CN113445030B - Method for improving cleanliness of graphene film - Google Patents
Method for improving cleanliness of graphene film Download PDFInfo
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- CN113445030B CN113445030B CN202010216388.4A CN202010216388A CN113445030B CN 113445030 B CN113445030 B CN 113445030B CN 202010216388 A CN202010216388 A CN 202010216388A CN 113445030 B CN113445030 B CN 113445030B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
Abstract
The invention provides a method for improving the cleanliness of a graphene film and the graphene film, wherein the method comprises the steps of carrying out high-temperature treatment on the graphene film in a vacuum environment; the high-temperature treatment temperature is 800-1050 ℃, and the graphene film is prepared by a chemical vapor deposition method. According to the method provided by the embodiment of the invention, the cleanliness of the graphene film can be improved to a large extent, and the uniformity of the cleanliness is good.
Description
Technical Field
The invention relates to a graphene film, in particular to a method for improving the cleanliness of graphene.
Background
Graphene is a two-dimensional atomic crystal material of a monoatomic layer composed of carbon atoms, has excellent electronic and optoelectronic properties, and has attracted widespread attention from the academic and industrial circles since discovery. From the standpoint of material preparation, chemical vapor deposition is the preferred method for preparing high quality graphene films: the substrate is usually placed in a high-temperature chamber, a carbon source and a reducing gas are introduced, the carbon source is cracked into carbon fragments under the catalysis of copper for nucleation, growth and splicing of graphene into a film, and a graphene film is formed. In the process, the carbon source is not fully cracked, and impurities such as amorphous carbon and the like are generated on the surface of the graphene while the graphene is generated, so that the quality of the graphene film is seriously influenced.
Disclosure of Invention
One main object of the present invention is to provide a method for improving the cleanliness of a graphene film, which comprises the steps of performing high-temperature treatment on the graphene film in a vacuum environment; the high-temperature treatment temperature is 800-1050 ℃, and the graphene film is prepared by a chemical vapor deposition method.
According to one embodiment of the present invention, the temperature of the high temperature treatment is 1000 to 1050 ℃.
According to an embodiment of the present invention, the pressure of the vacuum environment is 20Pa or less.
According to an embodiment of the present invention, the pressure of the vacuum environment is 3Pa or less.
According to one embodiment of the present invention, the time of the high temperature treatment is 5 to 300 minutes.
According to one embodiment of the invention, a growth substrate is arranged on the graphene film.
According to an embodiment of the invention, the growth substrate is selected from copper foil, nickel foil, copper nickel foil, silicon dioxide or sapphire.
The embodiment of the invention provides a graphene film, which is prepared by the method.
According to the method provided by the embodiment of the invention, the cleanliness of the graphene film can be improved to a large extent, and the uniformity of the cleanliness is good.
Drawings
FIG. 1a is a TEM image of a graphene film obtained according to an embodiment of the present invention;
FIG. 1b is a TEM image of a graphene film obtained according to the comparative example of the present invention;
fig. 2a to 2f are TEM images of graphene films obtained according to embodiments of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the present invention will be described in detail in the following description. It will be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention, and that the description and illustrations herein are intended to be by way of illustration only and not to be construed as limiting the invention.
The embodiment of the invention provides a method for improving the intrinsic cleanliness of a graphene film, which comprises the steps of carrying out high-temperature treatment on the graphene film in a vacuum environment; wherein the temperature of the high-temperature treatment is 800-1050 ℃, and the graphene film is prepared by a chemical vapor deposition method.
In one embodiment, a growth substrate is disposed on the graphene film.
According to the method provided by the embodiment of the invention, a plurality of graphene films growing on the surfaces of metal and nonmetal substrates such as copper foil, nickel foil, copper-nickel foil, silicon dioxide, sapphire and the like can be treated simultaneously.
The method of the embodiment of the invention has better compatibility and universality for the surface cleaning of the graphene film transferred to the surface of the high-temperature-resistant functional substrate, so that the graphene film before and after the transfer can be processed in a large area.
In an embodiment, the catalytic cracking effect of the copper foil of the growth substrate of graphene on the carbon source and amorphous carbon and/or desorption of amorphous carbon pollutants under high vacuum can be utilized, and after the growth of graphene is completed, the graphene film is subjected to high-temperature vacuum treatment for a certain time to remove impurities such as amorphous carbon existing on the surface of graphene, so that the cleanliness of the surface of the graphene film is improved.
In one embodiment, the pressure of the vacuum environment for performing the high temperature treatment may be 20Pa or less, for example, 18Pa, 15Pa, 12Pa, 10Pa, 8Pa, 5Pa, 3Pa, 1Pa, or the like.
In one embodiment, the pressure of the vacuum environment for performing the high temperature treatment may be 3Pa or less.
In one embodiment, all gases are turned off after the graphene is grown, and the vacuum pump is pumped to below 20Pa to perform high temperature treatment.
The method of the embodiment of the invention can be directly carried out after the graphene film is grown, and is simple to operate.
In one embodiment, the high temperature treatment is performed at a temperature of 800 to 1050 ℃, e.g., 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, etc.
In one embodiment, the high temperature treatment time may be 5 to 300 minutes, for example, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, 180 minutes, 200 minutes, 240 minutes, 270 minutes, etc.
The graphene film obtained by the method of the embodiment of the invention has the advantages that the cleanliness is improved to a great extent, and the uniformity of the cleanliness is good; meanwhile, the method is simple and convenient, has obvious effect, and is suitable for various systems for preparing the graphene by chemical vapor deposition.
An embodiment of the present invention provides a high cleanliness graphene film on a growth substrate, such as a copper foil substrate.
The method for improving the cleanliness of the graphene film according to an embodiment of the present invention is further described below with reference to the accompanying drawings and specific examples. Wherein, the raw materials used are all commercially available.
Examples
Placing large-area common industrial copper foil (10 x 60 cm) 2 ) After annealing and growing the graphene film, all gases are closed, simultaneously, the vacuum pump is pumped to bottom pressure of 3Pa, the sample is subjected to vacuum treatment for 30 minutes at the growth temperature of 1050 ℃ of graphene, then the sample is cooled, the cleanliness of the graphene film subjected to vacuum high-temperature treatment is subjected to transmission electron microscope characterization, and the cleanliness reaches 80%, and is particularly shown in fig. 1a and 2a to 2f.
Comparative example
Placing large-area common industrial copper foil (10 x 60 cm) 2 ) And after the process of annealing and growing the graphene film, which is the same as that of the embodiment, the temperature is directly reduced, and the generated graphene cleanliness is subjected to transmission electron microscope characterization, wherein the cleanliness is about 40%, and the method is specifically shown in fig. 1b.
FIGS. 1a and 1b are Transmission Electron Microscope (TEM) images of graphene films obtained in examples and comparative examples, respectively, in which dark areas are amorphous carbon covered areas; compared with the prior art, the area of the dark area in the graph 1a is far smaller than that in the graph 1b, which shows that the amorphous carbon coverage area of the graphene film is greatly reduced and the cleanliness is greatly improved after the graphene film is subjected to vacuum high-temperature treatment.
In addition, the graphene subjected to high-temperature treatment at intervals of 10cm on the copper foil of the embodiment is subjected to transmission electron microscope characterization, the cleanliness is over 80%, the uniformity is good, and particularly, the method can be seen from fig. 2a to 2f, and the fact that the graphene cleanliness after vacuum treatment is improved in a large area and the uniformity is good (amorphous carbon area is darker) is shown.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.
Claims (6)
1. A method for improving the cleanliness of a graphene film comprises the steps of carrying out high-temperature treatment on the graphene film in a vacuum environment; wherein the temperature of the high-temperature treatment is 800-1050 ℃, and the graphene film is prepared by a chemical vapor deposition method;
a growth substrate is arranged on the graphene film, and the growth substrate is copper foil;
and (3) utilizing the catalytic cracking effect of the growth substrate copper foil of the graphene on the carbon source and the amorphous carbon, and/or desorbing the amorphous carbon pollutants under high vacuum, and carrying out high-temperature vacuum treatment on the graphene film for a certain time after the graphene is grown so as to remove the amorphous carbon impurities existing on the surface of the graphene, thereby improving the cleanliness of the surface of the graphene film.
2. The method according to claim 1, wherein the high temperature treatment is at a temperature of 1000 to 1050 ℃.
3. The method of claim 1, wherein the vacuum environment has a pressure of 20Pa or less.
4. The method of claim 1, wherein the vacuum environment has a pressure of 3Pa or less.
5. The method of claim 1, wherein the high temperature treatment is for a period of 5 to 300 minutes.
6. A graphene film produced by the method of any one of claims 1 to 5.
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| JP2013087023A (en) * | 2011-10-20 | 2013-05-13 | Kri Inc | Method of producing graphene thin film using microwave |
| CN104477903A (en) * | 2014-12-22 | 2015-04-01 | 上海集成电路研发中心有限公司 | Preparation method of graphene film |
| CN104803377A (en) * | 2015-04-01 | 2015-07-29 | 中国科学院上海微***与信息技术研究所 | Method for improving surface cleanliness of graphene at high temperature and high pressure |
| ES2677157B1 (en) * | 2016-12-28 | 2019-05-31 | Consejo Superior Investigacion | PROCEDURE FOR EXFOLIATION AND TRANSFER OF GRAFENE FROM A SILICON CARBIDE SUBSTRATE DOPED TO ANOTHER SUBSTRATE |
| CN110883017B (en) * | 2018-09-10 | 2020-12-29 | 北京石墨烯研究院 | Method and device for statically cleaning graphene surface |
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