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Red emitting cubic Y 2 O 3 :Eu 3+ nanophosphor with an average particle size in the range of 10-20 nm was synthesized using a more facile gel-polymer pyrolysis process. The maximum relative luminescence yield obtained for the nanophosphor prepared with a urea and PVA combination is about 30% in relation to the bulk Y 2 O 3 :Eu 3+ industrial red phosphor. The photoluminescence excitation spectrum monitoring the dominant hypersensitive 5 D 0 f 7 F 2 red emission of Eu 3+ comprises two parts, viz., the dominant Eu 3+ -O 2 chargetransfer band and a weak excitonic band (or its tail) corresponding to the Y 3+ -O 2-host matrix absorption. The relative strengths of these two bands have a strong dependence on the particle size. Furthermore, in this nanocrystalline insulator system having a band gap of about 6 eV, it is possible to observe a size dependent blue shift (∼600 cm -1 ) in the photoluminescence excitation band corresponding to the Urbach tail region of the yttria host matrix. Both the bulk and nanocrystalline Y 2 O 3 :Eu 3+ show storage luminescence, a phenomenon previously unknown in this system. The mechanisms responsible for this appear to be different in these systems. The storage luminescence in the bulk system can be attributed to lattice defects, whereas that in the nanocrystalline counterpart is from a meta-stable, photoinduced surface-states arising from chemisorbed species.

Fluorescence properties have been studied for Mn:ZnS crystallites with average diameter of 4 nm prepared by an aqueous colloidal method under 266 nm light excitation. The intensity ratio of the blue band at ∼430 nm to the orange band at ∼590 nm has decreased after the preparation on a time scale of hours in aqueous solution. On the other hand, hyperfine structures of Mn 2+ in the electron paramagnetic resonance spectrum have increased markedly on the same time scale in solution samples. These phenomena are attributed to the redistribution of defect centers in nanocrystals. Such phenomena have not been observed in samples incorporated into poly(vinyl alcohol). The orange emission is mainly due to the 6 A 1 r 4 T 1 transition of Mn 2+ , while the blue emission is tentatively assigned to the donor-acceptor pair transition in which the acceptor is related to the Zn 2+ vacancy. Fluorescence decay times of the blue and orange bands have been found to be ∼10 ns and ∼1 ms, respectively, the latter being the same as in the bulk samples. A weak fluorescent component with fast kinetics observed in the orange region has been identified as a tail of the blue band. No lifetime shortening of the Mn 2+ emission due to quantum confinement has been observed, contrary to reports in the literature.

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M5(PO4)3X apatites are well known for their technological importance as phosphors, laser hosts and biocompatible materials. Divalent-europium-activated alkaline earth chloroapatites are of special importance for their application as the blue component in high-efficiency trichromatic fluorescent lamps. In these apatites, Eu2+ yields narrow-band emission in the blue region corresponding to the 4f65d to 8S7/2 allowed electric dipole transition. It has been found that the dominant emission band observed can be assigned to Eu2+ occupying MII sites of the apatite system having C1h symmetry. In the case of barium chloroapatites one could also observe Eu2+ emission from a second type of site (MI) that is available in the apatite system. The weak emission observed in the latter can be attributed to the intense spectral overlap with the former site(s) and thermal quenching effects. The exchange coupling between the 4f6 and 5d electrons of Eu2+ manifests itself in 'stair-case' features in the excitation spectrum and the strength of the exchange interaction is highly dependent on the host apatite(s). Also, in the Eu2+, Mn2+ co-doped system, energy transfer is found to occur from the former to the latter and the transfer is regulated by an exchange process. Various results based on these facts are discussed in detail.

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Luminescent Y3Al5O12: Ce3+ [yttrium aluminum garnet (YAG):Ce3+] nanoceramics (5–50 nm) have been prepared through a facile sol-gel pyrolysis route. A blueshift of about 720 cm−1 in the reflectance spectra near the absorption edge can be observed for YAG:Ce3+ nanoparticles (having an average particle size around 5 nm) with respect to the submicron powders (∼0.9 μm). Furthermore, the scope of application for this important luminescent system can be extended by isostructural substitution with heavier cations such as Ba2+. This substitution giving rise to an oxygen-vacancy defect complex, that exhibits certain size-sensitive exciton-impurity energy-transfer property in YAG:Ce3+ nanoparticles.