Techniques for low temperature direct graphene growth on glass

• US 10,145,005 B2
• Filed: 06/03/2016
• Issued: 12/04/2018
• Est. Priority Date: 08/19/2015
• 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): Osele, Mark A
• Assistant Examiner(s): Harm, Nickolas R
• Application Number:
  US15/172,511
• Publication Number:
  US 20170051399A1
• Time in Patent Office: 914 Days
• Field of Search: 156247, 156701, 156714, 156750
• CPC Class Codes: B32B 38/10 Removing layers, or parts of layers, mechanically or chemically
• CPC Class Codes: B32B 43/006 Delaminating
• CPC Class Codes: C01B 32/186 by chemical vapour deposition [CVD]
• CPC Class Codes: C01B 32/194 After-treatment
• CPC Class Codes: C23C 14/221 Ion beam deposition C23C14/46, C23C14/48 take precedence
• CPC Class Codes: C23C 14/48 Ion implantation
• CPC Class Codes: C23C 16/06 characterised by the deposition of metallic material
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/50 using electric discharges generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: Y10T 156/11 Methods of delaminating, per se; i.e. , separating at bonding face
• CPC Class Codes: Y10T 156/1168 Gripping and pulling work apart during delaminating
• CPC Class Codes: Y10T 156/19 Delaminating means

Abstract

Certain example embodiments relate to methods for low temperature direct graphene growth on glass, and/or associated articles/devices. In certain example embodiments, a glass substrate has a layer including Ni formed thereon. The layer including Ni has a stress pre-engineered through the implantation of He therein. It also may be preconditioned via annealing and/or the like. A remote plasma-assisted chemical vapor deposition technique is used to form graphene both above and below the Ni-inclusive film. The Ni-inclusive film and the top graphene may be removed via tape and/or the like, leaving graphene on the substrate. Optionally, a silicon-inclusive layer may be formed between the Ni-inclusive layer and the substrate. Products including such articles, and/or methods of making the same, also are contemplated.

Claims

1. A method of making a coated article including a graphene-inclusive thin film supported by a glass substrate, the method comprising:

forming a layer comprising Si on the substrate;

forming a layer comprising Ni on the layer comprising Si;

engineering stress in the layer comprising Ni via He ion implantation and annealing;

following the engineering of stress, growing graphene on both major surfaces of the layer comprising Ni via plasma-related chemical vapor deposition; and

mechanically removing the layer comprising Ni and the graphene on the major surface of the layer comprising Ni opposite the substrate, at least some graphene initially formed at an interface of the layer comprising Si and the layer comprising Ni remaining on the substrate on the layer comprising Si following the mechanical removal, in making the graphene-inclusive thin film,

wherein the annealing is performed, and the graphene is grown, at 450-550 degrees C., the graphene is grown in 1-5 minutes, and He exposure associated with the He ion implantation is no more than 5 minutes.

2. The method of claim 1, wherein the plasma-related chemical vapor deposition is remote plasma-assisted chemical vapor deposition.

3. The method of claim 1, wherein the plasma-related chemical vapor deposition is plasma-enhanced chemical vapor deposition.

4. The method of claim 1, wherein the plasma-related chemical vapor deposition uses acetylene and hydrogen as separate source gasses.

5. The method of claim 1, wherein the layer comprising Ni is formed by e-beam deposition.

6. The method of claim 1, wherein the layer comprising Ni is 200-300 nm thick.

7. The method of claim 1, wherein the mechanical removal is delamination.

8. The method of claim 1, wherein the mechanical removal removes at least some of the graphene on the major surface of the layer comprising Ni closest the substrate.

9. The method of claim 1, wherein the layer comprising Si is oxided.

10. The method of claim 1, wherein the layer comprising Si is 10-300 nm thick.

11. The method of claim 1, wherein the layer comprising Ni is formed on the substrate at least partially under vacuum, and He ion implantation also is performed at least partially under vacuum.

12. The method of claim 11, wherein the annealing and/or the graphene growing is performed at least partially under vacuum.

13. The method of claim 11, wherein the at least partial vacuum is maintained from formation of the layer comprising Ni through graphene growth.

14. A method of making a coated article including a graphene-inclusive thin film supported by a glass substrate, the method comprising:

forming a layer comprising Ni on the substrate;

implanting He ions in the layer comprising Ni;

heating the layer comprising Ni with the He ions implanted therein, the implanting and the heating creating a desired stress profile in the layer comprising Ni;

following creation of the desired stress profile in the layer comprising Ni, providing a hydrocarbon source gas and a separate hydrogen source gas to a remote plasma-assisted chemical vapor deposition apparatus to facilitate graphene growth on major surfaces of the layer comprising Ni opposite the substrate and adjacent the substrate; and

delaminating the layer comprising Ni from the substrate, the delamination removing the layer comprising Ni from the substrate together with graphene grown on the major surface of the layer comprising Ni opposite the substrate while leaving on the substrate graphene grown on the major surface of the layer comprising Ni adjacent the substrate, in making the graphene-inclusive thin film,

wherein the heating is performed, and graphene is grown, at 450-550 degrees C., the graphene is grown in 1-5 minutes, and He exposure associated with the He ion implantation is no more than 5 minutes.

15. The method of claim 14, wherein the layer comprising Ni is formed by e-beam deposition.

16. The method of claim 14, further comprising forming a silicon-inclusive layer on the substrate, the layer comprising Ni being formed on the silicon-inclusive layer.

17. The method of claim 16, wherein the silicon-inclusive layer is 10-300 nm thick.

18. A method of making a coated article including a graphene-inclusive thin film supported by a glass substrate, the method comprising:

forming a buffer layer on the substrate;

forming a metal catalyst layer on the buffer layer;

pre-engineering stress in the metal catalyst layer via He ion implantation and thermal annealing;

following the pre-engineering of stress, growing graphene on both major surfaces of the metal catalyst layer using a remote plasma-assisted chemical vapor deposition apparatus operating in connection with separate hydrocarbon and hydrogen gasses provided at different flow rates;

removing the metal catalyst layer from the substrate together with graphene grown on the major surface of the metal catalyst layer opposite the substrate, while leaving on the substrate graphene grown on the major surface of the metal catalyst layer adjacent the substrate, in making the graphene-inclusive thin film; and

wherein the annealing is performed, and the graphene is grown, at 450-550 degrees C., the graphene is grown in 1-5 minutes, and He exposure associated with the He ion implantation is no more than 5 minutes.

19. A method of making a coated article including a graphene-inclusive film supported by a glass substrate, the method comprising:

forming a layer comprising Si on the glass substrate;

forming a layer comprising Ni on the glass substrate and on the layer comprising Si;

engineering stress in the layer comprising Ni via He ion implantation and annealing;

following the engineering of stress, growing graphene on both major surfaces of the layer comprising Ni; and

removing the layer comprising Ni and the graphene on the major surface of the layer comprising Ni opposite the glass substrate, at least some graphene initially formed at an interface of the layer comprising Si and the layer comprising Ni remaining on the glass substrate on the layer comprising Si following the removal, in making the graphene-inclusive film,

wherein the annealing is performed, and the graphene is grown, at 450-550 degrees C., the graphene is grown in 1-5 minutes, and He exposure associated with the He ion implantation is no more than 5 minutes.