Les carbones amorphes hydrogénés (a–C:H ou HAC) constituent une composante importante de la poussière interstellaire. Ces grains hydrocarbonés sont observés au travers de bandes d’absorption IR à 3.4, 6.9 et 7.3 microns, caractéristiques des vibrations des liaisons C-H aliphatiques. Leurs signatures spectrales sont détectées dans le milieu interstellaire diffus de différentes lignes de visée de la Voie Lactée, mais aussi de nombreuses autres galaxies. Cette thèse porte sur l’étude de ces a–C:H interstellaires, à la fois au travers d’observations de ces poussières, et grâce à la synthèse et la caractérisation d’analogues de laboratoire.Une première partie de mon travail de thèse est consacrée à l’observation de la bande à 3.4 microns des a–C:H du milieu interstellaire diffus galactique en direction de la source IRAS 18511+0146. La bande d’absorption des modes d’élongation C-H détectée dans cette direction, vers différentes lignes de visée proches les unes des autres, présente des profondeurs optiques similaires et les plus fortes observées dans la Voie Lactée en dehors du centre galactique. Différentes interprétations de la profonde bande dans cette direction sont discutées.Des analogues de ces poussières carbonées aliphatiques ont été synthétisés en laboratoire, sous forme de films, grâce à un plasma, et reproduisent bien les bandes IR observées dans le milieu interstellaire diffus. Ces échantillons ont été caractérisés par spectroscopie d’absorption dans l’UV-visible et l’IR.Puisque les a–C:H émettent un rayonnement visible après absorption de photons UV ou visibles, une partie de la thèse est consacrée à une étude systématique de cette photoluminescence. Pour la première fois, les rendements absolus et intrinsèques de photoluminescence d’a–C:H sont déterminés pour une large gamme de longueurs d’onde d’excitation. Les propriétés de la photoluminescence des a–C:H sont confrontées aux observations de l’Emission Rouge Etendue, une large bande d’émission interstellaire dont les porteurs ne sont pas identifiés.Afin de déduire l’influence des rayons cosmiques sur ces poussières carbonées, les analogues produits ont été irradiés par différents ions énergétiques dont le dépôt d’énergie est similaire à celui du rayonnement cosmique interstellaire. Les effets induits ont été suivies par IR. L’analyse de la déshydrogénation des a–C:H observée au travers de la disparition progressive des bandes des C-H aliphatiques permet de déduire l’évolution de ces poussières interstellaires et de leurs signatures spectrales sous l’effet des rayons cosmiques. La destruction induite par les rayons cosmiques est comparée aux effets de l’exposition aux photons UV et aux atomes d’hydrogène afin d’interpréter l’évolution de la bande d’absorption à 3.4 microns observée dans le milieu interstellaire diffus, mais pas dans les nuages denses. / The hydrogenated amorphous carbons (a–C:H or HAC) are an important component of interstellar dust. These hydrocarbon grains are observed through IR absorption bands at 3.4, 6.9 and 7.3 microns, due to aliphatic C-H bond vibrations. Their spectral signatures are detected in the diffuse interstellar medium along several sight lines in the Milky Way and in many external galaxies. This thesis deals with the study of such interstellar a–C:H, both through their astrophysical observation and the synthesis and characterisation of laboratory analogues.A first part of this PhD work concerns the 3.4 microns band observation in the galactic diffuse interstellar medium in the direction of IRAS 18511+0146 source. The C-H stretching mode absorption band detected toward several lines of sight of this cluster has the strongest optical depths observed in the Milky Way outside the galactic center. Different interpretations for this deep absorption band in this direction are discussed.Analogues of the amorphous carbonaceous dust component have been produced in the laboratory with a plasma source. Their IR spectra are in excellent agreement with the absorption bands observed in the diffuse interstellar medium. The samples have been characterised by UV-visible and IR absorption spectroscopy.Since a–C:H emit a visible radiation when they absorb UV or visible photons, a systematic study of this photoluminescence is performed. For the first time, the absolute and intrinsic photoluminescence yield of a–C:H is measured for a broad range of excitation wavelengths. The photoluminescence properties of a–C:H is compared to observations of the Extended Red Emission, a large interstellar emission band whose carriers are not identified.To infer the influence of cosmic rays on this carbonaceous dust, the produced analogues have been irradiated by different swift ions, similar to interstellar cosmic rays. The induced modifications have been monitored by their IR spectrum. The a–C:H dehydrogenation is observed through the progressive disappearance of the aliphatic C-H bands. Its analysis allows us to deduce the evolution of the a–C:H dust and its spectral signatures under cosmic ray exposition. The destruction due to cosmic rays is compared to the effects induced by exposure to UV photons and hydrogen atoms, in order to interpret the evolution of the absorption band at 3.4 microns observed in the diffuse interstellar medium, but not in dense clouds.

Cette thèse est une contribution à la modélisation et à l'étude expérimentale de cavités à cristaux photoniques à fente développées en vue d’un intégration hybride de matériaux actifs sur silicium. Parmi les travaux de conception, nous avons d'abord utilisé la méthodes des ondes planes et la méthode des différences finies (FDTD) pour concevoir une série de cavités SOI à hétérostructures, mécaniquement robustes, infiltrées par des liquides d’indices (n environ 1,5), présentant des longueurs d'onde de résonance dans la gamme des télécommunications (1,3 μm - 1,6 μm), des facteurs de qualité de plusieurs dizaines de milliers, et des volumes modaux proches de 0,03 (lambda/n)3. Nous avons ensuite étudié analytiquement et numériquement le couplage entre une cavité à cristaux photoniques à fente et un guide d'onde à fente par la théorie des modes couplés, complétée par des simulations FDTD, qui ont permis de confirmer la possibilité d'exciter efficacement les modes de fente des cavités à partir d'un guide externe. Enfin, nous avons étudié numériquement et semi-analytiquement des géométries de molécules photoniques constituées de deux cavités à cristaux photoniques à fentes couplées, dont l’écart fréquentiel entre les supermodes a pu être ajusté en amplitude et en signe. Nous avons utilisé une méthode perturbative (« Tight binding ») pour estimer les distributions spatiales des modes des molécules photoniques et prédire leurs fréquences dans plusieurs configurations de cavités à cristaux photoniques à fentes couplées.Ce travail exploratoire a été complété par une partie expérimentale qui a porté sur l'étude d'une famille de cavités de hétérostructure à cristaux photoniques à fente. Les cavités à cœur creux fabriquées ont montré des facteurs de qualité (Q) de plusieurs dizaines de milliers, associés à des volumes modaux de l’ordre de V=0,03 (λ/n)^3 après infiltration de la fente et des trous des structures par des liquides d'indice de réfraction proches de 1,46. Des facteurs Q/V supérieurs à 600 000 et atteignant 1 000 000 dans le meilleur des cas (vers lambda=1,3µm) ont ainsi été observés. Cette phase expérimentale préliminaire a donné ensuite lieu à deux types de développements.Tout d'abord, les propriétés des cavités à cristaux photoniques à fentes ont été étudiées pour des applications en détection d'indice en volume, et testées en utilisant différents liquides d'indice de réfraction compris entre 1,345 à 1,545. Les résonateurs étudiés ont présenté des sensibilités de ~ 235 nm / RIU et des facteur de mérite de détection d'indice de l’ordre de 3700, à l’état de l’art pour des résonateurs silicium intégrés à cœur creux.Dans une autre direction, le potentiel des résonateurs diélectriques à fente a été exploré en vue d’une intégration des matériaux actifs sur silicium. Un polymère dopé aux nanotubes de carbone semiconducteurs a été déposé comme matériau de couverture en vue d’étudier le renforcement de la photoluminescence (PL) des nano-émetteurs sous pompage optique vertical à lambda=740nm. Les expériences conduites ont permis de corréler le renforcement de la PL des nanotubes avec les modes de résonance des cavités et de démontrer le couplage partiel de cette PL vers des guides SOI longs de plusieurs millimètres (collection par la tranche vers lambda=1.3µm), apportant une preuve de principe d’une possible intégration des nanotubes émetteurs en photonique sur silicium. / This Ph.D. work is a contribution to the modeling and the experimental study of slot photonic crystal cavities for hybrid on-silicon integration. Among the design works, we first have used plane the wave expansion and finite-difference time-domain methods to design a series of mechanically robust (non-free membrane) SOI slot photonic crystal heterostructure cavities with resonance wavelengths in the telecommunication range, i.e. from 1.3 µm – 1.6 µm, with Q-factors of around several tens of thousands and mode volumes around 0.03(lambda/n)^3 after being infiltrated by cladding materials with typical index values around 1.5. We have then analytically and numerically studied the coupling between a slot photonic crystal cavity and a slot photonic crystal waveguide by using the coupled mode theory and FDTD simulation. Then we confirmed the ability to excite the cavity slot modes from a waveguide by using FDTD simulation. Finally, as a preliminary step towards the use of several coupled slotted cavities for future hybrid integration schemes, we have numerically and semi-analytically investigated photonic molecules made of two coupled slot photonic crystal cavities providing two different supermodes (bonding and antibonding ones) with controllable wavelength splitting. We successfully employed the tight-binding (TB) approach, which relies on the overlap of the two tightly confined cavity electric fields, to predict the supermodes frequencies and spatial distributions in several coupled slot photonic crystal cavity configurations.This exploratory work was supplemented by an experimental part, which focused on the investigation of a family of slot photonic crystal heterostructure cavities. The fabricated silicon on insulator hollow core cavities showed quality factors of several tens of thousands, i.e. from 18,000 to 31,000 and mode volume V of ~0.03(λ/n)3 after being infiltrated with liquids of ~1.46 refractive index, yielding Q/V ratio larger than 600,000, and reaching 1,000,000 in the best case (at λ ≈ 1.3 μm).This preliminary experimental stage gave rise to two types of additional developments.Firstly, the properties of the studied slot photonic crystal cavities have been investigated for index sensing applications by using different liquids with refractive index values ranging from 1.345 to 1.545. The considered photonic crystal resonators have demonstrated quality factors of several tens of thousands with sensitivities of ~235 nm/RIU and index sensing FOMs around 3,700, i.e. at the state of the art considering hollow core silicon integrated resonators.Secondly, in the view of the integration of active materials on silicon, the potential of these hollow core nanoresonators has been considered to enhance the photo-luminescence (PL) of semiconductor single-walled carbon nanotubes (SWNTs) integrated in thin films deposited on top of silicon. We have brought the first experimental demonstration of SWNTs PL collection (around lambda=1.28 µm) under vertical pumping at short wavelength (lambda=740 nm) from a slotted resonator into millimeter long integrated silicon waveguides, providing a first proof-of-concept step towards nanotube/Si-PhC integration as an active photonic platform. The reported works demonstrate the feasibility of integrating telecommunication wavelength nanotube emitters in silicon photonics as well as emphasize the role of slot photonic crystal cavities for on-chip hybrid integration.

Les matériaux hybrides organiques inorganiques ont attirés l'attention vue qu'ils présentent des propriétés optiques et optoélectroniques fascinantes comme la forte photoluminescence même à température ambiante. Cet axe de recherche relativement nouveau, sur cette famille de matériaux, offre une variété d’opportunités technologiques. Dans ce contexte, nous nous sommes intéressés par l'étude des propriétés optiques des deux matériaux hybrides organiques inorganiques (C6H11NH3)2[PbI4] et (C6H11NH3)2[PbBr4], et principalement leurs propriétés de luminescence. Les résultats montre que sous excitation dans l'ultraviolet, (C6H11NH3)2[PbBr4] émet de la lumière blanche, même à température ambiante, ce qui présente un grand intérêt de l'utilisation de ces matériaux comme source d'émission de la lumière blanche. L'origine de cette émission a été étudié par différentes techniques comme la photoluminescence résolution en temps. / Inorganic organic hybrid materials have attracted a great attention do to their special structure and important optical such as the high luminescence, even at room temperature. This relatively new research on this family of materials, offers a variety of technological opportunities. In this context, we are interested in the study of optical properties of both inorganic and organic hybrid materials (C6H11NH3)2[PbI4] and (C6H11NH3)2[PbBr4], and mainly their luminescence properties. The results shows that under ultraviolet excitation, (C6H11NH3)2[PbBr4] show a strong white light emission, even at room temperature, which open a great interest in the use of these materials as a source of the white light emission. The origin of this large emission has been studied by different techniques such as the time resolved photoluminescence measurements .

<p dir="ltr">In the realm of two-dimensional (2D) materials, monolayer (ML) transition metal dichalcogenides (TMDCs) have gained significant interest due to their direct bandgap transition, high carrier mobility, strong light-matter interaction, and robust spin and valley degrees of freedom, starkly contrasting their bulk counterparts. Owing to their large surface-to-volume ratio, the integration of ML TMDCs with other various 2D semiconductors and microcavities offers opportunities to study fundamental photo-physics processes at the heterointerfaces, paving the way for implementation of next-generation devices.</p><p dir="ltr">Chapter 1 provides a concise introduction to 2D materials, particularly TMDCs, and their fascinating optical and electronic properties. It examines the role of excitons in 2D materials, and the impact of energy transfer (ET) and charge transfer (CT) on exciton’s properties in TMDC through the construction of 2D van der Waals (vdW) heterostructures and coupling with optical microcavities. This chapter also delves into the potential enhancement of TMDCs’ optical properties by integrating 2D hybrid lead halide perovskites and ultra-thin three-dimensional (3D) halide perovskites with TMDCs. Furthermore, it sets the general context for light-matter interaction, another form of ET, considering both weak and strong coupling regimes.</p><p dir="ltr">Chapter 2 outlines the optical techniques employed to gather data for this work. A focus is placed on ultrafast optical techniques like transient absorption spectroscopy, which allow for direct probing and analysis of ET and CT dynamics at the heterointerface.</p><p dir="ltr">Photoinduced interfacial CT plays a critical role in the field of energy conversion involving vdW heterostructures constructed by inorganic nanostructures and organic materials. However, the control of atomic-scale stacking configurations to modulate charge separation at interfaces remains challenging. Chapter 3 aims to illustrate tunability of interfacial charge separation in a Type-II heterojunction between ML-WS₂ and an organic semiconducting molecule by rational design of relative stacking configurations using 2D perovskites as scaffoldings. This chapter investigates how different molecular stacking, face-to-face versus face-to-edge, affects CT at the heterointerface. Our findings reveal that the CT process heavily depends on the relative stacking configurations at the organic-TMDCs heterointerface, with charge separation being notably slowed down for face-to-edge configuration compared to face-to-face configuration. These investigations open new opportunities for designing efficient charge separation processes in energy conversion applications by judiciously engineering interfaces between organic and inorganic semiconductors, using 2D perovskites as scaffolds.</p><p dir="ltr">Though TMDCs’ large surface-to-volume ratios make them excellent platforms for studying interfacial properties, the presence of bulky ligands on the surface of 2D perovskite poses a challenge, impeding direct interfacial coupling in their heterostructures. Chapter 4 details the fabrication of ML-WS₂ and ultra-thin CH₃NH₃PbX₃ (MAPbX₃, X=Br, I) heterostructures with tunable energy levels, to study the dynamics of CT and ET at these hybrid interfaces. Notably, heterojunctions of WS₂ with pure MAPbBr₃ and MAPbI₃ were elucidated as Type-I and Type-II respectively, using photoluminescence (PL) and time-resolved photoluminescence (TR-PL) measurements. Transit absorption (TA) spectroscopy investigations unambiguously revealed a rapid ET facilitated by CT in the WS₂/MAPbBr₃ heterostructure, with a time constant of ~20 ps, and a predominantly CT in the WS₂/MAPbI₃ heterostructure with a time constant of ~50 femtosecond (fs). The successful interfacing of low-dimensional perovskites with an extensive array of traditional 2D materials such as TMDCs opens up possibilities for novel optoelectronic properties and applications within the field of 2D material systems. Furthermore, the ultrafast and efficient ET and CT processes hold promise for the creation of advanced energy conversion devices.</p><p dir="ltr">In the last chapter, we successfully fabricated a ML-WS₂ in conjunction with a silver (Ag) nanoparticle (NP) array. Our findings affirmed a weak light-matter coupling between ML-WS₂ and the Ag NP array, as evidenced by angle-resolved photoluminescence spectroscopy. Furthermore, an enhancement in the bright exciton emission from ML-WS₂ was observed at reduced temperatures. The analysis of PL enhancement factor at varying temperatures suggested that an upper bound of the enhancement factor for the bright exciton could reach ~51 or even higher at 7 K, given the imperfect uniformity of the electric filed generated around the NPs. This discovery carries significant implications for the manipulation of excitons in TMDCs and expands their potential applications in the field of optoelectronics.</p>

Doctor of Philosophy / Department of Physics / Jingyu Lin / Time-resolved deep ultraviolet (DUV) Photoluminescence (PL) spectroscopy system has been employed to systematically monitor crystalline quality, identify the defects and impurities, and investigate the light emission mechanism in III-nitride semiconducting materials and photonic structures. A time correlated single photon counting system and streak camera with corresponding time resolutions of 20 and 2 ps, respectively, were utilized to study the carrier excitation and recombination dynamics. A closed cycle He-flow cryogenic system was employed for temperature dependent measurements. This system is able to handle sample temperatures in a wide range (from 10 to 900 K). Structural, electrical, and morphological properties of the material were monitored by x-ray diffraction (XRD), Hall-effect measurement, and atomic force microscopy (AFM), respectively. Most of the samples studied here were synthesized in our laboratory by metal organic chemical vapor deposition (MOCVD). Some samples were bulk AlN synthesized by our collaborators, which were also employed as substrates for homoepilayer growth. High quality AlN epilayers with (0002) XRD linewidth as narrow as 50 arcsec and screw type dislocation density as low as 5x10[superscript]6 cm[superscript]-2 were grown on sapphire substrates. Free exciton transitions related to all valence bands (A, B, and C) were observed in AlN directly by PL, which allowed the evaluation of crystal field (Δ[subscript]CF) and spin-orbit (Δ[subscript]SO) splitting parameters exerimentally. Large negative Δ[subscript]CF and, consequently, the difficulties of light extraction from AlN and Al-rich AlGaN based emitters due to their unique optical polarization properties have been further confirmed with these new experimental data. Due to the ionic nature of III-nitrides, exciton-LO phonon Frohlich interaction is strong in these materials, which is manifested by the appearance of phonon replicas accompanying the excitonic emission lines in their PL spectra. The strength of the exciton-phonon interactions in AlN has been investigated by measuring the Huang-Rhys factor. It compares the intensity of the zero phonon (exciton emission) line relative to its phonon replica. AlN bulk single crystals, being promising native substrate for growing nitride based high quality device structures with much lower dislocation densities (<10[superscript]4 cm[superscript]-2), are also expected to be transparent in visible to UV region. However, available bulk AlN crystals always appear with an undesirable yellow or dark color. The mechanism of such undesired coloration has been investigated. MOCVD was utilized to deposit ~0.5 μm thick AlN layer on top of bulk crystal. The band gap of strain free AlN homoepilayers was 6.100 eV, which is ~30 meV lower compared to hetero-epitaxial layers on sapphire possessing compressive strain. Impurity incorporation was much lower in non-polar m-plane growth mode and the detected PL signal at 10 K was about an order of magnitude higher from a-plane homo-epilayers compared to that from polar c-plane epilayers. The feasibility of using Be as an alternate p-type dopant in AlN has been studied. Preliminary studies indicate that the Be acceptor level in AlN is ~330 meV, which is about 200 meV shallower than the Mg level in AlN. Understanding the optical and electronic properties of native point defects is the key to achieving good quality material and improving overall device performance. A more complete picture of optical transitions in AlN and GaN has been reported, which supplements the understanding of impurity transitions in AlGaN alloys described in previous reports.

Pendant que la menace potentielle du bioterrorisme augmente, il y a grand besoin d'un outil qui peut détecter les agents biologiques contaminants dans l'environnement de façon rapide, fiable et précise. Par contre, les méthodes traditionnelles utilisées nécessitent l'utilisation de laboratoires d'analyse sophistiquée, souvent dans des installations centralisées, ce qui demande un capital considérable et une main-d'oeuvre hautement qualifiée. Il est possible de développé des dispositifs basés sur les biocapteurs à faible coût et très efficace à la détection d'agents biologiques. De plus, ils peuvent être utilisés dans d'autres domaines, au jour le jour, tel pour la surveillance de contaminants dans les produits comestibles. Dans le but de résoudre ce problème, une nouvelle approche pour la fabrication d'un biocapteur optique a été développée. Celui-ci serait capable de détecter, de façon directe, des micro-organismes qui seraient immobilisés à sa surface plus rapidement et plus aisément qu'avec les méthodes conventionnelles. En effet, les expériences présentées visent la fabrication d'un biocapteur suite à la déposition de molécules biochimiques sur une hétérostructure de GaAs/ALGaAs. Le biocapteur ainsi produit tire parti de la photoluminescence émise par ce semi-conducteur quantique III-V pour la détection de microorganismes immobilisés spécifiquement et négativement chargés. La présente recherche est basée sur des techniques novatrices de biocapteurs pour lesquelles il existe peu de littérature. Les travaux expérimentaux et les explications théoriques se révèlent ainsi de nature très exploratoires. Les résultats préliminaires obtenus ont d'ailleurs été similaires aux prédictions initiales. De plus, les détails théoriques et explications physiques permettent de comprendre l'origine des résultats obtenus et d'établir, de manière convaincante, les procédures à suivre pour une architecture optimale. Je rapporte ainsi l'étude de la bio-fonctionnalisation du GaAs (001) visant l'immobilisation d'anticorps polyclonaux selon deux architectures différentes. De plus, les architectures proposées ont leurs régions actives ouvertes à l'environnement, pour permettre des mesures en continues et, en plus d'être des systèmes offrant la possibilité de multiplexage, offrent un potentiel de mesures en parallèle, pour un grand nombre de mesures en simultanées. Les résultats obtenus démontrent l'immobilisation réussie ainsi que la détection effectuée du virus de l' influenza A et des bactéries Escherichia coli et Legionella pneumophila respectivement. Enfin, les avantages et les limites de chaque architecture ont ensuite été détaillés.

Semiconductor surfaces coupled to molecular structures derived from organic chemistry form the basis of an emerging class of field-effect devices. In addition to molecular electronics research, these interfaces are developed for a variety of sensor applications in the electronic and optical domains. Of practical interest are self-assembled monolayers (SAMs) comprised of n-alkanethiols [HS(CH[subscript 2])[subscript n]R], which couple to the GaAs(001) surface through S-GaAs covalent bond formation. These SAMs offer potential functionality in terms of the requisite sensor chemistry and the passivation effect such coupling is known to afford. In this thesis, the SAM-GaAs interface is investigated in the context of a photonic biosensor based on photoluminescence (PL) variation. The scope of the work is categorized into three parts: i) the structural and compositional analysis of the surface using X-ray photoelectron spectroscopy (XPS), ii) the investigation of electronic properties at the interface under equilibrium conditions using infrared (IR) spectroscopy, the Kelvin probe method, and XPS, and iii) the analysis of the electro-optic response under steady-state photonic excitation, specifically, the surface photovoltage (SPV) and PL intensity. Using a partial overlayer model of angle-resolved XPS spectra in which the component assignments are shown to be quantitatively valid, the coverage fraction of methyl-terminated SAMs is shown to exceed 90%. Notable among the findings are a low-oxide, Ga-rich surface with elemental As present in sub-monolayer quantities consistent with theoretical surface morphologies. Modal analysis of transmission IR spectra show that the SAM molecular order is sufficient to support a Beer-Lambert determination of the IR optical constants, which yields the observation of a SAM-specific absorbance enhancement. By correlation of the IR absorbance with the SAM dipole layer potential, the enhancement mechanism is attributed to the vibrational moments added by the electronic polarizability in the static field of the SAM. Lastly, the surface Fermi level position is determined by XPS and is used to interpret SPV results in terms of a thiol-induced reduction of the surface cross-section for minority carrier-capture. Numerical analysis confirms this result based on the carrier transport theory of PL intensity by means of a reduction of the surface recombination velocity.

This study investigates the photoluminescence (PL), cathodoluminescence (CL), radioluminescence (RL) and ionoluminescence (IL) of natural and synthetic minerals. The natural minerals (fluorapatite, leucophanite, meliphanite and zircon) are mostly from Ilímaussaq Alkaline Complex in South Greenland, Langesundsfjord in Norway and from different localities within Scotland. Synthetic fluorapatite (manufactured as part of the present study) and zircon doped with rare earth elements (REE) were used to compare single and multidoped materials. This study has shown that many of the generally accepted applications of luminescence are not as straightforward as often suggested by the current literature. For example, the study demonstrates how site distribution of REE, based on luminescence, is greatly affected by the dopant level and structural changes, and that different conclusions can be drawn on the same sample depending on method applied. Furthermore, it is clearly demonstrated that using luminescence as a tool for quantitative trace element determination is not going to be a standard technique in the near future if ever. The two main findings supporting this conclusion are the non-linear intensity decrease between different REE activators in the same sample and a large variation between activators at the concentration at which self-quenching starts. In contrast to the general perception that luminescence related to REE is mostly independent of the host, this study has shown a strong interaction between host and REE activators. This conclusion is supported by the change in the activator’s coordination polyhedron observed with single-crystal and powder X-ray diffraction combined with full chemical characterisation. When combining the weak interaction between some REE with the strong host interaction this study has shown the potential for designing new types of colour tuneable and “white light” LEDs based on natural minerals. This study also reveals that zircon doped with Gd³⁺ and Eu³⁺ can potentially have quantum-cutting properties.

Gold nanoparticles (GNP) have been widely used as optical imaging and photothermal therapy agents due to their biocompatibility, simplicity of conjugation chemistry, optical tunability and efficient light conversion to heat. A number of in vitro and in vivo studies have demonstrated that they can be used as effective thermal therapy and imaging contrast agents to treat and diagnose cancer. As clinical applications of GNPs for cancer imaging and therapy have gained interest, efforts for understanding their accumulation kinetics has become more important. Given the recent demonstration of intrinsic two-photon induced photoluminescence (TPIP) of gold nanoshells (GNSs) and gold nanorods (GNRs), TPIP imaging is an efficient tool for investigating the microscopic distribution of the GNPs at intra-organ level. The following work explores these GNPs’ physical and optical properties for effective use of GNPs in TPIP imaging and examines the feasibility of using intrinsic TPIP imaging to investigate GNP’s biodistribution in bulk tumors and thin tissue slices processed for standard histology. Our results showed that GNPs yield a strong TPIP signal, and we found that the direct luminescence-based contrast imaging of GNPs can image both GNPs and nuclei, cytoplasm or vasculature simultaneously. Also, we present the effect of GNP morphology on their distribution within organs. Collected images showed that GNPs had a heterogeneous distribution with higher accumulation at the tumor periphery. However, GNRs had deeper penetration into tumor than GNRs due to their shape and size. In addition, GNPs were observed in unique patterns close to vasculature. Finally, we introduce single- and multiple-dose administrations of GNPs as a way of increasing GNP accumulation in tumor. Our results show that multiple dosing can increase GNP accumulation in tumor 1.6 to 2 times more than single dosing. Histological analysis also demonstrated that there were no signs of acute toxicity in tumor, liver and spleen excised from the mice receiving 1 injection, 5 injections of GNPs and trehalose injection. / text

Cette thèse est consacrée au couplage fort exciton-photon à température ambiante dans les microcavités massives à base de ZnO élaborées par épitaxie par jets moléculaires sur substrat Si(111). Une étude théorique préliminaire montre que le continuum d'absorption des résonances excitoniques est responsable du fort amortissement observé sur la branche haute de polaritons, sans toutefois affecter la branche basse de polaritons. Le couplage fort à température ambiante du mode de cavité ainsi que des modes de Bragg de la microcavité a ensuite été démontré par spectroscopie résolue en angle. De plus, nous observons la présence d'un goulot d'étranglement (bottleneck) sur le mode de Bragg de polaritons. Ce dernier peut être supprimé en faisant varier la densité d'excitons ou la température. Nous comparons nos résultats expérimentaux aux prévisions théoriques faites en vue de l'obtention d'un régime laser à polaritons.