Estudos de interface têm presenciado um recente crescimento devido as novas propriedades físico-químicas, que puderam ser explorados com o advento de técnicas com resolução ao nível molecular/atômico. Dessas técnicas, dois ramos que merecem destaque são as Microscopias de Varredura por Ponta de Prova e Espectroscopias Óticas. Neste trabalho fazemos uso de algumas destas técnicas (o Microscópio de Tunelamento de Elétrons e Espectroscopia Vibracional por Geração de Soma de Freqüências) para estudar a adsorção de moléculas alifáticas e aromáticas em Au. Dois casos são abordados: como a rugosidade do substrato influencia no mecanismo de automontagem de monocamadas de alcanotióis e a automontagem de derivados de uracil em interfaces eletroquímicas. No primeiro caso, mostra-se que a quantidade de defeitos moleculares na monocamada adsorvida e extremamente sensível a rugosidade do substrato utilizado. Unem-se os resultados das técnicas acima aos resultados de sondas eletroquímica para se chegar a um modelo. Também e estudado a dependência das etapas de fisisorção e quimisorção em função da concentração da solução de alcanotiól. Para o segundo caso, um derivado halogenado do uracil (5-fluorouracil), mostra-se como a substituição química na base nitrogenada leva a diferentes mecanismos de formação de monocamadas na interface eletroquímica. Imagens de Microscopia de Tunelamento de Elétrons com resolução atômica e molecular mostram que em densidade de cargas negativas as moléculas estão fisisorvidas, porém não formam estruturas periódicas em contraste com uracil e timina, entretanto em densidades de cargas positivas formam estruturas periódicas quimisorvidas, assim como uracil e timina. E discutido como são diferentes os mecanismos de interação intermolecular: no caso dos alcanotiois preponderando às interações de van der Waals e no caso dos derivados de uracil pelas ligações via pontes de hidrogênio são dominantes. / Interface science has experienced a new rebirth since the development of new probes with atomic/molecular resolution, giving new insights about the physical-chemical properties, which differ substantially from the bulk. Among these techniques, two branches deserve special attention: the Scanning Probe Microscopies and Optical Spectroscopy. In this work, two derivatives of theses techniques (the Scanning Tunnelling Microscopy and Vibrational Spectroscopy by Sum-Frequency Generation) are combined giving new insights about the molecular adsorption onto Au. Two examples are focused: how roughness plays a key role in the structure of self-assembled alkanethiol monolayer and the uracil derivatives self-assembling at electrochemical interfaces. For the former, it has been shown that the amount of defects on the adsorbed monolayer is highly sensitive to substrate roughness. Combining the results of each technique with a well-known electrochemical probe, a physical model is proposed. The physisorbed and chemisorbed states are studied as a function of alkanethiol solution concentration as well. For the later case, the chemical substitution of uracil leads to drastically different results for the physisorbed phase (negative charge densities), compared to uracil and thymine. In the chemisorbed phase (positive charge densities) imaging with molecular resolution is achieved showing a quasi-hexagonal structure, similar to the structure of thymine and uracil. It is discussed what are the main driving forces for the self-assembling mechanism: van der Waal interactions for the alkanethiols and hydrogen bonding for uracil derivatives.

Exploiting coordination bonding of aromatic carboxylic acids at metal surfaces, this thesis explores new directions in the design and application of self-assembled monolayers (SAMs). The SAMs are investigated using a multi-technique approach comprising of a complementary combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In addition, the X-ray standing wave technique (XSW) was used to characterise the substrates. The process of layer formation and the final structures of the SAMs are found to be strikingly dependent on the combination of molecule and substrate, which is discussed in terms of the intermolecular and molecule-substrate interactions, bonding geometries and symmetry of the organic molecules. This is illustrated by the dramatic difference between molecular adsorption on Ag and Cu for molecules such as biphenyl-3,4',5-tricarboxylic acid and biphenyl-4-acetic acid. In the case of self-assembly on Cu, the molecule-substrate interactions play a decisive role in the resulting SAM structure, whereas on Ag, the intermolecular interactions dominate over the weaker molecule-substrate binding. This exploration of the balance of interactions that lead to the formation of these SAM structures lays the foundation for a systematic design of the structures and properties of aromatic carboxylic acid based monolayers. Finally, different applications and properties of some SAMs were investigated, namely coordination of a Pd(II) complex to a pyridine/pyrazole terminated molecule adsorbed on Ag. Evidence of coordination of Pd(II) to single molecules was provided by STM, XPS and NEXAFS spectroscopy. Additionally, controlled STM tip induced modification of local areas of a 1,3,5-tris(4-carboxyphenyl)benzene SAM on Ag was performed, opening an exciting prospect for nanoscale molecular manipulation.

Les principaux objectifs de cette thèse sont la fabrication et la caractérisation structurale à haute résolution de nanorubans de graphène à bords atomiquement lisses ainsi que leur intégration dans des composants et l'étude du transport électronique. En premier lieu, nous montrons que des nanorubans de graphène cristallins de largeur inférieure à 100 nm et avec des qualités structurales supérieures l'état de l'art peuvent être découpé par un faisceau électronique focalisé d'énergie modérée en présence d'oxygène. Les caractéristiques des rubans obtenus sont également supérieures à l'approche précédente utilisant la vapeur d'eau. Dans un deuxième temps, la structure des nanorubans est caractérisée jusqu'à l'échelle atomique par microscopie électronique en transmission corrigée des aberrations sphériques. Nous montrons que la cristallinité des nanorubans, tant en leur centre que le long des bords de découpe, est préservée. Les performances de notre approche atteignent l'état de l'art et sa reproductibilité permet de fabriquer des rubans longs de plusieurs centaines de nanomètres mais de largeur aussi fine que 16 nm. Ensuite, nous avons transposé la découpe de nanoruban suspendus à une configuration partiellement suspendue sur substrat SiO2/Si permettant de les intégrer dans des composants adaptés aux mesures de transport électronique à basse température et sous champ magnétique. Le transport électronique dans les rubans contactés de 60 x 300 nm présente un gap et des oscillations en balayage de grille arrière qui sont en accord avec un mécanisme de blocage de Coulomb dans un domaine de taille de l'ordre de la taille du ruban. Si ces résultats montrent la persistance de barrières tunnel, ses bords semblent de qualité suffisante pour ne pas induire de confinement supplémentaire. Au-delà des composants mésoscopiques, notre méthode de fabrication des rubans par gravure électronique sous oxygène ouvre des perspectives dans deux domaines en émergence. Elle est compatible avec l'ultravide et parfaitement adaptée au développement d'une technologie atomique à base de graphène. Une caractérisation de la contamination du graphène ainsi qu'une caractérisation électrique de dispositifs de graphène qui a été fait par microscopie à effet tunnel multisonde en ultra vide. Enfin, les rubans de graphène que nous produisons ont les dimensions et qualités structurales requises pour observer un comportement plasmonique du graphène dans le visible et ainsi interagir avec des structures plasmoniques métalliques. Ce couplage a été examiné en étudiant le signal Raman du graphène au voisinage de colloïdes d'or. / The main objectives of this thesis are the fabrication and high-resolution structural characterisation of graphene nanoribbons with atomically smooth edges as well as their device integration and electronic transport study. In first place, we show that crystalline graphene nanoribbons with width under 100 nm and structural properties better than the state of the art can be patterned by a focused electron beam in presence of oxygen. The structural characteristics of the ribbons are also better than the old process using water vapour. Secondly, nanoribbons structure is characterized down to the atomic scale by spherical aberration corrected transmission electron microscopy. We show that the nanoribbons crystallinity, of the centre as well as along the cut edges, is preserved. The performance of our process reaches the state of the art and its reproducibility allows to produce ribbons with length of hundreds of nanometer but as narrow as 16 nm. After that, we have transposed the suspended nanoribbon etching to a partially suspended configuration on a SiO2/Si substrate allowing the integration in devices suitable for electronic transport measurements at low temperature and under magnetic field. The electronic transport in contacted ribbons of 60x300 nm shows a gap and oscillations on backgate scanning measurements that are in agreement with a Coulomb blockade mechanism with dot sizes in the range of the ribbon surface. Even though those results show the persistence of tunnel barriers, the edges quality look good enough to avoid additional confinement. Other than mesoscopic devices, our ribbon fabrication process by electronic beam under oxygen atmosphere opens perspectives in two emergent fields. The process is ultra high vacuum compatible and perfectly adapted to the development of an atomic graphene based technology. A characterisation of contaminants of graphene samples as well as electrical characterisation of graphene devices has been performed in a multiprobe scanning tunnelling microscope in ultra high vacuum. Finally, our graphene nanoribbons have the right dimensions and structural qualities required for the observation of plasmonic behaviour of graphene in visible light and so interact with metallic plasmonic structures. This coupling has been analysed by studying the Raman signal of graphene at the close environment of gold colloids.

This thesis deals with the combined ultra-high vacuum (UHV) and electrochemical (EC) studies of selected iron oxide surfaces, namely Fe3O4(001) and -Fe2O3(012). The state-of- the-art knowledge regarding these surfaces is briefly reviewed, and importance of understanding these materials in the electrochemical environment is discussed. The design of the transfer system between UHV and EC environment is presented; individual features of the system are thoroughly discussed and the system is used for testing the stability of the Fe3O4(001) (2×2)R45° surface reconstruction in ambient conditions. The experimental results presented in this thesis show that the Fe3O4(001) (2×2)R45° reconstruction, utilized as an adatom array for single atom catalysis studies, survives both exposure to air and to liquid water, if the exposure is achieved in well-controlled fashion. Further, this thesis presents the first-ever atomic scale scanning tunneling microscopy (STM) study of the -Fe2O3(012) surface, which is important for photoelectrochemical water splitting. STM images of two surface reconstructions of the -Fe2O3(012) surface known to date are presented. A bulk terminated model of the (1×1) reconstruction is confirmed and a novel surface structure model for the (2×1) reconstructed surface is proposed. Adsorption studies of H2O and O2 on the (2×1) reconstructed surface are documented by timelapse STM.

Dans cette thèse, nous utilisons différentes nanostructures plasmoniques pour contrôler l'émission de lumière excitée électriquement. Notre émission électrique provient d'une "nanosource STM" qui utilise le courant tunnel inélastique entre la pointe d'un microscope à effet tunnel (STM) et un échantillon métallique, pour exciter localement les plasmons polaritons de surface localisés et propagatifs. L’interaction de notre nanosource STM et d'une lentille plasmonique circulaire (une série de fentes concentriques gravées dans un film d'or épais) produit une microsource radialement polarisée de faible dispersion angulaire (≈ ± 4 °). L'influence des paramètres structuraux sur la propagation angulaire de la microsource résultante est également étudiée. En outre, une faible dispersion angulaire (<± 7 °) pour une grande plage de longueurs d'onde (650-850 nm) est obtenue. Ainsi, cette microsource électrique de lumière presque collimatée a une réponse spectrale large et est optimale sur une large plage d'énergie, en particulier en comparaison avec d'autres structures plasmoniques résonantes telles que les nanoantennes Yagi-Uda. L'interaction de notre nanosource STM et d'une lentille plasmonique elliptique (une seule fente elliptique gravée dans un film d'or épais) est également étudiée. Lorsque l'excitation STM est située au point focal de la lentille plasmonique elliptique, un faisceau lumineux directionnel à faible divergence est acquis. De plus, expérimentalement, nous trouvons qu'en changeant l'excentricité de la lentille plasmique elliptique, l'angle d'émission varie. On constate que plus l'excentricité de la lentille elliptique est grande, plus l'angle d'émission est élevé. Cette étude permet de mieux comprendre comment les nanostructures plasmoniques façonnent l'émission de lumière. L'interaction de SPP excités par STM et d'une structure de pile multicouche planaire plasmonique est également étudiée. Il est démontré qu'en utilisant l'excitation STM, nous pouvons sonder la structure de bande optique de la pile Au-SiO₂-Au. Nous trouvons que l'épaisseur du diélectrique joue un rôle important dans la modification du couplage entre les modes. Nous comparons également les résultats obtenus par excitation laser et STM de la même structure de pile. Les résultats indiquent que la technique STM est supérieure en sensibilité. Ces résultats mettent en évidence le potentiel de la STM en tant que technique de nanoscopie optique sensible pour sonder les bandes optiques des nanostructures plasmoniques. Enfin, l'interaction d'une nanosource STM et d'une plaque triangulaire individuelle est également étudiée. Nous trouvons que lorsque l'excitation STM est centrée sur la plaque triangulaire, il n'y a pas d'émission de lumière directionnelle. Cependant, lorsque la nanosource STM est située sur le bord du triangle, on obtient une émission de lumière directionnelle. Cette étude nous fournit une nouvelle voie pour atteindre l'émission de lumière directionnelle. Nous étudions également l'exploration du LDOS optique du triangle avec la nanosource STM. Ainsi, nos résultats montrent que la manipulation de la lumière est réalisée par des interactions SPP-matière. En utilisant des nanostructures plasmoniques, nous contrôlons la collimation, la polarisation et la direction de la lumière provenant de la nanosource STM. / In this thesis, we use different plasmonic nanostructures to control the emission of electrically-excited light. Our electrical emission is from an “STM-nanosource” which uses the inelastic tunnel current between the tip of a scanning tunneling microscope (STM) and a metallic sample, to locally excite both localized and propagating surface plasmon polaritons. The interaction of our STM-nanosource and a circular plasmonic lens (a series of concentric slits etched in a thick gold film) produces a radially polarized microsource of low angular spread (≈±4°). The influence of the structural parameters on the angular spread of the resulting microsource is also investigated. In addition, a low angular spread (<±7°) for a large wavelength range (650-850 nm) is achieved. Thus this electrically-driven microsource of nearly collimated light has a broad spectral response and is optimal over a wide energy range, especially in comparison with other resonant plasmonic structures such as Yagi-Uda nanoantennas. The interaction of our STM-nanosource and an elliptical plasmonic lens (a single elliptical slit etched in a thick gold film) is also studied. When the STM excitation is located at the focal point position of the elliptical plasmonic lens, a directional light beam of low angular spread is acquired. Moreover, in the experiment we find that by changing the eccentricity of the elliptical plasmonic lens, the emission angle is varied. It is found that the larger the eccentricity of the elliptical lens, the higher the emission angle. This study provides a better understanding of how plasmonic nanostructures shape the emission of light. The interaction of STM-excited SPPs and a planar plasmonic multi-layer stack structure is also investigated. It is demonstrated that using STM excitation we can probe the optical band structure of the Au-SiO₂-Au stack. We find that the thickness of the dielectric plays an important role in changing the coupling between the modes. We also compare the results obtained by both laser and STM excitation of the same stack structure. The results indicate that the STM technique is superior in sensitivity. These findings highlight the potential of the STM as a sensitive optical nanoscopic technique to probe the optical bands of plasmonic nanostructures. Finally, the interaction of an STM-nanosource and an individual triangular plate is also studied. We find that when the STM excitation is centered on the triangular plate, there is no directional light emission. However, when the STM-nanosource is located on the edge of the triangle, directional light emission is obtained. This study provides us a novel avenue to achieve directional light emission. We also study probing the optical LDOS of the triangle with the STM-nanosource. Thus, our results show that the manipulation of light is achieved through SPP-matter interactions. Using plasmonic nanostructures, we control the collimation, polarization, and direction of the light originating from the STM-nanosource.

NaCl et KCl sont des matériaux à large bande interdite d’énergie, qui sont de plus en plus utilisés sous forme de couches minces en sciences des surfaces et dans des études de spectroscopie de molécules individuelles, pour découpler électroniquement des molécules organiques d’un substrat métallique. De plus, la réactivité de NaCl et KCl, sous forme de cristaux massifs, sous irradiation électronique ou photonique, a été beaucoup étudiée depuis les années 1970s. Dans ce mémoire de thèse, nous présentons les résultats d’une étude détaillée de couches minces de NaCl et de KCl sur Ag(001) par microscopie et spectroscopie à effet tunnel (STM/STS), diffraction des électrons lents (LEED) et spectroscopie d’électrons Auger (AES) sous ultravide. Afin d’obtenir des couches minces de haute qualité sur une surface métallique et de contrôler les propriétés de ces couches (épaisseur, taille et orientation des domaines, etc.), nous étudions en détails la formation de la couche en fonction des paramètres de croissance. De plus, les mesures de topographie STM montrent que l’épaisseur apparente et le contraste STM des couches isolantes dépendent de la différence de potentiel pointe-surface. Nous décrivons les modifications induites par irradiation électronique d’halogénures d’alcalins dans le régime de couches ultraminces. Les cinétiques et produits de réaction sont examinés dans le cas de couches de NaCl sur Ag(001). Les modifications structurales et chimiques sous faisceau d’électrons d’énergie 52-60 eV et 3 keV sont étudiées en utilisant respectivement le LEED et l’AES. Les effets de l’irradiation sur la géométrie et l’épaisseur des couches (allant de 2 à 5 couches atomiques) sont mesurés en STM. Nous observons que la déplétion en chlore induite par l’irradiation suit une cinétique différente de celles précédemment décrites pour les couches épaisses et cristaux massifs de NaCl. Les atomes de sodium produits par la dissociation de NaCl diffusent vers les zones nues de la surface Ag(001), où ceux-ci forment des superstructures Na-Ag connues pour le système Na/Ag(001). La modification des couches est le résultat de deux processus, pouvant être interprétés comme une désorganisation rapide de la couche avec l’arrachement de molécules de NaCl des bords d’îlots, et une perte lente de l’ordre structural à l’intérieur des îlots de NaCl due à la formation de trous par déplétion du chlore. La cinétique de la croissance des superstructures Na-Ag est expliquée par la diffusion limitée sur la surface irradiée, en raison de l’agrégation de molécules de NaCl désordonnées aux bords de marches du substrat. Nous avons également entrepris l’étude par STM de molécules de PTCDA déposées sur le substrat métallique Ag(001) et sur le système KCl/Ag(001). Nous obtenons une monocouche de PTCDA sur Ag(001) qui présente un arrangement avec une maille carrée. Sur les films de KCl, des molécules de PTCDA isolées ainsi que des structures empilées compactes ont été trouvées. / NaCl and KCl are wide band gap materials that are increasingly used as thin films in surface science and single-molecule spectroscopy studies to electronically decouple organic molecules from a metal substrate. In addition, the reactivity of bulk NaCl and KCl crystals under electron irradiation has been widely studied since the year 1970 s. In this dissertation, we report a detailed investigation on the structures of two different thin films of NaCl and KCl grown on the Ag(001) substrate by scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES) in ultrathin vacuum condition. In order to obtain high-quality thin films and to control the properties of these films on the metal surface (film thickness, domain size, domain orientation, etc), we study in detail the film growth, especially as a function of the growth parameters. In addition, the apparent height measurements by STM show that the apparent thickness and the STM contrast of these two insulating films are bias dependent. We report on an electron-induced modification of alkali halides in the ultrathin film regime. The reaction kinetics and products of the modifications are investigated in the case of NaCl films grown on Ag(001). Their structural and chemical modification upon irradiation with electrons of energy 52–60 eV and 3 keV is studied using LEED and AES, respectively. The irradiation effects on the film geometry and thickness (ranging from between two and five atomic layers) are examined using STM. We observe that Cl depletion follows different reaction kinetics, as compared to previous studies on thick NaCl films and bulk crystals. Na atoms produced from NaCl dissociation diffuse to bare areas of the Ag(001) surface, where they form Na-Ag superstructures that are known for the Na/Ag(001) system. The modification of the film is shown to proceed through two processes, which are interpreted as a fast disordering of the film with removal of NaCl from the island edges and a slow decrease of the structural order in the NaCl with formation of holes due to Cl depletion. The kinetics of the Na-Ag superstructure growth is explained by the limited diffusion on the irradiated surface, due to aggregation of disordered NaCl molecules at the substrate step edges. We have also investigated the deposition of PTCDA molecules on the metallic substrate Ag(001) and on the KCl/Ag(001) system using STM. We obtain a monolayer of PTCDA molecules on Ag(001) that is arranged in a square unit cell. On KCl films, both individual PTCDA molecules and a densely packed structure are found.

Polyzyklische organische Moleküle und deren Derivate sind eine Klasse von Nanostrukturen, die wegen diverser möglicher Anwendungen in molekularer und organischer Elektronik viel Aufmerksamkeit in der Wissenschaft erregt haben. Um ihre einzigartigen Eigenschaften in vollem Umfang auszunutzen, muss man das Verhalten von molekularen Systemen auf der Nanoskala verstehen und eine Reihe von Herstellungsverfahren entwickeln. In dieser Arbeit werden molekulare Nanostrukturen durch den Bottom-Up-Ansatz der Oberflächensynthese erzeugt. Als Untersuchungsmethode gilt Rastertunnelmikroskopie (STM) bei tiefen Temperaturen und im Ultrahochvakuum als Werkzeug der Wahl. Drei verschiedene molekulare Systeme werden ausführlich erforscht, mit dem Ziel organische Nanostrukturen mit gewünschten Eigenschaften und atomarer Präzision zu erzeugen. Im ersten Teil dieser Arbeit wird eine Cyclodehydrierungsreaktion erfolgreich für die Synthese von asymmetrischen Starphen verwendet. Es wird dann gezeigt, dass dieses Molekül als unimolekulares NAND-Logikgatter fungieren kann. Dabei wird die Positionierungsänderung der elektronischen Resonanz nach der Zufügung einzelner Goldatome an die Inputs des Moleküls gemessen. Eine Kombination aus atomarer und molekularer Lateralmanipulation mithilfe der Spitze des Rastertunnelmikroskops sowie Rastertunnelspektroskopie wird verwendet, um dieses Verhalten zu demonstrieren. Die steuerbare Verschiebung von molekularen Resonanzen entsteht wegen der asymmetrischen Form des Starphens und wurde theoretisch vorhergesagt. Molekulare Drähte werden im zweiten Teil der Arbeit durch die oberflächenassistierte Ullmann-Kupplung hergestellt. Ihr Baustein besteht aus abwechselnden Donor- und Akzeptorgruppen und wurde speziell vorgesehen, um leitfähige flexible molekulare Drähte herzustellen. Die Leitfähigkeit wird durch Ziehen einzelner Drähten von der Oberflächen mit der STM-Spitze gemessen. Theoretische Berechnungen der komplexen Bandstruktur der molekularen Drähte bestätigen die experimentellen Ergebnisse und unterstützen dabei die Wichtigkeit der Balance zwischen Akzeptor- und Donorgruppen für die Leitfähigkeit der Drähte. Basierend auf diesen Resultaten werden neue Strukturen zur Herstellung vorgeschlagen. Der letzte Teil befasst sich schließlich mit einer unimolekularen Reaktion, die zur Erzeugung einer anomalen Kombination von Pentagon- und Heptagonringen in einem einzelnen organischen Molekül führt. Solche 5-7-Einheiten sind analog zu Stone-Wales-Defekten in Graphen und können elektronische Eigenschaften beachtlich ändern. Die exakte intramolekulare Struktur der Reaktionsprodukte wird durch hochauflösende STM-Bildgebung mit funktionalisierter Spitze eindeutig zugeordnet und zusätzlich durch DFT-Rechnungen bestätigt. / Polycyclic organic molecules and their derivatives present the class of nanostructures that are currently in the focus of scientific research due to their perspectives for the versatile applications in molecular and organic electronics. To exploit their unique properties to full extent, one has to understand the behavior of molecular systems at the nanoscale and to develop a set of fabrication methods. In this work, molecular nanostructures are fabricated using the bottom-up on-surface synthesis approach, which allows precision of the desired products and control over their properties through careful precursors design. To study the reaction flow and the properties of the formed structures, scanning tunneling microscopy (STM) at low temperature and in ultra-high vacuum is the tool of choice. In this work, three molecular systems are studied in detail, with the focus of fabricating atomically precise nanostructures with tailored properties. A cyclodehydrogenation reaction is successfully applied to synthesize an asymmetric starphene molecule in the first part of the work. It is then shown that this molecule can function as a unimolecular NAND logic gate with its response to the attached single Au atoms measured as the position of the electronic resonance. A combination of the atomic and molecular lateral manipulation with the STM tip and scanning tunneling spectroscopy (STS) is used to demonstrate this behavior. The effect of the controllable shifting of the molecular resonances is due to the asymmetric shape of the starphene molecule and was initially predicted theoretically. More complex structures, molecular wires, are presented in the second part of the work by using the surface-assisted Ullmann coupling reaction. The monomer unit, consisting of the alternant donor and acceptor parts, was specifically designed to achieve highly-conductive flexible molecular wires. The conductance is measured by pulling the single wires with the STM tip off the surface. Theoretical calculations of the complex band structure of the wires confirm the obtained results and support the discussion of the importance of the balance between the strength of acceptor and donor units for the conductance of the resultant wires. Based on this, some model structures are proposed. Finally, the last part deals with a unimolecular reaction to create an anomalous combination of pentagon and heptagon rings in a single organic molecule. Such 5-7 moieties are analogous to the Stone-Wales defects in graphene and may significantly alter the electronic properties. The precise intramolecular structure of the reaction products is unambiguously assigned by high-resolution STM imaging with functionalized tips and further confirmed by DFT calculations.

The electronic and geometrical structure of single difluoro-bora-1,3,5,7-tetraphenyl-aza-dipyrromethene (aza-BODIPY) molecules adsorbed on the Au(111) surface is investigated by low temperature scanning tunneling microscopy and spectroscopy in conjunction with ab initio density functional theory simulations of the density of states and of the interaction with the substrate. Our DFT calculations indicate that the aza-BODIPY molecule forms a chemical bond with the Au(111) substrate, with distortion of the molecular geometry and significant charge transfer between the molecule and the substrate. Nevertheless, most likely due to the low corrugation of the Au(111) surface, diffusion of the molecule is observed for applied bias in excess of 1 V. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

No description available.

The high temperature adsorption of oxygen and the room temperature adsorption of CO on the Pt3Sn(111) and Pt3Sn(110) surfaces have been investigated by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES). Beforehand the structure of the clean surfaces has been reviewed. After exposure to several 1000 L O2 at sample temperatures of about 750 K on both Pt3Sn(111) and (110) an ultra-thin Sn-O surface layer is formed. For the (111) X-ray photoelectron spectroscopy (XPS) indicates that this layer does not yet exhibit oxide properties. STM topographs of the Sn-O phase show on both surfaces meshes of highly corrugated protrusions commensurate with the substrate. In the case of the (111), after additional thermal annealing with STM and LEED a (4 × 4) reconstruction is observed, that is due to a (2 × 2) supermesh of depressions in the p(2 × 2) mesh of protrusions. This structure is similar to findings reported for the oxidation of Sn/Pt(111) surface alloys. X-ray photoelectron diffraction (XPD) measurements in comparison with simulations yield a tentative model for the (111) Sn-O layer. On the Pt3Sn(110) surface after oxygen exposure a c(2 × 2) hexagonal grid of protrusions with regard to the (2 × 1) substrate is observed with STM and LEED. STM reveals the existence of domains due to two equivalent positions of the Sn-O layer relative to the substrate. The domain boundaries zigzag around the [1-10] direction. The Sn-O layer can on both surfaces be removed by thermal annealing to more than 1050 K. After CO adsorption at room temperature on both Pt3Sn(111) and (110) adsorbate structures are observable with the STM. On the (111) two different types of structures are found: ordered patches of protrusions and unordered clusters. These structures are seen only on (√3 × √3)R30° substrate regions, not on p(2 × 2) regions. Surprisingly on the (110) the CO molecules mostly arrange in dimers. For both (111) and (110) saturation coverage is already reached at about 30% of a closed monolayer. The CO can be desorbed by slightly heating the samples to about 400 K. STM topographs show that on both surfaces CO adsorbes in Pt sites, not on Sn. It was possible to observe the CO adsorption on the (110) directly live with the STM. The observed adsorption processes hint to a dimer formation mechanism where a preadsorbed monomer and a CO molecule form the gas phase or a precursor phase stick together. When on partially Sn-O phase covered Pt3Sn(111) and (110) surfaces CO is adsorbed at room temperature, the respective structures coexist. Neither is CO observed on the Sn-O phase nor does a reaction between CO and O occur.