Since the discovery of graphene, substantial effort has been put toward the synthesis and production of 2D materials. Developing scalable methods for the production of high-quality exfoliated nanosheets has proved a significant challenge. To date, the most promising scalable method for achieving these materials is through the liquid-based exfoliation (LBE) of nanosheetsin solvents. Thin films of nanosheets in dispersion can be modified with additives to produce 2D inks for printed electronics using inkjet printing. This is the most promising method for the deposition of such materials onto any substrate on an industrial production level. Although well-developed metallic and organic printed electronic inks exist on the market, there is still a need to improve or develop new inks based on semiconductor materials such as transition metal dichalcogenides (TMDs) that are stable, have good jetting conditions and deliver good printing quality.The inertness and mechanical properties of layered materials such as molybdenum disulfide (MoS2) make them ideally suited for printed electronics and solution processing. In addition,the high electron mobility of the layered semiconductors, make them a candidate to become a high-performance semiconductor material in printed electronics. Together, these features make MoS2 a simple and robust material with good semiconducting properties that is also suitable for solution coating and printing. It is also environmentally safe.The method described in this thesis could be easily employed to exfoliate many types of 2D materials in liquids. It consists of two exfoliation steps, one based on mechanical exfoliation of the bulk powder utilizing sand paper, and the other inthe liquid dispersion, using probe sonication to liquid-exfoliate the nanosheets. The dispersions, which were prepared in surfactant solution, were decanted, and the supernatant was collected and used for printing tests performed with a Dimatix inkjetprinter. The printing test shows that it is possible to use the MoS2 dispersion as a printed electronics inkjet ink and that optimization for specific printer and substrate combinations should be performed. There should also be advances in ink development, which would improve the drop formation and break-off at the inkjet printing nozzles, the ink jetting and, consequently, the printing quality. / Sedan upptäckten av grafen har mycket arbete lagts på framställning och produktion av 2D-material. En viktig uppgift har varit att ta fram skalbara metoder för produktion av högkvalitativa  nanosheets via exfoliering. Den mest lovande skalbarametoden hittills har varit vätskebaserad exfoliering av nanosheets i lösningsmedel. Tunna filmer av nanosheets i dispersion kan anpassas med hjälp av tillsatser och användas för tillverkning av halvledare strukturer med inkjet-skrivare, vilket är den mest lovande metoden för på en industriell produktions nivå beläggaden typen av material på substrat. Även om det finns välutvecklade metalliska och organiskabläck för tryckt elektronik, så finns det fortfarande ett behov av att förbättra eller utveckla nya bläck baserade på halvledarmaterial som t.ex. TMD, som är stabila, har goda bestryknings  egenskaper och ger bra tryckkvalitet. Den inerta naturen tillsammans med de mekaniska egenskaperna som finns hosskiktade material, som t.ex. molybdendisulfid (MoS2), gör demlämpliga för flexibel elektronik och bearbetning i lösning. Dessutom gör den höga elektronmobiliteten i dessa 2D-halvledaredem till en stark kandidat som halvledarmaterial inom trycktelektronik. Det betyder att MoS2 är ett enkelt och robust material med goda halvledaregenskaper som är lämpligt för bestrykning från lösning och tryck, och är miljömässigt säker.Den metod som beskrivs här kan med fördel användas föratt exfoliera alla typer av 2D-material i lösning. Exfolieringensker i två steg; först mekanisk exfoliering av torr bulk med sandpapper, därefter används ultraljudsbehandling i lösning för att exfoliera nanosheets. De dispersioner som framställts i lösning med surfaktanter dekanterades och det övre skiktetanvändes i trycktester med en Dimatix inkjet-skrivare.Tryckprovet visar att det är möjligt att använda MoS2 -dispersion som ett inkjet-bläck och att optimering för särskildaskrivar- och substratkombinationer borde göras, såsom förbättringav bläcksammansättningen med avseende på droppbildning och break-off vid skrivarmunstycket, vilket i sin tur skulleförbättra tryckkvaliteten. / KM2 / Paper Solar Cells

[pt] O Princípio da Postergação, quando inicialmente apresentado por Alderson (1950), propunha que o momento do embarque, e o local da configuração final do produto na distribuição, fossem adiados até que um pedido do cliente fosse recebido. Embora diversos autores tenham estudado as condições que levam à postergação da configuração final do produto e os benefícios da diferenciação de produtos e processos, poucos estudos foram feitos sobre a operacionalização da teoria da postergação em uma cadeia de suprimentos específica, que retrate os benefícios identificados pelos executivos. A revisão literária abrangeu mais de 50 anos de estudos sobre o princípio da postergação, o que resultou na proposta de um arcabouço integrativo. O foco do estudo está no ambiente upstream da cadeia de suprimentos específica de maneira que retrate os benefícios identificados pelos executivos, i. e. entre fábricas - distante do consumidor final. O estudo teve como objetivo investigar aplicação do Princípio da Postergação na cadeia de suprimentos das tintas para impressão, por meio de três dimensões: as condições que levaram à prática da postergação de forma; o local onde a configuração final deve ocorrer; os benefícios identificados diante desse tipo de postergação das tintas para impressão. Para atender a este objetivo, a pesquisa teve características exploratória e confirmatória, quando foram desenvolvidos sete estudos de caso, sendo seis fabricantes de embalagens gráficas e um fabricante de tintas para impressão. Foram realizadas entrevistas pessoais em cada empresa, com executivos diretamente envolvidos em decisões de configuração da tinta. A análise identificou padrões de comportamento nos estudos de caso. Os resultados propiciaram uma avaliação dos pressupostos existentes na literatura, permitindo a confirmação de alguns já existentes e a formulação de novos a serem testados em futuras pesquisas. / [en] The Principle of Postponement, early presented by Alderson (1950), proposes that the time of shipment and the location of product final configuration in the distribution of a product be delayed until a customer order is received. Although many authors have studied when form postponement is justified and the benefits of products and processes differentiation, few substantial efforts have been made to operationalize the theory of postponement in a specific supply chain in order to describe the benefits identified by the executive managers. The literature review has covered over 50 years of postponement research what resulted in a proposed integrative framework. Focus is placed on the upstream part of the supply chain, i.e. between factories - far from the consumer. The objective of this study was to investigate the Principle of Postponement in the press ink supply chain, through three dimensions: The conditions when postponement is justified; the place in the supply chain where final configuration should occur and the benefits of form postponement identified by the managers. To attend this objective, the research was classified as exploratory and confirmatory since seven case studies were developed. Six of them were packaging manufacturers and one was in a press ink manufacturer. Interviews were made with executive managers involved with decisions about ink configuration. The analysis identified patterns in the case studies. The results enabled evaluation of existing propositions in the literature, allowing the confirmation of some and the formulation of new proposition to be tested in future researches.

This thesis explores the application of two-dimensional (2D) materials such as graphene and single layer hexagonal boron nitride (h-BN) which are produced by liquid phase exfoliation for use in printed electronics and energy composite applications. In Chapter 2 I give a broad overview of the electrical, mechanical and optical properties of 2D materials among other nanomaterials that were used in the thesis such as carbon nanotubes and conductive polymers. Additionally I review the techniques and theory behind the exfoliation and dispersion of functional layered materials. In Chapter 3 I present the coating and printing techniques which were used in this thesis along with the experimental techniques and methods which I use to characterise my inks, films and devices. Chapter 4 is the first experimental chapter of the thesis and demonstrates the printing of 2D material heterostructures to create fully printed dieletrically gated field effect transistors with 2D materials on textile and polymer substrates. In this chapter I also demonstrate reprogrammable volatile memory, p and n type inverters, complementary inverters, and logic gates which pave the way to fully printed integrated circuits, operational at room temperature and pressure with 2D materials processed in liquid. In Chapter 5, I review spray coating (a highly industrial scalable printing technique), in terms of the optimisation of its parameters to achieve thin films of nanomaterials on three-dimensional (3D) surfaces. I then demonstrate that it is possible to create large area (∼750 cm2) transparent conducting films around curved surfaces with spray coating enabling a semi-transparent (around 360°) spherical touch sensor for interactive devices. Chapter 6 explores printed photonics for applications in terahertz (THz) frequencies. Here I demonstrate the feasibility of liquid phase exfoliated graphene to create THz saturable absorbers (SAs) which could enable many applications in THz frequencies such as tomography or time-resolved spectroscopy that require mode-locked (i.e. enabling a train of short pulses to be derived from continuous-wave operation) THz pulses. I also demonstrate that these SAs can be inkjet printed on demand providing unprecedented compactness in a quantum cascade laser system. Finally in Chapter 7, I look at the application of graphene in microbial fuel cells (MFC). I demonstrate that enhanced MFC output arises from the interplay of the improved surface area, enhanced conductivity, and catalytic surface groups of a graphene based electrode. As a final step graphene based anodes and cathodes which were entirely platinum free were combined to create an environmentally sustainable energy source.

Depuis les années 2000, l'impression fonctionnelle connait un grand succès pour la fabrication de composants électroniques. Elle se positionne de manière complémentaire par rapport aux technologies du silicium et vise principalement les marchés de l'électronique grande surface (écrans, panneaux photovoltaïques) et de l'électronique flexible (RFID, capteurs, textiles intelligents). Dans ce travail, des couches d'argent imprimées par jet d'encre ont été caractérisées en fonction des conditions d'impression et de recuit. L'évolution de leur microstructure, de leurs propriétés électriques et mécaniques a été étudiée. Dans ce cadre, des méthodes expérimentales ont été développées et validées par la bonne corrélation entre les mesures et les modèles. La maîtrise des propriétés de ces couches et l'optimisation de leur procédé de fabrication nous ont conduits à concevoir, fabriquer et caractériser plusieurs composants flexibles: un filtre passe bande centré à 17 GHz sur un substrat polyimide, un micro-capteur de vide fonctionnant sur le principe de Pirani et un bouton-poussoir d'épaisseur inférieure à 250 µm pour des claviers souples. Enfin, des condensateurs RF ont été réalisés par la superposition de couches imprimées diélectriques (BaSrTi) et conductrices (Ag). Les performances des prototypes réalisés sont proches de l'état de l'art et ouvrent la voie à de nouvelles applications pour les technologies d'impression. Cette étude démontre le potentiel des couches d'argent imprimées par jet d'encre pour la fabrication de dispositifs flexibles. / In the last decade, functional printing has gained a large interest for the manufacturing of electronic components. It stands aside to silicon technologies and specifically targets markets of large area devices (screens, photovoltaics) and flexible electronics (RFID antennas, sensors, smart textiles). In this work, inkjet printed silver layers are characterized depending on the printing conditions and the required post-printing annealing. The evolution of their microstructure, electrical and mechanical properties is investigated as a function of the annealing temperature. The correlation of the measurements with theoretical models supports the experimental methods that were developed. The knowledge of the printed silver layers assets and the optimization of the printing process lead to the design, fabrication and characterization of flexible electronics devices: a 17 GHz band-pass filter printed on polyimide, a flexible vacuum micro-sensor working on the Pirani principle, and a 250 µm thick membrane switch for keyboards. Finally, all printed RF capacitors were realized by stacking Barium Strontium Titanate (dielectric) and silver printed layers. These prototypes exhibit performances near the state-of-the-art and suggest new opportunities for printing technologies. This thesis offers a thorough study of inkjet printed silver layers and assess their potential for the manufacturing of flexible devices.

Ces travaux examinent le potentiel d’un papier à fort lissé pour la production de masse de tags RFID-HF imprimés. Les caractérisations menées sur le papier Powercoat HD mettent en évidence une haute tolérance à la température et une faible rugosité. De fait, il se présente ainsi comme une sérieuse alternative à l’utilisation des films polymères (PET, PEN, PI, etc.), permettant de développer pleinement les performances électriques d’encres conductrices métalliques.Deux procédés d’impression industriels ont été considérés, la flexographie et la sérigraphie ayant tout deux fait leurs preuves depuis plusieurs décennies pour l’impression graphique à hautes cadences. Le potentiel de leur utilisation pour l’impression à grande échelle de dispositifs électroniques à bas-coût est discuté dans ces travaux. De plus, les performances électriques d’encres commerciales à base d’argent sont étudiées en fonction de la taille des particules qui les composent. En effet, l’utilisation de particules métalliques à l’échelle nanométrique pourra faciliter l’activation des mécanismes de diffusion atomique, améliorant ainsi le contact physique entre les particules et favorisant la conduction électrique. En parallèle, les encres à microparticules sont moins coûteuses et leurs conditions d’utilisation moins contraignantes. Toutefois, la coalescence des particules métalliques après l’impression ne pourra être initiée sans un traitement thermique de recuit.Le recuit est usuellement réalisé dans une étuve ou un tunnel à air chaud, la température doit alors rester inférieure à la tolérance du substrat. Cela permet d’atteindre des performances électriques qui restent limitées pour des durées de procédé de l’ordre de plusieurs minutes. Afin de tenir compte des contraintes industrielles d’une production à grande échelle et de permettre d’obtenir les meilleures performances électriques en un temps réduit, l’un des principaux axes de recherche exploré consiste au déploiement des technologies émergentes de recuit photonique proche infrarouge (NIR) et lumière intense pulsée (IPL). Ces dernières sont basées sur l’absorption de l’énergie lumineuse par le film d’encre provoquant ainsi sont échauffement rapide. L’important différentiel d’absorption entre les encres et le substrat contribue, en outre, à une sélectivité de ces procédés permettant de limiter la dégradation du support tout en atteignant au niveau de l’encre, des températures pouvant être supérieures à 300°C. Pour chaque procédé de recuit, l’influence des différents paramètres sur les performances électriques finales a pu être étudiée par la mise en place d’un suivi in-situ de la résistance, permettant un échantillonnage allant jusqu’à 250 kHz.Finalement, des boucles RFID-HF ont été imprimées, recuites dans les conditions précédemment optimisées puis caractérisées. Une estimation des coûts de production a été menée afin de distinguer les contributions liées à l’encre, au support et à la puce électronique en silicium. Les résultats obtenus mettent en évidence le potentiel du papier Powercoat HD, couplé à une impression en flexographie et à un recuit proche infrarouge, permettant alors la production à grande échelle de tags RFID-HF pour un coût matière de l’ordre de 5 centimes d’euros. / This work examines the potential of a very smooth paper for the mass production of printed RFID-RF tags. Characterizations on Powercoat HD paper demonstrate high temperature tolerance and very low roughness. It thus represents a serious alternative to the use of polymeric films (PET, PEN, PI, etc.), enabling the electrical performance of metallic conductive inks to be fully developed.Two industrial printing processes have been considered, flexography and screen printing, and their use were discussed for the printing of low-cost electronic devices. Moreover, the electrical performances of commercial silver based inks are studied according to the size of their particles. Indeed, the use of metal particles at the nanometric scale can facilitate the activation of the atomic diffusion mechanisms, thus improving the physical contact between the particles and promoting electrical conduction. In parallel, microparticles inks are cheaper and their conditions of use less restrictive. In any case, the coalescence of the metal particles after printing cannot be initiated without a thermal sintering treatment.Sintering is usually carried out in an oven or hot air tunnel, the temperature must therefore remain below the tolerance of the substrate. This leads to limited electrical performances for long process duration of several minutes. In order to take into account the industrial constraints of large-scale production and to achieve the best electrical performance in a short time, one of the main explored research areas is the deployment of emerging near-infrared (NIR) and intense pulsed light (IPL) photonic technologies. These latter are based on the absorption of light energy by the ink film thus causing rapid heating. The important absorption differential between the inks and the substrate allows high heating selectivity which makes it possible to limit the degradation of the substrate while the ink temperatures may be greater than 300 ° C. For each sintering process, the influence of the various parameters on the final electrical performance has been studied by setting up an in-situ resistance monitoring, allowing sampling frequency up to 250 kHz.Finally, RFID-HF loops were printed, sintered under previously optimized conditions and then characterized. An estimate of the production costs was carried out in order to distinguish the contributions related to the ink, the substrate and the silicon chip. The obtained results demonstrate the potential of Powercoat HD paper, coupled with flexographic roll-to-roll printing and near-infrared technology, enabling the large-scale production of RFID-HF tags at a material cost of the order of 5 euros cents.

This diploma thesis deals with material printing using roll to roll material printer. Several kinds of printing inks were prepared and their parameters, like viscosity and homogeneity were optimized. Corona treated PET foil was used as the flexible substrate. Thin layers of function material were prepared by coating by using the smooth cylinder and slot die method. Layers homogeneity was characterized by optical density. Layer thickness was measured by profilometer.

Ces travaux de thèse portent sur la synthèse de particules hybrides à partir de pigments inorganiques pour la formulation d’encres électrophorétiques colorées. Les pigments doivent répondre à un cahier des charges spécifique à ce type d’application. Ils doivent avoir une taille sub-micronique, une faible densité et un haut indice de réfraction afin d’exalter les phénomènes de diffusion. Les pigments bleus et cyan de structure spinelle CoAl2O4 et NiAl2O4 ont été synthétisés par voie Pechini. Dans les deux cas, des phénomènes de démixtion influençant la couleur ont été observés. Cependant, de par la différence de rayon ionique entre le Co2+ et le Ni2+ (rCo2+ < rNi2+), les origines en sont différentes. Dans le premier cas il a fallu éliminer les ions Co3+ stabilisés en site [6] pour obtenir une phase pure où la majorité des ions cobalt occupent les sites [4]. Dans le second cas l’ajout d’ions Al3+ a été nécessaire pour stabiliser une phase spinelle pure en présence de lacunes cationiques et d’ions Ni2+ occupant partiellement les sites [4] et [6]. Ensuite, nous avons développé des pigments magenta et jaunes de structure olivine explorant la solution solide LiCoxNi1-xPO4. Dans ces composés, l’étude des transitions électroniques corrélées à la structure et à l’environnement des ions chromophores Ni2+ et Co2+ en site [6] a permis de montrer des champs cristallins proches et un effet néphélauxétique presque identique. Finalement l’analyse de l’état de valence du chrome dans les structures de type rutile SnxCr1-xO2 a permis de synthétiser des pigments violets. Dans un second temps, la surface des pigments a été modifiée avec des chaines silanes de type n-trimethoxysilane afin de favoriser la dispersion des pigments dans un milieu apolaire. Puis les pigments modifiés ont été polymérisés dans l’Isopar G par polymérisation radicalaire contrôlée par les nitroxydes avec du méthacrylate de méthyle afin de diminuer la densité globale des particules hybrides et ainsi obtenir des encres stables. L’étude de l’influence des conditions expérimentales a été effectuée sur chaque pigment afin de formuler des encres colorées et chargées sans ajout de contrôleur de charge. La réalisation d’un dispositif électrophorétique à deux couleurs bleu et blanc a finalement pu être développé. / This work deals with the hybrid particles synthesis, using inorganic pigment for the coloured electrophoretic inks formulation. To comply with this type of application, pigments must have a sub-micrometer size, a low density and a high refractive index in order to exalt the diffusion phenomena. Blue and cyan spinel structure pigments CoAl2O4 and NiAl2O4 have been synthesized by Pechini process. In both these oxides, steric and electronic effects allowed stabilizing pure phases with enhanced colouring effects. In the case of CoAl2O4, we have to avoid the occurrence of Co3+ (LS) whereas for NiAl2O4, excess of Al3+ is necessary to get pure phases with nanosized crystallites. Then, magenta and yellow olivine structure pigments have been developed with the exploration of the solid solution LiCoxNi1-xPO4. In these compounds, the study of the electronic transitions combined with Ni2+ and Co2+ chromophores ions structure and environment in [6] site leads to comparable crystal field and so an almost similar nephelauxetic effect for both ions. Finally, the investigation of the valence state and the environment of chromium in rutile type structure Sn1-xCrxO2 allowed the synthesis of purple pigments. In a second part, the pigment surface has been modified with n-trimethoxysilane chains to improve the pigment dispersion in apolar media. Then, modified pigments have been polymerised in Isopar-G by nitroxyde mediated radical polymerisation with methyl methacrylate to decrease the hybrids density and to obtain stable inks. The impact of the experimental conditions has been studied on each pigments in order to formulate coloured and charged inks without any charge control agent. A two-colour electrophoretic device (blue/white) has been finally tested.

Self-assembled microsphere monolayers (SMMs) hold significant promise for micro- and nanopatterning. Here we exploit, for the first time, SMMs as stamps for microcontact printing (μCP) and demonstrate this to fabricate patterned initiator templates that can subsequently be amplified into polymer brushes by surface initiated atom transfer radical polymerization (SI-ATRP). SMM stamps avoid the need for expensive and sophisticated instrumentation in pattern generation, and provide a broad range of accessible surface chemistries and pitch size control.

As permanent tattoos are becoming more popular and common, an increased number of allergic reactions to tattoos is reported. The purpose of this project was to analyze tattoo inks for hazardous substances, and whether they comply to current Swedish and European legislative requirements. The tattoo inks were qualitatively analyzed for pigments, and quantitatively analyzed for metals. A total of 73 tattoo inks were collected from various sources such as a tattoo ink supplier, online retailers, and provided directly from tattoo artists. The labels of each tattoo ink bottle were inspected to investigate their compliance with the Council of Europe and the Swedish Medical Products Agency. Matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI-ToF-MS) was used to qualitatively analyze 20 selected tattoo inks for different pigments. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantitatively analyze trace metals in 70 of the samples. A large majority (90%) of the tested samples violated the requirements and criteria in the European resolution ResAP 2008(1), such as information on name and address of the manufacturer, minimum date of durability, sterility, batch number, and storage. Patch and allergy testing were incorrectly recommended for many samples in a way that is not accepted by dermatologists. In a worst-case scenario, this testing could be a sensitizing step. Also, it can not prevent future allergic reactions from occurring or provide any juridical insurance. Only one brand, World Famous, fulfilled the requirements for labeling for six of the seven samples (one sample failed due to a faulty declared pigment). The brands Tang Dragon and Dynamic did not fulfill any of the requirements listed in ResAP 2008(1). The list of ingredients was incorrect for all samples from Tang Dragon (bought prior to 2019 online). Also, six of the other 50 samples from different brands (World Famous, Intenze, Fusion Tattoo Ink, Eternal Ink, Solid Ink) declared at least one pigment incorrectly in their ingredients list. 25% of the declared and theoretically detectable pigments were detected by means of MALDI-ToF-MS, whereas the other pigments were either absent or below the limit of detection. Future analyses should include an MS/MS analysis. Polyethylene glycol (PEG) was identified qualatively in 15 of the 20 samples analyzed with MALDI-ToF-MS but was not listed in any of the ingredients lists. ICP-QQQ-MS is a very sensitive technique and could both detect and verify the presence of all metal-containing pigments, as well as the level of impurities. Copper was clearly more present in green and blue colors, regardless of the brand. The metal content was evidently dependent on the brand for arsenic, aluminum, bismuth, chromium, nickel, zinc, and strontium. Elevated levels of barium and strontium (partially very high levels: up to 727 mg/kg barium and up to 8.06 g/kg strontium) were found in several samples. High amounts of aluminum (4 to 11,0 g/kg) and titanium (as judged from white precipitates and ingredients lists) were present in most samples. Nickel (0.1 to 41 mg/kg) and chromium (0.1 to 139 mg/kg) were also present in the samples. Some other impurities were also present (arsenic – 3.8 mg/kg, mercury – 1.6 mg/kg, and lead – 5.4 mg/kg for one sample, respectively). Known sensitizing pigments were declared and partially confirmed by MALDI-ToF-MS in 17 of 53 samples of the brands Radiant Colour, Eternal Ink, Fusion Tattoo Ink, and Kuro Sumi. Four samples (from Intenze, Eternal Ink, and Kuro Sumi) also declared pigments listed as non-suitable substance according to the European Commission regulation on cosmetic products from 2009.

No description available.