Cr3+ and Cr4+ luminescence in glass ceramic silica

This paper reports on the effect of glass ceramic silica matrix on [CrO4](4-) and Cr2O3 NIR and visible luminescence. Chromium-containing silica was obtained by precipitation from water-glass and chromium nitrate acid solution with thermal treatment at 1000 degrees C. From XRD results silica and silica-chromium samples are crystalline. The chromium emission spectrum presents two main broad bands: one in the NIR region (1.1-1.7 mu m) and other in the visible region (0.6-0.7 mu m) assigned to Cr4+ and to Cr3+, respectively. This thermal treated glass ceramic silica-chromium sample stabilizes the [CrO4](4-) where Cr4+ substitutes for Si4+ and also hexacoordinated Cr3+ group probably as segregated phase in the system. It can be pointed out that luminescence spectroscopy is a powerful toot for detecting the two chromium optical centers in the glass ceramic silica. (C) 2008 Elsevier B.V. All rights reserved.

Cr3+ and Cr4+ luminescence in glass ceramic silica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of CdF2 addition on thermal stability and upconversion luminescence properties in Tm3+-Yb3+ codoped oxyfluoride silicate glasses

Tm3+-Yb3+ codoped oxyfluoride silicate glasses suitable for upconversion laser has been fabricated. In this paper, effect of CdF2 addition on thermal stability and upconversion luminescence properties in Tm3+-Yb3+ codoped oxyfluoride silicate glasses have been systematically investigated. The experimental results indicate that, with the substitution CdF2 for PbF2, the glass thermal stability increases and the UV cutoff edge moves to short-wave band slightly. With increasing CdF2 content, the blue and red upconversion luminescence intensity increases slightly at first, and then increases rapidly. While the near infrared (NIR) upconversion emission intensity increases notably at first and then increases slightly. However, the blue and NIR luminescence intensity are much stronger than that of red, indicating these oxyfluoride silicate glasses are more preferable for blue and NIR emissions than red emission. The possible upconversion mechanisms for the blue, red and NIR fluorescence are also estimated and evaluated. (c) 2006 Elsevier B.V. All rights reserved.

Unusual broadening of the NIR luminescence of Er3+-doped Nb2O5 nanocrystals embedded in silica host: Preparation and their structural and spectroscopic study for photonics applications

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

Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

MnO4(3-) NIR luminescence in Ba2SiO4

Ba2SiO4: MnO43- luminescence is reported and compared to similar host lattices based on PO43-, VO43- and AsO43-, where Mn5+ substitutes for p(5+),V5+ Or AS(5+). The observed energy position of MnO43- 1E state in SiO44- is in accordance with interelectronic repulsion caused by Mn5+-O bond length. At 77 K the E-1 splitting is 119 cm(-1), which is in agreement with 1.8 degrees, the average deviation of O-M-O angles from the regular tetrahedron. These values are adjusted to Ca point symmetry. The vibronic-structure spectra evidenced a progression with a frequency assigned to the nu(2)(E) bending mode of MnO43-.

Effect of Calcination Temperature on Structural, Photoluminescence, and Thermo luminescence Properties of Y2O3:Eu3+ Nanophosphor

Red light emitting cubic Y1.95Eu0.05O3 nanophosphors have been synthesized by a low temperature solution combustion method using ethylene diamine tetra acetic acid (EDTA) as fuel. The systematic studies on the effect of calcination temperature on its structural, photoluminescence (PL), and thermoluminescence (TL) properties were reported. The crystallinity of the samples increases, and the strain is reduced with increasing calcination temperature. SEM micrographs reveal that samples lose their porous nature with an increase in calcination temperature. PL spectra show that the intensity of the red emission (611 nm) is highly dependent on the calcination temperature and is found to be 10 times higher when compared to as-formed samples. The optical band gap (E-g) was found to reduce with an increase of calcination temperature due to reduction of surface defects. The thermoluminescence (TL) intensity was found to be much enhanced in the 1000 degrees C calcined sample. The increase of PL and TL intensity with calcination temperature is attributed to the decrease of the nonradiative recombination probability, which occurs through the elimination of quenching defects. The trap parameters (E, b, s) were estimated from Chen's glow peak shape method and are discussed in detail for their possible usage in dosimetry.

Stimuli-responsive colorimetric and NIR fluorescence combination probe for selective reporting of cellular hydrogen peroxide

Hydrogen peroxide (H2O2) is a key reactive oxygen species and a messenger in cellular signal transduction apart from playing a vital role in many biological processes in living organisms. In this article, we present phenyl boronic acid-functionalized quinone-cyanine (QCy-BA) in combination with AT-rich DNA (exogenous or endogenous cellular DNA), i.e., QCy-BA subset of DNA as a stimuli-responsive NIR fluorescence probe for measuring in vitro levels of H2O2. In response to cellular H2O2 stimulus, QCy-BA converts into QCy-DT, a one-donor-two-acceptor (D2A) system that exhibits switch-on NIR fluorescence upon binding to the DNA minor groove. Fluorescence studies on the combination probe QCy-BA subset of DNA showed strong NIR fluorescence selectively in the presence of H2O2. Furthermore, glucose oxidase (GOx) assay confirmed the high efficiency of the combination probe QCy-BA subset of DNA for probing H2O2 generated in situ through GOx-mediated glucose oxidation. Quantitative analysis through fluorescence plate reader, flow cytometry and live imaging approaches showed that QCy-BA is a promising probe to detect the normal as well as elevated levels of H2O2 produced by EGF/Nox pathways and post-genotoxic stress in both primary and senescent cells. Overall, QCy-BA, in combination with exogenous or cellular DNA, is a versatile probe to quantify and image H2O2 in normal and disease-associated cells.

Optical transitions and upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

Er3+-doped halide modified tellurite glasses were synthesized by conventional melting and quenching method. The Judd-Ofelt analysis was performed on the absorption spectra and the transition probabilities, excited state lifetimes, and the branching ratios were calculated and discussed. The intense infrared and visible fluorescence spectra under 980 nm excitation were obtained. Strong upconversion signal was observed at pumping power as low as 30 mW in the glasses with halide ions. The upconversion mechanisms and power dependent intensities were discussed, which showed two-photon process are involved for the green and red emissions. The decay times of the emitting states and the corresponding quantum efficiency were determined and explained. (C) 2004 American Institute of Physics.

Broadband amplification and upconversion luminescence properties of Er3+/Yb3+ co-doped fluorophosphate glass

Broadband and upconversion properties were studied in Er3+/Yb3+ co-doped fluorophosphate glasses. Large Omega(6) and S-ed/(S-ed + S-md) values and the flat gain profile over 1530-1585 nm indicate the good broadband properties of the glass system. And a premise of using Omega(6) as a parameter to estimate the broadband properties of the glasses is proposed for the first time to our knowledge. Results showed that fluorescence intensity, upconversion luminescence intensity, the intensity ratio of red/green light (656 nm/545 nm) are closely related to the Yb3+:Er3+ ratio and Er3+ concentration, and the corresponding calculated lifetime of F-4(9/2) and S-4(3/2) states for red and green upconversion samples proves this conclusion. The upconversion mechanism is also discussed. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of PbCl2 addition on structure, OH- content, and upconversion luminescence in Yb3+/Er3+-codoped germanate glasses

Yb3+/ Er3+-codoped oxychloride germanate glasses have been synthesized by a conventional melting and quenching method. Structural properties were obtained based on Raman-spectra investigation, indicating that PbCl2 plays an important role in the formation of the glass network and has an important influence on the phonon density and the maximum phonon energy. The Judd - Ofelt intensity parameters and quantum efficiencies were calculated based on the Judd - Ofelt theory and lifetime measurements. The enhanced upconversion luminescence intensity of Er3+ with increasing PbCl2 content could not be explained only by the maximum phonon-energy change of the host glasses. For the first time, the effect of PbCl2 addition on phonon density, OH- content, and upconversion luminescence in oxychloride glasses has been discussed and evaluated. The results show that the effect of phonon density and OH- content on upconversion luminescence in oxychloride glasses is much stronger than that of the decrease of the maximum phonon energy. The possible upconversion luminescence mechanisms have also been estimated and are discussed.

Direct synthesis and intense luminescence of Y2O3 : Eu nanophosphors by complexation combustion

In this paper, we report the synthesis of high-luminance Y2O3:Eu nanocrystal through a citrate-nitrate complexation combustion method at a low temperature of 200-280 degrees C. The as-combusted Y2O3:Eu phosphors are almost equiaxed crystallites with an average size of 30-40 run, and have an intense red luminescence. The present fuel-deficient method suggests that by control of the ratio of citric acid to nitrates, it is valuable for the fabrication of Y2O3 nanoparticles without heat treatment. This process should be applicable to a wide range of nanocrystal oxides.

Concentration dependence of the Er3+ visible and infrared luminescence in Y2-x Erx O3 thin films on Si

Y2-x Erx O3 thin films, with x varying between 0 and 0.72, have been successfully grown on crystalline silicon (c-Si) substrates by radio-frequency magnetron cosputtering of Y2 O 3 and Er2 O3 targets. As-deposited films are polycrystalline, showing the body-centered cubic structure of Y2 O3, and show only a slight lattice parameter contraction when x is increased, owing to the insertion of Er ions. All the films exhibit intense Er-related optical emission at room temperature both in the visible and infrared regions. By studying the optical properties for different excitation conditions and for different Er contents, all the mechanisms (i.e., cross relaxations, up-conversions, and energy transfers to impurities) responsible for the photoluminescence (PL) emission have been identified, and the existence of two different well-defined Er concentration regimes has been demonstrated. In the low concentration regime (x up to 0.05, Er-doped regime), the visible PL emission reaches its highest intensity, owing to the influence of up-conversions, thus giving the possibility of using Y2-x Er x O3 films as an up-converting layer in the rear of silicon solar cells. However, most of the excited Er ions populate the first two excited levels 4I11/2 and 4I13/2, and above a certain excitation flux a population inversion condition between the former and the latter is achieved, opening the route for the realization of amplifiers at 2.75 μm. Instead, in the high concentration regime (Er-compound regime), an increase in the nonradiative decay rates is observed, owing to the occurrence of cross relaxations or energy transfers to impurities. As a consequence, the PL emission at 1.54 μm becomes the most intense, thus determining possible applications for Y2-x Erx O 3 as an infrared emitting material. © 2009 American Institute of Physics.