L’objective est d’améliorer l’activité photocatalytique de TiO2 sous irradiations UV et Visible. Pour contourner les limites de TiO2 intrinsèque nous envisageons une fabrication de nanocomposite plasmonique à base de nanofils de TiO2 périodiquement organisés et assemblés avec des nanoparticules plasmoniques. Pour la fabrication des nanofils de TiO2 mécaniquement stables, deux approches ont été réalisées. La première approche est basée sur la croissance sélective en phase vapeur, la deuxième approche consiste en l’utilisation d’un moule de membranes AAO et d’un dépôt de films conformes par ALD. En parallèle les films de TiO2déposés par ALD sont assemblés avec les nanoparticules plasmoniques d’or. Les différentes architectures de TiO2 sont valorisées par des tests photocatalytiques (UV et Visible) sur les polluants modèles. Une nouvelle approche de la fabrication des films mesoporeux d’H-TiO2 avec efficacité photocatalytique à la fois sous irradiation UV et Visible est développée. / The objective of this thesis is to improve the photo-response of well-known photocatalytic material such as TiO2, which is usually only active in the UV range. The basic idea is to assemble several approaches within one device to improve the photocatalytic properties: fabrication of periodically-organised TiO2 nanostructures and their assembly with plasmonic nanoparticles. Two fabrication strategies were investigated for these purposes. The first approach consists of selective vapour phase growth. The second approach implements the use of an AAO template. In parallel, TiO2 films deposited by ALD and assembled with plasmonic gold nanoparticles are investigated. The photocatalytic measurements on various TiO2 architectures were performed in both irradiation ranges UV and Vis. A new fabrication approach of mesoporous H-TiO2 films was developed giving promising results of photocatalytic efficiency improvement in both UV and Visible ranges.

Plasmonic cavities confine optical fields at metal-dielectric interfaces via collective charge oscillations of free electrons within metals termed surface plasmon polaritons (SPPs). SPPs are confined in nanometre gaps formed between two metallic surfaces which creates an optical resonance. This optical resonance of the system is controlled by the geometry and the material of the nanogap. The focus of this work is to understand and utilize these confined optical modes to probe and manipulate the dynamics of single-molecules at room temperature. In this thesis, nanogap cavities are constructed by placing nanoparticles on top of a metal-film separated by molecular spacers. Such nanogaps act as cavities with confined optical fields in the gap. Precise position and orientation of single-molecules in the gap is obtained by supramolecular guest-host assembly and DNA origami breadboards. The interaction of light and single-molecules is studied in two different regimes of interaction strength. In the perturbative regime molecular light emission from electronic and vibrational states is strongly enhanced and therefore is used for the detection of single-molecules. In this regime the energy states remain unaltered, however profound effects emerge when the gap size is reduced to < 1 nm. New hybridized energy states which are half-light and half-matter are then formed. Dispersion of these energies is studied by tuning the cavity resonance across the molecular resonance, revealing the anti-crossing signature of a strongly coupled system. This dressing of molecules with light results in the modification of photochemistry and photophysics of single-molecules, opening up the exploration of complex natural processes such as photosynthesis and the possibility to manipulate chemical bonds.

Le cadre de cette thèse est la simulation numérique de l'interaction de la lumière avec des surfaces métalliques rugueuses pouvant être à l'origine de fortes localisation du champ électromagnétique du à des résonances plasmoniques. Les profils accidentés de ces surfaces ont des tailles caractéristiques de quelques nanomètres de largeur et de quelques dizaines de nanomètres de hauteur. La principale difficulté dans la simulation de tels phénomènes réside dans la diff'erence d'échelle entre la longueur d'onde de l'onde incidente et la taille des rugosités ainsi que les variations brutales du champ magnétique à la surface. Une méthode de simulation adaptée est la résolution numérique d'équations intégrales de surface ayant un profil périodique. Cette méthode a été implémentée en C++ et la part principale de ce travail a été le calcul de la fonction de Green pseudo-périodique. L'intensité du faisceau réfracté ainsi que les cartes de champ proche peuvent être calculées rigoureusement à partir de la solution obtenue. A l'aide de cette méthode, on a montré que des résonances plasmoniques situées dans les cavités d'un réseaux ayant des rainures de forme Gaussienne de taille nanométrique ont un comportement électrostatique similaire à celles des cavités rectangulaires, notamment une réflectivité spéculaire très faible en condition de résonance. Les performances actuelles des ordinateurs limitent cependant les études à des réseaux de petite période. Afin de dépasser ces limitations, on a fait appel à des bases de fonctions permettant de décomposer une fonction en ses parties de résolutions différentes: les ondelettes. Ce travail se conclue par une discussion sur le potentiel de deux utilisations différentes des ondelettes pour la résolution d'équation intégrales. / The framework of this thesis is the numerical simulation of the interaction of light with rough metallic surfaces which can be the origin of giant enhancements of the electromagnetic field due to plasmonic resonances. The abrupt profile of these surfaces have characteristic sizes of a few nanometers of width and a few tens of nanometers of height. The main difficulty in the simulation of such phenomena is in the scale difference of the wavelength of the incident wave and the size of the roughness as well as the abrupt variations of the magnetic field at the surface. A suited method of simulation is the numerical resolution of surface integral equations for periodic profile of the surface. This method was implemented in C++ and the main part of this work was the calculation of the pseudo-periodic Green function. The intensity of the refracted beam and that of the electromagnetic field maps are rigorously calculated from the obtained solution. We showed by applying this method that plasmonic resonances situated in the cavity of gratings with Gaussian shaped grooves of nanometric sizes have an electrostatic behaviour similar to that of the rectangular grooves, in particular, a very low specular reflectivity at the resonance. The current performances of computers limit the studies to gratings with a small period. In order to overcome these limitations, we considered a function basis enabling to decompose a functions into its components of different resolutions: the wavelets. This work ends with a discussion on the potential of two different applications of the wavelets to the resolution of integral equations.

Les plasmons de surface (SP) sont des modes du champ électromagnétique confinés à l'interface entre un métal et un diélectrique. De par leur nature hybride, les SP permettent de concentrer et manipuler la lumière à des échelles sub-longueur d'onde. Ces propriétés sans précédent suscitent un grand intérêt, en particulier pour le transport et le traitement de l'information quantique mais aussi pour le contrôle de l'émission spontanée d'émetteurs fluorescents. Les études présentées dans ce manuscrit s'intéressent au couplage de nanostructures plasmoniques avec des nanoparticules luminescentes. L'outil utilisé est un microscope optique en champ proche (SNOM) dans lequel la nano-source de lumière est un nano-objet fluorescent attaché en bout de pointe (sonde active). Cette technique permet à la fois d'augmenter la résolution théorique accessible en SNOM mais aussi de positionner la sonde avec une précision nanométrique et de l'exciter directement grâce à la lumière laser injectée dans la fibre optique. En utilisant uniquement la lumière émise par l'objet, ces pointes ouvrent la voie à des études originales en nano-optique et en plasmonique. Dans ce travail de thèse, deux aspects distincts ont été abordés. D'une part, nous avons étudié les propriétés des plasmons de surface dans le régime de la plasmonique quantique en utilisant pour cela une sonde active fabriquée à base d'un émetteur de photons uniques, le centre NV (nitrogen-vacancy) contenu dans les nano-diamants. Les résultats fondamentaux obtenus sur ce système permettent d'envisager de nombreuses expériences en plasmonique quantique. D'autre part, le travail de développement des sondes actives à base de nanocristaux de YAG (yttrium-aluminum garnet) dopés au cérium a été poursuivi. Ces sondes nous ont permis de démarrer de nouvelles études sur les résonances plasmoniques localisées de particules colloïdales en or. / Surface plasmons (SPs) are modes of the electromagnetic field confined at the interface between a metal and a dielectric. Due to their hybrid nature, the SPs can be used to concentrate and handle light on subwavelength scales. These unprecedented properties draw great interest, in particular for quantum information transport and processing and also for the control of spontaneous emission of fluorescent emitters. The studies presented in this manuscript report the coupling of plasmonic nanostructures with luminescent nanoparticles. The tool we use is a scanning near-field optical microscope (SNOM), in which the nano-source of light is a fluorescent nano-object attached at the end of the probe (active tip). This technique allows not only to reach a better optical resolution in SNOM but also to position the nano-emitter with a nanometre precision and to excite it directly thanks to the laser light injected into the optical fibre. By using only the light emitted by the object, these tips open the way to original studies in nano-optics and plasmonics. In this work, two distinct aspects were studied. First, we studied the properties of the SPs in the quantum plasmonics regime. For this purpose, we used an active tip based on single photons emitters which are the NV centres (nitrogen-vacancy centre) hosted in nanodiamonds. The fundamental results obtained on this system make it possible to consider many other quantum plasmonics experiments. In addition, a different type of active tips based on Cerium-doped YAG (yttrium-aluminum garnet) nanoparticules was developed. These probes allow us to start new studies on localised plasmonic resonances in colloidal gold particles.

Cette thèse porte sur la manipulation du moment angulaire de la lumière à l'échelle sub-micronique. Le moment angulaire total de la lumière est composé d'une partie de spin, relié au degré de liberté de polarisation circulaire de la lumière, et d'une partie orbitale, relié au degré de libertés spatiaux de la lumière que sont sa direction de propagation (locale et globale) et sa distribution spatiale d'intensité. Le couplage spin-orbite existant entre ces deux contributions permet alors de manipuler les degrés de libertés spatiaux de la lumière par un simple contrôle de son état de polarisation circulaire. Dans cette thèse, nous avons étudié et exploité ce couplage à l'échelle sub-micronique dans deux nouveaux phénomènes que nous avons mis en évidence. Le premier met à profit ce couplage pour permettre d'exciter de manière unidirectionnelle des modes plasmoniques guidés. Une étude complète (numérique, expérimentale et analytique) de ce phénomène nouveau, basé sur un couplage entre le moment de spin du photon incident et le moment orbital extrinsèque des modes plasmoniques guidés dans la courbure d'un guide, est présentée. La deuxième étude présente une voie pour tirer parti du transfert de moment orbital de la lumière à un gaz d'électrons libres dans un métal afin de générer et contrôler le sens et la géométries de boucles de courants sub-microniques dans des structures métalliques. Ce contrôle permettrait la génération d'optomaimants nanométriques, entièrement contrôlés par la lumière, pouvant être modulés aux fréquences optiques. Ce travail a été soutenu par le LABEX Action. / This thesis focuses on the manipulation of the angular momentum of light at the nanoscale.The total angular momentum of light is composed of a spin component, connected to the polarization degree of freedom of light, and an orbital component, related to the spatial degrees of freedom of the light which are its propagation direction (local and global) and its intensity distribution. The spin-orbit coupling between these two contributions allows the control of the spatial degrees of freedom of light by a simple manipulation of its circular polarization state. In this thesis, we have studied and applied this coupling at the nanoscale anbd we have highlighted two new phenomenas. The first one takes part of this coupling to allows unidirectional excitation of plasmonic guided modes. A complete study (numerical, experimental and analytical) of this new phenomenon, based on a coupling between the spin of the incident photon and the extrinsic orbital momentum of the plasmonic guided modes within the curvature of a waveguide, is presented. The second study propose a way to benefit from the transfer of the angular momentum of light to the free electrons gas in a metal to generate and control the direction and the geometry of nanoscale current loops in metallic structures. this control would at optical frequencies. This work was supported by the LABEX Action.

Le contrôle des ondes électromagnétiques joue un rôle fondamental dans les technologies photoniques actuelles. De nos jours, on assiste à une demande croissante de composants agiles capable d'absorber efficacement les ondes électromagnétiques dans divers gamme de fréquences. Habituellement, ces absorbeurs s'appuient sur les résonances plasmoniques qui apparaissent dans les métaux nobles dans la gamme visible. Cependant, l'extension des propriétés plasmoniques aux spectres infrarouge et THz nécessite des matériaux adéquats ayant un comportement métallique à ces fréquences. Dans ce travail, nous étudions numériquement et expérimentalement les structures métal-isolant-métal (MIM) réalisées à partir de semi-conducteur hautement dopé Si: InAsSb qui a un comportement métallique dans la gamme infrarouge. Dans la deuxième partie, nous avons amélioré l'efficacité des résonateurs MIM en utilisant des métamatériaux hyperboliques qui miniaturisent les résonateurs. Dans la dernière partie, nous proposons un design universel ultra-mince qui permet de dépasser les contraintes associées au choix des matériaux et permettant la réalisation d'un absorbeur fonctionnant sur une gamme spectrale allant de l'infrarouge aux micro-onde. / The control of light absorbance plays a fundamental role in today's photonic technologies. And the urge to design and develop flexible structures that can absorb electromagnetic waves is very growing these days. Usually, these absorbers relies on plasmonic resonances that arise in noble metals in the visible range. However, the extension of the plasmonic properties to the infrared and THz spectra requires adequate materials that have a metallic behavior at these frequencies. In this work, we study numerically and experimentally the metal-insulator-metal (MIM) structures realized from highly doped semiconductor Si:InAsSb that has a metallic behavior in the infrared range. In the second, part we improved the efficiency of the MIM resonators by using hyperbolic metamaterials that also miniaturize the resonators. In the last part, we propose an ultra-thin universal design that overcomes the material barrier so that the total absorption can be achieved for different spectral ranges without changing the material.

L’exaltation de fluorescence par un métal est de plus en plus utilisée pour augmenter la sensibilité de détection dans les systèmes utilisant la fluorescence. Au cours de ce travail de thèse, nous avons étudié ce phénomène dans des nanoparticules hybrides Métal@SiO2 possédant des émetteurs de fluorescence immobilisés sur la silice. Dans un premier temps, nous avons élaboré les nanoparticules cœur-coquille Métal@SiO2 (Métal = Au ou Ag) en utilisant différentes méthodes et en les comparant pour choisir la plus adaptée selon le diamètre du cœur métallique. Dans un deuxième temps, nous avons étudié les propriétés de fluorescence exaltée des nanoparticules hybrides. Deux types d’émetteurs de fluorescence ont été sélectionnés : des nanoparticules semi-conductrices (SiC) et des fluorophores organiques (cyanine 3 et fluorescéine). Après fonctionnalisation de la silice, les émetteurs de fluorescence ont été greffés à la surface des nanoparticules Métal@SiO2. L’exaltation de leur fluorescence a été analysée en fonction de leur densité surfacique, de leur distance par rapport au cœur métallique (fixée par l’épaisseur de silice), du diamètre du cœur métallique et de la longueur d’onde d’excitation. Le facteur d’exaltation le plus important (de l’ordre de 103) a été obtenu avec une faible épaisseur de silice (10 nm) pour les nanoparticules de SiC dont le rendement quantique intrinsèque est très faible (inférieur à 1%). Enfin, la surface de nanoparticules hybrides a été fonctionnalisée avec des nanoparticules d’oxyde de fer de manière à obtenir une combinaison de propriétés optiques (fluorescentes et plasmoniques) et magnétiques à l’intérieur d’une même nanoparticule hybride. / For the past decade, metal-enhanced fluorescence (MEF) has attracted much attention as it improved the sensitivity of fluorescence detection. In this work, MEF was investigated in hybrid Metal@SiO2 nanoparticles with fluorescent emitters immobilized onto silica. In the first part, core-shell Metal@SiO2 (Metal = Au or Ag) nanoparticles were elaborated and several elaboration methods were compared. A comparison was given in order to choose the most suitable method depending on metal core diameter. The second part was dedicated to MEF properties of hybrid nanoparticles. Two kinds of fluorescent emitters were selected: quantum dots (SiC) and organic dyes (cyanine 3 and fluorescein). After silica surface modification, fluorescent emitters were linked to Metal@SiO2 nanoparticles. MEF phenomenon was investigated by tuning the distance between metal and fluorescent emitter (fixed by silica thickness), metal diameter, the fluorescent emitter surface density, and the excitation wavelength. The highest enhancement factor (almost 103) was obtained for a low silica thickness (10 nm) with SiC nanoparticles whose intrinsic quantum yield is very low (lower than 1%). Finally, we functionalized the surface of hybrid nanoparticles with iron oxide nanoparticles to obtain a combination of optical (fluorescence and plasmonics) and magnetic properties inside one hybrid nanoparticle.

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.

The nature of surface-enhanced Raman scattering (SERS) on nanostructured surfaces is explored using both inorganic and organic-based systems and a variety of environmental perturbation mechanisms. Experimental optical characterisation systems are developed and existing systems extended to facilitate this exploration. SERS of inorganic semiconducting quantum dots (QDs) is observed for the first time, paving the way for their use as spatially well-defined SERS markers. Tuning of the Raman excitation wavelength allows comparison between resonance and nonresonance QD SERS and identifies enhancement due to the plasmonic nanostructure. A gentle mechano-chemical process (carbon dioxide snow jet) is used to rearrange adsorbed organic thiol monolayers on a gold plasmonic nanostructure. The necessity of nanoscale roughness to the large SERS enhancement on pit-like plasmonic nanostructures is shown and demonstrates a new method to boost SERS signals (> 500 %) on plasmonic nanostructures. A multiplexed time-varied exposure technique is developed to track this molecular movement over time and highlights the different origins of the SERS peak and its accompanying background continuum. Using low-temperature cryogenics (down to 10 K) the SERS peak and background continuum intensity are shown to increase as the plasmonic metal damping reduces with temperature. Temperature dependent measurements of QD (resonance) SERS are shown to have strong wavelength dependence due to the excitonic transitions in QDs. Changes to the QD fluorescence at low temperature allows striking comparison between the Raman and fluorescence processes. The role of charge transfer and electromagnetic enhancement in the SERS intensity of p-aminothiophenol (pATP) is investigated on nanostructured plasmonic surfaces coupled to metallic nanoparticles. The results support the importance of charge transfer effects to the SERS of pATP, and highlight the difference between those of electromagnetic origin. Addition of nanoparticles to the nanostructured surface was seen to enhance SERS signals by up to 100×.

The region between the infrared and microwave region in the electromagnetic spectrum, the Terahertz (THz) gap, provides an exciting opportunity for future wireless communications as this band has been under utilised. This doctoral work takes a two-pronged approach into closing the THz gap with low-dimensional materials. The first attempt addresses the need for a compact THz source that can operate at room temperature. The second approach addresses the need to build optical elements such as filters and modulators in the THz spectrum. Terahertz quantum cascade lasers (THz QCLs) are one of the most compact, powerful sources of coherent radiation that bridge the terahertz gap. However, their cryogenic requirements for operation limit the scope of the applications. This is because of the electron-electron scattering and heating of the 2-dimensional free electron gas which leads to significant optical phonon scattering of the hot electrons. Theoretical studies in laterally confined QCL structures have predicted enhanced lifetime of the upper state through suppression of the non-radiative intersubband relaxation of carriers, which leads to lower threshold, and higher temperature performance. Lithographically defined vertical nanopillar arrays with electrostatic radius less than tens of nm offer a possible route to achieve lateral confinement, which can be integrated into QCL structures. A typical gain medium in a QCL consists of at least 100 repeat periods, with a thickness of 6-14 micron. For practical implementation of the top-down approach, restrictions are imposed by aspect ratios that can be achieved in present dry-etching systems. Typically, for sub-200 nm radius pillars, the thickness ranges from 1-3.5 micron. It is therefore necessary to work with THz QCLs based on 3-4 quantum well active regions, so as to maximise the number of repeat periods (hence gain) within an ultra-thin active region. After an introductory chapter, Chapter 2 presents a theoretical treatise on the realistic electrostatic potential in a lithographically defined nanopillar by scaling from a single quantum well (resonant tunnelling diode) to a THz QCL. Chapter 2 also discusses, the effect of lateral confinement on the intersubband states and the plasmonic mode in a THz QCL. One of the key experimental challenges in scaling down from QCLs to quantum-dot cascade lasers is the electrical injection into the nanopillars. This involves insulation and planarisation of the high aspect-ratio nanopillar arrays. Furthermore, the choice of the planarising layer is critical since it determines the loss of any optical mode. This experimental challenge is solved in Chapter 3. Chapter 4 presents the electro-optic performance of low-repeat period QCLs with an active region thickness that is less than 3.5 micron. Another topic of recent interest in the THz optics community is plasmonics in graphene. This is because the bound electromagnetic modes (plasmons) are tightly confined to the surface and can also be tuned with carrier concentration. Plasmonic resonance at terahertz frequencies can be achieved by gating graphene grown via chemical vapour deposition (CVD) to a high carrier concentration. THz time domain spectroscopy of such gated monolayer graphene shows resonance features around 1.6 THz superimposed on the Drude-like frequency response of graphene which may be related to the inherent poly-crystallinity of CVD graphene. Chapter 5 discusses these results, as an understanding of these features is necessary for the development of future THz optical elements based on CVD graphene. Chapter 5 finally describes how the gate tunability of THz transmission through graphene can be exploited to indirectly modulate a THz QCL. Chapter 6 presents ideas from this doctoral work, which can be developed in future to address the issues of enhanced temperature performance of THz QCLs and to realise realistic THz devices based on graphene.