Rozprawy doktorskie na temat „Charge transfer device”

There is a need for monolithic devices capable of spatial resolution in imaging and ionizing radiation detection. In this thesis, a GaAs acoustic charge transport device (ACT) was studied for this purpose. A new method of charge injection has been demonstrated for the ACT. Using near-infrared optical pulses incident through thin semi-transparent chromium windows, electron-hole-pairs were separated by the electric field in a depleted n-type channel region of the device. For light penetration less than the depth of the electron potential minimum, and for small injection levels, calculations indicated that electrons and holes were separated at their saturation velocities. Holes moving toward the surface of the substrate could recombine with electrons at an evaporated Schottky metal plate. Electrons moving toward the channel centre were bunched and transported by the electric field coupled to a <110> propagating surface acoustic wave (SAW) on (100) cut GaAs. Quantum efficiency, defined as the number of electrons collected at the output per incident photon on the GaAs surface, was greater than 9% at an optical wavelength of 730 nm. When compensation was made for the loss and reflection due to the chromium windows, the quantum efficiency was in excess of 24%. Charge transfer efficiency was greater than 0.992 with the ACT clocked at 360 MHz. The demonstrated optical injection technique may be of use in future ACT imaging devices.
Applied Science, Faculty of
Electrical and Computer Engineering, Department of
Graduate

The research described in this dissertation conclusively demonstrates the superior qualitative and quantitative performance of spectroscopic systems which employ a new class of optical detectors--charge transfer device (CTD) detectors. An overview of the operation and characteristics of these detectors, as well as theoretical models predicting their performance are presented. The evaluation of a unique prototype single element CID detector, a commercially available linear CCD detector, and a prototype two-dimensional CCD detector are described. Outstanding characteristics include the ability of the single element CID to quantitate photon fluxes ranging over eleven orders of magnitude, a quantum efficiency of the linear CCD in excess of 90%, and a read noise of the two-dimensional CCD of under 5 electrons. In addition, the use of the linear CCD for molecular fluorescence spectroscopy is demonstrated. A direct comparison of CCD and CID detection for atomic emission spectroscopy using a custom echelle system is described. The second part of these investigations focus on the design of spectrometers compatible with the format of these multichannel detectors. While a large number of spectrometer designs exist, the spectrometer and detector combination which produces the highest possible signal-to-noise ratio (SNR) spectra for a given experimental system is almost always desired. The investigations into optimum spectrometer design have led to the use of a unique spatial interferometer system. The performance of a common path interferometer using a linear charge-coupled device detectors is presented and compared to conventional dispersive systems. The throughput, resolution, and other practical factors are discussed. The common path system has a much larger light gathering ability compared to dispersive systems; however, spatial interferometry suffers from the multiplex disadvantages encountered with other forms of UV/Vis interferometry. A unique crossed interferometric dispersive arrangement allows the simultaneous acquisition of the spectral information while greatly reducing these multiplex disadvantages. Preliminary work on the crossed interferometric system is presented demonstrating significant reduction of these multiplex disadvantages.

In organic solar cells, the understanding of loss mechanisms, especially the energetic losses driven by the offset at type-II heterojunction and recombination, are crucial to improve the device performance. The best-performing organic solar cells are polymer:fullerene blends, and despite an abundance of donor materials, phenyl-C61/71-butyric acid methyl ester (PCBM) remains the most-used acceptor material. In this thesis, we use fullerene multiadducts as new acceptor materials that allow us to study energetic losses in polymer:fullerene blends by tuning the offset at the heterojunction. In addition, we analyse their performance in blends with high-performance polymer donors. The first chapter of results addresses design rules for fullerene multiadducts and energetic disorder. By adding multiple sidechains to the fullerene cage, the LUMO level can be raised by up to 400 meV compared to PCBM, which allows increased open circuit voltages. Fullerene multiadducts, however, are a mixture of different isomers with increased packing and energetic disorder and show reduced electron transport. Using Differential Pulse Voltammetry measurements, we quantify the amount of energetic disorder present in a variety of fullerene multiadducts. In the second results chapter, the fullerene multiadducts are employed in photovoltaic devices with poly(3-hexylthiophene) (P3HT) and other donor polymers. While most fullerene multiadducts perform reasonably well with P3HT as donor, their performance in blends with other donor polymers is usually much lower when compared to blends with PCBM as acceptor. We find that for many polymer:fullerene blends with multiadducts, the offset of the organic heterojunction is too small to allow efficient charge generation, especially for donor polymers optimised for PCBM. Even if the offset in the blend is sufficiently high, the lower electron mobility of the fullerene multiadducts is likely to reduce device performance, only donors featuring high hole mobility and high crystallinity show reasonable performance. Energetic losses in organic solar cells and limits of the charge transfer (CT) state energy are studied in the third results chapter of the thesis. We establish that electroluminescence (EL) from the CT state originates from transport levels in the density of states and that the spectrum shifts very little with increased injection currents. This allows us to use the EL emission peak as a proxy for the energy of the CT state. By employing indenofullerene multiadducts in blends with various polymers, we consistently find an additional loss pathway via polymer or fullerene exciton formation. If the energy of the CT state approaches the smaller optical bandgap of either component in the blends (Eopt,min), photocurrent and fill factor are likely to be reduced by increased recombination. We find this reduced performance in a number of blends, which allows us to empirically determine an limit of the open circuit voltage for efficient solar cell relative to Eopt,min for these systems.

The use of scientifically operated charge-transfer device array detectors are investigated for several spatial and spectroscopic optical imaging applications in chemical analysis and are described in this dissertation. The improved optical detection capabilities of this class of solid state detectors, made up of both charge-injection and charge-coupled device (CCD) detectors, offers a number of significant advantages over previous optical detection technologies utilized for these applications. The results obtained from the investigation of the use of a scientifically operated charge-injection device based echelle spectrograph system for the on-line monitoring of heteropoly acids, after chromatographic separation, for the indirect determination of phosphate, silicate and arsenate are presented. The obtained results represent an improvement over direct aspiration into an emission source for these nonmetals, showing excellent linearity over three orders of magnitude. Results from the evaluation of a scientific CCD detector based technique for the luminescence imaging of latent fingerprint residues on glass and paper, after chemical treatment with fluorescence enhancement agents, is presented. The use of a scientific CCD for fingerprint imaging is demonstrated to be a viable alternative to those methodologies requiring the use of high power laser excitation sources and photographic film imaging. Results of the use of a scientific CCD for the spectroscopic determination of seawater pH are also presented. Discussion is given to general system design, detector characteristics and modes of operation which will result in a ship board instrument capable of making both sensitive fluorometric and precise absorbance measurements. Additional investigations presented include the use of a scientific CCD for the in situ detection of DNA fragments separated in agarose electrophoretic slab gels and aflatoxins separated on thin-layer chromatographic plates. Scientific CCD detection, in contrast to previous optical detection techniques, is demonstrated here to provide for a competitive means of component detection in these media, offering significant advantages in speed, precision and ease of analysis.

La present tesi esta focalitzada tant en la síntesi de molècules orgàniques òpticament actives així com en la seva aplicació i caracterització en dispositius fotovoltaics, concretament per a les cel·les solars sensibilitzades amb colorant (DSSC en anglès). Les DSSC són cel·les foto-electroquímiques formades per colorant ancorat a un semiconductor (normalment TiO2) i en presencia d'un electròlit. En aquests dispositius, cada component té un efecte clau en la eficiència final de la cel·la, degut als processos de transferència electrònica que tenen lloc la interfície TiO2/colorant/electròlit. Aquests processos varen ser estudiat en gran detall utilitzant porfirines, perilens i D -  - A com a colorants, per poder així definir uns paràmetres amb els quals l'eficiència final del dispositiu es pugui correlacionar amb l'estructura molecular del colorant. Entendre aquesta relació entre l'estructura química i l'eficiència del dispositiu permet un millor diseny de futures molecules per a DSSC.
The present thesis focuses on the synthesis of organic chromophores as well as their use in optoelectronic devices, particulary in Dye Sensitized Solar Cells (DSSC). This kind of solar cell is based on a photoactive unit, a dye, anchored to a nanostructured metal-oxide semiconductor, usually TiO2, in a redox electrolyte media and sandwiched between two contact electrodes. In DSSC devices, each component (semiconductor, sensitizer and electrolyte) plays an important role in determining the final device efficiency, in a large part due to the charge transfer processes that take place at the TiO2/dye/electrolyte interface. Therefore, these charge transfer kinetics were studied using porphyrins, perylenes and donor -  - acceptor organic dyes in order to understand and establish a relationship between the molecular structure and the device performance. Improved understanding of this relationship is crucial for improved molecular design of future dyes for DSSC.

The rapidly increasing power conversion efficiencies (PCEs) of organic solar cells (OSCs) above 10% were made possible by concerted international research activities in the last few years, aiming to understand the processes that lead to the generation of free charge carriers following photon absorption. Despite these efforts, many details are still unknown, especially how these processes can be improved already at the drawing board of molecular design. To unveil this information, dicyanovinyl end-capped oligothiophene derivatives (DCVnTs) are used as a model system in this thesis, allowing to investigate the impact of small structural changes on the molecular properties and the final solar cells. On thin films of a methylated DCV4T derivative, the influence of the measurement temperature on the charge carrier generation process is investigated. The observed temperature activation in photoinduced absorption (PIA) measurements is attributed to an increased charge carrier mobility, increasing the distance between the charges at the donor/acceptor (D/A) interface and, thus, facilitating their final dissociation. The correlation between the activation energy and the mobility is confirmed using a DCV6T derivative with lower mobility , exhibiting a higher activation energy for charge carrier generation. Another parameter to influence the charge carrier generation process is the molecular structure. Here, alkyl side chains with varying length are introduced and their influence on the intramolecular energy levels as well as the absorption and emission properties in pristine and blend films with the acceptor C60 are examined. The observed differences in intermolecular order (higher order for shorter side chains) and phase separation in blend layers (larger phase separation for shorter side chains) are confirmed in PIA measurements upon comparing the temperature dependence of the triplet exciton lifetimes. A proposed correlation between the side chain length and the coupling between D and A, which is crucial for efficient charge transfer, is not confirmed. The presented flat heterojunction solar cells underline this conclusion, giving similar photocurrent densities for all compounds. Differences in PCE are related to shifts of the energy levels and the morphology of the blend layer in bulk heterojunction devices. Furthermore, the impact of the electric field on the charge carrier generation yield is investigated in a proof-of-principle study, introducing PIA measurements in transmission geometry realized using semitransparent solar cells. The recombination analysis of the photogenerated charge carriers reveals two recombination components. Trapped charge carriers or bound charge pairs at the D/A interface are proposed as an explanation for this result. The miscibility of D and A, which can be influenced by heating the substrate during layer deposition, is of crucial importance to obtain high PCEs. In this work, the unusual negative influence of the substrate temperature on DCV4T:C60 blend layers in solar cells is investigated. By using optical measurements and structure determination tools, a rearrangement of the DCV4T crystallites is found to be responsible for the reduced absorption and, therefore, photocurrent at higher substrate temperature. The proposed blend morphology at a substrate temperature of 90° C is characterized by a nearly complete demixing of the D and A phases. This investigation is of particular relevance, because it shows the microscopic origins of a behavior that is contrary to the increase of the PCE upon substrate heating usually reported in literature. Finally, the optimization steps to achieve a record PCE of 7.7% using a DCV5T derivative as donor material are presented, including the optimization of the substrate temperature, the active layer thickness, and the transport layers
Der rasante Anstieg des Wirkungsgrads von organischen Solarzellen über die Marke von 10% war nur durch länderübergreifende Forschungsaktivitäten während der letzten Jahre möglich. Trotz der gemeinsamen Anstrengungen, die Prozesse, die zwischen der Absorption der Photonen und der Ladungsträgererzeugung liegen, genauer zu verstehen, sind einige Fragen jedoch immer noch ungelöst, z.B. wie diese Prozesse schon auf dem Reißbrett durch die gezielte Änderung bestimmter Molekülstrukturen optimiert werden können. Um dieses Ziel zu erreichen, werden in dieser Arbeit Dicyanovinyl-substituierte Oligothiophene (DCVnTs) verwendet. Diese Materialien bieten die Möglichkeit, kleine strukturelle Änderungen vorzunehmen, deren Einfluss auf die molekularen und auf die Solarzelleneigenschaften untersucht werden soll. Der Einfluss der Messtemperatur auf den Prozess der Ladungsträgertrennung wird hier an einer methylierten DCV4T-Verbindung in einer dünnen Schicht untersucht. Die bei photoinduzierter Absorptionsspektroskopie (PIA) beobachtete Aktivierung dieses Prozesses mit zunehmender Temperatur wird auf eine erhöhte Ladungsträgerbeweglichkeit zurückgeführt. Der dadurch erhöhte effektive Abstand der Ladungen an der Grenzfläche zwischen Donator (D) und Akzeptor (A) erleichtert die endgültige Trennung der Ladungsträger. Durch den Vergleich mit einer DCV6T-Verbindung wird der Zusammenhang zwischen der Aktivierungsenergie und der Beweglichkeit bekräftigt. Die kleinere Beweglichkeit äußert sich dabei in einer größeren Aktivierungsenergie. Darüber hinaus kann der Ladungsträgergenerationsprozess auch von der Molekülstruktur abhängen. In dieser Arbeit wird untersucht, wie sich die Länge von Alkylseitenketten auf die Energieniveaus der Moleküle, aber auch auf die Absorptions- und Lumineszenzeigenschaften der Materialien in reinen und in Mischschichten mit dem Akzeptor C60 äußert. Die ermittelten Unterschiede bezüglich der Molekülordnung (geordneter für kürzere Seitenketten) und der Phasengrößen in Mischschichten (größere Phasen bei kürzerer Kettenlänge) werden in der Untersuchung der Temperaturabhängigkeit der Lebensdauer von Triplettexzitonen mittels PIA-Messungen bestätigt. Für Solarzellen ist von Bedeutung, ob sich die Seitenkettenlänge auf die Wechselwirkung zwischen D und A auswirkt. Der vermutete Zusammenhang wird hier nicht bestätigt. Ein ähnlicher Photostrom für alle untersuchten Verbindungen in Solarzellen mit planaren Heteroübergängen unterstreicht diese Schlussfolgerung. Unterschiede im Wirkungsgrad werden auf Änderungen der Energieniveaus und die Morphologie in Mischschichtsolarzellen zurückgeführt. Des Weiteren wird in einer Machbarkeitsstudie der Einfluss des elektrischen Felds auf die Generationsausbeute freier Ladungsträger untersucht. Dafür werden halbtransparente Solarzellen verwendet, die es ermöglichen, PIA-Messungen in Transmissionsgeometrie durchzuführen. Als mögliche Erklärung für das Auftreten zweier Rekombinationskomponenten in der Analyse des Rekombinationsverhaltens der durch Licht erzeugten Ladungsträger werden eingefangene Ladungsträger und gebundene Ladungsträgerpaare an der D/A-Grenzfläche genannt. Das Mischverhalten von D und A kann durch ein Heizen des Substrates während des Verdampfungsprozesses eingestellt werden, was von entscheidender Bedeutung für eine weitere Steigerung des Wirkungsgrades ist. Für DCV4T:C60-Mischschichtsolarzellen wird jedoch eine Verschlechterung des Wirkungsgrads zu höheren Substrattemperaturen beobachtet. Durch optische Messungen und Methoden zur Schichtstrukturbestimmung wird dieser Effekt auf eine Umordnung der DCV4T-Kristallite für hohe Substrattemperaturen und die damit verbundene Verringerung der Absorption und damit auch des Photostroms zurückgeführt. Bei einer Substrattemperatur von 90° C sind die D- und A-Komponenten fast vollständig entmischt. Dieses Beispiel ist von besonderer Bedeutung, weil hier die Ursachen für ein Verhalten aufgezeigt werden, das entgegen den Beispielen aus der Literatur eine Abnahme des Wirkungsgrads beim Aufdampfen der aktiven Schicht auf ein geheiztes Substrat zeigt. Schließlich werden die Optimierungsschritte dargelegt, mit denen Solarzellen mit einer DCV5T-Verbindung als Donatormaterial auf einen Rekordwirkungsgrad von 7,7% gebracht werden. Dabei wird die Substrattemperatur, die Dicke der aktiven Schicht und die Transportschichten angepasst

Cette étude analyse la commutation de blocage d'un igbt utilise en commutation quasi-résonnante a zéro de courant. Deux igbt de structure technologique différente ont été étudiés, le premier est à base non homogène et a couche tampon, le second à base homogène et contrôlé d'injection de charges par l'émetteur. L'évolution de la charge stockée dans la base du transistor bipolaire interne au blocage est suivie et analysée à l'aide de simulations et d'expérimentations. Différents éléments interviennent sur l'évacuation de la charge stockée donc sur les pertes au blocage, qu'ils soient propres au composant (coefficients d'injection ou durées de vie) ou a sa commande (maintien du canal lors de la conduction de la diode antiparallèle). Ce qui permet de comprendre pourquoi les pertes au blocage sont plus faibles en commutation a zero de courant qu'en commutation commandée. Une caractérisation électrique et thermique de l'igbt permet ensuite de quantifier l'influence des conditions de commutation sur les pertes au blocage. Des limites de fonctionnement sont ainsi définies, pour s'affranchir de l'emballement thermique, principale cause de destruction des igbt a couche tampon en zcs a fréquence de découpage élevée

Organic solar cells have great potential for cost-effective and large area electricity production, but their applicability is limited by the relatively low efficiency. In this dissertation I report investigations of novel materials and the underlying principles of organic solar cells, carried out at the University of St Andrews between 2011 and 2015. Key results of this investigation: • The charge carrier mobility of organic semiconductors in the active layer of polymer solar cells has a rather small influence on the power conversion efficiency. Cooling solar cells of the polymer:fullerene blend PTB7:PC₇₁BM from room temperature to 77 K decreased the hole mobility by a factor of thousand but the device efficiency only halved. • Subphthalocyanine molecules, which are commonly used as electron donor materials in vacuum-deposited active layers of organic solar cells, can, by a slight structural modification, also be used as efficient electron acceptor materials in solution-deposited active layers. Additionally these acceptors offer, compared to standard fullerene acceptors,advantages of a stronger light absorption at the peak of the solar spectrum. • A low band-gap polymer donor material requires a careful selection of the acceptor material in order to achieve efficient charge separation and a maximum open circuit voltage. • Metal structures in nanometer-size can efficiently enhance the electric field and light absorption in organic semiconductors by plasmonic resonance. The fluorescence of a P3HT polymer film above silver nanowires, separated by PEDOT:PSS, increased by factor of two. This could be clearly assigned to an enhanced absorption as the radiative transition of P3HT was identical beside the nanowires. • The use of a processing additive in the casting solution for the active layer of organic solar cells of PTB7:PC₇₁BM strongly influences the morphology, which leads not only to an optimum of charge separation but also to optimal charge collection.

The investigations described within this dissertation foretell the imminent revolution in optical analytical spectroscopy and conclusively demonstrate superior qualitative and quantitative analysis performance of a new system for atomic spectroscopy as compared to present, state-of-the-art instrumentation. The advent of a new class of multichannel detectors, the silicon charge transfer devices (CTDs) is shown to significantly impact ultraviolet, visible, and near-infrared analytical spectroscopy. An overview of the operation, characteristics, and performance of CTDs is presented including the results of the characteristics of a CTD detector system developed during these investigations. Theoretical comparisons of the performance obtainable in spectroscopic systems employing CTD detectors versus conventional detectors, including equations identifying the factors limiting sensitivity, demonstrate that CTDs offer superior performance. The second part of this dissertation describes the application of a particular CTD, the charge injection device (CID), to a very challenging spectroscopic problem, as far as light detection is concerned, simultaneous multielement analytical atomic emission spectroscopy. This widely employed technique for qualitative and quantitative elemental analysis requires sensitive and wide dynamic range detection of a large number of spectral resolution elements. This research resulted in the development of a novel echelle spectrometer employing a CID detector which has been demonstrated to be capable of solving many of the problems currently encountered in analytical atomic spectroscopy. The system achieves superior sample throughput rates, flexibility, accuracy and precision as compared to sequential spectrometers employing a single detector and to polychromators employing relatively few fixed detectors. The research included the development of a unique method of operating the CID, which is used to cope with the very wide dynamic range signals encountered in atomic spectroscopy, and has resulted in a spectroscopic instrument able to qualify simultaneously major and trace components of extremely complex samples with greater sensitivity and accuracy than possible with conventional instrumentation. New, very flexible, and extremely rapid methods of qualitative analysis have also been developed which virtually eliminate the possibility of spectral line misassignment. The atomic emission spectroscopic system is applicable in a variety of analytical areas as diversified as high sensitivity detection of near infrared spectral lines and element-specific detection of chromatographic eluents.

Nous avons déterminé l'alignement des niveaux énergétiques d’un solide moléculaire organique, transporteurs de trous, avec un oxyde d'indium dopé à l’étain (ITO), un conducteur transparent. Les molécules étudiées, basées sur une structure dipyranylidène (DIP), diffèrent par leur hétéroatome (O, S et Se). La spectroscopie de photoémission X a été utilisée pour déterminer cet alignement, et nous avons étudié l'orientation moléculaire par spectromicroscopie d'absorption X. Des calculs DFT ont été réalisés pour interpréter les données spectroscopiques. Nous avons constaté la présence d'un transfert de charge, au moins pour les dérivés oxygénés et soufrés. Celui-ci a lieu des molécules vers l’ITO, lorsqu'ils sont en contact intime avec le substrat. Nous avons déterminé la barrière d'injection des trous entre le niveau de Fermi de l’ITO et la HOMO du solide organique. Notre approche expérimentale met l'accent sur la relation entre les propriétés structurelles et les propriétés électroniques. Ces résultats ont été obtenus pendant des runs synchroton en France (SOLEIL), en Italie (ELETTRA) et en Suisse (SLS)
The energy level alignment of hole-transport organic molecular solids with indium tin oxide (ITO), a transparent conducting oxide, has been characterized. The studied molecules, based on the dipyranylidene (DIP) structure, differ by the heteroatom (O, S and Se). Synchrotron photoemission electron spectroscopy has been used to determine the alignment, and we investigated the molecular orientation via X-ray absorption spectromicroscopy. By interpreting spectroscopic data in the light of DFT calculations, we found evidence of the presence of charge transfer from the molecules to the ITO, when they are in intimate contact with the substrate, at least for the O and S-DIPs. The hole injection barrier between the ITO Fermi level and the organic HOMO was obtained. Our experimental approach emphasizes the relationship between structural and electronic properties. These results were obtained during beamtimes in France (SOLEIL), Italy (ELETTRA) and Switzerland (SLS)

The fast progress in biological study has attracted a growing interest in mimicking the signal processing functions of biological neural systems, which can be implemented in hardware and used to inspire new techniques for real time computations. On the other hand, the ITRS roadmap for Si indicates that alternative paradigms for building computational machines will be required within about 10 years and the massive parallelism of neural systems represents an attractive option. However most implementation approaches are restrictive in physical dimensions and characteristics towards biological networks in hardware. Thus there is a pressing need for compact. low power neural building blocks with operational characteristics that closely mimic realistic neuron cells. In this thesis, a charge coupled synapse is developed as a core building block for spiking neural networks in hardware. The proposed silicon synapse is based on a two-phase charge transfer device with associated localized memory capability. The correspondence between the fundamental semiconductor processes and the required biological functionality is illustrated by theory.

Charge transfer efficiency at the organic/transparent conducting oxide (TCO) interface is one of the key parameters controlling the overall efficiency of organic photovoltaics (OPVs). Modification of this interface with a redox-active organic surface modifier may further enhance the charge transfer across the interface by providing a charge-transfer pathway between the electrode and the organic active layer. Functionalized perylene diimide molecules (PDI) are useful for modifying metal oxide/acceptor interfaces for inverted solar cell devices because their LUMO energy level is close to some commonly used acceptor molecules. The effects of PDI structural parameters on the interfacial charge transfer processes across the organic/ITO interface were investigated. Six different PDI monolayers with different structural parameters were deposited on ITO surfaces to investigate the relationship between molecular orientation, linker length, aggregation and charge transfer process. The PDI orientation, degree of PDI aggregation and charge transfer process acrosses PDI/ITO interfaces were characterized by polarized ATR spectroscopy, PM-ATR spectroscopy and photoelectrochemistry. Both linker length and orientation affected the tunneling distance between PDI and ITO, therefore affecting the charge transfer rate constant across the PDI/ITO interfaces. PDI aggregation forced a more out-of-plane orientation of PDI molecules and increased the overall measured charge transfer rate constant. However, PDI aggregation also increased the excited state recombination rate which ultimately led to decrease of the charge collection efficiency. The first application of a PM-TIRF platform to characterize the electron-transfer processes of PDI monomeric films across the organic/electrode interface is presented. The PM-TIRF technique provides higher sensitivity as well as the capability to measure very fast charge transfer events, compared to other commonly used potential-modulated spectroscopy techniques. PDI-phenyl-PA monomeric films exhibited a more in-plane orientation compared with aggregated films and showed a smaller charge transfer rate constant across the PDI/ITO interfaces compared with PDI films with higher degrees of aggregation after normalizing the tunneling distance contributions.

The background and operation of charge transfer devices is reviewed, and a computer model simulation of focal plane arrays is presented. The model provides an option to predict the performance of a focal plane. With this program, any of the allowed materials, detectors, readout structures, or preamplifiers that make up a focal plane, may be selected to create new designs for analysis. Only surface channel devices are considered, and only references to the spectral dependence are presented. The computer model's operation and validity is supported by over 70 equations and more than 50 figures, including actual computer screen printouts. Standard equations followed by brief discussions are used to support the menu driven program. The structure and operation of the computer model is presented, but not the actual software source code.

The wireless transfer of power is the enabling technology for realizing a true internet-of-things. Broad sensor networks capable of monitoring environmental pollutants, health-related biological data, and building utility usage are just a small fraction of the myriad of applications which are part of an ever evolving ubiquitous lifestyle. Realizing these systems requires a means of powering their electronics sans batteries. Removing the batteries from the billions or trillions of these envisioned devices not only reduces their size and lowers their cost, but also avoids an ecological catastrophe. Increasing the efficiency of microwave-to-DC power conversion in energy-harvesting circuits extends the range and reliability of passive sensor networks. Multi-frequency waveforms are one technique that assists in overcoming the energy-harvesting circuit diode voltage threshold which limit the energy-conversion efficiency at low RF input powers typically encountered by sensors at the fringe of their coverage area. This thesis discusses a systematic optimization approach to the design of energy-conversion circuits along with multi-frequency waveform excitation. Using this methodology, a low-power 5.8 GHz rectenna showed an output power improvement of over 20 dB at -20 dBm input power using a 3-POW (power-optimized waveform) compared to continuous waveforms (CW). The resultant efficiency is the highest reported efficiency for low-power 5.8 GHz energy harvesters. Additionally, new theoretical models help to predict the maximum possible range of the next generation of passive electronics based upon trends in the semiconductor industry. These models predict improvements in diode turn-on power of over 20 dB using modern Schottky diodes. This improvement in turn-on power includes an improvement in output power of hundreds of dB when compared to CW.

A self-consistent, full-band, electrothermal ensemble Monte Carlo device simulation tool has been developed. It is used to study charge transport in bulk GaN, and to design, analyze, and improve the performance of AlGaN/GaN high electron mobility transistors (HEMTs) and avalanche photodiodes (APDs). Studies of electron transport in bulk GaN show that both peak electron velocity and saturated electron velocity are higher for transport in the basal plane than along the c-axis. Study of the transient electron velocity also shows a clear transit-time advantage for electron devices exploiting charge transport perpendicular to the c-axis. The Monte Carlo simulator also enables unique studies of transport under the influence of high free carrier densities but with low doping density, which is the mode of transport in AlGaN/GaN HEMTs. Studies of isothermal charge transport in AlGaN/GaN HEMTs operating at high gate bias show a drain current droop with increasing drain-source bias. The cause of the droop is investigated and a design utilizing source- or gate-connected field plate is demonstrated to eliminate the drain current droop. Electrothermal aspects of charge transport in AlGaN/GaN HEMTs are also investigated, and the influence of non-equilibrium acoustic and optical phonons is quantified. The calculated spatial distribution of non-equilibrium phonon population reveals a hot spot in the channel that is localized at low drain-source bias, but expands towards the drain at higher bias, significantly degrading channel mobility. Next, Geiger mode operation of wurtzite GaN-based homojunction APDs is investigated. The influences of dopant profile, active region thickness, and optical absorption profile on single photon detection efficiency (SPDE) are quantified. Simulations of linear mode gain as a function of multiplication region thickness and doping profile reveal that weakly n-type active regions may be exploited to achieve higher avalanche gain, without penalty to either applied bias or active region thickness. A separate absorption and multiplication APD (SAM-APD) utilizing a AlGaN/GaN heterojunction is also investigated. The presence of strong piezo-electric and spontaneous polarization charges at the heterojunction enables favorable electric field profile in the device to reduce dark current, improve excess noise factor, improve quantum efficiency, and improve breakdown probability. To maximize SPDE, a new device structure with a buried absorber is proposed and improved SPDE is demonstrated. Lastly, a new approach for the direct generation of self-sustaining millimeter-wave oscillations is proposed. In contrast to Gunn diodes, which exploit a bulk-like active region, periodic oscillation is achieved in the proposed structures through the creation, propagation and collection of traveling dipole domains supported by fixed polarization charge and the associated two-dimensional electron gas along the plane of a polar heterojunction. Numerical simulation of induced oscillations in a simple triode structure commonly used for AlGaN/GaN HEMTs reveals two distinct modes of self-sustaining millimeter-wave oscillation.

A compact air separator demonstrator based on centrifugally enhanced distillation has been studied. The full size device is meant to be used on board of a Two Stage To Orbit vehicle launcher. The air separation system must be able to extract oxygen in highly concentrated liquid form (LEA, Liquid Enriched Air) from atmospheric air. The LEA is stored before being used in a subsequent rocket propulsion phase by the second stage of the launcher. Two reference vehicles are defined, one with a subsonic first stage and one with a supersonic first stage. In both cases, oxygen collection is performed during a cruise phase (M 0.7 and M 2.5 respectively). The aim of the project is to demonstrate the feasibility of the air separation system, investigate the separation cycle design, and assess that the separator design selected is suitable for the reference vehicles.

The project is described from original base ideas to design, construction, extended testing and analysis of experimental results. Preliminary computations for a realistic layout have been performed and the motivations for the choices made during the process are explained. Test rig design, separator design and technical discussion are provided for a subscale pilot unit. Mass transport parameters and flooding limits have been estimated and experimentally measured. Performance has been assessed and shown to be sufficient for the reference Two Stage To Orbit vehicles. The technology developed is found suitable without further optimization, although some volume and mass reduction would be desirable for the supersonic first stage concept. There are many ways of optimisation that can be further investigated. The aim of this program, however, is not to fully optimize the device, but to demonstrate that a device based on a simple, robust, low-risk design is already suitable for the launch vehicles. On top of that analysis, directions for improvements are suggested and their potentials estimated. A complete assessment of those improvements requires further maturation of the technological concept through further testing and practical implementations.

Directions for future work, general conclusions and a vehicle development roadmap have also been provided.

Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

This document describes the development of spectroscopic techniques which benefit from the use of charge-transfer devices. Both charge-coupled devices (CCD's) and charge-injection devices (CID's) are used in the techniques presented here such as atomic emission spectroscopy and latent fingerprint imaging. The use of a CID echelle system for axial viewing of the inductively coupled plasma (ICP) demonstrates the enhancement in sensitivity that can be obtained over tangential viewing. More importantly though, are the advantages afforded by simultaneous multi-element detection. Axial viewing of the ICP has shown to not only improve upon the detection limits of several metals by, in some cases, a half order of magnitude, but also to increase the amount of light collected and thus reduce the time of analysis. Along with this, the effect of interferences upon the detection of various metals is, at worst, equivalent to that of an ICP with tangential viewing. Further enhancement of sensitivity in atomic analysis can be achieved by atomic fluorescence with an ICP. Although in the past, hollow cathode lamps have proven to be insufficient, advanced designs of hollow cathode lamps presented here have demonstrated an increase in the intensity of lines of copper best suited for use in ICP atomic fluorescence. Lastly, a latent fingerprint has been imaged with the use of a scientific CCD and a flashlight where in the past such a technique was accomplished with high power lasers. By using a CCD, the immediate digitization of information combined with the sensitivity and image processing capabilities offer a portable means by which to image latent fingerprints on poor surfaces.

Due to size effects, the microtechnologies that are used to manufacture micro-sensors, allowed a drastic reduction of electrical power consumption. This feature contributed to the emergence of the concept of autonomous sensors, which have the ability to take the energy needed for their operation from the environment where they are located. Among the different energy sources, our choice was made on ambient mechanical vibrations. The electromechanical conversion is done within a transducer integrated with a micromechanical structure. In this work, we have designed and fabricated an electrostatic transducer based on silicon-glass technology, which required the development of a dedicated deep etching process. The device was tested experimentally and we have obtained a conversion of mechanical energy into electrical energy, corresponding to a power of 61 nW, with a device whose surface area is only 66 mm². This device is the first miniaturized silicon converter based on electrostatic transduction which does not use an electret

Thesis (MEng) -- Stellenbosch University, 2014.
ENGLISH ABSTRACT: Solar energy is a time dependent, high-temperature radiant energy resource. The utility of a solar thermal energy system increases if the hot temperature source is available when it is needed most. This is realized by the thermal storage of the solar energy. Thermal storage gives greater versatility to a solar energy system by decoupling the heat source from the heat sink. A large quantity of energy may be stored during the melting process in a phase change material (PCM) within a small temperature range. This molten PCM can then deliver its absorbed heat at a constant temperature in a heating application. In this study a phase change storage system (PCS) is developed and proposed for a solar water heating application. This PCS system stores more heat per unit mass than would be possible with water across the same temperature range. The heat transfer rate in and out of many PCMs is slow because of the low thermal conductivity of the PCM. However, heat transfer enhancers (HTE), such as heat pipes and fins may be added to enhance heat absorption and heat removal rates. Heat pipes have the inherent capability to transfer heat at high rates across large distances, even where the temperature difference is small. In this thesis a description is given of a PCS system consisting of paraffin wax as the PCM and which uses rectangular heat pipes in conjunction with aluminium fins to enhance heat transfer. The storage design is modular and each module has the characteristic that enhanced heat transfer in and out of the PCM is possible when the module is heated or cooled. It also has the capability to quickly absorb or alternatively to supply heat at a nearly constant temperature during the phase change of the module. A rectangular module was designed and built. The module was then analysed under controlled heat absorption and heat removal cycles. The heat up experiment involved an electrical kettle as the hot temperature source. The heat sink was a mains water heat exchanger. The experimental results were compared to those of a transient numerical model, which calculates theoretically how the module will perform thermally under the given test conditions. The numerical model of the experimental set-up was validated when it was found that the numerical model results resemble the experimental results. The numerical model was then adapted to simulate a novel solar water heater (SWH) with an additional PCS container. The improvement over previous designs is that the additional storage container can be heated to a higher temperature than the allowable geyser temperature. The system also heats up and cools down at a faster rate than would be possible without the HTEs. From the numerical simulation the size and performance of such a system is determined. This numerical analysis indicated that a phase change storage system in a SWH application will increase the hot water delivered by a given solar collector and geyser by increasing the storage capacity and by heating up the geyser overnight for early morning hot water use.
AFRIKKANSE OPSOMMING: Son energie is ‘n tyd afhanklike, hoë temperatuur radiasie energiebron. Die bruikbaarheid van ‘n sontermiese energie sisteem verhoog indien die hoë temperatuur bron beskikbaar is wanneer dit die meeste benodig word. Dit kan verwesenlik word deur die sonenergie termies te stoor. Termiese storing bied groter veelsydigheid aan ‘n sontermiese stelsel deur effektief die hittebron te ontkoppel van die hitte sink. ‘n Groot hoeveelheid energie kan, gedurende die smeltingsproses in ‘n faseveranderingsmateriaal binne ‘n nou temperatuurband gestoor word. Hierdie gesmelte materiaal kan weer op sy beurt in die waterverhittingstoepassing, die geabsorbeerde hitte teen ‘n konstante temperatuur oordra. In hierdie studie word ‘n sonwaterverwarmer stelsel wat aangepas is deur ‘n addisionele latente hittestoor daaraan te heg, voorgestel. Hierdie faseverandering hittestoor kan meer hitte stoor as wat water in dieselfde temperatuur band sou kon. Die hitteoordrag tempo na en van baie van die faseveranderingsmateriale (FVM) is egter as gevolg van die lae termiese geleidingskoëfisient, stadig. Hierdie eienskap kan gelukkig verbeter word deur hittepype en hitteoordrag verhogings materiaal soos vinne by te voeg. Hittepype het die inherente eienskap om hitte teen ‘n hoë tempo oor groot afstande, oor te dra, selfs oor ‘n klein temperatuurverskil. In hierdie tesis word ‘n ondersoek rakende ‘n faseverandering storingsisteem wat bestaan uit paraffien was as die FVM en reghoekige hittepype wat te same met met aluminium finne gebruik word om die hitteoordragtempo te verhoog, beskryf. Die stoorontwerp is modulêr en elke module het die kenmerk van hoë hitteoordrag na en van die FVM. Die module het verder ook die eienskap om vining hitte te absorbeer of hitte af te gee. Dit gebeur teen ‘n konstante temperatuur gedurende die faseverandering van die FVM. Presies so ‘n reghoekige module is ontwerp en gebou en onder beheerde hitte absorbering- en hitte verwyderingsiklusse analiseer. Tydens die verhittings eksperiment is ‘n elektriese ketel van gebruik gemaak wat gedien het as die hoë temperatuur bron. Die hitte sink was ‘n hitteruiler wat kraanwater van ‘n konstante hoogte tenk ontvang het. Die resultate van die volledige toets is met die resultate van tydafhanklike numeriese model vergelyk. Hierdie numeriese model bereken teoreties wat die module se storing verrigting onder gegewe toets omstandighede sal wees. Die numeriese model se resultate het goed vergelyk met die resultate van die eksperimente. Die numeriese model van die module is toe aangepas om ‘n sonwaterverwarmer met addisionele stoortenk wat fase verandering materiaal gebruik, te simuleer. Hierdie ontwerp is anders as vorige ontwerpe in die sin dat hoër temperature as wat die warmwatertoestel kan hanteer, in die faseverandering storingstenk, bereik kan word. Die sisteem kan ook as gevolg van die hitteoordrag verhoging materiaal, vinniger verhit of afkoel en teen ‘n vinniger tempo. Die simulasie van die sonwaterverwarmer met FVM word gebruik om die grootte en verrigting van die sisteem te bepaal. Hierdie numeriese model toon aan dat wanneer ‘n addisionele faseverandering storingstelsel in ‘n sonwaterverwarmer toepassing gebruik word, die warm water wat die verbruiker uit die sisteem kan verkry, kan verhoog. Die rede hiervoor is dat meer hitte gestoor kan word, wat beskikbaar gemaak word aan die warm water tenk.

Thesis (PhD) -- Stellenbosch University, 2014.
ENGLISH ABSTRACT: Currently the reduction of the levelised cost of electricity (LCOE) is the main goal of concentrating solar power (CSP) research. Central to a cost reduction strategy proposed by the American Department of Energy is the use of advanced power cycles like supercritical steam Rankine cycles to increase the efficiency of the CSP plant. A supercritical steam cycle requires source temperatures in excess of 620°C, which is above the maximum storage temperature of the current two-tank molten nitrate salt storage, which stores thermal energy at 565°C. Metallic phase change materials (PCM) can store thermal energy at higher temperatures, and do not have the drawbacks of salt based PCMs. A thermal energy storage (TES) concept is developed that uses both metallic PCMs and liquid metal heat transfer fluids (HTF). The concept was proposed in two iterations, one where steam is generated directly from the PCM – direct steam generation (DSG), and another where a separate liquid metal/water heat exchanger is used – indirect steam generation, (ISG). Eutectic aluminium-silicon alloy (AlSi12) was selected as the ideal metallic PCM for research, and eutectic sodium-potassium alloy (NaK) as the most suitable heat transfer fluid. Thermal energy storage in PCMs results in moving boundary heat transfer problems, which has design implications. The heat transfer analysis of the heat transfer surfaces is significantly simplified if quasi-steady state heat transfer analysis can be assumed, and this is true if the Stefan condition is met. To validate the simplifying assumptions and to prove the concept, a prototype heat storage unit was built. During testing, it was shown that the simplifying assumptions are valid, and that the prototype worked, validating the concept. Unfortunately unexpected corrosion issues limited the experimental work, but highlighted an important aspect of metallic PCM TES. Liquid aluminium based alloys are highly corrosive to most materials and this is a topic for future investigation. To demonstrate the practicality of the concept and to come to terms with the control strategy of both proposed concepts, a storage unit was designed for a 100 MW power plant with 15 hours of thermal storage. Only AlSi12 was used in the design, limiting the power cycle to a subcritical power block. This demonstrated some practicalities about the concept and shed some light on control issues regarding the DSG concept. A techno-economic evaluation of metallic PCM storage concluded that metallic PCMs can be used in conjunction with liquid metal heat transfer fluids to achieve high temperature storage and it should be economically viable if the corrosion issues of aluminium alloys can be resolved. The use of advanced power cycles, metallic PCM storage and liquid metal heat transfer is only merited if significant reduction in LCOE in the whole plant is achieved and only forms part of the solution. Cascading of multiple PCMs across a range of temperatures is required to minimize entropy generation. Two-tank molten salt storage can also be used in conjunction with cascaded metallic PCM storage to minimize cost, but this also needs further investigation.
AFRIKAANSE OPSOMMING: Tans is die minimering van die gemiddelde leeftydkoste van elektrisiteit (GLVE) die hoofdoel van gekonsentreerde son-energie navorsing. In die kosteverminderingsplan wat voorgestel is deur die Amerikaanse Departement van Energie, word die gebruik van gevorderde kragsiklusse aanbeveel. 'n Superkritiese stoom-siklus vereis bron temperature hoër as 620 °C, wat bo die 565 °C maksimum stoor temperatuur van die huidige twee-tenk gesmelte nitraatsout termiese energiestoor (TES) is. Metaal fase veranderingsmateriale (FVMe) kan termiese energie stoor by hoër temperature, en het nie die nadele van soutgebaseerde FVMe nie. ʼn TES konsep word ontwikkel wat gebruik maak van metaal FVM en vloeibare metaal warmteoordrag vloeistof. Die konsep is voorgestel in twee iterasies; een waar stoom direk gegenereer word uit die FVM (direkte stoomopwekking (DSO)), en 'n ander waar 'n afsonderlike vloeibare metaal/water warmteruiler gebruik word (indirekte stoomopwekking (ISO)). Eutektiese aluminium-silikon allooi (AlSi12) is gekies as die mees geskikte metaal FVM vir navorsingsdoeleindes, en eutektiese natrium – kalium allooi (NaK) as die mees geskikte warmteoordrag vloeistof. Termiese energie stoor in FVMe lei tot bewegende grens warmteoordrag berekeninge, wat ontwerps-implikasies het. Die warmteoordrag ontleding van die warmteruilers word aansienlik vereenvoudig indien kwasi-bestendige toestand warmteoordrag ontledings gebruik kan word en dit is geldig indien daar aan die Stefan toestand voldoen word. Om vereenvoudigende aannames te bevestig en om die konsep te bewys is 'n prototipe warmte stoor eenheid gebou. Gedurende toetse is daar bewys dat die vereenvoudigende aannames geldig is, dat die prototipe werk en dien as ʼn bevestiging van die konsep. Ongelukkig het onverwagte korrosie die eksperimentele werk kortgeknip, maar dit het klem op 'n belangrike aspek van metaal FVM TES geplaas. Vloeibare aluminium allooie is hoogs korrosief en dit is 'n onderwerp vir toekomstige navorsing. Om die praktiese uitvoerbaarheid van die konsep te demonstreer en om die beheerstrategie van beide voorgestelde konsepte te bevestig is 'n stoor-eenheid ontwerp vir 'n 100 MW kragstasie met 15 uur van 'n TES. Slegs AlSi12 is gebruik in die ontwerp, wat die kragsiklus beperk het tot 'n subkritiese stoomsiklus. Dit het praktiese aspekte van die konsep onderteken, en beheerkwessies rakende die DSO konsep in die kollig geplaas. In 'n tegno-ekonomiese analise van metaal FVM TES word die gevolgtrekking gemaak dat metaal FVMe gebruik kan word in samewerking met 'n vloeibare metaal warmteoordrag vloeistof om hoë temperatuur stoor moontlik te maak en dat dit ekonomies lewensvatbaar is indien die korrosie kwessies van aluminium allooi opgelos kan word. Die gebruik van gevorderde kragsiklusse, metaal FVM stoor en vloeibare metaal warmteoordrag word net geregverdig indien beduidende vermindering in GLVE van die hele kragsentrale bereik is, en dit vorm slegs 'n deel van die oplossing. ʼn Kaskade van verskeie FVMe oor 'n reeks van temperature word vereis om entropie generasie te minimeer. Twee-tenk gesmelte soutstoor kan ook gebruik word in samewerking met kaskade metaal FVM stoor om koste te verminder, maar dit moet ook verder ondersoek word.

L’objectif de cette thèse est la préparation de matériaux hybrides polymères conjugués (P3HT et un copolymère dérivé) - nanotubes de carbone, ainsi que leur caractérisation par des méthodes spectroscopiques et par microscopie électronique. Des nanohybrides non-covalents sont obtenus par la sonication des deux composants dans le THF. L’interaction entre ces composants entraîne l’enroulement du polymère autour des nanotubes ainsi que la formation d'agrégats de polymère sur leur surface. L’effet de différents paramètres, tels que la masse molaire du polymère, ont été étudiés. Des nanohybrides covalents sont obtenus en utilisant un copolymère portant une aniline au bout de la chaîne alkyle. Les spectroscopies optique et Raman suggèrent un faible taux de fonctionnalisation ainsi qu’une conformation plus désordonnée des chaînes de polymères par rapport aux nanohybrides non-covalents. Des études préliminaires montrent que le copolymère peut fonctionnaliser aussi des dispositifs à base de nanotubes de carbone. Le bas taux de fonctionnalisation ne permet pas de conclure sur la modification des propriétés électroniques, mais les défauts induits permettent l’observation d’un photocourant
The objective of this thesis is the preparation of conjugated polymers (P3HT and a derivated copolymer) – carbon nanotubes hybrid materials and their characterization through different spectroscopies and transmission electron microscopy. Non-covalent nanohybrids can be obtained by sonicating both components together in THF. The interaction between both components leads to the wrapping of the polymer around the carbon nanotubes as well as the formation of polymer aggregates on the surface of the nanotubes. The effect of different parameters such as the polymer chain length are described. Covalent nanohybrids can be obtained using a specially designed copolymer bearing an aniline at the end of its side chain. Optical and Raman spectroscopies indicate a low level of functionalization, and suggest that the polymer chains are in a more disordered state compared to non-covalent nanohybrids. Preliminary studies show that the obtained copolymer can be used for functionalizing carbon nanotube based devices. Modification of electrical properties of the devices were small and compatible with the low functionalization degree, but the induced defects allow observation of a photocurrent

Le transport de charges dans une série de copolymères à faible bande interdite basés sur l'alternance de motifs riches en électrons (thiophène, thiénothiophène) et d'unités déficients en électrons (benzothiadiazole) et dans leurs mélanges avec un dérivé du fullerène (PCBM-C60) a été étudié. Les polymères sont différenciés par la structure moléculaire de leur coeur conjugué et par la nature, la position et la densité de leurs chaines latérales. Dans les polymères purs, la mobilité a été étudiée en fonction de la densité de charges par le biais de l'analyses de caractéristiques électriques de transistors à effet de champ et de dispositifs à un seul type de porteurs dont le courant est limité par la charge d'espace. En utilisant le modèle de transport de charges développé par Vissenberg et al., nous avons pu estimer le degré de désordre dans le film organique et corréler le transport de charge avec le degré d'ordre structural mesuré par la diffraction des Rayons-X. Ces polymères ont été conçus pour être utilisés dans la couche active des cellules solaires organiques. Grâce à l'étude du transport de charges dans les mélanges à différents ratios massiques polymères:fullerène, nous avons mis en évidence l'effet considérable de la structure moléculaire sur le ratio optimal polymère:fullerène. Aussi, nous avons pu montrer que la nature des chaînes latérales joue un rôle important dans l'obtention d'un chemin de percolation optimal à la conduction des électrons.

On presente une etude prospective pour un nouveau processeur optique effectuant le traitement des donnees de radar a vision laterale (sar) en temps reel. L'etage de correlation du calculateur optique, base sur un fonctionnement particulier des matrices ccd dit "add and shift" est valide experimentalement. On envisage egalement l'utilisation de ce processeur pour le traitement des signaux differents

Etude de deux appareils de mesure de spectres optiques. Realisation d'un appareil a reseau grave et a dtc. Le cycle de mesure et la resolution obtenue sont 10 ms et 0,2 nm. Developpement d'un ensemble de programmes. Proposition de l'appareil a compensateur de babinet en vue de realiser des analyseurs compacts. - lasers a semiconducteurs : etude de leurs caracteristiques en relation avec les equations de continuite. Simulation des forces de langevin. Amelioration des equations classiques de continuite. Etude du fonctionnement continu, comportement transitoire, problemes de commution de gain, de chirping. Caracteristiques dynamiques en modulation d'intensite directe

Automatisation du controle de qualite par vision. Les pieces sont positionnees par un mecanisme a quatre barres. Les traitements d'image permettent d'obtenir des resolutions superieures aux precisions des cameras

Les exigences en matière de stabilité et de linéarité des instruments utilisés en radioastronomie sont particulièrement sévères. Ce mémoire présente la conception et la réalisation d'un détecteur continuum adapté à ce cahier des charges. Une étude théorique démontre que le détecteur à diode Schottky ne répond pas à ces besoins. L'instrument finalement réalisé, construit à partir d'une diode tunnel, possède un bruit proche de la limite physique fondamentale. Il reste cependant très simple. Le chapitre suivant est consacré à l'étude et à la réalisation de l'électronique d'acquisition d'un spectrographe acousto-optique à large bande et à l'etude de ses caractéristiques dans des conditions d'utilisation réelles. Il inclut la description d'une méthode simple qui permet de s'affranchir des erreurs de linéarité différentielle du convertisseur analogique-numérique. La validation des caractéristiques du spectrographe s'appuie sur la comparaison avec deux batteries de filtres identiques. Sur le plan scientifique, il présente l'observation d'objets du système solaire entourés d'une atmosphère et l'interprétation des résultats dans le cas de Titan.

The main subject of the thesis is the development of several methodologies aimed to qualify mechanical components through thermoelasticity. Such essay begins with the analysis of the thermoelastic method of measure. We come to develop a new measure methodology of stress maps on mechanical rotation components through two test cases; they show their application to the stress analysis on the joint of water meter and fan cooling.

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.

The rapidly increasing power conversion efficiencies (PCEs) of organic solar cells (OSCs) above 10% were made possible by concerted international research activities in the last few years, aiming to understand the processes that lead to the generation of free charge carriers following photon absorption. Despite these efforts, many details are still unknown, especially how these processes can be improved already at the drawing board of molecular design. To unveil this information, dicyanovinyl end-capped oligothiophene derivatives (DCVnTs) are used as a model system in this thesis, allowing to investigate the impact of small structural changes on the molecular properties and the final solar cells. On thin films of a methylated DCV4T derivative, the influence of the measurement temperature on the charge carrier generation process is investigated. The observed temperature activation in photoinduced absorption (PIA) measurements is attributed to an increased charge carrier mobility, increasing the distance between the charges at the donor/acceptor (D/A) interface and, thus, facilitating their final dissociation. The correlation between the activation energy and the mobility is confirmed using a DCV6T derivative with lower mobility , exhibiting a higher activation energy for charge carrier generation. Another parameter to influence the charge carrier generation process is the molecular structure. Here, alkyl side chains with varying length are introduced and their influence on the intramolecular energy levels as well as the absorption and emission properties in pristine and blend films with the acceptor C60 are examined. The observed differences in intermolecular order (higher order for shorter side chains) and phase separation in blend layers (larger phase separation for shorter side chains) are confirmed in PIA measurements upon comparing the temperature dependence of the triplet exciton lifetimes. A proposed correlation between the side chain length and the coupling between D and A, which is crucial for efficient charge transfer, is not confirmed. The presented flat heterojunction solar cells underline this conclusion, giving similar photocurrent densities for all compounds. Differences in PCE are related to shifts of the energy levels and the morphology of the blend layer in bulk heterojunction devices. Furthermore, the impact of the electric field on the charge carrier generation yield is investigated in a proof-of-principle study, introducing PIA measurements in transmission geometry realized using semitransparent solar cells. The recombination analysis of the photogenerated charge carriers reveals two recombination components. Trapped charge carriers or bound charge pairs at the D/A interface are proposed as an explanation for this result. The miscibility of D and A, which can be influenced by heating the substrate during layer deposition, is of crucial importance to obtain high PCEs. In this work, the unusual negative influence of the substrate temperature on DCV4T:C60 blend layers in solar cells is investigated. By using optical measurements and structure determination tools, a rearrangement of the DCV4T crystallites is found to be responsible for the reduced absorption and, therefore, photocurrent at higher substrate temperature. The proposed blend morphology at a substrate temperature of 90° C is characterized by a nearly complete demixing of the D and A phases. This investigation is of particular relevance, because it shows the microscopic origins of a behavior that is contrary to the increase of the PCE upon substrate heating usually reported in literature. Finally, the optimization steps to achieve a record PCE of 7.7% using a DCV5T derivative as donor material are presented, including the optimization of the substrate temperature, the active layer thickness, and the transport layers.:Abstract - Kurzfassung Publications Contents 1 Introduction 2 Elementary Processes in Organic Semiconductors 2.1 Introduction 2.2 Optical Excitations in Organic Materials 2.2.1 Introduction 2.2.2 Radiative Processes: Absorption and Emission 2.2.3 Non-radiative Relaxation Processes 2.2.4 Triplet Excitons and Intersystem Crossing 2.3 Polarization Effects and Disorder 2.4 Transport Processes in Disordered Organic Materials 2.4.1 Charge Transport 2.4.1.1 The Bässler Model 2.4.1.2 Marcus Theory for Electron Transfer 2.4.1.3 Small Polaron Model 2.4.1.4 Functional Dependencies of the Charge Carrier Mobility 2.4.2 Diffusive Motion 2.4.3 Exciton Transfer Mechanisms 2.4.4 Characteristics of Exciton Diffusion 2.5 Charge Photogeneration in Pristine Materials 3 Organic Photovoltaics 3.1 General Introduction to Solar Cell Physics 3.2 Introduction to the Donor/Acceptor Heterojunction Concept 3.3 The Open-Circuit Voltage in Organic Solar Cells 3.4 Doping of Organic Semiconductors 3.5 Introduction to the p-i-n Concept 3.6 Charge Transfer Excitons in Donor/Acceptor Heterojunction Systems 3.6.1 Introduction 3.6.2 Verification of Charge Transfer Excitons in Donor/Acceptor Systems 3.7 The Process Cascade for Free Charge Carrier Generation in Donor/Acceptor Heterojunction Systems 3.7.1 The Initial Charge Transfer Step 3.7.2 The Binding Energy of the Charge Transfer Exciton 3.7.3 \"Hot\" Charge Transfer Exciton Dissociation 3.7.4 \"Cold\" Charge Transfer Exciton Dissociation 3.7.5 Supposed Influence Factors on Charge Transfer Exciton Dissociation 3.7.6 Recombination Pathways for Charge Transfer Excitons 3.7.7 Free Charge Carrier Formation and Recombination 4 Experimental Methods 4.1 Sample Preparation 4.2 Material Characterization Methods 4.2.1 Optical Characterization 4.2.2 Cyclic Voltammetry 4.2.3 Ultraviolet Photoelectron Spectroscopy 4.2.4 Atomic Force Microscopy 4.2.5 Grazing Incidence X-Ray Diffraction 4.2.6 Organic Field-Effect Transistor 4.3 Photoinduced Absorption Spectroscopy 4.3.1 Introduction 4.3.2 Derivation of the PIA Signal 4.3.3 Recombination Dynamics 4.3.4 Intensity Dependence of the PIA Signal 4.4 Solar Cell Characterization 4.4.1 External Quantum Efficiency 4.4.2 Spectral Mismatch Correction 4.4.3 Current-Voltage Characteristics 4.4.4 Optical Device Simulations 4.4.5 Optical Device Transmission Measurements 5 The Oligothiophene Material System 5.1 Introduction 5.2 Thermal Stability 5.3 Energy Levels 5.4 Optical Properties of the Pristine Materials 5.5 The Donor/Acceptor Couple: DCVnT and C60 5.6 Solar Cell Devices 5.7 Summary 6 Temperature Dependence of Charge Carrier Generation 6.1 Introduction 6.2 Principal Introduction to the PIA Measurements 6.2.1 Interpretation of the Spectra 6.2.2 Interpretation of the Frequency Scans 6.3 Temperature Dependence of the Spectra 6.4 Discussion of the Temperature Dependent Processes in the Blend Layer 6.5 Temperature Activated Free Charge Carrier Generation 6.5.1 Evaluation of the Activation Energy for the DCV4T-Me:C60 Blend 6.5.2 Comparison to a Sexithiophene Derivative (DCV6T-Me) 6.6 Summary 7 Side Chain Investigation on Quaterthiophene Derivatives 7.1 Energy Levels 7.2 Optical Properties 7.2.1 Solution and Pristine Films 7.2.2 Mixed Films with C60 7.3 Influence of the Side Chain Length on the Intermolecular Coupling 7.3.1 PIA Spectra of Pristine and Blend Layers at 10K 7.3.2 Recombination Analysis for Pristine and Blend Films at 10K 7.4 The Influence of the Side Chain Length on the Offset Charge Carrier Generation Rate at Low Temperature 7.5 In the High-Temperature Limit: Implications for Solar Cell Devices 7.5.1 PIA Spectra in Pristine and Blend Films at 200K 7.5.2 Recombination Analysis: Triplet Excitons and Free Charge Carriers 7.6 Solar Cells 7.6.1 Flat Heterojunction Devices 7.6.2 Bulk Heterojunction Devices 7.7 Summary 8 Electric-Field Dependent PIA Measurements on Complete Solar Cell Devices 8.1 Introduction 8.2 Semitransparent Organic Solar Cells 8.3 Photoinduced Absorption Measurements 8.4 Summary and Outlook 9 The Effect of Substrate Heating During Layer Deposition on the Performance of DCV4T:C60 BHJ Solar Cells 9.1 Introduction 9.2 The Importance of Morphology Control for BHJ Solar Cells 9.3 The Impact of Substrate Heating on DCV4T:C60 BHJ Solar Cells 9.4 Absorption and Photoluminescence 9.5 Topographical Investigations (AFM) 9.6 X-ray Investigations 9.6.1 1D GIXRD Measurements 9.6.2 2D GIXRD Measurements 9.7 Proposed Morphological Picture and Confirmation Measurements 9.7.1 Morphology Sketch of the DCV4T:C60 Blend Layer 9.7.2 Confirmation Measurements 9.8 The Equivalence of Temperature and Time 9.9 Summary 10 Record Solar Cells Using DCV5T-Me33 as Donor Material 10.1 Introduction 10.2 The Influence of the Substrate Temperature 10.3 Determination of the Optical Constants 10.4 Stack Optimization 10.5 Summary and Outlook 11 Conclusions and Outlook 11.1 Summary of the Photophysical Investigations 11.2 Summary of Device Investigations 11.3 Future Challenges Appendix A Detailed Description of the Experimental Setup for PIA Spectroscopy Appendix B Determination of the Triplet Level by Differential PL Measurements Appendix C Additional Tables and Figures Appendix D Reproducibility of the Solar Cell Results (Statistics) Appendix E Lists Bibliography Acknowledgments
Der rasante Anstieg des Wirkungsgrads von organischen Solarzellen über die Marke von 10% war nur durch länderübergreifende Forschungsaktivitäten während der letzten Jahre möglich. Trotz der gemeinsamen Anstrengungen, die Prozesse, die zwischen der Absorption der Photonen und der Ladungsträgererzeugung liegen, genauer zu verstehen, sind einige Fragen jedoch immer noch ungelöst, z.B. wie diese Prozesse schon auf dem Reißbrett durch die gezielte Änderung bestimmter Molekülstrukturen optimiert werden können. Um dieses Ziel zu erreichen, werden in dieser Arbeit Dicyanovinyl-substituierte Oligothiophene (DCVnTs) verwendet. Diese Materialien bieten die Möglichkeit, kleine strukturelle Änderungen vorzunehmen, deren Einfluss auf die molekularen und auf die Solarzelleneigenschaften untersucht werden soll. Der Einfluss der Messtemperatur auf den Prozess der Ladungsträgertrennung wird hier an einer methylierten DCV4T-Verbindung in einer dünnen Schicht untersucht. Die bei photoinduzierter Absorptionsspektroskopie (PIA) beobachtete Aktivierung dieses Prozesses mit zunehmender Temperatur wird auf eine erhöhte Ladungsträgerbeweglichkeit zurückgeführt. Der dadurch erhöhte effektive Abstand der Ladungen an der Grenzfläche zwischen Donator (D) und Akzeptor (A) erleichtert die endgültige Trennung der Ladungsträger. Durch den Vergleich mit einer DCV6T-Verbindung wird der Zusammenhang zwischen der Aktivierungsenergie und der Beweglichkeit bekräftigt. Die kleinere Beweglichkeit äußert sich dabei in einer größeren Aktivierungsenergie. Darüber hinaus kann der Ladungsträgergenerationsprozess auch von der Molekülstruktur abhängen. In dieser Arbeit wird untersucht, wie sich die Länge von Alkylseitenketten auf die Energieniveaus der Moleküle, aber auch auf die Absorptions- und Lumineszenzeigenschaften der Materialien in reinen und in Mischschichten mit dem Akzeptor C60 äußert. Die ermittelten Unterschiede bezüglich der Molekülordnung (geordneter für kürzere Seitenketten) und der Phasengrößen in Mischschichten (größere Phasen bei kürzerer Kettenlänge) werden in der Untersuchung der Temperaturabhängigkeit der Lebensdauer von Triplettexzitonen mittels PIA-Messungen bestätigt. Für Solarzellen ist von Bedeutung, ob sich die Seitenkettenlänge auf die Wechselwirkung zwischen D und A auswirkt. Der vermutete Zusammenhang wird hier nicht bestätigt. Ein ähnlicher Photostrom für alle untersuchten Verbindungen in Solarzellen mit planaren Heteroübergängen unterstreicht diese Schlussfolgerung. Unterschiede im Wirkungsgrad werden auf Änderungen der Energieniveaus und die Morphologie in Mischschichtsolarzellen zurückgeführt. Des Weiteren wird in einer Machbarkeitsstudie der Einfluss des elektrischen Felds auf die Generationsausbeute freier Ladungsträger untersucht. Dafür werden halbtransparente Solarzellen verwendet, die es ermöglichen, PIA-Messungen in Transmissionsgeometrie durchzuführen. Als mögliche Erklärung für das Auftreten zweier Rekombinationskomponenten in der Analyse des Rekombinationsverhaltens der durch Licht erzeugten Ladungsträger werden eingefangene Ladungsträger und gebundene Ladungsträgerpaare an der D/A-Grenzfläche genannt. Das Mischverhalten von D und A kann durch ein Heizen des Substrates während des Verdampfungsprozesses eingestellt werden, was von entscheidender Bedeutung für eine weitere Steigerung des Wirkungsgrades ist. Für DCV4T:C60-Mischschichtsolarzellen wird jedoch eine Verschlechterung des Wirkungsgrads zu höheren Substrattemperaturen beobachtet. Durch optische Messungen und Methoden zur Schichtstrukturbestimmung wird dieser Effekt auf eine Umordnung der DCV4T-Kristallite für hohe Substrattemperaturen und die damit verbundene Verringerung der Absorption und damit auch des Photostroms zurückgeführt. Bei einer Substrattemperatur von 90° C sind die D- und A-Komponenten fast vollständig entmischt. Dieses Beispiel ist von besonderer Bedeutung, weil hier die Ursachen für ein Verhalten aufgezeigt werden, das entgegen den Beispielen aus der Literatur eine Abnahme des Wirkungsgrads beim Aufdampfen der aktiven Schicht auf ein geheiztes Substrat zeigt. Schließlich werden die Optimierungsschritte dargelegt, mit denen Solarzellen mit einer DCV5T-Verbindung als Donatormaterial auf einen Rekordwirkungsgrad von 7,7% gebracht werden. Dabei wird die Substrattemperatur, die Dicke der aktiven Schicht und die Transportschichten angepasst.:Abstract - Kurzfassung Publications Contents 1 Introduction 2 Elementary Processes in Organic Semiconductors 2.1 Introduction 2.2 Optical Excitations in Organic Materials 2.2.1 Introduction 2.2.2 Radiative Processes: Absorption and Emission 2.2.3 Non-radiative Relaxation Processes 2.2.4 Triplet Excitons and Intersystem Crossing 2.3 Polarization Effects and Disorder 2.4 Transport Processes in Disordered Organic Materials 2.4.1 Charge Transport 2.4.1.1 The Bässler Model 2.4.1.2 Marcus Theory for Electron Transfer 2.4.1.3 Small Polaron Model 2.4.1.4 Functional Dependencies of the Charge Carrier Mobility 2.4.2 Diffusive Motion 2.4.3 Exciton Transfer Mechanisms 2.4.4 Characteristics of Exciton Diffusion 2.5 Charge Photogeneration in Pristine Materials 3 Organic Photovoltaics 3.1 General Introduction to Solar Cell Physics 3.2 Introduction to the Donor/Acceptor Heterojunction Concept 3.3 The Open-Circuit Voltage in Organic Solar Cells 3.4 Doping of Organic Semiconductors 3.5 Introduction to the p-i-n Concept 3.6 Charge Transfer Excitons in Donor/Acceptor Heterojunction Systems 3.6.1 Introduction 3.6.2 Verification of Charge Transfer Excitons in Donor/Acceptor Systems 3.7 The Process Cascade for Free Charge Carrier Generation in Donor/Acceptor Heterojunction Systems 3.7.1 The Initial Charge Transfer Step 3.7.2 The Binding Energy of the Charge Transfer Exciton 3.7.3 \"Hot\" Charge Transfer Exciton Dissociation 3.7.4 \"Cold\" Charge Transfer Exciton Dissociation 3.7.5 Supposed Influence Factors on Charge Transfer Exciton Dissociation 3.7.6 Recombination Pathways for Charge Transfer Excitons 3.7.7 Free Charge Carrier Formation and Recombination 4 Experimental Methods 4.1 Sample Preparation 4.2 Material Characterization Methods 4.2.1 Optical Characterization 4.2.2 Cyclic Voltammetry 4.2.3 Ultraviolet Photoelectron Spectroscopy 4.2.4 Atomic Force Microscopy 4.2.5 Grazing Incidence X-Ray Diffraction 4.2.6 Organic Field-Effect Transistor 4.3 Photoinduced Absorption Spectroscopy 4.3.1 Introduction 4.3.2 Derivation of the PIA Signal 4.3.3 Recombination Dynamics 4.3.4 Intensity Dependence of the PIA Signal 4.4 Solar Cell Characterization 4.4.1 External Quantum Efficiency 4.4.2 Spectral Mismatch Correction 4.4.3 Current-Voltage Characteristics 4.4.4 Optical Device Simulations 4.4.5 Optical Device Transmission Measurements 5 The Oligothiophene Material System 5.1 Introduction 5.2 Thermal Stability 5.3 Energy Levels 5.4 Optical Properties of the Pristine Materials 5.5 The Donor/Acceptor Couple: DCVnT and C60 5.6 Solar Cell Devices 5.7 Summary 6 Temperature Dependence of Charge Carrier Generation 6.1 Introduction 6.2 Principal Introduction to the PIA Measurements 6.2.1 Interpretation of the Spectra 6.2.2 Interpretation of the Frequency Scans 6.3 Temperature Dependence of the Spectra 6.4 Discussion of the Temperature Dependent Processes in the Blend Layer 6.5 Temperature Activated Free Charge Carrier Generation 6.5.1 Evaluation of the Activation Energy for the DCV4T-Me:C60 Blend 6.5.2 Comparison to a Sexithiophene Derivative (DCV6T-Me) 6.6 Summary 7 Side Chain Investigation on Quaterthiophene Derivatives 7.1 Energy Levels 7.2 Optical Properties 7.2.1 Solution and Pristine Films 7.2.2 Mixed Films with C60 7.3 Influence of the Side Chain Length on the Intermolecular Coupling 7.3.1 PIA Spectra of Pristine and Blend Layers at 10K 7.3.2 Recombination Analysis for Pristine and Blend Films at 10K 7.4 The Influence of the Side Chain Length on the Offset Charge Carrier Generation Rate at Low Temperature 7.5 In the High-Temperature Limit: Implications for Solar Cell Devices 7.5.1 PIA Spectra in Pristine and Blend Films at 200K 7.5.2 Recombination Analysis: Triplet Excitons and Free Charge Carriers 7.6 Solar Cells 7.6.1 Flat Heterojunction Devices 7.6.2 Bulk Heterojunction Devices 7.7 Summary 8 Electric-Field Dependent PIA Measurements on Complete Solar Cell Devices 8.1 Introduction 8.2 Semitransparent Organic Solar Cells 8.3 Photoinduced Absorption Measurements 8.4 Summary and Outlook 9 The Effect of Substrate Heating During Layer Deposition on the Performance of DCV4T:C60 BHJ Solar Cells 9.1 Introduction 9.2 The Importance of Morphology Control for BHJ Solar Cells 9.3 The Impact of Substrate Heating on DCV4T:C60 BHJ Solar Cells 9.4 Absorption and Photoluminescence 9.5 Topographical Investigations (AFM) 9.6 X-ray Investigations 9.6.1 1D GIXRD Measurements 9.6.2 2D GIXRD Measurements 9.7 Proposed Morphological Picture and Confirmation Measurements 9.7.1 Morphology Sketch of the DCV4T:C60 Blend Layer 9.7.2 Confirmation Measurements 9.8 The Equivalence of Temperature and Time 9.9 Summary 10 Record Solar Cells Using DCV5T-Me33 as Donor Material 10.1 Introduction 10.2 The Influence of the Substrate Temperature 10.3 Determination of the Optical Constants 10.4 Stack Optimization 10.5 Summary and Outlook 11 Conclusions and Outlook 11.1 Summary of the Photophysical Investigations 11.2 Summary of Device Investigations 11.3 Future Challenges Appendix A Detailed Description of the Experimental Setup for PIA Spectroscopy Appendix B Determination of the Triplet Level by Differential PL Measurements Appendix C Additional Tables and Figures Appendix D Reproducibility of the Solar Cell Results (Statistics) Appendix E Lists Bibliography Acknowledgments

碩士
國立交通大學
電子研究所
82
Presented here is an analysis simulation tool for Charge- coupled devices(CCD), including charge capacity model and charge transfer inefficiency analytical model with and without considering effective fat zero (dark current). The surface potential with no minority carrier in our simulation is so easy to get by Fourier series, without using numerical method and the CPU time is very greatly reduced. We firstly propose a simple charge capacity model to simulate signal-charge distribution and verified by numerical results. And we propose a new method to determine the minimum fringing field from the final time constant. By this new method and charge-signal distribution we can explain the controversy of the result of the short gate length. In addition, simulation results shows that a trade-off between the transfer efficiency and the magnitude of signal charge due to the charge screening effect. Finally, a analytical model of wide range temperature is proposed and simulation results matches the experimental data very good. By this model, we can obtain a complete energy- dependent interface state distribution.

Dissertação de Mestrado Integrado em Engenharia Electrotécnica e de Computadores apresentada à Faculdade de Ciências e Tecnologia
Wireless power transfer technology has been widely used in many areas. This thesis implements a wireless charging system for consumer electronics for mobile applications such as laptops and tablets. The working on a wireless power transfer system is comparable to that of an air core transformer with the leakage compensated by means of capacitances. Compensation has been applied to both the primary and secondary of the transformer. This would help boost power transfer. Theoretically described the basic series-series compensation topology used. The resonant wireless power transfer is demonstrated in this thesis. The efficiency of such a system is analyzed and the results are promising, however, there are significant opportunities for improvement.This thesis consists of five chapters:chapter 1 is talking about the history, classification and applications of wireless power transfer. Chapter 2 is talking about Introduction about the fundamentals of wireless power transfer system, the theoretical study of the compensation topology and determines the important elements of such a system to help the design of a wireless power transfer system to be good.Chapter 3 Defines the parameters of the desired design by using Matlab codes and Matlab model simulation and comparison for the results.Chapter 4 Implement the study of the experimental system, and compare the result with its own simulated and calculated results.Chapter 5 at the end, we will see the conclusion of the project and the future work.Wireless power transfer technology has been widely used in many areas. This thesis implements a wireless charging system for consumer electronics for mobile applications such as laptops and tablets. The working on a wireless power transfer system is comparable to that of an air core transformer with the leakage compensated by means of capacitances. Compensation has been applied to both the primary and secondary of the transformer. This would help boost power transfer. Theoretically described the basic series-series compensation topology used. The resonant wireless power transfer is demonstrated in this thesis. The efficiency of such a system is analyzed and the results are promising, however, there are significant opportunities for improvement.This thesis consists of five chapters:chapter 1 is talking about the history, classification and applications of wireless power transfer. Chapter 2 is talking about Introduction about the fundamentals of wireless power transfer system, the theoretical study of the compensation topology and determines the important elements of such a system to help the design of a wireless power transfer system to be good.Chapter 3 Defines the parameters of the desired design by using Matlab codes and Matlab model simulation and comparison for the results.Chapter 4 Implement the study of the experimental system, and compare the result with its own simulated and calculated results.Chapter 5 at the end, we will see the conclusion of the project and the future work.
Wireless power transfer technology has been widely used in many areas. This thesis implements a wireless charging system for consumer electronics for mobile applications such as laptops and tablets. The working on a wireless power transfer system is comparable to that of an air core transformer with the leakage compensated by means of capacitances. Compensation has been applied to both the primary and secondary of the transformer. This would help boost power transfer. Theoretically described the basic series-series compensation topology used. The resonant wireless power transfer is demonstrated in this thesis. The efficiency of such a system is analyzed and the results are promising, however, there are significant opportunities for improvement.This thesis consists of five chapters:chapter 1 is talking about the history, classification and applications of wireless power transfer. Chapter 2 is talking about Introduction about the fundamentals of wireless power transfer system, the theoretical study of the compensation topology and determines the important elements of such a system to help the design of a wireless power transfer system to be good.Chapter 3 Defines the parameters of the desired design by using Matlab codes and Matlab model simulation and comparison for the results.Chapter 4 Implement the study of the experimental system, and compare the result with its own simulated and calculated results.Chapter 5 at the end, we will see the conclusion of the project and the future work.Wireless power transfer technology has been widely used in many areas. This thesis implements a wireless charging system for consumer electronics for mobile applications such as laptops and tablets. The working on a wireless power transfer system is comparable to that of an air core transformer with the leakage compensated by means of capacitances. Compensation has been applied to both the primary and secondary of the transformer. This would help boost power transfer. Theoretically described the basic series-series compensation topology used. The resonant wireless power transfer is demonstrated in this thesis. The efficiency of such a system is analyzed and the results are promising, however, there are significant opportunities for improvement.This thesis consists of five chapters:chapter 1 is talking about the history, classification and applications of wireless power transfer. Chapter 2 is talking about Introduction about the fundamentals of wireless power transfer system, the theoretical study of the compensation topology and determines the important elements of such a system to help the design of a wireless power transfer system to be good.Chapter 3 Defines the parameters of the desired design by using Matlab codes and Matlab model simulation and comparison for the results.Chapter 4 Implement the study of the experimental system, and compare the result with its own simulated and calculated results.Chapter 5 at the end, we will see the conclusion of the project and the future work.

Finally in combination with c-AFM and EFM, the high-k materials breakdown behaviors are also interrogated. The breakdown processes are classified into three stages: pre-breakdown (pre-BD), soft breakdown (SBD) and hard breakdown (HBD). And a HfOx nano-pattern is fabricated with the aid of AFM. The dot growth characteristics on the pulse amplitude, duration and humidity are scrutinized.
In this thesis, the single CdS nanobelt devices are fabricated successfully. The photosensitivity at 1V is up to 8 x 103 A/W and the electron mobility reaches to tens of cm/V·s. Based on these excellent optoelectronic properties, the CdS nanobelt becomes a good choice for interrogation on the charge transport characteristics on a nanometer scale. The transistor measurements show that the performance of CdS nanobelt device can be influenced by illuminations and ambient conditions, which result from the metal/CdS nanobelt contact and nanobelt surface redox reactions.
The intrinsic carrier transport characteristics in CdS nanobelt can be investigated by reconstructing of the local surface band diagram with the aid of SSPM. A ∼0.50 eV upward band bending can be obtained in the dark. The surface depletion length induced by the negative surface oxygen adsorbates is estimated to ∼66nm if a concentration of 1017 cm -3 shallow donors is assumed in the CdS nanobelt. This depletion length is close to the height of the ultra-thin CdS nanobelt. These adsorbates result in the surface depletion region expansion and the conduction channel reduction, which is responsible for the CdS conductance drop. Above the band-gap illumination or to the oxygen-deficient environment can effectively reduce the surface band bending and the depletion region, finally increase the conduction channel, which is one of the main reasons for the large photosensitivity and highly oxygen sensitivity for the single CdS nanobelt device.
To sustain Moore's law scaling trend beyond COMS, one-dimensional (1D) nanostructures, e.g. carbon nanotubes and semiconductor nanowires, are proposed to act as fundamental nanoscale blocks in the future electronic and optoelectronic devices. Therefore it is very crucial to understand the unique nature of electronic properties for 1D nanostructures in designing novel nanoelectronic devices and optimizing the device performance. In this thesis, the charge transport properties of nanostructure devices are studied. A method called photo-assisted scanning surface potential microscopy (SSPM) is developed, which yields a direct measurement of the electrostatic potential distributions across the 'biased' nanostructured device under different illumination conditions. Our efforts provide significant understanding of the nature of charge transport in nanoelectronics.
We can simply fabricate the MSM device using single CdS nanobelt. A positive Schottky barrier is found at the electrode/CdS nanobelt junction because of the unequal work function or the Fermi level pinning by the surface states. The barrier height is estimated to be 0.38 eV by fitting the temperature dependent I-V curves. A big potential drop at the junction can be visualized by SSPM. The calculated contact resistance for the electron injection is much larger than that for the CdS nanobelt, which illustrates that the transport properties of CdS nanobelt device are dominated by the charge injection process. The change in contact resistance and nanobelt resistance under the above bandgap illumination are measured by photo-assisted SSPM. The experimental results show that in the dark, the charge transport for the CdS nanobelt device is dominated by electron injection, while under high light intensity, the charge transport is governed by the intrinsic nature of CdS nanobelt.
With the aid of SPM, the charge injection and carrier transport characteristics of the individual CdS nanobelt device are systematically interrogated and comprehensively demonstrated, which are useful for designing and fabricating the nanostructured electronic and optoelectronic devices.
An, Jin.
Adviser: Jiambin Xu.
Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3674.
Thesis (Ph.D.)--Chinese University of Hong Kong, 2008.
Includes bibliographical references.
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstracts in English and Chinese.
School code: 1307.

Despite the poor understanding of charge transfer in conducting polymers, conducting-polymer-based devices have achieved considerable commercial success. This success is based largely on the reproducibility of the measurable properties. It is the purpose of this study to further clarify charge transfer characteristics of conducting polymers under varying conditions. We studied a conducting polymer called polyaniline. Polyaniline was available in its doped conducting form called emeraldine salt and in its undoped form called emeraldine base. Three types of polyaniline were studies, electrosynthesized (doped by HCI), chemically synthesized (doped by HCI) and commercial polyaniline obtained from Adlrich Company and doped by camphor sulfonic acid. Initially we investigated whether charge transfer was ionic or electronic by observing the change in resistance with time for a fixed applied current. It was concluded that condition in this material is electronic. Electrical measurements were obtained using the four-point probe and the Montgomery methods. The samples investigated were in pellet and film forms. We investigated charge transfer over the temperature regime 30-450 K by applying the following methods: scanning electron microscopy to investigate the surfaces of pellet and film samples, Fourier transform infrared spectroscopy and Raman spectroscopy to investigate the effect of annealing on the molecular structure of the polymer and thermal analysis to investigate the loss of substances from the polymer as a result of the annealing process. The conductivity of the material was also analyzed over the entire temperature regime. The following were observed: • Conductivity in polyaniline is governed my monomer units. • The decrease in conductivity with increase annealing temperature is related to moisture loss, loss of dopant ions and polymer degradation. • The variable range hopping model in three dimensions, satisfactorily describes charge transfer mechanism in polyaniline. • Conductivity in polyaniline is temperature activated. • Conductivity varies with position on the sample surface. • The effect of pellet pressing pressure to conductivity is negligible. • Current-voltage characteristics for polyaniline exhibit non-ohmic behavior at high current values, (>0.2 mA for T <80 K), applied between the current probes of a four-point probe measuring instrument.
Dissertation (MSc (Physics))--University of Pretoria, 2006.
Physics
unrestricted

博士
國立臺灣大學
化學工程學研究所
104
Organic-field-effect-transistor (OFET) -type memory devices have been extensively studied due to their flexibility, scalability, and solution processability. Functional polymer containing semiconducting elements is considered as one of the most promising charge storage materials for organic field-effect transistors and organic-based memory devices, since it features a systematic route towards materials with novel architectures, functions, and physical properties. However, there is limited study on the correlations of the nanostructure and the electronic characteristic. In this thesis, we report the OFET memory devices using the dielectric layer of cross-linked core-shell block copolymers containing conjugating segments in the cores, and reveal the effect of both block composition and nanostructure on the memory characteristics. We further explored the random copolymers consisting of both pendant electron-donating and -withdrawing groups as charge storage layer in the OFET memory devices. In addition, for comparing with the synthetic polymer electrets, the solution-associated supramolecules are also applied in the OFET memory devices as charge storage dielectrics. The important discovery of this thesis was summarized in the follows. 1. Non-Volatile Field-Effect Transistor Memory Devices using Charge Storage Cross-Linked Core-Shell Nanoparticles as Polymer Electrets (Chapter 2): Solution processable cross-linked core-shell nanoparticles containing conjugated elements are firstly explored as charge storage materials for transistor-type (OFET) memories. These uniform nanoparticles containing cross-linked electron-donating or donor-acceptor cores presented efficient flash-type memory characteristics. The devices using donor-acceptor nanoparticles presented both electron- and hole-trapping abilities, along with the memory window of 38 V, the retention ability of over 10^4 s, and endurance of over 100 cycles. 2. Multilevel Non-Volatile Organic Transistor Memory Devices using Pendent Donor-Acceptor Random Copolymer Electrets (Chapter 3): Non-volatile transistor memories were fabricated using n-type semiconductor BPE-PTCDI and dielectric layer of non-conjugated random copolymers with pendant electron-donating 9-(4-vinylphenyl)carbazole (VPK) and electron-withdrawing 2-phenyl-5-(4-vinylphenyl)-1,3,4-oxadiazole (OXD) moieties. The pendent structure provided restricting regions with well-defined donor-acceptor interfaces, which is not happened in the case of PVPK/POXD polymer blend. The multilevel data storage and endurance characteristics obtained by applying different voltage pulses suggested that the devices using random copolymer P(VPKxOXDy) as electrets possessed ambipolar and controllable non-volatile flash-type memory behaviors even when the working voltage was as low as 10 V. 3. High-Performance Non-Volatile Transistor Memory Devices using Charge-Transfer Supramolecular Electrets (Chapter 4): Non-volatile OFET memory devices using charge-transfer (CT) supramolecules of poly(4-vinylpyridine) (P4VP) with two different chromophores, 3-(dicyanomethylidene)indan-1-one (1CN-IN) or 1,3-bis(dicyanomethylidene)indan (2CN-IN) were demonstrated. The intermolecular CT interaction effectively introduced the chromophores as charge trapping sites into the P4VP matrix, leading to a controllable flash-type memory behavior. The 2CN-IN with one more electron-withdrawing dicyanomethylene group, compared to 1CN-IN, provided a better electron-trapping ability and thus obtained a larger memory window. The device based on P4VP(2CN-IN)0.30 electret exhibited the largest memory window of 79 V with the excellent retention ability of up to 10^7 s and endurance of over 100 cycles. Our study demonstrated the significance of interfacial charge-transfer mechanism and molecular nanostructure on the charge transporting and memory characteristics for novel organic electronic devices.

Nowadays, from lifestyle to sports and health to security, wearable technology is an inevitable trend that, through the human-machine interaction, has the capability of transforming businesses by making them smarter, more informative, and more communicative. In this study, commercial textile fibers have been functionalized with Polypyrrole (PPy) to achieve an electronic system that can convert external mechanical energy into electrical energy. PPy is a biocompatible π-conjugated polymer. The main principle behind the devices’ operation is the charge transfer mechanism that occurs between the π-conjugated polymer and the metal (electrode) layer when the system suffers mechanical stress. Furthermore, the PPy functionalized textile has been weaved to an e-cloth, through a custom-built weaving machine. This e-cloth can generate current under human-motion interaction. The best results achieved in this study, in terms of power density and current density, were 2.29 Wm-2 and 23.9 mA m-2 , respectively. Considering the best device, we were able to light up to 50 LEDs connected in series. With this device, we were also able to charge a 33F capacitor up to 1V, in 225 seconds. All the devices built have kept electrical stability during the six months of the work. The main application explored in this study was the detection of human movements through motion interactive energy harvesting technology.

The main subject of this thesis is the synthesis and investigation of the properties and potential applications of a new class of hybrid compounds consisting of a rigid, electroactive 4,4’-bipyridinium core capped by nucleobase terminal groups with hydrogen bonding abilities. A new series of small molecules consisting in a 4,4’-bipyridinium unit carrying thymine or/and adenine as capping groups was synthetized. The synthesis strategy implied the regioselective alkylation of thymine and adenine bases respectively, followed by coupling of the alkylated precursors to 4,4’-bipyridine unit via Menschutkin reaction. Electrochemical, spectroelectrochemical and optical investigations revealed an intramolecular charge transfer (CT) relationship between nucleobases as donors and 4,4’-bipyridinium unit as acceptor which is accompanied by a change in color and a shift of the reduction potentials (approx. 60 mV). The viologen-nucleobase derivatives, particularly viologens capped by thymine, were used as building blocks to create self-assembled functional nanostructures in the presence of complementary templates such as oligonucleotides or ssPNA analogues via thymine-adenine interactions. The viologen-thymine derivatives were found to partially precipitate oligonucleotides or plasmid DNA by mean of coulombic interactions and form stable polyplexes that could be used as potential gene delivery vectors. It was found that the number of positive charges, as well as the number of thymine units per viologen-thymine derivative determines whether the interaction with DNA is dominated by electrostatic or by hydrogen bonding interactions. New electroactive ionic liquid crystals were prepared by ion pairing of viologen-nucleobase dicationic species with amphiphilic 3,4,5-tris(dodecyloxy)benzene sulfonate anion. The nucleobases with ability to self-associate by hydrogen bonding were found to influence not just the thermotropic behavior, by decreasing transition temperature from crystalline to mesophase state, but also the supramolecular arrangement in solution. A versatile approach to functionalize mesoporous TiO2 film with viologen-nucleobase derivatives was developed consisting of hydrogen bonding layer-by-layer deposition of viologen-nucleobase derivatives on TiO2 surface using the thymine-adenine molecular recognition as driving force for immobilization. This method is promising and represents an easy way to construct optoelectronic device components as was demonstrated with the construction of a switchable electrochromic device.

Photosynthesis involves the absorption of photons by light-harvesting pigments and the subsequent transfer of excitation from the absorption centre to the reaction centre. This highly efficient phenomenon of excitation transfer has traditionally been explained by the Forster mechanism of incoherent hopping of excitation from one chromophore to another. Recently 2D electronic spectroscopic evidences were gathered by Fleming and coworkers on the photosynthetic Fenna-Matthews-Olson (FMO) complex in green sulfur bacteria [1]. Subsequent simulation studies by the same group [2] led to the proposition of a quantum-mechanical, coherent, wave-like transfer of excitation among the chromophores. However, Fleming's conclusions regarding retention of coherence appeared surprising because, the complex would interact with the numerous degrees of freedom of the protein scaffold surrounding it, leading to decoherence, which is expected to be rapid. Thus, we were interested in proposing an analytical treatment to rationalize the excitation transfer. Traditional approaches employed for studying excitation energy transfer involve the master equation techniques where the system-bath coupling is perturbative and is truncated after a few orders. It is important to note that the system-bath coupling causes both decoherence and population relaxation. Such a perturbative approximation is difficult to justify for the photosystem, as the system-bath coupling and the interchromophoric electronic coupling have comparable values. Also, these treatments are largely numerical studies and demand involved calculations. Thus, exact calculations for such a system (7-level) are very difficult. Consequently, we were interested in developing an analytical approach where the coupling is treated as non-perturbative. We devised a novel analytical treatment which employs a unitary transformation analogous to the one used for the theory of nonadiabatic effects in chemical reactions [3]. Our treatment rests on an adiabatic basis which are eigenstates calculated at each nuclear position (i.e. at each configuration of the bath) bearing a parametric dependence in Qi, where Qi denotes the shift of the exciton at site `i' due to the environment. The treatment is justified because in the case of coherent transfer, the excitation would travel mostly amongst the adiabatic states and the effects of non-adiabaticity are small. We observed that the system-bath coupling, after the unitary transformation, could be decoupled at the lowest order into two parts: a) an adiabatic contribution, which accounts solely for decoherence (this is evaluated almost exactly in our approach) and b) a non-adiabatic contribution which accounts for population relaxation from one adiabatic state to another (treated by a Markovian master equation). When we applied our technique to the FMO complex, our prediction for population evolution at the chromophores showed excellent correspondence with those obtained by Nalbach and coworkers using path-integral calculations [4], which are exact. These were calculations where the environment was modelled using a Drude spectral density. Our method allowed the calculations to be readily performed for different temperatures as well. It should be specifically emphasized that, unlike the involved and cumbersome path-integral calculations by Nalbach and coworkers [4] or the hierarchical equation calculations by Ishizaki et al. [2], our method is simple, easy to apply and computationally expedient. Further it became evident that the ultra-efficiency of energy transfer in photosynthetic complexes is not completely captured by coherence alone but is the result of an interplay of coherence and the dissipative influence of the environment (also known as ENAQT or Environment Assisted Quantum Transport [5]). An added advantage of our analytical treatment was the flexibility it offered. Thus, we could use our formalism to perform expedient analyses on the behavior of the system under various conditions. For example, we may wish to evaluate the consequences of introducing correlations among the bath degrees of freedom on the efficiency of transfer to the reaction centre. To this end, we applied our formalism by introducing correlations among the bath degrees of freedom and then by introducing anticorrelations among the bath degrees of freedom. The conclusions were interesting, for they suggested that the efficiency of transfer to the reaction centre was enhanced by the presence of anti-correlations, when compared with an uncorrelated bath. Uncorrelated baths, in turn, had a higher efficiency of energy transfer than correlated baths [6]. Thus, the population evolution is fastest for the anti-correlated bath, followed by the uncorrelated bath and is slowest for the correlated bath. Similar conclusions have been reached at by Tiwari et al. [7]. We could also extend the formalism for studying the system under different spectral densities for the environment, apart from just the Drude spectral density which is popularly used in literature associated with FMO calculations. For instance, the FMO system could be analyzed for the Adolphs-Renger spectral density [3, 8]. Once again our results showed excellent agreement with those reported by Nalbach. We also analyzed the FMO system under the spectral density proposed by Kleinekathofer and coworkers [9]. It was found that these latter spectral densities had more profound participation from the environment, therefore coherences were destroyed more effectively and population relaxation was faster. The excitation transfer to the final site (site closest to the reaction centre in the FMO complex) was found to be faster for the Adolphs and Renger spectral density and the spectral density proposed by Kleinekathofer and coworkers, when compared to the Drude spectral density. Also, the excitation transfer was fastest when we modelled the environment using the Kleinekathofer spectral density. This reinforced the previous conclusions that the dissipative effects of the environment promote a faster energy transport. Being an almost analytical approach, our technique could be applied to systems with larger number of levels as well. A good example of such a case is the MEH-PPV polymer. 2D electronic-spectroscopic experiments performed on this polymer in solution speculate that the excitation energy transfer might be coherent even at physiological temperatures [10]. A prototype for studying this system might be a conjugated polymer with around 80-100 chromophores. Linewidths and Lineshapes in the vicinity of Graphene It has been reported that a vibrating dipole may de-excite by transferring energy non-radiatively to a neighboring metal surface [11]. It is also understood that due to its delocalized pi-cloud, graphene has a continuum of energy states and can behave like a metal sheet and accept energies. Thus, we proposed that if a vibrationally excited dipole de-excites in the vicinity of a graphene sheet, graphene may get electronically excited and thus serve as an effective quencher for such vibrational excitations. Depending on the distance of the dipole from the graphene sheet, the transfer might be intense enough to be spectroscopically probed. We have investigated the rate of such an energy transfer. We use the Dirac cone approximation for graphene, as this enables us to obtain analyt-ical results. The Fermi Golden rule was used to evaluate the rate of energy transfer from the excited dipole to the graphene sheet [12]. The calculations were performed for both the instances: a) energy transfer from a dipole to undoped graphene and, b) energy trans-fer from a dipole to doped graphene. For undoped graphene, the carrier (electron) charge density in the conduction band is zero and we would only have transitions from the valence band to the conduction band. As a consequence of absence of carrier charge density in CB (conduction band), the screening of Coulombic interactions in the graphene plane is ineffective. Thus, one could use the non-interacting polarizability for undoped graphene in the rate expression [13]. However, when we consider the case of doped graphene where EF is shifted upwards into CB, the conduction band electrons will contribute to screening. In this case, we have two sets of transitions: a) from ki in VB (valence band) to kf in CB and b) ki in CB to kf in CB, where ki and kf are the wavevectors which correspond to the initial and final electronic states in graphene. So we have used the polarizability propagator in the random phase approximation [14] to calculate the rate following the approach of [13]. It is also known that the imaginary part of the frequency domain dipole-dipole corre-lation function is a measure of the lineshape [15]. We were, thus, interested in evaluating the lineshape for these transitions. For evaluating the correlation function, we used the partitioning technique developed by L•owdin [16] and subsequently extracted the lineshape from its imaginary part. Using this method, we calculated lineshape for the vibrational excitation of CO molecule in the vicinity of an undoped graphene lattice. The linewidth for this system also was obtained. It could be seen that the vibrational linewidth for 1 CO in the vicinity (5 A) of undoped graphene (EF = 0:00eV ) is small (0:012 cm ) but could be observed experimentally. The lineshape calculations were also extended to cases where it is possible to have atomic transitions by placing an electronically excited atom in the vicinity of the graphene sheet. We considered the following two cases: a) 3p ! 2s transition in hydrogen atom, at a distance of 12 A from the graphene sheet and, b) 4p ! 3s transition in hydrogen atom, at a distance of 20 A from the graphene sheet. The linewidths for atomic transitions could be easily probed in these cases ( 55 cm 1 for 3p ! 2s and 56 cm 1 for 4p ! 3s). In the preceding calculations, the transi-tion dipoles were considered perpendicular to the graphene surface. It is worthwhile to note that if the transition dipoles are considered parallel to the graphene surface, the respective linewidths would be half of those obtained for the case where the transition dipoles are perpendicular. Another interesting possibility would be to consider a lanthanide metal complex placed within a few nanometers from graphene. Lanthanides are known to have sharp f-f transitions [17] and consequently, one could easily observe the effects of broadening due to energy transfer to the electronic system of graphene. Energy Eigenmodes for arrays of Metal Nanoparticles In the final part of the thesis we consider organized assemblies of metal nanoparti-cles, specifically helical and cylindrical assemblies and investigate the plasmonic excitation transfer across these assemblies. These were motivated by recent studies which reported growth of chiral asymmetric assemblies of nanoparticles on D and L- isomers of dipheny-lalanine peptide nanotubes [18]. The plasmons in the helical/cylindrical assemblies are expected to couple with each other via electromagnetic interactions. We construct the Hamiltonian for such systems and evaluate the eigenmodes and energies pertaining to these modes in the wave vector space. We also perform calculations for the group velocity for each eigenmode as this gives us an idea of which eigenmode transports excitation the fastest.

Quantum chemical computations provide convenient and effective ways for molecular design using computers. In this dissertation, the molecular designs of optimal nonlinear optical (NLO) materials were investigated through three aspects. First, an inverse molecular design method was developed using a linear combination of atomic potential approach based on a Hückel-like tight-binding framework, and the optimizations of NLO properties were shown to be both efficient and effective. Second, for molecules with large first-hyperpolarizabilities, a new donor-carbon-nanotube paradigm was proposed and analyzed. Third, frequency-dependent first-hyperpolarizabilities were predicted and interpreted based on experimental linear absorption spectra and Thomas-Kuhn sum rules. Finally, molecular interferometers were designed to control charge-transfer using vibrational excitation. In particular, an ab initio vibronic pathway analysis was developed to describe inelastic electron tunneling, and the mechanism of vibronic pathway interferences was explored.

Dissertation