Les diodes organiques électroluminescentes (OLEDs) représentent une évolution de la technologie des diodes électroluminescentes (LED) dans lesquelles l'émission de couleur provient de molécules organiques. Ce travail porte sur la synthèse et l'étude de nouvelles molécules dans le but de leur utilisation (i) comme couche active dans les OLED fluorescentes ou (ii) comme matériau hôte dans les OLEDs phosphorescentes (PhOLEDs). Tout d'abord, une introduction à ce domaine important de l'électronique organique est présentée et suivie de la synthèse de nouveaux semi-conducteurs organiques dérivés d'oligophénylènes d'architecture 3π-2spiro ou 2π-1spiro. L'analyse détaillée de leurs propriétés physico-chimiques est ensuite présentée. Les performances des OLEDs et/ou PhOLEDs bleues utilisant ces nouvelles matrices sont alors décrites et montrent l'intérêt des designs choisis pour les molécules. / Organic light emitting diodes (OLEDs) represent an evolution of the light emitting diode (LED) technology in which light is emitted from an organic molecule. This work is focused on the synthesis and the study of new molecules, which will be used (i) as emissive layer in fluorescent OLEDs, or (ii) as host material in phosphorescent OLED (PhOLED). First of all an introduction of the important field of organic electronics is presented, followed by the presentation of the synthesis of new organic semi-conductors (3π-2spiro or 2π-1spiro hydrocarbons). A detailed analysis of their properties was performed and after incorporation in the devices, the performances of blue OLEDs and PhOLEDs are compared. The performances recorded attests that this molecular design is of great interest.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24903号 / 工博第5183号 / 新制||工||1989(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 梶 弘典, 教授 関 修平, 教授 寺村 謙太郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Mit Seitenkettenpolystyrenen wurde ein neues Synthesekonzept für phosphoreszente polymere LED-Materialien aufgestellt und experimentell verifiziert. Zunächst erfolgten auf Grundlage strukturell einfacher Verbindungen Untersuchungen zum Einfluss von Spacern zwischen aktiven Seitengruppen und dem Polystyrenrückgrat. Es wurden Synthesemethoden für die Monomere etabliert, durch die aktive Elemente - Elektronen- und Lochleiter - mit und ohne diesen Spacer zugänglich sind. Durch Kombination dieser Monomere waren unter Hinzunahme von polymerisierbaren Iridium-Komplexen in unterschiedlicher Emissionswellenlänge statistische Terpolymere darstellbar. Es wurde gezeigt, dass die Realisierung bestimmter Verhältnisse zwischen Loch-, Elektronenleiter und Triplettemitter in ausreichender Molmasse möglich ist. Die Glasstufen der Polymere zeigten eine deutliche Strukturabhängigkeit. Auf die Lage der Grenzorbitale übten die Spacer nahezu keinen Einfluss aus. Die unterschiedlichen Makromoleküle kamen in polymeren Licht emittierenden Dioden (PLEDs) zum Einsatz, wobei ein deutlicher Einfluss der Spacereinheiten auf die Leistungscharakteristik der PLEDs festzustellen war: Sowohl Effizienz, Leuchtdichte wie auch Stromdichte waren durch den Einsatz der kompakten Makromoleküle ohne Spacer deutlich höher. Diese Beobachtungen begründeten sich hauptsächlich in der Verwendung der aliphatischen Spacer, die den Anteil im Polymer erhöhten, der keine Konjugation und damit elektrisch isolierende Eigenschaften besaß. Diese Schlussfolgerungen waren mit allen drei realisierten Emissionsfarben grün, rot und blau verifizierbar. Die besten Messergebnisse erzielte eine PLED aus einem grün emittierenden und spacerlosen Terpolymer mit einer Stromeffizienz von etwa 28 cd A-1 (bei 6 V) und einer Leuchtdichte von 3200 cd m-2 (bei 8 V). Ausgehend von obigen Ergebnissen konnten neue Matrixmaterialien aus dem Bereich verdampfbarer Moleküle geringer Molmasse in das Polystyrenseitenkettenkonzept integriert werden. Es wurden Strukturvariationen sowohl von loch- wie auch von elektronenleitenden Verbindungen als Homopolymere dargestellt und als molekular dotierte Systeme in PLEDs untersucht. Sieben verschiedene lochleitende Polymere mit Triarylamin-Grundkörper und drei elektronendefizitäre Polymere auf der Basis von Phenylbenzimidazol konnten erfolgreich in den Polymeransatz integriert werden. Spektroskopische und elektrochemische Untersuchungen zeigten kaum eine Veränderung der Charakteristika zwischen verdampfbaren Molekülen und den dargestellten Makromolekülen. Diese ladungstransportierenden Makro-moleküle wurden als polymere Matrizes molekular dotiert und lösungsbasiert zu Einschicht-PLEDs verarbeitet. Als aussichtsreichstes Lochleiterpolymer dieser Reihe, mit einer Strom-effizenz von etwa 33 cd A-1 (bei 8 V) und einer Leuchtdichte von 6700 cd m-2 (bei 10 V), stellte sich ein Triarylaminderivat mit Carbazolsubstituenten heraus. Als geeignetstes Matrixmaterial für die Elektronenleitung wurde ein meta-verknüpftes Di-Phenylbenzimidazol ausfindig gemacht, das in der PLED eine Stromeffizienz von etwa 20 cd A-1 (bei 8 V) und eine Leuchtdichte von 7100 cd m-2 (bei 10 V) erzielte. Anschließend wurden die geeignetsten Monomere zu Copolymeren kombiniert: Die lochleitende Einheit bildete ein carbazolylsubstituiertes Triarylamin und die elektronen-leitende Einheit war ein disubstituiertes Phenylbenzimidazol. Dieses Copolymer diente im Folgenden dazu, PLEDs zu realisieren und die Leistungsdaten mit denen eines Homopolymer-blends zu vergleichen, wobei der Blend die bessere Leistungscharakteristik zeigte. Mit dem Homopolymerblend waren Bauteileffizienzen von annähernd 30 cd A-1 (bei 10 V) und Leuchtdichten von 6800 cd m-2 neben einer Verringerung der Einsatzspannung realisierbar. Für die abschließende Darstellung bipolarer Blockcopolymere wurde auf die Nitroxid-vermittelte Polymerisation zurückgegriffen. Mit dieser Technik waren kontrollierte radikalische Polymersiationen mit ausgewählten Monomeren in unterschiedlichen Block-längen durchführbar. Diese Blockcopolymere kamen als molekular dotierte Matrizes in phosphoreszenten grün emittierenden PLEDs zum Einsatz. Die Bauteile wurden sowohl mit statistischen Copolymeren, wie auch mit Homopolymerblends in gleicher Zusammensetzung aber unterschiedlichem Polymerisationsgrad hinsichtlich der Leistungscharakteristik verglichen. Kernaussage dieser Untersuchungen ist, dass hochmolekulare Systeme eine bessere Leistungscharakteristik aufweisen als niedermolekulare Matrizes. Über Rasterkraft-mikroskopie konnte eine Phasenseparation in einem Größenbereich von etwa 10 nm für den hochmolekularen Homopolymerblend nachgewiesen werden. Für die Blockcopolymere war es nicht möglich eine Phasenseparation zu beobachten, was vorwiegend auf deren zu geringe Blocklänge zurückgeführt wurde. / A new synthetic approach for the synthesis of side chain polystyrenes was established and their use as phosphorescent polymers for polymer light emitting diodes (PLEDs) is shown by experiments. An assay was introduced to clarify influences on electroluminescent behavior for RGB-colored phosphorescent terpolymers with N,N-Di-p-tolyl-aniline as hole-transporting unit, 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tert-BuPBD) as electron-transporting unit, and different iridium complexes in RGB-colors as triplet emitting materials. All monomers were attached with spacer moieties to the “para” position of a polystyrene. PLEDs were built to study the electro-optical behavior of these materials. The gist was a remarkable influence of hexyl-spacer units to the PLED performance. For all three colors only very restricted PLED performances were found. In comparison RGB-terpolymers were synthesized with directly attached charge transport materials to the polymer backbone. For this directly linked systems efficiencies were 28 cd A−1 @ 6 V (green), 4.9 cd A−1 @ 5 V (red) and 4.3 cd A−1 @ 6 V (bluish). In summary it is assumed that an improved charge percolation pathways regarding to the higher content of semiconducting molecules and an improved charge transfer to the phosphorescent dopand in the case of the copolymers without spacers are responsible for the better device performance comparing the copolymers with hexyl spacers. It was found that the approach of the directly connected charge transport materials at the nonconjugated styrene polymer backbone is favored for further investigations as shown in the following. A series of styrene derived monomers with triphenylamine-based units, and their polymers have been synthesized and compared with the well-known structure of polymer of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine with respect to their hole-transporting behavior in PLEDs. A vinyltriphenylamine structure was selected as a basic unit, functionalized at the para positions with the following side groups: diphenylamine, 3-methylphenyl-aniline, 1- and 2-naphthylamine, carbazole, and phenothiazine. The polymers are used in PLEDs as host polymers for blend systems. It is demonstrated that two polymers are excellent hole-transporting matrix materials for these blend systems because of their good overall electroluminescent performances and their comparatively high glass transition temperatures. For the carbazole-substituted polymer (Tg = 246 °C), a luminous efficiency of 35 cd A−1 and a brightness of 6700 cd m−2 at 10 V is accessible. The phenothiazine-functionalized polymer (Tg = 220 °C) shows nearly the same outstanding PLED behavior. Hence, both these polymers outperform the well-known polymer of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine, showing only a luminous efficiency of 7.9 cd A−1 and a brightness of 2500 cd m−2 (10 V). Furthermore, novel styrene functionalized monomers with phenylbenzo[d]imidazole units and the corresponding homopolymers are prepared. The macromolecules are used as matrices for phosphorescent dopants to prepare PLEDs. The devices exhibit current efficiencies up to 38.5 cd A−1 at 100 cd m−2 and maximum luminances of 7400 cd m−2 at 10 V. Afterwards the most efficient monomers of this investigations were combined and statistical copolymers were synthesized. As hole-transporting monomer the carbazole substituted triarylamine and as electron-transporting monomer a disubstituted phenylbenzoimidazole was selected. This statistical copolymer was used in the following as matrix material for phosporescent PLEDs and the device performance was compared with a matrix system of a polymer blend matrix system of corresponding homopolymers. With this homopolymer blend efficiencies of about 30 cd A-1 at 10 V and luminances of 6800 cd m-2 beside a decreased onset voltage were realized. Finally bipolar blockcopolymers of structural basic monomers were synthesized via nitroxide mediated polymerization. With these technique and the chosen hole- and electron-transporting monomers a controlled radical polymerization was realized leading to blockcopolymers in different block lengths. These blockcopolymers were used as molecular doped matrix systems in green phosphoreszent PLEDs. The devices were compared in regard to their performances with PLEDs made of statistical copolymers and homopolymer blends. It was found that high molecular systems show a better device performance compared to low molecular polymer matrices. With atomic force microscopy it is shown that a phase separation takes place for the high molecular blend of homopolymers. For the synthesized blockcopolymers no phase separation could be verified, mainly because of the comparatively low molecular weight of these systems.

Abstract This thesis reports the investigation of color tuning of two types of organic light emitting devices, transistors (OLETs) and diodes (OLEDs). Voltage tunable two color light emission was demonstrated for OLETs. For OLEDs, two kinds of color tuning methods were presented. For these, color tuning was realized using thermal annealing which changes the light emission color of the devices permanently. The two color light emission of the OLETs, employing a three-layer heterostructure device configuration, occurs in red and green. The device structure was first utilized for producing red light emission originating from a light emission layer made of Alq3:DCM that was deposited between the hole and electron transport layers made of DH-4T and DFH-4T, respectively. After modifying the fabrication process in order to raise the device performance by acquiring smoother active layers green light could also be produced by the devices. Green light emission originated from the electron transport layer. This took place during the electron transport mode, while the red emission was apparent while hole transport was active. The color of the light emission was therefore demonstrated as being tunable by voltage. For OLEDs, devices with one active polymeric layer, undoped and doped, were investigated. The undoped OLEDs had the light emission layer made of blue light emitting polyfluorene PFO. The OLEDs suffered from keto-defects shifting their light emission color from blue to greenish shade, a common problem occurring in widely used blue light emitting polyfluorenes. The work conducted and reported in this thesis demonstrated that thermal annealing can be used for diminishing this undesired green emission. For the doped OLEDs with the light emission layer made of a PFO:F8BT blend, color tuning was realized using thermal annealing as well. As a result of exposure to thermal treatment, the light emission color of these devices which was green as fabricated was converted to white. The phenomenon behind this effect was explained by phase separation between the host and dopant polymers of the light emission layer. / Tiivistelmä Tässä väitöskirjatyössä tutkitaan orgaanisten valoa emittoivien transistoreiden (OLET) ja diodien (OLED) värinsäätöä. Työssä tehtiin kolmikerrosrakenteisia OLETeja, jotka kykenevät emittoimaan valoa kahdella värillä ja joiden emittointiväri on jännitesäädettävissä. OLEDien osalta toteutettiin kaksi erilaista värinsäätömenetelmää, joissa molemmissa hyödynnettiin kuumennusta pysyvän värinvaihdon aikaansaamiseksi. Tutkitut OLETit emittoivat punaista ja vihreää valoa. Aluksi tutkittiin vastaavia komponentteja, jotka emittoivat vain punaista valoa. Näissä komponenteissa punaisen valon tuotti keskimmäinen valoemitterinä toiminut kerros (Alq3:DCM), jonka ala- ja yläpuolella olivat aukko- ja elektronijohtavat kerrokset (DH-4T ja DFH-4T). Komponenteilla saatiin tuotettua myös vihreää valoa, kun valmistusprosessia kehitettiin tasaisempien aktiivisten materiaalikerrosten valmistamiseksi. Vihreän valon todettiin olevan elektronijohtavan kerroksen tuottamaa. Kaksiväriemittoiva OLET tuotti vihreää valoa ollessaan elektronijohtavassa tilassa, ja punaista valoa aukkojohtavassa tilassa, emittointivärin ollessa näin jännitesäädettävissä. Työssä tutkittujen OLEDien valon emittointi perustui polymeerikerrokseen, joka oli toisissa OLEDeissa seostamaton ja toisissa seostettu. Seostamattomien OLEDien aktiivinen kerros oli tehty sinistä valoa tuottavasta polyfluoreenista (PFO), jossa usein ilmenee keto-virheitä, joiden vuoksi PFO:sta tehtyjen OLEDien valo muuttuu sinisestä vihertäväksi. Työssä osoitettiin, että kuumennusta voidaan käyttää sinisen emittointivärin palauttamiseen. Seostettujen OLEDien (PFO:F8BT) osalta kuumennusta käytettiin komponenttien emittointivärin muuttamiseksi alkuperäisestä emittointiväristä vihreästä valkoiseksi. Tämä ilmiö selitettiin valoa emittoivan kerroksen polymeerien välisellä faasierkaantumisella.

Ce travail porte dans un premier temps sur l’optimisation du matériau constituant la couche d’injection des trous dans les diodes électroluminescentes organiques (OLEDs) et les cellules solaires organiques (OPVCs). Les Polyanilines (PANIs) utilisées dans ce travail sont dispersées dans différents solvants organiques ou dans l'eau. L’effet de l’épaisseur, de la morphologie et de la conductivité des films de PANI sur l’efficacité des cellules solaires a été étudié. Les résultats montrent que la conductivité et l’épaisseur des films de PANI affectent énormément l’efficacité des dispositifs OLEDs ou OPVCs. Le dopant et le solvant utilisés dans la synthèse de la dispersion de PANI jouent aussi un rôle important. Dans un second temps, différentes PANIs ainsi que des latex de PEDOT et des nanotubes de carbone ont été utilisés seuls en tant qu'électrode dans le but d'accéder à des dispositifs "tout polymère". L’influence du pH, de la conductivité, du travail de sortie, la nature du dopant et du solvant sur les propriétés de l’injection de charge ont été analysés. / The optimization of hole injection materials in organic light emitting diodes (OLEDs) and organic photovoltaic cells (OPVCs) is reported. Water and organic solvent-based PANIs were used. We have studied the influence of the thickness, the morphology and the conductivity of PANI films in (OPVCs) performances. The results show that the conductivity and the thickness of the PANI film greatly affect (OLED) and (OPVCs) effectiveness. The dopant and the solvent used in the synthesis of PANI dispersion also play an important role. PANI and PEDOT dispersions as well as carbon nanotube were also used as electrodes without ITO. The effect of pH, conductivity, the work function, the nature of the dopant and the solvent in the injection property were analyzed.

<p>U okviru doktorske disertacije predstavljene su elektronska i fononska struktura odabranih organometalnih materijala koji u svom sastavu imaju metale cink, kobalt ili bakar i organsko jedinjenje piridoksalaminogvanidin (PLAG). Predstavljene su realizacija i karakteristike organske svetleće diode zasnovane na najboljem od ispitivanih materijala. Urađena je detaljna analiza fotoluminescentnih spektara i njihovo razlaganje na proste komponente koristeći Lorencov model. Izvršeno je poređenje sa od ranije poznatim materijalom koji pokazuje visok stepen luminescencije. S obzirom da istraživanja vezana za organske svetleće diode uzimaju sve veći zamah i da ove diode postaju sve prisutnije u industrijskoj serijskoj proizvodnji, napravljena je detaljna analiza ove tehnologije i mehanizama koji se kriju iza nje. Urađeno je podrobno istraživanje kako na nivou elektrona u datim supstancama, tako i na nivou sloja organske svetleće diode. Na kraju je izvršena analiza rada diode sa integrisanim slojem sa materijalom koji u sebi sadrži cink i PLAG.</p> / <p>In this thesis electronic and phonon structure of specific organometallic<br />materials which have zinc, cobalt, copper metals and organic compound<br />pyridoxalaminoguanidin are presented. Implementation and characteristics of<br />organic light emitting diode based on the best material among examined<br />ones are also showed up. Detailed analysis of photoluminescence spectra<br />was done and its decomposition to its elementar components using<br />Lorentzian multipeak method. Comparison to well-known material that shows<br />high level of luminescence was implemented. In accordance to the fact that<br />research of organic light emitting diodes expands and that these diodes start<br />to be more present in industrial serial production, detailed analysis of this<br />technology and mechanisms behind it are made. Thorough research was<br />done both on electron level in these substances and organic light emitting<br />diode layer level. Finally, analysis of diode operation with integrated layer<br />made of material which includes zinc and pyridoxalaminoguanidin compound<br />is implemented.</p>

Porous metal oxides formed by supercritical carbon dioxide (SCCO2) treatments at low temperature were used for displays, solar cells, and light emitting diodes (LEDs) applications. The SCCO2 fluid, also known as green solvents, exhibits low viscosity, low surface tension and high diffusivity as gases, and high density and solubility same with liquids. In this thesis, we successfully fabricated porous antimony-doped tin oxide (ATO) and porous indium tin oxide (ITO) by the SCCO2 treatments. In addition, the treatment can also be used to improve the work function and surface energy of ITO anode of an organic LED (OLED). The performance of the OLEDs was drastically enhanced in comparison with that of the devices without any ITO surface treatments. First, the porous ATO films were formed by the SCCO2 treatment for absorption of silver molecules in silver electro deposition devices. The porosity, resistivity and average optical transmittance of the porous ATO film in visible wavelength were 43.1%, 3 £[-cm and 90.4%, respectively. For the silver electro deposition devices with the porous ATO film, the transmittance contrast ratio of larger than 12 in visible spectrum was obtained at an operating voltage of 1.5 V. Furthermore, for the 0.25 cm2 device, the switching time of 4.5 seconds was achieved by applying a square-wave voltage ranging from 1.5 to -0.2 V between the electrodes. On the other hand, the porous ITO with low refractive index was prepared by SCCO2/IPA treatment on gel-coated ITO thin films. The high refractive index of the ITO film was achieved by long-throw radio-frequency magnetron sputtering technique at room temperature. The index contrast (£Gn) was higher than 0.6 between porous ITO and sputtered ITO films. The large £Gn is useful for fabricating conductive anti-reflection (AR) and high reflection (HR) structures using the porous ITO on sputtered ITO bilayers. The weighted average reflectance and transmittance of 4.3% and 83.1% were achieved for the double-layer ITO AR electrode with a sheet resistance of 1.1 K£[/¡E. For HR structures, the reflectance and sheet resistance were 87.9% and 35 £[/¡E with 4 periods ITO bilayers. Finally, the SCCO2 treatments with strong oxidizer H2O2 were proposed to modify surface property of ITO anode of a fluorescent OLED. The highest work function and surface energy of 5.5 eV and 74.8 mJ/m2 was achieved by the SCCO2/H2O2 treatment. For the OLED with 15 min SCCO2 treatment at 4000 psi, the turn-on voltage and maximum power efficiency of 6.5 V and 1.94 lm/W were obtained. The power efficiency was 19.3% and 33.8% higher than those of the OLEDs with oxygen plasma treated and as-cleaned ITO anodes.

In this work, well-defined and stable thin films based on polythiophene and its derivative, are employed as the hole-injection contact of organic light-emitting diodes (OLED). The polymer films are obtained by the electropolymerization or the electrochemical doping/dedoping of a spin-coated layer. Their electrical properties and energetics are tailored by electrochemical adjustment of their doping levels in order to improve the hole-injection from the anode as well as the performance of small molecular OLEDs. By using dimeric thiophene and optimizing the electrodeposition parameters, a thin polybithiophene (PbT) layer is fabricated with well-defined morphology and a high degree of smoothness by electro-polymerization. The introduction of the semiconducting PbT contact layer improves remarkably the hole injection between ITO anode and the hole- transport layer (NPB) due to its favourable energetic feature (HOMO level of 5.1 eV). The vapor-deposited NPB/Alq3 bilayer OLEDs with a thin PbT interlayer, show a remarkable reduction of the operating voltage as well as enhanced luminous efficiency compared to the devices without PbT. Investigations have also been made on the influence of PbT thickness on the efficiency and I-V feature as well as device stability of the OLED. It is demonstrated that the use of an electropolymerization step into the production of vapor deposited molecular OLED is a viable approach to obtain high performance OLEDs. The study on the PbT has been extended to poly(3,4-ethylenedioxythiophene) (PEDT) and the highly homogenous poly(styrenesulfonate) (PSS) doped PEDT layer from a spin-coating process has been applied. The doping level of PEDT:PSS was adjusted quantitatively by an electrochemical doping/dedoping process using a p-tuoluenesulfonic acid containing solution, and the redox mechanism was elucidated. The higher oxidation state can remain stable in the dry state. The work function of PEDT:PSS increases with the doping level after adjusting at an electrode potential higher than the value of the electrochemical equilibrium potential (Eeq) of an untreated film. This leads to a further reduction of the hole-injection barrier at the contact of the polymeric anode/hole transport layer and an ideal ohmic behavoir is almost achieved at the anode/NPB interface for a PEDT:PSS anode with very high doping level. Molecular Alq3-based OLEDs were fabricated using the electrochemically treated PEDT:PSS/ITO anode, and the device performance is shown to depend on the doping level of polymeric anode. The devices on the polymer anode with a higher Eeq than that for the unmodified anode, show a reduction of operating voltage as well as a remarkable enhancement of the luminance. Furthermore, it is found that the operating stability of such devices is also improved remarkably. This originates from the removal of mobile ions such as sodium ions inside the PEDT:PSS by electrochemical treatment as well as the planarization of the ITO surface by the polymer film. By utilizing an Al/LiF cathode with an enhanced electron injection and together with a high Eeq- anode, a balanced injection and recombination of hole and electron is achieved. It leads to a further reduction of the operating voltage and to a drastic improvement of EL efficiency of the device as high as 5.0 cd/A. The results demonstrate unambiguously that the electrochemical treatment of a cast polymer anode is an effective method to improve and optimize the performance of OLEDs. The method can be extended to other polythiophene systems and other conjugated polymers in the fabrication of the OLEDs as well as organic transistors and solar cells.

A numerical model and results for the quantitative simulation of multilayer organic light emitting diode (OLED) and organic solar cell (OSC) are presented. In the model, effects like bipolar charge carrier drift and diffusion with field-dependent mobilities, trapping, dopants, indirect and direct bimolecular recombination, singlet Frenkel exciton diffusion, normal decay and quenching effects are taken into account. For an adequate description of multilayer devices with energetic barriers at interfaces between two adjacent organic layers, thermally assisted charge carrier hopping through the interface, interface recombination, and formation of interface charge transfer (CT) states have been introduced in the model. For the simulation of OSC, the generation of carrier pairs in the mixed layer or at the interface is additionally implemented. The light absorption profile is calculated from optical simulations and used as an input for the electrical simulation. The model is based on three elements: the Poisson equation, the rate equations for charge carriers and the rate equations for singlet Frenkel excitons. These equations are simultaeously solved by spatial and temporal discretisation using the appropriate boundary conditions and electrical parameters. The solution is found when a steady state is reached, as indicated by a constant value of current density. The simulation provides a detailed look into the distribution of electric field and concentration of free and trapped carriers at a particular applied voltage. For organic light emitting diodes, the numerical model helps to analyze the problems of different structures and provides deeper insight into the relevant physical mechanisms involved in device operation. Moreover, it is possible to identify technological problems for certain sets of devices. For instance, we could show that ? in contrast to literature reports - the contact between Alq3 and LiF/Al did not show ohmic behaviour for the series of devices. The role of an additional organic blocking layer between HTL and EML was presented. The explanation for the higher creation efficiency for singlet excitons in the three-layer structure is found in the separation of free holes and electrons accumulating close to the internal interface 1-Naphdata/Alq3. The numerical calculation has demonstrated the importance of controlled doping of the organic materials, which is a way to obtain efficient light emitting diodes with low operating voltage. The experimental results has been reproduced by numerical simulation for a series of OLEDs with different thicknesses of the hole transport layer and emitting layer and for doped emitting layers. The advantages and drawbacks of solar cells based on flat heterojunctions and bulk heterojunctions are analyzed. From the simulations, it can be understood why bulk-heterojunctions typically yield higher photocurrents while flat heterojunctions typically feature higher fill factors. In p-i-n ?structures, p and n are doped wide gap materials and i is a photoactive donor-acceptor blend layer using, e.g,. zinc phthalocyanine as a donor and C60 as an acceptor component. It is found that by introducing trap states, the simulation is able to reproduce the linear dependence of short circuit currents on the light intensity. The apparent light-induced shunt resistance often observed in organic solar cells can also be explained by losses due to trapping and indirect recombination of photogenerated carriers, which we consider a crucial point of our work. However, these two effects, the linear scaling of the photocurrent with light intensity and the apparent photoshunt, could also be reproduced when field-dependent geminate recombination is assumed to play a dominant role. First results that show a temperature independent short circuit photocurrent favour the model based on trap-mediated indirect recombination.

Phases organiques luminescentes qui sont incorporés dans une matrice inorganique conductrice est proposé dans cette étude pour la couche active d'une diode émettant de la lumière hybride. Dans ce composite, le colorant organique joue le rôle de site de recombinaison radiative de porteurs de charge qui sont injectées dans la matrice de transport ambipolaire inorganique. Comme l'un des combinaisons de matériaux de candidat, bicouche et des films minces composites de ZnSe et un complexe d'iridium rouge (Ir(BPA)) émetteur de lumière organique ont été préparé in situ par UHV technique d'évaporation thermique. Les alignements de bande d'énergie mesurée par spectroscopie de photoélectrons (PES) pour le ZnSe/Ir(BPA)et deux couches de ZnSe+Ir(BPA) révèlent que le composite HOMO et LUMO du colorant organique sont positionnées dans la largeur de bande interdite de ZnSe. Cette gamme offre les forces motrices énergiques nécessaires pour les transferts d'électrons et de trous de ZnSe à Ir(BPA). Par l'interprétation des données du PES,la composition chimique des interfaces ont également été déterminés. Le ZnSe/Ir(BPA) interface est réactive, même si elle est d'une pureté de matériaux de haute.Pendant ce temps, l'Ir (BPA)/ZnSe interface ne présente pas la pureté matériel. Ceci est représenté à la nature de ZnSe évaporation comme Zn particuliers et des fluxSE2, associée à des interactions chimiques avec le Ir(BPA) substrat. L'interface est,de ce fait, composé d'une multitude de phases, les phases de Se0, ZnSe rares, réduit Se et oxydé molécules de colorant, et de Zn qui sont intercalées atomes dans leIr(BPA) substrat. PES des composites ZnSe+Ir(BPA) révèle des tendances similaires à l'Ir(BPA)/ZnSe interface. A des émissions de lumière rouge surfaciques et intermittents fanées ont été observés à partir de dispositifs qui incorporent couches alternées séquences de ZnSe et Ir(BPA) pour la couche active. / Luminescent organic phases that are embedded in a conductive inorganicmatrix is proposed in this study for the active layer of a hybrid light-emitting diode. Inthis composite, the organic dye acts as the radiative recombination site for chargecarriers that are injected into the inorganic ambipolar transporting matrix. As one ofthe candidate material combinations, bilayer and composite thin films of ZnSe and ared iridium complex (Ir(BPA)) organic light emitter were prepared in situ via UHVthermal evaporation technique. The energy band alignments measured byphotoelectron spectroscopy (PES) for the ZnSe/Ir(BPA) bilayer and ZnSe+Ir(BPA)composite reveal that the HOMO and LUMO of the organic dye are positioned in theZnSe bandgap. This lineup provides the required energetic driving forces for electronand hole transfers from ZnSe to Ir(BPA). By interpreting PES data, the chemicalcomposition of the interfaces were also determined. The ZnSe/Ir(BPA) interface isreactive even though it is of high material purity. Meanwhile, the Ir(BPA)/ZnSeinterface does not exhibit material purity. This is accounted to the nature of ZnSeevaporation as individual Zn and Se2 fluxes, coupled with chemical interactions withthe Ir(BPA) substrate. The interface is, thereby, composed of an abundance of Se0phases, sparse ZnSe phases, reduced Se and oxidized dye molecules, and Znatoms that are intercalated into the Ir(BPA) substrate. PES of the ZnSe+Ir(BPA)composites reveals similar trends to the Ir(BPA)/ZnSe interface. A faded areal andintermittent red light emissions were observed from devices that incorporatedalternating layer sequences of ZnSe and Ir(BPA) for the active layer.