In this research, we studied the phenomenon of energy transfer of polymer phosphorescent light-emitting diodes, PPLEDs. This thesis was divided into three parts: devices constructed by new-type host polymer blended with phosphorescent material, devices constructed by host polymer PVK blended with phosphorescent materials, and devices constructed by new-type phosphorescent polymer materials. The phenomenon of energy transfer between host polymer BP105 and phosphorescent dye Ir(ppy)3 was studied. Second, we chose PVK as a host polymer material, and Ir(ppy)3 as a phosphorescent guest material, to observe whether it can improve efficiency of devices by using energy transfer process. At last we manufactured devices constructed by new-type host polymer blended or bonded with new-type phosphorescent materials, and compared their emitting and energy transfer efficiency. A glycerol-modified PEDOT:PSS layer that used as an anode buffer layer in PLED using super yellow as the emitter was also been studied. It was found the glycerol-modified device showed a larger current density and improved luminescent efficiency then that of the unmodified device.

Ce travail de thèse décrit l'utilisation de complexes de platine(II) dans les diodes électroluminescentes organiques (OLEDs). Ces complexes ([Pt(II) (tetra-tert-butylSalophen)] et [Pt(II) Salophen]) ont été caractérisés par les méthodes usuelles (1H RMN, spectroscopie UV-visible, électrochimie, diffraction des rayons X pour le [Pt(II) (tetra-tert-butylSalophen)]). Des calculs DFT ont corroboré les données expérimentales qui ont guidé le choix du Tris(8-hydroxyquinolinato) aluminum (Alq3) en tant que matrice. Des dispositifs bistables, susceptibles d'être utilisés en tant que mémoires, ont été obtenus lors du dopage, à 5%, d'OLEDs monocouches. La modulation de ce phénomène par l'ajout d'une couche de N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD) d'épaisseur contrôlée, a été mis en évidence. Des OLEDs bicouches (NPD/Alq3:Pt) émettant dans la gamme spectrale 640-750 nm (rouge profond), et présentant des rendements supérieurs à 20 %, ont ainsi été réalisées. En dopant la couche de NPD, des OLED jaunes présentant un comportement électro-chromatique ont été élaborées. Sous l'effet du dopage par ces complexes, l'augmentation de la durée de vie des OLEDs a aussi été démontrée. / This thesis describes the integration of platinum(II) complexes within organic light emitting diodes (OLEDs). These complexes ([Pt(II) (tetra-tert-butylSalophen)] and [Pt(II) Salophen]) were characterized by the usual methods ( 1H NMR, UV-Vis spectroscopy, electrochemistry and X-ray diffraction for [Pt(II) (tetra-tert-butylSalophen)]). DFT calculations support the experimental data which guided the selection of Tris(8-hydroxyquinolinato) aluminum (Alq3)as host. 5% doping in monolayer OLEDs gave bistable devices which may be used as memory. Modulation of this phenomenon was allowed by adding a controlled layer of N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD). Bilayer OLEDs (NPD/Alq3:Pt) were shown to emit in the deep-red range between 640-750nm with efficiencies higher than 20%. Upon doping with complexes, an enhancement in the lifetime of OLEDs was highlighted.

Phosphorescent organic light emitting diodes (PHOLEDs) based on efficient electrophosphorescent dopant, platinum(II)-pyridyltriazolate complex, bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) have been studied and improved with respect to power efficiency, external efficiency, chromacity and efficiency roll-off. By studying the electrical and optical behavior of the doped devices and functionality of the various constituent layers, devices with a maximum EQE of 20.8±0.2 % and power efficiency of 45.1±0.9 lm/W (77lm/W with luminaries) have been engineered. This improvement compares to devices whose emission initially could only be detected by a photomultiplier tube in a darkened environment. These devices consisted of a 65 % bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) doped into 4,4'-bis(carbazol-9-yl)triphenylamine (CBP) an EML layer, a hole transporting layer/electron blocker of 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), an electron transport layer of 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), and a LiF/Al cathode. These devices show the acceptable range for warm white light quadrants and qualify to be called "warm white" even w/o adding another emissive layer. Dual EML devices composed of neat Pt(ptp)2 films emitting orange and CBP: Pt(ptp)2 film emitting blue-green produced a color rendering index (CRI) of 59 and color coordinates (CIE) of (0.47,0.49) at 1000Cd/m² with power efficiency of 12.6±0.2 lm/W and EQE of 10.8±0.2 %. Devices with two blue fluorescent emission layers as singlet filters and one broad yellow emission layer from CBP: Pt(ptp)2 displayed a CRI of 78 and CIE of (0.28,0.31) at 100Cd/m² with maximum power efficiency of 6.7±0.3 lm/W and EQE of 5.7±0.2 %.

The development of new charge transport materials for use in phosphorescent organic light-emitting diodes (OLEDs) remains an important area of research. In this thesis, several examples of carbazole-containing norbornene-based side-chain polymers were synthesized and studied. In addition, several examples of ambipolar transport moieties were produced by combining hole- (carbazole) and electron- (oxadiazole or triazole) transport groups and examined as both small molecules and as norbornene-based side-chain polymers. UV-visible absorption, fluorescence spectroscopy, cyclic voltammetry, and other methods were used to evaluate the properties of the charge transport materials for use as hole- and/or host layers. It was found that side-functionalization produced polymers with photophysical and electrochemical properties corresponding to the charge transport side groups attached. In addition, several crosslinkable hole-transporting materials (copolymer or small molecule-based) incorporating either benzocyclobutenes, trifluorovinyl ethers, oxetanes, or bis(styrene)s were developed. Thin-films of the crosslinkable materials were shown to be readily insolubilized by thermal treatment permitting the deposition of a subsequent layer from solution onto the crosslinked layer. OLEDs fabricated using several of these materials produced efficient devices. Overall, it was shown that side-chain functionalization can be used to afford solution-processable charge transport polymers where the properties are determined mainly by the side group attached. As such, this approach could be extended to additional examples of charge transport moieties.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22460号 / 工博第4721号 / 新制||工||1737(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 近藤 輝幸, 教授 大江 浩一, 教授 中村 正治 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Ce travail porte sur la réalisation d'un micro-écran OLED haute luminance sur silicium. L'efficacité limitée des structures WOLED associées à des filtres colorés est un frein au développement de cette technologie pour des applications dans des dispositifs de type « see-through ». Nous proposons une approche tirant parti de l'effet de microcavité optique présent dans les écrans OLED à émission vers le haut pour générer des couleurs sans filtres. Les modulations de cavité à l'échelle du sous-pixel étant assurées par l'insertion d'oxyde transparent conducteur entre l'anode et l'OLED.L'étude offre selon un raisonnement cohérent de suivre les différentes phases de la réalisation d'un démonstrateur de ce type. Seront abordées dans la première partie les étapes technologiques de structuration de l'oxyde à l'échelle d'un sous-pixel de 16µm². Nous traiterons ensuite du développement d'un empilement OLED tandem utilisant des émetteurs fluorescent et phosphorescents. Une approche par simulation optique sera utilisée pour l'optimisation de cette architecture à un fonctionnement sur microcavité. Puis la discussion autour de la mise en commun des blocs technologiques précédents permettra d'aborder des écueils spécifiques au micro-écran OLED et de proposer des pistes de résolution. / This study focuses on the realization of a high brightness OLED micro-écran on silicon. The limited efficiency of White-OLED combined with color filters prevents the use of this technology in “see-through” applications. We propose a novel approach getting benefits from the optical micro-cavity effect in Top-Emitting OLED to generate colors without using color filters. Cavity modulations at a sub-pixel scale are realized by using a Transparent Conducting Oxide between the anode and the OLED.Following a step-by-step reasoning the work offers to follow all the phases of the realization of a prototype using this principle. In the first part, the technological steps of the processing of oxide cavities with a surface of 16µm² will be discussed. Then we will work on the development of a tandem OLED structure using both fluorescent and phosphorescent emitters optimized for micro-cavities. To this end optical simulation will be used. The two technological blocs will finally be put together to enlighten some issues specific for micro-écran technology and to give some clues to solve them.

<p>Phosphorescent metal complexes can be incorporated into amyloid-like fibrils, and these fibrils can be decorated with conjugated polyelectrolytes (CPEs). In this study, <em>fac</em>-tris[2-phenylpyridinato-<em>C</em>²,N]irdium(III) complexes [Ir(piq)₃] were used as the phosphorescence emitter and Sodium-poly(3-thiophene acetic acid) (PTAA-Na) compounds were used as CPEs. Herein we study the energy transfer processes between the iridium complexes and the CPEs. To investigate these mechanisms, the analysis of the emission quenching and time-resolved measurements were done. Our measurements show that energy can be transfered from singlet state of PTAA to the singlet state of Ir(piq)₃. Moreover, incorporation of iridium into amyloid fibrils decreases the importance of energy transfer by the Dexter mechanism. Finally we propose a geometry of interaction to explain the obtained results.</p>

Phosphorescent metal complexes can be incorporated into amyloid-like fibrils, and these fibrils can be decorated with conjugated polyelectrolytes (CPEs). In this study, fac-tris[2-phenylpyridinato-C2,N]irdium(III) complexes [Ir(piq)3] were used as the phosphorescence emitter and Sodium-poly(3-thiophene acetic acid) (PTAA-Na) compounds were used as CPEs. Herein we study the energy transfer processes between the iridium complexes and the CPEs. To investigate these mechanisms, the analysis of the emission quenching and time-resolved measurements were done. Our measurements show that energy can be transfered from singlet state of PTAA to the singlet state of Ir(piq)3. Moreover, incorporation of iridium into amyloid fibrils decreases the importance of energy transfer by the Dexter mechanism. Finally we propose a geometry of interaction to explain the obtained results.

Organic semiconductors are very attractive for thin film Organic Photodetectors (OPDs) since they possess a number of desirable attributes for optical sensing including high absorption coefficients over visible and ultraviolet wavelengths and compatibility with large-area deposition processes such as ink-jet, screen printing, and solution processing. OPDs, in general, utilize a vertical device architecture where the photoactive organic semiconductor layers are sandwiched between top and bottom electrodes that provide electrical contact. More recently, an interest in utilizing a lateral device architecture instead of the vertical one, has emerged. In this architecture, the two contacts are positioned on the two sides of the photoactive material with respect to the direction of the incoming signal, separated by a small gap. However, the factors governing lateral OPDs’ photo-response are still not well understood. In this thesis, we fabricate top-contact lateral OPDs using a thermal evaporation only fabrication process. We study the factors governing both the dark and photo currents of lateral OPDs. The effect of the wide gap between the two electrodes on the current-voltage characteristics is discussed and the role of space charge limited conduction is investigated. The contributions in the photoresponse of light scattering through the active layers as well as the back reflection of light at the metallic contacts are emphasized. The reproducibility over repeated operation cycles of both dark and photo currents values is explored. Exposure to light of the lateral OPD is found to lead to a significant increase in the dark current. The role of the conductivity enhancement in the channel due to light-induced trap filling is investigated. External quantum efficiency and detectivity estimates are given for deep ultraviolet lateral (DUV) OPDs. A comparison with vertical DUV OPDs performances is provided. Finally, the use of a phosphorescent sensitizer doped in the absorbing bottom layer to improve top-contact lateral OPDs efficiency is discussed.