Ge1-xSnx alloys are among a small class of benign semiconductors with composition tunable bandgaps in the near-infrared spectrum. As the amount of Sn is increased the band energy decreases and a transition from indirect to direct band structure occurs. Hence, they are prime candidates for fabrication of Si-compatible electronic and photonic devices, field effect transistors, and novel charge storage device applications. Success has been achieved with the growth of Ge1-xSnx thin film alloys with Sn compositions up to 34%. However, the synthesis of nanocrystalline alloys has proven difficult due to larger discrepancies (~14%) in lattice constants. Moreover, little is known about the chemical factors that govern the growth of Ge1-xSnx nanoalloys and the effects of quantum confinement on structure and optical properties. A synthesis has been developed to produce phase pure Ge1-xSnx nanoalloys which provides control over both size and composition. Three sets of Ge1-xSnx nanocrystals have been studied, 15–23 nm, 3.4–4.6 nm and 1.5–2.5 nm with Sn compositions from x = 0.000–0.279. Synthetic parameters were explored to control the nucleation and growth as well as the factors that have led to the elimination of undesired metallic impurities. The structural analysis of all nanocrystals suggests the diamond cubic structure typically reported for Ge1-xSnx thin films and nanocrystalline alloys. As-synthesized Ge1-xSnx nanoalloys exhibit high thermal stability and moderate resistance against sintering up to 400–500 °C and are devoid of crystalline and amorphous elemental Sn impurities.

Master of Science / Department of Chemical Engineering / Larry E. Erickson / Photocatalytic oxidation (PCO) is a promising and emerging technique in controlling indoor air contaminants, including volatile organic compounds (VOCs). It has broad air cleaning and deodorization applications in indoor environments ranging from residential and office buildings to healthcare and nursing facilities as well as spacecrafts, aircraft cabins and clean rooms in the agricultural and food industry. Numerous studies have been conducted to improve the effectiveness and performance of this technology. These include development of new configurations, energy-efficient catalysts and other parameters to control the process. However, only limited research has been conducted under realistic indoor environmental conditions. One of the most recent developments in photocatalysis is the synthesis of 2% C- and V-doped TiO[subscript]2, which is active under both dark and visible light conditions. However, like most research conducted in photocatalysis, the study on the reactivity of this catalyst has been performed only under laboratory conditions. This study investigated the possible application of the novel C and V co-doped TiO[subscript]2 in cleaning indoor air. Mathematical modeling and simulation techniques were employed to assess the potential use of some of the promising systems that utilize the catalyst (i.e., packed bed and thin films) as well as the effect of mass transfer limitations in the degradation of acetaldehyde, one of the VOCs that can be found in offices, residential buildings and other facilities.

Regarding the vegetation, the most affected areas by high levels of surface ozone (O3) are the mountain ridges. Our study has been carried out in the Jizerske hory Mts. High O3 levels together with the convenient environmental conditions for stomatal conductance could be a threat for the health of recovering ecosystems in this area. The aims of this study was both to assess the influence of O3 on vegetation in the Czech mountains and to provide recommendations and outlooks for possible future using of relatively new methods (visible symptoms and stomatal O3 flux modelling) used for O3 impact assessment on native vegetation in the field; that means physiologically relevant methods for the determination of O3 influence. During 2006 and 2007, O3-like visible symptoms were assessed on the leaves of seven species at four sites. Symptoms on only two species (Fagus sylvatica L. and Rubus idaeus L.) have been determined as O3-induced. To our knowledge, it is the first study in the Czech Republic in which the O3-like symptoms on native plants have been verified by the Ozone Validation Centre for Central Europe. Our results based on O3-induced symptoms indicate that ambient O3 is likely to have a much lower impact than expected, considering the measured O3 concentrations (measured with passive samplers) and...

The purpose of the study is to investigate the formative assessment work in Swedish compulsory special school, for students who read focus subject. The questions are how special educators working with formative assessment in different ways, and how they make the knowledge requirements visible by artefacts as the use of image support, alternative communication, digital tools and more. Theoretical approach consists of previous research on formative assessment. Sociocultural perspective has been used to analyse the results. Qualitative methods in the form of five observations and five interviews were used for the collection of empirical data. Results show that educators are working consistently with formative assessment in different ways and that teacher’s give students feedback for learning forward. In the categories peer assessment and the visibility of the knowledge requirements, it appears on the basis that it appears less in teaching. The study's implications based on the results is to make visible the objectives for students and help them to their own development. It also contributes to further research on the importance of students with intellectual disabilities may need alternative individual adaptations for perceiving information and communication about learning objectives and criteria. The work of visible learning and make students involved in their own development becomes more complicated when the curriculum and syllabuses exist only as text documents. Teachers need to create own image support in the student's immediate environment to increase the possibility for communication about the student's knowledge of the formative process

Este trabalho é dividido em duas partes. Na primeira parte são estudadas moléculas isoladas, na segunda, moléculas em meio solvente. Em sua primeira parte, métodos de mecânica quântica de alto nível de correlação são utilizados para caracterizar o estado fundamental da molécula de CaC. Propriedades elétricas e óticas desta molécula, como também da molécula de MgH, são obtidas usando-se o método de campo finito. O estudo dessas moléculas é de interesse para a Astrofísica. A segunda parte deste trabalho foca o estudo teórico do solvatocromismo da molécula de 4-[(4-dimethylamino)phenyl)imino]-2, 5-cyclohexadien-1-one, ou DIA (Dimethylaminoindoaniline). Esta molécula apresenta também uma grande variação da sua primeira hiperpolarizabilidade medida em solução. Sabe-se que ela existe em solução como uma combinação de duas formas extremas: a forma com separação de cargas eno e a forma neutra ceto. Após otimizarmos teoricamente as estruturas dessas duas formas, realizamos uma simulação Monte Carlo em um número de moléculas de solventes polares e apoiares. A análise da estrutura do solvente, em torno de cada soluto, é realizada usando-se funções de distribuição radial de pares. É feita, também, a análise das pontes de hidrogênio para cada estrutura eno ou ceto. Estruturas supermoleculares, envolvendo o soluto com as moléculas mais próximas e, em separado. com as moléculas ligadas por pontes de hidrogênio, são usadas como entrada para cálculos semi-empíricos de mecânica quântica da primeira transição eletrônica de absorção e da primeira hiperpolarizabilidade. Apenas superestruturas estatisticamente descorrelacionadas foram usadas no cálculo. Os resultados são analisados e comparados com resultados experimentais em solução e com resultados teóricos em fase gasosa. Todas as interpretações sugerem que a estrutura eno é responsável pelos espectros experimentais de absorção UV-visível, tanto em solvente polares quanto em apoiares. A estrutura eno tem também uma primeira hiperpolarizabilidade calculada que concorda adequadamente com aquelas observadas em alguns solventes. Para clorofórmio a primeira hiperpolarizabilidade do DIA é dez vezes maior que em outros solventes. / This work is divided in two parts. In the first part isolated molecules are studied, in the second part the interest is in molecules in solvent media. In the first part of this work, high level quantum mechanical correlation methods are employed to characterise the ground state of the CaC molecule. Electrical and optical properlies of this molecule and also of the MgH molecule are obtained using the finite field method. The study of these molecules is of interest to Astrophysics. The second part of this work focuses on the theoretical study of the solvatochromism of the 4-[(4-dimelhylamino)phenyl)imino]-2, 5-cyclohexadien-1-one molecule, or DIA (Dimethylaminoindoaniline). This molecule also presents a large variation of its measured first hyperpolarizability in solution. It is known that in solution this molecule exists in a combination of two extreme forms, the chargeseparated eno form and the neutral kelo form. After these two structures are theoretically optimised, a Monte Carlo simulation is performed in a number of polar and non-polar solvent molecules. Analysis of1 the solvent structure around each solute is performed using radial distribution function. Hydrogen bonding analysis for each eno or keto structure is also carried out. Supermolecular structures involving the solute and the nearest solvent molecules and, separately, the hydrogen bonded molecules, are used as input to quantum mechanical semi-empirical calculations of the first electronic absorption transition and the first hyperpolarizability. Only statistically non-correlated superstructures were used in the calculation. The results are analysed and compared to experimental results in solution and theoretical results in gas-phase. All interpretations suggest that the eno structure is responsible for the experimental UV-Visible absorption spectrum, both in polar and non-polar solvents. The eno structure has also a calculated first hyperpolarizability that agrees well with that observed for some solvents. For chloroform the first hyperpolarizability of DIA is ten times greater than in other solvents.

A titânia (TiO2) é um material amplamente estudado devido ao seu baixo teor de toxicidade, alta disponibilidade e por apresentar propriedades que permitem ser utilizado em uma variedade de aplicações fotocatalíticas. Sua atividade fotocatalítica frente à degradação de poluentes orgânicos, por exemplo, pode ser melhorada quando se prepara uma mistura de fases desse material, como o TiO2 P-25 apresenta. Entretanto, seu elevado valor de band gap lhe permite ser utilizado apenas quando incidido com radiação eletromagnética de alta energia (&#955;< 390 nm). O presente trabalho demonstra que quando TiO2 P-25 é sintetizado em forma de filmes mesoporosos, seu band gap é reduzido e passa a apresentar atividade fotocatalítica sob incidência de luz visível. Essa redução é atribuída ao tratamento térmico que é aplicado no processo de preparo do material. Para comprovar sua atividade na ausência de radiação UV, um estudo foi conduzido a partir da análise da taxa de fotodegradação das moléculas 2-naftol, alaranjado de metila e 2,4,6-trimercapto- 1,3,5-triazina por espectrometria de massas utilizando o composto hexafluorofosfato de amônio como padrão interno. A metodologia desenvolvida pode também ser aplicada para conduzir outros ensaios semi-quantitativos por espectrometria de massas. Foi observado que os filmes de TiO2 promovem fodo-oxidação de 2-naftol sob incidência de luz visível e na presença de gás oxigênio após 6 horas de reação. A fotodegradação do alaranjado de metila e do 2,4,6-trimercapto-1,3,5-triazina também foi confirmada, entretanto em uma taxa mais lenta. O processo também foi observado pela identificação de um subproduto da foto-oxidação do alaranjado de metila no espectro de massas e a partir do decaimento do seu pico de absorção em 468 nm por espectrofotometria no UV-Vis. Foi observado também que a titânia pode ter sua atividade fotocatalítica reduzida ao elevar o pH do meio. Além disso, foram produzidos filmes de titânia modificados com nanopartículas de ouro a partir da utilização de ácido tioglicólico como mediador e por drop casting. Os dois métodosformaram filmes homogêneos de nanopartículas de ouro sobre o TiO2, e estes foram utilizados nos ensaios fotocatalíticos. Entretanto, a presença do metal prejudicou a eficiência fotocatalítica da titânia inibindo sua atividade quando excitada com luz visível. Dessa forma, filmes puros de TiO2 P-25, além de ativos sob incidência de uma faixa espectral mais ampla da radiação solar, apresentam a vantagem de funcionarem como catalisadores heterogêneos de reações de fotodegradação de moléculas orgânicas podendo ser facilmente removidos do meio reacional ao final do processo. / Titania (TiO2) is a widely studied material due to its low toxicity, high availability and to have properties that allow it to be used in a variety of photocatalytic applications. Its photocatalytic activity against the degradation of organic contaminants, for instance, can be even improved when preparing a mixture of phases of this material, as TiO2 P- 25 presents. However, its high band gap allows it to be used only when affected by high energy electromagnetic radiation (&#955;< 390 nm). The present work demonstrates that when TiO2 P-25 is synthesized in the form of mesoporous films, its band gap is reduced, and it starts to present photocatalytic activity under visible light. This reduction is attributed to the heat treatment that is applied during the preparation process of the material. In order to verify its activity in the absence of UV radiation, a study was conducted based on the analysis of the photodegradation rate of 2-naphthol, methyl orange and 2,4,6-trimercapto-1,3,5-triazine molecules by mass spectrometry using the compound ammonium hexafluorophosphate as an internal standard. The developed methodology can also be applied to conduct other semiquantitative assays via mass spectrometry. It was observed that TiO2 films induced 2-naphthol photooxidation under visible light and in the presence of oxygen gas after 6 hours of reaction. Photodegradation of methyl orange and 2,4,6-trimercapto-1,3,5-triazine was also confirmed, yet at a slower rate. The process was also observed by the identification of a methyl orange photooxidation by-product in the mass spectrum and from the decay of its absorption peak at 468 nm by UV-Vis spectrophotometry. It was also observed that titania may have its photocatalytic activity reduced by raising the pH of the medium. Furthermore, it was also produced titania films modified with gold nanoparticles through use of thioglycolic acid as a mediator and by drop casting method. Both techniques formed homogeneous films of gold nanoparticles over TiO2, and their photocatalytic activity were also evaluated. Nevertheless, the presence of the metal impaired the photocatalytic efficiency of titania by inhibiting its activity when excited by visible light. All in all, pure TiO2 P-25 films work under incidence of a wider range of the solar spectrum and has also the advantage of functioning as heterogeneous catalysts for photodegradation reactions of organic molecules and can be easily removed from the reaction medium at the end of the process.

No description available.

A titânia (TiO2) é um material amplamente estudado devido ao seu baixo teor de toxicidade, alta disponibilidade e por apresentar propriedades que permitem ser utilizado em uma variedade de aplicações fotocatalíticas. Sua atividade fotocatalítica frente à degradação de poluentes orgânicos, por exemplo, pode ser melhorada quando se prepara uma mistura de fases desse material, como o TiO2 P-25 apresenta. Entretanto, seu elevado valor de band gap lhe permite ser utilizado apenas quando incidido com radiação eletromagnética de alta energia (&#955;< 390 nm). O presente trabalho demonstra que quando TiO2 P-25 é sintetizado em forma de filmes mesoporosos, seu band gap é reduzido e passa a apresentar atividade fotocatalítica sob incidência de luz visível. Essa redução é atribuída ao tratamento térmico que é aplicado no processo de preparo do material. Para comprovar sua atividade na ausência de radiação UV, um estudo foi conduzido a partir da análise da taxa de fotodegradação das moléculas 2-naftol, alaranjado de metila e 2,4,6-trimercapto- 1,3,5-triazina por espectrometria de massas utilizando o composto hexafluorofosfato de amônio como padrão interno. A metodologia desenvolvida pode também ser aplicada para conduzir outros ensaios semi-quantitativos por espectrometria de massas. Foi observado que os filmes de TiO2 promovem fodo-oxidação de 2-naftol sob incidência de luz visível e na presença de gás oxigênio após 6 horas de reação. A fotodegradação do alaranjado de metila e do 2,4,6-trimercapto-1,3,5-triazina também foi confirmada, entretanto em uma taxa mais lenta. O processo também foi observado pela identificação de um subproduto da foto-oxidação do alaranjado de metila no espectro de massas e a partir do decaimento do seu pico de absorção em 468 nm por espectrofotometria no UV-Vis. Foi observado também que a titânia pode ter sua atividade fotocatalítica reduzida ao elevar o pH do meio. Além disso, foram produzidos filmes de titânia modificados com nanopartículas de ouro a partir da utilização de ácido tioglicólico como mediador e por drop casting. Os dois métodosformaram filmes homogêneos de nanopartículas de ouro sobre o TiO2, e estes foram utilizados nos ensaios fotocatalíticos. Entretanto, a presença do metal prejudicou a eficiência fotocatalítica da titânia inibindo sua atividade quando excitada com luz visível. Dessa forma, filmes puros de TiO2 P-25, além de ativos sob incidência de uma faixa espectral mais ampla da radiação solar, apresentam a vantagem de funcionarem como catalisadores heterogêneos de reações de fotodegradação de moléculas orgânicas podendo ser facilmente removidos do meio reacional ao final do processo. / Titania (TiO2) is a widely studied material due to its low toxicity, high availability and to have properties that allow it to be used in a variety of photocatalytic applications. Its photocatalytic activity against the degradation of organic contaminants, for instance, can be even improved when preparing a mixture of phases of this material, as TiO2 P- 25 presents. However, its high band gap allows it to be used only when affected by high energy electromagnetic radiation (&#955;< 390 nm). The present work demonstrates that when TiO2 P-25 is synthesized in the form of mesoporous films, its band gap is reduced, and it starts to present photocatalytic activity under visible light. This reduction is attributed to the heat treatment that is applied during the preparation process of the material. In order to verify its activity in the absence of UV radiation, a study was conducted based on the analysis of the photodegradation rate of 2-naphthol, methyl orange and 2,4,6-trimercapto-1,3,5-triazine molecules by mass spectrometry using the compound ammonium hexafluorophosphate as an internal standard. The developed methodology can also be applied to conduct other semiquantitative assays via mass spectrometry. It was observed that TiO2 films induced 2-naphthol photooxidation under visible light and in the presence of oxygen gas after 6 hours of reaction. Photodegradation of methyl orange and 2,4,6-trimercapto-1,3,5-triazine was also confirmed, yet at a slower rate. The process was also observed by the identification of a methyl orange photooxidation by-product in the mass spectrum and from the decay of its absorption peak at 468 nm by UV-Vis spectrophotometry. It was also observed that titania may have its photocatalytic activity reduced by raising the pH of the medium. Furthermore, it was also produced titania films modified with gold nanoparticles through use of thioglycolic acid as a mediator and by drop casting method. Both techniques formed homogeneous films of gold nanoparticles over TiO2, and their photocatalytic activity were also evaluated. Nevertheless, the presence of the metal impaired the photocatalytic efficiency of titania by inhibiting its activity when excited by visible light. All in all, pure TiO2 P-25 films work under incidence of a wider range of the solar spectrum and has also the advantage of functioning as heterogeneous catalysts for photodegradation reactions of organic molecules and can be easily removed from the reaction medium at the end of the process.

Technology for wireless information access has enabled innovation of 'smart' portable consumer devices. These have been widely adopted and have become an integral part of our daily lives. They need ubiquitous connectivity to the internet to provide value added services, maximize their functionality and create a smarter world to live in. Cisco's visual networking index currently predicts wireless data consumption to increase by 61% per year. This will put additional stress on the already stressed wireless access network infrastructure creating a phenomenon called 'spectrum crunch'. At the same time, the solid state devices industry has made remarkable advances in energy efficient light-emitting-diodes (LED). The lighting industry is rapidly adopting LEDs to provide illumination in indoor spaces. Lighting fixtures are positioned to support human activities and thus are well located to act as wireless access points. The visible spectrum (380 nm - 780 nm) is yet unregulated and untapped for wireless access. This provides unique opportunity to upgrade existing lighting infrastructure and create a dense grid of small cells by using this additional 'optical' wireless bandwidth. Under the above model, lighting fixtures will service dual missions of illumination and access points for optical wireless communication (OWC). This dissertation investigates multiple-input multiple-output (MIMO) optical wireless broadcast system under unique constraints imposed by the optical channel and illumination requirements. Sample indexed spatial orthogonal frequency division multiplexing (SIS-OFDM) and metameric modulation (MM) are proposed to achieve higher spectral efficiency by exploiting dimensions of space and color respectively in addition to time and frequency. SIS-OFDM can provide significant additional spectral efficiency of up to (Nsc/2 - 1) x k bits/sym where Nsc is total number of subcarriers and k is number of bits per underlying spatial modulation symbol. MM always generates the true requested illumination color and has the potential to provide better color rendering by incorporating multiple LEDs. A normalization framework is then developed to analyze performance of optical MIMO imaging systems. Performance improvements of up to 45 dB for optical systems have been achieved by decorrelating spatially separate links by incorporating an imaging receiver. The dissertation also studies the impact of visual perception on performance of color shift keying as specified in IEEE 802.15.7 standard. It shows that non-linearity for a practical system can have a performance penalty of up to 15 dB when compared to the simplified linear system abstraction as proposed in the standard. Luminous-signal-to-noise ratio, a novel metric is introduced to compare performance of optical modulation techniques operating at same illumination intensity. The dissertation then introduces singular value decomposition based OWC system architecture to incorporate illumination constraints independent of communication constraints in a MIMO system. It then studies design paradigm for a multi-colored wavelength division multiplexed indoor OWC system.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-10-02T20:17:04Z No. of bitstreams: 1 ThiagoSantos.pdf: 1103502 bytes, checksum: 16ad7405a0ab31d83423293c43110ee8 (MD5) / Made available in DSpace on 2017-10-02T20:17:04Z (GMT). No. of bitstreams: 1 ThiagoSantos.pdf: 1103502 bytes, checksum: 16ad7405a0ab31d83423293c43110ee8 (MD5) Previous issue date: 2017-09-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão / Instituto Nacional de Ciência e Tecnologia em Bioanalítica / A photoelectroanalytical sensor was developed, based on deoxyribonucleic acid (DNA) and anatase titanium dioxide (TiO2) nanoparticles sensitized with bis(ethylenedithio)tetrathiofulvalene (BEDT-TTF) for determination of the adrenaline, also denominated as epinephrine. The photosensor composite developed was denominated as BEDT-TTF/DNA/TiO2/ITO and shows a high photocurrent for the adrenaline under light emitting diode (LED) irradiation in comparison to each component of the composite material. Under optimized conditions, the BEDTTTF/DNA/TiO2/ITO sensor shows a linear response range from 10 nmol L-1 up to 100 μmol L-1 with a sensitivity of 8,1 nA L μmol-1 and limit of detection of 1 nmol L-1 for the adrenaline. The photoelectrochemical sensor showed high photocurrent to adrenaline in comparison to photocurrent response to ascorbic acid and uric acid. The BEDT-TTF/DNA/TiO2/ITO photoelectrochemical sensor was successfully applied to urine samples, with recovery values between 96 and 106%. / Um sensor fotoeletroanalítico foi desenvolvido, baseado em ácido desoxirribonucleico (DNA) e nanopartículas de dióxido de titânio anatase (TiO2) sensibilizadas com bis(etilenoditio)tetratiofulvaleno (BEDT-TTF) para a determinação de adrenalina, também denominada como epinefrina. O fotossensor compósito desenvolvido foi denominado como BEDT-TTF/DNA/TiO2/ITO e exibiu uma elevada fotocorrente para a adrenalina sob a irradiação do diodo emissor de luz (LED) em comparação com cada componente do material compósito. Sob condições otimizadas, o sensor BEDT-TTF/DNA/TiO2/ITO exibiu um intervalo de resposta linear de 10 nmol L-1 para 100 μmol L-1 com uma sensibilidade de 8,1 nA L μmol-1 e limite de detecção de 1 nmol L-1 para a adrenalina. O sensor fotoeletroquímico mostrou elevada fotocorrente para a adrenalina em comparação com a resposta de fotocorrente para ácido ascórbico e ácido úrico. O fotossensor BEDTTTF/DNA/TiO2/ITO foi aplicado com sucesso em amostras de urina, com valores de recuperação entre 96 e 106%.