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L'enjeu de ce travail est la réalisation de circuits électroniques sur des pièces polymères injectées à forme 3D, appelées MIDs, par microtamponnage (μTP). Le μTP, est une technique de localisation de substances (chimiques ou biologiques) par contact mécanique d'un tampon structuré sur un substrat. Il permet de localiser les pistes conductrices des MIDs en utilisant deux protocoles : le μTP passif et le μTP actif. La première méthode consiste à déposer de manière localisée un thiol par μTP sur la surface de la pièce préalablement métallisée. Le thiol permet de protéger les pistes métalliques qui doivent être conservées après gravure humide. Dans la seconde, un catalyseur (du palladium) est déposé par μTP, suivi de la métallisation electroless des pistes. La problématique du μTP 3D a été étudiée à l'aide d'un tampon épousant la forme de la pièce. Nos résultats expérimentaux couplés à des simulations par éléments finis de la déformation du tampon lors de sa compression au moment du contact avec la pièce, nous ont permis de déterminer les paramètres clefs du procédé : l'alignement du tampon par rapport à la pièce, la gestion du contact et la fabrication du tampon. Il a été mis en évidence que la tolérance de l'alignement est de l'ordre de 100μm pour des motifs structurés de 250μm de hauteur. Un tampon composé d'un support rigide surmonté d'une couche mince structurée permet de limiter ses déformations lors de sa compression. Les enseignements tirés nous ont permis de réaliser nos premiers circuits par μTP à l'aide d'une machine originale développée au laboratoire. La problématique de l'épaississement des couches de cuivre adhérentes sur des pièces en LCP est également abordée, un protocole d'épaississement ayant été validé / The main challenge of this work was the production of electronic circuits on injected 3Dshaped polymer components, called MIDs, by microcontact printing (μCP). μCP is a substance (chemical or biological) localisation technique through mechanical contact between a patterned stamp and a substrate. It enables the MIDs’ conductor tracks to be located using two techniques: passive μCP and active μCP. The first method involves locally depositing a thiol by μCP on the substrate’s surface, which has previously been coated with a thin metallic film. The thiol protects the metallic tracks, which must be preserved after wet chemical etching. Regarding the second method, a catalyst (palladium) is deposited by μCP, followed by the electroless metallization of the tracks. The 3D μCP issue was studied using a stamp, which matched the shape of the substrate. Our experimental results combined with finite element simulations of stamp deformation during compression and whilst in contact with the substrate, revealed the key parameters of the process: stamp/substrate alignment, contact control and stamp manufacturing. We found that the alignment tolerance was around 100μm for a 250μm thickness structured design. A stamp with a rigid support covered in a structured thin film minimises deformation during compression. Thanks to the lessons learned, we carried out our first circuits using μCP with a new machine, which was developed in the laboratory. We also addressed the problem of thickening adhesive copper layers on LCP components, as a thickening procedure had already been validated

The exceptional self-assembly properties of DNA as well as its ability to interact with different kinds of chemical compounds and biological structures make this biomolecule to an interesting object for the fabrication of artificial nanostructures. In this work several methods for a DNA-based self-assembly of electronic nanocircuitry are explored. For this, four basic steps, which turned out to be essential within a circuit assembly process, are addressed: (i) The formation of multi-branched DNA junctions by a simple building-block procedure. (ii) The site-specific attachment of nanoobjects (gold colloids) at the center of DNA junctions. (iii) The integration of DNA into microstructured gold electrode arrays, in particular the stretching of single DNA molecules between two electrodes. For this a simple, but reliable methods for the functionalization of gold electrodes by using aminoethanethiol was developed, which enables end-specific attachment of the DNA but does not require DNA modification. (iv) The metallization of DNA. A synthesis procedure was developed, which results in the formation of continuous chains of 5nm platinum clusters along the DNA. The metal deposition process turned out to take place exclusively at the DNA while background metallization is completely suppressed.

The exceptional self-assembly properties of DNA as well as its ability to interact with different kinds of chemical compounds and biological structures make this biomolecule to an interesting object for the fabrication of artificial nanostructures. In this work several methods for a DNA-based self-assembly of electronic nanocircuitry are explored. For this, four basic steps, which turned out to be essential within a circuit assembly process, are addressed: (i) The formation of multi-branched DNA junctions by a simple building-block procedure. (ii) The site-specific attachment of nanoobjects (gold colloids) at the center of DNA junctions. (iii) The integration of DNA into microstructured gold electrode arrays, in particular the stretching of single DNA molecules between two electrodes. For this a simple, but reliable methods for the functionalization of gold electrodes by using aminoethanethiol was developed, which enables end-specific attachment of the DNA but does not require DNA modification. (iv) The metallization of DNA. A synthesis procedure was developed, which results in the formation of continuous chains of 5nm platinum clusters along the DNA. The metal deposition process turned out to take place exclusively at the DNA while background metallization is completely suppressed.

Thema der vorgelegten Dissertation ist der Mechanismus der Keimbildung und des Wachstums von Platinclustern in Lösung und auf Biopolymeren nach der Reduktion von Platin-Salzen. Die Untersuchung wird auf atomarer Skala durch ab-initio Molekulardynamik mit der Methode von Car und Parrinello durchgeführt. In einem klassischen, generell akzeptierten Mechanismus erfolgt die Aggregation von Pt-Atomen nur nach kompletter Reduktion der Pt(II)-Komplexen zum metallischen Pt(0)-Zustand. Im Gegensatz dazu, in der hier beobachteten Reaktionsablauf entstehen stabile Pt-Pt-Bindungen schon nach einem einzigen Reduktionsschritt. Darüber hinaus wird es gefunden, dass kleine Pt-Cluster durch Addition von unreduzierten PtCl2(H2O)2-Komplexen wachsen können. Das stimmt mit einem experimentell beocbachteten autokatalytischen Clusterwachstumsmechanismus überein. Es wird weiterhin gefunden, dass Pt(II)-Komplexe, die kovalent an DNA oder an Proteine gebunden sind, als sehr effiziente Nukleationszentren für das weitere Metallclusterwachstum wirken können. Das ist eine Konsequenz des starken Donor-Charakters der organischen Liganden, in derer Anwesenheit stärkere Metall-Metall-Bindungen als frei in der Lösung gebildet werden können. In der Tat, in Metallisierungsexperimenten können 5 Nanometer dünne, mehrere Mikrometer lange, regelmässige Clusterkette erzeugt werden, die rein heterogen auf das Biomolekulare Templat gewachsen sind. / In this thesis we investigate the molecular mechanisms of platinum cluster nucleation and growth in solution and on biopolymers by means of first-principles molecular dynamics. In contrast with a classical picture where clusters nucleate by aggregation of metallic Pt(0) atoms, we find that Pt--Pt bonds can form between dissolved Pt(II) complexes already after a single reduction step. Furthermore, we observe that small clusters grow by addition of unreduced PtCl2(H2O)2 complexes, consistently with an autocatalytic growth mechanism. Moreover Pt(II) ions covalently bound to biopolymers are found to act as preferred nucleation sites for the formation of clusters. This is a consequence of the strong donor character of the organic ligands which induce the formation of stronger metal-metal bonds than those obtained in solution. In fact, in metallization experiments we obtain a clean and purely heterogeneous metallization of single DNA molecules leading to thin and uniform Pt cluster chains extended over several microns.

Due to their inherent BW capacity, optical interconnect (OI) offers a means of replacement to BW limited copper as bottlenecks begin to appear within the various interconnect levels of electronics systems. Low-cost optically enabled printed circuit boards are a key milestone on many electronics roadmaps, e.g. iNEMI. Current OI solutions found in industry are based upon optical fibres and are capable of providing a suitable platform for inter-board applications especially on the backplane. However, to allow component assembly onto high BW interconnects, an integral requirement for intra-board applications, optically enabled printed circuit boards containing waveguides are essential. Major barriers to the deployment of optical printed circuit boards include the compatibility of the technique, the cost of acquiring OI and the optical power budget. The purpose of this PhD research programme is to explore suitable techniques to address these barriers, primarily by means of laser material processing using UV and IR source lasers namely 248 nm KrF Excimer, 355 nm UV Nd:YAG and 10.6 μm IR CO2. The use of these three main lasers, the trio of which dominates most PCB production assembly, provides underpinning drive for the deployment of this technology into the industry at a very low cost without the need for any additional system or system modification. It further provides trade-offs among the suitable candidates in terms of processing speed, cost and quality of waveguides that could be achieved. This thesis presents the context of the research and the underlying governing science, i.e. theoretical analysis, involving laser-matter interactions. Experimental investigation of thermal (or pyrolitic) and bond-breaking (or photolytic) nature of laser ablation was studied in relation to each of the chosen lasers with regression analysis used to explain the experimental results. Optimal parameters necessary for achieving minimum Heat Affected Zone (HAZ) and surface/wall roughness were explored, both of which are key to achieving low loss waveguides. While photochemical dominance - a function of wavelength and pulse duration - is desired in laser ablation of photopolymers, the author has been able to find out that photothermallyprocessed materials, for example at 10.6 μm, can also provide desirable waveguides. Although there are literature information detailing the effect of certain parameters such as fluence, pulse repetition rate, pulse duration and wavelength among others, in relation to the etch rate of different materials, the machining of new materials requires new data to be obtained. In fact various models are available to try to explain the laser-matter interaction in a mathematical way, but these cannot be taken universally as they are deficient to general applications. For this reason, experimental optimisation appears to be the logical way forward at this stage of the research and thus requiring material-system characterisation to be conducted for each case thereby forming an integral achievement of this research. In this work, laser ablation of a single-layer optical polymer (Truemode™) multimode waveguides were successfully demonstrated using the aforementioned chosen lasers, thus providing opportunities for rapid deployment of OI to the PCB manufacturing industry. Truemode™ was chosen as it provides a very low absorption loss value < 0.04 dB/cm at 850 nm datacom wavelength used for VSR interconnections - a key to optical power budget - and its compatibility with current PCB fabrication processes. A wet-Truemode™ formulation was used which required that optical polymer layer on an FR4 substrate be formed using spin coating and then UV-cured in a nitrogen oxygen-free chamber. Layer thickness, chiefly influenced by spinning speed and duration, was studied in order to meet the optical layer thickness requirement for multimode (typically > 9 μm) waveguides. Two alternative polymers, namely polysiloxane-based photopolymer (OE4140 and OE 4141) from Dow Corning and PMMA, were sparingly utilized at some point in the research, mainly during laser machining using UV Nd:YAG and CO2 lasers. While Excimer laser was widely considered for polymer waveguide due to its high quality potential, the successful fabrication at 10.6 μm IR and 355 nm UV wavelengths and at relatively low propagation loss at datacom wavelength of 850 nm (estimated to be < 1.5 dB/cm) were unprecedented. The author considered further reduction in the optical loss by looking at the effect of fluence, power, pulse repetition rate, speed and optical density on the achievable propagation but found no direct relationship between these parameters; it is therefore concluded that process optimisation is the best practice. In addition, a novel in-plane 45-degree coupling mirror fabrication using Excimer laser ablation was demonstrated for the first time, which was considered to be vital for communication between chips (or other suitable components) at board-level.

Les nanoparticules (NPs) métalliques présentent un grand intérêt dans de nombreuses applications, pour lesquelles un contrôle précis de la taille, de la composition et de la morphologie est requis. Cependant, ce contrôle demeure un défi. Les liquides ioniques (LIs) sont des sels fondus liquides à température ambiante. Ils possèdent des propriétés uniques, à michemin entre le liquide (ce sont des solvants, de bons électrolytes,…) et du solide (ils ne s’évaporent pas). Les LIs sont connus pour être des solvants intelligents, qui permettent, par décomposition de précurseur organométallique, de former des NPs de taille calibrée et contrôlée. Ceci en absence de ligands organiques contrairement aux solvants conventionnels. Cependant, le mécanisme de leur formation reste mal connu. Dans cette thèse, nous identifions les facteurs clés influant sur la taille finale des NPs. Cela permettra de développer des voies de synthèse de NPs de tailles prédéterminées. Par ailleurs, le silicium poreux (PSi) est un matériau prometteur qui peut trouver de multiples utilisations dans les systèmes intégrés ou dans les secteurs photovoltaïque et biomédical. Ses propriétés peuvent être ajustées par l'introduction de métaux dans ses pores. Dans ce cas également, les LIs peuvent être avantageusement utilisés. Dans ce travail, la métallisation de PSi par Cu est réalisée par imprégnation du PSi puis décomposition d’une solution de CuMes dans le LI. En fait, il est observé que c’est le PSi qui décompose le précurseur. Pour cette raison, l’utilisation d’analogues solubles du PSi est étudiée pour remplacer H2 dans la synthèse des NPs. Cela pourrait permettre d’améliorer encore le contrôle de ce procédé / Among nano-objects, metallic nanoparticles (NPs) certainly have a prominent position. This is because they offer a variety of compositions, sizes, shapes and structures that make them suitable for a variety of applications. In the same time, the accurate control of their size, shape and structure is still a challenge, mainly because NPs do not correspond to the thermodynamic stable state of metals. Recently, ionic liquids (ILs) have been shown to stabilize metallic NPs without the need of ligands required in conventional solvents. ILs are liquid molten salt at room temperature. These compounds uniquely combine properties of the liquid (they are good solvents, electrolytes…) and of the solid (they do not evaporate). In the process of decomposing organometallic precursors into metallic NPs, ILs play a central role in controlling the size and ensuring narrow size distribution. However, the corresponding mechanism remains unclear. This PhD work aims at identifying key factors influencing the final size (average and distribution) of metallic NPs chemically formed in ILs. Among nanoporous materials, porous silicon (PSi) is popular due to its exceptional characteristics for microelectronics, integrated optoelectronics, microelectromechanical systems (MEMS), layer transfer technology, solar and fuel cells, biomedicine, etc. Its properties are modified by introducing different materials into its pores. Unique properties of ILs may also be advantageous. In this work, the process used to synthesize metallic NPs is adapted into an easy, efficient, versatile, and safe process to metallise PSi. The metallisation of PSi by Cu is tentatively conducted by impregnation with a solution of CuMes in IL followed by the decomposition of the precursor. In fact, CuMes is shown to be readily decomposed by PSi. Finally, this knowledge is transposed back to the synthesis of metallic NPs, replacing H2 by chemical analogues of PSi as alternative reducing agents. This approach is believed to bring even more control in this process

Thema der vorgelegten Dissertation ist der Mechanismus der Keimbildung und des Wachstums von Platinclustern in Lösung und auf Biopolymeren nach der Reduktion von Platin-Salzen. Die Untersuchung wird auf atomarer Skala durch ab-initio Molekulardynamik mit der Methode von Car und Parrinello durchgeführt. In einem klassischen, generell akzeptierten Mechanismus erfolgt die Aggregation von Pt-Atomen nur nach kompletter Reduktion der Pt(II)-Komplexen zum metallischen Pt(0)-Zustand. Im Gegensatz dazu, in der hier beobachteten Reaktionsablauf entstehen stabile Pt-Pt-Bindungen schon nach einem einzigen Reduktionsschritt. Darüber hinaus wird es gefunden, dass kleine Pt-Cluster durch Addition von unreduzierten PtCl2(H2O)2-Komplexen wachsen können. Das stimmt mit einem experimentell beocbachteten autokatalytischen Clusterwachstumsmechanismus überein. Es wird weiterhin gefunden, dass Pt(II)-Komplexe, die kovalent an DNA oder an Proteine gebunden sind, als sehr effiziente Nukleationszentren für das weitere Metallclusterwachstum wirken können. Das ist eine Konsequenz des starken Donor-Charakters der organischen Liganden, in derer Anwesenheit stärkere Metall-Metall-Bindungen als frei in der Lösung gebildet werden können. In der Tat, in Metallisierungsexperimenten können 5 Nanometer dünne, mehrere Mikrometer lange, regelmässige Clusterkette erzeugt werden, die rein heterogen auf das Biomolekulare Templat gewachsen sind. / In this thesis we investigate the molecular mechanisms of platinum cluster nucleation and growth in solution and on biopolymers by means of first-principles molecular dynamics. In contrast with a classical picture where clusters nucleate by aggregation of metallic Pt(0) atoms, we find that Pt--Pt bonds can form between dissolved Pt(II) complexes already after a single reduction step. Furthermore, we observe that small clusters grow by addition of unreduced PtCl2(H2O)2 complexes, consistently with an autocatalytic growth mechanism. Moreover Pt(II) ions covalently bound to biopolymers are found to act as preferred nucleation sites for the formation of clusters. This is a consequence of the strong donor character of the organic ligands which induce the formation of stronger metal-metal bonds than those obtained in solution. In fact, in metallization experiments we obtain a clean and purely heterogeneous metallization of single DNA molecules leading to thin and uniform Pt cluster chains extended over several microns.