Communications: Nanomagnetic shielding: High-resolution NMR in carbon allotropes.

The understanding and control of the magnetic properties of carbon-based materials is of fundamental relevance in applications in nano- and biosciences. Ring currents do play a basic role in those systems. In particular the inner cavities of nanotubes offer an ideal environment to investigate the magnetism of synthetic materials at the nanoscale. Here, by means of (13)C high resolution NMR of encapsulated molecules in peapod hybrid materials, we report the largest diamagnetic shifts (down to -68.3 ppm) ever observed in carbon allotropes, which is connected to the enhancement of the aromaticity of the nanotube envelope upon doping. This diamagnetic shift can be externally controlled by in situ modifications such as doping or electrostatic charging. Moreover, defects such as C-vacancies, pentagons, and chemical functionalization of the outer nanotube quench this diamagnetic effect and restore NMR signatures to slightly paramagnetic shifts compared to nonencapsulated molecules. The magnetic interactions reported here are robust phenomena independent of temperature and proportional to the applied magnetic field. The magnitude, tunability, and stability of the magnetic effects make the peapod nanomaterials potentially valuable for nanomagnetic shielding in nanoelectronics and nanobiomedical engineering.

Electron beam induced structural transformations of SWNTs and DWNTs grown on Si3N4/Si substrates.

Electron beam induced structural transformations are investigated in single-wall carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs) and crossed nanotube junctions. The nanotubes studied here are synthesized by the chemical vapor deposition method. The response of the nanotubes to an electron beam is found to be influenced by the presence of coatings of amorphous carbon, graphene fragments and structural defects on the tube surface. The dependence of structural modifications on electron beam irradiation dose is measured. While nanotubes with amorphous carbon, graphene fragment coverage and/or defects undergo rapid transformation leading to structure disintegration, those without such coverage or defects are more resistant to beam damage. In addition, it is shown that the amorphous carbon coverage on the double-wall nanotubes can be transformed into graphene layers during electron beam irradiation of coated nanotubes. Finally, the relative stability of nanotube side-wall and end-walls are investigated through sub-threshold energy and above threshold energy irradiation of a model system, C60-filled nanotubes (Peapods). The data indicates that electron beams could be used to join nanotubes end-to-end without damaging the side-walls.

Filling single-wall carbon nanotubes with d- and f-metal chloride and metal nanowires.

Nanowires of magnetic metals (Fe, Co, Ho, Gd) have been synthesized inside the hollow interiors of single-wall carbon nanotubes (SWNTs) by filling SWNTs with precursor metal chlorides and subsequent reduction. SWNTs have been filled by either the melt-phase sealed-tube reaction or a solution-phase method. Among the metal chlorides investigated in this study, HoCl3 and GdCl3 filled the SWNTs to a significantly higher extent. The nanowires have been imaged by transmission electron microscopy (TEM), high-resolution transmission electron microscopy, and scanning transmission electron microscopy (STEM). X-ray energy dispersive spectroscopy carried out in conjunction with TEM and STEM confirmed the presence of metal chloride and metal nanowires.

Mapping the one-dimensional electronic States of nanotube peapod structures.

Arrays of C60 molecules nested inside single-walled nanotubes represent a class of nanoscale materials having tunable properties. We report electronic measurements of this system made with a scanning tunneling microscope and demonstrate that the encapsulated C60 molecules modify the local electronic structure of the nanotube. Our measurements and calculations also show that a periodic array of C60 molecules gives rise to a hybrid electronic band, which derives its character from both the nanotube states and the C60 molecular orbitals.

Orientational disorder in solvent-free solid c70.

The high-temperature structure of solvent-free C(70) has been determined with high-resolution x-ray powder difraction and electron microscopy. Samples crystallized from solution form hexagonal close-packed crystals that retain an appreciable amount of residual toluene, even after prolonged heating. Samples prepared by sublimation, which contain no detectable solvent, are primarily face-centered cubic with some admixture of a hexagonal phase. The relative volume of the hexagonal phase can be further reduced by annealing. The structures of both phases are described by a model of complete orientational disorder. The cubic phase contains an appreciable density of stacking faults along the [111] direction.

On high-resolution transmission electron microscopy in an unstable magnetic environment.

Owing to the particular environment of the JEM4000EX HREM at the University of Pennsylvania, it became necessary to control the magnetic environment around the microscope. The unstable magnetic environment included two components, a slowly wandering vertical DC magnetic field and an AC magnetic field. The effects of these fields on the microscope performance were to introduce an uncertainty in the objective lens defocus value over a series of images and to reduce the attainable resolution of the microscope, respectively. A solution is presented in which these fields are stably reduced well within the limits of sensitivity of the JEOL, Ltd. JEM4000EX for high-resolution imaging. This solution is based on a feedback loop using a pseudo-Helmholtz coil to generate a well-defined vertical magnetic field.