The binding of strontium and europium by an aquatic fulvic acid--ion exchange distribution and ultrafiltration studies

The complexation of an aquatic fulvic acid, FA, with Sr(2+) and Eu(3+) was studied at 0.10 and O1.O1M NaClO(4) using trace levels of metal ([Sr(2+)] = 10(-9)M and [Eu(3+)] = 10(-11)M) and a constant FA concentration (0.12 g/l) by an ultrafiltration technique (UF) and an ion exchange distribution method (IEDS). The overall complex formation function, beta(OV) for the two metals was calculated and its dependence on pH, ionic strength and method was investigated. The absolute value of log beta(OV), the pH dependence and the influence of the ionic strength on the complexation differed depending on the metal ion and experimental technique employed. By considering the functional group heterogeneity of the FA molecule, it was possible to predict the most predominantly bound site (keto-enol) and resolve the complex formation function for this site and EU(3+) (IEDS: 9.43 +/- 0.29 l/eq at 0.10M and 10.58 +/- 0.72 l/eq at 0.01M; UF: 7.19 +/- 1.51 l/eq at 0.01M and 6.88 +/- 0.91 l/eq at 0.01M). The results are discussed in the light of possible intrinsic problems of the two experimental methods.     

Europium complexation by an aquatic fulvic acid - effects of competing ions

Effects of competing ions, Fe (2+)Fe (3+) and Al(3+), on Eu(3+) complexation with an aquatic fulvic acid (FA), have been investigated using an ion exchange technique. The influence of different concentrations (10(-6), 10(-4) M) of the competing ions on the distribution coefficient for Eu was measured, and the overall complex formation function, beta(ov), was resolved for the Eu systems with Fe and Al. All systems showed pH-dependent beta(ov)-functions. The presence of 10(-4) M concentration of competing ion reduced the resolved complex formation function (logbeta(ov)) for Eu complexation with fulvic acid by 0.6 and 0.4 log units at pH 5 for Fe and Al, respectively. this indicates that Fe has a more perturbing effect on Eu-FA complexation than Al. In similar competition studies Sr and Eu were found not to perturb each others complexation with fulvic acid, suggesting therefore that the two metals probably bind to different sites on the fulvic acid molecule.     

LaOF:Eu3+ nanocrystals: hydrothermal synthesis, white and color-tuning emission properties

Uniform LaOF and LaOF : Eu(3+) nanocrystals of the γ-form have been successfully synthesized under mild conditions via a facile hydrothermal method followed a heat treatment of their bastnaesite-type precursor (LaCO(3)F). The synthetic details, investigations into the phase purity and the presence of the oxocarbonate anion CO(3)(2-) proven by IR measurements and EDX, as well as X-ray powder diffraction data, are given. Photoluminescence (PL) and cathodoluminescence (CL) spectra were utilized to characterize the luminescence properties of the LaCO(3)F : Eu(3+) and LaOF : Eu(3+) samples. Under ultraviolet light excitation, the LaCO(3)F : Eu(3+) precursor shows an orange emission of Eu(3+) (dominated by (5)D(0)→(7)F(1)), while the product of heat treatment, LaOF : Eu(3+), shows the characteristic emissions of Eu(3+) ((5)D(J)→(7)F(J')J, J' = 0, 1, 2, 3 transitions). Under the excitation of UV and low-voltage electron beams, the emission color (including white) of LaOF : Eu(3+) can be tuned by adjusting the doping concentration of Eu(3+). The corresponding luminescence mechanisms have been discussed in detail.     

A new emission band of Eu2+ and its efficient energy transfer to Mn2+ in Sr2Mg3P4O15:Mn2+, Eu2+

Eu(2+) singly and Eu(2+), Mn(2+) co-doped Sr(2)Mg(3)P(4)O(15) exhibit not only the well known blue emission band of Eu(2+) peaking at 448 nm but also a new band at 399 nm in violet. They are attributed to Eu(2+) on different Sr(2+) sites. The Eu(2+) for the violet band can transfer energy to the red emitting Mn(2+) more efficiently than Eu(2+) for the blue band. The new Eu(2+) band could enable Sr(2)Mg(3)P(4)O(15):Mn(2+), Eu(2+) to be a promising phosphor for enriching the red component of white LEDs.     

Mesoporous rare earth fluoride nanocrystals and their photoluminescence properties

YF(3) and YF(3):Eu(3+) mesoporous hexagonal nanocrystals were successfully synthesized via a simple hydrothermal process based on the in situ assembly of the as-synthesized YF(3) and YF(3):Eu(3+) nanoparticles. The well defined mesoporous nanostructures are formed by phenanthroline assisted assembly of ～20 nm nanoparticles, and 2-4 nm pores are contained as indicated by N(2) adsorption-desorption studies. The obtained YF(3):Eu(3+) mesoporous hexagonal nanoplates show a significant photoluminescence intensity enhancement compared with other shaped YF(3):Eu(3+) nanocrystals.     

Synthesis and photoluminescence properties of Ce3+ and Eu2+-activated Ca7Mg(SiO4)4 phosphors for solid state lighting

Ce(3+) and Eu(2+) singly doped and Ce(3+)/Eu(2+)-codoped Ca(7)Mg(SiO(4))(4) phosphors are synthesized by the conventional solid state reaction. The Ce(3+) activated sample exhibits intense blue emission under 350 nm excitation, the composition-optimized Ca(7)Mg(SiO(4))(4)?:?4%Ce(3+) shows better color purity than the commercial blue phosphor, BaMgAl(10)O(17)?:?Eu(2+) (BAM?:?Eu(2+)) and exhibits superior external quantum efficiency (65%). The Ca(7)Mg(SiO(4))(4)?:?Eu(2+) powder shows a broad emission band in the wavelength range of 400-600 nm with a maximum at about 500 nm. The strong excitation bands of the Ca(7)Mg(SiO(4))(4)?:?Eu(2+) in the wavelength range of 250-450 nm are favorable properties for applications as light-emitting-diode conversion phosphors. Furthermore, the energy transfer from the Ce(3+) to Eu(2+) ions is observed in the codoped samples, the resonance-type energy transfer is determined to be due to the dipole-dipole interaction mechanism and the critical distance is obtained through the spectral overlap approach and concentration quenching method.     

Novel red-emitting Ba2Tb(BO3)2Cl:Eu phosphor with efficient energy transfer for potential application in white light-emitting diodes

A novel red-emitting Ba(2)Tb(BO(3))(2)Cl:Eu phosphor possessing a broad excitation band in the near-ultraviolet (n-UV) region was synthesized by the solid-state reaction. Versatile Ba(2)Tb(BO(3))(2)Cl compound has a rigid open framework, which can offer two types of sites for various valence's cations to occupy, and the coexistence of Eu(2+)/Eu(3+) and the red-emitting luminescence from Eu(3+) with the aid of efficient energy transfer of Eu(2+)-Eu(3+)(Tb(3+)) and Tb(3+)-Eu(3+) have been investigated. Ba(2)Tb(BO(3))(2)Cl emits green emission with the main peak around 543 nm, which originates from (5)D(4) → (7)F(5) transition of Tb(3+). Ba(2)Tb(BO(3))(2)Cl:Eu shows bright red emission from Eu(3+) with peaks around 594, 612, and 624 nm under n-UV excitation (350-420 nm). The existence of Eu(2+) can be testified by the broad-band excitation spectrum, UV-vis reflectance spectrum, X-ray photoelectron spectrum, and Eu L(3)-edge X-ray absorption spectrum. Decay time and time-resolved luminescence measurements indicated that the interesting luminescence behavior should be ascribed to efficient energy transfer of Eu(2+)-Eu(3+)(Tb(3+)) and Tb(3+)-Eu(3+) in Ba(2)Tb(BO(3))(2)Cl:Eu phosphors.     

A facile reduction of Eu3+ to Eu2+ in gadolinium monosulfide nanoparticles using a mixed solvent of oleic acid/hexadecylamine

We prepared GdS:Eu(3+) by simple thermal decomposition under 1-dodecanethiol. A reduction process was observed from Eu(3+) to Eu(2+) when oleic acid and hexadecylamine were injected into GdS:Eu(3+). Under UV excitation, GdS:Eu(3+) showed an intense orange-red emission and GdS:Eu(2+) showed a broad green band.     

Disappearance and recovery of luminescence in Bi3+, Eu3+ codoped YPO4 nanoparticles due to the presence of water molecules up to 800 °C

YPO(4) nanoparticles codoped with Eu(3+) (5 at. %) and Bi(3+) (2-10 at. %) have been synthesized by a simple coprecipitation method using a polyethylene glycol-glycerol mixture, which acts as capping agent. It has been found that the incorporation of Bi(3+) ions into the YPO(4):Eu(3+) lattice induces a phase transformation from tetragonal to hexagonal, and also a significant decrease in Eu(3+) luminescence intensity was observed. This is related to the association of the water molecules in the hexagonal phase of YPO(4) in which the nonradiative process from the surrounding water molecules around Eu(3+) is dominating over the radiative process. On annealing above 800 °C, luminescence intensity recovers due to significant removal of water. 900 °C annealed Bi(3+) codoped YPO(4):Eu(3+) shows enhanced luminescence (2-3 times) as compared to that of YPO(4):Eu(3+). When sample was prepared in D(2)O (instead of H(2)O), 4-fold enhancement in luminescence was observed, suggesting the extent of reduction of multiphonon relaxation in D(2)O. This study illustrates the stability of water molecules even at a very high temperature up to 800 °C in Eu(3+) and Bi(3+) codoped YPO(4) nanoparticles.     

Preparation of Gd(2)O(3) : Eu(3+) and Gd(2)O(2)S : Eu(3+) phosphor fine particles using an emulsion liquid membrane system

Size- (submicrometer-sized) and morphology- (spherical) controlled composite Gd-Eu oxalate particles were prepared in an emulsion liquid membrane (water-in-oil-in-water emulsion) system. The oxalate particles thus prepared were calcined in air to obtain Gd(2)O(3) : Eu(3+) phosphor particles and in sulfur atmosphere to obtain Gd(2)O(2)S : Eu(3+) phosphor particles. These submicrometer-sized spherical phosphor particles showed photoluminescence properties with emission peak at 614 nm for Gd(2)O(3) : Eu(3+) and 628 nm for Gd(2)O(2)S : Eu(3+).     

Luminescence and microstructures of Eu(3+)-doped Ca9LiGd(2/3)(PO4)7

A red-emitting phosphor, Eu(3+)-doped Ca(9)LiGd(2/3)(PO(4))(7), was synthesized by the conventional high-temperature solid-state reaction. X-ray powder diffraction (XRD) analyses confirmed the pure crystalline phase of Whitlockite-type structure. The excitation spectra of Eu(3+) doped Ca(9)LiGd(2/3)(PO(4))(7) were measured in the VUV and UV region indicating an efficient energy transfer process from the host and Gd(3+) to Eu(3+) ions. Upon excitation with VUV and UV radiation, the phosphor showed strong red emission around 611 nm corresponding to the forced electric dipole (5)D(0)→(7)F(2) transition of Eu(3+) ions. The VUV- and UV-excited luminescence spectra of Ca(9)LiGd(2/3)(PO(4))(7):Eu(3+) together with the dependence of the integrated emission intensities on the doping levels were investigated. The Eu(3+) ions were investigated by a tunable laser as an excitation source. The excitation spectra of (7)F(0)→(5)D(0) transitions suggest that there are two families of inequivalent sites for Eu(3+) in this host. The concentration quenching and crystallographic site-occupancy of Eu(3+) ions in Ca(9)LiGd(2/3)(PO(4))(7) host were discussed on the basis of the site selective excitation and emission spectra, the luminescence decay and its crystal structure.     

The thermal stabilities of luminescence and microstructures of Eu2+-doped KBaPO4 and NaSrPO4 with β-K2SO4 type structure

Eu(2+)-doped monophosphates NaSrPO(4) and KBaPO(4) with the β-K(2)SO(4) structure were synthesized using the conventional high temperature solid state reaction. The X-ray powder diffraction, photoluminescence excitation, and emission spectra and decay curves were measured. The phosphors can be efficiently excited by UV-visible light from 220 to 430 nm to realize emission in the visible range. The natures of the Eu(2+) emission, e.g., the chromaticity coordinates, the Stokes shifts, and the luminescence absolute quantum efficiencies, were reported. The luminescence quenching temperatures and the thermal activation energies for NaSrPO(4):Eu(2+) and KBaPO(4):Eu(2+) were obtained from the temperature dependent (10-435 K) luminescence intensities and decay curves. KBaPO(4):Eu(2+) presents only one emission center; however, Eu(2+) ions have a "disordered environment" in NaSrPO(4) lattices. The relationship between the luminescence thermal stabilities and the crystal structures was discussed. The crystallographic occupations of rare earth ions doped in these hosts were analyzed by the site-selective emission spectra and the excitation spectra of Eu(3+) ions in the (7)F(0)→(5)D(0) transitions using a pulsed, tunable, and narrow-band dye laser. In KBaPO(4), the Eu(3+) ions could be distributed in the host with a high "ordered state" in only one site in the lattices. However, the multiple site structure of Eu(3+) ions with highly disordered distributions in NaSrPO(4) lattices was suggested.     

Energy transfer and tunable luminescence properties of Eu3+ in TbBO3 microspheres via a facile hydrothermal process

Tb (1- x) BO 3: xEu (3+) ( x = 0-1) microsphere phosphors have been successfully prepared by a simple hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL), low-voltage cathodoluminescence (CL), and time-resolved emission spectra as well as lifetimes were used to characterize the samples. The as-obtained phosphor samples present sphere-like agglomerates composed of nanosheets with highly crystallinity in spite of the moderate reaction temperature of 200 degrees C. Under ultraviolet excitation into the 4f (8) --> 4f (7)5d transition of Tb (3+) at 245 nm (or 284 nm) and low-voltage electron beams' excitation, TbBO 3 samples show the characteristic emission of Tb (3+) corresponding to (5)D 4 --> (7)F 6, 5, 4, 3 transitions; whereas TbBO 3:Eu (3+) samples mainly exhibit the characteristic emission of Eu (3+) corresponding to (5)D 0 --> (7)F 0, 1, 2, 3, 4 transitions due to an efficient energy transfer occurs from Tb (3+) to Eu (3+). The increase of Eu (3+) concentration leads to the increase of the energy-transfer efficiency from Tb (3+) to Eu (3+) but also enhances the probability of the interaction between neighboring Eu (3+), which results in the concentration quenching. The PL color of TbBO 3: xEu (3+) phosphors can be easily tuned from green, yellow, orange, to red-orange by changing the doping concentration ( x) of Eu (3+), making the materials have potential applications in fluorescent lamps for advertizing signs and other color display fields.     

Nanocrystalline CaYAlO4:Tb3+/Eu3+ as promising phosphors for full-color field emission displays

Eu(3+) and/or Tb(3+)-doped CaYAlO(4) phosphor samples were synthesized by Pechini-type sol-gel method. X-Ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) and cathodoluminescence (CL) spectra were used to characterize the samples. For CaYAlO(4):Tb(3+), it is shown that the Tb(3+)-doping concentration has a significant effect on the (5)D(3)/(5)D(4) emission intensity of Tb(3+), which is attributed to the cross relaxation from (5)D(3) to (5)D(4). Under the 4f(8)→ 4f(7)5d excitation of Tb(3+) or low-voltage electron beams excitation, the CaYAlO(4):Tb(3+) phosphors show tunable luminescence from blue to cyan, and then to green with the change of Tb(3+)-doping concentration. The CaYAlO(4):Eu(3+) samples exhibit a reddish-orange emission of Eu(3+) corresponding to (5)D(0,1)→(7)F(0,1,2,3) transitions. Furthermore, a white emission can be realized in the single phase CaYAlO(4) host by reasonably adjusting the doping concentrations of Tb(3+) and Eu(3+) under low-voltage electron beams excitation. Compared with the commercial blue (Y(2)SiO(5):Ce(3+)) and green (ZnO:Zn) phosphors, CaYAlO(4):0.1%Tb(3+) and CaYAlO(4):5%Tb(3+) phosphors have higher CL intensity and stability under continuous electron bombardment. Due to the excellent CL properties and good CIE chromaticity coordinates, the as-prepared Tb(3+)/Eu(3+)-doped CaYAlO(4) nanocrystalline phosphors have potential application in FEDs devices.     

Effect of thermal annealing on the kinetics of rehydroxylation of Eu3+:La2O3 nanocrystals

Europium-doped lanthanum oxide (5 mol % Eu(3+):La(2)O(3)) was prepared by calcining europium-doped lanthanum hydroxide (5 mol % Eu(3+):La(OH)(3)) previously synthesized by a simple hydrothermal method. Interestingly, we observed different emission Eu(3+) signatures depending on the phase of the host (lanthanum oxide or hydroxide) by cathodoluminescence. Taking into account that lanthanum oxide easily rehydroxylates in air, for the first time, we report the use of cathodoluminiscence as a novel characterization technique to follow the lanthanum oxide rehydroxylation reaction versus time according to different annealing procedures. Additionally, differential thermal-thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction techniques were used to identify the phases formed from the Eu(3+):La(OH)(3) depending on temperature and to study the evolution of La(2)O(3) to La(OH)(3) versus time. The results showed that the higher the temperature and the longer the annealing time, the higher the resistance to rehydroxylation of the Eu(3+):La(2)O(3) sample.     

Combinatorial search for green and blue phosphors of high thermal stabilities under UV excitation based on the K(Sr1-x-y)PO4:Tb3+ xEu2+y system

The present investigation aims at the synthesis of KSr 1-x-y PO 4:Tb(3+) x Eu(2+) y phosphors using the combinatorial chemistry method. We have developed square-type arrays consisting of 121 compositions to investigate the optimum composition and luminescence properties of KSrPO 4 host matrix under 365 nm ultraviolet (UV) light. The optimized compositions of phosphors were found to be KSr 0.93PO 4:Tb(3+) 0.07 (green) and KSr 0.995PO 4:Eu(2+) 0.005 (blue). These phosphors showed good thermal luminescence stability better than commercially available YAG:Ce at temperature above 200 degrees C. The result indicates that the KSr 1-x-y PO 4:Tb(3+) x Eu (2+)y can be potentially useful as a UV radiation-converting phosphor for light-emitting diodes.     

Electrospinning synthesis and luminescence properties of one-dimensional La(9.33)(SiO4)6O2: Ln3+ (Ln = Ce, Eu, Tb) microfibers

One-dimensional La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers were fabricated by a simple and cost-effective electrospinning method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and low voltage cathodoluminescence (CL) as well as kinetic decay were used to characterize the resulting samples. SEM and TEM results indicated that the diameter of the microfibers annealed at 1000 °C for 3 h was 200-245 nm. The microfibers were further composed of fine and closely linked nanoparticles. La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors showed the characteristic emission of Ce(3+) (5d → 4f), Eu(3+) ((5)D(0)→(7)F(J)) and Tb(3+) ((5)D(3,4)→(7)F(J)) under ultraviolet excitation and low-voltage electron beams (3-5 kV) excitation. An energy transfer from Ce(3+) to Tb(3+) was observed in the La(9.33)(SiO(4))(6)O(2): Ce(3+), Tb(3+) phosphor under ultraviolet excitation and low-voltage electron beam excitation. Luminescence mechanisms were proposed to explain the observed phenomena. Blue, red and green emission can be realized in La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers by changing the doping ions. So the La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors have potential applications in full-color field emission displays.     

Site-selective time-resolved laser fluorescence spectroscopy of Eu3+ in calcite

Three samples of calcite homogeneously doped with Eu(3+) were synthesized in a mixed-flow reactor. By means of selective excitation of the 5D0-->7F0 transition at low temperatures (T<20 K), three different Eu(3+) species (species A, B, and C, respectively) could be discriminated. For each one, the emission spectrum and lifetime were obtained after selective excitation of the single species. On the basis of these data, species C could be identified as Eu(3+) incorporated into the calcite lattice on the (nearly) octahedral Ca(2+) site. Species B was also identified as Eu(3+) incorporated into the calcite lattice, but the ligand field shows a much weaker symmetry. Species A, however, is not incorporated into the crystal's bulk, having 1-2 H(2)O ligands left in its first coordination sphere and showing very little symmetry, and is considered as Eu(3+) adsorbed onto the calcite surface. The emission spectra of species C for Eu:calcite grown in the presence of Na(+) were found to differ from those of Eu:calcite synthesized in the presence of K(+). The latter revealed a strong distortion in site symmetry, which was not observed in the samples grown in Na(+) solutions. This finding provides spectroscopic evidence in favor of an incorporation mechanism based on the charge-balanced coupled substitution of Na(+)+Eu(3+)<-->2Ca(2+).     

3D flower-like Y(2)O(3):Eu(3+) nanostructures: template-free synthesis and its luminescence properties

In this work, a facile route using simple hydrothermal reaction and sequential calcinations to synthesize 3-dimensional flower-like Y(2)O(3):Eu(3+) nanoarchitectures without employing templates or matrix for self-assembly is presented. The flower-like nanostructures are composed of nanosheets with thickness of about 30 nm, which is verified by the field-emission electron microscopy (FESEM). Influencing factors such as the dosage of reactants, the solvent, and pH are systematically investigated. The time-dependent experiments indicate a self-assembly mechanism. This method is also applicable in the preparation of other lanthanide oxides. The PL spectra of the as-synthesized Y(2)O(3):Eu(3+) are systematically studied. Both the Eu(3+) concentration and the calcinations temperature have great effect on the luminescence intensity of (5)D(0)-(7)F(2) transition. The decay curve of the (5)D(0) transition shows that the lifetime of the as-obtained Y(2)O(3):Eu(3+) is about 2.4 ms.