CN108083267B - Preparation method of electron-doped double-layer graphene - Google Patents
Preparation method of electron-doped double-layer graphene Download PDFInfo
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- CN108083267B CN108083267B CN201810025805.XA CN201810025805A CN108083267B CN 108083267 B CN108083267 B CN 108083267B CN 201810025805 A CN201810025805 A CN 201810025805A CN 108083267 B CN108083267 B CN 108083267B
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Abstract
Electronically doped bilayer grapheneThe invention relates to graphene, in particular to a preparation method of electron-doped double-layer graphene, which is used for modulating the electrical property of graphene by evaporating melamine molecules on the surface of the double-layer graphene through thermal evaporation. The preparation method of the electronic-doped double-layer graphene is characterized in that the preparation method prepares large-area double-layer graphene by a chemical vapor deposition method, and then uses a thermal evaporation technology to evaporate a layer of melamine molecules on the surface of the double-layer graphene to modulate the electrical properties of the graphene. The method is mainly different from the method for preparing the single-layer graphene in that the amount of hydrogen and argon mixed gas is increased, the preparation time is prolonged, and the thickness of the film covered on the surface of the double-layer graphene in the step 3) can be controlled by adjusting the amount of melamine; the doping of melamine enables the conductivity type of graphene to be modulated from strong p type to weak p type, and the graphene is large-area graphenenType doping provides a viable solution.
Description
Technical Field
The invention relates to graphene, in particular to a preparation method of electron-doped double-layer graphene, which is used for modulating the electrical property of graphene by evaporating melamine molecules on the surface of the double-layer graphene through thermal evaporation.
Background
Graphene is a polymer made of carbon atomssp 2The tracks are hybridized to form a honeycomb-structured two-dimensional material. Since the discovery of graphene and the fabrication of the first graphene field effect transistor in comstatin norvochov and anderley hom in 2004, there has been extensive interest in the field of photodetectors due to their high carrier mobility, broad spectral absorption, and fast response, howeverThe intrinsic single-layer graphene has a small switching ratio and low response rate of the graphene-based photoelectric detector due to zero band gap and weak light absorption (2.3%), so that the application of the graphene-based photoelectric detector in the photoelectric field is limited, and the opening of the band gap of the graphene to increase the switching ratio is very important for the application of the graphene in the photoelectric field. The double-layer graphene has higher carrier mobility except that the double-layer graphene has a quantum abnormal Hall effect similar to that of the single-layer graphene and has higher light absorption strength than that of the single-layer graphene, and an energy band of the double-layer graphene can be opened by applying a vertical electric field or doping.
The chemical vapor deposition method is one of the best methods for preparing large-area and high-quality single-layer graphene at present, but the preparation of the double-layer graphene is difficult due to the self-limiting effect, and only a few experimental groups prepare the high-quality double-layer graphene. Therefore, in order to apply graphene to the field of photoelectric detection, it is necessary to prepare double-layer graphene to enhance light absorption and dope the double-layer graphene to realize electrical modulation.
Disclosure of Invention
The invention aims to solve the problem that the existing preparation of the double-layer graphene is difficult, and provides a preparation method of the electron-doped double-layer graphene, which is used for preparing the electrical property of the graphene by evaporating melamine molecules on the surface of the double-layer graphene through thermal evaporation.
The preparation method of the electronic-doped double-layer graphene is characterized in that the preparation method prepares large-area double-layer graphene by a chemical vapor deposition method, and then evaporates a layer of melamine molecules on the surface of the double-layer graphene by a thermal evaporation technology to modulate the electrical properties of the graphene, and the preparation method comprises the following specific steps:
1) preparing double-layer graphene on the copper foil by adopting a chemical vapor deposition method: putting the copper foil substrate into a tube furnace, and then vacuumizing to below 1 Pa; introducing hydrogen and argon mixed gas into the tubular furnace at a flow rate of 60sccm, and heating to 1000 ℃ within 120 minutes; then introducing methane in an amount of 20sccm for 60 minutes, wherein the pressure in the tubular furnace is kept at 1500 Pa; then cooling to room temperature, turning off the hydrogen and argon mixed gas, and taking out the double-layer graphene sample growing on the surface of the copper foil;
2) and transferring double-layer graphene: spin-coating a layer of polymethyl methacrylate solution on the double-layer graphene sample obtained in the step 1), and then heating and evaporating the solution to dryness for 20 minutes in a drying oven at the temperature of 80 ℃ to form a firm film; soaking the copper foil coated with the polymethyl methacrylate solution and grown with the double-layer graphene in a ferric chloride solution to etch the copper foil for 1 to 2 hours; after etching, transferring the copper foil into deionized water by using a glass slide to be soaked for 30 minutes, and cleaning the residual ferric chloride and copper on the surface; and transferring the film with the graphene after the copper foil is etched onto a target substrate, and removing the polymethyl methacrylate solution by using acetone to obtain the double-layer graphene transferred on the target substrate.
3) And melamine evaporation: and (2) taking melamine as a doping agent, and evaporating the melamine onto the surface of the double-layer graphene by using a thermal evaporation method to form a layer of film, so as to obtain the electron-doped double-layer graphene.
The method is mainly different from the method for preparing the single-layer graphene in that the amount of hydrogen and argon mixed gas is increased, the preparation time is prolonged, and the thickness of the film covered on the surface of the double-layer graphene in the step 3) can be controlled by adjusting the amount of melamine; the doping of melamine enables the conductivity type of graphene to be modulated from strong p type to weak p type, and the graphene is large-area graphenenType doping provides a viable solution.
The preparation method of the electron-doped double-layer graphene has the following advantages:
1) the whole technical route is innovative, the preparation method has the characteristics of simple equipment and process, high preparation efficiency, low cost, obvious effect and the like, the surface doping of the double-layer graphene is realized by combining a classical CVD method and a thermal evaporation method, the electrical modulation is realized, and the defect of low carrier mobility caused by substitutional doping is avoided;
2) the operation of preparing the doped double-layer graphene is feasible, the prepared doped double-layer graphene can realize the modulation effect of the conductivity type of the double-layer graphene from a strong p type to a weak p type, and the direction and the reference are indicated for the n type modulation of the graphene;
3) the melamine contains carbon-nitrogen bonds, so that the melamine has an absorption effect on ultraviolet and can be used in an ultraviolet detector.
Drawings
FIG. 1 is an AFM diagram of chemical vapor deposition for preparing bilayer graphene.
Fig. 2 is a raman spectrum of double-layer graphene prepared by a chemical vapor deposition method.
Fig. 3 shows field effect test results of double-layer graphene and doped double-layer graphene.
Detailed Description
Example 1: a preparation method of electron-doped double-layer graphene is characterized in that large-area double-layer graphene is prepared by a chemical vapor deposition method, a layer of melamine molecules is evaporated on the surface of the double-layer graphene by a thermal evaporation technology to modulate the electrical properties of the graphene, and the preparation method comprises the following specific steps:
1) preparing double-layer graphene on the copper foil by adopting a chemical vapor deposition method: putting the copper foil substrate into a tube furnace, and then vacuumizing to below 1 Pa; introducing hydrogen and argon mixed gas into the tubular furnace at a flow rate of 60sccm, and heating to 1000 ℃ within 120 minutes; then introducing methane in an amount of 20sccm for 60 minutes, wherein the pressure in the tubular furnace is kept at 1500 Pa; then cooling to room temperature, turning off the hydrogen and argon mixed gas, and taking out the double-layer graphene sample growing on the surface of the copper foil;
2) and transferring double-layer graphene: spin-coating a layer of polymethyl methacrylate solution on the double-layer graphene sample obtained in the step 1), and then heating and evaporating the solution to dryness for 20 minutes in a drying oven at the temperature of 80 ℃ to form a firm film; soaking the copper foil coated with the polymethyl methacrylate solution and grown with the double-layer graphene in a ferric chloride solution to etch the copper foil for 1 to 2 hours; after etching, transferring the copper foil into deionized water by using a glass slide to be soaked for 30 minutes, and cleaning the residual ferric chloride and copper on the surface; transferring the film with the graphene after the copper foil is etched to a target substrate, and removing the polymethyl methacrylate solution by using acetone to obtain double-layer graphene transferred on the target substrate;
3) and melamine evaporation: melamine is used as a doping agent, and is evaporated on the surface of double-layer graphene by a thermal evaporation method to form a layer of film. Namely weighing 0.5 g of melamine powder, and evaporating the melamine powder on the surface of the double-layer graphene under a vacuum condition to obtain the electron-doped double-layer graphene.
In the actual preparation process, the thickness of the film covered on the surface of the double-layer graphene in the step 3) can be controlled by adjusting the amount of melamine.
As shown in fig. 1, an AFM image of double-layer graphene prepared by chemical vapor deposition method transferred to a target substrate shows that a discontinuous thin film is formed on the surface of the target substrate in addition to a wrinkled film, and the surface appearance of the double-layer graphene thin film is shown.
As shown in fig. 2, which is a raman spectrogram of a double-layer graphene film, D peak intensities of a plurality of points obtained by a raman test are very weak, so that it can be determined that the defect rate of the grown graphene is low and the quality of a graphene sample is high; intensity ratio for 2D peak to G peak (I)2D/IG1), it is obvious that the number of layers of the graphene is two-layer.
After the surface of the graphene is doped with a layer of melamine molecules, the field effect transistor is subjected to an electrical performance test, as shown in fig. 3, the electrical performance test in the air shows that: the doping of the melamine enables the conductivity type of the graphene to be modulated from a strong p type to a weak p type, and a reference scheme is provided for preparing large-area graphene n-type doping in the future.
Claims (1)
1. A preparation method of electron-doped double-layer graphene is characterized in that the preparation method prepares large-area double-layer graphene by a chemical vapor deposition method, and then evaporates a layer of melamine molecules on the surface of the double-layer graphene by a thermal evaporation technology to modulate the electrical properties of the graphene, and the preparation method specifically comprises the following steps:
1) preparing double-layer graphene on the copper foil by adopting a chemical vapor deposition method: putting the copper foil substrate into a tube furnace, and then vacuumizing to below 1 Pa; introducing hydrogen and argon mixed gas into the tubular furnace at a flow rate of 60sccm, and heating to 1000 ℃ within 120 minutes; then introducing methane in an amount of 20sccm for 60 minutes, wherein the pressure in the tubular furnace is kept at 1500 Pa; then cooling to room temperature, turning off the hydrogen and argon mixed gas, and taking out the double-layer graphene sample growing on the surface of the copper foil;
2) and transferring double-layer graphene: spin-coating a layer of polymethyl methacrylate solution on the double-layer graphene sample obtained in the step 1), and then heating and evaporating the solution to dryness for 20 minutes in a drying oven at the temperature of 80 ℃ to form a firm film; soaking the copper foil coated with the polymethyl methacrylate solution and grown with the double-layer graphene in a ferric chloride solution to etch the copper foil for 1 to 2 hours; after etching, transferring the copper foil into deionized water by using a glass slide to be soaked for 30 minutes, and cleaning the residual ferric chloride and copper on the surface; transferring the film with the graphene after the copper foil is etched to a target substrate, and removing the polymethyl methacrylate solution by using acetone to obtain double-layer graphene transferred on the target substrate;
3) and melamine evaporation: and (2) taking melamine as a doping agent, and evaporating the melamine onto the surface of the double-layer graphene by using a thermal evaporation method to form a layer of film, so as to obtain the electron-doped double-layer graphene.
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| CN105752965A (en) * | 2016-01-26 | 2016-07-13 | 无锡格菲电子薄膜科技有限公司 | Etching method for directly forming multi-layer graphene film in graphene prepared through CVD method |
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| CN103072978A (en) * | 2013-02-04 | 2013-05-01 | 杭州格蓝丰纳米科技有限公司 | Chemical vapor deposition method for preparing dual-layer graphene |
| EP3181516A1 (en) * | 2015-12-16 | 2017-06-21 | Samsung Electronics Co., Ltd | Multilayer graphene, method of forming the same, device including the multilayer graphene, and method of manufacturing the device |
| CN105752965A (en) * | 2016-01-26 | 2016-07-13 | 无锡格菲电子薄膜科技有限公司 | Etching method for directly forming multi-layer graphene film in graphene prepared through CVD method |
| CN106087051A (en) * | 2016-06-02 | 2016-11-09 | 南京大学 | The preparation method of synchronous growth wafer scale AB stacking bilayer graphene and equipment thereof |
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