New probes based on carbon nano-cones for scanning probe microscopies.

All-graphenic carbon morphologies grown on individual carbon nanotubes (CNTs) consisting of short-fiber segments bearing sharp micro-/nano-cones at both ends were mounted as new probes for scanning probe microscopies (SPM). Three mounting procedures were tested, two based on focused ion and/or electron beam processes operated in scanning electron microscopes, and another based on an irradiation-free procedure under an optical microscope. The benefits and drawbacks of all the methods are described in details. The extent to which the structural integrity of the carbon material of the cones was affected by each of the mounting processes was also investigated using Raman spectroscopy and high-resolution transmission electron microscopy. The carbon cones were found to be sensitive to both ion and electron irradiation to an unusual extent with respect to structurally-close nano-objects such as multi-wall CNTs. This was assumed to be due to the occurrence of a large number of free graphene-edges at the cone surface. The suitability of such carbon cones as SPM probes is demonstrated, the characteristics of which make them potentially superior to Si-, diamond-, or CNT-probes.

Texture, Nanotexture, and Structure of Carbon Nanotube-Supported Carbon Cones.

Graphene-based carbon micro-/nano-cones were prepared by depositing pyrolytic carbon onto individual carbon nanotubes as supports using a specific chemical vapor deposition process. They were investigated by means of high-resolution scanning electron microscopy, low-voltage aberration-corrected transmission electron microscopy, Raman spectroscopy, and molecular dynamics modeling. While the graphenes were confirmed to be perfect, the cone texture was determined to be preferably scroll-like, with the scroll turns being parallel to the cone axis. Correspondingly, many of the concentrically displayed graphenes (actually scroll turns) exhibit the same helicity vector. When radii of curvature are large enough, this could allow for coherent stacking to locally take place in spite of the lattice shift induced by the curvature. A particular care was taken on investigating the cone apexes, in which a specific type of graphene termination was observed, here designated as the "zip" defect. Calculations determined a plausible stable structure that such a defect type may correspond to. This defect was found to generate a very low Raman ID/ID' band ratio (1.5), for which physical reasons are proposed. Combining our results and that of the literature allowed proposing an identification chart for a variety of defects able to affect the graphene lattice or edges.

Intense Raman D Band without Disorder in Flattened Carbon Nanotubes.

Above a critical diameter, single- or few-walled carbon nanotubes spontaneously collapse as flattened carbon nanotubes. Raman spectra of isolated flattened and cylindrical carbon nanotubes have been recorded. The collapse provokes an intense and narrow D band, despite the absence of any lattice disorder. The curvature change near the edge cavities activates a D band, despite framework continuity. Theoretical calculations based on Placzek approximation fully corroborate this experimental finding. Usually used as a tool to quantify defect density in graphenic structures, the D band cannot be used as such in the presence of a graphene fold. This conclusion should serve as a basis to revisit materials comprising structural distortion where poor carbon organization was concluded on a Raman basis. Our finding also emphasizes the different visions of a defect between chemists and physicists, a possible source of confusion for researchers working in nanotechnologies.

Photolysis-Driven, Room Temperature Filling of Single-Wall Carbon Nanotubes.

An alternative process for opening and filling single-wall carbon nanotubes (SWCNTs) based on UV photolysis is proposed. The filling of SWCNTs with MoCl5 and iodine were successfully achieved at room temperature after subjecting SWCNTs with MoCl5 or I2 dissolved in chloroform to UV light for 6 hours. Transmission electron microscopy (TEM) and Electron Energy Loss Spectroscopy (EELS) were used to characterise both the encapsulated materials and the host tube. A mechanism for the related opening and filling events is proposed, along with a possible yet unprecedented structure for the encapsulated MoCl5 material whose the peculiar polymeric configuration could be enforced by the steric constrains resulting from the limited, 1D cavity available in SWCNT core.

200 keV cold field emission source using carbon cone nanotip: Application to scanning transmission electron microscopy.

We report the use of a pyrolytic carbon cone nanotip as field emission cathode inside a modern 200 kV dedicated scanning transmission electron microscope. We show an unprecedented improvement in the probe current stability while maintaining all the fundamental properties of a cold field emission source such as a small angular current density together with a high brightness. We have also studied the influence of the low extraction voltage, as enabled by the nanosized apex of the cones, on the electron optics properties of the source that prevent the formation of a virtual beam cross-over of the gun. We have addressed this resolution-limiting issue by coming up with a new electron optical source design.

Reductive dismantling and functionalization of carbon nanohorns.

Reduction of carbon nanohorn (CNH) aggregates with potassium naphthalenide resulted in their dismantling and individualization. Furthermore, the reduced CNHs were functionalized via addition of electrophiles.

Determining the work function of a carbon-cone cold-field emitter by in situ electron holography.

Cold-field emission properties of carbon cone nanotips (CCnTs) have been studied in situ in the transmission electron microscope (TEM). The current as a function of voltage, i(V), was measured and analyzed using the Fowler-Nordheim (F-N) equation. Off-axis electron holography was employed to map the electric field around the tip at the nanometer scale, and combined with finite element modeling, a quantitative value of the electric field has been obtained. For a tip-anode separation distance of 680 nm (measured with TEM) and a field emission onset voltage of 80 V, the local electric field was 2.55 V/nm. With this knowledge together with recorded i(V) curves, a work function of 4.8±0.3 eV for the CCnT was extracted using the F-N equation.

Inhibition of microbial growth by carbon nanotube networks.

In the last years carbon nanotubes have attracted increasing attention for their potential applications in the biomedical field as diagnostic and therapeutic nano tools. Here we investigate the antimicrobial activity of different fully characterized carbon nanotube types (single walled, double walled and multi walled) on representative pathogen species: Gram-positive Staphylococcus aureus, Gram-negative Pseudomonas aeruginosa and the opportunistic fungus Candida albicans. Our results show that all the carbon nanotube types possess a highly significant antimicrobial capacity, even though they have a colony forming unit capacity and induction of oxidative stress in all the microbial species to a different extent. Moreover, scanning electron microscopy analysis revealed that the microbial cells were wrapped or entrapped by carbon nanotube networks. Our data taken together suggest that the reduced capacity of microbial cells to forming colonies and their oxidative response could be related to the cellular stress induced by the interactions of pathogens with the CNT network.

Resonant laser-induced formation of double-walled carbon nanotubes from peapods under ambient conditions.

The selective excitation of fullerenes encapsulated in single-walled carbon nanotubes (SWCNTs) is carried out by irradiating them using a UV laser, the wavelength of which corresponds exactly to their maximum of absorption. Under such conditions, fullerenes strongly absorb the laser energy, open, and break, while the containing SWCNT merely acts as both a nanoreactor and a mold which is only weakly heated by the laser. The containing tube confines the fullerene fragments, promotes their reconstruction into an inner tube, and protects them from air oxidation. This leads to the overall formation of double-walled carbon nanotubes (DWCNTs). The transformation is found to strongly depend on the laser irradiance and dose. This proves that the related mechanism is a multiphoton photolysis, different from the previous heat-induced transformation attempts found in the literature, whether the heat is produced by means of a thermostat, infrared laser, or nonresonant UV laser. The actual peapod-to-DWCNT transformation is monitored by Raman spectroscopy and high-resolution transmission electron microscopy.

Highly electroconductive multiwalled carbon nanotubes as potentially useful tools for modulating calcium balancing in biological environments.

Aiming to explore the mechanisms modulating cell-carbon nanotube interactions, we investigated whether Ca(2+) ion balancing between intra- and extracellular environments could be affected by multiwalled carbon nanotubes (MWCNTs). We analyzed the effects induced by two different kinds of MWCNTs (as prepared and annealed at 2400°C) on the intracellular Ca(2+) ion levels in rat electrically sensitive cells and on the intercellular junction integrity of rat adenocarcinoma colon cells and platelet aggregation ability, which depend on the Ca(2+) concentration in the medium. MWCNTs, purified by annealing and more electroconductive as compared to nonannealed MWCNTs, affected Ca(2+) ion balancing between extra- and intracellular environments and induced changes on Ca(2+) ion-dependent cellular junctions and platelet aggregation, behaving as the calcium chelator ethylene glycol tetraacetic acid. This could be due to the sorption of cationic Ca(2+) ions on CNTs surface because of the excess of negatively charged electrons on the aromatic units formed on MWCNTs after annealing. From the ClinicAL Editor: The authors investigated whether Ca(2+) ion balance between intra- and extracellular space can be modulated by multiwalled carbon nanotubes (MWCNTs). Annealed nanotubes induced changes on Ca(2+) dependent cellular junctions and platelet aggregation, behaving similary to ethylene glycol tetraacetic acid, an established calcium chelator.

Fluidized bed chemical vapor deposition of silicon on carbon nanotubes for Li-ion batteries.

Silicon was deposited on balls of entangled multi-walled carbon nanotubes (CNT) with a mean diameter of several hundreds of microns, by Fluidized Bed Chemical Vapor Deposition from silane (SiH4). The weight total percentage of deposited silicon was between 30 and 70%, to test their efficacy in Li-ion battery anodes. TEM and SEM imaging revealed that silicon deposits were of the form of nanoparticles uniformly dispersed on the whole CNT surface. The diameter of these nanoparticles increases with the deposited silicon percentage from 18 to 36 nm whereas their density remains constant at 5 10(22) nanoparticles/g of CNT. This indicates a low affinity of chemical species born from silane pyrolysis with the CNT surface for nucleation. The increase of the silicon nanoparticles diameter leads to the decrease of the specific surface area and the porous volume of the balls, probably due to the filling of the pores of the CNT network by silicon. A slight increase of the mean diameter of the balls was observed for the two highest silicon percentages, certainly due to the ability of the CNT network to be deformed under the mechanical stress induced by the silicon nanoparticles growth.

Contact angle hysteresis at the nanometer scale.

Using atomic force microscopy with nonconventional carbon tips, the pinning of a liquid contact line on individual nanometric defects was studied. This mechanism is responsible for the occurrence of the contact angle hysteresis. The presence of weak defects which do not contribute to the hysteresis is evidenced for the first time. The dissipated energy associated with strong defects is also measured down to values in the range of kT, which correspond to defect sizes in the order of 1 nm.

Electrical detection of individual magnetic nanoparticles encapsulated in carbon nanotubes.

We report on low-temperature electrical transport measurements of single-walled carbon nanotubes (SWNTs) filled in their inner core with one-dimensional cobalt nanoparticles. The electrical transport properties of the hybrid devices are strongly sensitive to the magnetization reversal of isolated magnetic nanoparticles, resulting in strong hysteretic variations of the magnetoconductance. The magnetic anisotropy of a one-dimensional encapsulated cobalt nanoparticle is investigated, establishing an unusually strong dominating contribution of magnetic surface anisotropy.

Nanoelectromechanical coupling in fullerene peapods probed by resonant electrical transport experiments.

Fullerene peapods, which are carbon nanotubes encapsulating fullerene molecules, can offer enhanced functionality with respect to empty nanotubes. Their prospective applications include, for example, data storage devices, single-electron transistors and spin-qubit arrays for quantum computing. However, the present incomplete understanding of how a nanotube is affected by entrapped fullerenes is an obstacle for peapods to reach their full potential in nanoscale electronic applications. In this paper, we investigate the effect of C(60) fullerenes on low-temperature electron transport through peapod quantum dots. Compared with empty nanotubes, we find an abnormal temperature dependence of Coulomb blockade oscillations, indicating the presence of a nanoelectromechanical coupling between electronic states of the nanotube and mechanical vibrations of fullerenes. This provides a method to detect the C(60) presence and to probe the interplay between electrical and mechanical excitations in peapods, which thus emerge as a new class of nanoelectromechanical systems.

Fullerene interaction with carbon nanohorns.

The interaction between carbon buckminsterfullerene (C60) and carbon nanohorns (also referred to as nanocones) with different tip angles is investigated theoretically. Attachment of C60 to both the interior and the exterior of the horns are considered. Calculations cover a range of cone angles from flat graphene, through 114 degrees, 84 degrees, 60 degrees, 39 degrees and 20 degrees to fullerene pair interaction. Full DFT/LDA calculations are performed and the influence of dispersion forces are considered independently using a numerical potential. Fullerenes bind weakly to the external nanocone wall with approximately 2.9 angstroms spacing (0.5-0.9 eV binding energy), showing no discernable trend with cone tip angle. Fullerene binding inside cones is significantly stronger (> 3 eV), primarily due to strong dispersion force interactions, with higher (approximately 3.1 angstroms) fullerene-nanohorn spacing. In this case, the binding energy increases with number of pentagons in the tip. In all cases the fullerenes will be freely rotating below liquid nitrogen temperatures. For pristine cones and fullerenes, the fullerenes will experience a driving force towards (away) from the nanohorn tip when inside (outside) the nanohorn.

Solutions of negatively charged graphene sheets and ribbons.

Negatively charged graphene layers from a graphite intercalation compound spontaneously dissolve in N-methylpyrrolidone, without the need for any sonication, yielding stable, air-sensitive, solutions of laterally extended atom-thick graphene sheets and ribbons with dimensions over tens of micrometers. These can be deposited on a variety of substrates. Height measurements showing single-atom thickness were performed by STM, AFM, multiple beam interferometry, and optical imaging on Sarfus wafers, demonstrating deposits of graphene flakes and ribbons. AFM height measurements on mica give the actual height of graphene (ca. 0.4 nm).