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.

Sol-gel fabrication, patterning and photoluminescent properties of LaPO4 : Ce3+, Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped LaPO4 nanocrystalline thin films and their patterning were fabricated by a sol-gel process combined with soft lithography on silicon and quartz glass substrates. The results of XRD indicated that the films began to crystallize at 700 degreesC. The 1000 degreesC annealed single layer films are transparent by eyes, uniform and crack-free with a thickness of about 200 nm and an average grain size of 100 nm. Patterned thin film with different band widths (5-50 mum) were obtained by micro-molding in capillaries technique. The luminescence and energy transfer properties of Ce3+ and Tb3+ were studied in LaPO4 films.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

Luminescent self-assembled thin films based on rare earth-heteropolytungstate

earth (Eu3+, Dy3+)-heteropolytungstate thin films were fabricated by self-assembly method successfully. The thin films give off strong fluorescence, which can be observed by eyes upon UV irradiation. The characteristic emission behaviors of the rare earth ions in self-assembled thin film were investigated compared with those of the corresponding solids. It is noticed that the intensity ratio between D-5(0) --> F-7(2) and D-5(0) --> F-7(1) of Eu3+ and the intensity ratio between F-4(9/2) --> H-6(13/2) and F-4(9/2) --> H-6(15/2) of Dy3+ in the self-assembled films are different from those of the corresponding solids. Furthermore, the self-assembled films present shorter fluorescence lifetimes than the corresponding solids. The reasons for these results have been discussed.

Photochromic behavior and luminescent properties of novel hybrid organic-inorganic film doped with Preyssler's heteropoly acid H-12[EuP5W30O110] and polyvinylpyrrolidone

A novel hybrid photochromic composite film composed of Preyssler's heteropoly acid H-12[EuP5W30O110] (EuP5W30) and polyvinylpyrrolidone (PVP) was prepared by dip-coating method. Atomic force microscopy (AFM) was used to investigate the surface topography. The change of characteristic peak in the infrared spectra (IR) was investigated. The TG curve showed three steps of weight loss and approximately revealed the composition of the hybrid film. Ultraviolet-visible adsorption spectra (UV-VIS) and electron resonance spectrum (ESR) were used to investigate the photochromic behavior and mechanism of hybrid film. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(o)-F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent thin film with polyoxometalates (POMs).

Electrochemiluminescence of tris(2,2 '-bipyridyl)ruthenium (II) ion-exchanged in polyelectrolyte-silica composite thin-films

The organic-inorganic hybrid, PSS-silica composite material was developed for the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) on glassy carbon electrode via ion-exchange (PSS stands for poly(sodium 4-styrene-sulfonate)). The electrochemiluminescence (ECL) and electrochemistry of Ru(bpy)(3)(2-) immobilized in the composite thin films have been investigated with tripropylamine (TPA) as the coreactant. The immobilized Ru(bpy)(3)(2-) underwent a surface process. The modified electrode was used for the ECL detection of TPA and showed high sensitivity. Detection limit was 0,1 mumol L-1 for TPA (S/N = 3) with a linear range from 0.5 mumol L-1 to 5 mmol L-1 (R = 0.998), Moreover, the resulting modified electrode was stable over six months and the good stability may be due to the strong interaction between Ru(bpy)(3)(2-) and the high ion-exchange able PSS-silica composite films on GCE. Compared with other materials. the PSS-silica composite films containing incorporated Ru(bpy)(3)(2-) showed improved sensitivity and long-term stability, Thus, such composite thin film can be a promising material for the construction of ECL sensor.

An organic-inorganic hybrid ultrathin film: preparation and characterization of copper phthalocyanine derivative-ferric oxide nanoparticles

A nanoparticulate ferric oxide-copper tris(2,4-di-tert-amylphenoxy)-8-quinolinolylphthalocyanine hybrid ultrathin film was constructed from alternate layers by the Langmuir-Blodgett technique. The composition, morphology and structure of the film were studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, atomic force microscopy, small-angle X-ray diffraction, visible spectroscopy and polarized UV-Vis spectroscopy. All the above analyses suggest that the thin film is a kind of one-dimensional superlattice, composed of organic and inorganic components. The XPS data reveal that the nanoparticulate ferric oxide exists as an alpha-Fe2O3 phase in the films. Gas-sensing measurements show that the hybrid LB film has very fast response-recovery characteristics towards 2 ppm C2H5OH vapor.

Silica sol-gel composite film as an encapsulation matrix for the construction of an amperometric tyrosinase-based biosensor

An amperometric tyrosinase enzyme electrode for the determination of phenols was developed by a simple and effective immobilization method using sol-gel techniques. A grafting copolymer was introduced into sol-gel solution and the composition of the resultant organic-inorganic composite material was optimized, the tyrosinase retained its activity in the sol-gel thin film and its response to several phenol compounds was determined at 0 mV vs. Ag/AgCl (sat. KCI). The dependences of the current response on pH, oxygen level and temperature were studied, and the stability of the biosensor was also evaluated. The sensitivity of the biosensor for catechol, phenol and p-cresol was 59.6, 23.1 and 39.4 muA/mM, respectively. The enzyme electrode maintained 73% of its original activity after intermittent use for three weeks when storing in a dry state at 4 degreesC. (C) 2000 Elsevier Science S.A. All rights reserved.

Study of ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine composite LB film

The ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine (CuPcA(2)) composite ultrathin film was obtained by LB (Langmuir-Blodgett) technique. Structure of the composite LB film was characterized by X-ray photoelectron spectra, transmission electron microscopy, infrared spectra and visible spectra. Gas sensitivity measurements indicate that the composite LB film is sensitive to 100-200 ppm C2H5OH at room temperature. (C) 2000 Elsevier Science S.A. All rights reserved.

Preparation, structure, and properties of three-dimensional ordered alpha-Fe2O3 nanoparticulate film

alpha-Fe2O3 nanoparticulate films could be formed on the surface of alpha-Fe2O3 hydrosol after aging of the hydrosol or by compressing of the nanoparticles on the sol surface, in. which a three-dimensional ordered structure was constructed by the Langmuir-Blodgett; technique and colloid chemical methods. The structure of the LB film was characterized by AFM, TEM, XPS, and UV-vis spectra and small-angle X-ray diffraction. Gas-sensing measurement shows that the LB film has good sensitivity to alcohols at room temperature,

Molecular and supramolecular deformations and disclinations in a liquid crystalline copolyether thin films under an electrostatic field

An alignment study of a liquid crystalline copolyether TPP-7/11(5/5) thin films has been carried out in a 10 kV . cm(-1) electrostatic field parallel to the thin film surface normal. This copolyether possesses a negative dielectric anisotropy. The chain molecules are homogeneously aligned in the electric field and they form two-dimensionally ordered lamellae in a tilted columnar phase when the samples were cooled to room temperature. It is observed that the chain molecules are splayed to form bent lamellae and the chain direction is perpendicular to the tangential direction of the lamellar surfaces. These lamellae thus become replicas of the chain orientation, Due to the flexoelectric effect and density fluctuation on the thin film free surface, disclinations having topological strength s = 1, c = pi /4 and defect walls form. These s = 1 disclinations possesses both left- and right-handednesses. Discussion of the defect formations have been attempted.

Electrostatic-field-induced chain alignment of liquid crystalline copolyether TPP thin films

A liquid crystalline (LC) copolyether has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,11-dibromoundecane with a 50/50 (both in %) equal composition of the 7- and 11-methylene monomers [coTPP-7/11(5/5)]. A mono-domain with a homeotropic alignment can be induced by a thin film surface in the LC phase. When an electrostatic field is applied to the surface-induced mono-domains parallel to the thin film surface normal, the molecular alignment undergoes a change from the homeotropic to uniaxial homogeneous arrangement. However, when the field is applied to a direction perpendicular to the thin film surface normal. the molecular alignment is about 10 degrees -tilt with respect to the homeotropic alignment toward the a*-axis. This is because the permanent dipole moment of the copolyether is not right vertical to the molecular direction. The calculation of molecular dipoles indicates that the permanent dipole moment of this copolyether is about 70 degrees away from the molecular axis, which leads to a negative dielectric anisotropy. It is speculated that the 10 degrees- rather than 20 degrees -tilt is due to a balance between the alignment induced by the electrostatic field and the surface. In the electrostatic field, molecules are subjected to a torque tau, which is determined by the permanent dipole moment P and the electrostatic field E: tau = P x E. The molecular realignment in both parallel and perpendicular directions to the thin film surface normal is determined by satisfying the condition of tau = P x E = 0. (C) 2001 Elsevier Science Ltd. All rights reserved.

Characteristics of the conductive polyimide film surfaces induced by ultraviolet laser beam

A conducting layer with the conductivity of 1.2 Omega(-1)cm(-1) stripped in a solvent from KrF-laser-irradiated polyimide thin film is taken as a sample to determine the microstructure of the conducting layer. Fourier-transform infrared and X-ray photoelectron spectroscopies show the formation of the carbon-rich clusters after irradiation. The element analysis gives the atomic ratio of C:H:N:O for the carbon-rich cluster as 60:20:3:1. Wide-angle X-ray diffraction indicates that the conducting layer is mainly amorphous carbon with a small amount of the short-range ordered carbon-rich clusters. This study suggests a structural model with three-layer carbon sheets linked together in a random fashion for the short-range ordered carbon-rich clusters. The interplanar spacing is 3.87 Angstrom and the layer diameter 25 Angstrom. The transport model of variable-range hopping in three dimensions is used to explain the conducting behavior of the conducting layer. In our case, the short-range ordered carbon-rich clusters are assumed to be conducting islands dispersed in the amorphous carbon-rich cluster matrix.

Polyimide thin films as compensators for liquid crystal displays

The disadvantages of NW-TN-LCD (normally white twisted nematic liquid crystal display) are discussed. The reason that the negative birefringent polyimide thin films are used to compensate NW-TN-LCD to decrease off-axis leakage, improve contrast ratios and enlarge viewing angeles is explained. A certain polyimide thin film is taken as an example to show the compensation effect on NW-TN-LCD. (C) 1997 by John Wiley & Sons, Ltd.

Compensation effect of polyimide thin films on normally white twisted nematic liquid crystal displays

The disadvantages of Normally White Twisted Nematic Liquid Crystal Display (NW-TN-LCD) were discussed. The reason that the negative birefringent polyimide thin films were used to compensate NW-TN-LCD to decrease off-axis leakage, improve contrast ratios and enlarge viewing angles was explained in this paper. A certain polyimide thin film was taken as an example to show compensation effect on NW-TN-LCD.