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Issue 37, 2013
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Energy-transfer from Gd(iii) to Tb(iii) in (Gd,Yb,Tb)PO4 nanocrystals

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The photoluminescence properties of (Gd,Yb,Tb)PO4 nanocrystals synthesized via a hydrothermal route at 150 °C are reported. Energy-transfer from Gd3+ to Tb3+ is witnessed by the detailed analyses of excited-state lifetimes, emission quantum yields, and emission and excitation spectra at room temperature, for Tb3+ concentrations ranging from 0.5 to 5.0 mol%. Absolute-emission quantum yields up to 42% are obtained by exciting within the 6I7/2–17/2 (Gd3+) manifold at 272 nm. The room temperature emission spectrum is dominated by the 5D47F5 (Tb3+) transition at 543 nm, with a long decay-time (3.95–6.25 ms) and exhibiting a rise-time component. The 5D37F6 (Tb3+) rise-time (0.078 ms) and the 6P7/28S7/2 (Gd3+) decay-time (0.103 ms) are of the same order, supporting the Gd3+ to Tb3+ energy-transfer process. A remarkably longer lifetime of 2.29 ms was measured at 11 K for the 6P7/28S7/2 (Gd3+) emission upon excitation at 272 nm, while the emission spectrum at 11 K is dominated by the 6P7/28S7/2 transition line, showing that the Gd3+ to Tb3+ energy-transfer process is mainly phonon-assisted with an efficiency of ∼95% at room temperature. The Gd3+ to Tb3+ energy transfer is governed by the exchange mechanism with rates between 102 and 103 s−1, depending on the energy mismatch conditions between the 6I7/2 and 6P7/2 levels of Gd3+ and the Tb3+ 5I7, 5F2,3 and 5H5,6,7 manifolds and the radial overlap integral values.

Graphical abstract: Energy-transfer from Gd(iii) to Tb(iii) in (Gd,Yb,Tb)PO4 nanocrystals

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The article was received on 21 Mar 2013, accepted on 15 Jul 2013 and first published on 17 Jul 2013

Article type: Paper
DOI: 10.1039/C3CP52365A
Phys. Chem. Chem. Phys., 2013,15, 15565-15571

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    Energy-transfer from Gd(III) to Tb(III) in (Gd,Yb,Tb)PO4 nanocrystals

    M. L. Debasu, D. Ananias, J. Rocha, O. L. Malta and L. D. Carlos, Phys. Chem. Chem. Phys., 2013, 15, 15565
    DOI: 10.1039/C3CP52365A

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