This works studies novel emergent quantum phases. Here, the local electronic structure of a spin-orbit assisted Mott insulator, Sr₂IrO₄ and of the member of the iron-based superconductors (IBS), Li doped NaFeAs, are investigated using low-temperature scanning tunnelling microscopy and spectroscopy (STM/S).

[pt] A integração do grafeno nos dispositivos nanoeletrônicos depende da disponibilidade de processos de deposição de forma direta sobre o substrato. A deposição direta pode fornecer grafeno uniforme, com alta qualidade e em grande área sobre substratos semicondutores como sílicio ou germânio. Nesta tese, foi sintetizado grafeno diretamente sobre germânio dopado tipo p e com uma orientação cristalina (100) empregando a deposição química na fase vapor. Foi estudada a influência da relação de fluxo entre os gases CH4 e H2 no crescimento de grafeno. As técnicas empregadas para verificar a qualidade das amostras e o tipo de crescimento obtido foram a espectroscopia Raman, microscopia de varredura eletrônica, de tunelamento e de força atômica, e a espectroscopia de tunelamento. Determinamos que para as condições empregadas, o crescimento de grafeno sobre germânio é autolimitado, com a deposição de apenas uma única camada, com poucos defeitos na sua rede cristalina e com o nível de Fermi característico de um material com dopagem tipo n. / [en] The integration of graphene into nanoelectronic devices is dependent on the availability of direct deposition processes, which can provide uniform, large-area and high-quality graphene on semiconductor substrates such as Ge or Si. In this dissertation, we synthesized graphene directly on ptype Ge(100) substrates by chemical vapor deposition. The influence of the CH4:H2 flow ratio on the graphene growth was investigated. Raman Spectroscopy, Raman mapping, Scanning Electron Microscopy, Atomic Force Microscopy and Scanning Tunnelling Microscopy/Scanning Tunnelling Spectroscopy were the techniques employed to verify the quality of the samples and the type of growth. We determined that for the conditions employed, the growth of graphene is self-limited, with only a single layer deposition, with few defects in its crystalline lattice and with Fermi level characteristic of a material with doping type n.

In multiband superconductors, different bands at the Fermi surface contribute to the superconductivity with different magnitudes of superconducting gaps on different portions of the Fermi surface. Each band in a multiband superconductor has a condensate with an amplitude and phase that weakly interacts with the other bands’ condensate. The coupling strength between the bands determines whether one or two superconducting transition temperatures are observed, and it is the key to many peculiar properties. In general, if there are two gaps of different magnitude, there are two different length scales associated with the suppression of these gaps in applied magnetic fields, for example. Therefore, effects of multigap superconductivity can be observed in superconducting vortices, which are twirls of supercurrents that are generated when a superconductor is placed in a magnetic field. Furthermore, the two superconducting order parameters in different bands are characterized by a magnitude and phase. In multiband superconductors, there are collective excitations corresponding to fluctuations of the relative phase of two order parameters, so-called the Leggett mode. The first material identified as multiband superconductor is Magnesium Diboride (MgB2) in 2001 with a critical temperature Tc of 39 K. MgB2 is a superconducting material with the highest transition temperature among all conventional BCS superconductors. It has two superconducting gaps \Delta_\pi ~ 2 meV and \Delta_\sigma\ ~ 7 meV and they arise from the existence of two bands \pi and \sigma bands of boron electrons. The discovery of superconductivity in MgB2 renewed interest in the field of multiband superconductivity. MgB2 has attracted many scientists’ attention both for the fundamental importance of understanding the multiband superconductivity and possible applications such as magnets, power cables, bolometers, Josephson junction-based electronic devices, and radio-frequency cavities. Afterward, other materials have been identified as multiband superconductors such as NbSe2, the family of iron-based superconductors, heavy fermion superconductors, multilayer cuprates, borocarbides, etc. This dissertation uses tunneling experiments to highlight multiband superconductivity features in two systems, namely MgB2 thin films and ultrathin films of Pb. Further, we use multiple techniques to study a superconducting material, nitrogen-doped niobium, used for superconducting radio-frequency cavities. For the project on MgB2, MgB2/Native-Oxide/Ag planar junctions are fabricated and characterized down to 2.1 K and in the magnetic field parallel to the sample surface up to 6 Tesla. This work investigates how pairbreaking affects the magnitude and phase of the order parameter in a multiband superconductor. The tunneling spectra are analyzed in the framework of a two-band model developed by our theory collaborator Prof. Alex Gurevich, Old Dominion University. The model allows the extraction of the pair-breaking parameters among other quantities. The analysis shows that the order parameter in the ? band is quickly suppressed in the field, the ? band is cleaner than the ? band. The ratio of pairbreaking parameter in the ? band to the ? band rapidly increases at fields higher than ~0.1 T and then plateau at higher fields. This transition around 0.1 T magnetic field suggests a phase decoupling in the two bands of MgB2. Below the transition, the two bands are phase-locked, so mostly, the superconductivity in the ? band is affected, and after phase decoupling, both bands are affected by the applied field. These results are important for a basic understanding of multiband superconductors and the application implications of this material. This phase decoupling has a new and profound consequence on the superconducting state of a multiband superconductor that has been theoretically predicted and never observed experimentally. For the Pb project, ultrathin films of Pb in ultrahigh vacuum conditions are deposited by e-beam evaporation and characterized with low-temperature scanning tunneling microscopy and spectroscopy (STM/STS). The STM/STS allows measuring the electronic density of states with the highest spatial resolution down to atomic scale. The shape of a superconducting vortex core is determined by the superconducting gap and the Fermi velocity, and the STM allows to map anisotropies of these quantities spatially. The vortex cores of Pb film show a complex shape that evolves from triangular at short distances from the center to a six-fold symmetric star shape farther away from the center. These details are very subtle, and they can be highlighted only if one works within the clean limit (to avoid the averaging effect of the scattering) and by fabricating the heterostructure that pins the vortices spatially. The complex vortex core shape reflects the anisotropy of the two bands that contribute to superconductivity in this material. For the project on Niobium, cold and hot spots from nitrogen-doped Nb cutouts are characterized by low temperature scanning tunneling microscopy and spectroscopy (STM/STS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The radiofrequency (RF) measurements of the quality factor and temperature mapping on an N-doped Nb superconducting resonator cavity are carried out at Jefferson Laboratory before cutting out the samples. This work aims to identify possible sources of excess dissipation in hot spots and relate them to the surface chemical composition and superconducting properties. The temperature mapping revealed a strong effect of the cavity cooldown rate on the intensities of hot spots and their spatial distribution, which indicates a significant contribution of trapped vortices to the RF dissipation. SEM images acquired on the cold and hot spots using a secondary electron detector show absence of residual hydride scars and niobium nitrides on their surface. Angle-resolved XPS measurements on the native surface of these samples revealed higher oxidized Nb 3d states on the N-doped Nb cold spots, which is supported by XPS depth profiles done on the samples by Argon ion sputtering. Argon ion sputtering of oxidized Nb removes oxygen preferentially from Nb2O5 and diffuses to bulk, thickening the lower oxidation state layers. The proximity theory framework’s tunneling spectra analysis suggests hot spots have stronger pairbreaking due to a weakly reduced pair potential, a thicker metallic suboxide layer, and a wide distribution of the contact resistance. STM imaging of vortex cores shows a triangular vortex lattice in both samples, and the coherence length is nearly the same in hot and cold spots. The experimental data analysis suggests weakly degraded superconducting properties at the surface of hot spot regions are not the primary sources of RF losses. Instead, they are the regions where vortices nucleate first and get trapped during cooling down. These experimental techniques and findings will be crucial in helping to qualify new recipes for SRF cavity production and to boost their performance. / Physics

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.

Dans cette thèse, nous avons abordé par la microscopie/spectroscopie tunnel l'étude de deux phénomènes mettant en jeu les interactions entre électrons : la supraconductivité et la transition Métal/Isolant de Mott. L'étude par microscopie/spectroscopie tunnel du graphite intercalé supraconducteur CaC6 a permis qu'il s'agissait d'un supraconducteur bien décrit par la théorie BCS conventionnelle, avec un gap à température nulle de 1,6+/0,2 meV. Toutefois, un léger élargissement des structures spectroscopiques témoignait d'une légère anisotropie du paramètre d'ordre dans le plan ab. Nous avons pu extraire par l'imagerie du réseau de vortex une longueur de cohérence extrapolée à température nulle de 38 nanomètres. La seconde partie du manuscrit est constitué par l'étude de la transition Isolant-Métal induites par pulses électriques dans GaTa4Se8, qui est un isolant de Mott faible, proche de la transition Isolant Métal. L'application du pulse électrique entraine l'apparition de zones métalliques dans une matrice isolante au sein du volume du matériau, ce qui fournit une explication des modèles phénoménologiques développés suite aux mesures de transport. De plus, l'application de rampes de tension lors des mesures spectroscopiques induit une transition Isolant-Métal locale, et pour des tensions encore plus élevées (V > 1.0V), on observe un gonflement de la surface sous l'effet du champ électrique. L'étude du composé dopé en électrons de formule Ga0,91Zn0,15Ta4Se8 montre que si le dopage induit effectivement une métallicité, la transition observée sous pulse se rapproche plus d'une transition induite par une modification du rapport t/U que d'une transition induite par dopage. Ce manuscrit pose la question de savoir si ces phénomènes sont intrinsèques à GaTa4Se8 ou généralisables aux autres isolants de Mott faibles.

Afin de mieux comprendre les différents processus qui apparaissent à la transition supraconducteur-isolant (SIT), nous avons sondé simultanément les propriétés électroniques globales et locales de films minces de NbN, élaborés ex-situ sur un substrat de saphir. La transition a été approchée en réduisant l'épaisseur des échantillons, augmentant la résistance par carré de l'état normal à plusieurs kiloOhms. Les Tc correspondant aux films étudiés varient de Tc≈15K qui est proche de TC-bulk à Tc≈3.8K (Tc/TC-bulk≈0.23). Dans la gamme 0.4TC-bulk<Tc<TC-bulk, les mesures de résistances sont en accord avec la loi de Finkelstein pour la réduction de Tc induite par le désordre et les interactions électron-électron. Les mesures de spectroscopie tunnel locale (STS) montrent l'émergence d'une granularité dans les propriétés supraconductrices en réduisant la Tc, ainsi que le développement d'un fort fond Altshuler-Aronov dans les spectres tunnel dI/dV(V), ce qui est en accord avec le scenario de Finkelstein. Pour l'échantillon le plus désordonné (Tc≈3.8K), des mesures de résistance in-situ et de STS en simultané nous ont permis de suivre sur la même zone de l'échantillon, l'évolution des propriétés supraconductrices en fonction de la température et du champ magnétique, qui ont démontré un comportement percolatif de la transition dans l'état normal de mauvais métal. Cette étude locale a été confirmée par le changement de dimensionnalité des fluctuations Aslamasov-Larkin au-dessus de Tc de 2D à 0D. En outre, une telle étude est particulièrement intéressante pour comprendre les différents phénomènes qui limitent le fonctionnement des détecteurs de photon unique basé sur les films de NbN. / In order to better understand the various processes taking place at the superconductor-insulator transition (SIT), we have probed simultaneously the global and local electronic properties of NbN ultrathin films, elaborated ex-situ on sapphire substrate. The transition was approached by reducing the films thickness, increasing the normal state square resistance to several kiloOhms. The corresponding Tc's of the studied films ranged from about Tc≈15K, which is close to TC-bulk, to Tc≈3.8K (Tc/TC-bulk≈0.23). In the range 0.4TC-bulk<Tc<TC-bulk resistivity measurements are consistent with Finkelstein's reduction of Tc induced by disorder and electron-electron repulsion. Local scanning tunneling spectroscopy (STS) measurements show the emergence of granularity in the superconducting properties upon Tc reduction, as well as the progressive development of a strong Altshuler-Aronov background in the dI/dV(V) tunneling spectra, in agreement with Finkelstein scenario. For the most disordered film (Tc≈3.8K), simultaneous in-situ resistivity and STS measurements allowed us to follow at the same sample area the evolution of these emergent granular superconducting properties as a function of temperature and magnetic field, which demonstrate a percolative behavior of the transition to the bad-metal normal state. This local picture finds an interesting signature in the change of the dimensionality of the Aslamasov-Larkin fluctuations above Tc from 2D to 0D. Besides, such a study is particularly interesting to better understand the various phenomena occurring in and limiting the behavior of single-photon detectors patterned out of NbN films.

Ce travail de thèse s’est inscrit dans un cadre fondamental d’étude de la formation contrôlée d’oxydes en couches ultra-minces. Un bâti ultra-vide dédié à la croissance contrôlée de ces oxydes et à leur analyse in-situ (STM-STS, AES et LEED) a été développé. Par une méthode originale de phases alternées de dépôt d’une monocouche atomique de Mg et oxydation à RT, les mécanismes impliqués dans la formation de deux systèmes à fort potentiel applicatif : MgO/Si(100) et MgO/Ag(111) ont été étudiés .Le système MgO/Si(100) a révélé la formation d’une couche ultra-mince de Mg2Si à l’interface entre le MgO et le substrat. En bon accord avec les calculs thermodynamiques réalisés, une cristallisation de cette couche interfaciale dans un processus de dissociation partielle du Mg2Si en MgO à température ambiante a été observée. Identifiée ex-situ par TEM, la relation d’épitaxie associée à cette cristallisation a permis de conclure à la formation d’une hétérostructure MgO / Mg2Si (11-1) / Si(001), témoignant d’une grande qualité d’interface avec le silicium et de la formation d’une couche ultra-mince et amorphe de MgO homogène et isolante (gap de 6 eV).Pour le système MgO/Ag(111), nos résultats expérimentaux couplés aux calculs ab initio de nos partenaires du LAAS ont révélé l’absence de formation d’un alliage de surface ainsi qu’une croissance « liquid-like » du magnésium à RT. Un double empilement O/Mg/O/Mg/Ag(111) suivi d’un recuit UHV à 430°C a ensuite permis la stabilisation d’une couche ultra-mince polaire de MgO(111) qui a été caractérisée par LEED et STM-STS. Les propriétés physico-chimiques et origines possibles de stabilité de cet oxyde polaire ont ensuite été discutées. / This PhD work was dedicated to studying the fundamental mechanisms driving the controlled growth of ultra-thin oxide films. An experimental set-up was designed to finely control the growth parameters under UHV conditions while allowing the study of such oxide layers in situ with STM-STS, AES and LEED. Using an original method based on alternate cycles of Mg monolayer adsorption and RT oxidation, we focused on the formation of systems exhibiting a wide range of potential applications: MgO/Si(100) and MgO/Ag(111). The MgO/Si(100) system revealed the growth of an ultra-thin Mg2Si layer at the interface between the MgO and the silicon. In agreement with thermodynamic calculations, a crystallization of this interlayer driven by a partial decomposition of the Mg2Si to a MgO oxide was shown to occur at RT. From ex situ TEM experiments, the involved epitaxial relationship highlighted the formation of an MgO / Mg2Si (11-1) / Si(001) heterostructure. A sharp interface with the silicon was formed, as much as an ultra-thin and amorphous MgO layer exhibiting both a good homogeneity and a high insulating character (bandgap of 6 eV).In the MgO/Ag(111) system, no interfacial alloy formation and a « liquid-like » growth for the Mg were evidenced at RT, using our experimental results coupled with the ab initio calculations performed by our co-workers at LAAS laboratory. Later, a double-layering O/Mg/O/Mg/Ag(111) grown at RT followed by UHV annealing at 430°C resulted in the stabilization of a polar MgO(111) ultra-thin film, which was characterized using LEED and STM-STS. The physicochemical properties of this polar oxide and the potential origin of its stability were discussed.

Trotz einer Vielzahl von Forschungsarbeiten auf dem Gebiet der Phthalocyanin-basierten organischen Verbindungen fehlt nach wie vor ein umfassendes Verständnis des Zusammenspiels zwischen strukturellen und elektronischen Eigenschaften, die sich bei der Abscheidung dieser Stoffe auf anorganische kristallinen Substraten ausbilden. Vor diesem Hintergrund wurden für die vorliegende Arbeit vier metallbasierte Phthalocyanine ausgewählt und mittels organischer Molekularstrahl-Abscheidung (OMBD) im Ultrahochvakuum (UHV) auf Ag (111) Einkristalle adsorbiert. Für die anschließende eingehende Untersuchung dieser Proben wurden insbesondere Rastertunnelmikroskopie (STM) und -spektroskopie (STS) angewandt. Ergänzend kamen Ultraviolett- und Röntgen-Photoelektronenspektroskopie (UPS und XPS) zum Einsatz, wodurch komplementäre Informationen gewonnen wurden. Die aus diesen Untersuchungen resultierenden Ergebnisse liefern einen wesentlichen Beitrag zum oben genannten Forschungsgebiet. Die in dieser Arbeit untersuchten Metall-Phthalocyanine (MePc) wurden so ausgewählt, dass eine möglichst große Vielfalt an geometrischen und elektronischen Eigenschaften abgedeckt wurde. Planare cobaltbasierte Phthalocyanin-Moleküle wurden in zwei Konfigurationen untersucht: einerseits das protonierte CoPc, das sich als organischer p-Halbleiter verhält, und andererseits das vollständig fluorinierte F16CoPc, das n-Halbleitereigenschaften besitzt. Bei beiden Systemen zeigte sich an der Position des Cobaltions eine Kopplung zwischen den Molkülorbitalen des Adsorbats und den Elektronenzuständen des Substrates. Das nichtplanare Zinn-Phthalocyanin ist von besonderem Interesse aufgrund seiner beiden möglichen Adsorptionskonformationen up und down, bei denen sich das Sn-Ion oberhalb beziehungsweise unterhalb des Phthalocyaninliganden befindet. Damit stellt dieses System einen möglichen Kandidaten für Anwendungen als molekularer Schalter oder als Speichereinheit dar. In der vorliegenden Studie werden lokalisierte Schaltvorgänge einzelner Moleküle zusammen mit der Möglichkeit einer kontrollierten molekularen Nanostrukturierung gezeigt. Lutetium (III) bisphthalocyanin wurde ausgewählt als Vertreter einer neuen Gruppe von MePc, die eine Sandwichstruktur ausbilden, bei der zwei π-konjugierte Phthalocyaninliganden über ein Seltenerd-Ion miteinander verbunden sind. Die Untersuchung dieses Systems liefert wichtige neue Erkenntnisse, wie zum Beispiel ein umfassendes Verständnis der Vorgänge bei der Selbstassemblierung innerhalb der ersten und zweiten organischen Monolage. Zudem wurde bei der Charakterisierung des Tunneltransports durch einzelne Moleküle mittels STS ein negativer differentieller Widerstand (NDR) gefunden, der von der Anzahl molekularer Lagen abhängt.