Nanotube solution treated with molecular additive, nanotube film having enhanced adhesion property, and methods for forming the nanotube solution and the nanotube film

• US 9,634,251 B2
• Filed: 03/09/2012
• Issued: 04/25/2017
• Est. Priority Date: 02/27/2012
• Status: Active Grant

• Current Assignee: ZEON Corporation
• Original Assignee: Nantero Incorporated
• Inventors: Roberts, David A., Sen, Rahul, Sites, Peter, Kocab, J. Thomas, Smith, Billy, Gu, Feng
• Primary Examiner(s): Nguyen, Tri V
• Application Number:
  US13/416,820
• Publication Number:
  US 20130224934A1
• Time in Patent Office: 1,873 Days
• Field of Search: 252500-5181, 2525213, 977742, 977811, 977815
• 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 2202/22 Electronic properties
• CPC Class Codes: C01B 32/17 Purification
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• CPC Class Codes: C09D 1/00 Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01L 21/02532 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/02606 Nanotubes carbon nanotubes H10K85/211
• CPC Class Codes: H01L 21/02628 using solutions
• CPC Class Codes: H10K 71/12 using liquid deposition, e.g. spin coating
• CPC Class Codes: H10K 85/221 Carbon nanotubes
• CPC Class Codes: Y10S 977/75 Single-walled
• CPC Class Codes: Y10S 977/845 Purification or separation of fullerenes or nanotubes
• CPC Class Codes: Y10S 977/932 for electronic or optoelectronic application

Abstract

The present disclosure provides a nanotube solution being treated with a molecular additive, a nanotube film having enhanced adhesion property due to the treatment of the molecular additive, and methods for forming the nanotube solution and the nanotube film. The nanotube solution includes a liquid medium, nanotubes in the liquid medium, and a molecular additive in the liquid medium, wherein the molecular additive includes molecules that provide source elements for forming a group IV oxide within the nanotube solution. The molecular additive can introduce silicon (Si) and/or germanium (Ge) in the liquid medium, such that nominal silicon and/or germanium concentrations of the nanotube solution ranges from about 5 ppm to about 60 ppm.

Claims

1. A nanotube solution for forming highly adhesive, low defect nanotube fabrics, comprising:

a liquid medium;

a purified dispersion of nanotubes in said liquid medium; and

a selected concentration of molecular additive in the liquid medium, said molecular additive containing one or more group IV elements;

a dispersion of molecular silica in said liquid medium;

wherein said selected concentration of molecular additive is capable of promoting the formation of molecular silica within said nanotube solution while inhibiting the formation of colloidal silica particles;

wherein said molecular silica is capable of providing an enhanced adhesion property within a nanotube fabric formed from said nanotube solution; and

wherein said nanotube solution is substantially free of impurities, wherein the impurities consist of polymers and surfactants.

2. The nanotube solution of claim 1, wherein said molecular additive comprises a soluble form of an oxygen containing compound of said one or more group IV elements.

3. The nanotube solution of claim 1, wherein said molecular additive comprises a soluble form of a silicon oxide compound.

4. The nanotube solution of claim 1, wherein said molecular additive comprises a water soluble silsesquioxane cage molecule.

5. The nanotube solution of claim 1, wherein said dispersion of molecular silica is less than 60 ppm.

6. The nanotube solution of claim 1, wherein said liquid medium is an aqueous solvent, or alternatively a non-aqueous solvent, or alternatively their mixtures.

7. The nanotube solution of claim 1, wherein said nanotubes are carbon nanotubes, and said carbon nanotubes are one of single-wall carbon nanotubes, multi-wall carbon nanotubes having two or more concentric tubes, and any mixtures thereof.

8. The method of claim 7, wherein said carbon nanotubes are functionalized carbon nanotubes.

9. A method for forming a nanotube film having an enhanced adhesion property, comprising:

depositing a nanotube layer on a substrate, using the nanotube solution of claim 1.

10. The method of claim 9, further comprising baking the substrate in air at a temperature ranging from about 100°

C. to about 300°

C.

11. The nanotube solution of claim 1 wherein said molecular additive comprises one of SiO₂, SiCl₄, and H₂SiCl₂.

12. The nanotube solution of claim 1 wherein said molecular additive comprises Si(O-Et)₄.

13. The nanotube solution of claim 1 wherein said nanotube solution has a concentration of trace metals of less than 1.5 parts per billion (ppb).

14. A nanotube solution for forming highly adhesive, low defect nanotube fabrics, comprising:

a purified dispersion of nanotubes in a liquid medium; and

a selected concentration of a molecular additive in said liquid medium, wherein said molecular additive includes molecules that provide source elements for forming a group IV oxide within said nanotube solution;

a dispersion of a molecular scale group IV oxide particles in said liquid medium;

wherein said selected concentration of molecular additive is capable of promoting the formation of molecular scale group IV oxide particles within said nanotube solution while inhibiting the formation of colloidal scale particles;

wherein said molecular scale group IV oxide particles are capable of providing an enhanced adhesion property within a nanotube fabric formed from said nanotube solution;

wherein said nanotube solution is substantially free of impurities, wherein the impurities consist of polymers and surfactants.

15. The nanotube solution of claim 14, wherein said group IV oxide includes one of silicon oxide, germanium oxide, and a combination thereof.

16. The nanotube solution of claim 14, wherein said molecular additive introduces a group IV element in said liquid medium, the group IV element being one selected from the group consisting of Si, Ge, Sn, and Pb.

17. The nanotube solution of claim 14, wherein said desired group IV oxide concentration is predetermined such that molecular scale nanoparticulates of less than 3 nm are prevented from coalescing and that no larger aggregate particulates are visible in a nanotube film formed from the nanotube solution, using scanning electron or optical microscopes.

18. The nanotube solution of claim 14, wherein said molecular additive comprises a germanium containing molecule for forming germanium oxides within the nanotube solution.

19. The nanotube solution of claim 18, wherein the molecular additive introduces germanium in the liquid medium.

20. The nanotube solution of claim 18, wherein the germanium containing molecule comprises one or more of GeO₂ hydrate, GeCl₄, germanium tetrachloride, germylsesquioxane, and germanium tetra-ethoxide.

21. The nanotube solution of claim 14, wherein the molecular additives comprise a mixture of a silicon source and a germanium source in a predetermined proportion.

22. The nanotube solution of claim 14 wherein said nanotube solution has a concentration of trace metals of less than 1.5 parts per billion (ppb).