Method for cutting single-wall carbon nanotubes through fluorination

• US 7,029,646 B2
• Filed: 04/08/2003
• Issued: 04/18/2006
• Est. Priority Date: 04/08/2002
• Status: Expired due to Fees

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Margrave, John L., Gu, Zhenning, Hauge, Robert H.
• Primary Examiner(s): Hendrickson, Stuart L.
• Assistant Examiner(s): Stadler, Rebecca M.
• Application Number:
  US10/408,886
• Publication Number:
  US 20040009114A1
• Time in Patent Office: 1,106 Days
• Field of Search: 423/447.1, 423/447.6, 423/447.7, 977/DIG.1
• US Class Current: 423/447.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• CPC Class Codes: C01B 32/176 Cutting

Abstract

A method for cutting single-wall carbon nanotubes involves partially fluorinating single-wall carbon nanotubes and pyrolyzing the partially fluorinated nanotubes in an inert atmosphere or vacuum up to about 1000° C. The nanotubes are optionally purified before cutting. The partial fluorination involves fluorinating the nanotubes to a carbon-fluorine stoichiometry of CF_x, where x is up to about 0.3. The invention also relates to the derivatization of fluorinated and cut single-wall carbon nanotubes. The single-wall carbon nanotubes can be cut to any length depending on the fluorination and pyrolysis conditions. Short nanotubes are useful in various applications, such as field emitters for flat panel displays and as “seeds” for further nanotube growth.

Claims

1. A method of cutting single-wall carbon nanotubes comprising:

(a) reacting a fluorinating agent with single-wall carbon nanotubes to form partially-fluorinated single-wall carbon nanotubes; and

(b) pyrolyzing the partially-fluorinated single-wall carbon nanotubes to yield cut single-wall carbon nanotubes.

2. The method of claim 1 wherein the fluorinating agent is selected from the group consisting of F₂, ClF₃, BrF₃, IF₅, HF, XeF₂, XeF₄, XeF₆, and combinations thereof.

3. The method of claim 1 further comprising purifying the single-wall carbon nanotubes.

4. The method of claim 1, wherein the fluorinating agent is F₂.

5. The method of claim 1, wherein the fluorinating agent is HF.

6. The method of claim 1, wherein hydrogen is combined with the fluorinating agent.

7. The method of claim 1, wherein the fluorinating agent is diluted with a gas selected from the group consisting of nitrogen, inert gas, argon and combinations thereof.

8. The method of claim 1, wherein the fluorinating agent is present at a concentration in the range of about 0.001 vol % and 100 vol %.

9. The method of claim 1, wherein the fluorinating agent is present at a concentration in the range of about 0.02 vol % and about 10 vol %.

10. The method of claim 1, wherein the fluorinating is done at a temperature in a range of about −

80°

C. and about 400°

C.

11. The method of claim 1, wherein the fluorinating is done at temperature in a range of about 50°

C. and about 250°

C.

12. The method of claim 1, wherein the fluorinating is done at a temperature in the range of about 50°

C. and about 150°

C.

13. The method of claim 1, wherein the partially-fluorinated single-wall carbon nanotubes have a CF_x stoichiometry, wherein x is in the range of about 0.01 and about 0.3.

14. The method of claim 1, wherein the partially-fluorinated single-wall carbon nanotubes have a CF_x stoichiometry, wherein x is in the range of about 0.1 and about 0.2.

15. The method of claim 1 further comprising removing a portion of the fluorine from the partially-fluorinated single-wall carbon nanotubes.

16. The method of claim 1 further comprising heating the partially-fluorinated single-wall carbon nanotubes in an inert atmosphere.

17. The method of claim 16, wherein the heating is done at a temperature in the range of about 30°

C. and about 200°

C.

18. The method of claim 16 wherein the heating is done for a time in the range of about 1 and about 24 hours.

19. The method of claim 16 wherein the heating is performed before the pyrolyzing.

20. The method of claim 1, wherein the pyrolyzing is conducted in a gaseous atmosphere selected from the group consisting of nitrogen, inert gas, argon and combinations thereof.

21. The method of claim 1, wherein the pyrolyzing is conducted in a vacuum environment.

22. The method of claim 1, wherein the pyrolyzing is done in a temperature range of about 50°

C. and about 1500°

C.

23. The method of claim 1, wherein the pyrolyzing is done in a temperature range of about 50°

C. and about 1000°

C.

24. The method of claim 1, wherein the cut single-wall carbon nanotubes comprise less than about 0.2 atom % fluorine.

25. The method of claim 1 further comprising derivatizing the cut single-wall carbon nanotubes with a functional group.

26. The method of claim 25, wherein the functional group is provided by a compound selected from the group consisting of amines, alkyllithiums, Grignard reagents, alcohols, peroxides and combinations thereof.

27. The method of claim 1 further comprising fluorinating the cut single-wall carbon nanotubes to generate fluorinated cut single-wall carbon nanotubes.

28. The method of claim 27 further comprising derivatizing the fluorinated cut single-wall carbon nanotubes with a functional group.

29. The method of claim 28, wherein the functional group is provided by a compound selected from the group consisting of amines, alkyllithiums, Grignard reagents, aluminum alkyls, boranes and combinations thereof.

30. The method of claim 1, wherein the fluorinating agent has a partial pressure in a range of about 1 mTorr and about 1000 Torr.