<p>This thesis deals with synthesis and characterization of newoligothiophenes and derivatives thereof, for use as organicsemiconductors in optical and electronic applications, such asfield-effect transistors and light-emitting diodes. Much workis devoted to the development of new synthetic strategies forinteresting building blocks, to beused for synthesizing suchmaterials. One series of regio-defined oligothiophenes, up tothe octamer, has been prepared and evaluated. Photoluminescencequantum efficiencies of these were 22-31 % in solution, butdropped to 2-5 % in the solid state. Another project deals withthe development of oligothiophenes with in-chain chirality.These may find use in polarized lightemitting diodes. Finally,two oligothienyl-substituted porphyrins have been synthesizedand are currently evaluated for use in light-emitting diodesand possibly in solar cells.</p>

In the past decade, GaN-based nitrides have had a considerable impact in solid state lighting and high speed high power devices. InGaN-based LEDs have been widely used for all types of displays in TVs, computers, cell phones, etc. More and more high power LEDs have also been introduced in general lighting market. Once widely used, such LEDs could lead to the decrease of worldwide electrical consumption for lighting by more than 50% and reduce total electricity consumption by > 10%. However, there are still challenges for current state-of-the art InGaN-based LEDs, including ‘efficiency droop’ issues that cause output power quenching at high current injection levels (> 100 A/cm2). In this dissertation, approaches were investigated to address the major issues related to state-of-the-art nitride LEDs, in particular related to (1) efficiency droop investigations on m-plane and c-plane LEDs: enhanced matrix elements in m-plane LEDs and smaller hole effective mass favors the hole transport across the active region so that m-plane LEDs exhibit 30% higher quantum efficiency and negligible efficiency droop at high injection levels compared to c-plane counterparts; (2) engineering of InGaN active layers for achieving high quantum efficiency and minimal efficiency droop: lower and thinner InGaN barrier enhance hole transport as well as improves the quantum efficiencies at injection levels; (3) double-heterostructure (DH) active regions: various thicknesses were also investigated in order to understand the electron and hole recombination mechanism. We also present that using multi-thin DH active regions is a superior approach to enhance the quantum efficiency compared with simply increasing the single DH thickness or the number of quantum wells (QWs, 2 nm-thick) in multi-QW (MQW) LED structures due to the better material quality and higher density of states. Additionally, increased thickness of stair-case electron injectors (SEIs) has been demonstrated to greatly mitigate electron overflow without sacrificing material quality of the active regions. Finally, approaches to enhance light extraction efficiency including using Ga doped ZnO as the p-GaN contact layer to improve light extraction as well as current spreading was introduced.

Neste trabalho investigamos as propriedades térmicas (difusividade, condutividade, variação do caminho óptico com a temperatura, etc) e processos de perdas devido a interações entre íons em materiais lasers vítreos e cristalinos. Desde que a eficiência quântica de fluorescência, , está diretamente relacionada com esses mecanismos que levam a supressão da luminescência, os estudos foram realizados principalmente observando os efeitos desses agentes sobre . Espectros de lente térmica (LT) foram usados para determinar , eficiência de transferência de energia matriz-íon, e para analisar efeitos de sítios de defeitos sobre . Um novo método usando a técnica de LT foi proposto para determinar e o coeficiente de temperatura do caminho óptico. Com esta nova abordagem analisamos em materiais vítreos os mecanismos de supressão da luminescência em função da concentração de íons de Nd. Também a usamos para estudar efeitos de radicais de OH e outras impurezas em matrizes vítreas de fosfato dopadas com Yb3+. Processos de conversão ascendente Auger, os quais são importantes em sistemas lasers de alta potência, foram investigados em vidros e cristais dopados com Nd3+. Nos vidros o estudo foi realizado em função da concentração de íons dopantes. Neste estudo a técnica de LT mostrou ser muito sensível, apresentando resultados com erros bem menores que os existentes na literatura. Seguindo o estudo de perdas, investigamos distorção óptica induzida pela luz em função da temperatura, potência de excitação e polarização no cristal ferroelétrico SBN. Usando a técnica de LT, investigamos as propriedades térmicas através da transição de fase ferroelétrica-paraelétrica em cristais de SBN. Complementando, esta tese contribui significativamente para a caracterização de materiais laser, considerando que vários dos mecanismos de perdas estudados propriamente devem ser levados em conta em projetos de laser. Este trabalho também apresenta a técnica de lente térmica como uma ferramenta valiosa para tal estudo. / In this work we investigate the thermal properties (diffusivity, conductivity, temperature coefficient of the optical path length change, etc) and loss processes owing to ion-ion interactions in laser glassy and crystalline materials. Since the fluorescence quantum efficiency, , is directly related to these mechanisms that lead to luminescence quenching, the studies were performed mainly observing the effects of these processes on . Thermal lens (TL) spectra were used to determine , energy transfer efficiency between matrix-ion, and to analyze effects of \"dead site\" on . A new method based on the TL technique was proposed to determine q and the temperature coefficient of the optical path length change. This new approach was used to investigate concentration quenching mechanisms in glassy materials. It was also used to study effects of OH radicals and other impurities in Yb3+ doped phosphate glasses. Upconversion Auger processes, which are very important for high power laser systems, were investigated in Nd3+ -doped glasses and crystals. In glasses the study was performed as a function of doping ions. In this study the TL showed to be very sensitive, presenting results with uncertainties much smaller than previous literatures. Following the study of losses, we investigate light induced optical distortion as a function of temperature, excitation power, and polarization in SNB ferroelectric crystal. Using the TL technique, the thermal properties through the phase transition ferroelectric-paraelectric in SBN crystals were investigated. In addition, this thesis significantly contributes for characterization of laser materials with potential applications, considering that severa1 of the loss mechanisms studied here must be considered in laser design. This work also presents the TL technique as a valuable to01 for the present study.

The rise of organometal halide perovskite materials with extremely intriguing properties have opened a new horizon in the design of high speed and low price optoelectronic devices. The bandgap in the crystalline structure of these materials can be easily tuned for various applications and their dominant non-excitonic dynamics eliminate the requirement of a bulk or heterostructure for charge carrier separation. These unique properties increase the photo-sensitivity of perovskite-based optoelectronics and provide them with a low time constant, resulting in high precision fast devices. Realization of perovskite-based devices translates directly to inexpensive and simplified architectures of optoelectronic systems. In perovskite-based devices, costly silicon or wide bandgap semiconductor fabrication technology is largely replaced by solution processable methods. Their bandgap tunability allows the reduction of the required optical accessories and interconnects in optoelectronic components. For instance, a tuned perovskite-based detector can substitute a narrowband detecting system consisting of a conventional detector and its required optical accessories such as lenses and color filters. These properties of perovskite-based devices lead to the realization of inexpensive, low power and high-performance optoelectronic systems. In this work, the design of a narrowband, low noise, high performance and stable photodetector based on organic-inorganic hybrid perovskite structure is proposed. The full width at half maximum (FWHM) of the device would be in the nanometer range. The response of the device can be tuned using either different ratios of the lead salts or synthetic dyes (macromolecules) in the crystalline structure for color discrimination in machine vision and imaging applications. Non-excitonic photocarrier generation, tunability of the optical bandgap and low voltage requirements for charge carrier generation are the keys to the utility of this optoelectronic device. The goals of this project were to identify the required functional materials (lead salts and synthetic dyes based on their molecular structures) and optimize their performance; the study of their effect on the charge collection narrowing mechanism and bandwidth specifications defined for detectivity, linear dynamic range (LDR) and photoresponse speed. To achieve these goals, it was proposed to study the light detection properties as well as spectroscopic and semiconductor parameter characteristics of fabricated devices. The design considerations of such devices are versatile and may be modulated for different applications.

A near infrared waveguide photodetector in Si-based ternary Si₁−x−yGexCy alloy was demonstrated for 0.85~1.06 µm wavelength fiber-optic interconnection system applications. Two sets of detectors with active absorption layer compositions of Si₀.₇₉Ge₀.₂C₀.₀₁ and Si₀.₇₀Ge₀.₂₈C₀.₀₂ were designed. The active absorption layer has a thickness of 120~450 nm. The external quantum efficiency can reach ~3% with a cut-off wavelength of around 1.2 µm. / Singapore-MIT Alliance (SMA)

This aim of this dissertation is to fabrication microlens arrays (MLA) by silicon mold using dry etching technique and imprint on the PET substrate by direct imprinting microlens structures on Polyethylene terephthalate (PET) substrates using Si molds.The MLA on PET substrates can be used to increase light emitting efficiency from OLED. The MLA was formed by first etching the silicon wafers using SF6 process gas in an RIE/ECR system using isotropic etching technique.The concave undercuts obtained after the dry etching was removed by wet-etching the wafer in HF and HNO3 solutions.Finally,the fabricated silicon mold was used to imprint the microlens structure on the PET substrates.The microlens array with 10 £gm and 25 £gm radius on PET substrate were successfully fabricated using the technique.The surface coverage of the MLA of beter than 90% was obtained. In addition,the outcoupling efficiency of an OLED can be increased using the MLA.The brightness enhancement factor of 1.67 was achieved using in the MLA comparision to the simulation result of 1.73.

Using low-temperature (650¢J) Ce3+:YAG doped glass (LTCeYDG) phosphor layer instead of conventional Ce:YAG doped silicone phosphor layer applied to high-power phosphor-converted white-light-emitting diodes (PC-WLEDs) is demonstrated.The glass transition temperature (Tg) of silicone is 150¢J but glass is 750¢J,it shows the glass were employed in high power LED than silicon. The uniformity of phosphor powder doped glass is an important item to discriminates between good and bad. Quantize the uniformity of glass phosphor by image processing software and Distribution Uniformity (Du). Calculate the uniformity of phosphor powder mix with glass powder which has different particle size and measurement optical properties of glass phosphor which has different uniformity. The Du of glass phosphor are 64.46%, 84.65%, 85.24% , 91.85% and the quantum efficiency are 18.49%, 28.31%, 29.73%, 28.56% ,respectively. By using Ceramic tube and low temperature glass powder sintering glass phosphor is a new fabrication. Compare with last fabrication, new fabrication reduce 100¢Jfabrication temperature from 750¢J to 650¢J, 70% material savings and high luminous efficiency. The quantum efficiency and lumen per watt were improved about 7 percentage point from 22.3% to 29.1% and 4.2 lm/W from 36.4 lm/W to 40.68 lm/W. We used the XRD to analyze the glass phosphor of last fabrication and new fabrication and the results show that the higher thermal stress destroys the structure of YAG, lower fabrication temperature used to get higher luminous efficiency.

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.

This thesis presents an investigation into the factors which control the gain and amplification properties in conjugated materials. Conjugated polymers and perylene dyes are highly fluorescent, are easy to process into thin films, and exhibit strong amplification over a broad gain bandwidth making them ideal for use in lasers and amplifiers. The stimulated emission created when thin films of the red emitting polymer poly(2-methoxy-5-(2'-ethylhexyloxy)- p-phenylenvinylene) (MEH-PPV) were photoexcited with high energy laser pulses was investigated. This was characterised by a dramatic narrowing of the emission spectrum which has been assigned to amplified spontaneous emission (ASE). The emission was found to have a gaussian profile and the gain coefficient was found to be 4 cm-1.The temperature dependence of the absorption, photoluminescence and ASE of films of MEH-PPV was measured. The effect of film morphology on the photophysical properties was investigated by using films cast from two spinning solvents, chlorobenzene (CB) and tetrahydrofuran (THE). Film morphology was found to greatly affect the temperature dependence. A particularly important property is the spectral position of the ASE and the factors which affect it. By controlling the film thickness close to the cut-off thickness for waveguiding in the polymer film it was shown that the peak position of the ASE could be tuned by 31 nm. Modelling of the waveguide modes in the polymer films was used to explain this effect. The cut-off wavelength for each film was measured and good agreement with the theory was found. In order to investigate ways in which energy transfer could be used to control the emission, two perylene dyes were used as a donor-acceptor pair in a host matrix of poly methymethacralate (PMMA). The position of the ASE was found to depend on the acceptor concentration. Measurements of the photoluminescence quantum yield and time-resolved luminescence measurements showed that the energy transfer coefficient was 5x10(^11)mol(^-1)d(^3)

Neste trabalho investigamos as propriedades térmicas (difusividade, condutividade, variação do caminho óptico com a temperatura, etc) e processos de perdas devido a interações entre íons em materiais lasers vítreos e cristalinos. Desde que a eficiência quântica de fluorescência, , está diretamente relacionada com esses mecanismos que levam a supressão da luminescência, os estudos foram realizados principalmente observando os efeitos desses agentes sobre . Espectros de lente térmica (LT) foram usados para determinar , eficiência de transferência de energia matriz-íon, e para analisar efeitos de sítios de defeitos sobre . Um novo método usando a técnica de LT foi proposto para determinar e o coeficiente de temperatura do caminho óptico. Com esta nova abordagem analisamos em materiais vítreos os mecanismos de supressão da luminescência em função da concentração de íons de Nd. Também a usamos para estudar efeitos de radicais de OH e outras impurezas em matrizes vítreas de fosfato dopadas com Yb3+. Processos de conversão ascendente Auger, os quais são importantes em sistemas lasers de alta potência, foram investigados em vidros e cristais dopados com Nd3+. Nos vidros o estudo foi realizado em função da concentração de íons dopantes. Neste estudo a técnica de LT mostrou ser muito sensível, apresentando resultados com erros bem menores que os existentes na literatura. Seguindo o estudo de perdas, investigamos distorção óptica induzida pela luz em função da temperatura, potência de excitação e polarização no cristal ferroelétrico SBN. Usando a técnica de LT, investigamos as propriedades térmicas através da transição de fase ferroelétrica-paraelétrica em cristais de SBN. Complementando, esta tese contribui significativamente para a caracterização de materiais laser, considerando que vários dos mecanismos de perdas estudados propriamente devem ser levados em conta em projetos de laser. Este trabalho também apresenta a técnica de lente térmica como uma ferramenta valiosa para tal estudo. / In this work we investigate the thermal properties (diffusivity, conductivity, temperature coefficient of the optical path length change, etc) and loss processes owing to ion-ion interactions in laser glassy and crystalline materials. Since the fluorescence quantum efficiency, , is directly related to these mechanisms that lead to luminescence quenching, the studies were performed mainly observing the effects of these processes on . Thermal lens (TL) spectra were used to determine , energy transfer efficiency between matrix-ion, and to analyze effects of \"dead site\" on . A new method based on the TL technique was proposed to determine q and the temperature coefficient of the optical path length change. This new approach was used to investigate concentration quenching mechanisms in glassy materials. It was also used to study effects of OH radicals and other impurities in Yb3+ doped phosphate glasses. Upconversion Auger processes, which are very important for high power laser systems, were investigated in Nd3+ -doped glasses and crystals. In glasses the study was performed as a function of doping ions. In this study the TL showed to be very sensitive, presenting results with uncertainties much smaller than previous literatures. Following the study of losses, we investigate light induced optical distortion as a function of temperature, excitation power, and polarization in SNB ferroelectric crystal. Using the TL technique, the thermal properties through the phase transition ferroelectric-paraelectric in SBN crystals were investigated. In addition, this thesis significantly contributes for characterization of laser materials with potential applications, considering that severa1 of the loss mechanisms studied here must be considered in laser design. This work also presents the TL technique as a valuable to01 for the present study.