This thesis explores structural and electronic properties of layered materials at the nanometre scale. Room temperature and low temperature ultrahigh vacuum scanning probe microscopy (scanning tunneling microscopy, scanning tunneling spectroscopy, atomic force microscopy) is used as the primary characterization method. The main findings in this thesis are: (a) observations of the atomic lattice and imaging local lattice defects of semiconducting ReS2 by scanning tunneling microscopy, (b) measurement of the electronic band gap of ReS2 by scanning tunneling spectroscopy, and (c) scanning tunneling microscopy study of 1T-TaS2 lattice and chemically functionalizing its defects with magnetic molecules.

Les isolants topologiques 3D sont un nouvel état de la matière décrit par un volume iso-lant électriquement et recouvert par des états de surface métalliques. Une jonction Joseph-son topologique (TJJ) formée autour de ces états de surface peut théoriquement contenirun mode lié d’Andreev ayant une périodicité doublée par rapport aux modes liés d’An-dreev conventionnels 2p périodiques. Le mode d’Andreev 4p périodique serait la briqueélémentaire de l’ordinateur quantique topologique. Ainsi, nous étudions la dynamique dece mode particulier lors de mesures de Shapiro sur des jonctions Josephson fabriquées surdes isolants topologiques à base de bismuth.A?n d’identi?er les e?ets d’un mode 4p-périodique dans une mesure de Shapiro, nousutilisons un model phénoménologique permettant de simuler la caractéristique courant-tension d’une TJJ lors de telles mesures. Nous prédisons deux signatures du mode 4p-périodique et estimons leur robustesse face aux e?ets de chau?age par e?et Joule et face àun modèle d’empoisonnement thermiquement activé du mode 4p-périodique.Par des mesures de Shapiro, nous étudions la dynamique des TJJ basées sur le matériausimple qu’est le Bi2Se3. L’observation des deux mêmes signatures précédemment anticipéespar nos simulations, à savoir un ordre d’apparition non conventionnel des pas de Shapiroainsi que la persistance d’un supercourant à la fermeture du plateau de Shapiro n = 0prouve la présence d’un mode 4p-périodique.Notre étude s’est également portée sur un autre isolant topologique le BiSbTeSe2. Nousavons e?ectué sa croissance par cristallisation liquide-solide et avons mis en évidence,par des mesures d’interférométrie supraconductrice une supraconductivité de surface sanstransport électronique par le volume. / Three dimensional topological insulators (3D TI) are a new state of matter composedof an electrically insulating bulk covered by metallic surface states. Theoretically, a topo-logical Josephson junction composed of these surface states can host an Andreev Boundstate (ABS) that has twice the periodicity of the conventional 2p periodic ABSs. The4p periodic ABS is expected to be the building block of topological quantum computing.Therefore, we study the dynamic of this particular ABS by performing Shapiro measure-ment on Josephson junctions built with bismuth based 3D TI.To identify the e?ects of a 4p periodic ABS in a Shapiro measurement, we use a phe-nomenological model that simulates the voltage-current characteristics of a TJJ. We predicttwo signatures of the 4p periodic ABS and estimate their robustness against Joule heatingand thermally activated quasiparticle poisoning of the 4p periodic mode.We study the Josephson junctions dynamics by performing Shapiro measurements onjunctions built on Bi2Se3. We observe the two previously anticipated signatures, whichare the non-conventional appearance order of the Shapiro steps and the remaining of asupercurrent at the closing of the Shapiro step n = 0. They prove the presence of a 4pperiodic ABS.We also study the topological insulator BiSbTeSe2 that we have grown by using themelting growth method. By superconducting interferometric measurements, we show asuperconducting surface transport without bulk electronic conduction.

Submitted by LUIZ HENRIQUE BUGATTI GUESSI null (lhbguessi@gmail.com) on 2016-03-05T22:01:32Z No. of bitstreams: 1 Dissertação_Final_full_Luiz_Henrique_Guessi.pdf: 8393900 bytes, checksum: 733e3b310e036a5d66ec11c8c11f985e (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-03-07T18:18:44Z (GMT) No. of bitstreams: 1 guessi_lhb_me_rcla.pdf: 8393900 bytes, checksum: 733e3b310e036a5d66ec11c8c11f985e (MD5) / Made available in DSpace on 2016-03-07T18:18:44Z (GMT). No. of bitstreams: 1 guessi_lhb_me_rcla.pdf: 8393900 bytes, checksum: 733e3b310e036a5d66ec11c8c11f985e (MD5) Previous issue date: 2016-02-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Foi discutido teoricamente a Densidade Local de Estados (LDOS) de uma folha de grafeno hospedando duas impurezas distantes localizadas no centro da célula hexagonal. Ao acoplar lateralmente a ponta do Microcópio de Varredura por Tunelamento (STM) sobre o átomo de carbono, dois novos notáveis efeitos foram detectados: i) uma estrutura de multiníveis na LDOS e ii) padrões de batimentos na LDOS induzida. Também foram mostrados que ambos os fenômenos ocorrem próximos aos pontos de Dirac e são altamente anisotrópicos. Além disso, foram propostos experimentos de condutância empregando o STM como uma sonda para a observação de tais manifestações exóticas na LDOS do grafeno induzida pela correlação entre as impurezas. / We discuss theoretically the Local Density of States (LDOS) of a graphene sheet hosting two distant adatoms located at the center of the hexagonal cells. By putting laterally a Scanning Tunneling Microscope (STM) tip over a carbon atom, two remarkable novel effects can be detected: i) a multilevel structure in the LDOS and ii) beating patterns in the induced LDOS. We show that both phenomena occur nearby the Dirac points and are highly anisotropic. Furthermore, we propose conductance experiments employing STM as a probe for the observation of such exotic manifestations in the LDOS of graphene induced by inter-adatoms correlations.

abstract: Charge transport in molecular systems, including DNA (Deoxyribonucleic acid), is involved in many basic chemical and biological processes. Studying their charge transport properties can help developing DNA based electronic devices with many tunable functionalities. This thesis investigates the electric properties of double-stranded DNA, DNA G-quadruplex and dsDNA with modified base. First, double-stranded DNA with alternating GC sequence and stacked GC sequence were measured with respect to length. The resistance of DNA sequences increases linearly with length, indicating a hopping transport mechanism. However, for DNA sequences with stacked GC, a periodic oscillation is superimposed on the linear length dependence, indicating a partial coherent transport. The result is supported by the finding of delocalization of the highest occupied molecular orbitals of Guanines from theoretical simulation and by fitting based on the Büttiker’s theory. Then, a DNA G4-duplex structures with a G-quadruplex as the core and DNA duplexes as the arms were studied. Similar conductance values were observed by varying the linker positions, thus a charge splitter is developed. The conductance of the DNA G-tetrads structures was found to be sensitive to the π-stacking at the interface between the G-quadruplex and DNA duplexes by observing a higher conductance value when one duplex was removed and a polyethylene glycol (PEG) linker was added into the interface. This was further supported by molecular dynamic simulations. Finally, a double-stranded DNA with one of the bases replaced by an anthraquinone group was studied via electrochemical STM break junction technique. Anthraquinone can be reversibly switched into the oxidized state or reduced state, to give a low conductance or high conductance respectively. Furthermore, the thermodynamics and kinetics properties of the switching were systematically studied. Theoretical simulation shows that the difference between the two states is due to a difference in the energy alignment with neighboring Guanine bases. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

Nos últimos 30 anos o crescimento paralelo das Ciências de Superfície tradicionais, em ambiente de ultra-alto vácuo (UHV), com a Eletroquímica levou ao nascimento de um novo campo interdisciplinar: Física de Superfície e Eletroquímica. Técnicas de ambas as áreas dão informações complementares e assim, quando realizadas em conjunto podem fornecer muitas respostas em nível atômico, estrutural e eletrônico quando o eletrodo está em contato com a solução eletrolítica. A intenção primordial dessa Dissertação foi o estudo fundamental das fases ricas em oxigênio presentes na superfície de Ru(0001) através de caracterizações eletroquímicas e morfológicas utilizando um sistema que permitiu o acoplamento de uma célula eletroquímica miniatura de fluxo a câmaras de UHV. Inicialmente exibi-se a modificação e a construção de equipamentos necessários para a preparação do sistema binário Au-Pt(111) e do óxido monocristalino Ru2O(110). Imagens de STM em escala morfológica mostraram o crescimento anisotrópico do filme de RuO2(110) sobre um substrato monocristalino de Ru(0001). Resultados obtidos através da técnica de Voltametria Cíclica na eletrooxidação de CO em RuO2(110) corroboraram cálculos teóricos sobre a estrutura da superfície quando esta em ambiente úmido. Superfícies modelos baseadas em ouro, crescido epitaxialmente sobre um substrato de Pt(111), foram preparadas no sistema de UHV. Dados eletroquímicos foram correlacionados às composições superficiais destas, mostrando o efeito do substrato prevalecendo sobre o efeito eletrônico. / In the last 30 years the parallel growth of the traditional Surface Science, under UHV environment, and Electrochemistry gave rise to a new interdisciplinary field: Surface Science and Electrochemistry. Techniques from both sciences give complementary information. Thus, in tandem, they are able to elucidate many atomic, structural and electronic phenomena, of an electrode in contact with a solution. The main goal of this Dissertation was the fundamental study of the Oxygen-rich Ru(0001) surface through electrochemical and morphologic characterizations using a coupled system which allowed the attachment of a miniature flow cell to UVH-chambers. Initially it is shown the construction and modifications of required equipments for the preparation of the binary system Au-Pt(111) and single crystal RuO2(110) oxide. Attainable morphological STM images demonstrated the anisotropic growth of the RuO2(110) over a Ru(0001) substrate. Results of the electrooxidation of CO on RuO2(110), obtained by means of Cyclic Voltammetry, corroborated theoretical calculations concerning the oxide superficial structure in a humid environment. Model surfaces based on Au, epitaxialy grown on a Pt(111) substrate, were prepared under UHV conditions. Electrochemical data and superficial composition were correlated, confirming that the substrate effect overcomes electronic strain effects.

The ability to isolate single atomic layers of van der Waals materials has led to renewed interest in the electronic and optical properties of these materials as they can be fundamentally different at the monolayer limit. Moreover, these 2D crystals can be assembled together layer by layer, with controllable sequence and orientation, to form artificial materials that exhibit new features that are not found in monolayers nor bulk. Twisted bilayer graphene is one such prototype system formed by two monolayer graphene layers placed on top of each other with a twist angle between their lattices, whose electronic band structure depends on the twist angle. This thesis presents the efforts to explore the electronic and optical properties of twisted bilayer graphene by Raman spectroscopy and scanning tunneling microscopy measurements. We first synthesize twisted bilayer graphene with various twist angles via chemical vapor deposition. Using a combination of scanning tunneling microscopy and Raman spectroscopy, the twist angles are determined. The strength of the Raman G peak is sensitive to the electronic band structure of twisted bilayer graphene and therefore we use this peak to monitor changes upon doping. Our results demonstrate the ability to modify the electronic and optical properties of twisted bilayer graphene with doping. We also fabricate twisted bilayer graphene by controllable stacking of two graphene monolayers with a dry transfer technique. For twist angles smaller than one degree, many body interactions play an important role. It requires eight electrons per moire unit cell to fill up each band instead of four electrons in the case of a larger twist angle. For twist angles smaller than 0.4 degree, a network of domain walls separating AB and BA stacking regions forms, which are predicted to host topologically protected helical states. Using scanning tunneling microscopy and spectroscopy, these states are confirmed to appear on the domain walls when inversion symmetry is broken with an external electric field. We observe a double-line profile of these states on the domain walls, only occurring when the AB and BA regions are gaped. These states give rise to channels that could transport charge in a dissipationless manner making twisted bilayer graphene a promising platform to realize controllable topological networks for future applications.

Les nanostructures auto-organisées sont essentielles dans le domaine des nanotechnologies, car elles fournissent un moyen simple de créer des structures périodiques avec des dimensions nanométriques. Dans ce travail, nous introduisons une nouvelle méthode de préparation de la surface Cu(110)-(2×1)O, qui permet un contrôle de sa morphologie. La périodicité varie de 6.5 à 11 nm pour recouvrement en oxygène entre 0.1 et 0.4 (saturation est 0.5). On a obtenu des périodicités allant jusqu'au 100 nm. La préparation est basée sur la pré-adsorption de faibles quantités de soufre. La présence de soufre change les propriétés élastiques et/ou électrostatiques de la surface et modifie ainsi son auto-organisation. Nous avons effectué une étude détaillée au moyen de la microscopie à effet tunnel (STM) et développé un modèle mathématique décrivant nos données expérimentales. Une surface auto-organisée accordable fournit un système idéal pour étudier l'interaction entre la réactivité et la structure. Nous avons étudié la sulfuration sur la surface nanostructurée, Cu(110)-(2×1)O. Le mécanisme réactionnel dépend de la largeur des bandes oxydées. Sulfuration d'une nanostructure à bandes CuO étroites conduit au détachement de chaînes reconstruites Cu-O et dans le cas de bandes larges, le mécanisme réactionnel est une combinaison du détachement de chaînes et de la formation d'îlots de la phase S-c(2×2) sur les bandes CuO. Nous présentons une étude STM de la formation de ces îlots, ainsi que leur stabilité sous ultra vide. Les îlots sont mobiles et subissent une maturation (Ostwald et Smoluchowski). Dans le cas d'une surface pas complètement saturé, les îlots disparaissent progressivement. / Self-organized nanostructures are essential for the field of nanotechnology, since they provide a simple way to create periodic structures with nanodimensions. In the present work, we have developed a new preparation method for the Cu(110)-(2×1)O nanostructure, which allows tuning of its morphology. For oxygen coverages between 0.1 and 0.4 (saturation coverage 0.5), the periodicity of the nanostructure varies from 6.5 to 11 nm. We have been able to expand the possibilities of the system and reach periodicities up to 100 nm for half oxygen coverage. The preparation method consists in co-adsorption of low amounts of sulfur. We have shown that the presence of sulfur influences the elastic and/or electrostatic properties of the surface and thus changes its self-organization. We present a detailed scanning tunneling microscopy (STM) study of this new preparation method and a mathematical model describing our experimental data. A tunable self-organized surface provides an ideal playground for testing the reactivity and structure interplay. We introduce a study of the sulfidation of the nanostructured Cu(110)-(2×1)O surface. The reaction mechanism has been found to depend on the width of the oxidized stripes. Sulfidation of narrow CuO stripes proceeds via Cu-O chain abstraction and in the case of wide CuO stripes, the reaction mechanism is a combination of the chain detachment and S-c(2×2) island formation on the CuO stripes. We present a thorough STM study of the S island formation and their stability under UHV conditions. The S islands are mobile and undergo ripening (Ostwald and Smoluchowski). Additionally, island decay has been observed for sub-saturation S coverages.

Dans les supraconducteurs de type II, le champ magnétique pénètre le matériau sous forme de vortex, tourbillon de courants supraconducteurs circulant autour d'un c¿ur normal. Dans les travaux de cette thèse, nous montrons comment le confinement d'un système à une échelle comparable à la longueur de cohérence ? nanométrique modifie sensiblement ses propriétés supraconductrices.Cette étude est menée dans des nanostructures de plomb déposé in-situ sur un substrat de silicium (111), puis mesurées par spectroscopie à effet tunnel, sous UHV, à 300 mK et sous champ magnétique.En confinement extrême (taille latérale D<<10 ?), le système créé des vortex Géants, objets quantiques prédits théoriquement depuis 45 ans. En confinement plus faible (D~10 ?), les vortex peuvent être piégés, s'organisent ensuite en réseau triangulaire d'Abrikosov, puis s'interpénètrent avec le champ magnétique croissant.Les îlots de Pb cristallins supraconducteurs sont reliés entre eux par une monocouche de mouillage de Pb, ici désordonnée et non supraconductrice. Au voisinage des îlots, cette couche acquiert des caractéristiques spectroscopiques spécifiques qui reflètent la supraconductivité induite par proximité et les interactions entre électrons de type Altshuler-Aronov. L'évolution spatiale des spectres tunnel sont simulés en combinant les équations d'Usadel et la théorie du blocage de Coulomb dynamique.En réduisant la distance entre les îlots, l'effet de proximité autour de chacun se recouvre, ce qui forme une jonction Josephson. Sont étudiés finement le nombre, la position, le spectre et la forme des c¿urs de vortex Josephson sous champ magnétique, à travers une grande panoplie de jonctions. / In type II superconductors, the applied magnetic field penetrates the material in quanta of flux called vortices, vortices of superconducting currents circulating around a normal core. In the work of this thesis, we show how the confinement of a system to a scale comparable to the nanometric coherent length ? substantially modifies its superconducting properties.This study is carried out in nanostructures of lead deposited in-situ on a silicon (111) substrate, then studied by scanning tunneling spectroscopy, under UHV, at 300 mK, and under magnetic field. In extremely confinement (lateral size D<<10 ?), systems create Giant vortices, quantum objects predicted 45 years ago. In the weakly confinement (D~10 ?), vortices may be pinned, then are organized in the triangular Abrikosov lattice, finally interpenetrate in surface superconductivity with the increasing magnetic field. Crystalline superconducting Pb islands are here connected by a disordered non-superconducting wetting layer of Pb. In the vicinity of each superconducting island, the wetting layer acquires specific tunnelling characteristics which reflect the interplay between the proximity induced superconductivity and the inherent electron correlations of this ultimate diffusive two-dimensional metal. Spatial evolution of the tunnel spectra are simulated by combining the Usadel equations and the theory of dynamic Coulomb blockade. With reducing the distance between the islands, the proximity effect around each overlaps and forms a Josephson junction. Thanks to the tunneling spectroscopy, number, position, the spectrum and the form of Josephson vortex cores are studied in detail for a large variety of junctions.

Orientador: Abner de Siervo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-24T13:15:36Z (GMT). No. of bitstreams: 1 Fatayer_ShadiPassam_M.pdf: 3223190 bytes, checksum: f98805b3695907c808260ec6d392c1b8 (MD5) Previous issue date: 2014 / Resumo: O estudo de sistemas moleculares em cima de substratos metálicos tem atraído uma crescente atenção da comunidade científica. O melhor entendimento sobre as características de auto-organização e a habilidade de controlá-las em moléculas tem gerado formas mais baratas e rápidas de usar a abordagem bottom-up em nanociência. Dentre os diversos estudos feitos, podemos citar o desenvolvimento de sensores de gás que utilizam do sinal magnético de uma camada auto-organizada de moléculas e da ligação de pequenas moléculas como CO ou NO que promovem a emergência de magnetismo na amostra. Outro aspecto interessante do estudo de sistemas moleculares se encontra na similariedade das moléculas que podem ser utilizadas com moléculas encontradas nos processos recorrentes na natureza, por exemplo, as clorofilas e hemoglobinas. Isto significa que ao estudar moléculas simples é possível mimetizar um comportamento parecido com o das moléculas citadas. Neste sentido, em nosso trabalho estudamos dois tipos de moléculas ¿ Porfirinas e Ftalocianinas ¿ e as propriedades estruturais quando depositadas em diferentes substratos metálicos. As porfirinas foram analisadas em uma superfície de baixo índice de Miller, Cu(111), e tiveram seu comportamento comparado com o análogo em superfícies vicinais, Au(332) e Au(788). As porfirinas formam estruturas em 1D quando depositadas em pequenas quantidades, dependendo da natureza do substrato e a largura de seu terraço. Em maiores coberturas, as porfirinas formam diferentes estruturas de empacotamento fechado em 2D, de simetrias quadrada e paralelogrâmica. Eletronicamente observou-se a modificação do entorno químico do níquel quando a molécula de NiTPP é adsorvida no Cu(111). As ftalocianinas foram depositadas em diferentes substratos visando a produção de co-organização de dois tipos de moléculas num padrão tabuleiro de xadrez. Após a obtenção do padrão de tabuleiro de xadrez, nós realizamos experimentos para elucidar os mecanismos que possibilitam formar tais estruturas. Com o intuito de estudar auto-organização molecular, nós empregamos técnicas sensíveis a superfícies como a Microscopia de Tunelamento, Espectroscopia de Tunelamento e Espectroscopia de Fotoemissão por Raios-X. Tais técnicas possibilitam a obtenção das propriedades estruturais e eletrônicas das nanoestruturas formadas / Abstract: The study of molecular systems on top of metal substrates has gathered increased atten-tion of the scientific community. Better understanding over different self-assembly haracteristics and the ability to control them in molecules has led to the development of quicker and cheaper routes of the use of the bottom-up approach in nanoscience. Among the diverse studies, we can cite the development of gas sensors that use the mag-netic signal of a self-assembled layer of molecules and the eventual binding of small molecules such as CO or NO leading to the emergence of magnetism on the sample. Another interesting aspect of the study of molecular systems is the similarity of molecules commonly used with molecules found in nature processes, e.g. chlorophylls and hemeglobins. This means that by studying simple molecules one can try to mimic the natural processes of those natural molecules. In this sense, in our work we have studied two classes of molecules ¿ Porphyrins and Phthalocyanines ¿ and their structural properties when deposited on different metal substrates. The porphyrins were analyzed on a low-index miller surface, Cu(111) and compared to their be-havior when deposited on vicinal substrates, Au(332) and Au(788). The porphyrins were ob-served to form 1D structures when deposited in small quantities depending on the nature of the substrate and its terrace width. At higher coverages, porphyrins formed different close-packed 2D structures, with square and parallelogram symmetry. Electronically was observed the modifica-tion of the chemical environment of nickel when NiTPP is adsorbed on Cu(111). The phthalo-cyanines were deposited on different substrates as well, towards the goal of producing co-assembling of two types of molecules as chessboard arrays. After the chessboard array was obtained, we gathered knowledge about the mechanisms that formed such structures. Towards the goal of studying molecular self-assembly, we have employed proper surface sensitive techniques such as Scanning Tunneling Microscopy, Scanning Tunneling Spectroscopy and X-Ray Photoelectron Spectroscopy. Such techniques allowed us to obtain the structural and electronic properties of the nanostructures formed / Mestrado / Física / Mestre em Física

The electronic and magnetic properties of nanographenes strongly depend on their size, shape and topology. While many nanographenes present a closedshell electronic structure, certain molecular topologies may lead to an open-shell structure. Triangular-shaped nanographenes with zigzag edges, which exist as neutral radicals, are of considerable interest both in fundamental science and for future technologies aimed at harnessing their intrinsic high-spin magnetic ground states for spinbased operations and information storage. Their synthesis, however, is extremely challenging owing to the presence of unpaired electrons, which confers them with enhanced reactivity. We report a combined in-solution and onsurface synthesis of π-extended triangulene, a non-Kekulé nanographene with the structural formula C33H15, consisting of ten benzene rings fused in a triangular fashion. The distinctive topology of the molecule entails the presence of three unpaired electrons that couple to form a spin quartet ground state. The structure of individual molecules adsorbed on an inert gold surface is confirmed through ultrahigh-resolution scanning tunneling microscopy. The electronic properties are studied via scanning tunneling spectroscopy, wherein unambiguous spectroscopic signatures of the spin-split singly occupied molecular orbitals are found. Detailed insight into its properties is obtained through tight-binding, density functional and many-body perturbation theory calculations, with the latter providing evidence that π-extended triangulene retains its open-shell quartet ground state on the surface. Our work provides unprecedented access to open-shell nanographenes with high-spin ground states, potentially useful in carbon-based spintronics.