We report on inkjet printing of aqueous colloidal suspensions containing monodisperse silica and/or polystyrene nanosphere particles and a systematic study of the morphology of the deposits as a function of different parameters during inkjet printing and solvent evaporation. The colloidal suspensions act as a model ink for an understanding of layer formation processes and resulting morphologies in inkjet printing in general. We investigated the influence of the surface energy and the temperature of the substrate, the formulation of the suspensions, and the multi-pass printing aiming for layer stacks on the morphology of the deposits. We explain our findings with models of evaporation-driven self-assembly of the nanosphere particles in a liquid droplet and derive methods to direct the self-assembly processes into distinct one- and two-dimensional deposit morphologies.

We report on the detailed electrical investigation of all-inkjet-printed thin-film transistor (TFT) arrays focusing on TFT failures and their origins. The TFT arrays were manufactured on flexible polymer substrates in ambient condition without the need for cleanroom environment or inert atmosphere and at a maximum temperature of 150 °C. Alternative manufacturing processes for electronic devices such as inkjet printing suffer from lower accuracy compared to traditional microelectronic manufacturing methods. Furthermore, usually printing methods do not allow the manufacturing of electronic devices with high yield (high number of functional devices). In general, the manufacturing yield is much lower compared to the established conventional manufacturing methods based on lithography. Thus, the focus of this contribution is set on a comprehensive analysis of defective TFTs printed by inkjet technology. Based on root cause analysis, we present the defects by developing failure categories and discuss the reasons for the defects. This procedure identifies failure origins and allows the optimization of the manufacturing resulting finally to a yield improvement.

A wearable body temperature sensor would allow for early detection of fever or infection, as well as frequent and accurate hassle-free recording. This thesis explores the design of a body-temperature-sensing device inkjet-printed on a flexible substrate. All structures were first modeled by first-principles, theoretical calculations, and then simulated in HFSS. A variety of planar square inductor geometries were studied before selecting an optimal design. The designs were fabricated using multiple techniques and compared to the simulation results. It was determined that inductance must be carefully measured and documented to ensure good functionality. The same is true for parallel-plate and interdigitated capacitors. While inductance remains relatively constant with temperature, the capacitance of the device with a temperature-sensitive dielectric layer will result in a shift in the resonant frequency as environmental or ambient temperature changes. This resonant frequency can be wirelessly detected, with no battery required for the sensing device, from which the temperature can be deduced. From this work, the optimized version of the design comprises of conductive silver in with a temperature-sensitive graphene oxide layer, intended for inkjet-printing on flexible polyimide substrates. Graphene oxide demonstrates a high dielectric permittivity with good sensing capabilities and high accuracy. This work pushes the state-of-the-art in applying these novel materials and techniques to enable flexible body temperature sensors for future biomedical applications.

Die Kombination aus anorganischen Nanopartikeln und Mikrogelen in einem hybriden System erlaubt die Herstellung von Materialien mit vielseitigen neuen Eigenschaften. Im Idealfall weisen solche hybriden Materialien neben den Eigenschaften von beiden indivduellen Systemen zusätzlich synergetische Effekte auf, welche aus den Interaktionen zwischen dem anorganischen Nanopartikel und dem Mikrogel resultieren. Im ersten Teil dieser Arbeit wird eine neuartige und eingängige Methode zur Herstellung von Cu2O@PNIPAM Kern-Schale Nanoreaktoren präsentiert. Die PNIPAM Schale schützt dabei die Cu2O Nanopartikel effektiv vor Oxidation. Die Cu2O@PNIPAM wurden als Photokatalysator zum Abbau von Methylorange unter sichtbarem Licht eingesetzt. Im Vergleich zu den reinen Cu2O Nanopartikeln konnte eine signifikante Steigerung der katalytischen Aktivität festgestellt werden. Desweiteren kann die photokatalytische Aktivität mittels Temperatur durch die thermosensitive PNIPAM Schale abgestimmt werden. Verhältnismäßig geringe Konzentrationen einer Cu2O@PNIPAM wässrigen Lösung (1,5 Gew%) können direkt als neuartige Tinte genutzt werden. Keine zusätzlichen Additive oder organische Lösungsmittel sind für die Strahldruckprozesse vonnöten. Gedruckte Bauelemente bestehend aus den Cu2O@PNIPAM wurden als Gas Sensoren eingesetzt und zeigten eine geringere Nachweisgrenze für NO2 als die reinen Cu2O Nanowürfel. Im zweiten Teil der Arbeit wurden katalytisch aktive Au Nanopartikel an copolymerisierten α –Cyclodextrin (α-CD) Einheiten in einem Poly(N-vinylcaprolactan) (PVCL) Mikrogel immobilisiert. Diese hybriden Partikel sind sehr aktive Katalysatoren für die Reduktion von aromatischen Nitroverbindungen. Die Reduktion von 4-Nitrophenol (Nip) und 2,6-Dimethyl-4-nitrophenol (DMNip) wurden als Modellreaktionen ausgewählt. Durch selektive Bindungseingenschaften der Nitroverbindungen an die α-CD Einheiten konnten verschiedene katalytische Aktivitäten für Nip and DMNip festgestellt werden. / The combination of inorganic nanoparticles and organic microgels in one hybrid system allows for the preparation of new materials with multifunctional properties. Ideally, such hybrid materials reflect both the properties of its individual components and synergetic effects due to the interaction between inorganic nanoparticles and microgels. In the first part of this thesis, the fabrication of Cu2O@Poly(N-isopropylacrylamide) (PNIPAM) core-shell nanoreactors has been presented. It was found that the PNIPAM shell effectively protects the Cu2O nanocubes from oxidation. The core-shell microgels have been used as photocatalyst for the decomposition of methyl orange and a significant enhancement in the catalytic activity has been observed compared with the bare Cu2O nanocubes. Most importantly, the photocatalytic activity of the core-shell nanoreactors can be further tuned by the thermosensitive PNIPAM shell. The aqueous solution of Cu2O@PNIPAM core-shell nanoparticles with quite low solid content (1.5wt. %) can be also directly used as a novel ink material for the inkjet printing without adding any other surfactants and organic solvents. The gas sensor device printed by core-shell nanoparticles is more sensitive to NO2 than that made from the bare Cu2O nanocubes. In the second part, a kind of hybrid microgel has been fabricated by immobilization of catalytically active Au nanoparticles in the α-cyclodextrin (α-CD) modified poly(N-vinylcaprolactam) (PVCL) microgels without addition of reducing agent and surfactant. The hybrid microgels can work efficiently as catalyst for the reduction of aromatic nitro-compounds by using the reduction of 4-nitrophenol (Nip) and 2,6-dimethyl-4-nitrophenol (DMNip) as model reactions. Due to the selective binding property of α-CDs to nitro compounds, the synthesized hybrid microgels show different catalytic activity for the target compounds, 4-nitrophenol (Nip) and 2,6-dimethyl-4-nitrophenol (DMNip), during the catalytic reactions.

Depuis une vingtaine d'années, des composants électroniques flexibles sont développés. Ces composants étant amenés à se tordre, à s'étirer et à se fléchir au cours de leur utilisation, le développement de composants ayant une bonne fiabilité mécanique est primordial. Ce travail s'est concentré sur les films métalliques d'argent déposés par impression jet d'encre ou sérigraphie sur des substrats de polyimide, servant à l’interconnexion électrique entre composants actifs. Deux mécanismes d’endommagement sont observables dans ces systèmes : la fissuration et le flambement par délaminage.Premièrement, pour caractériser expérimentalement ces deux phénomènes, des tests de traction sont réalisés sous microscope optique, afin de suivre l'évolution des fissures au cours de la déformation et sous interféromètre optique, afin de suivre les cloques de délaminage. Une analyse d'images est réalisée afin d'obtenir l'évolution de l'espacement entre fissures au cours de la déformation. L'existence de deux régimes de fissuration est observée : la fissuration longue et droite pour les films épais et la fissuration courte et en forme de zigzag pour les films minces. Le suivi des profils de cloques permet d'obtenir l'évolution de leur forme au cours de la déformation.Ensuite, afin d'éclairer les observations expérimentales, les phénomènes à l'étude sont modélisés par élément finis. Ainsi l'origine des deux régimes de fissuration est expliquée par un effet géométrique de l'épaisseur du film. Un modèle élastoplastique bidimensionnel de relaxation de contraintes dans le film permet d'obtenir un encadrement de l'espacement entre fissures au cours de la déformation. À partir du suivi des cloques, un modèle tridimensionnel permet de réaliser une identification des paramètres de la zone cohésive à l'interface film/substrat, où une énergie d'adhésion de 2 J.m-2, une contrainte critique de 20 MPa et un paramètre de mixité modale de 0,4 sont déterminés. Ces valeurs sont en accord avec la littérature. / Over the past 20 years, new improvements in materials and processes led to the development of printed flexible electronics. Flexible electronics devices subjected to bending, twisting, or stretching during their lifetime, the development of device with high reliability is therefore of great importance for the efficiency of electrical connection. This work investigates the mechanical reliability of inkjet or screen-printed Ag thin films on polyimide substrates dedicated to the electrical interconnection of active components. Expected mechanical failure modes are film cracking and buckling delamination.First of all, in order to characterized the two mechanisms, tensile tests are performed under an optical microscope to follow cracks and under an optical interferometer to follow buckles. In order to obtain crack spacing evolution during deformation, an image processing is realized. Two types of cracks are observed: long and straight cracking for thick films and small and zigzag shape cracking for thin films. The evolution of buckles shape with imposed tensile deformation is characterized.In a second time, in order to understand experimental observations, mechanical failure modes are analysed with finite elements models. The origin of the two types of cracking are explained by a geometrical effect of film thickness. A elastoplastic shear lag bidimensional model gives upper and lower bonds of crack spacing during deformation. A three-dimensional model allows identification of cohesive zone model parameters at film/substrate interface, from experimental buckle shape. An adhesion energy of 2 J.m-2 , a critical strength of 20 MPa and a mode mixity parameter of 0.4 are determined. These values are in good agreement with literature.

Les dispositifs thermoélectriques, légers et flexibles, peuvent être particulièrement intéressants aujourd’hui dans le contexte de l’émergence de l’informatique ubiquitaire, ainsi que de la crise environnementale liée à la consommation d’énergie électrique. Cependant, beaucoup de problèmes doivent encore être résolus pour rendre les dispositifs de récupération de chaleur commercialement viables. Dans cette thèse nous avons élaboré une méthode de conception et de fabrication par impression jet d’encre de générateurs flexibles à base de semi-conducteurs organiques et hybrides. En premier lieu, les travaux ont été consacrés au développement de matériaux thermoélectriques efficaces, stables et synthétisés par voie liquide. Les stratégies d’optimisation employées reposent sur la modulation de la concentration de porteurs de charge et le contrôle de la morphologie microscopique du matériau. En second lieu, nous avons effectué un travail de conception et de modélisation de dispositifs thermoélectriques ainsi que de leurs paramètres géométriques en utilisant des outils numériques. La modélisation numérique a été réalisée par la méthode des éléments finis 3D et par couplage d’effets physiques multidimensionnels. L’aboutissement de notre projet a été la formulation des matériaux en encres pour la fabrication de générateurs thermoélectriques par la technique de dépôt par impression jet d’encre. Différentes structures et architectures ont été expérimentalement caractérisées et systématiquement comparées aux évaluations numériques. Ainsi, nous présentons une approche intégrale de conception et de fabrication de dispositifs thermoélectriques opérant à des températures proches de l’ambiant. / Flexible lightweight printed thermoelectric devices can become particularly interesting with the advent of ubiquitous sensing and within the context of current energy and environmental issues. However, major drawbacks of state of the art thermoelectric materials must be addressed to make waste heat recovery devices commercially feasible. In this PhD thesis, we’ve elaborated and described a method to fabricate optimized, fully inkjetprinted flexible thermoelectric generators based on organic and hybrid semiconductors. This research project can be divided into three stages: First is the development of effective, stable and solution-processed p-type and n-type thermoelectric materials. Our effort in optimizing thermoelectric materials were based on modulation of charge carrier concentration and on control of morphology. Second, design and modeling of thermoelectric devices and their geometric parameters using numerical simulation methods. Numerical simulations were based on a 3D-finite element analysis and simulation software for coupled physical problems to model and design thermoelectric devices. Finally, formulation of materials into ink in order to produce thermoelectric generators by inkjet printing deposition. Various structures and architectures were experimentally characterized and systematically compared to numerical evaluations. Hence, we produced an extensive study on designing and producing thermoelectric devices operating at near ambient temperature and conditions.

Artificial light surrounds us in a manifold of shapes. It is mainly utilized for illumination, but also for graphical communication of complex and evolving messages and information, among other things. It can be generated in different ways with incandescent lamps and fluorescent tubes constituting two common examples. Organic solid state light-generation technologies, which boast advantages such as solution processability, thin and flexible form factors, and large versatility, are modern additions to the field. But regardless of the means of generation, whenever light is to be used to communicate information, as signage or displays, it needs to be patterned. Unfortunately patterning is often complicated and expensive from a fabrication point of view, or renders the devices inefficient. To bridge the gap between present technologies and the need for low-cost and low-complexity patterned light emitters, it is important to develop new device architectures and/or fabrication procedures. In this thesis we show that patterned light emission can be attained from solution processable bilayer light-emitting electrochemical cells (LECs), in which the bilayer stack comprises an electrolyte and an organic semiconductor as the first and second layer, respectively. We investigate a subtractive direct-write approach, in which electrolyte is displaced and patterned by the contact motion of a thin stylus, as well as an additive inkjet-patterning technique. Both result in electroluminescent patterns, e.g., light-emitting sketches and microscopic signage with high pixel density. But they can also build macroscopic patterned regions with homogeneous emission depending on the design of electrolyte features. Using an in-operando optical microscopy study we have investigated the operational physics and some limiting factors of the bilayer LECs. More specifically we find that the electrolyte film homogeneity is a key property for high optical quality, and that the emitting region is defined by the location of the interfaces between electrolyte, anode, and organic semiconductor. We observe that the cationic diffusion length is less than one micrometer in our employed organic semiconductors, and rationalize the localized emission by cationic electric double-layer formation at the cathode, and the electronically insulating electrolyte at the anode. To date, the presented luminescent signage devices feature high-resolution patterns, in both pixelated and line-art form, and show great robustness in terms of fabrication and material compatibility. Being LECs, they have the potential for truly low-cost solution processing, which opens up for new applications and implementations. However, these first reports on patterned bilayer LECs leave plenty of room for improvements of the optical and electronic characteristics. For instance, if the optoelectronic properties of the devices were better understood, a rational design of microscopic electrolyte features could provide for both more efficient LECs, and for more homogeneous light emission from the patterned regions.

L'objectif de cette thèse était de démontrer les potentialités de l'impression à jet d'encre pour le pilotage d'une HLED contenant des clusters métalliques phosphorescents dans le rouges, par des transistors organiques à effet de champs. Pour atteindre ce but, le projet a été divisé en deux parties : I) La fabrication et l'optimisation de transistors organiques de type n par photolithographie puis le transfert technologique vers l'impression à jet d'encre. II) Parallèlement au développement des transistors, je me suis attaché à la conception de matériaux hybrides luminescents pour la réalisation d'HLED. Pour la partie transistor, nous avons obtenu une meilleure compréhension des facteurs influençant l'injection de charges mais aussi la stabilité électrique pour un transistor de géométrie grille basse/contacts bas avec le fullerène C60 évaporé. Nous avons démontré que la résistance de contact est d'une part gouvernée par la morphologie du SCO au niveau des électrodes et d'autre part indépendante du travail de sortie du métal. En outre, nous avons vu que la stabilité électrique des transistors est fortement impactée par la nature du contact source et drain. L'optimisation des transistors fabriqués par photolithographie, qui a essentiellement consisté à modifier les interfaces, nous a permis de développer des transistors de type n performants avec des mobilités à effet de champ saturées allant jusqu'à 1,5 cm2/V.s pour une température maximum de procédé de 115 °C. Le transfert vers un transistor fabriqué par impression à jet d'encre a ensuite été effectué. Nous avons ensuite démontré que les morphologies de l'électrode de grille et de l'isolant, fabriqués par impression à jet d'encre, ont un impact négligeable sur les performances des transistors. Pour notre structure imprimée, l'injection de charges aux électrodes S/D est en fait le facteur clé pour la réalisation de transistors performants. Finalement, des matériaux phosphorescents rouges à base de cluster métalliques octaédrique de molybdène ont été développés. Le copolymère hybride résultant présentait un rendement quantique de photoluminescence de 51 %. La réalisation de l'HLED a ensuite été effectuée par combinaison d'une LED bleue commercial et du copolymère dopé avec des clusters octaédriques de molybdène pour des applications possibles en biologie ou dans l'éclairage. / The objective of this thesis was to demonstrate the potentialities of inkjet printing for driving an HLED containing red phosphorescent metallic clusters, with organic field effect transistors. To achieve this goal, the project was divided into two parts: I) The fabrication and optimization of n-type organic transistors by photolithography and then transfer to inkjet printing. II) Parallel to the development of transistors, I focused on designing luminescent hybrid materials for HLED realization. Concerning transistors, we obtained a better understanding of the factors influencing the charge injection but also the electrical stability for bottom gate/ bottom contact geometry transistor with evaporated C60 semiconductor. We have demonstrated that the contact resistance is on the one hand governed by the morphology of the SCO at the electrodes and on the other hand independent of the metal work function. In addition, we have observed that transistors electrical stability of is strongly impacted by the source and drain contact nature. The optimization of photolithography transistors, which essentially consisted of modifying the interfaces, allowed us to develop efficient n-type transistors with saturated field effect mobilities of up to 1.5 cm2/V.s for a maximal process temperature of 115 °C. The technological transfer to inkjet printed transistors was then performed. We then demonstrated that gate electrode and insulator morphologies deposited by inkjet printing, have a negligible impact on transistors performances. For our printed structure, charges injection at the S/D electrodes is in fact the key factor for high performance transistors realization. Finally, red phosphorescent materials based on molybdenum octahedral metal cluster have been developed. The resulting hybrid copolymer showed photoluminescence quantum yield up to 51%. The realization of the HLED was then carried out by combining a commercial blue LED and the copolymer doped with octahedral molybdenum clusters for possible applications in biology or lighting.

Inkjet printing has emerged from a digital graphic arts printing technology to become a versatile tool for the patterned deposition of functional materials. This thesis contributes to the research in the area of functional inkjet printing by focusing on two different topics: (i) inkjet printing of colloidal suspensions to study the principles of deposit formation and to develop deposits with photonic properties based on self-assembly, and (ii) the development of a reliable manufacturing process for all-inkjet-printed thin-film transistors, highlighting the importance of selection of materials and inks, print pattern generation, and the interplay between ink, substrate and printing conditions. (i) Colloidal suspensions containing nanospheres were applied as ink formulation in order to study the fundamental processes of layer formation and to develop structures with periodically arranged nanospheres allowing the modulation of electromagnetic waves. Evaporation-driven self-assembly was found to be the main driver for the formation of the final deposit morphology. Fine-tuning of inkjet process parameters allows the deposition of highly ordered structures of nanospheres to be arranged as monolayer, multilayer or even three-dimensional assemblies with a microscopic spherical shape. (ii) This thesis demonstrates the development of a manufacturing process for thin-film transistors based on inkjet printing. The knowledge obtained from the study with the colloidal nanospheres is used to generate homogeneous and continuous thin films that are stacked well-aligned to each other to form transistors. Industrial printheads were applied in the manufacturing process, allowing for the up-scaling of the manufacturing by printing of several thousands of devices, and thus the possibility to study the process yield as a function of printing parameters. The discrete droplet-by-droplet nature of the inkjet printing process imposes challenges on the control of printed patterns. Inkjet printing of electronic devices requires a detailed understanding about the process and all of the parameters that influence morphological or functional characteristics of the deposits, such as the selection of appropriate inks and materials, the orientation of the print pattern layout to the deposition process and the reliability of the inkjet process.

The diploma thesis deals with the determination of thickness and refractive index of thin organic films using image analysis. In the theoretical part there are described principles of the methods, which are used to prepare the films (spin coating, inkjet printing, vapour deposition), the characteristics of thin films, ways of finding out the thickness and refractive index of substances (weight methods, electric methods, method based on measurement of absorption coefficient of light, interference microscopy, ellipsometry) and also image analysis (harmonic and wavelet analysis). Interference microscope Epival - Interpako (Carl Zeiss Jena), digital camera Nikon Coolpix 5400 and computer were used for the determination of thickness and refractive index. The thicknesses of layers were set on the basis of interference images of edges and grooves – both from the side of the metal contact and the side of underlying glass. The refractive indices of thin layers were then set using the recorded figures. In the final part of the thesis there are discussed the results of interference images photographed along the full length of the aluminium contact which are used for measuring electrical characteristics of DPP structures. The produces are thicknesses and refractive indices of individual layers.