Rational Design, Synthesis, and Optical Properties of Film-Forming, Near-Infrared Absorbing, and Fluorescent Chiromophores with Multidonors and Large Heterocyclic Acceptors

A new series of film-forming, low-bandgap chromophores (1a,b and 2a,b) were rationally designed with aid of a computational study., and then synthesized and characterized. To realize absorption and emission above the 1000 nm wavelength, the molecular design focuses on lowering the LUMO level by fusing common heterocyclic units into a large conjugated core that acts an electron acceptor and increasing the charge transfer by attaching the multiple electron-donating groups at the appropriate positions of the acceptor core. The chromophores have bandgap levels of 1.27-0.71 eV, and accordingly absorb at 746-1003 nm and emit at 1035-1290 nm in solution. By design, the relatively high molecular weight (up to 2400 g mol(-1)) and non-coplanar structure allow these near-infrared (NIR) chromophores to be readily spin-coated as uniform thin films and doped with other organic semiconductors for potential device applications. Doping with [6,6]-phenyl-C-61 butyric acid methyl ester leads to a red shift in the absorption on]), for la and 2a. An interesting NIR electrochromism was found for 2a, with absorption being turned on at 1034 nm when electrochemically switched (at 1000 mV) from its neutral state to a radical cation state. Furthermore, a large Stokes shift (256-318 nm) is also unique for this multidonor-acceptor type of chromophore.

Nanocrystalline LaAlO3:Sm3+ as a Promising Yellow Phosphor for Field Emission Displays

Nanocyrstalline LaAlO3:Sm3+ phosphors were prepared through a Pechini-type sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence, and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphors. XRD results reveal that the sample begins to crystallize at 600 degrees C, and pure LaAlO3 phase can be obtained at 700 degrees C. FE-SEM images indicate that the Sm3+-doped LaAlO3 phosphors are composed of aggregated spherical particles with sizes ranging from 40 to 80 nm. Under the excitation of UV light (245 nm) and low-voltage electron beams (1-3 kV), the Sm3+-doped LaAlO3 phosphors show the characteristic emissions of the Sm3+ ((4)G(5/2)-H-6(5/2), H-6(7/2), H-6(9/2) transitions) with a yellow color. The CL intensity (brightness) of the Sm3+-doped LaAlO3 phosphor is higher than that of the commercial product [Zn(Cd)S:Ag+] (yellow) to some extent.

Y2O3 : Eu3+ microspheres: Solvothermal synthesis and luminescence properties

Y2O3 : Eu3+ microspheres, with an average diameter of 3 mu m, were successfully prepared through a large-scale and facile solvothermal method followed by a subsequent heat treatment. X-ray diffraction, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectra, thermogravimetric and differential thermal analysis, inductive coupled plasma atomic absorption spectrometric analysis, scanning electron microscopy, transmission electron microscopy, photoluminescence spectra, as well kinetic decays, and cathodoluminescence spectra were used to characterize the samples. These microspheres were actually composed of randomly aggregated nanoparticles. The formation mechanisms for the Y2O3 : Eu3+ microspheres have been proposed on an isotropic growth mechanism. The Y2O3 : Eu3+ microspheres show a strong red emission corresponding to D-5(0) -> F-7(2) transition (610 nm) of Eu3+ under ultraviolet excitation (259 nm) and low-voltage electron beams excitation (1-5 kV), which have potential applications in fluorescent lamps and field emission displays.

Nanocrystalline LaGaO3 : Tm3+ as an efficient blue phosphor for field emission displays with high color purity

Nanocrystalline Tm3+-doped LaGaO3 phosphors were prepared through a Pechini-type sol-gel process [M. P. Pechini, U.S. Patent No. 3,330,697 (11 July 1967)]. X-ray diffraction, field emission scanning electron microscopy, photoluminescence, and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphors. Under the excitation of ultraviolet light and low voltage electron beams (0.5-3 kV), the Tm3+-doped LaGaO3 phosphors show the characteristic emissions from the LaGaO3 host lattice and the Tm3+ (D-1(2), (1)G(4)-F-3(4), and H-3(6) transitions), respectively. The blue CL of the Tm3+-doped LaGaO3 phosphors, with a dominant wavelength of 458 nm, had better Commission International I'Eclairage chromaticity coordinates (0.1552, 0.0630) and higher emission intensity than the commercial product (Y2SiO5:Ce3+).

White light emission from Eu3+ in CaIn2O4 host lattices

CaIn2O4:xEu(3+) (x=0.5%,1.0%,1.5%) phosphors were prepared by the Pechini sol-gel process [U.S. Patent No. 3,330,697 (1967)] and characterized by x-ray diffraction and photoluminescence and cathodoluminescence spectra as well as lifetimes. Under the excitation of 397 nm ultraviolet light and low voltage electron beams, these phosphors show the emission lines of Eu3+ corresponding to D-5(0,1,2,3)-F-7(J) (J=0,1,2,3,4) transitions from 400 to 700 nm (whole visible spectral region) with comparable intensity, resulting in a white light emission with a quantum efficiency near 10%. The luminescence mechanism for Eu3+ in CaIn2O4 has been elucidated.

Luminescence functionalization of SBA-15 by YVO4 : Eu3+ as a novel drug delivery system

Luminescence functionalization of the ordered mesoporous SBA-15 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process, resulting in the formation of the YVO4:Eu3+@SBA-15 composite material. This material, which combines the mesoporous structure of SBA-15 and the strong red luminescence property of YVO4:Eu3+, can be used as a novel functional drug delivery system. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, N-2 adsorption, and photoluminescence spectra. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the YVO4:Eu3+ layer and the adsorption of ibuprofen (IBU, drug). The IBU-loaded YVO4:Eu3+@SBA-15 system still shows the red emission of Eu3+ (617 nm, D-5(0)-F-7(2)) under UV irradiation and the controlled drug release property. Additionally, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU in the system, making the extent of drug release easily identifiable, trackable, and monitorable by the change of luminescence. The system has great potential in the drug delivery and disease therapy fields.

Biofunctionalization of CeF3 : Tb3+ nanoparticles

CeF3: Tb3+ nanoparticles (short pillar-like morphology with an average length and width of 11 and 5 nm, respectively) were successfully prepared by a polyol process using diethyleneglycol (DEG) as solvent. After being functionalized with a SiO2-NH2 layer, these CeF3: Tb3+ nanoparticles can be conjugated with biotin molecules (activated by thionyl chloride) and further with avidin. The as-formed CeF3: Tb3+ nanoparticles, CeF3: Tb3+ nanoparticles functionalized with amino groups, biotin conjugated amino-functionalized CeF3: Tb3+ nanoparticles and biotinylated CeF3: Tb3+ nanoparticles bonded with avidin were characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), UV/vis absorption spectra and luminescence spectra, respectively. The biofunctionalization of the CeF3: Tb3+ nanoparticles has less effect on their luminescence properties, i.e. they still show strong green emission (from Tb3+, with D-5(4) - F-7(5) at 543 nm as the most prominent group), indicative of the great potential for these CeF3: Tb3+ nanoparticles to be used as biological fluorescence probes.

MCM-41 functionalized with YVO4 : Eu3+: a novel drug delivery system

Luminescence functionalization of ordered mesoporous MCM-41 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process. This material, which combines the mesoporous structure of MCM-41 and the strong red luminescence property of YVO4: Eu3+, has been studied as a host carrier for drug delivery/release systems. The structure, morphology, texture and optical properties of the materials were well characterized by x-ray diffraction ( XRD), Fourier infrared spectroscopy ( FT-IR), transmission electron microscopy ( TEM), N-2 adsorption and photoluminescence ( PL) spectra. The results indicated that the specific surface area and pore volume of MCM-41, which were directly correlated to the drug-loading amount and ibuprofen ( IBU) release rate, decreased in sequence after deposition of YVO4:Eu3+ and loading of IBU as expected. The IBU-loaded YVO4:Eu3+@ MCM-41 system still showed red luminescence under UV irradiation ( 365 nm) and a controlled release property for IBU. In addition, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU, making the extent of drug release easily identified, tracked and monitored by the change of luminescence, which demonstrates its potential application in drug delivery/release systems.

Host-sensitized luminescence of Dy3+, Pr3+, Tb3+ in polycrystalline SrIn2O4 for field emission displays

SrIn2O4:Dy3+/Pr3+/Tb3+ white/red/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence, cathodoluminescence spectra, and lifetimes were utilized to characterize the samples. XRD reveal that the samples begin to crystallize at 800 degrees C and pure SrIn2O4 phase can be obtained at 900 degrees C. FE-SEM images indicate that the SrIn2O4:Dy3+, SrIn2O4:Pr3+, and SrIn2O4:Tb3+ samples consist of fine and spherical grains with size around 200-400 nm. Under the excitation of ultraviolet light and low-voltage electron beams (1 - 5 kV), the SrIn2O4:Dy3+, SrIn2O4: Pr3+, and SrIn2O4: Tb3+ phosphors show the characteristic emissions of Dy3+ (F-4(9/2) - H-6(15/2) at 492 nm and 4F(9/2) - 6H(13/2) at 581 nm, near white), Pr3+ (P-3(0) - H-3(4) at 493 nm, D-1(2) - H-3(4) at 606 nm, and P-3(0) - H-3(6) at 617 nm, red) and Tb3+ (D-5(4) - F-7(6,5,4,3) transitions dominated by D-5(4) - F-7(5) at 544 nm, green), respectively. All of the luminescence resulted from an efficient energy transfer from the SrIn2O4 host lattice to the doped Dy3+, Pr3+, and Tb3+ ions, and the luminescence mechanisms have been proposed.

Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: Polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb3+-doped CaWO4 particles show the characteristic emission of Tb3+ D-5(4)-F-7(J) (J=6-3) transitions due to an energy transfer from WO42- groups to Tb3+.

Host-sensitized luminescence of Dy3+, Pr3+ , Tb3+ in polycrystalline CaIn2O4 for field emission displays

Caln(2)O(4):Dy3+/Pr3+/Tb3+ blue-white/green/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence (PL) and cathodoluminescencc (CL) spectra as well as lifetimes were utilized to characterize the samples. The XRD results reveal that the samples begin to crystallize at 800 degrees C 3-1 and pure CaIn2O4 phase can be obtained after annealing at 900 degrees C. The FE-SEM images indicate that the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ samples consist of spherical grains with size around 200-400nm. Under the excitation of ultraviolet light and low electron beams (1-5kV), the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ phosphors show the characteristic emissions of Dy3+ ((F9/2-H15/2)-F-4-H-6 and (F9/2-H13/2)-F-4-H-6 transitions, blue-white), Pr3+ ((P0-H4)-P-3-H-3, (D2-H4)-D-1-H-3 and (P1-H5)-P-3-H-3 transitions, green) and Tb3+ ((D4-F6,5,4,3)-D-5-F-7 transitions, green), respectively. All the luminescence is resulted from an efficient energy transfer from the CaIn2O4 host lattice to the doped Dy3+ ,Pr3+ and Tb3+ ions, and the corresponding luminescence mechanisms have been proposed.

Pechini sol-gel deposition and luminescent properties of SrLa1-xRExGa3O7 (RE = Eu, Tb) phosphor films

SrLa1-xRExGa3O7 (RE = EU3+, Tb3+) phosphor films were deposited on quartz glass substrates by a simple Pechim sol-gel method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy, field-emission scanning electron microscopy, photoluminescence spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 700 degrees C and crystallized fully at 900 degrees C. The results of FNR spectra were in agreement with those of XRD. Uniform and crack-free films annealed at 900 degrees C were obtained with average grain size of 80 nm, root mean square roughness of 46 nm and thickness of 130 nm The RE ions showed their characteristic emission in crystalline SrLa1-xRExGa3O7 films, i.e., Eu3+ D-0-F-7(J) (J = 0, 1, 2, 3, 4), Tb3+5D4 -(7) F-J (J = 6, 5, 4, 3) emissions, respectively. The optimum concentrations (x) of Eu3+ and Tb3+ were determined to be 50, and 80 mol% in SrLa(1-x)RE(x)GGa(3)O(7) films, respectively.

Photoluminescence and electroluminescence properties of a samarium complex Sm(TTA)(3)phen

The photoluminescence (PL) and electroluminescence (EL) properties of a samarium complex Sm(TTA)(3)phen (TTA = 2-thenoyltri-fluoroacetonate, phen = 1, 10-phenanthroline) were investigated. The results show that Sm(TTA)3phen could be used as promising luminescent and electron transporting material in the electroluminescent devices. The difference between PL and EL spectra was noticed and discussed. Besides, it is noteworthy that the choice of the hole transporting layer (HTL) showed significant effect on the device performance, which was explained by the low-lying highest occupied molecular orbit (HOMO) level of Sm(TTA)3phen and the different hole injection barrier at the HTL/EML (emitting material layer) interface.