Since the first isolation of graphene in 2004 interest in superconductivity and the superconducting proximity effect in monolayer or few-layer crystals has grown rapidly. This thesis describes studies of both the proximity effect in single and fewlayer graphene flakes, as well as the superconducting transition in few unit cell chalcogenide flakes. Optical and atomic force microscopy and Raman spectroscopy have been used to characterise the quality and number of molecular layers present in these flakes. Graphene structures with superconducting Al electrodes have been realised by micromechanical cleavage techniques on Si/SiO2 substrates. Devices show good normal state transport characteristics, efficient back-gating of the longitudinal resistivity, and low contact resistances. Several trials have been made to investigate proximity-induced critical currents in devices with junction lengths in the range 250-750 nm. Unfortunately, no sign of proximity supercurrents was observed in any of these devices. Nevertheless the same devices have been used to carefully characterise proximity doping, (due to the deposited electrode), and weak localisation/anti-localisation contributions to the conductivity in them. In addition this work has been extended to investigations of the superconducting transition in few unit-cell dichalcogenide flakes. Four-terminal devices have been realised by micromechanical cleavage from a 2H-NbSe2 single crystal onto Si/SiO2 substrates followed by the deposition of Cr/Au contacts. While very thin NbSe2 flakes do not appear to conduct, slightly thicker flakes are superconducting with an onset ܶ௖ that is only slightly depressed from the bulk value (7.2K). The resistance typically shows a small, sharp, high temperature transition followed by one or more broader transitions, which end in a wide tail to zero resistance at low temperatures. These multiple transitions appear to be related to disorder in the layer stacking rather than lateral inhomogeneity. The behaviour of several flakes has been characterised as a function of temperature, applied field and back-gate voltage. The resistance and transition temperatures are found to depend weakly on the gate voltage. Results have been analysed in terms of available theories for these phenomena.

Theoretical predictions of the AC conductivity of both monolayer and Bernal-stacked bilayer graphene have largely been in agreement with experimental observations. Due to the recent realization of AA-stacked samples, we provide theoretical predictions for this system. We begin this thesis with a review of the optical properties of graphene and provide a brief discussion of the previously studied Bernal-stacked bilayer. We then calculate the optical conductivity of AA-stacked bilayer graphene as a function of frequency for several interesting cases. We are primarily interested in the case of finite doping due to charging. Unlike the monolayer, we see a Drude absorption at charge neutrality as well as an interband absorption with strength twice that of the monolayer background conductivity which onsets at twice the interlayer hopping energy. We examine the behaviour as we vary the chemical potential relative to the interlayer hopping energy scale and compute the partial optical sum. We also consider the effect of adding a bias across the layers and find it serves merely to renormalize the interlayer hopping parameter. While interested in the in-plane conductivity we also provide the perpendicular conductivity of the AA-stacked bilayer. We then extend the ideas to the AAA-stacked trilayer. Based on proposed models for topological insulators discussed in the literature, we consider the effect of spin orbit coupling in both one and two layers on the optical properties of the AA-stacked bilayer which illustrates the effect of opening an energy gap in the band structure.

Le nitrure de bore hexagonal (hBN) est un semi-conducteur à grand gap (>6 eV) appartenant à la nouvelle famille des cristaux 2D. Ses propriétés isolantes et sa structure cristalline font de lui un matériau stratégique dans la réalisation d’hétérostructures 2D à base de graphène. L’objectif de cette thèse a été d’étudier les propriétés optiques et structurales des feuillets de hBN.Après une description des méthodes expérimentales, les propriétés du matériau massif - loin des interfaces - sont étudiées sur le cristal de référence synthétisé par croissance haute-pression haute-température au Japon. L’étude en microscopie électronique à transmission a permis d’identifier l’empilement AA’, caractéristique du hBN. Les 3 principales régions d’émission de luminescence du hBN sont identifiées et analysées dans le détail : excitons libres, excitons piégés et défauts profonds. L’efficacité radiative excitonique a été analysée sur des cristaux issus de différentes voies de synthèse mettant en évidence des qualités dispersées. L’origine des processus de luminescence est discutée en regard des différentes interprétations actuelles, théoriques et expérimentales.Le cœur de la thèse porte sur les propriétés des cristaux 2D de faibles épaisseurs obtenus par clivage mécanique, ceci jusqu’à la monocouche atomique. Les expériences réalisées en spectroscopie Raman basse fréquence, en spectroscopie de pertes d’énergie et en cathodoluminescence ont mis en évidence une série d’effets de basse dimensionnalité sur les propriétés vibrationnelles, diélectriques et excitoniques du hBN. L’étude des défauts introduits lors de l’étape d’exfoliation et leur impact sur les émissions de luminescence ont permis d’isoler les propriétés intrinsèques des cristaux 2D de hBN. Les premiers résultats obtenus sur des feuillets suspendus dans le vide sont présentés et les effets de déformation élastique et plastique sur la luminescence de hBN discutés.La dernière partie de cette thèse porte sur des cristaux de nitrure de bore rhomboédrique (rBN) où les feuillets atomiques forment un empilement ABC. Ces cristaux ont permis d’aborder l’effet de l’empilement des plans atomiques sur la luminescence du BN en hybridation sp². / Hexagonal boron nitride (hBN) is a wide bandgap semi-conductor (>6 eV) which belongs to the 2D crystals family. Its structure and insulating properties make him as a strategic component towards the conception of graphene-based 2D heterostructures. This thesis focuses on the structural and optical properties of hBN layers.After a brief description of experimental methods, bulk material properties have been investigated on the reference HPHT-grown crystal fabricated in Japan. The characteristic stacking AA’ sequence of the hexagonal BN phase has been identified by transmission electron microscopy. Characteristics features of the 3 main luminescence regions have been identified and analyzed into details: free excitons, bound excitons and deep defects. The radiative efficiency of excitons recombinations in hBN has been studied on crystals obtained through various synthesis routes. The origin of hBN luminescence processes is discussed on the basis of current theoretical and experimental interpretations.The main part of the thesis is dedicated to the study of nanometer-thick hBN crystals obtained by mechanical cleavage, down to the monolayer. Experiments carried out by low-frequency Raman spectroscopy, energy loss spectroscopy and cathodoluminescence demonstrated a series of low-dimensionality effects on the vibrational, dielectric and excitonic properties of hBN. Defects introduced during the exfoliation step have been studied, their impact on luminescence emissions allowed us to isolate the intrinsic properties of 2D hBN flakes. Preliminary results obtained on hBN layers suspended in vacuum are presented and the effects of elastic and plastic deformation on BN luminescence are discussed.The last part of the work focuses on rhombohedral boron nitride (rBN) crystals where the BN stacking sequence follows the ABC type. Studying these crystals made possible the investigation of the influence of the stacking sequence on sp² BN luminescence.

There has been growing interest in two-dimensional (2-D) crystals beyond graphene for next-generation nano-electronics. Transition metal dichalcogenides have been most widely studied, for their semiconducting characteristics and hence, potential applications. This interest has fueled many efforts to establish methods for synthesis of MoS2 layers, a most promising candidate, in controlled numbers over large areas. One of the most scalable methods is chemical vapor deposition (CVD). The current approaches to growth from the vapor phase are by and large very empirical. This thesis is hence concerned with the predictive synthesis of n-layered MoS2 using CVD uniformly over large areas and the correlation of growth parameters with the structural and electronic properties of the deposited films. A simple, relatively non-toxic and non-pyrophoric chemistry, consisting of Mo(CO)6 and H2S was first chosen for vapor phase synthesis. This chemistry allowed synthesis of MoS2 from precursors located outside of the growth reactor, a necessary condition for electronics device technology. Iterative thermodynamic modeling of the Mo-S-C-O-H system and growth was then done to identify the appropriate CVD process windows for the growth of pure MoS2, departures from stoichiometry, contamination and breakdown of equilibrium modelling. Remarkable agreement between theoretical modelling and actual growth has been observed leading to predictable deposition. Within these thermodynamic windows, the gas phase supersaturation were then reduced to obtain better kinetic control over crystal growth. It is shown that control of supersaturation at the very initial stages of growth is critical to reduce the nucleation density and hence obtain monolayers with small defect densities. In addition, it is shown that at higher temperatures the kinetics of nucleation and growth are determined by the supersaturation on the growth surface. Physico-chemical modelling reveals that this steady state supersaturation is determined by the kinetics of adsorption and desorption. All of this understanding has been used to realize a variety of structures from discrete crystalline islands- 30 nm to 150 microns- to deposits with controlled number of layers – n =1 to 6 or greater- uniformly over large areas on quartz and sapphire. Gas phase chemistry also affects the electrical characteristics of the as deposited layers. It is shown, for the first time, that by changing gas phase Mo to S ratios the stoichiometry of the deposited layers MoS2 can be made metal or chalcogen deficient. This yields MoS2 that can be either p-type or n-type. p-type and n-type MoS2 with mobilities up to 7.4 cm2/Vs and 40 cm2/Vs respectively are demonstrated. FETs fabricated on MoS(2-x) samples (increasing x) with varying stoichiometry showed a maximum on-current of 18 μA (4.5 μA/μm) in vacuum and 0.6 μA (0.15 μA/μm) in air for a drain bias Vds = 1 V. Sulphur deficiency also affect reliability. While samples with a higher concentration of sulphur vacancies have higher mobility in vacuum, the mobility degrades significantly in air and gets reversed on annealing in H2S. The details of such correlation between growth and electrical characteristics are discussed in this thesis.