Preparation and characterization of novel luminescent sol-gel films containing a RE3+ carboxylic acid complex

RE3+ (Eu3+, Tb3+) complexes with carboxylic acid (salicylic acid and benzoic acid) were introduced into the sol, which was prepared by the hydrolysis of tetraethoxysilane (TEOS). A sol-gel luminescent thin film (SG-LTF) was then prepared by dispersing the sol onto a silica substrate by a spin coating method. Multi-layer luminescent thin films were prepared by repeating the same process. The luminescent spectra, fluorescence lifetime and thermal stability of the SG-LTFs were investigated. For the reason of comparison polyvinylbutyral (PVB) was added into a N,N-dimethylformamide (DMF) solution in which the comparative RE3+ carboxylic acid complexes were previously dissolved to form the DMF/PVB solution and the PVB luminescent thin film (PVB-LTF) was prepared. The results show that a broad excitation band indicates the formation of RE complexes in the solid SG-LTFs. RE ions, which are restrained in the silica matrix, present longer lifetimes and higher thermal stability than that in the PVB-LTF containing the corresponding pure complexes. The different doping concentration of RE (III) complexes in the SG-LTFs and the different change of the emission intensities with the heat treatment temperature in the sol-gel thin film and the sol-gel bulk gel were also discussed in this paper.

A novel way to enhance electroluminescence performance based on soluble binary and ternary europium 1,1,1-trifluoroacetylacetonate

Five rare earth complexes (Gd(acae)(3), Gd(TFacaC)(3), Eu(acaC)(3), Eu(TFacaC)(3) and Eu(TFacaC)(3)bipy; acac, acetylacetone; TFacac, 1,1,1-trifluoroacetylacetone; bipy, 2,2'-bipyridyl) were synthesized. By comparing the phosphorescence spectra of Gd(acac)(3) and Gd(TFacac)(3) the effect of the replacement of hydrogen by fluorine was examined. Organic light-emitting devices (OLEDs) based on the corresponding europium complexes as emissive layers were also fabricated by the spin-coating method. The triple-layer-type device with the structure glass substrate/ITO (indium-tin oxide)/PVK [poly(N-vinylcarbazole)]/(PVKEu)-Eu-.(TFacac)(3)bipy:PBD[2-(4-bibipyyl)-5-(4-t-butylbipyl-1,3,4-oxadiazole)]/PBD/Al (aluminum) exhibits a brighter red luminescence than those devices with Eu(acac)(3) and Eu(TFacac)(3) complexes as emissive centers upon applying a d.c. voltage.

Red electroluminescent device with europium 1,1,1-trifluoroacetylacetonate complex as emissive center

By comparing the phosphorescence spectra of Gd(acac)(3) (acac: acetylacetone) and Gd(TFacac)(3) (TFacac: 1, 1, 1-trifluoro-acetylacetone), the effect of fluorine replacing of hydrogen was discussed. It can lower the triplet state energy of acac and make it more suitable to the D-5(1) energy state of europium. Organic electroluminescent (OEL) devices with corresponding europium complexes as emissive layers were fabricated. A triple laver-type device with a structure of glass substrate/indium-tin oxide (ITO)/poly(N-vinylcarbazole) (PVK)/PVK:Eu(TFacac)(3)phen:2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD)/PBD/Al exhibits bright red luminescence upon applying dc voltage, The device has the properties of a diode and the current-bias voltage line was obtained.

Sol-gel deposition and luminescent properties of oxyapatite Ca-2(Y,Gd)(8)(SiO4)(6)O-2 phosphor films doped with rare earth and lead ions

Rare-earth and lead ions (Eu3+, Tb3+, Dy3+, Pb2+) doped Ca2Y8 (SiO4)(6)O-2 and Ca2Gd8(SiO4)(6)O-2 thin films have been dip- coated on silicon and quartz glass substrates through the sol- gel route. X- Ray diffraction (XRD), TG- DTA, scanning electron microscopy (SEM), atomic force microscopy (AFM), FT- IR and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resulting films. The results of XRD reveal that these films remain amorphous below 700 degreesC, begin to crystallize at 800 degreesC and crystallize completely around 1000 degreesC with an oxyapatite structure. The grain structure of the film can be seen clearly from SEM and AFM micrographs, where particles with various shapes and average size of 250 nm can be resolved. Eu3+ and Tb3+ show their characteristic red (D-5(0)-F-7(2)) and green (D-5(4) - F-7(5)) emission in the films with a quenching concentration of 10 and 6 mol% (of Y3+), respectively. The lifetime and emission intensity of Eu3+ increase with the temperature treatment from 700 to 1100 degreesC, while those of Tb3+ show a maximum at 800 degreesC. Energy transfer phenomena have been observed by activating the oxyapatite film host- lattice Ca2Gd8(SiO4)(6)O-2 with Tb3+ (Dy3+). In addition, Pb2+ can sensitize the Gd3+ sublattice in Ca2Gd8(SiO4)(6)O-2.

Calculation of the electrostatic energy H-e(fd) on 4f(N-1)5d configuration of lanthanide ions

In LS coupling, the energy expressions of H-e(fd) of the chief low-energy levels of 4f(N-15)d (n < 9) configuration ions are calculated. H-e(fd) can be parameterized with F-K (k=2,4) and G(K)(k=1,3,5). f(k) and g(k), which are coefficients, times the corresponding parameter FK and GK leads to the energy expressions of H-e(fd).

Hydrothermal synthesis and spectral properties of the Eu doped KZnF3

The polycrystals of KZnF3 : Eu have been synthesized by hydrothermal method at 220 degreesC, The product was characterized by XRD, XPS and SEM. The emission and excitation spectra of europium ion were measured. The existence of Eu2+ ion was confirmed by ESR and spectroscopy. The sites were possibly occupied by Eu2+ ions, charge compensation in this crystal were also discussed.

Novel trichromatic phosphor codoped with two rare earth ions in a single matrix

The luminescence properties of CaBPO5: Eu, Tb phosphor and the sensitization of Ce3+ were investigated. The CaBPO5: Eu, Tb phosphors were synthesized in the ambient air and the emission spectra of Eu3+, Tb3+ and Eu2+ were Observed in the phosphor. The result shows that there is electron transfer between conjugate rare earth ions. Sensitization of Ce3+ can improve the intensity of emission of Tb3+ and Eu2+. A novel trichromatic lamp phosphor codoped with Eu3+-Tb3+ in matrix CaBPO5 is then predicted.

Europium ion labeling anti-HBs

A microsecond time-resolved laser fluorescence spectroscopic analysis set was developed, A chelate-cyclic anhydride of diethylenetrimin pentaacetic acid anhydride (DTPAA) was synthesized. An anti-HBs antibody was purified, A EU3+ -DTPAA-anti-HBs label was prepared by two step procedure. We described the optimal condtion with EU3+ as marker and DTPAA as chelate bounding to antibody molecule. Labeling parameters such as solvent pH, protein and chelate molar ratio, reaction time, separation method were discussed in detail.

In situ synthesis of terbium-benzoic acid complex in sol-gel derived silica by a two-step sol-gel method

Terbium complexes with benzoic acid and its derivatives o-hydroxybenzoic acid and p-hydroxybenzoic acid were in situ synthesized in sol-gel derived silica matrix via a two-step sol-gel process. The formation process of the complex was characterized by fluorescence spectra, absorption spectra and IR spectra. The gels that contain in situ synthesized complexes exhibit the characteristic emission bands of terbium ion. The fluorescence lifetimes of Tb3+ in the silica gels are longer than those in the pure complexes and in the solutions that contain the corresponding complexes. (C) 2000 Elsevier Science Ltd. All rights reserved.

Luminescent properties of Langmuir-Blodgett films of europium bisphthalocyanine

Eu(III)-octa-4-(tetrahydrofurfuroxy) phthalocyanine (EuPc2') was synthesied and characterized by elementary analysis, IR, MS, UV-vis spectra. EuPc2' has good film-forming ability from determination of isotherm of pi-A. The complex LB film was formed by depositing of EuPc2' on a quartz slide with the LB techniques of the Z-type, The luminescent properties of pure and doped LS films were determined. The results showed that pure films have good luminescent properties, the thicker the LB films, the stronger the fluorescent intensity. The films doped with o-phenanthroline (abbreviated as phen) made the relative intensity of fluorescent emission behavior enhance in comparison to that of pure LB film, But the amount of phen may be not too much. Our results showed that EuPc2':phen = 1: 10 (molar ratio) has the best fluorescent behavior. The electronic spectroscopic characterization of the LB films is also given.

Preparation and characterization of luminescent thin films doped with rare earth (Tb3+, Eu3+) complexes derived from a sol-gel process

Sol-gel derived luminescent thin films doped with rare earth (RE) complexes were prepared using an in-situ synthesis method with a two-step hydrolysis process and the luminescence spectra were measured. Fluorescence Lifetime and thermal stability were investigated. The results show that a broad excitation band indicates the formation of RE complexes in the solid thin films. RE ions, which are restrained in a silica matrix, present longer lifetime and higher thermal stability than that in DMF/PVB films containing the corresponding pure complexes. (C) 2000 Elsevier Science B.V. All rights reserved.

Networks with hexagonal circuits in co-ordination polymers of metal ions (Zn-II, Cd-II) with 1,1 '-(1,4-butanediyl)bis(imidazole)

Three new compounds, [ZnL1.5(H2O)(SO4)]. 6H(2)O 1, [ZnL1.5(H2O)(2)][NO3](2). 2H(2)O 2 and [CdL1.5(H2O)(2)(SO4)]. 4H(2)O 3 were obtained from self-assembly of the corresponding metal salts with 1,1'-(1,4-butanediyl)bis(imidazole) (L). In both 1 and 2 zinc ion is five-co-ordinated, showing a less-common trigonal bipyramidal co-ordination polyhedron, while cadmium ion of 3 is six-co-ordinated with a common octahedral arrangement. The sulfate ions of 1 and 3 are co-ordinated, however the nitrate ions of 2 are not. Each of the three compounds is composed of a (6, 3) network with the hexagonal smallest circuit containing six metal ions and six L; each L is co-ordinated to two metal ions, acting as a bridging ligand. In 1 the 2-D sheet of (6, 3) networks is interpenetrated in an inclined mode by symmetry related, identical sheets to give an interlocked 3-D structure, while the (6, 3) networks of both 2 and 3 stack in a parallel fashion to construct frameworks having channels.

Nanostructured hybrid organic-inorganic lanthanide complex films produced in situ via a sol-gel approach

Communication: Nanostructural hybrid organic-inorganic lanthanide complex films were prepared in situ by use of a novel sol-gel precursor containing pendant triethoxy-silyl and carboxyl groups (see Figure). The resulting transparent and crack-free films gave rise to strong red or green emission, even at low lanthanide ion concentration. Phase separation and lanthanide ion aggregation were controlled at the nanoscale.

Preparation of borates doped with divalent rare earth ions (RE2+) in air and spectroscopy of divalent rare earth ions (RE2+ = Sm, Eu, Tm, Yb)

The spectroscopic feature of divalent Sm2+, Eu2+, Tm2+ and Yb2+ is discussed in this paper. Especially the spectroscopic properties of some berates containing tetrahedral BO4 group such as SrB4O7, SrB6O10 and BaB8O13 doped with these divalent ions are reported. When the divalent alkaline earth ion in these berates is replaced partially by the above trivalent rare earth ion, the charge carried in the produced defects can be used as reductant to reduce the doped rare earth ion into divalent state at high temperature even in air. Therefore, a convenient and safe method is provided to prepared phosphors doped with these divalent rare earths.