CN113637952B - Method for preparing graphene film by chemical vapor deposition electron irradiation - Google Patents
Method for preparing graphene film by chemical vapor deposition electron irradiation Download PDFInfo
- Publication number
- CN113637952B CN113637952B CN202110928877.7A CN202110928877A CN113637952B CN 113637952 B CN113637952 B CN 113637952B CN 202110928877 A CN202110928877 A CN 202110928877A CN 113637952 B CN113637952 B CN 113637952B
- Authority
- CN
- China
- Prior art keywords
- substrate
- vacuum chamber
- plasma
- carbon
- argon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- C23C16/44—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 method of coating
- C23C16/48—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 method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/481—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 method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation by radiant heating of the substrate
-
- 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
- C23C16/44—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 method of coating
- C23C16/48—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 method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/487—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 method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using electron radiation
-
- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
- C23C16/511—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 method of coating using electric discharges using microwave discharges
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses chemical vapor deposition electrodepositionThe method for preparing the graphene film by sub-irradiation comprises the following steps: carrying out vacuum-pumping treatment on the vacuum chamber with the substrate; when the vacuum degree in the vacuum chamber is lower than a preset threshold value, introducing argon into the vacuum chamber to increase the air pressure of the vacuum chamber to 2 x 10 ‑2 ‑1*10 ‑1 (ii) a Ionizing the argon gas under the coupling action of a magnetic field and microwaves, and cleaning the substrate by adopting the generated argon plasma; introducing carbon source gas into the vacuum chamber, and generating carbon plasma under the activation action of the argon plasma; and adjusting the bias voltage of the substrate to be a positive bias voltage, attracting electrons in the carbon plasma to the surface of the substrate for auxiliary growth to form electron irradiation, and depositing the carbon plasma on the substrate to generate the graphene carbon film. According to the invention, the carbon source gas is ionized by ECR plasma, so that the carbon source gas is fully ionized, and the graphene carbon film can be grown on the substrate under the condition of not heating the substrate by the aid of electron irradiation.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to a method for preparing a graphene film by chemical vapor deposition electron irradiation.
Background
The carbon film containing the graphene structure has excellent performance in the research fields of electricity, magnetism, photoelectricity and the like, and the carbon film continuously makes breakthrough progress in the application fields of micromachines, electronic elements, optical elements, capacitance storage and the like.
The preparation of graphene is realized by mechanical stripping in the early stage, and with research and exploration, the preparation methods of graphene become various gradually, and include methods of redox graphite powder, vacuum epitaxial growth, chemical vapor deposition and the like. Among them, chemical vapor deposition is a common method for preparing defect-free multi-layer graphene at present. For the properties of carbon films containing graphene nanocrystals, the graphene structure plays a dominant role in the macroscopic properties of the carbon film. However, the growth process of graphene is difficult to regulate and control by the preparation technologies at present, and how to regulate and control the size and the structure of the graphene nanocrystalline carbon film by designing process parameters is a key problem influencing the growth and the application of graphene.
The existing method is to grow graphene on the surface of a low-solubility substrate or a high-solubility substrate, wherein the low-solubility substrate represents Cu, and the growth mechanism is a surface catalysis process and comprises the decomposition and surface diffusion of hydrocarbon; the high-solubility substrate is represented by Ni and Ru, the growth mechanism of the high-solubility substrate is a supersaturation precipitation mechanism, and the growth mechanism is specifically described as follows: and (2) decomposing the hydrocarbon on the surface of the substrate at high temperature and releasing carbon atoms, forming a carbide solid solution by the carbon atoms and the metal, diffusing the carbide solid solution into the substrate, precipitating the carbon atoms due to supersaturation after cooling, and diffusing the carbon atoms on the surface of the metal to form graphene. In the prior literature reports, the copper substrate can grow the three-dimensional graphene with good morphology without heating, but the silicon substrate surface needs to be heated to more than 550 ℃ for growing the three-dimensional graphene film, so that the complexity of the preparation method is increased, and the method cannot meet the requirements once the process requirement or the material system which is not suitable for heating exists when the method is combined with other processes. Therefore, it is required to develop a method for growing a three-dimensional graphene thin film on the surface of a silicon substrate without heating.
In the existing literature reports, the pressure value in the process of chemical vapor deposition of three-dimensional graphene is usually greater than 10Pa, a large gas flux is required for maintaining the pressure value, if the chemical vapor deposition of three-dimensional graphene can be realized in a range significantly lower than the pressure value, only a small gas flux is required in the same vacuum chamber volume, so that the gas can be saved, and the other benefit is that the growth process of the three-dimensional graphene film is softer and the form and quality of the three-dimensional graphene film are easy to control. Therefore, it is necessary to develop a method for growing a three-dimensional graphene thin film by low-pressure chemical vapor deposition.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, an object of the present invention is to provide a method for preparing a graphene carbon film that can be performed in a low pressure environment without heating a substrate.
The technical scheme of the invention is as follows:
a method for preparing a graphene film by chemical vapor deposition electron irradiation comprises the following steps:
fixing a substrate on a substrate frame, putting the substrate into a vacuum chamber, and vacuumizing the vacuum chamber;
when the vacuum degree in the vacuum chamber is lower than a preset threshold value, introducing argon into the vacuum chamber to increase the air pressure of the vacuum chamber to 2 x 10 -2 -1*10 -1 ；
Ionizing the argon gas under the coupling action of a magnetic field and microwaves, and cleaning the substrate by adopting the generated argon plasma;
introducing carbon source gas into the vacuum chamber, and generating carbon plasma under the activation action of the argon plasma;
and adjusting the bias voltage of the substrate to be a positive bias voltage, attracting electrons in the carbon plasma to the surface of the substrate for auxiliary growth to form electron irradiation, and depositing the carbon plasma on the substrate to generate the graphene carbon film.
The method for preparing the graphene film by chemical vapor deposition electron irradiation is characterized in that the carbon source gas is one or more of methane, ethylene and acetylene.
The method for preparing the graphene film by chemical vapor deposition electron irradiation is characterized in that the substrate is a silicon substrate.
The method for preparing the graphene film by the chemical vapor deposition electron irradiation comprises the step of introducing argon gas into the vacuum chamber, wherein the gas pressure is 1 x 10 -2 -1*10 -1 Pa。
The method for preparing the graphene film by the chemical vapor deposition electron irradiation comprises the step of introducing a carbon source gas into the vacuum chamber, wherein the ratio of argon to the carbon source gas is 8:1 or 8: 2.
The method for preparing the graphene film by chemical vapor deposition electron irradiation further comprises the following steps of before the substrate is fixed on the substrate frame:
and cleaning the substrate by using an acetone solution and drying.
Has the advantages that: compared with the prior art, the plasma source is generated by the ECR plasma and used for activating the ionized carbon source gas, carbon supply in the graphene carbon film is realized, and the growth of graphene is realized by adjusting the electron irradiation energy during deposition; in addition, since the carbon source gas is ionized by using the ECR plasma, the carbon source gas can be sufficiently ionized to form a high-density plasma, and the temperature of the substrate required for growth can be reduced by the assistance of electron irradiation, thereby realizing the growth of the graphene carbon film on the substrate without heating the substrate.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing a graphene film by chemical vapor deposition electron irradiation according to a preferred embodiment of the present invention.
FIG. 2 is a schematic structural diagram of an ECR-PECVD apparatus according to the present invention.
Fig. 3 is an electron micrograph of the graphene carbon film in example 1.
Fig. 4 is a Raman characterization chart of the graphene carbon film in example 1.
Fig. 5 is an electron micrograph of the graphene carbon film in example 2.
Fig. 6 is a Raman characterization plot of the graphene carbon film of example 2.
Detailed Description
The invention provides a method for preparing a graphene film by chemical vapor deposition electron irradiation, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The method for growing the graphene film by plasma electron irradiation has been reported in documents and patents, but in the existing methods, electron irradiation is introduced in the physical vapor deposition (sputtering) process, and a C-C single bond is converted into a C ═ C double bond through electron induction to form a graphene nanocrystalline structure. In chemical vapor deposition, however, there is no report of introducing electron irradiation. Compared with physical vapor deposition, the chemical vapor deposition method does not need a target material, is less influenced by the geometric shape of the substrate, and has good film uniformity, so that electron irradiation is introduced in the chemical vapor deposition process, the application range of the electron irradiation method in the growth of the graphene film can be expanded, and the report of using electron irradiation in the chemical vapor deposition graphene film does not exist at present.
Based on this, the present invention provides a method for preparing a graphene thin film by chemical vapor deposition electron irradiation, as shown in fig. 1, which comprises the steps of:
s10, fixing the substrate on the substrate frame, putting the substrate into a vacuum chamber, and vacuumizing the vacuum chamber;
s20, when the vacuum degree in the vacuum chamber is lower than a preset threshold value, introducing argon gas into the vacuum chamber to increase the pressure of the vacuum chamber to 2 x 10 -2 -1*10 -1 ；
S30, ionizing the argon gas under the coupling action of a magnetic field and microwaves, and cleaning the substrate by adopting the generated argon plasma;
s40, introducing a carbon source gas into the vacuum chamber, and generating carbon plasma under the activation action of the argon plasma;
and S50, adjusting the bias voltage of the substrate to be a positive bias voltage, attracting electrons in the carbon plasma to the surface of the substrate for auxiliary growth to form electron irradiation, and depositing the carbon plasma on the substrate to generate the graphene carbon film.
Specifically, the method for preparing the graphene thin film by chemical vapor deposition electron irradiation provided by the invention is realized based on an electron cyclotron resonance-plasma vapor deposition (ECR-PECVD) apparatus shown in fig. 2. The ECR-PECVD device comprises a pre-vacuum chamber 20 and a vacuum chamber 30 which are arranged at intervals through a separating valve 10, and a microwave input pipe 40 communicated with the vacuum chamber 30; a substrate frame 50 is arranged in the vacuum chamber 30, a left magnetic coil 31 is arranged at the left end of the vacuum chamber 30, a middle magnetic coil 32 is arranged at the middle part of the vacuum chamber, and a right magnetic coil 33 is arranged at the right end of the vacuum chamber.
In the embodiment, a substrate is cleaned and wiped by acetone solution, is naturally dried and then is arranged on a substrate frame and is conveyed into a vacuum chamber through a pre-vacuum chamber; pumping by a two-stage vacuum system of a mechanical pump and a molecular pump, and when the vacuum degree of a vacuum cavity body is lower than 1 x 10 -4 When Pa, argon gas with a certain flow rate is introduced, and the argon gas is stable; then, the magnetic coil current is turned on to generate a predetermined magnetic field, and the microwave is turned on to be excited withArgon plasma is generated by magnetic field coupling, and the argon plasma is stabilized for 10 to 20 minutes; before coating, performing surface cleaning on the substrate by using argon plasma; after cleaning, introducing a certain flow of carbon source gas, so that the carbon source gas is ionized under the assistance of argon plasma to form carbon plasma, and stabilizing for a period of time; then, a substrate power supply is switched on to generate a substrate bias voltage, and the surface of the substrate is bombarded to form electron irradiation. In the embodiment, controllable change of electron irradiation current density can be realized by adjusting microwave power, gas flow, substrate bias voltage and the like, and graphene is prepared and grown by electron irradiation, so that the temperature required by the substrate can be effectively reduced, and the selection range of the growing substrate can be expanded; the carbon source gas is ionized by ECR plasma, so that the carbon source gas is fully ionized, the temperature required by cracking the carbon source in the chemical vapor process is reduced, and the graphene carbon film can be successfully grown under extremely low pressure; in the embodiment, the positive bias is applied to the substrate to attract the electron current to irradiate the surface of the substrate, so that the temperature of the substrate required by growth can be reduced, and the graphene carbon film can be grown on the substrate without heating the substrate.
In some embodiments, in the step of ionizing the argon gas under the coupling effect of the magnetic field and the microwave, the power of the microwave is 400-500W.
In some embodiments, the carbon source gas is one or more of methane, ethylene, and acetylene, but is not limited thereto.
In some embodiments, the substrate is a silicon substrate, a silicon dioxide substrate, or a PI flexible substrate, but is not limited thereto.
In some embodiments, the step of adjusting the substrate bias voltage to a positive bias voltage, the positive bias voltage is equal to or less than 100V. In this embodiment, if the positive bias is too high, the growth of the graphene carbon film tends to be unstable.
In some embodiments, the step of introducing argon into the vacuum chamber has a pressure of 1 × 10 -2 -1*10 -1 Pa. By way of example, but not limitation, argon may be flowed at a rate of 5-10 sccm.
In some embodiments, the ratio of argon to carbon source gas in the step of introducing carbon source gas into the vacuum chamber is 8:1 or 8: 2. The flow rate of the carbon source gas is, for example, 1 to 3sccm, but is not limited thereto.
In some embodiments, a graphene carbon film is further provided, wherein the graphene carbon film is prepared by the preparation method of the graphene carbon film.
The following provides a further explanation of the method for preparing graphene thin film by electron irradiation in chemical vapor deposition according to the present invention with specific examples:
example 1
1. Fixing the cleaned silicon substrate on a substrate holder, and delivering into a high vacuum chamber via a secondary vacuum chamber with a vacuum degree lower than 1 × 10 -4 After Pa, argon gas with the flow rate of 8sccm is introduced through the flow controller to increase the air pressure in the cavity to 6.6 multiplied by 10 -2 Pa; applying 40/40/48A magnetic coil current and 470W microwave to the left, middle and right magnetic coils respectively as shown in FIG. 2, ionizing gas under the coupling action of magnetic field and microwave, and generating high density argon plasma; and the argon plasma is led out to the working cavity to form a focusing ECR plasma source; stabilizing for 10-20min, and performing the next step;
2. setting a negative bias voltage of 50V for the substrate bias voltage, opening a baffle between the plasma and the substrate, etching and cleaning the surface of the silicon substrate by using argon plasma, and carrying out ion cleaning for 3 minutes; introducing methane gas with the flow of 2sccm after cleaning, ionizing the methane gas under the activation action of the argon plasma to form carbon plasma, and stabilizing for 10 min;
3. and opening a substrate bias voltage during the film deposition, and using a positive bias voltage to realize electron irradiation so as to form carbon film deposition growth, wherein the positive bias voltage is 80V, and the growth time is 20 min.
The graphene carbon film obtained in example 1 was photographed by an electron microscope, and as shown in fig. 3, it can be seen from fig. 3 that a carbon film was grown on the surface of the silicon substrate. Further, Raman characterization was performed on the graphene carbon film prepared in example 1, and the result is shown in fig. 4, and it can be seen from fig. 4 that a graphene structure grows in the carbon film.
Example 2
1. Will be cleanedFixing clean silicon substrate on substrate holder, and feeding into high vacuum chamber via two-stage vacuum chamber with vacuum degree lower than 1 × 10 -4 After Pa, argon gas with the flow rate of 8sccm is introduced through the flow controller to increase the air pressure in the cavity to 6.6 multiplied by 10 -2 Pa; a magnetic coil current of 40/40/48A and a microwave of 470W are respectively applied to a left, middle and right magnetic coil as shown in FIG. 2, and gas is ionized under the coupling effect of a magnetic field and the microwave to generate high-density argon plasma; and leading the argon plasma out of the working cavity to form a focusing ECR plasma source; stabilizing for 10-20min, and performing the next step;
2. setting a negative bias voltage of 50V for the substrate bias voltage, opening a baffle between the plasma and the substrate, etching and cleaning the surface of the silicon substrate by using argon plasma, and carrying out ion cleaning for 3 minutes; introducing methane gas with the flow of 2sccm after cleaning, ionizing the methane gas under the activation action of the argon plasma to form carbon plasma, and stabilizing for 10 min;
3. and opening a substrate bias voltage during the film deposition, and using a positive bias voltage to realize electron irradiation so as to form carbon film deposition growth, wherein the positive bias voltage is 80V, and the growth time is 30 min.
The graphene carbon film obtained in example 2 was photographed by an electron microscope, and as a result, as shown in fig. 5, it can be seen from fig. 5 that a carbon film was grown on the surface of a silicon substrate, and the carbon film was thickened by increasing the deposition time. Further, Raman characterization was performed on the graphene carbon film obtained in example 2, and the result is shown in fig. 6, and it can be seen from fig. 6 that a graphene structure grows in the carbon film, and the size of the graphene structure in the carbon film increases.
Example 3
1. Fixing cleaned silicon substrate on substrate holder, and delivering into high vacuum chamber via two-stage vacuum chamber with vacuum degree lower than 1 × 10 -4 After Pa, argon gas with the flow rate of 6sccm is introduced through the flow controller to increase the air pressure in the cavity to 8 multiplied by 10 -2 Pa; applying 40/40/48A magnetic coil current and 450W microwave to the left, middle and right magnetic coils respectively as shown in FIG. 2, ionizing gas under the coupling action of magnetic field and microwave, and generating high density argon plasma; and adding argon or the likeLeading out the plasma into the working cavity to form a focusing ECR plasma source; stabilizing for 10-20min, and performing the next step;
2. setting a negative bias voltage of 50V for the substrate bias voltage, opening a baffle between the plasma and the substrate, etching and cleaning the surface of the silicon substrate by using argon plasma, and carrying out ion cleaning for 3 minutes; introducing methane gas with the flow of 3sccm after cleaning, ionizing the methane gas under the activation action of the argon plasma to form carbon plasma, and stabilizing for 10 min;
3. and opening substrate bias voltage during film deposition, using positive bias voltage to realize electron irradiation, forming a carbon film for deposition growth, and preparing the graphene carbon film, wherein the positive bias voltage is 80V, and the growth time is 20 min.
Example 4
1. Fixing cleaned silicon substrate on substrate holder, and delivering into high vacuum chamber via two-stage vacuum chamber with vacuum degree lower than 1 × 10 -4 After Pa, argon gas with a flow rate of 7sccm was introduced through the flow controller to raise the pressure in the chamber to 4X 10 -2 Pa; a magnetic coil current of 40/40/48A and a microwave of 400W are respectively applied to a left magnetic coil, a middle magnetic coil and a right magnetic coil which are shown in the figure 2, and gas is ionized under the coupling action of a magnetic field and the microwave to generate high-density argon plasma; and leading the argon plasma out of the working cavity to form a focusing ECR plasma source; stabilizing for 20min, and performing the next step;
2. setting a negative bias voltage of 50V for the substrate bias voltage, opening a baffle between the plasma and the substrate, etching and cleaning the surface of the silicon substrate by using argon plasma, and carrying out ion cleaning for 3 minutes; introducing methane gas with the flow of 1sccm after cleaning, ionizing the methane gas under the activation action of the argon plasma to form carbon plasma, and stabilizing for 10 min;
3. and opening substrate bias voltage during film deposition, using positive bias voltage to realize electron irradiation, forming a carbon film for deposition growth, and preparing the graphene carbon film, wherein the positive bias voltage is 60V, and the growth time is 30 min.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (3)
1. A method for preparing a graphene film by chemical vapor deposition electron irradiation is characterized by comprising the following steps:
fixing a substrate on a substrate frame, putting the substrate into a vacuum chamber, and vacuumizing the vacuum chamber;
when the vacuum degree in the vacuum chamber is lower than a preset threshold value, introducing argon into the vacuum chamber to increase the air pressure of the vacuum chamber to 2 x 10 -2 -1*10 -1 (ii) a The substrate is a silicon substrate, and the preset threshold value is 1 x 10 -4 Pa; the flow rate of the argon is 5-10 sccm;
ionizing the argon gas under the coupling action of a magnetic field and microwaves, and cleaning the substrate by adopting the generated argon plasma; the power of the microwave is 400-500W;
introducing carbon source gas into the vacuum chamber, and generating carbon plasma under the activation action of the argon plasma; the ratio of argon to carbon source gas is 8:1 or 8: 2; the flow rate of the carbon source gas is 1-3 sccm;
adjusting the substrate bias voltage to be a positive bias voltage, attracting electrons in the carbon plasma to the surface of the substrate for auxiliary growth to form electron irradiation, depositing the carbon plasma on the substrate, and generating the graphene carbon film; wherein the positive bias voltage is less than or equal to 100V;
the carbon source gas is one or more of methane, ethylene and acetylene.
2. The method for preparing graphene thin film by chemical vapor deposition electron irradiation according to claim 1, wherein in the step of introducing argon gas into the vacuum chamber, the pressure is 1 x 10 -2 -1*10 -1 Pa。
3. The method for preparing graphene film by chemical vapor deposition electron irradiation according to claim 1, further comprising the steps of, before fixing the substrate on the substrate holder:
and cleaning the substrate by using an acetone solution and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110928877.7A CN113637952B (en) | 2021-08-13 | 2021-08-13 | Method for preparing graphene film by chemical vapor deposition electron irradiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110928877.7A CN113637952B (en) | 2021-08-13 | 2021-08-13 | Method for preparing graphene film by chemical vapor deposition electron irradiation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113637952A CN113637952A (en) | 2021-11-12 |
| CN113637952B true CN113637952B (en) | 2022-08-30 |
Family
ID=78421617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110928877.7A Active CN113637952B (en) | 2021-08-13 | 2021-08-13 | Method for preparing graphene film by chemical vapor deposition electron irradiation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113637952B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890409B (en) * | 2022-04-21 | 2024-03-12 | 深圳大学 | Preparation method of patterned graphene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003096555A (en) * | 2001-09-21 | 2003-04-03 | Ntt Afty Corp | Method for forming carbon nano-cluster film |
| TWI458678B (en) * | 2011-12-30 | 2014-11-01 | Ind Tech Res Inst | Method of preparing graphene layers |
| KR20160086186A (en) * | 2015-01-09 | 2016-07-19 | 이윤택 | Manufacturing method of substrate graphene growth without using metal catalyst and substrate graphene growth without using metal catalyst |
| CN105624624B (en) * | 2016-02-25 | 2018-02-13 | 深圳大学 | A kind of ecr plasma sputter equipment and its sputtering method |
| CN112794316A (en) * | 2020-12-30 | 2021-05-14 | 浙江大学杭州国际科创中心 | Device and method for continuously preparing vertically-oriented graphene on large scale by using plasma |
-
2021
- 2021-08-13 CN CN202110928877.7A patent/CN113637952B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113637952A (en) | 2021-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106663609B (en) | High-power pulse magnetron sputtering process for realizing high-density high-SP 3 content layer | |
| CN101506095B (en) | Apparatus and method for manufacturing carbon structure | |
| EP2573047B1 (en) | Method for producing onion-like carbon | |
| JP4963539B2 (en) | Method for producing carbon nanotube and plasma CVD apparatus for carrying out the method | |
| JP4601954B2 (en) | Method for manufacturing a coated substrate | |
| CN108677144B (en) | Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film | |
| CN113637952B (en) | Method for preparing graphene film by chemical vapor deposition electron irradiation | |
| JP5089898B2 (en) | Carbon nanotube growth method | |
| JP2001048512A (en) | Preparation of perpendicularly oriented carbon nanotube | |
| JP2007186363A (en) | Method and apparatus for producing carbon nanotube | |
| JP4963584B2 (en) | Plasma CVD apparatus and plasma CVD method | |
| CN114134566B (en) | Method for improving heterogeneous epitaxial nucleation uniformity of diamond | |
| JP2004519108A (en) | Member manufacturing method and vacuum processing system | |
| JP5213099B2 (en) | Carbon nanotube growth method and carbon nanotube emitter on carbon fiber sheet | |
| JP4802321B2 (en) | Carbon nanotube growth method | |
| CN111593318A (en) | Diamond nanocrystalline/nitrogen-doped silicon carbide interface phase n-type semiconductor composite film and preparation method thereof | |
| JP2005340222A (en) | Current stabilizing method of field emission element, and manufacturing method of field emission element | |
| CN114921753B (en) | Carbon film deposition method based on mixed irradiation and carbon film | |
| WO2017183313A1 (en) | Gas supply device, film formation device, gas supply method, production method for carbon film, and manufacturing method for magnetic recording medium | |
| WO2021090793A1 (en) | Film forming apparatus and film forming method for dlc film | |
| US11773484B2 (en) | Hard mask deposition using direct current superimposed radio frequency plasma | |
| CN113621947B (en) | Diamond film etching method, patterned diamond film and application thereof | |
| JP5140296B2 (en) | Remote plasma CVD apparatus and carbon nanotube production method using this apparatus | |
| KR20090014512A (en) | Manufacturing method of diamond like carbon films doped with the third elements | |
| Park et al. | Very smooth ultrananocrystalline diamond film growth by a novel pretreatment technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |