CN109133046B - Method for transferring graphene by utilizing fullerene - Google Patents
Method for transferring graphene by utilizing fullerene Download PDFInfo
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- CN109133046B CN109133046B CN201811207190.9A CN201811207190A CN109133046B CN 109133046 B CN109133046 B CN 109133046B CN 201811207190 A CN201811207190 A CN 201811207190A CN 109133046 B CN109133046 B CN 109133046B
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/182—Graphene
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Abstract
The invention discloses a method for transferring graphene by utilizing fullerene, which comprises the following steps: 1) attaching a fullerene film on graphene attached to a growth substrate to obtain a growth substrate-graphene-fullerene composite structure; 2) placing the growth substrate-graphene-fullerene composite structure in a growth substrate corrosive liquid, and removing the growth substrate; 3) cleaning to obtain a clean graphene-fullerene composite film, and placing the graphene-fullerene composite film on a target substrate to obtain a target substrate-graphene-fullerene composite; 4) and removing the fullerene layer in the target substrate-graphene-fullerene compound to obtain the graphene attached to the target substrate, and finishing the transfer. According to the invention, fullerene is used as a transfer layer, so that introduced organic pollution can be reduced during the transfer of the transfer layer, and the transfer of high-cleanliness graphene onto a target substrate is ensured, and particularly, a more complete suspended graphene film can be obtained during the transfer of the high-cleanliness graphene onto a substrate with through holes.
Description
Technical Field
The invention relates to a method for transferring graphene by utilizing fullerene, belonging to the technical field of graphene transfer.
Background
Graphene is a polymer made of carbon atoms in sp2The hybrid tracks constitute hexagonal honeycomb lattice two-dimensional carbon nanomaterials originally separated from graphite by micromechanical exfoliation. The material has excellent optical, electrical and mechanical properties, is the material with the fastest electron transfer speed under the known room temperature condition, and is also the thinnest and firmest film material, so the material has important application prospect in the fields of micro-processing, photoelectricity, biomedicine and the like.
At present, the preparation method of graphene mainly comprises methods such as mechanical stripping, graphene oxide reduction, SiC epitaxial growth, and Chemical Vapor Deposition (CVD). The existing CVD process is mature, the preparation of large-area high-quality graphene can be realized, and the growth thickness of the graphene and the size of a graphene sheet can be easily controlled. In the method, metal is generally selected as a growth substrate of graphene, such as copper foil, nickel foil, aluminum foil, alloy and the like, and graphene is attached to the surface.
After the preparation of the graphene on the metal sheet is completed by the CVD method, the prepared graphene sheet is transferred to other insulating substrates, and then subsequent processing is performed according to application requirements. Therefore, in order to realize efficient application of graphene in related fields, transfer of graphene becomes an essential link. The existing common transfer method is to attach a layer of polymethyl methacrylate film on the prepared graphene as a transfer layer, and then remove the metal matrix under the graphene and the polymethyl methacrylate transfer layer respectively by methods such as wet etching and the like. In the method, because the solution is soaked for many times, especially the organic reagent needs to be soaked for a long time when the polymethyl methacrylate transfer layer is removed, organic pollution is introduced on the surface of the graphene film, and the application effect of the graphene film in the fields of biology and the like is influenced.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for transferring graphene by utilizing fullerene, which adopts fullerene as a transfer layer, can reduce introduced organic pollution when the transfer layer is removed, and ensures that the graphene with high cleanliness is transferred to a target substrate, including a substrate with through holes, and has higher integrity.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a method for transferring graphene by utilizing fullerene comprises the following steps:
1) attaching a fullerene film on graphene attached to a growth substrate to obtain a growth substrate-graphene-fullerene composite structure;
2) placing the growth substrate-graphene-fullerene composite structure in a growth substrate corrosive liquid, and removing the growth substrate;
3) cleaning to obtain a clean graphene-fullerene composite film, and placing the graphene-fullerene composite film on a target substrate to obtain a target substrate-graphene-fullerene composite;
4) and removing the fullerene layer in the target substrate-graphene-fullerene compound to obtain the graphene attached to the target substrate, and finishing the transfer.
Preferably, the method comprises the following steps:
the growth substrate in the step 1) is one of copper, nickel, platinum, iron, cobalt or aluminum.
The method for attaching the fullerene film in the step 1) is a thermal evaporation method, a chemical vapor deposition method or a metal surface growth method.
The growth substrate corrosive liquid in the step 2) is nitric acid aqueous solution, hydrochloric acid aqueous solution, ferric trichloride aqueous solution, Kohler reagent or the mixed solution of the above corrosive solutions.
And 3) placing the graphene-fullerene composite film on a target substrate in deionized water or an organic solvent.
The target substrate in the step 4) is silicon nitride, glass or quartz glass.
The surface structure of the target substrate in the step 4) is a flat structure or a structure containing through holes or a structure containing grooves.
And 4) removing the fullerene layer by an evaporation method in the step 4).
Among them, the following matters need to be noted in the transfer process:
the whole transfer process should be kept in a cleaner environment.
When the growth substrate corrosive liquid is corroded, the temperature of the corrosion reaction can be 0-80 ℃, the reaction can be carried out more rapidly by properly heating the corrosive liquid, and the reaction time is determined according to the corrosion condition of the growth substrate and is generally 5-6 hours.
After the graphene-fullerene composite membrane is transferred to a target substrate, the target substrate can be naturally air-dried due to residual moisture or organic solvent on the surface of the target substrate, and can also be placed in an oven, wherein the preferred temperature is 60-80 ℃.
When fullerene is removed by dry evaporation, a reaction chamber needs to be firstly vacuumized, inert gas is filled into the reaction chamber to reduce the oxygen content in the chamber, and then the reaction chamber is vacuumized again, and protective gas can be selected from nitrogen and argon. During the heating process, preheating is needed for half an hour at 400 ℃, then the temperature is gradually increased by taking 100 ℃ as a gradient, and the temperature is kept for at least 15 minutes at each gradient. The maximum temperature does not exceed 1000 ℃. The whole temperature rising process should be carried out slowly to prevent the fullerene from being carbonized due to the excessively fast temperature rising.
Has the advantages that: compared with the prior art, the method provided by the invention has the advantages that the fullerene is used as the transfer layer, so that the introduced organic pollution can be reduced when the transfer layer is removed, the high-cleanliness graphene is transferred to a target substrate, and particularly, a suspended graphene film with higher cleanliness and more integrity can be obtained when the high-cleanliness graphene is transferred to a substrate with through holes.
Detailed Description
The process of the present invention is further illustrated below with reference to specific examples.
Example 1
In the embodiment, the transferred graphene grows on a copper foil growth substrate by using a chemical vapor deposition method, a fullerene transfer layer is prepared by using a thermal evaporation method, the fullerene transfer layer is removed by using an evaporation method under a dry condition, the thickness of the obtained graphene layer is 1-2 layers, the size of the growth substrate is 1 x 2cm, and the thickness of the growth substrate is 0.05 mm.
And placing the copper foil in chemical vapor deposition equipment to grow the graphene. And then placing the copper foil-graphene compound in a vacuum coating machine, heating to 500 ℃, and thermally evaporating the fullerene film with the thickness of 50 nm. And suspending the obtained copper foil-graphene-fullerene composite film on the surface of an etching solution, wherein the etching solution is a ferric chloride solution with the mass fraction of 20%, heating the solution to 65 ℃ and keeping the temperature for 5 hours, and completely etching the copper foil. And diluting the corrosive liquid with deionized water for many times to obtain the graphene-fullerene composite film.
The graphene-fullerene film is lightly fished up by taking a silicon wafer with a 200nm thick silicon nitride film as a target substrate and is dried by an oven, and the heating temperature is set to be 60 ℃. The target substrate contained 49 through holes of 20nm diameter. And after the target substrate-graphene-fullerene composite structure is completely dried, placing the target substrate-graphene-fullerene composite structure in a vacuum coating machine again, roughly vacuumizing the target substrate-graphene-fullerene composite structure once by using a mechanical pump, and then introducing inert gas. Gradually heating the chamber, keeping the temperature at 600 ℃ for half an hour, performing temperature rise treatment on the sample by taking 50 ℃ as a gradient, and finishing heating when the temperature rises to 800 ℃. The heating process is terminated after about two hours, and the fullerene layer for transfer is removed, resulting in a clean graphene thin film attached to the target substrate.
Example 2
In the embodiment, the transferred graphene grows on an aluminum foil growth substrate by using a chemical vapor deposition method, a fullerene transfer layer is prepared by using the chemical vapor deposition method, the graphene transfer layer is removed by using an evaporation method in a dry method, the thickness of the obtained graphene layer is 1-2 layers, the size of the growth substrate is 1 x 2cm, and the thickness of the growth substrate is 0.05 mm.
And placing the aluminum foil in chemical vapor deposition equipment to grow graphene. And then, the aluminum foil-graphene composite is placed in the chemical vapor deposition equipment again, and the fullerene thin film with the thickness of 100nm is grown. And (3) dipping the other side of the aluminum foil with absorbent cotton, taking a small amount of dilute hydrochloric acid, repeatedly wiping, and suspending the obtained aluminum foil-graphene-fullerene composite membrane on the surface of the corrosive solution. The corrosion solution is a Kohler reagent and has the following formula: 190ml of distilled water, 5ml of nitric acid, 3ml of hydrochloric acid and 2ml of hydrofluoric acid. And keeping the composite film and the corrosive liquid for 5 hours, and completely corroding the aluminum foil. And diluting the corrosive liquid with acetone for many times to obtain the graphene-fullerene composite film.
And lightly taking out the graphene-fullerene film by using a flat quartz glass sheet with the thickness of 400 mu m as a target substrate, and drying the graphene-fullerene film by using an oven, wherein the heating temperature is set to be 60 ℃. And after the target substrate-graphene-fullerene composite structure is completely dried, placing the target substrate-graphene-fullerene composite structure in a vacuum coating machine again, roughly vacuumizing the target substrate-graphene-fullerene composite structure once by using a mechanical pump, and then introducing inert gas. Gradually heating the chamber, keeping the temperature at 600 ℃ for half an hour, performing temperature rise treatment on the sample by taking 50 ℃ as a gradient, and finishing heating when the temperature rises to 800 ℃. The heating process is terminated after about two hours, and the fullerene layer for transfer is removed, resulting in a clean graphene thin film attached to the target substrate.
Example 3
In the embodiment, the transferred graphene grows on a nickel foil growth substrate by using a chemical vapor deposition method, a fullerene transfer layer is prepared by using the chemical vapor deposition method, the graphene transfer layer is removed by using an evaporation method in a dry method, the thickness of the obtained graphene layer is 1-2 layers, the size of the growth substrate is 1 × 2cm, and the thickness of the growth substrate is 0.05 mm.
And placing the aluminum foil in chemical vapor deposition equipment to grow graphene. And then, the nickel foil-graphene composite is placed in the chemical vapor deposition equipment again, and the fullerene thin film with the thickness of 100nm is grown. And suspending the obtained nickel foil-graphene-fullerene composite membrane on the surface of the corrosive solution. The corrosion solution comprises 5% of ferric trichloride, 10% of acetic acid, 4% of hydrogen peroxide and the balance of deionized water. Keeping the composite film and the corrosive liquid for 10 hours, and completely corroding the nickel foil. And diluting the corrosive liquid with deionized water for many times to obtain the graphene-fullerene composite film.
The graphene-fullerene thin film was gently scooped up with a 400 μm thick glass plate as a target substrate and dried in an oven with the heating temperature set at 60 ℃. And after the target substrate-graphene-fullerene composite structure is completely dried, placing the target substrate-graphene-fullerene composite structure in a vacuum coating machine again, roughly vacuumizing the target substrate-graphene-fullerene composite structure once by using a mechanical pump, and then introducing inert gas. Gradually heating the chamber, keeping the temperature at 600 ℃ for half an hour, performing temperature rise treatment on the sample by taking 50 ℃ as a gradient, and finishing heating when the temperature rises to 800 ℃. The heating process is terminated after about two hours, and the fullerene layer for transfer is removed, resulting in a clean graphene thin film attached to the target substrate.
Example 4
In the embodiment, the transferred graphene grows on an aluminum foil growth substrate by using a chemical vapor deposition method, a fullerene transfer layer is prepared by using a metal surface growth method, the fullerene transfer layer is removed by using an evaporation method in a dry method, the thickness of the obtained graphene layer is 1-2 layers, the size of the growth substrate is 1 x 2cm, and the thickness of the growth substrate is 0.05 mm.
And placing the aluminum foil in chemical vapor deposition equipment to grow graphene. And placing the fullerene-metal composite growing on the metal surface on the graphene surface. And removing the metal layer on the fullerene by using a metal etching solution to obtain the fullerene-graphene-aluminum foil composite structure. And (3) dipping the other side of the aluminum foil with absorbent cotton, taking a small amount of dilute hydrochloric acid, repeatedly wiping, and suspending the obtained aluminum foil-graphene-fullerene composite membrane on the surface of the corrosive solution. The corrosion solution is a Kohler reagent and has the following formula: 190ml of distilled water, 5ml of nitric acid, 3ml of hydrochloric acid and 2ml of hydrofluoric acid. And keeping the composite film and the corrosive liquid for 5 hours, and completely corroding the aluminum foil. And diluting the corrosive liquid with acetone for many times to obtain the graphene-fullerene composite film.
And lightly taking out the graphene-fullerene film by using a silicon wafer with a 50nm silicon dioxide film as a target substrate, and drying the graphene-fullerene film by using an oven, wherein the heating temperature is set to be 60 ℃. And after the target substrate-graphene-fullerene composite structure is completely dried, placing the target substrate-graphene-fullerene composite structure in a vacuum coating machine again, roughly vacuumizing the target substrate-graphene-fullerene composite structure once by using a mechanical pump, and then introducing inert gas. Gradually heating the chamber, keeping the temperature at 600 ℃ for half an hour, performing temperature rise treatment on the sample by taking 50 ℃ as a gradient, and finishing heating when the temperature rises to 800 ℃. The heating process is terminated after about two hours, and the fullerene layer for transfer is removed, resulting in a clean graphene thin film attached to the target substrate.
Claims (7)
1. A method for transferring graphene by utilizing fullerene is characterized by comprising the following steps:
1) attaching a fullerene film on graphene attached to a growth substrate to obtain a growth substrate-graphene-fullerene composite structure;
2) placing the growth substrate-graphene-fullerene composite structure in a growth substrate corrosive liquid, and removing the growth substrate;
3) cleaning to obtain a clean graphene-fullerene composite film, and placing the graphene-fullerene composite film on a target substrate to obtain a target substrate-graphene-fullerene composite;
4) removing the fullerene layer in the target substrate-graphene-fullerene compound to obtain graphene attached to the target substrate, and finishing the transfer;
and 4) removing the fullerene layer by an evaporation method in the step 4).
2. The method for transferring graphene by using fullerene according to claim 1, wherein the growth substrate in step 1) is one of copper, nickel, platinum, iron, cobalt or aluminum.
3. The method for transferring graphene using fullerene according to claim 1, wherein the method for attaching the fullerene thin film in step 1) is a thermal evaporation method, a chemical vapor deposition method or a metal surface growth method.
4. The method of claim 1, wherein the etching solution for the growth substrate in step 2) is nitric acid aqueous solution, hydrochloric acid aqueous solution, ferric chloride aqueous solution, kohler's reagent or a mixture thereof.
5. The method for transferring graphene by using fullerene according to claim 1, wherein the step 3) is performed in deionized water or in an organic solvent while the graphene-fullerene composite thin film is placed on the target substrate.
6. The method for transferring graphene by using fullerene according to claim 1, wherein the target substrate in step 4) is silicon nitride, glass or quartz glass.
7. The method for transferring graphene by using fullerene according to claim 1, wherein the surface structure of the target substrate in step 4) is a flat structure or a structure containing through holes or a structure containing grooves.
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| US20130025662A1 (en) * | 2011-07-25 | 2013-01-31 | International Business Machines Corporation | Water Soluble Dopant for Carbon Films |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102315058A (en) * | 2010-07-07 | 2012-01-11 | 清华大学 | Transmission electron microscope microgrid and preparation method thereof |
| CN102897750A (en) * | 2011-07-29 | 2013-01-30 | 浙江大学 | PrPrearation method for graphene film |
| CN102795619A (en) * | 2012-09-04 | 2012-11-28 | 南开大学 | Graphene thin film transferring method based on physical adsorption |
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