5,560,898 A 10, 1996 Uchida et al. (75) Inventors: Richard E. Smalley, deceased, late of 5.641,466 A 6/1997 Ebbesen et al. Houston TX (US); Daniel T. Colbert, 5,697,827. A 12/1997 Rabinowitz N. TS's p 1 5,698,175. A 12/1997 Hiura et al. unnyvale, CA (US); Jie Liu Chape 5,730.940 A 3/1998 Nakagawa Hill, NC (US); Andrew G. Rinzler, 5,824,470 A 10, 1998 Baldeschwieler et al. Newberry, FL (US); Jason H. Hafner, 5,879.836 A 3, 1999 Ikeda et all Houston, TX (US); Ken Smith, Katy, w f e d a. al TX (US); Ting Guo, Davis, CA (US); 5,935,339 A 8, 1999 Hen erSOn et al. Pavel Nikolaev, Houston, TX (US); 5,985, 112 A 11/1999 Fischer Andreas Thess, Kusterdingen (DE) 6,183,714 B1 2/2001 Smalley et al. 6,331,262 B1 12/2001 Haddon et al. (73) Assignee: William Marsh Rice University, 6,448,412 B1 9/2002 Murphy et al. Houston, TX (US) 6,645.455 B2 11/2003 Margrave et al. 6,683,783 B1 1/2004 Smalley et al. (*) Notice: Subject to any disclaimer, the term of this 6,790,425 B1 9/2004 Smalley et al. patent is extended or adjusted under 35 6,824,755 B2 11/2004 Colbert et al. U.S.C. 154(b) by 0 days. 7,041,620 B2 5/2006 Smalley et al. 7.205,069 B2 * 4/2007 Smalley et al. .............. 429/129 This patent is Subject to a terminal dis claimer.
Carbon nanotubes produced in arcs have been found to have the form of multiwalled fullerenes, at least over short lengths. Sintering of the tubes to each other is the predominant source of defects that limit the utility of these otherwise perfect fullerene structures. The use of a water-cooled copper cathode minimized such defects, permitting nanotubes longer than 40 micrometers to be attached to macroscopic electrodes and extracted from the bulk deposit. A detailed mechanism that features the high electric field at (and field-emission from) open nanotube tips exposed to the arc plasma, and consequent positive feedback effects from the neutral gas and plasma, is proposed for tube growth in such arcs.
In this design, single-wall carbon nanotubes (SWNTs) have been coated in polymer molecules to create a new type of material that has low electrical conductivity, but still contains individual nanotubes, and small ropes of individual nanotubes, which are themselves good electrical conductors and serve as small conducting rods immersed in an electrically insulating matrix. The polymer is attached through weak chemical forces that are primarily non-covalent in nature, caused primarily through polarization rather than the sharing of valence electrons. Therefore, the electronic structure of the SWNT involved is substantially the same as that of free, individual (and small ropes of) SWNT. Their high conductivity makes the individual nanotubes extremely electrically polarizable, and materials containing these individual, highly polarizable molecules exhibit novel electrical properties including a high dielectric constant.
A method of aligning and assembling single-wall carbon nanotubes (SWNTs) to fabricate macroscopic structures has been invented. The method entails suspending SWNTs in a fluid, orienting the SWNTs by use of a magnetic and/or electric field, and then removing the aligned SWNTs from suspension in such a way as to assemble them while maintaining the alignment. SWNTs are essentially tubular extensions of fullerene molecules. It is desirable to assemble aligned SWNTs into macroscopic structures because the common alignment of the SWNTs in such a structure makes it possible to exploit, on a macroscopic scale, the unique mechanical, chemical, and electrical properties that individual oriented SWNTs exhibit at the molecular level. Because of their small size and high electrical conductivity, carbon nanotubes, and especially SWNTs, are useful for making electrical connectors in integrated circuits. Carbon nanotubes can be used as antennas at optical frequencies, and as probes in scanning tunneling microscopes, atomic-force microscopes, and the like. Carbon nanotubes can be used with or instead of carbon black in tires. Carbon nanotubes are useful as supports for catalysts. Ropes of SWNTs are metallic and, as such, are potentially useful in some applications in which electrical conductors are needed - for example, they could be used as additives in formulating electrically conductive paints. Finally, macroscopic assemblies of aligned SWNTs can serve as templates for the growth of more and larger structures of the same type. The great variety of tubular fullerene molecules and of the structures that could be formed by assembling them in various ways precludes a complete description of the present method within the limits of this article. It must suffice to present a typical example of the use of one of many possible variants of the method to form a membrane comprising SWNTs aligned substantially parallel to each other in the membrane plane. The apparatus used in this variant of the method (see figure) includes a reservoir containing SWNTs dispersed in a suspending agent (for example, dimethylformamide) and a reservoir containing a suitable solvent (for example, water mixed with a surfactant). By use of either pressurized gas supplied from upstream or suction from downstream, the suspension of SWNTs and the solvent are forced to mix and flow into a tank. A filter inside the tank contains pores small enough to prevent the passage of most SWNTs, but large enough to allow the passage of molecules of the solvent and suspending agent. The filter is oriented perpendicular to the flow path. A magnetic field parallel to the plane of the filter is applied. The success of the method is based on the tendency of SWNTs to become aligned with their longitudinal axes parallel to an applied magnetic field. The alignment energy of an SWNT increases with the length of the SWNT and the magnetic-field strength. In order to obtain an acceptably small degree of statistical deviation of SWNTs of a given length from alignment with a magnetic field, one must make the field strong enough so that the thermal energy associated with rotation of an SWNT away from alignment is less than the alignment energy.