Made available in DSpace on 2017-07-21T19:25:46Z (GMT). No. of bitstreams: 1 Joao Luiz Gomes Junior.pdf: 5004861 bytes, checksum: 0e45ece35c737cce76186e1babb5e257 (MD5) Previous issue date: 2015-03-26 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / In this work, the correlation between the structural morphology with thermal, optical and mechanical properties of (1 – x – y)TeO2-xLi2O-yMoO3 glasses was studied. The analysis was divided into three sets of samples, varying according to the composition for technique. The results reveal different behaviors for each set vitreous stabilities. The Raman spectroscopy and FTIR results showed a similar structural change between each set with decrease NBOs and new peaks position. The Raman and FTIR spectra results showed that with increasing content x and y, concomitantly, occur the conversion of TeO4 to TeO3+1 units, then, in addition to TeO3 units. Furthermore occurs change coordination in the structural units Mo atoms 4 to 6 and these structural changes. Li addition causes these structural changes. This fact confirmed by the Band Gap energy values, which increase with the increase of x and y, it decreases the optical basicity and refractive index values. By optical absorption measurements determined the Band Gap energy values of all samples. It was concluded that occur direct transitions allowed in all sets. The behavior of increasing Band Gap values and decreasing Optical basicity confirmed the decreasing in the NBO content leading to an indication of a more polymerized network for a variation of x mol%. Finally the behaviors elastic modulus and hardness, which shows decreased stiffness of the material with the incorporation of Li2O and MoO3 concomitantly, is presented. x / Este trabalho apresenta as correlações entre a morfologia estrutural e as propriedades térmicas, ópticas e mecânicas nos vidros (1 – x – y)TeO2 – xLi2O – yMoO3. Dividiram-se as análises em três conjuntos de amostras, de acordo com variação da composição, para cada técnica utilizada. Os resultados revelam diferentes comportamentos de estabilidades vítreas para cada conjunto. As medidas por espectroscopia de Raman e FTIR mostram mudanças estruturais similares entre cada conjunto com diminuição dos NBOs e novas posições de picos. Os resultados de Raman e FTIR mostram que com o aumento em conteúdo x e y ocorre a transformação de unidades TeO4 para TeO3 + 1 e, em seguida, para TeO3 além disso ocorre a mudança de coordenação do átomo de Mo de 4 para 6 e estas alterações estruturais têm sido relacionados com a adição de átomos de Li. Este fato é confirmado pelos valores de energia de Band Gap, que aumentam com o incremento de x e y, e diminuição dos valores de basicidade óptica e índice de refração. As energias de Band Gap, para todas as amostras, foram determinadas por medidas de absorção óptica na região do Ultravioleta. Foi concluído que ocorrem transições diretas permitidas em todos os conjuntos. E por fim apresenta-se os comportamentos de dureza e Módulo elástico, o que revela diminuição da rigidez do material com a incorporação de Li2O e MoO3 concomitantemente.

Optical properties of Tl4In3GaSe8, Tl4InGa3Se8, Tl4In3GaS8, Tl2InGaS4 and Tl4InGa3S8 chain and layered crystals were studied by means of photoluminescence (PL) and transmission-reflection experiments. Several emission bands were observed in the PL spectra within the 475-800 nm wavelength region. The results of the temperature- and excitation intensity-dependent PL measurements in 15-300 K and 0.13&times / 10-3-110.34 W cm-2 ranges, respectively, suggested that the observed bands were originated from the recombination of electrons with the holes by realization of donor-acceptor or free-to-bound type transitions. Transmission-reflection measurements in the wavelength range of 400-1100 nm revealed the values of indirect and direct band gap energies of the crystals studied. By the temperature-dependent transmission measurements in 10-300 K range, the rates of change of the indirect band gap of the samples with temperature were found to be negative. The oscillator and dispersion energies, and zero-frequency refractive indices were determined by the analysis of the refractive index dispersion data using the Wemple&ndash / DiDomenico single-effective-oscillator model. Furthermore, the structural parameters of all crystals were defined by the analysis of X-ray powder diffraction data. The determination of the compositional parameters of the studied crystals was done by energy dispersive spectral analysis experiments.

Les processus photocatalytiques à la surface d’oxydes métalliques semi-conducteurs font l’objet d’intensesrecherches au niveau mondial car ils constituent des alternatives efficaces, respectueuses de l’environnement etpeu coûteuses aux méthodes conventionnelles dans les domaines de la purification de l’eau et de l’air, et de laproduction « verte » d’hydrogène. Cependant, certaines limitations pour atteindre des efficacitésphotocatalytiques élevées ont été mises en évidence avec les matériaux semiconducteurs classiques du fait de larecombinaison rapide des porteurs de charge générés par illumination. Le développement de photocatalyseurs àbase d’héterostuctures obtenues par dépôt de métaux à la surface de matériaux semiconducteurs ou parassociation de deux semiconducteurs possédant des bandes d’énergie bien positionnées devrait permettre delimiter ces phénomènes de recombinaison via un transfert de charge vectoriel. Dans ce contexte, trois typesd’hétérostructures telles que des nanomatériaux à base d’hétérojonction semiconducteur n/semiconducteur n(SnO2/ZnO), metal/semiconducteur n (RuO2/TiO2 and RuO2/ZnO) et semiconducteur p/semiconducteur n(NiO/TiO2) ont été synthétisées avec succès par différentes voies liquides. Leur composition, leur texture, leurstructure et leur morphologie ont été caractérisées par spectroscopies FTIR et Raman, par diffraction des rayonsX, microscopie électronique en transmission (MET) et porosimétrie de sorption d’azote. Par ailleurs, unecombinaison judicieuse des données issues de mesures effectuées par spectroscopie UV-visible en réflexiondiffuse (DRS) et par spectroscopies de photoélectrons X (XPS) et UV (UPS) a permis de déterminer lediagramme d’énergie des bandes pour chaque système étudié. Les catalyseurs ainsi obtenus ont conduit à desefficacités photocatalytiques plus élevées qu’avec le dioxyde de titane P25 pour la dégradation de colorantsorganiques (bleu de méthylène, l’orangé de méthyle) et la production d’hydrogène. En particulier, lesnanocomposites RuO2/TiO2 et NiO/TiO2 contenant une quantité optimale de RuO2 (5 % en masse) et de NiO(1% en masse), respectivement, ont conduit aux efficacités photocatalytiques les plus importantes pour laproduction d’hydrogène. Ces excellentes performances photocatalytiques ont été interprétées en termesd’alignement adéquat des bandes d’énergies des matériaux associé à des propriétés texturales et structuralesfavorables. Ce concept de photocatalyseurs à base d’hétérojonctions semiconductrices d’activité élevée devrait àl’avenir trouver des débouchés industriels dans les domaines de l’élimination de l’environnement de composésorganiques indésirables et de la production « verte » d’hydrogène. / Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV–visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV-visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

Phases organiques luminescentes qui sont incorporés dans une matrice inorganique conductrice est proposé dans cette étude pour la couche active d'une diode émettant de la lumière hybride. Dans ce composite, le colorant organique joue le rôle de site de recombinaison radiative de porteurs de charge qui sont injectées dans la matrice de transport ambipolaire inorganique. Comme l'un des combinaisons de matériaux de candidat, bicouche et des films minces composites de ZnSe et un complexe d'iridium rouge (Ir(BPA)) émetteur de lumière organique ont été préparé in situ par UHV technique d'évaporation thermique. Les alignements de bande d'énergie mesurée par spectroscopie de photoélectrons (PES) pour le ZnSe/Ir(BPA)et deux couches de ZnSe+Ir(BPA) révèlent que le composite HOMO et LUMO du colorant organique sont positionnées dans la largeur de bande interdite de ZnSe. Cette gamme offre les forces motrices énergiques nécessaires pour les transferts d'électrons et de trous de ZnSe à Ir(BPA). Par l'interprétation des données du PES,la composition chimique des interfaces ont également été déterminés. Le ZnSe/Ir(BPA) interface est réactive, même si elle est d'une pureté de matériaux de haute.Pendant ce temps, l'Ir (BPA)/ZnSe interface ne présente pas la pureté matériel. Ceci est représenté à la nature de ZnSe évaporation comme Zn particuliers et des fluxSE2, associée à des interactions chimiques avec le Ir(BPA) substrat. L'interface est,de ce fait, composé d'une multitude de phases, les phases de Se0, ZnSe rares, réduit Se et oxydé molécules de colorant, et de Zn qui sont intercalées atomes dans leIr(BPA) substrat. PES des composites ZnSe+Ir(BPA) révèle des tendances similaires à l'Ir(BPA)/ZnSe interface. A des émissions de lumière rouge surfaciques et intermittents fanées ont été observés à partir de dispositifs qui incorporent couches alternées séquences de ZnSe et Ir(BPA) pour la couche active. / Luminescent organic phases that are embedded in a conductive inorganicmatrix is proposed in this study for the active layer of a hybrid light-emitting diode. Inthis composite, the organic dye acts as the radiative recombination site for chargecarriers that are injected into the inorganic ambipolar transporting matrix. As one ofthe candidate material combinations, bilayer and composite thin films of ZnSe and ared iridium complex (Ir(BPA)) organic light emitter were prepared in situ via UHVthermal evaporation technique. The energy band alignments measured byphotoelectron spectroscopy (PES) for the ZnSe/Ir(BPA) bilayer and ZnSe+Ir(BPA)composite reveal that the HOMO and LUMO of the organic dye are positioned in theZnSe bandgap. This lineup provides the required energetic driving forces for electronand hole transfers from ZnSe to Ir(BPA). By interpreting PES data, the chemicalcomposition of the interfaces were also determined. The ZnSe/Ir(BPA) interface isreactive even though it is of high material purity. Meanwhile, the Ir(BPA)/ZnSeinterface does not exhibit material purity. This is accounted to the nature of ZnSeevaporation as individual Zn and Se2 fluxes, coupled with chemical interactions withthe Ir(BPA) substrate. The interface is, thereby, composed of an abundance of Se0phases, sparse ZnSe phases, reduced Se and oxidized dye molecules, and Znatoms that are intercalated into the Ir(BPA) substrate. PES of the ZnSe+Ir(BPA)composites reveals similar trends to the Ir(BPA)/ZnSe interface. A faded areal andintermittent red light emissions were observed from devices that incorporatedalternating layer sequences of ZnSe and Ir(BPA) for the active layer.

Orientador: Prof. Dr. Jeverson Teodoro Arantes Junior / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, Santo André, 2018. / Investigamos, sistematicamente, as propriedades estruturais e eletrônicas do óxido de zinco nanoporoso sob tração e compressão biaxial utilizando cálculos de primeiros princípios baseados na Teoria do Funcional da Densidade. O sistema apresenta uma alta concentração de nanoporos lineares orientados nas direções cristalográcas [0001] e [01-10], bem como um lme no nanoporoso. Para compressões maiores do que 4% com relação ao parâmetro de rede, foi observada uma distorção estrutural nas regiões menos densas do material poroso, mostrando uma tendência à mudança de fase localizada. O coe- ciente de Poisson calculado dos nanoporos orientados na direção [0001] foi negativo. Isto signica que quando o material poroso foi tracionado, expandiu-se transversalmente. Já quando comprimido, o material contraiuse na direção transversal. Os materiais que possuem esta característica são conhecidos como materiais auxéticos. Nossos resultados mostram que o valor do gap de energia foi modulado pelas deformações biaxiais com uma tendência oposta ao bulk. A densidade dos estados eletrônicos conrmou nossas observações. A tendência estrutural inversa da superfície dos nanoporos é o principal mecanismo para o comportamento inverso do gap sob compressão e tração. Dentro do nosso conhecimento, este é o primeiro reporte de um comportamento inverso do gap de energia de estruturas de ZnO sob compressão e tração biaxial. Nossos resultados sugerem que a nanoporosidade, conjuntamente com tra- ção e compressão biaxial, podem ser empregadas como um método dentro da engenharia de gap para customizar materiais funcionais que requerem controle da atividade eletrônica. / This work investigated, systematically, the structural and electronic properties of nanoporous zinc oxide, under biaxial strain, through rst-principles methods, based on total energy ab initio calculations using Density Functional Theory. The system was in a massive nanopore concentration regime. We studied linear pores in [0001] and [01-10] direction and a porous thin lm. Using a biaxial tension above 4% of the ZnO bulk lattice parameter, we observed a distortion resulting in a local phase change region in the material's structure. The calculated Poisson's coecient was negative for the [0001] pore. When stretched, they become thicker in the perpendicular direction to the applied force. These materials are known as auxetic. Our results show that the energy band gap value is tuned by the strain with an uncommon opposite trend related to the bulk. The density of electronic states conrmed the energy gap modulation. The structural inverse trend of nanopores surface is the principal mechanism for gap inverse behavior under compressive and tensile strain. From the best of our knowledge, this is the rst report about opposite Egap trend in strained nanopores. Our results suggest that nanoporosity and biaxial strain could be employed as a method within the band gap engineering for tailored functional matexi rials that require control of the electronic activity.