Method for growing single-wall carbon nanotubes utilizing seed molecules

• US 6,756,025 B2
• Filed: 12/21/2001
• Issued: 06/29/2004
• Est. Priority Date: 08/08/1996
• Status: Active Grant

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Rinzler, Andrew G., Colbert, Daniel T., Hafner, Jason H., Dai, Hongjie
• Primary Examiner(s): BERMAN, JACK I
• Application Number:
  US10/027,568
• Publication Number:
  US 20020092983A1
• Time in Patent Office: 921 Days
• Field of Search: 423/447.3, 423/445.B
• US Class Current: 423/447.3
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 35/00 Methods or apparatus for measurement or analysis of nanostructures
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/06 Multi-walled nanotubes
• CPC Class Codes: C01B 2202/08 Aligned nanotubes
• CPC Class Codes: C01B 2202/24 Thermal properties
• CPC Class Codes: C01B 2202/34 Length
• CPC Class Codes: C01B 32/154 Preparation
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• CPC Class Codes: G01Q 70/12 Nanotube tips
• CPC Class Codes: G01Q 70/16 Probe manufacture
• CPC Class Codes: G11B 11/007 with reproducing by means directly associated with the tip of a microscopic electrical probe as defined in G11B9/14 details of heads G11B9/1409; disposition or mounting of heads G11B9/1418
• CPC Class Codes: G11B 9/1409 Heads
• CPC Class Codes: G11C 13/025 using fullerenes, e.g. C60, or nanotubes, e.g. carbon or silicon nanotubes
• CPC Class Codes: G11C 2213/81 Array wherein the array conductors, e.g. word lines, bit lines, are made of nanowires
• CPC Class Codes: H01J 2201/30469 Carbon nanotubes (CNTs)
• CPC Class Codes: Y10S 977/70 : Nanostructure
• CPC Class Codes: Y10S 977/75 : Single-walled
• CPC Class Codes: Y10S 977/789 : in array format
• CPC Class Codes: Y10S 977/843 : Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/845 : Purification or separation of fullerenes or nanotubes
• CPC Class Codes: Y10T 428/249977 : Specified thickness of void-containing component [absolute or relative], numerical cell dimension or density
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]

Abstract

This invention relates generally to a method for growing single-wall carbon nanotube (SWNT) from seed molecules. The supported or unsupported SWNT seed materials can be combined with a suitable growth catalyst by opening SWNT molecule ends and depositing a metal atom cluster. In one embodiment, a suspension of seed particles containing attached catalysts is injected into an evaporation zone to provide an entrained reactive nanoparticle. A carbonaceous feedstock gas is then introduced into the nanoparticle stream under conditions to grow single-wall carbon nanotubes. Recovery of the product produced can be done by filtration, centrifugation and the like.

Claims

1. A method for growing single-wall carbon nanotubes comprising:

a) providing seed molecules comprising segments of single-wall carbon nanotubes;

b) contacting the ends of the single-wall carbon nanotubes of the segments with at least one catalytic metal;

c) activating the catalytic metal;

d) adding a gaseous source of carbon to the single-wall carbon nanotubes and the catalytic metal;

e) subjecting the single-wall carbon nanotubes, the catalytic metal and the gaseous source of carbon to conditions to grow to the single-wall carbon nanotubes;

f) growing the segments of the single-wall carbon nanotubes; and

g) recovering the grown single-wall carbon nanotubes.

2. The method of claim 1 further comprising removing fullerene caps from the ends of at least some of the single-wall carbon nanotubes.

3. The method of claim 1 wherein the growing step grows the length of the segments by a factor of at least 100.

4. The method of claim 1 wherein the seed molecules are provided by cutting a previously-grown single-wall carbon nanotube fiber.

5. The method of claim 1 wherein the seed molecules are provided by cutting a mat comprising single-wall carbon nanotubes.

6. The method of claim 1 further comprising cutting the grown single-wall carbon nanotubes to form new seed molecules.

7. The method of claim 1 wherein the seed molecules are formed on supports.

8. The method of claim 1 wherein the seed molecules are part of a 3-dimensional structure.

9. The method of claim 1 wherein the see molecules are in the form of a powder.

10. The method of claim 1 wherein the contacting step comprises:

a) suspending or dissolving a catalyst precursor of the catalytic metal in a liquid;

b) suspending the seed molecules in the liquid; and

c) evaporating the liquid.

11. The method of claim 10 wherein the liquid comprises water.

12. The method of claim 10 wherein the catalyst precursor comprises a chemical selected from the group consisting of Fe(NO₃)₃, Ni(NO₃)₂, Co(NO₃)₂ and combinations thereof.

13. The method of claim 1 wherein the segments are derivatized with a moiety that binds to a catalytic metal.

14. The method of claim 1 wherein the segments are derivatized with a moiety that binds to a catalyst precursor comprises the catalytic metal.

15. The method of claim 14 wherein the catalyst precursor comprises a ligand-stabilized catalyst nanoparticle.

16. The method of claim 1 wherein the contacting step comprises heating the seed molecules and the catalytic metal in a gas stream to a temperature in a range between 250°

C. and 500°

C. to form an entrained particle stream.

17. The method of claim 16 wherein the entrained particle stream is subjected to reduction conditions at a temperature in a range between 300°

C. and 500°

C.

18. The method of claim 16 further comprising introducing of the entrained particle stream to a growth chamber.

19. The method of claim 1 wherein the gaseous source of carbon comprises a gas selected from the group consisting of carbon monoxide, hydrocarbon gases and combinations thereof.

20. The method of claim 1 wherein the growing step is at a temperature in the range between 500°

C. and 1000°

C.

21. The method of claim 1 wherein the growing step is at a total pressure of about one atmosphere.

22. The method of claim 21 wherein the partial pressure of the gaseous source of carbon is in a range between 1 and 100 Torr.

23. The method of claim 20 wherein a sweep gas is introduced into the growth chamber.

24. The method of claim 20 wherein the growth chamber temperature is maintained by a heating method selected from the group consisting of preheating the gaseous source of carbon, preheating a sweep gas, externally heating the growth chamber, applying localized heating in the growth chamber and combinations thereof.

25. The method of claim 24 wherein the heating is applied by a heat source selected from the group consisting of a laser, an induction coil and combinations thereof.

26. The method of claim 1 wherein the recovery step comprises a recovery method selected from the group consisting of filtration, centrifugation and combinations thereof.