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 origin of the nematic phase in the iron-based superconductors is still unknown, and an understanding of its microscopic mechanism could have important implications on the unconventional superconductivity in these materials. This thesis describes a series of experiments using scanning tunneling microscopy (STM) and spectroscopy (STS) to visualize the nematic electronic structure in NaFe1-xCoxAs as a function of energy, temperature, strain, and doping. We first start with background material on the iron-based superconductors and the iron pnictides in particular. We then extensively explore the physical details of NaFe1-xCoxAs which is the main material of study in this thesis. Additional attention is paid to the electronic structure due to its relation to quasiparticle interference (QPI) measurements made with STS. The theoretical underpinnings of STM and STS are then derived as well as further details of QPI. Many of the experiments described in this thesis were performed on a custom-built, low temperature STM which the author helped build. We describe the design of this system and report on benchmarking tests that were used to characterize the system's performance. Both pristine, undoped NaFeAs and LiFeAs were measured by STM, and we compare and contrast these two materials which come from the same structural family. The electronic local density of states (LDOS) of NaFeAs was measured at various temperatures in all three phases of the material (tetragonal paramagnetic, orthorhombic paramagnetic, and orthorhombic spin density wave (SDW)). The electronic structure in the SDW phase is highly anisotropic. QPI signals in this phase are found to be well-explained by comparison to a joint density of states (JDOS) model using the reconstructed bandstructure fit to angle-resolved photoemission spectroscopy data. The electronic anisotropy is found to persist into the nominally tetragonal phase. This persistence arises from built-in crystallographic strain coupling to high amplitude, unidirectional, antiferroic fluctuations. These fluctuations renormalize the bare Green's function which gives rise to anisotropic scattering. We then describe the construction of a novel device created for variable-strain STS. Antiphase domains in NaFeAs are visualized and found to change in size as a function of unidirectional strain. These domains are tracked as a function of temperature and found to disappear at exactly the nematic transition temperature proving that this is the temperature at which long-range order is lost. By measuring Co-doped samples, we find that the domains disappear before optimal doping in an underdoped sample with superconducting transition temperature of 18 K. However, the electronic structure remains anisotropic implying that nematic fluctuations persist. These fluctuations are found even in overdoped samples and disappear with superconductivity at heavy doping.

Quasiparticle interference (QPI) is a powerful technique within Scanning Tunneling Microscopy (STM) that is used to probe the electronic bandstructure of materials. This thesis presents two examples using QPI to measure the bandstructure in materials with exotic electronic states that can be tuned via outside parameters (temperature and strain). In Part I of the thesis, we discuss the temperature dependence of Fermi Arcs in 1T’-MoTe2, and then in Part II, the strain dependent nematic state in NaFeAs. The recent discovery of Weyl semimetals has introduced a new family of materials with topologically protected electronic properties and potential applications due to their anomalous transport effects. Even more useful is a Weyl semimetal that can be turned “on” and “off,” switching between a topological and trivial state. One possible material is MoTe2, which undergoes a phase transition at 240K. This thesis consists of experiments using Scanning Tunneling Microscopy (STM) and Spectroscopy (STS) at different temperatures to visualize changes in the electronic bandstructure of MoTe2 across the topological phase transition. We show that a signature of topologically protected Fermi Arcs is present at low temperatures but disappears at room temperature, in the trivial phase. We include an in-depth discussion of how to account for thermal effects when comparing these two types of measurements. In Part II, we discuss strain induced nematicity in NaFeAs, an iron pnictide. Nematic fluctuations and spin correlations play an important role in the phase diagram of the iron pnictides, a family of unconventional superconductors. Illuminating the mechanism behind this symmetry breaking is key to understanding the superconducting state. Previous work has shown that nematicity in the iron pnictides responds strongly to applied strain [1, 2]. In this thesis, I present results from a new experimental technique, elasto-scanning tunneling microscopy (E-STM), which combines in situ strain and atomic resolution STM/STS. For the first time, we are able to observe the effects of strain on nematicity at the local level. We perform E-STM measurements in both the spin density wave phase and the tetragonal phase of NaFeAs and measure a distinct response in each. We successfully use strain to manipulate domain boundaries in the spin density wave state and we find the intensity of nematic fluctuations is coupled to strain in NaFeAs in the tetragonal phase.

Transition metal dichalcogenides (TMDs) are crystalline layered materials that have significantly impacted the field of condensed matter physics. These materials were the first exfoliatable semiconductors to be discovered after the advent of graphene. The focus of this dissertation is utilizing multiple imaging and characterization techniques to improve and understand the impact of strain and lattice defects in these materials. These inclusions to the lattice, alter the semiconducting performance in controllable ways. A comprehensive study using scanning tunneling spectroscopy (STM), spectroscopy (STS), scanning transmission electron microscopy (STEM), and photoluminescence (PL) in this work will provide a breadth of ways to pinpoint and cross-examine the impact of these factors on these materials. In the first half of this work we focus on the control of lattice defects through two growth processes: chemical vapor transport (CVT) and self-flux. By fine tuning the growth procedure we are both able to determine the intrinsic defects of the material, their electronics, and consistently diminish their density. The second half uses an in-situ strain device to reversibly control and examine the effects of applied strain on transition metal dichalcogenide layers. Utilizing the scanning tunneling microscope to image the lattice, we characterize the change of lattice parameters and observe the formation of strain solitons within the lattice. Measuring these solitons directly we look at the dynamics of a special class of line defects, folds within the top layer of the material, that occur naturally as strain is relieved within the monolayer. With the available imaging techniques and theoretical models we uncover a host of properties of these materials that are only accessible within the high strain regime

Thin film arrays of molecules or supramolecules are active subjects of investigation because of their potential value in electronics, chemical sensing, catalysis, and other areas. Scanning probe microscopes (SPMs), including scanning tunneling microscopes (STMs) and atomic force microscopes (AFMs) are commonly used for the characterization and metrology of thin film arrays. As opposed to transmission electron microscopy (TEM), SPMs have the advantage that they can often make observations of thin films in air or liquid, while TEM requires highly specialized techniques if the sample is to be in anything but vacuum. SPM is a surface imaging technique, while TEM typically images a 2D projection of a thin 3D sample. Additionally, variants of SPM can make observations of more than just topography; for instance, magnetic force microscopy measures nanoscale magnetic properties. Thin film arrays are typically two-dimensionally periodic. A perfect, infinite two-dimensionally periodic array is mathematically constrained to belong to one of only 17 possible 2D plane symmetry groups. Any real image is both finite and imperfect. Crystallographic Image Processing (CIP) is an algorithm that Fourier transforms a real image into a 2D array of complex numbers, the Fourier coefficients of the image intensity, and then uses the relationship between those coefficients to first ascertain the 2D plane symmetry group that the imperfect, finite image is most likely to possess, and then adjust those coefficients that are symmetry-related so as to perfect the symmetry. A Fourier synthesis of the symmetrized coefficients leads to a perfectly symmetric image in direct space (when accumulated rounding and calculation errors are ignored). The technique is, thus, an averaging technique over the direct space experimental data that were selected from the thin film array. The image must have periodicity in two dimensions in order for this technique to be applicable. CIP has been developed over the past 40 years by the electron crystallography community, which works with 2D projections from 3D samples. Any periodic sample, whether it is 2D or 3D has an "ideal structure" which is the structure absent any crystal defects. The ideal structure can be considered one average unit cell, propagated by translation into the whole sample. The "real structure" is an actual sample containing vacancies, dislocations, and other defects. Typically the goal of electron and other types of microscopy is examination of the real structure, as the ideal structure of a crystal is already known from X-ray crystallography. High resolution transmission electron microscope image based electron crystallography, on the other hand, reveals the ideal crystal structure by crystallographic averaging. The ideal structure of a 2D thin film cannot be easily in a spatially selective fashion examined by grazing incidence X-ray or low energy electron diffraction based crystallography. SPMs straightforwardly observe thin films in direct space, but SPM accuracy is hampered by blunt or multiple tips and other unavoidable instrument errors. Especially since the film is often of a supramolecular system whose molecules are weakly bonded (via pi bonds, hydrogen bonds, etc.) both to the substrate and to each other, it is relatively easy for a molecule from the film to adhere to the scanning tip during the scan and become part of the tip during subsequent observation. If the thin film array has two-dimensional periodicity, CIP is a unique and effective tool both for image enhancement (determination of ideal structure) and for the quantification of overall instrument error. In addition, if a sample of known 2D periodicity is scanned, CIP can return information about the contribution of the instrument itself to the image. In this thesis we show how the technique is applied to images of two dimensionally periodic samples taken by SPMs. To the best of our knowledge, this has never been done before. Since 2D periodic thin film arrays have an ideal structure that is mathematically constrained to belong to one of the 17 plane symmetry groups, we can use CIP to determine that group and use it for a particularly effective averaging algorithm. We demonstrate that the use of this averaging algorithm removes noise and random error from images more effectively than translational averaging, also known as "lattice averaging" or "Fourier filtering". We also demonstrate the ability to correct systematic errors caused by hysteresis in the scanning process. These results have the effect of obtaining the ideal structure of the sample, averaging out the defects crystallographically, by providing an average unit cell which, when translated, represents the ideal structure. In addition, if one has recorded a scanning probe image of a 2D periodic sample of known symmetry, we demonstrate that it is possible to use the Fourier coefficients of the image transform to solve the inverse problem and calculate the point spread function (PSF) of the instrument. Any real scanning probe instrument departs from the ideal PSF of a Dirac delta function, and CIP allows us to quantify this departure as far as point symmetries are concerned. The result is a deconvolution of the "effective tip", which includes any blunt or multiple tip effects, as well as the effects caused by adhesion of a sample molecule to the scanning tip, or scanning irregularities unrelated to the physical tip. We also demonstrate that the PSF, once known, can be used on a second image taken by the same instrument under approximately the same experimental conditions to remove errors introduced during that second imaging process. The preponderance of two-dimensionally periodic samples as subjects of SPM observation makes the application of CIP to SPM images a valuable technique to extract a maximum amount of information from these images. The improved resolution of current SPMs creates images with more higher-order Fourier coefficients than earlier, "softer" images; these higher-order coefficients are especially amenable to CIP, which can then effectively magnify the resolution improvement created by better hardware. The improved resolution combined with the current interest in supramolecular structures (which although 3D usually start building on a 2D periodic surface) appears to provide an opportunity for CIP to significantly contribute to SPM image processing.

No description available.

The magnetic properties and growth mode of self-assembly alloy nonoclusters were interests to surface science. Our experiment focused on the growth behavior of Fe-Ag alloy nanoclusters on the ordered alumina templates. We carried out the experiment by scanning tuneling miscoscopy (STM) under an ultra high vacuum chamber with base pressure better than 5 x 10E-11 torr. The clean NiAl(001) surface was prepared by repeating argon sputtr and annealing. Subsequently, it was deposited 1000 L oxygen at elevated temperature to form the ordered alumina templates. Iron and silver nanoclusters were deposited simultaneously on Al2O3/NiAl(001) surface by electron-beam evaporators. We observed the alloy nanoclusters by STM at low temperature. By increasing the silver composition, the height and diameter of alloy nanoclusters was increase, but the increasing ratio of diameter is higher than that of height.

It is generally believed that the Si technology is going to hit a road block soon. Amongst all the potential candidates, graphene shows the most promise as replacement material for the aging Si technology. This has caused a tremendous stir in the scientific community. This excitement stems from the fact that graphene exhibits unique electronic properties. Physically, it is a two-dimensional network of sp₂bonded carbon atoms. The unique symmetry of two equivalent sublattices gives rise to a linear energy dispersion for the charge carriers. As a consequence, the charge carriers behave like massless Dirac particles with a constant speed of c/300, where c is the speed of light. The sublattice symmetry gives rise to unique half-integer quantum hall effect, Klein's paradox, and weak antilocalization. In this research work, I was able to successfully study the growth and electronic structure of EG on SiC(0001), in ultra-high vacuum and low-vacuum furnace environment. I used STM to study the growth at an atomic scale and macroscopic scale. With STM imaging, I studied the distinct properties of commonly observed interface region (layer 0), first graphene layer, and the second graphene layer. I was able to clearly resolve graphene lattice in both layer 1 and 2. High resolution imaging of the defects showed a unique scattering pattern. Raman spectroscopy measurements were done to resolve the layer dependent signatures of EG. The characteristic Raman 2D peak was found to be suppressed in layer 1, and a single Lorentzian was seen in layer 2. Ni metal islands were grown on EG by e-beam deposition. STM/ STS measurements were done to study the changes in doping and the electronic structure of EG with distance from the metal islands.

Graphene grown epitaxially on silicon carbide provides a potential avenue toward industrial-scale graphene electronics. A predominant aspect of the multilayer graphene produced on the carbon-terminated (000 -1) face of SiC is the rotational stacking faults between graphene layers and their associated moire-pattern superlattice. We use scanning tunneling microscopy (STM) and spectroscopy (STS) in high magnetic fields to obtain detailed information about the "massless Dirac fermions" that carry charge in graphene. In agreement with prior investigations, we find that for small magnetic fields, the rotational stacking effectively decouples the electronic properties of the top graphene layer from those below. However, in maps of the wavefunction density at magnetic fields above 5 Tesla, we discover atomic-scale features that were not previously known or predicted. A phenomenological theory shows that this high-field symmetry-breaking is a consequence of small cyclotron-orbit wavefunctions, which are sensitive to the local layer stacking structures internal to the moire superlattice cell. The broken symmetry is sublattice degeneracy, predicated by atomic scale variations that derive from the sublattice polarization of graphene wavefunctions.

Many properties of the thin films are different from the bulk value and in many cases, depend dramatically on the film thickness. In the metallic ultra-thin films epitaxially grown on the semiconductor substrate, the conduction electrons are confined by the vacuum and metal-semiconductor interface. When the film thickness is comparable to the electron Fermi wavelength, this confinement will produce discrete energy levels known as quantum well states (QWS), which dramatically modify the electronic structures of the thin film and this is called quantum size effect (QSE). QSE will have a profound effect on a lot of physical properties of the thin films. Among various systems exhibiting QSE, Pb/Si (111) is the most widely studied one and exhibits the richest phenomena in QSE. In this study, a home made low temperature Scanning Tunneling Microscopy/Spectroscopy (LT-STM/S) was used to study the superconductivities of the Pb thin films. Quantum oscillations of the superconductivity have been observed for the films down to 4 monolayer and the oscillation amplitude increases as the film gets thinner. To resolve the discrepancies between the superconductivities measured with ex-situ transport and in-situ STS. We also studied the influence of Au overlay on the Pb thin films with LT-STM/S, and found out the deposition of Au on Pb dramatically roughened the Pb films. Finally, we successfully grew large scale near perfect 2ML Pb films. There are two types of films which exhibit different Moiré patterns. LT-STS studies revealed there is big difference in the superconductivity Tc of these two films, both of which decreased dramatically from that of the 4ML film. / text