Carbon nanotubes (CNTs) have great potential in many applications due to their unique structure and properties. However, there are still many unsolved problems hampering their real applications. This thesis focuses on three important issues limiting their applications, namely: (1) direct growth of CNTs without additional catalyst, (2) secondary growth of carbon nanotubes on primary CNT bed without using extra catalyst, (3) and CNT alignment mechanisms during the growth.<p> The CNTs used in this thesis were prepared by hot filament chemical vapor deposition (CVD) reactor and characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), and Raman spectroscopy. Field electron emission (FEE) properties of the CNTs were also tested.<p> Oxidation-reduction method was adopted in direct growth of CNTs on Inconel 600 plates and proved effective. The effect of oxidation temperature on the growth of CNTs was studied. It was found that the oxidation temperature had an influence on CNT height uniformity and FEE properties: the higher the treatment temperature, the more uniform the resultant CNTs, and the better the FEE properties of the resultant CNTs. The contribution of different oxides formed at different temperatures were investigated to explain the effect of oxidation temperature on the CNT height uniformity.<p> Secondary CNTs were grown on primary ones by simply changing the carbon concentration. No additional catalyst was used during the whole deposition process. It was found that synthesizing primary CNTs at extremely low carbon concentration is key factor for the secondary growth without additional catalyst. The CNT sample grown with secondary nanotubes exhibited improved field emission properties.<p> The effect of bias voltage on growth of vertically aligned carbon nanotubes was investigated. The CNTs grown at -500V shows the best alignment. At the early growth stage, simultaneous growth of randomly oriented and aligned carbon nanotubes was observed. This was consistent with the alignment mechanism involving stress that imposed on catalyst particles on tube tips. Through the observation of CNT growth on the scratched substrates, catalyst particle size was found as another determining factor in the alignment of CNTs. Big catalyst particles promoted aligned growth of CNTs.

Carbon nanotubes (CNTs) have great potential in many applications due to their unique structure and properties. However, there are still many unsolved problems hampering their real applications. This thesis focuses on three important issues limiting their applications, namely: (1) direct growth of CNTs without additional catalyst, (2) secondary growth of carbon nanotubes on primary CNT bed without using extra catalyst, (3) and CNT alignment mechanisms during the growth.<p> The CNTs used in this thesis were prepared by hot filament chemical vapor deposition (CVD) reactor and characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), and Raman spectroscopy. Field electron emission (FEE) properties of the CNTs were also tested.<p> Oxidation-reduction method was adopted in direct growth of CNTs on Inconel 600 plates and proved effective. The effect of oxidation temperature on the growth of CNTs was studied. It was found that the oxidation temperature had an influence on CNT height uniformity and FEE properties: the higher the treatment temperature, the more uniform the resultant CNTs, and the better the FEE properties of the resultant CNTs. The contribution of different oxides formed at different temperatures were investigated to explain the effect of oxidation temperature on the CNT height uniformity.<p> Secondary CNTs were grown on primary ones by simply changing the carbon concentration. No additional catalyst was used during the whole deposition process. It was found that synthesizing primary CNTs at extremely low carbon concentration is key factor for the secondary growth without additional catalyst. The CNT sample grown with secondary nanotubes exhibited improved field emission properties.<p> The effect of bias voltage on growth of vertically aligned carbon nanotubes was investigated. The CNTs grown at -500V shows the best alignment. At the early growth stage, simultaneous growth of randomly oriented and aligned carbon nanotubes was observed. This was consistent with the alignment mechanism involving stress that imposed on catalyst particles on tube tips. Through the observation of CNT growth on the scratched substrates, catalyst particle size was found as another determining factor in the alignment of CNTs. Big catalyst particles promoted aligned growth of CNTs.

Carbon-infiltrated carbon nanotube (CICNT) forests are carbon nanotube (CNT) forests infiltrated with pyrolytic carbon to increase durability by becoming a solid material. This material can be tuned to maintain the nanotube geometry of a CNT forest and can also be fabricated on a variety of materials and geometries. Additionally, the present work has indicated that CICNT forests may resist bacterial proliferation and biofilm formation. This phenomenon is not due to the CICNT chemistry; it is presumably due to the CICNT nanostructure morphology. Thus, both silicon and stainless steel substrates were used to investigate CICNT's structural resistance to Methicillin-resistant Staphylococcus aureus (MRSA) biofilm. From in vitro experimental testing, CICNT on both these substrates resisted MRSA cell attachment and biofilm proliferation. The discovery of this non-pharmaceutical biofilm resistance expands the potential applications of CICNT to include medical devices that are prone to infection and/or devices that contribute to infection. Two representative applications were investigated: external fixator pins and scalpel blades. CICNT-coated versions of these applications underwent additional MRSA biofilm resistance testing as well as mechanical testing. In particular, external fixator pins were identified as a high potential application of CICNT surface coating technology. Previous work on both CNT and CICNT forests has largely been performed on planar structures. However, any potential medical device applications involve curved substrates. In particular, concave curvatures are challenging due to the potential for stress-related CICNT forest defects. Thus, the present work also included a study of the incidence rates and determining factors of these defects. SEM images of the cross-sections revealed different types of microscale forest defects while the top surface showed morphologies that are largely consistent with flat substrates. CICNT forest height and substrate curvature were identified as contributing factors to CICNT forest defect incidence rates. Thus, the present work advances the understanding of bacterial resistance and microstructure-related properties of CICNT surface coatings, with applications in medical devices.

Le graphène est un matériau bidimensionnel appartenant à la famille des allotropes du carbone. Il consiste en une couche atomique restant stable grâce à des liaisons chimiques fortes dans le plan entre les atomes de carbone. C'est un semi-conducteur sans bande interdite (gap) avec une dispersion d'énergie linéaire près des points de Dirac, ce qui facilite le transport balistique des porteurs de charge. De plus, tout comme n'importe quel semi-conducteur, il est possible de contrôler ses propriétés électriques sous l'influence d'un champ électrique externe, ce qui permet de modifier la densité de porteurs et leur type (électrons ou trous). Le graphène peut être élaboré par différentes techniques, mais nous avons considéré la croissance directe sur le carbure de silicium (SiC) par dépôt chimique en phase vapeur (CVD) avec une source de carbone externe, technique développée dans notre laboratoire depuis 2010. Cette approche est attrayante car elle permet de contrôler les propriétés du graphène en modifiant les paramètres de croissance. Notre objectif dans ce manuscrit est de donner une idée plus approfondie de cette technique de croissance et d'étudier son potentiel pour la croissance du graphène. À cette fin, nous avons discuté en détail de différents aspects de la croissance, en commençant par des simulations thermodynamiques pour comprendre la chimie gouvernant cette méthode. Nous avons également étudié l'influence des différents paramètres de croissance sur la formation du graphène et sur ses propriétés, tels que le temps de croissance, le débit de propane et d'autres paramètres. Cependant, nous nous sommes principalement concentrés sur deux paramètres majeurs : la quantité d'hydrogène dans le mélange gazeux, surtout que la croissance se fait sous hydrogène et argon, et la désorientation du substrat. Nos recherches ont révélé que la structure du graphène peut être modifiée en fonction de la proportion de l’hydrogène dans le mélange des gaz utilisé pour la croissance. Pour une faible proportion d’hydrogène, la croissance du graphène est associée à une reconstruction d'interface de (6√3×6√3), alors que pour une proportion élevée d’hydrogène, la couche de graphène est désordonnée dans le plan. Ces observations sont liées à l'intercalation de l'hydrogène à l'interface entre la couche de graphène et le substrat SiC, ce qui peut favoriser ou interdire la formation de la reconstruction (6√3×6√3) comme nous l'avons discuté dans le manuscrit. On s'attend à ce que la présence des deux structures de graphène ait un effet sur la contrainte dans la couche de graphène. Pour cette raison, nous avons discuté en détail les origines de la contrainte dans le graphène et tenté de corréler l'intercalation de l'hydrogène à l’interface avec la contrainte. Aussi, nous avons montré que l'angle de désorientation du substrat a une influence directe sur la croissance du graphène, affectant principalement la morphologie mais également la contrainte dans la couche du graphène. Enfin, nous avons pu produire du graphène de haute qualité, tout en démontrant la possibilité de contrôler ses propriétés électriques avec les conditions de croissance. Dans la deuxième partie de ce travail, nous avons étendu notre étude à la croissance du graphène sur les semi-conducteurs de type nitrures d’éléments III et en particulier le nitrure d’aluminium (AlN) massif ainsi que des couches hétéroépitaxiées d’AlN/SiC et AlN/Saphir, ce qui ouvre de nouvelles opportunités pour des applications innovantes. La croissance du graphène a été précédée d'une étude de recuit sur les différents échantillons d’AlN, dans le but d'améliorer leur qualité de surface, mais aussi pour tester leur stabilité à la température nécessaire pour la croissance du graphène. Bien que le film d’AlN ait été incapable de résister à la température élevée dans certains cas, une amélioration de la qualité cristalline a été détectée, attribuée à l'effet de recuit. / Graphene is a two-dimensional material belonging to the family of carbon allotropes, consisting of a stable single atomic layer owing to strong in-plane chemical bonds between carbon atoms. It can be identified as a gapless semiconductor with a linear energy dispersion near the Dirac points, which facilitates ballistic carrier transport. In addition, similarly to any semiconductor, it is possible to control its electrical properties under the influence of an external electric field, resulting in the tuning of its carrier density and doping type, i.e. electrons or holes. Graphene can be elaborated by different techniques and approaches. In this present work, we have considered the direct growth on silicon carbide (SiC) by chemical vapor deposition (CVD) with an external carbon source. This approach which has started to be developed in our laboratory since 2010 is very promising since it allows to control the graphene properties by manipulating the growth parameters. Our objective in this manuscript is to give further insights into this growth technique and to study its potential for the growth of graphene. For this purpose, we have discussed in details different aspects of the growth, starting with thermodynamic simulations to understand the chemistry behind our distinct growth approach. We have also investigated the influence of the different growth parameters, such as the growth time, the propane flow rate and other parameters on the growth of graphene and its properties. However, we mainly focused on two major factors: the hydrogen amount in the gas mixture, especially since the growth is carried out under hydrogen and argon, and the substrate’s miscut angle. Our investigations revealed that the graphene structure can be altered depending on the hydrogen percentage in the gas mixture considered for the growth. For low hydrogen percentage, the graphene growth is associated with a (6√3×6√3) interface reconstruction, whereas for high hydrogen percentage, the graphene layer is dominated by in-plane rotational disorder. These observations are related to the hydrogen intercalation at the interface between the graphene layer and the SiC substrate, which can allow or prohibit the formation of the (6√3×6√3) interface reconstruction as we have discussed thoroughly in this manuscript. The presence of two graphene structures was expected to impact the strain within the graphene layer. For this reason, we have discussed in details the origins of the strain in graphene and attempted to correlate the hydrogen intercalation at the interface to the strain amount. Furthermore, the substrate’s miscut angle was also found to have a direct influence on the growth of graphene, mainly affecting the morphology but also the strain within the graphene layer. In light of the different studies and results, we were able to combine the ideal growth parameters to produce state-of-the art graphene, while demonstrating the possibility of tuning its electrical properties with the growth conditions. In a second part of this work, we extended our study to the growth of graphene on III-nitrides semiconductors. We have considered substrates and templates such as bulk aluminum nitride (AlN), AlN/SiC and AlN/sapphire, which opens new opportunities for innovative applications. The growth of graphene was preceded by an annealing study on the different AlN substrates, in an attempt to enhance their surface quality, but also to test their stability at the temperatures necessary for the growth of graphene. Although the AlN film was found to be unable to withstand the high temperature in some cases, an enhancement of the crystalline quality was detected, attributed to the annealing effect.