La demande urgente d'innovations dans le domaine du stockage de l'énergie est liée au développement récent de la production d'énergie renouvelable ainsi qu'à la diversification des produits électroniques portables qui consomment de plus en plus d'énergie. Il existe plusieurs technologies pour le stockage et la conversion électrochimique de l'énergie, les plus notables étant les batteries aux ions lithium, les piles à combustible et les supercondensateurs. Ces systèmes sont utilisés de façon complémentaire des uns aux autres dans des applications différentes. Par exemple, les batteries sont plus facilement transportables que les piles à combustible et ont de bonne densité d'énergie alors que les supercondensateurs ont des densités de puissance plus élevés et une meilleure durée de vie. L'objectif principal de ces travaux est d'étudier les performances électrochimiques d'une nouvelle famille de matériaux bidimensionnel appelée MXène, en vue de proposer de nouvelles solutions pour le stockage de l'énergie. Pour y arriver, plusieurs directions ont été explorées. Dans un premier temps, la thèse se concentre sur les supercondensateurs dans des électrolytes aqueux et aux effets des groupes de surface. La seconde partie se concentre sur les systèmes de batterie et de capacités à ions sodium. Une cellule complète comportant une anode en carbone et une cathode de MXène a été développées. La dernière partie de la thèse présente l'étude des MXènes pour les supercondensateur en milieu organique. Une attention particulière est apportée à l'étude du mécanisme d'intercalation des ions entre les feuillets de MXène. Différentes techniques de caractérisations ont été utilisées, en particulier la voltampérométrie cyclique, le cyclage galvanostatique, la spectroscopie d'impédance, la microscopie électronique et la diffraction des rayons X. / An increase in energy and power densities is needed to match the growing energy storage demands linked with the development of renewable energy production and portable electronics. Several energy storage technologies exist including lithium ion batteries, sodium ion batteries, fuel cells and electrochemical capacitors. These systems are complementary to each other. For example, electrochemical capacitors (ECs) can deliver high power densities whereas batteries are used for high energy densities applications. The first objective of this work is to investigate the electrochemical performances of a new family of 2-D material called MXene and propose new solutions to tackle the energy storage concern. To achieve this goal, several directions have been explored. The first part of the research focuses on MXene behavior as electrode material for electrochemical capacitors in aqueous electrolytes. The next part starts with sodium-ion batteries, and a new hybrid system of sodium ion capacitor is proposed. The last part is the study of MXene electrodes for supercapacitors is organic electrolytes. The energy storage mechanisms are thoroughly investigated. Different characterization techniques were used in this work, such as cyclic voltammetry, galvanostatic charge-discharge, electrochemical impedance spectroscopy, scanning electron microscopy and X-ray diffraction.

abstract: Two dimensional (2D) Janus Transition Metal Dichalcogenides (TMDs) are a new class of atomically thin polar materials. In these materials, the top and the bottom atomic layer are made of different chalcogen atoms. To date, several theoretical studies have shown that a broken mirror symmetry induces a colossal electrical field in these materials, which leads to unusual quantum properties. Despite these new properties, the current knowledge in their synthesis is limited only through two independent studies; both works rely on high-temperature processing techniques and are specific to only one type of 2D Janus material - MoSSe. Therefore, there is an urgent need for the development of a new synthesis method to (1) Extend the library of Janus class materials. (2) Improve the quality of 2D crystals. (3) Enable the synthesis of Janus heterostructures. The central hypothesis in this work is that the processing temperature of 2D Janus synthesis can be significantly lowered down to room temperatures by using reactive hydrogen and sulfur radicals while stripping off selenium atoms from the 2D surface. To test this hypothesis, a series of controlled growth studies were performed, and several complementary characterization techniques were used to establish a process–structure-property relationship. The results show that the newly proposed approach, namely Selective Epitaxy and Atomic Replacement (SEAR), is effective in reducing the growth temperature down to ambient conditions. The proposed technique benefits in achieving highly crystalline 2D Janus layers with an excellent optical response. Further studies herein show that this technique can form highly sophisticated lateral and vertical heterostructures of 2D Janus layers. Overall results establish an entirely new growth technique for 2D Janus.layers, which pave ways for the realization of exciting quantum effects in these materials such as Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) state, Majorana fermions, and topological p-wave superconductors. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2020

<p>The demand for the faster information transport and better computational abilities is ever increasing. In the last few decades, the electronic industry has met this requirement by increasing the number of transistors per square inch. This lead to the scaling of devices to tens of nm. However, the speed of the electronics is limited to few GHz. Using light, the operating speed of photonic devices can be much larger than GHz. But the photonic devices are diffraction limited and hence the size of photonic device is much larger than the electronic components. Plasmonics is an emerging field with light-induced surface excitations, and can manipulate the light at nanoscale. It can bridge the gap between electronics and photonics. </p> <p>With the present scaling of devices to few nm, the scientific community is looking for alternatives for continued progress. This has opened up several promising routes recently, including two-dimensional materials, quantum computing, topological computing, spintronics and valleytronics. The discovery of graphene has led to the immense interest in the field of two-dimensional materials. Two dimensional-materials have extraordinary properties compared to its bulk. This work discusses the applications of plasmonics in this emerging field of two-dimensional materials and for heat assisted magnetic recording.</p> <p>Black phosphorus is an emerging low-direct bandgap two-dimensional semiconductor, with anisotropic optical and electronic properties. It has high mobility and is promising for photo detection at infrared wavelengths due to its low band gap. We demonstrate two different plasmonic designs to enhance the photo responsivity of black phosphours by localized surface plasmons. We use bowtie antenna and bowtie apertures to increase the absorption and polarization selectivity respectively. Plasmonic structures are designed by numerical electromagnetic simulations, and are fabricated to experimentally demonstrate the enhanced photo responsivity of black phosphorus. </p> <p>Next, we look at another emerging two-dimensional material, bismuth telluride selenide (Bi₂Te₂Se). It is a topological insulator with an insulating bulk but conducting electronic surface states. These surface states are Dirac like, similar to graphene and can lead to exotic plasmonic phenomena. We investigated the optical properties of Bi₂Te₂Se and found that the bulk is plasmonic below 650 nm wavelength. We study the distinct surface plasmons arising from the bulk and surface state of the topological insulator, Bi₂Te₂Se. The propagating surface plasmons at a nanoscale slit in Bi₂Te₂Se are imaged using near-field scanning optical microscopy. The surface state plasmons are studied with a below band gap excitation of 10.6 µm wavelength and the surface plasmons of the bulk are studied with a visible wavelength of 633 nm. The surface state plasmon wavelength is 100 times shorter than the incident wavelength in sharp contrast to the plasmon wavelength of the bulk. </p> <p>Next, we look at the application of plasmonics in heat assisted magnetic recording (HAMR). HAMR is one of the next generation data storage technology that can increase the areal density to beyond 1 Tb/in². Near-field transducer (NFT) is a key component of the HAMR system that locally heats the recording medium by concentrating light below the diffraction limit using surface plasmons. In this work, we use density-based topology optimization for inverse design of NFT for a desired temperature profile in the recording medium. We first perform an inverse thermal calculation to obtain the required volumetric heat generation (electric field) for a desired temperature profile. Then an inverse electromagnetic design of NFT is performed for achieving the desired electric field. NFT designs for both generating a small heated spot size and a heated spot with desired aspect ratio in recording medium are demonstrated. The effect of waveguide, write pole and moving recording medium on the heated spot size is also investigated. </p>

The enrichment of heavy hydrogen isotopes (deuterium, tritium) is required to fulfill their increasing application demands, e.g., in isotope related tracing, cancer therapy and nuclear reaction plants. However, their exceedingly low natural abundance and the close resemblance of physiochemical properties to protium render them extremely difficult to be separated. In this thesis, we investigate hydrogen isotope transport and separation via layered and two-dimensional materials. Three different theoretical challenges are undertaken in this work: (1) identification of the transported hydrogen species (proton H+ or protium H atom) inside interstitial space of layered materials (hexagonal boron nitride, molybdenum disulfide and graphite) and elucidation of their transport mechanism; (2) separation of hydron (proton H+, deuteron D+, and triton T+) isotopes through vacancy-free graphene and hexagonal boron nitride monolayers; (3) capture of the extremely rare light helium isotope (3He) with atomically thin two-dimensional materials. In the case of hydrogen transport, the essential challenges are investigation of its mechanism as well as the identification of transported particles. Regarding the case of hydron isotope separation, the essential questions are whether or not pristine graphene is permeable to the isotopes, and how quantum tunneling and topological Stone-Wales 55-77 defects affect their permeation and separation through graphene. In the last case, to capture the light helium isotope, quantum tunneling, which favors the lighter particles, is utilized to harvest 3He using graphdiyne monolayer. Our results provide novel theoretical insights into hydrogen particle transport inside the interstitial space of van der Waals materials; they uncover the mechanism of hydron isotope separation through 2D graphene and hexagonal boron nitride monolayers; and they predict the influence of pure quantum tunneling on the enrichment of 3He through graphdiyne membrane.

Cette thèse est consacrée à l'étude approfondie de formes exotiques de matériaux nano-structurés qui pourraient conduire à une avancée significative dans les nano-composants. Deux thèmes distincts ont été ainsi abordés. Le premier concerne les nano-clusters aromatiques de silicium synthétisés par plasma (SiNCs), tandis que le second est dédié aux structures silicium et germanium bi-dimensionnelles. Grâce à des simulations de type dynamique moléculaire et des calculs ab initio, ainsi que sur des recherches expérimentales, nous nous proposons d’explorer les propriétés intrigantes, mais à fort potentiel, de ces matériaux exotiques.Dans la première partie, nous commençons par des études théoriques et montrons qu'il est possible d'obtenir un comportement aromatique pour des SiNCs hydrogénés ayant une taille de ~1nm. Nous démontrons que les plasmas silane/hydrogène à basse température, proches de la formation de particules de poussière, présentent l'environnement idéal pour exploiter la tendance naturelle du silicium à la sur-coordination et donc pour la synthèse de structures à liaisons déficitaires en électrons. Ces nano-clusters qui se forment spontanément par auto-assemblage dans le plasma, ne possèdent pas de structure tétraédrique, sont plus stables que tous les autres SiNCs connus de cette taille et ont de fortes propriétés aromatiques dues à leur forte délocalisation électronique. Nous montrons également que les SiNCs non tétraédriques, présentent des modes de liaison à caractère métallique qui ressemblent fortement à celui d'un gaz d'électrons homogène dans des nano-clusters de métaux. Les SiNCs tétraédriques standards de cette taille ne peuvent absorber que dans l'ultraviolet, alors que nos calculs ont montré que des SiNCs purs, mais sur-coordonnés, absorbent dans la région spectrale ultraviolette, mais aussi dans le visible et l’infrarouge. Nous présentons ensuite une première preuve expérimentale pour nos prédictions théoriques. Nous avons mesuré in situ, dans un réacteur plasma l'absorption de la lumière visible des SiNCs. De plus, nos mesures réalisées en présence d'un champ électrique ont prouvées clairement que les SiNCs aromatiques possèdent un moment dipolaire permanent, que nous avons estimé entre 2 et 2,5 Debye, en excellent accord avec les calculs ab initio. Enfin, nos images de microscopie électronique à transmission des SiNCs, déposés dans des conditions de plasma optimisées, ont révélé la présence d'une autre forme exotique de silicium à structure hexagonale. Une telle structure se forme habituellement à des pressions extrêmement élevées appliquées sur des structures cubiques (diamant) de silicium. Nous souhaitons affirmer que c’est grâce à la «chimie au marteau» que ces conditions ont été atteintes.Dans la seconde partie, nous avons entrepris des études théoriques et expérimentales approfondies sur la croissance d'une nouvelle forme allotropique de silicium et de germanium: le silicène et le germanène, à savoir, une mono-couche d'atomes intégrée dans un réseau hexagonal qui ressemble fortement au graphène. Afin d'exclure tout mélange entre les atomes de silicium ou de germanium avec le substrat et de conserver leurs caractéristiques prometteuses comme de nouveaux matériaux de Dirac, nous avons effectué nos dépôts, sur un substrat de graphite chimiquement inerte. Une de nos découvertes cruciales est que les mono-couches de silicène ou de germanène interagissent avec le substrat de graphite uniquement via des forces de van der Waals. Cette interaction est suffisamment forte pour stabiliser les mono-couches, déposées même au-dessus de la température ambiante, mais suffisamment faible pour empêcher toute hybridation ou alliage entre le silicium ou le germanium et les atomes de carbone du substrat. Par conséquent, les propriétés électroniques exceptionnelles du silicène et du germanène, tels que les cônes de Dirac et les électrons sans masse, sont préservées même après leur dépôt sur les surfaces de graphite. / This thesis is devoted to the study of advanced, exotic forms of nanostructured materials that could lead to the next big advance for nanodevices. Two distinct topics have been considered. The first one is related to plasma-born aromatic silicon nanoclusters (SiNCs), while the second is dedicated to two-dimensional silicon and germanium materials. Based on molecular dynamics simulations and ab initio calculations, as well as, on experimental investigations, we explore a variety of intriguing properties of those exotic materials that are expected to be far superior to those of their conventional counterparts.In the first part of the thesis, we begin with theoretical studies and show that it is possible to obtain aromatic behavior in simple hydrogenated SiNCs with size of ~1nm. We demonstrate that low-temperature silane/hydrogen plasmas close to dust formation present the ideal environment to exploit the natural tendency of silicon to over-coordination for the construction of structures with electron-deficient bonds. Those nanoclusters form spontaneously by self-assembly in plasmas, do not possess tetrahedral structures, are more stable than any other known SiNCs of this size, and have strong aromatic-like properties due to their high electron delocalization. We demonstrate that non-tetrahedral SiNCs exhibit metallic-like bonding schemes that strongly resemble the one of a homogeneous electron gas in small metal clusters. Standard tetrahedral SiNCs of this size can absorb light only in the ultraviolet, while our calculations have shown that pure, but over-coordinated SiNCs absorb light in the ultraviolet, visible, and infrared spectral region. In this thesis, we present first experimental evidence that supports our theoretical predictions. Using incoherent broadband cavity enhanced absorption spectroscopy, we have measured the absorption of SiNCs, in situ, in a plasma reactor and found that they do absorb light in the visible region. In addition, our absorption measurements in the presence of an applied electric field have provided clear evidence that aromatic SiNCs possess a permanent dipole moment, and we have measured it to be between 2 and 2.5 Debye, in excellent agreement to prior ab initio calculations. Finally, our transmission electron microscopy images of such SiNCs, after their deposition under optimized plasma conditions, have revealed the presence of another exotic form of silicon with a primitive hexagonal structure. Such a structure usually forms after exposing diamond-cubic silicon to extremely high pressures. We tentatively claim that those conditions were, actually, achieved in our experiments due to the “chemistry with a hammer”.In the second part of the thesis, we have undertaken in-depth theoretical and experimental studies on the growth of a new allotropic form of silicon and germanium: a single layer of silicon or germanium atoms, only one atom thick and packed in a hexagonal lattice that closely resembles the lattice of graphene, namely silicene and germanene. In order to rule out any intermixing between silicon or germanium atoms and the underneath substrate atoms, as it was the case for metallic substrates, and to maintain their promising features to be new Dirac materials, we have performed our depositions on a chemically inert graphite substrate. One of our crucial findings is that the silicene or germanene monolayers interact with the graphite substrate via van der Waals forces only. The van der Waals interaction is strong enough to stabilize the deposited monolayers even above room temperature, but weak enough to prevent any hybridization or alloying between silicon or germanium and carbon atoms. Consequently, the outstanding electronic properties of free-standing silicene and germanene, such as Dirac cones and massless electrons, are preserved even after their deposition on graphite surfaces.

Lasers are increasingly used for a wide range of different applications for both civil and military purposes. Due to the distinct properties of laser light, use of lasers often comes with a risk of damage to the human eye and other optical sensors. Therefore, an effective laser protection is needed. 2D-materials is a relatively new class of materials, which have shown to possess many unique properties compared to its bulk counterparts. Some 2D-materials exhibit nonlinear optical (NLO) properties, and specifically optical power limiting (OPL) effects, and have therefore been researched for laser protection applications. In this work, two different 2D-materials, MXene Ti3C2 and graphene oxide (GO), have been combined with a hybrid organic-inorganic polymer, a so called melting gel (MG), to synthesise nanocomposites possessing OPL effects for laser protection applications. Different methods of incorporating the 2D-materials in the polymer matrix as well as the effect on optical properties of different concentrations of 2D-materials were investigated. The prepared nanocomposites were characterised using optical microscopy, spectroscopy and OPL measurements in order to investigate and quantify their linear and nonlinear optical properties. The MG was optically clear, mechanically stable and easy to synthesise, which makes it a suitable candidate as a matrix for a laser protection nanocomposite. Additionally, it was possible to dope the MG with the two different 2D-materials to create nanocomposites showing desirable optical properties in the visible spectrum. However, many samples showed signs of clustered 2D-particles indicating that the dispersion could be improved. Finally, OPL measurements, performed at 532 nm, showed that the MG itself exhibited OPL effects, both 2D-materials showed a stronger OPL effect than the non-doped MG and that GO-doped samples gave a better protection than the MXene samples.

<p>  </p> <p>Low-dimensional materials (LDMs) are substances that have at least one dimension with thicknesses in the nanometer (nm) scale. They have attracted tremendous research interests in many fields due to their unique properties that are absent in bulk materials. For instance, in quantum optics/photonics, LDMs offer unique advantages for effective light extraction and coupling with photonic/plasmonic structures; in chemistry, the large surface-to-volume ratio of LDMs enables more efficient chemical processes that are useful for numerous applications. In this thesis, several types of LDMs are studied and engineered with the goal to improve their impact in plasmonic and quantum photonic applications. Two-dimensional hexagonal boron nitride (hBN) is receiving increasing attention in quantum optics/photonics as it hosts various types of quantum emitters that are promising for quantum computing, quantum sensing, etc. In the first study, we explore and demonstrate a radiation- and lithography-free route to deterministically create single-photon emitters (SPEs) in hBN by nanoindentation with an atomic force microscopy. The method applies to hBN on flat, chip-compatible silicon-based substrates, and an SPE yield of up to 36% is achieved. This marks an important step toward the deterministic creation and integration of hBN SPEs with photonic and plasmonic devices. In the second study, the recently discovered negatively charged boron vacancy (V_B^-) spin defect in hBN is investigated. V_B^- defects are optically active with spin properties suitable for sensing at extreme scales. To resolve the low brightness issue of V_B^- defects, we couple them with an optimized nano-patch antenna structure and observe emission intensity enhancement that is nearly an order of magnitude higher than previous reports. Our achievements pave the way for the practical integration of V_B^- defects for quantum sensing. Zero-dimensional nanodiamond is another important host material for solid-state SPEs. Specifically, the negatively charged silicon vacancy (SiV) center in nanodiamonds exhibits optical properties that are suitable for quantum information technologies. In the third study, we, for the first time, demonstrate the creation of single SiV centers in nanodiamonds with an average size of ~20 nm using ion implantation. Stable single-photon emission is confirmed at room temperature, with zero-phonon line (ZPL) wavelengths in the range of 730 – 803 nm. This confirms the feasibility of single-photon emitter creation in nanodiamonds with ion implantation, and offers new opportunities to integrate diamond color centers for hybrid quantum photonic systems. Finally, we have also explored using metal-semiconductor hybrid nanoparticles for plasmon-enhanced photocatalysis. A core-shell nanoparticle structure is synthesized, with titanium nitride (TiN) and titanium dioxide (TiO₂) being the core and shell material respectively. It is observed that such core-shell nanoparticles effectively catalyze the generation of single oxygen molecules under 700-nm laser excitation. The main mechanism behind is the hot electron injection from the TiN core to the TiO₂ shell. Considering the chemical inertness and low cost of TiN, TiN@TiO₂ NPs hold great potential as plasmonic photosensitizers for photodynamic therapy and other photocatalytic applications at red-to-near-infrared (NIR) wavelengths.</p>

No description available.

Following a 15-year-long investigation on graphene, two-dimensional (2D) carbon-rich conjugated frameworks (CCFs) have attracted growing research interest as a new generation of multifunctional materials. Typical 2D CCFs include 2D π-conjugated polymers (also classified as 2D π-conjugated covalent organic frameworks) and 2D π-conjugated metal–organic frameworks, which are characterized by layer-stacked periodic frameworks with high in-plane π-conjugation. These unique structures endow 2D CCFs with regular porosities, large specific surface areas, and superior chemical stability. In addition, 2D CCFs exhibit certain notable properties (e.g., excellent electronic conductivity, designable topologies, and defined catalytic/redox-active sites), which have motivated increasing efforts to explore 2D CCFs for electrochemical energy applications. In this Perspective, the structural features and synthetic principles of 2D CCFs are briefly introduced. Moreover, we discuss recent achievements in 2D CCFs designed for various electrochemical energy conversion (electrocatalysis) and storage (supercapacitors and batteries) applications. Particular emphasis is placed on analyzing the precise structural regulation of 2D CCFs. Finally, we provide an outlook about the future development of synthetic 2D CCFs for electrochemical applications, which concerns novel monomer design, chemical methodology/strategy establishment, and a roadmap toward practical applications.

Micro– and subsequently nano–scale fabrication techniques have reshaped our world more drastically than almost any other development of the last half-century. Spurred by the invention of the transistor at Bell Labs in 1947, monolithic integrated circuits—or microchips in the colloquial lexicon—were developed in ’59, kickstarting the modern digital age as we know it. More recently, the maturation of classical computing technology and significant advancements in materials science have led to a boom of interest in and progress by the quantum sector on both computation and communication fronts. The explosive growth currently underway in the field of quantum information science (QIS) marks the dawning of a new age, which will undoubtedly transform our world in ways we have yet to imagine. This dissertation seeks to leverage advanced nanofabrication approaches, atomically thin materials, and state of the art microscopy techniques to develop room-temperature single photon sources for QIS applications. A basic overview of 2D materials is provided in Chapter 1. Particular emphasis is placed on the optical properties of tungsten diselenide (WSe2), which is followed by a brief discussion of quantum emitters in 2D and other material systems. Chapter 2 describes the scanning near-field optical microscopy (SNOM) technique we use to investigate the photoluminescence (PL) response of strained WSe₂ with resolution well below the classical diffraction limit. The third chapter is dedicated to the various fabrication methods explored and developed to produce the plasmonic substrates necessary for near-field optical studies. The first section focuses on the creation of extremely flat metallic surfaces, while the second deals with extremely sharp metallic stressors. These two platforms enable the investigations of nanobubbles—touched upon in Chapter 2—and nanowrinkles, which are the subject of discussion in Chapter 4. The strain confinement provided by these wrinkles leads to highly localized quantum dot-like states that exhibit excitation power saturation at room temperature. Together, these studies lay the groundwork for achieving high-temperature quantum emission in atomically thin semiconducting van der Waals materials.