ASICs estruturados com leiautes regulares representam uma das soluções para a perda de rendimento de fabricação de circuitos integrados em tecnologias nanométricas causada pela distorção de fotolitografia. Um método de projeto de circuitos integrados ainda mais restritivo resulta em ASICs estruturados configuráveis apenas pelas camadas de vias, que são compostos pela repetição do mesmo modelo de bloco em todas as camadas do leiaute, exceto as camadas de vias. A escolha do modelo de bloco tem grande influência nas características do circuito final, criando a demanda por novas ferramentas de CAD que possam avaliar e comparar tais modelos em seus diversos aspectos. Esta tese descreve um ambiente de CAD baseado em SAT, capaz de avaliar o aspecto de capacidade lógica em padrões de blocos configuráveis por vias. O ambiente proposto é genérico, podendo tratar quaisquer padrões de bloco definido pelo usuário, e se comporta de maneira eficiente quando aplicado aos principais padrões já publicados na literatura. / Structured ASICs with regular layouts comprise a design-based solution for IC manufacturing yield loss in nanometer technologies caused by photolithography distortions. Via-configurable structured ASICs is even a more restrictive digital IC design method, based on the repetition of a block template comprising all layout layers except the vias one. The choice of such a design strategy impacts greatly the final circuit characteristics, arising the need for specific CAD tools to allow template evaluation and comparison in different aspects. This work presents a SAT-based CAD environment for evaluating the logical capacity aspect of via-configurable block templates. The proposed environment is able to support any user-defined template, and behaves efficiently when applied to block templates presented in related literature.

Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH3)63+ in the aqueous phase could be reduced to Ru(NH3)62+. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH3)62+ could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH3)63+ by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E1/2 comparing the reaction undertaken in the recessed cavity and the bulk solution.

Movement of motor proteins along cytoskeletal filaments is fundamental for various cellular processes ranging from muscle contraction over cell division and flagellar movement to intracellular transport. Not surprisingly, the impairment of motility was shown to cause severe diseases. For example, a link between impaired intracellular transport and neurodegenerative diseases, such as Alzheimer’s, has been established. There, the movement of kinesin-1, a neuronal motor protein transporting vesicles along microtubules toward the axonal terminal, is thought to be strongly affected by roadblocks leading to malfunction and death of the nerve cell. Detailed information on how the motility of kinesin-1 deteriorates in the presence of roadblocks and whether the motor has a mechanism to circumvent such obstructions is scarce. In this thesis, kinesin-1 motility was studied in vitro in the presence of rigor kinesin-1 mutants, which served as permanent roadblocks, under controlled single-molecule conditions. The 25 nm wide microtubule track, consisting of 13 individual protofilaments, resembles a multi-lane environment for transport by processive kinesin-1 motors. The existence of multiple traffic-lanes, allows kinesin-1 to utilize different paths for cargo transport and potentially also for the circumvention of roadblocks. However, direct observation of motor encounters with roadblocks has been intricate in the past, mainly due to limitations in both, spatial and temporal resolution. These limitations, intrinsic to fluorescent probes commonly utilized to report on the motor positions, originate from a low rate of photon generation (low brightness) and a limited photostability (short observation time). Thus, studying kinesin-1 encounters with microtubule-associated roadblocks requires alternative labels, which explicitly avoid the shortcomings of fluorescence and consequently allow for a higher localization precision. Promising candidates for replacing fluorescent dyes are gold nanoparticles (AuNPs), which offer an enormous scattering cross-section due to plasmon resonance in the visible part of the optical spectrum. Problematic, however, is their incorporation into conventionally used (fluorescence) microscopes, because illumination and scattered light have the same wavelength and cannot be separated spectrally. Therefore, an approach based on total internal reflection (TIR) utilizing a novel parabolically shaped quartz prism for illumination was developed within this thesis. This approach provided homogenous and spatially invariant illumination profiles in combination with a convenient control over a wide range of illumination angles. Moreover, single-molecule fluorescence as well as single-particle scattering were detectable with high signal-to-noise ratios. Importantly, AuNPs with a diameter of 40 nm provided sub-nanometer localization accuracies within millisecond integration times and reliably reported on the characteristic 8 nm stepping of individual kinesin-1 motors moving along microtubules. These results highlight the potential of AuNPs to replace fluorescent probes in future single-molecule experiments. The newly developed parabolic prism-type TIR microscope is expected to strongly facilitate such approaches in the future. To study how the motility of kinesin-1 is affected by permanent roadblocks on the microtubule lattice, first, conventional objective-type TIRF microscopy was applied to GFP-labeled motors. An increasing density of roadblocks caused the mean velocity, run length, and dwell time to decrease exponentially. This is explained by (i) the kinesin-1 motors showing extended pausing phases when confronted with a roadblock and (ii) the roadblocks causing a reduction in the free path of the motors. Furthermore, kinesin-1 was found to be highly sensitive to the crowdedness of microtubules as a roadblock decoration as low as 1 % sufficed to significantly reduce the landing rate. To study events, where kinesin-1 molecules continued their runs after having paused in front of a roadblock, AuNPs were loaded onto the tails of the motors. When observing the kinesin-1 motors with nanometer-precision, it was interestingly found that about 60 % of the runs continued by movements to the side, with the left and right direction being equally likely. This finding suggests that kinesin-1 is able to reach to a neighboring protofilament in order to ensure ongoing transportation. In the absence of roadblocks, individual kinesin-1 motors stepped sideward with a much lower, but non-vanishing probability (0.2 % per step). These findings suggest that processive motor proteins may possess an intrinsic side stepping mechanism, potentially optimized by evolution for their specific intracellular tasks.

Movement of motor proteins along cytoskeletal filaments is fundamental for various cellular processes ranging from muscle contraction over cell division and flagellar movement to intracellular transport. Not surprisingly, the impairment of motility was shown to cause severe diseases. For example, a link between impaired intracellular transport and neurodegenerative diseases, such as Alzheimer’s, has been established. There, the movement of kinesin-1, a neuronal motor protein transporting vesicles along microtubules toward the axonal terminal, is thought to be strongly affected by roadblocks leading to malfunction and death of the nerve cell. Detailed information on how the motility of kinesin-1 deteriorates in the presence of roadblocks and whether the motor has a mechanism to circumvent such obstructions is scarce. In this thesis, kinesin-1 motility was studied in vitro in the presence of rigor kinesin-1 mutants, which served as permanent roadblocks, under controlled single-molecule conditions. The 25 nm wide microtubule track, consisting of 13 individual protofilaments, resembles a multi-lane environment for transport by processive kinesin-1 motors. The existence of multiple traffic-lanes, allows kinesin-1 to utilize different paths for cargo transport and potentially also for the circumvention of roadblocks. However, direct observation of motor encounters with roadblocks has been intricate in the past, mainly due to limitations in both, spatial and temporal resolution. These limitations, intrinsic to fluorescent probes commonly utilized to report on the motor positions, originate from a low rate of photon generation (low brightness) and a limited photostability (short observation time). Thus, studying kinesin-1 encounters with microtubule-associated roadblocks requires alternative labels, which explicitly avoid the shortcomings of fluorescence and consequently allow for a higher localization precision. Promising candidates for replacing fluorescent dyes are gold nanoparticles (AuNPs), which offer an enormous scattering cross-section due to plasmon resonance in the visible part of the optical spectrum. Problematic, however, is their incorporation into conventionally used (fluorescence) microscopes, because illumination and scattered light have the same wavelength and cannot be separated spectrally. Therefore, an approach based on total internal reflection (TIR) utilizing a novel parabolically shaped quartz prism for illumination was developed within this thesis. This approach provided homogenous and spatially invariant illumination profiles in combination with a convenient control over a wide range of illumination angles. Moreover, single-molecule fluorescence as well as single-particle scattering were detectable with high signal-to-noise ratios. Importantly, AuNPs with a diameter of 40 nm provided sub-nanometer localization accuracies within millisecond integration times and reliably reported on the characteristic 8 nm stepping of individual kinesin-1 motors moving along microtubules. These results highlight the potential of AuNPs to replace fluorescent probes in future single-molecule experiments. The newly developed parabolic prism-type TIR microscope is expected to strongly facilitate such approaches in the future. To study how the motility of kinesin-1 is affected by permanent roadblocks on the microtubule lattice, first, conventional objective-type TIRF microscopy was applied to GFP-labeled motors. An increasing density of roadblocks caused the mean velocity, run length, and dwell time to decrease exponentially. This is explained by (i) the kinesin-1 motors showing extended pausing phases when confronted with a roadblock and (ii) the roadblocks causing a reduction in the free path of the motors. Furthermore, kinesin-1 was found to be highly sensitive to the crowdedness of microtubules as a roadblock decoration as low as 1 % sufficed to significantly reduce the landing rate. To study events, where kinesin-1 molecules continued their runs after having paused in front of a roadblock, AuNPs were loaded onto the tails of the motors. When observing the kinesin-1 motors with nanometer-precision, it was interestingly found that about 60 % of the runs continued by movements to the side, with the left and right direction being equally likely. This finding suggests that kinesin-1 is able to reach to a neighboring protofilament in order to ensure ongoing transportation. In the absence of roadblocks, individual kinesin-1 motors stepped sideward with a much lower, but non-vanishing probability (0.2 % per step). These findings suggest that processive motor proteins may possess an intrinsic side stepping mechanism, potentially optimized by evolution for their specific intracellular tasks.

Cell adhesion to extracellular matrices (ECM) is critical to many cellular processes including differentiation, proliferation, migration, and apoptosis. Alterations in adhesive mechanisms are central to the behavior of cells in pathological conditions including cancer, atherosclerosis, and defects in wound healing. Although significant progress has been made in identifying molecules involved in adhesion, the mechanisms that dictate the generation of strong adhesive forces remain poorly understood. Specifically, the role of nanoscale geometry of the adhesive interface in integrin recruitment and adhesion forces remains elusive due to limitations in the techniques available for engineering cell adhesion environments. The objective of this project was to analyze the role of nanoscale geometry in cell adhesion strengthening to ECM. Our central hypothesis was that adhesive interactions are regulated by integrin clusters whose recruitment is determined by the nanoscale geometry of the adhesive interface and whose heterogeneity in size, spacing, and orientation modulates adhesion strength. The objective of this project was accomplished by 1) developing an experimental technique capable of producing nanoscale patterns of proteins on surfaces for cell adhesion arrays, 2) assessing the regulation of integrin recruitment by geometry of the adhesive interface, and 3) determining the functional implications of adhesive interface geometry by systematically analyzing the adhesion strengthening response to nanoscale patterns of proteins. A printing technique was developed that patterns proteins into features as small as 90nm with high contrast and high reproducibility. Cell adhesion arrays were produced by directly immobilizing proteins into patterns on mixed-SAMs surfaces with a protein-resistant background. Colocalization analysis of integrin recruitment to FN patterns demonstrated a concentrating effect of bound integrins at pattern sizes with areas equivalent to small nascent focal adhesions. At adhesion areas below 333 × 333 nm2, the frequency of integrin recruitment events decreased significantly indicating a threshold size for integrin clustering. Functionally, pattern sizes below the threshold were unable to participate in generation of adhesion strength. In contrast, patterns between the threshold and micron sizes showed a relationship between adhesion strength and area of individual adhesion points, independent of the total available adhesion area. These studies introduce a robust platform for producing nanoscale patterns of proteins in biologically relevant geometries. Results obtained using this approach yielded new insights on the role of nanoscale organization of the adhesive interface in modulating adhesion strength and integrin recruitment.

This critical review summarizes recent developments in the fabrication of patterned polymer brushes. As top-down lithography reaches the length scale of a single macromolecule, the combination with the bottom-up synthesis of polymer brushes by surface-initiated polymerization becomes one main avenue to design new materials for nanotechnology. Recent developments in surface-initiated polymerizations are highlighted along with diverse strategies to create patterned polymer brushes on all length scales based on irradiation (photo- and interference lithography, electron-beam lithography), mechanical contact (scanning probe lithography, soft lithography, nanoimprinting lithography) and on surface forces (capillary force lithography, colloidal lithography, Langmuir–Blodgett lithography) (116 references). / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

A l’ère du « big data » et de l’intelligence artificielle, les recherches pour trouver de nouvelles façons de stocker et traiter l’information se multiplient. Dans le domaine des mémoires non volatiles, cette émulation a conduit à l’émergence de nouveaux composants, dont les OxRAM (oxide-based resistive random access memories) auxquels nous nous sommes intéressés dans cette thèse. Il s’agit d’un empilement métal-oxyde-métal où la couche d’oxyde commute entre au moins deux états de résistance stables lorsqu’une tension est appliquée. Nos travaux ont porté sur l'étude électrique de dispositifs en croix, de dimensions submicroniques (500 x 500 nm2 ou 100 x 100 nm2) avec, comme oxyde diélectrique, le dioxyde d’hafnium HfO2 ou le dioxyde de titane TiO2. Pour l'élaboration des oxydes, nous avons mis en oeuvre le dépôt par jets moléculaires (ou MBE pour molecular beam epitaxy), technique très peu utilisée jusqu’ici dans la communauté des OxRAM. Cette technique d'ultravide permet d'obtenir des films très purs alors qu'avec l’ALD (pour atomic layer deposition), le précurseur employé induit une contamination en carbone, azote ou chlore. L'une des clés de l’optimisation des propriétés électriques se trouve dans le contrôle de la quantité et de la distribution des lacunes d’oxygène. A cet effet, nous avons exploré l’incorporation de divers éléments aux couches de HfO2 et TiO2. La microstructure et la composition des films d'oxyde ainsi dopés ont été analysées, puis les dispositifs OxRAM ont été fabriqués et leurs caractéristiques électriques (courant-tension) ont été étudiées. Pour les OxRAM à base de HfO2 (mettant en jeu un mécanisme filamentaire), nous avons tout d'abord optimisé l'élaboration de HfO2 par MBE. Nous avons obtenu des dispositifs dont les propriétés électriques se situent au niveau de l'état de l'art international, notamment pour la fenêtre mémoire. Grâce à la croissance par MBE, nous obtenons une plus petite tension de forming et une plus grande fenêtre mémoire que pour des composants similaires, que nous avons fabriqués à partir de films préparés par ALD. Nous suggérons un lien entre contaminants carbonés et largeur de la fenêtre mémoire. Par rapport à l'état de l'art, nos objectifs étaient d’abaisser les courants de fonctionnement et d’atténuer la variabilité entre nombreux cycles ainsi qu'entre composants. Nous avons pour cela examiné les effets de l'ajout dans HfO2 des éléments Al, La ou Ti (de quelques % jusqu'à 30 %), par co-dépôt avec Hf. Grâce à ces additions, nous parvenons à réduire le courant de reset, la tension de forming et la variabilité du courant de reset. De plus, les mesures XPS (pour X-ray photoelectron spectroscopy) montrent une augmentation du taux de lacunes dans les couches La-HfO2, Ti-HfO2 et Al-HfO2. Concernant les composants à base de TiO2 (impliquant des mécanismes de type interfacial à l'une des deux interfaces avec les électrodes, dite active), nos objectifs étaient de diminuer les courants de fonctionnement et d’augmenter le nombre d’états de résistance accessibles stables. A cette fin, nous avons privilégié, là aussi, des stratégies matériaux. Nous avons modifié l'interface active du dispositif en y incorporant des hétéroéléments (Ne, N et B) par implantation ionique. La teneur en lacunes d’oxygène a été analysée par XPS tandis que la mobilité des lacunes a été quantifiée via leur énergie d’activation de diffusion Ea. Afin de déterminer Ea, nous avons mis au point un protocole expérimental original. Ainsi, nous avons établi que l'azote, dopant de type p dans TiO2, accroît la mobilité des lacunes tandis que le bore, dopant de type n, l’entrave et le néon, inerte, n'a pas d'incidence. L'énergie d'activation est minimale (0,4 eV) pour une implantation en azote de 1018 ions/cm3. La mobilité des lacunes n'est cependant pas le seul paramètre à améliorer : le transport des électrons à travers la barrière Schottky TiO2/Pt joue également un rôle crucial. [...] / In the age of big data and artificial intelligence, researches to find new ways to process and store the information multiply. In the field of non-volatile memories, this emulation has led to the emergence of new components, such as OxRAM (for oxide-based random access memories) in which we have been interested in during this PhD. It is a metal-oxide-metal stack where the oxide layer is able to switch between at least two stable resistance states under an applied voltage. In this work, we have studied sub-micrometer cross-point devices (500 x 500 nm2 or 100 x 100 nm2) with hafnium dioxide (HfO2) or titanium dioxide (TiO2) as dielectric oxide. The oxides have been deposited by molecular beam epitaxy (MBE), a technique that has rarely been used so far in the OxRAM community. With this ultra-vide technique, we can obtain very pure films whereas with atomic layer deposition (ALD), precursors induce carbon, nitrogen or chlorine contaminations. For the electrical properties optimization, one of the keys is the concentration and distribution control of oxygen vacancies. Regarding that, we have explored the incorporation of various elements in HfO2 and TiO2 layers. The microstructure and the composition of these doped films have been analyzed, afterward OxRAM devices have been fabricated and their electrical characteristics (current-voltage) have been studied. For HfO2-based OxRAM (involving a filamentary mechanism), we have firstly optimized the MBE HfO2 deposition. The devices then obtained have electrical properties which are as good as those of the state-of-the-art components, in particular for the memory window. Moreover, these MBE deposited devices have a smaller forming voltage and a larger memory window than equivalent components that we have fabricated with ALD grown layers. So, we suggest a link between carbon impurities and memory width. In light of the state of the art, our objectives were to lower working currents and to reduce the variability between numerous cycles and between components too. To this end, we have examined the effects of adding Al, La or Ti elements in HfO2 (from few % to 30 %), by co-deposition with Hf. Thanks to these additions, we manage to decrease the reset current, the forming voltage and the variability of the reset current. Furthermore, X-ray photoelectron spectroscopy (XPS) measurements show an increase of vacancies amount in La-HfO2, Ti-HfO2 and Al-HfO2 layers. Concerning TiO2-based components (for which the mechanism is interfacial and takes place at one of the two electrode interfaces, said active), our goals were to diminish working currents and to augment the number of accessible stable resistance states. For this purpose, we have also focused on material strategies. We have modified the active interface by heteroelements ion implantation (Ne, N and B). The oxygen vacancies content has been analyzed by XPS while the vacancies mobility has been quantified via their activation energy diffusion Ea. In order to determine Ea, we have developed an original experimental protocol. In this way, we establish that nitrogen, which is a p-type dopant in TiO2, heightens the oxygen vacancies mobility, whereas boron, which is a n-dopant, hinders it and the neon, inert, does not have any effect on vacancies mobility. The activation energy is minimal (0.4 eV) for a nitrogen dose of 1018 ions/cm3. However, the oxygen vacancies mobility is not the only parameter that we have to improve: the electronic transport through the TiO2/Pt Schottky barrier plays also a crucial role. The results achieved during this PhD attest to the pertinence of the MBE utilization and of an analysis that combines ionic and electronic aspects in order to improve the resistive switching phenomenon understanding and the OxRAM performances.

No description available.

Ce travail concerne la modélisation, à l’échelle moléculaire, de l’interaction entre des nanoparticules carbonées et le rayonnement électromagnétique. Le but est d’aider à la compréhension des propriétés optiques des particules de suie afin de mieux quantifier l’influence des suies sur l’atmosphère et le climat. L’étude de l’interaction rayonnement/particules de suie fraîche a été effectuée par la méthode PDI ; il a été montré que : i) le coefficient d’absorption massique (MAC) des particules de suie dépend de la répartition des atomes dans la particule et de leurs liaisons, en particulier entre 200 et 350 nm ; ii) le MAC diffère selon que le cœur de la particule carbonée est occupé ou non par des plans graphitiques ; iii) un modèle analytique n’est pas adapté pour calculer le MAC d’une nanoparticule carbonée présentant des défauts structuraux. De plus, des méthodes de chimie quantique ont été utilisées pour caractériser le vieillissement des suies. Les résultats montrent que : i) NO, Cl, et HCl sont physisorbées sur une surface carbonée parfaite alors que sur une surface défective, ces espèces sont chimisorbées et conduisent à une modification de la surface ; ii) la présence de Cl conduit à un piégeage fort des molécules d’eau supérieur à celui obtenu lorsqu’un site oxygéné est présent sur la surface carbonée, expliquant ainsi le caractère hydrophile des suies émises lors d’incendies dans des milieux industriels. Enfin, la méthode PDI a été appliquée au calcul de la polarisabilité de HAP afin d’interpréter des spectres d’absorption des grains carbonés du milieu interstellaire, en incluant des molécules pour lesquelles aucune donnée n’était actuellement disponible. / This work concerns the modeling, at the molecular level, of the interaction between carbonaceous particles of nanometric size and the electromagnetic radiation. The goal is to improve our understanding of the optical properties of soot particles, to better quantify the influence of soot on the atmosphere and on climate change. The study of the interaction between radiation and fresh soot particles was carried out using the point dipole interaction method; it has been shown that: i) the mass absorption coefficient (MAC) of these soot nanoparticles may significantly depend on their atomistic details, especially between 200 and 350 nm; ii) the MAC depends on whether the heart of the carbonaceous particle is occupied or not by graphite planes; iii) an analytical model is not suitable for calculating the MAC of carbonaceous nanoparticles having structural defects. In addition, quantum chemical methods have been used to characterize the ageing of soot. The results obtained are i) NO, Cl, and HCl are physisorbed on a perfect carbonaceous surface whereas on a defective surface, these species are chemisorbed and lead to a modification of the surface; ii) on a carbonaceous surface, the presence of adsorbed Cl atoms leads to a strong trapping of the surrounding water molecules. This may be related to the highly hydrophilic nature of soot emitted during fires in industrial environments. Finally, the PDI method was applied to calculate the polarizability of PAHs to help at interpreting the absorption spectra of carbonaceous grains in the interstellar medium, including molecules for which no data was currently available.

This critical review summarizes recent developments in the fabrication of patterned polymer brushes. As top-down lithography reaches the length scale of a single macromolecule, the combination with the bottom-up synthesis of polymer brushes by surface-initiated polymerization becomes one main avenue to design new materials for nanotechnology. Recent developments in surface-initiated polymerizations are highlighted along with diverse strategies to create patterned polymer brushes on all length scales based on irradiation (photo- and interference lithography, electron-beam lithography), mechanical contact (scanning probe lithography, soft lithography, nanoimprinting lithography) and on surface forces (capillary force lithography, colloidal lithography, Langmuir–Blodgett lithography) (116 references). / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.