published_or_final_version / Chemistry / Master / Master of Philosophy

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The fundamental atomic and electronic behaviour of clean silicon surfaces has been studied within a simple tight-binding picture of bonding in solids. Of the various contributions to the surface binding energy, the lowering in the promotion energy (i.e. rehybridization) which accompanies localized Jahn-Teller distortions has been identified as a major electronic driving force underlying the stability of silicon surfaces. The structure of Si(113) has been experimentally determined by the technique of scanning tunnelling microscopy (STM). Despite its high index, the Si(113) surface is found to be highly stable. STM images of both empty and filled states provide strong evidence for a particular structural model with a 3x2 unit cell. The STM results are explained in terms of a general rehybridization principle, suggested by the earlier theoretical study, which accounts for the low surface energy as well as the observed spatial distribution of empty and filled states. In addition, the STM images reveal a high density of domain boundaries which introduce energy states that pin the Fermi level and explain earlier reports of a 3x1 reconstruction for this surface. Voltage-dependent STM image simulations for the Si(113)3x2 surface have been carried out using a simple tight-binding description of surface electronic structure. Quantitative agreement with experiment is obtained confirming the qualitative rehybridization arguments used previously. The local barrier for tunnelling electrons is shown to have an important effect on the interpretation of STM images. The high stability of clean Si(l 13) is shown by STM to be disrupted by adsorption of submonolayer amounts of atomic hydrogen which saturates dangling bonds. Mass transport of silicon occurs and structural models are proposed for the resultant mixed 2x2 and 2x3 surface.

This thesis demonstrates the effective use of low temperature molecular beam epitaxy to encapsulate planar Si:P (phosphorus-in-silicon) devices lithographically patterned by scanning tunnelling microscopy (STM) without significant redistribution of the dopants. To achieve this goal, low temperature magnetotransport is used in combination with STM, Auger electron spectroscopy and secondary ion-mass spectrometry to analyse Si:P ??-doped samples fabricated under different doping and growth conditions. An important aspect of this project is the use of large 1 ?? 1 cm2 Si(001) samples which are about five times larger than standard STM samples. The larger sample size is necessary for post-STM fabrication lithography processes in a cleanroom but presents problems for preparing atomically clean surfaces. The ability to prepare clean and atomically flat Si(001) surfaces for STM lithography on such 1 ?? 1 cm2 samples is demonstrated, and it is shown that Si:P ??-doped layers fabricated on these surfaces exhibit complete electrical activation. Two dopant sources (gaseous PH3 and solid GaP source) were investigated to assess their compatibility with STM-lithography on the H:Si(001) surface. The findings show that while the PH3 and GaP sources result in near identical electrical qualities, only PH3 molecules are compatible with H-resist based lithography for controlled nano-scale doping. For achieving complete activation of the P dopants, it is shown that an anneal to ??? 350 ???C to incorporate P atoms into the Si surface prior to encapsulation is critical. While it is known that the presence of H during growth degrades the quality of Si epitaxy, investigations in this thesis indicate that it has no significant effect on dopant activation. Systematic studies performed to assess the impact of growth temperature recommend an encapsulation temperature of 250 ???C for achieving optimal electrical qualities with minimal dopant segregation. In addition, it is shown that rapid thermal anneals (RTAs) at temperatures &lt 700 ???C provide only marginal improvement in the electrical quality of Si:P ??-doped samples encapsulated at 250 ???C, while RTA temperatures &gt 700 ???C should be avoided due to the high probability of dopant redistribution. To elucidate the nature of 2D transport in Si:P ??-doped devices, a detailed analysis of the low temperature magnetotransport for Si:P ??-doped layers with doping densities in the range ??? 0.2 ??? 2 ?? 1014 cm???2 was carried out. Using conventional 2D theories for disordered systems, both weak localisation (WL) and electron-electron interactions (EEI) are shown to contribute almost equal corrections to the 2D conductivity. In particular, it is found that EEI can introduce a significant correction in the Hall coefficient RH (hence Hall density) especially in the low density/temperature regime and the need to correct for this when using the Hall density to estimate the activated electron density is highlighted. While the electronic mean free path in such highly doped ??-layers is typically &lt 10 nm making ballistic transport in these devices difficult to observe, the phase coherence length can extend to almost 200 nm at about 0.3???0.5 K for doping densities of ??? 1 ??? 2 ?? 1014 cm???2. Finally, the optimised encapsulation strategy developed in this thesis is applied to a 2D square device fabricated by STM. The device exhibits Ohmic conductivity with complete dopant activation. An analysis of its low temperature magnetotransport shows that the device behaves similarly to a Si:P ??-doped layer encapsulated under similar conditions, thus highlighting that the STM patterning process had no adverse effect on device quality.

Thesis (M.S.)--Rochester Institute of Technology, 2009. / Typescript. Includes bibliographical references (leaves 57-59).

Thesis (Ph. D.)--University of Alberta, 2009. / Title from PDF file main screen (viewed on Oct. 19, 2009). "A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy, Department of Physics, University of Alberta." Includes bibliographical references.

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Douglas J. Doren, Dept. of Chemistry and Biochemistry. Includes bibliographical references.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2007. / Vita. Includes bibliographical references (leaves 116-130). Also available in electronic version.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 183-190).

The electron transfer mechanisms of multiheme cytochromes were examined with scanning tunneling microscopy (STM). To simulate bacterial metal reduction mediated by proteins in direct contact with mineral surfaces, monolayers of purified decaheme cytochromes from the metal-reducing bacterium Shewanella oneidensis were prepared on Au(111) surfaces. Recombinant tetracysteine sequences were added to two outermembrane decaheme cytochromes (OmcA and MtrC) from S. oneidensis MR-1 to ensure chemical immobilization on Au(111). STM images of the cytochrome monolayers showed good coverage and their shapes/sizes matched that predicted by their respective molecular masses. Current-voltage (I-V) tunneling spectroscopy revealed that OmcA and MtrC exhibit characteristic tunneling spectra. Theoretical modeling of the single-molecule tunneling spectra revealed a distinct tunneling mechanism for each cytochrome: OmcA mediates tunneling current coherently whereas MtrC temporarily traps electrons via orbital-mediated tunneling. These mechanisms suggest a superexchange electron transfer mechanism for OmcA and a redox-specific (i.e. heme-mediated) electron transfer mechanism for MtrC at mineral surfaces during bacterial metal reduction. Additionally, a novel electrochemical STM configuration was designed to measure tunneling current from multiheme cytochromes to hematite (001) surfaces in various electrolyte solutions. Current-distance (I-s) profiles on hematite (001) reveal predictable electric double layer structure that changes with ionic strength. The addition of the small tetraheme cytochrome c (STC) from S. oneidensis on insulated Au tips resulted in modified tunneling profiles that suggest STC significantly modulates the double layer. This observation is relevant to understanding metal reduction in cases where terminal metal-reducing enzymes are unable to come in direct contact with reducible mineral surfaces. Electronic coupling to the mineral surface might therefore be mediated by a localized ion swarm specific to the mineral surface. / Ph. D.