Modeling of single-walled carbon nanotubes, multi-walled nanotubes and nanotube reinforced polymer composites using both the Finite Element method and the Molecular Dynamic simulation technique is presented. Nanotubes subjected to mechanical loading have been analyzed. Elastic moduli and thermal coefficient of expansion are calculated and their variation with diameter and length is investigated. In particular, the nanotubes are modeled using 3D elastic beam finite elements with six degrees of freedom at each node. The difficulty in modeling multi walled nanotubes is the van der Waal's forces between adjacent layers which are geometrically non linear in nature. These forces are modeled using truss elements. The nanotube-polymer interface in a nano-composite is modeled on a similar basis. While performing the molecular dynamic simulations, the geometric optimization is performed initially to obtain the minimized configuration and then the desired temperature is attained by rescaling the velocities of carbon atoms in the nanotube. Results show that the Young's modulus increases with tube diameter in molecular mechanics whereas decreases in molecular dynamics since the inter-atomic potential due to chemical reactions between the atoms is taken into consideration in molecular dynamics unlike in molecular mechanics.

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.

Dans le vaste domaine des nanosciences et nanotechnologies, les nanotubes de carbone (NTC) suscitent un intérêt particulier en raison de leur structure originale qui leur confère des propriétés exceptionnelles. Alors que le nombre d'applications ainsi que la quantité de NTC produite ne cessent d'augmenter chaque année, il est essentiel de comprendre les mécanismes régissant la formation de ces nanomatériaux afin de contrôler leur structure et leur organisation, optimiser les rendements, diminuer les risques sanitaires et environnementaux et améliorer les performances des matériaux et composants sous-jacents. Parmi les techniques de synthèse répertoriées, la CVD d'aérosol (Chemical Vapor Deposition) développée au laboratoire MSSMat, permet la croissance continue de NTC multi-feuillets de haute qualité sur divers substrats par l'injection simultanée de sources carbonées liquide (xylène) et gazeuse (acétylène) et de précurseur catalytique (ferrocène) dans un réacteur porté à une température comprise entre 400 et 1000°C. L'objectif de cette étude a consisté à examiner les différentes étapes de la formation des NTC dès l'injection des précurseurs jusqu'à la fin de la croissance. Grâce une nouvelle approche expérimentale faisant intervenir plusieurs diagnostics in situ couplés à des modèles numériques, nous avons pu suivre l'évolution des différents réactifs et produits lors de synthèses dans des conditions thermodynamiques (flux de gaz et températures) et chimiques (concentrations des différents précurseurs) variées. De fait, après avoir examiné l'évolution spatiale des gouttelettes formées lors de l'injection, la germination des nanoparticules en phase gazeuse a été étudiée par incandescence induite par laser (L2I) et spectroscopie de plasma induit par laser (LIPS). Une relation entre la taille de ces particules et celle des NTC a ainsi pu être mise en évidence. Les réactions chimiques pendant la synthèse ont ensuite été analysées par spectrométrie de masse et chromatographie en phase gazeuse. Différents mécanismes réactionnels ont ainsi pu être identifiés en fonction des sources de carbone utilisées, alors que l'effet de l'hydrogène sur la croissance, soit accélérateur ou soit inhibiteur selon les conditions, a été étudié. Les rôles du substrat ont par ailleurs été examinés en comparant la croissance et la morphologie des NTC obtenus sur différentes surfaces telles que des plaques de quartz, des fibres de carbone ou des micro-particules d'alumine, de carbure de silicium, de carbure de titane et de graphène de formes variées. L'effet catalytique de certains substrats ou mélanges de substrats sur la croissance des NTC a d'ailleurs été mis en évidence, de même que l'importance du rapport surface/volume des substrats sur les rendements massiques des NTC. La cinétique de croissance des NTC a finalement été étudiée et différents mécanismes à l'origine de la désactivation des catalyseurs ont été identifiés. Enfin, les différentes nanostructures hybrides issues de la croissance de NTC sur différents substrats ont servi à concevoir des matériaux composites multi-fonctionnels à hautes-performances dont les propriétés électriques, thermiques et mécaniques ont été analysées.

In the first part of this dissertation, we study mainly novel boron structures and their electronic and mechanical properties, using ab initio calculations. The electronic structure and construction of the boron buckyball B80, and boron nanotubes as the α-sheet wrapped around a cylinder are studied. The α-sheet is considered so far to be the most stable structure energetically out of the two dimensional boron assemblies. We will argue however that there are other sheets close in energy, using cluster expansion method. The boron buckyball is shown to have different possible isomers. Characterization of these isomers according to their geometry and electronic structure is studied in detail. Since the B80 structure is made of interwoven double-ring clusters, we also investigate double-rings with various diameters. We investigate the properties of nanotubes obtained from α-sheet. Computations confirm their high stability and identify mechanical stiffness parameters. Careful relaxation reveals the curvature-induced buckling of certain atoms off the original plane. This distortion opens up the gap in narrow tubes, rendering them semi-conducting. Wider tubes with the diameter d  1.7 nm retain original metallic character of the α-sheet. We conclude this part by investigation into hydrogen storage capacity of boron-rich compounds, namely the metallacarboranes. In the second part of dissertation, we switch our focus to electronic and transport properties of carbon nano-structures. We study the application of carbon nanotubes as electro-chemical gas sensors. The effect of physisorption of NO2 gas molecules on electron transport properties of semi-conducting carbon nanotubes is studied using ab initio calculations and Green’s function formalism. It is shown that upon exposure of nanotube to different concentrations of gas, the common feature is the shift in conductance towards lower energies. This suggests that physisorption of NO2 will result in a decrease (increase) in conductance of p-type (n-type) nanotubes with Fermi energies close to the edge of valence and conduction band. Finally we study the effect of torsion on electronic properties of carbon nano-ribbons, using helical symmetry of the structures.

No description available.

Single-walled carbon nanotubes (SWCNTs) are promising for use in solar cells and photodetectors because of their strong optical absorption in most of the solar spectrum. There have been many reports about the photovoltaic effect in nanoelectronic devices based on individual SWCNTs, but they have been limited by complicated fabrication and miniscule absorption. There has been a growing trend for merging SWCNTs into micro-and macroscopic devices to provide more practical applications. Here we report the photoresponse of macroscopic SWCNT films with a p-n junction at room temperature. Photovoltage (PV) and photocurrent (PC) due to the photothermoelectric (PTE) effect were observed at the junction, and they were larger by one order of magnitude as compared with their values at the metal-SWCNT interfaces. Various factors affecting PV amplitude and response time have been studied, including junction length, substrate, and doping level. The maximal responsivity we observed was 1V/W with samples on Teflon tape, while a fast response time 80 S was observed with samples on AlN substrates. Hence an optimal combination of photoresponse time and amplitude can be found by proper choice of substrate. It was found that PV increased nonlinearly with increase in n-doping concentration, indicating the existence of an optimal doping level. This result also suggests the possibility to further improve photoresponse by changing p-doping level. Finally, we checked the photoresponse in wide wavelength range (360-900 nm), and PV was observed throughout, indicating that the device could potentially be used as a broadband photodetector.

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.

Due to entropy and Van der Waals¡¦ interaction, carbon nanotubes tend to aggregate degrading their excellent opto-electronic properties and limiting their applications. Chemical derivatizations were applied to the multi-wall carbon nanotube (MWCNT) by esterificating with different lengths of aliphatic pendants (COOC4H9, COOC10H21, and COOC18H37) to decrease the MWCNT aspect ratio to facilitate its dispersion, and to observe its percolation behavior. FTIR analysis revealed the more relevant absorption peaks of C-H at 2917 cm-1, 2846 cm-1 and C=O at 1733 cm-1 from the derivatization. H1-NMR showed that the aliphatic pendant functionalized MWCNT from the signals of OCH2 at £_ = 3.64 ppm, CH2 at £_ = 1.25 ppm, and CH3 at £_ = 0.88 ppm. Raman scattering indicated that esterification caused the ID/IG absorption peak area ratio to decrease. In applications, the electric conductivity was measured on thin-films of MWCNT:Poly-(3-hexylthiophene) (P3HT) as a function of nanotube content. Accompanied with nanotube doping concentration increased, the electric conductivity parallel to film surface (£m||) could range from an undoped value 1.4¡Ñ10-6 S/cm up to 1.2¡Ñ10-2 S/cm. The conductivity percolation threshold concentration decreased as the MWCNT aspect ratio increased due to the average distance between the nanotubes becoming sufficiently small for charges to hopping through P3HT. By incorporating [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), bulk heterojunction photovoltaic (PV) cells of ITO/PEDOT:PSS/MWCNT:[PC61BM:P3HT]/LiF/Al were fabricated. By varying the ratio of MWCNT to the PC61BM:P3HT (0.8:1) mixtures, the PV cells showed the maximum power conversion efficiency (£bp) close to 4 % with MWCNT-COOC4H9 at a doping concentration of 0.01 wt. %.

Boron-doped carbon nanotubes are predicted to behave as semiconductors over a large range of diameters and chiralities and might thus constitute a suitable class of material for nanoelectronics technology. Boron-doped CNTs were reported as by-products when BC2N nanotubes were prepared by an arc-discharge method. The potential doping of CNTs with different kinds of atoms might provide a mechanism for controlling their electronic properties. We have synthesized boron-doped carbon nanotubes (CNTs) directly on copper catalyst by decomposition of B(OCH3)3 in chemical vapor deposition method. The results were characterized and analyzed by scanning electron microscopy (SEM), Raman, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), solid-state NMR and TGA.

A method offering precise control over the synthesis conditions to obtain carbon nanotube (CNT) samples of a single chirality (metallic or semi-conducting) is presented. Using this nanolithographic method of catalyst deposition, the location of CNT growth is also precisely defined. This technique obviates three significant hurdles that are preventing the exploitation of CNT in micro- and nano-devices. Microelectronic applications (e.g., interconnects, CNT gates, etc.) require precisely defined locations and spatial density, as well as precisely defined chirality for the synthesized CNT. Conventional CVD synthesis techniques typically yield a mixture of CNT (semi-conducting and metallic types) that grow at random locations on a substrate in high number density, which leads to extreme difficulty in application integration. Dip Pen Nanolithography (DPN) techniques were used to deposit the catalysts at precisely defined locations on a substrate and to precisely control the catalyst composition as well as the size of the patterned catalyst. After deposition of catalysts, a low temperature Chemical Vapor Deposition (CVD) process at atmospheric pressure was used to synthesize CNT. Various types of catalysts (Ni, Co, Fe, Pd, Pt, and Rh) were deposited in the form of metal salt solutions or nano-particle solutions. Various characterization studies before and after CVD synthesis of CNT at the location of the deposited catalysts showed that the CNT were of a single chirality (metallic or semiconducting) as well as a single diameter (with a very narrow range of variability). Additionally, X-ray photoelectron spectroscopy (XPS) was used to characterize the deposited samples before and after the CVD, as was lateral force microscopy (LFM) for determination of the successful deposition of the catalyst material immediately after DPN as well as following the CVD synthesis of the samples. The diameter of the CNT determines the chirality. The diameter of the CNT measured by TEM was found to be consistent with the chirality measurements obtained from Raman Spectroscopy for the different samples. Hence, the results showed that CNT samples of a single chirality can be obtained by this technique. The results show that the chirality of the synthesized CNT can be controlled by changing the synthesis conditions (e.g., size of the catalyst patterns, composition of the catalysts, temperature of CVD, gas flow rates, etc.).