Thesis (Ph.D.)--York University, 1999. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 155-161). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pNQ43453

Thesis (Ph. D.)--Ohio State University, 2004. / Title from first page of PDF file. Document formatted into pages; contains xvii, 208 p.; also includes graphics (some col.). Includes bibliographical references (p. 189-208).

Thesis (M.S.)--Ohio State University, 2005. / Includes bibliographical references (leaves 69-74). Available online via OhioLINK's ETD Center

In this thesis, a wide breadth of topics related to the field of surface science are addressed using density functional theory (DFT). Specifically, five studies with relevance to molecular electronics and heterogeneous catalysis are presented, with a particular focus on interadsorbate interactions, reactivity and characterisation of molecules on transition metal surfaces. The first part of this work focuses on giving strong theoretical underpinning to the atomic-scale observations provided by scanning tunnelling microscopy (STM) experiments conducted by my group colleagues. The theoretical calculations presented here provide support to the experimental evidences but also serve to unravel information that is inaccessible from the experiments. On the one hand, the variety of results obtained in this thesis using standard DFT methods serve to highlight the capabilities of the computationally low-demanding methods for modelling processes occurring on metal surfaces. On the other hand, we notice that these workhorse methods in DFT have inherent limitations for providing an accurate description of some properties, in particular binding energies. This, further improvements in the level of theory are necessary for advancing the computational accuracy of standard DFT methods in materials science. The second part of this thesis is devoted to highlight the high level of accuracy obtained by the new theoretical approaches in the field of materials science. Due to the recent implementation of new algorithms combined with the increasing computer power that is available to the scientific community, these sophisticated methods are becoming more accessible for modelling solid-state systems. Here, the recent implementation of the random-phase approximation (RPA) for solids is employed to perform to benchmark study on the adsorption of benzene on different close-packed transition metal surfaces. The development of new theoretical tools is also essential to improve our predictive capabilities in surface science. A novel approach to correct vibrational intensities by including anharmonicities using density functional perturbation theory (DFPT) is proposed. The new method is tested for the adsorption of different organic molecules on various transition metal surfaces. The results obtained by this implementation demonstrate excellent improvements for predicting accurate spectra of molecules on surfaces.

abstract: Understanding charge transport in single molecules covalently bonded to electrodes is a fundamental goal in the field of molecular electronics. In the past decade, it has become possible to measure charge transport on the single-molecule level using the STM break junction method. Measurements on the single-molecule level shed light on charge transport phenomena which would otherwise be obfuscated by ensemble measurements of groups of molecules. This thesis will discuss three projects carried out using STM break junction. In the first project, the transition between two different charge transport mechanisms is reported in a set of molecular wires. The shortest wires show highly length dependent and temperature invariant conductance behavior, whereas the longer wires show weakly length dependent and temperature dependent behavior. This trend is consistent with a model whereby conduction occurs by coherent tunneling in the shortest wires and by incoherent hopping in the longer wires. Measurements are supported with calculations and the evolution of the molecular junction during the pulling process is investigated. The second project reports controlling the formation of single-molecule junctions by means of electrochemically reducing two axial-diazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in-situ between the molecule and gold electrodes. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond. Finally, the third project investigates the role that molecular conformation plays in the conductance of oligothiophene single-molecule junctions. Ethyl substituted oligothiophenes were measured and found to exhibit temperature dependent conductance and transition voltage for molecules with between two and six repeat units. While the molecule with only one repeat unit shows temperature invariant behavior. Density functional theory calculations show that at higher temperatures the oligomers with multiple repeat units assume a more planar conformation, which increases the conjugation length and decreases the effective energy barrier of the junction. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2013

This thesis presents the development of a selective-etch fabrication process to create sub-10 nanometre metallic gaps and the subsequent use of the gaps to study the electronics of nanocrystals and molecules. A complete picture of the success of the process required both examination by scanning electron microscopy as well as probing the current response to an applied bias at low temperature. The empty gaps were fully characterised before self-assembling 7 nm CdSe nanocrystals onto the metal with the help of linker molecules. The I-V characteristics of the empty gaps showed a reduction of the tunnelling barrier height from the expected value (~5.1 eV, the work function of Au) when the results were fitted to the Simmons tunnelling model for a metal-insulator-metal system. Results indicate that after the barrier height is surpassed, a transition from direct to field-effect (Fowler-Nordheim) tunnelling occurs. After CdSe assembly, the collected I-V characteristics of the system at 77 K showed varied results. Many devices displayed conductance peaks at low voltages comparable to the results of the shadow evaporation process for 4.2 nm nanocrystals (also documented in this thesis). Several devices revealed switching between multiples of fundamental curves, suggesting conduction through multiples of nanocrystals.

Modern studies on charge transfer reaction and conductivity measurements of DNA have shown that the electrical behavior of DNA ranges from that of an insulator to that of a wide bandgap semiconductor. Based on this property of DNA, a metal-semiconductor-metal photodetector is fabricated using a self-assembled layer of deoxyguanosine derivative (DNA base) deposited between gold electrodes. The electrodes are lithographically designed on a GaN substrate separated by a distance L (50nm < L < 100nm). This work examines the electrical and optical properties of such wide-bandgap semiconductor based biomaterial systems for their potential application as photodetectors in the UV region wherein most of the biological agents emit. The objective of this study was to develop a biomolecular electronic device and design an experimental setup for electrical and optical characterization of a novel hybrid molecular optoelectronic material system. AFM results proved the usage of Ga-Polar substrate in conjugation with DG molecules to be used as a potential electronic based sensor. A two-terminal nanoscale biomolectronic diode has been fabricated showing efficient rectification ratio. A nanoscale integrated ultraviolet photodetector (of dimensions less than 100 nm) has been fabricated with a cut-off wavelength at ~ 320 nm.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19734号 / 工博第4189号 / 新制||工||1646(附属図書館) / 32770 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 辻 康之, 教授 村田 靖次郎, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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