Large area deposition of graphene via hetero-epitaxial growth, and products including the same

• US 10,167,572 B2
• Filed: 08/07/2009
• Issued: 01/01/2019
• Est. Priority Date: 08/07/2009
• Status: Expired due to Fees

• Current Assignee: Guardian Glass LLC (KOCH Industries Incorporated)
• Original Assignee: Guardian Glass LLC (KOCH Industries Incorporated)
• Inventors: Veerasamy, Vijayen S.
• Primary Examiner(s): McCracken, Daniel
• Application Number:
  US12/461,346
• Publication Number:
  US 20110033688A1
• Time in Patent Office: 3,434 Days
• Field of Search: 4272496, 4272491, 423448
• 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 32/186 by chemical vapour deposition [CVD]
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/105 by irradiation or electric discharge
• CPC Class Codes: C30B 25/18 characterised by the substrate
• CPC Class Codes: C30B 29/02 Elements

Abstract

Certain example embodiments of this invention relate to the use of graphene as a transparent conductive coating (TCC). In certain example embodiments, graphene thin films grown on large areas hetero-epitaxially, e.g., on a catalyst thin film, from a hydrocarbon gas (such as, for example, C₂H₂, CH₄, or the like). The graphene thin films of certain example embodiments may be doped or undoped. In certain example embodiments, graphene thin films, once formed, may be lifted off of their carrier substrates and transferred to receiving substrates, e.g., for inclusion in an intermediate or final product. Graphene grown, lifted, and transferred in this way may exhibit low sheet resistances (e.g., less than 150 ohms/square and lower when doped) and high transmission values (e.g., at least in the visible and infrared spectra).

Claims

1. A method of making a graphene thin film, the method comprising:

providing a back support substrate;

disposing a catalyst thin film, directly or indirectly, on the back support substrate;

introducing a hydrocarbon inclusive gas proximate to the catalyst thin film;

heating the back support substrate to cause the hydrocarbon inclusive gas to at least partially separate the carbon in the hydrocarbon inclusive gas and promote graphene growth in and/or on the catalyst thin film; and

actively cooling the back support substrate to promote crystallization of graphene, directly or indirectly, on an outermost surface of the catalyst thin film, in making the graphene thin film, said active cooling being performed in connection with an inert gas and in accordance with a cooling temperature profile that, as a whole, is non-constant, non-uniform, and non-linear in speed, and cools the back substrate from 900 degrees C. to 700 degrees C.

2. The method of claim 1, wherein the catalyst thin film has a substantially single-orientation large-grain crystal structure, the crystals in the catalyst thin film having a length along a major axis on the order of 10s of microns.

3. The method of claim 1, wherein the catalyst thin film comprises metal.

4. The method of claim 3, wherein the catalyst thin film comprises at least one of:

nickel, cobalt, iron, permalloy, a nickel-chromium alloy, copper, and combinations thereof.

5. The method of claim 4, wherein the catalyst thin film comprises a nickel-chromium alloy, and wherein the amount of chromium is 3-15% of the nickel-chromium alloy.

6. The method of claim 1, wherein the hydrocarbon inclusive gas includes C₂H₂ gas.

7. The method of claim 1, wherein the hydrocarbon inclusive gas includes CH₄ and Ar gasses.

8. The method of claim 1, wherein the hydrocarbon inclusive gas is introduced at a pressure of 5-150 mTorr.

9. The method of claim 1, wherein the back support substrate is heated to a temperature of 800-900 degrees C. during the heating.

10. The method of claim 1, wherein the cooling is performed using an inert gas.

11. The method of claim 10, wherein the cooling reduces the temperature of the back support substrate to 700 degrees or lower.

12. The method of claim 1, further comprising:

enhancing graphene visibility on the outmost surface of the catalyst thin film via phase contrast; and

determining when to stop the cooling based on the enhanced graphene visibility.

13. The method of claim 12, wherein the enhancing of the graphene visibility includes, after formation of the graphene, disposing a polymer-based material on the catalyst thin film over the graphene.

14. The method of claim 1, further comprising exposing at least a portion of the graphene thin film to hydrogen atom etchants in order to etch down at least the exposed portion of the graphene thin film.

15. The method of claim 1, wherein the graphene thin film is an n-level HEG graphene thin film, with n=2-3.

20. The method of claim 1, wherein the cooling comprises a quenching process.

16. A method of hetero-epitaxially growing a graphene thin film in making a graphene thin film, the method comprising:

providing a back support;

disposing a metal catalyst thin film, directly or indirectly, on the back support substrate;

introducing a hydrocarbon inclusive gas proximate to the metal catalyst thin film at a pressure of 5-150 mTorr;

heating the back support substrate to a temperature greater than about 700 degrees C. to cause the hydrocarbon inclusive gas to at least partially separate the carbon in the hydrocarbon inclusive gas;

growing graphite on the metal catalyst thin film;

exposing the metal catalyst thin film to hydrogen atom etchants from a non-liquid source to form graphane; and

further exposing the graphane to further hydrogen atom etchants from the non-liquid source to form graphene, in making the graphene thin film.

17. The method of claim 16, wherein the catalyst thin film comprises at least one of:

nickel, cobalt, iron, permalloy, a nickel-chromium alloy, copper, and combinations thereof.

18. The method of claim 16, wherein the hydrocarbon inclusive gas includes C₂H₂ gas, or CH₄ and Ar gasses.

19. A method of making a graphene thin film, the method comprising:

providing a back support substrate;

disposing a catalyst thin film, directly or indirectly, on the back support substrate, wherein the catalyst thin film comprises a nickel-chromium alloy, and wherein the amount of chromium is 3-15% of the nickel-chromium alloy;

introducing a hydrocarbon inclusive gas proximate to the catalyst thin film;

heating the back support substrate to cause the hydrocarbon inclusive gas to at least partially separate the carbon in the hydrocarbon inclusive gas and promote graphene growth in and/or on the catalyst thin film; and

cooling the back support substrate to promote crystallization of graphene, directly or indirectly, on an outermost surface of the catalyst thin film, in making the graphene thin film, in connection with a quenching process.

21. The method of claim 19, wherein the catalyst thin film has a substantially single-orientation large-grain crystal structure, the crystals in the catalyst thin film having a length along a major axis on the order of 10s of microns.

22. The method of claim 19, wherein the cooling is performed in accordance with a temperature profile that involves active cooling at a non-constant and non-linear rate over the entirety of the cooling.