Molecular self-assembly of cadmium-triazolate complexes via hydrogen bonding: Synthesis, structures and photoluminescent properties

Two new cadmium coordination polymers namely Cd(HAmTrz-COO)(4)(NH4+)(2)] 1; and Cd(HAmTrz)(2)I-2](n) 2; (HAmTrz-COOH = 3-amino-1,2,4-triazole-5-carboxylic acid), have been prepared based on HAmTrz-COOH as ligand. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction technique. In coordination-complex 1 four triazole ligands coordinate via N1 nitrogen leading to a tetrahedral geometry around cadmium ion, while in 2 the ligand prefers to coordinate to the metal in a bidentate bridging mode. The structures of both the coordination polymers can be envisaged as 3D hydrogen bonded networks. Thermogravimetric analysis shows that 2 is more stable than 1 owing to different coordination numbers of cadmium atoms. Photoluminescence properties of both the compounds have been investigated in the solid state. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and photoluminescent properties of ZnS nanocrystals doped with copper and halogen

A novel wet-chemical precipitation method is optimized for the synthesis of ZnS nanocrystals doped with Cu+ and halogen. The nanoparticles were stabilized by capping with polyvinyl pyrrolidone (PVP). XRD studies show the phase singularity of ZnS particles having zinc-blende (cubic) structure. TEM as well as XRD line broadening indicate that the average crystallite size of undoped samples is similar to2 nm. The effects of change in stoichiometry and doping with Cu+ and halogen on the photoluminescence properties of ZnS nanophosphors have been investigated. Sulfur vacancy (Vs) related emission with peak maximum at 434 nm has been dominant in undoped ZnS nanoparticles. Unlike in the case of microcrystalline ZnS phosphor, incorporation of halogens in nanoparticles did not result V-Zn related self-activated emission. However, emission characteristics of nanophosphors have been changed with Cu+ activation due to energy transfer from vacancy centers to dopant centers. The use of halogen as co-activator helps to increase the solubility of Cu+ ions in ZnS lattice and also enhances the donor-acceptor type emission efficiency. With increase in Cu+ doping, Cu-Blue centers (CuZn-Cui+), which were dominant at low Cu+ concentrations, has been transformed into Cu-Green (Cu-Zn(-)) centers and the later is found to be situated near the surface regions of nanoparticles. From these studies we have shown that, by controlling the defect chemistry and suitable doping, photoluminescence emission tunability over a wide wavelength range, i.e., from 434 to 514 nm, can be achieved in ZnS nanophosphors. (C) 2003 Elsevier B.V. All rights reserved.

Structural and phase dependent thermo and photoluminescent properties of Dy(OH)(3) and Dy2O3 nanorods

Hexagonal Dy(OH)(3) and cubic Dy2O3 nanorods were prepared by hydrothermal method. Dy(OH)(3) nanorods was directly obtained at 180 degrees C for 20 h after hydrothermal treatment whereas subsequently heat treatment at 750 degrees C for 2 h gives pure cubic Dy2O3. SEM micrographs reveal that needle shaped rods with different sizes were observed in both the phases. TEM results also confirm this. The TL response of hexagonal Dy(OH)(3) and cubic Dy2O3 nanorods have been analyzed for gamma-irradiation over a wide range of exposures (1-5 kGy). TL glow peak intensity increases with gamma dose in both the phases. The activation energy (E), order of kinetics (6), and frequency factor (s) for both the phases have been determined using Chen's peak shape method. The simple glow curve shape, structure and linear response to gamma-irradiation over a large span of exposures makes the cubic Dy2O3 as a useful dosimetric material to estimate high exposures of gamma-rays. (c) 2012 Elsevier Ltd. All rights reserved.

Effect of different fuels on structural, thermo and photoluminescent properties of Gd 2O 3 nanoparticles

Gd 2O 3 nanoparticles (27-60nm) have been synthesized by the low temperature solution combustion method using citric acid, urea, glycine and oxalyl dihydrazide (ODH) as fuels in a short time. The structural and luminescence properties have been carried out using powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman, UV-Vis, photoluminescence (PL) and thermoluminescence (TL) techniques. The optical band gap values were estimated for as formed and 800°C calcined samples. The band gap values in as-formed and calcined samples were found to be in the range 4.89-5.59eV. It is observed that, the band gap values are lower for as-formed products and it has been attributed to high degree of structural defects. However, in calcined samples, structure becomes more order with reduced structure defects. Upon 270nm excitation, deep blue UV-band at �390nm along with blue (420-482nm), green (532nm) and red emission (612nm) was observed. The 390nm emission peak may be attributed to recombination of delocalized electron close to the conduction band with a single charged state of surface oxygen vacancy. TL measurements were carried out on Gd 2O 3 prepared by different fuels by irradiating with γ-rays (1kGy). A well resolved glow peak at 230°C was observed for all the samples. It is observed that TL intensity is found to be higher in for urea fuel when compared to others. From TL glow curves the kinetic parameters were estimated using Chen's peak shape method and results are discussed in detail. © 2012 Elsevier B.V.

Facile green fabrication of iron-doped cubic ZrO2 nanoparticles by Phyllanthus acidus: Structural, photocatalytic and photoluminescent properties

Cubic ZrO2: Fe3+ (0.5-4 mol%) nanoparticles (NPs) were synthesized via bin-inspired, inexpensive and simple route using Phyllanthus acidus as fuel. PXRD, SEM, TEM, FTIR, UV absorption and PL studies were performed to ascertain the formation of NPs. Rietveld analysis confirmed the formation of cubic structure. The influence of Fe3+ on the structure, morphology, UV absorption, PL emission and photocatalytic activity of NPs were investigated. The CIE chromaticity coordinates (0.36, 0.41) show that NPs could be a promising candidate for white LEDs. The influence of Fe3+ on ZrO2 matrix for photocatalytic degradation of AO7 was evaluated under UVA and Sunlight irradiation. The enhanced photocatalytic activity of spherical shaped ZrO2: Fe3+ (2 mol%) under UVA light was attributed to dopant concentration, crystallite size, narrow band gap, textural properties and capability for reducing the electron-hole pair recombination. The trend of inhibitory effect in the presence of different radical scavengers were followed the order SO42- > Cl- > C2H5OH > HCO3- > CO32-. The recycling catalytic ability of the ZrO2: Fe3+ (2 mol%) was also evaluated with a negligible decrease in the degradation efficiency even after the sixth successive run. (C) 2014 Elsevier B.V. All rights reserved.

Structural and photoluminescent properties of ternary Zn1-xCdxO crystal films grown on Si(111) substrates

The ternary Zn1-xCdxO (0less than or equal toxless than or equal to0.6) alloying films with highly c-axis orientation have been deposited on Si(111) substrates by direct current reactive magnetron sputtering method. X-ray diffraction measurement indicates that the wurtzite-type structure of ZnO can be stabilized up to nominal Cd content x similar to 0.6 without cubic CdO phase separation. The lattice parameter c of Zn1-xCdxO increases almost linearly from 5.229 Angstrom (x = 0) to 5.247 Angstrom (x = 0.6), indicating that Cd substitution takes place on the Zn lattice sites. The photoluminescence spectra of the Zn1-xCdxO thin films measured at 12 K display a substantial red shift (similar to0.3 eV) in the near-band-edges (NBEs) emission of ZnO: from 3.39 eV of ZnO to 3.00 eV of Zn0.4Cd0.6O. The direct modulation of band gap caused by Zn/Cd substitution is responsible for the red shift effect in NBE emission of ZnO. (C) 2003 Elsevier Science B.V. All rights reserved.

Structural and photoluminescent properties of ZnO films deposited by radio frequency reactive sputtering

Zinc oxide films with c-axis preferred orientation were deposited on silicon (100) substrates by radio frequency (RF) reactive sputtering. The properties of the samples were characterized by X-ray diffractometer, X-ray photoelectron spectroscopy and fluorescent-spectrophotometer. The effect of sputtering power and substrate temperature on the structural and photoluminescent (PL) properties of the ZnO films was investigated. The results indicated that when the sputtering power is 100 W and the substrate temperature is 300-400 degrees C, it is suitable for the growth of high c-axis orientation and small strain ZnO films. A violet peak at about 380 nm and a blue band at about 430 nm were observed in the room temperature photoluminescence spectra, and the origin of blue emission was investigated.

Hydrothermal synthesis and photoluminescent properties of stacked indium sulfide superstructures

Unusual hierarchical stacked superstructures of cubic beta-In2S3 were fabricated via a facile hydrothermal process in the presence of a surfactant cetyltrimethylammonium bromide CTAB; the 3D superstructures were developed by helical propagation of surface steps from microflakes of 10-20 nm thickness.

Synthesis and photoluminescent properties of silica-coated LaCeF3 : Tb nanocrystals

La0.45Ce0.45F3:Tb (10 mol% Tb) nanoparticles was synthesized via sonochemical method and then coated with silica (SiO2) shells through a microemulsion process, resulting in the formation of core/shell structured LaCeF3:Tb/SiO2 nanoparticles. The obtained core/shell LaCeF3:Tb/SiO2 nanoparticles are spherical and uniform in size (average size about 60 nm), strongly fluorescent, and long fluorescence lifetime (1.87 ms). This kind of nanoparticles was water-soluble, which could be applied in biological labeling and other fields.

Facile sonochemical synthesis and photoluminescent properties of lanthanide orthophosphate nanoparticles

Uniform lanthanide orthophosphate LnPO(4) (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) nanoparticles have been systematically synthesized via a facile, fast, efficient ultrasonic irradiation of inorganic salt aqueous solution under ambient conditions without any surfactant or template. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) spectra as well as kinetic decays were employed to characterize the samples. The SEM and the TEM images show that the hexagonal structured lanthanide orthophosphate LnPO(4) (Ln = La, Ce, Pr, Nd. Sm, Eu, Gd) products have nanorod bundles morphology, while the tetragonal LnPO(4) (Ln = Tb, Dy, Ho) samples prepared under the same experimental conditions are composed of nanoparticles. HRTEM micrographs and SAED results prove that these nanostructures are polycrystalline in nature.

Comparative study on the photoluminescent properties of siliceous MCM-41 with silica particles and xerogels

The samples of as-synthesized siliceous MCM-41, extracted MCM-41, amorphous silica particles and silica xerogels were heat treated from room temperature to 1000degreesC. Their photoluminescence (PL) spectra at room temperature excited by 254nm and 365nm ultraviolet light (UV) were investigated and compared. Excited by 254nm UV the MCM-41 samples do not display PL but amorphous silica particles and silica xerogels show PL, which changes with the heat treatment conditions for the samples. However, when excited by 365nm UV the PL spectra for the MCM-41 and the amorphous samples are similar. The carbon impurity and E' center mechanisms can be ruled out as the origin of PL in siliceous MCM-41 under UV excitation. The PL of MCM-41 series samples probably originates from oxygen-related defect center like dropSi-O-. according to the present work.

Effects R3+ on the photoluminescent properties of Ca2R8(SiO4)(6)O-2 : A (R = Y, La, Gd; A= Eu3+, Tb3+) phosphor films prepared by the sol-gel process

Using CaCO3, metal oxides (all dissolved by nitric acid) and tetraethoxysilane Si(OC2H5)(4) (TEOS) as the main starting materials, Ca2R8(SiO4)(6)O-2:A (R = Y, La, Gd; A = EU3+, Tb3+) phosphor films have been dip-coated on quartz glass substrates through the sol-gel process. X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the 1000 degreesC annealed films are isomorphous and crystallize with the silicate oxyapatite structure. AFM and SEM studies revealed that the phosphor films consisted of homogeneous particles ranging from 30 to 90 nm, with an average thickness of 1.30 mum. The Eu3+ and Tb3+ show similar spectral properties independent of R 3, in the films due to their isomorphous crystal structures. However, both the emission intensity and lifetimes of Eu3+ and Tb3+ in Ca2R8(SiO4)(6)O-2 (R = Y, La, Gd) films decrease in the sequence of R = Gd > R = Y > R = La, which have been explained in accordance with the crystal structures.

Facile synthesis and photoluminescent properties of redispersible CeF3, CeF3 : Tb3+, and CeF3 : Tb3+/LaF3 (core/shell) nanoparticles

CeF3, CeF3:Tb3+, and CeF3:Tb3+/LaF3 (core/shell) nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), UV-vis absorption spectra, photoluminescence (PL) spectra, and lifetimes. The results of XRD indicate that the obtained CeF3, CeF3:Tb3+, and CeF3:Tb3+/LaF3 (core/shell) nanoparticles crystallized well at 200 degrees C in diethylene glycol (DEG) with a hexagonal structure. The TEM images illustrate that the CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 7 nm. The growth of the LaF3 shell around the CeF3:Tb3+ core nanoparticles resulted in an increase of the average size (11 nm) of the nanopaticles as well as in a broadening of their size distribution. These nanocrystals can be well-dispersed in ethanol to form clear colloidal solutions. The colloidal solutions of CeF3 and CeF3:Tb3+ show the characteristic emission of Ce3+ 5d-4f (320 nm) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 542 nm as the strongest one) transitions, respectively. The emission intensity and lifetime of the CeF3:Tb3+/LaF3 (core/shell) nanoparticles increased with respect to those of CeF3:Tb3+ core particles.

Facile sonochemical synthesis of CePO4 : Tb/LaPO4 core/shell nanorods with highly improved photoluminescent properties

A simple, efficient and quick method has been established for the synthesis of CePO4:Tb nanorods and CePO4:Tb/LaPO4 core/shell nanorods via ultrasound irradiation of inorganic salt aqueous solution under ambient conditions for 2 h. The as-prepared products were characterized by means of powder x-ray diffraction (PXRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction ( SAED), x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectra and lifetimes. TEM micrographs show that all of the as-prepared cerium phosphate products have rod-like shape, and have a relatively high degree of crystallinity and uniformity. HRTEM micrographs and SAED results prove that these nanorods are single crystalline in nature. The emission intensity and lifetime of the CePO4:Tb/LaPO4 core/shell nanorods increased significantly with respect to those of CePO4: Tb core nanorods under the same conditions. A substantial reduction in reaction time as well as reaction temperature is observed compared with the hydrothermal process.

Photoluminescent properties of sol-gel derived (La, Gd)MgB5O10 : Ce3+/Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped (La,Gd)MgB5O10 nanocrystalline thin films were deposited on silica glass substrates by a sol-gel dip-coating process using triethyl borate B(OC2H5)(3) as the boron source. The results of XRD indicated that the films have fully crystallized after annealing at 800 degrees C. The films are transparent, uniform and crack free with a thickness of about 300 nm, consisting of particles with an average grain size of 50 nm. The luminescence and energy transfer properties of Ce3+ and Tb3+ have been studied in the films. It is confirmed that the excitation energy of Ce3+ transfers to the Gd3+, migrates over the Gd3+ sublattices, trapped by the Tb3+ and resulted in its characteristic green emission (D-5(4)-F-7(5) at 543 nm) in GdMgB5O10 nanocrystalline films as in the powder phosphors.