When a temperature differential is applied across a semiconductor, a thermal voltage develops across it in response. The ratio of this thermal voltage to the applied temperature differential is the Seebeck coefficient, a transport coefficient that complements measurements of electrical and thermal conductivity. The physical interpretation of the Seebeck coefficient is the entropy per charge carrier divided by its charge and is hence a direct measurement of the carrier entropy in the solid state. This PhD thesis has three major outcomes. The first major outcome is a demonstration of how the Seebeck coefficient can be used as a tool to quantify the role of energetic disorder in organic semiconductors. To this end, a microfabricated chip was designed to perform accurate measurements of the Seebeck coefficient within the channel of the active layer in a field-effect transistor (FET). When measured within an FET, the Seebeck coefficient can be modulated using the gate electrode. The extent to which the Seebeck coefficient is modulated gives a clear idea of charge carrier trapping and the distribution of the density of states within the organic semiconductor. The second major outcome of this work is the observation that organic semiconducting polymers show Seebeck coefficients that are temperature independent and strongly gate voltage modulated. The extent to which the Seebeck coefficient is modulated in the polymer PBTTT is found to be larger than that in the polymer IDTBT. Taken together with conventional charge transport measurements on IDTBT, the voltage modulated Seebeck coefficient confirms the existence of a vanishingly small energetic disorder in this material. In the third and final outcome of this thesis, the magnitude of the Seebeck coefficient is shown to be larger for organic small molecules as compared to organic polymers. The basis for this is not yet clear. There are reports that such an observation is substantiated through a larger contribution from vibrational entropy that adds to the so called entropy-of-mixing contribution so as to boost the magnitude of the Seebeck coefficient in organic small molecules. As of now, this remains an open question and is a potential starting point for future work. The practical implications of this PhD thesis lie in building cost-effective and environmentally friendly waste-heat to useful energy converters based on organic polymers. The efficiency of heat to energy conversion by organic polymers tends to be higher than that for conventional semiconductors owing to the presence of narrow bands in organic polymer semiconductors.

Les fibres amyloïdes sont des biomatériaux prometteurs pour la bioélectronique, en particulier pour l’interfaçage avec les systèmes biologiques. Ces fibres, formées par l’auto-assemblage de protéines, sont aisément synthétisables et modifiables/fonctionnalisables. Elles possèdent de surcroît des propriétés physiques remarquables notamment en termes de stabilité et de résistance mécanique. Nous avons étudié les mécanismes de conductions de charges dans les fibres formées par la protéine HET-s(218-289), seules fibres amyloïdes dont la structure atomique soit connue. Les échantillons ont été caractérisés électriquement et électrochimiquement sous la forme de films « secs ». L’influence de plusieurs paramètres sur la conductivité, entre autres la température, l’humidité ou encore la lumière, a été investiguée. Nous avons montré que l’organisation de la protéine en fibres permet la mise en place de processus de transport de charges intrinsèques. De plus, l’eau joue un rôle essentiel dans ces mécanismes et les principaux porteurs de charges sont certainement des protons. En parallèle, une simulation de dynamique moléculaire appuyée notamment par des expériences de diffusions des neutrons, a mis en évidence une forte interaction entre l’eau et les fibres. Deux canaux d’eau stabilisés par liaisons hydrogènes se formeraient le long des fibres. Ces derniers peuvent permettre le transport de protons par un mécanisme de type Grotthuss. Des réactions électrochimiques, en particulier l’électrolyse de l’eau, seraient la source des protons transportés grâce aux fibres. Cela conduit à l’instauration d’un courant catalytique à partir d’un seuil de tension de polarisation. Enfin, deux effets photo-électriques ont été observés lorsque les fibres sont irradiées entre 200 et 400 nm. Le premier est un photo-courant qui serait dû à la photolyse de l’eau adsorbée dans les échantillons. Le second, qualifié de « photo-courant inverse », se produit plus spécifiquement à la longueur d’onde de 280nm et seulement en présence de dioxygène. Il engendre une diminution de la conductivité. Cela serait dû à une réaction entre l’état triplet des tryptophanes des fibres et le dioxygène, captant in fine des protons. / Amyloid fibers are very promising biomaterials for bioelectronics, especially for interfacing with biological systems. These self-assembled proteins fibers are easy to synthetize, to tune and to functionalize. Their physical properties such as stability and mechanical strength are noticeable. We studied charge transport processes in HET-s(218-289), the only amyloid fibers we know the atomic structure. The samples were characterized as “dried” films by electrical measurement and electrochemistry. The influence of several parameters such as temperature, humidity or light was investigated. We demonstrated that the fiber organization allows intrinsic charge transport mechanisms in which water plays a crucial role. Furthermore, the dominant charge carriers would be protons. Molecular dynamic simulation and neutron diffusion experiments run in parallel show strong water-fibers interactions. In particular, H-bonded water wires can be formed along the fibers and support proton transport according to a Grotthuss-like mechanism. Proton production would result from electrochemical reactions, especially from water electrolysis. Therefore a catalytic current is detected when the bias exceeds a certain threshold. In addition, two photoelectric phenomena were observed when the fibers are irradiated with near UV light (200-400nm). The first one is a photocurrent probably due to water photo-splitting. The other occurs specifically at 280nm wavelength and in the presence of molecular oxygen. It leads to a decrease of the sample conductivity. This likely results from chemical reaction(s) between triplet-state tryptophan and oxygen that consumes protons.

<div> Design rules and application spaces for closed-shell conjugated polymers have been well established in the field of organic electronics, and this has allowed for significant breakthroughs to occur in myriad device platforms [e.g., organic field-effect transistors (OFETs) and organic light-emitting devices (OLEDs)]. Conversely, organic electronic materials that are based on the emerging design motif that includes open-shell stable radicals have not been evaluated in such detail, despite the promise these materials show for charge transfer, light-emission, and spin manipulation platforms. Moreover, recent results have demonstrated that the materials performance of hybrid systems will allow for future applications to harness both of these platform design archetypes to generate composites that combine the performance of current state-of-the-art conjugated polymer systems with the novel functions provided by open-shell species. Thus, establishing the underlying physical phenomena associated with the interactions between both classes of materials is imperative for the effective utilization of these soft materials.</div><div><br></div><div> In the first part of this work, Förster resonance energy transfer (FRET) is demonstrated to be the dominant mechanism by which energy transfer occurs from a common conjugated polymer to various radical species using a combination of experimental and computational approaches. Specifically, this is determined by monitoring the fluorescence quenching of poly(3hexylthiophene) (P3HT) in the presence of three radical species: (1) the galvinoxyl; (2) the 2phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO); and (3) the 4-hydroxy-2,2,6,6tetramethylpiperidine-1-oxyl (TEMPO) radicals. Both in solution and in the solid-state, the galvinoxyl and PTIO radicals show quenching on par with that of a common fullerene electronaccepting derivative. Conversely, the TEMPO radical shows minimal quenching at similar concentrations. Using both ultrafast transient absorption spectroscopy and computational studies, FRET is shown to occur at a significantly faster rate than other competing processes. These findings suggest that long-range energy transfer can be accomplished in applications when radicals that can act as FRET acceptors are utilized, forming a new design paradigm for future applications involving both closed- and open-shell soft materials.</div><div><br></div><div> Following this, addition of the galvinoxyl radical to P3HT is shown to alter the thin film transistor response from semiconducting to conducting. This is accompanied by a modest enhancement in electrical conductivity. This interaction is not seen with either the TEMPO or PTIO radicals. While an increase in charge carrier concentration is observed, the interaction is not otherwise consistent with a simple charge-transfer doping mechanism, due to the mismatched reduction and oxidation potentials of the two species. Additionally, no freeze-out of charge carriers is observed at reduced temperatures. It is also not due to parallel conduction through the radical fraction of the bulk composite, as the radical species is non-conductive. Hole mobility is enhanced at lower concentrations of the radical, but it decreases at higher concentrations due to the reduced fraction of conductive material in the polymer bulk. Despite the increase in mobility at lower concentrations, the activation energy for charge transport is increased by the presence of the radical. This suggests that the radical is not improving the charge transport through filling of deep trap states or by reducing the activation energy for the charge transport reaction; however, the galvinoxyl radical is likely filling shallow trap states within the P3HT for the composite thin film.</div><div><br></div><div> Finally, a novel analysis technique for polymer relaxation is investigated through dielectric spectroscopy of model polyalcohols. An understanding of relaxation phenomena and the physics of amorphous solids in general remains one of the grand open challenges in the field of condensed matter physics. This problem is particularly relevant to organic electronics as many organic electronic materials are found in the amorphous state, and their physical relaxation can lead to undesirable effects such as hysteresis and instability. Current procedures describe relaxation phenomena in terms of empirical functions, but the physical insights provided by this representation are limited. The new approach instead represents the dielectric response as a spectrum of Debye processes. Rather than varying the spectral strength at fixed time points as traditional spectral analysis implicitly does, this approach instead varies the characteristic time of each spectral element while the strength remains fixed. This allows the temperature dependence on relaxation time of each spectral element to be determined, and the <i>α</i>- and <i>β</i>-relaxation are interpreted in light of this analysis. </div><div> </div>

These days, organic photovoltaic devices (OPV) have received a large interest from both academic and industrial researchers as alternative energy source to replace petroleum and nuclear fission. New organic semi-conductors (OSC) are actively researched since these materials can be purified and processed by solution techniques that are cheaper than those required for silicon. The current record efficiency is 8.3%. Further improvement of the OPV performances is desired in order to decrease both the pay-back time of the device and the price of the energy produced. On that purpose, academic research is focused on two main axes: (i) develop new organic materials characterized by high charge mobilities for both p-type (holes) and n-type (electrons) semi-conduction and (ii) increase as much as possible the contact surface between both p-type and n-type OSC (p-n junction), where the electric charges are created. <p>In the frame of this PhD thesis, we proposed to investigate this second aspect by building the interface at a nanoscopic scale, creating a molecular heterojunction. Liquid crystalline (LC) materials composed of donor-acceptor dyads were chosen as OSC since they can lead to complex supramolecular structures made of two interpenetrated networks: the first one is related to the donor and provides holes transport, while the second one is related to the acceptor and affords electrons conduction. In this context, we decided to synthesize new donor-acceptor molecules composed of a phthalocyanine (donor) covalently connected to a fullerene (acceptor) through a non-conjugated bridge and to investigate their supramolecular assembly in solution and solid state. This specific molecular structure was inspired from a mesogenic phthalocyanine developed earlier in our laboratory and the very popular fullerene derivative referred to as PCBM. <p>Four dyads with different bridge lengths were prepared via multi-step synthesis. Two key steps are: (i) the formation of low-symmetry A3B phthalocyanines bearing three mesogenic substituents and one hydroxyl-terminated chain and (ii) the esterification of these phthalocyanines with the carboxylic acid homologue of PCBM.<p>In solution, no electron transfer from the phthalocyanine to the fullerene is evidenced in the ground state. On the contrary fluorescence quenching indicates that a photo-induced charge transfer takes place. Also, cyclic voltammetry measurements confirmed that both phthalocyanine and fullerene moieties act as independent & / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Les semiconducteurs organiques (OSC) tels que les composés organiques photovoltaïques (OPVs), les diodes électroluminescentes organiques (OLEDs) ou encore les transistors organiques à effet de champ (OFETs) constituent un domaine de recherche très attractif en raison de leur potentiel en tant que couches actives dans les dispositifs optoélectroniques. Les composés aromatiques polycycliques ainsi que les hétéroaromatiques sont considérés comme des matériaux prometteurs pour les OSC en raison de leurs conductivités électriques potentielles, de leurs propriétés optiques ainsi que de leurs assemblages géométriques. Ces deux systèmes et leurs propriétés photophysiques ont été étudiés dans les trois chapitres de cette thèse. Dans le premier chapitre, une étude sur un ensemble d'acènes linéaires, angulaires et condensés consistant en des liens hétéroatomes avec des agrégations uniques a été décrite et analysée. Les hétéroacènes N-fusionnés angulaires et π-étendus sont la classe principale étudiée dans le deuxième chapitre. Leurs synthèses sont basées sur la réaction de couplage de Suzuki-Miyaura et la réaction de Cadogan. Outre les acènes et les hétéroacènes N-fusionnés, les N-hétéroaromatiques ont fait l'objet d'une attention particulière dans le domaine de matériaux. L'un d'entre eux est la classe des quinazolines utilisées comme partie acceptrice d'électrons dans les structures push-pull pour le transfert de charge intramoléculaire (TCI). L'étude des relations entre les structures dérivées du motif quinazoline de type donneur d'électron-accepteur-donneur (D-A-D) et leurs propriétés de photoluminescence est le principal travail mentionné dans le troisième chapitre. / Organic semiconductors (OSCs) are a highly attractive research field due to their potentials as active layers in optoelectronic devices such as organic field-effect transistors (OFETs), organic photovoltaic (OPVs) and organic light emitting diodes (OLEDs). Polycyclic aromatic compounds as well as heteroaromatics are considered as promising materials for OSCs due to their semi conductivity properties, optical properties and geometric structures. The mentioned systems and their photophysical properties were investigated in three chapters of my thesis. In the first chapter, a study on a set of linear, angular and condensed acenes consisting of heteroatom linkages with unique aggregations was described and analyzed. The angular and π-extended N-fused heteroacenes are the main class studied in the second chapter. Their synthesis is based on the Suzuki-Miyaura coupling and the Cadogan reactions. Besides acenes and N-fused heteroacenes, N-heteroaromatics have gained attention in material area. One of them is the quinazoline class that is known as an electron withdrawing unit in push-pull structures for intramolecular charge transfer (ICT). The investigation of the relationships between the electron donor-acceptor-donor (D-A-D) quinazoline-based structures and their photoluminescence properties is the main work mentioned in the third chapter.

In the last 25 years, organic or "plastic" solar cells have gained commercial interest as a light-weight, flexible, colorful, and potentially low-cost technology for direct solar energy conversion into electrical power. Currently, organic solar cells with a maximum power conversion effciency (PCE) of 12% can compete with classical silicon technology under certain conditions. In particular, a variety of strongly absorbing organic molecules is available, enabling custom-built organic solar cells for versatile applications. In order to improve the PCE, the charge carrier mobility in organic thin films must be improved. The transport characterization of the relevant materials is usually done in neat layers for simplicity. However, the active layer of highly efficient organic solar cells comprises a bulk heterojunction (BHJ) of a donor and an acceptor component necessary for effective charge carrier generation from photo-generated excitons. In the literature, the transport properties of such blend layers are hardly studied. In this work, the transport properties of typical BHJ layers are investigated using space-charge limited currents (SCLC), conductivity, impedance spectroscopy (IS), and thermally stimulated currents (TSC) in order to model the transport with numerical drift-diffusion simulations. Firstly, the influence of an exponential density of trap states on the thickness dependence of SCLCs in devices with Ohmic injection contacts is investigated by simulations. Then, the results are applied to SCLC and conductivity measurements of electron- and hole-only devices of ZnPc:C60 at different mixing ratios. Particularly, the field and charge carrier density dependence of the mobility is evaluated, suggesting that the hole transport is dominated by exponential tail states acting as trapping sites. For comparison, transport in DCV5T-Me33:C60, which shows better PCEs in solar cells, is shown not to be dominated by traps. Furthermore, a temperature-dependent IS analysis of weakly p-doped ZnPc:C60 (1:1) blend reveals the energy-resolved distribution of occupied states, containing a Gaussian trap state as well as exponential tail states. The obtained results can be considered a basis for the characterization of trap states in organic solar cells. Moreover, the precise knowledge of the transport-relevant trap states is shown to facilitate modeling of complete devices, constituting a basis for predictive simulations of optimized device structures.:1 Introduction 2 Organic Semiconductors and Solar Cells 2.1 Structural, Optical, and Energetic Properties 2.2 Charge Carrier Transport 2.2.1 Classical Transport Models 2.2.2 Hopping and Tunneling Transport 2.2.3 Limitations of Transport Characterization 2.3 Doping 2.4 Single Carrier Devices 2.4.1 Theory of Space-Charge Limited Currents 2.4.2 Electrical Potential Mapping by Thickness Variation 2.4.3 Influence of the Contacts 2.5 Organic Solar Cells 2.5.1 Principles 2.5.2 The p-i-n Concept 2.5.3 Recombination 2.5.4 Electrical Characterization 3 Numerical Drift-Diffusion Simulations 3.1 Modeling Organic Semiconductors 3.2 System of Differential Equations 3.3 Simulation Algorithm and Modules 4 Exploiting Contact Diffusion Currents for Trap Characterization in Organic Semiconductors 4.1 Motivation 4.2 Drift-Diffusion Model 4.3 Results and Discussion 4.4 Conclusion 5 Transport Characterization of Donor-Acceptor Blend Layers 5.1 Motivation 5.2 Device Fabrication 5.3 Hole Transport in ZnPc:C60 Blends with Balanced Mixing Ratios 5.3.1 Current-Voltage Measurements 5.3.2 Drift-Diffusion Model 5.3.3 Modeling Results 5.3.4 Discussion 5.4 Hole Transport in Fullerene-Rich ZnPc:C60 Blends 5.4.1 Results and Discussion 5.5 Electron Transport in ZnPc:C60 (1:1) 5.5.1 Results and Discussion 5.6 Transport in Blend Layers with the High Efficiency Donor DCV2-5T-Me33 5.6.1 Hole Transport in DCV2-5T-Me33:C60 5.6.2 Electron Transport in DCV2-5T-Me33:C60 5.7 Conclusions for Transport in Blend Layers 6 Doping-Enabled Density of States Determination in Donor-Acceptor Blend Layers 6.1 Motivation 6.2 Theory 6.3 Methods 6.4 Results 6.4.1 Impedance Spectroscopy 6.4.2 Fermi level, Mott-Schottky Analysis, and Band Diagram 6.4.3 DOOS Determination 6.4.4 Thermally Stimulated Currents 6.4.5 Solar Cell Characteristics 6.5 Discussion 6.6 Conclusions on the DOS of ZnPc:C60 (1:1) 7 Conclusion and Outlook Materials, Symbols, Abbreviations Bibliography / Organische oder "Plastik"-Solarzellen haben in den letzten 25 Jahren eine rasante Entwicklung durchlaufen. Kommerziell sind sie vor allem wegen ihres geringen Gewichts, Biegsamkeit, Farbigkeit und potentiell geringen Herstellungskosten interessant, was zukünftig auf spezielle Anwendungen zugeschnittene Solarzellen ermöglichen wird. Die Leistungseffzienz von 12% ist dabei unter günstigen Bedingungen bereits mit klassischer Siliziumtechnologie konkurrenzfähig. Um die Effzienz weiter zu steigern und damit die Wirtschaftlichkeit zu erhöhen, muss vor allem die Ladungsträgerbeweglichkeit verbessert werden. In organischen Solarzellen werden typischerweise Donator-Akzeptor-Mischschichten verwendet, die für die effziente Generation freier Ladungsträger aus photo-induzierten Exzitonen verantwortlich sind. Obwohl solche Mischschichten typisch für organische Solarzellen sind, werden Transportuntersuchungen der relevanten Materialien der Einfachheit halber meist in ungemischten Schichten durchgeführt. In der vorliegenden Arbeit wird der Ladungstransport in Donator-Akzeptor-Mischschichten mithilfe raumladungsbegrenzter Ströme (space-charge limited currents, SCLCs), Leitfähigkeit, Impedanzspektroskopie (IS) und thermisch-generierter Ströme (thermally stimulated currents, TSC) untersucht und mit numerischen Drift-Diffusions-Simulationen modelliert. Zunächst wird mittels Simulation der Einfluss exponentiell verteilter Fallenzustände auf das schichtdickenabhängige SCLC-Verhalten unipolarer Bauelemente mit Ohmschen Kontakten untersucht. Die Erkenntnisse werden dann auf Elektronen- und Lochtransport in ZnPc:C60-Mischschichten mit verschiedenen Mischverhältnissen angewendet. Dabei wird die Beweglichkeit als Funktion von elektrischem Feld und Ladungsträgerdichte dargestellt, um SCLC- und Leitfähigkeitsmessungen zu erklären, was mit einer exponentiellen Fallenverteilung gelingt. Zum Vergleich werden dieselben Untersuchungen in DCV2-5T-Me33:C60, dem effizientesten der bekannten Solarzellenmaterialien dieser Art, wiederholt, ohne Anzeichen für fallendominierten Transport. Des weiteren werden erstmals schwach p-dotierte ZnPc:C60-Mischschichten mit temperaturabhängiger IS untersucht, um direkt die Dichte besetzter Lochfallenzustände zu bestimmen. Dabei werden wiederum exponentielle Fallenzustände sowie eine Gaußförmige Falle beobachtet. Insgesamt tragen die über Fallenzustände in Mischschichten gewonnenen Erkenntnisse zum Verständnis von Transportprozessen bei und bilden damit eine Grundlage für die systematische Identifizierung von Fallenzuständen in Solarzellen. Außerdem wird gezeigt, dass die genaue Beschreibung der transportrelevanten Fallenzustände die Modellierung von Bauelementen ermöglicht, auf deren Grundlage zukünftig optimierte Probenstrukturen vorhergesagt werden können.:1 Introduction 2 Organic Semiconductors and Solar Cells 2.1 Structural, Optical, and Energetic Properties 2.2 Charge Carrier Transport 2.2.1 Classical Transport Models 2.2.2 Hopping and Tunneling Transport 2.2.3 Limitations of Transport Characterization 2.3 Doping 2.4 Single Carrier Devices 2.4.1 Theory of Space-Charge Limited Currents 2.4.2 Electrical Potential Mapping by Thickness Variation 2.4.3 Influence of the Contacts 2.5 Organic Solar Cells 2.5.1 Principles 2.5.2 The p-i-n Concept 2.5.3 Recombination 2.5.4 Electrical Characterization 3 Numerical Drift-Diffusion Simulations 3.1 Modeling Organic Semiconductors 3.2 System of Differential Equations 3.3 Simulation Algorithm and Modules 4 Exploiting Contact Diffusion Currents for Trap Characterization in Organic Semiconductors 4.1 Motivation 4.2 Drift-Diffusion Model 4.3 Results and Discussion 4.4 Conclusion 5 Transport Characterization of Donor-Acceptor Blend Layers 5.1 Motivation 5.2 Device Fabrication 5.3 Hole Transport in ZnPc:C60 Blends with Balanced Mixing Ratios 5.3.1 Current-Voltage Measurements 5.3.2 Drift-Diffusion Model 5.3.3 Modeling Results 5.3.4 Discussion 5.4 Hole Transport in Fullerene-Rich ZnPc:C60 Blends 5.4.1 Results and Discussion 5.5 Electron Transport in ZnPc:C60 (1:1) 5.5.1 Results and Discussion 5.6 Transport in Blend Layers with the High Efficiency Donor DCV2-5T-Me33 5.6.1 Hole Transport in DCV2-5T-Me33:C60 5.6.2 Electron Transport in DCV2-5T-Me33:C60 5.7 Conclusions for Transport in Blend Layers 6 Doping-Enabled Density of States Determination in Donor-Acceptor Blend Layers 6.1 Motivation 6.2 Theory 6.3 Methods 6.4 Results 6.4.1 Impedance Spectroscopy 6.4.2 Fermi level, Mott-Schottky Analysis, and Band Diagram 6.4.3 DOOS Determination 6.4.4 Thermally Stimulated Currents 6.4.5 Solar Cell Characteristics 6.5 Discussion 6.6 Conclusions on the DOS of ZnPc:C60 (1:1) 7 Conclusion and Outlook Materials, Symbols, Abbreviations Bibliography

In this thesis, methods for improving charge carrier mobility and deposition conditions for the solution shearing of organic semiconductors for organic field-effect transistors (OFETs) are investigated. Electrical performance for OFETs is currently still limited by the charge carrier mobility, especially when high fabrication speeds are required. In this work, adaptations are made to the solution shearing method to enhance charge carrier mobility values and to increase the deposition speed and film uniformity of semiconductor films. The solution shearing method can be easily adapted to large-scale roll-to-roll fabrication, a low-cost and high throughput fabrication process. In this work, the fabrication of OFETs with both crystalline small-molecule and donor-acceptor polymer semiconductors as the active layer is performed, and significant improvements in charge carrier mobility and film formation are achieved. Specifically, the crystalline small-molecule semiconductor TIPS-pentacene is blended with the inert dielectric polystyrene, and solution shearing parameters are optimized to obtain highly-aligned crystalline films. The thin film with optimized morphology is deposited on a very thin polymer dielectric film, demonstrating the feasibility of high-performance OFETs (effective mobility of ~1.2 cm2 V-1s-1) and an ultra-low operating voltage (~1 V) – at the time a record value. To improve crystal growth, the solution shearing method is modified to add vibrations to the liquid during the coating process. The new coating method, named “piezoshearing”, allows the application of vibrations to the liquid during deposition through the attachment of a piezo actuator to the shearing blade. The piezoshearing is implemented to enhance crystal growth during the solution shearing of crystalline materials, and tests of piezoshearing for the material 2,7-Dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) demonstrate that substrate coverage can be increased due to induced stick-and-slip caused by the piezoshearing. Due to the unfavorable wetting conditions of semiconducting donor-acceptor polymer solutions on the commonly used low surface energy OFET substrates, conventional solution shearing is problematic. With piezoshearing, film deposition can be significantly improved. In particular, through piezoshearing the so-called stick-and-slip instabilities are mitigated, allowing the doubling of the shearing speed, and the deposition of smooth and ultrathin films (~7 nm). In addition to enabling higher coating speeds, piezoshearing also lowers the polymer material consumption by up to ~ 70% in comparison to the conventional solution shearing method. For some materials, piezoshearing is also found to increase the charge carrier mobility in OFET devices by up to two orders of magnitude. The piezoshearing is utilized for viscous polymer solutions, which are challenging to coat, and usually, result in non-uniform films. Three donor-acceptor polymer systems were tested, and morphology changes are observed for all materials when piezoshearing is applied. For one of the polymeric solutions, an increase in crystallinity is achieved, possibly accompanied by a change in the degree of alignment of the polymer chains. For two other polymer solutions with higher molecular weight chains, very smooth films were obtained with the piezoshearing – saving 30% of material. Without the application of vibrations, such materials yield very non-uniform films, with significant thickness variations, which is unsuitable for OFET devices. In summary, this work leads to significant improvements in the solution shearing of organic semiconductor materials by adding vibrations in the kHz range to the deposition process. The effects and benefits of utilizing the piezoshearing are demonstrated, and suggestions for further improvement and studies are made.:Contents 7 1.Introduction 11 Motivation 11 Outline 12 2.Theoretical Principles of Organic Electronic Materials and Devices 13 Organic Electronics 13 Organic Semiconductors 14 Charge Transport Mechanisms in Organic Semiconductors 16 Organic Field-effect Transistors 19 Operation 19 The Metal-Semiconductor Interface 22 The Dielectric 25 Film Morphology and Charge Transport in OFETs 27 Small Molecules 27 Semicrystalline Polymers 29 3.Solution Shearing and Control of Film Morphology 33 The Solution Shearing Method 34 Capillary Flow and the Pinned Contact Line. 36 Marangoni Flow 36 Shear Flow 37 Film Formation in Solution Shearing 38 Small Molecules 38 Polymers 43 Stick-and-slip Instabilities 50 Contact Angle Hysteresis and Stick-and-slip 52 Vibration-assisted Thin-film Solution Fabrication Methods 53 Effects on a Liquid stemming from Vibration 53 Relevant Characteristics 57 Vibrations and Thin-film Formation 58 Combining the Solution Shearing and Vibrations 61 4.Experimental Methods 63 Device Fabrication 63 Substrate Preparation 63 Electrode Evaporation . 65 Piezoshearing Setup 65 Thin-film Characterization 68 Cross-Polarized Optical Microscopy 68 Grazing Incidence Wide-Angle X-ray Scattering 71 Electrical characterization 77 Characterization 77 Mobility estimation and overestimation discussion 77 5.Alignment Improvement from Blending the Small molecule TIPS- pentacene with an inert Polymer 81 Introduction 81 Optimization of film morphology for TIPS-pentacene . 82 Device Fabrication 82 Electrical Characterization .. 83 Film morphology characterization 86 Fabrication of Ultra-low-voltage Operation Devices 96 Figure of Merit of this Study 97 6.Piezoshearing of Crystalline Materials 101 Introduction 101 Piezoshearing of Pristine TIPS-pentacene 102 Film Fabrication 102 Thin-film Characterization 102 TIPS-pentacene blended with PS in Toluene: Better Performing Devices 104 Piezoshearing of C8-BTBT 105 7.Addressing Stick-and-Slip Instabilities in solution-sheared films for Introduction 109 Device Fabrication 110 The Effect of Piezoshearing on Stick-and-Slip Instabilities 111 Increasing Shearing Speed 111 Thin-film Characterization 114 Electrical Characterization 116 Energy Barriers and Overcoming them with Vibration 119 Acceleration Threshold for Mitigating Stick-and-slip 122 8.Piezoshearing of Viscous Polymer Solutions 127 Introduction 127 Device Fabrication 128 DPP4DE-TT and Film Morphology 129 DPP6DO-TT, DPP6DO-T, and Faraday Instabilities 137 Thin-film Characterization 141 Piezoshearing as a Parametric Oscillator System 145 Solid Friction 146 Viscosity 146 Transition Between Regimes 147 9.Conclusion and Outlook 149 Conclusion 149 Outlook 150

Dotierung ist ein technologisches Schlüsselverfahren zur Kontrolle der Ladungsträgerdichte und der Position des Fermi-Levels in Halbleitern. Für organische Halbleiter hat sich die Verwendung von starken molekularen Elektronenakzeptoren und -donatoren als p- bzw. n-Dotanten als zuverlässigster Ansatz erwiesen. In der vorliegenden Arbeit wird eine Reihe von Themen im Zusammenhang mit der molekularen Dotierung von organischen Halbleitern untersucht. Zuerst wird die Eignung zweier verschiedener Materialparameter zur Vorhersage der Ionenpaarbildung bei der molekularen Dotierung überprüft: i) Redox-Potentiale, gemessen durch Cyclovoltammetrie (CV), und ii) Ionisationsenergie (IE) / Elektronenaffinität (EA), gemessen mittels (inverser) Photoelektronenspektroskopie (PES/IPES). Optische Absorptionsmessungen zeigen, dass Redox-Potentiale besser geeignet sind passende Materialpaare zu identifizieren als IE/EA-Werte. Zweitens wird die n-Dotierung eines prototypischen, p-artigen Co-Polymers durch metallorganische Dimere erforscht. Eine Kombination von PES/IPES, optischen Absorptions- und Leitfähigkeitsmessungen zeigt, dass das p-Polymer durch Dotierung zu einem n-Polymer transformiert werden kann. Drittens wird die p-Dotierung des Polymers P3HT durch ein bor-basiertes organisches Salz analysiert. Ein multi-experimenteller Ansatz zeigt die Bildung von Polaronen bei niedrigen und von Bipolaronen bei hohen Dotanten-Konzentrationen von über zehn Prozent. Zuletzt wird die Modifikation von elektronenselektiven Kontakten in organisch-anorganischen Metallhalogenid-Perowskit-Solarzellen (PSCs) untersucht, um Elektronensammel-Verluste zu minimieren. Hierzu wird eine Zwischenschicht aus metallorganischen Dimeren zwischen Elektrode und org. Elektronentransportschicht (ETL) eingebracht, um einen ohmschen Kontakt herzustellen. PSCs, die aus derart modifizierten elektronenselektiven Kontakte bestehen, weisen erhöhte Wirkungsgrade auf. / Doping is a key technological procedure to control the charge carrier density and Fermi level position in semiconductors. For organic semiconductors, the use of strong molecular electron acceptors and donors as p-type and n-type dopants, respectively, has emerged as the most reliable approach. In the present thesis, a variety of topics related to the molecular doping of organic semiconductors will be investigated. First, the suitability of two different material parameters to predict ion pair formation in molecular doping is explored: i) redox-potentials measured by cyclic voltammetry (CV) and ii) ionization energy (IE) / electron affinity (EA) measured by (inverse) photoelectron spectroscopy (PES/IPES). Optical absorption spectroscopy measurements reveal redox-potentials to be better suited to identify matching material pairs than IE/EA values. Secondly, the n-type doping of a prototypical p-type co-polymer by an organometallic dimer is studied. Combined PES/IPES, optical absorption and conductivity measurements show that the p type polymer can be rendered n-type upon doping. Thirdly, the p-type doping of the polymer P3HT by a boron based organic salt is investigated. A multi-experimental approach shows the formation of polarons at low and bipolarons at high dopant concentrations above ten percent. Finally, the modification of electron-selective contacts in organic-inorganic metal halide perovskite solar cells (PSCs) is studied in order to minimize electron collection losses. Here, an interlayer of organometallic dimers is introduced between electrode and organic electron transport layer in order to form an Ohmic contact. PSCs employing such modified electron-selective contacts show increased power conversion efficiencies.

Organic field-effect transistors (OFETs) are essential devices for the realization of novel electronic applications based on organic materials. Recent years have brought tremendous improvements regarding the organic semiconductor (OSC) with charge carrier mobilities around 10 cm²/Vs. Yet, several challenges are needed to be addressed in order to enable technologies of the future that are based on high-performance organic transistors. In this work, C8-BTBT, a high-mobility material that has gained increasing interest in the last few years, is used to prepare films with state-of-the art charge-carrier mobility and above. For this purpose, the solution-shearing method—a meniscus-guided technique that is capable to produce highly aligned, crystalline films—is applied. Based on these charge-transport layers with an estimated intrinsic mobility of up to 12 cm²/Vs, several strategies towards their exploitation for high-performance organic transistors are investigated. Among the relevant parameter, channel length, contact resistance and gate dielectric capacitance are the three aspects that are addressed. The solution-shearing method is further applied to the realization of solution-deposited polymer dielectrics. High-capacitance films with maximum values of about 280 nF/cm² are fabricated and used to produce low-voltage OFETs that can operate at -1V. In order to increase the devices’ transconductance, a novel patterning methodology to achieve sub-micrometre channel lengths is investigated. Using this technique, working devices with a channel length of 500 nm are shown. The compatibility of this process with the solution-shearing method for the fabrication of high-performance semiconducting and gate dielectric films is one of its major advantages. One of the limiting device parameters is the contact resistance as is clearly observable by the restricted current scaling that is observed for lower channel length. Hence, the interface of OSC and source/drain contacts is investigated. Even though an ultimate solution for very low contact resistance remains to be developed, important aspects for its further enhancement are deduced in this work. As an important first experimental result, this thesis describes a short-channel device architecture that is compatible with solution-shearing of high-performance films with its full potential yet to be explored in future work. / Organische Feld-Effekt Transistoren (OFETs) sind grundlegende Bestandteile für die Entwicklung neuerartiger Technologien auf der Basis von organischen Halbleitermaterialien. Insbesondere während der letzten Jahre haben diese Materialien einschlägige Verbesserungen erfahren und erreichen heute Ladungsträgermobilitäten um die 10 cm²/Vs. Um dies für die Umsetzung neuartiger Technologien zu nutzen, müssen jedoch noch einige Herausforderungen überwunden werden. Diese Arbeit leistet einen Beitrag in diese Richtung. Unter Anwendung eines der wohl populärsten Halbleitermaterialien der letzen Jahre mit der chemischen Bezeichnung C8-BTBT, wird die Herstellung von hochqualitativen Halbleiterfilmen mittels Flüssigprozessierung gezeigt. Mit der sogenannten „Solution-Shearing“ Methode – eine Abscheidetechnik, die über die Kontrolle eines trocknenden Meniskus hochkristalline und ausgerichtete Schichten erzeugen kann – ist es möglich Dünnschichtbauelemente mit abgeschätzten, intrinsischen Ladungsträgermobilitäten von bis zu 12 cm²/Vs zu erzeugen. Um diese hoch-qualitativen Filme für die Herstellung von leistungsfähigen Transistoren zu nutzen, werden mehrere relevante Parameter betrachtet, darunter die Kanallänge, der Kontaktwiderstand und das Gate-Dielektrikum. Im Speziellen wird die Abscheidung des Dielektrikums mittels der „Solution-Shearing“ Methode untersucht. Es kann gezeigt werden, dass dies für die Herstellung von qualitativ hochwertigen Filmen mit Kapazitäten bis zu 280 nF/cm² genutzt werden kann. Angewendet in OFETs erlauben diese Schichten den Betrieb bei sehr geringen Spannungen von -1V. Um die Transkonduktanz der Transistoren zu erhöhen wird zudem eine mit der „Solution-Shearing“ Methode kompatible Source/Drain-Strukturierungsmethode untersucht. Diese ermöglicht Kanallängen unter einem Mikrometer und konnte hier für die Herstellung von funktionierenden Transistoren mit einer Kanallänge bis zu nur 500 nm angewendet werden. Eine der limitierenden Transistorkenngrößen ist der Kontaktwiderstand, wie durch die abweichende Skalierung des Stromes mit verringerter Kanallänge deutlich wird. Aus diesem Grund wurde auch die Grenzfläche zwischen Halbleiter und Source/Drain-Kontakten näher untersucht. Allerdings verbleibt die Entwicklung einer effektiven Methode zur Reduzierung des Kontaktwiderstandes ein Projekt für zukünftige Untersuchungen, auch wenn die vorliegende Arbeit einige wichtige Anhaltpunkte für mögliche Strategien liefert. Als wichtiges erstes Resultat liefert die vorliegende Arbeit eine Beschreibung zur Herstellung funktionsfähiger Kurzkanal-OFETs mittels „Solution-Shearing“, deren volles Potential aber in der Zukunft weiter untersucht werden muss.

The field of organic semiconductors considerably gained research interest due to promising applications in flexible, large-area, lightweight and semitransparent electronic devices, such as light-emitting diodes, solar cells, or transistors. The working mechanism of such devices depends on the combination of different neat or blended organic films, whose physical properties substantially differ from those of inorganic semiconductors. Weak intermolecular electronic coupling and large energetic disorder result in a thermally activated charge carrier hopping between localized electronic states. Therefore, many processes in organic devices are determined by properties of single molecules. The major goal of this thesis is to disclose relationships between electronic properties of organic thin films and molecular parameters, helping to provide specific design rules for new molecules. In the first part of this thesis, the impact of molecular quadrupole moments on the transport energies of charge carriers is investigated by photoelectron spectroscopy. The results reveal for a variety of planar small molecules that charge-quadrupole interactions along the pi-pi-stacking geometry induce large energy changes with molecular orientation at surfaces and interfaces of crystalline films. Furthermore, these electrostatic interactions enable a continuous tuning of energy levels in crystalline intermixed blends by more than 1 eV. In blends exhibiting separated phases, quadrupole moments induce electrostatic gradients from the interface to the bulk phase. These two effects are exploited in organic solar cells consisting of a ternary blend of two intermixed donors blended with one acceptor. By changing the mixing ratio of the two donors, the open-circuit voltage can be continuously tuned. Additionally, the dissociation barrier of electron-hole pairs at the interface can be varied, reflecting in a change in photocurrent. In the second part, molecular n-doping is investigated, facing the particular issue of air sensitivity. The analysis of two air stable precursor molecules of n-dopants reveals very good doping properties after their thermal evaporation, partly even better than for a reference air sensitive dopant. For high doping concentrations, temperature-dependent conductivity measurements show that the thermal activation energy of many compounds can be described by an empirical function of two molecular parameters, the relaxation energy of matrix anions and the Coulomb binding energy of integer charge transfer complexes (ICTCs) between matrix anions and dopant cations. The investigation of the density of states indicates that charge transport at high doping concentrations predominantly occurs by a rearrangement between different ICTC configurations and is limited by their energetic disorder, which can be reduced substantially by adding electron withdrawing side groups to the matrix molecules. The exposure of several n-doped semiconductors to air reveals that the air stability increases with larger ionization energies of ICTCs. This effect is attributed to an universal trap introduced upon air exposure. Its energy is estimated to be 3.9 eV, setting a general limit for air stable n-doping. / Organische Halbleiter bieten vielversprechende Anwendungsmöglichkeiten in ultraleichten, flexiblen, großflächigen und semitransparenten elektronischen Bauteilen wie beispielsweise in Leuchtdioden, Solarzellen oder Transistoren. Die Funktionsweise solcher Bauteile basiert auf der Kombination verschiedener organischer Moleküle in dünnen Schichten, deren physikalische Eigenschaften sich stark von herkömmlichen anorganischen Halbleitern unterscheiden. Die schwache elektronische Kopplung zwischen einzelnen Molekülen und die große energetische Unordnung in organischen Halbleitern bewirken einen temperaturaktivierten Transport von Ladungsträgern zwischen lokalisierten elektronischen Zuständen. Daher werden viele Prozesse in organischen Halbleiterbauelementen von molekularen Eigenschaften bestimmt. Das Hauptziel dieser Dissertation ist es, verschiedene elektronische Eigenschaften dünner organischer Filme mit molekularen Parametern in Verbindung zu bringen, was als Grundlage für die gezielte Entwicklung neuer Moleküle dienen soll. Im ersten Teil dieser Arbeit wird mittels Photoelektronenspektroskopie der Einfluss molekularer Quadrupolmomente auf die Transportenergien von Ladungsträgern untersucht. Für eine große Anzahl verschiedener planarer Moleküle zeigt sich, dass die Wechselwirkung von Ladungen mit Quadrupolmomenten entlang der pi-pi-Stapelrichtung große Veränderungen der Energieniveaus an der Oberfläche und der Grenzfläche von kristallinen Filmen bewirkt, beispielsweise wenn sich die Molekülorientierung ändert. Dieser elektrostatische Effekt ermöglicht es, die Energieniveaus in einer homogen durchmischten Schicht zweier Molekülarten kontinuierlich über eine Größenordnung von mehr als 1 eV durchzustimmen. In Mischungen mit einer Phasentrennung können molekulare Quadrupolmomente einen elektrostatischen Gradienten an der Grenzfläche zwischen den Phasen ausbilden. Diese beiden Effekte werden in Solarzellen ausgenutzt, die aus einer Mischung von zwei Donatormolekülen und einem Akzeptormolekül bestehen. Durch Variation des Mischverhältnisses der zwei Donatoren lässt sich die Leerlaufspannung kontunierlich anpassen. Zusätzlich lässt sich die Energiebarriere für die Ladungsträgertrennung an der Grenzfläche reduzieren, was zu einem höheren Photostrom führt. Im zweiten Teil wird molekulare n-Dotierung untersucht, bei der das spezielle Problem der Luftsensitivität berücksichtigt werden muss. Zwei luftstabile Ausgangsmoleküle von n-Dotanden weisen nach ihrer thermischen Verdampfung sehr gute Dotiereigenschaften auf, welche für ein Molekül sogar besser als bei entsprechenden luftsensitiven Referenzdotanden sind. Temperaturabhängige Leitfähigkeitsmessungen zeigen, dass die thermische Aktivierungsenergie bei hohen Dotierkonzentrationen durch eine empirische Funktion von zwei molekularen Parametern beschrieben werden kann, welche die Relaxationsenergie von Anionen des Matrixmoleküls und die Coulombbindungsenergie des Ionenpaars aus Matrix- und Dotandenmolekül sind. Die Untersuchung der Zustandsdichte dieser hochdotierten Halbleiter deutet darauf hin, dass sich der Ladungstransport durch eine Umbesetzung dieser Ionenpaare beschreiben lässt. Der Transport ist dabei durch die energetische Unordnung der Ionenpaare limitiert, welche sich allerdings durch das Hinzufügen von elektronenziehenden Seitengruppen an die Matrixmoleküle deutlich reduzieren lässt. Der Kontakt verschiedener n-dotierter Halbleiter mit Luft zeigt, dass sich die Luftstabilität dieser mit größerer Ionisationsenergie der Anionen des Matrixmaterials verbessert. Diese Beobachtung wird dadurch erklärt, dass durch den Kontakt mit Luft ein universeller Fallenzustand mit der Energie von 3.9 eV entsteht. Dieser setzt eine allgemeine Grenze für luftstabile n-Dotierung.