Nanomanipulation and fabrication by ion beam molding

Nanoscale manipulation is a basic ability needed to realize many of the nanotechnology applications. We demonstrate an ion bean molding technique to shape the configuration of nanostructures. As an example, the native curvature of a carbon nanotube in an atomic force microscope tip and its undesirable angle with respect to the surface are removed by this technique to render the nanotube straight. The straightened nanotube is effectively used in a semiconductor profilometry application. The ion beam molding technique is also shown to be effective in creating a desirable net shape of nanotubes. As mechanical deformation determines electrical and other properties of nanotubes, such manipulation may be of use in nanodevice fabrication.     

Atomically resolved mechanical response of individual metallofullerene molecules confined inside carbon nanotubes

The hollow core inside a carbon nanotube can be used to confine single molecules and it is now possible to image the movement of such molecules inside nanotubes. To date, however, it has not been possible to control this motion, nor to detect the forces moving the molecules, despite experimental and theoretical evidence suggesting that almost friction-free motion might be possible inside the nanotubes. Here, we report on precise measurements of the mechanical responses of individual metallofullerene molecules (Dy@C82) confined inside single-walled carbon nanotubes to the atom at the tip of an atomic force microscope operated in dynamic mode. Using three-dimensional force mapping with atomic resolution, we addressed the molecules from the exterior of the nanotube and measured their elastic and inelastic behaviour by simultaneously detecting the attractive forces and energy losses with three-dimensional, atomic-scale resolution.     

Microwave‐Assisted Regeneration of Single‐Walled Carbon Nanotubes from Carbon Fragments

Direct growth of chirality‐controlled single‐walled carbon nanotubes (SWNTs) with metal catalyst free strategy, like cloning or epitaxial growth, has suffered from the low efficiency. The underlying problem is the activation of seed edge. Here an unexpectedly efficient microwave‐assisted pathway to regenerate SWNTs from carbon fragments on SiO₂/Si substrate is demonstrated via Raman spectroscopy and atomic force microscope (AFM) characterization. In this attempt, microwave irradiation provides fast heating to remove polar groups bonded to carbon nanotubes and reduce the spontaneous closure of tubes’ open ends. The survived SWNT and carbon fragments connected to it after plasma treatment are simply microwaved and then they serve as the template for regeneration. Scanning electron microscope and AFM characterizations indicate that the efficiency of the regeneration can reach 100%. And the regenerated SWNT has been proved without any change in chirality compared to the original SWNT. Electrical measurements on regenerated carbon nanotube films indicate 1 and 2 times increase in on/off ratio and on‐state current respectively than original carbon nanotube films obtained from solution‐phase separation, confirming the improvement of SWNT's quality. The microwave‐assisted regeneration is found to be highly effective and would be applied to improve the cloning efficiency of carbon nanotubes potentially.     

Studying electrical transport in carbon nanotubes by conductance atomic force microscopy

An introduction to conductance atomic force microscopy in the context of carbon nanotubes is provided where the main problems and performances of this technique are discussed. The conductance measured in SWNT as a function of the loading force applied by an AFM metallized tip is reported. These experiments allow us to study the process of the electrical contact formation between the tip and the nanotube. This will also lead to a study of the electromechanical properties of nanotubes for radial deformations.     

Nanocrystallized steel surface by micro-shot peening for catalyst-free carbon nanotube growth

Nanocrystallized steel surface by micro-shot peening (MSP) were applied to carbon nanotube growth in this study. Micro-shot peening treatment severely deformed steel surface and nanocrystallized surface layer was formed by the plastic deformation. The grain sizes of the nanocrystallized layer were 10-30 nm after 300 s of MSP treatment. On the nanocrystallized surface, carbon nanotubes were formed with thermal chemical vapour deposition without catalysts. Before carbon nanotube growth, the nanocrystallized steel surface was reduced with H₂/N₂ gas at 600 °C. The carbon nanotube growth was performed at 600 °C with C₂H₂ gas carried by H₂/N₂ gas. The carbon nanotubes formed on the nano-structured surface was multi-walled carbon nanotube and the diameter was 10-20 nm. The reduction process before carbon nanotube growth was essential to form carbon nanotubes on the nanocrystallized surface with MSP.     

Boron Nitride Nanotubes

The current status of research on boron nitride nanotubes (BNNTs)—carbon nanotube structural analogues—is discussed. Latest achievements in BNNT synthesis, morphology, and atomic structure analysis as well as physical, chemical, and functional property evaluations are reviewed. Similarities and differences between structural parameters and properties of BNNTs in comparison with conventional carbon nanotubes are particularly highlighted. Recent breakthroughs in BNNT filling, doping and functionalization, morphology, and electronic structure engineering are examined. Finally, prospective BNNT applications for fabricating field‐effect transistors, gas accumulators, and reinforcing polymer films are presented.     

Direct Intermolecular Force Measurements between Functional Groups and Individual Metallic or Semiconducting Single‐Walled Carbon Nanotubes

Many electronic applications of single‐walled carbon nanotubes (SWNTs) require electronic homogeneity in order to maximally exploit their outstanding properties. Non‐covalent separation is attractive as it is scalable and results in minimal alteration of nanotube properties. However, fundamental understanding of the metallicity‐dependence of functional group interactions with nanotubes is still lacking; this lack is compounded by the absence of methods to directly measure these interactions. Herein, a novel technology platform based on a recently developed atomic force microscopy (AFM) mode is reported which directly quantifies the adhesion forces between a chosen functional group and individual nanotubes of known metallicity, permitting comparisons between different metallicity. These results unambiguously show that this technology platform is able to discriminate the subtle adhesion force differences of a chosen functional group with pure metallic as opposed to pure semiconducting nanotubes. This new method provides a route towards rapid advances in understanding of non‐covalent interactions of large libraries of compounds with nanotubes of varying metallicity and diameter; presenting a superior tool to assist the discovery of more effective metallicity‐based SWNT separation agents.     

Influence of surface chemistry on inkjet printed carbon nanotube films

Carbon nanotube ink chemistry and the proper formulation are crucial for direct-write printing of nanotubes. Moreover, the correct surface chemistry of the self-assembled monolayers that assist the direct deposition of carbon nanotubes onto the substrate is equally important to preserve orientation of the printed carbon nanotubes. We report that the successful formulation of two single walled carbon nanotube (SWNT) inks yields a consistent, homogenous printing pattern possessing the requisite viscosities needed for flow through the microcapillary nozzles of the inkjet printer with fairly modest drying times. The addition of an aqueous sodium silicate allows for a reliable method for forming a uniform carbon nanotube network deposited directly onto unfunctionalized surfaces such as glass or quartz via inkjet deposition. Furthermore, this sodium silicate ingredient helps preserve applied orientation to the printed SWNT solution. Sheet resistivity of this carbon nanotube ink formula printed on quartz decreases as a function of passes and is independent of the substrate. SWNTs were successfully patterned on Au. This amine-based surface chemistry dramatically helps improve the isolation stabilization of the printed SWNTs as seen in the atomic force microscopy (AFM) image. Lastly, using our optimized SWNT ink formula and waveform parameters in the Fuji materials printer, we are able to directly write/print SWNTs into 2D patterns. Dried ink pattern expose and help orient roped carbon nanotubes that are suspended in ordered arrays across the cracks.     

Amplitude response of single-wall carbon nanotube probes during tapping mode atomic force microscopy: Modeling and experiment

Imaging of surfaces with carbon nanotube probes in tapping mode results frequently in complex behavior in the amplitude-distance curves monitored. Using molecular mechanics simulations, we calculate the force exerted on a nanotube pressed against a smooth surface as it undergoes deformation and buckling. This nonlinear force is then used in a macroscopic equation, describing the response of a damped harmonic oscillator, to predict the amplitude response of a nanotube AFM probe. Similarities between the prediction and experiment suggest that the complex amplitude response seen in the experiment may be explained by the nonlinearity in the force exerted on the nanotube and thus must not necessarily be related to the structure of the surface.     

Characterizing the Structure and Properties of Individual Wire‐Like Nanoentities

A new approach to the characterization of the mechanical and electrical properties of individual nanowires and nanotubes is demonstrated by in‐situ transmission electron microscopy (TEM). The technique allows a one‐to‐one correlation between the structure and properties of the nanowires. Recent developments include the determination of the Young's modulii of carbon nanotubes and semiconductor nanowires, femtogram nanobalance of a single fine particle, field emission of carbon nanotubes, and quantum ballistic conductance in carbon nanotubes.     

Manipulation of individual double-walled carbon nanotubes packed in a casing shell

Controlled placement of carbon nanotubes is important for carbon-based nanodevice assembly. However, it is difficult to manipulate individual nanotubes because of their extremely small dimensions. Ultra-fine tubes are often in the form of bundles and are hard to efficiently move on a surface due to the strong adhesion among themselves and between the tubes and the substrate. This paper presents a novel manipulation approach of individual double-walled carbon nanotubes encased in a thick amorphous carbon shell. With an atomic force microscope, we are able to freely displace the nanotubes within a casing shell, and unpack it from the shell on a silicon surface. The theoretical analysis demonstrates that the unpacking process is determined by the difference of the static friction between the shell and the substrate and the resistance force between the shell and the embedded nanotube.     

Frictionless sliding of single-stranded DNA in a carbon nanotube pore observed by single molecule force spectroscopy

Smooth inner pores of carbon nanotubes (CNT) provide a fascinating model for studying biological transport. We used an atomic force microscope to pull a single-stranded DNA oligomer from a carbon nanotube pore. DNA extraction from CNT pores occurs at a nearly constant force, which is drastically different from the elastic profile commonly observed during polymer stretching with atomic force microscopy. We show that a combination of the frictionless nanotube pore walls and an unfavorable DNA solvation energy produces this constant force profiles.     

Nanoscale uniaxial pressure effect of a carbon nanotube bundle on tip-enhanced near-field Raman spectra

In situ measurement of tip-enhanced near-field Raman spectra of an isolated single-wall carbon nanotube (SWNT) bundle has been demonstrated by applying a uniaxial pressure up to approximately 2 GPa to the bundle via a metal-coated atomic force microscope tip. We investigated the pressure dependences of Raman frequencies and the intensity of the radial breathing mode bands, the D-band and the G-band, which were related to deformation of SWNTs caused by the tip pressure.     

Micro orientation and anisotropy of conductivity in liquid crystalline polymer films filled with carbon nanotubes

In this communication we report the preferential orientation of single wall carbon nanotubes (SWNT) in a nematic liquid crystalline (LC) polymer matrix. The alignment of the nanotubes was characterized through anisotropy of electrical conductivity of the composite measured in directions parallel and perpendicular to the nematic director. The anisotropy of the nanocomposite films strongly depends on the nanotube concentration in the range from 1 to 10% and vanished at higher loads. The electrical conductivity of nanocomposites is related to their structural features revealed by atomic force microscopy and Raman spectroscopy experiments and is explained by a strong coupling between the nanotubes and the polymer matrix.     

Physical properties of carbon nanotubes radiated by proton beams: Gas adsorption and electron microscopy studies

Single walled carbon nanotues (SWCNTs) of high purity and multi walled carbon nanotubes (MWCNTs) were radiated by high energies of proton and electron beams. The surface physical properties were examined by XRD and TEM for both irradiated and non-radiated samples to compare the effect of radiation. The possible changes of surface characteristics were investigated by isotherm gas adsorption technique using Ar which can probe the local structure in an order of atomic scale. A series of Ar gas adsorption results measured below 77 K revealed significant changes in surface properties of carbon nanotubes by the bombardment of proton beams, which may induce the local surface defects. It is speculated that reactions on carbon nanotubes radiated by beams were led by kinetic energy transfer of the bombardments.     

Evidence for metal-semiconductor transitions in twisted and collapsed double-walled carbon nanotubes by scanning tunneling microscopy

The atomic and electronic structure of a twisted and collapsed double-walled carbon nanotube was characterized using scanning tunneling microscopy and spectroscopy. It was found that the deformation opens an electronic band gap in an otherwise metallic nanotube, which has major ramifications on the use of carbon nanotubes for electronic applications. Fundamentally, the importance of the intershell interaction in this double-walled carbon nanotube points to the potential of a reversible metal-semiconductor junction, which can have device applications, as well as a caution in the design of semiconductor components based on carbon nanotubes. Lattice registry effects between the two neighboring walls evidenced by atomically resolved images confirm earlier first principle calculations indicating that the helicity influences the collapsed structure and show excellent agreement with the predicted twisted-collapse mode.     

Peeling force spectroscopy: exposing the adhesive nanomechanics of one-dimensional nanostructures

The physics of adhesion and stiction of one-dimensional nanostructures such as nanotubes, nanowires, and biopolymers on different material substrates is of great interest for the study of biological adhesion and the development of nanoelectronics and nanocomposites. Here, we combine theoretical models and a new mode in the atomic force microscope to investigate quantitatively the physics of nanomechanical peeling of carbon nanotubes and nanocoils on different substrates. We demonstrate that when an initially straight nanotube is peeled from a surface, small perturbations can trigger sudden transitions between different geometric configurations of the nanotube with vastly different interfacial energies. This opens up the possibility of quantitative comparison and control of adhesion between nanotubes or nanowires on different substrates.     

Separation Techniques for Carbon Nanotubes

Single‐walled carbon nanotubes have considerable potential as building blocks in future nanoscale electronics. The tubes exist in two modifications, metallic and semiconducting, which might be used in a range of electronic applications. One of the grand challenges is to separate metallic from semiconducting tubes in substantial quantities. In this respect, this article gives a brief overview over the separation techniques in this new field of nanotube research.     

Field emission properties of carbon nanotubes coated with boron nitride

Field emission properties of carbon nanotubes coated with a single layer of boron nitride are calculated using the first-principles pseudopotential method. At lower bias voltage, the emission current of the coated nanotube is comparable to that of the bare carbon nanotube and is dominated by the contribution from localized states at the tip of the tube. At higher voltage, newly generated hybridized states between the carbon nanotube tip and the even-membered boron nitride rings contribute significantly to the emission current because they experience a low tunneling barrier compared with the bare carbon nanotube case. Our results suggest that the insulator coating can, besides protecting the nanotube tip from the attack of gas molecules, substantially enhance the field emission current.