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Engineering carbon nanotubes and nanotube circuits using electrical breakdown.

Carbon nanotubes display either metallic or semiconducting properties. Both large, multiwalled nanotubes (MWNTs), with many concentric carbon shells, and bundles or "ropes" of aligned single-walled nanotubes (SWNTs), are complex composite conductors that incorporate many weakly coupled nanotubes that each have a different electronic structure. Here we demonstrate a simple and reliable method for selectively removing single carbon shells from MWNTs and SWNT ropes to tailor the properties of these composite nanotubes. We can remove shells of MWNTs stepwise and individually characterize the different shells. By choosing among the shells, we can convert a MWNT into either a metallic or a semiconducting conductor, as well as directly address the issue of multiple-shell transport. With SWNT ropes, similar selectivity allows us to generate entire arrays of nanoscale field-effect transistors based solely on the fraction of semiconducting SWNTs.

Journal Article↗

Application of host-guest chemistry in nanotube-based device fabrication: photochemically controlled immobilization of azobenzene nanotubes on patterned alpha-CD monolayer/Au substrates via molecular recognition.

Azobenzene-functionalized nanotubes recognized and attached onto well-defined complementary regions of thiolated alpha-CD SAM/Au substrates via host-guest molecular recognition. The binding between the azobenzene nanotubes and the alpha-CD SAM/Au substrates was controlled by UV irradiation. The light-induced attachment-detachment of the azobenzene nanotubes on the alpha-CD SAMs was reversible. Some of the nanotubes were capable of interconnecting two Au substrates. This smart building block may be applied to build photoactive nanometer-sized mechanical switches in electronics.

Azo Compounds↗

Quantum chemical treatment of large nanotubes via use of line group symmetry: structural preferences of magnesium dichloride nanotubes.

Nanotubes with diameters in the magnitude of 10 nm can be treated by quantum chemical methods, made possible by utilization of line group symmetries. The methodology presented here is applied for magnesium dichloride nanotubes. The structural preferences of MgCl2 nanotubes are strongly dependent on the tube diameter. The rolled layer of a crystalline sheet becomes favorable above a diameter of 3.4 nm, below which alternative stable coordination modes dominate. Application of the methodology for other nanotubular compounds, including multiwalled nanotubes, is expected to be straightforward.

Journal Article↗

Self-assembly of single-walled carbon nanotubes into multiwalled carbon nanotubes in water: molecular dynamics simulations.

We report discoveries from a series of molecular dynamics simulations that single-walled carbon nanotubes, with different diameters, lengths, and chiralities, can coaxially self-assemble into multiwalled carbon nanotubes in water via spontaneous insertion of smaller tubes into larger ones. The assembly process is tube-size-dependent, and the driving force is primarily the intertube van der Waals interactions. The simulations also suggest that a multiwalled carbon nanotube may be separated into single-walled carbon nanotubes under appropriate solvent conditions. This study suggests possible bottom-up self-assembly routes for the fabrication of novel nanodevices and systems.

Journal Article↗

Formation of ice nanotube with hydrophobic guests inside carbon nanotube.

A composite ice nanotube inside a carbon nanotube has been explored by molecular-dynamics and grand canonical Monte Carlo simulations. It is made from an octagonal ice nanotube whose hollow space contains hydrophobic guest molecules such as neon, argon, and methane. It is shown that the attractive interaction of the guest molecules stabilizes the ice nanotube. The guest occupancy of the hollow space is calculated by the same method as applied to clathrate hydrates.

Journal Article↗

DNA functionalization of carbon nanotubes for ultrathin atomic layer deposition of high kappa dielectrics for nanotube transistors with 60 mV/decade switching.

For single-walled carbon nanotube (SWNT) field effect transistors, vertical scaling of high kappa dielectrics by atomic layer deposition (ALD) currently stands at approximately 8 nm with a subthreshold swing S approximately 70-90 mV/decade at room temperature. ALD on as-grown pristine SWNTs is incapable of producing a uniform and conformal dielectric layer due to the lack of functional groups on nanotubes and because nucleation of an oxide dielectric layer in the ALD process hinges upon covalent chemisorption on reactive groups on surfaces. Here, we show that by noncovalent functionalization of SWNTs with poly-T DNA molecules (dT40-DNA), one can impart functional groups of sufficient density and stability for uniform and conformal ALD of high kappa dielectrics on SWNTs with thickness down to 2-3 nm. This enables approaching the ultimate vertical scaling limit of nanotube FETs and reliably achieving S approximately 60 mV/decade at room temperature, and S approximately 50 mV/decade in the band-to-band tunneling regime of ambipolar transport. We have also carried out microscopy investigations to understand ALD processes on SWNTs with and without DNA functionalization.

DNA↗

Exposure to carbon nanotube material: aerosol release during the handling of unrefined single-walled carbon nanotube material.

Carbon nanotubes represent a relatively recently discovered allotrope of carbon that exhibits unique properties. While commercial interest in the material is leading to the development of mass production and handling facilities, little is known of the risk associated with exposure. In a two-part study, preliminary investigations have been carried out into the potential exposure routes and toxicity of single-walled carbon nanotube material (SWCNT)--a specific form of the allotrope. The material is characterized by bundles of fibrous carbon molecules that may be a few nanometers in diameter, but micrometers in length. The two production processes investigated use-transition metal catalysts, leading to the inclusion of nanometer-scale metallic particles within unrefined SWCNT material. A laboratory-based study was undertaken to evaluate the physical nature of the aerosol formed from SWCNT during mechanical agitation. This was complemented by a field study in which airborne and dermal exposure to SWCNT was investigated while handling unrefined material. Although laboratory studies indicated that with sufficient agitation, unrefined SWCNT material can release fine particles into the air, concentrations generated while handling material in the field were very low. Estimates of the airborne concentration of nanotube material generated during handling suggest that concentrations were lower than 53 microg/m(3) in all cases. Glove deposits of SWCNT during handling were estimated at between 0.2 mg and 6 mg per hand.

Aerosols↗

Exposure to carbon nanotube material: assessment of nanotube cytotoxicity using human keratinocyte cells.

Carbon nanotubes are new members of carbon allotropes similar to fullerenes and graphite. Because of their unique electrical, mechanical, and thermal properties, carbon nanotubes are important for novel applications in the electronics, aerospace, and computer industries. Exposure to graphite and carbon materials has been associated with increased incidence of skin diseases, such as carbon fiber dermatitis, hyperkeratosis, and naevi. We investigated adverse effects of single-wall carbon nanotubes (SWCNT) using a cell culture of immortalized human epidermal keratinocytes (HaCaT). After 18 h of exposure of HaCaT to SWCNT, oxidative stress and cellular toxicity were indicated by formation of free radicals, accumulation of peroxidative products, antioxidant depletion, and loss of cell viability. Exposure to SWCNT also resulted in ultrastructural and morphological changes in cultured skin cells. These data indicate that dermal exposure to unrefined SWCNT may lead to dermal toxicity due to accelerated oxidative stress in the skin of exposed workers.

Cells, Cultured↗

Formation of silicon carbide nanotubes and nanowires via reaction of silicon (from disproportionation of silicon monoxide) with carbon nanotubes.

One-dimensional silicon-carbon nanotubes and nanowires of various shapes and structures were synthesized via the reaction of silicon (produced by disproportionation reaction of SiO) with multiwalled carbon nanotubes (as templates) at different temperatures. A new type of multiwalled silicon carbide nanotube (SiCNT), with 3.5-4.5 A interlayer spacings, was observed in addition to the previously known beta-SiC (cubic zinc blende structure) nanowires and the biaxial SiC-SiO(x) nanowires. The SiCNT was identified by high-resolution transmission microscopy (HRTEM), elemental mapping, and electron energy loss spectroscopy (EELS). The multiwalled SiCNT was found to transform to a beta-SiC crystalline structure by electron beam annealing under TEM.

Journal Article↗

Micelle-encapsulated carbon nanotubes: a route to nanotube composites.

We report a general approach toward dispersing single-walled carbon nanotubes (SWNTs) in solvents and polymer materials, by encapsulating SWNTs within cross-linked micelles. Micelles made from polystyrene-block-poly(acrylic acid) (PS-b-PAA), an amphiphilic block copolymer, are first assembled around SWNTs by gradually adding H2O to a suspension of nanotubes in dimethylformamide. The hydrophilic, outer shells of these micelles are then chemically cross-linked with a difunctional linker molecule. Pure encapsulated SWNTs (e-SWNTs) can then be separated from empty cross-linked micelles by consecutive cycles of centrifugation and redispersion. Atomic force and transmission electron microscopies of the resulting nanostructures demonstrate that individual nanotubes (rather than bundles) have been completely encased in polymer shells whose thickness is slightly larger than that of empty micelles. e-SWNTs encapsulated in PS-b-PAA can be permanently redispersed in H2O, in organic solvents, and in both hydrophobic and hydrophilic polymer matrices with minimal sonication. Micelle encapsulation could improve the compositing of SWNTs in a wide variety of polymer materials for structural, electronic, and thermal applications.

Journal Article↗

New nanotube synthesis strategy--application of sodium nanotubes formed inside anodic aluminium oxide as a reactive template.

Formation of Na nanotubes inside the channels of anodic aluminium oxide (AAO) membranes has been achieved by decomposing NaH thermally on AAO. The as-produced material, Na@AAO, is applied as a reactive template to prepare other tubular materials. Reacting Na@AAO with gaseous C6Cl6 generates carbon nanotubes (ca. 250 nm, wall thickness of 20 nm, tube length of 60 microm) inside the AAO channels. Highly aligned bundles of nearly amorphous carbon nanotubes are isolated after AAO is removed.

Journal Article↗

Low temperature emission spectra of individual single-walled carbon nanotubes: multiplicity of subspecies within single-species nanotube ensembles.

Low-temperature photoluminescence (PL) studies of individual semiconducting single-walled carbon nanotubes reveal ultranarrow peaks (down to 0.25 meV linewidths) that exhibit blinking and spectral wandering. Multiple peaks appear within bands previously assigned to nanotubes of certain chiralities, indicating the existence of numerous subspecies within single-chirality specimens. The sharp PL features show two types of distinctly different shapes (symmetric versus asymmetric) and temperature dependences (weak versus strong), which we attribute to the presence of unintentionally doped nanotubes along with undoped species.

Journal Article↗

Cytotoxicity of carbon nanomaterials: single-wall nanotube, multi-wall nanotube, and fullerene.

A cytotoxicity test protocol for single-wall nanotubes (SWNTs), multi-wall nanotubes (with diameters ranging from 10 to 20 nm, MWNT10), and fullerene (C60) was tested. Profound cytotoxicity of SWNTs was observed in alveolar macrophage (AM) after a 6-h exposure in vitro. The cytotoxicity increases by as high as approximately 35% when the dosage of SWNTs was increased by 11.30 microg/cm2. No significant toxicity was observed for C60 up to a dose of 226.00 microg/cm2. The cytotoxicity apparently follows a sequence order on a mass basis: SWNTs > MWNT10 > quartz > C60. SWNTs significantly impaired phagocytosis of AM at the low dose of 0.38 microg/cm2, whereas MWNT10 and C60 induced injury only at the high dose of 3.06 microg/cm2. The macrophages exposed to SWNTs or MWNT10 of 3.06 microg/cm2 showed characteristic features of necrosis and degeneration. A sign of apoptotic cell death likely existed. Carbon nanomaterials with different geometric structures exhibit quite different cytotoxicity and bioactivity in vitro, although they may not be accurately reflected in the comparative toxicity in vivo.

Animals↗

The role of metal-nanotube contact in the performance of carbon nanotube field-effect transistors.

Single-wall carbon nanotube field-effect transistors (CNFETs) have been shown to behave as Schottky barrier (SB) devices. It is not clear, however, what factors control the SB size. Here we present the first statistical analysis of this issue. We show that a large data set of more than 100 devices can be consistently accounted by a model that relates the on-current of a CNFET to a tunneling barrier whose height is determined by the nanotube diameter and the nature of the source/drain metal contacts. Our study permits identification of the desired combination of tube diameter and type of metal that provides the optimum performance of a CNFET.

Computer Simulation↗

Photoluminescence mapping of "as-grown" single-walled carbon nanotubes: a comparison with micelle-encapsulated nanotube solutions.

Band gap photoluminescence (PL) is observed from "as-grown" single-walled carbon nanotubes (SWNTs) in solid form. The relative PL intensities for six specific semiconducting SWNTs are compared directly to those of the micelle-encapsulated SWNTs' solutions to investigate the influence of the micelle dispersion process on PL measurements. The results indicate that sodium dodecyl sulfate (SDS) and sodium cholate (SC) selectively solubilize smaller-diameter nanotubes, whereas sodium dodecylbenzene sulfonate (SDBS) solution does not exhibit significant diameter selectivity within the diameter range studied here (d(t) = 0.829-0.966 nm).

Colloids↗

Measurement of wetting properties of individual boron nitride nanotubes with the wilhelmy method using a nanotube-based force sensor.

The wetting properties of individual boron nitride nanotubes (BNNTs) were studied with the Wilhelmy method in ambient conditions. A nanotube-based force sensor having a force resolution of 0.1 nN, calibrated with the wetting force method, was used to study the interactions between BNNTs and liquids in situ. The static contact angles of the liquids on BNNTs were evaluated, and the surface tension of the BNNT along with its surface tension components was determined based on the Owens and Wendt method and the van Oss-Chaudhury-Good acid-base theory.

Boron Compounds↗

Comparison of diatoms, exfoliated graphite, single-wall nanotubes, multiwall nanotubes, and silica for the synthesis of the nanomagnet Mn12.

We have completed a preliminary series of experiments that compare the silicate shells of the marine organism diatoms to Single-Wall NanoTubes (SWNT), Multi-Wall NanoTubes (MWNT), Exfoliated Graphite (EG), and silica as templates for producing nanostructures of the manganese acetate cluster Mn12 (Mn12[CH3(COO)16(H2O)4O12].(2)CH3COOH.4H2O). Mn12 exhibits magnetic properties because of the molecular arrangement within the cluster and exhibits no exchange couplings between the individual clusters. Data from scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and laser diffraction are discussed in terms of research that can expand the use of diatoms and other materials as templates for nanostructures.

Crystallization↗