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.

White organic light-emitting diodes (OLEDs) are promising candidates for future solid-state lighting applications and backplane illumination in large-area displays. One very specific feature of OLEDs, which is currently gaining momentum, is that they can enable tunable white light emission. This feature is conventionally realized either through the vertical stacking of independent OLEDs emitting different colors or in lateral arrangement of OLEDs. The vertical design is optically difficult to optimize and often results in efficiency compromises between the units. In contrast, the lateral concept introduces severe area losses to dark regions between the subunits, which requires a significantly larger overall device area to achieve equal brightness. Here we demonstrate a color-tunable, two-color OLED device realized by side-by-side alignment of yellow and blue p-i-n OLEDs structured down to 20 μm by a simple and up-scalable orthogonal photolithography technique. This layout eliminates the problems of conventional lateral approaches by utilizing all area for light emission. The corresponding emission of the photo-patterned two-unit OLED can be tuned over a wide range from yellow to white to blue colors. The independent control of the different units allows the desired overall spectrum to be set at any given brightness level. Operated as a white light source, the microstructured OLED reaches a luminous efficacy of 13 lm W−1 at 1000 cd m−2 without an additional light outcoupling enhancement and reaches a color rendering index of 68 when operated near the color point E. Finally, we demonstrate an improved device lifetime by means of size variation of the subunits.

White organic light-emitting diodes (OLEDs) are promising candidates for future solid-state lighting applications and backplane illumination in large-area displays. One very specific feature of OLEDs, which is currently gaining momentum, is that they can enable tunable white light emission. This feature is conventionally realized either through the vertical stacking of independent OLEDs emitting different colors or in lateral arrangement of OLEDs. The vertical design is optically difficult to optimize and often results in efficiency compromises between the units. In contrast, the lateral concept introduces severe area losses to dark regions between the subunits, which requires a significantly larger overall device area to achieve equal brightness. Here we demonstrate a color-tunable, two-color OLED device realized by side-by-side alignment of yellow and blue p-i-n OLEDs structured down to 20 μm by a simple and up-scalable orthogonal photolithography technique. This layout eliminates the problems of conventional lateral approaches by utilizing all area for light emission. The corresponding emission of the photo-patterned two-unit OLED can be tuned over a wide range from yellow to white to blue colors. The independent control of the different units allows the desired overall spectrum to be set at any given brightness level. Operated as a white light source, the microstructured OLED reaches a luminous efficacy of 13 lm W−1 at 1000 cd m−2 without an additional light outcoupling enhancement and reaches a color rendering index of 68 when operated near the color point E. Finally, we demonstrate an improved device lifetime by means of size variation of the subunits.

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.

A new dual-boron-cored luminogen ligated with a nitrogen-containing multidentate ligand and four bulky phenyl rings was readily synthesized. The unique molecular structure endows this BN-containing luminogen with rich photophysical properties in either solution or in the solid state, including a large Stokes shift, aggregation induced emission activity and reversible piezochromism. Furthermore, this BN-containing luminogen exhibits good capabilities for imaging living cells and sensing of fluoride anions.

We discuss approaches to increase the light outcoupling efficiency in organic microcavity (MC) lasers and organic light-emitting diodes (OLEDs). We find that the introduction of metals into the cavities leads to additional Tamm-plasmon polariton modes, while the corrugation of metal contacts, such as perforated m-size holes or a periodic array of metal stripes, leads to 2D confinement of the cavity modes, which in turn reduces the lasing threshold in MCs. Furthermore, we elucidate light loss mechanisms in OLEDs and reveal how external dielectric layers and periodic gratings can be used to enhance outcoupling from the OLED cavity.

Over the last decades organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) have gained considerable attention as efficient, flexible, lightweight, and potentially low-cost technology for lighting and display applications or as a renewable energy source, respectively. However, achieving long-term stability remains challenging. Revealing and understanding aging processes is therefore of great interest. This work presents fundamental investigations to understand and circumvent organic device degradation. In the first part, single materials used in organic devices were investigated. By tailoring an attenuated total reflection infrared (ATR-IR) spectrometer to the specific needs and subsequent measurements, it is shown that the tris(8-hydroxyquinoline)aluminum (Alq3) molecule, a well known fluorescent green emitter, degrades during air exposure by the formation of carbonyl groups. By using a laser desorption/ionization time of flight mass spectrometer (LDI-TOF-MS) it was shown that a,w-bis-(dicyanovinylen)-sexithiophen (DCV6T-Bu4), a well known small-molecule material which is used as part of the active layer, reacts with oxygen during ultraviolet (UV) irradiation. By using climate boxes and a sun simulator the impact of dry and humid air as well as sunlight on C60, a widely-used acceptor molecule in organic solar cells, was investigated. The breaking of the C60 cage to C58 and C56 and the further reaction of these components with oxygen as well as the dimerization of C58 and C56 molecules were found. The degradation products such as C58O increase with air exposure time but they are independent of the humidity level of the ambient air as well as sunlight irradiation. Subsequent annealing leads to a decrease of the C58O concentration. Many efficient n-dopants are prone to degradation in air, due to the low ionization potentials, thereby limiting the processing conditions. It was found that the air exposure of the highly efficient n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) leads to oxidation reactions of the molecule to [W(hpp)2 + O] and other degradation products. The decay constant of W2(hpp)4 and the matching mean growth time of the [W(hpp)2 + O] degradation as well as a second very quick degradation of the dopant could be determined. The two decay constants can be explained by the assumption that W2(hpp)4 molecules, which are involved in the charge transfer, do degrade slower due to the fact that the charge transfer leads to a downshift of the energy levels of the W2(hpp)4 molecule. Apart from the properties of the organic materials, other effects such as the impact of different purification systems on the material purity as well as the dependence of material purity on the OLED lifetime has been investigated. No correlations between the purification grade and the amount of impurities were found. OLEDs which contain N,N\'-di(naphthalen-1-yl)-N,N\'-diphenyl-benzidine (alpha-NPD) purified in a vertically interlaced stainless steel sublimation systems shows slightly higher external quantum efficiencies compared to tube-based vacuum sublimation systems. The devices which contain alpha-NPD purified by a sublimation system have an extended lifetime. Finally, the impact of residual gases during device fabrication on OLED lifetime and electrical characteristics was investigated. It was found that water vapor introduces an additional series resistance to the OLED, while the other gases do not influence the electric characteristics. The presence of nitrogen or oxygen impacts the lifetime of the OLEDs by the same amount. Nitrogen is non-reactive, this leads to the conclusion that the influence of nitrogen and oxygen on the OLED lifetime is of non-chemical nature, such as changes in the morphology of the organic layers. Water vapor introduces an additional, even faster degradation process within the first hours of OLED operation. As major sources of device degradation, the dimerization of 4,7-diphenyl-1,10-phenanthroline (BPhen) as well as the complexation reaction of alpha-NPD with a bis(1-phenylisoquinoline)iridium(III) (Ir(piq)2) fragment was identified.

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.

A series of phosphorescent bimetallic platinum(II) complexes is presented, which were synthesized by the combination of bidentate cyclometalated N-heterocyclic carbene ligands and different bridging diphenylformamidinates. The complexes were characterized by standard techniques and additionally two solid-state structures could be obtained. Photoluminescence measurements revealed the strong emissive behavior of the compounds with quantum yields of up to 90 % and emission lifetimes of approx. 2 μs. The effect of the substitution pattern in the bridging ligands on the structural and photophysical properties of the complexes was examined in detail and rationalized by density functional theory calculations (PBE0/6-311G*).

The efficiency of organic light-emitting diodes (OLEDs) typically decreases with increasing current density. This so-called roll-off impedes the market entry of OLEDs in high-brightness applications such as general lighting. One of the most important processes causing roll-off is exciton annihilation, which evolves upon high exciton densities. This mechanism is especially pronounced in phosphorescent molecules due to their long triplet lifetime. In order to reduce the roll-off in phosphorescent OLEDs, this thesis focusses on decreasing the local exciton density by modifying the exciton lifetime, the spatial exciton distribution, and the tendency of emitters to form aggregates. The obtained results lead to a deeper understanding of efficiency roll-off and help sustaining the OLED efficiency at high brightness. The emitter lifetime can be influenced by the optical environment around the emitting dipoles through the Purcell effect. In order to study this effect, the distance between emitter and metal cathode is varied for two different OLED stacks. A strong influence of emitter position and orientation on roll-off is observed and explained by modelling the data with triplet-triplet annihilation theory. Furthermore, design principles for optimal high-brightness performance are established by simulating the roll-off as a function of emitter-cathode distance, emissive dipole orientation, and radiative efficiency. Next, a method is developed that allows extracting the spatial exciton distribution. Therefore, a thin sensing layer that locally quenches excitons is introduced into the emission layer at varying positions. The resulting quenching profile is then fitted using a comprehensive theory based on the diffusion equation, which renders the exciton distribution and diffusion length with nanometer resolution. This method is applied to an emission layer comprising an ambipolar host material. Contrary to expectations which suggest that ambipolar materials exhibit broad exciton formation, a narrow emission zone close to the electron transport layer is found. Additional explorations of structures that might broaden the emission zone point to a narrow emission zone in double emission layers and broader exciton formation in mixed emission layers. Previous investigations revealed a strong correlation between emitter aggregation and molecular dipole moment of the emitter. Within this thesis, the range of studied emitters is significantly extended. It is shown that homoleptic emitters show a stronger tendency to form aggregates than heteroleptic compounds. This is probably not only related to their higher dipole-dipole potential, but also to the molecular structure. Systematic analysis of the deposition parameters shows that aggregate formation depends on the underlying material and increases with increasing substrate temperature and decreasing evaporation rate. The two green emitters Ir(ppy)3 and Ir(ppy)2(acac) are additionally studied by means of X-ray diffraction. Both emitters form crystallite grains and exhibit a preferred orientation. Doping the emitters into an amorphous host, both orientation and crystallite formation retain at the investigated doping concentrations above 20 wt%. This result is a first step toward further understanding of the mechanism of transition dipole orientation. / Die Effizienz organischer Leuchtdioden (OLEDs) nimmt üblicherweise mit ansteigender Stromdichte ab. Dieser so genannte Roll-Off erschwert den Markteintritt von OLEDs in Bereichen, die hohe Helligkeiten erfordern, wie beispielsweise in der Beleuchtung. Einer der wichtigsten Prozesse, die zu Roll-Off führen, ist die Annihilation von Exzitonen. Diese nimmt mit steigender Exzitonendichte zu und ist vor allem in phosphoreszenten OLEDs aufgrund der dort vorhandenen langen Triplettlebensdauer ein großer Verlustfaktor. Im Rahmen dieser Dissertation werden Methoden vorgestellt, die mittels Reduzierung der Exzitonendichte den Roll-Off in phosphoreszenten OLEDs verringern können. Dazu gehören die Veränderung der Exzitonenlebensdauer, die Untersuchung der räumlichen Verteilung der Exzitonen und die Erforschung der Bildung von Emitteraggregaten. Die gewonnenen Ergebnisse führen zu einem besseren Verständnis des Effizienz Roll-Offs und helfen, die Effizienz von OLEDs bei hohen Helligkeiten zu verbessern. Die Emitterlebensdauer kann über den Purcell-Effekt durch Veränderung des die emittierenden Dipole umgebenden elektromagnetischen Felds beeinflusst werden. Dieser Effekt wird genutzt, indem der Abstand zwischen Emitter und Metallelektrode für zwei verschiedene OLED-Aufbauten variiert wird. Der Roll-Off ist stark abhängig von der Position und Orientierung des Emitters und kann durch Modellierung der Daten auf Basis von Triplett-Triplett-Annihilation erklärt werden. Durch Simulation des Roll-Offs in Abhängigkeit des Emitter-Kathode-Abstands, der Orientierung und der strahlenden Effizienz der emittierenden Dipole werden Prinzipien zur optimalen Leistung von OLEDs bei hohen Helligkeiten entwickelt. Als nächstes wird eine Methode eingeführt mittels derer die räumliche Exzitonenverteilung extrahiert werden kann. Dafür wird eine dünne Sensorschicht in die Emissionsschicht eingebracht, die lokal Exzitonen auslöscht. Unter Variation der Position des Sensors wird ein Profil der Auslöschungsintensität bestimmt. Die gemessene Intensität wird mittels einer umfassenden Theorie auf Grundlage der Diffusionsgleichung angepasst, wodurch sich die räumliche Verteilung der Exzitonen und die Diffusionslänge mit einer Auflösung von 1nm ergibt. Die Methode wird auf eine Emissionsschicht angewandt, die das ambipolare Matrixmaterial CBP enthält. Entgegen der Erwartung, dass die Exzitonenbildung in ambipolaren Materialien weiter ausgedehnt ist, ist die gemessene Emissionszone sehr schmal und befindet sich an der Grenze zur Elektronentransportschicht. Um eine Verbreiterung des Emissionsprofils zu ermöglichen, werden weitere Strukturen untersucht. Dabei wird eine schmale Emissionszone in Doppelemissionsschichten beobachtet, wohingegen gemischte Emissionsschichten zu einer Verbreiterung der Exzitonenbildung führen können. Vorangegangene Untersuchungen deckten einen Zusammenhang zwischen der Aggregation von Emittermolekülen und dem Dipolmoment des Emitters auf. In dieser Arbeit werden weitere Emittermoleküle untersucht, wobei eine stärkere Aggregation von homoleptischen Emittern im Vergleich zu heteroleptischen festgestellt wird. Dies ist einerseits im höheren Dipol-Dipol-Potential der homoleptischen Verbindungen und andererseits in der Molekülstruktur begründet. Eine systematische Analyse der Herstellungsparameter zeigt, dass die Aggregatbildung von dem darunter liegenden Material abhängt und mit steigender Substrattemperatur und sinkender Verdampfungsrate zunimmt. Die zwei Grünemitter Ir(ppy)3 und Ir(ppy)2(acac) werden zusätzlich mittels Röntgenspektroskopie untersucht. Beide Emitter bilden kristalline Körner und weisen eine bevorzugte Orientierung auf. Sowohl die Kristallbildung als auch die Orientierung bleiben erhalten, wenn die Emitter mit mehr als 20 Gewichtsprozent in das Matrixmaterial CBP dotiert werden. Dieses Ergebnis ist ein erster Schritt zum besseren Verständnis der in vielen Iridium-Emittern beobachteten Orientierung des Übergangsdipolmoments.