CN114655944A - Graphene/carbon nanotube composite film and preparation method thereof - Google Patents
Graphene/carbon nanotube composite film and preparation method thereof Download PDFInfo
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- CN114655944A CN114655944A CN202210214468.5A CN202210214468A CN114655944A CN 114655944 A CN114655944 A CN 114655944A CN 202210214468 A CN202210214468 A CN 202210214468A CN 114655944 A CN114655944 A CN 114655944A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/24—Thermal properties
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
Abstract
The embodiment of the invention discloses a graphene/carbon nanotube composite film and a preparation method thereof, belonging to the technical field of carbon nanomaterials. A preparation method of a graphene/carbon nanotube composite film comprises the following steps: and (3) constructing a Ti/Co array on the surface of the copper foil with the graphene, growing the carbon nano tube in situ, and etching to remove the copper foil to obtain the graphene/carbon nano tube composite film. The method can effectively solve the problem that the bonding force of the graphene and the carbon nano tube is weak, and the composite film with the tightly bonded graphene and the carbon nano tube is prepared and has excellent electric conduction and heat conduction performance.
Description
Technical Field
The embodiment of the invention relates to the technical field of carbon nano materials, in particular to a graphene/carbon nano tube composite film and a preparation method thereof.
Background
The graphene single-layer or few-layer graphene prepared by the chemical vapor deposition method has excellent light transmission and electrical properties, but has large surface resistance, and is easy to cause film breakage in the separation and transfer process, so that the conductivity and the strength of the graphene are reduced. As a family material, the carbon nanotube has high electron mobility along the axial direction, has excellent properties such as large specific surface area, high tensile strength and elastic modulus, is often used as a first choice for a transparent conductive and heat-conducting film and an electrode material, but has structural defects such as diameter and chirality; introducing impurities in the preparation process; the combination mode among the carbon nano tubes and the like have great influence on the electric conduction and heat conduction performance of the film prepared from the carbon nano tubes. The gaps of the carbon nanotube bundles increase the light transmittance of the carbon nanotube film, but also weaken the conduction of electrons and phonons (lattice vibration) among the bundles, thereby reducing the electric and heat conduction performance of the film. The graphene is used as a two-dimensional plane structure, and the defects of the carbon nano tube are well made up. Therefore, the graphene/carbon nanotube composite film prepared by compounding the graphene and the carbon nanotubes is beneficial to exerting the continuous network structure of the carbon nanotube film, and can fill gaps by using the graphene to enhance the conduction of electrons, phonons and external force (energy).
The graphene/carbon nanotube compounding method is divided into an in-situ compounding method and an ex-situ compounding method. The ex-situ method comprises the steps of firstly preparing graphene and carbon nanotubes respectively by using a chemical vapor deposition method, then combining the graphene and the carbon nanotubes by using some chemical reagents to prepare the graphene/carbon nanotube composite film, wherein the method has great damage to the structures of the graphene and the carbon nanotubes, and further influences the electric and heat conduction performance of the composite film. In-situ compounding is realized by controlling the chemical vapor deposition reaction conditions and growing graphene in situ between the tube bundle gaps of the carbon nanotubes. Generally, in-situ compounding is carried out by carburizing Ni foil to prepare graphene, and carbon nanotubes are supported, so that graphene and carbon nanotubes are weakly combined, and mainly due to the fact that the carbon nanotubes cover an area and are entangled among tube bundles, carbon atoms are prevented from crystallizing and nucleating on a substrate, and therefore, only tiny particles which are aggregated among the tube bundles can be scattered on the tube bundles or in gaps. Meanwhile, as the thickness of the graphene is continuously increased, the graphene film gradually disappears between the tube bundles, and further effective compounding of the graphene and the carbon nanotubes is influenced.
In view of this, the invention is particularly proposed.
Disclosure of Invention
Therefore, the embodiment of the invention provides a preparation method of a graphene/carbon nanotube composite film and the composite film prepared by the method.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
according to a first aspect of the embodiments of the present invention, there is provided a method for preparing a graphene/carbon nanotube composite film, the method including: and (3) constructing a Ti/Co array on the surface of the copper foil with the graphene, growing the carbon nano tube in situ, and etching to remove the copper foil to obtain the graphene/carbon nano tube composite film.
The invention discovers that the method can improve the binding force of the graphene and the carbon nano tube, so that the graphene and the carbon nano tube are tightly bound, and the prepared composite film has excellent electric conduction and heat conduction performance.
Further, the method for constructing the Ti/Co array comprises the following steps: annealing the copper foil in a hydrogen/argon atmosphere at the temperature of 900-1100 ℃, coating an adhesion promoter and a photoresist, baking for 90-120s at the temperature of 90-110 ℃, and obtaining a carbon nano tube growth array through a photo mask and a mask aligner on an array layout under UV exposure; developing by using a developing solution, washing by using deionized water, baking again, sputtering a Ti buffer layer and a Co catalyst layer by using metal particles, and treating the surface of the copper foil by using acetone.
Further, the adhesion promoter is HMDS; the photoresist is AZ 5214E.
Further, the developing solution is prepared by mixing the following components in a volume ratio of 1: (2-4) a mixed solution of AZ400K and deionized water; the developing time is 45-60 s.
Further, the thickness of the Ti buffer layer is 30-45nm, and the thickness of the Co catalyst layer is 3-10 nm.
Further, the temperature for the second baking is 135-145 ℃, and the time is 2-3 min.
Further, the carbon nano tube is grown in situ by adopting a hot wire chemical vapor deposition method.
Specifically, the copper foil with Ti/Co array is placed in hydrogen atmosphere with vacuum degree of 0.1-0.15MPa, the substrate copper foil is heated to 560 ℃ and 600 ℃, the temperature is kept for 15-25min, and then NH is introduced3After 10-20min, reducing the temperature of the substrate to 360-400 ℃; heating the tungsten filament to 2200 ℃ at 2000-4Growing carbon nanotube, and cooling to room temperature in hydrogen atmosphere after 15-30 min.
Further, the NH3With a concentration of 100-300ppmN2(ii) a Said H2：CH4：NH3The flow ratio of (A) to (B) is 3:1: 3.
According to a second aspect of the embodiments of the present invention, there is provided a graphene/carbon nanotube composite film manufactured by the above method.
The embodiment of the invention has the following advantages:
(1) according to the invention, the graphene is utilized to increase the relation between the carbon nanotube bundles, the continuity of the carbon nanotube film is exerted, and the transmission of electrons between the bundles is enhanced;
(2) according to the graphene/carbon nanotube composite film prepared in situ, the carbon nanotubes continue to grow on the surface where the graphene grows, the graphene and the carbon nanotubes are tightly combined, and the carbon nanotubes play a supporting role in the etching process, so that the damage to the graphene film is reduced;
(3) the method provided by the invention has strong operability and is easy to realize, and the prepared graphene/carbon nano tube composite film has good optical and electrical properties and has wide application prospect in electric conduction and heat conduction.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a graphene/carbon nanotube composite film, which comprises the following steps:
(1) taking a piece of SiO with the area of 5cm multiplied by 8cm and the thickness of 70 mu m2Slicing;
(2) placing a piece of copper foil with the thickness of 25 mu m and the area of 2cm multiplied by 4cm, on which graphene grows, on SiO2The wafer is annealed in hydrogen/argon atmosphere at 1000 ℃;
(3) uniformly coating an adhesion promoter Hexamethyldisilane (HMDS) on the treated copper foil;
(4) spin-coating photoresist AZ5214E on the copper foil coated with the adhesion promoter HMDS, and baking for 90s at 100 ℃;
(5) exposing the copper foil under UV, and obtaining a carbon nano tube growth array through a photo mask and a mask aligner on the array layout;
(6) adopting a volume ratio of 1: 2, treating the photoresist 45s on the copper foil by using a mixture of a photoetching developing solution AZ400K and deionized water, and then washing by using the deionized water;
(7) baking for 2min at 145 ℃, sputtering a Ti buffer layer with the thickness of 45nm and a Co catalyst layer with the thickness of 10nm by using metal particles, and then treating the surface of the copper foil with acetone to form a Ti/Co array on the surface of the copper foil with graphene;
(8) heating the copper foil with the Ti/Co array to 580 ℃ under the vacuum degree of 0.15MPa and hydrogen environment, keeping the temperature for 20min, and then introducing NH with the concentration of 100ppm3After 15min, reducing the temperature of the substrate to 380 ℃; heating the tungsten filament to 2100 deg.C, and introducing CH4Growing carbon nanotube, cooling to room temperature in hydrogen atmosphere after 15min, wherein H2：CH4：NH3The concentration ratio of (A) to (B) is 3:1: 3;
(9) and etching by using a copper etching agent to remove the copper foil, thus obtaining the graphene/carbon nanotube composite film.
Example 2
The embodiment provides a preparation method of a graphene/carbon nanotube composite film, which comprises the following steps:
(1) taking a piece of SiO with the area of 6cm multiplied by 8cm and the thickness of 50 mu m2Slicing;
(2) placing a piece of copper foil which grows with graphene and has the thickness of 25 mu m and the area of 3cm multiplied by 3cm on SiO2The wafer is annealed in hydrogen/argon atmosphere at 1000 ℃;
(3) uniformly coating an adhesion promoter Hexamethyldisilane (HMDS) on the treated copper foil;
(4) spin-coating a photoresist AZ5214E on the copper foil coated with the adhesion promoter HMDS, and baking at 100 ℃ for 90 s;
(5) exposing the copper foil under UV, and obtaining a carbon nano tube growth array through a photo mask and a mask aligner on the array layout;
(6) the volume ratio is 1: 2, treating the photoresist on the copper foil for 60s by using a mixture of AZ400K and deionized water, and washing by using the deionized water;
(7) baking for 2min at 145 ℃, sputtering a Ti buffer layer with the thickness of 30nm and a Co catalyst layer with the thickness of 3nm by using metal particles, and then treating the surface of the copper foil with acetone to form a Ti/Co array on the surface of the copper foil with graphene;
(8) heating the copper foil with the Ti/Co array to 580 ℃ under the condition of vacuum degree of 0.15MPa and hydrogen, keeping the temperature for 20min, and then introducing NH with the concentration of 180ppm3After 20min, reducing the temperature of the substrate to 380 ℃; heating the tungsten filament to 2100 deg.C, and introducing CH4Growing carbon nanotube, and cooling to room temperature in hydrogen atmosphere after 20min, wherein H2：CH4：NH3The concentration ratio of (A) to (B) is 3:1: 3;
(9) and etching and removing the copper foil by using a copper etching agent to obtain the graphene/carbon nano tube composite film.
Example 3
The embodiment provides a preparation method of a graphene/carbon nanotube composite film, which comprises the following steps:
(1) taking a piece of SiO with the area of 8cm multiplied by 10cm and the thickness of 20 mu m2Slicing;
(2) placing a piece of copper foil with the thickness of 30 mu m and the area of 4cm multiplied by 5cm, on which graphene grows, on SiO2The wafer is annealed in hydrogen/argon atmosphere at 1000 ℃;
(3) uniformly coating an adhesion promoter Hexamethyldisilane (HMDS) on the treated copper foil;
(4) spin-coating photoresist AZ5214E on the copper foil coated with the adhesion promoter HMDS, and baking for 90s at 100 ℃;
(5) exposing the copper foil under UV, and obtaining a carbon nano tube growth array through a photo mask and a mask aligner on the array layout;
(6) the volume ratio is 1: 2, treating the photoresist on the copper foil for 60s by using a mixture of AZ400K and deionized water, and washing by using the deionized water;
(7) baking for 2min at 145 ℃, sputtering a Ti buffer layer with the thickness of 30nm and a Co catalyst layer with the thickness of 3nm by using metal particles, and then treating the surface of the copper foil with acetone to form a Ti/Co array on the surface of the copper foil with graphene;
(8) heating the copper foil with the Ti/Co array to 580 ℃ under the vacuum degree of 0.15MPa and hydrogen environment, keeping the temperature for 20min, and then introducing NH with the concentration of 300ppm3After 15min, reducing the temperature of the substrate to 380 ℃; heating the tungsten filament to 2100 deg.C, and introducing CH4Growing carbon nanotube, cooling to room temperature in hydrogen atmosphere after 30min, wherein H2：CH4：NH3The concentration ratio of (A) to (B) is 3:1: 3;
(9) and etching by using a copper etching agent to remove the copper foil, thus obtaining the graphene/carbon nanotube composite film.
Test example 1
The electric conductivity and thermal conductivity of the graphene/carbon nanotube composite films prepared in examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1
| Sample (I) | Conductivity S/m | Thermal conductivity W/(m.K) |
| Example 1 | 2556 | 1.37 |
| Example 2 | 1483 | 0.72 |
| Example 3 | 1745 | 1.05 |
The result shows that the graphene/carbon nanotube composite film prepared by the method of the embodiment of the invention has excellent electric and thermal conductivity, wherein the graphene/carbon nanotube composite film prepared by the embodiment 1 has the best electric and thermal conductivity.
Although the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a graphene/carbon nanotube composite film is characterized by comprising the following steps:
and (3) constructing a Ti/Co array on the surface of the copper foil with the graphene, growing the carbon nano tube in situ, and etching to remove the copper foil to obtain the graphene/carbon nano tube composite film.
2. The method for preparing the graphene/carbon nanotube composite film according to claim 1, wherein the method for constructing the Ti/Co array comprises:
annealing the copper foil in a hydrogen/argon atmosphere at 900-1100 ℃, coating an adhesion promoter and a photoresist, baking for 90-120s at 90-110 ℃, and obtaining a carbon nano tube growth array through a photo mask and a mask aligner on an array layout under UV exposure; developing by using a developing solution, washing by using deionized water, baking again, sputtering a Ti buffer layer and a Co catalyst layer by using metal particles, and treating the surface of the copper foil by using acetone.
3. The method for preparing a graphene/carbon nanotube composite film according to claim 2, wherein the adhesion promoter is HMDS; the photoresist is AZ 5214E.
4. The method for preparing the graphene/carbon nanotube composite film according to claim 2, wherein the developing solution is a mixture of the following components in a volume ratio of 1: (2-4) a mixed solution of AZ400K and deionized water; the developing time is 45-60 s.
5. The preparation method of the graphene/carbon nanotube composite film according to claim 2, wherein the thickness of the Ti buffer layer is 30-45nm, and the thickness of the Co catalyst layer is 3-10 nm.
6. The method of claim 2, wherein the re-baking is performed at 135-145 ℃ for 2-3 min.
7. The method for preparing the graphene/carbon nanotube composite film according to claim 1, wherein the carbon nanotubes are grown in situ by a hot-wire chemical vapor deposition method.
8. The method as claimed in claim 7, wherein the Cu foil with Ti/Co array is placed in a hydrogen atmosphere with a vacuum degree of 0.1-0.15MPa, the substrate Cu foil is heated to 560-600 deg.C and kept at the temperature for 15-25min, and NH is introduced into the substrate3After 10-20min, reducing the temperature of the substrate to 360-400 ℃; heating the tungsten filament to 2200 ℃ of 2000-4Growing carbon nanotube, and cooling to room temperature in hydrogen atmosphere after 15-30 min.
9. The method of claim 8, wherein the NH is added to the graphene/carbon nanotube composite film3N at a concentration of 100-300ppm2(ii) a Said H2：CH4：NH3The flow ratio of (A) to (B) is 3:1: 3.
10. A graphene/carbon nanotube composite film produced by the production method according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103050346A (en) * | 2013-01-06 | 2013-04-17 | 电子科技大学 | Field emission electron source and preparation method of carbon nanotube graphene composite structure thereof |
| CN104036878A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Preparation method of graphene-carbon nanotube three-dimensional structure material |
| US20150004373A1 (en) * | 2013-06-27 | 2015-01-01 | National Taiwan University Of Science And Technology | Carbon nanotube-graphene composite, method of forming the same, and electronic device |
| CN111180292A (en) * | 2020-01-13 | 2020-05-19 | 东南大学 | Graphene/metamaterial composite nanostructure-based field emission cathode and preparation method thereof |
| CN112537769A (en) * | 2020-12-02 | 2021-03-23 | 北海惠科光电技术有限公司 | Graphene carbon nanotube composite film, preparation method thereof and thin film transistor array |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050346A (en) * | 2013-01-06 | 2013-04-17 | 电子科技大学 | Field emission electron source and preparation method of carbon nanotube graphene composite structure thereof |
| US20150004373A1 (en) * | 2013-06-27 | 2015-01-01 | National Taiwan University Of Science And Technology | Carbon nanotube-graphene composite, method of forming the same, and electronic device |
| CN104036878A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Preparation method of graphene-carbon nanotube three-dimensional structure material |
| CN111180292A (en) * | 2020-01-13 | 2020-05-19 | 东南大学 | Graphene/metamaterial composite nanostructure-based field emission cathode and preparation method thereof |
| CN112537769A (en) * | 2020-12-02 | 2021-03-23 | 北海惠科光电技术有限公司 | Graphene carbon nanotube composite film, preparation method thereof and thin film transistor array |
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