Structural and optical properties of GdAlO3:RE3+ (RE = Eu or Tb) prepared by the Pechini method for application as X-ray phosphors

In this work, GdAlO3:RE3+ (RE = Eu or Tb) was successfully prepared by the Pechini method at lower temperatures when compared to others methods as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. The differential thermal analysis (DTA) shows a crystallization peak at 850 degrees C. The samples are composed by monocrystalline particles (50-120 nm) exhibiting the formation of aggregates among them, which indicates the beginning of the sinterization process. This feature indicates a strong tendency to the formation of aggregates, which is a suitable ability for the close-packing of particles, and hence a potential application in X-ray intensifying screens. Luminescence measurements indicate Gd3+ -> RE3+ energy transfer. The Eu3+ emission spectra exhibit all the characteristics D-5(0) -> F-7(j) transitions and the observed profile suggests that RE3+ ions occupy at least one site without center of symmetry. For terbium-doped samples, the D-5(3) -> F-7(j) (blue emission) and D-5(4) -> F-7(j) (green emission) transitions were observed and the ratio between them may depend on the Tb3+ content due to cross-relaxation processes. (C) 2009 Elsevier B.V. All rights reserved.

Eu3+ as a spectroscopic probe in phosphors based on spherical fine particle gadolinium compounds

This work reports on the luminescence spectroscopy sensitivity in the determination of the phase purity in gadolinium compounds using Eu3+ as a probe. Cubic Gd2O3 and hexagonal Gd2O2S doped with Eu3+ spherical fine particles were obtained from doped gadolinium basic carbonates with morphological control and were also characterized by IR and XRD. Doped samples present Eu3+ characteristic transitions, with specific energy positions related to each phase. Emission and excitation spectra patterns were established for oxide and oxysulfide compounds, then oxysulfate and oxide impurities generated during oxysulfide preparation were monitored. From emission spectra some experimental intensity parameters were also calculated. All spectroscopic results reflect the presence or not of impurities in all compounds. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Study of the annealing temperature effect on the structural and luminescent properties of SrWO4:Eu phosphors prepared by a non-hydrolytic sol-gel process

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

UVC emitting phosphors obtained by spray pyrolysis

The broadband inter-configurational (4f(1)5d(1)-->4f(2)) emission of Pr(3+) doped in lanthanum orthophosphate (LaPO(4)) and in calcium pyrophosphate (Ca(2)P(2)O(7)) has been investigated under plasma excitation. The synthesis by spray pyrolysis at moderate temperature followed by a controlled annealing proves to be a very efficient way to produce good quality UVC emitting phosphor Ca(1.92)Pr(0.04)Na(0.04)P(2)O(7) (alpha phase). The emission of this phosphor in the wavelength range 200-350 nm has been measured with a prototype device, which can be employed for anti-microbial testing. (C) 2010 Elsevier B.V. All rights reserved.

Full-color phosphors from amine-functionalized crosslinked hybrids lacking metal activator ions

Sol-gel derived hybrids that contain OCH2CH2 (polyethylene glycol, PEG) repeat units grafted onto a siliceous backbone by urea, -NHC(=O)NH-, or urethane, -NHC(=O)O-, bridges have been prepared. It is demonstrated that the white light PL of these materials results from an unusual convolution of a longer lived emission that originates in the NH groups of the urea/urethane bridges with shorter lived electron-hole recombinations occurring in the nanometer-sized siliceous domains. The PL efficiencies reported here (maximum quantum yields at room temperature of ≈ 0.20 ± 0.02 at a 400 nm excitation wavelength) are in the same range as those for tetramethoxysilane-formic acid, and APTES-acetic acid, sol-gel derived phosphors. The high quantum yields combined with the possibility of tuning the emission to colors across the chromaticity diagram present a wide range of potential applications for these hybrid materials.

The effect of Eu3+ concentration on the Y2O3 host lattice obtained from citrate precursors

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

Yttrium oxysulfide nanosized spherical particles doped with Yb and Er or Yb and Tm: efficient materials for up-converting phosphor technology field

This work reports on the preparation, structural and luminescent studies of nanosized up-converter phosphors Y2O2S:Yb(4%), Er(0.1%) and Y2O2S:Yb(4%), Tm(0.1%),both from polymeric and basic carbonate precursors. The precursors were submitted to a sulphuration process that was previously developed for oxysulfide preparation from basic carbonate. From XRD data, all phosphors presented the oxysulfide phase and the mean crystallite size estimated from the Scherrer formula in the range of 15-20 nm. Polymeric precursor leads to the smallest crystallite size independent on the doping ion. SEM and TEM results confirmed that basic carbonate leads to spherical particles with narrow size distribution and mean diameter of 150 nm, and polymeric precursor smaller spherical particles with diameter between 20 and 40 nm. Up-conversion studies under 980 nm laser excitation showed that Er-doped phosphors present strong green emission related to H-2(11/2), S-4(3/2) --> I-4(15/2) Er transitions as well as the red ones, F-4(9/2) --> I-4(15/2). Tm-doped samples show strong blue emission assigned to (1)G(4) --> H-3(6) and also the red ones, related to (1)G(4) --> F-3(4). Therefore, the sulphuration method was successfully applied to prepare nanosized and nanostructured blue and green up-converter oxysulfide phosphors starting from basic carbonate and polymeric precursors. (C) 2003 Elsevier B.V. All rights reserved.

Microwave synthesis of YAG : Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl3, YCl3 and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800 C during I h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 C. For the samples pretreated at 800 degrees C, the YAG phase appears in 30s. The excitation spectra present a maximum of 394 nm corresponding to the L-5(6) level and emission spectra of Eu III ion present bands characteristic transitions arising from the D-5(0) -> F-7(J) (J= 1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole D-5(0) -> F-7(1) transition presents more intensity than the electric dipole D-5(0) -> F-7(2) transition. This methodology showed efficiency in obtaining YAG phase. (c) 2006 Elsevier B.V. All rights reserved.

Luminescence of europium(III) and manganese(II) in barium and zinc orthosilicate

The aim of this work is to report on the luminescence properties of BaZnSiO4 activated by Eu3+ and Mn2+ ions. Doped and undoped powder samples were prepared by solid-state reaction starting from oxides and carbonates or Ba2SiO4:Eu3+ and Zn2SiO4:Mn2+ precursors. X-ray diffraction powder data, IR vibrational, and UV-vis luminescence spectroscopies were carried out. Results showed that doped and undoped samples from both types of precursors have the same structure and crystallize with a superstructure of hexagonal kalsilite. Vibrational spectroscopy has confirmed the formation of a silicate group, which outlines differences between products and silicate precursors. The observed luminescence assigned to Eu3+ and Mn2+ transitions covered most parts of the visible spectrum, an important requirement for phosphors in fluorescent low-pressure mercury vapor lamps.

Effects of dispersion by Gd3+ upon europium diphenylphosphinate luminescence

A series of binary diphenylphosphinates with Eu3+ and Gd3+ were prepared. The compounds have the general formula Gd1-xEux(DPP)(3), where x ranges from 0 to 1. The spectroscopic measurements show interesting behavior. The intensity of the D-5(0) --> F-7(2) transitions decreases relative to D-5(0) --> F-7(1) With an increase in europium dispersion. Inside the temporal domain, the same decrease is observed with increasing delay after excitation. The lifetimes are also affected, which can be seen in the x = 1 compound, where the decay is a first-order process and lifetime values are 4.81 ms. In the binary compound, as an effect of dispersion, the lifetime of the D-5(0) level measured at the D-5(0) --> F-7(1) transition increases with europium dispersion, and the average along the series is 6.25 ms. The decay measured at the D-5(0) --> F-7(2) transitions reveals a second-order process with lifetimes ranging from 1.90 to 6.00 ms. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Determination of the local site occupancy of Eu3+ ions in ZnAl2O4 nanocrystalline powders

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.

Sistema para realização de medidas de luminescência com excitação por raios X

In this work is presented a versatile system for X-ray excited optical luminescence (XEOL) measurements. The apparatus was assembled from a sample holder connected to an optical fiber responsibly for the acquisition of the scintillation signal. The spectrum is registered with a CCD coupled in a spectrograph provided with diffraction gratings. The system performance was analyzed by exciting GdAlO3:Eu3+ 3.0 at.% with X-rays from a diffractometer and measuring the emission spectra. The system can be used to obtain precise and reliable spectroscopic properties of samples with various conformations without the loss of the required safety when dealing with ionizing radiations.

Luminescent multifunctional biocellulose membranes

Luminescent biocellulose membranes were obtained by incorporation of ethanolic solutions of the europium compounds [Eu(BTFAC)3(H2O)2], [Eu(BTFA) 3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] (BTFAC- 4,4,4-Trifluoro-1- phenyl-1,3-butanedione DBSO- dibenzyl sulfoxide, PTSO- p-Tolyl sulfoxide and FSO- phenyl sulfoxide). Selfsustainable semi-transparent composite membranes were obtained showing strong emission under UV exctiation. The antenna hole played by the ligands was observed to be more efficient in the composite membranes than in the precursor complexes which by themselves are also strong red emitter compounds. These new multifuctional membranes could find application in different areas as phosphors and UV→Visible energy converting devices. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).