CN108069416B - Ultra-clean graphene and preparation method thereof - Google Patents
Ultra-clean graphene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses ultra-clean graphene and a preparation method thereof. The method for preparing the ultra-clean graphene comprises the following steps: and after the foamy copper is placed above and attached to the copper substrate, introducing carbon source gas and hydrogen to carry out chemical vapor deposition, and obtaining the ultra-clean graphene on the surface of the copper substrate, which is in contact with the foamy copper, after the deposition is finished. The preparation method is simple, can be used for large-scale production, has continuous clean area reaching the sub-centimeter level, and can be applied to the aspects of electronics, optics and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to ultra-clean graphene and a preparation method thereof.
Background
Graphene is a two-dimensional thin film material formed by arranging single-layer carbon atoms according to a hexagonal symmetric honeycomb structure. Due to the excellent properties of graphene in electrical, optical, thermal, and mechanical aspects, graphene has attracted much attention in various fields such as physics, chemistry, biology, and materials since its discovery. For example, single layer graphene has a dirac-tapered band structure, where energy and momentum are linearly dispersed at the fermi level. This unique energy band structure determines that graphene has extremely high carrier mobility, and thus graphene is gradually becoming a favorable alternative to conventional silicon-based electronic materials. Since graphene is a thin film material with a single atomic layer, the light absorption rate is only 2.3%, and in combination with excellent conductivity and flexibility, graphene becomes a possible material of a next-generation flexible transparent conductive material. Meanwhile, the graphene has a perfect hexagonal symmetrical structure, extremely high electron transmittance, extremely high electrical conductivity and thermal conductivity, so that the graphene has extremely high imaging resolution and radiation resistance as a transmission grid, and is widely applied.
The existing methods for preparing graphene mainly comprise a mechanical stripping method, a graphene reduction and oxidation method and a chemical vapor deposition method. This is where the continuous graphene domain size obtained based on mechanical exfoliation methods is typically on the order of microns and is not suitable for large-scale production. The graphene prepared by the redox method has more defects caused by the chemical reduction reaction process, and the oxidized group is difficult to completely reduce so as to cause serious doping, thereby seriously limiting the application of the graphene in the field of electronics. The chemical vapor deposition method is suitable for preparing the graphene film material on a large scale, but a large amount of amorphous carbon pollutants exist on the surface of the prepared graphene, and the existence of the pollutants causes the light transmittance and the electrical conductivity of the graphene to be obviously reduced. Meanwhile, the continuous clean size under a transmission electron microscope is only in the nanometer level, and the imaging and observation range of the graphene as the transmission grid substrate is severely limited. Therefore, it becomes important how to prepare clean and contaminant-free ultra-clean graphene in a large area by using a chemical vapor deposition method.
Disclosure of Invention
The invention aims to provide ultra-clean graphene and a preparation method thereof.
The method for preparing the ultra-clean graphene comprises the following steps:
and after the foamy copper is placed above and attached to the copper substrate, introducing carbon source gas and hydrogen to carry out chemical vapor deposition, and obtaining the ultra-clean graphene on the surface of the copper substrate, which is in contact with the foamy copper, after the deposition is finished.
In the method, the aperture of the foam copper is 0.1-2.0 mm;
the distance between the foam copper and the copper substrate is not more than 0.1 mm;
the copper substrate is a single crystal copper sheet, a polycrystalline copper sheet or a copper foil; the copper substrate can perform catalytic cracking function on carbon source gas.
The thickness of the copper substrate is 2-100 μm.
The carbon source gas is methane, ethane or ethylene; the purity of the carbon source gas is not less than 99.999%.
In the chemical vapor deposition step, the flow rate of the carbon source gas is 0.05sccm-7sccm (standard-state cubic center per minute), specifically 0.36sccm, 1sccm or 7 sccm;
the flow rate of the hydrogen is 10-1000sccm, specifically 11sccm or 500 sccm; the ratio of the hydrogen gas to the carbon source gas determines the graphene domain size, which is in the micrometer to millimeter scale. In addition, in the chemical vapor deposition process, hydrogen can dilute a precursor carbon source, and meanwhile, the hydrogen-rich environment plays a role in activating carbon-hydrogen bonds and regulating monolayer growth on microscopic chemical kinetics.
The deposition temperature is 980-1040 ℃, and specifically can be 1020 ℃;
the deposition time is not less than 30s, specifically 30s, 300s or 24 h;
the chemical vapor deposition step is carried out in an inert atmosphere (e.g., an argon atmosphere);
the flow rate of the inert gas is 100sccm-200 sccm;
the pressure of the deposition is 20Pa-700Pa, and specifically 48Pa, 50Pa or 500 Pa.
The method further comprises the steps of: annealing the system prior to the chemical vapor deposition step.
Specifically, the annealing is performed in a reducing atmosphere or a hydrogen atmosphere;
the flow rate of the reducing gas is 100sccm to 300sccm, specifically 100 sccm.
The pressure of the system is 30Pa-300Pa, and specifically can be 100 Pa;
the annealing temperature is 900-1100 ℃, specifically 1020 ℃ or 1040 ℃;
the annealing time is 30min-120min, specifically 30min or 50 min.
The crystal domain of the copper substrate after annealing treatment can reach hundreds of microns.
The method further comprises the steps of: after the chemical vapor deposition step, the system is cooled.
Specifically, in the cooling step, the cooling rate is greater than 80 ℃/min, such as 90 ℃/min.
The method further comprises the steps of: before the annealing step, carrying out surface cleaning on the copper substrate and the foam copper;
and the surface cleaning step is to sequentially use dilute hydrochloric acid with the mass percentage concentration of 5% and water to clean the surface of the copper substrate and the foam copper.
The ultra-clean graphene is specifically an ultra-clean single crystal graphene or an ultra-clean polycrystalline graphene film.
In addition, the ultra-clean graphene prepared by the method also belongs to the protection scope of the invention; the ultra-clean graphene is specifically an ultra-clean single crystal graphene or an ultra-clean polycrystalline graphene film.
Compared with the prior art, the invention has the beneficial effects that: (1) by introducing the foam copper, the ultra-clean graphene with a continuous area at the micron level can be obtained, and amorphous adsorbates introduced in the growth process are effectively reduced; (2) the graphene is safe, cheap and easily available in raw materials, simple and effective in preparation method, and can realize efficient lossless transfer from a copper substrate to a transmission substrate due to the excellent structure of the graphene, so that the graphene can be used as a transmission grid. (3) The sub-centimeter-level single-crystal graphene (namely a single domain) can be spliced into a single-layer graphene film through further growth, and the area of a sample of the single-layer graphene film is only related to the size of the copper foil, so that large-area preparation can be realized, and the method can be popularized to large-scale production.
Drawings
FIG. 1 is a schematic view of a reactor for growing ultra-clean graphene.
Fig. 2 is a stacked structure of a copper foam and a copper foil for growing ultra-clean graphene, the copper foam itself structure.
Fig. 3 is a comparison of sample cleanliness and light absorbance obtained after ultra-clean graphene and ordinary graphene are transferred onto a quartz plate with the aid of PMMA.
FIG. 4 is a TEM photograph showing the continuous clean area of 1 μm in example 1 and example 2
Fig. 5 is a large-area high-resolution photograph of the ultra-clean graphene prepared in example 1 under a high-resolution transmission electron microscope.
Fig. 6 is a raman spectroscopy characterization of the unsettled graphene without glue transferred onto the porous substrate for example 1 and example 2, respectively.
Fig. 7 is a photograph of a transmission microscope of graphene that was not normally grown using copper foam. The continuous area is only a few to a few tens of nanometers.
Fig. 8 is an atomic force microscope characterization of graphene on a copper substrate without the normal growth of copper foam.
Detailed Description
The method of the present invention is illustrated by the following specific examples, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The schematic view of the reaction apparatus configuration of single crystal graphene used in the following examples and the schematic view of the step of growing large single crystal graphene are shown in fig. 1 and 2, respectively, and number 1 in fig. 2 is a copper foil substrate and number 2 is a copper foam.
Example 1 preparation of ultra clean graphene
(1) Cleaning copper foil (produced by Alfa Aesar company, purity 99.8% and thickness 25 μm) with dilute hydrochloric acid with mass fraction of 5% and deionized water in sequence, placing the copper foil and the foam copper in close contact in a sleeve with a magnetic control device, placing the sleeve in a tubular furnace, increasing the system pressure to 100Pa under a hydrogen atmosphere with flow of 100sccm, and keeping the furnace body temperature at 1020 ℃ for 30 min;
(2) keeping the temperature of the furnace body at 1020 ℃, changing the hydrogen gas with the flow rate of 11sccm, introducing the methane gas with the flow rate of 7sccm, keeping the system pressure at 50Pa, and keeping the system pressure for 30 s;
(3) pulling the sleeve loaded with the copper foil out of the high-temperature area by using a magnet, rapidly cooling the temperature of the sample to room temperature at a cooling rate of 90 ℃/min, and finishing the growth of the sample;
(4) and taking out the grown copper foil sample, and removing the graphene on the back surface of the copper substrate, which is in contact with the foam copper, through plasma bombardment. The PMMA is transferred to a substrate such as a silicon wafer, a quartz wafer and the like by using a traditional PMMA auxiliary transfer method for subsequent characterization. The transmission grid is used for replacing the traditional high polymer auxiliary graphene to realize glue-free transfer, and a transmission sample is prepared for subsequent characterization.
Fig. 3 is a comparison of sample cleanliness and absorbance obtained after transferring ultra-clean graphene and normal graphene onto a quartz plate with the aid of PMMA, and it can be seen that the absorbance of the clean sample is significantly lower than that of the normal sample, indicating that there is less contaminant residue on the surface of the ultra-clean graphene.
Fig. 4 is a transmission electron microscope photograph of example 1 with a continuous clean area of 1 micron, the darker color under the transmission electron microscope is an amorphous carbon adsorbate caused by growth, the ultra-clean graphene thin film has no distribution of such adsorbate within a continuous one micron range, and the clean graphene shows uniform contrast, indicating no pollutant adsorption. The continuous clean area reaches the micrometer scale.
Fig. 5 is a high-resolution photograph of the ultra-clean graphene prepared in example 1 under a high-resolution transmission electron microscope. The hexagonal symmetrical skeleton structure of the graphene can be clearly seen through high-resolution imaging of the graphene, so that the graphene is free of pollutant adsorption, and the product is a polycrystalline graphene film.
Fig. 6 is a raman spectroscopy characterization of ultra clean graphene transferred onto a target mesh substrate. The results of the characterization by raman analysis are shown in fig. 6: the graphene prepared by the method has no D peak, which indicates that the quality is high and is undoped, and the integral mild ratio of the 2D peak to the G peak is far greater than 2, which indicates that the graphene is a perfect single layer and has no adsorbate and substrate interference.
Example 2 preparation of ultra clean graphene
(1) The mass ratio of the components is 3: 1 phosphoric acid and ethylene glycol solution were used as an electrolyte, and a copper foil (99.8% purity, 25 μm thickness, produced by Alfa Aesar) was connected to the positive electrode and polished for 30min at a direct current of 0.5A. Placing copper foil and foam copper in close contact in a sleeve with a magnetic control device, placing the sleeve in a tubular furnace, raising the temperature of the furnace body to 1040 ℃ under the hydrogen atmosphere with the flow of 300sccm, and keeping the system pressure at 300Pa for 50 min;
(2) keeping the temperature of the furnace body at 1040 ℃, changing the hydrogen gas with the flow rate of 500sccm, introducing the methane gas with the flow rate of 0.36sccm, keeping the system pressure at 500Pa, and keeping for 24 hours;
(3) pulling the sleeve loaded with the copper foil out of the high-temperature area by using a magnet, rapidly cooling the temperature of the sample to room temperature, and finishing the growth of the sample;
(4) and taking out the grown copper foil sample, and removing the graphene on the back surface of the copper substrate, which is in contact with the foam copper, through plasma bombardment. The PMMA is transferred to a substrate such as a silicon wafer, a quartz wafer and the like by using a traditional PMMA auxiliary transfer method for subsequent characterization. The transmission grid is used for replacing the traditional high polymer auxiliary graphene to realize glue-free transfer, and a transmission sample is prepared for subsequent characterization.
Fig. 3 is a comparison of sample cleanliness and absorbance obtained after transferring ultra-clean graphene and normal graphene onto a quartz plate with the aid of PMMA, and it can be seen that the absorbance of the clean sample is significantly lower than that of the normal sample, indicating that there is less contaminant residue on the surface of the ultra-clean graphene.
Fig. 4 is a transmission electron microscope photograph of example 1 with a continuous clean area of 1 micron, the darker color under the transmission electron microscope is an amorphous carbon adsorbate caused by growth, the ultra-clean graphene thin film has no distribution of such adsorbate within a continuous one micron range, and the clean graphene shows uniform contrast, indicating no pollutant adsorption. The continuous clean area reaches the micrometer scale.
Fig. 5 is a high-resolution photograph of the ultra-clean graphene prepared in example 1 under a high-resolution transmission electron microscope. The high-resolution imaging of the graphene can clearly see the hexagonal symmetrical skeleton structure of the graphene, so that the graphene is free from pollutant adsorption, and the product is an isolated graphene large single crystal.
Fig. 6 is a raman spectroscopy characterization of ultra clean graphene transferred onto a target mesh substrate. The results of the characterization by raman analysis are shown in fig. 6: the graphene prepared by the method has no D peak, which indicates that the quality is high and is undoped, and the integral mild ratio of the 2D peak to the G peak is far greater than 2, which indicates that the graphene is a perfect single layer and has no adsorbate and substrate interference.
Example 3 preparation of ultra clean graphene
(1) Cleaning copper foil (produced by Alfa Aesar company, purity 99.8% and thickness 25 μm) with dilute hydrochloric acid with mass fraction of 5% and deionized water in sequence, placing the copper foil and the foam copper in close contact in a sleeve with a magnetic control device, placing the sleeve in a tubular furnace, increasing the system pressure to 100Pa under a hydrogen atmosphere with flow of 100sccm, and keeping the furnace body temperature at 1020 ℃ for 30 min;
(2) keeping the temperature of the furnace body at 1020 ℃, changing the hydrogen gas with the flow rate of 11sccm, introducing the methane gas with the flow rate of 1sccm, keeping the system pressure at 48Pa, and keeping the system pressure for 300 s;
(3) pulling the sleeve loaded with the copper foil out of the high-temperature area by using a magnet, rapidly cooling the temperature of the sample to room temperature at a cooling rate of 90 ℃/min, and finishing the growth of the sample;
(4) and taking out the grown copper foil sample, and removing the graphene on the back surface of the copper substrate, which is in contact with the foam copper, through plasma bombardment. The PMMA is transferred to a substrate such as a silicon wafer, a quartz wafer and the like by using a traditional PMMA auxiliary transfer method for subsequent characterization. The transmission grid is used for replacing the traditional high polymer auxiliary graphene to realize glue-free transfer, and a transmission sample is prepared for subsequent characterization. The obtained results have no substantial difference from example 1 and are not described in detail.
Comparative example 1 preparation of graphene on copper substrate without ordinary growth of copper foam
The only difference between the preparation method and that shown in example 1 is that no copper foam is used, and the growth of graphene on the copper foil alone is shown in fig. 7, and it can be seen from fig. 7 that: the foam copper structure is not used, the copper steam is not supplied enough, and the sp is rich in a large amount3Carbon clusters of the bonds are generated in the air atmosphere and are further deposited on the surface of the graphene, so that the graphene is polluted. Seen under a transmission electron microscope, the pollutants are in aggregation distribution, so that the continuous area of the clean graphene is only dozens of nanometers. While the atomic force microscopy analysis shown in FIG. 8 also confirms thisAdsorbates exist on the surface of graphene and are directly generated in the growth process.
Claims (10)
1. A method for preparing ultra-clean graphene comprises the following steps:
placing foamy copper above a copper substrate and attaching the foamy copper, introducing carbon source gas and hydrogen to carry out chemical vapor deposition, and obtaining the ultra-clean graphene on one surface of the copper substrate, which is in contact with the foamy copper, after the deposition is finished;
the carbon source gas is methane, ethane or ethylene;
in the chemical vapor deposition step, the flow rate of the carbon source gas is 0.05sccm-7 sccm;
the flow rate of the hydrogen is 10-1000 sccm;
the deposition temperature is 980-1040 ℃;
the deposition time is not less than 30 s;
the chemical vapor deposition step is carried out in an argon atmosphere;
the flow rate of the argon gas is 100sccm-200 sccm;
the pressure of the deposition is 20Pa to 700 Pa.
2. The method of claim 1, wherein: the aperture of the foam copper is 0.1-2.0 mm;
the distance between the foam copper and the copper substrate is not more than 0.1 mm;
the copper substrate is a single crystal copper sheet, a polycrystalline copper sheet or a copper foil;
the thickness of the copper substrate is 2-100 mu m.
3. The method of claim 1, wherein: the method further comprises the steps of: annealing the copper foam and the copper substrate prior to the chemical vapor deposition step.
4. The method of claim 3, wherein: the annealing is carried out in a hydrogen atmosphere;
the flow rate of the hydrogen is 100sccm-300 sccm;
the pressure of the system is 30Pa-300 Pa;
the annealing temperature is 900-1100 ℃;
the annealing time is 30min-120 min.
5. The method of claim 1, wherein: the method further comprises the steps of: after the chemical vapor deposition step, the copper foam and the copper substrate are cooled.
6. The method of claim 5, wherein: in the cooling step, the cooling rate is more than 80 ℃/min.
7. The method of claim 3, wherein: the method further comprises the steps of: before the annealing step, carrying out surface cleaning on the copper substrate and the foam copper;
and the surface cleaning step is to sequentially use dilute hydrochloric acid with the mass percentage concentration of 5% and water to clean the surface of the copper substrate and the foam copper.
8. The method according to any one of claims 1-7, wherein: the ultra-clean graphene is a single crystal graphene or polycrystalline graphene film.
9. Ultra-clean graphene prepared by the method of any one of claims 1 to 8.
10. The ultra clean graphene according to claim 9, wherein: the ultra-clean graphene is a single crystal graphene or polycrystalline graphene film.
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| CN108726510B (en) * | 2017-04-20 | 2020-06-30 | 北京大学 | Large-area ultra-clean graphene, macro preparation method thereof and rapid evaluation method of cleanliness of large-area ultra-clean graphene |
| CN110540197B (en) * | 2018-05-29 | 2021-03-12 | 北京石墨烯研究院 | Method for cleaning graphene surface by using carbon nano material |
| CN108892132A (en) * | 2018-07-26 | 2018-11-27 | 中国电子科技集团公司第十三研究所 | Prepare auxiliary device, the graphene and preparation method thereof of graphene |
| CN114752914A (en) * | 2021-01-11 | 2022-07-15 | 上海新池能源科技有限公司 | Preparation method of copper-based graphene and conductor, and wire and cable |
| CN112899768B (en) * | 2021-01-20 | 2022-09-23 | 南方科技大学 | Method for preparing single crystal copper |
| CN112921396A (en) * | 2021-01-26 | 2021-06-08 | 南方科技大学 | Preparation method of single crystal graphene film |
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