The impetus of unsustainable consumption coupled with major environmental concerns has renewed our society's investment in new energy production methods. Solar energy is the poster child of clean, renewable energy. Its favorable environmental attributes have greatly enhanced demand resulting in a spur of development and innovation. Photovoltaics, which convert light directly into usable electrical energy, have the potential to transform future energy production. The benefit of direct conversion is nearly maintenance free operation enabling deployment directly within urban centers. The greatest challenge for photovoltaics is competing economically with current energy production methods. Lowering the cost of photovoltaics, specifically through increasing the conversion efficiency of the active absorbing layer, may enable the invisible hand to bypass bureaucracy. To accomplish the ultimate goal of increased efficiency and lowered cost, it is essential to develop new material systems that provide enhanced output or lowered cost with respect to current technologies. However, new materials require new understanding of the physical principles governing device operation. It is my hope that elucidating the dynamics and charge transfer mechanisms in novel photovoltaic material systems will lead to enhanced design principles and improved material selection. Presented is the investigation of electron dynamics in two materials systems that show great promise as active absorbers for photovoltaic applications: inorganic semiconductor quantum dots and organic semiconductors. Common to both materials is the strong Coulomb interaction due to quantum confinement in the former and the low dielectric constant in the latter. The perceived enhancement in Coulomb interaction in quantum dots is believed to result in efficient multiexciton generation (MEG), while discretization of electronic states is proposed to slow hot carrier cooling. Time-resolved two-photon photoemission (TR2PPE) is utilized to directly map out the hot electron cooling and multiplication dynamics in PbSe quantum dots. Hot electron cooling is found to proceed on ultrafast time scales (< 2ps) and carrier multiplication proceeds through an inefficient bulk-like interband scattering. In organic semiconductors, the strong Coulomb interaction leads to bound electron-hole pairs called excitons. TR2PPE is used to monitor the separation of excitons at the model CuPc/C₆₀ interface. Exciton dissociation is determined to proceed through "hot" charge transfer states that set a fundamental time limit on charge separation. TR2PPE is used to investigate charge and energy transfer from organic semiconductors undergoing singlet fission, an analog of multiple exciton generation. The dynamic competition between one and two-electron transfer is determined for the tetracene/C₆₀ and tetracene/CuPc interfaces. These findings allow for the formulation of design principles for the successful harvesting of hot or multiple carriers for solar energy conversion. / text

Universal quantum computation requires precision control of the dynamics of qubits. Frequently accurate quantum control is impeded by systematic drifts and other errors. Compensating composite pulse sequences are a resource efficient technique for quantum error reduction. This work describes compensating sequences for ion-trap quantum computers. We introduce a Lie-algebraic framework which unifies all known fully-compensating sequences and admits a novel geometric interpretation where sequences are treated as vector paths on a dynamical Lie algebra. Using these techniques, we construct new narrowband sequences with improved error correction and reduced time costs. We use these sequences to achieve laser addressing of single trapped 40Ca+ ions, even if neighboring ions experience significant field intensity. We also use broadband sequences to achieve robust control of 171Yb+ ions even with inhomogeneous microwave fields. Further, we generalize compensating sequences to correct certain multi-qubit interactions. We show that multi-qubit gates may be corrected to arbitrary accuracy if there exists either two non-commuting controls with correlated errors or one error-free control. A practical ion-trap quantum computer must be extendible to many trapped ions. One solution is to employ microfabricated surface-electrode traps, which are well-suited for scalable designs and integrated systems. We describe two novel surface-electrode traps, one with on-chip microwave waveguides for hyperfine 171Yb+ qubit manipulations, and a second trap with an integrated high numerical aperture spherical micromirror for enhanced fluorescence collection.

Low-dimensional systems in condensed matter physics exhibit a rich array of correlated electronic phases. One-dimensional systems stand out in this regard. Electrons cannot avoid each other in 1D, enhancing the effects of interactions. The resulting correlations leave distinct spatial imprints on the electronic density that can be imaged with scanning probes. Disorder, however, can destroy these delicate interacting states by breaking up the electron liquid into localized pieces. Thus, to generate fragile interacting quantum states, one requires an extremely clean system in which disorder does not overcome interactions, as well as a high degree of tunability to design potential landscapes. Furthermore, to directly measure the resulting spatial correlations, one requires an exceptionally sensitive scanning probe, but the most sensitive probes presently available are also invasive, perturbing the system and screening electron-electron interactions. / Engineering and Applied Sciences

Στο επίκεντρο της παρούσας διπλωματικής εργασίας, βρίσκεται η μελέτη μη γραμμικών οπτικών ιδιοτήτων, σύνθετων δομών κβαντικών τελειών οξειδίου του ψευδαργύρου (ZnO). Αρχικά θα κάνουμε μια γρήγορη επισκόπηση των ιδιοτήτων των νανοδομημένων συστημάτων, περίπτωση των οποίων αποτελούν οι ημιαγώγιμες κβαντικές τελείες, καθώς και οι σύνθετες νανοδομές του ZnO, ενώ θα επισημάνουμε και τον στόχο που καλείται να εκπληρώσει η εργασία μας. Προκειμένου να υπολογίσουμε την ηλεκτρονική δομή του συστήματος που εξετάζουμε, χρησιμοποιούμε την μέθοδο PMM (Potential Morphing Method), τις βασικές αρχές της οποίας παραθέτουμε στο δεύτερο κεφάλαιο. Στο επόμενο κεφάλαιο παρουσιάζουμε το θεωρητικό μας μοντέλο, βασισμένο στην μέθοδο των πλατών πιθανότητας για τον αναλυτικό υπολογισμό της γραμμικής (1) και της μη γραμμικής οπτικής επιδεκτικότητας (3), οι οποίες και αποτυπώνουν τις οπτικές ιδιότητες του συστήματος μας. Τέλος περιγράφουμε την δομή του σύνθετου συστήματος κβαντικών τελειών πυρήνα/κελύφους (core/shell quantum dots), παραθέτουμε τα αποτελέσματα του υπολογισμού της ηλεκτρονικής δομής και παρουσιάζουμε την συμπεριφορά της γραμμικής, της μη γραμμικής καθώς και της ολικής επιδεκτικότητας του συστήματος που εξετάζουμε, μέσω διαγραμμάτων και του απαραίτητου σχολιασμού των αποτελεσμάτων μας. / At the center of our interest in this thesis lies the study of nonlinear optical properties of complex Zinc Oxide (ZnO) quantum dots structures. At first we will have a short review of the nanostructured systems properties in general and then we will discuss the properties of semiconductor quantum dots as well as the complex ZnO nano-structures. We will also notify the goal of this thesis. In order to calculate the electronic structure of our investigating system we will use the PMM (Potential Morphing Method) method, the basic principles of which we quote on the second chapter. In the next chapter we present our theoretical model, based in the probability amplitudes method, for the analytical calculation of both the linear (1) and nonlinear susceptibility (3) which illustrate the optical properties of our system. At the end we describe our complex core/shell quantum dots system, we quote the results of the electronic structure calculation and we present the behaviour of linear, nonlinear as well as the total susceptibility of our system through graphs and the necessary discussion of our results.

This dissertation develops technology for microfluidic point-of-care immunoassay devices. This research (2004–2007) improved microfluidic immunoassay performance by reducing reagent consumption, decreasing analysis time, increasing sensitivity, and integrating processes using a lab-on-a-chip. Estimates show that typical hospital laboratories can save $1.0 million per year by using microfluidic chips. Our first objective was to enhance mixing in a microfluidic channel, which had been one of the main barriers to using these devices. Another goal of our studies was to simplify immunoassays by eliminating surfactants. Manufacturers of latex immunoassays add surfactants to prevent non-specific aggregation of microspheres. However, these same surfactants can cause false positives (and negatives) during diagnostic testing. This work, published in Appendix A (© 2006 Elsevier) shows that highly carboxylated polystyrene (HCPS) microspheres can replace surfactants and induce rapid mixing via diffusion in microfluidic devices. Our second objective was to develop a microfluidic device using fiber optics to detect static light scattering (SLS) of microspheres in Appendix B (© 2007 Elsevier). Fiber optics were used to deliver light emitting diode (LED) or laser light. A miniature spectrometer was used to measure 45° forward light scattering collected by optical fiber. Latex microspheres coated with PR3 proteins were used to test for the vasculitis marker, anti-PR3. No false negatives or positives were observed. A limit of detection (LOD) of 50 ng mL⁻¹ was demonstrated. This optical detection system works without fluorescence or chemiluminescence markers. It is cost effective, small, and re-usable with simple rinsing. The final objective in this dissertation, published in Appendix C (© 2007 Elsevier), developed a multiplex immunoassay. A lab-on-a-chip was used to detect multiple antibodies using microsphere light scattering and quantum dot (QD) emission. We conjugated QDs onto microspheres and named this configuration “nano-on-micro” or “NOM”. Upon radiation with UV light, strong light scattering is observed. Since QDs also provide fluorescent emission, we are able to use increased light scattering for detecting antigen-antibody reactions, and decreased QD emission to identify which antibody is present.

Multivalent interactions are common in nature, such as influenza virus infecting epithelial cells, clearance of pathogens by antibody-mediated attachment to macrophages, etc. To mimic nature, we utilized a bottom-up approach to develop various multivalent self-assembling systems based on leucine-zipper peptides. We tethered several pairs of leucine-zipper peptides to PAMAM dendrimers to form leucine-zipper dendrimers (LZDs). We conjugated Fos/Jun to the dendrimer to make D0Fos4 and D0Jun4, and studied the interactions between these LZDs and their cognate peptide target, either Jun or Fos. Our experiments showed that the D0Fos4 can non-covalently assemble four copies of Jun, and this approach can be further used for the rapid non-covalently assembling of multimeric ligands. We also pursued the multivalent target of GPCRs with a Fos/Jun assembly, and found the complex can potentially be used as a molecular switch to target GPCRs with controlled ligand activity. In a related project for bio-material design based on self-assembly of LZDs, we synthesized a different pair of LZDs, D-Ez4 and D-Kz4, and established that they can assemble at neutral pH to form helical fibrils which display higher order self-organized structures, providing a new methodology for bio-material design. In another effort for studying multivalent interactions, we conjugated three copies of the F23, mini-protein that binds the HIV-1 capsid protein, to a trimesic acid and obtained a trivalent inhibitor, Tri-F23. Tri-F23 showed enhanced binding in ELISA against gp120, but was not significantly more effective preventing HIV entry. This methodology provides a new strategy for developing multivalent inhibitors for preventing HIV-1 infection at the entry level. In a related area, we are developing imaging agents based on quantum dots that can detect GPCRs on whole cells and at the single molecule level. To this end, a new method was developed for biocompatible amphphilic polymers to coat quantum dots. This amphiphilic polymer facilitates rapid quantum dot conjugation to any ligand with a free thiol or engineered cysteine. Several GPCR targeted peptides have been utilized for imaging receptors on whole cells and as single molecules. These efforts will guide the rational design of multivalent ligands for targeting GPCRs and other cell surface proteins.

Due to their extraordinary electronic properties, Quantum Dots (QDs) are potentially very useful nanoscale devices and research tools. As their electrons are confined in all three dimensions, the energy spectra of QDs is descrete, similar to atoms and molecules. Because the gaps between these energy levels is inversely related to the size of the QD, very small QDs are desirable. Carbon nanotubes have long been touted as fundamental units of nanotechnology, due to their structural, optical and electronic properties, many of which are a result of the confinement of electrons in the trans-axial plane of the nanotube. It is known that their band gap structure is altered under deformation of their cross section. It is proposed that one way to fabricate a very small quantum dot is by confining electrons in the nanotube so that they may not freely move along its length. A structure to produce this confinement has been described elsewhere, namely the carbon nanotube cross, consisting of two carbon nanotubes, with the the one draped over the other at ninety degrees. It is thought that this structure will induce local physical deformations in the nanotube, resulting in local changes in electronic structure of the top nanotube at the junction of the cross. These band gap shifts may cause metal-semiconductor transitions, resulting in tunnel barriers that axially the confine electrons in the nanotube. This thesis investigates the possibility that the carbon nanotube cross may exhibit QD behavior at the junction of the cross, due to these local band gap shifts. A device for carbon nanotube growth, using Chemical Vapor Deposition, has been designed, and may be built using microfabrication techniques. This device consists of electrodes (for electrical measurements of the nanotubes) and catalyst regions (to initiate nanotube growth), lithographically patterned in a configuration that promotes carbon nanotube formation. Unfortunately, due to fabrication issues, this effort is a work in progress, and these devices have not yet been constructed. However, an experimental methodolgy has been developed, which provides a framework for eventually building a carbon nanotube cross, and investigating the possibility of QD behavior at the junction of the cross. This structure has also been investigated computationally. Molecular dynamics simulations were used to obtain equilibrium geometries of the carbon nanotube cross, and it was found that their are many different meta stable states, corresponding to different types of nanotube, and different physical arrangements of these nanotubes. The electronic structure of the carbon nanotube cross was calculated using the density functional theory. Band gap energies similar to experimental values were obtained. A one-to-one spatial correlation between deformation and band gap and conduction band shifts were observed in the top carbon nanotube of the nanotube cross. Small tunnel barriers, inferred from both the calculated band gap and LUMO energies, are observed, and could well be sufficient to confine electrons along the axis of the nanotube. The results described in this thesis, while not definitive, certainly indicate that a QD probably would form at the junction of a carbon nanotube cross, and that further investigation, both experimental and computational, is warranted.

Imaging tools in cellular and molecular biology have long relied on organic fluorophores to observe microorganisms or various cell constituents. The advent of semiconductor nanoparticles known as quantum dots (QDs) has offered the possibility to use this new class of fluorescent probes with very advantageous optical properties in cell biology. The imaging of transmembrane potential and ionic currents is of significant importance for monitoring the activity of the cell. It remains possible with relatively complicated instruments and methods such as patch clamping. A complementary approach to view the dynamics of ion channels with modern and efficient fluorophores is therefore of great interest to the field of biology in general. / We developed a construct based on the FRET signal between QDs and organic fluorescent dyes to monitor the conformational changes of voltage gated sodium channels. The amino acid histidine was used as a "landing platform" for QDs and the bacterial sodium channel NaChBac was chosen for testing. This study focused on the preliminary steps of the project and aimed to characterize the electrophysiological behavior of the histidine-tagged channel. The whole-cell configuration of patch clamping was the tool we used to understand the differences between the wild-type and the histidine-tagged variants of the channels. We also explore the possibility to land QDs on the histidine tag.

Fluorescence molecular imaging has been triggering interest in the scientific community for the last decade due to its great potential for improved early cancer detection and image-guided treatment. Semiconductor nanoparticles, also known as quantum dots, have been identified as potential contrast agents for molecular imaging, but there is a lack of quantitative contrast optimization studies that would enable precise and robust dosimetry calculations. These calculations are crucial to determine the feasibility, risk and cost of any contrast-enhanced clinical imaging procedure. This thesis presents a first attempt at developing a quantitative dosimetry framework for quantum dot-based contrast-enhanced fluorescence molecular imaging, by combining novel experimental methods and validated mathematical models. Three studies were completed to develop the dosimetry framework. In the first study, we design a novel homogenized optical tissue phantom approach to investigate with precision the effects of various photophysical parameters, such as the excitation and emission wavelengths, tissue absorption and scattering coefficient spectra, tissue autofluorescence spectra, target fluorescence spectra and target depth, on the detected contrast. In the second study, we use the approach to investigate the influence of tissue optical absorption and scattering on contrast behavior for various ex vivo tissue samples, and develop performance metrics to quantify the optimization results. In the third study, we perform vascular fluorescence contrast-enhanced imaging in the dorsal skinfold window chamber mouse model to investigate the effects of pharmacokinetics, blood absorption, vessel diameter and injected dose on the detected contrast. We also describe the relationship between the injected volume and vascular contrast, and transfer the performance metrics developed previously to estimate the minimum injection dose under various conditions. These studies are expected to serve as a stepping stone to further develop contrast optimization and dosimetry models for the emerging field of fluorescence molecular imaging.

Fluorescence molecular imaging has been triggering interest in the scientific community for the last decade due to its great potential for improved early cancer detection and image-guided treatment. Semiconductor nanoparticles, also known as quantum dots, have been identified as potential contrast agents for molecular imaging, but there is a lack of quantitative contrast optimization studies that would enable precise and robust dosimetry calculations. These calculations are crucial to determine the feasibility, risk and cost of any contrast-enhanced clinical imaging procedure. This thesis presents a first attempt at developing a quantitative dosimetry framework for quantum dot-based contrast-enhanced fluorescence molecular imaging, by combining novel experimental methods and validated mathematical models. Three studies were completed to develop the dosimetry framework. In the first study, we design a novel homogenized optical tissue phantom approach to investigate with precision the effects of various photophysical parameters, such as the excitation and emission wavelengths, tissue absorption and scattering coefficient spectra, tissue autofluorescence spectra, target fluorescence spectra and target depth, on the detected contrast. In the second study, we use the approach to investigate the influence of tissue optical absorption and scattering on contrast behavior for various ex vivo tissue samples, and develop performance metrics to quantify the optimization results. In the third study, we perform vascular fluorescence contrast-enhanced imaging in the dorsal skinfold window chamber mouse model to investigate the effects of pharmacokinetics, blood absorption, vessel diameter and injected dose on the detected contrast. We also describe the relationship between the injected volume and vascular contrast, and transfer the performance metrics developed previously to estimate the minimum injection dose under various conditions. These studies are expected to serve as a stepping stone to further develop contrast optimization and dosimetry models for the emerging field of fluorescence molecular imaging.