Controlled patterning and growth of single wall and multi-wall carbon nanotubes

• US 6,858,197 B1
• Filed: 03/13/2002
• Issued: 02/22/2005
• Est. Priority Date: 03/13/2002
• Status: Expired due to Fees

• Current Assignee: The United States of America As Represented By The Secretary of Agriculture, U.S.A. as represented by the Administrator of the National Aeronautics and Space Administration
• Original Assignee: United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
• Inventors: Delzeit, Lance D.
• Primary Examiner(s): Hendrickson, Stuart L.
• Assistant Examiner(s): Lish, Peter J
• Application Number:
  US10/099,247
• Time in Patent Office: 1,077 Days
• Field of Search: 423/447.1, 423/447.3, 423/445.R
• US Class Current: 423/447.3
• 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 2202/06 Multi-walled nanotubes
• CPC Class Codes: C01B 2202/36 Diameter
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: D01F 9/1271 Alkanes or cycloalkanes
• CPC Class Codes: D01F 9/1272 Methane
• CPC Class Codes: D01F 9/1273 Alkenes, alkynes
• CPC Class Codes: D01F 9/1275 Acetylene
• CPC Class Codes: Y10S 977/75 Single-walled
• CPC Class Codes: Y10S 977/843 Gas phase catalytic growth, i.e. chemical vapor deposition

Abstract

Method and system for producing a selected pattern or array of at least one of a single wall nanotube and/or a multi-wall nanotube containing primarily carbon. A substrate is coated with a first layer (optional) of a first selected metal (e.g., Al and/or Ir) and with a second layer of a catalyst (e.g., Fe, Co, Ni and/or Mo), having selected first and second layer thicknesses provided by ion sputtering, arc discharge, laser ablation, evaporation or CVD. The first layer and/or the second layer may be formed in a desired non-uniform pattern, using a mask with suitable aperture(s), to promote growth of carbon nanotubes in a corresponding pattern. A selected heated feed gas (primarily CH₄ or C₂H_n with n=2 and/or 4) is passed over the coated substrate and forms primarily single wall nanotubes or multiple wall nanotubes, depending upon the selected feed gas and its temperature. Nanofibers, as well as single wall and multi-wall nanotubes, are produced using plasma-aided growth from the second (catalyst) layer. An overcoating of a selected metal or alloy can be deposited, over the second layer, to provide a coating for the carbon nanotubes grown in this manner.

Claims

1. A method for producing at least one of a single wall nanotube, a multi-wall nanotube and a nanofiber containing primarily carbon, the method comprising:

providing a substrate of a selected material in a heated chamber, a first layer of a first selected thickness of material that is produced primarily by sputtering a combination of Al and Ir onto the substrate, and a second layer of a second selected thickness of material, drawn from a second group of materials including at least one of Fe, Co and Ni, that is deposited on the first layer that is deposited on the substrate, where at least one of the first layer and the second layer is deposited with a selected non-uniform layer pattern;

providing a hydrocarbon-containing (“

HC-containing”

) gas containing at least one of CH₄, C₂H₄ and C₂H₂, heated to a selected temperature in a mange between 400°

C. and 1000°

C. within the chamber, and passing the HC-containing gas over a selected portion of the coated substrate; and

allowing at least one layer deposited on the substrate to remove H atoms and molecules from the HC-containing gas and to deposit C particles as part of at least one of a single wall nanotube, a multi-wall nanotube and a nanofiber on the coated substrate, in an array defined in part by the selected pattern.

2. The method of claim 1, further comprising producing at least one single wall nanotube having a diameter in a range between 0.5 nm and 5 nm.

3. The method of claim 1, further comprising:

providing, as said HC-containing gas, a gas that is primarily at least one of C₂H₄ and C₂H₂, heated to a selected temperature in a range 650°

C.≦

T≦

900°

C., and

allowing said substrate coating layers to remove said H atoms and molecules and to deposit said C particles to form at least one multi-wall nanotube on said coated substrate, in said array defined in part by said selected pattern.

4. The method of claim 1, further comprising producing at least one multi-wall nanotube having a diameter in a range between 2 nm and 100 nm.

5. The method of claim 1, further comprising:

providing as said HC-containing gas a gas that is primarily at least one of C₂H₄ and C₂H₂, heated by a plasma to a selected temperature in a range 400°

C.≦

T≦

600°

C., and

allowing said substrate coating layers to remove said H atoms and molecules and to deposit said C particles to form at least one nanofiber on said coated substrate, in said array defined in part by said selected pattern.

6. The method of claim 1, further comprising producing at least one nanofiber having a diameter in a range between 15 nm and 200 nm.

7. The method of claim 1, further comprising:

providing, as said HC-containing gas, a gas that is primarily CH₄, heated in a plasma to a selected temperature in a range 800°

C.≦

T≦

1100°

C., and

allowing said substrate coating layers to remove said H atoms and molecules and to deposit said C particles to form at least one single wall nanotube on said coated substrate, in said array defined in part by said selected pattern.

8. The method of claim 7, further comprising producing at least one single wall nanotube having a diameter in a range between 0.5 nm and 5 nm.

9. The method of claim 1, further comprising:

providing as said HC-containing gas a gas that is primarily at least one of C₂H₄ and C₂H₂, heated in a plasma to a selected temperature in a range 650°

≦

T≦

900°

C., and

allowing said substrate coating layers to remove said H atoms and molecules and to deposit said C particles to form at least one multi-wall nanotube on said coated substrate, in said array defined in part by said selected pattern.

10. The method of claim 9, further comprising producing at least one multi-wall nanotube having a diameter in a range between 2 nm and 100 nm.

11. The method of claim 1, further comprising depositing said second layer pattern using a second layer mask having at least one aperture.

12. The method of claim 11, further comprising selecting said second layer pattern from a group of aperture patterns consisting of at least one polygon, at least one alphanumeric character, a spiral, two or more selected sectors of an oval, an irregular boundary having at least one linear segment, and an irregular boundary having at least one curvilinear segment.

13. The method of claim 1, further comprising providing said second substrate coating with said second thickness in a range between 0.1 nm and 20 nm.

14. The method of claim 1, further comprising providing said second substrate coating primarily by sputtering of a target containing at least one of Fe, Co and Ni.

15. The method of claim 1, further comprising providing said second substrate coating primarily by sputtering of a target containing at least two of Fe, Co and Ni.

16. The method of claim 1 further comprising depositing said first layer pattern using a first layer mask having at least one aperture.

17. The method of claim 16, further comprising selecting said first layer pattern from a group of aperture patterns consisting of at least one polygon, at least one alphanumeric character, a spiral, one or more selected sectors of an oval, an irregular boundary having at least one linear segment, and an irregular boundary having at least one curvilinear segment.

18. The method of claim 1, further comprising providing said first substrate coating with said first thickness in a range between 0.1 nm and 20 nm.

19. The method of claim 1, further comprising providing said first substrate coating primarily by at least one of ion beam sputtering, arc discharge, laser ablation, chemical vapor deposition and evaporation of a target containing at least one of Al and Ir.

20. The method of claim 1, further comprising including in an exposed layer a selected amount of Mo.

21. The method of claim 1, further comprising selecting said substrate material from a group of substrate materials consisting of highly oriented pyrolytic graphite (HOPG), amorphous carbon, fused quartz, glass, zeolite and mica.