Production of carbon nanotubes

• US 8,715,790 B2
• Filed: 07/26/2002
• Issued: 05/06/2014
• Est. Priority Date: 07/27/2001
• Status: Expired due to Fees

• Current Assignee: University of Surrey
• Original Assignee: University of Surrey
• Inventors: Haq, Sajad, Silva, Sembukutiarachilage Ravi, Boskovic, Bojan O.
• Primary Examiner(s): Turocy, David
• Assistant Examiner(s): Miller, Michael G
• Application Number:
  US10/484,894
• Publication Number:
  US 20040253167A1
• Time in Patent Office: 4,302 Days
• Field of Search: None
• US Class Current: 427/577
• 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 32/162 characterised by catalysts

Abstract

A method of forming carbon nanotubes by plasma enhanced chemical vapor deposition using a carbon containing gas plasma, wherein the carbon nanotubes are not formed on a substrate at a temperature 300° C. or above.

Claims

1. A method of forming carbon nanotubes in an apparatus by plasma enhanced chemical vapor deposition, comprising:

(a) providing an earthed electrode and a powered electrode in a chamber of the apparatus, the earthed electrode and the powered electrode being arranged substantially parallel and being spaced apart such that a space is provided between the earthed electrode and the powered electrode;

(b) supporting a substrate on the earthed electrode such that the substrate occupies a part of the space between the earthed electrode and the powered electrode with a surface of the substrate facing said space, and providing a catalyst on said surface of a substrate;

(c) feeding a carbon containing gas via an inlet into the chamber;

(d) striking a plasma from the carbon containing gas in the space between the earthed electrode and the powered electrode by applying energy to the powered electrode, wherein the energy comprises at least one of radio-frequency energy and microwave-frequency energy; and

(e) forming carbon nanotubes from the plasma on the surface of the substrate facing the plasma, wherein the apparatus comprises a temperature control system that includes both heating elements and cooling elements, and wherein the temperature control system maintains the earthed electrode and the powered electrode at a temperature below 300°

C. throughout (a)-(e), thus maintaining the substrate at said temperature.

2. A method according to claim 1, wherein the substrate is not separately heated.

3. A method according to claim 1, wherein the substrate is kept at a temperature of 200°

C. or below.

4. A method according to claim 3, wherein the substrate is kept at a temperature of 150°

C. or below.

5. A method according to claim 4, wherein the substrate is kept at a temperature of 100°

C. or below.

6. A method according to claim 5, wherein the substrate is kept at a temperature of 50°

C. or below.

7. A method according to claim 6, wherein the substrate is kept at substantially room temperature.

8. A method according to claim 1, further comprising cooling the substrate during the forming the carbon nanotubes.

9. A method according to claim 8, wherein the substrate is kept at a temperature below 0°

C.

10. A method according to claim 8, further comprising cooling the substrate with liquid nitrogen.

11. A method according to claim 1, wherein the catalyst is placed directly on the substrate surface.

12. A method according to claim 1, wherein the carbon nanotubes are grown from the catalyst as deposited on the substrate.

13. A method according to claim 1, wherein the substrate is placed on an earthed electrode of a plasma generator, within the sheathed region of the plasma.

14. A method according to claim 13, wherein the potential difference between the substrate/catalyst and the plasma is less than 100 volts.

15. A method according to claim 14, wherein the potential difference between the material/catalyst and the plasma is less than 70 volts.

16. A method according to claim 15, wherein the potential difference between the material/catalyst and the plasma is less than 40 volts.

17. A method according to claim 13, further comprising cooling an electrode.

18. A method according to claim 17, wherein the electrode is cooled by water.

19. A method according to claim 1, wherein the catalyst is a metal.

20. A method according to claim 19, wherein the metal is a transition metal.

21. A method according to claim 20, wherein the transition metal includes a metal, or mixture of metals, from the group comprising nickel (Ni), cobalt (Co) and iron (Fe).

22. A method according to claim 1, wherein the catalyst is in the form of a powder, a film, or island arrays.

23. A method according to claim 22, wherein the island arrays are etched island arrays of which the particle sized is between 2 nm and 100 nm.

24. A method according to claim 1, wherein the substrate comprises a material selected from:

an organic material, a fabric, a plastics material, a polymer, and paper.

25. A method according to claim 1, wherein the plasma is of an ionized gas or gas mixture, or in the form of a beam.

26. A method according to claim 1, wherein the plasma is generated by radio-frequency current and microwave-frequency current.

27. A method according to claim 1, wherein the plasma is generated using a pulsed supply.

28. A method according to claim 1, wherein the plasma is generated by a primary power source and combined with at least one secondary power source.

29. A method according to claim 1, wherein the carbon containing gas is a hydrocarbon gas.

30. A method according to claim 29, wherein the hydrocarbon gas is methane, acetylene, ethylene, or any mixture of the said gases.

31. A method according to claim 1, wherein the carbon containing gas is carbon monoxide or carbon dioxide.

32. A method according to claim 1, wherein the carbon containing gas is non-destructive and non-etching of the substrate or apparatus when in a plasma state.

33. A method according to claim 1, wherein the carbon containing gas is combined with a carrier gas.

34. A method according to claim 33, wherein the carrier gas is from the group comprising nitrogen, hydrogen, argon, and ammonia.

35. A method according to claim 1, further comprising the plasma under vacuum conditions.

36. A method according to claim 1, further comprising inserting the carbon nanotubes into a liquid to self-organise the carbon nanotubes into ropes.

37. A method according to claim 36, wherein the liquid is water.

38. A method according to claim 1, further comprising an acid treatment step for removal of excess catalyst particles.

39. A method according to claim 38, further comprising a wash step to remove the acid.

40. A method according to claim 1, wherein a proportion of formed nanotubes are in at least one of the following forms:

bi-directional, branched, multiple-coaxial, coiled, or densely packed ropes of nanotubes.

41. A method of forming carbon nanotubes in an apparatus by plasma enhanced chemical vapor deposition, comprising:

(a) providing a catalyst on the surface of a substrate, wherein the substrate is supported by an earthed electrode and a surface of the substrate faces a powered electrode;

(b) feeding a carbon containing gas via an inlet into a chamber of the apparatus containing the substrate;

(c) striking a plasma from the carbon containing gas in a space between the earthed electrode and a powered electrode by applying energy to the powered electrode, wherein the energy is selected from the group comprising;

radio-frequency current, microwave-frequency current, and combinations thereof; and

(d) forming carbon nanotubes from the plasma on the surface of the substrate facing the powered electrode, wherein the apparatus comprises a temperature control system that includes both heating elements and cooling elements, and wherein the temperature control system maintains the substrate at a temperature below 300°

C. throughout (a)-(d),

and wherein the method further comprises cooling the substrate during the forming the carbon nanotubes, and wherein the substrate is kept at a temperature below 0°

C.