Contribution of structural order-disorder to the room-temperature photoluminescence of lead zirconate titanate powders

Intense and broad visible photoluminescent (PL) band was observed at room temperature in structurally disordered PbZr0.53Ti0.47O3 powders. The lead zirconate titanate PbZr0.53Ti0.47O3 powders prepared by the polymeric precursor method and heat treated at different temperatures were structurally characterized at long range by means of X-ray diffraction. The PL was measured at room temperature samples heat treated at different temperatures. Experimental measurements and quantum-mechanical calculations showed that the high structural order and the high structural disorder in PbZr0.53Ti0.47O3 lattice are not favorable to the intense PL emission. Only samples containing simultaneous structural order and disorder in their lattice present the intense visible PL emission at room temperature. (C) 2007 Published by Elsevier B.V.

Room temperature photoluminescence of BCT prepared by Complex Polymerization Method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A DFT rationalization of the room temperature photoluminescence of Li2TiSiO5

Li2TiSiO5 powders were synthesized by the polymeric precursor method. The calcination temperatures were progressively increased until the complete crystallization of the phase occurring at 870 degreesC. For the first time, a strong photoluminescence was measured at room temperature with a 488 nm excitation wavelength for the non-crystalline samples. This photoluminescence in disordered phases has been interpreted by means of high-level quantum mechanical calculations based on density functional theory. Two periodic models have been used to represent the crystalline and disordered powders. They allowed to calculate electronic properties consistent with experimental data and to explain the relations between photoluminescence and structural disorder. (C) 2004 Elsevier B.V. All rights reserved.

Room-temperature photoluminescence in structurally disordered SrWO4

Intense and broad visible photoluminescent (PL) band in structurally disordered SrWO4 compounds was observed at room temperature. The polycrystalline scheelite strontium tungstate (SrWO4) samples prepared by the polymeric precursor method at different temperatures of annealing were structurally characterized by x-ray diffraction and Fourier transform Raman spectroscopy measurements. Quantum-mechanical calculations showed that the local disorder in the cluster of the network modifiers Sr has a very important role in the charge transfer. The experimental and theoretical results are in good agreement, indicating that the generation of the intense visible PL band can be related to short-range order-disorder degree in the scheelite structure. (c) 2006 American Institute of Physics.

Room-temperature photoluminescence of BaTiO3: Joint experimental and theoretical study

Strong photoluminescent emission has been measured at room temperature for noncrystalline BaT'O-3 (BT) perovskite powders. A joint experimental and theoretical study has been carried out to rationalize this phenomenon. From the experimental side, BT powder samples have been synthesized following a soft chemical processing, their crystal structure has been confirmed by x-ray data and the corresponding photoluminescence (PL) properties have been measured. Only the structurally disordered samples present PL at room temperature. From the theoretical side, first-principles quantum-mechanical techniques, based on density-functional theory at the B3LYP level, have been employed to study the electronic structure of crystalline (BT-c) and asymmetric (BT-a) models. Theoretical and experimental results are found to be consistent and their confrontation leads to an interpretation of the PL apparition at room temperature in the structurally disordered powders.

Conditions giving rise to intense visible room temperature photoluminescence in SrWO4 thin films: the role of disorder

The nature of intense visible photoluminescence at room temperature of SrWO4 (SWO) non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The SWO thin films were synthesized by the polymeric precursors method. Their structural properties have been obtained by X-ray diffraction data and the corresponding photoluminescence (PL) spectra have been measured. The UV-vis optical spectra measurements suggest the creation of localized states in the disordered structure. The photoluminescence measurements reveal that the PL changes with the degree of disorder in the SWO thin film. To understand the origin of visible PL at room temperature in disordered SWO, we performed quantum-mechanical calculations on crystalline and disordered SWO periodic models. Their electronic structures are analyzed in terms of DOS, hand dispersion and charge densities. We used DFT method with the hybrid non-local B3LYP approximation. The polarization induced by the symmetry break and the existence of localized levels favors the creation of trapped holes and electrons, giving origin to the room temperature photoluminescence phenomenon in the SWO thin films. (c) 2004 Elsevier B.V. All rights reserved.

Experimental and theoretical investigation of the room-temperature photoluminescence of amorphized Pb(ZrTi)O-3

Ultrafine PbZr0.20Ti0.80O3 was omorphized through high-energy mechanical milling. The structural evolution through the omorphization process was accompanied by various characterization techniques, such as X-ray diffraction, Fourier-transformed IR spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. A strong photoluminescence was measured at room temperature for amorphized PbZr0.20Ti0.80O3, and interpreted by means of high-level quantum mechanical calculations in the density functional theory frame-work. Three periodic models were used to represent the crystalline and amorphized PbZr0.20Ti0.80O3, and they allowed the calculation of electronic properties that are consistent with the experimental data and that explain the appearance of photoluminescence.

Room-temperature photoluminescence in amorphous SrTiO3-The influence of acceptor-type dopants

Room-temperature photoluminescence (PL) was observed in undoped and 2 mol% Cr-, Al- and Y-doped amorphous SrTiO3 thin films. Doping increased the PL, and in the case of Cr significantly reduced the associated PL wavelength. The optical bandgaps, calculated by means of UV-vis absorption spectra, increased with crystallinity and decreased with the doping level. It was considered that yttrium and aluminum substituted Sr2+, whereas chromium replaced Ti4+. It is believed that luminescence centers are oxygen-deficient BO6 complexes, or the same centers with some other defects, such as oxygen or strontium vacancies, or BO6 complexes with some other defects placed in their neighborhood. The character of excitation and the competition for negatively charged non-bridging oxygen (NBO) among numerous types of BO6 defect complexes in doped SrTiO3 results in various broadband luminescence peak positions. The results herein reported are an indicative that amorphous titanates are sensitive to doping, which is important for the control of the electro-optic properties of these materials. The probable incorporation of Cr into the Ti site suggests that the existence of a double network former can lead to materials displaying a more intense photoluminescence.

The role of structural order-disorder for visible intense photoluminescence in the BaZr0.5Ti0.5O3 thin films

The nature of the intense visible room temperature photoluminescence of BaZr0.5Ti0.5O3 non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The photoluminescence measurements reveal that the emission intensity changes with the degree of disorder in the BaZr0.5Ti0.5O3 lattice. First principles quantum mechanical techniques, based on density functional theory at B3LYP level, have been employed to study the electronic structure of a crystalline model and of structurally disordered models in order to detect the influence of disorder on the electronic structure. An analysis of the electronic charge distribution reveals local polarization in the disordered structures. The relevance of the present theoretical and experimental results on the photoluminescence behavior of BZT is discussed. (C) 2005 Elsevier B.V. All rights reserved.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

Europium(III) Concentration Effect on the Spectroscopic and Photoluminescent Properties of BaMoO4:Eu

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

Relaxation effects on the negatively charged Mg impurity in zincblende GaN

The electronic structure of Mg impurity in zincblende (c-)GaN is investigated by using the ab initio full potential linear-augmented plane-wave method and the local density-functional approximation. Full geometry optimization calculations, including nearest and next-nearest neighbor displacements, are performed for the impurity in the neutral and negatively charged states. A value of 190 ± 10 meV was obtained for the Franck-Condon shift to the thermal energy, which is in good agreement with that observed in recent low temperature photoluminescence and Hall-effect measurements. We conclude that the nearest and next-nearest neighbors of the Mg impurity replacing Ga in C-GaN undergo outward relaxations which play an important role in the determination of the center acceptor energies.

Estudo teórico - experimental do titanato de cálcio - 'CA''TI''OIND.3'

Pós-graduação em Química - IQ

Intense blue and green photoluminescence emissions at room temperature in barium zirconate powders

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Theoretical and experimental study of disordered Ba0.45Sr0.55TiO3 photoluminescence at room temperature

Disordered and crystalline Ba0.45Sr0.55TiO3 (BST) powder processed at low temperature was synthesized by the polymeric precursor method. The single-phase perovskite structure of the ceramics was identified by the Raman and X-ray diffraction techniques. Photoluminescence at room temperature was observed only in a disordered BST sample. Increasing the calcination time intensified the photoluminescence (PL), which reached its maximum value in the sample heat treated at 300 degrees C for 30 h. This emission may be correlated with the structural disorder. Periodic ab initio quantum-mechanical calculations using the CRYSTAL98 program can yield important information regarding the electronic and structural properties of crystalline and disordered solids. The experimental and theoretical results indicate the presence of intermediary energy levels in the band gap. This is ascribed to the break in symmetry, which is responsible for visible photoluminescence in the material's disordered state at room temperature. (c) 2005 Elsevier B.V. All rights reserved.