A coupling-limited approach for the Ullmann reaction-like on-surface synthesis of a two-dimensional covalent organic network starting from a halogenated metallo-porphyrin is demonstrated. Copper-octabromo-tetraphenylporphyrin molecules can diffuse and self-assemble when adsorbed on the inert Au(111) surface. Splitting-off of bromine atoms bonded at the macrocyclic core of the porphyrin starts at room temperature after the deposition and is monitored by X-ray photoelectron spectroscopy for different annealing steps. Direct coupling between the reactive carbon sites of the molecules is, however, hindered by the molecular shape. This leads initially to an ordered non-covalently interconnected supramolecular structure. Further heating to 300 °C and an additional hydrogen dissociation step is required to link the molecular macrocycles via a phenyl group and form large ordered polymeric networks. This approach leads to a close-packed covalently bonded network of overall good quality. The structures are characterized using scanning tunneling microscopy. Different kinds of lattice defects and, furthermore, the impact of polymerization on the HOMO–LUMO gap are discussed. Density functional theory calculations corroborate the interpretations and give further insight into the adsorption of the debrominated molecule on the surface and the geometry and coupling reaction of the polymeric structure. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

In this thesis, graphene (i.e. monolayer carbon film) and carbon clusters supported on a transition metal surface are systematically studied by local probe techniques, with respect to their structures, electronic properties and formation mechanisms. The main tools used are low-temperature scanning tunnelling microscopy and spectroscopy (STM and STS), which are introduced in Chapter 2. The mechanism of the resonance tunnelling at electron energies higher than the work function of the surface is discussed in detail, and a qualitative explanation of the Gundlach oscillations in the corresponding spectroscopy is presented. Epitaxial graphene synthesised on the Rh(111) surface by ethylene dehydrogenation is investigated by STM in Chapter 4. Such carbon film exhibits a hexagonal Moiré pattern due to a lattice mismatch between graphene and the rhodium substrate. The periodicity and local registries of the graphene/Rh(111) superstructure are carefully analysed. Based on a thorough discussion about the “commensurate vs. incommensurate” nature of the Moiré pattern in surface science field, the graphene/Rh(111) system is identified to have a non-simple-commensurate superstructure. The surface electronic properties and geometric buckling of graphene/Rh(111) are investigated by resonance tunnelling spectroscopy (RTS) and density functional theory (DFT) calculations in Chapter 5. Spectroscopy measurements reveal a modulation of the electronic surface potential (or work function Φ) across the supercell of epitaxial graphene. Based on the microscopy/spectroscopy data and the extended DFT calculations, we examined the electronic coupling of the various local C-Rh registries, and identified both experimentally and theoretically the local atomic configurations of maximum and minimum chemical bonding between graphene and the rhodium substrate. We studied in Chapter 6 the growth mechanism of graphene on Rh(111) at elevated temperatures. This part starts by investigating the dehydrogenation of ethylene into ethylidyne. When the dehydrogenation process is complete, monodispersed carbon species, identified as 7C6, are found to dominate the cluster population on the rhodium terraces. A significant coalescence of the 7C6 clusters into graphene islands occurs at temperatures higher than 873 K. The structural and electronic properties of the 7C6 carbon clusters are examined by high-resolution STM and STS, and compared with coronene molecules, i.e. the hydrogenated analogues of 7C6. DFT calculations are further used to explain the stability of 7C6 supported on the Rh(111) surface, and also the structural characteristics of such magic-sized carbon clusters.

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal.

La physique mésoscopique est actuellement dominée par des mesures de transport permettant d'extraire les propriétés électroniques globales des systèmes étudiés. La spectroscopie tunnel permet d'avoir un accès direct à la densité d'états locale (LDOS). Nous pouvons donc sonder les évolutions spatiale des propriétés électroniques notamment à l'interface entre 2 matériaux possédant des propriétés différentes. Au cours de cette thèse, nous avons développé un microscope à sonde locale qui combine microscopie à force atomique (AFM) et microscopie à effet tunnel (STM) et qui fonctionne à 100mK. L'AFM permet de localiser un nanocircuit unique sur un substrat isolant grâce à un Length Extension Resonator (LER). Nous pouvons ensuite mesurer la spectroscopie tunnel locale du nanocircuit conducteur. La résolution énergétique obtenue avec ce système est de 70µeV. Nous avons montré la faisabilité expérimentale d'une telle étude en mesurant l'effet de proximité sur un îlot de cuivre (métal normal) connecté par deux électrodes supraconductrices en aluminium à l'équilibre, hors-équilibre et sous champ magnétique. Nous avons également mesuré la LDOS du graphène sur Ir(111) qui présente des propriétés proches du graphène intrinsèque avec un dopage de type p de l'ordre de 0.34eV. Nous avons observé que ce dopage fluctue spatialement avec la présence de poches de charges avec une taille typique de l'ordre de 9nm. Ces observations sont similaires à des résultats déjà reportés sur des systèmes graphène sur SiO2. Cependant, le profil des poches que nous avons mesuré montre une forte corrélation avec la topographie due à une modulation du potentiel électrostatique induit par le métal sous le graphène. Une analyse plus fine a permis également de réveler la présence d'interférences de quasiparticules se traduisant par une inhomogénéité de la DOS. La taille typique des structures est de l'ordre de la longueur d'onde de Fermi avec une dépendance linéaire avec l'énergie selon E=ħvFk avec vF = 8.3±0.7x10^5m/s proche de la vitesse de Fermi théorique de 1x10^6m/s. Cela met évidence la présence de diffusion intravallée et prouve le caractère de fermions de Dirac sans masse des particules du graphène sur Ir(111). / Mesoscopic physic is currently dominated by transport measurements that extract overall electronic properties of the studied sytstems. Tunneling spectroscopy gives access to the local density of states (LDOS). Hence, we can probe the spatial evolution of the electronic properties especially at the interface between two materials with different properties. During this thesis, we built-up a scanning probe microscope at 100mK that combine both atomic force microscopy (AFM) and scanning tunneling microscopy (STM). AFM helps to locate a single nanocircuit on insulating substrate thanks to a Length Extension Resonator (LER). We can then measure the tunneling spectroscopy on the conductive nanocircuit. The energy resolution of the system is of 70µeV. We show the experimental proof of such a system by measuring the proximity effect in copper island (normal island) connected by two superconducting leads in aluminum at equilibrium, out of equilibrium and with a magnetic field. We also measured the LDOS of graphene on Ir(111) that displays electronic properties close to the one of intrinsic graphene with p-doping of about 0.34eV. We observe spatial inhomogeneities of this doping forming charge puddles with a typical size af about 9nm. Those observations are close to previous results reported on graphene on SiO2. However, the profile of the measured puddles shows a strong correlation with the topography due to the modulation of the electrostatic potential induced by the metal below the graphene. A closer look to the DOS shows quasiparticles interferences forming DOS inhomogeneities. The typical size of the DOS structures is of the order of the Fermi wavelength with a linear dependence with energy as E=ħvFk with vF = 8.3±0.7x10^5m/s which is close to the theoretical Fermi velocity of 1x10^6m/s. This point out the presence intravalley scattering and demonstrate the fact that particles in graphene on Ir(111) are Dirac fermions without mass.

L’interaction de molécules organiques avec les surfaces semiconductrices permet de contrôler les propriétés physiques de ces dernières et ce, soit à travers une modification locale en utilisant des molécules individuelles, soit par la passivation de la surface par une mono-couche complète. Aussi, le contrôle de l’interaction moléculaire nous permet de modifier les propriétés intrinsèques des molécules à travers un découplage électronique partiel ou complet entre les orbitales moléculaires et la surface. Pour atteindre ces objectifs, cette thèse présente l’étude expérimentale de l’adsorption de molécules sur la surface semiconductrice à large gap de 6H-SiC(0001)-3x3. Les expériences ont été réalisées à l’aide d’un microscope à effet tunnel opérant dans les conditions d’Ultra-Haut Vide et de température ambiante (UHV RT-STM). Les résultats ont été comparés à des études théoriques employant des calculs selon la théorie de la fonctionnelle de la densité (DFT). Trois molécules on été étudié durant ce travail de thèse : C60, Caltrope et Trima. Les études STM et DFT montre que les molécules individuelles de C60 sont chimisorbé à la surface de carbure de silicium SiC(0001)-3x3 à travers la formation d’une seule liaison Si-C avec un seul adatome de silicium, contrairement aux autres surfaces semiconductrices où la molécule se chimisorbe en formant plusieurs liaisons. Trois sites d’adsorption par rapport à l’adatome de Si de la maille de surface ont été observés. Pour expliquer les observations STM, les forces de Van der Waals entre la molécule de C60 et les atomes de la surface voisins ont du être pris en compte dans les calculs DFT. Il a été observé aussi que les molécules de C60 forment de petits clusters même à de faibles taux de couverture ce qui indique la présence d’un état précurseur de la molécule et des interactions intermoléculaires non négligeable. La molécule de Caltrope, nouvellement synthétisée, a été étudié aussi bien sur la surface de Silicium que celle de SiC. Le dépôt de cette molécule complexe ne peut être réalisé selon la méthode d’évaporation classique sans induire sa dissociation et a donc nécessité l'emploi de techniques d’évaporation spécifiques. Nos résultats expérimentaux montrent un comportement remarquable: le dépôt de molécule individuelle est induit sur la surface de manière efficace par la pointe du STM démontrant ainsi l’idée d’imprimerie moléculaire. Suite à son adsorption sur la surface de silicium à travers une seule liaison, la molécule de Caltrope se comporte comme un moteur moléculaire activé thermiquement. La troisième molécule a être étudié est la molécule de Trima. Elle a été sélectionnée à cause de sa taille comparable à la distance des ad-atomes de silicium de la surface de SiC. La structure chimique de la molécule qui se termine par un groupement cétone rend possible la fonctionnalisation de la surface. Ceci est révélé par les calculs DFT de la densité de charge. La distribution de charge montre qu’il n’y a pas de partage entre les atomes d’oxygènes de la molécule et les ad-atomes de la surface et donc nous avons un évidence claire pour la formation d’une liaison dative. / The interaction of organic molecules with a semiconductor surface enables the physical properties of the surface to be controlled, from a local modification using individual isolated molecules to passivation using a complete monolayer. Controlling the molecular interaction also allows us to modify the intrinsic properties of the molecules by partial or complete electronic decoupling between the molecular orbitals and the surface. To this end, this thesis presents experimental studies of the adsorption of molecules on the wide band gap 6H-SiC(0001)-3×3 substrate. The experiments were performed using Ultra-High Vacuum Room Temperature Scanning Tunneling Microscopy (UHV RT STM) and the results were compared with comprehensive theoretical Density Functional Theory (DFT) calculations. Three different molecules were studied in this thesis: C60, Caltrop and Trima. The STM and DFT studies show that individual C60 fullerene molecules are chemisorbed on the silicon carbide SiC(0001)-3×3 surface through the formation of a single Si-C bond to one silicon adatom, in contrast to multiple bond formation on other semiconducting surfaces. We observed three stable adsorption sites with respect to the Si adatoms of the surface unit cell. To explain the STM observations, Van der Waals forces between the C60 molecule and the neighboring surface atoms had to be included in the DFT calculations. The C60 molecules are also observed to form small clusters even at low coverage indicating the presence of a mobile molecular precursor state and non negligible intermolecular interactions. The second newly designed Caltrop molecule was studied on both the Si and SiC surfaces. Intact adsorption of this complex organic molecule cannot be realized using classical adsorption methods and requires the use of specific evaporation techniques. Our experimental results show remarkable behavior: The STM tip efficiently deposits single molecules one at a time, demonstrating the concept of single molecule printing. After adsorption on the Si surface through one bond, the Caltrop operates as a thermally activated molecular rotor. The third molecule to be studied is the Trima molecule. This molecule was chosen because it is commensurable in size with the surface Si adatom distance. The chemical termination of the molecule with a ketone group enables the successful functionalization of the SiC surface. The Trima molecule provides a rare and clear-cut example of the formation of two dative bonds between the oxygen atoms of the carbonyl groups and the Si adatoms of the SiC surface. This is revealed by the DFT calculations of the charge density. The charge distribution shows that there is no sharing of electrons between the oxygen atoms of the molecule and the surface which is clear evidence for the formation of a dative bond.

The foci of this thesis are the metal oxides Cu2O, ZnO and Fe3O4 and their interaction with water and sulfur dioxide (SO2). The intention is to study SO2-induced atmospheric corrosion on a molecular level. All studies are based on photoelectron spectroscopy (PES) and scanning tunneling microscopy (STM) measurements. The band structure of Cu2O in the Γ-M direction has been probed by angle-resolved PES (ARPES). It reveals a more detailed picture of the bulk band structure than earlier data and gives the first experimental evidence of a dispersive hybridized Cu 3d-Cu 4s state. The experimental data is compared to band structure calculations. The structure of clean metal oxide surfaces and impact of sample preparation have been studied. Oxygen vacancies can form a (√3x√3)R30° reconstruction on Cu2O(111). Oxygen atoms adjacent to copper vacancies, steps or kinks are shown to be adsorption sites for both water and SO2. Annealing temperature influences the defect density and hydrogen content in ZnO, which can have large impact on the surface properties of ZnO(0001). Water is shown to adsorb dissociatively on ZnO(0001) and partly dissociatively on Cu2O(111). The dissociation occurs at undercoordinated oxygen sites on both surfaces. Water stays adsorbed on ZnO(0001) at room temperature but on Cu2O(111), all water has desorbed at 210 K. SO2 interacts with one or two undercoordinated O-sites on all studied oxide surfaces forming SO3 or SO4 species respectively. SO4 on Fe3O4(100) follows the (√2x√2)R45° reconstruction. On Cu2O(111) and ZnO(0001), SO2 adsorbs on defect sites. An SO3 to SO4 transition is observed on Cu2O(111) when heating an SO3 adsorbate layer from 150 K to 280K. Coadsorption of water and SO2 on ZnO(0001) and Fe3O4(100) has been studied briefly. Water blocks SO2 adsorption sites on ZnO(0001). On Fe3O4(100) and on one type of reduced ZnO(0001) sample, SO2 dissociation to atomic sulfur or sulfide occurs to a higher extent on water exposed surfaces than on clean surfaces. Water thus appears to increase the charge density on some surfaces. Further studies are needed to reveal the cause of this unexpected effect. / <p>QC 20110516</p>

This thesis details the development of expertise and tools required for the study of amino acids deposited on Au(111), with a primary focus on the design and testing of a Knudsen cell for controlled deposition of L-cysteine and L-methionine. An ultra-high vacuum preparation chamber designed by Dr. Katie Mitchell and built by Torrovap Industries Inc. was installed. This chamber is connected to the existing scanning tunneling microscopy chamber via a gate valve, and both chambers can operate independently. Various instruments such as a mass spectrometer, quartz crystal microbalance, ion source, and sample manipulator were installed on the preparation chamber. Scanning tunneling microscopy was performed on both homemade and commercial Au(111) thin films. High resolution images of "herringbone" reconstruction and individual atoms were obtained on the commercial thin films, and optimal tunneling conditions were determined. A Knudsen cell was designed to be mounted on the preparation chamber. The Knudsen cell operates over the temperature range 300-400K, with temperatures reproducible to ±0.5K, and stable to ±0.1K over a five minute period. Reproducible deposition rates of less than 0.2Ǻ/s were obtained for both L-cysteine and L-methionine. Electron impact mass spectrometry and heat of sublimation measurements were performed to characterize the effusion of L-cysteine and L-methionine from the Knudsen cell. The mass spectrometry results suggest that L-cysteine was decomposing at 403K while L-methionine was stable during effusion. Heats of sublimation of 168.3±33.2kJ/mol and 156.5±10.1kJ/mol were obtained for L-cysteine and L-methionine respectively.

This thesis details the development of expertise and tools required for the study of amino acids deposited on Au(111), with a primary focus on the design and testing of a Knudsen cell for controlled deposition of L-cysteine and L-methionine. An ultra-high vacuum preparation chamber designed by Dr. Katie Mitchell and built by Torrovap Industries Inc. was installed. This chamber is connected to the existing scanning tunneling microscopy chamber via a gate valve, and both chambers can operate independently. Various instruments such as a mass spectrometer, quartz crystal microbalance, ion source, and sample manipulator were installed on the preparation chamber. Scanning tunneling microscopy was performed on both homemade and commercial Au(111) thin films. High resolution images of "herringbone" reconstruction and individual atoms were obtained on the commercial thin films, and optimal tunneling conditions were determined. A Knudsen cell was designed to be mounted on the preparation chamber. The Knudsen cell operates over the temperature range 300-400K, with temperatures reproducible to ±0.5K, and stable to ±0.1K over a five minute period. Reproducible deposition rates of less than 0.2Ǻ/s were obtained for both L-cysteine and L-methionine. Electron impact mass spectrometry and heat of sublimation measurements were performed to characterize the effusion of L-cysteine and L-methionine from the Knudsen cell. The mass spectrometry results suggest that L-cysteine was decomposing at 403K while L-methionine was stable during effusion. Heats of sublimation of 168.3±33.2kJ/mol and 156.5±10.1kJ/mol were obtained for L-cysteine and L-methionine respectively.

Multilayer epitaxial graphene has been shown to contain "massless Dirac fermions" and is believed to provide a possible route to industrial-scale graphene electronics. We used scanning tunneling microscopy (STM) and spectroscopy (STS) in high magnetic fields to obtain local information on these fermions. A new STS technique was developed to directly measure graphene's energy-momentum relationship and resulted in the highest precision measurement of graphene's Dirac cone. STS spectra similar to ideal graphene were observed, but additional anomalies were also found. Extra peaks and an asymmetry between electron and hole states were shown to be caused by the work function difference between the Iridium STM tip and graphene. This tip effect was extracted using modeled potentials and performing a least square fit using degenerate perturbation theory on graphene's eigenstates solved in the symmetric gauge. Defects on graphene were then investigated and magnetic field effects were shown to be due to a mixture of potential effect from defects and the tip potential. New defect states were observed to localize around specific defects, and are believed to interact with the STM tip by Stark shifting in energy. This Stark shift gives a direct measurement of the capacitive coupling between the tip and graphene and agrees with the modeled results found when extracting the tip potential.

In this work, a Au(100) single crystal was used as substrate for organic molecular beam epitaxy. Highly ordered organic thin films of the molecules 3,4,9,10-perylenetetracarboxylic-3,4,9,10-dianhydrid (PTCDA) and hexa-peri-hexabenzo-coronene (HBC) as well as organic-organic heterostructures on reconstructed Au(100) were prepared. The molecular arrangement was characterized in Scanning Tunneling Microscopy and Low Energy Electron Diffraction investigations. Scanning Tunneling Spectroscopy data were recorded on monolayer and submonolayer PTCDA films. Measurements on closed PTCDA layers at different fixed tip sample separations revealed a peak +0.95V. Other measurements performed consecutively on a PTCDA island and on uncovered Au(100) areas showed that this peak is indeed caused by the PTCDA molecules. Another set of consecutive measurements on herringbone and square phase PTCDA islands indicates that in the normalized differential conductivity the peak shape and peak position depend on the molecular arrangement. The STS data are compared to UPS and IPES results, already published. In the case of highly ordered films of HBC on Au(100) it was possible to derive the energetic positions of the HBC frontier orbitals and the energies of the molecular states next to these frontier orbitals from Tunneling Spectroscopy measurements. These measurements were performed using two different tip materials. The results are compared to UPS measurements, to theoretical calculations of the electronic conductance based on a combination of the Landauer transport formalism with a density-functional-parametrized tight-binding scheme within the Local Density Approximation (LDA) as well as semiempirical quantum chemistry calculations. / Für die hier dargestelleten Arbeiten wurde ein Au(100) Einkristall als Substrat für die organische Molekularstrahlepitaxie verwendet. Hochgeordnete organische Dünnschichten der Moleküle 3,4,9,10-Perylen-tetracarbonsäure-3,4,9,10-dianhydrid (PTCDA) und Hexa-peri-hexabenzo-coronen (HBC) sowie organisch-organische Heteroschichten wurden auf der Au(100) Oberfläche abgeschieden. Die Struktur der Schichten wurde mittels Rastertunnelmikroskopie (STM) und Niederenergetischer Elektronenbeugung (LEED) untersucht. Tunnelspektroskopiedaten wurden für Monolagen sowie Submonolagen von PTCDA aufgenommen. Messungen an geschlossenen PTCDA Filmen zeigen für verschiedene Probe-Spitze-Abstände ein Maximum in der normierten differentiellen Leitfähigkeit bei +0.95V. Aufeinanderfolgende Messungen auf PTCDA-Inseln und unbedeckten Gebieten der Au(100) Oberfläche zeigen eindeutig, dass dieses Maximum auf die PTCDA Moleküle zurückzuführen ist. Weitere Messungen an PTCDA Inseln unterschiedlicher Struktur (Fischgrätenstruktur bzw. quadratische Struktur) belegen einen Zusammenhang zwischen der Anordnung der Moleküle und der Peakposition bzw. Peakform in der normierten differentiellen Leitfähigkeit. Die STS Daten werden mit UPS und IPES Ergebnissen aus der Literatur verglichen. Im Falle hochgeordneter HBC Schichten auf Au(100) war es möglich, neben dem höchsten besetzten und niedrigsten unbesetzten Molekülorbital auch die energetische Position der jeweils nächsten Orbitale zu bestimmen. Diese Messungen wurden mit zwei unterschiedlichen Spitzenmaterialien durchgeführt. Die Ergebnisse für HBC auf Au(100) werden mit UPS Daten sowie mit theoretischen Rechnungen verglichen.