High quality large scale single and multilayer graphene production by chemical vapor deposition

Patent metadata

Field	Value
Publication number	US-10023468-B2
Application number	US-201313734823-A
Country	US
Kind code	B2
Filing date	Jan 4, 2013
Priority date	Jan 6, 2012
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

Systems and methods for synthesizing continuous graphene sheets are provided. The systems and methods include passing a catalyst substrate through a heated chemical vapor deposition chamber and exposing the substrate to a reaction gas mixture of hydrogen and hydrocarbon at a preselected location within the chamber. The reaction gas mixture can include hydrogen having a partial pressure of between about 0 Torr and 20 Torr, hydrocarbon having a partial pressure of between about 20 mTorr and about 10 Torr, and one or more buffer gases. The buffer gases can include argon or other noble gases to maintain atmospheric pressure within the chemical deposition chamber. The resulting graphene can be made with continuous mono and multilayers (up to six layers) and have single crystalline hexagonal grains with a preselected nucleation density and domain size for a range of applications.

First claim

The invention claimed is:

1. A method of making a monolayer or multilayer of poly-crystalline and single crystalline graphene comprising:
providing a chemical vapor deposition chamber including a pre-deposition region and a deposition region in fluid communication with each other at atmospheric pressure;
providing a continuous copper substrate for movement through the chemical vapor deposition chamber;
drawing the copper substrate through the pre-deposition region of the chemical vapor deposition chamber at atmospheric pressure and in the presence of hydrogen gas to anneal the copper substrate;
introducing a hydrocarbon gas and a buffer gas at a nozzle opening coextensive with the deposition region of the chemical vapor deposition chamber to mix with hydrogen gas escaping from the pre-deposition region at the nozzle opening, thereby forming a reaction gas mixture in the deposition region, the reaction gas mixture being at atmospheric pressure;
drawing the copper substrate through the deposition region of the chemical vapor deposition chamber while introducing the hydrocarbon gas at the nozzle opening so that the copper substrate continuously reacts with the reaction gas mixture in the deposition region, the reaction gas mixture having a partial pressure of hydrogen gas at 10-20 Torr and a partial pressure of hydrocarbon gas at 23-100 mTorr with a ratio of hydrogen gas partial pressure to hydrocarbon gas partial pressure of greater than 400 to form a monolayer or multilayer of graphene including crystal hexagonal grains, wherein the hydrogen gas contributes to the annealing of the copper substrate in the pre-deposition region and contributes to the formation of active surface-bound carbon species in the deposition region; and
continuously extracting the copper substrate from the chemical vapor deposition chamber, the extracted copper substrate supporting the monolayer or multilayer of graphene including crystal hexagonal grains.

2. The method according to claim 1 wherein the hydrocarbon gas includes about 30 ppm methane gas.

3. The method according to claim 1 further including continuously extracting the copper substrate from the chemical vapor deposition chamber with a poly-crystalline or single-crystalline graphene.

4. The method according to claim 1 wherein the hexagonal grains have an average grain size of between about 3 μm and about 1000 μm.

5. The method according to claim 1 wherein the number of continuous multilayers of graphene is between 2 and 6.

6. The method according to claim 1 further including heating the copper substrate to approximately 1000° C. using an infrared or plasma arc lamp.

7. The method according to claim 1 further including heating the copper substrate using inductive coils.

8. A method of synthesizing graphene comprising:
providing a chemical vapor deposition chamber including a pre-deposition region and a deposition region in fluid communication with each other at atmospheric pressure;
providing a continuous catalyst substrate for movement through the chemical vapor deposition chamber;
annealing the catalyst substrate in hydrogen gas within the pre-deposition region of the chemical vapor deposition chamber at atmospheric pressure and in the presence of hydrogen gas while passing the catalyst substrate therethrough;
introducing a hydrocarbon gas and a buffer gas at a nozzle opening coextensive with the deposition region of the chemical vapor deposition chamber to mix with hydrogen gas escaping from the pre-deposition region at the nozzle opening, thereby forming a reaction gas mixture in the deposition region, the reaction gas mixture being at atmospheric pressure;
drawing the catalyst substrate through the deposition region of the chemical vapor deposition chamber while introducing the hydrocarbon gas at the nozzle opening so that the annealed catalyst substrate continuously reacts with the reaction gas mixture, the reaction gas mixture having a partial pressure of the hydrocarbon gas between about 23 mTorr and about 100 mTorr, and having a partial pressure of the hydrogen gas between about 10 Torr and about 20 Torr with a ratio of hydrogen gas partial pressure to hydrocarbon gas partial pressure of greater than 400, wherein the hydrogen gas contributes to the annealing of the catalyst substrate in the pre-deposition region and contributes to the formation of active surface-bound carbon species in the deposition region; and
continuously extracting the catalyst substrate from the chemical vapor deposition chamber, the extracted catalyst substrate supporting a monolayer or multilayer of graphene including crystal hexagonal grains.

9. The method according to claim 8 wherein the hydrocarbon gas is selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, heptane, octane, benzene, toluene and combinations thereof.

10. The method according to claim 8 wherein the catalyst substrate includes a copper foil.

11. The method according to claim 8 wherein annealing the catalyst substrate includes gradually heating the catalyst substrate to approximately 1000° C.

12. The method according to claim 11 wherein heating the catalyst substrate is performed using one of a plasma arc lamp, a resistive furnace, an infrared lamp and an inductive coil.

13. The method according to claim 8 wherein the buffer gas includes helium to maintain atmospheric pressure within the chemical vapor deposition chamber.

14. The method according to claim 8 further including bonding the synthesized graphene to a polymeric or dielectric substrate.

15. The method according to claim 14 further including separating the catalyst substrate after bonding the synthesized graphene to the polymeric or dielectric substrate.

16. A method of synthesizing graphene:
providing a chemical vapor deposition chamber including a pre-deposition region and a laterally-extending deposition region in fluid communication with each other at atmospheric pressure;
passing a continuous copper substrate through the pre-deposition region of the chemical vapor deposition chamber at atmospheric pressure;
annealing the copper substrate within the pre-deposition region of the chemical vapor deposition chamber in H 2 gas while drawing the copper substrate therethrough;
introducing a hydrocarbon gas and a buffer gas at a nozzle opening coextensive with the deposition region of the chemical vapor deposition chamber to mix with hydrogen gas escaping from the pre-deposition region at the nozzle opening, thereby forming a reaction gas mixture in the deposition region, the reaction gas mixture being at atmospheric pressure;
passing the annealed copper substrate through the deposition region of the chemical vapor deposition chamber while introducing the hydrocarbon gas at the nozzle opening so that the copper substrate continuously reacts with the reaction gas mixture in the deposition region to form poly-crystalline or single-crystalline graphene on the annealed copper substrate, the hydrocarbon gas having a partial pressure between about 23 mTorr and about 100 mTorr, the H 2 gas having a partial pressure between about 10 Torr and about 20 Torr with a ratio of H 2 gas partial pressure to hydrocarbon gas partial pressure of greater than 400, wherein the H 2 gas contributes to the annealing of the copper substrate in the pre-deposition region and contributes to the formation of active surface-bound carbon species in the deposition region; and
continuously extracting the copper substrate from the chemical vapor deposition chamber, the extracted copper substrate supporting a monolayer or multilayer of gra

Assignees

• Ut Battelle Llc

Inventors

• Vlassiouk Ivan V
• Smirnov Sergei N
• Peter William H
• Sabau Adrian S
• Dai Sheng
• Fulvio Pasquale F
• Ivanov Ilia N
• Lavrik Nickolay V
• Datskos Panagiotis G

Classifications

• C01B2204/04

  Specific amount of layers or specific thickness · CPC title

• C01B32/186 Primary

  by chemical vapour deposition [CVD] · CPC title

• C01B2204/02

  Single layer graphene · CPC title

• C01B2204/32

  Size or surface area · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title