Den Fokus dieser Arbeit bildet die Untersuchung und die konzeptionelle Verbesserung der wichtigsten Eigenschaften organischer Leuchtdioden (OLED) – die Lebensdauer und die Quantenausbeute, welche sich durch die interne und externe Quanteneffizienz kategorisieren lässt. Es werden monochrome pin- Strukturen betrachtet, welche die Basis für Displays und weiße Multifarben- OLEDs darstellen. Die Auswirkung der Ladungsbalance auf die interne Quanteneffizienz wird untersucht. Dabei finden Triplettemitter Verwendung, da diese aus spinstatistischen Gründen viermal effizienter als fluoreszente Substanzen sind. Für hohe Effizienzen ist die ambipolare Ladungs- und Exzitonenverteilung in der Emissionsschicht mit breiter und zentraler Rekombinationszone anzustreben. Dies wird durch einen energetisch barrierefreien Schichtaufbau über die Auswahl der Matrix-, Blocker- und Transportmaterialien bezüglich geeigneter Transportniveaus und Ladungsträgerbeweglichkeiten erreicht. Bei roten OLEDs wird durch den Austausch des Lochblockers mit geeignetem LUMO die Elektroneninjektion in die löcherleitende Emissionsschicht erhöht und dadurch die Ladungsbalance maximiert. Damit werden externe Quanteneffizienzen von 20% erzielt, was dem Maximum der internen Quanteneffizienz von 100% entspricht. Des Weiteren werden neue Konzepte zur höheren Lichtauskopplung entwickelt. Aufgrund interner Totalreflexionen bleiben 80% der Photonen in Organikund Substratmoden gefangen was die externe Quanteneffizienz begrenzt. Eine deutliche Reduzierung dieser Moden wird bei OLEDs mit stärkeren Mikrokavitäten durch ITO/Silber-Anoden festgestellt. Die energetische und räumliche Umverteilung der Photonen verringert Totalreflexionen womit die Auskopplung bzw. die externe Quanteneffizienz um den Faktor 1,5 erhöht wird. Für rote OLEDs werden dadurch Rekordwerte von 26% externer Quanteneffizienz und einer Leistungseffizienz von 81 lm/W erzielt. Die auftretende winkelabhängige Farbverschiebung kann durch streuende Mikrolinsenfolien reduziert werden. Für verbesserte Auskopplung ohne Farbverschiebung werden Streukonzepte mit rauen Schichten getestet. Kristalline Schichten innerhalb der Organik beeinflussen allerdings den elektrischen Teil der OLED. Dies wird durch extrinsische Verlagerung der Streuschicht ausgeschlossen. Weiterhin wird die intrinsische Degradation von OLEDs mit phosphoreszenten Iridium-Emittern untersucht. Als Hauptursache werden strominduzierte chemische Reaktionen zwischen Emittermolekülen und anderen umgebenden Substanzen identifiziert. Die Akkumulation von Ladungsträgern und Exzitonen fördert diese Reaktionen. Als Zerstörungsmechanismus wird die Dissoziation der Iridium-Emitter mit folgender irreversibler Komplexbildung der Fragmente mit Umgebungsmaterialien wie dem Lochblocker festgestellt. Die OLED-Lebensdauer korreliert dabei doppelt- logarithmisch mit der Anzahl der Komplexe. Die chemische Reaktivität der Umgebungsmaterialien bestimmt die Stärke der Komplexbildung. Mit inerten Substanzen konnte bei roten OLEDs mit 10 Millionen Stunden bei Display-Helligkeit ein Weltrekord erzielt werden. Die geringe Degradation erfordert Extrapolationsmethoden. Es wird ein gestreckt exponentielles Verhalten der Helligkeitsabnahme beobachtet. Eine neue Fehleranalyse der Extrapolation ermöglicht die Angabe von Lebensdauer-Infima bei sehr stabilen OLEDs.

The first part of this dissertation deals with the application of a luminescence quenching method to measure diffusion and permeation coefficients of oxygen in polymers. Most luminescence oxygen sensors do not follow linearity of the Stern-Volmer (SV) equation due to heterogeneity of luminophore in the polymer matrix, thus the complexity of data analysis is increased. To circumvent this limitation, inverted fluorescence microscopy is utilized in this work to investigate the SV response of the sensors at the micron-scale. In these diffusion experiments, oxygen concentration is measured by luminescence changes in regions with high SV constants and good linearity. Thus, we avoid numerical complexity of combining nonlinear SV equation with a diffusion model. This technique allows us to measure oxygen diffusion properties in different type of polymers like transparent, opaque, free-standing polymers and polymers that cannot be cast into free standing films and polymer composites. In the second part of this thesis, we have explored the effect of Ag-Cu alloy nanoparticles on the emission intensity of luminophores at their close proximity. Alloy nanoparticles offer additional degrees of freedom for tuning their optical properties by altering atomic composition and atomic arrangement and thus can be an attractive option for manipulating signal of a wide range of luminophores. In this work, surface plasmon resonance spectrum of Ag-Cu alloy nanoparticles deposited by sputtering was easily tuned in wide wavelength range by varying one experimental condition- annealing temperature. Large metal enhanced luminescence for different luminophores viz Alexa Fluor 594 and Alexa Fluor 488 were achieved at the vicinity of Ag-Cu nanoparticles when maximum spectral overlap between SPR spectra of Ag-Cu nanoparticles and the emission and absorption spectra of the luminophores occur. We also studied the effect of composition of Ag-Cu nanoparticles synthesized by the polyol process on the luminescence of low quantum yield dye Cy3. In the third part of this thesis, quenching effect of Cu nanoparticles on CdSe/ZnS nanocrystal quantum dots has been explored. As Cu nanoparticles have comparable dielectric properties with gold nanoparticles, they are expected to show similar quenching effects. It was found that Cu is an efficient quencher of fluorescence from CdSe/ZnS quantum dots and the quenching effect is due to resonance energy transfer from quantum dots to Cu nanoparticles.

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In the past few years, intensive research efforts have been devoted to studying new approaches to controlling the photon emission of quantum emitters (QEs), especially for telecommunication applications. These approaches rely on tailoring the QE\'s radiation, usually assessed via well-known figures-of-merit such as lifetime (τ) and quantum efficiency (η). Controlling the QE\'s photon emission is important because the faster its photons are emitted, the greater is the number of times it returns to the excited state per second. Therefore, it is crucial to create additional decay channels to reduce τ, which necessarily requires increasing the Purcell factor (P). One of the most promising approaches to increase P involves a new class of metamaterials, known as hyperbolic metamaterials (HMM). This class of materials exhibits pronounced anisotropy, with the parallel and perpendicular permittivity tensor elements (with respect to the anisotropy axis) presenting opposite signs, resulting in an open hyperboloidal isofrequency surface (IS). This unusual IS shape leads to the most outstanding feature of HMMs, namely, the existence of photonic modes with wavenumber (k) much larger than those in free-space (k0), known as high-k modes. By engineering these modes, it is possible to manipulate the HMM photonic density of states (PDoS), thus controlling the QE\'s radiation parameters. The simplest approach to designing HMM is by means of a planar stack of alternating thin metal and dielectric layers. However, the finite thickness of these layers induces spatial dispersion, making the extraction of effective parameters (homogenization) of these media a challenging task. In this context, we propose in this thesis a new constitutive parameter retrieval approach that takes spatial dispersion into account for all electromagnetic parameters of the medium. We demonstrate that the real part of the dispersion curve flattens out (correspondingly with a large imaginary part) because of the absence of propagating modes inside the metamaterial. This flat region is strongly dependent on the layer thicknesses and is a direct manifestation of spatial dispersion. Moreover, we demonstrate that the QE\'s lifetime calculation is overestimated if this effect is not taken into account in the homogenization procedure, which is detrimental for telecommunication applications. Moreover, we demonstrate how to enhance P by a factor greater than 100 with the use of HMMs. However, most of the QE dissipated power couples into the HMM as high-k modes (which do not propagate in free-space). Therefore, the energy is thermally dissipated inside the HMM with a consequent reduction of η . Some authors have resorted to nano-patterned HMMs (NPHM) to convert the high-k modes into free-space modes (k≤k0) aiming at increasing η. However, much of the NPHMs designs still rely on computationally costly three dimensional (3D) numerical simulations. Thus, we also propose in this thesis a new semi-analytical method to model, both in two- and three-dimensions (2D and 3D, respectively), the radiation emission of QEs interacting with nano-patterned structures. The low computational cost of this method makes it attractive for mapping P and η as function of the QE and NPHM relative position. This mapping is a helpful tool to understand the decay behavior of the whole system since QEs are arbitrarily distributed and oriented inside the NPHM. The analytically calculated decay curve allows the systems effective quantum efficiency (ηeff) and Purcell factor (Peff) to be directly obtained assuming multiple arbitrarily distributed electromagnetic sources. In this sense, we propose here a new procedure to optimize the NPHM geometrical parameters to maximize ηeff while achieving the desired Peff. We apply the proposed model to an NPHM composed of nine Ag/SiO2 layers, with the polymer host layer embedded with Rhodamine 6G, to maximize ηeff for a specified tenfold increase of Peff. This procedure allowed ηeff to be increased by 69% and 170% for one- and two-dimensional nano-patterning, respectively. Moreover, the time required to build the P and η maps (used in the calculation of the decay behavior) is reduced by approximately 96% when compared to those numerically calculated via FDTD. This procedure paves the way to the realization of new high-speed and efficient light sources for telecommunication applications. / Nos últimos anos, intensivo esforço tem sido devotado para o estudo de novas método para o controla da missão de fótons de emissores quânticos (EQs), especialmente para aplicações em telecomunicações. Estes métodos dependem da adaptação da radiação dos EQs, geralmente avaliadas por meio das bem conhecidas figuras de mérito, como o tempo de meia vida (τ) e a eficiência quântica (η). O controle da emissão de fótons é importante pois quanto mais rápido os fótons são emitidos, maior é o número de vezes que o EQ retorna ao seu estado excitado por segundo. Portanto, é crucial criar canais de decaimento adicionais para reduzir τ, o que necessariamente requer o aumento do fator de Purcell (P). Uma das abordagens mais promissoras para aumentar P envolve uma nova classe de metamateriais, conhecida como metamateriais hiperbólicos (MHs). Esta classe de materiais apresenta pronunciada anisotropia, onde os elementos paralelo e perpendicular do tensor de permissividade (em relação ao eixo de anisotropia) apresentam sinais opostos, resultando em uma superfície de isofrequência (SI) hiperboloidal aberta (IS). Essa forma incomum de SI leva à característica mais marcante dos MHs, a existência de modos fotônicos com número de onda (k) muito maior do que aqueles no espaço livre (k0), conhecidos como modos alto-k. Ao manipular esses modos, é possível manipular a densidade de estados fotônicos (DES) dos MHs, controlando assim os parâmetros de radiação do QE. A abordagem mais simples para a criação de MHs é por meio de uma pilha plana de camadas metálicas e dielétricas alternadas. Entretanto, a espessura finita dessas camadas induz a dispersão espacial, tornando a extração de parâmetros efetivos (homogeneização) destes meios uma tarefa desafiadora. Neste contexto, propomos nesta tese uma nova abordagem de recuperação de parâmetros constitutivos a dispersão espacial de todos os parâmetros eletromagnéticos do meio é levada em consideração. Nós demonstramos que a parte real da curva de dispersão se aplaina (correspondentemente com uma grande parte imaginária) devido à ausência de modos propagantes dentro do metamaterial. Esta região plana é fortemente dependente das espessuras das camadas e é uma manifestação direta da dispersão espacial Além disso, nós mostramos que se a dispersão espacial não for corretamente considerada no processo de homogeneização, o tempo de meia vida do EQ pode ser superestimado, o que é prejudicial para aplicações de telecomunicações. Além disso, demonstramos como melhorar P por um fator maior que 100 com o uso de MHs. a maior parte da potência dissipada pelos EQs são acopladas nos MHs como modos de alto-k (que não se propagam no espaço livre). Portanto, a energia é dissipada termicamente no interior do MH, resultando em uma redução de η. Alguns autores recorreram a MHs nano-estruturados (MHNE) para converter os modos alto-k em modos de espaço livre (k≤k0) visando o aumento de η. No entanto, muitos dos projetos do NPHM ainda dependem de simulações numéricas tridimensionais (3D) computacionalmente dispendiosas. Assim, também propomos nesta tese um novo método semi-analítico para modelar, tanto em duas como em três dimensões (2D e 3D, respectivamente), a emissão de radiação de EQs interagindo com estruturas nano-estruturadas. O baixo custo computacional deste método faz com que seja atrativo para o mapeamento de P e η em função da posição relativa do EQ e do MHNE. Esse mapeamento é uma ferramenta útil para entender o comportamento de decaimento de todo o sistema, já que os EQs são arbitrariamente distribuídos e orientados dentro do MHNE. A curva de decaimento calculada analiticamente permite que a eficiência quântica efetiva do sistema (ηeff) e o fator de Purcell (Peff) sejam obtidos diretamente, assumindo múltiplas fontes eletromagnéticas arbitrariamente distribuídas. Neste sentido, propomos aqui um novo procedimento para otimizar os parâmetros geométricos do MHNE visando a maximização de ηeff enquanto Peff é aumentado à um valor desejado. Aplicamos o modelo proposto a um MHNE composto por nove camadas de Ag/SiO2, com a camada de polímero embutida com Rodamina 6G, visando maximizar ηeff para um aumento de dez vezes de Peff. Este procedimento permitiu que o ηeff fosse incrementado em 69% e 170% para nano-estruturas uni e bidimensionais, respectivamente. Além disso, o tempo necessário para construir os mapas P e η (utilizados no cálculo da curva de decaimento) é reduzido em aproximadamente 96% quando comparado com os calculados numericamente via FDTD. Este procedimento abre caminho para o desenvolvimento de novas fontes de luz de alta velocidade e eficiência para aplicações de telecomunicações.

In the past few years, intensive research efforts have been devoted to studying new approaches to controlling the photon emission of quantum emitters (QEs), especially for telecommunication applications. These approaches rely on tailoring the QE\'s radiation, usually assessed via well-known figures-of-merit such as lifetime (τ) and quantum efficiency (η). Controlling the QE\'s photon emission is important because the faster its photons are emitted, the greater is the number of times it returns to the excited state per second. Therefore, it is crucial to create additional decay channels to reduce τ, which necessarily requires increasing the Purcell factor (P). One of the most promising approaches to increase P involves a new class of metamaterials, known as hyperbolic metamaterials (HMM). This class of materials exhibits pronounced anisotropy, with the parallel and perpendicular permittivity tensor elements (with respect to the anisotropy axis) presenting opposite signs, resulting in an open hyperboloidal isofrequency surface (IS). This unusual IS shape leads to the most outstanding feature of HMMs, namely, the existence of photonic modes with wavenumber (k) much larger than those in free-space (k0), known as high-k modes. By engineering these modes, it is possible to manipulate the HMM photonic density of states (PDoS), thus controlling the QE\'s radiation parameters. The simplest approach to designing HMM is by means of a planar stack of alternating thin metal and dielectric layers. However, the finite thickness of these layers induces spatial dispersion, making the extraction of effective parameters (homogenization) of these media a challenging task. In this context, we propose in this thesis a new constitutive parameter retrieval approach that takes spatial dispersion into account for all electromagnetic parameters of the medium. We demonstrate that the real part of the dispersion curve flattens out (correspondingly with a large imaginary part) because of the absence of propagating modes inside the metamaterial. This flat region is strongly dependent on the layer thicknesses and is a direct manifestation of spatial dispersion. Moreover, we demonstrate that the QE\'s lifetime calculation is overestimated if this effect is not taken into account in the homogenization procedure, which is detrimental for telecommunication applications. Moreover, we demonstrate how to enhance P by a factor greater than 100 with the use of HMMs. However, most of the QE dissipated power couples into the HMM as high-k modes (which do not propagate in free-space). Therefore, the energy is thermally dissipated inside the HMM with a consequent reduction of η . Some authors have resorted to nano-patterned HMMs (NPHM) to convert the high-k modes into free-space modes (k≤k0) aiming at increasing η. However, much of the NPHMs designs still rely on computationally costly three dimensional (3D) numerical simulations. Thus, we also propose in this thesis a new semi-analytical method to model, both in two- and three-dimensions (2D and 3D, respectively), the radiation emission of QEs interacting with nano-patterned structures. The low computational cost of this method makes it attractive for mapping P and η as function of the QE and NPHM relative position. This mapping is a helpful tool to understand the decay behavior of the whole system since QEs are arbitrarily distributed and oriented inside the NPHM. The analytically calculated decay curve allows the systems effective quantum efficiency (ηeff) and Purcell factor (Peff) to be directly obtained assuming multiple arbitrarily distributed electromagnetic sources. In this sense, we propose here a new procedure to optimize the NPHM geometrical parameters to maximize ηeff while achieving the desired Peff. We apply the proposed model to an NPHM composed of nine Ag/SiO2 layers, with the polymer host layer embedded with Rhodamine 6G, to maximize ηeff for a specified tenfold increase of Peff. This procedure allowed ηeff to be increased by 69% and 170% for one- and two-dimensional nano-patterning, respectively. Moreover, the time required to build the P and η maps (used in the calculation of the decay behavior) is reduced by approximately 96% when compared to those numerically calculated via FDTD. This procedure paves the way to the realization of new high-speed and efficient light sources for telecommunication applications. / Nos últimos anos, intensivo esforço tem sido devotado para o estudo de novas método para o controla da missão de fótons de emissores quânticos (EQs), especialmente para aplicações em telecomunicações. Estes métodos dependem da adaptação da radiação dos EQs, geralmente avaliadas por meio das bem conhecidas figuras de mérito, como o tempo de meia vida (τ) e a eficiência quântica (η). O controle da emissão de fótons é importante pois quanto mais rápido os fótons são emitidos, maior é o número de vezes que o EQ retorna ao seu estado excitado por segundo. Portanto, é crucial criar canais de decaimento adicionais para reduzir τ, o que necessariamente requer o aumento do fator de Purcell (P). Uma das abordagens mais promissoras para aumentar P envolve uma nova classe de metamateriais, conhecida como metamateriais hiperbólicos (MHs). Esta classe de materiais apresenta pronunciada anisotropia, onde os elementos paralelo e perpendicular do tensor de permissividade (em relação ao eixo de anisotropia) apresentam sinais opostos, resultando em uma superfície de isofrequência (SI) hiperboloidal aberta (IS). Essa forma incomum de SI leva à característica mais marcante dos MHs, a existência de modos fotônicos com número de onda (k) muito maior do que aqueles no espaço livre (k0), conhecidos como modos alto-k. Ao manipular esses modos, é possível manipular a densidade de estados fotônicos (DES) dos MHs, controlando assim os parâmetros de radiação do QE. A abordagem mais simples para a criação de MHs é por meio de uma pilha plana de camadas metálicas e dielétricas alternadas. Entretanto, a espessura finita dessas camadas induz a dispersão espacial, tornando a extração de parâmetros efetivos (homogeneização) destes meios uma tarefa desafiadora. Neste contexto, propomos nesta tese uma nova abordagem de recuperação de parâmetros constitutivos a dispersão espacial de todos os parâmetros eletromagnéticos do meio é levada em consideração. Nós demonstramos que a parte real da curva de dispersão se aplaina (correspondentemente com uma grande parte imaginária) devido à ausência de modos propagantes dentro do metamaterial. Esta região plana é fortemente dependente das espessuras das camadas e é uma manifestação direta da dispersão espacial Além disso, nós mostramos que se a dispersão espacial não for corretamente considerada no processo de homogeneização, o tempo de meia vida do EQ pode ser superestimado, o que é prejudicial para aplicações de telecomunicações. Além disso, demonstramos como melhorar P por um fator maior que 100 com o uso de MHs. a maior parte da potência dissipada pelos EQs são acopladas nos MHs como modos de alto-k (que não se propagam no espaço livre). Portanto, a energia é dissipada termicamente no interior do MH, resultando em uma redução de η. Alguns autores recorreram a MHs nano-estruturados (MHNE) para converter os modos alto-k em modos de espaço livre (k≤k0) visando o aumento de η. No entanto, muitos dos projetos do NPHM ainda dependem de simulações numéricas tridimensionais (3D) computacionalmente dispendiosas. Assim, também propomos nesta tese um novo método semi-analítico para modelar, tanto em duas como em três dimensões (2D e 3D, respectivamente), a emissão de radiação de EQs interagindo com estruturas nano-estruturadas. O baixo custo computacional deste método faz com que seja atrativo para o mapeamento de P e η em função da posição relativa do EQ e do MHNE. Esse mapeamento é uma ferramenta útil para entender o comportamento de decaimento de todo o sistema, já que os EQs são arbitrariamente distribuídos e orientados dentro do MHNE. A curva de decaimento calculada analiticamente permite que a eficiência quântica efetiva do sistema (ηeff) e o fator de Purcell (Peff) sejam obtidos diretamente, assumindo múltiplas fontes eletromagnéticas arbitrariamente distribuídas. Neste sentido, propomos aqui um novo procedimento para otimizar os parâmetros geométricos do MHNE visando a maximização de ηeff enquanto Peff é aumentado à um valor desejado. Aplicamos o modelo proposto a um MHNE composto por nove camadas de Ag/SiO2, com a camada de polímero embutida com Rodamina 6G, visando maximizar ηeff para um aumento de dez vezes de Peff. Este procedimento permitiu que o ηeff fosse incrementado em 69% e 170% para nano-estruturas uni e bidimensionais, respectivamente. Além disso, o tempo necessário para construir os mapas P e η (utilizados no cálculo da curva de decaimento) é reduzido em aproximadamente 96% quando comparado com os calculados numericamente via FDTD. Este procedimento abre caminho para o desenvolvimento de novas fontes de luz de alta velocidade e eficiência para aplicações de telecomunicações.

Dans le domaine de la photodétection infrarouge (IR) haute performance refroidie, le photodétecteur à superréseaux (SR) InAs/GaSb est une filière émergente qui peut compléter les technologies déjà établies. Grâce à des années de recherche, l'Institut d'Electronique du Sud (IES) de l'Université de Montpellier a développé une expertise sur la croissance du matériau SR InAs/GaSb par épitaxie par jets moléculaires et sur la fabrication technologique des photodiodes pin dont les performances sont à l'état de l'art mondial dans le moyen IR (3-5µm). Au cours de cette thèse, nous avons étudié deux périodes différentes de SR comme zone active de photodiodes pin ayant une longueur d'onde de coupure à 5 µm à 80K : une riche en InAs (InAs-rich) et l'autre riche en GaSb (GaSb-rich). Ces structures SR présentent des caractéristiques électriques et électro-optiques très différentes. Notamment, les densités de courant de la structure InAs-rich sont très bonnes, de l'ordre de 10-8A/cm2 à 80K, alors que celles de la structure GaSb-rich sont deux décades plus élevées. L'objectif de cette thèse était donc d'analyser les performances de ces photodiodes. Pour cela, nous avons développé une méthode de simulation avec l'outil TCAD SILVACO. Appliquée tout d'abord aux structures InAs-rich, nous avons mis en évidence que ces diodes sont limitées à basse température (typiquement < 120K) par le courant de génération-recombinaison et/ou par le courant tunnel assisté par pièges. La durée de vie extraite de la simulation suit une variation en T-1/2, démontrant que les mécanismes limitant les photodiodes est la génération-recombinaison SRH. Appliquée aux structures GaSb-rich, l'approche SILVACO ne peut expliquer les résultats en courant. Nous démontrons que ces résultats sont fortement liés à la présence du champ électrique dans la zone d'absorption du composant. Cela génère à faible polarisation, un fort courant tunnel, au travers des états Wannier-Stark localisés, qui pénalise fortement le courant d'obscurité et cela malgré des améliorations obtenues au niveau du matériau. Pour finir, nous établissons des règles de dimensionnement de structures à barrière et nous proposons une structure à SR pour le lointain infrarouge. / Among the high performance cooled infrared (IR) photodetector systems, the InAs/GaSb superlattice (SL) is an emerging material which may complement the currently technologies already established. Over the last 10 years, the Institut d'Electronique du Sud (IES) of the University of Montpellier has developed skills in both the growth of SL materials by molecular beam epitaxy and the process fabrication of pin photodiodes. The photodiode fabricated by the IES group are at the state of the art in the mid IR (3 – 5 μm). During this thesis, we studied two structures with different SL periods for the pin active zone showing the same cut-off wavelength of 5 μm at 80K: the structure called InAs-rich structure presents InAs layer thicker than the GaSb layer in each SL period while this configuration is reversed in the case of the GaSb-rich structure. These SL structures have very different electrical and electro-optical characteristics. In particular, the current densities of the InAs-rich structure are very good, about 10-8 A/cm2 at 80K - two orders of magnitude greater than that of GaSb-rich. The aim of this thesis work was therefore to analyze the performance of these photodiodes. For this purpose, we developed a simulation method with the SILVACO TCAD tool. Using this tool, we found that the InAs-rich diodes are limited at low temperatures (typically under 120K) by generation recombination and/or by assisted tunneling currents. The lifetimes extracted from the simulation follows the T-1/2 law, which demonstrates that the limiting mechanism is SRH recombination. However, we found that we could not study the current densities of the GaSb-rich structure using the same procedure. We demonstrate that these results are strongly related to the presence of the electric field in the absorption zone of the device. This electric field generates, at low biases, a strong tunneling current through localized Wannier-Stark states, which strongly limits the overall current despite material improvements. Finally, we define the design conditions to achieve an optimized SL barrier structure and propose a design for SL structures targeting the long wavelength domain.

Made available in DSpace on 2014-06-11T19:26:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-02-10Bitstream added on 2014-06-13T20:47:02Z : No. of bitstreams: 1 graca_jp_me_jabo.pdf: 256015 bytes, checksum: 389bd2988baccfc63d2527a482a1e26f (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A cana-de-açúcar (Saccharum spp.) é uma das principais culturas das regiões tropicais, cuja produtividade agrícola pode ser afetada pelo déficit hídrico. Para investigar o processo de tolerância e sensibilidade ao déficit hídrico, diferentes parâmetros fisiológicos foram avaliados em cultivares de cana-de-açúcar tolerantes (SP83-2847 e CTC15) e sensível (SP86-155) ao déficit hídrico. A deficiência hídrica afetou todo o aparato fotossintético das plantas de forma diferenciada dentro e entre as cultivares. A taxa fotossintética e condutância estomática diminuíram significativamente para todas as cultivares submetidas ao estresse. Nas plantas controle das cultivares (cv) tolerantes SP83-2847 e CTC15 observou-se que a taxa fotossintética apresentou valores mais altos em comparação a cultivar sensível SP86-155. Resultados do teor relativo de água mostraram que a cultivar CTC15 apresentou melhor condição hídrica durante o período de déficit hídrico. A eficiência quântica do fotossistema II da cultivar SP83-2847 mostrou maior estabilidade nos últimos dias do tratamento experimental, sugerindo que o decréscimo do teor relativo de água estimulou o ajuste da capacidade fotossintética frente às alterações da disponibilidade hídrica. De modo geral, as cultivares SP83-2847 e CTC15, consideradas tolerantes, sob déficit hídrico exibiram melhor desempenho em relação a cultivar sensível SP86-155. Os dados permitem sugerir que tais parâmetros fisiológicos podem ser empregados na avaliação e distinção de genótipos de cana-de-açúcar tolerantes e sensíveis ao déficit hídrico. / The sugarcane (Saccharum spp.) is one of the main crops cultivated in tropical areas, whose agricultural productivity can be affected by drought. To investigate the tolerance and sensitivity process to water deficit, various physiological parameters were evaluated in sugarcane cultivars considered tolerant (SP83-2847 and CTC15) and sensitive (SP86-155) to drought. The water deficit affected the entire photosynthetic apparatus of all plants in different manners, inside and among cultivars. The photosynthetic rate and stomatal conductance decreased significantly for all cultivars, submitted to water stress. In control plants of the tolerant cultivars SP83-2847 and CTC15, it was observed that the photosynthetic rate showed better values in comparison to sensitive cultivar SP86-155. According to relative water content results of the cultivar CTC15 showed better condition water performance during the drought. The quantum efficiency photosystem II of the cultivar SP83-2847 showed greater stability in recent days of the experimental treatment, suggesting that the decline in the relative water content stimulated the adjustment of photosynthetic capacity to face the changes in water availability. Thus, cultivars SP83-2847 and CTC15, considered tolerant under water deficit, showed better performance in comparison to sensitive cultivar SP86-155. The data suggest that these physiological parameters can be used in the evaluation and distinction of drought tolerant and sensitive sugarcane genotypes.

abstract: This dissertation addresses challenges pertaining to multi-junction (MJ) solar cells from material development to device design and characterization. Firstly, among the various methods to improve the energy conversion efficiency of MJ solar cells using, a novel approach proposed recently is to use II-VI (MgZnCd)(SeTe) and III-V (AlGaIn)(AsSb) semiconductors lattice-matched on GaSb or InAs substrates for current-matched subcells with minimal defect densities. CdSe/CdTe superlattices are proposed as a potential candidate for a subcell in the MJ solar cell designs using this material system, and therefore the material properties of the superlattices are studied. The high structural qualities of the superlattices are obtained from high resolution X-ray diffraction measurements and cross-sectional transmission electron microscopy images. The effective bandgap energies of the superlattices obtained from the photoluminescence (PL) measurements vary with the layer thicknesses, and are smaller than the bandgap energies of either the constituent material. Furthermore, The PL peak position measured at the steady state exhibits a blue shift that increases with the excess carrier concentration. These results confirm a strong type-II band edge alignment between CdSe and CdTe. The valence band offset between unstrained CdSe and CdTe is determined as 0.63 eV±0.06 eV by fitting the measured PL peak positions using the Kronig-Penney model. The blue shift in PL peak position is found to be primarily caused by the band bending effect based on self-consistent solutions of the Schrödinger and Poisson equations. Secondly, the design of the contact grid layout is studied to maximize the power output and energy conversion efficiency for concentrator solar cells. Because the conventional minimum power loss method used for the contact design is not accurate in determining the series resistance loss, a method of using a distributed series resistance model to maximize the power output is proposed for the contact design. It is found that the junction recombination loss in addition to the series resistance loss and shadowing loss can significantly affect the contact layout. The optimal finger spacing and maximum efficiency calculated by the two methods are close, and the differences are dependent on the series resistance and saturation currents of solar cells. Lastly, the accurate measurements of external quantum efficiency (EQE) are important for the design and development of MJ solar cells. However, the electrical and optical couplings between the subcells have caused EQE measurement artifacts. In order to interpret the measurement artifacts, DC and small signal models are built for the bias condition and the scan of chopped monochromatic light in the EQE measurements. Characterization methods are developed for the device parameters used in the models. The EQE measurement artifacts are found to be caused by the shunt and luminescence coupling effects, and can be minimized using proper voltage and light biases. Novel measurement methods using a pulse voltage bias or a pulse light bias are invented to eliminate the EQE measurement artifacts. These measurement methods are nondestructive and easy to implement. The pulse voltage bias or pulse light bias is superimposed on the conventional DC voltage and light biases, in order to control the operating points of the subcells and counterbalance the effects of shunt and luminescence coupling. The methods are demonstrated for the first time to effectively eliminate the measurement artifacts. / Dissertation/Thesis / Ph.D. Electrical Engineering 2012

Title: Advanced spectroscopic characterization of quantum dot ensembles Author: Michael Greben Department: Department of Chemical Physics and Optics Supervisor of the doctoral thesis: Prof. Jan Valenta, Ph.D. Abstract: Semiconductor quantum dots (QDs) are small crystallites whose sizes (of the order of nm) cause spatial confinement of carriers in all 3 dimensions. As result, QDs often reveal very different physical properties in comparison with their bulk counterparts. From the optical point of view, the broadening of bandgap with QD-size shrinking is particularly interesting. It is a purely quantum mechanical effect that results from quantum confinement (QC), i.e. dimensional limitations of excitons. A strong spatial confinement leads to a relaxation of momentum (Heisenberg uncertainty principle), consequently, larger overlap of the wave-functions of carriers results in significant increase of probability of radiative recombination. Therefore ensembles of QDs are promising candidates for new generations of photonic and photovoltaic devices. This PhD thesis is primary focused on detailed spectroscopic characterization of ensembles of direct (PbS) and indirect (Si) semiconductor QDs in both colloidal (toluene) and matrix-embedded (oxide or oxinitrides multilayers) forms. The oleic- acid capped PbS QDs were...

The photocathode is one of the key components of particle accelerator facilities that provides electrons for experiments in many disciplines such as biomedicine, security imaging, and condensed matter physics. The requirements for the electron emitting material, the so-called photocathode, are rather high because these materials should provide a high quantum efficiency, a low thermal emittance, a fast response, and a long operational lifetime. At present, none of the state-of-the-art photocathodes can fully meet all the desired requirements. Therefore, new materials that can be used as potential photocathodes are urgently needed for future developments in accelerator research. Semiconductor photocathodes such as cesium telluride are the preferred materials in particle accelerators. These photocathodes provide high quantum efficiencies of above 10 %, making them highly attractive. The crystal growth of cesium telluride, as a compound semiconductor photocathode, requires the deposition of cesium and tellurium on a suitable substrate with an ideal chemical ratio, which seems elaborate and difficult to handle. In contrast, III-V semiconductors, such as gallium arsenide and gallium nitride (GaN), represent another type of semiconductor photocathode. These commercially available semiconductors are already grown on a substrate and only require a thin film of cesium and optional oxygen to obtain a photocathode. An atomically clean surface is necessary to achieve a negative electron affinity surface, which is the main prerequisite for high quantum efficiency. In this work, p-GaN grown on sapphire by metal-organic chemical vapor deposition, was wet chemically cleaned, and transferred into an ultra-high vacuum chamber, where it underwent a subsequent thermal cleaning. The cleaned p-GaN samples were activated with Cs to obtain p-GaN:Cs photocathodes and their performance was monitored with respect to their quality, especially concerning their quantum efficiency and storage lifetime. The surface topography and morphology were examined ex-situ by atomic force microscopy and scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Treatments at different temperatures resulted in various quantum efficiency values and storage lifetimes. Moderate temperatures of 400–500 °C were found to be more beneficial for the p-GaN surface quality, which was reflected by achieving higher quantum efficiency values. After the thermal cleaning, the samples were activated with a thin layer of cesium at an average pressure of 1 x E-9 mbar. The surface morphology was studied with scanning electron microscopy and energy dispersive X-ray spectroscopy after the samples were thermally cleaned and activated with cesium. The results showed that the surface appeared inhomogeneous when the samples were cleaned at a high temperature above 600 °C. A thermal cleaning from the back side through the substrate represented another possibility but did not yield higher quantum efficiency values. An in-situ analysis method facilitates following and understanding the changes in the surface electronic states before, during, and after any treatment of p-GaN:Cs photocathodes. For this purpose, an X-ray photoelectron spectrometer was applied that was built into an ultra-high vacuum system to prepare and characterize photocathodes. It allowed the in-situ monitoring of the photocathode surfaces beginning immediately after their cleaning and throughout the activation and degradation processes. The realization of the adaption of an X-ray photoelectron spectroscopy chamber to the preparation chamber presented a significant constructional challenge. Thus, this work paid special attention to the technical aspects of in-situ sample transportation between these chambers without leaving the ultra-high vacuum environment. The p-GaN surface was cleaned with different solutions and studied by X-ray photoelectron spectroscopy and atomic force microscopy, revealing that cleaning with a so-called 'piranha' solution in combination with rinsing in ethanol works best for the p-GaN surface. A cleaning step that solely uses ethanol is also possible and represents a simple cleaning procedure that is manageable in all laboratories. Afterward, the cleaned p-GaN samples underwent a subsequential thermal vacuum cleaning at various temperatures to achieve an atomically clean surface. Each treatment step was followed by X-ray photoelectron spectroscopy analysis without leaving the ultra-high vacuum environment, revealing residual oxygen and carbon on the p- GaN surface. A thermal treatment under vacuum did not entirely remove these organic contaminations, although the thermal cleaning reduced their peak intensities. The remaining oxygen and carbon contaminants were assumed to be residuals derived from the metal-organic chemical vapor deposition process. After the cesium activation, a shift toward a higher binding energy was observed in the X-ray photoelectron spectroscopy spectra of the related photoemission peaks. This shift indicated that the cesium was successfully adsorbed to the p-GaN surface. Before the cesium activation, adventitious carbon at a binding energy of approximately 284 eV was found, which was also present after the cesium activation but did not shift in its binding energy. It was also shown that the presence of remaining carbon significantly influenced the photocathode’s quality. After the cesium deposition, a new carbon species at a higher binding energy (approximately 286 eV) appeared in the carbon 1s spectrum. This new species showed a higher binding energy than adventitious carbon and was identified as a cesium carbide species. This cesium carbide species grew over time, resulting in islands on the surface. The X-ray photoelectron spectroscopy data facilitated the elucidation of the critical role of thiscesium carbide species in photocathode degradation. Typically, the quantum efficiency of photocathodes decays exponentially. Conversely, an immense quantum efficiency loss was observed after the p-GaN:Cs photocathodes were studied by X-ray photoelectron spectroscopy. The origin of the quantum efficiency loss derived from X-rays as an external influence and was not caused by the sample’s transportation. Therefore, potential X-ray damages to the p-GaN:Cs photocathodes were investigated. These experiments showed that the adsorbed cesium and its adhesion to the p-GaN surface were strongly influenced by X-ray irradiation. The cesium photoemission peaks shifted toward a lower binding energy, while the relative cesium concentration did not. This shift indicated that X-ray irradiation accelerated the external aging of the p-GaN photocathodes and thus it was proposed to use lower X-ray beam power or cool the samples to prevent X-ray damage to cesiated photocathodes. This work shows that an exclusive activation with cesium is feasible and that a re-activation of the same sample is possible. Quantum efficiency values of 1–12% were achieved when the p-GaN, grown on sapphire, was activated. The capability of an X-ray photoelectron spectroscopy analysis allowed the in-situ monitoring of the photocathode surface and shed light on the surface compositions that changed during the photocathodes’ degradation process.