Facilitated by the development of various direct-write techniques and functional polymeric materials including polymer based conductors and semiconductors, printed electronics are flourishing both commercially and as a research topic. This is not only because of their simpler manufacturing routes and lower cost, but also as a result of lower processing temperatures and better compatibility with flexible substrates, compared with conventional electronics. The development of conventional electronics has been guided by Moore s Law, the driver for which lies in the demand for electronic devices with better performance and portability at lower prices. Therefore, one can expect a similar trend for printed electronics to guide its development. Multi-layered printing can be adopted in printed electronics to achieve higher density integration, so that this development trend can be maintained. In such circumstances, creation of electrical connections between multiple layers emerges as an important issue for printed electronics. Inkjet-etched via holes are one potential solution to providing such electrical interconnections, and which can provide good integration with other inkjet-printed features simply by switching nozzles. This thesis aims to elicit a better understanding of the physics involved in inkjet etching and investigate the capability of the inkjet etching technique. In the thesis, the factors that can affect the size of via holes produced by inkjet etching are evaluated, which is significant for evaluating the capability of this technique to deliver industrially relevant features. Identified factors include droplet ejection frequency, droplet diameter, solvent properties and substrate temperature. Droplet ejection frequency, i.e. the reciprocal of the time interval between drops, determines the extent of evaporation of the solvent between two consecutive drop impacts. Droplet diameter determines the radius of the wetted area after the droplet I impacts on the surface and spreads into a sessile drop. Solvents with different evaporation properties result in different size evolution with the number of drops dispensed, as does droplet ejection frequency. Higher substrate temperatures can reduce the drop diameter during flight and decrease the evaporation time on polymer surfaces, which can shrink the size of via holes. Another important issue is achieving complete polymer penetration as residual polymer creates an electrical conduction barrier after such holes are subsequently filled with conductive materials or act as a barrier to filling by electroplating. Experiments have been carried out to test the effect of outer diameter and polymer thickness on polymer penetration. Electroplating is utilised to test the completeness of via hole penetration. A mechanism using the Marangoni effect to explain the protrusion drying pattern other than a hole in the polymer layer is proposed.

Over the last decade, two dimensional (2D) materials have attracted considerable attention from both the scientific and engineering community due to their unique properties. One important advance of 2D materials is that they can be exfoliated into nanosheets suspended in a liquid phase and that this allows the formulation of 2D nanomaterials inks. Such inks can be deposited as functional components through low-cost inkjet printing techniques. Many 2D materials based inks have been produced over the years. This thesis investigates the use of inkjet printing to deposit 2D materials such as graphene oxide (GO) and black phosphorus (BP).GO, a derivative of graphene, has been widely used to produce graphene-based conductors via inkjet printing owing to its good stability in readily available solvents such as water. In this work, highly conductive reduced graphene oxide (rGO) films with bulk conductivity in excess of 2 × 10^4 Sm-1 have been prepared by inkjet printing a GO aqueous ink, with mean flake size 35.9 micro metre, through a 60 micro metre inkjet printing nozzle followed by a reduction step. Experimental results showed that individual GO flakes up to 200 micro metre diameter can be successfully printed with no instances of nozzle blocking or poor printing performance. The mechanism by which this occurs is believed to be GO sheet folding during drop formation followed by elastic unfolding during drop impact and spreading. In addition, the influence of GO flake size on rGO film conductivity has been investigated. It was found that the rGO film conductivity increased about 60% when the mean flake size of the GO flakes in the ink increases from 0.68 micro metre to 35.9 micro metre. The drying behaviour of printed GO droplets has been studied on eight GO aqueous inks in which the mean flake size of GO was varied over a range from 0.68 to 35.9 micro metre. It was found that the coffee ring effect (inhomogeneous drying of a droplet to leave a ring like deposit) of dried droplets of the GO ink weakened and disappeared when the flake size increasing. It was found that, with a printed deposit around 340 micro metre in diameter, the coffee ring effect (CRE) was suppressed with the mean flake size > 10.3 micro metre. The critical flake size for CRE suppression reduced to 5.97 and 3.68 micro metre when the substrate temperature was 40 and 50 °C, respectively. It was further found that the CRE weakened with decreasing printed drop size, with the critical flake size reducing to 1.58 micro metre with a printed drop diameter of 30 micro metre.The interaction between BP nanometre thickness flakes and humid atmospheres was investigated using an inkjet printed BP sensor. The BP sensor showed was very sensitive to changes in humidity with a response time of a few seconds and the effect is reproducible in minutes. However, long term exposure to humid air with a relative humidity (RH) > 11% leads to a significant chemical change in the BP films, with Fourier transform infra-red spectroscopy (FTIR) indicating partial hydrolysis of the BP to form phosphate and phosphonate ions. Low temperature heat treatment of BP films under dry conditions after exposure to elevated RH leads to a partial recovery of the impedance response and reversion to a chemical state similar to that before exposure to a humid environment. The recovery of BP properties is most complete after exposure to lower humidity environments (RH < 11%), although exact replication of the original impedance response and FTIR spectrum was not possible.

La compréhension des mécanismes pilotant la cinétique d'évaporation d'une gouttelette sessile sur un substrat inerte a notablement progressé ces dernières années. Ainsi, l'influence de l'angle de contact de la goutte, de la conductivité thermique du solide, de sa rugosité, de la convection thermocapillaire à l'intérieur de la goutte, ou de la convection dans la vapeur environnante, sont maintenant bien compris. Parallèlement, la façon dont des dépôts de type ‘tâche de café' se forment pendant l'évaporation de fluides complexes (suspension colloïdale, sang …) a été étudiée en détail.Toutes ces études ont été réalisées avec des solides non-réactifs. Nous proposons ici d'étudier le comportement d'une goutte d'eau s'évaporant sur un substrat soluble. Dans cette configuration, trois phénomènes sont en interaction complexe : la dissolution/précipitation du substrat à l'interface solide-liquide, la diffusion/convection des espèces dissoutes dans la gouttelette, l'évaporation de l'eau à l'interface liquide-air. Nous avons travaillé avec des solides à dissolution rapide, des monocristaux de NaCl et KCl, à température et humidité contrôlées. Pour tester l'influence des instabilités thermo- et soluto-gravitationnelles, nous avons réalisé des expériences au sol et en micropesanteur, lors de plusieurs campagnes de vols paraboliques CNES.Nous avons observé que la dissolution induisait un ancrage de la ligne triple au tout début de l'évaporation, conduisant à une décroissance linéaire de l'angle de contact avec le temps. A la fin de l'évaporation, un dépôt périphérique apparaît. Cette configuration permet ainsi de faire apparaître des dépôts de type ‘tâche de café' à partir d'une goutte d'eau pure. Ces dépôts sont la preuve d'un écoulement radial de l'intérieur vers l'extérieur au sein de la goutte. L'observation de gouttes ensemencées de particules fluorescentes s'évaporant sur un monocristal de sel a permis de mettre en évidence des écoulements capillaires complexes au sein de celle-ci. La morphologie des dépôts périphériques est très variée, passant continument de la forme de parois inclinées à celle de demi-tore creux, lorsque le volume initial de la goutte ou la température varient / Recent progresses have led to a better understanding of the mechanisms driving the evaporation kinetics of a sessile droplet of simple liquid on an inert substrate. For instance, the influence of the contact angle of the droplet, of the thermal conductivity of the solid, of its roughness, of the thermocapillary convection inside the droplet, or of the convection in the vapor are now better understood. Besides, the way coffee-stain-like deposits form during the evaporation of complex fluids (colloidal suspension, blood …) has now been studied in detail.All these studies have been carried out with non-reacting solids. We propose here the investigation of the behavior of a water droplet evaporating on a soluble substrate. In this configuration, three phenomena are strongly interacting: dissolution/precipitation of the substrate at the solid-liquid interface, diffusion/convection of the dissolved species in the droplet, evaporation of water at the liquid-air interface. We have worked with fast-dissolving solids, NaCl and KCl single crystals, with controlled temperature and humidity. To test the influence of thermogravitational instabilities, experiments on the ground and in microgravity (parabolic flights) have been carried out.We have observed that the dissolution induces a pinning of the triple line at the early beginning of the evaporation, leading to a decrease of the contact angle linear in time. At the end of the evaporation, a peripheral deposit (coffee-ring-like) resulting from the salt migration and precipitation, is always present, proof of an outward flow inside the droplet. The observation of drops seeded with fluorescent particles evaporating on a dissolving solid (NaCl single crystal) has highlighted complex capillary flows inside the liquid. The shape of this ring-like deposit is very diversified and vary with the substrate temperature and the initial volume of the droplet

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.

Due to the increasing interest in low-cost, lightweight, and wearable technologies, flexible and printed electronics has become an intensive field of research during the last two decades. This research is mainly focused on the development of solution-processed organic materials, the evolution of diverse appropriate printing technologies and the enhancement of electronic device performance. Compared to conventional electronics, printed technologies allow for cheaper and easier processing but much poorer resolution, which results in comparatively large organic field effect transistor (OFET) channel lengths of a few ten microns. Reducing the channel length requires the use of additional methods such as wetting-based and non-printed approaches. The minimisation of the channel length is crucial in order to obtain higher frequencies and increasing currents. Therefore, overcoming the resolution limitation is one of the challenging topics in the field of printed electronics. In this thesis, a new approach for the realisation of fully inkjet-printed small-channel OFETs is investigated. For this purpose, a piezoelectric Drop-on-Demand (DOD) inkjet printer with 10 pl printheads is employed. This approach involves a self-aligned, dewetting-based technique for the reproducible fabrication of source and drain electrodes with homogeneous and well-controllable channel lengths down to 4 μm. For the realisation of these electrodes, a water-based, hydrophobic nanoparticle (NP) dispersion is initially printed and dried at room temperature in order to spontaneously form a thin hydrophobic twin-line of few microns due to the so-called coffee ring effect (CRE). This mechanism is responsible for the migration of the NPs from the center to the edge of the printed line during evaporation. An alcohol-based silver NP ink is subsequently printed on the hydrophobic lines and self-aligned to split into two separated source and drain electrodes. Dispersions with different materials such as polytetrafluoroethylene (PTFE) and fluoroplastic NPs, different particle sizes and concentrations are evaluated in order to optimize the twin line deposition and the dewetting of the silver ink. Optimum dispersions are printed, then characterised on untreated polyethylene naphthalate (PEN) foils and oxygen plasma treated dielectrics such as cross-linked poly-4-vinylphenol (c-PVP) and cross-linked polymethyl methacrylate (c-PMMA). To evaluate the influencing parameters on the twin-line deposition, a model is developed for the calculation of the printed rivulet width and the electrode gap, which is determined by the width of the hydrophobic ring. These dimensions are investigated as functions of the printing parameters, NP concentration, line geometry, and wetting properties. Multiple simulations are used to determine the influence of each parameter on the twin-line deposition and calculate the critical channel length, below which the dewetting of the conductive ink on the hydrophobic line is no more possible. Based on the simulation results, the optimum parameters are used to control the gap between the printed source and drain electrodes. The underlying mechanism is finally employed for the realisation of fully inkjet-printed OFETs on plastic substrates with small channel lengths and a bottom gate bottom contact configuration (BGBC). For this purpose, a silver NP ink is used for the electrodes, a PTFE NP dispersion is printed on c-PVP and a small-molecule 6,13-Bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) solution is used for the semiconducting layer. Multiple small-channel OFET arrays are furthermore fabricated with a good reproducibility of the channel length and a high yield, which proves the industrial applicability of the proposed approach. / Die Integration kostengünstiger, leichter und tragbarer Technologien gewinnt zunehmend an Interesse. Dies führt kontinuierlich zu einer rasanten Zunahme der Forschungsaktivitäten im Bereich der flexiblen und gedruckten Elektronik. Der Fokus liegt hierbei überwiegend auf der Entwicklung organischer Materialien, Herstellung von geeigneten Druckverfahren und Verbesserung der Leistungsfähigkeit gedruckter elektronischer Bauteile. Ein ausschlaggebender Vorteil der gedruckten gegenüber der konventionellen Elektronik liegt darin, dass sie eine preiswerte und einfache Prozessierung ermöglicht. Die Beeinträchtigung dieser jungen Technologie ist immer noch die schwächere Auflösung, welche zur Erstellung von organischen Feldeffekttransistoren (OFETs) mit vergleichbar größeren Kanallängen von einigen zehn Mikrometern führt. Die Reduzierung der Kanallänge erfordert die Verwendung zusätzlicher Hilfsmethoden z.B. oberflächenspannungsstrukturiertes Drucken oder “non-printing”-Technologien. Die Minimierung der Kanallänge ist entscheidend, um höhere Frequenzen und Ströme zu erzielen. Daher ist die Optimierung der Auflösung ein wesentlicher Parameter, um die Technologie weiter zu entwickeln. Die vorliegende Arbeit stellt ein neu entwickeltes Verfahren zur Realisierung von All-Inkjet-gedruckten OFETs mit kleinen Kanallängen dar. Hierbei wird ein Drop- on-Demand (DOD) Inkjet-Drucker mit 10pl-Druckköpfen eingesetzt. Dieses Verfahren basiert auf einem oberflächenspannungsabhängigen Ansatz für die reproduzierbare Erstellung von Source- und Drainelektroden mit homogenen und kontrollierbaren Kanallängen bis 4 μm. Beim Erstellen dieser Elektroden wird zuerst eine wasserbasierte Dispersion mit hydrophoben Nanopartikeln gedruckt und bei Raumtemperatur getrocknet. Während der Trocknungsphase wird der sogenannte Kaffeeringeffekt (CRE) zu Nutze gemacht. So führt der CRE zur Migration der Nanopartikeln vom Zentrum bis zum Rand der gedruckten Struktur. Diese gerichtete Migration bewirkt eine spontane Erstellung einer dünnen hydrophoben Doppellinie mit einer Breite von nur wenigen Mikrometern. In einem weiteren Schritt wird eine alkoholbasierte Silbernanopartikeltinte über die hydrophobe Linie gedruckt. Aufgrund der niedrigen Oberflächenenergie der darunter befindlichen hydrophoben Linie, teilt sich die leitfähige Tinte in zwei voneinander getrennte Strukturen, die zunächst als Source- und Drainelektroden eingesetzt werden. Um dieses Verfahren zu optimieren, werden im Rahmen dieser Arbeit Dispersionen mit verschiedenen hydrophoben Materialien wie Teflon- oder fluoroplastische Nanopartikeln unterschiedlicher Partikelgrößen und Konzentrationen untersucht. Die optimale Dispersion wird darauffolgend auf unbehandelten PEN-Folien und sauerstoffplasmabehandelten Dielektrika wie vernetztem Poly-4-Vinylphenol (c- PVP) und vernetztem Polymethylmethacrylat (c-PMMA) gedruckt und anschließend charakterisiert. Um den Einfluss verschiedener Parameter auf dieses Verfahren zu evaluieren, wurde ein Modell für die Berechnung der Breiten der gedruckten Struktur und der getrockneten hydrophoben Doppellinie, die den Elektrodenabstand bestimmt, entwickelt. Diese Dimensionen werden in Abhängigkeit verschiedener Druckparameter, Nanopartikelkonzentrationen, Liniengeometrien und Benetzungseigenchaften untersucht. Zunächst werden Simulationen durchgeführt, um den Einfluss von jedem Parameter auf die Doppellinienentstehung zu bestimmen. Dieses Modell ist ebenfalls erforderlich für die Berechnung der kritischen Kanallänge, unter welcher keine Entnetzung der leitfähigen Tinte auf der hydrophoben Linie mehr möglich ist. Die gewonnenen Simulationsergebnisse bzw. die optimalen Parameter werden für die Kontrolle des Abstands zwischen den Source- und Drainelektroden beim Drucken eingesetzt. Das beschriebene Verfahren wird zur Realisierung von All-Inkjet-gedruckten OFETs mit kleinen Kanallängen auf Plastiksubstraten in einer Bottom-Gate-Bottom-Contact-Konfiguration (BGBC) verwendet. Die benutzten Materialien bestehen aus einer Silbernanopartikeltinte für die Source-, Drain- und Gateelektroden, c-PVP für das Dielektrikum und TIPS-Pentacen für den Halbleiter. Multiple OFET-Arrays werden zum Schluss mit hoher Reproduzierbarkeit der Kanallängen und hoher Ausbeute gedruckt, um die industrielle Anwendbarkeit des vorgestellten Verfahren zu zeigen.

Inkjet printing has attracted much attention in recent years as a versatile manufacturing tool, suitable for printing functional materials. This facile, low-cost printing technique with high throughput and accuracy is considered promising for a wide range of applications including but not limited to optical and electronic devices, sensors, solar cells, biochips, and displays. The performance of such functional devices is significantly influenced by the deposit morphology and printing resolution. Therefore, fabrication functional devices with precise footprints by inkjet printing requires deep understanding of ink properties, material interactions, and material self-assembly. In conventional inkjet printing process, where sessile droplets are directly printed on substrates, particle depositions are usually associated with the well-known, undesirable coffee-ring effect due to the high solvent evaporation rate at the edges of the printed droplets. Such particle accumulation phenomenon in vicinity of the three-phase contact lines of sessile droplets is considered detrimental to inkjet printing applications. This study investigates the material interactions and self-assembly of colloidal inks in inkjet printing applications at different length scales. The potential of inkjet printing has been exploited through employing the dual-droplet inkjet printing of colloidal particles to investigate the self-assembly of colloidal nanoparticles at the air-liquid interface and at the three-phase contact line of sessile droplets, which provide better understanding of the particle deposition morphologies after solvent evaporation. Different from conventional inkjet printing, the dual-droplet printing involves jetting wetting droplets, containing colloidal nanoparticles dispersed in solvents with high vapor pressure, over supporting droplets composed of water only. By tuning the surface tensions and controlling the jetting parameters of the jetted droplets, monolayers with closely-packed deposition of colloidal nanoparticles are demonstrated. Various solutions are proposed to totally suppress or mitigate the coffee-ring effect in inkjet printing applications through tuning the pH value of the supporting droplets in the dual-droplet inkjet printing to control the multibody interactions (i.e., particle-particle, particle-interface, and particle-substrate interactions) or by applying magnetic field to direct the self-assembly of colloidal particles in conventional inkjet printing. In addition, the influence of various forces such as drag force, van der Waals force, electrotactic force, and capillary force on the particle deposition and assembly in vicinity of the three-phase contact line area were investigated for both the conventional and dual-droplet inkjet printing techniques. Finally, fabrication of functional devices such as stretchable conductors have also been demonstrated by inkjet printing of silver nanowires into elastomer substrate, where the viscous liquid elastomer layer shaped the printed silver wire lines into tens of micrometers in dimeter. The silver nanowires align along the printing direction during solvent evaporation, resulting in wires with good mechanical stability and electrical performance. The printing techniques and the outcomes presented in this study can be harnessed in engineering and manufacturing a wide range of technological applications ranging from high-performance optical and electronic devices to stretchable conductors and sensors.

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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.