This thesis aims to provide insights into two challenging problems in the field of molecular electronics: Understanding the role of the electronic and the mechanical properties of electrodes in determining the charge transport dynamics of molecular devices and achieving the optical control of charge transport through single-molecule junctions by exploiting the optical properties of electrodes. We start by investigating the impact of electrode band structure on the charge transport characteristics of molecular devices. To this end, we conduct two independent, yet highly related studies. In the first study, we demonstrate how the metallic band structure dictates the molecular orbital coupling at metal-molecule interfaces by studying charge transport through pyridine-based single-molecule junctions with Au and Ag electrodes using a newly developed scanning tunneling microscope-based spectroscopy technique and performing density functional theory calculations. We find that pyridine derivatives couple well to Au electrodes compared with Ag electrodes. The density functional theory calculations show that the increase in the molecular orbital coupling to Au compared with Ag is due to an enhanced density of d-states near the Fermi level resulting from relativistic effects. Second, we study the interfacial charge transport properties of molecular devices with metal, semimetal and semiconductor electrodes using X-ray photoemission based spectroscopy techniques. In particular, we probe the hot electron dynamics of 4,4'-bipyrdine on Au (metal), epitaxial graphene (semimetal) and graphene nanoribbon (semiconductor) surfaces. We find that charge transfer from the molecule to the substrate is fastest on the metal surface and slowest on the semiconductor surface. We attribute this trend to a reduced electronic interaction between the molecule and the surface as a results of a decrease in the density of electronic states near the Fermi level as the metallic character of the substrate is reduced. Furthermore, we provide evidence for fast phase decoherence of hot electrons via an interaction with the substrate in these systems. Third, we shed light onto the origin of flicker noise in single-molecule junctions, tunnel junctions and gold point-contacts at room temperature. We find that the switching of gold atoms between metastable sites in the electrodes due to the thermal energy leads to conductance fluctuations in these systems. We further demonstrate how the flicker noise characteristics of single-molecule junctions can be used to infer the nature of the electronic interaction at metal-molecule interfaces. Specifically, we find that flicker noise exhibits a power dependence on junction conductance that can distinguish between through-space and through-bond charge transport. This work demonstrates how the mechanical properties of electrodes affect charge transport through single-molecule junctions and how noise can be used to understand the electronic properties of metal-molecule interfaces. Lastly, we explore the possibility of driving currents through single-molecule junctions using electromagnetic radiation. To this end, we perform photocurrent measurements on single-molecule junctions, tunnel junctions and gold point-contacts obtained using the scanning tunneling microscope-based break-junction technique. We find that the primary source of photocurrents in these systems is the laser induced local heating and the subsequent thermal expansion when probed using a lock-in type technique in which the light intensity is being modulated. We further develop an experimental method that differentiates between the photocurrents due to thermal expansion and the optical currents in single-molecule junctions, and provide evidence for optical currents due to electron-photon interaction during charge transport through single-molecule junctions. By using this method we estimate the plasmonic electric field enhancement factor in single-molecule junctions formed by 4,4'-bipyridine. Our estimate is in very good agreement with values inferred from tip enhanced Raman spectroscopy measurements and field emission measurements. We believe that the results presented in this thesis provide original insights into the fundamentals of the physics that govern charge transport across metal-molecule interfaces. Furthermore, the new experimental techniques introduced in this thesis offer new ways for investigating the rich physics present in nanoscale systems.

Batteries are complex, multidisciplinary, electrochemical energy storage systems that are crucial for powering our society. During operation, all battery technologies suffer from voltage losses due to energetic penalties associated with the electrochemical processes (i.e., ohmic resistance, kinetic barriers, and mass transport limitations). A majority of the voltage losses can be attributed to processes occurring on/in the battery electrodes, which are responsible for facilitating the electrochemical reactions. A major challenge in the battery field is developing strategies to mitigate these losses. To accomplish this, researchers must i) identify the processes limiting the performance of the electrode, ii) characterize the main, performance-limiting processes to understand the underlying mechanisms responsible for the poor performance, and iii) mitigate the voltage losses by developing strategies which target these underlying mechanisms. In this thesis, three studies are presented which highlight the role of electrochemical engineers in alleviating the performance limiting processes in battery electrodes. Each study is focused on a different step of the research approach (i.e., identification, characterization, and mitigation) and analyzes an electrode from a different battery system. The first part of the thesis is focused on identifying the processes limiting the capacity in nanocomposite lithium-magnetite electrodes. To accomplish this, the mass transport processes and phase changes occurring within magnetite electrodes during discharge and voltage recovery are investigated using a combined experimental and modeling approach. First, voltage recovery data are analyzed through a comparison of the mass transport time-constants associated with different length-scales in the electrode. The long voltage recovery times are hypothesized to result from the relaxation of concentration profiles on the mesoscale, which consists of the agglomerate and crystallite length-scales. The hypothesis was tested through the development of a multi-scale mathematical model. Using the model, experimental discharge and voltage recovery data are compared to three sets of simulations, which incorporate crystal-only, agglomerate-only, or multi-scale transport effects. The results of the study indicate that, depending on the crystal size, the low utilization of the active material (i.e., low capacity) is caused by transport limitations on the agglomerate and/or crystal length-scales. For electrodes composed of small crystals (6 and 8 nm diameters), it is concluded that the transport limitations in the agglomerate are primarily responsible for the long voltage recovery times and low utilization of the active material. In the electrodes composed of large crystals (32 nm diameter), the slow voltage recovery is attributed to transport limitations on both the agglomerate and crystal length-scales. Next, the multi-scale model is further expanded to study the phase changes occurring in magnetite during lithiation and voltage recovery experiments. Phase changes are described using kinetic expressions based on the Avrami theory for nucleation and growth. Simulated results indicate that the slow, linear voltage change observed at long times during the voltage recovery experiments can be attributed to a slow phase change from α¬-LixFe3O4 to β¬-Li4Fe3O4. In addition, simulations for the lithiation of 6 and 32 nm Fe3O4 suggest the rate of conversion from α¬-LixFe3O4 to γ-(4 Li2O + 3 Fe) decreases with decreasing crystal size. The next part of the thesis presents a study aimed at characterizing the formation of PbSO4 films on Pb in H2SO4, which has been previously identified as a performance-limiting process in lead-acid batteries. Transmission X-ray microscopy (TXM) is utilized to monitor, in real time, the initial formation, the resulting passivation, and the subsequent reduction of the PbSO4 film. It is concluded with support from quartz-crystal-microbalance experiments that the initial formation of PbSO4 crystals occurs as a result of acidic corrosion. Additionally, the film is shown to coalesce during the early stages of galvanostatic oxidation and to passivate as a result of morphological changes in the existing film. Finally, it is observed that the passivation process results in the formation of large PbSO4 crystals with low area-to-volume ratios, which are difficult to reduce under both galvanostatic and potentiostatic conditions. In a further extension of this study, TXM and scanning electron microscopy are combined to investigate the effects of sodium lignosulfonate on the PbSO4 formation and the initial growth of PbSO4 crystals. Sodium lignosulfonate is shown to retard, on average, the growth of the PbSO4 crystals, yielding a film with smaller crystals and higher crystal densities. In addition, an analysis of the growth rates of individual, large crystals showed an initial rapid growth which declined as the PbSO4 surface coverage increased. It was concluded that the increase in PbSO4 provides additional sites for precipitation and reduces the precipitation rate on the existing crystals. Finally, the potential-time transient at the beginning of oxidation is suggested to result from the relaxation of a supersaturated solution and the development of a PbSO4 film with increasing resistance. The final part of the thesis presents a study aimed at mitigating the ohmic losses during pulse-power discharge of a battery by the adding a second electrochemically active material to the electrode. Porous electrode theory is used to conduct case studies for when the addition of a second active material can improve the pulse-power performance. Case studies are conducted for the positive electrode of a sodium metal-halide battery and the graphite negative electrode of a lithium-ion battery. The replacement of a fraction of the nickel chloride capacity with iron chloride in a sodium metal-halide electrode and the replacement of a fraction of the graphite capacity with carbon black in a lithium-ion negative electrode were both predicted to increase the maximum pulse power by up to 40%. In general, whether or not a second electrochemically active material increases the pulse power depends on the relative importance of ohmic-to-charge transfer resistances within the porous structure, the capacity fraction of the second electrochemically active material, and the kinetic and thermodynamic parameters of the two active materials.

No description available.

Ho, Yee Man Martina = 硒化鎘三維納米結構之製作及其感應脫氧核糖核酸之應用潛能 / 何綺雯. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstract also in Chinese. / Ho, Yee Man Martina = Xi hua ge san wei na mi jie gou zhi zhi zuo ji qi gan ying tuo yang he tang he suan zhi ying yong qian neng / He Qiwen. / Chapter Chapter 1 --- Introduction / Chapter 1 --- Photovoltaic properties of CdSe --- p.1 / Chapter 1.1 --- Quantum size effect --- p.1 / Chapter 1.2 --- Synthesis of CdSe nanostructures --- p.3 / Chapter 1.3 --- Electrochemical sensing of CdSe nanostructures --- p.4 / Chapter 1.3.1 --- Surface passivation and functionalization of CdSe nanostructures --- p.5 / Chapter 1.4 --- Electronic properties of nanocrystalline semiconductor electrode --- p.6 / Chapter 1.4.1 --- Band alignment --- p.6 / Chapter 1.4.2 --- Interfacial charge transfer process --- p.9 / Chapter 1.4.3 --- Surface traps and adsorbed molecules --- p.10 / Chapter 1.4.4 --- DNA molecules as a capping group --- p.11 / Chapter 1.5 --- Literatures review in DNA sensing --- p.12 / Chapter 1.6 --- Present study --- p.14 / Chapter 1.6.1 --- Objective --- p.14 / Chapter 1.6.2 --- General methodology --- p.15 / Chapter Chapter 2 --- Experimental / Chapter 2.1 --- Introduction into the instrumentation of this project --- p.21 / Chapter 2.2 --- CHI Electrochemical workstation --- p.22 / Chapter 2.2.1 --- Linear sweep voltammetry --- p.24 / Chapter 2.2.2 --- Cyclic voltammetry --- p.24 / Chapter 2.2.3 --- Multiple potential step --- p.25 / Chapter 2.3 --- CEM Microwave-assisted chemical synthesizer --- p.27 / Chapter 3.1 --- Morphological examination by scanning electron microscopy --- p.28 / Chapter 3.2 --- Elemental analysis by energy dispersive x-ray spectroscopy --- p.30 / Chapter 3.3 --- Crystal structure analysis by x-ray diffraction --- p.31 / Chapter 3.4 --- Surface compositional analysis by x-ray photoelectron spectroscopy --- p.32 / Chapter 3.5 --- Transmission electron microscopy --- p.34 / Chapter Chapter 3 --- Synthesis of 3D nanostructured CdSe multipod electrodes / Chapter 3.1 --- Introduction into the synthesis of CdSe MP electrode --- p.35 / Chapter 3.2 --- Recipe for the synthesis of CdSe NPs --- p.36 / Chapter 3.3 --- The synthesis of CdSe MPs --- p.37 / Chapter 3.3.1 --- Tuning the experimental parameters: Reaction temperature --- p.37 / Chapter 3.3.2 --- Tuning the experimental parameters: Reaction hold time --- p.46 / Chapter 3.3.3 --- Tuning in experimental parameters: Precursor molar ratio --- p.50 / Chapter 3.4 --- The fabrication of MP CdSe on a conductive substrate --- p.54 / Chapter 3.4.1 --- The electrodeposition of CdSe thin films on ITO/glass substrates --- p.55 / Chapter 3.4.2 --- The growth of CdSe MPs on CdSe/ ITO/glass --- p.57 / Chapter 3.5 --- The characterization of MP CdSe electrode --- p.57 / Chapter Chapter 4 --- Electrical and opto-electric characteristics of CdSe MP electrodes and their applications as platforms for the DNA recognition / Chapter 4.1 --- Introduction to the property characterization of CdSe MP electrodes --- p.62 / Chapter 4.2 --- DNA surface attachment --- p.64 / Chapter 4.2.1 --- Mechanism of DNA surface anchoring --- p.65 / Chapter 4.3 --- I-V characterization in PBS --- p.69 / Chapter 4.3.1 --- Experimental procedures of the I-V tests in PBS --- p.70 / Chapter 4.3.2 --- Results and discussions of I-V tests in PBS --- p.72 / Chapter 4.3.2.1 --- Exercising as-prepared CdSe MP electrode --- p.74 / Chapter 4.3.2.2 --- I-V characteristics of CdSe MP electrodes before and after ssDNA attachment --- p.75 / Chapter 4.3.2.3 --- I-V characteristics of CdSe MP electrodes before and after the dsDNA attachment --- p.76 / Chapter 4.3.2.4 --- "Photo-response of bare CdSe MP, ssDNA/CdSe MP and dsDNA/CdSe electrodes" --- p.77 / Chapter 4.4 --- "Photovoltaic I-V measurement in I3""/I"" redox electrolyte" --- p.79 / Chapter 4.4.1 --- Experimental procedures --- p.79 / Chapter 4.4.2 --- Results and discussions --- p.80 / Chapter 4.5 --- Possible application implied by the results --- p.88 / Chapter 4.5.1 --- DNA base pair mismatch identification --- p.91 / Chapter 4.5.2 --- Field-assisted DNA hybridization acceleration process --- p.92 / Chapter Chapter 5 --- Conclusions / Chapter 5.1 --- Conclusions --- p.95

Les polymères à empreintes moléculaires sont des matériaux aux propriétés de reconnaissance spécifiques qui peuvent être mis à profit pour la détection d’une large gamme d’analytes. Ainsi, depuis quelques années, des travaux décrivent leur utilisation dans des capteurs en raison de leur capacité à piéger une cible définie.L’objectif de ce travail est d’ajouter des propriétés redox à des polymères à empreintes moléculaires pour détecter le Bisphénol A (BPA) par des méthodes électrochimiques simples. Ces polymères électroactifs sont synthétisés par polymérisation par précipitation d’une sonde redox, le méthacrylate deméthylferrocène (Fc), et du diméthacrylate d’éthylène glycol (EDMA) en présence du BPA pour le polymère imprimé (e-MIP-Fc) et en son absence pour le polymère non-imprimé (e-NIP-Fc).L’introduction d’un deuxième monomère fonctionnel, la 4-vinyl pyridine (4-VP), conduit à deux autres polymères imprimé (e-MIP-Fc-VP) et non-imprimé (e-NIP-Fc-VP). Les propriétés d’adsorption des polymères ainsi obtenus sont caractérisés en batch à l’aide de la LC-MS et présentent une capacité de reconnaissance du BPA avec un facteur d’empreinte de 2,5 et 1,3 respectivement pour l’e-MIP-Fc-VP et e-MIP-Fc justifiant de l’efficacité de l’empreinte. Leurs caractérisations par voltampérométrie cyclique confirment d’une part la bonne intégration du monomère ferrocényle dans les e-MIP/e-NIP et d’autre part la capacité de ces polymères à révéler la présence ou pas de la cible. Les particules e-MIP-Fc ont ensuite été intégrées dans des dispositifs type micro électrode ou transistor OECT (Organic ElectroChemical Transistor). Les premiers résultats, mêmes s’ils doivent être confirmés, s’avèrent encourageants avec,comme attendu, des modifications des propriétés électriques en présence du BPA. L’e-MIP-Fc-VP après mélange avec de la pâte de carbone, a été utilisé en sérigraphie pour obtenir une électrode de travail modifiée dans des électrodes sérigraphiées (Screen Printed Electrode). Ces électrodes permettent la reconnaissance du BPA avec des limites de détection et de quantification de 60 pM et 190 pM respectivement pour une gamme de concentrations comprise entre 0,15 et 1,84 nM, ouvrant ainsi des perspectives intéressantes pour la détection du BPA en milieu aqueux. / Molecularly imprinted polymers are materials with specific recognition properties that can be used for the detection of a wide range of template. In recent years, many works have been reported on their use in sensors because of their capability to specifically bind a defined analyte.The aim of this work is to assign to the molecularly imprinted polymers redox properties in order to detect Bisphenol A (BPA) by using easy electrochemical techniques. These electroactive polymers are synthesizedby precipitation polymerization of ferrocenylmethyl methacrylate (Fc) and ethylene glycol dimethacrylate(EDMA) in the presence of BPA for the imprinted polymer (e-MIP-Fc) and in its absence for the nonimprinted polymer (e-NIP-Fc). The copolymerization of the previous monomer with 4-vinylpyridine (4-VP) leads to two other imprinted (e-MIP-Fc-VP) and non-imprinted (e-NIP-Fc-VP) polymers. The resulting polymers are characterized in batch using LC-MS and have ability to recognize BPA with an imprinting factor of 2.5 and 1.3 respectively for e-MIP-Fc-VP and e-MIP-Fc the proving the recognition efficiency ofthese polymers. Their cyclic voltammetry recording confirm first, the good integration of the redoxferrocenyl monomer inside the polymers e-MIP/e-NIP during the polymerization, and on the other hand,the capability of these polymers to reveal the presence of BPA in the solution. The e-MIP-Fc particles were then integrated inside devices like microelectrode and OECT (Organic ElectroChemical Transistor). The first results, even if they must be confirmed, are positive regarding the modification of the electrical properties of these devices in the presence of BPA. The e-MIP-Fc-VP particles, after mixing with a carbon paste, were screen-printed to obtain a modified working electrode in a screen-printed electrode device. This electrode enable the recognition of BPA with limits of detection and quantification of 60 pM and 190 pM respectively, for a concentration range between 0.15 and 1.84 nM, thus opening up interesting perspectives for the detection of BPA in aqueous medium.

This thesis outlines a study of the physical changes that hybridisation imposes on single-stranded DNA (ssDNA) immobilised by one end to a substrate, and of how such physical changes can be exploited to detect specific sequences of DNA in a target solution. The system studied was composed of a mixed monolayer of 20mer ssDNA with C6 alkanethiolate modifications on their 3??? ends and short-chain hydroxyterminated alkanethiolates, on a gold substrate. It was prepared using the self-assembly properties of alkanethiols on gold. Atomic force microscopy images showed that the end-immobilised ssDNA is flexible enough to lie over the diluent hydroxy-terminated self-assembled monolayer (SAM). Hybridisation was shown to cause the DNA to become more rigid and stand up off the substrate due to an increase in persistence length. Such physical changes of the DNA upon hybridisation were significant enough to be exploited in the development of a DNA recognition interface. The recognition interface was designed with the view of keeping it both simple to make and simple to use, and was coupled with electrochemical transduction. A label-free recognition interface was developed that relied on the oxidation of the sulfur head group of the alkanethiolate SAM to detect hybridisation (firstly air oxidation and then electrochemical oxidation). It produced a positive signal upon hybridisation with complementary target DNA. Improvements in the reliability and robustness of the recognition interface were made using a labelled approach. The labelled version employed electroactive molecules as labels on the 5??? ends of the probe DNA strands. Two labels were investigated ??? anthraquinone and ferrocene. The flexibility of the ssDNA ensured that the redox labels were able to directly access the underlying gold electrode. Hybridisation was expected to remove the labels from the electrode due to an increase in the DNA???s persistence length, and thus perturb the electrochemical signal. The use of ferrocene as a label provided a ???proof-of-concept??? for the system. The labelled recognition interface provides a foundation for the future development of a simple, reliable, and selective DNA hybridisation biosensor.

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Jingguang G. Chen, Dept. of Chemical Engineering. Includes bibliographical references.

Women are four to eight times more likely to injure their anterior cruciate ligament (ACL) compared to men. It is most commonly injured through a non-contact mechanism during game time situations. During landings, women display valgus collapse, where a less active gluteus medius muscle (GMed) may be unable to control the internal rotation of the thigh, causing an increase in knee joint abduction angle, augmenting the risk of ACL injury. This study’s purpose was to determine the difference between 12 male and 12 female athletes in muscle activity, specifically the GMed, and the 3D kinematics and kinetics of the lower-limb during drop jump landings from three heights; maximum vertical jump height, tibial length, and a commonly used height of 40cm. Results showed that females had greater hip adduction and knee abduction angles compared to men. The GMed activity showed no significant differences between sexes at each drop jump height.

Hot microelectrodes are very small electrodes (usually 1 100 µm in diameter), which have a surface temperature much higher than the temperature in the bulk solution. In this work, the heating is achieved by applying an alternating potential of very high frequency (100 MHz 2 GHz) and of high amplitude (up to 2.8 Vrms) to the microelectrode. As a result, very fast (on the order of milliseconds) changes in the temperature of the electrolyte solution surrounding the electrode can be achieved. Due to the size of the heated microelectrodes, the hot zone in solution is small. Therefore, the solution can be easily overheated and temperatures above the boiling point can be reached.<p> The purpose of this research was to investigate and understand the phenomena occurring at ac polarized microelectrodes and to propose new applications of these electrodes. Using both steady-state and fast-scan (10 V/s) cyclic voltammetry measurements, mass transport of redox species has been studied at ac heated microelectrodes. It has been established that the convection at hot-disk microelectrodes is driven primarily by the electrothermal flow of an electrolyte solution. In addition, other effects such as ac dielectrophoresis and Soret (nonisothermal) diffusion are also observed. Numerical simulations have been employed to predict the distribution of temperature in the hot zone, the direction and magnitude of the electrothermal force and the solution flow rate, as well as the voltammetric response of hot-disk microelectrodes. The results of the simulations agree well with the experimental observations. Theoretical findings of this PhD work are very important for the understanding of the fundamentals of high temperature electrochemistry, particularly mass transport. The proposed explanation of the convection mechanism is most likely applicable not only to ac polarized microelectrodes, but also to the microwave heated microelectrodes, since the only difference between these two heating methods is in the way of delivering electrical energy (wired vs. wireless). The results of the studies of Soret diffusion indicate that it contributes significantly to mass transfer of redox species at hot microelectrodes. Taking into account that the magnitude of the Soret effect has been considered negligible by other electrochemists, the results obtained in this work prove the opposite and show that Soret diffusion affects both the faradaic current and the half-wave potential of the redox reaction. Therefore, the Soret effect can not be ignored if working with hot microelectrodes.<p> Hot microelectrodes can have a number of interesting applications. The results of the initial investigations indicate that these electrodes can be successfully used in the arrangement for Scanning Electrochemical Microscopy (such a novel technique is termed Hot-Tip SECM). In addition, the observed dielectrophoretic and electrothermal convection effects can enhance the performance of the electrochemical sensors based on hot microelectrodes. This can lead to the improvement of the detection limits of many biologically important analytes, such as proteins, bacteria and viruses.

Organic semiconductors have the advantage over traditional inorganic semiconductors, such as Si or GaAs, in that they do not require perfect single crystal films to operate in real devices. Complicated multi-layer structures with nanometer scale thicknesses can thus be easily fabricated from organic materials using low-cost roll-to-roll manufacturing techniques. However, the discrete nature of organic semiconductors also implies that they typically contain almost no intrinsic charge carriers (i.e., electrons or holes), and thus act as insulators until electrical charges are injected into them. In electrical device applications this means that all of the holes and electrons within a device must be injected from the anode and cathode respectively. As a result, device stability, performance, and lifetime are greatly influenced by the interface between the organic materials and the electrode contacts. Despite the fundamental importance of the electrode/organic contacts, much of the basic physical understanding of these interfaces remains unclear. As a result, the current design of state-of-the-art organic optoelectronic devices tends to be based on trial and error experimentation, resulting in overly complicated structures that are less than optimal. In the present thesis, various electrode/organic interfaces relevant to device applications are studied using a variety of different techniques, including photoelectron spectroscopy and the iii temperature dependent current-voltage characteristics of single carrier devices. The fundamental understanding gleaned from these studies has been used to develop new strategies for controlling the energy-level alignment at electrode/organic interfaces. A universal method for tuning the work function of electrode materials using a halogenated organic solvent and UV light has been developed. Application of this technique in organic light emitting diodes enabled the first highly simplified two-layer device with a state-of-the-art record breaking efficiency.