Circularly Polarized Luminescence from Pure and Eu-Doped Trigonal TbPO4·nH2O Nanocrystals.

In this contribution, we describe the preparation, by means of a precipitation reaction from aqueous solution at 40 °C, and the structural characterization of nanocrystalline powders of trigonal Tb1-xEuxPO4·nH2O (with x = 0, 0.005, 0.01, 0.05, and 0.1; n tentatively assigned as 0.67) which crystallize in the two possible P3121 or P3221 enantiomorphic space groups. While the volume of the crystal lattice is not significantly affected by the Tb3+/Eu3+ substitution, the average crystallite size seems to depend on the Eu3+ dopant concentration and ranges from 13 to 30 nm. The desired handedness of the crystals has been induced by using, during the synthesis, one of the two possible enantiomers of tartaric acid (l or d). The analysis of the luminescence excitation and emission spectra, together with the decay kinetics of the 5D4 Tb3+ excited state, suggests the presence of a very efficient Tb3+ → Eu3+ energy transfer process in the Eu3+-doped orthophosphates. Upon excitation of Tb3+ ions at 368 nm, the enantiomorphic powders grown with l- or d-tartaric acid (i.e., l-TbPO4·0.67H2O/d-TbPO4·0.67H2O, l-Tb0.995Eu0.005PO4·0.67H2O/d-Tb0.995Eu0.005PO4·0.67H2O, and l-Tb0.9Eu0.1PO4·0.67H2O/d-Tb0.9Eu0.1PO4·0.67H2O) exhibited mirror circularly polarized luminescence signals in the visible spectral region (in the green and/or in the red).