Upconversion luminescence in transparent glass ceramics containing beta-PbF2 nanocrystals doped with erbium

Frequency upconversion luminescence in erbium-doped PbGeO3-PbF2-CdF2-based transparent glass ceramics (TGC) under 980 nm infrared excitation is investigated. Upconversion emission signals around 410, 525, 550, 660, and 850 nm were generated and identified as due to the H-2(9/2) H-2(11/2), S-4(3/2), and F-4(9/2) transitions to the I-4(15/2) ground-state, and S-4(3/2)-I-4(13/2), respectively. The erbium ions excited-state emitting levels were populated via a combination of stepwise ground-state absorption (GSA), excited-state absorption (ESA), and cross-relaxation processes. The results also disclosed that both blue (410 nm) and red (660 nm) upconversion emission signals in the transparent glass ceramic sample presented twice as much intensity as compared to its vitreous counterpart. (C) 2003 Elsevier B.V. All rights reserved.

Blue cooperative luminescence properties in Yb3+ doped GeO2-PbO-Bi2O3 vitreous system for the production of thin films

Germanate glasses are of interest for optoelectronic applications because they combine high mechanical strength, high chemical durability and temperature stability with a large transmission window (400 to 4500 nm) and high refractive index (2.0). GeO2-PbO-Bi2O3 glasses doped with Y-b(3+) were fabricated by melting powders in a crucible and then pouring them in a brass mold. Energy Dispersive Spectroscopy showed that the glass composition has a high spatial uniformity and that the Yb concentration in the solid sample is proportional to the Yb concentration in the melt, what was confirmed by absorption measurements. Intense blue emission at 507 nm was observed, corresponding to half of the wavelength of the near infrared region (NIR) emission; besides, a decay lifetime of 0.25 ms was measured and this corresponds to half of the decay lifetime in the infrared region; these are very strong indications of the presence of blue cooperative luminescence. Larger targets have been produced to be sputtered, resulting in thin films for three dimensional (3D) display and waveguide applications. (c) 2006 Elsevier B.V. All rights reserved.

Energy-transfer frequency upconversion in neodymium-sensitized praseodymium-doped PbGeO3-PbF2-CdF2 glass excited at 810 nm

Visible frequency upconversion emission through resonant energy-transfer involving neodymium and praseodymium ions in PbGeO3-PbF2-CdF2 glass excited by a semiconductor laser at 8 10 nm is investigated. Luminescence emission centered around 485, 530, 610, and 645 nm, which correspond to the P-3(0) -> H-3(4), P-3(1) + I-1(6) -> H-3(5), P-3(0) -> H-3(6) and P-1(0) -> F-3(2) transitions of praseodymium ions, respectively, are observed. The upconversion excitation of the Pr3+ ions excited-state emitting levels was accomplished by means of an ion-pair interaction involving ground-state absorption, multiphonon relaxation, and excited-state absorption of pump photons at 8 10 nm by the Nd3+ (I-4(9/2) -> H-2(9/2), F-4(5/2); F-4(3/2) -> P-2(1/2)) and direct energy-transfer to Pr3+ ((4)G(11/2) + K-2(11/2), H-3(4) -> I-4(9/2), P-3(1) + I-1(6)). The dependence of the upconversion emission intensity upon the excitation power, and neodymium concentration are also examined. (c) 2004 Elsevier B.V. All rights reserved.

Optical characteristics of Er3+-Yb3+ doped SnO2 xerogels

Er3+ doped SnO2 xerogels have been obtained from aqueous colloidal suspensions. Emission and excitation spectra were obtained and allowed the identification of two main families of sites for Er3+. In the first one Er3+ substitutes for Sn4+ in the SnO2 cassiterite structure. In the second Er3+ are found adsorbed at the SnO2 particle surface. For the first family of sites the technological important infrared Er3+ emission about 1.5 mum is efficiently excited through absorption at the SnO2 conduction band at 3.8 eV. on the other hand the emission due to adsorbed ions appears inhomogeneously broadened by the statistical distribution of sites available for Er3+ ions at the surface of the particles. Moreover it is not excited by the host. The emission of this second family of sites could be also excited by an energy transfer mechanism involving Yb3+ ions also adsorbed a posteriori at particles surface. Results are compared with spectra obtained for Eu3+ doped samples. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Morphological and luminescent studies on nanosized Er, Yb-Yttrium oxide up-converter prepared from different precursors

In this paper, we report luminescent and morphological studies with yttrium oxide samples doped with ytterbium and erbium. The samples were prepared by the combustion method and also from different precursors: oxalate, basic carbonate and polymeric resin. All powders were identified Lis being an yttrium oxide with a C-form structure, independent of the employed precursor. From mean crystallite size measurements, it was verified that oxides prepared through the polymeric precursor and combustion methods lead to the smallest crystallite size. Particle shape and size were investigated by SEM and TEM, and showed that both the oxalate precursor and the combustion methods do not provide oxide materials of suitable shape or size, on the other hand. The basic carbonate and polymeric precursors resulted in spherically shaped particles with an average diameter of 90 and 15 run. respectively, Upon 980 run diode laser excitation, green and red emission lines were detected for all samples and were assigned to the H-2(11/2) S-4(3/2) -> I-4(15/2) and (4)Fg(9/2) -> 4I(15/12) transitions, respectively. Such transitions are characteristic for Er3+ and result from energy transfer from Yb3+ energy levels, F-2(7/2) -> F-2(5/2). A relationship between the decrease in the mean crystallite size and the enhancement in red emission was also established as well as the influence of the presence of a high percentage of Yb-3 Both factors promote ET from Yb3+ (F-2(5/2)) to Er3+ (I-4(11/2)). (c) 2004 Elsevier B.V. All rights reserved.

Enhanced emission from Eu(III) beta-diketone complex combined with ether-type oxygen atoms of di-ureasil organic-inorganic hybrids

Organic-inorganic hybrids, named di-ureasils and described by polyether-based chains grafted to both ends to a siliceous backbone through urea cross linkages, were used as hosts for incorporation of the well-known coordination complex of trivalent europium (Eu3+) ions described by the formula [Eu(TTA)(3)(H2O)(2)] (where TTA stands for thenoyltrifluoroacetone). By comparing with Eu3+-doped di-ureasil without complex form the new materials prepared here enhanced the quantum efficiency for photoemission of Eu3+ ions. The enhancement can be explained by the coordination ability of the organic counterpart of the host structure which is strong enough to displace water molecules in [Eu(TTA)(3)(H2O)(2)] from the rare earth neighbourhood after the incorporation process. High intensity of Eu3+ emission was observed with a low non-radiative decay rate under ultraviolet excitation. The quantum efficiency calculated from the decay of D-5(0) emission was 74%, which in the same range of values previously obtained for the most efficient Eu3+ coordination compounds reported in literature. Luminescence, X-ray absorption and infrared absorption results considered together leads to a picture where the first coordination shell of Eu3+ is composed of the 6 oxygen atoms of the 3 beta-diketonate ligands and 2 ether-like oxygen atoms of the host. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Magnetic properties of acicular Fe1-xREx (RE = Nd, Sm, Eu, Tb; x=0, 0.05, 0.10) metallic nanoparticles

Acicular monodispersed Fe1-xREx (RE= Nd, Sm,Eu,Tb;x=0, 0.05, 0.10) metallic nanoparticles (60 +/- 5 nm in length and axial ratio similar to6) obtained by reduction of alumina-coated goethite nanoparticles-containing rare earth (RE) under hydrogen flow are reported. Alumina and maghemite thin layers on particle surface were used to protect the goethite particles against sintering and oxidation, respectively. Al and RE additions were obtained by successive heterocoagulation reactions. Aluminum sulfate (10 at.% based on Fe) was dissolved in water and the pH adjusted to 12.5 with NaOH solution. Goethite particles were suspended in this solution and CO2 gas was blown into the slurry to neutralize it to a pH 8.5 or less. Particles were purified and dehydrated to effect transformation to alumina-coated hematite nanoparticles, which were re-suspended in aqueous solution in which RE sulfate (0-0.15 at.% based on Fe) has been dissolved, and the pH increased by ammonia aqueous solution addition. Resulted alumina-coated RE-doped hematite nanoparticles were reduced to metal at 450 degreesC/12 h under hydrogen flow and passivated with nitrogen-containing ethanol vapor at room temperature. Acicular monodispersed metallic nanoparticle systems were obtained and the presence of Al and RE were confirmed by induced-coupled plasma spectrometry analysis. X-ray diffraction, Mossbauer spectroscopy, and magnetization data are in agreement with the nanosized alpha-Fe core in a bcc structure, having a spinel structure, gammaFe(2)O(3), with thickness similar to1.5 run on particle surface. Main magnetic parameters showed saturation magnetization decreases and significant increasing in the coercive field with the RE composition increases. Magnetic properties of these particles, similar to40% smaller than those commercially available, suggest a decrease in the bit-size for high-density magnetic or magneto-optics recording media application. (C) 2004 Published by Elsevier B.V.

The Role of the Eu3+ Concentration on the SrMoO4:Eu Phosphor Properties: Synthesis, Characterization and Photophysical Studies

SrMoO4 doped with rare earth are still scarce nowadays and have attracted great attention due to their applications as scintillating materials in electro-optical like solid-state lasers and optical fibers, for instance. In this work Sr1-xEuxMoO4 powders, where x = 0.01; 0.03 and 0.05, were synthesized by Complex Polymerization (CP) Method. The structural and optical properties of the SrMoO4:Eu3+ were analyzed by powder X-ray diffraction patterns, Fourier Transform Infra-Red (FTIR), Raman Spectroscopy, and through Photoluminescent Measurements (PL). Only a crystalline scheelite-type phase was obtained when the powders were heat-treated at 800 A degrees C for 2 h, 2 theta = 27.8A degrees (100% peak). The excitation spectra of the SrMoO4:Eu3+ (lambda(Em.) = 614 nm) presented the characteristic band of the Eu3 + 5L6 transition at 394 nm and a broad band at around 288 nm ascribed to the charge-transfer from the O (2p) state to the Mo (4d) one in the SrMoO4 matrix. The emission spectra of the SrMoO4:Eu3+ powders (lambda(Exc.) = 394 and 288 nm) show the group of sharp emission bands among 523-554 nm and 578-699 nm, assigned to the D-5(1)-> F-7(0,1and 2) and D-5(0)-> F-7(0,1,2,3 and 4), respectively. The band related to the D-5(0)-> F-7(0) transition indicates the presence of Eu3+ site without inversion center. This hypothesis is strengthened by the fact that the band referent to the D-5(0)-> F-7(2) transition is the most intense in the emission spectra.

Multiwavelength visible and white light generation by upconversion emission in Ho/Tm/Yb triply doped fluorogermanate glass-ceramic

Energy transfer excited multiwavelength visible upconversion emission and white light generation is described in a single sample of PbGeO(3)-PbF(2)-CdF(2) glass-ceramic triply doped With Ho/Tm/Yb under single infrared laser excitation. Blue (475 nm), green (540 mn), and red (650 nm), upconversion luminescence signals are generated, and the emissions are assigned, respectively, to thulium ((1)G(4)-(3)H(6)), and holmium ((5)S(2);(5)F(4)) -> (5)I(8), (5)F(5) -> (5)I(8)) ions transitions, both excited via successive energy transfers from ytterbium ions. It is experimentally shown that with a proper combination of the rare earth ions contents, white light may be produced, with the simultaneous generation of fluorescence with controllable intensities at the wavelengths of the three primary colours in a single sample and using a single near-infrared excitation source.

Effect of the ytterbium concentration on the upconversion luminescence of Yb3+/Er3+ co-doped PbO-GeO2-Ga2O3 glasses

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

Tm and Tm-Tb-doped germanate glasses for S-band amplifiers

The mechanism involved in the Tm(3+)((3)F(4)) -> Tb(3+)((7)F(0,1,2)) energy transfer as a function of the Tb concentration was investigated in Tm:Tb-doped germanate (GLKZ) glass. The experimental transfer rate was determined from the best fit of the (3)F(4) luminescence decay due to the Tm -> Tb energy transfer using the Burshtein model. The result showed that the 1700 nm emission from (3)F(4) can be completely quenched by 0.8 mol% of Tb(3+). As a consequence, the (7)F(3) state of Tb(3+) interacts with the (3)H(4) upper excited state of TM(3+) slighting decreasing its population. The effective amplification coefficient beta(cm(-1)) that depends on the population density difference Delta n = n((3)H(4))-n((3)F(4)) involved in the optical transition of Tm(3+) (S-band) was calculated by solving the rate equations of the system for continuous pumping with laser at 792 nm, using the Runge-Kutta numerical method including terms of fourth order. The population density inversion An as a function of Tb(3+) concentration was calculated by computational simulation for three pumping intensities, 0.2, 2.2 and 4.4 kWcm(-2). These calculations were performed using the experimental Tm -> Tb transfer rates and the optical constants of the Tm (0.1 mol%) system. It was demonstrated that 0.2 mol% of Tb(3+) propitiates best population density inversion of Tin(3+) maximizing the amplification coefficient of Tm-doped (0.1 mol%) GLKZ glass when operating as laser intensity amplification at 1.47 mu m. (C) 2007 Elsevier B.V. All rights reserved.

Luminescence properties of Eu(3+)- and Mg(2+)-doped LiTaO(3) obtained via the polymeric precursor method

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

Violet-blue emissions due to frequency up-conversion in Nd3+-doped fluoroindate glasses

We report the observation of intense frequency up-conversion in Nd3+-doped fluoroindate glasses pumped by the second harmonic of a cw mode-locked Nd: YAG laser. Mechanisms for generating the observed emissions are discussed.

Synthesis, characterization and spectroscopy of the europium doped lanthanum trimetaphosphate

Orthorhombic modification of europium doped lanthanum trimetaphosphate has been prepared. The compound was obtained by precipitation of rare earth chloride solution with trimetaphosphoric acid. The characterizations were made using X-ray diffractometry, chemical analysis and infrared spectroscopy. Excitation and emission spectra were recorded at liquid nitrogen and room temperatures. Assignments of the 5D0→7FJ (J=0, 1, 2, 3, 4, 5) transitions were made and an unusual high 5D0→7F4 transition intensity with six split lines has been observed. Structural distortion of the crystal lattice may be caused by the Eu3+ ion inclusion. The simple overlap model was applied for the calculation of the total splitting of the 5D0→7F1 transition, the 5D0→7F0/5D 0→7F2 transition intensity ratio and the Ωλ (λ=2.4) intensity parameters. Theoretical predictions showed to be in good accordance with the experimental data. © 1988 Elsevier Science S.A.

Red, green, and blue upconversion luminescence in ytterbium-sensitized praseodymium-doped lead-cadmium-germanate glass

Blue, green, red, and near-infrared upconversion luminescence in the wavelength region of 480 - 740 nm in Pr3+/Yb3+-codoped lead-cadmium-germanate glass under 980 nm diode laser excitation, is presented. Upconversion emission peaks around 485, 530, 610, 645, and 725 nm which were ascribed to the 3P0 - 3HJ (J=4, 5, and 6), and 3P0 - 3FJ (J=2, and 3,4), transitions, respectively, were observed. The population of the praseodymium upper 3P0 emitting level was accomplished through a combination of ground-state absorption of Yb3+ ions at the 2F7/2, energy-transfer Yb3+(2F 5/2) Pr3+(3H4), and excited-state absorption of Pr3+ ions provoking the 1G4 - 3P0 transition. The dependence of the upconversion luminescence upon the Yb3+-concentration and diode laser power, is also examined, in order to subsidize the proposed upconversion excitation mechanism.