Ces dernières années sont apparues de nouvelles techniques permettant le contrôle de la charge de nano-objets individuels (atome, molécule, agrégat métallique ou semi-conducteur, ...) déposés sur substrats isolants. Cet aboutissement a été rendu possible par le perfectionnement des méthodes de microscopie à effet tunnel (STM) et à force atomique (AFM). En combinant ces outils, les précurseurs ont réussi à maîtriser l'état de charge d'un atome d'or déposé sur une bicouche de NaCl(001) sur substrat Cu(111). Par la suite, ce type de manipulation a été étendu à des systèmes moléculaires notamment au CEMES avec Cu(dbm)2. Ce sujet s'inscrit dans la continuité de ces études. L'objectif était d'analyser l'impact de l'augmentation de l'épaisseur du film isolant sur les mécanismes de charge. Cette problématique requière une quantification de l'état de charge du système ainsi qu'une mesure de l'épaisseur d'isolant. Dans ce travail, nous avons pu étudier des films de KBr et NaCl déposés sur des surfaces de Cu(111) et Ag(111). Pour ces études, que ce soit en courant tunnel (STM) ou en gradient de force (NC-AFM), le contrôle de l'état de pointe est essentiel. Lorsque l'on travaille sur substrat isolant, la pointe a tendance à collecter des contaminants qui en changent les propriétés électroniques. Or, pour charger un système de manière reproductible, il nous faut impérativement contrôler la métallicité de l'apex. Cette maîtrise passe par une re-préparation fréquente de la pointe sur une surface métallique, difficile à trouver dans le cas d'un film épais. Pour pallier à cette rareté, nous avons mis en place un masque de dépôt permettant un contrôle du gradient de l'épaisseur du film isolant tout en préservant des zones de métal libre. Cela nous a permis de réaliser nos mesures avec un état de pointe mieux contrôlé. L'instabilité de l'état de pointe nous a également conduit à effectuer des spectroscopies à courant régulé de type Z(V). En contrôlant ce courant, il est alors possible de minimiser l'interaction entre la pointe et le film isolant, préservant ainsi plus longtemps la pointe. Ces spectroscopies Z(V) permettent également d'augmenter la tension de mesure jusqu'à atteindre le régime d'émission de champ. Nous avons observé par cette méthode une variation de la modulation de l'amplitude des résonances d'émission de champ (FER) en fonction de l'épaisseur du film isolant. Une modélisation numérique par différences finies a été développée afin de comprendre ce phénomène. [..] / In recent years, new techniques have emerged to control the charge of individual nano-objects (atom, molecule, metal aggregate or semiconductor, etc.) deposited on insulating substrates. This achievement has been made possible by the refinement of Tunneling Microscopy (STM) and Atomic Force (AFM) methods. By combining these tools, the precursors succeeded in controlling the state of charge of a gold atom deposited on a NaCl (001) bilayer on a Cu (111) substrate. Subsequently, this type of manipulation has been extended to molecular systems, in particular at the CEMES with Cu(dbm)2. This subject is part of the continuity of these studies. The objective was to analyze the impact of the increase of the thickness of the insulating film on the charge mechanisms. This problem requires a quantification of the state of the system charge as well as a measurement of the insulation thickness. In this work, we have been able to study KBr and NaCl films deposited on Cu(111) and Ag(111) surfaces. For these studies, whether in tunnel current (STM) or force gradient (NC-AFM), the control of the tip state is essential. When working on an insulating substrate, the tip tends to collect contaminants that change their electronic properties. However, to charge a system in a reproducible way, we must imperatively control the metallicity of the apex. This control requires a frequent re-preparation of the tip on a metal surface, difficult to find in the case of a thick film. To overcome this scarcity, we have implemented a deposition mask allowing a control of the gradient of the thickness of the insulating film while preserving clean metal zones. This allowed us to carry out our measurements with a better controlled state of the tip. The instability of the tip state has also led us to perform Z (V) regulated current spectroscopies. By controlling this current, it is then possible to minimize the interaction between the tip and the insulating film, thus making the tip last longer. These Z (V) spectroscopies also make it possible to increase the measurement voltage until reaching the field emission regime. We have observed a variation of the modulation of the field emission resonances (FER) amplitude as a function of the thickness of the insulating film. [...]

The electronic structure of clean pyrite {100} and covellite {001} surfaces have been investigated in ultra-high vacuum (UHV) for the purpose of understanding the nature of sulfide surface reactivity. Using primarily scanning tunneling microscopy and spectroscopy (STM/STS), the electronic structure at atomic sites on these surfaces was directly probed, and chemical insight into the results was provided by ab-initio calculations. Pyrite is the most abundant sulfide at the earth's near surface. Its oxidation influences a wide variety of natural and industrial chemical process, but very little is known about the stepwise oxidation reactions involved. For this reason, the first two chapters are directed at understanding the surface electronic structure and fundamental reactivity of pyrite surfaces at the atomic scale. UPS spectra show a characteristic peak at ~ 1 eV forming the top of the valence band for the near surface. Ab-initio calculated densities of states for the bulk crystal suggest that this band is comprised primarily of non-bonding Fe 3d t_2g and lesser S 3p and Fe 3d e_g states. Ab-initio slab calculations predict that the broken bonding symmetry at the surface displaces a Fe 3d_Z2 dangling bond state into the bulk band gap. Evidence confirming the presence of this surface state is found in low bias STM imaging and normalized single-point tunneling spectra, which are in remarkable agreement with calculations of the LDOS at surface Fe and S sites. The results predict that due to the dangling bond surface states, Fe sites are energetically favored for redox interaction with electron donors or acceptor species. STM/STS observations of O₂/H₂O exposed surfaces are consistent with this assertion, as are ab-initio cluster calculations of adsorption reactions between O₂/H₂O derived species and the {100} surface. Furthermore, an enhancement in the "rate" of oxidation was discovered using UPS on pyrite surfaces exposed to a mixture of O₂/H₂O. Cluster calculations of adsorption energies reveal a similar result for the case where both O₂ and H₂O are dissociated on the surface and sorbed to Fe sites. Covellite, similar to pyrite, is a natural semiconducting metal sulfide. In contrast, however, precious metal bearing solutions have a curiously lower affinity for covellite surfaces than for pyrite. At the same time, its unique combination of low resistivity and perfect basal cleavage represented a unique opportunity to improve our ability to interrogate metal sulfide surfaces using STM/STS at the atomic scale. Ab-initio calculations predict that cleaving covellite exposes two slightly different surfaces, one is expected to have dangling bonds, the other is not. Atomic-scale STM images and LEED patterns indicate that the surface structure is laterally unreconstructed. The STM images are predicted to show Cu sites as high tunneling current sites on the dangling bond covered surface, and S sites on the other. Based on tunneling spectra and tip-induced effects therein, reasonable arguments are presented which allow one to uniquely differentiate between the two possible surfaces. For both pyrite and covellite, the combination of experiment and theoretical calculations afforded much more insightful conclusions than either would have alone. The calculations provided the necessary chemical framework with which to make interpretations of the experimental data and, in this sense, contribute information obtainable by no other means. This point is further developed in an investigation of Si-O interactions and the electron density distribution in the model silicate coesite, which is presented in the appendix. In addition, it breaks new ground by delving into differences and similarities between periodic vs. cluster calculations of minerals. / Ph. D.

No description available.

Scanning probe microscopy techniques were used to investigate the desorption of hydrogen passivated silicon to form SiO2 etch masks The application of the etch masks were planned on being used to manufacture silicon nanowires. Low concentration hydrofluoric acid was used to passivate the surface. The surface was selectively depassivated by SPM techniques. Scanning tunneling microscopy (STM) and atomic force microscopy (AFM) were used to create the masks. The STM system used was found to desorb hydrogen from the surface faster than the STM could image and was considered incapable in the configuration investigated. This led to the use of atomic force microscopy (AFM). Using a conductive tip in contact mode, lithography on the passivated surface was performed. The topography of the lithography was compared to similar works and found to be similar in size. The width was found to be 80nm and the thickness 1nm. The depassivated layers were confirmed to be oxide through electronic force microscopy (EFM). Finally, voltages were swept with the tip in contact with the surface to find the bandgap of the oxide. It was found that the voltage sweeps were severely modifying the tip along with producing inconsistent desorption thicknesses ranging from 0.2 to 12nm. Despite the results from the voltage sweeps, the lithography procedure performed using the AFM was found to be successful.

The present project aimed to characterize the role of serial order within the working memory and language domains by first addressing a) whether serial order processing is domain-general and then b) whether serial order processing underlies vocabulary acquisition. Experiment 1 revealed that order memory in the visuo-spatial domain is qualitatively similar to order memory for verbal memoranda by reporting visuo-spatial equivalents of two well-known effects in verbal STM for serial order, repetition inhibition (e.g., Crowder, 1968) and repetition facilitation (Crowder, 1968). The effects were, however, accompanied by critical differences that may be due to modality-specific processes. Experiment 2 directly investigated whether verbal and visuo-spatial STM rely on common ordering mechanisms using a delayed recall dual-task design that contrasted two types of visuo-spatial interference tasks during a concurrent verbal serial order memory task (digit sequence memory). The visuo-spatial tasks probed either serial order STM or non-serial order (item) STM. Serial-order specific interference effects with the concurrent verbal serial order STM task were found. In experiment 3, we replicated the investigations of Experiment 2 using a word-learning paradigm as a concurrent task in place of the verbal serial order STM task that was previously used. Again interference by a visuo-spatial STM task was found only when it required memory for serial order. In sum, the results suggest that verbal and visuo-spatial STM subsystems rely on common mechanisms for serial order processing. These in turn appear to communicate with domain-specific processing substrates involved in item-level memory representations. Furthermore, the results indicate that such domain-general serial ordering mechanisms are also involved in novel word-learning. Taken together, the present findings provide crucial constraints for modeling of order representations. They also offer insight into mechanisms shared by vocabulary acquisition and STM tasks. / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.

Neste trabalho apresenta-se uma avaliação do desempenho da implementação de memória transacional da linguagem Clojure, utilizada como biblioteca de sincronização para uso em conjunto com outras aplicações dentro da máquina virtual de Java. É implementada uma camada de interface entre as estruturas de dados de Clojure e o benchmark STMBench7 e são discutidos alguns aspectos que geram sobrecarga no desempenho. / In this work a performance evaluation of Clojure transactional memory implementation is presented, using it as a synchronization library to work together with other applications on Java virtual machine. It is implemented an interface layer between Clojure data structures and STMBench7 benchmark, and issues about overhead in performance are discussed.

Die heterogene Katalyse spielt in der industriellen chemischen Synthese sowie in umwelttechnischen Prozessen eine herausragende Rolle. Viele Katalysatoren zeichnen sich durch eine hohe strukturelle Komplexität aus, welche ein detailliertes Verständnis von entscheidenden Parametern sowie zugrunde liegenden Reaktionsmechanismen meist verhindert. Daher ist die Untersuchung von geeigneten Modellsystemen unerlässlich. Im Rahmen dieser Arbeit wurde ein dünner, kristalliner Aluminiumoxid-Film auf NiAl(110) mittels Rastertunnelmikroskopie (STM) und -spektroskopie (STS) bei 5K untersucht. Dieser Film konnte bereits in zahlreichen Studien als Modell für Alumi-niumoxid-Trägermaterialien etabliert werden, obwohl seine atomare Struktur nicht bekannt war. Hier wurden nun atomar aufgelöste STM-Bilder des Films aufgenommen, die sich später verschiedenen Lagen des Films zugeordnen ließen. Ferner konnten Antiphasendomänengrenzen (APDB), d.h. regelmäßig auftretende Liniendefekte des Oxidfilms, mit STM und STS charakterisiert werden. Es gelang somit, deren elektronische und geometrische Struktur zu korrelieren. Im zweiten Teil der Arbeit wurde das Adsorptionsverhalten des Aluminiumoxid-Films gegenüber einzelnen Au-Atomen untersucht. Nach der Präparartion waren Au-Monomere, Dimere und kleine Cluster auf der Oberfläche vorhanden, die mit STM und STS untersucht wurden. Die Ergebnisse zeigen, dass das NiAl(110)-Substrat an der Bindung von Au-Atomen auf dem Oxid-Film beteiligt ist, und dass dünne Filme offenbar ein anderes Adsorptionsverhalten aufweisen können als die entsprechenden Bulk-Oxide. Im dritten Teil dieser Arbeit wurden die Eigenschaften von Metall-Clustern (Ag, Pd) auf dem Aluminiumoxid-Film in Abhängigkeit von ihrer Größe untersucht. Leitfähigkeits-Spektren zeigen eine charakteristische Signatur, die am besten mit einer Coulomb-Blockade erklärt werden kann. Somit reflektieren die Spektren eher Eigenschaften des Tunnelkontakts als intrinsische Cluster-Eigenschaften. / Heterogeneous catalysis plays an important role in industrial synthesis and in environmental chemistry. Due the difficulties related with the investigation of working catalysts, the study of well-defined model systems is very important to gain a fundamental understanding of the principles and reaction mechanisms. Within the scope of this work, a well-ordered, thin alumina film on NiAl(110) has been investigated by scanning tunneling microscopy (STM) and spectroscopy (STS) at 5K. This film was established as model for bulk alumina supports in previous studies, though its exact structure remained unknown. Here, atomically resolved STM images of the film have been obtained, which could later be assigned to distinct atomic layers. Furthermore, anitiphase domain boundaries (APDB), regularly appearing line defects in the oxide film, were characterized by STM and STS. These studies provide a detailed understanding of how their geometric and electronic structure are related. The second part of this thesis addressed the adsorption behavior of the alumina film toward single Au atoms. The sample preparation yielded Au monomers, dimers and small clusters on the surface, which were investigated with STM and STS. Accordingly, the NiAl(110) substrate participates in the binding of Au atoms, demonstrating that adsorption properties of thin oxide films can deviate significantly from bulk oxides, whereby the metal adatom seems to play an important role. The third part of this work presents size-dependent STM/STS studies on metal clusters (Ag, Pd) deposited onto alumina/NiAl(110). Conductance spectra reveal a distinct signature, which can be explained by a Coulomb blockade effect. Another interpretation based on quantized electronic levels, is also discussed, but cannot account for all experimental findings. Thus, the spectroscopic data reflect most likely no intrinsic properties of the metal clusters but are due to the specific behavior of a double-barrier tunneling junction.

O objetivo deste trabalho foi a construção de um microscópio de tunelarnento (STM) e sua aplicação a alguns tipos de materiais. Todas suas partes constituintes - cabeça de medida, sistema de isolamento contra vibrações, circuito eletrônico de retroalirnentação e programa computacional de controle - foram desenvolvidas c montadas em nosso laboratório. O aparelho foi testado e calibrado por medidas de interferência óptica e através de imagens da estrutura cristalina de grafite obtidas com o próprio instrumento. Foi realizado um estudo sobre filmes finos de ouro, otirnizando-se o processo de deposição por sputtering, para sua utilização corno cobertura de amostras isolantes a serem investigadas por microscopia eletrônica de varredura (SEM) ou de tunelarnento. Um método de preparo de amostras sernicondutoras foi proposto e utilizado no estudo inicial de pontos quânticos de InAs crescidos pela técnica de epitaxia por feixe molecular (MBE). / The aim of this work was the construction of a scanning tunneling microscope (STM) and its application to some interesting physical systems. All its parts- measurement head, antivibration system, electronic feedback circuit and control software were developed and mounted in our laboratory. The instrument was tested and calibrated by optical interferometry and using images of the atomic structure of graphite obtained with the microscope itself. A systematic study of thin sputtered Au films was carried out in order to optimize the sputtering process for its use in the coverage of insulating samples to be investigated by scanning electron microscopy (SEM) and STM. We also proposed a new method to prepare semiconducting surfaces for STM measurements in air, which was used to study InAs quantum dots grown by molecular beam epitaxy (MBE).