Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Preparation and luminescence properties of ormosil hybrid materials doped with Tb(Tfacac)(3)phen complex via a sol-gel process

In this paper, silica-based transparent organic-inorganic hybrid materials were prepared via the sol-gel process. Tetraethoxysilane (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) were used as the inorganic and organic precursors, respectively. The terbium complex, Tb(Tfacac)(3)phen (Tfacac = 1,1,1-trifluoroacetylacetone, phen = 1, 10-phenanthroline) was successfully doped into organically modified silicate (ormosil) matrix derived from TEOS and GPTMS, and the luminescent properties of the resultant ormosil composite phosphors [ormosil/Th(Tfacac)(3)phen] were investigated compared with those of the Tb(Tfacac)(3)phen incorporated into SiO2 derived from TEOS (labeled as silica/Tb(Tfacac)(3)phen). Both kinds of the materials show the characteristic green emission of Tb3+ ion. The luminescence behavior of the resultant composite products was dependent on the matrix composition. The optimized lanthanide complex concentration in the ormosil/Tb(Tfacac)(3)phen was increased compared with in silica/Tb(Tfacac)(3)phen. Furthermore, the lifetime of Tb3+ in Tb(Tfacac)(3)phen, silica/Tb(Tfacac)(3)phen and ormosil/Tb(Tfacac)(3)phen follows the sequence: onmosil/Tb(Tfacac)(3)phen>silica/Tb(Tfacac)(3)phen>pure Tb(Tfacac)(3)phen.

LB films of 2-n-heptadecanoylbenzoic-rare earth and their luminescence properties

Several ultrathin luminescent Langmuir-Blodgett (LB) films have been prepared by using the subphase containing the rare earth ions (Eu3+, Tb3-). The effect of the rare earth ions on the monolayer of 2-n-heptadecanoylbenzoic acid (HBA) was investigated. IR and UV spectra showed the rare earth ions were bound to the carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction. UV absorbance intensity increases linearly with the number of LB films layers, which indicate that the LB films are homogeneously deposited. The LB films can give off strong fluorescence. and the signal can be detected from a single layer. The characteristic luminescence behaviors of LB films have been discussed compared with those of the complexes.

Luminescent thin film of doped terbium complex obtained by sol-gel method

The transparent luminescent thin films of doped terbium complex were obtained by sol-gel method. The result indicates that rare earth carboxylates with poor solubility can be homogeneously doped into sol matrix in situ. The fluorescence spectra show that the thin film material emits the characteristic narrow band emission of Tb3+ under the UV excitation.

Luminescent film with terbium-complex-bridged polysilsesquioxanes

A luminescent film with terbium-complex-bridged polysilsesquioxanes has been prepared by sol-gel processing of a new bifunctional monomer that combines the role of a sol-gel molecular precursor with a Tb3+ ion coordinate donor. The emission from Tb3+ ion due to ligand-to-metal energy transfer was observed by UV excitation.

Preparation and characterization of a layered transparent luminescent thin film of silica-CTAB-Tb(acac)(3) composite with mesostructure

A layered luminescent mesostructured thin film of silica-CTAB-Tb(acac)(3) composite has been synthesized by a dip-coating process through an in situ sol-gel method. The terbium (Tb3+) ion and beta-diketone organic ligand acetylacetone (acac) were introduced into the precursor solution, respectively. The as-synthesized composite film was transparent, colorless and possessed a layered structure. After the composite film was dried at 50 degreesC for a few minutes Tb(acac)(3) complex was synthesized in the mesostructured thin film, which can be indicated by the luminescence of the composite film under the UV lamp. The properties of the samples were characterized by XRD, absorption, Fourier transform infrared spectroscopy, and luminescent spectra.

Preparation and luminescence properties of LB films based on 4-hexadecyloxybenzoic terbium

LB films of 4-hexadecyloxybenzoic-terbium by using the subphase containing Tb3+ were prepared. The monolayer behavior of 4-hexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.

Multi-color long-lasting phosphorescence of rare earth ions in CdSiO3 matrix

A series of rare earth ions doped CdSiO3:RE3+(RE=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) multi-color long-lasting phosphorescence phosphors are prepared by the conventional high-temperature solid-state method. The results of XRD measurement indicate that the products fired under 1050degreesC for 3 h have a good crystallization without any detectable amount of impurity phase. Rare earth ions doped CdSiO3 phosphors possess excellent luminescence properties. When rare earth ions such as Y3+, La3+, Gd3+, Lu3+, Ce3+, Nd3+, Ho3+, Er3+, Tm3+ and Yb3+ are introduced into the CdSiO3 host, one broadband centered at about 420 nm resulting from traps can be observed. In the case of other earth ions such as Pr3+, Sm3+, Eu3+, Tb3+ and Dy3+, their characteristic line emitting as well as the similar to420 nm broadband luminescence can be obtained. The mixture of their characteristic line emitting with the similar to420 nm broadband luminescence results in various afterglow color.

The optical spectroscopic properties of rare earth-activated barium orthophosphate in VUV-Vis range

The optical properties of rare earth ions-activated barium orthophosphate phosphors, Ba-3(PO4)(2):RE (RE = Ce3+, Sm3+, Eu3+, Eu2+, and Tb3+), were investigated in vacuum ultraviolet (VLTV)-Vis range. A band-band transition Of PO43- in Ba-3(PO4)(2) is observed in the region of 150-170 nm. The partial reduction of Eu3+ to Eu2+ was observed and confirmed by luminescent spectra under the VUV-UV excitation. It is proposed that the electronegative defects that formed by aliovalent substitution of Eu3+ on the Ba2+ site in the host are responsible for the reduction process.

VUV-UV excited luminescent properties of calcium borophosphate doped with rare earth ions

The VUV-UV spectra of rare earth ions activated calcium borophosphate, CaBPO5:RE (RE = Ce3+, sm(3+), Eu2+, Eu3+, Tb3+ and Dy3+) were determined. The bands at about 155 nm in the VUV excitation spectra are attributed to the host lattice absorptions. The bands at 166 and 190 nm for the sample CaBPO5:Sm have been considered as related to the f-d transition and the charge transfer band (CTB) of Sm3+ ions, and the band at 169 nm for the sample CaBPO5:Dy is assumed to be connected with the f-d transition of the Dy3+ ions in CaBPO5. The partial reduction of Eu3+ CaBPO5:Eu prepared by high temperature solid state reaction in air is confirmed by the VUV-UV spectra.

Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propylthiethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by H-1 NMR IR and MS, The monomer acts as a ligand for Tb3+ ion and as a sol-gel precursor. Band emission front Tb3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the D-5(4) level of Tb3+ ion falls in the exciting range to sensitize Tb3+ ion fluorescence.

Preparation, photo and electroluminescence properties of novel rare earth aromatic carboxylates

Novel soluble rare earth aromatic carboxylates were prepared. The triplet energy level of organic ligand was measured. The photoluminescence properties of the Tb3+ and EU3+ aromatic carboxylates and lifetimes were investigated, which indicated that these rare earth complexes have high quantum efficiency. Because of their excellent solubility, polymer-doping rare earth carboxylates were fabricated as thin Films by spin-coating method and their luminescence properties were studied. Some rare earth organic light-emitting diodes were successfully fabricated which performed high pure color. The maximum luminance of the device of ITO/PVK/PVK :Th (AS)(3)Phen: PBD/PBD/Al is 32 cd(.)m(-2) at 28 V.

Sol-gel derived silicate oxyapatite phosphor films doped with rare earth ions

Rare-earth (Eu3+, Tb3+)-doped Ca2Y8(SiO4)(6)O-2 luminescent thin films were dip-coated on silicon and quartz glass substrates through a sol-gel route. X-ray diffraction (XRD), scanning electron microscopy (SEM) and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resultant 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 micrographs, where particles with various shape and average size of 250 nm can be resolved. The Eu3+ and Tb3+ ions 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 of Eu-3divided by increases with the heat treatment temperature front 700 to 1100 degreesC.

Hybrid luminescent films obtained by covalent anchoring terbium complex to silica-based network

New monomer N-(4-carboxyphenyl)-NL-(propyltriethoxysilyl)urea (1) which acts as both a ligand for Th3+ ion and a sol-gel precursor has been synthesized and characterized by H-1 NMR, and MS. Hybrid luminescent thin films consisting of organoterbium covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. Strong line emission of Tb3+ ion was observed from the hybrid luminescent films under UV excitation.

Luminescence properties of transparent hybrid thin film covalently linked with lanthanide complexes

Novel hybrid thin films covalently doped with Eu3+ (Tb3+) have been prepared via direct routes involving co-condensation of tetraethoxysilane and phen-Si in the presence of Eu3+ (Tb3+) by spin-casting and their luminescence properties have been investigated in detail. Lanthanide ions can be sensitized by anchored phenanthroline in hybrid thin films. Excitation at the ligand absorption wavelength (272 nm) resulted in the strong emission of the lanthanide ions i.e. Eu3+ D-5(0)-F-7(J) (J=0, 1, 2, 3, 4) emission lines and Tb3+ D-5(4)-F-7(J) (J = 6, 5, 4, 3) due to the energy transfer from the ligands to the lanthanide ions.