White Light and Multicolor Emission Tuning in Triply Doped Yb3+/Tm3+/Er3+ Novel Fluoro-phosphate Transparent Glass-ceramics

New Yb3+, Er3+ and Tm3+ doped fluoro-phosphate glasses belonging to the system NaPO3–YF3–BaF2–CaF2 and containing up to 10 wt% of rare-earth ion fluorides were prepared and characterized by differential scanning calorimetry, absorption spectroscopy and up-conversion emission spectroscopy under excitation with a 975 nm laser diode. Transparent and homogeneous glass-ceramics have been reproducibly obtained with a view to manage the red, green and blue emission bands and generate white light. X-ray diffraction as well as electron microscopy techniques have confirmed the formation of fluorite-type cubic nanocrystals at the beginning of the crystallization process while complex nanocrystalline phases are formed after a longer heat-treatment. The prepared glass-ceramics exhibit high optical transparency even after 170 h of thermal treatment. An improvement of up-conversion emission intensity – from 10 to 160 times larger – was measured in the glass-ceramics when compared to the parent glass, suggesting an important incorporation of the rare-earth ions into the crystalline phase(s). The involved mechanisms and lifetime were described in detail as a function of heat-treatment time. Finally, a large range of designable color rendering (from orange to turquoise through white) can be observed in these materials by controlling the laser excitation power and the crystallization rate.

Al3+ environments in nanostructured ZnAl2O4 and their effects on the luminescence properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Excitation mechanisms and effects of dopant concentration in Gd2O2S : Tb3+ phosphor

Gadolinium oxysulfide powders doped with different Tb3+ concentrations were prepared from sulfur vaporization on rare earths' basic carbonate precursors. Single-phase Gd2O2S samples were obtained, with Tb3+ doping up to 9 at%. The study of the excitation mechanisms revealed that the Tb3+ emission might occur after the direct Tb3+ excitation either by energy transfer from Gd3+ or from the phosphor host. The characteristic terbium emission lines were observed, resulting from the radiative decay from D-5(3) or D-5(4), to F-7(j) levels. The cross-relaxation phenomenon was observed and its effects on the materials emission color were discussed based on the CIE diagram. By using time-resolved spectroscopy, D-5(3) -> F-7(J) and D-5(4) -> F-7(J) transitions were separated. (c) 2007 Elsevier B.V. All rights reserved.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

Spectral redistribution of waveguided emission in BEH-PPV films

We report on spectral redistribution of the photoluminescence (PL) emission from the edge of thin-film planar waveguides of the conjugated polymer BEH-PPV [Poly(2,5-bis(2'-ethyl-hexyl)-1,4-phenylenevinylene] induced by self-absorption in the polymer film. The PL spectra present drastic changes and displace to longer wavelengths with increasing self-absorption. We observe an enhancement of the absolute PL intensity at longer wavelengths, which was interpreted as due to re-emission of self-absorbed photons. The significant efficiency for the PL re-emission suggests the use of self-absorption as a mechanism for tuning the emission into the near infrared.