Effect of Ce3+ Ion on the X-Ray Induced Fluorescence Emission from CaS

The effect of Ce3+ on the fluorescence emission from CaS:Ce3+ phosphor is studied using X-ray excitation. Apart from the emission in the visible region, the phosphor also shows fluorescence emission in the ultraviolet region. Variation in wavelengths and intensities of these emissions due to change in dopant concentration is also analysed.

CE3+���ER3+/Yb3+������TeO2-WO3-ZnO���������������������������

Ce3+ ions were introduced into the Er3+/Yb3+ -codoped TeO2-WO3-ZnO glasses, and the effect of Ce3+ on the emission properties at 1.5 mu m band and the upconversion luminescence of Er3+ in the glasses was investigated. With the increasing of Ce3+ concentration, the emission intensity of Er3+ at 1.5 mu m band increases firstly, and then decreases. The optimal doping concentration of Ce3+ is about 2.07 x 10(20)/cm(3). As for the Er3+ emission at 1.5-mu m band, the fluorescence lifetime decreases a little from 3.4ms to 3.0ms, while the full width at half maximum (FWHM) hardly changes with the increase of Cc 3+ concentration. Due to the effective cross relaxation between Ce3+ and Er3+ : Er3+ (I-4(11/2)) + Ce3+ (F-2(5/2)) -> Er3+ (I-4(13/2)) + Ce3+ (F-2(7/2)), the upconversion emission intensity of Er3+ is reduced greatly. But when Ce3+ -doping concentration is too high, the other cross relaxation between Ce3+ and Er3+ : Er3+ (4I(13/2)) + Ce3+ (F-2(5/2)) -> Er3+ (I-4(15/2)) + Ce3+ (F-2(7/2)) happens, which depopulates the I-4(13/2) level of Er3+ and results in the decrease of the emission intensity and fluorescence lifetime of Er3+ at 1.5 mu m band.

Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation

Infrared to ultraviolet and visible upconversion luminescence was demonstrated in trivalent cerium doped YAlO3 crystal (Ce3+: YAP) under focused infrared femtosecond laser irradiation. The fluorescence spectra show that the upconverted luminescence comes from the 5d-4f transitions of trivalent cerium ions. The dependence of luminescence intensity of trivalent cerium on infrared pumping power reveals that the conversion of infrared radiation is dominated by three-photon excitation process. It is suggested that the simultaneous absorption of three infrared photons pumps the Ce3+ ion into upper 5d level, which quickly nonradiatively relax to lowest 5d level. Thereafter, the ions radiatively return to the ground states, leading to the characteristic emission of Ce3+. (c) 2005 Optical Society of America.

Thermoluminescence characteristics of NaSr4(BO3)(3):Ce3+ under beta-ray irradiation

The thermoluminescence (TL) properties of Ce3+ doped NaSr4(BO3)(3) phosphor under the beta-ray irradiation were reported. The polycrystalline sample was synthesized by high temperature solid-state reaction. The TL glow curve of NaSr4(BO3)(3):Ce3+ phosphor was composed of only one peak. TL kinetic parameters of NaSr4(BO3)(3):Ce3+ were deduced by the peak shape method, the activation energy (E) was 0.590 eV and the frequency factor was 1.008x10(6) s(-1). TL dose response was linear in the range of measurement. The 3-dimensional (3D) TL emission spectrum was also recorded, the emission spectrum consisted of two bands located at 441 and 479 nm respectively, corresponding to the characteristic 4f(0)5d(1)-> F-2((5/2,7/2)) transitions of the Ce3+ ion. The fading behavior of the NaSr4(BO3)(3):Ce3+ phosphor over a period of 15 d was also studied.

Ce3+ -> Eu2+ energy transfer in BaLiF3 phosphor

Photoluminescence characteristics and the energy transfer between Ce3+ and Eu2+ in BaLiF3 host lattice have been investigated. A series of concentrations of Ce3+ ion with a fixed Eu2+ concentration in doubly doped BaLiF3:Ce3+,Eu2+ have been studied. According to the defects forming after Eu2+ and Ce3+ entering the host lattice, cerium ions occupy the positions of nearest neighbors of the europium ions. The energy transfer probability and critical distance are calculated. (C) 1999 Elsevier Science Ltd. All rights reserved.

THE INVESTIGATION ON THE EMISSION CENTERS AND SUBSTITUTING SITES IN KMGF3-CE3+

With the method of high temperature solid state reaction and stockbarger, we synthesized a series of powder phosphors of KMgF3-Ce3+, KMg1-alphaMalphaF3-Ce3+(M = Be2+, Ca2+) and the single crystal of KMgF3-Ce3+. We tested their excitation and emission spectra, found two emission centers in KMgF3-Ce3+ and demonstrated that they resulted from different charge compensating ways. By the structural analysis on KMgF3-Ce-3+ from a four-cycle diffractometer and spectral analysis on KMg1-alphaMalphaF3-Ce3+(M = Be2+, Ca2+), we deduced that Ce3+ ion only.substituted K+ site in KMgF3.

Time-resolved spectroscopy studies of Gd2SiO5 : Ce3+ from spherical particles

This paper reports on time-resolved emission and excitation spectra measurement studies of Gd2SiO5:Ce3+ in powder or pellet samples, from spherical particles, in order to assign the Ce3+ ion transitions into two different symmetry sites. Samples were obtained from solid-state reaction of the spherical particles oxides, SiO2 and Gd2O3:Ce3+. From time-resolved spectroscopy measurements Ce3+ ion transitions occupying the two different gadolinium crystallographic sites in Gd2SiO5 were separated and assigned. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effect of air annealing on the spectral properties of Ce : Y3Al5O12 single crystals grown by the temperature gradient technique

Five absorption hands, at 227, 300 340, 370 and 457nm, were observed in the optical absorption spectrum of Ce:Y3Al5O12 (Ce:YAG) crystals grown by the temperature gradient technique (TGT). The absorption bands at 227, 340, and 457 nm were identified Lis belonging to the Ce3+ -ion in the YAG crystal. A near UV optical emission band at 398nm was observed. with an excitation spectrum containing two bands, at 235 and 370nm. No fluorescence was detected under 300 nm excitation. The pair of absorption bands at 235 and 370 nm and the absorption band at 300 nm were attributed to the F- and F+-type color centers, respectively. The color centers model was also applied to explain the spectral changes in the Ce:YAG (TGT) crystal, including the reduction in the Ce 31 -ion absorption intensity, after annealing in an oxidizing atmosphere (air). (C) 2004 Elsevier B.V. All rights reserved.

Czochralski growth and crystal structure of cerium-doped Lu2Si2O7 scintillator

Cerium-doped lutetium pyrosilicate crystal, Ce:Lu2Si2O7 (Ce:LPS), was grown by the Czochralski method. The segregation coefficient of Ce3+ ion was studied by the ICP-AES method. X-ray diffraction analysis showed that the structure of Ce:LPS crystal was monoclinic symmetry with space group of C2/m. Perfect cleavage planes (110) and imperfect cleavage planes (001) were observed by optical microscope. The reasons why it is difficult to grow crack-free crystals were studied. After optimized growth parameters, a Ce:LPS crystal with dimension of Phi 25 x 30 mm was grown, which is colorless, high optical quality, cracking-free and no inclusions. The transmittance of Ce:LPS crystal from 380 to 800 nm is over 82% and there is no observable absorption. (c) 2005 Elsevier B.V. All rights reserved.

Gamma-irradiation effects on Ce-doped YAG crystals grown by Cz and TGT method

Gamma-rays radiation effects on Ce:YAG crystals grown by Czochralski (Cz) and temperature gradient techniques (TGT) have been studied by means of optical absorption and luminescence spectra. Valence of Ce3+ ion changes during the gamma-ray irradiation process and this result indicates Ce4+ ion may exist in both Cz-Ce:YAG and TGT-Ce:YAG crystals. Thermally stimulated luminescence measurements reveal intense thermoluminescence peaks in gamma-irradiated Ce:YAG crystals and trap parameters were calculated by general-order kinetics expression. (C) 2006 Elsevier B.V. All rights reserved.

Synthesis, photoluminescence, thermoluminescence and dosimetry properties of novel phosphor KSr4(BO3)(3):Ce

Polycrystalline powder sample of KSr4(BO3)(3) was synthesized by high-temperature solid-state reaction. The influence of different rare earth dopants, i.e. Tb3+, TM3+ and Ce3+, on thermoluminescence (TL) of KSr4(BO3)(3) Phosphor was discussed. The TL, photoluminescence (PL) and some dosimetric properties of Ce3+-activated KSr4(BO3)(3) phosphor were studied. The effect of the concentration of Ce3+ on TL intensity was investigated and the result showed that the optimum Ce3+ concentration was 0.2 mol%. The TL kinetic parameters of KSr4(BO3)(3):0.002 Ce3+ phosphor were calculated by computer glow curve deconvolution (CGCD) method. Characteristic emission peaking at about 407 and 383 nm due to the 4f(0)5d(1) -> F-2((5/2),(7/2)) transitions of Ce3+ ion were observed both in PL and three-dimensional (3D) TL spectra. The dose-response of KSr4(BO3)(3):0.002 Ce3+ to gamma-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of KSr4(BO3)(3):0.002 Ce3+ was also investigated.

Preparation and luminescent properties of rare earth ions in M2B5O9Cl : Re(M = Ca, Sr, Ba; Re=Eu, Tb)

M2B5O9X: Re(M = Ca, Sr, Ba; X = Cl, Br; Re = Eu, Th) phosphors were synthesized via solid state method. The products were characterized with X-ray powder diffraction and luminescence spectrometer. The luminescent properties as well. as the influences of the matrix composition and other doping ions on the luminescence of the rare earth ions of the co-doped phosphors were investigated. The coexistence of Eu3+, Eu2+ and Th3+ were observed in these matrices. The phenomenon may be explained by the electron transfer theory. The sensitization of Ce3+ ion improves the intensity of emission of Eu2+, and Tb3+. The competition between electron transfer among conjugate rare earth ions and energy migration might be the reasons for the observation. We predict a novel trichromatic phosphor co-doped with Eu3+ Tb3+ in M2B5O9X.

LUMINESCENCE AND ENERGY-TRANSFER OF RARE-EARTH-METAL IONS IN MG2Y8(SIO4)(6)O-2

The photoluminescence of Ce3+, Tb3+ and Sm3+, and energy transfer from Ce3+ to Tb3+, Dy3+ and Sm3+ in Mg2Y8(SiOd(4))(6)O-2 are reported and discussed. The Ce3+ ion shows blue luminescence under UV excitation, and occupies simultaneously the 4f site and 6h site in the host lattice. The optimum concentrations for the D-5(3) and D-5(4) emissions of Tb3+ and the (4)G(5/2) emission of Sm3+ are determined to be 0.04, 0.20 and 0.10 mol in every mol of Mg2Y8(SiO4)(6)O-2, respectively. The critical distances responsible for the cross-relaxation between the D-5(3)-D-5(4) and F-7(6)-F-7(0) transitions of Tb3+ and between the (4)G(5/2)-F-4(9/2) and H-6(5/2)-F-4(9/2) transitions of Sm3+ are estimated to be 1.43 and 1.06 nm, respectively. Both Tb3+ and Dy3+ can be sensitized by Ce3+, but Ce3+ and Sm3+ quench each other.

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.

Caracteriza����o de sistemas v��treos baseados no formador B2O3 e P2O5 dopados com CeO2

Coordena����o de Aperfei��oamento de Pessoal de N��vel Superior (CAPES)