Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

Morphology controlled synthesis of wurtzite ZnS nanostructures through simple hydrothermal method and observation of white light emission from ZnO obtained by annealing the synthesized ZnS nanostructures

A controllable synthesis of phase pure wurtzite (WZ) ZnS nanostructures has been reported in this work at a low temperature of similar to 220 degrees C using ethylenediamine as the soft template and by varying the molar concentration of zinc to sulphur precursors as well as by using different precursors. A significant reduction in the formation temperature required for the synthesis of phase pure WZ ZnS has been observed. A strong correlation has been observed between the morphology of the synthesized ZnS nanostructures and the precursors used during synthesis. It has been found from Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) image analyses that the morphology of the ZnS nanocrystals changes from a block-like to a belt-like structure having an average length of similar to 450 nm when the molar ratio of zinc to sulphur source is increased from 1 : 1 to 1 : 3. An oriented attachment (OA) growth mechanism has been used to explain the observed shape evolution of the synthesized nanostructures. The synthesized nanostructures have been characterized by the X-ray diffraction technique as well as by UV-Vis absorption and photoluminescence (PL) emission spectroscopy. The as-synthesized nanobelts exhibit defect related visible PL emission. On isochronal annealing of the nanobelts in air in the temperature range of 100-600 degrees C, it has been found that white light emission with a Commission Internationale de I'Eclairage 1931 (CIE) chromaticity coordinate of (0.30, 0.34), close to that of white light (0.33, 0.33), can be obtained from the ZnO nanostructures obtained at an annealing temperature of 600 degrees C. UV light driven degradation of methylene blue (MB) dye aqueous solution has also been demonstrated using as-synthesized nanobelts and similar to 98% dye degradation has been observed within only 40 min of light irradiation. The synthesized nanobelts with visible light emission and having dye degradation activity can be used effectively in future optoelectronic devices and in water purification for cleaning of dyes.

Ethylenediamine assisted synthesis of wurtzite zinc sulphide nanosheets and porous zinc oxide nanostructures: near white light photoluminescence emission and photocatalytic activity under visible light irradiation

Porous fungus-like ZnO nanostructures have been synthesized by simple thermal annealing of the hydrothermally synthesized sheet-like ZnS(en)(0.5) complex precursor in air at 600 degrees C. Structural and morphological changes occurring during ZnS(en)(0.5) -> ZnS -> ZnO transformations have been observed closely by annealing the as-synthesized precursor at 100-600 degrees C. Wurtzite ZnS nanosheets and ZnS-ZnO composites are obtained at temperatures of 400 degrees C and 500 degrees C, respectively. Thermal decomposition and oxidation of the ZnS(en) 0.5 nanosheets have been confirmed by differential scanning calorimetry and thermo-gravimetric analysis. The visible light driven photocatalytic degradation of methylene blue dye has been demonstrated in the synthesized samples. ZnS-ZnO composite shows the highest dye degradation efficiency of 74% due to the formation of surface complex as well as higher visible light absorption as a result of band-gap narrowing effect. The porous ZnO nanostructures show efficient visible photoluminescence (PL) emission with a colour coordinate of (0.29, 0.35), which is close to that of white light (0.33, 0.33). The efficient visible PL emission as well as visible light driven photocatalytic activity of the materials synthesized in the present work might be very attractive for their applications in future optoelectronic devices, including in white light emitting devices.

Infrared to visible up-conversion in biocellulose yttrium vanadate nanoparticle composite membranes. Demonstration of chloroaluminum phthalocyanine light emission under up-converted light excitation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Trap-State Dynamics in Visible-Light-Emitting ZnO:MgO Nanocrystals

Oleate-capped ZnO:MgO nanocrystals have been synthesized that are soluble in nonpolar solvents and which emit strongly in the visible region (450−600 nm) on excitation by UV radiation. The visible emission involves recombination of trap states of the nanocrystalline ZnO core and has a higher quantum yield than the band gap UV exciton emission. The spectrally resolved dynamics of the trap states have been investigated by time-resolved emission spectroscopy. The time-evolution of the photoluminescence spectra show that there are, in fact, two features in the visible emission whose relative importance and efficiencies vary with time. These features originate from recombination involving trapped electrons and holes, respectively, and with efficiencies that depend on the occupancy of the trap density of states.

Cobalt(II) complexes of terpyridine bases as photochemotherapeutic agents showing cellular uptake and photocytotoxicity in visible light

Cobalt(II) complexes of terpyridine bases Co(L)(2)](ClO4)(2) (1-3), where L is 4'-phenyl-2,2':6',2''-terpyridine (ph-tpy in 1), 4'-(9-anthracenyl)-2,2':6',2''-terpyridine (an-tpy in 2) and 4'-(1-pyrenyl)-2,2':6',2''-terpyridine (py-tpy in 3), are prepared and their photo-induced DNA and protein cleavage activity and photocytotoxic property in HeLa cells studied. The 1 : 2 electrolytic and three-electron paramagnetic complexes show a visible band near 550 nm in DMF-Tris-HCl buffer. The complexes 1-3 show emission spectral bands at 355, 421 and 454 nm, respectively, when excited at 287, 368 and 335 nm. The quantum yield values for 1-3 in DMF-H2O (2 : 1 v/v) are 0.025, 0.060 and 0.28, respectively. The complexes are redox active in DMF-0.1 M TBAP. The Co(III)-Co(II) and Co(II)-Co(I) couples appear as quasi-reversible cyclic voltammetric responses near 0.2 and -0.7 V vs. SCE, respectively. Complexes 2 and 3 are avid binders to calf thymus DNA giving K-b value of similar to 10(6) M-1. The complexes show chemical nuclease activity. Complexes 2 and 3 exhibit oxidative cleavage of pUC19 DNA in UV-A and visible light. The DNA photocleavage reaction of 3 at 365 nm shows formation of singlet oxygen and hydroxyl radical species, while only hydroxyl radical formation is evidenced in visible light. Complexes 2 and 3 show non-specific photo-induced bovine serum albumin protein cleavage activity at 365 nm. The an-tpy and py-tpy complexes exhibit significant photocytotoxicity in HeLa cervical cancer cells on exposure to visible light giving IC50 values of 24.2 and 7.6 mu M, respectively. Live cell imaging study shows accumulation of the complexes in the cytosol of HeLa cancer cells.

Mitochondria targeting Photocytotoxic Oxidovanadium( IV) Complexes of Curcumin and ( Acridinyl) dipyridophenazine in Visible Light

Oxidovanadium(IV) complexes, VO(acac)(L)Cl] (1), VO(cur)(L)Cl] (2), and VO(scur)(L)Cl] (3) {acac = acetylacetonate, cur = curcumin monoanion, scur = diglucosylcurcumin monoanion, L = 11-(9-acridinyl)dipyrido3, 2-a:2',3'-c]phenazine (acdppz)}, were prepared and characterized. The complexes are non-electrolytic in DMF and 1:1 electrolytic in aqueous DMF. The one-electron paramagnetic complexes showed a d-d band near 725 nm in aqueous DMF and green emission near 520 nm in aqueous DMSO. The complexes exhibited an irreversible V-IV/V-III redox response near -0.85 V versus SCE in aqueous DMF. The complexes showed good binding strengths to calf thymus DNA (K-b: 3.1x10(5)-9.6x10(5) M-1) and efficient pUC19 DNA photocleavage activity in red light of 705 and 785 nm by singlet oxygen (O-1(2)) pathway. Complexes 1 and 2 exhibited significant photocytotoxicity (IC50: 0.1-1.0 M) in visible light (400-700 nm) with low dark toxicity (IC50: >20 M) in HeLa and HaCaT cells. Complex 3 was cytotoxic in both light and dark. DNA ladder formation experiments indicated cell death via apoptotic pathway. Confocal microscopy done with 1 and 2 revealed primarily cytosolic localization of the complexes with significant presence of the complex in the mitochondria as evidenced from the imaging data using mitotracker red.

Facile synthesis of PbWO4: Applications in photoluminescence and photocatalytic degradation of organic dyes under visible light

Stolzite polymorph of PbWO4 catalyst was prepared by the facile room temperature precipitation method. Structural parameters were refined by the Rietveld analysis using powder X-ray data. PbWO4 was crystallized in the scheelite-type tetragonal structure with space group I4(1)/a (No. 88). Field emission scanning electron microscopy revealed leaf like morphology. Photoluminescence spectra exhibit broad blue emission (425 nm) under the excitation of 356 nm. The photocatalytic degradation of Methylene blue, Rhodamine B and Methyl orange dyes were measured under visible illumination. The 100% dye degradation was observed for MB and RhB dyes within 60 and 105 min. The rate constant was found to be in the decreasing order of MB > RhB > MO which followed the 1st order kinetic mechanism. Therefore, PbWO4 can be a potential candidate for blue component in white LEDs and also acts as a catalyst for the treatment of toxic and non-biodegradable organic pollutants in water. (C) 2014 Elsevier B.V. All rights reserved.

Tb3+/Yb3+ heavily-doped tellurite glasses with efficient green light emission

Without introducing concentration quenching phenomenon, a few wt% of Tb3+ and Yb3+ ions were doped into a group of easily-fiberized tellurite glasses characterized by loose polyhedron structures and rich interstitial positions. Intense green upconversion emission from Tb3+ ions centered at 539 nm due to transition 5D4→7F5 was observed by direct excitation of Yb3+ ions with a laser diode at 976 nm. Optimizing the concentration ratio of Tb3+/Yb3+, a tellurite glass with composition of 80TeO2-10ZnO-10Na2O (mol%)+1.0wt% Tb2O3+3.0wt% Yb2O3 was found to present the highest green light intensity and therefore is especially suitable for efficient green fiber laser development.

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.

Rare-earth nitroquinolinates: Visible-light-sensitizable near-infrared emitters in aqueous solution

Water-soluble, stable, and easily synthesizable 1:4 complexes of rare-earth ions with 8-hydroxy-5-nitroquinolinate ligands have been prepared. These complexes can be sensitized by visible light with wavelengths up to 480 nm and show near-infrared emission in aqueous solution. The incorporation of a nitro group in the quinoline moiety shifts its absorption bands to longer wavelengths and also increases its molar absorptivity by a factor of 2.5, thereby significantly enhancing its light-harvesting power. The presence of the nitro group also increases the solubility of the resulting complexes, making them water-soluble. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007.

Search for Rapid Changes in the Visible-Light Corona during the 21 June 2001 Total Solar Eclipse

Some 8000 images obtained with the Solar Eclipse Coronal Imaging System (SECIS) fast-frame CCD camera instrument located at Lusaka, Zambia, during the total eclipse of 21 June 2001 have been analysed to search for short-period oscillations in intensity that could be a signature of solar coronal heating mechanisms by MHD wave dissipation. Images were taken in white-light and Fe xiv green-line (5303 ) channels over 205 seconds (frame rate 39 s(-1)), approximately the length of eclipse totality at this location, with a pixel size of four arcseconds square. The data are of considerably better quality than those that we obtained during the 11 August 1999 total eclipse (Rudawy et al.: Astron. Astrophys. 416, 1179, 2004), in that the images are much better exposed and enhancements in the drive system of the heliostat used gave a much improved image stability. Classical Fourier and wavelet techniques have been used to analyse the emission at 29 518 locations, of which 10 714 had emission at reasonably high levels, searching for periodic fluctuations with periods in the range 0.1 -aEuro parts per thousand 17 seconds (frequencies 0.06 -aEuro parts per thousand 10 Hz). While a number of possible periodicities were apparent in the wavelet analysis, none of the spatially and time-limited periodicities in the local brightness curves was found to be physically important. This implies that the pervasive Alfv,n wave-like phenomena (Tomczyk et al.: Science 317, 1192, 2007) using polarimetric observations with the Coronal Multi-Channel Polarimeter (CoMP) instrument do not give rise to significant oscillatory intensity fluctuations.

Light emission and excitonic effect of boron nitride nanotubes observed by photoluminescent spectra

Photoluminescent (PL) and optical absorption spectra of high-yield multi-wall BN nanotubes (BNNTs) were systematically investigated at room temperature in comparison with commercial hexagonal BN (h-BN) powder. The direct band gap of the BNNTs was determined to be 5.75 eV, just slightly narrower than that of h-BN powder (5.82 eV). Two Frenkel excitons with the binding energy of 1.27 and 1.35 eV were also determined. However, they were not a distinctive characteristic of the BNNTs as reported previously. Observed broad UV–visible–NIR light emission demonstrates the potential of the BNNTs as a nano light source.