CN115571872B - Method for removing PMMA layer on graphene surface based on non-solvent system - Google Patents
Method for removing PMMA layer on graphene surface based on non-solvent system Download PDFInfo
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Abstract
The invention discloses a method for removing a PMMA layer on a graphene surface based on a non-solvent system, which belongs to the technical field of graphene transfer and comprises the following steps: placing the PMMA/graphene/inorganic nonmetallic substrate in a closed system containing a non-inorganic salt solid desiccant, and standing; placing the dried PMMA/graphene/inorganic nonmetallic substrate in sodium ethoxide-ethanol solution with a water absorbent for standing; and taking out and clamping the PMMA/graphene/inorganic nonmetallic substrate from the solution, placing the PMMA/graphene/inorganic nonmetallic substrate in absolute ethyl alcohol, and drying the solution after ultrasonic cleaning to obtain the graphene film loaded on the inorganic nonmetallic substrate. According to the method, good solvents or soluble solvents of PMMA are not introduced, and the PMMA layer can be effectively removed after graphene is transferred.
Description
Technical Field
The invention belongs to the technical field of graphene transfer, and particularly relates to a method for removing a PMMA layer on a graphene surface based on a non-solvent system.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The wet transfer technology is a common and widely used transfer method of graphene, and mainly comprises the steps of coating the surface of the graphene with a polymer in a spin mode, supporting the graphene film to carry out etching dissolution of the substrate and carrying out new substrate loading. For the newly constituted PMMA/graphene/inorganic nonmetallic substrate, a good solvent for PMMA such as acetone is generally used for dissolution to achieve a method of eliminating the auxiliary polymer support layer. However, due to the high solubility of good solvents such as acetone or anisole, PMMA is easily deposited on the surface of graphene at random with volatilization of the solvent once entering a solvent system coating the whole substrate, and is finally difficult to be thoroughly removed.
Therefore, it is necessary to develop a method for removing the PMMA layer on the surface of graphene based on a non-solvent system, which avoids the introduction of a good solvent or a soluble solvent of PMMA, so that the PMMA layer cannot be precipitated and deposited on the surface of graphene again due to dissolution, but at the same time, the PMMA layer can be eliminated to obtain clean graphene, thereby avoiding a series of problems that are difficult to thoroughly eliminate due to PMMA dissolution.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method for removing a PMMA layer on the surface of graphene based on a non-solvent system, and the method can realize the elimination of PMMA after the graphene is transferred without introducing a good solvent or a soluble solvent of PMMA.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in one aspect, a method for removing a PMMA layer on a graphene surface based on a non-solvent system comprises the following steps:
(1) Placing the PMMA/graphene/inorganic nonmetallic substrate in a closed system containing a non-inorganic salt solid desiccant, and standing;
(2) Placing the dried PMMA/graphene/inorganic nonmetallic substrate in sodium ethoxide-ethanol solution with a water absorbent for standing;
(3) And taking out and clamping the PMMA/graphene/inorganic nonmetallic substrate from the solution, and carrying out ultrasonic cleaning in absolute ethyl alcohol and drying to obtain the graphene film loaded on the inorganic nonmetallic substrate.
The beneficial effects of the invention are as follows:
the method for eliminating the PMMA layer is carried out based on a good solvent or a soluble solvent which does not introduce PMMA, and utilizes the strong alkalinity of ethoxy in sodium ethoxide to carry out a series of chemical reactions including electron-deficient reaction sites which attack carbonyl groups and the like, so that the PMMA film is subjected to macroscopic shrinkage, and the effect of releasing graphene is achieved. In addition, the whole reaction system uses absolute ethyl alcohol as a solvent, on one hand, the absolute ethyl alcohol is an active solvent of sodium ethoxide, so that the sodium ethoxide can be dissolved and ethoxy is continuously provided to keep the activity of the sodium ethoxide, and meanwhile, the inactivation of the sodium ethoxide caused by the introduction of water (steam) is avoided; on the other hand, the solvent is a non-solvent of PMMA (a non-solvent system of PMMA formed by the solvent and sodium ethoxide), and the solvent cannot dissolve the PMMA and is equivalent to being separated from the reaction system, so that the PMMA is prevented from entering the reaction system in a solute form, and the subsequent solvent is volatilized to cause wide residue similar to acetone treatment. The method can realize stripping of the PMMA film from the surface of the graphene on the basis of insoluble PMMA, the PMMA film is suspended or dispersed in absolute ethyl alcohol, and the whole elimination process can be finished by continuously replacing pure absolute ethyl alcohol and carrying out ultrasonic flushing, so that the method is simple and convenient to operate, the flow is rapid and feasible, and a new direction is widened for a graphene transfer method.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic flow chart of a method for removing a PMMA layer on a graphene surface based on a non-solvent system;
FIG. 2 is an optical microscope image of PMMA/graphene/inorganic nonmetallic substrate after drying in example 1 of the present invention;
FIG. 3 is an optical microscope image of a PMMA/graphene/inorganic nonmetallic substrate of example 1 of the present invention after it has been placed in a sodium ethoxide-ethanol solution with solid particles of sodium carbonate;
FIG. 4 is an optical microscope image of PMMA/graphene/inorganic nonmetallic substrate of example 1 of the present invention after being subjected to ethanol ultrasound;
fig. 5 is a micrometer-scale optical microscope image of graphene after PMMA removal in the comparative example.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In view of the technical problem that in the current graphene transfer, PMMA is dissolved in a good solvent and is redeposited on the surface of graphene along with solvent volatilization, so that the problem of difficulty in thorough removal is solved.
The invention provides a method for removing a PMMA layer on a graphene surface based on a non-solvent system, which comprises the following steps:
(1) Placing the PMMA/graphene/inorganic nonmetallic substrate in a closed system containing a non-inorganic salt solid desiccant, and standing;
(2) Placing the dried PMMA/graphene/inorganic nonmetallic substrate in sodium ethoxide-ethanol solution with a water absorbent for standing;
(3) And taking out and clamping the PMMA/graphene/inorganic nonmetallic substrate from the solution, and carrying out ultrasonic cleaning in absolute ethyl alcohol and drying to obtain the graphene film loaded on the inorganic nonmetallic substrate.
According to the invention, a series of chemical reactions including electron-deficient reaction sites which attack carbonyl groups and the like are carried out by utilizing the strong basicity of ethoxy in sodium ethoxide, so that the PMMA film is subjected to macroscopic shrinkage, and the effect of releasing graphene is achieved. In addition, the whole reaction system uses absolute ethyl alcohol as a solvent, on one hand, the absolute ethyl alcohol is an active solvent of sodium ethoxide, so that the sodium ethoxide can be dissolved and ethoxy is continuously provided to keep the activity of the sodium ethoxide, and meanwhile, the inactivation of the sodium ethoxide caused by the introduction of water (steam) is avoided; on the other hand, the solvent is a non-solvent of PMMA (a non-solvent system of PMMA formed by the solvent and sodium ethoxide), and the solvent cannot dissolve the PMMA and is equivalent to being separated from the reaction system, so that the PMMA is prevented from entering the reaction system in a solute form, and the subsequent solvent is volatilized to cause wide residue similar to acetone treatment. The invention realizes the stripping of the PMMA film from the surface of the graphene on the basis of insoluble PMMA, and the PMMA film is suspended or dispersed in absolute ethyl alcohol, and the whole elimination process can be completed by continuously replacing pure absolute ethyl alcohol and carrying out ultrasonic flushing.
In some examples of this embodiment, in (1), the preparation method of PMMA/graphene/inorganic nonmetallic substrate is: cutting and fixing metal-based graphene grown by a chemical vapor deposition method, spin-coating PMMA, and thermally curing to obtain a PMMA/graphene/metal substrate; placing PMMA/graphene/metal substrate in etching liquid to etch away the metal substrate, and taking out; and cleaning the PMMA/graphene film and transferring the PMMA/graphene film to an inorganic nonmetallic substrate to obtain the PMMA/graphene film.
Wherein the PMMA comprises a liquid PMMA solution and PMMA solution which is prepared according to any mass fraction.
In some examples of this embodiment, in (1), the inorganic nonmetallic substrate is an inorganic nonmetallic substrate that does not chemically react with sodium ethoxide and ethanol; preferred include, but are not limited to, si/SiO 2 Quartz.
Wherein the sodium ethoxide comprises liquid sodium ethoxide solution and sodium ethoxide-ethanol solution prepared according to any mass fraction.
In some examples of this embodiment, in (1), the non-inorganic salt solid state desiccant includes, but is not limited to, a color changing silica gel desiccant, a coarse pore silica gel desiccant, a fine pore silica gel desiccant, a type C silica gel desiccant. According to the invention, the PMMA/graphene/inorganic nonmetallic substrate is dried by adopting a drying agent, so that the phenomenon that sodium ethoxide is inactivated due to the fact that moisture is introduced when the PMMA/graphene/inorganic nonmetallic substrate is placed in a sodium ethoxide-ethanol solution is avoided.
In some examples of this embodiment, in (1), the standing time is 0.5 hours or more.
In some examples of this embodiment, in (2), the water absorbing agent includes, but is not limited to, sodium carbonate, sodium bicarbonate, calcium chloride, magnesium sulfate, sodium sulfate, copper sulfate. According to the invention, the water absorbing agent absorbs water to construct an anhydrous environment, so that the inactivation of sodium ethoxide caused by the introduction of water is further avoided.
Wherein the sodium carbonate is non-hydrated crystalline sodium carbonate powder or granules.
Alternatively, the sodium bicarbonate is a non-hydrated crystalline sodium bicarbonate powder or granule.
In some examples of this embodiment, (2) the sodium ethoxide mass fraction in the sodium ethoxide-ethanol solution is 1% to 21%, preferably 1% to 5%.
Wherein the sodium ethoxide comprises liquid sodium ethoxide solution and sodium ethoxide-ethanol solution prepared according to any mass fraction.
In some examples of this embodiment, in (2), the standing time is 0.5 hours or longer.
In some examples of this embodiment, (3), the ultrasonic cleaning is performed in the following manner: the PMMA/graphene/inorganic nonmetallic substrate is completely covered by absolute ethyl alcohol, the clamping tool and the PMMA/graphene/inorganic nonmetallic substrate are not contacted with a container which is subjected to high-frequency vibration after being opened by ultrasonic, and after ultrasonic cleaning is carried out for a period of time, the operation is repeated for 2-3 times again by replacing the absolute ethyl alcohol.
Wherein the period of time is more than or equal to 2s.
In some examples of this embodiment, in (3), blow-drying is specifically: drying the substrate along the direction parallel to the substrate surface by using unheated inert gas.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating a liquid PMMA solution by using an instrument such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 The substrate is placed in a closed state containing a color-changing silica gel desiccantStanding in the system for 2 hours;
(2) Drying PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 2% of non-hydrated crystalline sodium carbonate powder for standing for 2 hours;
(3) Taking out and clamping the PMMA/graphene/Si/SiO 2 substrate, wherein the clamping tool is not contacted with the high-frequency vibration container containing absolute ethyl alcohol after ultrasonic opening of the PMMA/graphene/Si/SiO 2 substrate, and the PMMA/graphene/Si/SiO is not contacted with the PMMA/graphene/Si/SiO 2 substrate 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 2s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Example 2
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating a liquid PMMA solution by using an instrument such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in ammonium persulfate etching solution to etch the copper substrate, and then fishing with quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 2 hours;
(2) Drying PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 2% of non-hydrated crystalline sodium carbonate powder for standing for 2 hours;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, and is placed in the absolute ethyl alcohol to be ultrasonically cleaned for 2s, and the absolute ethyl alcohol is replacedAlcohol and repeating the operation twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Example 3
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating PMMA-acetone solution with the mass fraction of 4% by using instruments such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 2 hours;
(2) PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 2% of non-hydrated crystalline sodium carbonate powder for standing for 2 hours;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 2s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Example 4
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method,spin-coating the liquid PMMA solution by using an instrument such as a spin coater and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 1 hour;
(2) PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 2% of non-hydrated crystalline sodium carbonate powder for standing for 2 hours;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 2s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Example 5
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating a liquid PMMA solution by using an instrument such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 2 hours;
(2) PMMA/graphene/Si/SiO 2 The substrate was placed in 3% ethanol by mass with non-hydrated crystalline sodium carbonate powderStanding the sodium-ethanol solution for 1.5 hours;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 2s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Example 6
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating a liquid PMMA solution by using an instrument such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 2 hours;
(2) PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 1.5% of non-hydrated crystalline sodium carbonate powder for standing for 3 hours;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 2s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate was removed from the absolute ethanol and nitrogen at ambient temperature was used to align the substrate with the substrateBlow-drying to obtain Si/SiO-loaded material 2 A graphene film over a substrate.
Example 7
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating a liquid PMMA solution by using an instrument such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 2 hours;
(2) PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 4% of non-hydrated crystalline sodium carbonate powder for standing for 1 hour;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 2s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Example 8
The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system comprises the following specific steps:
(1) Cutting and fixing copper-based graphene grown by a chemical vapor deposition method, spin-coating a liquid PMMA solution by using an instrument such as a spin coater, and finally performing heat curing treatment; placing PMMA/graphene/copper substrate in acidified ferric chloride etching solution to etch the copper substrate, and then fishing out the copper substrate by using quartz plates and the like; multiple timesCleaning PMMA/graphene film with deionized water and transferring to Si/SiO 2 A substrate; the PMMA/graphene/Si/SiO after the transfer is carried out 2 Placing the substrate in a closed system containing a color-changing silica gel drying agent, and standing for 2 hours;
(2) PMMA/graphene/Si/SiO 2 Placing the substrate in a sodium ethoxide-ethanol solution with a mass fraction of 2% of non-hydrated crystalline sodium carbonate powder for standing for 2 hours;
(3) PMMA/graphene/Si/SiO 2 Substrate removal and clamping, clamping tool and PMMA/graphene/Si/SiO 2 The substrate is not contacted with a container containing absolute ethyl alcohol, PMMA/graphene/Si/SiO, which is subjected to high-frequency vibration after ultrasonic opening 2 The substrate is completely covered by absolute ethyl alcohol, the substrate is placed in the absolute ethyl alcohol for ultrasonic cleaning for 5s, the absolute ethyl alcohol is replaced, and the operation is repeated twice again;
(4) Clamping graphene/Si/SiO 2 The substrate leaves absolute ethyl alcohol and is dried by using normal temperature nitrogen along the direction parallel to the surface of the substrate, thus obtaining the Si/SiO load 2 A graphene film over a substrate.
Comparative example
(1) Cutting and fixing metal-based graphene grown by a chemical vapor deposition method, spin-coating PMMA (polymethyl methacrylate) by using an instrument such as a spin coater, and finally performing heat curing treatment; placing the PMMA/graphene/metal substrate coated with the PMMA/graphene/metal substrate in etching liquid such as acidified ferric chloride and the like to etch a metal surface, and then fishing out the metal surface by using a quartz plate; multiple washes of PMMA/graphene film with deionized water and transfer to Si/SiO 2 A substrate;
(2) Soaking PMMA/graphene/Si/SiO with good solvent or soluble agent of PMMA such as acetone 2 A substrate for a period of time;
(3) Taking out the substrate, and drying or baking to obtain a graphene film loaded on the inorganic nonmetallic substrate, wherein PMMA impurities remain in the graphene film;
as can be seen from comparison of fig. 4 and 5, the method of dissolution using PMMA good solvent or soluble solvent in the comparative example causes the general PMMA residues to be randomly deposited on the surface of graphene, which causes a number of adverse effects including electrical properties of graphene. The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system in the embodiment 1 can fundamentally avoid the problem of PMMA dissolution-residue, thereby obtaining a clean graphene film loaded on an inorganic non-metal substrate.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. The method for removing the PMMA layer on the surface of the graphene based on the non-solvent system is characterized by comprising the following steps of:
(1) Placing the PMMA/graphene/inorganic nonmetallic substrate in a closed system containing a non-inorganic salt solid desiccant, and standing;
(2) Placing the dried PMMA/graphene/inorganic nonmetallic substrate in sodium ethoxide-ethanol solution with a water absorbent for standing;
(3) And taking out and clamping the PMMA/graphene/inorganic nonmetallic substrate from the solution, and carrying out ultrasonic cleaning in absolute ethyl alcohol and drying to obtain the graphene film loaded on the inorganic nonmetallic substrate.
2. The method for removing a PMMA layer on a graphene surface based on a non-solvent system according to claim 1, wherein in (1), the preparation method of the PMMA/graphene/inorganic non-metal substrate is as follows: cutting and fixing metal-based graphene grown by a chemical vapor deposition method, spin-coating PMMA, and thermally curing to obtain a PMMA/graphene/metal substrate; placing PMMA/graphene/metal substrate in etching liquid to etch away the metal substrate, and taking out; and cleaning the PMMA/graphene film and transferring the PMMA/graphene film to an inorganic nonmetallic substrate to obtain the PMMA/graphene film.
3. The method for removing a graphene surface PMMA layer based on a non-solvent system according to claim 2, wherein the PMMA comprises a liquid PMMA solution and a PMMA solution configured in an arbitrary mass fraction.
4. The method for removing PMMA layers on a graphene surface of claim 1, wherein in (1), the inorganic nonmetallic substrate is an inorganic nonmetallic substrate that does not chemically react with sodium ethoxide and ethanol.
5. The method for removing a graphene surface PMMA layer based on a non-solvent system of claim 4, wherein the inorganic non-metallic substrate comprises Si/SiO 2 Or quartz.
6. The method for removing a PMMA layer from a graphene surface of claim 4, wherein the sodium ethoxide comprises a liquid sodium ethoxide solution and a sodium ethoxide-ethanol solution configured in any mass fraction.
7. The method of claim 1, wherein (1) the non-inorganic salt solid desiccant comprises a color changing silica gel desiccant, a coarse pore silica gel desiccant, a fine pore silica gel desiccant, or a C-type silica gel desiccant.
8. The method for removing PMMA layer on a graphene surface according to claim 1, wherein in (1), the standing time is 0.5 hour or more.
9. The method for removing PMMA layer of a graphene surface based on a non-solvent system of claim 1, wherein in (2), the water absorbing agent comprises sodium carbonate, sodium bicarbonate, calcium chloride, magnesium sulfate, sodium sulfate or copper sulfate.
10. The method of removing a graphene surface PMMA layer based on a non-solvent system of claim 9, wherein the sodium carbonate is a non-hydrated crystalline sodium carbonate powder or particle;
or, the sodium bicarbonate is non-hydrated crystalline sodium bicarbonate powder or particles.
11. The method for removing a PMMA layer from a graphene surface of claim 1, wherein in (2), the mass fraction of sodium ethoxide in the sodium ethoxide-ethanol solution is 1% to 21%.
12. The method for removing a PMMA layer from a graphene surface of claim 11, wherein in (2), the mass fraction of sodium ethoxide in the sodium ethoxide-ethanol solution is 1% to 5%.
13. The method for removing PMMA layer on a graphene surface according to claim 1, wherein in (2), the standing time is 0.5 hour or more.
14. The method for removing PMMA layer on graphene surface based on non-solvent system according to claim 1, wherein in (3), the ultrasonic cleaning is performed in the following manner: the PMMA/graphene/inorganic nonmetallic substrate is completely covered by absolute ethyl alcohol, the clamping tool and the PMMA/graphene/inorganic nonmetallic substrate are not contacted with a container which is subjected to high-frequency vibration after being opened by ultrasonic, and after ultrasonic cleaning is carried out for a period of time, the operation is repeated for 2-3 times again by replacing the absolute ethyl alcohol.
15. The method for removing a PMMA layer on a graphene surface according to claim 14, wherein the period of time is greater than or equal to 2s.
16. The method for removing PMMA layer on graphene surface based on non-solvent system according to claim 1, wherein in (3), the blow-drying is specifically: drying the substrate along the direction parallel to the substrate surface by using unheated inert gas.
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| CN102351175A (en) * | 2011-11-03 | 2012-02-15 | 东南大学 | High-quality transfer method of graphene prepared by chemical vapor deposition method |
| CN102682918A (en) * | 2011-03-17 | 2012-09-19 | 铼钻科技股份有限公司 | Method for manufacturing transparent electrode |
| CN102719803A (en) * | 2012-07-09 | 2012-10-10 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing and transferring graphene transparent film |
| CN103588199A (en) * | 2013-11-21 | 2014-02-19 | 上海理工大学 | Method for preparing graphene membrane material through in-site metal catalytic decomposition and transfer |
| CN109641188A (en) * | 2016-06-28 | 2019-04-16 | 纳米技术有限公司 | The Van der Waals heterojunction structure equipment for forming 2D thin slice by the prefabricated nanoparticle of chemical cleavage and being prepared using same procedure |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102682918A (en) * | 2011-03-17 | 2012-09-19 | 铼钻科技股份有限公司 | Method for manufacturing transparent electrode |
| CN102351175A (en) * | 2011-11-03 | 2012-02-15 | 东南大学 | High-quality transfer method of graphene prepared by chemical vapor deposition method |
| CN102719803A (en) * | 2012-07-09 | 2012-10-10 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing and transferring graphene transparent film |
| CN103588199A (en) * | 2013-11-21 | 2014-02-19 | 上海理工大学 | Method for preparing graphene membrane material through in-site metal catalytic decomposition and transfer |
| CN109641188A (en) * | 2016-06-28 | 2019-04-16 | 纳米技术有限公司 | The Van der Waals heterojunction structure equipment for forming 2D thin slice by the prefabricated nanoparticle of chemical cleavage and being prepared using same procedure |
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