We demonstrate a new approach for fabricating alternating current driven organic electroluminescent devices using the concept of doping in organic semiconductors. Doped charge transport layers are used for generation of charge carriers within the device, hence eliminating the need for injecting charge carriers from external electrodes. The device is an organic-inorganic hybrid: We exploit the mechanical strength and chemical stability of inorganic semiconductors and combine it with better optical properties of organic materials whose emission color can be chemically tuned so that it covers the entire visible spectrum. The device consists of an organic electroluminescence (EL) layer composed of unipolar/ambipolar charge transport materials doped with organic dyes (10 wt% ) as well as molecularly doped charge generation layers enclosed between a pair of transparent insulating metal oxide layers. A transparent indium doped tin oxide (ITO) layer acts as bottom electrode for light outcoupling and Aluminium (Al) as top reflective electrode. The electrodes are for applying field across the device and to charge the device, instead of injection of charge carriers in case of direct current (DC) devices. Bright luminance of up to 5000 cd m-2 is observed when the device is driven with an alternating current (AC) bias. The luminance observed is attributed to charge carrier generation and recombination, leading to formation of excitons within the device, without injection of charge carriers through external electrodes.

Poly-p-phenylenebenzazoles (PBXs) are heterocyclic aromatic rigid-rod liquid-crystalline polymers with fully conjugated backbone having excellent thermo-oxidative, as well as dimensional stabilities. PBXs are considered to be multifunctional polymers of superior mechanical tenacity, non-linear optical response, and electrical properties. The fully conjugated PBX polymers are deemed to have excellent opto-electronic properties. In the last decade, molecular light emitting diodes (LEDs) have been investigated intensively for having distinct advantages as an advanced opto-electronic technology. This dissertation leads to rigid-rod polymer thin-films and mono-layer devices fabricated from acidic solutions. Photoluminescence (PL) spectra for poly-p-phenylenebenzobisthiazole (PBT) freestanding film were measured over a temperature range of 67 K to 300 K showing distinct electron-phonon interaction. Using an Mg cathode, the mono-layer PBT LEDs displayed a diodic electric response with a threshold voltage as low as 1 V. A blue shift in the maximum emission wavelength of the electroluminescence (EL) spectra was also observed with increasing electrical injection energy. For the multi-layer LEDs based on PBT using the same electrodes, the p-type/n-type bi-layer structure showing the most enhanced EL emission, and the tri-layer heterojunction had the least threshold voltage using the same electrodes. Our results indicated that the heterojunction architecture could be applied to balance charge carriers for increasing EL intensity. Meanwhile, the investigation also revealed the advantage in using the extra PBT layer for increasing both EL emission intensity and injection efficiency by lowering its threshold voltage. Two schemes for making uniaxial freestanding films and LED devices for polarized optical absorption and emission were processed from uniaxial poly-p-phenylenebenzobisoxazole (PBO) fiber. The PL of the uniaxial PBO films demonstrated an emission intensity ratio I¡ü/I¡æas high as 5. Anisotropically processed mono-layered PBO LED showed a markedly decreased threshold voltage from 7 V of the isotropic PBO device to 5 V. The polarization effects in optical absorption, PL and EL emissions were acquired and correlated with the uniaxial orientation of the rigid-rod PBO polymer. The molecular modification investigated the opto-electronic properties of poly-2,2'-m-phenylene-5,5'-bibenzimidazole (Pbi) with PBT physical blends, and monolithic 6F-PBO-OH-co-6F-PBO-di(OC10H21) copolymers. Partially conjugated polymer Pbi and fully conjugated polymer PBT were mixed for luminescence study. Their absorption spectra showed superposition of individual absorption response indicating no inter-molecular energy transfer. However, the PL and the EL emission demonstrated a blue shift with increasing Pbi content. This was attributed to the rigid-rod configuration or the aggregation of PBT perturbed by mixing with coil-like Pbi. It was recognized that the backbone of the fully conjugated rigid-rod PBT was collinear having more charge delocalization than that of not fully conjugated coil-like Pbi. The diode threshold voltage of the physical blends varied from 4 V to 14 V with decreasing PBT content. Another molecular modification was changing the composition of 6F-PBO copolymers. Their PL emission exhibited excellent chromatic tuning range from green to blue emission. The Commission Internationale de l¡¦Eclairage (C. I. E.) coordinates of the copolymer EL emission were from (0.25, 0.53) to (0.24, 0.31) covering a wide visible range and demonstrating a white light emission. Atomic substitution of the rigid-rod polymers was utilized to examine individual atomic contribution for luminescence emission. The hydrogen bond effect for PBO-OH and PBO was evidenced in a major Stoke¡¦s shift to a longer wavelength because of protonic transfer on the excited state. Elemental electronegativities affected the delocalization of the £k electron leading to a blue shift in absorption spectra as shown in case of PBO and PBT. The PBO molecule was more collinear and co-planar, providing more charge delocalization than PBT. However the absorption edge of the PBT was about 30 nm higher than that of PBO. This suggested that the electronegativities affected the molecular delocalization. Using the solid-state physics with pseudofunction (PSF) calculation, there was good match between absorption spectra and calculated excitation energies for the rigid-rod polymer systems.

The aim of this work was to find a correlation between the electrical, optical and microstructural properties of thin SiO2 layers containing group IV nanostructures produced by ion beam synthesis. The investigations were focused on two main topics: The electrical properties of Ge- and Si-rich oxide layers were studied in order to check their suitability for non-volatile memory applications. Secondly, photo- and electroluminescence (PL and EL) results of Ge-, Si/C- and Sn-rich SiO2 layers were compared to electrical properties to get a better understanding of the luminescence mechanism.

Parmi toutes les méthodes de confinement des porteurs dans les trois directions de l'espace, la croissance auto organisée de boîtes quantiques semble être la meilleure. La méthode de fabrication de ces nanostructures est l'épitaxie par jets moléculaires ; elle permet l'obtention de cristaux d'une grande qualité, de manière cohérente avec leur environnement. Cette technique d'auto organisation dite de Stranski Krastanov génère cependant des nanostructures de tailles diverses ; le spectre de leur luminescence s'en retrouve élargi, altérant les performances des composants à base de boîtes quantiques. Une solution consiste à localiser leur croissance en structurant à l'échelle nanométrique le substrat : lorsqu'elles sont régulièrement espacées, leur taille et leur géométrie sont plus homogènes. La technique employée, la nanoimpression, présente l'avantage majeur de ne pas altérer la cristallinité du substrat. Ces travaux mettent en exergue le fait que la luminescence des boîtes quantiques après reprise d'épitaxie sur ces surfaces nanostructurées par nanoimpression est intense. Les boîtes quantiques sont ici appliquées à un domaine en plein essor : l'électronique de spin. Le principe est d'utiliser le spin de l'électron pour coder l'information. Trois problèmes majeurs doivent être surmontés pour ce faire : l'injection de porteurs polarisés en spin dans le semiconducteur, le transport de ces porteurs polarisés, et enfin la recombinaison radiative, le cas échéant, pour émettre des photons polarisés avec un bon rendement. Dans cette thèse, nous présentons un composant qui permet de qualifier l'ensemble de ces paramètres, la spinLED. Les temps caractéristiques de relaxation de spin dans le semiconducteur sont courts, de l'ordre de 100ps ; il a été nécessaire d'adapter la structure de la spinLED pour la rendre compatible aux caractérisations en hyperfréquence, jusqu'à 20GHz.

Les systèmes photovoltaïques à concentration, ou CPV, reposent sur le principe de la concentration des rayons du soleil sur une cellule photovoltaïque à très haut rendement. Le CPV reste jeune face au photovoltaïque (PV) classique qui accumule plus de 30 ans de retour d'expérience.La pérennisation de cette technologie CPV ne passera que par la démonstration d'une certaine maturité. Aussi, la question de la fiabilité de ces systèmes est plus que jamais d'actualité. Dans ce contexte, le Commissariat à L'Energie Atomique et aux Energies Alternatives (CEA) a répondu à la sollicitation lancée par des fabricants de modules CPV français sur la thématique de la conception et de la fiabilisation de modules CPV par une collaboration de ses différents laboratoires, dont le Laboratoire des Modules Photovoltaïques (LMPV). C'est au sein de ce laboratoire que s'effectuent les travaux de thèse. La diversité des éléments constituant un module CPV a poussé les travaux de thèse à se concentrer sur le coeur fonctionnel des modules : les assemblages CPV. Une première partie des travaux de thèse a consisté à mettre en place les bons outils de caractérisation, en partant parfois d'une feuille blanche. La mesure de caractéristique IV dans l'obscurité, la mesure de réponse spectrale, la tomographie RX ou encore l'électroluminescence sont autant de moyens de caractérisation de cellules multi-jonctions amenés par les travaux de thèse. Les efforts conduits sur l'électroluminescence auront permis l'invention d'une nouvelle technique de caractérisation des interfaces cellule/ substrat des assemblages CPV, concrétisée par le dépôt d'un brevet. Une collaboration entre le laboratoire d'accueil et l'Institut de l'Energie Solaire (IES) à Madrid a permis l'accès à la mesure de performance des assemblages CPV sous éclairement. Tous ces moyens ont rendu possible une caractérisation fine des assemblages CPV et ont permis de s'intéresser à leur robustesse-fiabilité, deuxième partie des travaux de thèse. Deux types d'assemblages CPV ont été étudiés durant les travaux de thèse. Le premier, basé sur un substrat Direct Bonded Copper (DBC) correspond à l'état de l'art et est le plus utilisé dans l'industrie CPV. Le deuxième, en rupture technologique avec l'état de l'art, repose sur un Substrat Métal Isolé (SMI), et a été intégralement développé par le CEA et ses partenaires industriels. L'étude de la robustesse de ces assemblages CPV a été faite par l'emploi de tests de vieillissement accéléré dont la nature est justifiée par le retour d'expérience et la définition des spécifications environnementales. Aucune défaillance n'a été observé sur chacun des types d'assemblage. Les assemblages SMI se comportent comme les assemblages DBC, considérés comme références. Les travaux de thèse offrent donc un premier retour d'expérience propre au laboratoire d'accueil et la mise en place d'une infrastructure complète de caractérisation d'assemblage CPV permet aujourd'hui au CEA d'être un acteur clé du CPV en France.

This work focusses on the high brightness performance of phosphorescent organic light-emitting diodes (OLEDs). The use of phosphorescent emitter molecules in OLEDs is essential to realize internal electron-photon conversion efficiencies of 100 %. However, due to their molecular nature, the excited triplet states have orders of magnitude longer time constants compared to their fluorescent counterparts which, in turn, strongly increases the probability of bimolecular annihilation. As a consequence, the efficiencies of phosphorescent OLEDs decline at high brightness – an effect known as efficiency roll-off, for which it has been shown to be dominated by triplet-triplet annihilation (TTA). In this work, TTA of the archetype phosphorescent emitter Ir(ppy)3 is investi- gated in time-resolved photoluminescence experiments. For the widely used mixed system CBP:Ir(ppy)3, host-guest TTA – an additional unwanted TTA channel – is experimentally observed at high excitation levels. By using matrix materials with higher triplet energies, this effect is efficiently suppressed, however further studies show that the efficiency roll-off of Ir(ppy)3 is much more pronounced than predicted by a model based on Förster-type energy transfer, which marks the intrinsic limit for TTA. These results suggest that the emitter molecules show a strong tendency to form aggregates in the mixed film as the origin for enhanced TTA. Transmission electron microscopy images of Ir(ppy)3 doped mixed films give direct proof of emitter aggregates. Based on these results, two concepts are developed that improve the high brightness performance of OLEDs. In a first approach, thin intrinsic matrix interlayers are incorporated in the emission layer leading to a one-dimensional exciton confinement that suppresses exciton migration and, consequently, TTA. The second concept reduces the efficiency roll-off by using an emitter molecule with slightly differ- ent chemical structure, i.e. Ir(ppy)2(acac). Compared to Ir(ppy)3, this emitter has a much smaller ground state dipole moment, suggesting that the improved performance is a result of weaker aggregation in the mixed film. The knowledge gained in the investigation of triplet-triplet annihilation is further used to develop a novel emission layer design for white organic LEDs. It comprises three phosphorescent emitters for blue, green, and red emission embedded in a multilayer architecture. The key feature of this concept is the matrix material used for the blue emitter FIrpic: Its triplet energy is in resonance with the FIrpic excited state energy which enables low operating voltages and high power efficiencies by reducing thermal relaxation. In order to further increase the device efficiency, the OLED architecture is optically optimized using high refractive index substrates and thick electron transport layers. These devices reach efficiencies which are on par with fluorescent tubes – the current efficiency benchmark for light sources. / Diese Arbeit richtet ihren Fokus auf die Untersuchung der Leistungsfähigkeit von phosphoreszenten, Licht-emittierenden organischen Dioden (OLEDs) im Bereich hoher Betriebshelligkeiten. Phosphoreszente Emittermoleku ̈le werden in OLEDs eingesetzt, um interne Elektron-Photon Konversionseffizienzen von 100% zu erreichen. Begründet in ihrer chemischen Struktur, weisen die angeregten Triplett-Zustände dieser Emitter um Größenordnungen längere Zeitkonstanten als die Emission fluo- reszenter Materialien auf, sodass die Wahrscheinlichkeit bimolekularer Auslöschung stark ansteigt. Dies resultiert in einem deutlichen Effizienzrückgang phosphoreszenter OLEDs bei großen Leuchtdichten. Dieser als Roll-off bekannter Effekt wird bei hohen Anregungsdichten hauptsächlich durch Triplett-Triplett Annihilation (TTA) bestimmt. In der Arbeit wird TTA an einem Modellmolekül, dem phosphoreszenten Emit- ter Ir(ppy)3, in zeitaufgelösten Photolumineszenz Experimenten untersucht. Für das bekannte Emittersystem CBP:Ir(ppy)3 wird bei hohen Anregungsdichten Host-Guest TTA beobachtet, was einen zusätzlichen, ungewünschten TTA Kanal darstellt. Dieser Effekt wird durch das Verwenden von Matrix Materialien mit höherer Triplett Energie vermieden, jedoch zeigt sich in weiteren Untersuchungen, dass der Roll-off deutlich stärker ist als von einem auf Förster Energieübertrag basierendem Modell vorhergesagt, welches selbst ein intrinsisches Limit für TTA in phosphoreszenten Systemen beschreibt. Die Diskrepanz zwischen experimenteller Beobachtung und Modellvorhersage wird durch eine starke Tendenz des Emitters, Aggregate zu bilden, erklärt, was TTA deutlich verstärkt. Diese Aggregate werden mit Hilfe von Transmissionselektronenmikroskopie an Ir(ppy)3-dotierten Mischsystemen direkt nachgewiesen. Basierend auf diesen Resultaten werden zwei Konzepte entwickelt, um die Effizienz phosphoreszenter Systeme bei hohen Helligkeiten zu verbessern. Im ersten Ansatz werden dünne intrinsische Schichten des Matrixmaterials in die Emissionsschicht eingebaut, was die Exzitonenbewegung in einer Raumrichtung und damit auch TTA stark unterdrückt. Das zweite Konzept reduziert den Effizienz Roll-off durch die Verwendung eines phosphoreszenten Emitters Ir(ppy)2(acac) mit einer leicht abgeänderten Molekularstruktur. Im Vergleich mit Ir(ppy)3 weist dieser ein deutlich kleineres Dipolmoment im molekularen Grundzustand auf, wodurch die Aggregation vermindert wird. Aufbauend auf den Ergebnissen der TTA wird ein neuartiges Emissionsschicht-Design für weißes Licht entwickelt. In diesem Konzept werden drei phosphoreszente Materialien für blaue, grüne und rote Farbe in eine Vielschicht-Architektur eingebracht. Das Hauptmerkmal der Emissionsschicht ist die Wahl des Matrix-Materials für dem blauen Emitter FIrpic: Seine Triplett Energie liegt resonant zu dem FIrpic Triplett Zustand, wodurch niedrige Betriebsspannungen und hohe Leistungseffizienzen ermöglicht werden, da die thermische Relaxierung reduziert wird. Um die Ef- fizienz dieser weißen OLEDs weiter zu erhöhen, wird die entwickelte OLED Architektur zusätzlich durch die Verwendung von hochbrechenden Substraten und dicken Elektronen-Transportschichten optisch optimiert. Bei beleuchtungsrelevanten Helligkeiten erreichen diese OLEDs das Effizienzniveau von Leuchtstoffröhren – letztere stellen heute den Effizienz-Maßstab dar.

Organic light-emitting diodes (OLEDs) have drawn much attention in the last two decades. In recent years, the power efficiency of OLEDs has been increased to exceed the efficiency of fluorescent light bulbs. However, such high-efficiency devices are typically based on small molecules that have to be evaporated in vacuum. A much higher fabrication throughput and therefore lowered costs are expected if high-efficiency OLEDs were processed from solution. This thesis shows how solution-processed electrophosphorescent multilayer OLEDs can be achieved by starting with an evaporated three-layer device structure and replacing layer by layer with a solution-processed layer. First, the hole-transport layer was replaced by a polymer and high efficiencies were observed when using a hole-transport polymer with a high ionization potential and a low hole mobility. Then, the emissive layer was replaced by a copolymer consisting of hole-transport groups and emissive complexes in its side-chains. OLEDs with four different colors are shown where the orange devices showed the highest efficiency. The orange copolymer was further optimized by making changes to the chemical nature of the polymer, such as different molecular weight, different concentrations of the emissive complex and different linkers between the side-chains and the polymer backbone. Finally, a three-layer solution-processed OLED was fabricated by crosslinking the hole-transport and the emissive layer, and by spin-coating an electron-transport polymer on top. Moreover, using the photocrosslinking properties of the emissive layer, solution-processed multilayer OLEDs of two different colors were patterned using photolithography to fabricate a white-light source with a tunable emission spectrum. Furthermore, with more and more organic semiconductors being integrated into the circuitry of commercial products, good electrical models are needed for a circuit design with predictive capabilities. Therefore, a model for the example of an organic single-layer diode is introduced in the last chapter of this thesis. The model has been implemented into SPICE and consists of an equivalent circuit that is mostly based on intrinsic material properties, which can be measured in independent experiments. The model has been tested on four different organic materials, and good agreement between model and experimental results is shown.

[pt] Este trabalho teve como objetivo fabricar e caracterizar Transistores Orgânicos Emissores de Luz (OLETs, Organic light-Emitting Transistors). Os OLETs combinam em um único dispositivo a funcionalidade elétrica de um transistor de efeito de campo orgânico e a capacidade de geração de luz, representando uma nova classe de dispositivos orgânicos com alto potencial de inovação em aplicações, como sistemas ópticos de comunicação, tecnologia de displays avançada, lasers orgânicos, fontes de luz em nanoescala e optoeletrônica orgânica integrada. Portanto, esta tese possui um caráter pioneiro, tanto para grupo de pesquisa quanto para o país, uma vez que ocorre a junção dos conhecimentos e domínio adquiridos sobre OFETs e OLEDs. Efetivamente, este trabalho de doutorado consistiu na fabricação e caracterização sistemática de diversos dispositivos OLET utilizando variadas arquiteturas e diversos materiais, comerciais e não comerciais, como o NT4N, o P13 e uma bicamada de C8-BTBT com TcTa:Ir(ppy)3. Os dispositivos foram caracterizados através de medidas elétricas e óticas, obtendo-se as curvas características. Também foram determinados seus parâmetros e propriedades de funcionamento, com destaque para as mobilidades de carga e para as eficiências obtidas. Houve também o entendimento e a implementação de um tratamento térmico na camada dielétrica, sendo parte fundamental da fabricação dos dispositivos. Os dispositivos fabricados apresentaram diferentes graus de desempenho, com destaque para a arquitetura bicamada, por apresentar a maior potência luminosa (4 microwatt) e a maior eficiência (0,5 por cento), sendo suficientes para inserir os dispositivos fabricados na categoria de dispositivos orgânicos altamente eficientes. Tal fato demonstra que o domínio da fabricação e da caracterização desta nova classe de dispositivos foi alcançado. / [en] The aim of this work was to achieve the knowledge of the fabrication and the characterization of Organic Light Emitting Transistors, OLETs, considered as one of the innovative technologies nowadays. The OLETs combine in a single device the electrical functionality of an organic field-effect transistor (OFET) and the light-generating capability. They represent a promising new class of organic devices with high potential for innovation in applications such as communication systems, advanced display technology, organic lasers, nanoscale light sources and integrated organic optoelectronics. In some way, this thesis has a pioneer character, both for our research group and for the country, since it combines different knowledge and skills about OFETs and OLEDs to achieve a new device. Actually, this work involved the systematic manufacture and characterization of several OLETs using different architectures employing commercial and noncommercial materials, such NT4N, P13 and a bilayer of C8-BTBT with TcTa:Ir(ppy)3. The devices were then characterized by electrical and optical measurements. The working parameters and properties were determined as well, highlighting the charge carrier mobilities and efficiencies obtained. The understanding and the implementation of a specific heat treatment in the dielectric layer was a fundamental part of this work for the manufacture of the devices which have different degrees of performance. With emphasis on the bilayer architecture, that presented the highest luminous power (4 microwatt) and efficiency (0,5 percent), inserting the devices manufactured in the category of highly efficient organic devices. Such fact shows that the fabrication and characterization of this new class of devices has been achieved.

Made available in DSpace on 2014-10-09T12:27:51Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:48Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:51Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:48Z (GMT). No. of bitstreams: 0 / Complexos contendo íons de terras raras são de grande interesse na fabricação de dispositivos eletroluminescentes como é o caso do diodo emissor de luz construído com compostos orgânicos (OLED). Esses dispositivos, utilizando íons de terras raras trivalentes (TR3+) como centros emissores, exibem alta luminescência com bandas espectrais extremamente finas devido à estrutura dos seus níveis de energia, tempos de vida longos e a alta eficiência quântica. Este trabalho relata a preparação de complexos de β-dicetonatos (tta - tenoiltrifluoroacetonato e acac - acetilacetonato) de terras raras (Tb3+, Eu3+ e Gd3+) contendo ligante macrocíclico éter coroa (DB18C6 - dibenzo18coroa6) e de filmes poliméricos de UO22+. Os materiais obtidos foram caracterizados por titulação complexométrica com EDTA, análise elementar de CH, espectroscopia de absorção na região do infravermelho, análise termogravimétrica, difratometria de raios X (método do pó) e espectroscopia de luminescência. Na manufatura do dispositivo OLED construído neste trabalho utilizou-se a técnica de deposição física de filmes finos por fase vapor (PVD, Physical Vapor Deposition). / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP