CN115806288B - Method for promoting secondary growth of graphene and application of method in preparation of double-layer graphene - Google Patents
Method for promoting secondary growth of graphene and application of method in preparation of double-layer graphene Download PDFInfo
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- CN115806288B CN115806288B CN202211634985.4A CN202211634985A CN115806288B CN 115806288 B CN115806288 B CN 115806288B CN 202211634985 A CN202211634985 A CN 202211634985A CN 115806288 B CN115806288 B CN 115806288B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000034655 secondary growth Effects 0.000 title claims abstract description 22
- 230000001737 promoting effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000012010 growth Effects 0.000 claims abstract description 36
- 238000005530 etching Methods 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 47
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 29
- 239000011889 copper foil Substances 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000001020 plasma etching Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 18
- 239000002356 single layer Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for promoting secondary growth of graphene and application of the method in preparation of double-layer graphene. According to the method, the limited space formed by metal is used as a graphene growth substrate, graphene is grown by a chemical vapor deposition method, and secondary growth of graphene on the inner surface of the limited space is promoted by primary growth, etching and secondary growth, so that double-layer graphene is obtained.
Description
Technical Field
The invention belongs to the field of graphene preparation, and particularly relates to a method for promoting secondary growth of graphene and application of the method in preparation of double-layer graphene.
Background
Graphene is a cellular two-dimensional crystal material formed by six-membered rings of carbon in a plane, the carrier mobility of the graphene exceeds 10,000cm 2 V-1s-1 at room temperature, the thermal conductivity can reach 5300W/(m.K), the performance is far superior to that of silicon in a traditional microelectronic device, the graphene can play an important role in a semiconductor device in the future, and the zero band gap property of single-layer graphene limits the development and industrial application of graphene-based electronic devices.
Unlike single-layer graphene, double-layer graphene is a two-dimensional system formed by stacking an upper layer and a lower layer, and when a vertical electric field is applied to AB stacked double-layer graphene, the band gap of double-layer graphene is easily opened. So the preparation of the high-quality double-layer graphene has great significance for promoting the development of graphene-based electronic devices. However, graphene directly grown on the outer surface of the metal can bring more additional defects, wrinkling impurities and the like to the graphene due to the etching effect of excessive hydrogen and the evaporation of the metal. How to obtain high quality and/or high coverage bilayer graphene on the inner surface of a substrate is a technical problem addressed in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for promoting graphene secondary growth, which comprises the following steps: and taking a limited space formed by metal as a graphene growth substrate, etching the outer surface of the limited space after annealing and first growing graphene, and then growing graphene for the second time to promote the growth of double-layer graphene on the inner surface of the limited space.
According to an embodiment of the invention, the metal is selected from copper or nickel.
According to an embodiment of the invention, the confined space has a closed cavity formed of metal, such as a closed pocket made of copper foil or nickel foil. The limited space can be opened, and double-layer graphene can be conveniently taken out.
According to an embodiment of the invention, the wall thickness of the confinement space is greater than the depth of the etching, for example, the wall thickness is 25 microns.
According to an embodiment of the invention, the metal is preferably a polished metal. For example, the polishing conditions include: the metal is used as an anode to be put into polishing solution for treatment; preferably, the polishing liquid comprises the components: phosphoric acid, ethanol, isopropanol, deionized water and urea; for another example, the copper foil is placed as an anode in a polishing liquid, and the copper foil is subjected to a treatment at a voltage of 10V for 30-60 seconds.
According to an embodiment of the present invention, the annealing conditions include: the annealing time is 30-60 minutes, the annealing temperature is 1000-1050 ℃, and the annealing atmosphere is argon and hydrogen. By annealing, surface defects in the metal confinement space can be reduced.
According to an embodiment of the invention, the annealing, the first growing and the second growing are all performed in a tube furnace quartz tube.
According to an embodiment of the invention, the conditions of the first growth and the second growth are the same. For example, the conditions for each growth include: methane is used as a carbon source, the growth time is 20-60 minutes, the growth temperature is 1000-1050 ℃, and argon and hydrogen are used as carrier gases. For example, the flow rate of methane is 0.1-10sccm, the flow rate of argon is 1-500sccm, and the flow rate of hydrogen is 1-200sccm.
According to an embodiment of the present invention, the etching may be selected from plasma etching, such as oxygen plasma etching. In one embodiment, the etching conditions include: introducing 5sccm of oxygen, power 90%, and etching for 3-20 min. The purpose of the etching is to remove the graphene from the outer surface of the confined space to expose the surface metal. Further, the exposed surface metal can catalyze redundant carbon sources, carbon active groups penetrate through the surface metal to diffuse into the confined space, secondary nucleation and growth of the inner surface graphene are assisted, and double-layer graphene is obtained.
According to an embodiment of the present invention, the method for promoting graphene secondary growth includes the steps of: prefabricating the polished copper foil into a closed pocket, placing the copper pocket into a tubular furnace for annealing, performing chemical vapor deposition to grow graphene for the first time, taking out the copper pocket after the first growth is finished, performing plasma etching on the copper pocket to remove graphene on the outer surface, and then performing chemical vapor deposition to grow graphene for the second time to promote the growth of double-layer graphene on the inner surface.
The invention also provides a preparation method of the double-layer graphene, which comprises the method for promoting the secondary growth of the graphene. Preferably, the bilayer graphene can be obtained by the method for promoting the secondary growth of the graphene.
Advantageous effects
The double-layer graphene is grown in a relatively stable confined space. Specifically, a limited space formed by metals such as copper, nickel and the like is used as a graphene growth substrate, graphene is grown by a chemical vapor deposition method, and secondary growth of graphene on the inner surface of the limited space is promoted through primary growth, etching and secondary growth, so that high-quality and high-coverage double-layer graphene is obtained.
Drawings
FIG. 1 is a schematic flow chart of a method for promoting graphene secondary growth;
FIG. 2 is a graph comparing copper surfaces before (a) and after (b) etching;
fig. 3 is a scanning electron microscope contrast diagram of graphene on the inner surface of a copper pocket before (a) and after (c) etching growth, graphene (b) simply and repeatedly grown twice, and a scanning electron microscope photograph (d) of the multi-layer graphene obtained after controlling time and times.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
In the embodiment, a chemical vapor deposition system is used as a growth system, a copper pocket is used as a graphene growth substrate, and double-layer graphene is grown on the inner surface of the copper pocket in an etching secondary growth mode.
First, a copper foil (thickness: 25 μm, purity: 99.9%) of 4X 5cm size was put into a prepared polishing liquid (phosphoric acid: 75mL, ethanol: 75mL, isopropanol: 15mL, deionized water: 150mL, urea: 1.5 g), and subjected to an electrochemical polishing treatment under a direct current voltage of 10V for 30-60 s.
And folding the polished copper foil into a copper pocket with the shape shown in figure 1, placing the copper pocket in the middle of a quartz tube of a tube furnace, controlling a vacuum pump to enable the pressure in the quartz tube to be reduced to 3 multiplied by 10 -3 torr, introducing 100sccm argon and 100sccm hydrogen, and carrying out annealing treatment on the copper pocket for 30-60 minutes under the environment of 1000-1050 ℃ to reduce the surface defects of the copper foil.
After the annealing was completed, 1sccm of methane was introduced as a carbon source, and 10sccm of hydrogen was used as an assist gas, followed by growth for 2 hours.
And after the first growth is finished, the inner surface and the outer surface of the copper pocket are grown to obtain graphene layers, after the copper pocket is cooled to room temperature, the copper pocket is taken out and put into an oxygen plasma generator, and the copper is etched for 3-20 minutes in an oxygen atmosphere of 1-10sccm under 90% power, so that the graphene on the outer surface of the copper pocket is removed to expose the copper on the surface. Fig. 2 shows that the etching functions to expose the copper on the outer surface, (a) a monolayer of graphene is laid on the copper foil before the etching, and (b) after the etching, the surface graphene sample is removed, and the metal copper is exposed.
And (3) putting the etched copper pocket into a quartz tube, growing for 0.1-12h under the same conditions, cooling to room temperature after the process is finished, and taking out the secondarily grown copper pocket.
Fig. 3 (a) is a scanning electron micrograph of the inner surface of a once-grown copper pocket, and the wrinkles show that a graphene continuous film is formed.
In fig. 3 (b), the simple repeated growth is performed by placing the polished copper pocket in a tube furnace, annealing in an argon-hydrogen atmosphere for 30 minutes, introducing 1sccm methane as a growth gas source, and growing for 2 hours, and restarting the procedure after the above process is completed, and repeating the growth once. The characterization photo shows that the surface is still a single-layer fold, and after the graphene is completely covered, copper metal is not used as a catalyst after multiple growth, and the graphene does not continue to grow.
In fig. 3 (c), a bilayer graphene (BLG) is formed on the inner surface of the secondarily grown copper pocket, which illustrates that the outer surface of the copper foil exposed by etching can play a role in catalyzing the redundant carbon source, carbon active groups diffuse into the pocket through the copper foil, secondary nucleation growth on the inner surface is assisted, and a flat and wrinkle-free bilayer graphene is obtained, and the coverage area of the bilayer graphene is significantly larger than that of the monolayer graphene (SLG).
Further, the growth atmosphere and the number of times of growth are controlled to achieve the layer-number controllable growth of graphene, as shown in fig. 3 (d).
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. 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 (10)
1. A method for promoting secondary growth of graphene, comprising the steps of: taking a limited space formed by copper foil or nickel foil as a graphene growth substrate, after annealing and first growing graphene are completed, etching the outer surface of the limited space by plasma so as to remove the graphene on the outer surface of the limited space, and then carrying out second growth of the graphene so as to promote the growth of double-layer graphene on the inner surface of the limited space;
The annealing conditions include: the annealing time is 30-60 minutes, the annealing temperature is 1000-1050 ℃, and the annealing atmosphere is argon and hydrogen;
the wall thickness of the limit space is larger than the etching depth;
The conditions for each growth included: methane is used as a carbon source, the growth time is 20-60 minutes, the growth temperature is 1000-1050 ℃, argon and hydrogen are used as carrier gases, the flow rate of the methane is 0.1-10sccm, the flow rate of the argon is 1-500sccm, and the flow rate of the hydrogen is 1-200sccm.
2. The method of promoting graphene secondary growth according to claim 1, wherein the confined space has a closed cavity formed of copper foil or nickel foil.
3. The method for promoting the secondary growth of graphene according to claim 2, wherein the confinement space is a closed pocket made of copper foil or nickel foil.
4. A method of promoting graphene regrowth according to claim 3, wherein the copper foil or nickel foil is polished metal, and the polishing conditions include: placing copper foil or nickel foil serving as an anode into polishing solution for treatment; the polishing solution comprises the following components: phosphoric acid, ethanol, isopropanol, deionized water and urea.
5. The method for promoting the secondary growth of graphene according to claim 4, wherein the copper foil or the nickel foil is placed as an anode in a polishing liquid, and the copper foil is subjected to a treatment at a voltage of 10V for 30-60 s.
6. The method of promoting secondary growth of graphene according to claim 1, wherein the conditions of the first and second growth are the same.
7. The method for promoting the secondary growth of graphene according to claim 1, wherein the etching is oxygen plasma etching.
8. The method of claim 1, wherein the etching conditions include: introducing 5sccm of oxygen, power 90%, and etching for 3-20 min.
9. The method for promoting the secondary growth of graphene according to claim 1, comprising the steps of: prefabricating the polished copper foil into a closed pocket, placing the copper pocket into a tubular furnace for annealing, performing chemical vapor deposition to grow graphene for the first time, taking out the copper pocket after the first time growth, performing plasma etching on the copper pocket to remove the graphene on the outer surface, and then performing chemical vapor deposition to grow graphene for the second time to promote the growth of double-layer graphene on the inner surface of the pocket.
10. A method for preparing bilayer graphene, comprising the method for promoting secondary growth of graphene according to any one of claims 1 to 9.
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| CN109485035A (en) * | 2018-11-12 | 2019-03-19 | 南京大学 | A kind of double-deck or three layers of graphene preparation method |
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| CN103730523B (en) * | 2014-01-06 | 2016-05-11 | 山东师范大学 | A kind of graphene-based mercury cadmium telluride composite film material and preparation method thereof |
| CN106335897B (en) * | 2016-08-26 | 2019-02-26 | 中国人民大学 | A kind of large single crystal bilayer graphene and preparation method thereof |
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| Towards intrinsically pure graphene grown on copper;Xu, XZ, et al;《Nano research》;20220228;第15卷(第2期);全文 * |
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