Combined experimental and theoretical study to understand the photoluminescence of Sr1-xTiO3-x

A joint experimental and theoretical study has been carried out to rationalize the results of visible photoluminescence measurements at room temperature on Sr1-xTiO3-x (ST) perovskite thin films. From the experimental side, ST thin films, x = 0 to 0.9, have been synthesized following soft chemical processing, and the corresponding photoluminescence properties have been measured. First principles quantum mechanical techniques, based on density functional theory at the B3LYP level, have been employed to study the electronic structure of a crystalline, stoichiometric (x = 0) ST-s model and a nonstoichiometric (SrO-deficient, x not equal 0) and structurally disordered ST-d model. The relevance of the present theoretical and experimental results of the photoluminescence behavior of ST is discussed. The optical spectra and the calculations indicate that the symmetry-breaking process on going from ST-s to ST-d creates electronic levels in the valence band. Moreover, an analysis of the Mulliken charge distribution reveals a charge gradient in the structure. These combined effects seem to be responsible for the photoluminescence behavior of deficient Sr1-xTiO3-x.

The role of network modifiers in the creation of photoluminescence in CaTiO3

We discuss the nature of visible photoluminescence (PL) at room temperature in amorphous calcium titanate in the light of the results of recent experimental and quantum mechanical theoretical studies. Our investigation of the electronic structure involved the use of first-principle molecular calculations to simulate the variation of the electronic structure in the calcium titanate crystalline phase, which is known to have a direct band gap, and we also made an in-depth examination of amorphous calcium titanate. The results of our theoretical calculations of amorphous calcium titanate indicate that the formation of fivefold coordination in the amorphous system may introduce delocalized electronic levels in the highest occupied and the lowest unoccupied molecular orbitals. These delocalized electronic levels are related to the formation of a tail in the absorbance spectrum curve. The results indicate that amorphous calcium titanate has the conduction band near the band gap dominated by Ca states contribution. Experimental optical absorption measurements showed the presence of a tail. These results are interpreted by the nature of these exponential optical edges and tails, associated with defects promoted by the disordered structure of the amorphous material. We associate them with delocalized states in the band gap. (C) 2002 Elsevier B.V. B.V. All rights reserved.

NEAR-RESONANT SCATTERING FROM NONSYMMETRIC DIMERS - APPLICATIONS TO SUBSTITUTED POLYANILINES

In this work we show that, beyond the prediction of the random dimer model [Wu and Phillips, Phys. Rev. Lett. 66, 1366 (1991)], it is possible to have near resonant scattering from nonsymmetric dimers. It is shown by direct density of states calculations as well as by a procedure similar to the random dimer model that protonated chains of alkyl-substituted polyanilines support extended electronic states at the Fermi energy when a disordered distribution of symmetric or asymmetric bipolarons is present. An extension of the random dimer model to include resonant scattering by nonsymmetric dimers is proposed.

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.

The influence of the physigraphic and geologic condition aspects on the environmental degradation in the city of Guaratingueta

The present paper deals with environmental degradation in the city of Guaratingueta, Brazil; as a result of disordered urban settlement and development. Three site areas in the city resting on different geologic units were selected for the analyses, i.e.: precambrian rocks, tertiary sedimentary basin, and recent quaternary soil deposits. It has been found that geological and geotechnical aspects are fundamental to form the basis for environmental preservation and urban planning.

Electrical characterization of in situ polymerized polyaniline thin films

The alternating conductivity, sigma*(f) = sigma'(f) + i sigma ''(f), of in situ polymerized polyaniline thin films doped with hydrochloric acid, deposited on top of an interdigitated gold line array previously deposited on glass substrates, were measured in the frequency (f) range between 0.1 Hz to 10 MHz and in the temperature range from 100 to 430 K. The results for sigma'(f) are typical of a disordered solid material: for frequencies lower than a certain hopping frequency gamma(hop), log[sigma'(f)] is frequency-independent rising almost linearly for in logf > gamma(hop). A master curve was thus obtained by plotting the real component of the conductivity using normalized scales sigma'(f)/sigma(dc) and f/gamma(hop) which is indicative of a single process operating in the whole frequency range. An expression encompassing the conduction through a disordered structure taken from previous random free energy barrier model for hopping carriers, as well a dielectric function to represent the capacitive behavior of the PAni was employed to fit the experimental results. The dielectric constant and activation energy for hopping carriers were obtained as function of the polymer doping level. (c) 2007 Elsevier B.V. All rights reserved.

Diagnosis and environmental planning for Paranagud - PR - Brazil

The main goal of this study was to identify and analyse environmental problems related to human occupation at the south part of the city of Paranagua PR, Brazil, aiming the diagnosis and conceptual evaluation of landscape use. For landscape use assessments and degradation diagnosis purposes, the environment was classified considering mainly geological and geomorphologic characteristics, such as declivity and sediment origin. The identification of potential environmental impacts was made by aerial photographs, Landsat-TM images, photographic records, surface sediment samples, water-column samples, and mainly observation visits to each classified unit. Surface sediment samples were taken with a Petit-Ponar sampler, in 13 station located in Paranagua Bay. In order to characterize the contamination level on sediments, the concentration of the following elements were analysed: arsenic (As), copper (Cu), cadmium (Cd), nickel (Ni), lead (Ph) e zinc (Zn). For the extraction of these elements, samples were treated with HCl 0.1N for 12 hours. This method has the advantage of determining contaminants which are weakly bind to the sediment, thus more available to the system. Analysis were performed by atomic absorption spectroscopy. According to the adopted criteria, sectors were classified as hills, mangroves, continental sediments and beach ridges urban and port industrial. Water quality and concentrations of metallic elements were determined at three sectors one control and two with the influence of urban and port/industrial activities, respectively the major upland impacts found were: deforestation due to disordered occupation, and solid waste emission through domestic and industrial sewage. The diagnosis of the actual situation was used as a basis for a management plan, once it allows the identification of impacts, and consequent environmental irregularities. Based on this considerations, suggestions for land use and management were presented, which offers a better approach for recuperation and protection of the studied ecosystem.

Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

Photoluminescent BaMoO4 nanopowders prepared by complex polymerization method (CPM)

The BaMoO4 nanopowders were prepared by the Complex Polymerization Method (CPM). The structure properties of the BaMoO4 powders were characterized by FTIR transmittance spectra, X-ray diffraction (XRD), Raman spectra, photoluminescence spectra (PL) and high-resolution scanning electron microscopy (HR-SEM). The XRD, FTIR and Raman data showed that BaMoO4 at 300 degrees C was disordered. At 400 degrees C and higher temperature, BaMoO4 crystalline scheelite-type phases could be identified, without the presence of additional phases, according to the XRD, FTIR and Raman data. The calculated average crystallite sizes, calculated by XRD, around 40 nm, showed the tendency to increase with the temperature. The crystallite sizes, obtained by HR-SEM, were around of 40-50 nm. The sample that presented the highest intensity of the red emission band was the one heat treated at 400 degrees C for 2 h, and the sample that displayed the 'highest intensity of the green emission band was the one heat treated at 700 degrees C for 2 h. The CPM was shown to be a low cost route for the production of BaMoO4 nanopowders, with the advantages of lower temperature, smaller time and reduced cost. The optical properties observed for BaMoO4 nanopowders suggested that this material is a highly promising candidate for photoluminescent applications. (C) 2005 Elsevier B.V. All rights reserved.

Blue-green and red photoluminescence in CaTiO3 : Sm

Blue-green and red photoluminescence (PL) emission in structurally disordered CaTiO3:Sm (CT:Sm) powders was observed at room temperature with laser excitation at 350.7 nm. The perovskite-like titanate CT:Sm powders prepared by a soft chemical processing at different temperatures of annealing were structurally characterized by X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES). The results indicate that the generation of the broad PL band is related to order-disorder degree in the perovskitelike structure. (c) 2006 Elsevier B.V. All rights reserved.

NUMERICAL STUDY OF TRANSPORT IN A DISSIPATIVE MEDIUM

A numerical study of propagation of a particle through a one-dimensional dissipative medium is presented. The medium is composed of several dissipative sections, which are characterized by their friction coefficients eta. In particular, we have considered two types of friction coefficients distributed orderly or disorderly along the chain. For the same relative proportion of the coefficients, we have found that transport can be enhanced in the disordered distribution in comparison with the ordered one. We also show how this can be considered an approximated way to treat the propagation in a dissipative medium with a position-dependent friction coefficient.

Photoluminescent property of mechanically milled BaWO4 powder

Crystalline BaWO4 (BWO) powder obtained by the polymeric precursor method was structurally disordered by means of high-energy mechanical milling. For the first time a strong and broad photoluminescence (PL) has been measured at room temperature for mechanically milled BWO powder and interpreted by ground-state quantum mechanical calculations in the density functional theory framework. Two periodic models have been studied; one representing the crystalline form and the other one representing the disordered BWO powder. These models allowed the calculation of electronic properties, which are consistent with the experimental results, showing that structural disorder in the lattice is an important condition to generate an intense and broad PL band. (c) 2006 Elsevier B.V. All rights reserved.

Contribution of structural order-disorder to the green photoluminescence of PbWO4

An intense and broad visible photoluminescence (PL) band was observed at room temperature in structurally disordered PbWO4 thin films. The scheelite lead tungstate (PbWO4) films prepared by the polymeric precursor method and annealed at different temperatures were structurally characterized by means of x-ray diffraction and atomic force microscopy analysis. Quantum-mechanical calculations showed that the local disorder of the network modifier (Pb) has a very important role in the charge transfer involved in the green PL emission. The experimental and theoretical results are in good agreement, both indicating that the generation of the intense visible PL band is related to simultaneous structural order and disorder in the scheelite PbWO4 lattice.

BaZrO3 Photoluminescence Property: An Ab Initio Analysis of Structural Deformation and Symmetry Changes

This article reports a theoretical study based on experimental results for barium zirconate, BaZrO3 (BZ) thin films, using periodic mechanic quantum calculations to analyze the symmetry change in a structural order-disorder simulation. Four periodic models were simulated using CRYSTAL98 code to represent the ordered and disordered BZ structures. The results were analyzed in terms of the energy level diagrams and atomic orbital distributions to explain and understand the BZ photoluminescence properties (PL) at room temperature for the disordered structure based on structural deformation and symmetry changes. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 111: 694-701, 2011