Diese Dissertation besteht aus zwei Teilen von Studien. Der erste Teil demonstriert die Steuerung der Elektron-Kern-Spin-Systems in II-VI Halbleiter Quantum Dots (QDs) durch elektrische Ströme über Mikrospulen. Mikrometer-große Leiterschleifen sind auf der Oberseite von Heterostrukturen mit geladenen CdSe/ZnS QDs hergestellt worden. Eine Strominjektion erzeugt magnetische Felder im Bereich von einige 10 mT, welche stark genug sind, um die Hyperfeinwechselwirkung in CdSe QDs modulieren zu können. Der Durchmesser des Spulen im Mikrometer-Bereich ermöglicht die Generation von schnellen Feld transienten im Bereich von wenigen ns. Mit diesen Vorteilen der Mikrospulen werden die Steuerungs des Spins der residenten Elektronen sowie das Auslesen des Kernspinzustandes durch elektrische Impulse nachgewiesen. Der zweite Teil befasst sich mit der Ladungsträger-Spindynamik in ZnO Quantum Well (QW) Strukturen und Epitaxieschichten, die mittels des optischen Übergang von negativ geladenen Exzitonen X− beziehungsweise des am neutralen Donator gebunden Exziton D0X untersucht werden. Der Loch-Spin kann direkt über die zirkular polarisierten Photolumineszenz der beiden Komplexe zurückverfolgt werde. Die Spin-Relaxationszeit von QW und Epiplyer verfolgt werden. Der Spin des Donatorelektronens wird über die Ausbleichung des Spin-selektive Anregungprozesses nachgewiesen. Es werden longitudinale Loch-Spinrelaxationszeiten von 80 bis 140 ps für D0X und X− gefunden. Deutlich längere longitudinalen Elektronen-Spin-Relaxationszeiten in Bereich von mehreren 100 ns werden gefunden, wenn die Hyperfeinwechselwirkung durch ein geeignetes externes Magnetfeld unterdrückt wird. Eine Feldstärke von 2 mT ist groß genug. Dies zeigt den extrem kleinen Wert des Overhauser-Feldes in ZnO auf, der durch die sehr begrenzte Anzahl von magnetischen Kernen in Wechselwirkung mit dem Elektronen innerhalb des Volumens des Donators verursacht wird. / This work is composed of two parts of studies. The first part represents an electron-nuclear spin control in II-VI semiconductor quantum dots (QDs) by electrical currents via micro coils. Micrometer single turn coils are fabricated on top of heterostructures with charged CdSe/ZnSe QDs. Current injection creates magnetic fields in the range of some 10 mT which is strong enough to modulate the hyperfine interaction in CdSe. The micrometer-range diameter of coil allows for generation of fast field transient in the range of few ns. Using these advantages of micro coils, local control of the resident electron spin as well as read out of the nuclear spin state are demonstrated by electrical pulses. The second part presents charged carrier spin dynamics in ZnO quantum wells and epilayers using the optical transition of the negatively charged exciton X− and the neutral donor bound exciton D0X, respectively. The hole spin can be directly traced by the circular polarized photoluminescence of both complexes. The spin relaxation of the resident electrons and donor electrons is accessed via the bleaching of the spin selective excitation process. Longitudinal hole spin relaxation times of 80 and 140 ps are found for D0X and X−, respectively. Much longer longitudinal electron spin relaxation times in the several 100 ns range are uncovered if the hyperfine interaction is suppressed by a proper external magnetic field. A field strength of 2 mT is large enough proving that the extremely small value of the Overhauser field in ZnO caused by the very restricted number of magnetic nuclei interacting with the electron inside the donor volume.

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Unconventional nanofabrication techniques; both those which have been newly developed and those under development, had brought inexpensive, facile, yet high quality means to fabricate nanostructures that have feature sizes of less than 100 nm in industry and academia. This dissertation focuses on developing unconventional fabrication techniques, building studying platforms, and studying the mechanisms behind them. The studies are divided into two main facets and four chapters. The first facet, in Chapter II and Chapter III, deals with the research and development of different nanofabrication techniques and nanostructures. These techniques include litho-synthesis, colloidal lithography, and photolithography. The nanostructures that were fabricated by these techniques include the metal nanoparticle arrays, and the self-assembled CdSe nanoring arrays. At the same time, the dissertation provides mechanisms and models to describe the physical and chemical nature of these techniques. The second area of this study, in Chapter III to Chapter V, presents the applications of these nanostructures in fundamental studies, i.e. the mechanisms of plasmon enhanced fluorescence and photo-oxidation kinetics of CdSe quantum dots, and applications such as molecular sensing and material fabrication. More specifically, these applications include tuning the optical properties of CdSe quantum dots, biomodification of CdSe quantum dots, and copper ion detection using plasmon and photo enhanced CdSe quantum dots. We have successfully accomplished our research goals in this dissertation. Firstly, we were able to tune the emission wavelength of quantum dots, blue-shifted for up to 45 nm, and their surface functionalization with photo-oxidation. A kinetic model to calculate the photo-oxidation rates was established. Secondly, we established a simple mathematical model to explain the mechanism of plasmon enhanced fluoresce of quantum dots. Our calculation and experimental data support the fluorescence resonance energy transfer (FRET) mechanism between quantum dots and the metal nanoparticles. Thirdly, we successfully pattered the CdSe quantum dots (diameter ~4 nm) into nanorings with tunable diameters and annular sizes on different substrates. We also established a physical model to quantitatively explain the mechanism with the forces that involved in the formation of the nanorings.

This thesis summarizes the methods of preparation and optical properties of hybrid assemblies of Au NPs and cadmium selenide (CdSe) QDs. First chap-ter deals with the literature survey and theoretical aspects of plasmonics and discussions on optical excitations of metal (plasmons) and semiconducting QDs (excitons). Variation of energy levels of CdSe QDs and its optical properties i e. absorption and emission properties under strong confinement regime have been discussed with respect to effective mass approximation (EMA) model. This is followed by the discussion on optical properties of Au NPs and rods, describing absorption properties, based on Mie theory. Size and shape depen-dent variation of absorption properties. Theoretical discussions of collective effects in QDs assemblies and plasmonic interactions with the QDs assemblies i.e. plasmonic Dicke effect and metal nanoantenna interaction with CdSe QDs arrays is provided. In the second chapter a discussion on experimental techniques used for the study is provided. It starts with a discussion on the synthesis methods for CdSe QDs and Au NPs/rods with different capping ligands. Different techniques of preparation of CdSe QDs assemblies and their hybrid with metallic nanoparti-cles has been discussed. Further discussion on optical microscopy techniques, confocal, near field scanning microscopy (NSOM), Brewster angle microscopy and electron microscopy techniques i. e transmission electron microscopy and scanning electron microscopy and thermogravimetry analysis of the samples is provided. In the third chapter the details of the different self-assembly methods of preparation of hybrid assemblies of CdSe QDs and Au NPs /rods are given. The different strategies are used for different type of hybrids. In first method of Langmuir-Blodgett (LB) , effect of different capping agents, core size, and number ratios of Au NPs/rods to CdSe QDs, effect of anisotropy of Au NPs on the LB films of CdSe QDs assemblies is discussed. In another method of dip coating several control parameters like dip time, concentration of the solution and dip speed of transferring an aligned GNRs is given. Finally a combination of LB and dip coating methods is described for transferring aligned GNRs over a compact layer of CdSe QDs. At the end, a section is devoted to hit and trials of self-assemblies of hybrid of GNRs and CdSe QDs using LB method, the failures of which resulted in devising a method which uses a combination of LB and dip coating. In fourth chapter effects of plasmons on the collective emission of CdSe QDs assemblies are investigated. A plasmonic tuning of photoluminescence from semiconducting QD assemblies using Au NP in different ratio and different packing density has been discussed. We have described how the emission from a closed pack assemblies, prepared with different packing densities depends on the packing density and extent of spectral overlap between QD photolumi-nescence and the metal nanoparticle absorbance. We have provided possible evidence for plasmon mediated coherent emission enhancement from some of these assemblies from the case of strong spectral overlap between CdSe QDs and Au nanoparticle. In fifth chapter, we have demonstrated non local far field enhancement of PL in QDs assemblies induced by isolated and partially aligned GNRs nano-antenna located on such assemblies. It is shown that the emission is also anisotropic with the maxima being near such GNRs assembly which decays to finite, nonzero and significantly large values even away from the vicinity of any such assemblies. For this novel effect it is shown to have a clear spec-tral dependence. It is shown to be maximum when the longitudinal surface plasmon resonance absorption maxima is resonant with the CdSe QD photolu-minescence maxima and the excitation wavelength and is always non-existent for the off resonant case. We have also shown that finite difference time do-main simulations could model some of the observed near field effects but the far field effects could not be modelled in such simulations.

Parce qu'ils présentent des propriétés remarquables par rapport à leurs équivalents massifs, les nanomatériaux occupent une place de plus en plus importante dans l'industrie et en médecine. Leur essor rapide a généré de nombreuses craintes dans l'opinion publique notamment au regard de certaines méconnaissances liées à leur toxicité. Notre projet vise l'utilisation du séléniure de cadmium (CdSe) comme matériau modèle afin d'établir une corrélation entre la structure chimique des nanoparticules, leur réactivité de surface, leur (photo)stabilité et leur toxicité. Des quantum dots (QDs) CdSe et alliages CdSe(S) ont été préparés en milieu aqueux à 100°C ou par voie hydrothermale de manière à ne différer que par leur structure chimique de coeur (alliage ternaire vs semi-conducteur binaire) alors que d'autres paramètres comme la taille, la charge ou la nature du ligand de surface, ont été maintenus constants. Des études de cytotoxicité menées sur Escherichia coli ont montré que la libération de Cd2+ jouait un rôle important dans la toxicité pour les deux QDs. Nos résultats ont également mis en évidence que les QDs CdSe(S) alliés étaient plus stables et moins toxiques que les QDs CdSe. Sans négliger l'importance de la libération d'ion Cd2+ par les nanoparticules, une corrélation entre la stabilité et la production d'espèces réactives de l?oxygène (EROs) a montré que la toxicité était en partie dépendante de la photostabilité des QDs. Notre étude met en perspective une relation entre la réactivité, la stabilité du coeur des nanoparticules, et la toxicité photo-induite / Due to their unique properties compared to their bulk counterparts, nanomaterials have gained considerable attention, especially in industry and medicine. Their fast development has generated many public concerns, especially because of a lack of knowledge regarding their toxicity. Our project aims to use cadmium selenide (CdSe) as a model material in order to initiate a research aiming at establishing a correlation between the nanoparticles chemical structure, their surface reactivity, their stability and their toxicity. CdSe and alloyed CdSe(S) quantum dots (QDs) were prepared in aqueous phase either at 100°C or under hydrothermal conditions in order to differ solely by their core chemical structure (ternary alloy vs binary semiconductor), while other parameters such as the size, the surface charge or the surface ligand, have been kept constant. Cytotoxicity studies carried out on Escherichia coli have shown that release of Cd2+ played a key role in the toxicity for both QDs. However, alloyed CdSe(S) QDs were also found more stable and less toxic than CdSe nanocrystals. Without disregarding the importance of Cd2+ ions release by the nanoparticles, a correlation between the stability and the production of reactive oxygen species (ROS) showed that toxicity was dependent on QDs photostability. Our study highlights a relationship between the core reactivity, stability and the photo-induced toxicity QD nanoparticles

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