Synthesis and Photoluminescence Properties of Novel Red Phosphors for White Light Emitting Diode Applications

Several series of Eu3+ based red emitting phosphor materials were synthesized using solid state reaction route and their properties were characterized. The present studies primarily investigated the photoluminescence properties of Eu3+ in a family of closely related host structure with a general formula Ln3MO7. The results presented in the previous chapters throws light to a basic understanding of the structure, phase formation and the photoluminescence properties of these compounds and their co-relations. The variation in the Eu3+ luminescence properties with different M cations was studied in Gd3-xMO7 (M = Nb, Sb, Ta) system.More ordering in the host lattice and more uniform distribution of Eu3+ ions resulting in the increased emission properties were observed in tantalate system.Influence of various lanthanide ion (Lu, Y, Gd, La) substitutions on the Eu3+ photoluminescence properties in Ln3MO7 host structures was also studied. The difference in emission profiles with different Ln ions demonstrated the influence of long range ordering, coordination of cations and ligand polarizability in the emission probabilities, intensity and quantum efficiency of these phosphor materials. Better luminescence of almost equally competing intensities from all the 4f transitions of Eu3+ was noticed for La3TaO7 system. Photoluminescence properties were further improved in La3TaO7 : Eu3+ phosphors by the incorporation of Ba2+ ions in La3+ site. New red phosphor materials Gd2-xGaTaO7 : xEu3+ exhibiting intense red emissions under UV excitation were prepared. Optimum doping level of Eu3+ in these different host lattices were experimentally determined. Some of the prepared samples exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. In the present studies, Eu3+ acts as a structural probe determining the coordination and symmetry of the atoms in the host lattice. Results from the photoluminescence studies combined with the powder XRD and Raman spectroscopy investigations helped in the determination of the correct crystal structures and phase formation of the prepared compounds. Thus the controversy regarding the space groups of these compounds could be solved to a great extent. The variation in the space groups with different cation substitutions were discussed. There was only limited understanding regarding the various influential parameters of the photoluminescence properties of phosphor materials. From the given studies, the dependence of photoluminescence properties on the crystal structure and ordering of the host lattice, site symmetries, polarizability of the ions, distortions around the activator ion, uniformity in the activator distribution, concentration of the activator ion etc. were explained. Although the presented work does not directly evidence any application, the materials developed in the studies can be used for lighting applications together with other components for LED lighting. All the prepared samples were well excitable under near UV radiation. La3TaO7 : 0.15Eu3+ phosphor with high efficiency and intense orange red emissions can be used as a potential red component for the realization of white light with better color rendering properties. Gd2GaTaO7 : Eu3+, Bi2+ red phosphors give good color purity matching to NTSC standards of red. Some of these compounds exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. However thermal stability and electrical output using these compounds should be studied further before applications. Based on the studies in the closely related Ln3MO7 structures, some ideas on selecting better host lattice for improved luminescence properties could be drawn. Analyzing the CTB position and the number of emission splits, a general understanding on the doping sites can be obtained. These results could be helpful for phosphor designs in other host systems also, for enhanced emission intensity and efficiency.

Multiple lyotropic polymorphism of a PEG-peptide diblock copolymer in aqueous solution

Nematic and hexagonal columnar liquid crystal phase formation by a PEG-peptide conjugate is reported. The results are relevant to peptide-polymer Conjugates and bionanomaterial self-assembly (with relevance to PEGylated peptides used in therapeutic applications). The use of modified fragments of the amyloid beta peptide is especially interesting with respect to amyloid fibrillization and its control.

Dynamics of shear-induced orientation transitions in block copolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Thermal and structural investigation of Er:YAl(3)(BO(3))(4) nanocrystalline powders

Pure Er:YAB (Er:YAl(3)(BO(3))(4)) nanometer-sized crystalline powder was produced from low cost chemical route, the polymeric precursor method. The initial homogeneous solutions were heat treated from 200 to 700A degrees C under oxygen atmosphere and the unique crystalline phase was synthesized at around 1150A degrees C. The thermal treatments and the initial stoichiometry play a very important role on the Er:YAB preparation. The thermal events of amorphous precursor resins and the crystallization process up to phase formation were investigated.

Synthesis optimization, structural evolution and optical properties of Y(0.9)Er(0.1)Al(3)(BO(3))(4) nanopowders obtained by soft chemistry methods

This paper describes the structural evolution of Y(0.9)Er(0.1)Al(3)(BO(3))(4) nanopowders using two soft chemistry routes, the sol-gel and the polymeric precursor methods. Differential scanning calorimetry, differential thermal analyses, thermogravimetric analyses, X-ray diffraction, Fourier-transform infrared, and Raman spectroscopy techniques have been used to study the chemical reactions between 700 and 1200 degrees C temperature range. From both methods the Y(0.9)Er(0.1)Al(3)(BO(3))(4) (Er:YAB) solid solution was obtained almost pure when the powdered samples were heat treated at 1150 degrees C. Based on the results, a schematic phase formation diagram of Er:YAB crystalline solid solution was proposed for powders from each method. The Er:YAB solid solution could be optimized by adding a small amount of boron oxide in excess to the Er:YAB nominal composition. The nanoparticles are obtained around 210 nm. Photoluminescence emission spectrum of the Er:YAB nanocrystalline powders was measured on the infrared region and the Stark components of the (4)I(13/2) and (4)I(15/2) levels were determined. Finally, for the first time the Raman spectrum of Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystalline phase is also presented. (C) 2008 Elsevier Masson SAS. All rights reserved.

Zn(0.97)M(0.03)O (M = Co, Fe, and V) pigments: thermal, structural, and optical characterization

Zinc oxide is a widely used white inorganic pigment. Transition metal ions are used as chromophores and originate the ceramic pigments group. In this context, ZnO particles doped with Co, Fe, and V were synthesized by the polymeric precursors method, Pechini method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of decomposition temperatures due to different exothermal events, which were identified as H(2)O elimination, organic compounds degradation and phase formation. The samples were structurally characterized by X-Ray diffractometry revealing the formation of single phase, corresponding to the crystalline matrix of ZnO. The samples were optically characterized by diffuse reflectance measurements and colorimetric coordinates L*, a*, b* were calculated for the pigment powders. The pigment powders presented a variety of colors ranging from white (ZnO), green (Zn(0.97)Co(0.03)O), yellow (Zn(0.97)Fe(0.03)O), and beige (Zn(0.97)V(0.03)O).

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test

Obtenção de ferrita de cobalto através de dois métodos de síntese: método de complexação combinando EDTA/Citrato e método hidrotérmico

In this work it was synthesized and characterized the cobalt ferrite (CoFe2O4) by two methods: complexation combining EDTA/Citrate and hydrothermal investigating the influence of the synthesis conditions on phase formation and on the crystallite size. The powders were mainly characterized by x-ray diffraction. In specific cases, it was also used scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), x-ray fluorescence (XRF) and isotherms of adsorption and desorption of nitrogen (BET method). The study of the crystallite size was based on the interpretation of x-ray diffractograms obtained and estimated by the method of Halder-Wagner-Scherrer and Langford. An experimental design was made in order to assist in quantifying the influence of synthesis conditions on the response variables. The synthesis parameters evaluated in this study were: pH of the reaction medium (8, 9 and 10), the calcination temperature (combined complexation method EDTA/Citrate 600°C, 800°C and 1000°C), synthesis temperature (hydrothermal method 120°C, 140°C and 160°C), calcination time (combined complexation method EDTA/Citrate - 2, 4 and 6 hours) and time of synthesis (hydrothermal method 6, 15 and 24 hours). By the hydrothermal method was possible to produce mesoporous powders with high purity, with an average crystallite size up to 7 nm, with a surface area of 113.44 m²/g in the form of pellets with irregular morphology. By using the method of combined complexation EDTA/Citrate, mesoporous powders were produced with greater purity, crystallite size up to 22nm and 27.95 m²/g of surface area in the form of pellets with a regular morphology of plaques. In the experimental design was found that the hydrothermal method to all the studied parameters (pH, temperature and time) have significant effect on the crystallite size, while to the combined complexation method EDTA/Citrate, only temperature and time were significant

Evolução microestrutural da cerâmica KSr2Nb5O15 dopada com CuO:B2O3

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

Disorder effects produced by the Mn and H incorporations on the optical absorption edge of Ga1-xMnxAs:H nanocrystalline films

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

Síntese análise das propriedades magnéticas da ferrita de NiMg e características de absorção de radiação

It was synthesized different Ni1-xMgxFe2O4 (0,2 ≤ x ≤ 0,7) compositions by use of citrate precursor method. Initially, the precursory citrates of iron, nickel and magnesium were mixed and homogenized. The stoichiometric compositions were calcined from 350°C to 1200°C at ambient atmosphere or in argon atmosphere. The calcined powders were characterized by XRD, TGA/DTG, FTIR, magnetic measures and reflectivity using the wave guide method. I was observed pure magnetic phase formation between 350°C and 500°C, with formation of ferrite and hematite after 600°C at ambient atmosphere. The calcined powder at argon atmosphere formed pure ferromagnetic phase at 1100°C and 1200°C. The Rietveld analyses calculated the cations level occupation and the crystallite size. The analyses obtained nanometric crystals (11-66 nm), that at 900°C/3h presents micrometric sizes (0,45 - 0,70 Om). The better magnetization results were 54 Am2/Kg for x= 0,2 composition, calcined at 350°C/3h and 30 min, and 55,6 Am2/Kg for x= 0,2 1200°C, calcined in argon. The hysteresis shows characteristics of soft magnetic material. Two magnetization processes were considered, superparamagnetism at low temperature and the magnetic domains formation at high temperatures. The materials presented absorption less or equal the 50 % in ranges specific frequency. As for the 2,0 and 3,0 thickness (in 11,0 - 11,8 GHz), the reflectivity of the x= 0,3, 0,5 and 0,4 compositions, all calcined at 900°C/3h showed agreement with MS and O. Various factors contribute for the final radiation absortion effect, such as, the particle size, the magnetization and the polymer characteristics in the MARE composition. The samples that presented better magnetization does not obtaining high radiation absorption. It is not clear the interrelaction between the magnetization and the radiation absorption in the strip of frequencies studied (8,2 - 12,4 GHz)

Síntese e caracterização de carreadores de oxigênio para combustão com recirculação química obtidos via reação de combustão assistida por microondas

Perovskites oxides win importance by its properties and commercials applications, they have a high thermal stability, have conductive properties, electrical, catalytic, electro catalytic, optical and magnetic, and are thermally stable. Because of these properties, are being widely studied as carriers of oxygen in the process of power generation with CO2 capture. In this work, the base carrier system La1-xMexNiO3 (Me = Ca and Sr) were synthesized by the method via the combustion reaction assisted by microwave. were synthesized from the combustion reaction method by microwave process. This method control the synthesi`s conditions to obtain materials with specific characteristics. The carriers calcined at 800 ° C/2h were analyzed by thermal analysis (TG-DTA), to verify its thermal stability, X-ray diffraction (XRD) to verify the phase formation, with subsequent refinement by the Rietveld method, to quantify the percentage of phases formed, the surface area by BET method was determined, scanning electron microscopy (SEM) was obtained to evaluate the material morphology and temperature programmed reduction (TPR) was done to observe the metallic phase of the nickel. After all proposed characterization and analysis of their results can be inferred to these oxides, key features so that they can be applied as carriers for combustion reactions in chemical cycles. The final products showed perovskite-type structures K2NiF4 (main) and ABO3.

Otimização da síntese de nanoferritas de nizn dopada com cobre e cobalto

Different compositions of Ni0,5-xCuxZn0,5Fe2O4 and Ni0,5-xCoxZn0,5Fe2O4 0 ≤ x ≤ 0.3 were synthesized ferrite y the citrate precursor method. The stoichiometric compositions were calcined in air at 350°C and then pressed into pellets and toroids. The pressed samples were sintered at temperatures of 1000, 1050 and 1100°C/3h in air control at the speed of heating and cooling. The calcined powders were characterized by XRD, TGA / DTG, FTIR, SEM and vibrating sample magnetometry (VSM) and the sintered samples by XRD, SEM, MAV, density and measurements of permeability and magnetic losses. There was pure phase formation ferrimagnetism applied at all temperatures except for A-I composition at all sintering temperatures and A-II only at a temperature of 1100°C. Crystallite sizes were obtained by Rietveld analysis, nanometer size from 11 to 20 nm for the calcined powders. For SEM, the sintered samples showed grain size between 1 and 10 micrometers. Bulk density (ρ) of sintered material presented to the Families almost linear behavior with increasing temperature and a tendency to decrease with increasing concentration of copper, different behavior of the B Family, where the increase in temperature decreased the density. The magnetic measurements revealed the powder characteristics of a soft ferrimagnetic material. Two processes of magnetization were considered, the superparamagnetism at low temperatures (350°C) and the formation of magnetic domains at higher temperatures. Obtaining the best parameters for P and B-II magnetic ferrites at high temperatures. The sintered material at 1000°C showed a relative permeability (μ) from 50 to 800 for the A Family and from 10 to 600 for the B Family. The samples sintered at 1100°C, B Family showed a variation from 10 to 1000 and the magnetic loss (tan δ) of A and B Families, around of 1. The frequency response of the toroidal core is in the range of 0.3 kHz. Several factors contribute to the behavior of microstructure considering the quantities μ and tan δ, such as the grain size, inter-and intragranular porosity, amount of grain boundary and the aspects of the dynamics of domain walls at high frequencies.

Structural characterization of 0.5PbMg(1/3)Nb(2/3)O(3)-0.5Ba(x)Pb((1-x))TiO(3) powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5PbMg(1/3)Nb(2/3)O(3)-0.5Ba(x)Pb((1-x))TiO(3) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 mn for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 degrees C for 4 h. (c) 2007 Elsevier Ltd. All rights reserved.