The dissociative adsorption of three carboxylic acids (acetic acid, propanoic acid, and acrylic acid), allyl alcohol, and allyl aldehyde on Si(100)2×1 at room temperature has been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The C 1s features obtained by XPS measurement for acetic acid, propanoic acid, and acrylic acid show that formation of bidentate carboxylate at a low exposure is followed by that of unidentate carboxylate at a higher exposure, with approximately equal population for both adstructures. The signatures of C 1s features attributed to methyl (285.7 eV), ethyl (285.3 eV), ethenyl (285.0 eV), and bidentate carboxyl (286.8 eV) and unidentate carboxyl (289.8-289.3 eV) carbons were observed for the studied carboxylic acids. The results showed that the carboxyl group is more reactive than the alkyl or alkenyl group towards the Si(100)2×1 surface, with O−H dissociation preferred over [2+2] C=C cycloaddition and the other plausible reaction products. This was also supported by our DFT calculation which showed that the bidentate carboxylate adstructure is the most stable configuration among the calculated adstructures for the aforementioned carboxylic acids. The combined temperature-dependent XPS and TPD studies provided strong evidence for the formation of ketene, acetaldehyde and CO from acetic acid, CO and ethylene from propanoic acid, and CO, ethylene, acetylene, and propene from acrylic acid. Furthermore, the TPD results provided further evidence for the preferred structure of the adsorbate from each of the carboxylic acid on the surface. In addition to carboxyl group, reactivity of the hydroxyl and carbonyl functional groups relative to that of ethenyl group was studied by investigating the reaction of allyl alcohol and allyl aldehyde on Si(100)2×1 at room temperature. The C 1s XPS results supported O−H dissociation for allyl alcohol and [2+2] C=O cycloaddition for allyl aldehyde over the [2+2] C=C cycloaddition. The similarity between the observed C 1s features for allyl alcohol and allyl aldehyde helped to identify the structure of the adsorption products of these two molecules on the surface. The presence of the related C 1s feature of C=C for allyl alcohol and allyl aldehyde, and the absence of C 1s feature of C=O for allyl aldehyde provided strong evidence to support that [2+2] C=C cycloaddition does not occur in the presence of hydroxyl or carbonyl groups. Furthermore, by comparing the experimental results and the adsorption energies of the adstructures calculated by DFT, it was concluded that these molecules do not react with the Si dimers through both of their functional groups, while the reaction of only one of the two functional groups is preferred on the surface. Formation of ethylene, acetylene, and propene from allyl alcohol and allyl aldehyde, simultaneously to CO from allyl alcohol, was concluded from the corresponding TPD results, which also confirm the structure of the adsorbates on the surface. The present research shows that reactions involving oxygen-containing functional groups are favoured over the other plausible reactions including [2+2] C=C cycloaddition on the Si(100)2×1. The preference of the surface to react with one of the two functional groups calls for future studies for the selective functionalization of Si(100)2×1 with potential applications in molecular electronics.

The dissociative adsorption of three carboxylic acids (acetic acid, propanoic acid, and acrylic acid), allyl alcohol, and allyl aldehyde on Si(100)2×1 at room temperature has been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The C 1s features obtained by XPS measurement for acetic acid, propanoic acid, and acrylic acid show that formation of bidentate carboxylate at a low exposure is followed by that of unidentate carboxylate at a higher exposure, with approximately equal population for both adstructures. The signatures of C 1s features attributed to methyl (285.7 eV), ethyl (285.3 eV), ethenyl (285.0 eV), and bidentate carboxyl (286.8 eV) and unidentate carboxyl (289.8-289.3 eV) carbons were observed for the studied carboxylic acids. The results showed that the carboxyl group is more reactive than the alkyl or alkenyl group towards the Si(100)2×1 surface, with O−H dissociation preferred over [2+2] C=C cycloaddition and the other plausible reaction products. This was also supported by our DFT calculation which showed that the bidentate carboxylate adstructure is the most stable configuration among the calculated adstructures for the aforementioned carboxylic acids. The combined temperature-dependent XPS and TPD studies provided strong evidence for the formation of ketene, acetaldehyde and CO from acetic acid, CO and ethylene from propanoic acid, and CO, ethylene, acetylene, and propene from acrylic acid. Furthermore, the TPD results provided further evidence for the preferred structure of the adsorbate from each of the carboxylic acid on the surface. In addition to carboxyl group, reactivity of the hydroxyl and carbonyl functional groups relative to that of ethenyl group was studied by investigating the reaction of allyl alcohol and allyl aldehyde on Si(100)2×1 at room temperature. The C 1s XPS results supported O−H dissociation for allyl alcohol and [2+2] C=O cycloaddition for allyl aldehyde over the [2+2] C=C cycloaddition. The similarity between the observed C 1s features for allyl alcohol and allyl aldehyde helped to identify the structure of the adsorption products of these two molecules on the surface. The presence of the related C 1s feature of C=C for allyl alcohol and allyl aldehyde, and the absence of C 1s feature of C=O for allyl aldehyde provided strong evidence to support that [2+2] C=C cycloaddition does not occur in the presence of hydroxyl or carbonyl groups. Furthermore, by comparing the experimental results and the adsorption energies of the adstructures calculated by DFT, it was concluded that these molecules do not react with the Si dimers through both of their functional groups, while the reaction of only one of the two functional groups is preferred on the surface. Formation of ethylene, acetylene, and propene from allyl alcohol and allyl aldehyde, simultaneously to CO from allyl alcohol, was concluded from the corresponding TPD results, which also confirm the structure of the adsorbates on the surface. The present research shows that reactions involving oxygen-containing functional groups are favoured over the other plausible reactions including [2+2] C=C cycloaddition on the Si(100)2×1. The preference of the surface to react with one of the two functional groups calls for future studies for the selective functionalization of Si(100)2×1 with potential applications in molecular electronics.

Behaviour of Group III (Al) and IV (Sn) metals on Si(100) surface was studied by Scanning Tunnelling Microscopy in a temperature range from 115 K to 350 K. Evolution of the length of Sn chains at room and elevated temperatures was studied by the method of repeated line scans. Activation energies and the respective frequency prefactors for detachment of different individual atoms from the chains' terminations were obtained by means of statistical processing. Kinetic Monte Carlo simulations were used to obtain activation energies for hops of Sn adatoms on the Si(100) surface at room temperature by fitting experimentally measured growth characteristics of Sn/Si(100). Three basic Al objects observed by Scanning Tunnelling Microscopy at room temperature on Si(100) were identified and thoroughly described. Direct observation of Al adatom hopping on Si(100)-c(4x2) at 115 K was used to evaluate the activation energies for individual hops in directions parallel with Si dimer rows and perpendicular to Si dimer rows. Kinetic Monte Carlo simulations were used to obtain activation energies for hops of Al adatoms on the Si(100) surface at room temperature by fitting experimentally measured growth characteristics of Al/Si(100).

The subject of the thesis is growth of aluminium structures one-dimensional chains on Si(100) surface. Growth characteristics of Al on Si(100) at room temperature and at higher temperature and various coverages were measured using STM. The results are discussed with respect to previous experiments and a way to find the value of activation energy of surface migration is proposed. An important part of the thesis is preparation and tests of a new low-temperature UHV apparatus for STM experiments. Functions of the apparatus are described. A way to prepare clean Si(100) surface as well as the methods of achieving atomic-scale resolution in STM were found in conditions previously unknown. A test of evaporators for Al and Sn is described. Al deposition has not been successful in the new apparatus yet. Sn deposition has been successful and low-temperature structures of tin on Si(100) were observed. They differ from room-temperature structures and contain kinks which were previously observed only in Al structures.

Surface diffusion of group III and IV metals on Si(100) is studied. Three methods for obtaining diffusion barriers are presented and discrepancies in published results are discussed. Room temperature growth of Al on Si(100) is studied using STM, observing a monomodal scaled island size distribution function. A Kinetic Monte Carlo simulation model is employed to obtain bonding energies and diffusion barriers for Al/Si(100). The best agreement between the measured and simulated characteristics is found for strongly anisotropic diffusion with barriers 0.60 eV in the direction orthogonal to the Si dimer rows and 0.80 eV in the parallel direction. Modifications of the cooling system required for observing metal adatom diffusion on Si(100) using STM are described and the first low-temperature experiment is carried out.

The thesis presents the research results obtained while studying novel chemical strategies for preparing Si(100)-based electrochemical platforms suitable for aqueous environments. A primary research aim was the preparation of well-passivated Si(100) surfaces amenable to further chemical derivatization. The preparation and functionalization of alkyne-terminated alkyl monolayers on Si(100) surfaces using the Huisgen 1,3-dipolar ???click??? cycloaddition of azides with surface-bound acetylenes is reported and shown to be a versatile, experimentally simple, chemically unambiguous modular approach to modified silicon surfaces. Covalently immobilized, structurally well-defined acetylenyl organic monolayers are prepared from a commercially available ??,??-diyne (1,8-nonadiyne) species using a one-step thermal hydrosilylation procedure. Subsequent derivatization of the alkyne-terminated monolayers in aqueous environments with representative azide species affords disubstituted surface-bound [1,2,3]-triazole species. Neither activation procedures nor protection/deprotection schemes are required, as is the case with more established grafting approaches for silicon surfaces. The described surface modification scheme has been used in preparing modified Si(100) electrode surfaces, where modular components such as ferrocene derivatives or electrochemically ???switchable??? linker molecules are introduced onto the passivated silicon surface. An implementation study to prepare modified light-addressable ???switchable??? Si(100) electrodes is also reported. Negligible oxidation of the substrate was generally observed after exposure to aqueous systems for extended periods (tens of hours), and the electroactive monolayers showed a robust and reversible behaviour. The proposed concept of modular components and high-yielding coupling procedures has been shown on Si(100) surfaces and also extended to illustrate the functionalization of porous silicon rugate filters.

1 Title: Interaction of group III and IV metals with Si(100) surface in temperature range from 20 to 800 K Author: Martin Setvín Department: Departement of Surface and Plasma Science Supervisor of the doctoral thesis: Doc. RNDr. Ivan Ošt'ádal CSc. Abstract: Interaction of group III and IV metals with Si(100) surface was studied by STM (Scanning Tunneling Microscopy) and AFM (Atomic Force Microscopy) in temperature range from 20 to 800 K. Adsorption and hopping of single metal adatoms on Si(100)-c(4×2) reconstruction can be observed by STM at low temperatures. Activation energies and frequency prefactors for hopping of single indium atoms were measured by two meth- ods - direct STM measurement at low temperature and Kinetic Monte Carlo simulations of layer growth at room temperature. Group III and IV atoms self-assemble into single atom wide chains on Si(100) surface at about room temperature. Atomic and electronic structure of the chains was investi- gated by means of STM and dynamic non-contact AFM. Keywords: Si(100), STM, AFM, adsorption, diffusion

A superfície (100) do Silício é estudada através de métodos de primeiros princípios, baseados na Teoria do Funcional da Densidade e no Método dos Pseud.opotenciais. Estudamos as propriedades eletrônicas e estruturais das principais reconstruções desta superfície. Obtivemos os principais sítios ligantes para pequenas estruturas de Germânio adsorvidas sobre ela. Para um átomo adsorvido o sítio mais estável encontrado foi o sítio M, semelhante a resultados existentes na literatura. A diferença está na configuração dos dímeros de Si da superfície. Observamos que diferentes configurações destes dímeros nos forneciam diferentes sítios metaestáveis. O deslocamento dos dímeros da superfície é tratado então como um novo grau de liberdade para a adsorção de átomos, além da posição destes sobre a superfície. Também foi estudada a adsorção de alguns trímeros de Ge sobre a superfície, sendo que a estrutura encontrada como sendo a mais estável concorda muito bem com outros resultados teóricos e experimentais. / The (100) surface of Silicon is studied using First Principles methods, based on the Density Functional Theory and on the Pseudopotential method. We obtained the electronic and structural properties of the most important reconstructions of this surface and we also obtained the main bonding sites for the adsorption of small Ge structures on the surface. Site M was found as being the most stable for the monomers adsorption, similar to previous results on the literature. The main difference is on the buckling of the silicon surface dimers. We observed that different configurations of these buckling gave us different metastable adsorption sites. We then insert a new degree of freedom for this kind of adsorption, related to the buckling of the silicon surface dimers. \\Me also studied the adsorption of Ge trimers on the surface, and the structure found as being the most stable agree very well with previous theoretical and experimetal results.

A superfície (100) do Silício é estudada através de métodos de primeiros princípios, baseados na Teoria do Funcional da Densidade e no Método dos Pseud.opotenciais. Estudamos as propriedades eletrônicas e estruturais das principais reconstruções desta superfície. Obtivemos os principais sítios ligantes para pequenas estruturas de Germânio adsorvidas sobre ela. Para um átomo adsorvido o sítio mais estável encontrado foi o sítio M, semelhante a resultados existentes na literatura. A diferença está na configuração dos dímeros de Si da superfície. Observamos que diferentes configurações destes dímeros nos forneciam diferentes sítios metaestáveis. O deslocamento dos dímeros da superfície é tratado então como um novo grau de liberdade para a adsorção de átomos, além da posição destes sobre a superfície. Também foi estudada a adsorção de alguns trímeros de Ge sobre a superfície, sendo que a estrutura encontrada como sendo a mais estável concorda muito bem com outros resultados teóricos e experimentais. / The (100) surface of Silicon is studied using First Principles methods, based on the Density Functional Theory and on the Pseudopotential method. We obtained the electronic and structural properties of the most important reconstructions of this surface and we also obtained the main bonding sites for the adsorption of small Ge structures on the surface. Site M was found as being the most stable for the monomers adsorption, similar to previous results on the literature. The main difference is on the buckling of the silicon surface dimers. We observed that different configurations of these buckling gave us different metastable adsorption sites. We then insert a new degree of freedom for this kind of adsorption, related to the buckling of the silicon surface dimers. \\Me also studied the adsorption of Ge trimers on the surface, and the structure found as being the most stable agree very well with previous theoretical and experimetal results.

L'utilisation de différents niveaux de complexité dans les méthodes de la chimie théorique permet de discuter de la validité des modèles de reconstruction de la surface Si(100) et de créer des modèles de sous-oxydes. Notre étude ab-initio Hartree-Fock périodique est en faveur d'une reconstruction symétrique combinée à un arrangement anti-ferromagnétique 2x2 des spins des électrons des liaisons pendantes. Néanmoins la reconstruction asymétrique est quasi isoénergétique. Le traitement d'un large modèle moléculaire de sous-oxydes pseudo-périodique, permet de rendre compte des contraintes de la surface. L'importante relaxation trouvée dans cette étude est la combinaison d'une translation verticale et d'une rotation. Le réseau, la valence des espèces présentes peut influencer la cinétique de la relaxation. Le premier site d'oxydation est la liaison du dimère. Les atomes de silicium sont ensuite oxydés un par un.