Effect of density variation and non-covalent functionalization on the compressive behavior of carbon nanotube arrays

Arrays of aligned carbon nanotubes (CNTs) have been proposed for different applications, including electrochemical energy storage and shock-absorbing materials. Understanding their mechanical response, in relation to their structural characteristics, is important for tailoring the synthesis method to the different operational conditions of the material. In this paper, we grow vertically aligned CNT arrays using a thermal chemical vapor deposition system, and we study the effects of precursor flow on the structural and mechanical properties of the CNT arrays. We show that the CNT growth process is inhomogeneous along the direction of the precursor flow, resulting in varying bulk density at different points on the growth substrate. We also study the effects of non-covalent functionalization of the CNTs after growth, using surfactant and nanoparticles, to vary the effective bulk density and structural arrangement of the arrays. We find that the stiffness and peak stress of the materials increase approximately linearly with increasing bulk density.

Non-covalent functionalization using lithographically patterned polyelectrolyte multilayers for high-density microarrays

We describe a method to fabricate high-density biological microarrays using lithographic patterning of polyelectrolyte multi layers formed by spin assisted electrostatic layer-by-layer assembly. Proteins or DNA can be immobilized on the polyelectrolyte patterns via electrostatic attachment leading to functional microarrays. As the immobilization is done using electrostatically assembled polyelectrolyte anchor, this process is substrate independent and is fully compatible with a standard semiconductor fabrication process flow. Moreover, the electrostatic assembly of the anchor layer is a fast process with reaction saturation times of the order of a few minutes unlike covalent schemes that typically require hours to reach saturation. The substrate independent nature of this technique is demonstrated by functionalizing glass slides as well as regular transparency sheets using the same procedure. Using a model protein assay, we demonstrate that the non-covalent immobilization scheme described here has competitive performance compared to conventional covalent immobilization schemes described in literature. (C) 2012 Elsevier B.V. All rights reserved.

Covalent functionalization of polydisperse chemically-converted graphene sheets with amine-terminated ionic liquid

A facile method to obtain polydisperse chemically-converted graphene sheets that are covalently functionalized with ionic liquid was reported-the resulting graphene sheets, without any assistance from polymeric or surfactant stabilizers, can be stably dispersed in water, DMF, and DMSO.

Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement

Polydisperse, functionalized, chemically converted graphene (f-CCG) nanosheets, which can be homogeneously distributed into water, ethanol, DMF, DMSO and 3-aminopropyltriethoxysilane (APTS), were obtained via facile covalent functionalization with APTS. The resulting f-CCG nanosheets were characterized by FTIR, XPS, TGA, EDX, AFM, SEM, and TEM. Furthermore, the f-CCG nanosheets as reinforcing components were extended into silica monoliths. Compressive tests revealed that the compressive failure strength and the toughness of f-CCG-reinforced APTS monoliths at 0.1 wt% functionalized, chemically converted graphene sheets compared with the neat APTS monolith were greatly improved by 19.9% and 92%, respectively.

Reinforcement of silica with single-walled carbon nanotubes through covalent functionalization

Single-walled carbon nanotubes (SWCNTs) as reinforcing components were extended into silica monoliths and thin films via covalent functionalization for the first time. Silica materials have poor mechanical attributes, which limit their applications. Because of the extreme flexibility of SWCNTs and their large interfacial area, they may be very intriguing as reinforcing fillers for the silica matrix. To get more uniform dispersion and stronger interfacial interaction, SWCNTs were covalently functionalized with silane, and then integrated into silica via a sol - gel process, and their properties were also compared with those of pristine SWCNTs. Results show that the silane-functionalized nanotubes resulted in better mechanical properties ( for example, 33% increase in stress, and 53% increase in toughness), as well as higher electron-transfer kinetics.

Controlled Covalent Functionalization of Multiwalled Carbon Nanotubes using [4 + 2] Cycloaddition of Benzocyclobutenes

Surface modification of carbon nanotubes (CNTs) through covalent functionalization is vital for the development of high-performance composite materials, chemosensors, nanoelectronics, photovoltaic devices, as well as for a range of biomedical applications. Several methods have been developed to functionalize CNTs. The introduction of acid groups by acid digestion disrupts the structural integrity of CNTs. Apart from shortening the tubes, oxidatively generated acid groups are inhomogenously located at the tips of broken CNTs and, hence, functionalization using acid groups as precursors does not give a statistical distribution of functional groups throughout the surface of the CNTs.

Electronics and Optics of Graphene Nanoflakes: Edge Functionalization and Structural Distortions

The effects of edge covalent functionalization on the structural, electronic, and optical properties of elongated armchair graphene nanoflakes (AGNFs) are analyzed in detail for a wide range of terminations, within the framework of Hartree-Fock-based semiempirical methods. The chemical features of the functional groups, their distribution, and the resulting system symmetry are identified as the key factors that determine the modification of strutural and optoelectronic features. While the electronic gap is always reduced in the presence of substituents, functionalization-induced distortions contribute to the observed lowering by about 35-55% This effect is paired with a red shift of the first optical peak, corresponding to about 75% of the total optical gap reduction. Further, the functionalization pattern and the specific features of the edge-substituent bond are found to influence the strength and the character of the low-energy excitations. All of these effects are discussed for flakes of different widths, representing the three families of AGNFs.

One-step amino-functionalization of milled carbon fibre for enhancement of thermo-physical properties of epoxy composites

Development of new chemical approaches for preparation of engineered carbon-based fillers is critical for high-performance applications. Herein, an efficient method for covalent functionalization of polyacrylonitrile-based carbon fibre through azo radical addition under mild condition is demonstrated. In this way, isobutyronitrile radicals in situ produced from thermal decomposition of 2,2′-azobisisobutyronitrile (AIBN), were covalently grafted on milled carbon fibre (MCF) surface, assisted by microwave irradiation, as evidenced by FTIR, Raman, and TGA analysis. The grafted isobutyronitriles on MCF surface (n-MCF) were applied for further MCF amino-functionalization (a-MCF) via nucleophilic reaction of an amine-rich compound. Then, both pure MCF and a-MCF were incorporated into epoxy matrix; and its curing process and thermo-physical properties were investigated using DSC, rheometry, DMA, TGA, and flexural analysis. The Tg and flexural strength of epoxy/a-MCF composites, compared to epoxy/MCF, increased by ∼3.5% and ∼10.2%, resulting from good adhesion between a-MCF and epoxy matrix which confirmed by SEM observations.

Synthesis, Characterization and Properties of Single-Walled Carbon Nanohorns

Single-walled nanohorns (SWNHs) have been prepared by sub-merged arc discharge of graphite electrodes in liquid nitrogen. The samples were examined by scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. Nitrogen and boron doped SWNHs have been prepared by the sub-merged arc discharge method using melamine and elemental boron as precursors. Intensification of Raman D-band and stiffening of G-band has been observed in the doped samples. The electrical resistance of the SWNHs varies in opposite directions with nitrogen and boron doping. Functionalization of SWNHs through amidation has been carried out for solubilizing them in non-polar solvents. Water-soluble SWNHs have been produced by acid treatment and non-covalent functionalization with a coronene salt. SWNHs have been decorated with nanoparticles of Au, Ag and Pt. Interaction of electron donor (tetrathiafulvalene, TTF) and acceptor molecules (tetracyanoethylene, TCNE) with SWNHs has been investigated by Raman spectroscopy. Progressive softening and stiffening of Raman G-band has been observed respectively with increase in the concentration of TTF and TCNE.

Tailoring the interface in graphene/thermoset polymer composites: A critical review

With the emergence of scientific interest in graphene oxide (GO) in recent times, researchers have endeavored to incorporate GO in thermoset polymeric matrix to develop composites with extraordinary set of properties. The current state of research in graphene/thermoset polymer composites is highlighted here with a focus on the role of interface in dictating the overall properties of the composites. Different strategies like covalent and non-covalent functionalization of GO have been discussed with respect to improvement in mechanical, electrical, thermal and rheological properties. In addition, future prospects have been outlined. By assessing the current state of research in graphene/thermoset composites, it is obvious that graphene derivatives are promising materials in enhancing the structural properties of the nanocomposites at extremely low levels of filler loading. This opens new avenues in designing lightweight composites for myriad applications and by tailoring the interfacial adhesion with the polymer, ordered structure can be achieved at macroscopic processing scales. (C) 2015 Elsevier Ltd. All rights reserved.

First-principles study of the electronic and magnetic properties of defective carbon nanostructures

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Spectroscopic characteristics and cellular compatibility of protein wrapped single wall carbon nanotubes

Non-covalent functionalization of CoMoCAT single-wall carbon nanotubes (SWNTs) by bovine serum albumin (BSA) was achieved. Photoluminescence spectra for the functionalized nanotubes showed good dispersion by BSA functionalization. Raman spectra were taken for the sonicated SWNT-BSA solution to establish the signal versus concentration correlation. Cellular uptake of functionalized carbon nanotubes by mouse macrophage (RAW264.7) was then investigated using Raman spectroscopy. For a seeding density of 50% confluence in a culture solution containing 10 μg/ml of BSA-SWNTs, uptake of 200 μg/ml by the macrophages was recorded after 23hr incubation, indicating an active uptake of SWNTs. © 2012 IEEE.

Ferroelectric : CNTs structures fabrication for advanced functional nano devices

This work is about the combination of functional ferroelectric oxides with Multiwall Carbon Nanotubes for microelectronic applications, as for example potential 3 Dimensional (3D) Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Miniaturized electronics are ubiquitous now. The drive to downsize electronics has been spurred by needs of more performance into smaller packages at lower costs. But the trend of electronics miniaturization challenges board assembly materials, processes, and reliability. Semiconductor device and integrated circuit technology, coupled with its associated electronic packaging, forms the backbone of high-performance miniaturized electronic systems. However, as size decreases and functionalization increases in the modern electronics further size reduction is getting difficult; below a size limit the signal reliability and device performance deteriorate. Hence miniaturization of siliconbased electronics has limitations. On this background the Road Map for Semiconductor Industry (ITRS) suggests since 2011 alternative technologies, designated as More than Moore; being one of them based on carbon (carbon nanotubes (CNTs) and graphene) [1]. CNTs with their unique performance and three dimensionality at the nano-scale have been regarded as promising elements for miniaturized electronics [2]. CNTs are tubular in geometry and possess a unique set of properties, including ballistic electron transportation and a huge current caring capacity, which make them of great interest for future microelectronics [2]. Indeed CNTs might have a key role in the miniaturization of Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Moving from a traditional two dimensional (2D) design (as is the case of thin films) to a 3D structure (based on a tridimensional arrangement of unidimensional structures) will result in the high reliability and sensing of the signals due to the large contribution from the bottom electrode. One way to achieve this 3D design is by using CNTs. Ferroelectrics (FE) are spontaneously polarized and can have high dielectric constants and interesting pyroelectric, piezoelectric, and electrooptic properties, being a key application of FE electronic memories. However, combining CNTs with FE functional oxides is challenging. It starts with materials compatibility, since crystallization temperature of FE and oxidation temperature of CNTs may overlap. In this case low temperature processing of FE is fundamental. Within this context in this work a systematic study on the fabrication of CNTs - FE structures using low cost low temperature methods was carried out. The FE under study are comprised of lead zirconate titanate (Pb1-xZrxTiO3, PZT), barium titanate (BaTiO3, BT) and bismuth ferrite (BiFeO3, BFO). The various aspects related to the fabrication, such as effect on thermal stability of MWCNTs, FE phase formation in presence of MWCNTs and interfaces between the CNTs/FE are addressed in this work. The ferroelectric response locally measured by Piezoresponse Force Microscopy (PFM) clearly evidenced that even at low processing temperatures FE on CNTs retain its ferroelectric nature. The work started by verifying the thermal decomposition behavior under different conditions of the multiwall CNTs (MWCNTs) used in this work. It was verified that purified MWCNTs are stable up to 420 ºC in air, as no weight loss occurs under non isothermal conditions, but morphology changes were observed for isothermal conditions at 400 ºC by Raman spectroscopy and Transmission Electron Microscopy (TEM). In oxygen-rich atmosphere MWCNTs started to oxidized at 200 ºC. However in argon-rich one and under a high heating rate MWCNTs remain stable up to 1300 ºC with a minimum sublimation. The activation energy for the decomposition of MWCNTs in air was calculated to lie between 80 and 108 kJ/mol. These results are relevant for the fabrication of MWCNTs – FE structures. Indeed we demonstrate that PZT can be deposited by sol gel at low temperatures on MWCNTs. And particularly interesting we prove that MWCNTs decrease the temperature and time for formation of PZT by ~100 ºC commensurate with a decrease in activation energy from 68±15 kJ/mol to 27±2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 ºC for MWCNTs - PZT whereas for pure PZT traces of pyrochlore were still present at 650 ºC, where PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs - PZT synthesised at 500 ºC for 1 h was proved by PFM. In the continuation of this work we developed a low cost methodology of coating MWCNTs using a hybrid sol-gel / hydrothermal method. In this case the FE used as a proof of concept was BT. BT is a well-known lead free perovskite used in many microelectronic applications. However, synthesis by solid state reaction is typically performed around 1100 to 1300 ºC what jeopardizes the combination with MWCNTs. We also illustrate the ineffectiveness of conventional hydrothermal synthesis in this process due the formation of carbonates, namely BaCO3. The grown MWCNTs - BT structures are ferroelectric and exhibit an electromechanical response (15 pm/V). These results have broad implications since this strategy can also be extended to other compounds of materials with high crystallization temperatures. In addition the coverage of MWCNTs with FE can be optimized, in this case with non covalent functionalization of the tubes, namely with sodium dodecyl sulfate (SDS). MWCNTs were used as templates to grow, in this case single phase multiferroic BFO nanorods. This work shows that the use of nitric solvent results in severe damages of the MWCNTs layers that results in the early oxidation of the tubes during the annealing treatment. It was also observed that the use of nitric solvent results in the partial filling of MWCNTs with BFO due to the low surface tension (<119 mN/m) of the nitric solution. The opening of the caps and filling of the tubes occurs simultaneously during the refluxing step. Furthermore we verified that MWCNTs have a critical role in the fabrication of monophasic BFO; i.e. the oxidation of CNTs during the annealing process causes an oxygen deficient atmosphere that restrains the formation of Bi2O3 and monophasic BFO can be obtained. The morphology of the obtained BFO nano structures indicates that MWCNTs act as template to grow 1D structure of BFO. Magnetic measurements on these BFO nanostructures revealed a week ferromagnetic hysteresis loop with a coercive field of 956 Oe at 5 K. We also exploited the possible use of vertically-aligned multiwall carbon nanotubes (VA-MWCNTs) as bottom electrodes for microelectronics, for example for memory applications. As a proof of concept BiFeO3 (BFO) films were in-situ deposited on the surface of VA-MWCNTs by RF (Radio Frequency) magnetron sputtering. For in situ deposition temperature of 400 ºC and deposition time up to 2 h, BFO films cover the VA-MWCNTs and no damage occurs either in the film or MWCNTs. In spite of the macroscopic lossy polarization behaviour, the ferroelectric nature, domain structure and switching of these conformal BFO films was verified by PFM. A week ferromagnetic ordering loop was proved for BFO films on VA-MWCNTs having a coercive field of 700 Oe. Our systematic work is a significant step forward in the development of 3D memory cells; it clearly demonstrates that CNTs can be combined with FE oxides and can be used, for example, as the next 3D generation of FERAMs, not excluding however other different applications in microelectronics.

Fonctionnalisation covalente des nanotubes de carbone : propriétés, réversibilité et applications dans le domaine de l'électronique

Le sujet général de cette thèse est l’étude de la fonctionnalisation covalente des nanotubes de carbone (CNT) et son application en électronique. Premièrement, une introduction au sujet est présentée. Elle discute des propriétés des CNT, des différentes sortes de fonctionnalisation covalente ainsi que des principales techniques de caractérisation utilisées au cours de la thèse. Deuxièmement, les répercussions de la fonctionnalisation covalente sur les propriétés des nanotubes de carbone monoparoi (SWNT) sont étudiées. Deux types de fonctionnalisation sont regardés, soit le greffage de groupements phényles et le greffage de groupements dichlorométhylènes. Une diminution de l’absorption optique des SWNT dans le domaine du visible-proche infrarouge est observée ainsi qu’une modification de leur spectre Raman. De plus, pour les dérivés phényles, une importante diminution de la conductance des nanotubes est enregistrée. Troisièmement, la réversibilité de ces deux fonctionnalisations est examinée. Il est montré qu’un recuit permet de résorber les modifications structurales et retrouver, en majorité, les propriétés originales des SWNT. La température de défonctionnalisation varie selon le type de greffons, mais ne semble pas affectée par le diamètre des nanotubes (diamètre examinés : dérivés phényles, Ømoyen= 0,81 nm, 0,93 nm et 1,3 nm; dérivés dichlorométhylènes, Ømoyen = 0,81 nm et 0,93 nm). Quatrièmement, la polyvalence et la réversibilité de la fonctionnalisation covalente par des unités phényles sont exploitées afin de développer une méthode d’assemblage de réseaux de SWNT. Celle-ci, basée sur l’établissement de forces électrostatiques entre les greffons des SWNT et le substrat, est à la fois efficace et sélective quant à l’emplacement des SWNT sur le substrat. Son application à la fabrication de dispositifs électroniques est réalisée. Finalement, la fonctionnalisation covalente par des groupements phényles est appliquée aux nanotubes de carbone à double paroi (DWNT). Une étude spectroscopique montre que cette dernière s’effectue exclusivement sur la paroi externe. De plus, il est démontré que la signature électrique des DWNT avant et après la fonctionnalisation par des groupements phényles est caractéristique de l’agencement nanotube interne@ nanotube externe.

Transport électrique dans les nanotubes de carbone et leurs dérivés fonctionnalisés

Les nanotubes de carbone forment une structure quasi-unidimensionnelle de diamètre nanométrique, dont les propriétés mécaniques et électroniques, en particulier leur remarquable conductivité électrique, présentent un grand potentiel pour la conception de dispositifs électroniques. Les nanotubes fonctionnalisés, c’est-à-dire dont la paroi a été chimiquement modifiée, présentent aussi un intérêt majeur pour leur mise en œuvre facilitée et pour la formation d’une interface active entre le nanotube et l’environnement, cette dernière étant essentielle pour la conception de nanocapteurs chimiques et biologiques. La présente thèse porte sur l’étude des mécanismes gouvernant le transport électrique dans les nanotubes de carbone et leurs dérivés fonctionnalisés. Les travaux, de nature expérimentale, ont été réalisés sur des dispositifs électroniques constitués d’un nanotube individuel monoparoi ou biparoi, additionné de groupes fonctionnels au besoin. En première partie, on s’intéresse à l’effet de la dimensionnalité sur les mécanismes d’injection des porteurs de charge au niveau des contacts électriques avec le nanotube. En seconde partie, on étudie l’effet de la fonctionnalisation covalente sur les propriétés de transport électrique des nanotubes, et on montre notamment que l’impact de l’addition des greffons varie fortement selon leur valence et qu’il est possible d’obtenir des nanotubes fonctionnalisés avec une bonne conductance. En troisième partie, on explore les phénomènes de saturation du courant et de claquage électrique survenant à haut voltage. Enfin, on discute de l’impact des résultats obtenus sur l’avancement de la compréhension des mécanismes de transport électrique dans les systèmes hautement confinés, ainsi que des perspectives fondamentales et technologiques ouvertes par ces travaux.