Sand ramps are widespread but understudied landforms which have the potential to provide detailed palaeoenvironmental information in dryland regions. This thesis investigates the utility of sand ramps as late Quaternary palaeoenvironmental archives by addressing two research questions: (1) What are the main controls on sand ramp formation in southern Africa? (2) What does the sand ramp record tell us about late Quaternary palaeoenvironments in southern Africa? The distribution of sand ramps in southern Africa was surveyed using Google Earth™ and 75 features were identified in southern Namibia. Ten of these sand ramps, and an additional feature from South Africa, were studied in the field. Sediments and morphology were mapped and a total of 64 OSL dates, 96 sediment samples, 10 heavy mineral assemblages and OSL sensitivity data from 8 samples were examined. The distribution of sand ramps suggests formation is dependent on (1) sediment supply, (2) accommodation space, (3) persistent unidirectional wind and (4) a variable semi-arid to arid climate. Chronologies and sediment analyses indicate individual sand ramp accumulation is locally controlled by sediment supply modulated by the availability, and nature, of the accommodation space. Comparison between the Namibian and South African sand ramps suggests considerable regional variation in the factors controlling sediment supply. The Namibian sand ramps show an affinity to local ephemeral river channels. Periods of dated sand ramp activity in multiple features are interpreted as periods of increased regional fluvial activity. Significant activity occurred at ~21-12 ka (with peaks at 21-18.5 ka and 14.5-12 ka), ~8.5-7.5 ka and ~2 ka. Some activity is also indicated at 85-65 ka and 45-35 ka. These results correspond well to regional records. Overall, this study demonstrates that sand ramps can provide palaeoclimatic information on both the local and regional scale but only if a number of caveats are taken into consideration.

abstract: As the world energy demand increases, semiconductor devices with high energy conversion efficiency become more and more desirable. The energy conversion consists of two distinct processes, namely energy generation and usage. In this dissertation, novel multi-junction solar cells and light emitting diodes (LEDs) are proposed and studied for high energy conversion efficiency in both processes, respectively. The first half of this dissertation discusses the practically achievable energy conversion efficiency limit of solar cells. Since the demonstration of the Si solar cell in 1954, the performance of solar cells has been improved tremendously and recently reached 41.6% energy conversion efficiency. However, it seems rather challenging to further increase the solar cell efficiency. The state-of-the-art triple junction solar cells are analyzed to help understand the limiting factors. To address these issues, the monolithically integrated II-VI and III-V material system is proposed for solar cell applications. This material system covers the entire solar spectrum with a continuous selection of energy bandgaps and can be grown lattice matched on a GaSb substrate. Moreover, six four-junction solar cells are designed for AM0 and AM1.5D solar spectra based on this material system, and new design rules are proposed. The achievable conversion efficiencies for these designs are calculated using the commercial software package Silvaco with real material parameters. The second half of this dissertation studies the semiconductor luminescence refrigeration, which corresponds to over 100% energy usage efficiency. Although cooling has been realized in rare-earth doped glass by laser pumping, semiconductor based cooling is yet to be realized. In this work, a device structure that monolithically integrates a GaAs hemisphere with an InGaAs/GaAs quantum-well thin slab LED is proposed to realize cooling in semiconductor. The device electrical and optical performance is calculated. The proposed device then is fabricated using nine times photolithography and eight masks. The critical process steps, such as photoresist reflow and dry etch, are simulated to insure successful processing. Optical testing is done with the devices at various laser injection levels and the internal quantum efficiency, external quantum efficiency and extraction efficiency are measured. / Dissertation/Thesis / Ph.D. Physics 2010

abstract: Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices from GeSn films were fabricated using newly developed CMOS-compatible protocols, and the devices were characterized with respect to their electrical properties and optical response. The detectors were found to have a detection range that extends into the near-IR, and the detection edge is found to shift to longer wavelengths with increasing Sn content, mainly due to the compositional dependence of the direct band gap E0. With only 2 % Sn, all of the telecommunication bands are covered by a single detector. Room temperature photoluminescence was observed from GeSn films with Sn content up to 4 %. The peak wavelength of the emission was found to shift to lower energies with increasing Sn content, corresponding to the decrease in the direct band gap E0 of the material. An additional peak in the spectrum was assigned to the indirect band gap. The separation between the direct and indirect peaks was found to decrease with increasing Sn concentration, as expected. Electroluminescence was also observed from Ge/Si and Ge0.98Sn0.02 photodiodes under forward bias, and the luminescence spectra were found to match well with the observed photoluminescence spectra. A theoretical expression was developed for the luminescence due to the direct band gap and fit to the data. / Dissertation/Thesis / Ph.D. Physics 2011

Title: Photoluminescence of CdTe crystals Author: Jan Procházka Department: Institute of Physics of Charles University in Prague Supervisor: Doc. RNDr. Pavel Hlídek, CSc. Abstract: Energy levels connected with defects in nominally undoped crystals CdTe, indium- doped crystals and chlorine-doped crystals were studied using low-temperature photoluminescence. The crystals are intended for X- and gamma- ray detectors operated at room temperature. An effect of annealing in cadmium or tellurium vapor on luminescence spectra was investigated. Some changes were interpreted by filling of vacancies not only by atoms coming from gaseous phase but also by impurities from defects like interstitials, precipitates, inclusions, grain boundaries etc. The luminescence bands assigned to defects important for compensation mechanism were examined, namely A-centers (complexes of vacancy in cadmium sublattice and impurity shallow donor) and complexes of two donors bound to a vacancy. It was shown, that temperature dependence of the luminescence bands results from more complicated processes than a simple thermal escape of bound excitons or thermal excitation of electrons (holes) from defects to bands. We observed expressive "selective pair luminescence" bands (SPL) on partially compensated In-doped samples during sub-gap...

Pontos quânticos de carbono (C-dots) luminescentes na região do azul-verde aprisionados em matriz de sílica foram produzidos por um processo novo, baseado na pirólise de grupos contendo carbono dispersos nas bordas dos grãos de dimensões nanométricas de sílica (AEROSIL) previamente sinterizados a frio sob alta pressão, onde nenhuma técnica de passivação foi exigida. A análise de difração de elétrons de área selecionada (SAED – Selected Area Electron Diffraction) e espectroscopia de perda de energia de elétrons (EELS – Electron Energy Loss Spectroscopy) confirmaram a formação de C-dots contendo átomos de carbono com ligações do tipo sp2. Foram investigados diferentes valores de pressão (2,5, 4 e 7,7 GPa) para sinterização a frio e diferentes temperaturas de pirólise, a partir de 500 até 900°C. Resultados de análise térmica revelaram pequena perda de massa durante a pirólise das amostras, praticamente independente da pressão utilizada na sinterização. Espectroscopia na faixa do infravermelho revelou alterações nas bandas de aborção na faixa correspondente aos modos de vibração de CH2 e CH3, dependentes da temperatura e da pressão utilizadas. Os espectros de fotoluminescência (FL) foram fortemente dependentes do comprimento de onda de excitação e observou-se uma intensidade de emissão mais elevada no intervalo entre 500-550 nm para a amostra sinterizada a frio em 7,7 GPa e tratada termicamente a 800°C para excitação em 460 nm. Também foi investigado a contribuição da matriz de silica após a sinterização. / Quantum dots in the blue-green region embedded in a silica matrix were produced by a new process based on the pyrolysis of groups containing carbon dispersed on the edges of the grain of nanosized silica (AEROSIL) previously sintered under high pressure, where no passivation technique was required. The Selected Area Electron Diffraction (SAED) and Electron Energy Loss Spectroscopy (EELS) confirmed the formation of Cdots containing carbon atoms with sp2 bonds. Different pressure values (2,5, 4 and 7,7 GPa) were investigated for cold sintering and the pyrolsys was in the temperature range from 500 to 900°C. Results of thermal analysis revealed a small loss of mass during the pyrolysis of the samples, practically independent of the sintering pressure. Infrared spectroscopy revealed changes in the absorption bands in the range corresponding to the CH2 and CH3 vibration modes, depending on the temperature and pressure conditions. Photoluminescence (PL) spectra were strongly dependent on the excitation wavelength and a higher emission intensity was observed in the range 500-550 nm for the sample sintered at 7.7 GPa and pyrolysed at 800°C for excitation at 460 nm. The contribution of the silica matrix after sintering was also investigated.

O presente trabalho tem como objetivo a reconstrução da história evolutiva ao longo do Holoceno da planície costeira de cordões litorâneos estabelecidos sobre o vale fluvial do Rio Itabapoana/ES. A partir desse objetivo, foram realizadas as seguintes etapas metodológicas: Sensoriamento Remoto, Topografia, Geofísica e Geocronologia. Através da análise da imagem de satélite RapidEye, na composição colorida R5-G3-B1, foram discriminadas classes de cobertura vegetal. A relação entre a vegetação e o solo exposto proporcionou a identificação de três padrões distintos na planície costeira de cordões litorâneos. A obtenção de dados contínuos de altimetria através de um sistema global de navegação por satélite (GNSS), concentrado no caminhamento perpendicular à linha de costa, permitiu a elaboração e análise do perfil altimétrico dos cordões litorâneos, identificando-se três principais características: 1) nos primeiros 600 m tem-se um acréscimo na elevação; 2) em seguida, uma longa faixa “estável”, de pouca mudança na elevação; 3) por fim, o decréscimo da elevação nos últimos 500 m. Para caracterizar a arquitetura deposicional em subsuperfície dos cordões litorâneos, utilizou-se um Radar de Penetração no Solo (GPR) O registro obtido com GPR possibilitou a identificação de três padrões, representados pelas unidades retrogradacional e progradacional, onde o padrão de empilhamento compõe uma sequência de barreira regressiva ou progradante. Para a obtenção de uma relação cronoestratigráfica, seis amostras de sedimentos da fração arenosa de deposição eólica foram coletadas para a obtenção de idades absolutas a partir de Luminescência Opticamente Estimulada (LOE). Os cordões datados apresentaram idades holocênicas, com idades inferiores a 5.261 ± 396 anos. A integração dos resultados obtidos através dos métodos aplicados permitiu o reconhecimento de três padrões que levaram à interpretação de três fases decorrentes das variações do nível relativo do mar e do aporte sedimentar na evolução da planície. Essas fases representam os períodos de transgressão, regressão normal e regressão forçada. / The aim of this study is the reconstruction of the evolutionary history along the Holocene of the of beach ridges coastal plain established on the fluvial valley of Itabapoana River/ES. From this objective, the following methodological steps were performed: Remote Sensing, Topography, Geophysics and Geochronology. Through the analysis of the RapidEye satellite image, in the color composition R5-G3-B1, classes of vegetal cover were discriminated. The relationship between vegetation and exposed soil provided the identification of three distinct patterns of the beach ridges coastal plain. Obtaining continuous data of altimetry with a GNSS system, concentrated in the path perpendicular to the coastline, allowed the elaboration and analysis of the altimetric profile of the beach ridges. It was identified three main characteristics: 1) in the first 600 m there is an increase in elevation; 2) then along “stable” stretch, with little change in elevation; 3) lastly, the decrease of the elevation in the last 500 m. A Ground Penetrating Radar (GPR) was used to characterize the depositional architecture in the subsurface of the beach ridges The GPR record allowed the identification of three patterns, represented by the retrogradational and progradational units, in which the stacking pattern consists of a regressive or progradational barrier sequence. Six sediment samples of the sandy fraction of wind deposition were collected to obtain absolute ages from Optically Stimulated Luminescence (OSL). The dated ridges presented Holocene ages, with ages lower than 5,261 ± 396 years. The integration of the results obtained allowed the recognition of three patterns that led to the interpretation of three phases due to the variations of the relative sea level and the sedimentary budget in the evolution of the plain. These phases represent periods of transgression, normal regression and forced regression.

Made available in DSpace on 2014-06-11T19:25:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-02-08Bitstream added on 2014-06-13T20:14:05Z : No. of bitstreams: 1 sabaris_tpp_me_rcla.pdf: 3208215 bytes, checksum: 338f71066b13421e89faae60fd4c23ea (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho descreve sistematicamente a preparação de xerogéis de sílica dopados com rodamina B utilizando em baixa temperatura (ambiente), o processo sol-gel. As amostras foram obtidas após a sono-hidrólise do tetraetilortosilicato [TEOS, Si(OC2H5)4], em meio ácido pH~2, (HCl). A dopagem foi realizada adicionando-se soluções alcoólicas de rodamina previamente definidas à solução hidrolisada e o pH ajustado para ~ 5 (NH4OH). A secagem e o envelhecimento foram realizados à temperatura de 40 ºC por até 90 dias. Os xerogéis foram tratados em temperaturas de até 500 º em atmosfera de Hélio e Oxigênio. As caracterizações foram realizadas através da Espectroscopia de Absorção e Emissão UV/Vis , Infravermelho e Análise Térmica Diferencial (DTA). Os espectros de absorção apresentam bandas centradas em 557 nm e mostra o máximo de intensidade para as amostras sem tratamento térmico. Comportamento semelhante foi observado para os espectros de emissão. O espectro de infravermelho foi feito para o pó de rodamina puro e para o xerogel dopado e encontro-se que a maioria dos picos presentes para o pó puro eram ausentes no espectro do xerogel. Estudos de Análise Térmica Diferencial (DTA) foram realizados e não se pbservou nenhum pico associado à presença do corante no xerogel. / This work describe systematically the preparation of rhodamine B doped silica xerogels using the low temperature sol-gel process. The samples were obtained after hydrolysis under ultrasonic stimulation of tetraethylorthosilicate [TEOS, Si(OC2H5)4], in acid conditions pH~2, (HCl). The doping was carried out adiction of ethanolic rhodamine B previously defined to the hidrolysis solution and the pH of resulting sol was adjusted to ~5 (NH4OH). The drying and aging of samples were carried out at 40 ºC for until 90 days. The xerogels were treated in temperatures of until 500 ºC in atmospheres of Helium and Oxygen. The characterizations were carried out through Spectroscopy of Absorption and Emission UV/Vis, Infrared and Differential Thermal Analysis (DTA). Absorption spectra shows bands centered at 557 nm and shows maximum intensity for samples without treatment thermal. Identical behavior was observed in the emission spectra. IR spectra were taken for pure rhodamine powder and rhodamine doped silica xerogels and found that most of the peaks present in pure rhodamine powder spectrum were absent in the spectra of trapped rhodamine SiO2 xerogels. Studies of Thermal Differential Analysis (DTA) were carried out and no peaks were associated to the presence of the dye in the xerogel.

Made available in DSpace on 2014-06-11T19:35:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-09-25Bitstream added on 2014-06-13T19:45:04Z : No. of bitstreams: 1 francisco_cs_dr_araiq.pdf: 2557839 bytes, checksum: 6e50bdc3b6d442d52debf1600ec04bb1 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho foram sintetizados e caracterizados complexos de lantanídeos contendo ligantes organofosforados. Os ligantes utilizados neste trabalho foram: ácido difenilfosfínico (HDPP), ácido benzil(fenil)fosfínico (HBPP) e ácido (1,4-fenilenodimetileno)-bis-(fenilfosfínico) (H2PMPP). Os compostos foram obtidos através de reação de precipitação e síntese hidrotérmica em diferentes condições. Para os compostos obtidos através de reação de precipitação, observa- se uma tendência a formação de partículas esféricas e aglomerados. Os complexos sintetizados via síntese hidrotérmica apresentam partículas em forma de bastões e formação de aglomerados. Os espectros de luminescência indicam a presença de dois ou mais sítios de simetria para os difenilfosfinatos de ítrio dopados com európio (Y(DPP)3:Eu(%)). Para os benzil(fenil)fosfinatos (Y(BPP)3:Eu(%)) e (1,4- fenilenodimetileno)-bis-(fenilfosfinatos) (Y(PMPP)3:Eu(%)) de ítrio dopados com európio foi observada a presença da transição 5 D0→7 F0, indicando que o íon Eu3+ nestes compostos ocupa um sítio de simetria sem centro de inversão. As curvas de decaimento de estado excitado sugerem a presença de dois ou mais sítios de simetria nos complexos Y(DPP)3:Eu(%). Para os compostos Y(BPP)3:Eu(%) e Y2(PMPP)3:Eu(%) foi observada a contribuição de apenas um sítio de simetria. Os parâmetros de intensidades Ω2 e Ω4 dos complexos Y(DPP)3:Eu(%) indicam que o íon Eu3+ ocupa sitos de simetria semelhantes nos difenilfosfinatos, e nos compostos Y(BPP)3:Eu(%) e Y2(PMPP)3:Eu(%) indicam a presença de sítios de baixa simetria. A emissão do Eu3+ e Tb3+ nos Y(DPP)3:CeEuTb(%) aumenta em função da concentração do íon Ce3+ , indicando a ação do cério como íon sensibilizador nestes compostos através dos processos de transferência de energia, do íon Ce(III) para os íons ativadores Eu(III) e Tb(III)... / In this work lanthanides complexes containing organophosphorus ligands were synthesized and characterized. The following ligands were used diphenilphosphinic acid H(DPP), benzyl(phenyl)phosphinic acid (BPP) and (1,4- phenylenedimethylene)-bis-(phenylphosphinic) (PMPP). The compounds obtained through hydrothermal route presented a greater structural organization of the system regarding the obtained complexes by precipitation. For obtained compounds through precipitation, spherical- particle and cluster formation are observed. The synthesized compounds through hydrothermal rout presented particles in sticks form and cluster formation. The luminescence spectral indicatee the presence of two or more symmetry sites to europium-doped diphenylphosphinate of yttrium complexes (Y(DPP)3:Eu%). For europium-doped benzyl(phenyl)phosphinate (Y(BPP)3:Eu%) and europium doped (1-4-phenylenedimethylene)-bis- (phenylphosphinate) (Y2(PMPP)3:Eu%) complexes the presence only a non- centrossymetry site was observed. The presence of 5 D0→7 F0 an indicative of the low symmetry in about Eu(III) ion. The values of emission lifetime confirmed the presence of two or more symmetry sites to (Y(DPP)3:Eu%). The lifetime for (Y(BPP)3:Eu%) and (Y2(PMPP)3:Eu%) complexes confirmed the presence a non-centrossymmetry sites contribuition only. were observed the presence only a non-centrossymetry site, the presence of 0-0 transition is indicative that the symmetry in about Eu(III) low. The values of emission lifetime confirmed the presence a non-centrossymmetry site contribution only. xi The intensity parameters Ω2 e Ω4 indicate that Y(BPP)3:Eu(%) e Y(PMPP)3:Eu(%) present non-centrossimetric sites. The emission of Eu3+ and Tb3+ in the Y(DPP)3:CeEuTb(%)is favored with the increasing of the concentration cerium indicatin that energy transfer process process of Ce(III) to Eu (III) and Tb (III) is favored... (Complete abstract click electronic access below)

Doctor of Philosophy / Department of Chemistry / Christine M. Aikens / The remarkable optical and luminescence properties of noble metal nanoparticles (with diameters < 2 nm) attract researchers due to potential applications in biomedicine, photocatalysis, and optoelectronics. Extensive experimental investigations on luminescence properties of thiolate-protected gold and silver nanoclusters during the past decade have failed to unravel their exact photoluminescence mechanism. Herein, density functional and time-dependent density functional theory (DFT and TDDFT) calculations are performed to elucidate electronic-level details of several such systems upon photoexcitation. Multiple excited states are found to be involved in photoemission from Au₂₅(SR)₁₈– nanoclusters, and their energies agree well with experimental emission energies. The Au₁₃ core-based excitations arising due to electrons excited from superatom P orbitals into the lowest two superatom D orbitals are responsible for all of these states. The large Stokes shift is attributed to significant geometrical and electronic structure changes in the excited state. The origin of photoluminescence of Ag₂₅(SR)₁₈– nanoclusters is analogous to their gold counterparts and heteroatom doping of each cluster with silver and gold correspondingly does not affect their luminescence mechanism. Other systems have been examined in this work to determine how widespread these observations are. We observe a very small Stokes shift for Au₃₈(SH)₂₄ that correlates with a relatively rigid structure with small bond length changes in its Au₂₃ core and a large Stokes shift for Au₂₂(SH)₁₈ with a large degree of structural flexibility in its Au₇ core. This suggests a relationship between the Stokes shift of gold−thiolate nanoparticles and their structural flexibility upon photoexcitation. The effect of ligands on the geometric structure and optical properties of the Au₂₀(SR)₁₆ nanocluster is explored. Comparison of the relative stability and optical absorption spectra suggests that this system prefers the [Au₇(Au₈SR₈)(Au₃SR₄)(AuSR₂)₂] structure regardless of whether aliphatic or aromatic ligands are employed. The real-time (RT) TDDFT method is rapidly gaining prominence as an alternative approach to capture optical properties of molecular systems. A systematic benchmark study is performed to demonstrate the consistency of linear-response (LR) and RT-TDDFT methods for calculating the optical absorption spectra of a variety of bare gold and silver nanoparticles with different sizes and shapes.

A dosimetria in vivo têm se tornado um papel importante para o tratamento da irradiação total da pele dentro de um rigoroso programa de garantia de qualidade que deve ser parte integrante nos departamentos radioterápicos. A dosimetria em TSI é difícil, devido à complexidade do tratamento em avaliar a uniformidade da dose e medir a dose absorvida em profundidades rasas em toda extensão da superfície cutânea, tendo como consequência uma ampla variação na distribuição da dose. Os TLDs tem provado ser muito úteis para a distribuição e verificação da dose prescrita para o paciente, pois a dose pode diferir de local para local devido a geometria do corpo do paciente, sobreposições de estruturas e assimetrias do campo de radiação. A utilização de TLDs in vivo pode identificar variações da dose prescrita por apresentarem uma grande exatidão e precisão nas medidas. Nos setores de radioterapia vêm sendo empregado vários tipos de dosímetros, os mais utilizados são o Flureto de Lítio (TLD-100), onde obtém uma longa história neste tipo de aplicação. Novos materiais dosímetricos vêm ganhado grande importância na aplicação da dosímetria de feixes clínicos de elétrons, como o Sulfato de Cálcio dopado com Disprósio (TL) e o Óxido de Alumínio dopado com Carbono (OSL), este trabalho avalia o desempenho dosímetrico dos respectivos dosímetros termoluminescentes e a luminescência opticamente estimulada na aplicação da dosímetria de feixes clínicos de elétrons utilizados na irradiação total da pele. / In vivo dosimetry has become an important role for the treatment of total skin irradiation within a rigorous quality assurance program that should be an integral part of the radiotherapy departments. TSI dosimetry is difficult because of the complexity of the treatment in assessing dose uniformity and measuring the dose absorbed at shallow depths throughout the skin surface extent, resulting in a wide variation in dose distribution. The TLDs have proven to be very useful for the distribution and verification of the dose prescribed for the patient as the dose may differ from place to place due to patient body geometry, overlapping of structures and asymmetries of the radiation field. The use of TLDs in vivo can identify variations in the prescribed dose because its measurement accuracy and great precision. Several types of dosimeters have been used in the radiotherapy sectors, the most commonly used are Lithium Fluride (TLD-100), where it obtains a long history in this type of application. New dosimetric materials have gained great importance in the dosimetry of clinical electron beams, such as Dysprosium-doped Calcium Sulphate (TL) and Carbon doped (OSL) based Aluminum Oxide, This work evaluates the performance of the respective thermoluminescent dosimeters and the optically stimulated luminescence in the dosimetry of clinical electron beams used in total irradiation of the skin.