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The scanning tunneling microscope (STM) is one of the most advanced surface science tools capable of atomic resolution imaging and atomic manipulation. Unfortunately, STM has many time-consuming bottlenecks, like probe conditioning, tip instability, and noise artificing, which causes the technique to have low experimental throughput. This dissertation describes my efforts to address these challenges through automation and machine learning. It consists of two main sections each describing four projects for a total of eight studies. The first section details two studies on nanoscale sample fabrication and two studies on STM tip preparation. The first two studies describe the fabrication of graphene-based Josephson Junction devices and the factorial optimization of patterned carbon nanotube forest synthesis. The second two studies focus on the factorial optimization of electrochemical STM tip etching and automated STM tip functionalization via in-situ silicon nanocolumn growth. The second section details four studies on the use of neural networks for STM image and spectroscopy analysis. The third two studies are on the effectiveness of convolutional neural networks for identifying images of conditioned STM tips on the Au(111) surface and on the detection and metrology of atomic scale defects in single crystal tungsten diselenide, a transition metal dichalcogenide. The fourth two studies are on the use of variational autoencoders to autonomously classify scanning tunneling spectra of various materials, molecules, and surface structures and to identify bismuth and nickel atoms from cross sectional STM images of doped gallium arsenide.

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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.

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.