A combined theoretical and experimental study of electronic structure and optical properties of β-ZnMoO4 microcrystals

In this paper, a combined theoretical and experimental study on the electronic structure and photoluminescence (PL) properties of beta zinc molybdate (β-ZnMoO4) microcrystals synthesized by the hydrothermal method has been employed. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, Fourier transform Raman (FT-Raman) and Fourier transform infrared (FT-IR) spectroscopies. Their optical properties were investigated by ultraviolet-visible (UV-Vis) absorption spectroscopy and PL measurements. First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level have been carried out. XRD patterns, Rietveld refinement, FT-Raman and FT-IR spectra showed that these crystals have a wolframite-type monoclinic structure. The Raman and IR frequencies experimental results are in reasonable agreement with theoretically calculated results. UV-Vis absorption measurements shows an optical band gap value of 3.17 eV, while the calculated band structure has a value of 3.22 eV. The density of states indicate that the main orbitals involved in the electronic structure of β-ZnMoO4 crystals are (O 2p-valence band and Mo 4d-conduction band). Finally, PL properties of β-ZnMoO4 crystals are explained by means of distortions effects in octahedral [ZnO6] and [MoO6] clusters and inhomogeneous electronic distribution into the lattice with the electron density map. © 2013 Elsevier Ltd. All rights reserved.

Intense photoluminescence emission at room temperature in calcium copper titanate powders

A study was undertaken about the structural and photoluminescent properties at room temperature of CaCu3Ti4O12 (CCTO) powders synthesized by a soft chemical method and heat treated between 300 and 800 °C. The decomposition of precursor powder was followed by thermogravimetric analysis (TG-DTA), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman) and photoluminescence (PL) measurements. XRD analyses revealed that the powders annealed at 800 °C are becoming ordered and crystallize in the cubic structure. The most intense PL emission was obtained for the sample calcined at 700 °C, which is not highly disordered (300-500 °C) and neither completely ordered (800 °C). From the spectrum it is clearly visible that the lowest wavelength peak is placed around 480 nm and the highest wavelength peak at about 590 nm. The UV/vis absorption spectroscopy measurements showed the presence of intermediate energy levels in the band gap of structurally disordered powders. © 2012 Elsevier Ltd and Techna Group S.r.l.

Enhanced optical properties of germanate and tellurite glasses containing metal or semiconductor nanoparticles

Germanium- and tellurium-based glasses have been largely studied due to their recognized potential for photonics. In this paper, we review our recent studies that include the investigation of the Stokes and anti-Stokes photoluminescence (PL) in different glass systems containing metallic and semiconductor nanoparticles (NPs). In the case of the samples with metallic NPs, the enhanced PL was attributed to the increased local field on the rare-earth ions located in the proximity of the NPs and/or the energy transfer from the metallic NPs to the rare-earth ions. For the glasses containing silicon NPs, the PL enhancement was mainly due to the energy transfer from the NPs to the Er3+ ions. The nonlinear (NL) optical properties of PbO-GeO 2 films containing gold NPs were also investigated. The experiments in the pico- and subpicosecond regimes revealed enhanced values of the NL refractive indices and large NL absorption coefficients in comparison with the films without gold NPs. The reported experiments demonstrate that germanate and tellurite glasses, having appropriate rare-earth ions doping and NPs concentration, are strong candidates for PL-based devices, all-optical switches, and optical limiting. © 2013 Cid Bartolomeu de Araujo et al.

Synthesis, structural characterization and photophysical properties of highly photoluminescent crystals of Eu(III), Tb(III) and Dy(III) with 2,5-thiophenedicarboxylate

Lanthanide compounds of general formula [Ln2(2,5-tdc) 3(dmf)2(H2O)2] ·2dmf·H2O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc2- = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T1) of 2,5-tdc2- ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc2- ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω2 for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the 5D0 emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs). © 2013 Elsevier B.V. All rights reserved.

Rietveld refinement, morphology and optical properties of (Ba 1-xSrx)MoO4 crystals

In this article, the structural refinement, morphology and optical properties of barium strontium molybdate [(Ba1-x Sr x )MoO4 with x = 0, 0.25, 0.50, 0.75 and 1] crystals, synthesized by the co-precipitation (drop-by-drop) method, are reported. The crystals obtained were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, and Fourier transform-Raman (FT-Raman) and Fourier transform-infrared (FT-IR) spectroscopies. The shapes of the crystals were observed by means of field-emission scanning electron microscopy (FE-SEM). The optical properties were investigated using ultraviolet-visible (UV-Vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement, and FT-Raman and FT-IR spectra showed that all of the crystals are monophasic with a scheelite-type tetragonal structure. The refined lattice parameters and atomic positions were employed to model the [BaO8], [SrO8] and [MoO4] clusters in the tetragonal lattices. The FE-SEM images indicate that increased x content produces a decrease in the crystal size and modifications in the crystal shape. UV-Vis spectra indicated a decrease in the optical band gap with an increase in x in the (Ba1-x Sr x )MoO4 crystals. Finally, a decrease in the intensity of PL emission is apparent with an increase in x up to 0.75 in the (Ba1-x Sr x )MoO4 crystal lattice when excited by a wavelength of 350nm, probably associated with the degree of structural order-disorder. © 2013 International Union of Crystallography Printed in Singapore - all rights reserved.

Red shift and higher photoluminescence emission of CCTO thin films undergoing pressure treatment

CCTO thin films were deposited on Pt(1 1 1)/Ti/SiO2/Si substrates using a chemical (polymeric precursor) and pressure method. Pressure effects on CCTO thin films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and optical properties which revealed that a pressure film (PF) is denser and more homogeneous than a chemical film (CF). Pressure also causes a decrease in the band gap and an increase in the photoluminescence (PL) emission of CCTO films which suggests that the pressure facilitates the displacement of Ti in the titanate clusters and the charge transference from TiO6 to [TiO5V0z], [TiO5V0z] to [CaO11V0z] and [TiO5V0z] to [CuO4]x. © 2013 Elsevier B.V. All rights reserved.

Structural, electronic and optical properties of Fe(III) complex with pyridine-2,6-dicarboxylic acid: A combined experimental and theoretical study

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

Er3+-doped Y2O3 obtained by polymeric precursor: Synthesis, structure and upconversion emission properties

The relentless pursuit for materials containing rare earth ions with photoluminescent properties has led to several studies with applications in the development of new technologies. The main focus of this work is the preparation of Er3+-doped polycrystalline Y2O3 with photoluminescent properties using PEG as an organic precursor and heat-treated at different temperatures. The methodology used in this synthesis is highly attractive due to its high feasibility for improved technology and low cost for preparing materials. The behavior of the viscous resin has been evaluated and the final compounds exhibited the formation of a cubic polycrystalline phase, which is able to support variations in Er3+ doping concentrations up to 10 mol%, without significant changes in the polycrystalline parameters. The values of the nanocrystallite size calculated by Scherrer's equation showed direct dependence on the heat-treatment temperature as well as the Er3+ concentration. Intense emission in the visible region under excitation at 980 nm was attributed to an upconversion phenomenon assigned to the intraconfigurational f-f transitions of Er3+ ions. The upconversion mechanism was investigated and it was demonstrated that the higher intense emission in the red region in comparison to the emission in the green region is related to the crystallite size. The studies about the intensity showed the dependence of upconversion emission of power source, indicating that two-photon are responsible for the green and red photoluminescence. These polycrystalline materials exhibit properties that make them promising for use in solar energy systems, C-telecom band or solid-state laser devices. (C) 2014 Elsevier B.V. All rights reserved.

Toward an Understanding of the Growth of Ag Filaments on alpha-Ag2WO4 and Their Photoluminescent Properties: A Combined Experimental and Theoretical Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of Zn2+ ions on the structure, morphology and optical properties of CaWO4 microcrystals

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Titanate nanotubes produced from microwave-assisted hydrothermal synthesis: Photocatalytic and structural properties

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Sr2CeO4: Electronic and structural properties

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

Correlation between structural and electronic order-disorder effects and optical properties in ZnO nanocrystals

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

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO 3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 °C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 °C for 2 h. The degree of structural order−disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet− visible (UV−vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

Experimental and theoretical studies of photoluminescence in Zns obtained by microwave-assisted solvothermal method

A shift of the photoluminescence (PL) emission was observed in ZnS prepared by microwave assisted solvothermal method with the increase of the time in microwave. In this work we reported a study of the optical behavior linking with the structural disorder according to XRD and FEG-TEM results. The reduction of intrinsic defects in the lattice is responsible for the decrease of electronic levels in the band gap changing the PL profile. This effect was confirmed by electronic structure calculations.