METHODS FOR DIRECT PRODUCTION OF GRAPHENE ON DIELECTRIC SUBSTRATES, AND ASSOCIATED ARTICLES/DEVICES

• US 20140308523A1
• Filed: 12/31/2013
• Published: 10/16/2014
• Est. Priority Date: 03/15/2013
• Status: Active Grant

• Current Assignee: Guardian Glass LLC (KOCH Industries Incorporated), Board of Regents of the University of Michigan (University of Michigan)
• Original Assignee: Anastasios John Hart, Vijayen S. Veerasamy
• Inventors: VEERASAMY, Vijayen S., HART, Anastasios John, MCNERNY, Daniel Quinn
• Granted Patent: US 10,431,354 B2
• Time in Patent Office: Days
• US Class Current: 428/408
• 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: H01B 1/04 mainly consisting of carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01B 13/0016 for heat treatment
• CPC Class Codes: H01B 13/0026 Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
• CPC Class Codes: Y10T 29/49002 Electrical device making
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

Certain example embodiments of this invention relate to methods for large area graphene precipitation onto glass, and associated articles/devices. For example, a coated article including a graphene-inclusive film on a substrate, and/or a method of making the same, is provided. A metal-inclusive catalyst layer (e.g., of or including Ni and/or the like) is disposed on the substrate. The substrate with the catalyst layer thereon is exposed to a precursor gas and a strain-inducing gas at a temperature of no more than 900 degrees C. Graphene is formed and/or allowed to form both over and contacting the catalyst layer, and between the substrate and the catalyst layer, in making the coated article. The catalyst layer, together with graphene formed thereon, is removed, e.g., through excessive strain introduced into the catalyst layer as associated with the graphene formation. Products including such articles, and/or methods of making the same, also are contemplated herein.

Claims

1. A method of making a coated article comprising a graphene-inclusive film on a substrate, the method comprising:

disposing a metal-inclusive catalyst layer on the substrate;

exposing the substrate with the metal-inclusive catalyst layer thereon to a precursor gas and a strain-inducing gas at a temperature of no more than 900 degrees C., the strain-inducing gas inducing strain in the metal-inclusive catalyst layer; and

forming and/or allowing formation of graphene both over and contacting the metal-inclusive catalyst layer, and between the substrate and the catalyst metal-inclusive catalyst layer, in making the coated article.

2. The method of claim 1, further comprising removing the catalyst layer, as well as with graphene formed thereon.

3. The method of claim 2, wherein the removing is accomplished through excessive strain introduced in the catalyst layer as associated with graphene formation.

4. The method of claim 1, wherein the temperature is less than 800 degrees C.

5. The method of claim 1, wherein the temperature is less than 700 degrees C.

6. The method of claim 1, wherein the precursor gas comprises acetylene.

7. The method of claim 1, wherein the substrate with the catalyst layer thereon is exposed to at least helium and/or acetylene gasses, in plural successive stages.

8. The method of claim 7, wherein a first stage comprises providing at least helium gas at a first flow rate, and a second stage comprises providing at least helium gas at a second flow rate and acetylene gas at a third flow rate, the first and second stages being provided in that order.

9. The method of claim 8, wherein a third stage is provided following the second stage, the third stage providing virtually no helium and/or acetylene.

10. The method of claim 1, wherein the substrate with the catalyst layer thereon is exposed to at least the strain-inducing gas and/or a carbon source gas, in one or more stages.

11. The method of claim 10, wherein a first stage comprises providing at least the strain-inducing gas in order to induce strain in the catalyst layer, and a second stage comprises providing at least the strain-inducing gas at a second flow rate and the carbon source gas at a third flow rate, the first and second stages being provided in that order.

12. The method of claim 11, wherein the first flow rate is greater than the second and third flow rates, and the second flow rate is lower than the third flow rate.

13. The method of claim 1, wherein the substrate is a glass substrate or a silicon wafer.

14. The method of claim 1, further comprising patterning the catalyst layer to a desired pattern, the graphene-inclusive film, once formed on the coated article, generally corresponding to the desired pattern.

15. The method of claim 14, wherein the patterning is practiced prior to the exposing.

16. The method of claim 1, wherein the exposing is performed at a temperature of 700-900 degrees C., the 700-900 degree C. temperature being reached within two minutes.

17. The method of claim 16, wherein the 700-900 degree C. temperature is maintained for no more than 10 s of minutes.

18. A coated article made in accordance with the method of claim 1.

19. A method of making an electronic device, the method comprising:

providing a coated article made in accordance with the method of claim 1; and

building the coated article into the device.

20. An electronic device made in accordance with the method of claim 19.

21. A method of making a coated article comprising a graphene-inclusive film on a substrate, the method comprising:

disposing a metal-inclusive catalyst layer on the substrate;

rapidly heating to 700-900 degrees C. the substrate with the metal-inclusive catalyst layer thereon;

annealing in a He gas inclusive environment, the substrate with the metal-inclusive catalyst layer thereon, the He gas being provided at a pressure selected to engineer a desired stress in the metal-inclusive catalyst layer;

exposing the substrate with the catalyst layer thereon to a carbon-inclusive precursor gas; and

forming and/or allowing formation of graphene both over and contacting the metal-inclusive catalyst layer, and between the substrate and the metal-inclusive catalyst layer, in making the coated article.

22. The method of claim 21, wherein the He gas induces strain in the metal-inclusive catalyst layer sufficient to cause at least partial separation between the substrate and the metal-inclusive catalyst layer during graphene formation.

23. The method of claim 21, further comprising delaminating the metal-inclusive catalyst layer and the graphene thereon through excessive strain provided by the He gas.

24. The method of claim 21, wherein the rapid heating is accomplished in no more than 1 minute, the annealing is performed for no more than 10 minutes, and the exposure to the carbon-inclusive precursor gas is performed for no more than 5 minutes.

25. The method of claim 21, wherein the rapid heating is accomplished in no more than 30 seconds, the annealing is performed for 3-7 minutes, and the exposure to the carbon-inclusive precursor gas is performed for no more than 3 minutes.

26. The method of claim 21, wherein the substrate is a silicon wafer.

27. The method of claim 21, further comprising mechanically delaminating from the substrate the metal-inclusive catalyst layer and the graphene thereon.

28. The method of claim 27, wherein the mechanical delamination is accomplished automatically through excess strain being induced in the metal-inclusive catalyst layer.

29. The method of claim 27, wherein the mechanical delamination is accomplished ex situ without using a wet chemical process.

30. The method of claim 21, wherein the desired stress in the metal-inclusive catalyst layer that is engineered is a net compressive stress.

31. A method of making a coated article comprising a graphene-inclusive film on a substrate, the method comprising:

disposing a metal-inclusive catalyst layer on the substrate;

heating to 700-900 degrees C. the substrate with the metal-inclusive catalyst layer thereon;

exposing the substrate with the metal-inclusive catalyst layer thereon to a carbon-inclusive precursor gas;

forming and/or allowing formation of graphene both over and contacting the metal-inclusive catalyst layer, and between the substrate and the metal-inclusive catalyst layer; and

mechanically delaminating from the substrate the metal-inclusive catalyst layer and the graphene on the metal-inclusive catalyst layer, so that the graphene formed between the substrate and the metal-inclusive catalyst layer remains on the substrate following the mechanical delaminating, in making the coated article,

wherein the metal-inclusive catalyst layer is engineered to have a stress that facilitates the mechanical delaminating.