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 present a novel top-electrode spray-coating process for the solution-based deposition of silver nanowires (AgNWs) onto vacuum-processed small molecule organic electronic solar cells. The process is compatible with organic light emitting diodes (OLEDs) and organic light emitting thin film transistors (OLETs) as well. By modifying commonly synthesized AgNWs with a perfluorinated methacrylate, we are able to disperse these wires in a highly fluorinated solvent. This solvent does not dissolve most organic materials, enabling a top spray-coating process for sensitive small molecule and polymer-based devices. The optimized preparation of the novel AgNW dispersion and spray-coating at only 30 °C leads to high performance electrodes directly after the deposition, exhibiting a sheet resistance of 10.0 Ω □−1 at 87.4% transparency (80.0% with substrate). By spraying our novel AgNW dispersion in air onto the vacuum-processed organic p-i-n type solar cells, we obtain working solar cells with a power conversion efficiency (PCE) of 1.23%, compared to the air exposed reference devices employing thermally evaporated thin metal layers as the top-electrode.

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.

This work demonstrates an approach to develop low-cost, semi-transparent, long-term stable, and efficient organic photovoltaic (OPV) cells and organic light-emitting diodes (OLEDs) using various alternative electrodes such as conductive polymers, doped ZnO, and carbon nanotubes. Such electrodes are regarded as good candidates to replace the conventional indium tin oxide (ITO) electrode, which is expensive, brittle, and limiting the manufacturing of low-cost, flexible organic devices. First, we report long-term stable, efficient ITO-free OPV cells and transparent OLEDs based on poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) electrodes by using a solvent post-treatment or a structure optimization. In addition, a high performance internal light out-coupling system for white OLEDs based on PEDOT:PSS-coated metal oxide nanostructures is developed. Next, we demonstrate highly efficient ITO-free OPV cells and OLEDs with optimized ZnO electrodes doped with alternative non-metallic elements. The organic devices based on the optimized ZnO electrodes show significantly improved efficiencies compared to devices with standard ITO. Finally, we report semi-transparent OPV cells with free-standing carbon nanotube sheets as transparent top electrodes. The resulting OPV cells exhibit very low leakage currents with good long-term stability. In addition, the combination of various kinds of bottom and top electrodes for semi-transparent and ITO-free OPV cells is investigated. These results demonstrate that alternative electrodes-based OPV cells and OLEDs have a promising future for practical applications in efficient, low-cost, flexible and semi-transparent device manufacturing. / Die vorliegende Arbeit demonstriert einen Ansatz zur Verwirklichung von kostengünstigen, semi-transparenten, langzeitstabilen und effizienten Organischen Photovoltaik Zellen (OPV) und Organischen Leuchtdioden (OLEDs) durch die Nutzung innovativer Elektrodensysteme. Dazu werden leitfähige Polymere, dotiertes ZnO und Kohlenstoff-Nanoröhrchen eingesetzt. Diese alternativen Elektrodensysteme sind vielversprechende Kandidaten, um das konventionell genutzte Indium-Zinn-Oxid (ITO), welches aufgrund seines hohen Preises und spröden Materialverhaltens einen stark begrenz Faktor bei der Herstellung von kostengünstigen, flexiblen, organischen Bauelementen darstellt, zu ersetzten. Zunächst werden langzeitstabile, effiziente, ITO-freie Solarzellen und transparente OLEDs auf der Basis von Poly(3,4-ethylene-dioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS) Elektroden beschrieben, welche mit Hilfe einer Lösungsmittel-Nachprozessierung und einer Optimierung der Bauelementstruktur hergestellt wurden. Zusätzlich wurde ein leistungsfähiges, internes Lichtauskopplungs-System für weiße OLEDs, basierend auf PEDOT:PSS-beschichteten Metalloxid-Nanostrukturen, entwickelt. Weiterhin werden hoch effiziente, ITO-freie OPV Zellen und OLEDs vorgestellt, bei denen mit verschiedenen nicht-metallischen Elementen dotierte ZnO Elektroden zur Anwendung kamen. Die optimierten ZnO Elektroden bieten im Vergleich zu unserem Laborstandard ITO eine signifikant verbesserte Effizienz. Abschließend werden semi-transparente OPV Zellen mit freistehenden Kohlenstoff-Nanoröhrchen als transparente Top-Elektrode vorgestellt. Die daraus resultierenden Zellen zeigen sehr niedrige Leckströme und eine zufriedenstellende Stabilität. In diesem Zusammenhang wurde auch verschiedene Kombinationen von Elektrodenmaterialen als Top- und Bottom-Elektrode für semi-transparente, ITO-freie OPV Zellen untersucht. Zusammengefasst bestätigen die Resultate, dass OPV und OLEDs basierend auf alternativen Elektroden vielversprechende Eigenschaften für die praktische Anwendung in der Herstellung von effizienten, kostengünstigen, flexiblen und semi-transparenten Bauelement besitzen.

Single self-assembled semiconductor quantum dots (QDs) are able to emit single-photons and entangled-photons pairs. They are therefore considered as potential candidate building blocks for quantum information processing (QIP) and communication. To exploit them fully, the ability to precisely control their optical properties is needed due to several reasons. For example, the stochastic nature of their growth ends up with only little probability of finding any two or more QDs emitting indistinguishable photons. These are required for two-photon quantum interference (partial Bell-state measurement), which lies at the heart of linear optics QIP. Also, most of the as-grown QDs do not fulfil the symmetries required for generation of entangled-photon pairs. Additionally, tuning is required to establish completely new systems, for example, 87Rb atomic-vapors based hybrid semiconductoratomic (HSA) interface or QDs with significant heavy-hole (HH)-light-hole (LH) mixings. The former paves a way towards quantum memories and the latter makes the optical control of hole spins much easier required for spin- based QIP. This work focuses on the optical properties of a new type of QDs optimized for HSA experiments and their broadband tuning using strain. It was created by integrating the membranes, containing QDs, onto relaxor-ferroelectric actuators and was quantified with a spatial resolution of ~1 µm by combining measurements of the µ-photoluminescence of the regions surrounding the QDs and dedicated modeling. The emission of a neutral exciton confined in a QD usually consists of two fine-structure-split lines which are linearly polarized along orthogonal directions. In our QDs we tune the emission energies as large as ~23meV and the fine-structure-splitting by more than 90 µeV. For the first time, we demonstrate that strain is able to tune the angle between the polarization direction of these two lines up to 40° due to increased strain-induced HH-LH mixings up to ~55%. Compared to other quantum emitters, QDs can be easily integrated into optoelectronic devices, which enable, for example, the generation of non-classical light under electrical injection. A novel method to create sub-micrometer sized current-channels to efficiently feed charge carriers into single QDs is presented in this thesis. It is based on focused-laserbeam assisted thermal diffusion of manganese interstitial ions from the top GaMnAs layer into the underlying layer of resonant tunneling diode structures. The combination of the two methods investigated in this thesis may lead to new QDbased devices, where direct laser writing is employed to preselect QDs by creating localized current-channels and strain is used to fine tune their optical properties to match the demanding requirements imposed by QIP concepts.

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*).

Metallhalogenid Perowskite sind eine aufkommende Klasse von Halbleitermaterialien, die einige der besten Eigenschaften von organischen und anorganischen Halbleitern vereinen. Die Materialien kombinieren eine hohe Leitfähigkeit und modulierbare Bandlücke mit hohem Absorptionskoeffizienten und Löslichkeit in organischen Lösungsmitteln. Verarbeitungsmethoden wie Tintenstrahldruck ermöglichen somit die Herstellung von kristallinen Halbleitern mit direkter Bandlücke aus Lösung. Zunächst werden in einem kombinatorischen Druckprozess drei Perowskittinten, aus drei separaten Druckköpfen, während des Druckprozesses gemischt. Es resultiert eine Reihe von Perowskitfilmen mit genau definierten Zusammensetzungen. Die Kontrolle über die resultierenden Materialeigenschaften wird durch die Herstellung einer Reihe wellenlängenselektiver Fotodetektoren und Langpassfiltern demonstriert, die zu einem tintenstrahlgedruckten dispersionselementfreien Spektrometer kombiniert werden. Weiterhin wird mit den Möglichkeiten eines Tintenstrahldruckers für großflächige Bearbeitung ein etabliertes Verfahren für Tintenstrahl-gedruckte Perowskit-LEDs (PeLEDs) hochskaliert. Mit dem gleichen Druckverfahren und der gleichen Tintenzusammensetzung wurde die aktiv emittierende Fläche von 4 mm² auf 1600 mm² erhöht. Es konnte ein homogener Perowskit Dünnfilm für PeLEDs gedruckt werden, ohne einen Anstieg des Leckstroms mit steigender Fläche zu verursachen. Zuletzt werden die Strukturierungsmöglichkeiten des Tintenstrahldrucks genutzt um zweifarbige PeLEDs herzustellen. Auf einer primären Perowskitschicht wird eine zweite Perowskit-Vorläufertinte aufgebracht. Während des Betriebs erfährt der gemischte Halogenid-Perowskit eine Phasenseparierung und zeigt nur tiefrote Emission von iodidreichen Domänen vor einem hellgrünen emittierenden Hintergrund, dessen Helligkeit nicht durch den Strukturierungsprozess vermindert wird. / Metal halide perovskites are an emerging semiconductor material class that combines some of the best properties of inorganic and organic semiconductors. The material pairs high conductivity and composition-based bandgap tunability with solution processability and high absorption coefficients. Deposition methods like inkjet printing thus allow for the fabrication of crystalline, direct bandgap semiconductors from solution for various applications. First, in a combinatorial printing approach, three perovskite precursor inks, from three separate printheads, are mixed during the printing process. By controlling the perovskite composition, material properties such as the bandgap can be tuned. This is demonstrated by fabrication of a range of wavelength-selective photodetectors and longpass filters, which are combined to yield an inkjet-printed, dispersion element-free spectrometer. Furthermore, using the large-scale capabilities of an inkjet printer, a previously established procedure for inkjet-printed perovskite LEDs (PeLEDs) is upscaled. The actively emitting area is increased from 4 mm² to 1600 mm² using the same printing procedure and ink formulation. This achieved a homogeneous perovskite film, that showed no increase in leakage current, independent of size. Finally, using the patterning capabilities of inkjet printing, dual coloured red/green PeLEDs are fabricated in a sequential printing process. On a primary perovskite layer, a second perovskite precursor ink is deposited. Under operation in a PeLED, the mixed halide perovskite experiences phase segregation and only shows deep red emission from iodide-rich domains against a bright green emitting background, which still performs as well as a non-patterned device.

Tesis por compendio / [ES] La alcaparra (Capparis spinosa L.) es un arbusto característico de la región mediterránea, del que se aprovechan sus botones florales y frutos. Uno de los inconvenientes más importantes para su cultivo es la dificultad en su propagación. El fruto es una baya con muchas semillas, que presentan un porcentaje de germinación que no supera el 5%. Las semillas son de color marrón oscuro, de 2 a 3 mm y la cubierta tiene una capa lignificada con paredes radiales engrosadas. La baja germinación se relaciona con distintos tipos de latencia, que no ha sido científicamente atribuida a ningún tipo concreto. El objetivo de esta tesis es estudiar las distintas fases del proceso de germinación para determinar el tipo de latencia, cómo superarla, y establecer pautas para una propagación viable mediante semillas. Los ensayos se realizaron en el Departamento de Producción Vegetal de la Universitat Politècnica de València, utilizando semillas de producción propia y de lotes comerciales. Para determinar el tipo de latencia, se estudió el proceso de imbibición durante la germinación, la resistencia mecánica de la cubierta seminal y el endospermo frente a la protusión de la radícula, y el efecto de la aplicación de giberelinas. La absorción de agua sigue las dos primeras fases del modelo trifásico típico de absorción de agua en la germinación y la hidratación comienza por la región hilo-micropilar. La imbibición no es un factor limitante para su germinación, alcanzando un contenido de humedad del 32%, con el que se obtienen porcentajes de germinación superiores al 90%. Por tanto, no tienen una cubierta impermeable al agua, es decir, no muestran latencia física. Las semillas comerciales presentan menor viabilidad y germinación que las de producción propia, lo que se ha evidenciado con el deterioro en la cubierta seminal que se relaciona con los procesos de extracción, limpieza y almacenamiento. Para obtener altos porcentajes de germinación se requiere el uso de giberelinas, lo que indica la presencia de latencia fisiológica. Se recomienda el uso de 500 mg L-1 de ácido giberélico (AG) para humedecer el sustrato de germinación. El AG desencadena el incremento del contenido de giberelinas activas endógenas y la disminución del ácido abscísico. La germinación consta de dos eventos separados temporalmente, el agrietamiento de la cubierta, en el área hilo-micropilar y luego la perforación del endospermo micropilar, por donde emerge la radícula. Las giberelinas activas no disminuyen la fuerza de punción para perforar el endospermo, sino que aumentan el potencial de crecimiento del embrión, logrando una mayor germinación y en menor tiempo. La viabilidad y germinación de semillas recién extraídas de frutos recolectados en su dehiscencia alcanzan valores muy elevados. Si la recolección de los frutos se retrasa y la pulpa se seca, la viabilidad y la germinación disminuyen, por lo que, como regla general, se aconseja recolectar los frutos al menos una vez por semana, e inmediatamente extraer las semillas y ponerlas a germinar. En el ensayo de flotación, las semillas que flotan y que presentan buena germinación son muy pocas (0.24%), por lo que se recomienda desecharlas. La germinación no es afectada por la iluminación con diferentes longitudes de onda, por lo que puede realizarse en oscuridad, lo que puede suponer un ahorro económico para semilleros comerciales. La irradiación con láser He-Ne durante tiempos cortos de exposición mejora el porcentaje de germinación en semillas previamente humedecidas, pero no sustituye a la adición de AG al sustrato, complementando su efecto. Con la ultrasonicación se escarifica la testa sin afectar al tegmen, y se acelera la imbibición inicial, aunque la humedad alcanzada en las semillas es la misma que en el control. Existe una correlación lineal y negativa, entre la germinación y la temperatura alcanzada con estos tratamientos. / [CA] La tàpera (Capparis spinosa L.) és un arbust característic de la regió mediterrània, que s'aprofita pels seus botons florals i fruits. Un dels principals inconvenients que presenta el seu cultiu, es la dificultat que presenta la seua propagació. El fruit és una baia que té moltes llavors, que presenten una germinació que no sol superar el 5%. Les llavors són de color marró fosc, mesuren 2 - 3 mm, i la coberta té una capa lignificada amb parets radials engrossides. La baixa germinació s'ha relacionat amb diferents tipus de latència, però fins ara no ha estat científicament atribuïda a cap tipus concret. L'objectiu d'aquesta tesi és estudiar les diferents fases de la germinació per determinar el tipus de latència, com superar-la, i establir les pautes per a una propagació viable mitjançant les seves llavors. Els assajos s'han realitzat en el Dep. Producció Vegetal de la Universitat Politècnica de València, utilitzant llavors de producció pròpia, i de lots comercials. Per determinar el tipus de latència, s'ha estudiat el procés d' imbibició que es produeix durant la germinació, la resistència mecànica que exerceixen la coberta seminal i l'endosperma enfront de la protrusió de la radícula, i l' efecte de l'aplicació de gibberel·lines. L'absorció d'aigua segueix les dues primeres fases del model trifàsic típic d'absorció d'aigua en la germinació, i la hidratació comença per la regió micropilar. La imbibició no és un factor limitant per a la seua germinació, aconseguint un contingut d'humitat del 32%, permet percentatges de germinació superiors al 90%. Per tant, les llavors no tenen una coberta impermeable a l'aigua, és a dir, no mostren latència física. Les llavors comercials presenten menor viabilitat i germinació que les de producció pròpia, relacionat amb el seu deteriorament, que ha estat evident a la coberta; conseqüència dels processos d'extracció, neteja i emmagatzematge. Per obtenir alts percentatges de germinació es requereix l'ús de gibberel·lines, la qual cosa indica la presència de latència fisiològica. Es recomana l'ús d'una solució de 500 mg L-1 d'àcid gibberèl·lic (AG). L'AG desencadena l'augment del contingut de gibberel·lines actives endògenes i una disminució d'àcid abscísic. La germinació consta de dos esdeveniments separats temporalment, l'esquerdament de la coberta, que comença a l'àrea micropilar i a continuació es produeix la perforació de l'endosperma micropilar, per on emergeix la radícula. Les gibberel·lines actives no disminueixen la força de punció necessària per perforar l'endosperma, sinó que augmenten el potencial de creixement de l'embrió, aconseguint major germinació i en menor temps. La viabilitat i el percentatge de germinació de les llavors obtinguts de fruits recol·lectats en la seva dehiscència assoleixen valors molt elevats. Si la recol·lecció dels fruits es retarda i la polpa s'asseca, la viabilitat i la germinació disminueixen, per la qual cosa, com a regla general, per a la producció de llavor comercial s'aconsella recol·lectar els fruits almenys una vegada per setmana, i immediatament extreure les llavors i posar-les a germinar. En l 'assaig de flotació, les llavors que floten i que presenten capacitat germinativa són molt poques (0,24%), recomanant-se rebutjar les llavors flotants. La germinació no és afectada per la il·luminació amb llums de diferents longituds d'ona, per la qual cosa la germinació pot realitzar-se en foscor, i, pot suposar un estalvi econòmic en planters comercials. La irradiació amb làser He-Ne durant temps curts d'exposició millora el percentatge de germinació de les llavors prèviament humitejades, però no substitueix l' addició d'AG al substrat, sinó que complementa el seu efecte. Amb la ultrasonicació, s'escarifica la testa sense afectar el tegmen i s'accelera la imbibició inicial, però la humitat assolida en les llavors és la mateixa que el control. Hi ha una correlació lineal i negativa, entre la germinació i la temperatura assolida amb estos tractaments. / [EN] The caper (Capparis spinosa L.) is a shrub characteristic of the Mediterranean region. It is use for its flower buds and fruits. One of the main drawbacks of its cultivation, is the difficulty presented by its propagation, both vegetative and through seeds. The fruit is a berry containing many seeds, these have a very low germination percentage, which usually is at most 5%. The seeds are dark brown colour, measure 2 - 3 mm, and the cover has a lignified layer with thickened radial walls. Low germination power has been linked to different types of dormancies, but, it has not been scientifically attributed to any specific type. This thesis aims to study the different phases of the germination process to determine the type of dormancy, how to overcome it, and to establish guidelines for viable propagation through their seeds. The tests have been carried out in the Universitat Politècnica de València Plant Production Department, mainly using own-produced seeds, and seeds from commercial lots. To determine the type of dormancy, the imbibition process that occurs during germination has been studied, as well as the mechanical resistance exerted by the seed coat and the endosperm against the protrusion of the radicle and the effect of the external gibberellins application. Water uptake follows the first two phases of the typical three-phase water uptake pattern in seed germination, and seed hydration begins in the hilum-micropillar region. Imbibition is not a limiting factor for germination, reaching a moisture content of 32%, which allows germination percentages higher than 90%. Therefore, caper seeds do not have a waterproof coat; that is, they do not show physical dormancy. Commercial seeds showed lower viability and germination than those of own production, which has been related to seed deterioration. This deterioration, which has been evident in the seed coat, is related to their extraction, cleaning, and storage processes. Obtaining high percentages of germination requires gibberellins, which indicates the presence of physiological dormancy. The use of 500 mg L-1 of gibberellic acid (GA) is recommended to moisten the germination substrate. GA triggers an increase in endogenous active gibberellins content and a decrease in abscisic acid. The germination consists of two temporarily separated events: the cracking of the coat in the hilum-micropillar area, and then the perforation of the micropillar endosperm, where the radicle emerges. Active gibberellins do not decrease the puncture force needed to pierce the endosperm but increase the growth potential of the embryo, achieving higher germination percentages in less time. The viability and germination of seeds freshly extracted from fruits harvested in their dehiscence reach very high values. If the harvest of the fruits is delayed and the pulp dries, the viability and the percentage of germination decrease so, as a rule, for the production of commercial seed, it is advisable to collect the fruits at least once a week and immediately extract the seeds and put them to germinate. In the flotation test, floating seeds with germination capacity are very few (0.24%), so it is recommended to discard them. The germination is not affected by different wavelengths lights, so it can be carried out in darkness, which can mean economic savings in commercial nurseries. He-Ne laser irradiation during short exposure times improves the germination of previously moistened seeds but does not replace the addition of GA to the substrate but complements its effect. With the ultrasonication treatment, the testa is scarified without affecting the tegmen, and the initial imbibition is accelerated, although the seed moisture is the same as in the control. There is a linear and negative correlation between germination and the temperature reached with these treatments. / Foschi, ML. (2023). Mejora de la germinación para la propagación sexual de la alcaparra (Capparis spinosa L.) [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/202596 / Compendio

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.