O espalhamento de ondas eletromagnéticas por partículas isoladas, com propriedades ópticas e formatos arbitrários, encontra aplicações nas mais diversas áreas do conhecimento. Usualmente, o espalhamento eletromagnético é investigado via grandezas auferidas na região de campo distante. Para partículas inomogêneas, no entanto, as ressonâncias nas seções de choque de espalhamento podem não corresponder a um aumento de intensidade do campo eletromagnético nas vizinhanças imediatas da partícula (região de campo próximo). Esse efeito pode ser induzido em nanopartículas dielétricas com revestimentos plasmônicos e foi recentemente explicado em termos da ressonância de Fano. Essa ressonância resulta da interferência entre um modo eletromagnético não ressonante (processo de fundo) e um modo discreto ressonante (ressonância de plásmon), produzindo um formato assimétrico de linha espectral. Para o entendimento de como os modos de superfície no campo próximo acoplam-se às ressonâncias nas seções de choque, é necessário o cálculo de funcionais dos campos eletromagnéticos internos às partículas ou em suas vizinhanças imediatas. Neste estudo, calculamos a energia eletromagnética no interior de centros espalhadores nas geometrias esférica e cilíndrica. Fazemos aqui o vínculo dos campos internos às grandezas de espalhamento no campo distante via seção de choque de absorção e conservação de energia. Aplicamos nossos resultados a metamateriais dispersivos, estudando as propriedades do espalhamento por esferas revestidas e por esferas quirais, no regime de refração negativa, e por cilindros revestidos sob incidência oblíqua de radiação. Mediante a energia interna às partículas, demonstramos novos efeitos de aumento de intensidade de campo interno fora da ressonância de espalhamento e fornecemos resultados analíticos para a análise dessas ressonâncias, tanto em espalhamento simples quanto múltiplo. / Electromagnetic wave scattering by single particles with both shapes and optical properties arbitrary finds applications in several areas of knowledge. Usually, the electromagnetic scattering is investigated via measured quantities in the far-field region. However, for inhomogeneous particles, resonances in scattering cross sections may not correspond to the electromagnetic field enhancement in the vicinity of a particle (near-field). This effect can be induced in dielectric nanoparticles with plasmonic coatings, and it has recently been explained in terms of the Fano resonance. The Fano resonance results from the interference between a non-resonant electromagnetic mode (background or continuous) and a resonant discrete mode (localized plasmon resonance), leading to an asymmetric lineshape. To understand how the surface modes in the near-field are connected to the cross section resonances, functionals of the electromagnetic fields within scatterers or in their vicinity are required. In this study, we calculate the electromagnetic energy inside scatterers in both cylindrical and spherical geometries. We obtain a connection between the internal energy and the scattering quantities in the far-field via absorption cross section and energy conservation. We apply our results to dispersive metamaterials, studying scattering properties of coated and chiral spheres in the negative refraction regime, and coated cylinders under oblique incidence of radiation. By the electromagnetic energy inside particles, we demonstrate new off-resonance field enhancement effects and provide analytical tools to analyze these resonances in both single and multiple scattering regimes.

O espalhamento de ondas eletromagnéticas por partículas isoladas, com propriedades ópticas e formatos arbitrários, encontra aplicações nas mais diversas áreas do conhecimento. Usualmente, o espalhamento eletromagnético é investigado via grandezas auferidas na região de campo distante. Para partículas inomogêneas, no entanto, as ressonâncias nas seções de choque de espalhamento podem não corresponder a um aumento de intensidade do campo eletromagnético nas vizinhanças imediatas da partícula (região de campo próximo). Esse efeito pode ser induzido em nanopartículas dielétricas com revestimentos plasmônicos e foi recentemente explicado em termos da ressonância de Fano. Essa ressonância resulta da interferência entre um modo eletromagnético não ressonante (processo de fundo) e um modo discreto ressonante (ressonância de plásmon), produzindo um formato assimétrico de linha espectral. Para o entendimento de como os modos de superfície no campo próximo acoplam-se às ressonâncias nas seções de choque, é necessário o cálculo de funcionais dos campos eletromagnéticos internos às partículas ou em suas vizinhanças imediatas. Neste estudo, calculamos a energia eletromagnética no interior de centros espalhadores nas geometrias esférica e cilíndrica. Fazemos aqui o vínculo dos campos internos às grandezas de espalhamento no campo distante via seção de choque de absorção e conservação de energia. Aplicamos nossos resultados a metamateriais dispersivos, estudando as propriedades do espalhamento por esferas revestidas e por esferas quirais, no regime de refração negativa, e por cilindros revestidos sob incidência oblíqua de radiação. Mediante a energia interna às partículas, demonstramos novos efeitos de aumento de intensidade de campo interno fora da ressonância de espalhamento e fornecemos resultados analíticos para a análise dessas ressonâncias, tanto em espalhamento simples quanto múltiplo. / Electromagnetic wave scattering by single particles with both shapes and optical properties arbitrary finds applications in several areas of knowledge. Usually, the electromagnetic scattering is investigated via measured quantities in the far-field region. However, for inhomogeneous particles, resonances in scattering cross sections may not correspond to the electromagnetic field enhancement in the vicinity of a particle (near-field). This effect can be induced in dielectric nanoparticles with plasmonic coatings, and it has recently been explained in terms of the Fano resonance. The Fano resonance results from the interference between a non-resonant electromagnetic mode (background or continuous) and a resonant discrete mode (localized plasmon resonance), leading to an asymmetric lineshape. To understand how the surface modes in the near-field are connected to the cross section resonances, functionals of the electromagnetic fields within scatterers or in their vicinity are required. In this study, we calculate the electromagnetic energy inside scatterers in both cylindrical and spherical geometries. We obtain a connection between the internal energy and the scattering quantities in the far-field via absorption cross section and energy conservation. We apply our results to dispersive metamaterials, studying scattering properties of coated and chiral spheres in the negative refraction regime, and coated cylinders under oblique incidence of radiation. By the electromagnetic energy inside particles, we demonstrate new off-resonance field enhancement effects and provide analytical tools to analyze these resonances in both single and multiple scattering regimes.

Neste trabalho, estudamos a influência de canais de espalhamento inelástico no transporte eletrônico. Primeiramente, expomos o formalismo de Landauer usual para o cálculo da corrente elétrica em sistemas em que o espalhamento é puramente elástico. Como exemplo, calculamos a corrente para um potencial delta de Dirac a partir de suas probabilidades de transmissão. A amostra correspondente é aquela de uma camada muito fina com impurezas (não-magnéticas) contida em uma heterostrutura semicondutora. Mostramos que a distorção do potencial quântico devido à voltagem aplicada pode ser desprezada no cálculo da corrente elétrica, abaixo da energia de Fermi do emissor. Subsequentemente, acoplamos o potencial delta a um oscilador harmônico quântico para modelar a presença de fônons no sistema. Encontramos modos inelásticos de transmissão que se tornam acessíveis para energias cada vez maiores, múltiplas do quantum hω. Devido à conservação de probabilidade, a abertura de cada novo canal corresponde a bicos\" nas probabilidades de transmissão dos modos abaixo deste, em função da energia de incidência do elétron. No caso de uma delta atrativa, ressonâncias assimétricas com perfil de Fano são observadas. Adaptamos o formalismo de Landauer, incluindo canais inelásticos independentes. Seguindo um trabalho anterior de Emberly e Kirczenow (2000), mostramos que existe uma forma de se levar em conta possíveis coincidências nos estados de espalhamento finais aplicando o princípio de exclusão de Pauli. Isto leva as distribuições dos estados de espalhamento a estarem fora de equilíbrio, já que dependem umas das outras. Resolvendo o problema auto-consistentemente, somos capazes de obter a corrente elétrica a partir das probabilidades de transmissão do potencial quântico. Nossos resultados demonstram que as ressonâncias de Fano do potencial atrativo dão origem a uma diminuição da inclinação da corrente elétrica contra a voltagem aplicada, já que elétrons são presos\" ao potencial por um tempo infinito. Mostramos este efeito num regime de voltagens baixas em comparação com a energia de Fermi, para o qual desprezamos a distorção do potencial quântico devido à voltagem aplicada. Além disso, uma comparação com os resultados do formalismo de Landauer mostra que uma discrepância significativa é observada para o caso de o oscilador estar inicialmente excitado e fortemente acoplado ao elétron. / In this work, we study the influence of inelastic scattering channels in electronic transport. We first present the usual Landauer formalism, for calculating the electric current in systems where the scattering is purely elastic. As an example, we calculate the current for a Dirac delta potential from its transmission probabilities. The corresponding sample is that of a very thin layer with (non-magnetic) impurities within a semiconductor heterostructure. We show that the distortion of the quantum potential due to the applied voltage can be ignored in the calculation of an electric current below the Fermi energy of the emitter. Then we couple the delta potential to a quantum harmonic oscillator to model the presence of phonons in the system. We find inelastic transmission modes that become available for increasing energies, multiple of the quantum hω. Due to conservation of probability, the opening of each new channel corresponds to kinks\" in the transmission probabilities of lower modes as a function of the energy of the impinging electrons. In the case of an attractive delta potential, asymmetric resonances with a Fano-like profile are observed. We adapt the Landauer formalism by including the independent inelastic channels. Following a previous work by Emberly and Kirczenow (2000), we show that there is a way to take into account the possible coincidences in the final scattering states using Pauli\'s exclusion principle. This causes the distributions of the scattering states to be out of equilibrium, as they depend on each other. Solving the problem self-consistently, we are able to obtain the electric current from the transmission probabilities of the quantum potential. Our results demonstrate that the Fano resonances of the attractive potential gives rise to a decrease of the slope in the electric current versus the applied voltage, as the electrons are trapped\" in the potential for a finite amount of time. We have shown this effect in a low voltage regime with respect to the Fermi energy, for which we ignore the distortion of the quantum potential due to the applied voltage. Furthermore, a comparison with the results from the Landauer formalism shows that a significant discrepancy is seen for the oscillator initially in its excited mode and strongly coupled to the electron.

Cette thèse a porté sur les principes de guidage, les propriétés linéaires et les outils de conception autour des fibres à cristal photonique à coeur creux (HC-PCF) à couplage inhibé (IC). Le guidage IC a été démontré comme une manifestation photonique de Q-BiC (état quasi lié dans un continuum) en étudiant des profils asymétriques et dépendants en polarisation dit Fano présentant une bande passante spectrale de 30 GHz. En utilisant le concept de IC, nous reportons la caractérisation linéaire de fibres IC HC-PCF supérieures à l’état de l’art. Par une optimisation de la forme du coeur, une fibre Kagome IC HC-PCF a démontré des pertes très faibles de 8,5 dB/km à 1030 nm associées à une bande passante à 3 dB de 225 nm. Une autre conception avec des entretoises de silice amincies à 300 nm a permis d’atteindre des pertes de 30 dB/km à 780 nm avec une bande de transmission fondamentale record décalée à 670 nm et capable de couvrir toutes les gammes spectrales du Ti:Sa, Yb et Er. Nous avons également travaillé sur la conception et la fabrication de IC HC-PCF présentant une gaine dont la structure est un réseau unique de tubes fins isolés. Une de ces fibres a permis de démontrer une transmission jusqu'à 220 nm avec des pertes records de 7,7 dB/km à ~ 750 nm, tandis qu’une seconde réalisation s’est traduit par une bande fondamentale de plus d’une octave allant de 600 à 1200 nm avec des pertes de 10-20 dB/km. Finalement, cette dernière fibre a été étudiée plus en détail pour déterminer les sources à l’origine des pertes due à la rugosité de surface présente à l’interface du contour du coeur. / This thesis reported on guiding principles, linear properties and conceptual design tools of inhibited coupling (IC) guiding hollow-core photonic crystal fibers (HC-PCF). IC guidance was proved as photonic manifestation of Q-BiC (quasi bound-state-in-a-continuum) by investigating asymmetric and polarization dependent Fano profiles with bandwidth of 30 GHz in high resolution transmission spectra. By using IC design concept, we reported on linear characterization of state-of-the-art IC HC-PCFs. Based on core shaping optimization, a Kagome IC HC-PCF demonstrated ultra-low loss down to 8.5 km/km at 1030 nm associated with a 225 nm wide 3-dB bandwidth. Another Kagome design with thinner silica struts of 300 nm exhibited lowest loss of 30 dB/km at 780 nm along with record level fundamental bandwidth spreading down to 670 nm and able to cover the entire Ti:Sa, Yb and Er laser spectral ranges. We also reported on design and fabrication of single-ring tubular lattice IC HC-PCFs. One of these fibers demonstrated transmission down to 220 nm with a record transmission loss of 7.7 dB/km at ~750 nm, while the second one exhibited ultra-broad fundamental band with loss range of 10-20 dB/km over one octave spanning from 600 to 1200 nm. Finally, the second tubular fiber was further investigated for fundamental loss sources due to surface roughness around its core-contour.

Floquet’s theorem, a temporal analogue of Bloch’s theorem, is used for studying a time-dependent potential. With applications in cold atoms on optical lattices, quantum dots and more, there is a growing interest in Floquet engineering exotic materials and phases. By solving the time-dependent Schrödinger equation scattering amplitudes are derived from which the transmission spectrum are generated. The driving field induces Floquet sidebands into which the particle can inelastically scatter. Fano resonances are observed when the incoming particle and a bound state of the staticpotential differ by some energy quanta. This process is mediated by the driving field. The scattering matrix and transmission spectra are reproduced from previous work on electron gas, graphene, and a semi-metal admitting a point of quadratic band touching (QBT). The QBT system is extended with linear tilting along the potential, which proves to be another good quantum number for tunable control.

Light interaction with matter has long been an area of interest throughout history, spanning many fields of study. In recent decades, the investigation of light-matter interactions with nanostructures has become an intense area of research in the field of photonics. Metallic nanostructures, in particular, are of interest due to the interesting properties that arise when interacting with light. The properties are a result of the excitation of surface plasmons which are the collective oscillation of the conduction electrons in the metal. Since the conduction electrons can be thought of as harmonic oscillators, they are quantized in a similar fashion. Just as a photon is a quantum of oscillations of an electromagnetic field, the plasmon is a quantum of electron oscillations of a metal. There are three types of plasmons: 1. Bulk plasmons, also called volume plasmons, are longitudinal density fluctuations which propagate through a bulk metal with an eigenfrequency of �� called the plasma frequency. 2. Localized surface plasmons are non-propagating excitations of the conduction electrons of a metallic nanoparticle coupled to an electromagnetic field. 3. Surface plasmon polaritons are evanescent, dispersive propagating electromagnetic waves formed by a coupled state between a photon and the excitation of the surface plasmons. They propagate along the surface of a metal-dielectric interface with a broad spectrum of eigenfrequencies from � = 0 to � = ��⁄√2. iv Plasmonics is a subfield of photonics which focuses on the study of surface plasmons and the optical properties that result from light interacting with metal films and nanostructures on the deep subwavelength scale. In this thesis, plasmonic nanostructures are investigated for optical waveguides and other nanophotonic applications through computational simulations primarily base on electrodynamic theory. The theory was formulated by several key figures and established by James Clerk Maxwell after he published a set of relations which describe all classical electromagnetic phenomena, known as Maxwell’s equations. Using methods based on Maxwell’s equations, the optical properties of metallic nanostructures utilizing surface plasmons is explored. In Chapter 3, light propagation of bright and dark modes of a partially and fully illuminated silver nanorod is investigated for waveguide applications. Then, the origin of the Fano resonance line shape in the scattering spectra of a silver nanorod is investigated. Next, in Chapter 4, the reflection and transmission of a multilayer silver film is simulated to observe the effects of varying the dielectric media between the layers on light propagation. Building on the multilayer film work, metal-insulator-metal waveguides are explored by perforating holes in the bottom layer of a two layer a silver film to investigate the limits of subwavelength light trapping, confinement, and propagation. Lastly, in Chapter 5, the effect of surface plasmons on the propagation direction of electromagnetic wave around a spherical silver nanoparticle which shows an effective negative index of refraction is examined. In addition, light manipulation using a film of silver prisms with an effective negative index of refraction is also investigated. The silver prisms demonstrate v polarization selective propagation for waveguide and optical filter applications. These studies provide insight into plasmonic mechanisms utilized to overcome the diffraction limit of light. Through better understanding of how to manipulating light with plasmonic nanostructures, further advancements in nanophotonic technologies for applications such as extremely subwavelength waveguides, sensitive optical detection, optical filters, polarizers, beam splitters, optical data storage devices, high speed data transmission, and integrated subwavelength photonic circuits can be achieved.

No description available.

Les recherches présentées dans ce mémoire ont été rendues possible grâce à la contribution financière du CRSNG, par à leur Programme de subventions à la découverte (SD) et leur Programme de bourses d’études supérieures du Canada au niveau de la maîtrise (BESC M); du FRQNT, par leur Programme de bourse de maîtrise (B1); et du CLS, par leur Graduate and Post-Doctoral Student Travel Support Program. / Le graphène est un nano-matériau très prometteur grâce à ses excellentes propriétés mécaniques, optiques et électriques. Toutefois, la plupart de ses applications les plus novatrices requièrent de l'altérer, mais la compréhension du graphène altéré est encore limitée. Certaines applications envisagées sont en optique infrarouge. Or, notre compréhension actuelle du graphène ne permet pas d’expliquer l’apparition des pics infrarouges qui sont observés dans les bicouches et dans les monocouches fonctionnalisées. Le comportement du graphène fonctionnalisé est particulièrement contre-intuitif, puisque l’ajout de greffons le rend plus transparent, et non pas plus opaque! Un modèle proposé par Bruno Rousseau, un étudiant post-doctorant du professeur Michel Côté à l'Université de Montréal, suggère une explication à ce phénomène: bien que les phonons du graphène ne puissent pas coupler directement avec la lumière, ils coupleraient indirectement avec celle-ci grâce à des collisions sur les électrons, qui eux, peuvent coupler avec les photons. Ce couplage indirect peut produire des interférences parfois constructives, parfois destructives, de telle sorte que ce mécanisme peut autant produire des pics d’absorbance que de transparence. Dans le cadre de ce mémoire, nous avons entrepris de vérifier expérimentalement la validité de ce modèle, et nous concluons qu’il semble prédire adéquatement le comportement de l’activité infrarouge des bicouches de graphène et des monocouches fonctionnalisées. Nous avons aussi étudié les méthodes par lesquelles nous synthétisions ces différents types de graphène afin de les optimiser. Enfin, nous avons déterminé des techniques, basées sur la spectroscopie Raman, permettant de bien caractériser l’intensité de l’altération causée par ces méthodes. / Graphene is a promising nanomaterials thanks to its excellent mechanical, optical and electrical properties. However, its most innovative applications require that it be altered, but the understanding altered graphene is still limited. Some applications are considered in infrared optics. However, our current understanding of graphene does not explain the appearance of the infrared peaks that are observed in bilayers and grafted monolayers. The behaviour of grafted graphene is especially baffling, since the addition of grafts makes it more transparent, not less! A model proposed by Bruno Rousseau, a postdoctoral student of Professor Michel Côté at Université de Montréal, suggests an explanation for this phenomenon: although the phonons of graphene cannot couple directly with light, they could couple indirectly through collisions with the electrons, which can couple with photons. This indirect coupling may produce constructive and destructive interference, depending on the conditions, so this mechanism can produce absorbance peaks as much as transparency peaks. In this master’s thesis, we have undertaken to experimentally verify the validity of this model, and we conclude that it seems to adequately predict the behaviour of the infrared activity of graphene bilayers and grafted monolayers. We also studied the methods by which we synthesized these different types of graphene to optimize them. Finally, we determined techniques based on Raman spectroscopy to characterize the intensity of the alteration induced by these methods.

Les nanotubes de carbone et le graphène sont des nanostructures de carbone hybridé en sp2 dont les propriétés électriques et optiques soulèvent un intérêt considérable pour la conception d’une nouvelle génération de dispositifs électroniques et de matériaux actifs optiquement. Or, de nombreux défis demeurent avant leur mise en œuvre dans des procédés industriels à grande échelle. La chimie des matériaux, et spécialement la fonctionnalisation covalente, est une avenue privilégiée afin de résoudre les difficultés reliées à la mise en œuvre de ces nanostructures. La fonctionnalisation covalente a néanmoins pour effet de perturber la structure cristalline des nanostructures de carbone sp2 et, par conséquent, d’affecter non seulement lesdites propriétés électriques, mais aussi les propriétés optiques en émanant. Il est donc primordial de caractériser les effets des défauts et du désordre dans le but d’en comprendre les conséquences, mais aussi potentiellement d’en exploiter les retombées. Cette thèse traite des propriétés optiques dans l’infrarouge des nanotubes de carbone et du graphène, avec pour but de comprendre et d’expliquer les mécanismes fondamentaux à l’origine de la réponse optique dans l’infrarouge des nanostructures de carbone sp2. Soumise à des règles de sélection strictes, la spectroscopie infrarouge permet de mesurer la conductivité en courant alternatif à haute fréquence des matériaux, dans une gamme d’énergie correspondant aux vibrations moléculaires, aux modes de phonons et aux excitations électroniques de faible énergie. Notre méthode expérimentale consiste donc à explorer un espace de paramètres défini par les trois axes que sont i. la dimensionnalité du matériau, ii. le potentiel chimique et iii. le niveau de désordre, ce qui nous permet de dégager les diverses contributions aux propriétés optiques dans l’infrarouge des nanostructures de carbone sp2. Dans un premier temps, nous nous intéressons à la spectroscopie infrarouge des nanotubes de carbone monoparois sous l’effet tout d’abord du dopage et ensuite du niveau de désordre. Premièrement, nous amendons l’origine couramment acceptée du spectre vibrationnel des nanotubes de carbone monoparois. Par des expériences de dopage chimique contrôlé, nous démontrons en effet que les anomalies dans lespectre apparaissent grâce à des interactions électron-phonon. Le modèle de la résonance de Fano procure une explication phénoménologique aux observations. Ensuite, nous établissons l’existence d’états localisés induits par la fonctionnalisation covalente, ce qui se traduit optiquement par l’apparition d’une bande de résonance de polaritons plasmons de surface (nanoantenne) participant au pic de conductivité dans le térahertz. Le dosage du désordre dans des films de nanotubes de carbone permet d’observer l’évolution de la résonance des nanoantennes. Nous concluons donc à une segmentation effective des nanotubes par les greffons. Enfin, nous montrons que le désordre active des modes de phonons normalement interdits par les règles de sélection de la spectroscopie infrarouge. Les collisions élastiques sur les défauts donnent ainsi accès à des modes ayant des vecteurs d’onde non nuls. Dans une deuxième partie, nous focalisons sur les propriétés du graphène. Tout d’abord, nous démontrons une méthode d’électrogreffage qui permet de fonctionnaliser rapidement et à haute densité le graphène sans égard au substrat. Par la suite, nous utilisons l’électrogreffage pour faire la preuve que le désordre active aussi des anomalies dépendantes du potentiel chimique dans le spectre vibrationnel du graphène monocouche, des attributs absents du spectre d’un échantillon non fonctionnalisé. Afin d’expliquer le phénomène, nous présentons une théorie basée sur l’interaction de transitions optiques intrabandes, de modes de phonons et de collisions élastiques. Nous terminons par l’étude du spectre infrarouge du graphène comportant des îlots de bicouches, pour lequel nous proposons de revoir la nature du mécanisme de couplage à l’œuvre à la lumière de nos découvertes concernant le graphène monocouche. / Carbon nanotubes and graphene are sp2 hybridized carbon nanostructures which electrical and optical properties raise considerable interest for the design of a new generation of electronic devices and optically active materials. However, many challenges remain before their implementation in industrial processes on a large scale. Materials chemistry, especially covalent functionalization, is a privileged avenue to resolve the difficulties related to the processing of these nanostructures. Covalent functionalization, however, disrupts the sp2 carbon nanostructures’ crystalline structure, and pertubs not only said electrical properties, but also the deriving optical properties. It is therefore essential to characterize the effects of defects and disorder in order to understand their consequences, but also to potentially exploit the benefits. This thesis deals with the optical properties in the infrared of carbon nanotubes and graphene, with the aim to understand and explain the fundamental mechanisms at the origin of the optical response in the infrared of sp2 carbon nanostructures. Subject to strict selection rules, infrared spectroscopy measures the high frequency AC conductivity of materials in an energy range corresponding to molecular vibrations, phonon modes and low energy electronic excitations. Our experimental method is therefore to explore a parameter space defined by the three axes that are i. the dimensionality of the material, ii. the chemical potential, and iii. the disorder level, which allows us to identify the various contributions to optical properties in the infrared of sp2 carbon nanostructures. At first, we focus on the infrared spectroscopy of single-walled carbon nanotubes as a function of doping and disorder level. We start by amending the commonly accepted origin of single-walled carbon nanotubes vibrational spectra. Using controlled chemical doping experiments, we show that the anomalies in the carbon nanotube spectra appear through electron-phonon interactions. The Fano resonance model provides a phenomenological explanation for the observations. Then, we establish the existence of localized states induced by covalent functionalization, which appear as a surface plasmon polariton resonance (nanoantenna) contributing to the terahertz conductivity peak. Control of the disorder level in carbon nanotube films allows us to observe the evolution of the nanoantenna resonance. We therefore conclude to an effective segmentation of the nanotubes by the grafts. Finally, we show that disorder activates phonon modes that are usually forbidden by infrared spectroscopy’s selection rules. Disorder-induced infrared activity originates from elastic collisions on defects that give access to phonon modes with non-zero wave vectors. In a second part, we focus on the properties of graphene. First, we demonstrate an electrografting method to rapidly functionalize graphene with high-density, regardless of the substrate. Subsequently, we use electrografting to show that disorder activates chemical potential dependent anomalies in the vibrational spectra of single-layer graphene. These anomalies are absent in the spectra of pristine samples. In order to explain this phenomenon, we present a theory based on the interaction of intraband optical transitions, phonon modes and elastic collisions. We conclude by studying the infrared spectra of graphene with bilayer islands, for which we propose to review the nature of the coupling mechanism in the light of our findings on single-layer graphene.

Les nanotubes de carbone et le graphène sont des nanostructures de carbone hybridé en sp2 dont les propriétés électriques et optiques soulèvent un intérêt considérable pour la conception d’une nouvelle génération de dispositifs électroniques et de matériaux actifs optiquement. Or, de nombreux défis demeurent avant leur mise en œuvre dans des procédés industriels à grande échelle. La chimie des matériaux, et spécialement la fonctionnalisation covalente, est une avenue privilégiée afin de résoudre les difficultés reliées à la mise en œuvre de ces nanostructures. La fonctionnalisation covalente a néanmoins pour effet de perturber la structure cristalline des nanostructures de carbone sp2 et, par conséquent, d’affecter non seulement lesdites propriétés électriques, mais aussi les propriétés optiques en émanant. Il est donc primordial de caractériser les effets des défauts et du désordre dans le but d’en comprendre les conséquences, mais aussi potentiellement d’en exploiter les retombées. Cette thèse traite des propriétés optiques dans l’infrarouge des nanotubes de carbone et du graphène, avec pour but de comprendre et d’expliquer les mécanismes fondamentaux à l’origine de la réponse optique dans l’infrarouge des nanostructures de carbone sp2. Soumise à des règles de sélection strictes, la spectroscopie infrarouge permet de mesurer la conductivité en courant alternatif à haute fréquence des matériaux, dans une gamme d’énergie correspondant aux vibrations moléculaires, aux modes de phonons et aux excitations électroniques de faible énergie. Notre méthode expérimentale consiste donc à explorer un espace de paramètres défini par les trois axes que sont i. la dimensionnalité du matériau, ii. le potentiel chimique et iii. le niveau de désordre, ce qui nous permet de dégager les diverses contributions aux propriétés optiques dans l’infrarouge des nanostructures de carbone sp2. Dans un premier temps, nous nous intéressons à la spectroscopie infrarouge des nanotubes de carbone monoparois sous l’effet tout d’abord du dopage et ensuite du niveau de désordre. Premièrement, nous amendons l’origine couramment acceptée du spectre vibrationnel des nanotubes de carbone monoparois. Par des expériences de dopage chimique contrôlé, nous démontrons en effet que les anomalies dans lespectre apparaissent grâce à des interactions électron-phonon. Le modèle de la résonance de Fano procure une explication phénoménologique aux observations. Ensuite, nous établissons l’existence d’états localisés induits par la fonctionnalisation covalente, ce qui se traduit optiquement par l’apparition d’une bande de résonance de polaritons plasmons de surface (nanoantenne) participant au pic de conductivité dans le térahertz. Le dosage du désordre dans des films de nanotubes de carbone permet d’observer l’évolution de la résonance des nanoantennes. Nous concluons donc à une segmentation effective des nanotubes par les greffons. Enfin, nous montrons que le désordre active des modes de phonons normalement interdits par les règles de sélection de la spectroscopie infrarouge. Les collisions élastiques sur les défauts donnent ainsi accès à des modes ayant des vecteurs d’onde non nuls. Dans une deuxième partie, nous focalisons sur les propriétés du graphène. Tout d’abord, nous démontrons une méthode d’électrogreffage qui permet de fonctionnaliser rapidement et à haute densité le graphène sans égard au substrat. Par la suite, nous utilisons l’électrogreffage pour faire la preuve que le désordre active aussi des anomalies dépendantes du potentiel chimique dans le spectre vibrationnel du graphène monocouche, des attributs absents du spectre d’un échantillon non fonctionnalisé. Afin d’expliquer le phénomène, nous présentons une théorie basée sur l’interaction de transitions optiques intrabandes, de modes de phonons et de collisions élastiques. Nous terminons par l’étude du spectre infrarouge du graphène comportant des îlots de bicouches, pour lequel nous proposons de revoir la nature du mécanisme de couplage à l’œuvre à la lumière de nos découvertes concernant le graphène monocouche. / Carbon nanotubes and graphene are sp2 hybridized carbon nanostructures which electrical and optical properties raise considerable interest for the design of a new generation of electronic devices and optically active materials. However, many challenges remain before their implementation in industrial processes on a large scale. Materials chemistry, especially covalent functionalization, is a privileged avenue to resolve the difficulties related to the processing of these nanostructures. Covalent functionalization, however, disrupts the sp2 carbon nanostructures’ crystalline structure, and pertubs not only said electrical properties, but also the deriving optical properties. It is therefore essential to characterize the effects of defects and disorder in order to understand their consequences, but also to potentially exploit the benefits. This thesis deals with the optical properties in the infrared of carbon nanotubes and graphene, with the aim to understand and explain the fundamental mechanisms at the origin of the optical response in the infrared of sp2 carbon nanostructures. Subject to strict selection rules, infrared spectroscopy measures the high frequency AC conductivity of materials in an energy range corresponding to molecular vibrations, phonon modes and low energy electronic excitations. Our experimental method is therefore to explore a parameter space defined by the three axes that are i. the dimensionality of the material, ii. the chemical potential, and iii. the disorder level, which allows us to identify the various contributions to optical properties in the infrared of sp2 carbon nanostructures. At first, we focus on the infrared spectroscopy of single-walled carbon nanotubes as a function of doping and disorder level. We start by amending the commonly accepted origin of single-walled carbon nanotubes vibrational spectra. Using controlled chemical doping experiments, we show that the anomalies in the carbon nanotube spectra appear through electron-phonon interactions. The Fano resonance model provides a phenomenological explanation for the observations. Then, we establish the existence of localized states induced by covalent functionalization, which appear as a surface plasmon polariton resonance (nanoantenna) contributing to the terahertz conductivity peak. Control of the disorder level in carbon nanotube films allows us to observe the evolution of the nanoantenna resonance. We therefore conclude to an effective segmentation of the nanotubes by the grafts. Finally, we show that disorder activates phonon modes that are usually forbidden by infrared spectroscopy’s selection rules. Disorder-induced infrared activity originates from elastic collisions on defects that give access to phonon modes with non-zero wave vectors. In a second part, we focus on the properties of graphene. First, we demonstrate an electrografting method to rapidly functionalize graphene with high-density, regardless of the substrate. Subsequently, we use electrografting to show that disorder activates chemical potential dependent anomalies in the vibrational spectra of single-layer graphene. These anomalies are absent in the spectra of pristine samples. In order to explain this phenomenon, we present a theory based on the interaction of intraband optical transitions, phonon modes and elastic collisions. We conclude by studying the infrared spectra of graphene with bilayer islands, for which we propose to review the nature of the coupling mechanism in the light of our findings on single-layer graphene.