Methods of making spatially aligned nanotubes and nanotube arrays

• US 8,367,035 B2
• Filed: 08/28/2012
• Issued: 02/05/2013
• Est. Priority Date: 03/03/2006
• Status: Active Grant

• Current Assignee: Board of Trustees of The University of Illinois
• Original Assignee: Board of Trustees of The University of Illinois
• Inventors: Rogers, John A., Kocabas, Coskun, Shim, Moonsub, Kang, Seong Jun, Park, Jang-Ung
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): MARTINEZ, BRITTANY M
• Application Number:
  US13/596,343
• Publication Number:
  US 20120321785A1
• Time in Patent Office: 161 Days
• Field of Search: 423/445.R, 423/447.1, 423/447.2, 423/447.3, 423/447.5, 423/460, 423/461, 977/842, 977/843, 977/890, 977/891, 977/892, 977/845, 977/888, 977/932
• 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 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 2202/08 Aligned nanotubes
• CPC Class Codes: C01B 2202/34 Length
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: H10K 10/464 Lateral top-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 10/466 Lateral bottom-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 71/191 characterised by provisions for the orientation or alignment of the layer to be deposited
• CPC Class Codes: H10K 85/221 Carbon nanotubes

Abstract

The present invention provides arrays of longitudinally aligned carbon nanotubes having specified positions, nanotube densities and orientations, and corresponding methods of making nanotube arrays using guided growth and guided deposition methods. Also provided are electronic devices and device arrays comprising one or more arrays of longitudinally aligned carbon nanotubes including multilayer nanotube array structures and devices.

Claims

1. A method for making an array of longitudinally aligned carbon nanotubes;

said method comprising the steps of;

providing a guided growth substrate having a receiving surface, wherein said guided growth substrate is a single crystalline Y-cut or rotated Y-cut quartz substrate having a cut angle selected from the range of 0 degrees to 42.75 degrees;

wherein said guided growth substrate is characterized by a principle guided growth axis in the plane of said receiving surface;

patterning said receiving surface with a carbon nanotube growth catalyst to generate bands of catalyst separated from each other by regions of said receiving surface having substantially no catalyst present, wherein said bands of catalyst are oriented to intersect the principle guided growth axis and have a surface concentration of catalyst selected from the range of 1000 particles μ

m<sup>−

2</sup> to 10 particles μ

m<sup>−

2</sup>; and

wherein said regions of said receiving surface having substantially no catalyst present have a surface concentration of catalyst less than or equal to 1 particle μ

m<sup>−

2</sup>; and

growing longitudinally aligned carbon nanotubes on said receiving surface of said guided growth substrate via guided growth, wherein said nanotubes grow between the bands of catalyst along nanotube growth axes parallel to the principle guided growth axis of said guided growth substrate, thereby making said array of longitudinally aligned carbon nanotubes.

2. The method of claim 1 wherein said guided growth substrate is said Y-cut quartz substrate.

3. The method of claim 1 wherein said rotated Y-cut quartz substrate is an AT-cut quartz substrate.

4. The method of claim 1 wherein said rotated Y-cut quartz substrate is a ST-cut quartz substrate.

5. The method of claim 1 wherein said cut angle of said rotated Y-cut quartz substrate is tilted toward a Z-cut quartz plane.

6. The method of claim 1 wherein said guided growth substrate provides for energetically favorable van der Waals interactions for growth and alignment between growing longitudinally aligned carbon nanotubes and the guided growth substrate.

7. The method of claim 1 wherein said bands of catalyst are parallel bands of catalyst.

8. The method of claim 1 wherein said bands of catalyst are longitudinally oriented along longitudinal catalyst alignment axes oriented perpendicular to the principle guided growth axis of the guided growth substrate.

9. The method of claim 1 wherein said bands of catalyst have lengths and widths each selected from the range of 100 nanometers to 100 microns.

10. The method of claim 1 wherein said bands of catalyst comprise first and second bands of catalyst, and said first and second bands of catalyst are separated along an axis parallel to the principle guided growth axis by a distance selected from the range of 100 nanometers to 500 microns.

11. The method of claim 1 wherein said bands of catalyst comprise ferritin, nickel, molybdenum, palladium, yttrium, iron, copper, molybdenum, or cobalt.

12. The method of claim 1 wherein said step of growing longitudinally aligned carbon nanotubes on said receiving surface of said guided growth substrate is carried out by exposure of said carbon nanotube growth catalyst patterned on said receiving surface to a precursor gas.

13. The method of claim 1 wherein said step of growing longitudinally aligned carbon nanotubes on said receiving surface of said guided substrate is carried out by chemical vapor deposition.

14. The method of claim 1 wherein said step of growing longitudinally aligned carbon nanotubes on said receiving surface of said guided growth substrate generates single walled carbon nanotubes.

15. The method of claim 1 wherein the array has a density of the longitudinally aligned carbon nanotubes between said bands of catalyst greater than or equal to 1 nanotube μ

m<sup>−

1</sup>.

16. The method of claim 1 wherein the array has a density of the longitudinally aligned carbon nanotubes between said bands of catalyst greater than or equal to 5 nanotubes μ

m<sup>−

1</sup>.

17. The method of claim 1 wherein at least 95% of said longitudinally aligned carbon nanotubes of said array are parallel to each other within 10 degrees.

18. The method of claim 1 wherein at least 95% of said longitudinally aligned carbon nanotubes of said array have deviations from perfect linearity along their entire lengths that are less than or equal to 50 nanometers per micron of length.

19. The method of claim 1 wherein the array of longitudinally aligned carbon nanotubes has an area selected from the range of 100 nm² to 10 cm².

20. The method of claim 7 wherein said step of patterning said receiving surface with the carbon nanotube growth catalyst comprises the steps of:

depositing said catalyst onto selected deposition areas of said receiving surface corresponding to said parallel bands of catalyst, and

preventing catalyst accumulation on areas of said receiving surface between said parallel bands of catalyst.

21. The method of claim 7 wherein said step of patterning said receiving surface with the carbon nanotube growth catalyst comprises the steps of:

providing a catalyst layer of said nanotube growth catalyst to said receiving surface; and

removing said catalyst from selected areas of said catalyst layer corresponding to the regions of said receiving surface having substantially no catalyst present, thereby generating the parallel bands of catalyst.

22. The method of claim 1 further comprising annealing the guided growth substrate to a temperature equal to or greater than 900 degrees Celsius for an annealing time equal to or greater than 8 hours prior to said step of growing said longitudinally aligned carbon nanotubes on said receiving surface of said guided growth substrate.

23. The method of claim 1 further comprising the step of transferring said array of longitudinally aligned carbon nanotubes from said receiving surface of said guided growth substrate to a surface of a different substrate.

24. The method of claim 23 wherein said step of transferring said array of longitudinally aligned carbon nanotubes from said receiving surface of said guided growth substrate to said surface of said different substrate is achieved by contact printing, microcontact printing, transfer printing, dry transfer printing or solution printing said array of longitudinally aligned carbon nanotubes.

25. The method of claim 23 wherein said different substrate is a flexible substrate.

26. The method of claim 23 wherein said different substrate is a polymer substrate, a dielectric substrate, a metal substrate, a ceramic substrate, a glass substrate or a semiconductor substrate.

27. The method of claim 23 wherein said different substrate is prepatterned with device components.

28. The method of claim 27 wherein said device components of said different substrate are one or more electrodes, metal layers, dielectric layers, semiconductor layers, diodes, insulators, or nanotube layers.

29. The method of claim 1 further comprising applying a laminating or coating layer to the array of longitudinally aligned carbon nanotubes.

30. The method of claim 1 further comprising providing one or more electrodes in contact with at least a portion of the longitudinally aligned carbon nanotubes in the array.

31. The method of claim 1 further comprising the step of oxidizing said carbon nanotube growth catalyst, reducing said carbon nanotube growth catalyst or both oxidizing and reducing said carbon nanotube growth catalyst prior to said step of growing longitudinally aligned carbon nanotubes on said receiving surface of said guided growth substrate.