Sol-gel synthesis and photoluminescent properties of LaPO4 : A (A = Eu3+, Ce3+, Tb3+) nanocrystalline thin films

Rare-earth ion (Eu3+, Tb3+, Ce3+)- doped LaPO4 nanocrystalline thin films and their patterning were fabricated by a Pechini sol-gel process combined with soft lithography on silicon and silica glass substrates. X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM), scanning electron microcopy (SEM), optical microscopy, absorption and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicate that the films begin to crystallize at 700 degreesC and the crystallinity increases with increasing annealing temperature. The morphology of the thin film depends on the annealing temperature and the number of coating layers. The 1000 degreesC annealed single layer film is transparent to the naked eye, uniform and crack-free with a thickness of about 200 nm and an average grain size of 100 nm. Patterned thin films with different strip widths ( 5 - 50 mm) were obtained by micromolding in capillaries ( soft lithography). The doped rare earth ions show their characteristic emission in the nanocrystalline LaPO4 films, i.e., Eu3+ D-5(0)-F-7(J) (J = 1, 2, 3, 4), Tb3+ D-5(3,4) - F-7(J) ( J = 6, 5, 4, 3, 2) and Ce3+ 5d-4f transition emissions, respectively. Both the lifetimes and the PL intensities of Eu3+ and Tb3+ increase with increasing annealing temperature, and the optimum concentrations for them were determined to be 5 mol% and 16 mol% of La3+ in LaPO4 thin films, respectively. An energy transfer phenomenon from Ce3+ to Tb3+ has been observed in LaPO4 nanocrystalline thin films, and the energy transfer efficiency depends on the doping concentration of Tb3+ if the concentration of Ce3+ is fixed.

Patterning and photolumine scent properties of perovskite-type organic/inorganic hybrid luminescent films by soft lithography

Perovskite-type organic/inorganic hybrid layered compound (C6H5C2H4NH3)(2)PbI4 was synthesized. The patterning Of (C6H5C2H4NH3)(2)PbI4 thin films on silicon substrate was realized by the micromolding in capillaries (MIMIC) process, a kind of soft lithography. Bright green luminescent stripes with different widths (50, 15, 0.8 mum) have been obtained. The structure and optical properties Of (C6H5C2H4NH3)(2)PbI4 films were characterized by X-ray diffraction (XRD), UV/Vis absorption and photoluminescence excitation and emission spectra, respectively. It is shown that the organic-inorganic layered (C6H5C2H4NH3)(2)PbI4 film was c-axis oriented, paralleling to the substrate plane. Green exciton emission at 525 nm was observed in the film, and the explanations for it were given.

Patterning and optical properties rhodamine B-doped organic-inorganic silica films fabricated by sol-gel soft lithography

Rhodamine B (RB)-doped organic-inorganic silica films and their patterning were fabricated by a sol-gel process combined with a soft lithography. The resulted film samples were characterized by atomic force microscope (AFM), optical microscope and UV/Vis absorption and photoluminescence excitation and emission spectra. The effects of the concentration of the RB dye and heat treatment temperature on the optical properties of the hybrid silica films have been studied. Four kinds of patterning structures with film line widths of 5, 10, 20 and 50 mum have been obtained by micromolding in capillaries by a soft lithography technique. The RB-doped hybrid silica films present a red color, with an excitation and emission bands around 564 and 585 mum, respectively. With increasing the RB concentration, the emission intensity of the RB-doped hybrid silica films increases and the emission maximum presents a red shift. The emission intensity of the films decreases with increasing the heat treatment temperatures.

Multilayer assemblies consisting of tri-vanadium-substituted heteropolyanions and its electrocatalytic properties

We describe the controlled fabrication of ultrathin multilayer films consisting of tri-vanadium- substituted heteropolytungstate anions (denoted as P2W15V3) and a cationic polymer of quaternized poly (4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) (denoted as QPVP-Os) on the 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) surface based on layer-by-layer assembly. Cyclic voltammetry and UV-vis absorption spectrometry have been used to easily monitor the thickness and uniformity of thus-formed multilayer films. The V-centered redox reaction of P2W15V3 in the multilayer films can effectively catalyze the reduction of BrO3- and NO2-. The resulting P2W15V3/QPVP-Os multilayer film modified electrode behaves as a much promising electrochemical sensor because of the low overpotential for the catalytic reduction of BrO3- and NO2-, and the catalytic oxidation of ascorbic acid.

Synthesis, structure and luminescent properties of a new praseodymium(III) complex with beta-diketone

A new tetrakis praseodymium(tu) complex Pr(TFNB)(3)Phen has been synthesized, in which TFNB is 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione and Phen is 1,10-phenanthroline. Its crystal structure and luminescent spectra were successfully determined and investigated. The typical antenna effect existing in the luminescence of Pr(TFNB)(3)Phen was revealed by the study of the UV-Vis absorption spectra of ligands and the excitation spectrum of Pr(TFNB)(3)Phen.

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.

Preparation and luminescence properties of hybrid materials containing europium(III) complexes covalently bonded to a silica matrix

A new kind of luminescent organic-inorganic hybrid material (denoted Hybrid I) consisting of europium 1,10-phenanthroline complexes covalently attached to a silica-based network was prepared by a sol-gel process. 1,10-Phenanthroline grafted to 3-(triethoxysilyl)propyl isocyanate was used as one of the precursors for the preparation of an organic-inorganic hybrid materials. For comparison purposes, the hybrid material (denoted Hybrid II) in which phenanthroline was not grafted onto the silica backbone of the frameworks was also prepared. Elemental analysis; NMR, FT-IR, UV/vis absorption, and luminescence spectroscopies, and luminescence decay analysis were used to characterize the obtained hybrid materials. It is shown that the homogeneity of Hybrid I is superior to that of Hybrid II, and a higher concentration europium can be incorporated into Hybrid I than Hybrid II. Excitation at the ligand absorption wavelength (283 nm) resulted in the strong emission of the Eu3+ D-5(0)-F-7(J) (J = 0-4) transition lines as a result of the efficient energy transfer from the ligands to the EU3+ in Hybrid I. The number of water molecules coordinated to the europium ion was estimated, and the structure of the as-synthesized Hybrid I was predicted on the basis of the experimental results.

Vacuum ultraviolet optical properties of (La,Gd)PO4 : RE3+ (RE = Eu, Tb)

Vacuum ultraviolet excitation spectra of phosphors (La,Gd)PO4:RE3+ (RE = Eu or Tb) and X-ray photoelectron spectra of LaPO4 and GdPO4 are investigated. The vacuum ultraviolet excitation intensity of (La,Gd)PO4:RE3+ is enhanced with the increasing of Gd3+ content, which implies that Gd3+ plays an intermediate role in energy transfer from host absorption band to RE3+. When Gd3+ is doped into LaPO4:Eu, charge transfer band (CT band) begins to shift to higher energy region and the overlap degree of CT band and the host absorption band gets greater with more Gd3+ doped into LaPO4. These results suggest that the dopant (Gd3+) gives an important influence on energy transfer efficiency. The top of LaPO4 valance band is formed by the 2p level of O2-, whereas that of GdPO4 valance band is formed by the 2p level of O2- and the 4f level of Gd3+, showing the differences in band structures between LaPO4 and GdPO4.

Preparation and nonlinear optical properties of ultrathin composite films containing both a polyoxometalate anion and a binuclear phthalocyanine

An ultrathin composite film containing both polyoxometalate anion [PMo12O40](3-) ( PMo12) and a planar binuclear phthalocyanine, bi-CoPc, has been prepared by the electrostatic layer-by-layer self-assembly method. UV-vis measurements revealed regular film growth with each four-layer {PMo12/bi-CoPc/PSS/PAH} adsorption. The lm structure was characterized by small-angle X-ray reflectivity measurements, X-ray photoelectron spectra, and AFM images. The nanothick film shows a third-order nonlinear optical response of chi((3)) = 4.21 x 10(-12) esu. Experimental investigations also indicate that the combination of polyoxometalate anions [PMo12O40](3-) with the phthalocyanine bi-CoPc in multilayer films can enhance the third-order NLO susceptibility and modify the third-order NLO absorption of bi-CoPc.

Fabrication, patterning, and optical properties of nanocrystalline YVO4 : A (A = Eu3+, Dy3+, Sm3+, Er3+) phosphor films via sol-gel soft lithography

Nanocrystalline YVO4:A (A = Eu3+, Dy3+, Sm3+, Er3+) phosphor films and their patterning were fabricated by a Pechini sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM) and optical microscopy, UV/vis transmission and absorption spectra, photoluminescence (PL) spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 400 degreesC and the crystallinity increased with the increase of annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of grains with an average size of 90 nm. Patterned gel and crystalline phosphor film bands with different widths (5-60 mum) were obtained. Significant shrinkage and a few defects were observed in the patterned films during the heat treatment process. The doped rare earth ions (A) showed their characteristic emission in crystalline YVO4 phosphor films because of an efficient energy transfer from vanadate groups to them. The Sm3+ and Er3+ ions also showed upconversion luminescence in a YVO4 film host. Both the lifetimes and PL intensity of the rare earth ions increased with increasing annealing temperature from 400 to 800 degreesC, and the optimum concentration for Eu3+ was determined to be 7 mol % and those for Dy3+, Sm3-, and Er3+ were 2 Mol % of Y3- in YVO4 films, respectively.

Studies on enzymological properties of antibody elicited by meso-tetra(alpha, alpha, alpha, alpha-O-phenylacetyl benzene)porphyrin

meso-Tetra (alpha, alpha, alpha, alpha-O-phenylacetyl benzene) porphyrin was used as a complete antigen to elicit monoclonal antibody 1F2 through the immunization and cell fusion techniques. McAb 1F2 obtained was demonstrated very pure by HPLC and MALDI/TOFMS. The retention time of McAb 1F2 was 2. 63 min. The subtype of McAb 1F2 was IgG2a. The relative molecular weight was 156 678. 8. When the McAb 1F2-porphyrin was formed, the maximal absorption of the porphyrin soret region had a redshift from 408 to 416 nm and hyperchromical effect, showing that the antigen-antibody combination was rigid and intense, and the abzyme constancy was high. But compared with HRP, the activity of the abzyme was only 4. 687 5 U/mg and 1. 899 % of that of HRP. Its K-m was 20. 29 mmol/L, k(cat) 396. 82 min(-1), k(cat)/K-m. 1. 955 7 X 10(4) L . mol(-1) . min(-1).

Liquid crystalline and light emitting polyacetylenes: Synthesis and properties of biphenyl-containing poly(1-alkynes) with different functional bridges and spacer lengths

Biphenyl- (Biph-) containing 1-alkynes (3 and 4) and their polymers (1 and 2) with varying bridge groups and spacer lengths were synthesized and the effects of the structural variation on their properties, especially their mesomorphism and photoluminescence behaviors, were studied. The acetylene monomers 3(3) [HCdropC(CH2)(3)O-Biph-OCO(CH2)(10)CH3] and 4(m) [HCdropC(CH2)(m)OCO-Biph-OCO(CH2)(10)-CH3, m = 3, 4] were prepared by sequential etherization and esterification reactions of 1-alkynes. While 3(3) exhibits enantiotropic crystal E and SmB mesophases, its structural cousin 4(3) displays only a monotropic SmB phase. Enantiotropic SmA and SmB mesophases are, however, developed when the spacer length is increased to 4. Polymerizations of the monomers are effected by Mo-, W-, Rh-, and Fe-based catalysts, with the WCl6-Ph4Sn catalyst giving the best results (isolation yield up to 85% and M-w up to 59000). The polymers were characterized by IR, UV, NMR, TGA, DSC, POM, XRD, and PL analyses. Compared to 1(3), 2(3) shows a red-shifted absorption, a higher T-i, and a better packed interdigitated bilayer SmA(d) structure, while the mesophase of 2(4) involves monolayer-packing arrangements of the mesogens. Upon photoexcitation, 1(3) emits almost no light but 2(m) gives a strong ultraviolet emission (lambda(max) similar to 350 nm), whose intensity increases with the spacer length.

Seed-mediated growth of large, monodisperse core-shell gold-silver nanoparticles with Ag-like optical properties

Large, monodisperse core-shell Au-Ag nanoparticles with Ag-like optical properties have been prepared by the seeding growth method in micellar media.

Preparation, patterning and luminescence properties of rare earth-doped YVO4 nanocrystalline phosphor films via sol-gel soft lithography

In this presentation, nanocrystalline YVO4:A (A=Eu3+, Dy3+, SM3+, Er3+) phosphor films and their patterning were fabricated by a Pechini sol-gel process combined with a soft lithography (micro-molding in capillaries). XRD, FT-IR, AFM and optical microscope, absorption spectra, photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 400 degrees C and the crystallinity increased with the increase of annealing temperatures. Transparent nonpattemed phosphor films were uniform and crack free, which mainly consisted of grains with an average size of 90nm. Patterned crystalline phosphor film bands with different widths (5-30 mu m) were obtained. The doped rare earth ions (A) showed their characteristic emission in crystalline YVO4 phosphor films due to an efficient energy transfer from vanadate groups to them. The Sm3+ and Er3+ ions also showed upconversion luminescence in YVO4 film host. The optimum concentration for Eu3+ was determined to be 7 mol% and those for Dy3+, Sm3+, Er3+ were 2 Mol% of Y3+ in YVO4 films, respectively.

Sol-gel preparation and luminescence properties of nano-structured hybrid materials incorporated with europium complexes

Microporous silica gel has been prepared by the sol-gel method utilizing the hydrolysis and polycondensation of tetraethylorthosilicate (TEOS). The gel has been doped with the luminescent ternary europium complex Eu(TTA)(3)(.)phen: where HTTA=1-(2-thenoyl)-3,3,3-trifluoracetone and phen=1,10-phenanthroline. By contrast to the weak f-f electron absorption bands of Eu3+, the complex organic ligand exhibits intense near ultraviolet absorption. Energy transfer from the ligand to Eu3+ enables the production of efficient, sharp visible luminescence from this material. Utilizing the polymerization of methyl methacrylate, the inorganic/polymer hybrid material containing Eu(TTA)(3)(.)phen has also been obtained. SEM micrographs show uniformly dispersed particles in the nanometre range. The characteristic luminescence spectral features of europium ions are present in the emission spectra of the hybrid material doped with Eu(TTA)(3)(.)phen.