Various colloidal delivery systems, including polymeric nanoparticles, metal colloids, liposomes, and microemulsions have been reported to enhance the delivery of therapeutic agents following intranasal administration. However, the mechanisms involved in the uptake of these nanomaterials, especially those in the ultrafine size ranges (diameter < 20 nm) through nasal mucosa and their subsequent biodistribution in the body are not well characterized. The objectives of this study address the knowledge gap regarding ultrafine nanoparticle transfer in the nasal mucosa by quantifying nanoparticle uptake and biodistibution patterns in the presence and absence of known inhibitors of endocytic processes. The uptake of ~ 10 nm fluorescent quantum dots (QDs) was investigated by measuring the concentration of QDs following exposure to bovine respiratory and olfactory mucosal explants. An inductively coupled optical emission spectroscopy method was developed to measure the amount of QDs within the tissues. The results demonstrated that carboxylate-modified QDs (COOH-QDs) show ~2.5 fold greater accumulation in the epithelial and submucosal regions of the olfactory tissues compared to the respiratory tissues. Endocytic inhibitory studies showed that in respiratory tissues clathrin-dependent, macropinocytosis and caveolae-dependent endocytosis process were all involved in the uptake of COOH-QDs. Whereas in olfactory tissues, clathrin-dependent endocytosis was the major endocytic pathway involved in uptake of COOH-QDs. Additional energy-independent pathways appeared to also be active in the transfer of COOH-QDs into the olfactory mucosa. Interestingly, PEGylated quantum dots (PEG-QDs) of similar size ~15 nm were not internalized into the bovine nasal tissues. In vivo fluorescence imaging was used to study the biodistribution of quantum dots following nasal instillation in mice. These studies showed that majority of COOH-QDs remain in the nasal tissues for relatively long periods of time (up to 24 h) whereas PEG-QDs showed no such accumulation. Biodistribution studies of gold nanoparticles (~15 nm) in mice using micro-CT showed that gold nanoparticles were transferred to the posterior turbinate region and a fraction of the administered dose distributed to regions in close proximity to the olfactory bulb. Both NIR imaging and micro-CT imaging were useful tools for visualization of in vivo nanoparticle distribution. A diazepam-containing microemulsion (dispersed phase ~40 nm) was formulated to investigate the uptake mechanisms utilized for fluid-phase colloidal dispersions in the nasal mucosa. The resulting diazepam-containing microemulsion showed enhanced transfer of the drug into the bovine nasal respiratory and olfactory tissues. It is unclear if endocytosis of the fluid-phase nanodispersions played a role in drug absorption from the microemulsions in a manner similar to the uptake of solid-phase nanoparticles, however, since there was significant loss of the epithelial cell layer following exposure to the microemulsion formulation which likely altered the barrier properties of the epithelium. These studies have increased the fundamental understanding of ultrafine nanoparticle uptake in the nasal tissues and the resulting nanoparticle biodistribution patterns. While ultrafine nanoparticles may have limited application in the development of efficient drug delivery systems, an understanding of the size-dependent and tissue-dependent processes responsible for the uptake of particulates into mucosal tissues will contribute to the rational development of nanoparticulate drug delivery strategies investigating the nasal and other routes of administration.

The focus of this dissertation is on the interactions of compounds containing group 12 and 16 elements. This work is presented in three major parts. First, the interaction of the synthetic dithiol N,N’-bis(2-mercaptoethyl)isophthalamide), abbreviated BDTH2, with selenite. Second, the interaction of cysteine with Cd(II) and the biologically relevant Cd-Cysteine crystal structure. Third, the green synthesis of CdSe quantum dots (QDs). The interaction of BDTH2 with selenite is different from the interactions with other metals and metalloids previously studied. Under ambient conditions, BDTH2 is oxidized to the disulfide, BDT(S-S), while selenite is reduced to elemental selenium. However, under carefully controlled conditions, the reaction of BDTH2 with selenite produces a mixture of BDT(S-S) and the covalently bound Se(II) species, BDT(S-Se-S). While the mixture could not be separated, experimental 77Se NMR combined with computational analysis confirmed the presence of BDT(S-Se-S). The interaction of the amino acid cysteine with Cd(II) was studied as a means to sequester, and potentially recycle, Cd(II) from bulk CdS waste. Single crystals of Cd(Cys)Cl·H2O were grown, and the crystal structure determined. Surprisingly, this is only the second structure to be determined by X-ray crystallography of a compound containing the Cd-Cysteine unit. Not only does this structure have biological relevance, but it also corrects a structure proposed in 1965. Using the knowledge gained from studying the interaction of BDTH2 with selenite, a green synthesis of water-soluble CdSe QDs by the reaction of selenite with Cd(Cys)Cl·H2O in water at room temperature was developed. This green method for the synthesis of CdSe QDs was extended to ZnSe and HgSe QDs. The mechanism of CdSe formation was investigated using Cd(II) combined with various thiols.

This thesis describes the development and demonstration of a new technique for the fabrication of well-defined quantum dots in a bulk silicon substrate, for potential applications such as quantum computation in coupled quantum dots. Hall characterisation was performed on double-gated mesaMetal-Oxide- Semiconductor Field-Effect Transistors (MOSFETs) on a silicon-on-insulator (SOI) substrate, for the purpose of silicon quantum dots in etched nanowires on SOI. Carrier density and mobility results are presented, demonstrating top- and backgate control over the two inversion layers created at the upper and lower surfaces of the superficial silicon mesa. A new technique is developed enabling effective depletion gating of quantum dots in a bulk silicon substrate. A lower layer of aluminium gates is defined using electron beam lithography; the surface of these gates is oxidised using a plasma oxidation technique; and a further layer of aluminium gates is deposited. The lower gates form tunable tunnel barriers in the narrow inversion layer channel created by the upper MOSFET gate. The two layers of gates are electrically isolated by the localised layer of aluminium oxide. Low-temperature transport spectroscopy has been performed in both the many electron (∼100 electrons) and the few electron (∼10 electrons) regimes.Excited states in the bias spectroscopy provide evidence of quantum confinement. Preliminary temperature and magnetic field dependence data are presented. These results demonstrate that depletion gates are an effective technique for defining quantum dots in silicon. Furthermore, the demonstration of the first silicon radio-frequency single electron transistor is reported. The island is again defined by electrostatically tunable tunnel barriers in a narrow channel field effect transistor. Charge sensitivities of better than 10μe/√Hz are demonstrated at MHz bandwidth. These results establish that silicon may be used to fabricate fast, sensitive electrometers.

This thesis deals with electron correlation effects within low-dimensional, mesoscopic systems. We study phenomena within two different types of system in which correlations play an important role. The first involves the spectra and spin structure of small symmetric quantum dots, or &quoteartificial atoms&quote. The second is the &quote0.7 structure&quote, a well-known but mysterious anomalous conductance plateau which occurs in the conductance profile of a quantum point contact. Artificial atoms are manufactured mesoscopic devices: quantum dots which resemble real atoms in that their symmetry gives them a &quoteshell structure&quote. We examine two-dimensional circular artificial atoms numerically, using restricted and unrestricted Hartree-Fock simulation. We go beyond the mean-field approximation by direct calculation of second-order correlation terms; a method which works well for real atoms but to our knowledge has not been used before for quantum dots. We examine the spectra and spin structure of such dots and find, contrary to previous theoretical mean-field studies, that Hund's rule is not followed. We also find, in agreement with previous numerical studies, that the shell structure is fragile with respect to a simple elliptical deformation. The 0.7 structure appears in the conductance of a quantum point contact. The conductance through a ballistic quantum point contact is quantised in units of 2e^2/h. On the lowest conductance step, an anomalous narrow conductance plateau at about G = 0.7 x 2e^2/h is known to exist, which cannot be explained in the non-interacting picture. Based on suggestive numerical results, we model conductance through the lowest channel of a quantum point contact analytically. The model is based on the screening of the electron-electron interaction outside the QPC, and our observation that the wavefunctions at the Fermi level are peaked within the QPC. We use a kinetic equation approach, with perturbative account of electron-electron backscattering, to demonstrate that these simple features lead to the existence of a 0.7-like structure in the conductance. The behaviour of this structure reproduces experimentally observed features of the 0.7 structure, including the temperature dependence and the behaviour under applied in-plane magnetic fields.

This thesis examines the optical properties of nanoscale silicon and the sensitization of Er with Si. In this context, it predominantly investigates the role of defects in limiting the luminescence of Si nanocrystals, and the removal of these defects by hydrogen passivation. The kinetics of the defect passivation process, for both molecular and atomic hydrogen, are studied in detail. Moreover, the optical absorption of Si nanocrystals and the effect of annealing environment (during nanocrystal synthesis) on the luminescence are investigated. The effect of annealing temperature and hydrogen passivation on the coupling (energy transfer) of Si nanocrystals to optically active centres (Er) is also examined.¶ The electronic structure of silicon-implanted silica slides is investigated through optical absorption measurements. Before and after annealing to form Si nanocrystals, optical absorption spectra from these samples show considerable structure that is characteristic of the particular implant fluence. This structure is shown to correlate with the transmittance of the samples as calculated from the modified refractive index profile for each implant. Due to the high absorption coefficient of Si at short wavelengths, extinction at these wavelengths is found to be dominated by absorption. As such, scattering losses are surprisingly insignificant. To eliminate interference effects, photothermal deflection spectroscopy is used to obtain data on the band structure of Si in these samples. This data shows little variance from bulk Si structure and thus little effect of quantum confinement. This is attributed to the dominance of large nanocrystals in the absorption measurements.¶ The effect of annealing environment on the photoluminescence (PL) from silicon nanocrystals synthesized in fused silica by ion implantation and thermal annealing is studied as a function of annealing temperature and time. Interestingly, the choice of annealing environment (Ar, N2, or 5 % H2 in N2) is found to affect the shape and intensity of luminescence emission spectra, an effect that is attributed both to variations in nanocrystal size and the density of defect states at the nanocrystal/oxide interface.¶ The passivation kinetics of luminescence-quenching defects, associated with Si nanocrystals in SiO2, during isothermal and isochronal annealing in molecular hydrogen are studied by time-resolved PL. The passivation of these defects is modeled using the Generalized Simple Thermal model of simultaneous passivation and desorption, proposed by Stesmans. Values for the reaction-rate parameters are determined for the first time and found to be in excellent agreement with values previously determined for paramagnetic Si dangling-bond defects (Pb type centers) found at planar Si/SiO2 interfaces; supporting the view that non-radiative recombination in Si nanocrystals is dominated by such defects.¶ The passivation kinetics of luminescence-quenching defects during isothermal and isochronal annealing in atomic hydrogen are studied by continuous and time-resolved PL. The kinetics are compared to those for standard passivation in molecular hydrogen and found to be significantly different. Atomic hydrogen is generated using the alneal process, through reactions between a deposited Al layer and H2O or –OH radicals in the SiO2. The passivation and desorption kinetics are shown to be consistent with the existence of two classes of nonradiative defects: one that reacts with both atomic and molecular hydrogen, and the other that reacts only with atomic hydrogen. A model incorporating a Gaussian spread in activation energies is presented that adequately describes the kinetics of atomic hydrogen passivation and dissociation for the samples.¶ The effect of annealing temperature and hydrogen passivation on the excitation cross-section and PL of erbium in silicon-rich silica is studied. Samples are prepared by co-implantation of Si and Er into SiO2 followed by a single thermal anneal at temperatures ranging from 800 to 1100 degrees C, and with or without hydrogen passivation performed at 500 degrees C. Using time-resolved PL, the effective erbium excitation cross-section is shown to increase by a factor of 3, while the number of optically active erbium ions decreases by a factor of 4 with increasing annealing temperature. Hydrogen passivation is shown to increase the luminescence intensity and to shorten the luminescence lifetime at 1.54 micron only in the presence of Si nanocrystals. The implications of these results for realizing a silicon-based optical amplifier are also discussed.

L'efficacité de la thérapie photodynamique (PDT) est confrontée à plusieurs verrous : les photosensibilisateurs (PSs) utilisés en clinique ne sont pas adaptés à la fenêtre thérapeutique, ils subissent un photoblanchiment lors du traitement, et leur nature organique pose des problèmes de solubilité en milieu biologique. Ils présentent également une faible sélectivité envers les tissus tumoraux à traiter. Dans le cadre de cette thèse, trois approches visant une amélioration de la PDT appliquée à la cancérologie ont été développées : la vectorisation, l'adressage, et l'optimisation de nouveaux PSs. La synthèse de structure PS/vecteur a permis d'élaborer des structures hydrophiles capables de vectoriser des PSs hydrophobes. Des porphyrines ont ainsi été greffées sur des dendrimères polyamidoamine (PAMAM) dissymétriques. La conservation des propriétés photophysiques des PSs après leur couplage au dendrimère a été mise en évidence. Des quantum dots (QDs), grâce à la modularité de leurs propriétés photophysiques et leur capacité à résister au photoblanchiment, ont été synthétisés et utilisés comme nouvelle classe d'agents photosensibilisants. Ces QDs ont été préparés afin d'être hydrophiles et utilisables dans la fenêtre thérapeutique de la PDT. Une étude in vitro des QDs couplés à l'acide folique a mis en évidence leur activité photodynamique. Des études réalisées par une approche de plans d'expérience a permis de hiérarchiser les facteurs expérimentaux en fonction de leurs impacts sur l'activité photodynamique. Nous avons en particulier montré une amélioration de la sélectivité des conjugués envers les cellules surexprimant le récepteur à l'acide folique.

Nous avons étudié par diverses techniques de photoluminescence les propriétés optiques d'hétérostructures à base de composés III-N de structure wurtzite. Des expériences de photoluminescence résolues en polarisation nous ont permis de mettre en évidence l'influence des contraintes et du confinement sur la structure de bande d'une hétérostructure. L'étude de boites quantiques uniques GaN/AlN a pu être réalisée sur un système original : une boite quantique comme tranche d'un nanofil. Ce nouveau système nous a ainsi permis d'identifier les émissions de l'exciton et du biexciton. Nous avons également démontré le caractère d'émetteur de photon unique d'une boite quantique insérée dans un nanofil grâce à une expérience de corrélation de photon fonctionnant dans l'ultraviolet. Nous nous sommes également intéressés aux propriétés optiques de microdisques III-N et avons mesuré des facteurs de qualité atteignant 11000, ouvrant la porte à l'étude de l'effet Purcell dans ces structures. Finalement nous nous sommes penchés sur la dynamique des porteurs et du spin dans les hétérostructures GaN/AlN. Les boites quantiques se révèlent extrêmement efficaces pour éviter les recombinaisons non radiatives, les temps de déclin de la luminescence étant indépendants de la température même pour des boites présentant des déclins de l'ordre de la microseconde. Les boites quantiques semblent aussi être très efficientes pour supprimer les effets de diffusion sur le spin d'un exciton localisé. En effet des expériences d'alignement optique en pompage quasi résonnant nous ont permis de montrer que la polarisation induite était conservée sur la durée de vie de l'exciton et ce jusqu'à température ambiante.

<p>GaN quantum dots grown by molecular beam epitaxy are examined by micro-photoluminescence. The exciton and biexciton emission are identified successfully by power-dependence measurement. With two different samples, it can be deduced that the linewidth of the peaks is narrower in the thicker deposited layer of GaN. The size of the GaN quantum dots is responsible for the binding energy of biexciton (E^b_XX); E^b_XXdecreases with increasing size of GaN quantum dots. Under polarization studies, polar plot shows that emission is strongly linear polarized. In particular, the orientation of polarization vector is not related to any specific crystallography orientation. The polarization splitting of fine-structure is not able to resolve due to limited resolution of the system. The emission peaks can be detected up to 80 K. The curves of transition energy with respect to temperature are S-shaped. Strain effect and screening of electric field account for  blueshift of transition energy, whereas Varshni equation stands for redshifting. Both blueshifting and redshifting are compensated at temperature ranging from 4 K to 40 K.</p>

<p>It is very interesting to probe the rotational symmetry of semiconductor quantum dots for quantum information and quantum computation applications. We studied the effects of rotational symmetry in semiconductor quantum dots using configuration interaction calculation. Moreover, to compare with the experimental data, we studied the effects of hidden symmetry. The 2D single-band model and the 3D single-band model were used to generate the single-particle states. How the spectra affected by the breaking of hidden symmetry and rotational symmetry are discussed. The breaking of hidden symmetry splits the degeneracy of electron-hole single-triplet and triplet-singlet states, which can be clearly seen from the spectra.</p><p>The breaking of rotational symmetry redistributes the weight percentage, due to the splitting of p_x and p_y states, and gives a small brightness to the dark transition, giving rise to asymmetry peaks. The asymmetry peaks of 4X, 5X, and 6X were analyzed numerically. In addition, Auger-like satellites of biexciton recombination were found in the calculation. There is an asymmetry peak of the biexciton Auger-like satellite for the 2D single-band model while no such asymmetry peak occurs for the 3D single-band model. Few-particle effects are needed in order to determine the energy separation of the biexciton main peak and the Auger-like satellite.</p><p>From the experiments, it was confirmed that the lower emission energy peak of X^2- spectrum is split. The competed splitting of the X^2- spectra were revealed when temperature dependence was implemented. However, since the splitting is small, we suggest the X^2- peaks are broadened in comparison with other configurations according to single-band models. Furthermore, the calculated excitonic emission patterns were compared with experiments. The 2D single-band model fails to give the correct energy order of the peaks for the few-particle spectra; on the other hand the peaks order from 3D single-band model consistent with experimental data.</p>

In ‘clean' confined conductors (the so-called mesoscopic systems), the electronic phase and momentum can be preserved over very long distances compared to the system dimensions. This gives rise to peculiar transport properties, bearing signatures of electron interferences, ballistic electron trajectories, electron-electron interactions, regular-chaotic electron dynamics and (in some cases) spin-orbit coupling. Examples of such effects are the Universal Conductance Fluctuations (UCFs) and the Weak Localization observed in the low-temperature magnetoconductance of many confined electronic systems. Of central importance, the electronic phase coherence time and the spin-orbit coupling time determine the amplitude of these quantum effects. In the first part of this thesis, we use UCFs to extract these characteristic timescales in open ballistic quantum dots (QDs) fabricated from InGaAs heterostructures. We observe an intrinsic saturation of the coherence time at low temperature in the InGaAs QDs. The origin of this phenomenon has been intensely debated during the last decade. Based on our observations and previous experimental data in QDs, we propose an explanation: the dwell time becomes the limiting factor for electron interferences in QDs at low temperature. Then, we report on magnetoconductance measurements in a bismuth ballistic nano-cavity. The cavity is found to be zero-dimensional for phase coherent processes at low temperature. We evidence an anomalous reduction of the phase coherence time in the cavity with respect to data obtained in thin Bi films, while the spin-orbit coupling time is similar in both systems. Finally, we examine the current-voltage characteristics of asymmetric InGaAs nano-junctions in the nonlinear regime. We observe a new tunable rectification effect, whose amplitude and sign are governed by the conductances of the junctions' channels. We show that the effect is ballistic and exhibits new features with respect to predictions of available models.