LETTERS
Ring Formation in Single-Wall Carbon Nanotubes
Richard Martel, Herbert R. Shea, and Phaedon Avouris*
IBM Research DiVision, T. J. Watson Research Center, Yorktown Heights, New York 10598
ReceiVed: May 6, 1999; In Final Form: July 14, 1999
Nanotube rings were fabricated from straight single-wall carbon nanotubes (SWNTs) with yields exceeding
50%. The rings result from the folding of nanotubes onto themselves under ultrasonic irradiation to form
coils with a narrow distribution of radii (300-400 nm). A simple continuum elastic model is used to discuss
the thermodynamic stability of the rings. Their formation involves a balance between tube-tube van der Waals
adhesion and the strain energy resulting from the coiling-induced curvature. Our findings suggest that ring
formation is a kinetically controlled process where bubble cavitation, generated by ultrasonic irradiation,
provides the energy necessary to activate ring formation. The electrical conductance of the rings is measured
as a function of temperature and in the presence of a perpendicular magnetic field. While the rings consist of
bundles of many metallic and semiconducting SWNTs, they exhibit metallic behavior at low temperatures,
and quantum interference effects are clearly observed.
Self-organization and the formation of molecular superstruc-
tures is a subject of strong current interest.
1,2
This field is driven
in part by a desire to understand the formation of biological
structures such as proteins, cell membranes, etc., and in part
by technological needs. As the push to increased miniaturization
of structures and devices continues, conventional fabrication
techniques are hard pressed to keep up, and self-assembly and
self-organization techniques are sought to replace them.
2,3
One
of the most studied processes of self-organization is the coiling
and ring formation by bio-polymers such as DNA and pro-
teins.
4,5
These processes are complex, involving a number of
different types of interactions. Here we discuss a case of self-
organization that involves coiling and ring formation by carbon
nanotubes, materials known for their high flexural rigidity.
6,7
Unlike the coils of bio-polymers that are usually stabilized
through hydrogen bonding and ionic interactions, the coils of
nanotubes are stabilized solely by van der Waals forces.
8
Carbon nanotubes (NTs) are a new class of materials that
consist of one or several graphene sheets rolled up into a
seamless tube, forming single-wall (SWNTs) or multiwall
(MWNTs) nanotubes, respectively.
9-11
NT’s very high tensile
strength is comparable to that of diamond,
6,7
and depending on
their atomic structure, NTs behave electrically as metals or as
semiconductors.
12-14
The synthesis of carbon nanotubes is itself
a self-organization process, where carbon atoms self-assemble,
with or without the help of catalysts, to form the tubes.
15-17
An important characteristic of carbon nanotubes is the strong
van der Waals attraction between tubes, and between nanotubes
and the substrate on which they are deposited. These van der
Waals forces have important implications for the geometry and
detailed configuration of the tubes. In the case of SWNTs, the
van der Waals attraction between the NTs leads to a second
level of self-organization; the nanotubes bunch together to form
ropes, in which the NTs are closely packed in a triangular
lattice.
16
Within a rope, the tube-tube interactions are strong
enough to induce radial deformation of the tubes.
18
Similarly,
van der Waals interactions with the substrate have been found
to lead to both axial and radial deformations of adsorbed tubes
and, most importantly, to stabilize highly strained nanotube
* Author to whom correspondence should be addressed. E-mail:
avouris@us.ibm.com.
© Copyright 1999 by the American Chemical Society VOLUME 103, NUMBER 36, SEPTEMBER 9, 1999
10.1021/jp991513z CCC: $18.00 © 1999 American Chemical Society
Published on Web 08/19/1999