Method of growing a graphene coating or carbon nanotubes on a catalytic substrate

• US 11,447,391 B2
• Filed: 06/22/2016
• Issued: 09/20/2022
• Est. Priority Date: 06/23/2015
• Status: Active Grant

• Current Assignee: Polyvalor LP, Valorisation-Recherche, Limited Partnership
• Original Assignee: Polyvalor LP, Valorisation-Recherche, Limited Partnership
• Inventors: Choubak, Saman, Levesque, Pierre, Gagnon, Philippe, Martel, Richard, Desjardins, Patrick
• Primary Examiner(s): Louie, Mandy C
• Application Number:
  US15/189,545
• Publication Number:
  US 20160376156A1
• Time in Patent Office: 2,281 Days
• Field of Search: None
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/745 Iron
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/186 by chemical vapour deposition [CVD]
• CPC Class Codes: C23C 16/01 on temporary substrates, e.g. substrates subsequently removed by etching
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: C23C 16/45557 Pulsed pressure or control pressure

Abstract

A method of growing a graphene coating or carbon nanotubes on a catalytic substrate by chemical vapor deposition is provided. In the method, the chemical vapor deposition is carried out in an atmosphere in which a ratio P_ox/P_red is about 5×10⁻²⁶ or less, wherein P_ox is the partial pressure oxidizing species in the atmosphere and P_red is the partial pressure of reducing species in the atmosphere. A catalytic substrate coated with a graphene coating grown according to this method is also provided.

Claims

1. A method of growing a graphene coating on a catalytic substrate by chemical vapor deposition, wherein the catalytic substrate is a copper, copper-metal alloy, or semiconductor Ge catalytic substrate,

the method comprising using a low pressure chemical vapor deposition (LP-CVD) system having a manifold capable of ultra-high vacuum (UHV) conditions to perform the steps of:

a) heating said catalytic substrate at a growth temperature,

b) exposing the catalytic substrate heated at said growth temperature to a gaseous atmosphere of a hydrocarbon-containing gas in said LP-CVD system, wherein the system is sealed to have an air leak rate of <

1×

10<sup>−

7</sup> sccm, thereby growing the graphene coating on the catalytic substrate, and

c) cooling said catalytic substrate down to a temperature at which etching of the graphene coating by oxidizing species does not occur in said LP-CVD system, wherein the system is sealed to have an air leak rate of <

1×

10<sup>−

7</sup> sccm,

wherein steps b) and c) are carried out in the gaseous atmosphere in which the ratio

2. The method of claim 1, wherein the ratio

3. The method of claim 1, wherein all gases used during steps b) and c) are purified before use so as to comprise about 10 ppb or less of oxidizing species.

4. The method of claim 1, wherein steps b) and c) are carried out under a gaseous atmosphere of a reducing species.

5. The method of claim 1, wherein step a) is carried out under a gaseous atmosphere of a reducing species or a gaseous atmosphere of an inert species.

6. The method of claim 1, wherein step a) is carried out in the absence of the hydrocarbon-containing gas.

7. The method of claim 1, wherein step c) is carried out in the absence of the hydrocarbon-containing gas.

8. The method of claim 7, wherein after step b) and prior to step c), the gaseous atmosphere of the hydrocarbon-containing gas is interrupted and the hydrocarbon-containing gas is evacuated.

9. The method of claim 1, further comprising, before step a), an annealing step comprising heating the catalytic substrate at an annealing temperature and annealing the catalytic substrate at said annealing temperature.

10. The method of claim 9, wherein the annealing step is carried out under a gaseous atmosphere of a reducing species or a gaseous atmosphere of an inert species.

11. The method of claim 9, wherein the annealing step is carried out in the absence of the hydrocarbon-containing gas.

12. The method of claim 1, wherein step b) last about 5 minutes or less.

13. The method of claim 1, wherein the hydrocarbon-containing gas is a methane.

14. The method of claim 1, wherein all gases used during steps b) and c) are purified before use so as to comprise about 1 ppb or less of oxidizing species.

15. The method of claim 1, wherein the ratio

16. The method of claim 1, wherein the catalytic substrate is copper (Cu) or a Cu—

Ni alloy.

17. The method of claim 1, wherein step b) last about 3 minutes or less.

18. The method of claim 1, wherein step b) last about 1 minutes or less.

19. The method of claim 1, wherein, during step b), about 90% or more surface coverage is achieved within 10 seconds.