Depuis plus de 30ans, les chercheurs essaient de combiner le silicium et le GaAs. Le potentiel de l'intégration du GaAs sur Si est en effet considérable pour le remplacement des substrats coûteux de GaAs ou de Ge dans la fabrication de cellules PV, de photodétecteurs, de LED, de lasers…. Il en est de même pour le développement de nouveaux dispositifs opto- et électroniques par l'intégration monolithique de GaAs sur circuit silicium. Des défis majeurs persistant jusqu'à aujourd'hui doivent toutefois être surmontés.Dans le but de surmonter ces difficultés, nous proposons un concept intéressant qui permet l'hétéroépitaxie de III-V sur Si. Ce concept est basé sur la technique d’épitaxie latérale (ELO) par CBE depuis des ouvertures nanométriques réalisées dans un masque de silice ultra-mince. Cette technique nous a permis d’obtenir des microcristaux de GaAs sans défaut et parfaitement intégrés sur Si grâce à une nucléation depuis des ouvertures de très petits diamètres qui évitent la génération de dislocations dues au désaccord de maille. Le concept étant validé, nous avons poursuivi l’étude en utilisant une 2ème approche de nanostructuration technologique du masque et permettant la localisation des cristaux. L’obtention in fine d’une pseudo-couche de GaAs sur Si sans défaut ni contrainte serait particulièrement utile pour les diverses applications mentionnées. Seront donc présentés le concept d’intégration, puis les résultats de croissance par ces techniques, et des analyses matériaux complémentaire. Pour finir, sera détaillée la structure d’une cellule PV de GaAs/Si devant permettre d’atteindre un rendement de conversion de 29,2%, ainsi que les premiers résultats obtenus. / For over thirty years researchers have attempted to combine Si and GaAs. Alternative GaAs-on-Si substrates have a considerable market potential for replacing the costly GaAs or Ge substrate in producing traditional GaAs devices such as solar cells, photodetectors, LEDS, lasers, and microwave devices, and as a new technology for monolithic integration of GaAs elements and silicon integrated circuits. However, major challenges remaining until now must be overcome.In that way, we propose an interesting concept that allows III-V heteroepitaxy on silicon. This concept is based on the Epitaxial Lateral Overgrowth (ELO) by CBE from nanoscale holes through an ultra-thin silica layer. This technique allows us to obtain GaAs microcrystals without any defect and perfectly integrated on Si thanks to nanoscaled nucleation seeds which prevent dislocation generation due to lattice mismatch. The concept being validated, the study has continued using a 2nd approach of nanostructuration to allow crystal localization. The achievement of getting a GaAs pseudo-layer on silicon substrate without any defect or stain would be of great interest for the formerly mentioned applications.So the integration concept of III-V materials on silicon will be introduced, then growth resultants by these techniques, and material characterizations in order to qualify the integrated GaAs on silicon regarding to the opto- and electronic applications. Finally, the structure of a GaAs/Si tandem solar cell will be discussed. After proving this solar cell could reach a 29.2% conversion efficiency, first achievements will be revealed.

Depuis sa découverte, le graphène a attiré beaucoup d’intérêt et ses propriétés remarquables font de lui un matériau très étudié par la communauté scientifique. Ce travail de thèse porte non pas sur ces propriétés intrinsèques, mais sur les possibilités de dopage et de fonctionnalisation du graphène pour d’éventuelles applications futures. Le choix du graphène épitaxié sur SiC comme matériau de base nous a permis d’avoir des échantillons adaptés aux études spectroscopiques (XPS, ARPES, NEXAFS) effectuées au synchrotron SOLEIL. Ces études sont indispensables pour la caractérisation macroscopique du graphène dopé et fonctionnalisé. La croissance epitaxiale permet à la fois le dopage in-situ et ex-situ. Dans un premier temps nous avons étudié l’influence de l’azote, élément voisin du carbone. Nous avons opté pour une technique de dopage in-situ, ce qui nous a permis d’avoir du graphène dopé dans un seul et même processus de fabrication. De plus nous avons pu déterminer les conditions de croissance pour obtenir une couche de nitrure de silicium (Si3N4) entre le graphène et le substrat. D’autre part nous avons utilisé l’oxygène pour fonctionnaliser le graphène. En exposant le graphène vierge à l’oxygène atomique et moléculaire, on a pu étudier l’évolution des états vide du graphène en présence d’oxygène. Les bords des grains de graphène sont particulièrement adaptés pour la fonctionnalisation à cause de leur activité chimique. Nous avons ainsi synthétisé du graphène avec des grains de petites dimension (~100 nm) pour avoir une forte densité de bords dans l’échantillon. De cette manière nous avons pu détecter, par absorption des rayons X, la signature de ces états de bord. / Since its discovery, graphene has attracted tremendous interest and its remarkable properties make it a material intensively studied by the scientific community. This thesis is not directly concerned with its intrinsic properties, but the possibilities of doping and functionalization of graphene for future possible applications and devices. The choice of epitaxial graphene on SiC as basic material allowed us to have samples well adapted for spectroscopic studies (XPS, ARPES and NEXAFS) carried out on a synchrotron facility (SOLEIL). These studies are essential for the macroscopic characterization of doped graphene and its functionalization. Epitaxial growth provides us the possibility to dope graphene both in-situ and ex-situ. We first opted for an in-situ doping technique studying the influence of nitrogen as a chemical dopant on the growth process. This allowed us to fabricate doped graphene in a one-step process. By tuning the parameters for epitaxial growth the creation of a silicon nitride layer was also observed. We also used atomic and molecular oxygen for the functionalization of graphene. By exposing pristine graphene to oxygen in an ex-situ process, we were able to study the evolution of empty states of graphene and the consequences on the electronic structure. The edges of graphene crystallites are particularly adapted for functionalization because of their chemical activity. The epitaxial growth on a 3C-SiC substrate allowed us to synthesize graphene with a reduced lateral size (~100 nm) and to have a higher density of edges in our sample. In this way we were able to detect the signature of these edge states using non-local spectroscopic methods.

abstract: The first part of this dissertation reports the study of the vertical carrier transport and device application in InAs/InAs1-xSbx strain-balanced type-II superlattice. It is known that the low hole mobility in the InAs/InAs1-xSbx superlattice is considered as the main reason for the low internal quantum efficiency of its mid-wave and long-wave infrared photodetectors, compared with that of its HgCdTe counterparts. Optical measurements using time-resolved photoluminescence and steady-state photoluminescence spectroscopy are implemented to extract the diffusion coefficients and mobilities of holes in the superlattices at various temperatures from 12 K to 210 K. The sample structure consists of a mid-wave infrared superlattice absorber region grown atop a long-wave infrared superlattice probe region. An ambipolar diffusion model is adopted to extract the hole mobility. The results show that the hole mobility first increases from 0.2 cm2/Vs at 12 K and then levels off at ~50 cm2/Vs as the temperature exceeds ~60 K. An InAs/InAs1-xSbx type-II superlattice nBn long-wavelength barrier infrared photodetector has also been demonstrated with a measured dark current density of 9.5×10-4 A/cm2 and a maximum resistance-area product of 563 Ω-cm2 at 77 K under a bias of -0.5 V. The Arrhenius plot of the dark current density reveals a possible high-operating-temperature of 110 K.The second part of the dissertation reports a lift-off technology using a water-soluble sacrificial MgTe layer grown on InSb. This technique enables the seamless integration of materials with lattice constants near 6.5 Å, such as InSb, CdTe, PbTe, HgTe and Sn. Coherently strained MgTe with a lattice constant close to 6.5 Å acts as a sacrificial layer which reacts with water and releases the film above it. Freestanding CdTe/MgxCd1-xTe double-heterostructures resulting from the lift-off process show increased photoluminescence intensity due to enhanced extraction efficiency and photon-recycling effect. The lifted-off thin films show smooth and flat surfaces with 6.7 Å root-mean-square roughness revealed by atomic-force microscopy profiles. The increased photoluminescence intensity also confirms that the CdTe/MgxCd1-xTe double-heterostructures maintain the high optical quality after epitaxial lift-off. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

Titanium is one of the earth-abundant elements, and its oxides including titanium dioxide (TiO2) and strontium titanium oxide (SrTiO3) are widely used in technologies of electronics, energy conversion, catalysis, sensing, and so on. Generally, the Ti ions in these compounds have a valence of 4+ with the outer shell electron configuration of 3d0. In this thesis, we explore interface and titanite containing Ti3+ ions with 3d1 itinerate electrons, which we believe open new doors towards some new titanite-based technologies. In the first part of this thesis (Chapter 3), we will discuss the nanoscale chemical and valence evolution at a metal/oxide interface: Ti/SrTiO3. In many devices, metal-oxide interfaces are ubiquitous and play important roles in the performance of a wide range of electronic and optoelectronic devices. This motivated us to examine the microscopic structure of the interfaces between strontium titanium oxide and metals. In this work, one unit cell of cubic perovskite Ti2O3 was observed at the Ti/SrTiO3 interface, and oxygen diffusion depth of ~3.2 nm was observed in the sample fabricated at room temperature. Meanwhile, oxygen vacancy domains in the SrTiO3 substrates was observed and characterized by low angle annular dark field (LAADF) imaging and electron energy loss spectra (EELS). In the main part of this thesis, we will focus on the structure and physical properties of Ti2O3, a titanite which has received less attention so far in the research community. Different from TiO2 and SrTiO3, Ti2O3 has a much narrower band-gap (~0.1 eV), and we will discuss some preliminary results of its physical properties and potential applications. In Chapter 4, we will discuss the photothermal application and mid-infrared photodetectors using Ti2O3 nanoparticles based on its ultra-narrow bandgap. Photo-thermal effect via a Ti2O3/membrane structure is further applied to seawater desalination. A high temperature of 70 °C was achieved when this Ti2O3/membrane double layer structure floating on top surface of water subjected to the white light illumination of 7 kW/cm2. Furthermore, room temperature mid-infrared (10 μm) photodetectors based on Ti2O3/graphene hybrid structure was fabricated and studied. The photoresponsivity of this hybrid device, operated from 4.5 to 10 μm, is above ~ 100 A/W, which, to our knowledge, is the highest value for the mid-infrared photodetectors operating in the photocurrent (PC) mode. In chapter 5, structure, optical, transport properties of Ti2O3 epitaxial thin films on sapphire fabricated by pulsed laser deposition (PLD) will be discussed. By tailoring growth conditions, two different: trigonal and orthorhombic, of Ti2O3 were stabilized on Al2O3 substrates. More interestingly, the orthorhombic Ti2O3 has never been reported, and, moreover, superconductivity (~8 K) and high temperature ferromagnetism (up to 700 K) was discovered in this new stabilized phase. More details of the physical properties of Ti2O3 will be discussed in the following chapters of this dissertation.

Optoelectronics in the deep-ultraviolet (DUV) regime is still a growing research field that requires significant effort to understand the material properties and optimize the device structures to realize efficient DUV devices. Aluminum gallium nitride (AlGaN) is perhaps the most studied semiconductor to replace the environmentally hazardous mercury lamps; however, the external quantum efficiency of AlGaN based DUV devices is insufficient to replace the existing old-fashioned mercury UV lamps. Despite the tunability in the bandgap of AlGaN, the excessive strain accumulation associated with increased alloying of Al in AlGaN and the poor dopant activation due to the relatively large ionization energy of the donors and acceptors are not favorable for realizing efficient DUV emitters. In addition, the crossover among the light hole, heavy hole and split-off bands in the valance band for Al-rich AlGaN suppresses the transverse-electric polarization, which further worsens the external quantum efficiency. Furthermore, for DUV photodetection, commercially available Si-photodetectors suffer from poor responsivity for wavelengths shorter than 400 nm in contrast to the visible spectrum. Hence, the-state-of-art photodetectors in the DUV regime also need a significant upgrade, particularly for high-speed applications. Firstly, we utilized the high quantum confinement in plasma-assisted MBE grown ultrathin GaN QDisks to realize DUV (λ ≈ 260 nm) emission using a binary compound (GaN) in contrast to conventionally used ternary compound (AlGaN). More importantly, we experimentally demonstrated TE-dominant DUV emission, unlike Al-rich AlGaN, illustrating a unique pathway for realizing efficient DUV vertical emitters. Secondly, inspired by the light manipulation technique practiced in nature, we presented iridocytes on giant clams (Tridacna maxima), known for their symbiotic relationship with algae as a color downconverting material for DUV photodetection. Investigating the structural and optical properties of iridocytes found in Tridacna maxima, we established a robust UV communication allowing the data transfer rate of 100 Mbit/s within the forward error correction limit for modulated 375 nm-laser diode. Using a similar matrix implemented to 375 nm-laser, with high-power UV-C LED (λ ≈ 278 nm), we could establish an optical wireless communication that could allow a data-transmission rate of tens of Mbit/s within the forward error correction limit.

Après dopage, les oxydes de terres rares peuvent acquérir des propriétés optiques intéressantes pour les dispositifs d’optoélectronique du futur. Ces matériaux peuvent aussi être utilisés comme absorbant neutronique dans les réacteurs nucléaires. Que ce soit pendant le processus de dopage ou en réacteur, ces oxydes sont soumis à des conditions d’irradiation aux ions intenses. Il est alors important de comprendre leur comportement dans cet environnement extrême. C’est l’objectif de cette thèse durant laquelle a été menée une étude fondamentale de matériaux modèles (couches épitaxiées assimilables à des monocristaux) sous irradiation ionique. Les principaux résultats montrent qu’un changement de phase, de cubique à monoclinique, se produit sous irradiation. Cette transition, qui n’est pas directement pilotée par l’énergie déposée par les ions, a lieu en plusieurs étapes liées à des évolutions microstructurales distinctes. Enfin, la composition joue un rôle sur le changement de structure, l’oxyde de Gadolinium étant plus rapidement transformé que l’oxyde d’Erbium. / After doping, the rare earth oxides can acquire interesting optical properties for the optoelectronic devices of the future. These materials can also be used as neutron absorbers in nuclear reactors. Whether during the doping process or in the reactor, these oxides are subjected to irradiation conditions with intense ions. It is important to understand their behavior in this extreme environment. This is the objective of this thesis during which a fundamental study of model materials(epitaxial layers assimilable to single crystals)under ionic irradiation was conducted. The main results show that a phase change, from cubic to monoclinic, occurs under irradiation. This transition, which is not directly driven by the energy deposited by the ions, takes place in several stages linked to distinct microstructural evolutions. Finally, the composition plays a role in the change of structure, gadolinium oxide being more rapidly transformed than Erbium oxide.

Les études concernent le développement de dispositifs supraconducteurs de détection de photon unique. Le nitrure niobium (NbN) est un matériau adapté à l’élaboration de fils supraconducteurs de la cible du détecteur. Ces travaux ouvrent des perspectives sur l’élaboration de films de nitrure de niobium épitaxié sur saphir par la méthode de dépôt chimique en phase vapeur (CVD). L’élaboration des films minces (5-100 nm) est effectuée à haute température (1000°C à 1300°C) à partir de chlorure de niobium et d'ammoniaque dilués dans l'hydrogène (H2-NH3-NbCl5). Les substrats sont du saphir monocristallin (Al2O3) orienté (0002), du nitrure d'aluminium (AlN) orienté (0002) et de 'oxyde de magnésium (MgO) orienté (100).L'étude des relations d’épitaxie au cours de la croissance du nitrure de niobium sur le substrat de saphir a tout d'abord été effectuée. L’observation des microstructures et des orientations cristallines des différents films élaborés a permis de mettre en évidence les relations existant entre l'état de surface du substrat et le mode de croissance du NbN. Les perspectives d'utilisation de substrats monocristallins de type MgO et AlN sont présentées en conclusion.L’étude du procédé de croissance et les relations existant entre les conditions d'élaboration et la "qualité" des films minces a permis de dégager les fenêtres expérimentales conduisant à une croissance épitaxiale. L’énergie d’activation des réactions de croissance et les conditions de sursaturation propices à la croissance épitaxiale ont été calculées.L'étude des relations entre les propriétés structurales et les caractéristiques supraconductrices des films a permis de relier la température de transition supraconductrice à la densité de défauts atomiques, aux défauts microstructuraux, à l’épaisseur des films élaborés et à leur état de contrainte. Il existe une relation linéaire entre l’espace interréticulaire des plans parallèles au substrat et la température de transition supraconductrice.Enfin, l'étude de la durabilité des films ultraminces (5 – 8 nm) de nitrure de niobium a été menée. Dans cette étude les propriétés électriques et supraconductrices de films élaborés à 1000°C et 1200°C sur des substrats de saphir et de couches épitaxiales d'AlN ont été analysées sur une durée de six mois. Les propriétés des films évoluent surtout au cours du premier mois. Le dépôt effectué à haute température permet de limiter la dégradation rapide des films et de conserver leurs propriétés supraconductrices. / The studies concern the development of superconducting devices for single photon detection. Niobium nitride (NbN) is a material suitable for the production of superconducting wires for the detector target. This work is opening up perspectives on the development of epitaxial niobium nitride films on sapphire by the chemical vapor deposition (CVD) method. The production of thin films (5-100 nm) is carried out at high temperature (1000°C to 1300°C) from niobium chloride and ammonia diluted in hydrogen (H2-NH3-NbCl5). The substrate is oriented single crystalline sapphire (Al2O3) (0002), aluminum nitride (AlN) (0002) or magnesium oxide (MgO) (100).The study of epitaxial relationships during the growth of niobium nitride on the sapphire substrate was first performed. Observation of the microstructures and crystalline orientations of the various films processed made it possible to highlight the relationships between the surface state of the substrate and the growth mode of NbN. The potential for using single crystal substrates such as MgO and AlN is discussed in the conclusion.The study of the growth process and the relationships between the working conditions and the "quality" of thin films made it possible to identify the experimental windows leading to epitaxial growth. The activation energy of the growth reactions and the supersaturation conditions favorable to epitaxial growth were calculated.The study of the interactions between the structural properties and superconducting properties of films has allowed the superconducting transition temperature to be linked to the density of atomic defects, microstructural defects, the thickness of the films and their stress state. There is a linear relationship between the interplanar space of planes parallel to the substrate and the superconducting transition temperature.Finally, the durability of ultra-thin films (5 - 8 nm) of niobium nitride was studied. The electrical and superconducting properties of films processed at 1000°C and 1200°C on sapphire substrates and epitaxial layers of AlN were analyzed over a period of six months. The properties of films change most notably during the first month. High temperature deposition limits the rapid degradation of the films and preserves their superconducting properties.

2D semiconductors are one of the most promising materials for next-generation electronics. Realizing continuous 2D monolayer semiconductors with single-crystalline structure at the wafer scale is still a challenge. We developed an epitaxial phase conversion (EPC) process to meet these requirements. The EPC process is a two-step process, where the sulfurization process was carried out on pre-deposited Mo-containing films. Traditionally, two-step processes for 2D MoS2 and other chalcogenides have suffered low-quality film and non-discontinuity at monolayer thickness. The reason was regarded as the low lattice quality of precursor film. The EPC process solves these problems by carefully preparing the precursor film and carefully controlling the sulfurization process. The precursor film in the EPC process is epitaxial MoO2 grown on 2″ diameter sapphire substrate by pulsed laser deposition. This epitaxial precursor contains significantly fewer defects compared to amorphous precursor films. Thus fewer defects are inherited by the EPC MoS2 film. Therefore, EPC MoS2 film quality is much better. The EPC prepared monolayer MoS2 devices to show field-effect mobility between 10 ~ 30 cm2·V-1s-1, which is the best among the two-step process. We also developed a CLAP method further to reduce the defects in the precursor oxide film; thus, in-plane texture in the thicker MoS2 film was eliminated, and a single-crystalline structure was obtained in the wafer-scale MoS2 films. The potentially feasible technique to further improve the 2D film quality is pointed out for our next research plan. Meanwhile, the epitaxial phase conversion process was proposed to be as a universal growth method. Last but not least, we demonstrate several potential applications of the wafer-scale single-crystalline MoS2 film we developed, such as logic circuits, flexible electronics, and seeding layer of van der Waal or remote epitaxial growth.

Micro-electro-mechanical systems (MEMS) have become an essential component of a wide range ofelectronic devices over the last decades such as accelerometers, microphones, gas sensors, and filters.During this new millennium, a new radio frequency (RF) technology has been developed to satisfy thetough demands that arose due to the implementation of 5G wireless communication: bulk acoustic wave(BAW) filters.BAW devices use the piezoelectric effect, converting mechanical vibrations to electrical signals, topower wireless devices. BAW filters can operate between 3.5 GHz and 6 GHz, therefore, within therange of the new 5G. BAW technology offers lower insertion loss, higher heat dissipation, andperformances at higher power and frequency which increases the data speed considerably.This thesis will be focused on the study of the materials used in BAW devices. A common BAW filteris made from different layers distributed in a stack, from the bottom to the upper part, the BAW filteris composed of a substrate, a transducer layer made of a piezoelectric layer in between of two electrodes,and intermediate layers that can enhance the addition of the deposited layers on top called buffer layers,or the crystal quality of the films on top called seed layers.The main characteristic that a buffer layer must possess is an intermediate lattice parameter betweenthat of the substrate and the top layer. When these two layers present a high lattice mismatch, theinterface quality is rather poor. By using a buffer layer, and therefore, by adding two different interfaces,the crystal quality is improved by decreasing the internal stress and the crystal distortion. Buffer layermaterials depend on the type of materials that will be in contact with them.A seed layer is usually used to improve the crystal quality of a layer that requires extreme sputteringparameters to be used to be deposited possessing a high crystal quality and a preferred orientation. Seedlayers used in BAW devices, whose piezoelectric layer is made of AlScN or AlN, are usually made ofhighly c-axis oriented and highly crystalline AlN.The objective of this study is to analyze the deposition of AlN and HfN by means of reactive radiofrequency magnetron sputtering and reactive pulsed-direct current magnetron sputtering, respectively.AlN is largely used as a buffer layer and as a seed layer, however, the new approach of this report is tostudy the sputtering of HfN and compare it as a possible candidate to replace AlN as a seed layer.

The growth mechanism of chemical vapor deposition (CVD) grown homo-epitaxial diamond (110) and (111) films was studied using ultrahigh vacuum (UHV) scanning tunneling microscopy (STM). In addition, the field emission properties of diamond coated molybdenum microtips were studied as a function of exposure to different gases.