Molecular electronics is envisioned as a possible next step in device miniaturization. It is usually taken to mean the design and manufacturing of electronic devices and applications where organic molecules work as the fundamental functioning unit. It involves the easurement and manipulation of electronic response and transport in molecules attached to conducting leads. Organic molecules have the advantages over conventional solid state electronics of inherent small sizes, endless chemical diversity and ambient temperature low cost manufacturing. In this thesis we investigate the switching and conducting properties of photochromic dithienylethene derivatives. Such molecules change their conformation in solution when acted upon by light. Photochromic molecules are attractive candidates for use in molecular electronics because of the switching between different states with different conducting properties. The possibility of optically controlling the conductance of the molecule attached to leads may lead to new device implementations. The switching reaction is investigated with potential energy calculations for different values of the reaction coordinate between the closed and the open isomer. The electronic and atomic structure calculations are performed with density functional theory (DFT). It is concluded that there is a large potential energy barrier separating the open and closed isomer and that switching between open and closed forms must involve excited states. The conducting properties of the molecule inserted between gold leads is calculated within the Non Equilibrium Green Function theory. The transmission function is calculated for the two isomers with different basis sizes for the gold contacts, as well as the electrostatic potential, for finite applied bias voltages. We conclude that a Au 6s basis give qualitatively the same result as a Au spd basis close to the Fermi level. The transmission coefficient at the Fermi energy is around 10 times larger in the closed molecule compared to the open. This will result in a large difference in conductivity. It is also found that the large difference in conductivity will remain for small applied bias voltages. The results are consistent with earlier work. / QC 20101119

The physical limitations of miniaturization of the traditional silicon-based electronic devices have motivated growing interest in molecular electronics due to its promising potential in transcending Moore's Law. Since the concept of molecular rectifier was first proposed by Ratner and Aviram in 1974, a lot of efforts have been devoted to realizing nondestructive electrical contacts to the individual or ensemble molecules, such as liquid metal contact, break junctions, cross wire junctions, etc. Among them, rolled-up nanotechnology is compatible with the conventional photolithography processes and can provide an efficient strategy to fabricate fully integrated functional molecular devices on a chip via an array of damage-free soft contacts. This nanotechnology takes an important step towards implementing the miniaturization of molecular devices and promotes the development of molecular electronics. In this doctoral thesis, rolled-up nanotechnology is employed to develop functional molecular devices on chips. Enabled by these rolled-up soft contacts, fully integrated molecular rectifiers based on ultrathin molecular heterojunctions are developed for the first time, and they are able to convert alternating current to direct current with frequencies up to 10 MHz. This is also the first time that a nanoscale organic rectifier with an operating frequency exceeding 1 MHz has been fabricated. The remarkable unidirectional current behavior of the molecular devices mainly originates from the intrinsically different surfaces of bottom planar and top microtubular gold electrodes. While the excellent high-frequency response is guaranteed by the charge accumulation in the phthalocyanine molecular heterojunction, which not only improves the charge injection but also increases the carrier density. Then this rolled-up nanotechnology is further employed to explore multi-functional molecular devices. In this thesis, fully integrated process-programmable molecular devices are achieved for the first time, which can switch between photomultiplication photodiodes and bipolar memristors. The transition depends on the release of mobile ions initially stored in the bottom polymeric electrode and can be controlled by modulating the local electric field at the interface between the ultrathin molecular layer and the bottom electrode. Photogenerated-carrier trapping at a low interfacial electric field leads to photomultiplication with an ultrahigh external quantum efficiency (up to 104%). In contrast, mobile-ion polarization triggered by a high interfacial electric field results in ferroelectric-like memristive behaviour with both remarkable resistive on/off ratios and rectification ratios. The combination of the “soft-contact” enabled by rolled-up nanotechnology and the “ion reservoir” provided by the polymeric electrode opens up a novel strategy for integrating multi-functional molecular devices based on the synergistic electronic-ionic reaction to various stimuli.:List of abbreviations 6 Chapter 1 Introduction 8 1.1 Molecular electronics: a brief history 8 1.2 Motivation: why molecular electronics? 9 1.3 Objectives: developing integrated functional molecular devices 14 1.4 Dissertation structure 15 Chapter 2 Fabrication and characterization methods 17 2.1 Core nanotechnology adopted in this thesis: rolled-up nanomembrane contacts 17 2.2 Fabrications 18 2.2.1 Photolithography 18 2.2.2 Spin-coating 23 2.2.3 Electron-beam deposition 24 2.2.4 Sputter deposition 25 2.2.5 Atomic layer deposition 27 2.2.6 Low-temperature evaporation 28 2.3 Characterizations 30 2.3.1 Atomic force microscopy 30 2.3.2 Photoelectron spectroscopy 32 2.3.3 X-ray diffraction 35 Chapter 3 Integrated molecular rectifiers 37 3.1 Introduction 37 3.2 Construction of the organic heterojunction 39 3.3 Microfabrication of the molecular diode 46 3.4 Origination of the rectification 54 3.5 Frequency performance 61 3.6 Discussion 63 Chapter 4 Integrated process-programmable molecular devices 66 4.1 Introduction 66 4.2 Design and microfabrication of the molecular devices 69 4.2.1 Top tubular metallic electrodes 69 4.2.2 Bottom finger polymer electrodes 71 4.3 Function I: Molecular photomultiplication photodiodes 75 4.3.1 Traditional photodiodes and photomultiplication photodiodes 75 4.3.2 Performance of molecular photomultiplication photodiodes 78 4.3.3 Transition voltage spectroscopy 84 4.4 Function II: Molecular bipolar memristors 86 4.4.1 Ion doping-assisted injection 86 4.4.2 Performance of the molecular bipolar memristors 88 4.4.3 Mechanism of the resistance switching 97 4.5 Mechanism of the electric-field-driven transition 106 4.6 Conclusions 108 Chapter 5 Conclusions and outlook 110 5.1 Conclusions 110 5.1.1 Fully integrated molecular rectifiers 110 5.1.2 Fully integrated process-programmable molecular devices 111 5.2 Outlook 111 5.2.1 Improve the yield of the integrated molecular devices 111 5.2.2 Develop integrated molecular functional devices 112 References 113 List of figures and tables 129 Selbständigkeitserklärung 134 Theses 135 Acknowledgments 138 Research achievements 140 Curriculum-vitae 142

No description available.

Nesta tese são discutidos alguns aspectos importantes no desenvolvimento de sistemas fotovoltaicos moleculares. São abordados temas de interesse como a síntese de novos sensibilizadores para células solares sensibilizadas por corante, o desenvolvimento de novos materiais fotoativos, Química Supramolecular, bem como a aplicação de sistemas fotovoltaicos em eletrônica molecular, especificamente no desenvolvimento de portas lógicas moleculares e dispositivos de memória. A porfirina TBPyP, contendo quatro ligantes 2,2\'-bipiridina ligados covalentemente aos carbonos meso do anel porfirínico, foi sintetizada. Este derivado porfirínico serviu como bloco de construção de sistemas supramoleculares. A utilização desses sistemas como sensibilizadores em células solares (células de Grätzel) é discutido. Fios moleculares derivados da TBPyP foram obtidos via coordenação com íons de metais de transição e são investigados quanto à possibilidade de utilização em eletrônica molecular. Novos sistemas fotovoltaicos multicamada, utilizando filmes de porfirina depositados por evaporação a vácuo como elementos fotoativos e filmes de V2O5 como eletrodo passivo, foram estudados quanto a sua eficiência e quanto ao seu mecanismo de funcionamento. Os filmes finos de porfirina obtidos neste estudo foram testados como elelementos fotoativos em células fotovoltaicas com diferentes configurações, além daquelas utilizando filmes de V2O5. A obtenção de filmes híbridos compostos de nanopartículas de ouro e ligantes orgânicos foi desenvolvida e sua aplicação em sistemas fotovoltaicos bem como em dispositivos de memória investigada. Novas portas lógicas moleculares foram obtidas utilizando-se o arranjo de células de Grätzel convencionais sensibilizadas por clusteres trigonais de rutênio sintetizados para este fim. Seu princípio de funcionamento é discutido, bem como a seu potencial de integração em circuitos lógicos. / In this thesis some aspects concerning the development of molecular photovoltaic systems are discussed. Themes of current interest such as the synthesis of new sensitizers for dye-sensitized solar cells, the development of new photoactive materials, and Supramolecular Chemistry are treated, as well as the application of photovoltaic systems in molecular electronics, specifically in the development of molecular logic gates and memory devices. The porphyrin TBPyP, comprised of four 2,2\'-bipyridine ligands covalently linked to the porphyrin meso carbons, was synthesized. This porphyrin derivative was used as a building block on supramolecular systems. The utilization of these supramolecular species in solar cells (Grätzel cells) is discussed. The coordination of the porphyrin TBPyP with transition metal ions gave rise to molecular wires, which are investigated about its potential use in molecular electronics. New multilayer photovoltaic systems, using thermo-evaporated porphyrin films as photoactive elements and V2O5 films as passive electrodes, had their efficiency and mechanism studied. The confection of hybrid films comprised of gold nanoparticles and organic ligands was developed and its application in photovoltaic systems, as well as in memory devices, was investigated. New molecular logic gates were realized using the a Grätzel cell in its conventional configuration, sensitized by ruthenium trigonal clusters synthesized to this end.

Diese Arbeit präsentiert eine vollständige quantenmechanische Beschreibung eines Systems bestehend aus einem Molekül und einem metallischem Nanopartikel (MNP) in der Gegenwart eines Strahlungsfeldes. Zuerst wird ein System aus einem Molekül und einem Gold-MNP betrachtet. Das Emissionsund Absorptionsspektrum zeigt viele scharfe molekulare Schwingungssatelliten auf einem breiten Plasmonmaximum. Eine Verstärkung der Schwingungssatelliten um drei Größenordnungen ist auf effiziente Absorption und Emission durch die MNP zurückzuführen. Dann wird ein System aus einer molekularen Kette mit einem Gold-MNP untersucht. Alle zuvor genannten Phänomene treten auch hier auf, jedoch werden die Schwingungssatelliten durch das Exzitonenband der molekularen Kette ersetzt. Anschließend wird ein Nano-Laser aus vielen Molekülen und einem Gold-MNP betrachtet. Die Moleküle werden durch inkohärentes optisches Pumpen angeregt. Dabei wird eine starke Plasmonanregung durch die gemeinsame Kopplung an die Moleküle erreicht. Die Photonenemission des Lasers zeigt, dass die Intensität ansteigt, während die Linienbreite schmaler wird. Die Korrelationsfunktion in zweiter Ordnung für die Photonen in Verbindung mit der schmaler Emission könnte dabei sogar einen Hinweis auf Lasing geben. Zuletzt wird eine Nanoverbindung aus einem Molekül und zwei sphärischen metallischen Elektroden betrachtet. Das Molekül wird durch den sequentiellen Ladungstransfer angeregt. Durch die Kopplung an die Moleküle werden die Elektrodenplasmonen angeregt. Die Photonenemission der Verbindung zeigt, dass die scharfen molekularen Schwingungssatelliten um das Tausendfache verstärkt werden. Anschließend ist ein System aus zwei pyramidalen Elektroden, die seitlich von zwei Gold-MNP eingeschlossen werden, untersucht. Hier können die Schwingungssatelliten einzeln verstärkt werden, indem der Abstand zwischen den MNP variiert wird. Wir zeigen auch, dass das Lasing in einer Verbindung aus vielen Molekülen theoretisch möglich ist. / This thesis presents a unified quantum description of the combined molecule-metal nano-particle system in the presence of a radiation field. Firstly, a single molecule coupled to a gold nano-sphere is investigated. The emission and absorption spectrum show many sharp molecular vibrational satellites over one broad plasmon peak. The three orders of magnitude enhancement of the vibrational satellites is due to the great ability of the sphere to absorb and emit photons. Secondly, a molecular chain coupled to a gold nano-sphere is investigated. All the phenomena mentioned above appear also for such system, except that the vibrational satellites are replaced by the Frenkel exciton band of the molecular chain. Thirdly, a plasmonic nano-laser consisting of many dye molecules and a gold nano-sphere is considered. The molecules are initially excited by incoherent optical pump. The strong plasmon excitation of the sphere is achieved due to the concerted coupling with the molecules. The emission of the laser shows that the intensity is enlarged while the line-width is reduced. The second-order correlation function of photons together with the emission narrowing can be utilized to determine lasing operation. Finally, a nano-junction formed by a molecule and two spherical metallic leads is investigated. The molecule is excited through sequential electron transfer. The lead plasmons get excited due to the coupling with the excited molecule. The emission of the junction shows that the molecular vibrational satellites are about one thousand times enhanced by the lead plasmons. Then, a junction with two pyramidal metallic leads sandwiched by two gold nano-spheres is investigated. The simulations show that the molecular vibrational satellites can be selectively enhanced by varying the inter-sphere distance. It is also proved that the lasing can be realized by a junction with many molecules.

In dieser Dissertation wird die Selbstorganisation von pi-konjugierten (makro)molekularen Architekturen durch Chemisorption oder Physisorption in hochgeordnete supramolekulare nanoskopische und mikroskopische Strukturen auf festen Trägern untersucht. Ihre Struktur und Dynamik wurden auf molekularer Skala hauptsächlich mit Rastersondenmikroskopien, insbesondere mit Rastertunnel- und Rasterkraftmikroskopie, untersucht. Dies erlaubte die Charakterisierung einer Reihe von Phänomenen, die sowohl an Fest-Flüssig-Grenzflächen auftreten, wie beispielsweise die Dynamik der einzelnen molekularen Nanostäbchen (Ostwald Reifung) und die Fraktionierung steifer Polymerstäbchen durch Physisorption an der Grafitoberfläche aus der Lösung heraus, als auch in trockenen Filmen vorkommen wie die Selbstorganisation steifer Polymerstäbchen zu Nanobändern mit molekularen Querschnitten, die sich epitaktisch auf Oberflächen orientieren lassen und auch die Ausbildung gestapelter Architekturen von diskförmigen Molekülen. Außerdem wurden die elektronischen Eigenschaften der untersuchten Systeme mit Hilfe von Photoelektronenspektroskopie charakterisiert. Die entwickelten Nanostrukturen sind nicht nur für Nanokonstruktionen auf festen Oberflächen von Interesse, sondern besitzen auch Eigenschaften, die sie für Anwendungen in einer zukünftigen molekularen Elektronik prädestiniert, etwa für den Aufbau molekularer Drähte. / In this thesis the self-assembly of pi-conjugated (macro)molecular architectures, either through chemisorption or via physisorption, into highly ordered supramolecular nanoscopic and microscopic structures has been studied. On solid substrates structure and dynamics has been investigated on the molecular scale making use primarily of Scanning Probe Microscopies, in particular Scanning Tunneling Microscopy and Scanning Force Microscopy. This allowed to characterize a variety of phenomena occurring both at the solid-liquid interface, such as the dynamics of the single molecular nanorods (known as Ostwald ripening), the fractionation of a solution of rigid-rod polymers upon physisorption on graphite; and in dry films, i.e. the self-assembly of rigid-rod polymers into nanoribbons with molecular cross sections which can be epitaxially oriented at surfaces and the formation ordered layered architectures of disc-like molecules. In addition the electronic properties of the investigated moieties have been studied by means of Photoelectron Spectroscopies. The nanostructures that have been developed are not only of interest for nanoconstructions on solid surfaces, but also exhibit properties that render them candidates for applications in the field of molecular electronics, in particular for building molecular nanowire devices.

Nesta tese são discutidos alguns aspectos importantes no desenvolvimento de sistemas fotovoltaicos moleculares. São abordados temas de interesse como a síntese de novos sensibilizadores para células solares sensibilizadas por corante, o desenvolvimento de novos materiais fotoativos, Química Supramolecular, bem como a aplicação de sistemas fotovoltaicos em eletrônica molecular, especificamente no desenvolvimento de portas lógicas moleculares e dispositivos de memória. A porfirina TBPyP, contendo quatro ligantes 2,2\'-bipiridina ligados covalentemente aos carbonos meso do anel porfirínico, foi sintetizada. Este derivado porfirínico serviu como bloco de construção de sistemas supramoleculares. A utilização desses sistemas como sensibilizadores em células solares (células de Grätzel) é discutido. Fios moleculares derivados da TBPyP foram obtidos via coordenação com íons de metais de transição e são investigados quanto à possibilidade de utilização em eletrônica molecular. Novos sistemas fotovoltaicos multicamada, utilizando filmes de porfirina depositados por evaporação a vácuo como elementos fotoativos e filmes de V2O5 como eletrodo passivo, foram estudados quanto a sua eficiência e quanto ao seu mecanismo de funcionamento. Os filmes finos de porfirina obtidos neste estudo foram testados como elelementos fotoativos em células fotovoltaicas com diferentes configurações, além daquelas utilizando filmes de V2O5. A obtenção de filmes híbridos compostos de nanopartículas de ouro e ligantes orgânicos foi desenvolvida e sua aplicação em sistemas fotovoltaicos bem como em dispositivos de memória investigada. Novas portas lógicas moleculares foram obtidas utilizando-se o arranjo de células de Grätzel convencionais sensibilizadas por clusteres trigonais de rutênio sintetizados para este fim. Seu princípio de funcionamento é discutido, bem como a seu potencial de integração em circuitos lógicos. / In this thesis some aspects concerning the development of molecular photovoltaic systems are discussed. Themes of current interest such as the synthesis of new sensitizers for dye-sensitized solar cells, the development of new photoactive materials, and Supramolecular Chemistry are treated, as well as the application of photovoltaic systems in molecular electronics, specifically in the development of molecular logic gates and memory devices. The porphyrin TBPyP, comprised of four 2,2\'-bipyridine ligands covalently linked to the porphyrin meso carbons, was synthesized. This porphyrin derivative was used as a building block on supramolecular systems. The utilization of these supramolecular species in solar cells (Grätzel cells) is discussed. The coordination of the porphyrin TBPyP with transition metal ions gave rise to molecular wires, which are investigated about its potential use in molecular electronics. New multilayer photovoltaic systems, using thermo-evaporated porphyrin films as photoactive elements and V2O5 films as passive electrodes, had their efficiency and mechanism studied. The confection of hybrid films comprised of gold nanoparticles and organic ligands was developed and its application in photovoltaic systems, as well as in memory devices, was investigated. New molecular logic gates were realized using the a Grätzel cell in its conventional configuration, sensitized by ruthenium trigonal clusters synthesized to this end.

La réalisation d’un ordinateur quantique est l’un des objectifs scientifiques les plus ambitieux et prometteurs de ce début de siècle.La force du calcul quantique réside dans sa capacité à se placer dans une superposition d’états et à utiliser les interférences entre eux pour dépasser la limite intrinsèque des ordinateurs classiques, qui est la description discrète des phénomènes physiques pourtant continus. Cela leur permettrait théoriquement de simplifier et de résoudre des problèmes insolubles pour les ordinateurs classiques.La première étape dans la réalisation d’un ordinateur quantique est sa brique de base : le bit-quantique, ou qubit. Il s’agit de l’analogue quantique du bit classique, qui permet de stocker l’information sous la forme de 0 ou de 1. Dans le cas quantique, l’information est formée par la superposition de ces deux états, en un nombre infini de possibilités. Si cette étape a été réalisée à de nombreuses reprises par la communauté, en utilisant des qubits de différentes natures, le couplage entre plusieurs d’entre eux reste difficile et limité en nombre. En effet, le système quantique ainsi formé a tendance à perdre sa cohérence ; ou dit autrement, à se détruire.Parmi les nombreuses possibilités de qubit existant, j’utilise le spin nucléaire. Ils ont l’avantage d’être relativement bien découplés de leur environnement, ce qui permet de les protéger des sources extérieures de décohérence et ainsi d’avoir un temps de vie supérieur aux spins électroniques.Cet avantage a un prix : il est plus difficile d’accéder à leur lecture.Pour ce faire, j’ai fabriqué un transistor moléculaire afin de connecter une molécule unique à deux centres magnétiques, le Tb2Pc3, aux électrodes de source et drain. L’aimant monomoléculaire utilisé possède deux centres magnétiques (les ions Tb3+) dont les spins électroniques J=6 sont couplés entre eux via une interaction dipolaire. De plus, chacun d’entre eux est couplé à son spin nucléaire I=3/2 via l’interaction hyperfine. On a ainsi un couple de deux qudits (d=4), ce qui porte la dimension de l’espace de Hilbert à 16, et ce à l’intérieur d’une unique molécule.Dans un premier temps, j’ai élaboré le diagramme Zeeman de la molécule, qui est sa réponse énergétique à un champ magnétique extérieur. Je détaille ensuite la fabrication des échantillons, et notamment l’utilisation de la technique d’électromigration. Je présente ensuite les mesures en transport électrique, aux très basses températures (milliKelvins) et sous champ magnétique, qui permettent de détecter le retournement du couple de spins électroniques, dont la position est dépendante de l’état du couple de spins nucléaires : c’est ainsi qu’est réalisée la lecture des états du couple de qudits.Une étude de la dynamique du système est alors réalisée par des mesures de corrélations entre la position des retournements des spins électroniques entre deux balayages consécutifs. On obtient ainsi, à la fois une meilleure visualisation des états du système, mais aussi de sa relaxation entre deux balayages en champ magnétique.Enfin, j’ai pu extraire sa température effective à l’aide d’une distribution de Maxwell-Boltzmann. De l’ordre de 300 mT, elle est cohérente avec la littérature, ainsi qu’avec celles extraites sur deux autres transistors moléculaires obtenus à d’autres moments de ma thèse.En résumé, cette thèse montre pour la première fois l’utilisation d’un transistor à molécule unique pour accéder à lecture d’un couple de qudits. Le grand nombre de molécules existantes, et le grand nombre de qubits ou qudits qui pourrait y être couplé, fait de la spintronique moléculaire une voie très prometteuse vers de possibles futurs ordinateurs quantiques moléculaires.La prochaine étape sera d’opérer la manipulation cohérente d’un tel système, notamment via l’utilisation de l’effet Stark, comme cela a déjà été réalisé à l’aide d’une molécule ne comportant qu’un centre magnétique. / The realization of a quantum computer is one of the most ambitious and promising scientific objectives of the beginning of this century.The strength of quantum computing lies in its ability to use a superposition of states and the interferences between them to overcome the intrinsic limit of classical computers, which is the discrete description of the continuous physical phenomena. This would theoretically allow them to simplify and solve impossible problems for conventional computers.The first step in the realization of a quantum computer, is its basic block: the quantum-bit, or qubit. It is the quantum analogue of the classical bit, which stores information in the form of 0 or 1. In the quantum case, information is formed by the superposition of these two states, leading to an infinity of possibilities. If this step has been done many times by the community, using qubits of different natures, the coupling between several of them remains difficult and limited in number. Indeed, the quantum systems thus formed tend to lose their coherence; or said otherwise, to destroy itself.Among the many possibilities of existing qubit, I have used the nuclear spin. They have the advantage of being relatively well decoupled from their environment, which makes it possible to protect them from external sources of decoherence, and thus to have a longer lifetime than electronic spins.This advantage has a price: it is more difficult to access their reading.To do this, I have made a molecular transistor to connect a single molecule possessing two magnetic centers, the Tb2Pc3, to the source and drain electrodes. The monomolecular magnet used has two magnetic centers (the Tb3 + ions), whose electronic spins J = 6, are coupled to each other via a dipolar interaction. In addition, each of them is coupled to its nuclear spin I = 3/2 via the hyperfine interaction. We thus have a pair of two qudits (d = 4), which brings the size of the Hilbert space to 16, and this inside a single molecule.At first, I have developed the Zeeman diagram of the molecule, which is its energy response to an external magnetic field. Then, I detail the manufacture of the samples, and in particular the use of the electromigration technique. Next, I present the electrical transport measurements, at very low temperatures (milliKelvins) and under a magnetic field, which make it possible to detect the reversal of the electronic spins, which position is dependent on the state of the pair of nuclear spins: it is how the reading of the states of qudits couple is performed.A study of the dynamics of the system is then carried out by correlation measurements among the position of the reversals of the electronic spins between two consecutive scans. This gives a better visualization of the states of the system, but also its relaxation.Finally, I was able to extract its effective temperature, using a Maxwell-Boltzmann distribution. Of the order of 300 mT, it is consistent with the literature, as well as with those extracted on two other molecular transistors obtained at other times of my thesis.In summary, this thesis shows for the first time the use of a single-molecule transistor to access reading of a qudits couple. The large number of existing molecules, and the large number of qubits or qudits that could be coupled inside one of them, makes molecular spintronics a very promising way for possible future molecular quantum computers.The next step will be to operate the coherent manipulation of such a system, in particular via the use of the Stark effect, as it has already been done using a molecule having only a magnetic center.

Ce travail de thèse est focalisé sur l'interaction de molécules organométalliques avec des métaux de transition. Cette thématique a un large éventail d'applications dans plusieurs domaines tels que la réalisation de nanojonctions pour la nano-électronique, la bioimagerie et le stockage d'énergie magnétique, la nano-catalyse et les applications biomédicales. Dans ce cadre général, ce projet de thèse vise la modélisation à l’échelle atomique des interactions fondamentales entre les briques moléculaires afin de comprendre leur rôle dans l’assemblage et la fonctionnalisation des nanostructures. L’outil principal utilisé est la dynamique moléculaire à partir des premiers principes selon les approches Born-Oppenheimer et Car-Parrinello. La première partie de cette thèse présente une rétrospective du domaine afin de donner une vision d’ensemble des méthodes utilisées et de l’état de l’art dans ce domaine. Le deuxième chapitre donne les éléments de base de la théorie et les méthodes qui ont été utilisées dans la thèse, au développement desquels on a aussi contribué pendant ce projet de recherche. Les résultats obtenus et leur discussion critique constituent le corps principal de cette ouvrage de thèse. Ceci est organisé dans un chapitre unique (troisième chapitre), divisé en trois sous-chapitre pour des raisons de clarté. / The purpose of this study is to investigate the interaction of organometallic complexes with transition metals. This topic in question has a broad array of applications in a number of domain; realization of nanojunctions for molecular nanoelectronics, biological imaging and nanocatalysis. Within this general framework, this PhD project aims to model the fundamental interactions of molecular building blocks at the atomic level in order to understand their role in the assembly and functionalization of nanostructures. The principal tool used in this study is first-principles simulation methods such as the Born-Oppenheimer and Car-Parrinello molecular dynamics. The first chapter presents an emphasis of the current developments in the related field alongside of a retrospective on the historical developments that leads today's knowledge. The second chapter presents the basic elements of the theory behind the methods that were used in the thesis, whose development has also been contributed during this research project. Lastly, the third chapter which is organized in three sub-chapters enumerates and describes the results of the various systems studied.Molecular dynamics, constrained dynamics, molecular electronics, molecular junctions, ferrocene, fullerene, metal-organic precursors.

Die Verwendung einzelner Moleküle als aktive Elemente elektronischer Bauteile wird derzeit als potentielle Alternative zur halbleiterbasierten Nanoelektronik angesehen, da einzelne Moleküle a priori nur einige Nanometer groß sind. Auß erdem kann dabei eventuell eine vereinfachte Verarbeitung und Herstellung der Bauteile erreicht werden. In dieser Arbeit werden das Selbstaggregationsverhalten und die Elektrontransporteigenschaften konjugierter Moleküle mit Rastertunnelmikroskopie (RTM) und -spektroskopie (RTS) an einer Fest-Flüssig-Grenzfläche und unter Ultrahochvakuumbedingungen bei tiefen Temperaturen untersucht. Ihre mögliche Verwendung in hybrid-molekularen Bauteilen als auch Ansätze für eine mono-molekulare Elektronik werden erkundet. Insbesondere wird die Nano-Phasenseparation von Elektron-Donor-Akzeptor-Multiaden an der Fest-Flüssig-Grenzfläche demonstriert, die zur Integration verschiedener elektronischer Funktionen auf der Nanoskala benutzt werden kann. Desweiteren wird die Abhängigkeit der elektronischen Kopplung scheibenförmiger gestapelter Moleküle vom lateralen Versatz innerhalb des Stapels experimentell nachgewiesen. Dies eröffnet neue Möglichkeiten die elektronischen Eigenschaften solcher dreidimensionaler Architekturen gezielt zu beeinflussen. Außerdem werden die ersten RTM/RTS-Untersuchungen von Ladungstransferprozessen in einzelnen organischer Donor-Akzeptor-Komplexe präsentiert. Schließlich werden die Ladungstransferkomplexe mit dem Ansatz der Nano-Phasenseparation kombiniert, um den ersten Einzelmolekültransistor mit intergrierten Nanogates zu realisieren. In diesem prototypischen Bauteil wird die Strom-Spannungs-Kennlinie einer hybrid-molekularen Diode, die aus einem Hexa-peri-hexabenzocoronen (HBC) im Tunnelspalt eines RTMs besteht, durch einen kovalent an das HBC gebundenen Ladungstransferkomplex modifiziert. Dies wird als wichtiger Schritt in Richtung einer mono-molekularen Elektronik angesehen. / The use of single molecules as active components in electronic devices is presently considered a potential alternative to semiconductor-based nano-scale electronics since it directly provides precisely-defined nano-scale components for electronic devices which eventually allows for simple processing and devicefabrication. In this thesis the self-assembly and electron transport properties of conjugated molecules are investigated by means of scanning tunneling microscopy (STM) and spectroscopy (STS) at solid-liquid interfaces and under ultrahigh vacuum conditions and low temperatures. The use of the molecules in hybrid-molecular electronic devices and potential approaches to a mono-molecular electronics are explored. In particular, electron-donor-acceptor-multiads are shown to exhibit a nano-phase-segregation at the solid-liquid interface which allows for the integration of different electronic functions at the nano-scale. Furthermore, the dependence of the electronic coupling of stacked disk-like molecules on the lateral off-set in the stack is demonstrated experimentally which offers new possibilities for the control of the electronic properties of these three-dimensional architectures. In addition the first STM/STS experiments on charge transfer in single organic donor-acceptor complexes are presented. Finally, charge transfer complexes are combined with the approach of nano-phase-segregation to realize the first single-molecule transistor with integrated nanometer-sized gates. In this prototypical device the current through a hybrid-molecular diode made from a hexa-peri-hexabenzocoronene (HBC) in the junction of the STM is modified by charge transfer complexes covalently attached to the HBC in the gap. Since the donor which complexes the covalently attached acceptor comes from the ambient fluid the set-up represents a single-molecule chemical field-effect transistor with nanometer-sized gates. This is considered a major step towards mono-molecular electronics.