With the decrease of the RE atom size, the chemical pressure related to the decreasing volumes of the GaO4 tetrahedral, GaO6 octahedral and REO8 dodecahedral units drive the nano-garnets toward a more compacted structure, which is evidenced by the change of the vibrational phonon mode frequencies. The chemical pressure also increases the crystal-field strength felt by the RE3+ ions while decreases the orthorhombic distortion of the REO8 local environment. These effects alter the absorption and emission properties of the Nd3+ ion measured in the near-infrared luminescence range from 0.87 to 1.43 ¿m associated with the 4 F3/2¿4 IJ (J = 9/2, 11/2, 13/2) transitions. The 4 F3/2 luminescence decay curves show non-exponential behavior due to dipole-dipole energy transfer interactions among Nd3+ ions that increases with pressure.Authors are grateful to The Governments of Spain and India for the Indo-Spanish Joint Programme of Bilateral Cooperation in Science and Technology (PRI-PIBIN-2011-1153/DST-INT-Spain-P-38-11). Dr. Venkatramu is grateful to DAE-BRNS, Government of India for the award of DAE Research Award for Young Scientist (No. 2010/20/34/5/BRNS/2223). This work have been partially supported by MINECO under The National Program of Materials (MAT2013-46649-C4-2-P/-3-P/-4-P), The Consolider-Ingenio 2010 Program (MALTA CSD2007-00045), by Fundacion CajaCanarias (ENER-01), and by the EU-FEDER funds. V. Monteseguro wishes to thank MICINN for the FPI grant (BES-2011-044596). 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Local and average structures of the spin-glass pyrochlore Y2Mo2O7 from neutron diffraction and neutron pair distribution function analysis

The observation of canonical spin-glass behavior in the pyrochlore oxide Y2Mo2O7 has been a subject of considerable interest as the original structural studies were interpreted in terms of a well-ordered crystallographic model. It is widely held that the stabilization of the spin-glass state requires some level of positional disorder along with frustration. Recent reports from local probe measurements, extended x-ray-absorption fine structure (EXAFS) and Y-89 NMR, have been interpreted in terms of disorder involving the Mo-Mo distances (EXAFS) and multiple Y sites (NMR). This work reports results from temperature-dependent (15-300 K) neutron diffraction (ND) and neutron pair distribution function studies which can provide from the same data set information on both the average and local structures. The principal findings are that: (1) there is no crystallographic phase transition over the temperature region studied within the resolution of the ND data; (2) the diffraction data are well fitted using a fully ordered model but with large and anisotropic displacement parameters for three of the four atomic sites; (3) the pairwise real-space correlation function G(r) shows clear evidence that the principal source of disorder is associated with the Y-O1 atom pairs rather than the Mo-Mo pairs, in disagreement with the interpretation of the EXAFS results; (4) fits to the G(r) improve significantly when anisotropic displacements for all sites are included; (5) inclusion of a split-site position parameter for O1 improves, slightly, both the G(r) fits and the Rietveld fits to the ND data; and (6) for all models the fits become worse as the temperature decreases and as the fitting range decreases. These results are qualitatively consistent with the Y-89 NMR observations and perhaps recent muon-spin-relaxation studies. The issue of static versus dynamic disorder is not resolved, definitively. An estimate of the distribution of exchange constants due to the disorder is made using spin-dimer analysis and compared with the Saunders-Chalker model for the generation of spin-glass behavior from "weak" disorder on geometrically frustrated lattices