In this thesis, we focus on the structural identification of the interface using surface enhanced Raman spectroscopy (SERS) and inelastic electron tunnelling scattering (IETS). Two different molecular junctions, namely gold/ trans-1,2-bis (4-pyridyl) ethylene/gold junction and gold/4,4'-bipyridine/gold junctions in various conditions were studied and the corresponding configurations were determined. The enhancement in SERS was also studied by employing the time-dependent density functional theory. Furthermore, we studied some properties of the interface, such as the stability of the adsorbates and charge transfer properties of molecular junctions. The decrease in the stability of molecules was found when adsorbed on metallic surface and trapped in metallic junctions. Our studies explained several puzzles and by rational design, more stable molecular devices were obtained.

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The work in this thesis can be split into three areas. In the first, inelastic electron tunnelling spectroscopy (IETS) is used to investigate resistive and bias polarity dependent effects on vibrational mode energy in metal - aluminium oxide - metal tunnel junctions. It is shown that even when four point-probe techniques are used the ratio of width to thickness of the electrodes used in IET junctions has an effect on both the breadth and position of spectral lines. A simple treatment based upon work done by Giaever allows for such effects to be corrected. Work done on top metal and polarity effects in undoped IET junctions investigated the effect on the position of the 450 meV mode on reversing the applied bias. The investigation revealed that any dependence on the nature of the top-metal electrode was outside the accuracy of the work. Calculation of q/e for the hydroxyl group on alumina within the tunnel junction has been extended to include other electrode materials. A new and exciting facility within the university provided the impetus for the second area of work. A class 100 clean room housing a Langmuir Blodgett (LB) trough offered the opportunity to produce metal - insulator - Langmuir Blodgett film - metal tunnel junctions. It was realised at the outset that IETS using LB films would be difficult, previous workers had tried using a home-made tank with only limited success. However, the added sophistication of the new tank did not improve matters as was hoped. Although the results were disappointing, only a few junctions had resistances low enough to be usable in the spectrometer, the investigation produced some of the very few IET specra using junctions doped with LB films. The results also revealed the important role that imperfections and pin-holes play in the tunnelling process. The last area used IETS to investigate two commercially important and interesting polymers, hydrogels and polymeric electrolytes. Hydrogel have many applications in the field of implants, prosthetic, and cosmetics and have been studied and developed for many years. Polymeric electrolytes have many commercial applications especially in the field of solid-state batteries and conducting polymers. The way in which hydrogels swell as they absorb water is important, as is the way they adsorb onto a surface and much work has been done to investigate these characteristics using bulk samples. The study done by this group is the first to investigate the swelling and adsorption behaviour of a monolayer of the hydrogel poly 2-hydroxylethyl methacrylate. The results from both investigations indicate that ester cleavage occurs in p-HEMA and that water incorporated within a hydrogel has a limited structure with the first layer being thinner than the second and subsequent layers.

<p>A theoretical framework for calculating electron transport through molecular junctions is presented. It is based on scattering theory using a Green's function formalism. The model can take both elastic and inelastic scattering into account and treats chemical and physical bonds on equal footing. It is shown that it is quite reliable with respect to the choice of functional and basis set. Applications concerning both elastic and inelastic transport are presented, though the emphasis is on the inelastic transport properties. The elastic scattering application part is divided in two part. The first part demonstrates how the current magnitude is strongly related to the junction width, which provides an explanation why experimentalists get two orders of magnitude differences when performing measurements on the same type of system. The second part is devoted to a study of how hydrogenbonding affects the current-voltage (I-V) characteristics. It is shown that for a conjugated molecule with functional groups, the effects can be quite dramatic. This shows the importance of taking possible intermolecular interactions into account when evaluating and comparing experimental data. The inelastic scattering part is devoted to get accurate predictions of inelastic electron tunneling spectroscopy (IETS) experiments. The emphasis has been on elucidating the importance of various bonding conditions for the IETS. It is shown that the IETS is very sensitive to the shape of the electrodes and it can also be used to discriminate between different intramolecular conformations. Temperature dependence is nicely reproduced. The junction width is shown to be of importance and comparisons between experiment as well as other theoretical predictions are made.</p>

A theoretical framework for calculating electron transport through molecular junctions is presented. It is based on scattering theory using a Green's function formalism. The model can take both elastic and inelastic scattering into account and treats chemical and physical bonds on equal footing. It is shown that it is quite reliable with respect to the choice of functional and basis set. Applications concerning both elastic and inelastic transport are presented, though the emphasis is on the inelastic transport properties. The elastic scattering application part is divided in two part. The first part demonstrates how the current magnitude is strongly related to the junction width, which provides an explanation why experimentalists get two orders of magnitude differences when performing measurements on the same type of system. The second part is devoted to a study of how hydrogenbonding affects the current-voltage (I-V) characteristics. It is shown that for a conjugated molecule with functional groups, the effects can be quite dramatic. This shows the importance of taking possible intermolecular interactions into account when evaluating and comparing experimental data. The inelastic scattering part is devoted to get accurate predictions of inelastic electron tunneling spectroscopy (IETS) experiments. The emphasis has been on elucidating the importance of various bonding conditions for the IETS. It is shown that the IETS is very sensitive to the shape of the electrodes and it can also be used to discriminate between different intramolecular conformations. Temperature dependence is nicely reproduced. The junction width is shown to be of importance and comparisons between experiment as well as other theoretical predictions are made. / QC 20101118

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No description available.

Organic molecules such as porphyrins and alkanethiols are currently being investigated for applications such as sensors, light-emitting diodes and single electron transistors. Porphyrins are stable, highly conjugated compounds and the choice of metal ion and substituents bound to the macrocycle as well as other effects such as chemical surrounding and cluster size modulate the electronic and photonic properties of the molecule. Porphyrins and their derivatives are relatively non-toxic and their very rich photo- and electro-chemistry, and small HOMO-LUMO gaps make them outstanding candidates for use in molecularly-enhanced electronic applications. For these studies, self-assembled tri-pyridyl porphyrin thiol derivatives have been fully characterized on Au(111) surfaces. A variety of surface characterization techniques such as Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS) have been implemented in order to obtain information regarding the attachment orientation based on the angle and physical height of the molecule, conductivity which is determined based on the apparent height and current-voltage (I-V) measurements of the molecule, conductance switching behavior due to conformational or other effects as well as the stability of the molecular ensembles. Specifically, the transport properties of free base and zinc coordinated tri-pyridyl porphyrin thiol molecular islands inserted into a dodecanethiol matrix on Au(111) were investigated using STM and cross-wire inelastic electron tunneling spectroscopy (IETS). The zinc porphyrin thiol islands observed by STM exhibited reversible bias induced switching at high surface coverage due to the formation of Coulomb islands of ca. 10 nm diameter driven by porphyrin aggregation. Low temperature measurements (~ 4 K) from crossed-wire junctions verified the appearance of a Coulomb staircase and blockade which was not observed for single molecules of this compound or for the analogous free base. Scanning probe lithography via nanografting has been implemented to directly assemble nanoscale patterns of zinc porphyrin thiols and 16-mercapotohexadecanoic acid on Au surfaces. Matrix effects during nanopatterning including solvent and background SAMs have been investigated and ultimately ~ 10 nm islands of zinc porphyrins have been fabricated which is the optimal size for the observed switching effect.

La Spectroscopie par Effet Tunnel Inélastique (IETS) avec un Microscope à Effet Tunnel (STM) est une nouvelle technique de spectroscopie vibrationnelle, qui permet de caractériser des propriétés très fines de molécules adsorbées sur des surfaces métalliques. Des règles de selection d’excitation vibrationnelle basées sur la symétrie ont été proposées, cependant, elles ne semblent pas exhaustives pour expliquer la totalité du mécanisme et des facteurs en jeu; elles ne sont pas directement transposables pour les propriétés d'un adsorbat et sont lourdes d'utilisation. Le but de cette thèse est donc d'améliorer ces règles de selection par une étude théorique. Un protocole de simulation de l'IETS a été développé, paramétré, et évalué, puis appliqué pour calculer des spectres IETS pour différentes petites molécules, qui sont systématiquement liées, sur une surface de cuivre. Des principes additifs de l'IETS ont été developpés, notamment concernant l’extension dans le vide de l’état de tunnel, l'activation/ quench sélectif de certains modes du aux propriétés électroniques de certains fragments moléculaires, et l'application de certaines règles d'addition de signaux IETS. De plus, des empreintes vibrationnelles par des signaux IETS ont été determinées pour permettre de différentier entre les orientations des adsorbats, la nature chimique des atomes et les isomères de structures. Une stratégie simple utilisant les propriétés de distribution de la densité électronique de la molécule isolée pour prédire les activités IETS sans des couts importants de calculs a aussi été développée. Cette expertise a été utilisée pour rationaliser et interpréter les mesures expérimentales des spectres IETS pour des métalloporphyrines et métallophtalocyanines adsorbées. Ces études sont les premières études IETS pour des molécules aussi larges et complexes. L'approche expérimentale a permis de déterminer les limitations actuelles des simulations IETS. Les défauts associés à l'identification ont été résolus en faisant des simulations d'images STM complémentaires. / Inelastic Electron Tunneling Spectroscopy (IETS) with the Scanning Tunneling Microscope (STM) is a novel vibrational spectroscopy technique that permits to characterize very subtle properties of molecules adsorbed on metallic surfaces. Its proposed symmetry-based propensity selection rules, however, fail to fully capture its exact mechanism and influencing factors; are not directly retraceable to an adsorbate property and are cumbersome. In this thesis, a theoretical approach was taken to improve them. An IETS simulation protocol has been developed, parameterized and benchmarked, and consequently used to calculate IETS spectra for a set of systematically related small molecules on copper surfaces. Extending IETS principles were deduced that refer to the tunneling state’s vacuum extension, the selective activating/quenching of certain types of modes due to the moieties’ electronic properties, and the applicability of a sum rule of IETS signals. Also, fingerprinting IETS-signals that enable discrimination between adsorbate orientations, the chemical nature of atoms and structural isomers were determined and a strategy using straightforward electronic density distribution properties of the isolated molecule to predict IETS activity without (large) computational cost was developed. This expertise was used to rationalize and interpret experimentally measured IETS spectra for adsorbed metalloporphyrins and metallophthalocyanines, being the first IETS studies of this large size. This experimental approach permitted to determine the current limitations of IETS-simulations. The associated identification shortcomings were resolved by conducting complementary STM-image simulations.