A series of heteroleptic and homoleptic platinum(II) complexes has been synthesized and characterized towards their use in thin film devices such as organic light-emitting diodes (OLEDs) and organic thin film transistors (OTFTs). Pyridylpyrazolate- and pyridyltetrazolate-containing ligands were selected due to their structural rigidity and ease of functionalization. Single-crystal x-ray diffraction studies of two selected heteroleptic complexes show strong aggregation with preferential stacking into vertical columns with a varying degree of overlap of the neighboring square planar molecular units. It is shown that the close proximity of the molecules to one another in the stack increases semiconducting character, phosphorescence quantum yields, and shorter radiative lifetimes. The potential for these materials towards incorporation into high-efficiency doping free white OLEDs (DFW-OLEDs) for solid-state lighting and display applications has been realized and will be expanded upon by present and future embodiments of materials in this thesis.

No description available.

This dissertation addresses the following issues. Firstly, to reduce the efficiency roll-off at high current densities or brightness, of green, fluorescent organic light-emitting (OLEDs), we introduced a double-doped structure into the emissive layer. It includes two thin buffer layers and a broad emissive region stacked with two doped layers. This modification better controls charge injection/transport and recombination, boosting EL and PL efficiency. Secondly, aiming for highly efficient phosphorescent OLEDs surpassing the theoretical EQE limit of ~20%, a new class of platinum(II)-based phosphorescent complexes have been designed and synthesized serving as both emitters and electron transporters in straightforward undoped bi-/tri-layered devices. Achieving this without costly doping techniques, these OLEDs boast a relatively low turn-on voltage, extremely high power efficiency, and stable emission color dependent on applied voltages. This design anticipates reduced or no efficiency roll-off even at brightness levels exceeding 20,000 cd/m2, far surpassing DOE technology requirements (only 500-1500 cd/m2). This work sheds light on the influence of molecular design on crystalline packing and optoelectronic device performance and accelerates the development of efficient and stable Pt-based emitters.

Over the last three decades, the performance of OLEDs has been improved rapidly, however, as an important assessment for OLED, the EQE data are still quite low. As outlined in the theoretical background, the EQE is the product of out-coupling efficiency and internal quantum efficiency (IQE). Therefore, this thesis focuses on designing two types of polymers with different optical functionalities, to increase the EQE addressing the two aforementioned determining factors. Thus, the first part of the thesis addresses the light out-coupling efficiency in OLED devices. Here high refractive index (HRI) polymers are aimed for as potential material for the out-coupling layer, which are so far scarily reported for application in OLED devices, due to existing limitations, such as limited transparency, extra fluorescence, tedious synthesis, poor thermal stability and low solubility. However, if suitable polymers are becoming easily available, they will offer the unique advantage, compared to low molar mass HRI compounds, of being able to using cost-effective solution based technology for large area film preparation. In addition, polymeric materials will allow to introducing fully new concepts for increasing the light-out-coupling efficiency, like patterning allowing micro-lens preparation, or the incorporation of light scattering particles into the out-coupling layer. The approach described in this thesis is based on a previous work where HRI polymers were prepared via metal-free thiol-yne “A2+B3” polyaddition reaction, which led in an easy one-pot synthesis to hyperbranched polyvinylsulfides of high solubility and already reasonable high RI. For further increasing RI, in this work B3 as well as finally A2 monomers with high naphthalene content were chosen which should, in addition to the positive effect of the sulfur-containing units, render polymers with even higher RI, and hopefully also of high solubility due to the branching. A challenging aspect of this work was to find reaction conditions which allow the preparation of high molar mass as well as highly soluble, highly aromatic polymers by that A2+B3 approach, even so very sterically demanding monomers are used. In addition, the material properties should be fine-tuned by careful selection of the monomer ratio. It was expected that these new, easily available HRI polymers will be of high potential in OLED application. Thus, the work in this part of the thesis comprises on the one hand monomer and polymer synthesis as well as detailed characterization of the structure and the solution and thermal properties of the new materials. But on the other hand, the elucidation of the thin film preparation and the quality and optical properties of the resulting polymer films are major objectives. Finally, evaluation of the performance of the polymer films in an OLED device compared to conventionally low molar mass our-coupling layers was aimed for, which could be realized with the help of partners from the Institute of Applied Photophysics at TU Dresden. For increasing the IQE in OLEDs, this thesis focuses on the development of a new type of polymeric thermally activated delayed fluorescence (TADF) material. TADF materials have the potential of theoretical 100% IQE and are considered as key materials for the next generation of OLEDs. So far, a significant amount of low molar mass TADF molecules has been developed, however, only a limited number of design rules are reported so far for polymers, even though polymers would offer, as already outlined above, significant advantages with regard to processing cost-effectively more efficient OLEDs for large area application. The new concept described in this thesis for TADF polymers is based on a new monomer which exhibits individual promising structural units for achieving TAFD properties but does not emit TADF itself due to its large ΔEST (the energy gap between singlet S1 and triple T1 state). However, it has to be expected that once the monomer is polymerized, the resulting polymeric product will have reduced ΔEST due to the increased conjugation length and thus can be expected to emit TADF. This new concept has the potential to significantly increase the scope of polymeric materials with TADF properties. Thus the second part on the thesis focuses on the design of a new monomer based on carbazole units with a pendant benzophenone moiety and its polymerization and full structural elucidation with the help of model compounds involving intensive NMR and MALDI-TOF analysis. In addition to the expect TADF properties, the benzophenone unit will also provide the possibility for film stabilization and even photopatterning due to photo-crosslinking. Thus the study of film formation and photo-crosslinking of the new TADF polymers was a further objective of this thesis. Finally, first theoretical as well as experimental studies of the photo physical properties of the monomer, a low molar mass model compound and the polymer, again together with the partners from the Institute of Applied Photophysics, should provide evidence on the suitability of the new polymer design principle.

Il y a actuellement un vif intérêt pour des méthodes rigoureuses qui effectuent l’analyse électromagnétique des milieux diélectriques avec une distribution de permittivité diélectrique complexe. L’intérêt est motivé par des applications actuelles et futures dans la conception et la fabrication d’éléments optiques et optoélectroniques. Le niveau que les technologies de microstructuration ont maintenant atteint requiert des appels pour méthodes numériques rapides, économes en mémoire et rigoureuses capables de résoudre et d’optimiser des grandes parties de structures dont les caractéristiques représentent la fonction optique de la structure complète. Bien que la majorité des problèmes de modélisation en microoptique sont non périodiques (par exemple, une section d’une couche diffusante d’OLED, la cellule d’un réticule microélectronique, une microlentille diffractive de haute NA), ils peuvent être efficacement résolus par la périodisation de la distribution de l’indice. Une nouvelle méthode numérique puissante pour la modélisation exacte de structures périodiques 2D est décrite avec toutes les fonctionnalités et les expressions nécessaires à son exécution. La puissance de cette méthode est dans sa forme spécifique unique qui permet d’appliquer rapidement des algorithmes numériques et, par conséquent, de diminuer de façon spectaculaire la complexité de calcul en comparaison avec les méthodes établies. La comparaison avec des solutions de référence a montré que, d’abord, la nouvelle méthode donne les mêmes résultats que celles-ci sur les structures de référence et, d’autre part, que le temps de calcul nécessaire et le recours en mémoire représentent une percée vers la résolution de grandes structures périodiques ou périodisées. La méthode développée a été appliquée à analyser le problème de diffusion non périodique d’une couche diélectrique plan avec micro / nanoparticules sphériques. Une référence numérique proposée a démontré la possibilité d’obtenir environ 1% de précision. En outre, il a été développé un modèle numérique basé sur des matrices S pour la simulation des structures planes électroluminescentes. La validité de la méthode a été démontrée par comparaison avec les résultats expérimentaux. Enfin, les deux méthodes de calcul de la diffusion de la lumière et de simulation des structures multicouches ont été groupées, et une couche diffusante a été démontrée augmentait l’efficacité externe d’une OLED de quelques pour cents / There is presently a strong interest for rigorous methods that perform the electromagnetic analysis of dielectric media with complex dielectric permittivity distribution. The interest is motivated by both present and future applications in the design and manufacturing of optical elements and optoelectronic devices. The level that the microstructuring technologies have now reached calls for fast, memory sparing, and rigorous numerical methods capable of solving and optimizing large structure parts whose characteristics do represent the optical function of the whole structure. Although the majority of modeling problems in microoptics are non-periodic (e.g., a section of an OLED extraction layer, the cell of a microelectronic reticle, a high NA diffractive microlens) they can be efficiently solved by periodizing the index distribution. A new powerful numerical method for the exact modeling of 2D periodic structures is described with all features and expressions needed to implement it. The power of this method is in its unique specific form which permits to apply fast numerical algorithms and, consequently, to decrease dramatically the calculation complexity in comparison with established methods. The comparison with reference solutions has shown that, first, the new method gives the same results as the latter on benchmark structures and, secondly, that the needed calculation time and memory resort represent a breakthrough towards solving larger periodic or periodized structures. The developed method was applied to analyze nonperiodic scattering problem of a plane dielectric layer with spherical micro/nanoparticles. Proposed numerical benchmark demonstrated the possibility to get about 1% accuracy. In addition there was developed a numerical S-matrix based method for planar electroluminescent structures simulation. Validity of the method was demonstrated by comparison with experimental results. Finally both methods for the light scattering calculation and multilayer structures simulation were joined, and a scattering layer was demonstrated to increase an OLED external efficiency by several percent

Os dispositivos emissores de luz orgânicos OLEDs têm despertado um enorme interesse tanto da comunidade científica quanto das empresas presentes no mercado mundial de displays. As características de elevado ângulo de visão, alta eficiência energética, possibilidade de confecção de displays flexíveis que não necessitam retroiluminação, baixo peso, fácil processabilidade, dentre outras, fazem com que os displays fabricados com materiais orgânicos apresentem um enorme potencial para as mais diversas aplicações. O presente trabalho teve como objetivo contribuir para a construção e caracterização de displays monocromáticos à base de polímeros luminescentes depositados pela técnica Ink Jet. Para tanto foram preparados os padrões de linhas x colunas, formadores dos pontos luminosos (pixels) de matrizes passivas e desenvolvidos processos para deposição dos filmes finos de polímeros semicondutores. A utilização da deposição por Ink Jet aparece como uma técnica chave para a produção de dispositivos poliméricos. Nesta pesquisa, como material luminescente foi utilizado um polímero da família do polifluoreno, de fácil processamento e elevada eficiência luminosa, enquanto que como eletrodos foram utilizados o óxido de estanho e índio (ITO) e Alumínio. O ITO foi utilizado por possuir baixa resistividade elétrica, elevada função de trabalho e elevada transmitância na região do visível. O processo de encapsulamento do display se deu por meio do acondicionamento destes dispositivos em ambiente isento de oxigênio e umidade, evitando-se os efeitos já conhecidos da foto-oxidação das camadas poliméricas. Os dispositivos, uma vez preparados, foram caracterizados por meio de medidas ópticas (fotoluminescência), elétricas (eletroluminescência, condutividade) e de desempenho (eficiência luminosa e luminância). / Organic Light Emitters Diodes OLEDs is a promising field of study and a huge market opportunity to semiconductor players. Thanks to its potential characteristics to replace the main todays display technologies like lightweight, low voltage, wide viewing angle, high resolution, fast switching, broad color range and the possibility to fabricate flexible devices, makes the organic semiconductors a potential candidate to develop, in a near future, devices and systems that even could not be imagined before. This work aims to contribute to the manufacturing process field and to the characterization of displays made by ink jet deposition technique. To achieve this objective, line x column patterns were produced, in which the pixels are generated at the crossing of lines and columns. The ink jet printing of materials is playing an important role in industry because it provides a low-cost manufacture environment potential. In this work, we studied the morphology of the ink jet deposition of polyfluorene over Indium Tin Oxide (ITO) substrates treated by different procedures. Those materials where used because the polyfluorene polymer presents high light emission efficiency and easiness of processing. The electrodes were prepared with ITO (due its low resistivity, high work function and high transmittance in the visible spectrum) and aluminum. The processed displays were sealed inside an inert ambient with positive pressure to avoid the photo-oxidation of the semiconductor luminescent polymer layers. The devices were characterized by optical (photoluminescence), electrical (electroluminescence) and performance (brightness, luminous efficiency) measurements.

Este trabalho foi dividido em duas partes, sendo que na primeira (PARTE A) estão apresentadas as sínteses dos polímeros PPV, Cl-PPV, Br-PPV e dos co-polímeros (Cl-PPV)m / (PPV)n e (Br-PPV)m / (PPV)n nas seguintes relações m:n de 30:70; 50:50 e 70:30. Estes polímeros foram caracterizados por espectroscopia de infravermelho, UV-Visível e emissão de fluorescência. As modificações causadas nos polímeros, devido a dopagem com vapor de iodo e solução de cloreto férrico 0,12M em nitrometano também foram estudadas por estas mesmas técnicas. O acompanhamento da dopagem do PPV com vapor de iodo permitiu fazer a atribuição das bandas polarônicas e bipolarônicas por espectroscopia óptica. Também foram feitas medidas de voltametria cíclica que permitiram avaliar parâmetros eletrônicos importantes destes polímeros, tais como a Afinidade Eletrônica (HOMO), Potencial de Ionização (LUMO) e o GAP que é a diferença entre esses dois níveis de energia. Os co-polímeros apresentaram valores de energia do GAP menores que o PPV e níveis de energia de HOMO e de LUMO que podem ser apropriados para a utilização destes materiais em dispositivos eletroluminescentes (LED). Na PARTE B está apresentada a síntese de um composto inédito o 4- (2-fenoxi-p-xileno)-N-metil-1,8-naftalimida aqui chamado de NPOX. A caracterização do NPOX foi feita por espectroscopia de ressonância magnética v nuclear de próton (RMN 1H), espectrometria de massas (CG/MS), UV-Vis e Emissão de Fluorescência. O NPOX é solúvel em clorofórmio, que quando evaporado promove a formação de um filme transparente. Este filme tem emissão de fluorescência em 456 nm sendo excitado em 363 nm O filme também apresentou um comportamento semelhante a dos diodos demonstrado pela medida elétrica de corrente versus potencial (curva I x V). Estas propriedades abrem a possibilidade da utilização do NPOX como camada ativa, com emissão no azul, em OLED (Dispositivos Eletroluminescentes Orgânicos). / This work was separated in two parts, in the first, called PART A, the synthesis of the polymers PPV, Cl-PPV, Br-PPV and of the co-polymers (Cl-PPV)m / (PPV)n and (Br-PPV)m / (PPV)n in the following relationships m:n of 30:70; 50:50 and 70:30 are presented. These polymers were characterized by infrared spectroscopy, UVvisible and fluorescence emission. The modifications caused in the polymers due to the doping with iodine vapor and 0,12M ferric chloride in nitrometano solution were studied also by these same techniques. The doping of PPV with iodine vapor have been monitored by optical spectroscopy allowing us to do the attribution of the polaronic and bipolaronic bands. Measurements of cyclic voltametry revealed important electric properties of these polymers, such as the Electronic Affinity (HOMO), Ionization Potential (LUMO) and \" GAP \" that is the difference between those two energy levels. The co-polymers presented smaller values of GAP than PPV and HOMO and of LUMO energy levels that can be appropriate to the use these materials in Light-Emitting Devices (LED). In PARTE B, the synthesis of an unpublished compound is presented, the 4-(2-fenoxi-p-xileno)-N-methyl-1,8-naftalimida, here called as NPOX. The characterization of NPOX was made by of nuclear magnetic resonance of proton vii spectroscopy (1H NMR), Gas Cromatography/ Mass Spectrometry (GC/MS), UVVisible and Fluorescence Emission spectroscopy. NPOX is soluble in chloroform that when evaporated it promotes in a transparent film formation. This film has fluorescence emission in 456 nm when excited in 363 nm. The film also showed a similar behavior as diodes that was demonstrated by the electric measurement of current versus potential (I x V curve). These properties open the possibility of the use of NPOX as activate layer, with emission in the blue region, in OLED (Organic Light- Emitting Devices).

Os dispositivos emissores de luz orgânicos OLEDs têm despertado um enorme interesse tanto da comunidade científica quanto das empresas presentes no mercado mundial de displays. As características de elevado ângulo de visão, alta eficiência energética, possibilidade de confecção de displays flexíveis que não necessitam retroiluminação, baixo peso, fácil processabilidade, dentre outras, fazem com que os displays fabricados com materiais orgânicos apresentem um enorme potencial para as mais diversas aplicações. O presente trabalho teve como objetivo contribuir para a construção e caracterização de displays monocromáticos à base de polímeros luminescentes depositados pela técnica Ink Jet. Para tanto foram preparados os padrões de linhas x colunas, formadores dos pontos luminosos (pixels) de matrizes passivas e desenvolvidos processos para deposição dos filmes finos de polímeros semicondutores. A utilização da deposição por Ink Jet aparece como uma técnica chave para a produção de dispositivos poliméricos. Nesta pesquisa, como material luminescente foi utilizado um polímero da família do polifluoreno, de fácil processamento e elevada eficiência luminosa, enquanto que como eletrodos foram utilizados o óxido de estanho e índio (ITO) e Alumínio. O ITO foi utilizado por possuir baixa resistividade elétrica, elevada função de trabalho e elevada transmitância na região do visível. O processo de encapsulamento do display se deu por meio do acondicionamento destes dispositivos em ambiente isento de oxigênio e umidade, evitando-se os efeitos já conhecidos da foto-oxidação das camadas poliméricas. Os dispositivos, uma vez preparados, foram caracterizados por meio de medidas ópticas (fotoluminescência), elétricas (eletroluminescência, condutividade) e de desempenho (eficiência luminosa e luminância). / Organic Light Emitters Diodes OLEDs is a promising field of study and a huge market opportunity to semiconductor players. Thanks to its potential characteristics to replace the main todays display technologies like lightweight, low voltage, wide viewing angle, high resolution, fast switching, broad color range and the possibility to fabricate flexible devices, makes the organic semiconductors a potential candidate to develop, in a near future, devices and systems that even could not be imagined before. This work aims to contribute to the manufacturing process field and to the characterization of displays made by ink jet deposition technique. To achieve this objective, line x column patterns were produced, in which the pixels are generated at the crossing of lines and columns. The ink jet printing of materials is playing an important role in industry because it provides a low-cost manufacture environment potential. In this work, we studied the morphology of the ink jet deposition of polyfluorene over Indium Tin Oxide (ITO) substrates treated by different procedures. Those materials where used because the polyfluorene polymer presents high light emission efficiency and easiness of processing. The electrodes were prepared with ITO (due its low resistivity, high work function and high transmittance in the visible spectrum) and aluminum. The processed displays were sealed inside an inert ambient with positive pressure to avoid the photo-oxidation of the semiconductor luminescent polymer layers. The devices were characterized by optical (photoluminescence), electrical (electroluminescence) and performance (brightness, luminous efficiency) measurements.

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). / Complexes containing Rare Earth ions are of great interest in the manufacture of electroluminescent devices as organic light emitting devices (OLED). These devices, using rare earth trivalent ions (TR3+) as emitting centers, show high luminescence with extremely fine spectral bands due to the structure of their energy levels, long life time and high quantum efficiency. This work reports the preparation of Rare Earth β-diketonate complexes (Tb3+, Eu3+, Gd3+) and (tta - tenoyltrifluoroacetonate and acac - acetylacetonate) containing a ligand macrocyclic crown ether (DB18C6 - dibenzo18coroa6) and polymer films of UO22+. The materials were characterized by complexometric titration with EDTA, CH elemental analysis, near infrared absorption spectroscopy, thermal analysis, X-ray diffraction (powder method) and luminescence spectroscopy. For manufacturing the OLED it was used the technique of deposition of thin films by physical vapor (PVD, Physical Vapor Deposition).

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). / Complexes containing Rare Earth ions are of great interest in the manufacture of electroluminescent devices as organic light emitting devices (OLED). These devices, using rare earth trivalent ions (TR3+) as emitting centers, show high luminescence with extremely fine spectral bands due to the structure of their energy levels, long life time and high quantum efficiency. This work reports the preparation of Rare Earth β-diketonate complexes (Tb3+, Eu3+, Gd3+) and (tta - tenoyltrifluoroacetonate and acac - acetylacetonate) containing a ligand macrocyclic crown ether (DB18C6 - dibenzo18coroa6) and polymer films of UO22+. The materials were characterized by complexometric titration with EDTA, CH elemental analysis, near infrared absorption spectroscopy, thermal analysis, X-ray diffraction (powder method) and luminescence spectroscopy. For manufacturing the OLED it was used the technique of deposition of thin films by physical vapor (PVD, Physical Vapor Deposition).