Doctor of Philosophy / Department of Chemistry / Duy H. Hua / Carbon nanotubes are allotropes of carbon comprising of one or more grapheme sheets seamlessly joined together to form a cylinder. They are classified as single-walled carbon nanotubes (SWNTs) or multi-walled carbon nanotubes (MWNTs). They have potential applications ranging from conductive and high reinforcement material components, nano interconnection in electronic devices to drug delivery in biological systems. Current methods of production are high temperature arc-discharge, laser ablation of graphitic materials and chemical vapor deposition. These methods give tubes that are impure and highly heterogeneous in length, diameter and chirality thus leading to mixture metallic and semiconducting tubes. Effective application of such carbon nanotubes requires cumbersome, harsh and expensive purification and sorting into like forms. Such treatments usually compromised the structural integrity of the tubes and hence their mechanical and electrical properties. Also pristine carbon nanotubes are insoluble in most solvents. Solubility in basic organic solvents is crucial prior to their application, which requires some level of chemical manipulation or functionalization on the tubes. Currently methods of functionalization are unpredictable and limited to few oxidation reactions. A novel rational synthetic chemical approach to [12, 12] arm-chair carbon nano tube with pre-defined diameter and length has been explored utilizing cheap and simple organic building blocks and results achieved so far have been presented in this dissertation. Two approaches were employed to form the carbon-rich beltene (32) before its final conversion to the target single-walled carbon nanotube (SWNT) 1. A survey on carbon nanotubes and their related structures including their potential applications and properties are presented in chapter 1. In the second chapter an iron template-assisted olefin metathesis via a ferrocene intermediate served as an anchor for an effective cyclization. In chapter 3, an un-assisted olefin metathesis pathway was explored. Both approaches use a series of benzyl halide carbonylation coupling and Diels-Alder reactions to synthesize some of the key intermediates. The protocol presented in this dissertation may be used to produce functionalized carbon nanotubes with predefined length and diameter tailored for specific applications to be produced in kilogram scale for the first time since its discovery in 1991. Such an approach is expected to address most if not all of the problems associated with the traditional methods of producing carbon nanotubes.

Cette thèse est consacrée à l’étude du dépôt uniforme et de l’alignement à haute densité en nanotubes de carbone monoparois (NTCMP) sur différents substrats, à l’analyse qualitative des propriétés optiques excitoniques et aux modes de vibration des échantillons à NTCMP, et à la fabrication de guides d’onde optiques à base de NTCMP, en vue de composants photoniques pour les télécoms, autour de 1550 nm. Deux types de NTCMP ont été étudiés durant cette thèse : des NTCMP « HiPCO » (« high pressure carbon monoxide ») issus de la décomposition du monoxyde de carbone à haute pression, et des NTCMP « LV » (« laser vaporization ») provenant de l’ablation laser d’une cible en graphite. Plusieurs méthodes de dépôt de ces NTCMP ont été développées, telles que la méthode de dépôt assistée-par-tube, la méthode de dépôt en sillon, la méthode par pulvérisation, la méthode par centrifugation à grande vitesse, la méthode optimisée par centrifugation à vitesse réduite (MOCVR) et la méthode à jet d’encre. La qualité, l’épaisseur et l’uniformité des films de NTCMP sont caractérisées par observations au microscope électronique à balayage (MEB). Il est montré ici que l’uniformité des films à base de NTCMP HiPCO dépend fortement de la concentration en surfactants de la dispersion à base de NTCMP déposée. Des films uniformes de NTCMP LV ont été obtenus par la MOCVR et leur épaisseur couvre une gamme de 600nm à 900nm (avec une erreur <10%), qui dépend de la nature du substrat. L’alignement par diélectrophorèse (DEP) de NTCMP HiPCO et LV a été développé et optimisé. Ainsi, une nouvelle méthode (DEP « assistée-parchauffage ») est proposée afin d’obtenir un alignement à très haute densité en NTCMP. Cette méthode d’alignement par DEP assistée-par-chauffage a fait l’objet de travaux de simulation pour comprendre l’effet de la température. Les propriétés optiques excitoniques et les modes de vibration des NTCMP en solution et en film sur substrat ont été caractérisés par spectroscopies d’absorption, de photoluminescence (PL), d’excitation de la PL et Raman. Les niveaux de défauts et d’isolement des NTCMP HiPCO, les distributions en diamètre et en chiralité, les cartographies de l’uniformité et de l’épaisseur des films à base de NTCMP, et l’effet du laser à forte puissance, ont été qualitativement étudiés par spectroscopie Raman. Le rendement quantique interne en PL de NTCMP HiPCO en film est estimée à une valeur de 5%. Le transfert d’exciton entre NTCMP HiPCO individualisés, le rôle du polymère environnant sur les propriétés excitoniques des NTCMP LV, et les excitons sombres sont discutés dans cette thèse. Le design et la fabrication de guides optiques hybrides à une dimension, contenant une ou trois couches de NTCMP HiPCO, et de guides optiques à deux dimensions à base de NTCMP LV ont été menés. Les étapes de fabrication des guides optiques sont ici examinées en détails. La propagation à 1550nm de ces guides d’onde à base de NTCMP est observée. La propagation de la lumière dans les guides d’onde à base de NTCMP LV est une caractéristique préliminaire pour toute cavité optique et confère un fort potentiel aux NTCMP LV pour les composants photoniques de la future génération. / This thesis concentrates on the uniform deposition and highdensity alignment of single-walled carbon nanotubes (SWCNTs) on various substrates, the qualitative analysis of optical and excitonic properties, as well as vibrational modes of SWCNTbased samples by absorption, photoluminescence (PL) and Raman spectroscopies, and the fabrication of SWCNT-based optical waveguides towards photonics devices in the 1.55μm telecom window. Two types of SWCNT were studied during this thesis: “HiPCO” SWCNT from high pressure carbon monoxide conversion process (HiPCO) and “LV” SWCNT from catalytic growth of SWCNT assisted by laser vaporization (LV) of graphite. Several methods for the deposition of these SWCNTs were investigated and performed, including tube-assisted deposition method, groove deposition method, spraying method, high-speed spin coating method, improved low-speed spin coating method (ILSSCM) and inkjet printing method. The quality, thickness and uniformity of SWCNT films are characterized by scanning electron microscopy (SEM). The uniformity of HiPCO SWCNT-based film is shown to depend strongly on the surfactants concentration in deposited SWCNTbased dispersion. Uniform LV SWCNTbased films using ILSSCM were obtained with thicknesses ranging from 600nm to 900nm (with thickness error <10%), depending on substrates nature. Alignment of HiPCO and LV- SWCNTs using a dielectrophoresis method, combining microtechnological processes and SEM observations, is investigated and optimized. Thus, a new method (“heating-enhanced DEP”) for ultra-high alignment density of HiPCO SWCNTs is proposed. The effect of temperature in this heating-enhanced DEP process is further explained by simulation works. Optical and excitonic properties, vibrational modes of SWCNT solutions and films are characterized by absorption, PL and PL excitation, Raman spectroscopies. The defects and the isolation levels of HiPCO SWCNT, the chirality- and diameterdistributions of SWCNT, the uniformity and the thickness mapping of SWCNT-based films, and the effect of high energy laser are qualitatively analyzed by Raman spectra. We estimated the PL quantum efficiency value of HiPCO SWCNT film of around 5%. The exciton energy transfer between individualized HiPCO SWCNTs, the role of polymer environment on excitonic properties of LV SWCNTs, and the dark excitons are discussed in this thesis. One-layer and three-layers of HiPCO SWCNT-based onedimensional slab optical waveguides of hybrid core structures, and LV SWCNT-based twodimensional optical waveguides are designed and fabricated. The fabrication process steps of the optical waveguides are investigated in details. 1.55μm propagation in these SWCNT-based waveguides is highlighted. Single- or multi-mode emissions around 1.5μm and 1.6μm are observed in LV SWCNTbased optical waveguides. The light propagation in the LV SWCNT-based optical waveguide is the preliminary characteristic of an optical cavity, which confers great potential for future generation LV SWCNT-based photonics devices.

The outstanding electrical and mechanical properties of single-walled carbon nanotubes (SWCNTs) may offer solutions to realizing high-mobility and high-bendability thin-film transistors (TFTs) for the emerging flexible electronics. This thesis aims to develop low-cost ink-jet printing techniques for high-performance TFTs based on pristine SWCNTs. The main challenge of this work is to suppress the effects of “metallic SWCNT contamination” and improve the device electrical performance. To this end, this thesis entails a balance between experiments and simulations.   First, TFTs with low-density SWCNTs in the channel region are fabricated by utilizing standard silicon technology. Their electrical performance is investigated in terms of throughput, transfer characteristics, dimensional scaling and dependence on electrode metals. The demonstrated insensitivity of electrical performance to the electrode metals lifts constrains on choosing metal inks for ink-jet printing.   Second, Monte Carlo models on the basis of percolation theory have been established, and high-efficiency algorithms have been proposed for investigations of large-size stick systems in order to facilitate studies of TFTs with channel length up to 1000 times that of the SWCNTs. The Monte Carlo simulations have led to fundamental understanding on stick percolation, including high-precision percolation threshold, universal finite-size scaling function, and dependence of critical conductivity exponents on assignment of component resistance. They have further generated understanding of practical issues regarding heterogeneous percolation systems and the doping effects in SWCNT TFTs.   Third, Monte Carlo simulations are conducted to explore new device structures for performance improvement of SWCNT TFTs. In particular, a novel device structure featuring composite SWCNT networks in the channel is predicted by the simulation and subsequently confirmed experimentally by another research group. Through Monte Carlo simulations, the compatibility of previously-proposed long-strip-channel SWCNT TFTs with ink-jet printing has also been demonstrated.   Finally, relatively sophisticated ink-jet printing techniques have been developed for SWCNT TFTs with long-strip channels. This research spans from SWCNT ink formulation to device design and fabrication. SWCNT TFTs are finally ink-jet printed on both silicon wafers and flexible Kapton substrates with fairly high electrical performance. / QC 20100910

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

Fabrication of SWCNT-PMMA and Activated Charcoal- PMMA composites was carried out by the compression moulding technique. Then Mechanical and Electrical properties of the composites were investigated. The morphological studies of composites showed a) good dispersion of fillers and b) good interaction between fillers and matrix. Electrical conductivity of SWCNT-PMMA composites was increased by 9 orders of magnitude (at 0.8 % volume fraction of SWCNT) and that of AC-PMMA composites increased by 16 orders of magnitude (at 17 % volume fraction of AC). The percolation threshold of both composites turned out to be lower compared to the theoretical values. A significant improvement in mechanical properties was obtained ??? particularly in AC-PMMA composites which showed a 400 % improvement in Vickers microhardness ??? raising the polymer matrix abrasion property literally to that of Aluminium alloys (Dobrazanski et al 2006). In conclusion, it is to be noted that Activated Charcoal - PMMA composites have a great potential for cost effective conducting polymer composite production by the use of cheap filler: In addition, the compression moulding technique shows good potential for cost effective fabricating technique for amorphous polymers with high electrical and mechanical properties.

Ce travail est dédié à l’étude de l’encapsulation de molécules organiques photoactives dans des nanotubes de carbone mono-feuillets. L’effet de confinement sur les propriétés vibrationnelles , structurales, et les interactions entre les sous-systèmes est étudié en fonction de la taille des nanotubes. La première partie du manuscrit est consacrée à l’étude du confinement de diméthylquaterthiophènes dans les tubes. La dynamique vibrationnelle des molécules confinées est étudiée par diffusion inélastique des neutrons et par des simulations DFT. L’étude des interactions entre les deux sous-systèmes, en termes de transfert d’énergie et de transfert de charge, est réalisée en combinant des études de photoluminescence et de Raman. La nature des transferts de charge dépend de la taille du nanotube. Pour des tubes de petits diamètres (<1.1nm), un transfert de charge photo-induit est obtenu lorsque la longueur d’excitation correspond à l’absorption de la molécule. La deuxième partie est dédiée à l’étude de l’organisation structurale de molécules de phtalocyanine encapsulées à l’intérieur des nanotubes. Ce travail combine des études expérimentales par diffraction neutronique et spectroscopie Raman à pression ambiante et sous hautes pressions. Les études structurales sont confrontées à des simulations par dynamique moléculaire. / This work is dedicated to the study of the encapsulation of photoactive molecules within single wall carbon nanotubes. The confinement effect on vibrational, structural and interactions between host and guest is studied as a function of nanotube size. The first part of the manuscript is dedicated to the confinement of dimethyl quaterthiophene within carbon nanotubes. Vibrational dynamics for the encapsulated molecules is studied coupling neutron scattering and DFT simulations. Interactions molecule/nanotube, in terms of energy transfer and charge transfer are studied combining photoluminescence and Raman spectroscopies. The nature of charge transfers depends on the size of the nanotube. For small diameters (>1,1nm) a photoinduced charge transfer is obtained when the excitation wavelength matches the absorption of the molecule. The second part of the manuscript focuses on the structural organization of encapsulated phthalocyanine molecules. This work combines neutron diffraction and Raman spectroscopy experimental studies at room and high pressures. Structural studies are discussed together with molecular dynamics simulations.

In the last three decades carbon nanomaterials such as fullerenes, carbon nanotubes and graphene have attracted significant attention from the scientific community due to their unique electronic, optical, thermal, mechanical and chemical properties. Among them carbon nanotubes and graphene have been used in numerous applications for future nanoelectronics, biochemical sensors and energy harvesting technologies due to their unique properties including exceptionally high electronic conductivity and mechanical strength. Carbon nanotubes are cylindrical structures and considered to be large mesoscopic molecules with high aspect ratios. Graphene is a single atomic layer of crystalline graphite and prepared by stripping layers off the graphite using Scotch tape. Apart from this scotch tape method, chemical ex-foliation and reduction of graphite oxide produces large amounts of reduced graphene oxide which has similar properties as graphene. This thesis reports on the biosensors made of reduced graphene oxide and single walled carbon nanotubes based on their electronic properties. We also demonstrate the changes in electronic properties of single walled carbon nanotubes due to interactions with dendrimer molecules. Finally, the yielding and flow behaviour of graphene oxide nematic gel are discussed. Chapter 1 gives a general introduction about the preparation and characterization along with the electronic properties of the systems studied in this thesis, namely graphene oxide, reduced graphene oxide and single walled carbon nanotubes. We have also discussed about the experimental techniques such as Raman, UV-visibe and infrared spectroscopy, atomic force and scanning tunneling microscopy and different types of rheometers used in this thesis work. In Chapter 2, we discuss top-gated field effect transistor characteristics of the devices made of reduced graphene oxide monolayer by dielectrophoresis. Raman spectrum of RGO flakes shows a single 2D band at 2687 cm 1, characteristic of a single layer graphene. The two probe current - voltage measurements of RGO flakes, deposited in between the patterned electrodes using a.c. dielectrophoresis show ohmic behavior with a resistance of 37kΩ. The temperature dependence of the resistance (R) of RGO measured between temperatures 305K to 393K yields the temperature coefficient of resistance of -9.5 10 4/K. Ambipolar nature of graphene flakes is observed upto a doping level of 6 1012/cm2 and carrier mobility of 50cm2/V-sec. The source - drain current characteristics shows a tendency of current saturation at high source - drain voltage which is analyzed quantitatively by a diffusive transport model. In Chapter 3, We demonstrate the detection of glucose molecules by using reduced graphene oxide (RGO) and aminophenylboronic acid (APBA) complex with detection limit of 5 nM. APBA functionalized RGO (APBA-RGO) flakes, prepared by stirring the aqueous GO suspension in the presence of APBA molecules at 100◦C, were used as conducting channel in our field effect transistor (FET) devices. The APBA-RGO complex formation was confirmed by atomic force microscopy (AFM), x - ray photoelectron, Raman and UV-visible spectroscopic studies. Detection of glucose molecules was carried out by monitoring the changes in electrical conductance of the APBA-RGO flake in the FET device. FET devices made of non-covelently functionalized APBA-RGO complex (nc-APBA-RGO) exhibited enhanced sensitivity over the devices made of covalently functionalized APBA-RGO complex (c-APBA-RGO). Change in normalized conductance in the FET devices made of nc-APBA-RGO flakes ( 85%) is 4 times more than that of in the devices made of c-APBA-RGO flakes in response to aqueous glucose solution with different concentrations. Specificity of APBA-RGO complex to glucose was proved from the observation of negligible change in electrical conductance of the FET devices made of nc-APBA-RGO complex after exposure to 10 mM lactose solution. Chapter 4 reports unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two - terminal devices with yield > 99% are made at room temperature by forming continuous films of graphene of thickness 20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the lm. These memory devices are non - volatile, rewritable with ON/OFF ratios up to 105 and switching times up to 10 s. The devices made of MWNT films are rewritable with ON/OFF ratios up to 400. The resistive switching mechanism is proposed to be nanogap formation. In the first part of Chapter 5, we study the interactions between SWNT and PETIM dendrimer by measuring the quenching of inherent fluorescence of the dendrimer. Also, the dendrimer - nanotube binding results in the increased electrical resistance of the hole-doped SWNT due to charge transfer interaction between the dendrimer and the nanotube. This charge transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. Experimental studies were supplemented by all atom molecular dynamics simulations to provide a microscopic picture of the dendrimer - nanotube complex. The complexation was achieved through charge - transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen and n-propyl moieties of the dendrimer. We also studied the effect of acidic and neutral pH conditions on the binding affinities. In the second part, we show that SWNT decorated with sugar functionalized PETIM dendrimer is a very sensitive platform to quantitatively detect carbohydrate recognizing proteins, namely, lectins. The changes in electrical conductivity of SWNT in field effect transistor device due to carbohydrate - protein interactions forms the basis of this study. The mannose sugar attached PETIM dendrimers undergo charge - transfer interactions with the SWNT. The changes in the conductance of the dendritic sugar functionalized SWNT after addition of lectins in varying concentrations were found to follow the Langmuir type isotherm, giving the concanavalin A (Con A) - mannose affinity constant to be 8.5 106 M-1. The increase in the device conductance observed after adding 10 nM of Con A is same as after adding 20 µM of a non - specific lectin peanut agglutinin, showing the high specificity of the Con A - mannose interactions. The specificity of sugar-lectin interactions was characterized further by observing significant shifts in Raman modes of the SWNT. Chapter 6 reports the metal to semiconductor transition in metallic single-wall carbon nanotubes (SWNT) due to the wrapping of mannose attached poly (propyl ether imine) dendrimer (DM) molecule. Scanning tunneling spectroscopic (STS) measurements and ionic liquid top gated field effect transistor (FET) characteristics of the nanotube-dendrimer complex gives a band gap of 0.42eV, close to the E11 energy gap between the first van Hove singularities of 1.7nm diameter semiconducting nanotubes. The absence of Breit-Wigner-Fano (BWF) component in G band in the Raman spectrum of the nanotube-dendrimer complex corroborates the semiconductor nature of the tubes after wrapping with the dendrimer molecules. Dendrimer molecule breaks the symmetry in metallic SWNT by wrapping around it through the charge transfer interactions. In the first part of Chapter 7, we demonstrate a rigidity percolation transition and the onset of yield stress in a dilute aqueous dispersion of graphene oxide platelets (aspect ratio 5000) above a critical volume fraction of 3.75x10-4 with a percolation exponent of 2.4 ± 0.1.The viscoelastic moduli of the gel at rest measured as a function of time indicates the absence of structural evolution of the 3D percolated network of disks. However, a shear-induced aging giving rise to a compact jammed state and shear rejuvenation indicating a homogenous flow is observed when a steady shear stress (σ ) is imposed in creep experiments. We construct a shear diagram (σ vs volume fraction ϕ) and the critical stress above which shear rejuvenation occurs is identified as the yield stress σ y of the gel. The minimum steady state shear rate ƴm obtained from creep experiments agrees well with the end of the plateau region in a controlled shear rate flow curve, indicating a shear localization below ƴm. A steady state shear banding in the plateau region of the flow curve observed in particle velocimetry measurements in a couette geometry confirms that the dilute suspensions of GO platelets form a thixotropic yield stress fluid (TYSF). In the second part, we report that the creep experiments on a nematic liquid crystalline suspension of Graphene Oxide platelets which was established recently as a TYSF exhibit two characteristic timescales Tc and Tf marking the onset of yielding, and a final steady state of flow respectively. We show that both Tc and Tf exhibit a power law dependence on the applied stress σ which can be linked to the steady state flow behaviour of a TYSF. The smooth transition from Andrade creep to the onset of flow with ƴ~ t 0.7 at a critical strain ƴc for different applied stresses, is well captured by the master curve for the creep compliance, obtained through a simple scaling of the creep times with either Tc or Tf . We propose that the absence of diverging timescales for onset of flow as σ→ yield stress σy from above, is a characteristic feature of TYSF. The thesis concludes with a summary of the main results and a brief account of the scope of future work described in Chapter 8.

Different carbon nanostructures have different properties and different applications. It is needed to synthesize good quality and also on large scale. From the point of industrial applications, highly productive and low cost synthesis method is very essential. Research has been done extensively on the intrinsic and individual properties of both single walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWC-NTs) in the range of nanometer to micrometer length scale. The important question is how the properties change beyond this length scale and if they are used in group in the form of an array instead of the individual carbon nanotubes (CNTs). Some applications require large current output, large energy production etc. For such kind of applications, it becomes essential to use CNTs in large number in the form of arrays or array, instead of using large numbers of CNTs in individual level. Future nanotechnology scope requires large scale application using the very rich intrinsic properties of the CNTs and nanomaterials. Keeping these problems and challenges in front, this thesis work is devoted to the research of the large scale synthesis of mm long MWCNTs, having different morphology and studies on various physical properties of MWCNTs in the form of arrays. Synthesis of mm long aligned and buckled MWCNTs have been reported for the first time. Generally buckled CNTs were obtained by compressing the straight CNTs. Apart from this, different morphologies like, aligned straight, helical or coiled CNTs are also synthesized. Resistance of the individual CNT increases with the increase in length. Resistance versus length of an array of CNT also shows similar behaviour. The thermal conductivity of CNT array is observed to decrease with the increase of array diameter (diameter �100 µm). There are few reports of the similar behaviour with the experiments done on small diameter CNT arrays (diameter �100 nm). From these observations, it seems that in the arrays of CNT, their intrinsic individual property is preserved though the magnitudes are different. The conductance measurements done on buckled CNT array by compressing it to apply uniaxial strain, shows the conductance oscillation. This conductance oscillation seems to be originating from the band gap change due to strain when the CNTs bend during compression. Recent research focuses on the arrays of CNT as they can carry large current of the order of several milliamperes that make the arrays suitable in nanoscale electronics and in controlling macroscopic devices such as light emitting diodes and electromotors. Regarding this aspect, a part of this thesis work is devoted on the application of CNT array to field effect transistor (FET) and study of thermoelectric power generation using CNT arrays. The entire thesis is based on the works discussed above. It has been organized as follows: Chapter 1 deals with introduction about the different carbon nanostructures and different synthesis methods. A brief introduction about the different current-voltage (IV) characteristics of SWCNTs and MWCNTs, length and diameter dependence and effect of the mode of contacts, are given. Some applications of the array of CNTs like buckling effect on compression, stretching of CNT into the form of rope, and conduction change on compression are discussed. Application of CNT as FET, as a thermometer, and thermoelectric effect of CNT are discussed. The electromechanical effect of CNT is also discussed briefly. Chapter 2 deals with experimental setup for synthesis of different morphologies of carbon nanostructures. The samples are characterized using common characterization techniques like, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. A brief introduction about Raman Spectroscopy of CNT is given. Chapter 3 reports the unusual IV characteristics and breakdown of long CNT arrays. The current carrying ability and the threshold voltage as a function of array diameter are reported. The effect of the ambient like temperature and pressure are discussed. Chapter 4 deals with theoretical models to analyze the IV characteristics reported in Chapter 3. It has been shown that a set of classical equations are applicable to quantum structures and the band gap can be evaluated. Chapter 5 describes with application of CNT arrays as temperature sensors. It has been shown that CNT arrays of suitable diameters are used as temperature sensors after calibration. Chapter 6 reports the high current FET application of CNT arrays. Effects of temperature and ambient pressure are discussed. The type of the majority charge carrier is determined. Chapter 7 deals with application of CNT arrays as thermoelectric power generator to get large thermoelectric current. Effects of different array diameter are discussed. Modulation of thermoemf with gate voltage is discussed. The type of the majority charge carrier is determined. Chapter 8 reports the effect of compressive strain on buckled MWCNT arrays. Conductance is measured during the compression of the array. Quantum electromechanical conductance oscillation is observed. The structural changes are observed with SEM. Raman spectroscopic study supports the explanation of the effect. Chapter 9 provides the conclusion and overall summary of the thesis.

The thesis contains two parts. Part 1 describes the investigations on graphene and contains five sections. Section 1, gives a brief overview of graphene and other nanocarbons. The other four sections deal with various aspects of single-layer and few-layer graphene such as functionalization and solubilization, surface properties and gas adsorption, molecular charge transfer interaction and some properties and applications. Section 2 describes covalent and noncovalent functionalization and solubilization of few-layer graphene samples prepared by different methods as well as of single-walled carbon nanotubes (SWNTs). It includes covalent functionalization of graphene with organometallic reagents, noncovalent functionalization of graphene and SWNTs with surfactants as well as large aromatic molecules, and exfoliation of few-layer graphene by a water-soluble coronene carboxylate. Section 3 deals with surface properties and gas adsorption (mainly H2 and CO2) of few-layer graphenes. It is found that graphene samples with high surface area can adsorb even more than 3 wt% of H2 at high pressure which makes it promising material for gas-storage applications. Section 4 describes the molecular charge-transfer interaction of single and few-layered graphenes and SWNTs with different electron-donor and -acceptor molecules probed by both ITC measurements and Raman spectroscopy. Electron–acceptor molecules interact more strongly with graphene and SWNTs than the -donor molecules and nature of interaction of metallic SWNTs are different than the as-prepared ones. A Raman study of the interaction of single-layer graphene, prepared by micromechanical cleavage as well as chemical route, with an electron donor molecule such as tetrathiofulvalene (TTF) and an electron acceptor molecule such as tetracyanoethylene (TCNE) is examined. In Section 5, some properties and applications of graphene are discussed. These include fluorescence quenching phenomena observed with few-layer graphene samples on two fluorescent molecules such as coronene and perylene derivatives. Fabrication of a sensing device as well as of FETs prepared from doped and undoped few-layer and single-layer graphene samples forms part of this section. Part 2 of the thesis includes a brief introduction of hybrid open-framework material and synthesis, characterization and crystal structure of various open-framework metal carboxylates, starting with different transition and main group metals. The carboxylic acids used to form these frameworks vary such as simple aliphatic amino acids such as beta-alanine and aspartic acid or simple aliphatic hydroxyl carboxylic acid such as malic acid in its chiral and achiral forms or five-membered heterocyclic aromatic acid, such as imidazole dicarboxylic acid.