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<p>  </p> <p>From applications in nanoscale electronics to regenerative medicine, there is a strong need for control assembly processes at nanometer length scales.1,2 In this work, we investigate the application of microscale droplet delivery as a rapid and scalable approach to pattern the molecular assembly of nanoscale chemical patterns on highly oriented pyrolytic graphite (HOPG). Furthermore, it was also observed that variations in the blend of alkyl impurities present in technical-grade OLAm reagents influenced the temperature-dependent assembly behavior.13 This suggests a likely role of alkyl chain phase transitions in the ligand shell, particularly in more complex mixtures and for anisotropic nanocrystals.</p> <p>Oleylamine (OLAm) is a common technical-grade reagent used in nanocrystal synthesis. Most nanocrystal synthesis is done using technical grade Oleylamine (70% purity). Higher purity reagents are not readily available because in certain instances, technical grades are obtained from natural substances, resulting in differing impurities compared to those generated during preparative reactions using pure raw materials.3 Technical grade reagents of OLAm contain 70% of the cis chain OLAm and 30% of an unspecified mixture of Elaidylamine (ELAm) , Octadecylamine (ODAm) and segments of various lengths and saturated alkyl chains.4,5 Here, we use Differential Scanning Calorimetry thermograms to investigate the miscibility of binary mixtures of OLAm/ELAm, OLAm/ODAm, and ELAm/ODAm. Ternary mixtures of the lipids showed clear peaks for the trans and saturated impurities.</p> <p>We patterned graphite surfaces with amphiphiles via inkjet printing to quickly generate 1-nm-wide functional patterns. Inkjet printing allowed for long-scale hierarchical patterning. We investigated various ink formulations and the resulting printing quality of functional monolayers on 2D crystalline materials. </p>

The monitoring of pH and free chlorine concentration in drinking water is important for water safety and public health. However, existing laboratory-based analytical methods are laborious, inefficient, and costly. This thesis focuses on the development of an easy-to-use, sensitive, and low-cost drinking water quality monitoring system for pH and free chlorine. An inkjet printing technology with a two-step thermolysis process in air is developed to deposit palladium/palladium oxide (Pd/PdO) films as potentiometric pH sensing electrodes. The redox reaction between PdO and hydronium ions generates the sensor output voltage. A large PdO percentage in the film provides a high sensitivity of ~60 mV/pH. A defect-free Pd/PdO film with small roughness contributes to a fast response and a high stability. When the Pd ink is thermalized in low vacuum, the deposited Pd/PdO film shows a bilayer structure. The residual oxygen in the low vacuum environment assists the decomposition of organic ligands for Pd to form a thin and continuous layer beneath submicron Pd aggregates. The oxidized bilayer film behaves as a temperature sensor with a sensitivity of 0.19% resistance change per °C, which can be used to compensate the sensed pH signals. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is drawn by hand to form a free chlorine sensor. Free chlorine oxidises PEDOT:PSS, whose resistivity increment indicates the free chlorine concentration in the range of 0.5-500 ppm. Also, we simplified an amperometric free chlorine sensor based on amine-modified pencil leads. The simplified sensor is calibration-free, potentiostat-free, and easy-to-use. The pH, temperature, and free chlorine sensors are fabricated on a common substrate and connected to a field-programmable gate array board for data processing and display. The sensing system is user-friendly, cheap, and can accurately monitor real water samples. / Thesis / Doctor of Philosophy (PhD) / Sensitive, easy-to-use, and low-cost pH and free chlorine monitoring systems are important for drinking water safety and public health. In this thesis, we develop an inkjet printing technology to deposit palladium/palladium oxide films for potentiometric pH sensors and resistive temperature sensors. The different electrical and electrochemical properties of the palladium/palladium oxide films are realized by creating different film morphologies using different ink thermolysis atmospheres. The developed pH and temperature sensors are highly sensitive, fast in response, and stable. For free chlorine sensors, a hand drawing process is used to deposit poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), which is an indicator for the free chlorine concentration over a wide range. We also developed a calibration-free free chlorine sensors based on modified pencil leads. Such a free chlorine sensor is integrated with the pH and temperature sensors, and an electronic readout system for accurate on-site drinking water quality monitoring at low cost is demonstrated.

Silicones are industrially important polymers characterized by a wide spectrum of chemical and physical properties with a number of important applications including automotive components, construction materials, isolating parts in electronic devices, flexible electronics, and medical products. Development of additive manufacturing methods for silicones enable production of complex and custom designed shapes and structures at both the micro- and macro-scale, economically feasible. In general, such materials can be fabricated using stereolithographic, extrusion-based, or inkjet printing techniques, in which silicones are polymerized using either photo- or heat-initiators. Silicones can also be crosslinked based on chemical reactions. Although this approach is supposedly the simplest, it has not been widely applied in additive manufacturing, as suitable technology for mixing and curing reactive inks without clogging nozzles has not be developed yet. To address this issue, a new 3D printer, that enables the fabrication of highly reactive and low viscous materials, has been developed and tested experimentally. The proposed fabrication method involves the ejection of two reactive droplets simultaneously from individual dispensers, merging and mixing them in free space outside the nozzle followed by deposition of the merged drop in a patterned format on a substrate. It was shown that the printing process is robust and stable more than 4 hours and it can be used on demand. By incorporating an XYZ positioner, it was possible to deposit droplets in an overlapping fashion to print any programmable shape featuring homogeneous structure, with a small number of pores. Moreover, due to the almost instantaneous reaction between two components (< 10s), the fabrication of very high aspect ratio (AR > 50) objects is possible. Lastly, the presented method can be easily adapted to print in free space without the use of support materials. / Thesis / Master of Applied Science (MASc)

Inkjet printing has generated considerable interest as a technique for the patterning of functional materials in the liquid phase onto a substrate. Despite its high promise, the phenomena associated with inkjet printing remain incompletely understood. This research project investigates inkjet printing of cellulose nanocrystals (CNCs) as a possible method for the fabrication of cellulose micropatterns. CNCs were prepared from wood pulp by H₂SO₄ hydrolysis and characterized in terms of length, width, and thickness distributions by atomic force microscopy (AFM) and dynamic light scattering. Aqueous CNC suspensions were characterized in terms of shear viscosity with a rheometer. Glass substrates were cleaned with a detergent solution, aqua regia, or a solvent mixture, and characterized in terms of surface chemical composition, surface free energy, polarity, roughness, ζ-potential, and surface charge distribution in air by X-ray photoelectron spectroscopy, contact angle measurements, AFM, streaming potential, and scanning Kelvin probe microscopy (SKPM). Additionally, poly(ethylene glycol)-grafted glass substrates were prepared and characterized in terms of surface free energy, polarity, and roughness. Aqueous CNC suspensions were printed in different patterns onto the different glass substrates with a commercial, piezoelectric drop-on-demand inkjet printer. Inkjet deposited droplet residues and micropatterns were analyzed by AFM, scanning electron microscopy, and polarized-light microscopy. At low CNC concentrations (0.05 wt %), inkjet-deposited droplets formed ring-like residues due to the "coffee drop effect". The "coffee drop effect" could be suppressed by the use of higher CNC concentrations. The resulting dot-like droplet residues exhibited Maltese cross interference patterns between crossed polarizers, indicating a radial orientation of the birefringent, elongated CNCs in these residues. The observed Maltese cross interference patterns represent unprecedented indirect evidence for a center-to-edge radial flow in drying droplets. The degree of definition of the micropatterns depended strongly on the surface properties of the glass substrates. Well-defined micropatterns were obtained on aqua regia-cleaned substrates. In addition to the surface free energy and polarity, other factors seemed to play a role in the formation of the inkjet-printed micropatterns. If these factors can be identified and controlled, inkjet deposition of CNCs could become an attractive method for the fabrication of cellulose micropatterns. / Ph. D.

This dissertation will outline solution processable materials and fabrication techniques to manufacture flexible electronic devices from them. Conductive ink formulations and inkjet printing of gold and silver on plastic substrates were examined. Line patterning and mask printing methods were also investigated as a means of selective metal deposition on various flexible substrate materials. These solution-based manufacturing methods provided deposition of silver, gold and copper with a controlled spatial resolution and a very high electrical conductivity. All of these procedures not only reduce fabrication cost but also eliminate the time-consuming production steps to make basic electronic circuit components. Solution processable semiconductor materials and their composite films were also studied in this research. Electrically conductive, ductile, thermally and mechanically stable composite films of polyaniline and sulfonated poly (arylene ether sulfone) were introduced. A simple chemical route was followed to prepare composite films. The electrical conductivity of the films was controlled by changing the weight percent of conductive filler. Temperature dependent DC conductivity studies showed that the Mott three dimensional hopping mechanism can be used to explain the conduction mechanism in composite films. A molecular interaction between polyaniline and sulfonated poly (arylene ether sulfone) has been proven by Fourier Transform Infrared Spectroscopy and thermogravimetric analysis. Inkjet printing and line patterning methods also have been used to fabricate polymer resistors and field effect transistors on flexible substrates from poly-3-4-ethyleneoxythiophene/poly-4-sytrensulfonate. Ethylene glycol treatment enhanced the conductivity of line patterned and inkjet printed polymer thin films about 900 and 350 times, respectively. Polymer field effect transistors showed the characteristics of traditional p-type transistors. Inkjet printing technology provided the transfer of semiconductor polymer on to flexible substrates including paper, with high resolution in just seconds. / Ph. D.

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.

This study presents a method developed to achieve the roll-to-roll sintering of printed Ag patterns based on exposure to hot air, near-infrared, and mid-infrared sources. The sintering energy was quantified and evaluated based on theoretical and experimental calculations. Moreover, the effect of the sintering energy on the web tension was simultaneously considered. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

<p>This thesis presents work on two major areas of research. The first area of research involves the use of a dual-nozzle piezoelectric inkjet printing system to print bilayer aluminum bismuth (III) oxide nanothermite samples. The combinatorial printing method allows for separate fuel and oxidizer inks to be printed adjacent to each other at prescribed offset distances. The effect of the bilayer thickness on the burning rate of the samples is investigated using high-speed imaging. Analysis of the burning rate data revealed that there is no statistically significant relationship between these two parameters. This result was used to determine the dominant processes that control the propagation rate in nanothermite systems. It was concluded that convective processes dominate the burning rate rather than diffusive processes. The second area of research involved synthesizing inks suitable for inkjet printing using two promising high nitrogen energetic materials called BTATz and DAATO_3.5. The performance of the developed inks was characterized using four experiments. The thermal stability and exothermic behavior of the inks were determined using DSC and TGA analysis. The results revealed that the inks are more thermally stable than the base materials. The inks were used to print lines that were subsequently used to determine burning rates. DAATO_3.5 samples were determined to have faster burning rates than BTATz. Closed pressure bomb experiments were conducted to determine the gas producing capability of the high nitrogen inks. BTATz samples showed better performance in terms of peak static pressures and pressurization rates. 3D printed microthrusters were developed to test the thrust performance of the inks. Peak thrust, total impulse, and specific impulse values are reported and were determined to be suitable for use with Class 1 micro-spacecraft. Finally, a microthruster array prototype was developed to demonstrate the capability to use additive manufacturing to create high packing density arrays.</p>

Dans le cadre de la fabrication de dispositifs pour l’électronique organique à grande échelle, les besoins en matériaux conducteurs stables à l’air libre, de coût réduit et compatibles avec les techniques d’impression sont croissants. Ces matériaux sont destinés à remplacer les couches métalliques déposés par des méthodes telles que la gravure ou l’évaporation sous vide. Les travaux présentés dans cette thèse ont pour objectif la mise au point d’une encre imprimable stable à l’air libre, composée de polyaniline dispersée en phase aqueuse. L’originalité de cette thèse est de décrire l’intégralité de ce processus, depuis la synthèse chimique de la charge, à partir du monomère jusqu’à l’intégration de l’encre conductrice dans une cellule solaire organique sous forme d’électrode imprimée, en passant par la formulation de l’encre. La première partie des travaux consacrés à la synthèse chimique de la charge a permis d’obtenir un matériau nano structuré, de taille et morphologie contrôlée, dispersable en phase aqueuse et conducteur. Cette dispersion a ensuite été formulée pour lui conférer des propriétés compatibles avec l’impression jet d’encre et lever des verrous critiques comme la granulométrie. La phase d’essai d’impression jet d’encre a permis de valider l’étape de formulation et d’optimiser la morphologie des gouttelettes éjectées. Les couches minces imprimées ont permis d’atteindre des résistances surfaciques inférieures à 1000 Ω/□. Finalement l’encre conductrice a pu être imprimée en tant qu’électrode supérieure dans des cellules solaires organiques. / Considering large-scale development and fabrication of organic electronic devices, needs for low cost conductive printable materials are growing. These materials are designed to replace thin metallic layers deposited via gravure or thermal evaporation. The objective of the work presented in this report is to obtain a conductive and inkjet printable aqueous stable dispersion of polyaniline. Originality of this PhD work is to describe all the steps from the chemical synthesis of polyaniline starting from the monomer, until the integration of the conductive ink in an organic solar cell as a conductive top electrode, through formulation of the ink to meet inkjet printing requirements. During the first part of work dedicated to chemical synthesis of PANI, we managed to produce a nanostructured and conductive material, with controlled size and morphology, which was dispersed in water. This aqueous dispersion was formulated to meet inkjet printing requirements and break technological locks such as particle size in the PANI dispersion. Formulation step was then validated during printing trials, which allowed optimising shape of ejected droplets. Printed PANI thin layers showed sheet resistance below 1000 Ω/□ after 20 printing passes. Finally, conductive ink was printed as a top electrode in fully solution–processed printed organic solar cell.