The present thesis is focused on various methods of controlling electronic and geometrical structure of two-dimensional overlayers adsorbed on metal surfaces exemplified by graphene and hexagonal boron nitride (h-BN) grown on transition metal (TM) substrates. Combining synchrotron-radiation-based spectroscopic and various microscopic techniques with in situ sample preparation, we are able to trace the evolution of overlayer electronic and geometrical properties in overlayer/substrate systems, as well as changes of interfacial interaction in the latter.It is shown that hydrogen uptake by graphene/TM substrate strongly depends on the interfacial interaction between substrate and graphene, and on the geometrical structure of graphene. An energy gap opening in the electronic structure of graphene on TM substrates upon patterned adsorption of atomic species is demonstrated for the case of atomic oxygen adsorption on graphene/TM’s (≥0.35 eV for graphene/Ir(111)). A non-uniform character of adsorption in this case – patterned adsorption of atomic oxygen on graphene/Ir(111) due to the graphene height modulation is verified. A moderate oxidation of graphene/Ir(111) is found largely reversible. Contrary, oxidation of h-BN/Ir(111) results in replacing nitrogen atoms in the h-BN lattice with oxygen and irreversible formation of the B2O3 oxide-like structure.      Pronounced hole doping (p-doping) of graphene upon intercalation with active agents – halogens or halides – is demonstrated, the level of the doping is dependent on the agent electronegativity. Hole concentration in graphene on Ir(111) intercalated with Cl and Br/AlBr3 is as high as ~2×1013 cm-2 and ~9×1012 cm-2, respectively.     Unusual periodic wavy structures are reported for h-BN and graphene grown on Fe(110) surface. The h-BN monolayer on Fe(110) is periodically corrugated in a wavy fashion with an astonishing degree of long-range order, periodicity of 2.6 nm, and the corrugation amplitude of ~0.8 Å. The wavy pattern results from a strong chemical bonding between h-BN and Fe in combination with a lattice mismatch in either [11 ̅1] or [111 ̅] direction of the Fe(110) surface. Two primary orientations of h-BN on Fe(110) can be observed corresponding to the possible directions of lattice match between h-BN and Fe(110).     Chemical vapor deposition (CVD) formation of graphene on iron is a formidable task because of high carbon solubility in iron and pronounced reactivity of the latter, favoring iron carbide formation. However, growth of graphene on epitaxial iron films can be realized by CVD at relatively low temperatures, and the formation of carbides can be avoided in excess of the carbon-containing precursors. The resulting graphene monolayer creates a periodically corrugated pattern on Fe(110): it is modulated in one dimension forming long waves with a period of ~4 nm parallel to the [001] direction of the substrate, with an additional height modulation along the wave crests. The novel 1D templates based on h-BN and graphene adsorbed on iron can possibly find an application in 1D nanopatterning. The possibility for growing high-quality graphene on iron substrate can be useful for the low-cost industrial-scale graphene production.

Les architectures multicœurs changent notre façon d'écrire des programmes. L'écriture de programmes concurrents est bien connue pour être difficile. Traditionnellement, l'utilisation de verrous (locks) permettant au code de s'exécuter en exclusion mutuelle, a été l'abstraction la plus largement utilisée pour l'écriture des programmes concurrents. Malheureusement, il est difficile d'écrire des programmes concurrents efficaces et corrects reposant sur des verrous. En outre, les verrous présentent d'autres problèmes, notamment celui du passage à l'échelle. Le concept de mémoire transactionnelle a été proposé comme une solution à ces difficultés. Les transactions peuvent être considérées comme une abstraction de haut niveau, ou une méthodologie pour l'écriture de programmes concurrents, ce qui permet au programmeur de pouvoir déclarer des sections de code devant être exécutés de façon atomique, sans avoir à se soucier des détails de synchronisation. Malheureusement, bien qu'assurément plus facile à utiliser que les verrous, la mémoire transactionnelle souffre encore de problèmes de performance et de facilité d'utilisation. En fait, de nombreux concepts relatifs à l'utilisation et à la sémantique des transactions n'ont pas encore des normes convenues. Cette thèse propose de nouvelles solutions permettant de faciliter l'utilisation des mémoires transactionellles. La thèse débute par un chapitre qui donne un bref aperçu de la mémoire transactionnelle logicielle (STM) ainsi qu'une discussion sur le problème de la facilité d'utilisation. Les contributions à la recherche sont ensuite divisées en quatre chapitres principaux, chacun proposant une approche différente afin de rendre les STMs plus facile à utiliser.

Understanding changes in materials properties as a function of size is crucial for both fundamental science development and technological applications. Size restriction results in quantum confinement effects that modify both energy level structures and electron dynamics of solid materials. This study investigates individual quantum states in a single nanocrystal. Single electron charging effects in gold and semiconductor nanocrystals are observed. Charging effects are found to be dominant in samples, where the nanocrystals are weakly coupled to the substrate. For nanocrystals strongly coupled to the substrate, nanocrystal-substrate tunneling rate is larger than tip-nanocrystal tunneling rate. Therefore, the resulting peaks in the dI/dV spectrum are attributed to tunneling through the energy levels of the nanocrystal. A newly developed nanocrystals BEES technique is used successfully to further explore quantized energy levels and electron dynamics in single gold nanocrystals. BEES samples were grown successfully by depositing $unit[10]{nm}$ thick gold on silicon substrates. Nanocrystals are chemically attached to the gold substrate using a self assembled monolayer (SAM) of xyelendithiol molecules. Immobile and single isolated nanocrystals were imaged at low temperature. A BEES turn-on voltage of $unit[0.84]{V}$ was found on nanocrystal-free region of the substrate. The BEES spectrum acquired on a single gold nanocrystal is found to be attenuated by a factor of 10 when compared with BEES acquired on the substrate. The attenuation is attributed to electron relaxation to lower energy states before tunneling out of the nanocrystal. The measured hot electron lifetimes from experimental data were found to be on the order of $unit[16]{picoseconds}$, which is a long time compared to lifetimes in bulk metals or large nanocrystals. The long measured lifetimes result from the molecular-like energy level structures of these small nanocrystals.

This dissertation focuses on three separate studies. First, magnetization of the Mn12- acetate was studied by low temperature hysteresis loops and DC magnetization data on magnetically aligned Mn12-acetate micro-crystals. Secondly, Mn12-acetate thin films were fabricated and characterized by AFM and STM. Finally, magnetization of the film material was also studied. Enhanced alignment of Mn12-acetate micro-crystals as compared to prior studies was verified by observation of several sharp steps in low temperature hysteresis loops. It was found that ~ 0.5 T is sufficient to orient the micro-crystals in an organic solvent to a degree comparable to a single crystal. The degree of the alignment was controlled by varying the magnetic field at room temperature and during the cooling process. Subsequently, low temperature hysteresis loops and DC magnetizations were measured for each prepared orientation state of a sample. The high temperature magnetic anisotropy responsible for the alignment could not be measured, possibly due to its small magnitude. Mn12-acetate was deposited onto Si/SiO2 by a solution evaporation method. Atomic force microscopy studies revealed that 2 nm thick films of molecular level smoothness were formed. Mn12-acetate was also deposited onto a Highly Ordered Pyrolytic Graphite (HOPG) surface for scanning tunneling microscopy (STM) studies. A self-assembled triangular lattice was observed in the Mn12-acetate thin films by STM at room temperature under ambient conditions. These STM images show typical center to center intermolecular separations of about 6.3 nm and height corrugation of less than 0.5 nm. Magnetization measurements were not successful in Mn12-acetate thin films due to the small amount of material in the film and the large background signal from the substrate. Therefore, a sample for the magnetization measurements, called “film material”, was made by evaporating a dilute solution of Mn12-acetate powder in acetonitrile. Significant changes in magnetic properties of the film material were observed from magnetization measurements. The blocking temperature of the film material was found to increase to TB > 10 K at low magnetic fields.

An atomic level understanding of the structure and stability of model catalysts is essential for surface science studies in heterogeneous catalysis. Scanning tunneling microscopy (STM) can operate both in UHV and under realistic pressure conditions with a wide temperature span while providing atomic resolution images. Taking advantage of the ability of STM, our research focuses on 1) investigating the structure and stability of supported Au catalysts, especially under CO oxidation conditions, and 2) synthesizing and characterizing a series of alloy model catalysts for future model catalytic studies. In our study, Au clusters supported on TiO2(110) have been used to model supported Au catalysts. Our STM studies in UHV reveal surface structures of TiO2(110) and show undercoordinated Ti cations play a critical role in the nucleation and stabilization of Au clusters on TiO2(110). Exposing the TiO2(110) surface to water vapor causes the formation of surface hydroxyl groups and subsequently alters the growth kinetics of Au clusters on TiO2(110). STM studies on Au/TiO2(110) during CO oxidation demonstrate the real surface of a working catalyst. Au clusters supported on TiO2(110) sinter rapidly during CO oxidation, but are mostly stable in the single component reactant gas, either CO or O2. The sintering kinetics of supported Au clusters has been measured during CO oxidation and gives an activation energy, which supports the mechanism of CO oxidation induced sintering. CO oxidation was also found to accelerate the surface diffusion of Rh(110). Our results show a direct correlation between the reaction rate of CO oxidation and the diffusion rate of surface metal atoms. Synthesis of alloy model catalysts have also been attempted in our study with their structures successfully characterized. Planar Au-Pd alloy films has been prepared on a Rh(100) surface with surface Au and Pd atoms distinguished by STM. The growth of Au-Ag alloy clusters have been studied by in-situ STM on a cluster-to-cluster basis. Moreover, the atomic structure of a solution-prepared Ru3Sn3 cluster has been resolved on an ultra-thin silica film surface. The atomic structure and adsorption sites of the ultrathin silica film have also been well characterized in our study.

In this new era of mobile society and information explosion, people are continuously receiving different kinds of information representation at anytime and everywhere, how to quickly learn and absorb different kinds of information to become one¡¦s own knowledge is an important challenge for modern people. Due to the rapid advancement of mobile communication & wireless transmission technology, many scholars in academia were believed that these new technologies will have a great impact on the way of learning in the future. As a matter of fact, by effectively applying short-message services as learning content delivery (LCD) methods, including SMS and MMS, provided by mobile phone system to deliver different learning content representation (LCR) types, Mobile Learning (M-learning) can be implemented accordingly. However, the most important issue is whether M-learning based on these LCD methods and LCR types can really achieve good learning outcomes and be accepted by mobile learners. In this research we will explore the restraint of short-term memory (STM) ability of psychological learning process through technology-mediated learning theory on assessing learning outcomes in M-learning environment. The finding of this study is to match different LCR types with different LCD methods to fit learners¡¦ different STM abilities would cause higher learning outcomes in M-learning environment. Therefore, we suggest that Learners with lower verbal and lower nonverbal STM capacity, the most suitable way to help their learning is just providing them the basic learning materials; learners with higher verbal and lower nonverbal STM capacity, providing them additional written annotations will help them learn better; learners with lower verbal and higher nonverbal STM capacity, providing them additional pictorial annotations will help them learn better; and Learners with higher verbal and higher nonverbal STM capacity, the best way is to cater them both written annotations and pictorial annotations in M-learning environment.

The chemisorption and anodic oxidation of hydroquinone (H2Q) and benzoquinone (BQ) at palladium electrode surfaces was studied by a combination of electrochemistry (EC), Auger electron spectroscopy (AES), high-resolution electron- energy loss spectroscopy (HREELS) and electrochemical-scanning tunneling microscopy (EC-STM) on a smooth polycrystalline and well-defined (single-crystalline) Pd(100) electrode surface. The results point to the following more critical conclusions: (i) Chemisorption of H2Q from dilute (less than or equal to 0.1 mM) aqueous solutions forms surface- coordinated BQ oriented parallel albeit with a slight tilt. (ii) At high concentrations (greater than or equal to 1mM), chemisorption yields an edge-vertical oriented diphenolic species. (iii) The extent of anodic oxidation of the chemisorbed organic strongly depends upon its initial orientation; only the flat-adsorbed species are oxidized completely to carbon dioxide. (iv) The rate of anodic oxidation is likewise dependent upon the initial adsorbate orientation; the rate for vertically-oriented species is more than twice that of flat- adsorbed species. (v) The chemisorbed species are not oxidized (to the same extent) simultaneously; instead, oxidation occurs one molecule at a time. That is, molecules that survive the anodic oxidation and remain on the surface retain their original identities.

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.

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.

<p>The local corrosion behavior of duplex stainless steel (DSS)is affected by a wide variety of factors. Localized corrosionof DSS frequently starts at micrometer scale inclusions orprecipitates, which are often segregated in theaustenite-ferrite boundary regions. Moreover, due to thepartitioning of the key alloying elements of ferrite (Cr andMo) and austenite (N and Ni), the local interactions betweenthe phases must also be considered.</p><p>The aim of this doctoral study was to increase the knowledgeabout the local dissolution behavior of DSS in acidic-chlorideenvironments. The recent developments of new local probingtechniques have opened a new frontier in corrosion science,providing valuable local information not accessible in thepast. The local techniques used include electrochemicalscanning tunneling microscopy (EC-STM), scanning probe forcemicroscopy (SKPFM), magnetic force microscopy (MFM), andscanning Auger electron Spectroscopy (SAES), all withmicrometer or sub-micrometer resolution.</p><p>With EC-STM, it was possible to monitor local dissolutionprocesses on DSS in situ, and in real time. MFM was capable ofimaging the phase distribution in DSS without the need of thetraditional surface etching, while SKPFM revealed that theVolta potential difference between the two phases wasmeasurable and significant. SAES showed that the compositiongradient at the phase boundaries is narrower than 2µm.</p><p>Different types of DSSs have been studied, from low-alloyedDSS to superduplex. Higher contents of Cr, Mo and Nstrengthened both phases as well as the phase boundaries,resulting in phases having similar corrosion resistance thatshowed a more uniform dissolution behavior. However, the Voltapotential difference between the phases proved to be of thesame order for all the DSSs studied. Austenite was in generalassociated to regions displaying a more noble Volta potentialthan ferrite, resulting in a higher dissolution rate of theferrite next to the austenite phase.</p><p><b>Key words:</b>In situ, local dissolution, electrochemical,STM, SKPFM, MFM, SAES, duplex stainless steel, acidic-chloridesolution.</p>