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This thesis describes three different design projects that are intellectually connected by the fact that they all involve the development of apparatus to facilitate the precise control of sample temperature in modern microscopes. The first project is a low-temperature sample stage, for a beetle-type scanning tunnelling microscope. The design for this sample stage, and images taken on it with atomic resolution at 114 K are presented. This stage has the capability for variable-temperature sample cooling, which is also discussed. The second project is a set of low- and variable-temperature isothermal radiation shields for a new microscope that is currently being designed and assembled by our research group. These shields provide temperature control between 5 K and room temperature, with measured stability better than +/- 0.1 K. Controlled and stable temperature changes at rates up to 1.5 K per minute have been produced. The shields are modular and can easily accommodate future modifications. The design for the shields, along with their cooling and temperature control capabilities, is presented. The third project is a new stage design for heating, cleaning, and transferring metal and semiconductor samples. Also for use with the new microscope, this stage uses electron bombardment to provide precision temperature control between room temperature to temperatures in excess of 1250 C‰. With this stage, the sample temperature can be determined by measuring the power applied to the sample. The design of this stage, its heating performance, and a method to calculate the sample temperature is presented. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2008-06-03 12:47:18.808

Orientador: Daniel Mario Ugarte / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-17T22:12:05Z (GMT). No. of bitstreams: 1 Martins_BrunoVieiradaCunha_D.pdf: 17693367 bytes, checksum: cd2b98fba2b0d91ed107d569050c937f (MD5) Previous issue date: 2011 / Resumo: O estudo da estrutura de nanosistemas individuais requer o uso de equipamentos capazes de gerar imagens de sistemas com poucos átomos. No caso de nanopartículas metálicas produzidas por síntese química, uma questão relevante e ainda pouco estudada é a organização dos passivantes sobre sua superfície e como isso contribui para a definição de sua estrutura de equilíbrio. Para abordar este tema, devemos ser capazes de gerar imagens de resolução atômica em superfícies com alto grau de curvatura: a microscopia de tunelamento (STM) representa o instrumento mais adequado para este tipo de tarefa. Entretanto, o estudo detalhado requer o uso de métodos não-convencionais de microscopia STM (ex. modulação da tensão de bias ou de setpoint), sendo assim desejável que tenhamos total controle sobre a operação do instrumento. Este domínio preciso sobre as características funcionais consiste na principal razão que justifica a construção de um STM no próprio grupo. Este trabalho descreve o desenho, a construção e a caracterização de um STM de Ultra-Alto Vácuo (UHV). Todo o desenho e a construção foram integralmente realizadas no grupo de pesquisa. Apresentamos e justificamos os parâmetros escolhidos para o projeto, os quais definem o perfil do instrumento. O projeto mecânico consiste em um sistema elástico tipo ¿Parallel-Guiding-Spring Table¿(PSM). O sistema de varredura foi desenvolvido utilizando na configuração tipo tripod para os atuadores piezoelétricos. Desenvolvemos dois protótipos da cabeça STM, ambos compatíveis com UHV. Apresentamos o projeto e a construção da câmara de vácuo e do sistema de amortecimento de vibração. Na parte eletrônica, desenvolvemos um projeto que envolve blocos anal'ogicos de precisão e componentes digitais de 16 bits. O sistema funciona com baixa tensão, o que o torna mais estável e menos suscetível ao ruído e a variações térmicas. O sistema de controle embarcado e seu modelo analítico são analisados de modo a se determinar os parâmetros para operação estável. Caracterizamos todo o sistema e obtivemos imagens para superfícies de Grafite e Au como forma de verificar a performance do equipamento construído. Por fim discutimos as dificuldades do projeto e apresentamos soluções para os pontos que requerem certa otimização / Abstract: The study of the structure of individual nanosystems requires the use of equipments capable of generating images of systems containing just a few atoms. In the case of metallic nanoparticles produced by chemical synthesis, a relevant and not much studied question is the organization of the passivant molecules over the surface and how they contribute to the definition of the equilibrium structure. To adress this issue, we must be capable of generating atomic resolution images on surfaces with a high level of curvature: the Scanning Tunneling Microscopy (STM) represents the most adequate instrument for this job. Nevertheless, the detailed study requires the use of non-conventional methods of STM microscopy (ex. bias voltage and setpoint modulation), then it is desirable to have total control over the instrument operation. This precise domain over the functional characteristics consists in the main reason that motivated the construction of a STM in our group. This work describes the design, construction and characterization of an Ultra-High Vacuum (UHV) STM. The design and construction were both integrally done in our research group. We present and justify the chosed project parameters, which define the profile of the instrument. The mechanical project consists of an elastic system of the ¿Parallel-Guiding- Spring-Table Mechanism¿(PSM) type. The scanning system was developed using the tripod configuration for the piezoelectric actuators. We have developed two prototypes for the STM head, both compatible with UHV. We present the project and construction of the vacuum chamber and the vibration isolating system. For the electronics, we have developed a project that involves precision analog blocks and 16 bits digital components. The system works with low voltage, what turns it more stable e less succeptible to noise and thermal variations. The embedded control system and its model are analysed in order to determine the stable operation parameters. We have characterized the system in detail and obtained images for Graphite and Gold surfaces as a way to verify the performance of the constructed equipment. Finally, we discuss the difficulties of the project and present solutions for the points that require optimization / Doutorado / Física da Matéria Condensada / Doutor em Ciências

This thesis reports on the elemental growth of oxide thin films including TiO_x, BaO_x and Ba_xTi_yO_z by Ti/Ba deposition and oxidation. The films were grown on two different substrates, Au(111) and SrTiO₃(001), and studied using a variety of surface characterisation techniques. On the reconstructed Au(111) surface, three different TiO_x structures were obtained with increasing Ti amounts deposited: a (2 × 2) Ti₂O₃ honeycomb structure, a pinwheel structure that is the result of a Moiré pattern, and a triangular island TiO_1.30 structure. The structures arise from raised Ti coverages and have increased Ti densities. Although Ba deposited on the reconstructed Au(111) has a weak interaction with the substrate, the BaO_x thin films can grow epitaxially and lift the Au(111) reconstruction. Two well-ordered phases, a (6 × 6) and a (2√3 × 2√3) BaO_x structure, were obtained which may have octopolar-based surface structures. For Ba & Ti deposition on Au(111), a locally ordered (5 × 5) BaxTiyOz structure was observed in the sub-monolayer regime. What is more interesting is the possible formation of a BaO-TiO surface alloy with short-range ordering achieved by Ba deposition on the (2 × 2) Ti₂O₃-templated Au(111) surface. This is the first time that surface-alloying has been observed for oxides. When Ti is deposited onto the SrTiO₃(001) surface, it is incorporated into the substrate by forming a variety of Ti-rich SrTiO₃ surface reconstructions, such as c(4 × 2), (6 × 2), (9 × 2) and (√5 ×√5)-R26.6°. Ti deposition provides a completely different route to obtaining these reconstructions at much lower anneal temperatures than the previously reported preparation procedures involving sputtering and annealing the SrTiO₃ sample. Anatase islands with (1 × 3) and (1 × 5) periodicities were also formed by increasing the Ti deposition amount and post-annealing. Reconstructed SrTiO₃ substrate surface has a lattice that differs from the bulk crystal and affects the epitaxial growth of BaO, however, a locally ordered BaO_x structure was observed on the sputtered substrate with a growth temperature of 300 °C. Depositing Ba & Ti on SrTiO₃(001) results in the formation of BaO_x clusters and the Ti incorporation into the substrate, forming the familiar Ti-rich SrTiO₃ surface reconstructions.

For an electronic device well-designed interfaces are critical for the performance. Studies of interfaces down to an atomic level are thus highly motivated both from a fundamental and technological point of view. In this thesis, a surface science approach has been employed to study the formation of interfaces in systems relevant for transistor and solar cell applications. Surface science methodology entails ultra high vacuum environment, single crystalline surfaces, submonolayer control of deposited material, surface sensitive spectroscopy and atomic resolution microscopy. The primary experimental method for characterization is electron spectroscopy. This is a family of very powerful experimental techniques capable of giving information on the atomic level. Additionally, studies have been performed using scanning tunnelling microscopy. Combined these two methods can provide an atomic level characterisation of the geometric and electronic properties of the surface. The emphasis of this work is placed on ultra thin TiO2 and ZrO2 films grown on silicon substrates by means of ultra-high vacuum metal-organic chemical vapour deposition. ZrO2 has also been grown on SiC and FeCrAl. Deposition has been performed with different process parameters. The interface region of each film has been characterised. The band alignment, a most important issue with regard to the development of new transistor devices, for the ZrO2/Si(100) system has been explored. Decomposition pathways of the metal organic precursors have been studied in detail. Changing process parameters is shown to alter both the precursor decomposition pathway and the nature of the interface region, thus opening the possibility to tailor the material function. The titanium dioxide films grown in situ have shown to be excellent models of nanostructured electrode materials. In this spirit, interfaces of model systems for the solid-state dye-sensitized solar cell have been studied. Links between device performance and interface structure have been elucidated.

The discovery of high-temperature superconductivity in 1986 in copper-oxide materials have opened up new avenues to investigate new families of quantum materials that were previously not known. Understanding the mechanism of superconductivity in high-T[sub]c superconductors has been an important research theme in condensed matter physics, as it is believed to be essential to realize the next generation engineered materials that become superconducting at room temperature. Discovered in 2006, iron based superconductors are a new addition to the family of high-T[sub]c superconductors, these materials exhibit several interesting properties and show some vivid similarities with cuprates and other families of high-temperature superconductors. In this thesis, I will present the spin-polarized scanning tunneling microscopy (SPSTM) study carried out on the parent compound of iron chalcogenide high temperature superconductor Fe[sub](1+y)Te to investigate the bi-collinear antiferromagnetic order. Magnetic tips in this work are prepared using a novel preparation technique by picking up excess iron atoms and clusters of FeTe from the surface of the sample. Next, I will present the SP-STM results obtained in the spin glass phase of Fe[sub](1+y)SeₓTe₁₋ₓ visualizing the interplay between the short ranged bi-directional bi-collinear antiferromagnetic order and superconductivity at the atomic scale. In this thesis, I will also present the scanning tunneling microscopy and spectroscopy (STM/STS) study of the native and engineered defect bound states in the iron-pnictide superconductor LiFeAs. This study addresses the pairing symmetry of the superconducting order parameter and understanding of dip-hump features seen in STM spectra outside the superconducting gap in iron pnictide superconductor LiFeAs.

This thesis reports on the chemical vapour deposition (CVD) growth of carbon nanostructures (mainly carbon nanotubes (CNTs)) on perovskite oxide surfaces with the aid of various catalysts. Two types of perovskite oxide, single crystal SrTiO3 (001) and polycrystalline BaSrTiO₃, have been used as catalyst supports (in metal-catalyst-involved CVD routes) or as catalysts (via metal-catalyst-free CVD routes) for the growth of carbon nanostructures. In metal-catalyst-involved cases, SrTiO₃ (001) single crystal has been proven, for the first time, to serve as a substrate for the growth of CNTs. Fe and Ni catalysts can be tailored in a controllable manner on SrTiO3 (001) surfaces prior to the CNT synthesis, forming truncated pyramid shaped nanocrystals with uniform size distributions. The growth of vertically aligned CNT carpets was realised with the aid of Fe on SrTiO₃ (001) surfaces, and it was further found that the CNTs grow via a base growth model. Furthermore, it is possible to grow helical carbon nanostructures on BaSrTiO3 substrates by introducing a Sn catalyst into the system. The synthesised helical carbon nanostructures follow a tip growth mode, where the structural and chemical aspects of catalyst particles gave rise to a wide range of carbon morphologies. CNTs were also grown on single crystal SrTiO₃ (001) and polycrystalline BaSrTiO3 substrates via metal-catalyst-free routes. The surface-roughness-tailored growth of CNTs was surprisingly achieved on a series of engineered SrTiO₃ (001) surfaces, where a correlation between the surface roughness/morphology of the substrates and the relevant catalytic activity was revealed. The growth of CNTs arises because the catalyst fabrication methods lead to the formation of SrTiO₃ asperities with nanoscale curvatures, over which the CNTs are generated throughout a lift-off process. Facet-selective growth of CNTs was observed on polycrystalline BaSrTiO₃ surfaces, where BaSrTiO₃ (110) facets lead to the growth of CNTs on them, whereas the (001) facets result in no growth at all. This observation was further analysed in the content of the adsorption and diffusion of carbon species on distinct BaSrTiO₃ facets, before reaching the conclusion that the formation of CNTs occurs through a metal-free, stack-up process driven by the assembly of the carbon fragments.

Les travaux présentés dans ce manuscrit portent sur la croissance de réseaux 2D covalents nanoporeux sur des substrats métalliques monocristallins en conditions ultravide. La réalisation de tels réseaux bidimensionnels nanostructurés met en jeu l’assemblage de briques élémentaires par des réactions de polymérisation sur surface qui sont ensuite caractérisées par microscopie à effet tunnel. La réaction étudiée est la condensation par déshydratation des groupes acides boroniques de l’acide 1,4-benzènediboronique conduisant à la formation d’un réseau aux pores hexagonaux de 15Å. L’étude se focalise spécifiquement sur l’influence de la fonctionnalisation du monomère (l’ajout de substituants ou d’hétéroatomes sur le cycle aromatique) sur les propriétés de la molécule et son impact sur la croissance du réseau. Une seconde famille de molécule fonctionnalisée a été étudié à partir de l’acide 1-bromo-4-benzèneboronique, qui par la substitution d’un acide boronique par un brome permet de modifier le mécanisme de polymérisation et ainsi de ralentir la cinétique de réaction. Les travaux réalisés portent sur la synthèse des deux familles de molécules, sur la caractérisation de l’évolution de leurs propriétés (polymérisation, dégradation) et sur leur capacité à former des réseaux covalents 2D ordonnés. Il a ainsi été possible de déterminer de manière qualitative les paramètres critiques qui gouvernent l’assemblage des molécules pour optimiser la croissance de réseaux fonctionnalisés. / The work presented in this thesis relates to the growth of 2D covalent organic frameworks on single crystal metal substrates in UHV conditions. The realization of such nanostructured two-dimensional networks involves the assembly of building blocks by polymerization reactions on surface that are characterised by scanning tunnelling microscopy. The chosen reaction is the condensation by dehydration of boronic acid groups from the 1,4-benzenediboronique acid leading to the formation of a nanoporous network with 15 Å hexagonal pores. The study focuses specifically on the effect of the monomer functionalization (addition of substituents or hetero atoms on the aromatic ring) regarding the molecule properties and its impact on the network growth. A second functionalized molecule family has also been studied from the 1-bromo-4-benzene boronic acid in which a boronic acid is substituted by a bromine group. This allows kinetic control of the polymerization. The work done relates to the synthesis of the two kind of functionalized molecules, the characterization of the evolution of their properties (polymerization, degradation) and their ability to form ordered 2D covalent networks. It was thus possible to determine qualitatively the critical parameters that govern the assembly of molecules to optimize the growth of functionalized networks.

L’objectif de cette thèse a été axé sur le développement des systèmes capable de répondre à des stimuli externes, basés sur des unités photochromiques. Le but d’une telle quête est d’augmenter la complexité des dispositifs et des machines moléculaires synthétiques. Avec l’objectif de développer des dispositifs et des machines artificiels plus complexes, nous avons réalisé de systèmes comprenant de multiples interrupteurs moléculaires. En vue de la réalisation de cette thèse, des nouveaux systèmes multi-photochromiques, où hybrides photochrome/nanomatériaux contenant des fragments azobenzène, diaryléthène ou spiropyrane ont été réalisés et étudiés. D’abord, on s’est focalisés sur des systèmes multi-azobenzènes capables de subir de grands réarrangements géométriques lors de la photoisomérisation, ils pourraient être utilisés à l'avenir comme éléments constitutifs des matériaux host-guest ou metal-organic frameworks contrôlables par des stimuli lumineux. Dans un second exemple, des commutateurs photochromiques de type dithiényléthène ont été utilisés pour déclencher l'émission d'une porphyrine. Cette dyade à montré une modulation réversible de son émission, affichant un contraste particulièrement élevé. Comme dernier exemple, un dérivé de spiropyrane a été combiné avec des nanoparticules d’or anisotropes. En induisant l'isomérisation de l’interrupteur moléculaire dans les dispersions colloïdales des nanorods d’or en liquide, nous avons visualisé une grande variation du spectre d'extinction des colloïdes, dépendante de la longueur d’onde du mode LSPR et du recouvrement spectrale avec le photoswitch. / The aim of this thesis has been to develop systems capable of responding to external stimuli, based on photochromic units. The goal of such a quest is to increase the complexity of devices and synthetic molecular machines. With the goal of developing more complex artificial devices and machines, we have realised systems containing multiple molecular switches. For the realisation of this thesis, new multi-photochromic systems, or photochromes/nanomaterials hybrids containing azobenzene, diarylethene or spiropyran moieties have been realised and studied. Firstly, we focused on multi-azobenzene systems capable of undergoing large geometric rearrangements during photoisomerisation, as they may be used in the future as constituent elements of host-guest or metal-organic frameworks controllable by luminous stimuli. In a second example, dithienylethene-type photochromic switches have been used to trigger the emission of a porphyrin. This dyad exhibited a reversible modulation of its emission, displaying a particularly highly contrasted response. As a final example, a spiropyran derivative has been combined with anisotropic gold nanoparticles. By inducing the isomerisation of the molecular switch in the AuNR colloidal liquid dispersions, we visualised a large variation of the colloid extinction spectrum, dependent on the LSPR mode wavelength and the spectral overlap with the photoswitch.