Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Electron doping and phonon scattering in Ti1+xS2 thermoelectric compounds

Bulk polycrystalline samples in the series Ti1+xS2 (x = 0 to 0.05) were prepared using high temperature synthesis from the elements and spark plasma sintering. X-ray structure analysis shows that the lattice constant c expands as titanium intercalates between TiS2 slabs. For x=0, a Seebeck coefficient close to -300 μV/K is observed for the first time in TiS2 compounds. The decrease in electrical resistivity and Seebeck coefficient that occurs upon Ti intercalation (Ti off stoichiometry) supports the view that charge carrier transfer to the Ti 3d band takes place and the carrier concentration increases. At the same time, the thermal conductivity is reduced by phonon scattering due to structural disorder induced by Ti intercalation. Optimum ZT values of 0.14 and 0.48 at 300K and 700K, respectively, are obtained for x=0.025.

IxV Curves of Boron and Nitrogen Doping Zigzag Graphene Nanoribbons

We investigate the transport properties (IxV curves and zero bias transmittance) of pristine graphene nanoribbons (GNRs) as well as doped with boron and nitrogen using an approach that combines nonequilibrium Green`s functions and density functional theory (DFT) [NEGF-DFT]. Even for a pristine nanoribbon we verify a spin-filter effect under finite bias voltage when the leads have an antiparallel magnetization. The presence of the impurities at the edges of monohydrogenated zigzag GNRs changes dramatically the charge transport properties inducing a spin-polarized conductance. The IxV curves for these systems show that depending on the bias voltage the spin polarization can be inverted. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1379-1386, 2011

Confinement and surface effects in B and P doping of silicon nanowires

Several experimental groups have achieved effective n- and p-type doping of silicon nanowires (SiNWs). However, theoretical analyses on ultrathin SiNWs suggest that dopants tend to segregate to their surfaces, where they would combine with defects such as dangling bonds (DB), becoming electronically inactive. Using fully ab initio calculations, we show that the differences in formation energies among surface and core substitutional sites decrease rapidly as the diameters of the wires increase, indicating that the dopants will be uniformly distributed. Moreover, occurrence of the electronically inactive impurity/DB complex rapidly becomes less frequent for NWs of larger diameters. We also show that the high confinement in the ultrathin SiNWs causes the impurity levels to be deeper than in the silicon bulk, but our results indicate that for NWs of diameters larger than approximately 3 nm the impurity levels recover bulk characteristics. Finally, we show that different surfaces will lead to different dopant properties in the gap.

Effect of Eu(2)O(3) doping on Ta(2)O(5) crystal growth by the laser-heated pedestal technique

High energy band gap hosts doped with lanthanide ions are suitable for optical devices applications To study the potential of Ta(2)O(5) as a host compound pure and Eu(2)O(3)-doped Ta(2)O(5) crystal fibers were grown by the laser-heated pedestal growth technique in diameters ranging from 250 to 2600 pm and in lengths of up to 50 mm The axial temperature gradient at the solid/liquid interface of pure Ta(2)O(5) fibers revealed a critical diameter of 2200 gm above which the fiber cracks X-ray diffraction measurements of the pure Ta(2)O(5) single crystals showed a monoclinic symmetry and a growth direction of [1 (1) over bar 0] An analysis of the pulling rate as a function of the fiber diameter for Eu(2)O(3)-doped Ta(2)O(5) fibers indicated a well defined region in which constitutional supercooling is absent Photoluminescence measurements of pure Ta(2)O(5) crystals using excitation above the band gap (3 8 eV) were dominated by a broad unstructured green band that peaked at 500 nm Three Eu(3+)-related optical centers were identified in the doped samples with nominal concentrations exceeding 1 mol% Two of these centers were consistent with the ion in the monoclinic phase with different oxygen coordinations The third one was visible in the presence of the triclinic phase (C) 2010 Elsevier B V All rights reserved

The role of solvent on the doping of polyaniline with Fe(III) ions

The products formed from the reaction of emeraldine base polyaniline (EB-PANI) with Fe(III) ions in N-methyl-pyrrolidone (NMP), dimethylacetamide (DMA), dimethylformamide (DMF) and m-cresol media have been investigated using UV-VIS-NIR and resonance Raman (lambda(0) = 632.8 and 1064 nm) spectroscopies. Through these results it was verified that the different PANI forms in solution can be formed by the suitable choice of the solvent. The behavior of Fe(III)/EB-PANI in different solvents was rationalized in terms of the interactions among Fe(III) ions, EB-PANI and solvent. In basic NMP, DMA and DMF media, the reaction of Fe(III) with EB-PANI yields EB-PANI doping giving ES-PANI and/or the EB-PANI oxidation to PB-PANI. The formation of ES-PANI is favored in DMF while PB-PANI is formed in a greater extension in NMP and DMA. In acidic m-cresol, only ES-PANI is produced in Fe(III)/EB-PANI solutions indicating the important role played by the solvent in the nature of the product. (C) 2010 Elsevier B.V. All rights reserved.

Photocatalyst TiO(2)-Co: the effect of doping depth profile on methylene blue degradation

In this work, we study the effect of doping depth profile on the photocatalytic and surface properties of TiO(2) films. Two thin film layers of TiO(2) (200 nm) and Co (5 nm), respectively, were deposited by physical evaporation on glass substrate. These films were annealed for 1 s at 100 and 400 A degrees C and the Co layer was removed by chemical etching. Atomic force microscopy (AFM) phase images showed changes in the surface in function of thermal treatment. The grazing-incidence X-ray fluorescence (GIXRF) measurements indicated that the thermal treatment caused migration of Co atoms to below the surface, the depths found were between 19 and 29 nm. The contact angle showed distinct values in function of the doped profile or Co surface concentration. The UV-vis spectra presented a red shift with the increasing of thermal treatment. Photocatalytical assays were performed by methylene blue discoloration and the higher activity was found for TiO(2)-Co treated at 400 A degrees C, the ESI-MS showed the fragments formed during the methylene blue decomposition.

Sanções disciplinares aplicáveis em caso de doping a atletas profissionais e não profissionais

A presente pesquisa descritiva do tipo documental centrou-se em analisar as sanções disciplinares aplicadas em caso de doping, a atletas profissionais e não profissionais que atuam no Brasil. A amostragem foi levantada através de um processo de seleção não probabilística intencional, utilizando-se como sujeitos, 18 atletas de uma modalidade esportiva dita não profissional: atletismo e 19 de uma modalidade profissional: futebol, de ambos os sexos, os quais tenham sido flagrados pelo exame de controle de dopagem da Confederação Brasileira de Atletismo (CBAt) e da Confederação Brasileira de Futebol (CBF). Como instrumentos de análise, foram utilizados os diagnósticos de dopagem positiva, arquivados junto a CBAt e CBF; além dos processos julgados pelo Superior Tribunal de Justiça Desportiva (STJD) do atletismo entre os anos de 2003/2007 e os processos julgados pelo STJD do futebol no ano de 2007. Os resultados demonstram que as sanções aplicadas aos desportistas diferem muito entre as modalidades incluídas no estudo. Enquanto encontramos, no atletismo a aplicação de sanções em conformidade com o Código Mundial Anti Doping (CMAD) com penalidades de no mínimo de dois anos, no futebol encontrou-se grande número de absolvições ou aplicação de penalidades conforme o Código Brasileiro de Justiça Desportiva (CBJD) que prevê penalidades muito inferiores. Por outro lado verificou-se ser a modalidade Futebol a que mais realiza controles, sendo certo que durante o ano de 2007 o desporto profissional realizou 4832 testes, ao passo que o desporto dito não profissional realizou tão somente 281. O caráter multidisciplinar do trabalho 12 pôde ser caracterizado pelo emprego de técnicas que envolveram direito, educação física, farmacologia

Fabrication and characterization of chemical sensors made from nanostructured films of poly(o-ethoxyaniline) prepared with different doping acids

Chemical sensors made from nanostructured films of poly(o-ethoxyaniline) POEA and poly(sodium 4-styrene sulfonate) PSS are produced and used to detect and distinguish 4 chemicals in solution at 20 mM, including sucrose, NaCl, HCl, and caffeine. These substances are used in order to mimic the 4 basic tastes recognized by humans, namely sweet, salty, sour, and bitter, respectively. The sensors are produced by the deposition of POEA/PSS films at the top of interdigitated microelectrodes via the layer-by-layer technique, using POEA solutions containing different dopant acids. Besides the different characteristics of the POEA/PSS films investigated by UV-Vis and Raman spectroscopies, and by atomic force microscopy.. it is observed that their electrical response to the different chemicals in liquid media is very fast, in the order of seconds, systematical, reproducible, and extremely dependent on the type of acid used for film fabrication. The responses of the as-prepared sensors are reproducible and repetitive after many cycles of operation. Furthermore, the use of an "electronic tongue" composed by an array of these sensors and principal component analysis as pattern recognition tool allows one to reasonably distinguish test solutions according to their chemical composition. (c) 2007 Published by Elsevier B.V.

Influence of Heat Treatment and Oxygen Doping on the Mechanical Properties and Biocompatibility of Titanium-Niobium Binary Alloys

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Indirect optical transitions from carriers trapped on the delta doping and on the parabolic quantum well

In this work, doped AlGaAs/GaAs parabolic quantum wells (PQW) with different well widths (from 1000 angstrom up to 3000 angstrom) were investigated by means of photoluminescence (PL) measurements. In order to achieve the 2DEG inside the PQW Si delta doping is placed at both side of the well. We have observed that the thickness of this space layer plays a major rule on the characteristics of the 2DEG. It has to be thicker enough to prevent any diffusions of Si to the well and thin enough to allow electrons migration inside the well. From PL measurement, we have observed beside the intra well transitions, indirect transitions involving still trapped electron on the delta doping and holes inside the PQW. For the thinness sample, we have measured a well defined PL peak at low energy side of the GaAs bulk emission. With the increasing of the well thickness this peak intensity decreases and for the thickest sample it almost disappears. Our theoretical calculation indicated that carriers (electron and holes) are more placed at the center of the PQW. In this way, when the well thickness increases the distance between electrons on the delta doping and holes on the well also increases, it decreases the probability of occurrence of these indirect optical transitions. (C) 2012 Published by Elsevier B.V. Selection and/or peer-review under responsibility of Universidade Federal de Juiz de Fora, Brazil.

Theoretical analysis of the energy levels induced by oxygen vacancies and the doping process (Co, Cu and Zn) on SnO2 (110) surface models

Density functional calculation at B3LYP level was employed to study the surface oxygen vacancies and the doping process of Co, Cu and Zn on SnO2 (110) surface models. Large clusters, based on (SnO2)(15) models, were selected to simulate the oxidized (Sn15O30), half-reduced (Sn15O29) and the reduced (Sn15O28) surfaces. The doping process was considered on the reduced surfaces: Sn13Co2O28, Sn13Cu2O28 and Sn13Zn2O28. The results are analyzed and discussed based on a calculation of the energy levels along the bulk band gap region, determined by a projection of the monoelectron level structure on to the atomic basis set and by the density of states. This procedure enables one to distinguish the states coming from the bulk, the oxygen vacancies and the doping process, on passing from an oxidized to a reduced surface, missing bridge oxygen atoms generate electronic levels along the band gap region, associated with 5s/5p of four-/five-fold Sn and 2p of in-plane O centers located on the exposed surface, which is in agreement with previous theoretical and experimental investigations. The formation energy of one and two oxygen vacancies is 3.0 and 3.9 eV, respectively. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Effect of the doping medium on blends of polyurethane and polyaniline

Flexible and free-standing films from blends of polyurethane, based on castor oil, and polyaniline were obtained with various compositions by casting. Significant increase on conductivity followed by a considerable decrease on doping time was obtained by doping the films in N,N-dimethylformamide (DMF) solution with p-toluene sulphonic acid (TSA) or HCl instead of the conventional doping in aqueous solution. This doping efficiency is proposed to be due to an improved swelling of the blend structure caused by the solvent. The electrical conductivity increases significantly upon polyaniline content increase reaching 10(-2) S/cm for a polyaniline content of about 10% (w/w).

A homovalent doping in PMN ceramics by using lithium and scandium cations

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