Longtemps cantonnées au visible et au proche IR, des nanostructures résonantes sont à présent réalisées dans l’IR, notamment en vue d'applications spectroscopiques. Pour étudier la réponse de ces nanostructures des moyens de caractérisation spécifiques doivent être mise en œuvre. Nous considérons la réponse IR de nano-structures et développons des outils à même de les caractériser. Nous nous sommes intéressés à des échantillons pouvant présenter des modes localisés de surface associés à des Plasmons Polaritons au sein de semiconducteurs fortement dopés ou des Phonons Polaritons dans des matériaux semiconducteurs polaires comme SiC. Cette étude a été menée d’abord en champ lointain (Spectroscopie à Transformée de Fourier et analyse Kramers-Kronig) pour étudier la réponse collective des nanostructures. Nous montrons que la fonction diélectrique de l’échantillon structuré peut être représentée par un oscillateur de Lorentz amortit modifié. Une permittivité effective est aussi déterminée par l’emploi de matrices de transfert pour rendre compte de la réflectivité complexe. L’étude en champ proche permet ensuite d’obtenir une réponse individuelle des structures. Nous développons ici une méthode d’extraction novatrice de l’amplitude et de la phase du signal avec un rapport signal à bruit optimum. Après avoir théoriquement et expérimentalement démontré la pertinence de l’approche, la signature de SPP localisés a pu être observée par des cartographies de champ complexe en fonction de la longueur d’onde. Les images obtenues sont confrontées à des simulations électromagnétiques et discutées / We studied the response of a nano-structured material to an IR electromagnetic excitation. For a given geometry, this response is dictated by the dielectric function to which phonons and free carriers contribute. In case of defect-free semiconductors the phonon response is the dominant term; however when we consider doped semi-conductors the plasmon response plays a major role. In both case, the permittivity functions can be negative with small losses which permits a resonant coupling between the surface modes and the electromagnetic excitation. Our work focuses on the development of experimental tools to analyze both SPP and SPhP. This study was conducted in the far-field regime to see a collective response and in the near-field regime to study nano-structures individually. In far-field, the experimental spectroscopic response of the material was conducted by Fourier Transform Infrared Reflectivity and Kramers-Kronig analysis. Quantitative information on the dielectric function was extracted using a modified Lorentz damped oscillator to fit the reflectivity. An effective permittivity is also retrieved using a transfer matrix method. The near-field study was done in a two-step procedure. The first step was the development of an innovative detection technique with optimum signal to noise ratio. The second step was the implementation of this technique to NSOM after proving its success. LSPP were detected using the developed NSOM. A spectroscopic study was performed as well. Experimental results were compared to theoretical ones obtained with electromagnetic simulations

Near-field optical microscopy has attracted remarkable attention, as it is the only technique that allows the investigation of local optical properties with a resolution far below the diffraction limit. Especially, the scattering-type near-field optical microscopy allows the nondestructive examination of surfaces without restrictions to the applicable wavelengths. However, its usability is limited by the availability of appropriate light sources. In the context of this work, this limit was overcome by the development of a scattering-type near-field microscope that uses a widely tunable free-electron laser as primary light source. In the theoretical part, it is shown that an optical near-field contrast can be expected when materials with different dielectric functions are combined. It is derived that these differences yield different scattering cross-sections for the coupled system of the probe and the sample. Those cross-sections define the strength of the near-field signal that can be measured for different materials. Hence, an optical contrast can be expected, when different scattering cross-sections are probed. This principle also applies to vertically stacked or even buried materials, as shown in this thesis experimentally for two sample systems. In the first example, the different dielectric functions were obtained by locally changing the carrier concentration in silicon by the implantation of boron. It is shown that the concentration of free charge-carriers can be deduced from the near-field contrast between implanted and pure silicon. For this purpose, two different experimental approaches were used, a non-interferometric one by using variable wavelengths and an interferometric one with a fixed wavelength. As those techniques yield complementary information, they can be used to quantitatively determine the effective carrier concentration. Both approaches yield consistent results for the carrier concentration, which excellently agrees with predictions from literature. While the structures of the first system were in the micrometer regime, the capability to probe buried nanostructures is demonstrated at a sample of indium arsenide quantum dots. Those dots are covered by a thick layer of gallium arsenide. For the first time ever, it is shown experimentally that transitions between electron states in single quantum dots can be investigated by near-field microscopy. By monitoring the near-field response of these quantum dots while scanning the wavelength of the incident light beam, it was possible to obtain characteristic near-field signatures of single dots. Near-field contrasts up to 30 % could be measured for resonant excitation of electrons in the conduction band of the indium arsenide dots.

No description available.

Nonlinearities play critical roles in regulating natural processes. Effects like nuclear fission, stimulated emission in lasers, and chaos theory all derive from nonlinearities that govern their natural systems, giving humans perspectives on their origins and impacts of their nonlinearities. Similarly, nonlinear optics can provide interesting insights into investigating and characterizing new materials. In the materials sciences, nonlinearities can be broken up into two categories: incoherent and coherent nonlinearities. I explore how incoherent and coherent nonlinear optical processes reveal the multifaceted behavior of materials at the nanoscale. Furthermore, nonlinearities are strongly tied to the increasing imaging resolutions at the nanoscale. Yet, here, I show that nonlinearities improve resolutions for imaging purposes and provide insights into the local material properties that cannot be visualized with linear optics. For the first part of the thesis, Chapter 3 explores the uniquely dynamic optical sensitivities of avalanching nanoparticles (ANPs). ANPs recently emerged as promising nanomaterial candidates for local sensing of their environments. However, extreme incoherent nonlinearities of this sort are poorly understood, necessitating a comprehensive study into the origins of nonlinearities and, particularly, heterogeneous nonlinear emissions seen in ANPs. Through systematic investigations and computational fittings of over 300+ single particle studies, ANPs demonstrated extraordinary sensitivities to their local environment, including shell thicknesses, substrate, and ligands. Nanoscale effects perturb the extremely sensitive photon avalanching effect to the point that inhomogeneities during chemical synthesis also manifest into large optical heterogeneities, with avalanching thresholds varying from 4 kW cm⁻² to 12 kW cm⁻². Shell thicknesses of 5.6 nm and greater were found to greatly passivate the ANP from environmental effects, which aligns with what other researchers have demonstrated. For the latter part of the thesis, Chapters 4 and 5 utilize parametric nonlinearities to investigate material properties of emerging layered nanosheet materials. In Chapter 4, Bismuth tellurohalides, BiTeX, were shown to contain enormous nonlinearities that increase as the fundamental field moves towards the infrared. Quantitatively, BiTeI exhibits effective second-order nonlinearities that rival other nonlinear materials (𝛸⁽²⁾_𝑒𝑓𝑓 ∼ 2 (nm/V)). Furthermore, the second-order nonlinearities measured within BiTeI play outsize roles in allowing the visualization of permanent polar domains that have only been seen with scanning probe techniques. Through rigorous rotational second harmonic generation studies and second harmonic generation microscopy, BiTeI contained rather interesting domain behavior consistent with what experts predict in materials with Ising-type domains. Chapter 5 investigates Graphullerene, an emerging layered carbon allotrope, for its nonlinear optical properties. The types of disorders that are especially interesting are the second harmonic and third harmonic generation studies revealed in Graphullerene. Although much remains unknown about this new class of carbon materials, second-order nonlinearities confirm the type of strain theoretically predicted in Graphullerene. Furthermore, combined with linear temperature studies of photoluminescence in Graphullerene, vibronics correlate with the vibronics seen in C60 molecules. Nonlinear excitation spectroscopy in the second and third order reveals electronic resonances that correlate with the shoulders and peaks in Graphullerene. Lastly, the appendices consist of two projects that remain works in progress. Tapping near-field scanning optical microscopy (Tapping NSOM) and magneto-photoluminescence (MPL) represent two cutting-edge techniques I was thankfully involved in developing during my graduate studies. Tapping-NSOM represents a flavor of work where time-correlated NSOM can reveal the temporal dynamics of the probe itself, in addition to the excited state dynamics of a nanomaterial. The MPL spectroscopy was carried out at Los Alamos National Laboratory to investigate ANPs as optical magnetometers. Though much work remains to be completed before I can take these emerging spectroscopic techniques to the next application level, they were formative projects that shaped my experience as a graduate researcher in the spectroscopic sciences.

Collective phenomena can give quantum materials unusual properties not found in common materials. Electronic correlations are responsible for intriguing emergent effects like superconductivity, metal-to-insulator transitions, magnetism, etc. Also, anisotropic excitations of polar quantum matter can lead to hyperbolicity, when one crystal axis is metallic and another dielectric. Polaritons, half-light half-matter quasiparticles, have exotic properties in hyperbolic media and are influenced by electronic correlations. In this dissertation, we use infrared near-field optical nanoscopy to interrogate various quantum materials both with strong anisotropy and electronic correlations and study their interplay and tunability. We first understand how near-field microscopes read out optical anisotropy and use our theory to study the metal-to-insulator transition in polycrystalline VO₂. Next, we demonstrate extreme tunability of hyperbolic phonon polaritons in α-MoO₃ by interfacing graphene. Finally, we introduce two novel hyperbolic systems: CrSBr and MoOCl₂, which host magnetically-enhanced hyperbolic exciton polaritons and ultra-low-loss hyperbolic plasmon polaritons, respectively.

InGaN based blue and near-ultraviolet light emitting diodes and laser diodes have been successfully commercialized for many applications such as general lighting, display backlighting and high density optical storage devices. Despite having a comparably high defect density, these devices are known for their efficient operation, which is attributed to localization in potential fluctuations preventing carriers from reaching the centers of nonradiative recombination. Nitride research is currently headed towards improving deep ultraviolet AlGaN and green InGaN emitters with higher Al and In molar fractions. The efficiency of these devices trails behind the blue counterparts as the carrier localization does not seem to aid in supressing nonradiative losses. In addition, the operation of ternary nitride heterostructure based devices is further complicated by the presence of large built-in electric fields. Although the problem can be ameliorated by growing structures in nonpolar or semipolar directions, the step from research to production still awaits. In this thesis, carrier dynamics and localization effects have been studied in three different nitride ternary compounds: AlGaN epitaxial layers and quantum wells with high Al content, nonpolar m-plane InGaN/GaN quantum wells and lattice matched AlInN/GaN heterostructures. The experimental methods of this work mainly consist of spectroscopy techniques such as time-resolved photoluminescence and differential transmission pump-probe measurements as well as spatial photoluminescence mapping by means of scanning near-field microscopy. The comparison of luminescence and differential transmission measurements has allowed estimating the localization depth in AlGaN quantum wells. Additionally, it has been demonstrated that the polarization degree of luminescence from m-InGaN quantum wells decreases as carriers diffuse to localization centers.What is more, dual-scale localization potential has been evidenced by near-field measurements in both AlGaN and m-InGaN. Larger scale potential fluctuation have been observed directly and the depth of nanoscopic localization has been estimated theoretically from the recorded linewidth of the near-field spectra. Lastly, efficient carrier transport has been observed through AlInN layer despite large alloy inhomogeneities evidenced by broad luminescence spectra and the huge Stokes shift. Inhomogeneous luminescence from the underlying GaN layer has been linked to the fluctuations of the built-in electric field at the AlInN/GaN interface. / <p>QC 20121101</p>

Le graphène, une monocouche de graphite, est composé d'atomes de carbone avec une structure en nid d'abeilles. Ses propriétés exceptionnelles ont attiré un intérêt mondial, dont le Prix Nobel de Physique en 2010. Le graphène épitaxié sur métal à rapidement été identifié comme un moyen de production de graphène de haute qualité de taille métrique, et est le sujet d'intenses activités de recherche en sciences de surface pour caractériser ses propriétés. En outre, ces études concernent aussi des systèmes plus complexes avec pour base le graphène, par exemple les réseaux ordonnés de nanoparticules à sa surface. Tout cela a mené à l'étude de la croissance, de la structure et des défauts du graphène épitaxié avec un grande variété de techniques expériementales, tel que la microscopie par effet tunnel, spectroscopie par photo-émission résolue en angle ou encore la microscopie électronique à basse énergie. Ce travail de recherche se concentre sur le graphène obtenu par croissance sur la surface (111) d'un monocristal d'iridium dans des conditions d'ultra vide et étudié avec plusieurs techniques de mesure par diffraction (diffraction de surface des rayons X, diffraction des rayons X en incidence rasante, réflectivité des rayons X et diffraction des électrons à haute énergie en réflexion). Ces expériences ont été faites au synchrotron européen ESRF à Grenoble, en France. La première partie de cette étude a été de déterminer la structure du graphène à l'échelle atomique. Le système montre une tendance à la commensurabilité, mais sa structure précise dépend fortement des conditions de préparation et de la température appliqué au système. En outre, en combinant des techniques de diffraction à haute résolution, une caractérisation précise de la structure, qui fait débat dans la littérature, est dévoilée. Le système étudié présente aussi une surperstructure, typique du graphène épitaxié, nommé moiré pour ses similarités avec l'effet optique du même nom. Celle-ci est utilisée comme gabarit pour faire croître des nanoparticules monodisperses à la surface en réseau auto-organisé. Durant cette étude, trois types de nanoparticules ont été examinés, des particules de platine de deux tailles différentes et des particules composées de platine et de cobalt. Ces systèmes hybrides présentent un fort degré d'organisation, partiellement hérité de la superstructure du moiré. Les nanoparticules forme une interaction forte avec leur support et elles subissent des contraintes de surface causées par leurs petites tailles. Par ailleurs, les nanoparticules de platine-cobalt, dont la croissance est en deux étapes, gardent une structure en couche et non une structure d'alliage métallique. / Graphene, a monolayer of graphite, is composed of carbon atoms arranged in a honeycomb lattice. Its exceptional properties have attracted a worldwide interest, including the Novel Prize in Physics in 2010. Epitaxial graphene on a metal was rapidly identified as an efficient method for large-area production of high quality graphene, and also was the matter of intense activities exploiting surface science approaches to address the various properties of graphene and of advanced systems based on graphene, for instance ordered lattice of metal nanoparticles on graphene. This resulted in the study of growth, structure and defects of epitaxial graphene on a wide variety of substrates with various techniques such as scanning tunneling microscopy, angle-resolved photoemission spectroscopy or low-energy electron microscopy. This work focuses on graphene grown on the (111) surface of iridium in ultra-high vacuum conditions and studied with several diffraction techniques (surface X-ray diffraction, grazing incidence X-ray diffraction, X-ray reflectivity, and reflection-high energy electron diffraction). These experiments were performed at the European Synchrotron Radiation Facility in Grenoble, France. The first step in our study was to determine the structure of graphene at the atomic scale. The system was found to have a tendency to commensurability, but that the precise structure depends on temperature and on preparation conditions. Moreover, with the combination of high resolution diffraction techniques, a precise characterization about the debated structure of graphene perpendicular to the surface was unveiled. The system, exhibits a superstructure, typical of epitaxial graphene, called a moiré, as an equivalent of the moiré effect in optics. This is used as a template to grown nanoparticles on top of the system to achieve the self-organisation of monodisperse nanoparticles. In this study, three type of nanoparticles were investigated, two different size of pure platinum ones and bimetallic ones, platinum and cobalt. These hybrid systems show very high degree of order, partly inherited by the superstructure lattice. The nanoparticles were found to strongly bond to their support, experience substantial surface strain related to their small size, and that bimetallic ones grown in a sequential manner retain a chemically layered structure.

Le développement de dispositifs optiques intégrés dans des domaines tels que l'information quantique et la détection de molécules est actuellement dirigé vers l'intégration de nanosources (NS) sur des systèmes sur puce avec faible pertes de propagation. Cette thèse montre une contribution à la conception, à la fabrication et à la caractérisation de structures photonique-plasmoniques en vue de l'intégration d'une seule NS sur des puces optiques à travers le spectre visible. Nous recherchons à optimiser l’efficacité d’excitation et de collection de l'émission de la fluorescence d'une NS en combinant un nano-prisme en or et une structure formée par une couche de dioxyde de titane (TiO2) et un guide d'ondes à échange d'ions (IEW) sur verre. Le couplage entre les modes permet un transfert efficace de l'énergie entre un mode faiblement confiné dans l'IEW vers un mode plasmonique confiné dans un volume effectif de quelques nanomètres cubes. Ce mode confiné interagit avec une NS en améliorant son émission de fluorescence par l'effet de facteur Purcell. En utilisant le théorème de réciprocité de l'électromagnétisme, nous avons étudié le cas réciproque où la lumière émise par la NS peut être collectée dans les modes photoniques du IEW.La caractérisation a été réalisée en champ lointain et en champ proche avec en particulier l'utilisation d'un microscope optique de champ proche à sonde diffusante (SNOM). Nous avons proposé une configuration SNOM qui permet d'imiter l'interaction d'une NS et des systèmes guidés, cartographiant la densité locale des modes guidés (LDOM) / The development of integrated optical devices in areas such as quantum information and molecular sensing is currently directed towards the integration of nanosources (NS) into systems on a chip with low propagation losses. This thesis shows a contribution on the design, fabrication, and characterization of photonic-plasmonic structures towards the integration of a NS on optical chips across the visible spectrum. We pursue the efficient excitation and collection of the fluorescence emission of a NS by making use of the interaction between an electromagnetic field concentrator (gold nanoprism) and an integrated optics structure formed by a high-index layer of titanium dioxide (TiO2) and a low-contrast index ion exchanged waveguide on glass (IEW). The coupling mode allows an efficient transfer of the energy between a weakly confined mode in the IEW and a plasmonic mode confined in an effective volume of few cubic nanometers. This confined mode interacts with a NS enhancing its florescence emission through Purcell factor effect. Using the reciprocity theorem of electromagnetism, we studied the reciprocal case where the light emitted by the NS can be collected into the photonic modes of the IEW.The characterization was performed in the far and in the near field with the use of a scanning near-field optical microscopy (SNOM). We proposed a SNOM configuration that allows us to imitate the interaction of a NS and guided systems, mapping the local density of guided modes (LDOM)

The structure of a material, whether at the atomic scale or patterned at the nanoscale, is the basis of many of its physical properties—color, emission wavelength, optical nonlinearity, electrical conductivity, thermal conductivity, brittleness, and more. Therefore, one of the most important developments in photonics, electronics, and magnetics is the ability to manipulate the nanostructure of materials as a way to augment their natural qualities and adapt them to greater applications. The cleanroom debuted in the mid-20th century, alongside and followed by an assortment of precision nanofabrication instruments performing photolithography, electron-beam lithography, ion implantation, femtosecond laser machining, etc. While these techniques have demonstrated breakthroughs such as fabricating ever-smaller transistors keeping pace with the famous Moore’s Law, they require cleanroom facilities, multi-step processing, or leave behind debris or residue. Such impurities have an outsize effect on a burgeoning class of materials with desirable optical and electronic properties—two-dimensional (2D) layered van der Waals materials—as their dimensions approach the single-atom limit, leading a desire for additional approaches to material nanostructuring. In this thesis, we describe a novel approach to generating atomically sharp linear nanostructures in hexagonal boron nitride (hBN) via resonant optical phonon pumping with a pulsed mid-infrared laser and detail its development from discovery to a useful technique that complements established approaches to nanopatterning. The femtosecond laser is tuned to the material’s infrared-active transverse optical TO (E1u) phonon, located at ? = 7.3 ?? or 1367 cm-1, and its polarization aligned parallel to the crystal zigzag axis, in the direction of the phonon’s characteristic atomic motion. The optical field coherently drives and amplifies the intrinsic ionic motion toward bond breakage, resulting in a gentle tearing of the hBN flake along the crystal axis at the material damage threshold. All processing is performed in situ at room temperature under ambient conditions, free from cryogenics and vacuum setups, unlike in the conventional nanofabrication methods confined to the cleanroom. This phenomenon is termed “unzipping” to depict the rapid formation and emanation of a crack tens of nanometers wide from a point within the laser-excited area. The generation of these fea- tures is ascribed to the large atomic displacements and localized bond strain produced by strongly driving the crystal at an intrinsic resonance, which is absent under non-resonant irradiation and is greatly sensitive to the relative angle between the crystal orientation and the linear laser polarization. We perform detailed characterization of the unzipped features and their host hBN flakes us- ing atomic force microscopy (AFM) topographic imaging, scanning electron microscopy (SEM), atomic-scale lateral force microscopy (LFM), nanoindentation in the plastic deformation regime, and near-field optical probing (scattering-type scanning near-field optical microscopy, s-SNOM) to reveal their atomically sharp, six-fold symmetric, orientation-selective, defect-seeded nature. Then, we fabricated several nanostructures—gratings, Fabry-Perot resonators, and cleaved and shaped flakes—to demonstrate the technique in useful nanophotonics applications. The preliminary Fabry-Perot resonator, examined in the near-field with nanoscale Fourier-transform infrared spectroscopy (nano-FTIR), exhibited performance that is competitive with similar structures fabricated by cleanroom etching. Our initial approach achieved a quality factor of ? ≈ 70, already on par with ? = 50 to 100 achieved by conventional nanofabrication methods. The cleanliness, sharpness, and directionality of nanostructures fabricated in situ via unzipping, along with the ability to deterministically seed the location of its constituent line defects using nanoindentation, enable vast future applications in patterning hBN and other polar crystals that possess optically-addressable, high-energy optical phonon modes in the mid-infrared.

Les propriétés optique des nanoparticules ont ouvert de nouvelles voies dans de nombreux domaines, de l'optique fondamental avec la compréhension des interactions dans la matière, la biologie et la compréhension du fonctionnement des milieux cellulaires, en passant par la microscopie en champ proche, qui permet de sonder localement les propriétés physiques de divers nano-systèmes. Au cours de ce travail, nous avons réalisé l'étude de la génération de seconde harmonique (GSH) de nanoparticules de KTP ainsi que de dimères d'or isolés. Des mesures optiques du rayonnement émis par ces nano-objets montrent qu'ils sont parfaitement photostables. Par ailleurs, nous avons aussi étudié de nouvelles particules actives qui permettent d’obtenir un double signal, de luminescence ainsi que de GSH. Ces nanosources bimodales sont constituées des nanoparticules de KTP dopées avec des ions Europium. Dans une seconde partie, nous tentons de fabriquer des sondes optiques pour le champ proche en utilisant les nanocristaux non-linéaires de KTP, ceci dans le but de développer une nouvelle microscopie optique en champ proche capable de sonder localement et vectoriellement un champ électromagnétique. Une pointe de microscopie à force atomique est fonctionnalisée par une particule d'or, puis approchée d'un nanocristal de KTP. Des résultats préliminaires montrent qu'il est possible par cette méthode de sonder le champ électromagnétique présent autour d'une nanoparticule d'or. / The optical properties of nanoparticles have opened new avenues in many areas of optics with the fundamental understanding of the interactions in matter, biology and understanding of the functioning of cell media, through the near-field microscopy, which allows us to probe locally the physical properties of various nano-systems. In this work, the study of second harmonic generation (SHG) has been performed on isolated nanoparticles of KTP and dimers of gold. Optical measurements of radiation emitted by these particles show that nanoparticles are perfectly photostable.Furthermore, we also explored new active particles that deliver a double signal, luminescence and GSH. These nanosources bimodal nanoparticles consist of KTP doped with europium ions. In the second part, we try to manufacture optical probes for near field using nonlinear nanocrystals in this case the probe is KTP nanocrystals. A tip of atomic force microscopy is functionalized by a particle of gold, then approached a nanocrystal of KTP. Preliminary results showed that it was possible to probe the electromagnetic field present around a gold nanoparticle.