Process for preparing graphene based on metal film-assisted annealing and the reaction with Cl2

Patent metadata

Field	Value
Publication number	US-9048092-B2
Application number	US-201214350282-A
Country	US
Kind code	B2
Filing date	Sep 3, 2012
Priority date	Jan 3, 2012
Publication date	Jun 2, 2015
Grant date	Jun 2, 2015

Abstract

A method for preparing graphene by reaction with Cl 2 based on annealing with assistant metal film is provided, comprising the following steps: applying normal wash to a Si-substrate, then putting the Si-substrate into a reaction chamber of a CVD system and evacuating, rising the temperature to 950° C.-1150° C. gradually, supplying C 3 H 8 and carbonizing the Si-substrate for 3-10 min; rising the temperature to 1150° C.-1350° C. rapidly, supplying C 3 H 8 and SiH 4 , growing a 3C—SiC hetero-epitaxial film on the carbonized layer, and then reducing the temperature to ambient temperature under the protection of H 2 gradually, introducing the grown sample wafer of 3C—SiC into a quartz tube, heating to 700-1100° C., supplying mixed gas of Ar and Cl 2 , and reacting Cl 2 with 3C—SiC to generate a carbon film, applying the sample wafer of carbon film on a metal film, annealing at 900° C.-1100° C. for 10-30 min to reconstruct the carbon film into graphene; and taking out of the metal film from the sample wafer of graphene to obtain large area graphene. The graphene obtained by the method has large area, smooth surface, good continuity, and low porosity; and the product can be used to seal gas and liquid.

First claim

What is claimed is:

1. A process for preparing graphene based on metal film-assisted annealing and a reaction with Cl 2 , characterized in that said process comprises the following steps:
(1) cleaning a Si substrate;
(2) placing the cleaned Si substrate into a CVD system reactor, wherein the reactor is vacuumized, the temperature is gradually raised to a carbonization temperature of 950° C.-1150° C. under a protection of H 2 , and C 3 H 8 is flowed into the reactor, such that the Si substrate is carbonized for 3-10 min so as to grow a carbonization layer;
(3) raising the temperature to 1150° C.-1350° C. while C 3 H 8 and SiH 4 are flowed into the reactor, and a 3C—SiC heterogeneous epitaxial film is grown on the carbonization layer for 30-60 minutes, and then the temperature is gradually decreased to an ambient temperature under the protection of H 2 so as to complete the growth of the 3C—SiC epitaxial film,
(4) placing the 3C—SiC film into a quartz tube, and heating the 3C—SiC film to 700° C.-1100° C. as a mixed gas of Ar and Cl 2 is flowed into the quartz tube, and Cl 2 is reacted with the 3C—SiC film to obtain a carbon film,
(5) placing the carbon film onto a metal film that has catalysis for a reconfiguration of carbon to graphene, and annealing the carbon film and the metal film together for 10-30 minutes under a temperature of 900° C.-1100° C. in an Ar atmosphere, wherein the carbon film is reconfigured to graphene, and
(6) removing the metal film from the graphene sample so as to obtain graphene with a large area.

2. The process for preparing graphene according to claim 1 , characterized in that in step (2), the vacuum in the reactor is about 10 −7 mbar.

3. The process for preparing graphene according to claim 1 , characterized in that in step (2), the flow rate of C 3 H 8 is 30 sccm-40 sccm.

4. The process for preparing graphene according to claim 1 , characterized in that in step (3), the flow rate of the flowed SiH 4 and C 3 H 8 is respectively 15 sccm-25 sccm and 30 sccm-50 sccm.

5. The process for preparing graphene according to claim 4 , characterized in that the flow rates of SiH 4 and of C 3 H 8 are adjusted such that the ratio of C/Si=6.

6. The process for preparing graphene according to claim 1 , characterized in that in step (4), the flow rate of the flowed Ar and Cl 2 is respectively 95 sccm-98 sccm and 2 sccm-5 sccm.

7. The process for preparing graphene according to claim 1 , characterized in that in step (5), the flow rate of Ar when annealing is 25 sccm-100 sccm.

8. The process for preparing graphene according to claim 1 , characterized in that in step (5), the metal film is a Cu film.

9. The process for preparing graphene according to claim 8 , characterized in that the Cu film has a thickness of 250 nm-300 nm.

10. The process for preparing graphene according to claim 1 , characterized in that a dimension of the Si substrate is 2 inches-20 inches.

11. The process for preparing graphene according to claim 1 , characterized in that a dimension of the graphene sample is 2 inches-12 inches.

12. A graphene sample with a large area obtained by a process comprising the following steps:
(1) cleaning a Si substrate;
(2) placing the cleaned Si substrate into a CVD system reactor, wherein the reactor is vacuumized, the temperature is gradually raised to a carbonization temperature of 950° C.-1150° C. under a protection of H 2 , and C 3 H 8 is flowed into the reactor, such that the Si substrate is carbonized for 3-10 min so as to grow a carbonization layer;
(3) raising the temperature to 1150° C.-1350° C. while C 3 H 8 and SiH 4 are flowed into the reactor, and a 3C—SiC heterogeneous epitaxial film is grown on the carbonization layer for 30-60 minutes, and then the temperature is gradually decreased to an ambient temperature under the protection of H 2 so as to complete the growth of the 3C—SiC epitaxial film,
(4) placing the 3C—SiC film into a quartz tube, and heating the 3C—SiC film to 700° C.-1100° C. as a mixed gas of Ar and Cl 2 is flowed into the quartz tube, and Cl 2 is reacted with the 3C—SiC film to obtain a carbon film,
(5) placing the carbon film onto a metal film that has catalysis for a reconfiguration of carbon to graphene, and annealing the carbon film and the metal film together for 10-30 minutes under a temperature of 900° C.-1100° C. in an Ar atmosphere, wherein the carbon film is reconfigured to graphene sample, and
(6) removing the metal film from the graphene sample so as to obtain graphene with a large area.

Assignees

• Guo Hui
• Zhang Keji
• Zhang Yuming
• Deng Pengfei
• Lei Tianmin
• Univ Xidian

Inventors

• Guo Hui
• Zhang Keji
• Zhang Yuming
• Deng Pengfei
• Lei Tianmin

Classifications

• H10P14/2905

  Silicon, silicon germanium or germanium · CPC title

• H10P14/38

  characterised by treatments done after the formation of the materials · CPC title

• H10P14/24

  using chemical vapour deposition [CVD] · CPC title

• H10P14/3406 Primary

  Carbon, e.g. diamond-like carbon · CPC title

• C23C16/26 Primary

  Deposition of carbon only · CPC title