Semiconductor quantum dots tightly confine excited electron-hole pairs, called excitons, resulting in discrete energy levels similar to those of single atoms. Transition energies in the visible or near-infrared make quantum dots suitable for many applications in quantum optics and quantum information science, but to take advantage of all the properties of quantum dot emission, it is necessary to excite them coherently which has been a great challenge due to background scattering of the excitation laser. This dissertation presents the first coherent control of a single quantum dot with observation of its resonance fluorescence and decoherence phenomena. Strong continuous-wave excitation causes the dot to undergo several Rabi oscillations before emitting. These are visible as oscillations in the first- and second-order correlation functions of the emission, and the quantum dot states are "dressed", resulting in a Mollow triplet in the emission spectrum. Some resonantly excited dots, in addition to resonance fluorescence, also emit light from excited states several meV higher in energy. Such up-conversion fits existing theories of decoherence but has never been directly observed before. The up-conversion intensity is shown to be described well by a fairly simple three-level model with single-phonon absorption. The coherent phenomena of resonance fluorescence and the decoherence due to up-conversion paint a dual picture of single quantum dots wherein they can sometimes be treated as an ideal two-level system, but their interactions with the host crystal can lead to many complex behaviors. / text

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Modern communications technology has encouraged an intimate connection between Semiconductor Physics and Optics, and this connection shows best in the combination of electron-confining structures with light-confining structures. Semiconductor quantum dots are systems engineered to trap electrons in a mesoscopic scale (the are composed of [approximately] 10000 atoms), resulting in a behavior resembling that of atoms, but much richer. Optical microrseonators are engineered to confine light, increasing its intensity and enabling a much stronger interaction with matter. Their combination opens a myriad of new directions, both in fundamental Physics and in possible applications. This dissertation explores both semiconductor quantum dots and microresonators, through experimental work done with semiconductor quantum dots and microsphere resonators spanning the fields of Quantum Optics, Quantum Information and Photonics; from quantum algorithms to polarization converters. Quantum Optics leads the way, allowing us to understand how to manipulate and measure quantum dots with light and to elucidate the interactions between them and microresonators. In the Quantum Information area, we present a detailed study of the feasibility of excitons in quantum dots to perform quantum computations, including an experimental demonstration of the single-qubit Deutsch-Jozsa algorithm performed in a single semiconductor quantum dot. Our studies in Photonics involve applications of microsphere resonators, which we have learned to fabricate and characterize. We present an elaborate description of the experimental techniques needed to study microspheres, including studies and proof of concept experiments on both ultra-sensitive microsphere sensors and whispering gallery mode polarization converters. / text

Nano-structures, such as photonic crystal cavities and metallic antennas, allow one to focus and store optical energy into very small volumes, greatly increasing light-matter interactions. These structures produce resonances which are typically characterized by how well they confine energy both temporally (quality factor–Q) and spatially (mode volume–V). In order to observe non-linear effects, modified spontaneous emission (e.g. Purcell enhancement), or quantum effects (e.g. vacuum Rabi splitting), one needs to maximize the ratio of Q/V while also maximizing the coupling between the resonance and the active medium. In this dissertation I will discuss several projects related by the goal of controlling light-matter interactions using such nano-structures. In the first portion of this dissertation I will discuss the deterministic placement of self-assembled InAs quantum dots, which would allow one to precisely position an optically-active material, for maximum interaction, inside of a photonic crystal cavity. Additionally, I will discuss the use of atomic layer deposition to tune and improve both the resonance wavelength and quality factor of silicon based photonic crystal cavities. Moving from dielectric materials to metals allows one to achieve mode-volumes well below the diffraction limit. The quality factor of these resonators is severely limited by Ohmic loss in the metal; however, the small mode-volume still allows for greatly enhanced light-matter interaction. In the second portion of this dissertation I will investigate the coupling between an array of metallic resonators (antennas) and a nearby semiconductor quantum well. Using time-resolved pump-probe measurements I study the properties of the coupled system and compare the results to a model which allows one to quantitatively compare various antenna geometries.

Advances in optical imaging have provided methods for visualizing molecular expression in tumors in vivo, allowing the opportunity to study the complexity of the tumor microenvironment. The development of fluorescent contrast agents targeted to molecules expressed in cancer cells is critical for in vivo imaging of the tumors. Contrast agents emitting in the near infrared (NIR) allow for an increased depth of penetration in tissue due to decreased absorption and scattering. There is also significantly less autofluorescence from tissue in the NIR. Quantum dots are nanoscopic particles of semiconductors whose fluorescent emission wavelength is tunable by the size of the particle with desirable fluorescent qualities such as a wide range of excitation wavelengths, a narrow emission band, high quantum efficiency, high photostablility, and they can be produced to emit throughout the NIR imaging window. It has been shown that vascular endothelial growth factor receptor 2 (VEGFR2) is upregulated in many cancers, including colorectal, as it is important in tumor angiogenesis and is considered a predictor for clinical outcome and, in some instances, is used for targeted therapy with anti-angiogenic drugs. For these reasons, quantum dots bioconjugated to VEGFR2 antibodies have the potential to provide contrast between normal tissue and cancer, as well as a mechanism for evaluating the molecular changes associated with cancer in vivo. In this dissertation, we present on the design of two contrast agents using quantum dots targeted to VEGFR2 for use in the molecular imaging of colon cancer, both ex vivo and in vivo. First, as a preliminary ex vivo investigation into their efficacy, Qdot655® (655nm emission) were bioconjugated to anti-VEGFR2 antibodies through streptavidin/biotin linking. The resulting QD655-VEGFR2 contrast agent was used to label colon adenoma in vivo and imaged ex vivo with significant increase in contrast between diseased and undiseased tissue, allowing for fluorescence based visualization of the VEGFR2 expressing diseased areas of the colon with high sensitivity and specificity. Then, QD655-VEGFR2 was used in a longitudinal in vivo study to investigate ability to correlate fluorescence signal to tumor development over time using optical coherence tomography and laser induced fluorescence spectroscopy (OCT/LIF) dual-modality imaging. The contrast agent was able to target VGEFR2 expressing diseased areas of colon; however, challenges in fully flushing the unbound contrast agent from the colon before imaging arise when moving from ex vivo imaging to in vivo image. Lastly, lead sulfide (PbS) quantum dots were made by colloidal synthesis to emit at a 940 nm (QD940) and conjugated to anti-VEGFR2 primary antibodies through streptavidin/biotin linking. The resulting QD940-VEGFR2 contrast agent was then used to label cells in vitro. The QD940-VEGFR2 molecules were able to positively label VEGFR2 expressing cells and did not label VEGFR2 negative cells. Very low photoluminescence and large amounts of aggregation after conjugation of the quantum dot to streptavidin was detected. Improvements to the quantum dot stability through synthesis, capping and conjugation techniques must be made for this contrast agent to be effective as a contrast agent for cancer imaging.

Quantum-scale semiconductors embedded in an electrically-active matrix have the potential to improve photovoltaic (PV) device power conversion efficiencies by allowing the solar spectral absorption and photocarrier transport properties to be tuned through the control of short and long range structure. In the present work, the effects of phase assembly on quantum confinement effects and carrier transport were investigated in CdTe - ZnO nanocomposite thin films for use as a spectrally sensitized n-type heterojunction element. The nanocomposites were deposited via a dual-source, sequential radio-frequency (RF) sputter technique that offers the unique opportunity for in-situ control of the CdTe phase spatial distribution within the ZnO matrix. The manipulation of the spatial distribution of the CdTe nanophase allowed for variation in the electromagnetic coupling interactions between semiconductor domains and accompanying changes in the effective carrier confinement volume and associated spectral absorption properties. Deposition conditions favoring CdTe connectivity had a red shift in absorption energy onset in comparison to phase assemblies with a more isolated CdTe phase. While manipulating the absorption properties is of significant interest, the electronic behavior of the nanocomposite must also be considered. The continuity of both the matrix and the CdTe influenced the mobility pathways for carriers generated within their respective phases. Photoconductivity of the nanocomposite, dependent upon the combined influences of nanostructure-mediated optical absorption and carrier transport path, increased with an increased semiconductor nanoparticle number density along the applied field direction. Mobility of the carriers in the nanocomposite was further mediated by the interface between the ZnO and CdTe nanophases which acts as a source of carrier scattering centers. These effects were influenced by low temperature annealing of the nanocomposite which served to increase the crystallinity of the phases without modification of the as-deposited phase assembly and associated absorption properties. Integration of the nanocomposite as an n-type heterojunction element into a PV device demonstrated the ability to tune device response based on the spectral absorption of the nanocomposite sensitizer film as dictated by the phase assembly. Overall the various phase assemblies studied provided increased opportunity for optimization of the absorption and carrier transport properties of the nanocomposite thin films.

Κατά τη διάρκεια των τελευταίων ετών, το ενδιαφέρον πολλών επιστημόνων έχει στραφεί στη μελέτη της δυναμικής ηλεκτρονίων τα οποία είναι τοποθετημένα σε συζεύξεις κβαντικών τελειών. Στις μέρες μας, τέτοιου είδους κβαντικά συστήματα, όπου έχουν παγιδευτεί ηλεκτρόνια, μελετώνται με εντατικό ρυθμό. Ειδικότερα, στο πρώτο μέρος της εργασίας, μελετάμε τη δυναμική δύο αλληλεπι- δρώντων ηλεκτρονίων, τα οποία είναι παγιδευμένα σε μία δομή ζεύγους κβαντικών τελειών, κάτω από την επίδραση διχρωματικών ηλεκτρικών πεδίων. Η θεωρητική ανάλυση βασίζεται στην προσέγγιση του συστήματος δύο ενεργειακών επιπέδων και καταλήγουμε στις αναλυτικές συνθήκες εντοπισμού των δύο ηλεκτρονίων στην ίδια κβαντική τελεία. Τα αναλυτικά αποτελέσματα συγκρίνονται με τα αριθμητικά, τα οποία προκύπτουν από την επίλυση της χρονοεξαρτώμενης εξίσωσης Schrödinger. Στο δεύτερο μέρος της εργασίας αυτής, μελετάμε τον βέλτιστο έλεγχο για δυναμικό διπλής συμμετρικής κβαντικής τελείας, όπου έχει παγιδευτεί ένα ηλεκτρόνιο, κατά τη διάρκεια του οποίου το σύστημα αλληλεπιδρά με έναν παλμό ηλεκτρομαγνητικού πεδίου. Αρχικά χρησιμοποιούμε τις προσεγγίσεις του περιστρεφόμενου κύματος και του ακριβούς συντονισμού και προσεγγίζουμε το σύστημα με ένα σύστημα τριών ενεργειακών καταστάσεων. Στη συνέχεια, περιγράφουμε το σύστημα μέσω διαφορι- κών εξισώσεων, οι οποίες πρέπει να ικανοποιούνται από το βέλτιστο ηλεκτρομαγνη- τικό πεδίο. Τέλος, καταλήγουμε σε αναλυτικές εκφράσεις για το σχήμα του παλμού βέλτιστου ελέγχου, ο οποίος οδηγεί σε χρονικά μέση, αλλά και ολική μεγιστοποίηση του πληθυσμού μιας ενεργειακής στάθμης που έχουμε επιλέξει. / During the last years, the study of dynamics of electrons trapped by systems of quantum dots has attracted the interest of many scientists. Nowadays, such quantum systems, where electrons have been trapped, are being studied intensively. More specifically, in the first part of this thesis, we investigate the dynamics of two interacting electrons confined in a symmetric double quantum dot structure, under the influence of bichromatic electric fields. The theoretical analysis is based on an effective two-level system approach and the conditions for two-electron localization in the same quantum dot are analytically derived. The analytical results are compared to numerical results obtained from the solution of the time-dependent Schrödinger equation. In the second part of this thesis, we study the potential for optimal control of a symmetric double quantum dot structure, where a single electron has been trapped, interacting with a single pulsed electromagnetic field. We first use the rotating wave and resonant approximations and reduce the dynamics of the system to that of a degenerate three-level-type system. We also formulate the optimal control problem in terms of differential equations that have to be fulfilled by the optimal electromagnetic fields. We then obtain general analytical expressions for the optimal pulse shapes that lead to global maximization of the final population of the target state and of the timeaveraged population of the target state in the quantum dot structure.

Colloidal semiconductor nanoparticles (NPs) contain hundreds to thousands of atoms in a roughly spherical shape with diameters in the range of 1-10 nm. The extremely small particle size confines electron transitions and creates size tunable bandgaps, giving rise to the name quantum dots (QDs). The unique optoelectronic properties of QDs enable a broad range of applications in optical and biological sensors, solar cells, and light emitting diodes. The most common compound semiconductor combination is chalcogenide II-VI materials, such as ZnSe, CdSe, and CdTe. But III-V and group IV as well as more complicated ternary materials have been demonstrated. Coordinating organic ligands are used to cap the NP surface during the synthesis, as a mean of protecting, confining, and separating individual particles. This study investigated the impact of the ligand on particle growth and self-assembly into hierarchical structures. ZnSe QDs were synthesized using an aqueous route with four different thiol ligands, including 3-mercaptopropionic acid (MPA), thioglycolic acid (TGA), methyl thioglycolate (MTG), and thiolactic acid (TLA). The particle growth was monitored as a function of reaction time by converting the band gaps measured using UV-vis spectroscopy into particle sizes. A kinetic model based on a diffusion-reaction mechanism was developed to simulate the growth process. The growth data were fit to this model, yielding the binding strength in the order TLA < MTG ≈ TGA < MPA. This result showed the relationship between the QD growth rates and the chemical structures of the ligands. Ligands containing electron-withdrawing groups closer to the anchoring S atom and branching promoted growth, whereas longer, possibly bidendate, ligands retarded it. Removing TGA ligands from the surface of CdTe QDs in a controlled manner yielded new superstructures that were composed of either intact or fused particles. Purifying as-synthesized QDs by precipitating them using an anti-solvent removed most of the free ligand in solution. Aging this purified QD suspension for a week caused self-assembly of QDs into nanoribbons. The long time needed for self-assembly was due to the slow equilibrium between the ligands on QD surface and in solution. Accelerating the approach to equilibrium by diluting purifed CdTe QDs with organic solvents triggered rapid self-assembly of superstructures within a day, forming various nanostructures from nanoribbons to nanoflowers. The type of nanostructures that formed was determined by the solvation of TGA in the trigger solvent. Extracting the smallest portion of TGA in methanol promoted vectorial growth into ribbons consistent with dipole-dipole attractive and charge-charge repulsive interactions. Removing more of the TGA layer in IPA caused the dots to fuse into webs containing clustered ribbons and branches, and the directional nature of the superstructure was lost. Completely deprotecting the surface in acetone promoted photochemical etching and dissolved the QDs, yielding ower-like structures composed of CdS. Nanocrystal (NC) growth mediated by a ligand was also studied in the organic synthesis of FeS₂ nanocubes. Oleylamine was used not only as the ligand but also the solvent and reductant during the reaction. A one hour reaction between iron (II) chloride and elemental sulfur in oleylamine at 200 ℃ and a S to Fe ratio of 6 yielded phase pure pyrite cubes with dimensions of 87.9±14.1 nm. X-ray diffraction (XRD) spectra and Raman peaks for pyrite at 340, 375, and 426 cm⁻¹ confirmed phase purity. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results showed that the oleylamine remained on the FeS₂ surface as a ligand. The reaction mechanism includes the production of pyrrhotite Fe₁₋ᵪS (0≤x<0.5) via reduction of S⁰ to S²⁻ by oleylamine and the oxidation of pyrrhotite to pyrite with remaining S⁰.

Glaucoma is a leading cause of world blindness, often associated with elevated eye pressure. Current glaucoma treatments aim to lower eye pressure by improving aqueous humor outflow from the eye. Ocular lymphatics have been demonstrated to contribute to aqueous humor outflow in human and sheep. It is not known whether any glaucoma drugs target this lymphatic drainage. The mouse is a valuable model with similar aqueous humor dynamics and pharmacology as human. Using in vivo hyperspectral fluorescence imaging combined with intracameral quantum dot injection, we identified an ocular lymphatic drainage in mouse. Immunofluorescence and confocal microscopy revealed lymphatic channels in the ciliary body, sclera, and orbit that may be responsible for this lymphatic drainage. We showed that latanoprost, a prostaglandin F2&alpha; analog widely used to treat glaucoma, increases this ocular lymphatic drainage. Our findings provide the framework for future development of novel glaucoma drugs that stimulate the ocular lymphatic drainage.