Facile synthesis and multicolor luminescent properties of uniform Lu2O3:Ln (Ln=Eu3+, Tb3+, Yb3+/Er3+, Yb3+/Tm3+, and Yb3+/Ho3+) nanospheres

Multicolor Lu(2)O(3):Ln (Ln=Eu(3+), Tb(3+), Yb(3+)/Er(3+), Yb(3+)/Tm(3+), and Yb(3+)/Ho(3+)) nanocrystals (NCs) with uniform spherical morphology were prepared through a facile urea-assisted homogeneous precipitation method followed by a subsequent calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectrum (EDS), Fourier transformed infrared (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), and photoluminescence (PL) spectra as well as kinetic decays were employed to characterize these samples. The XRD results reveal that the as-prepared nanospheres can be well indexed to cubic Lu(2)O(3) phase with high purity. The SEM images show the obtained Lu(2)O(3):Ln samples consist of regular nanospheres with the mean diameter of 95 nm. And the possible formation mechanism is also proposed. Upon ultraviolet (UV) excitation, Lu(2)O(3):Ln (Ln=Eu(3+) and Tb(3+)) NCs exhibit bright red (Eu(3+), (5)D(0)→(7)F(2)), and green (Tb(3+), (5)D(4)→(7)F(5)) down-conversion (DC) emissions. Under 980 nm NIR irradiation, Lu(2)O(3):Ln (Ln=Yb(3+)/Er(3+), Yb(3+)/Tm(3+), and Yb(3+)/Ho(3+)) NCs display the typical up-conversion (UC) emissions of green (Er(3+), (4)S(3/2),(2)H(11/2)→(4)I(15/2)), blue (Tm(3+), (1)G(4)→(3)H(6)) and yellow-green (Ho(3+), (5)F(4), (5)S(2)→(5)I(8)), respectively.     

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.     

Synthesis and characterization of heterodinuclear Ln(3+)-Fe3+ and Ln(3+)-Co3+ complexes,bridged by cyanide ligand (Ln3+ = lanthanide ions). Nature of the magnetic interaction in the Ln(3+)-Fe3+ complexes

The reaction of Ln(NO3)3.aq with K3[Fe(CN)6] or K3[Co(CN)6] in N,N'-dimethylformamide (DMF) led to 25 heterodinuclear [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O and [Ln(DMF)4(H2O)3(mu-CN)Co(CN)5].nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr(3+)-Fe3+), (Tm(3+)-Fe3+), (Ce(3+)-Co3+), (Sm(3+)-Co3+), and (Yb(3+)-Co3+) have been structurally characterized; they crystallize in the equivalent monoclinic space groups P21/c or P21/n. Structural studies of these two families show that they are isomorphous. This relationship in conjunction with the diamagnetism of the Co3+ allows an approximation to the nature of coupling between the iron(III) and the lanthanide(III) ions in the [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O complexes. The Ln(3+)-Fe3+ interaction is antiferromagnetic for Ln = Ce, Nd, Gd, and Dy and ferromagnetic for Ln = Tb, Ho, and Tm. For Ln = Pr, Eu, Er, Sm, and Yb, there is no sign of any significant interaction. The isotropic nature of Gd3+ helps to evaluate the value of the exchange interaction.     

YF3:Ln3+ (Ln = Ce, Tb, Pr) submicrospindles: hydrothermal synthesis and luminescence properties

YF(3):Ln(3+) (Ln = Ce, Tb, Pr) microspindles were successfully fabricated by a facile hydrothermal method. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), lifetimes, photoluminescence (PL) and low-voltage cathodoluminescence (CL) were used to characterize the resulting samples. The lengths and diameters of YF(3):0.02Ce(3+) microspindles are around 760 nm and 230 nm, respectively. Adding dilute acid and trisodium citrate (Cit(3-)) are essential for obtaining YF(3) microspindles. A potential formation mechanism for YF(3) microspindles has been presented. PL spectroscopy investigations show that YF(3):Ce(3+) and YF(3):Tb(3+) microcrystals exhibit the characteristic emission of Ce(3+) 5d → 4f and Tb(3+ 5)D(4)→(7)F(J) (J = 6-3) transitions, respectively. In addition, the energy transfer from Ce(3+) to Tb(3+) was investigated in detail for YF(3):Ce(3+), Tb(3+) microspindles. Under the excitation of electron beams, YF(3):Pr(3+) show quantum cutting emission and YF(3):Ce(3+), Tb(3+) phosphors exhibit more intense green emission than the commercial phosphor ZnO:Zn.     

Uniform hollow Lu2O3:Ln (Ln = Eu3+, Tb3+) spheres: facile synthesis and luminescent properties

Uniform hollow Lu(2)O(3):Ln (Ln = Eu(3+), Tb(3+)) phosphors have been successfully prepared via a urea-assisted homogeneous precipitation method using carbon spheres as templates, followed by a subsequent calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed infrared (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), photoluminescence (PL) spectra, cathodoluminescence (CL) spectra, kinetic decays, quantum yields (QY), and UV-visible diffuse reflectance spectra were employed to characterize the samples. The results show that hollow Lu(2)O(3):Ln spheres can be indexed to cubic Gd(2)O(3) phase with high purity. The as-prepared hollow Lu(2)O(3):Ln phosphors are confirmed to be uniform in shape and size with diameter of about 300 nm and shell thickness of approximate 20 nm. The possible formation mechanism of evolution from the carbon spheres to the amorphous precursor and to the final hollow Lu(2)O(3):Ln microspheres has been proposed. Upon ultraviolet (UV) and low-voltage electron beams excitation, the hollow Lu(2)O(3):Ln (Ln = Eu(3+), Tb(3+)) spheres exhibit bright red (Eu(3+), (5)D(0)-(7)F(2)) and green (Tb(3+), (5)D(4)-(7)F(5)) luminescence, which may find potential applications in the fields of color display and biomedicine.     

Bifunctional Mixed-Lanthanide Cyano-Bridged Coordination Polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), Tb(3+)/Sm(3+))

A new family of mixed-lanthanide cyano-bridged coordination polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (where Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), and Tb(3+)/Sm(3+)) containing two lanthanide and one transition metal ions were obtained and characterized by X-ray diffraction, photoluminescence spectroscopy, magnetic analyses, and theoretical computation. These compounds are isotypical and crystallize in the tetragonal system P4/nmm forming two-dimensional grid-like networks. They present a magnetic ordering at low temperature and display the red Eu(3+) ((5)D(0) → (7)F(0-4)) and green Tb(3+) ((5)D(4) → (7)F(6-2)) characteristic photoluminescence. The Tb(0.5)Eu(0.5)(H(2)O)(5)[W(CN)(8)] compound presents therefore green and red emission and shows Tb(3+)-to-Eu(3+) energy transfer.     

Hydrothermal synthesis, dimension evolution and luminescence properties of tetragonal LaVO4:Ln (Ln = Eu3+, Dy3+, Sm3+) nanocrystals

Well-defined 1D and 3D t-LaVO(4):Ln (Ln = Eu(3+), Dy(3+), Sm(3+)) nanocrystals with regular and uniform shapes were synthesized through a simple hydrothermal route assisted by disodium ethylenediaminetetraacetic acid (Na(2)EDTA). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), as well as kinetic decay curves were employed to characterize the samples. The results show that the reaction time, pH value of the initial solution, and Na(2)EDTA/La(3+) molar ratio all have an important influence on the dimension and shapes of the final products. By introducing the "splitting mechanism" to the dimension and morphology evolution process from one-dimensional (1D) to three-dimensional (3D) t-LaVO(4) crystals, the nucleation and crystal growth processes were well demonstrated. The Ln(3+) ions doped t-LaVO(4) samples exhibit respective bright red, blue-white and orange luminescence of Eu(3+), Dy(3+), and Sm(3+) under ultraviolet excitation, and have potential application in the fields of colour display, UV laser and biomedicine. The results not only expand the knowledge of the properties of lanthanide orthovanadates luminescence, but also contribute to the principles of the crystal growth and dimension transition of this kind of inorganic material.     

Phase transition from hexagonal LnF3 (Ln = La, Ce, Pr) to cubic Ln0.8M0.2F2.8 (M = Ca, Sr, Ba) nanocrystals with enhanced upconversion induced by alkaline-earth doping

Complete phase transition from hexagonal LnF(3) (Ln(3+) = La(3+), Ce(3+), Pr(3+)) to monodisperse ultrasmall (～7 nm) cubic Ln(0.8)M(0.2)F(2.8) (M(2+) = Ca(2+), Sr(2+), Ba(2+)) disordered solid solution nanocubes was successfully achieved through alkaline-earth doping, which induced great intensification of the near-infrared to visible upconversion emissions of the optically active rare earth ions.     

Monodisperse mesocrystals of YF3 and Ce3+/Ln3+ (Ln=Tb, Eu) co-activated YF3: shape control synthesis, luminescent properties, and biocompatibility

A family of monodisperse YF(3), YF(3):Ce(3+) and YF(3):Ce(3+)/Ln(3+) (Ln=Tb, Eu) mesocrystals with a morphology of a hollow spindle can be synthesized by a solvothermal process using yttrium nitrate and NH(4) F as precursors. The effects of reaction time, fluorine source, solvents, and reaction temperature on the synthesis of these mesocrystals have been studied in detail. The results demonstrate that the formation of a hollow spindle-like YF(3) can be ascribed to a nonclassical crystallization process by means of a particle-based reaction route in ethanol. It has been shown that the fluorine sources selected have a remarkable effect on the morphologies and crystalline phases of the final products. Moreover, the luminescent properties of Ln(3+)-doped and Ce(3+)/Ln(3+) -co-doped spindle-like YF(3) mesocrystals were also investigated. It turns out that Ce(3+) is an efficient sensitizer for Ln(3+) in the spindle-like YF(3) mesocrystals. Remarkable fluorescence enhancement was observed in Ce(3+)/Ln(3+) -co-doped YF(3) mesocrystals. The mechanism of the energy transfer and electronic transition between Ce(3+) and Ln(3+) in the host material of YF(3) mesocrystals was also explored. The cytotoxicity study revealed that these YF(3) -based nanocrystals are biocompatible for applications, such as cellular imaging.     

The fabrication of one-dimensional Ca4Y6(SiO4)6O: Ln3+ (Ln=Eu, Tb) phosphors by electrospinning method and their luminescence properties

One-dimensional Ca(4)Y(6)(SiO(4))(6)O: Ln(3+) (Ln=Eu, Tb) microfibers were fabricated by a simple and cost-effective electrospinning method. X-ray diffraction (XRD) pattern and high-resolution transmission electron microscopy (HRTEM) confirmed that the fibers were composed of hexagonal Ca(4)Y(6)(SiO4)(6)O phase. Thermogravimetric and differential scanning calorimetry (TG-DSC) results showed that the Ca(4)Y(6)(SiO4)(6)O phase began to crystallize at 740°C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results indicated that the diameter of as-prepared microfibers ranged from 390 to 900 nm and the diameter of the microfibers annealed at 1000°C ranged from to 120 to 260 nm. Under ultraviolet and low-voltage electron beams (3-5 kV) excitation, the Ca(4)Y(6)(SiO(4))(6)O: Ln(3+) (Ln=Eu, Tb) samples showed the red and green emission, corresponding to (5)D(0)→(7)F(2) transition of Eu(3+) and (5)D(4)→(7)F(5) transition of Tb(3+), respectively.     

Controlling electron trap depth to enhance optical properties of persistent luminescence nanoparticles for in vivo imaging

Focusing on the use of nanophosphors for in vivo imaging and diagnosis applications, we used thermally stimulated luminescence (TSL) measurements to study the influence of trivalent lanthanide Ln(3+) (Ln = Dy, Pr, Ce, Nd) electron traps on the optical properties of Mn(2+)-doped diopside-based persistent luminescence nanoparticles. This work reveals that Pr(3+) is the most suitable Ln(3+) electron trap in the diopside lattice, providing optimal trap depth for room temperature afterglow and resulting in the most intense luminescence decay curve after X-ray irradiation. This luminescence dependency toward the electron trap is maintained through additional doping with Eu(2+), allowing UV-light excitation, critical for bioimaging applications in living animals. We finally identify a novel composition (CaMgSi(2)O(6):Eu(2+),Mn(2+),Pr(3+)) for in vivo imaging, displaying a strong near-infrared afterglow centered on 685 nm, and present evidence that intravenous injection of such persistent luminescence nanoparticles in mice allows not only improved but highly sensitive detection through living tissues.     

Luminescence properties and quenching mechanisms of Ln(Tf2N)3 complexes in the ionic liquid bmpyr Tf2N

The emission properties, including luminescence lifetimes, of the lanthanide complexes Ln(Tf(2)N)(3) (Tf(2)N = bis(trifluoromethanesulfonyl)amide); Ln(3+) = Eu(3+), Tm(3+), Dy(3+), Sm(3+), Pr(3+), Nd(3+), Er(3+)) in the ionic liquid bmpyr Tf(2)N (bmpyr = 1-n-butyl-1-methylpyrrolidinium) are presented. The luminescence quantum efficiencies, η, and radiative lifetimes, τ(R), are determined for Eu(3+)((5)D(0)), Tm(3+)((1)D(2)), Dy(3+)((4)F(9/2)), Sm(3+)((4)G(5/2)), and Pr(3+)((3)P(0)) emission. The luminescence lifetimes in these systems are remarkably long compared to values typically reported for Ln(3+) complexes in solution, reflecting weak vibrational quenching. The 1.5 μm emission corresponding to the Er(3+) ((4)I(13/2)→(4)I(15/2)) transition, for example, exhibits a lifetime of 77 μs. The multiphonon relaxation rate constants are determined for 10 different Ln(3+) emitting states, and the trend in multiphonon relaxation is analyzed in terms of the energy gap law. The energy gap law does describe the general trend in multiphonon relaxation, but deviations from the trend are much larger than those normally observed for crystal systems. The parameters determined from the energy gap law analysis are consistent with those reported for crystalline hosts. Because Ln(3+) emission is known to be particularly sensitive to quenching by water in bmpyr Tf(2)N, the binding properties of water to Eu(3+) in solutions of Eu(Tf(2)N)(3) in bmpyr Tf(2)N have been quantified. It is observed that water introduced into these systems binds quantitatively to Ln(3+). It is demonstrated that Eu(Tf(2)N)(3) can be used as a reasonable internal standard, both for monitoring the dryness of the solutions and for estimating the quantum efficiencies and radiative lifetimes for visible-emitting [Ln(Tf(2)N)(x)](3-x) complexes in bmpyr Tf(2)N.     

Highly uniform and monodisperse Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres: solvothermal synthesis and luminescence properties

Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres were successfully prepared through a facile and mild solvothermal method followed by a subsequent heat treatment. X-ray diffraction (XRD) results demonstrate that all the diffraction peaks of the samples can be well indexed to the pure hexagonal phase of Gd(2)O(2)S. The energy dispersive spectroscopy (EDS), element analysis, and FT-IR results show that the precursors are composed of the Gd, Eu, O, S, C, H, and N elements. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that these spheres are actually composed of randomly aggregated nanoparticles. The formation mechanism for the Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres has been proposed on an isotropic growth mechanism. Under ultraviolet excitation, Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres show red and green emission corresponding to the (5)D(0)→(7)F(2) transition of the Eu(3+) ions and the (5)D(4)→(7)F(5) transition of the Tb(3+) ions. Furthermore, this synthetic route may have potential applications for fabricating other lanthanide oxysulfides.     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

Tunable full-color-emitting Ca3Sc2Si3O12:Ce3+, Mn2+ phosphor via charge compensation and energy transfer

A tunable full-color-emitting Ca(3)Sc(2)Si(3)O(12):Ce(3+), Mn(2+) (CSS:Ce(3+),Mn(2+)) phosphor is obtained by addition of doped ions as charge compensation. White LEDs with high R(a) (> 90) are achieved using the single CSS:Ce(3+),Mn(2+) phosphor.     

Luminescence investigation on ultraviolet-emitting rare-earth-doped phosphors using synchrotron radiation

Three series of new ultraviolet-emitting Ca(9)Y(PO(4))(7):Ln(3+) (Ln = Ce, Gd, Pr) phosphors were synthesized, and their luminescence was investigated. Under vacuum ultraviolet excitation Ca(9)Y(PO(4))(7):Ce(3+) phosphors emit UVA light with one broad emission centered at 346 nm, on account of the 5d(1) → 4f(1) transition of Ce(3+) ions; the optimal doping concentration of these phosphors is 0.2 mol. Ca(9)Y(PO(4))(7):Gd(3+) phosphors show a strong 4f(7) → 4f(7) transition and a sharp UVB emission band at 312 nm; the optimal doping concentration of these phosphors is 0.7 mol. The PL spectra of Ca(9)Y(PO(4))(7):Pr(3+) show two broad UVC emission bands centered between 230 and 340 nm, owing to the 4f(1)5d(1) → 4f(2) transition of Pr(3+) ions; the optimal doping concentration of these phosphors is 0.2 mol. Under 172 nm excitation, we found that the luminescence intensity of the UVA-emitting Ca(9)Y(PO(4))(7):0.2Ce(3+) is 0.3675 times that of BaSi(2)O(5):0.05Pb(2+), that of the UVB-emitting Ca(9)Y(PO(4))(7):0.7Gd(3+) is 1.7 times that of YAl(3)(BO(3))(4):0.25Gd(3+), and that of the UVC-emitting Ca(9)Y(PO(4))(7):0.2Pr(3+) is 1.5 times that of LaPO(4):0.1Pr(3+). The thermal stability investigation indicated that the luminescence decay was only 9.2%, 18.2%, and 10.3% for Ca(9)Y(PO(4))(7):0.2Ce(3+), Ca(9)Y(PO(4))(7):0.7Gd(3+), and Ca(9)Y(PO(4))(7):0.2Pr(3+) at 250 °C relative to that at ambient temperature, respectively. The Ca(9)Y(PO(4))(7):Ln(3+) (Ln = Ce, Gd, Pr) phosphors exhibit high emission efficiency and excellent thermal stability.     

Selective detection of Fe2+ by combination of CePO4:Tb3+ nanocrystal-H2O2 hybrid system with synchronous fluorescence scan technique

A new method for quenching kinetic discrimination of Fe(2+) and Fe(3+), and sensitive detection of trace amount of Fe(2+) was developed by using synchronous fluorescence scan technique. The principle of this assay is based on the quenching kinetic discrimination of Fe(2+) and Fe(3+) in CePO(4):Tb(3+) nanocrytals-H(2)O(2) hybrid system and the Fenton reaction between Fe(2+) and H(2)O(2). Stable, water-soluble and well-dispersible CePO(4):Tb(3+) nanocrystals were synthesized in aqueous solutions, and characterized by transmission electron microscopy (TEM) and electron diffraction spectroscopy (EDS). We found that both Fe(2+) and Fe(3+) could quench the synchronous fluorescence of CePO(4):Tb(3+) nanocrytals-H(2)O(2) system, but their quenching kinetics velocities were quite different. In the presence of Fe(3+), the synchronous fluorescent intensity was unchanged after only one minute, but in the presence of Fe(2+), the synchronous fluorescent intensity decreased slowly until 28 min later. The Fenton reaction between Fe(2+) and H(2)O(2) resulted in hydroxyl radicals which effectively quenched the synchronous fluorescence of the CePO(4):Tb(3+) nanocrystals due to the oxidation of Ce(3+) into Ce(4+) by hydroxyl radicals. Under optimum conditions, the linear range for Fe(2+) is 3 nM-2 μM, and the limit of detection is 2.0 nM. The method was used to analyze water samples.     

Optimization of Pr3+, Tb3+, and Sm3+ co-doped (Y0.65Gd0.35)BO3:Eu0.05(3+) VUV phosphors through combinatorial approach

A combinatorial approach was used to systematically investigate the effect of trace Pr(3+), Tb(3+), or Sm(3+) on the VUV photoluminescence of Eu(3+) in the Pr(3+), Tb(3+), or Sm(3+) co-doped (Y(0.65)Gd(0.35))BO(3):E(3+)(0.05). We found that Pr(3+) and Tb(3+)increases the VUV photoluminescent efficiency, while Sm(3+) decreases the efficiency. The optimized composition was identified to be between 7 x 10(-6) and 3 x 10(-4), and the corresponding efficiency improvement is about 15%. Scale-up experiments confirmed the results in the combinatorial materials libraries.     

Luminescence and energy transfer in lu(3)al(5)o(12) scintillators co-doped with ce(3+) and tb(3+)

Lu(3)Al(5)O(12) (LuAG) doped with Ce(3+) is a promising scintillator material with a high density and a fast response time. The light output under X-ray or γ-ray excitation is, however, well below the theoretical limit. In this paper the influence of codoping with Tb(3+) is investigated with the aim to increase the light output. High resolution spectra of singly doped LuAG (with Ce(3+) or Tb(3+)) are reported and provide insight into the energy level structure of the two ions in LuAG. For Ce(3+) zero-phonon lines and vibronic structure are observed for the two lowest energy 5d bands and the Stokes' shift (2 350 cm(-1)) and Huang-Rhys coupling parameter (S = 9) have been determined. Tb(3+) 4f-5d transitions to the high spin (HS) and low spin (LS) states are observed (including a zero-phonon line and vibrational structure for the high spin state). The HS-LS splitting of 5400 cm(-1) is smaller than usually observed and is explained by a reduction of the 5d-4f exchange coupling parameter J by covalency. Upon replacing the smaller Lu(3+) ion with the larger Tb(3+) ion, the crystal field splitting for the lowest 5d states increases, causing the lowest 5d state to shift below the (5)D(4) state of Tb(3+) and allowing for efficient energy transfer from Tb(3+) to Ce(3+) down to the lowest temperatures. Luminescence decay measurements confirm efficient energy transfer from Tb(3+) to Ce(3+) and provide a qualitative understanding of the energy transfer process. Co-doping with Tb(3+) does not result in the desired increase in light output, and an explanation based on electron trapping in defects is discussed.     

Crystal structure and morphology evolution in the LaXO3, X = Al, Ga, In nano-oxide series. Consequences for the synthesis of luminescent phosphors

The LaXO(3):Tb(3+) (X = Al(3+), Ga(3+), In(3+)) perovskite nanoparticles were obtained using the nonhydrolytic treatment (Bradley reaction) of the molecular precursors of the La(O(i)Pr)(3), Al(O(i)Pr)(3), Ga(O(i)Pr)(3), In(5)O(O(i)Pr)(13), and Tb(acac)(3), respectively. It was shown that crystal structure and morphology evolution in the LaXO(3), X = Al, Ga, In nano-oxide series depended on the size and chemical properties of the X-metal atom. Formation of the LaInO(3):Tb(3+) nanoparticles is distinctly less thermodynamically demanding on contrary to the LaAlO(3):Tb(3+) and LaGaO(3):Tb(3+) since it provided crystalline product directly in the solution synthesis at 202 °C, which is the lowest reported synthesis temperature for this compound up-to-date. This behavior was ascribed to the effects directly connected with the dopant substitution (exchange of bigger La(3+) cation with smaller Tb(3+)) as well as reduction of the particle size. The size effects are mostly reflected in the expansion of the cell volume, changes of the cell parameters as well as shifting and broadening of the Raman bands. Indirectly, size reduction has also an effect on the luminescence properties through the higher probability of presence of surface and net defects as well as heterogeneous distribution of the Tb(3+) ions caused by high surface-to-volume ratio. The prepared nanophosphors show basically green emission with exception of white-green in case of the LaInO(3):Tb(3+). Strong emission quenching was found in the latter case being most likely a consequence of the nonradiative energy transfer between Tb(3+) and In(3+) as well as the presence of defects. In comparison to the Pechini's method, the LaXO(3) nanoparticles required significantly lower annealing temperature (700 °C) necessary for complete crystallization. Generally the resulting particles are distinctly smaller (5 to 25 nm) and less agglomerated (50-100 nm) depending on the reaction conditions as well as thermal treatment. For the first time, it was shown that the LaGaO(3):Tb(3+) nanopowder has crystallized in the high-temperature rhombohedral R3c phase.