CN110453280B - Preparation method of high-quality wafer-level graphene single crystal - Google Patents

Preparation method of high-quality wafer-level graphene single crystal Download PDF

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CN110453280B
CN110453280B CN201810432604.1A CN201810432604A CN110453280B CN 110453280 B CN110453280 B CN 110453280B CN 201810432604 A CN201810432604 A CN 201810432604A CN 110453280 B CN110453280 B CN 110453280B
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黄富强
程园
毕辉
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Shanghai Institute of Ceramics of CAS
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    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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Abstract

The invention provides a preparation method of a high-quality wafer-level graphene single crystal, which comprises the following steps: placing the metal foil subjected to plasma treatment in a reaction furnace, introducing inert atmosphere, heating to an annealing temperature, and introducing hydrogen for annealing treatment, wherein the metal foil is one of copper foil, nickel foil, molybdenum foil and cobalt foil; introducing a carbon source into the reaction furnace, adjusting the annealing temperature to the growth temperature of the graphene single crystal, starting the growth of the graphene single crystal, and cooling to room temperature after the growth is finished; the plasma treatment atmosphere is at least one of air, hydrogen, argon, oxygen and nitrogen, the power is 100-150W, the pressure is 400-500Pa, and the time is 1-30 minutes.

Description

Preparation method of high-quality wafer-level graphene single crystal
Technical Field
The invention relates to a preparation method of a high-quality wafer-level graphene single crystal, and belongs to the field of graphene single crystals.
Background
Since the discovery of graphene by two scientists at the university of manchester in the united kingdom in 2004 and the research and application thereof to date, graphene shows immeasurable application prospects with its excellent properties. The unique crystal structure of graphene endows the graphene with novel properties such as high thermal conductivity, high mechanical strength, high mobility, high light transmittance and the like.
Although graphene has great potential application in many fields, it is still far from the way of researching how to prepare high-quality and large-size graphene single crystals. Among the existing production methods, vapor deposition is generally employed. According to the method, metal is mainly used as a catalyst, the operation is simple, the graphene single crystal with good quality is prepared, but due to the fact that the nucleation density is high, the size is small, a large number of crystal boundaries exist, the excellent performance of the graphene single crystal is greatly reduced, and therefore the application of graphene is limited.
In order to reduce nucleation density and prepare high-quality and large-size graphene single crystals, the performance of the graphene single crystals is improved, and the practical application value of the graphene single crystals is fully exerted. In recent years, many researchers have made diligent efforts in this regard, and have made great progress. For example, copperThe foil is folded in half, rolled into a tube, and folded into a sealed small box. The copper foil is processed to form a closed or semi-closed structure, the dissolving amount of the inner side of the copper foil to a carbon source is reduced, and therefore the nucleation density is inhibited, but the narrow closed or semi-closed structure also prevents the graphene single crystal from growing and is inconvenient to transfer, and the utilization rate of the graphene single crystal is reduced[1],[2]. In addition, oxygen is introduced in the growth stage, and the growth is catalyzed by the oxygen, so that the method is favorable for growing large-size single crystals, but the method is difficult to operate, has low safety coefficient, and is not favorable for mass production of graphene single crystals[3],[4]. Recently, graphene single crystals are grown on single crystal Cu (111) mainly by introducing high-flow hydrogen gas, a long-time low-pressure environment, or by using high-end mobile equipment or the like to prepare single crystal Cu (111). The methods have the defects of danger, complex process, harsh conditions, time consumption, material consumption and the like[1],[5],[6]. Therefore, the search for a more excellent method for preparing the large-size high-quality graphene single crystal has great scientific significance and practical requirements.
Reference to the literature
[1]Hao Y,Wang L,Liu Y,et al.Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene[J].Nature nanotechnology,2016,11(5):426.；
[2]Li B W,Luo D,Zhu L,et al.Orientation‐Dependent Strain Relaxation and Chemical Functionalization of Graphene on a Cu(111)Foil[J].Advanced Materials,2018.；
[3]Chen J,Cui M,Wu G,et al.Fast growth of large single-crystalline graphene assisted by sequential double oxygen passivation[J].Carbon,2017,116:133-138.；
[4]Lin L,Sun L,Zhang J,et al.Rapid Growth of Large Single‐Crystalline Graphene via Second Passivation and Multistage Carbon Supply[J].Advanced Materials,2016,28(23):4671-4677.；
[5]Hu J,Xu J,Zhao Y,et al.Roles of Oxygen and Hydrogen in Crystal Orientation Transition of Copper Foils for High-Quality Graphene Growth[J].Scientific reports,2017,7:45358.；
[6]Xu X,Zhang Z,Dong J,et al.Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial Cu foil[J].Science Bulletin,2017,62(15):1074-1080.。
Disclosure of Invention
In one aspect, the present invention provides a method for preparing a high-quality wafer-level graphene single crystal, including:
placing the metal foil subjected to plasma treatment in a reaction furnace, introducing inert atmosphere, heating to an annealing temperature, and introducing hydrogen for annealing treatment, wherein the metal foil is one of copper foil, nickel foil, molybdenum foil and cobalt foil;
introducing a carbon source into the reaction furnace, adjusting the annealing temperature to the growth temperature of the graphene single crystal, starting the growth of the graphene single crystal, and cooling to room temperature after the growth is finished;
the plasma treatment atmosphere is at least one of air, hydrogen, argon, oxygen and nitrogen, the power is 100-150W, the pressure is 400-500Pa, and the time is 1-30 minutes.
According to the method, the surface of the metal foil (such as copper foil, nickel foil, molybdenum foil, cobalt foil and the like) is subjected to plasma treatment (the atmosphere is at least one of air, hydrogen, argon, oxygen and nitrogen, the pressure is 400-500Pa, and the time is 1-30 minutes), so that the flatness of the surface of the copper foil and the oxygen-containing components of the surface are optimized, the nucleation density of the graphene single crystal is effectively inhibited in the subsequent growth process of the graphene single crystal, and the high-quality wafer-level graphene single crystal is finally obtained. Specifically, the plasma contains a large number of energetic electrons, positive and negative ions, excited particles, and radicals having strong oxidizing properties, and these radicals having strong oxidizing properties adhere to the surface of the copper foil and have a micro-oxidizing effect on the metal foil. For example, the oxidizing component of the copper foil is CuO. In addition, in the plasma generating process, the instantaneous high energy generated by the high-frequency discharge is enough to open the chemical energy of gas molecules to decompose, so that the micro impurity molecules on the surface of the metal foil can be removed, and the cleanness and the flatness of the surface of the metal foil are improved. The oxidation of the surface of the metal foil initiates passivation and inhibits nucleation. The flatness and cleanliness of the copper foil surface are also intended to reduce nucleation, since single crystals tend to nucleate at this point of impurity.
Preferably, the thickness of the metal foil is 25 to 127 μm.
Preferably, when the metal foil is a copper foil, the annealing temperature is 1000-1080 ℃ and the growth temperature is 1000-1080 ℃; when the metal foil is a nickel foil, the annealing temperature is 1000-1440 ℃, and the growth temperature is 1000-1440 ℃; when the metal foil is a molybdenum foil, the annealing temperature is 1000-2600 ℃, and the growth temperature is 1000-2600 ℃; when the metal foil is a cobalt foil, the annealing temperature is 1000-1480 ℃, and the growth temperature is 1000-1480 ℃.
Preferably, the metal foil is subjected to electrochemical polishing before plasma treatment, and parameters of the electrochemical polishing include: the electrolyte solution is pure phosphoric acid, the constant voltage is 1-5V, and the polishing time is 1-30 minutes.
Preferably, the inert atmosphere is at least one of argon, nitrogen and helium, and the gas flow rate is 1 to 1000 sccm.
Preferably, the gas flow rate of the hydrogen used for the annealing treatment is 1 to 30 sccm.
Preferably, the annealing time is 1 to 60 minutes.
Preferably, the carbon source is at least one of a gaseous carbon source, a liquid carbon source and a solid carbon source; preferably, the gaseous carbon source is at least one of methane, ethane, ethylene, acetylene, propane and propyne, the liquid carbon source is at least one of methanol, ethanol, propanol and acetone, and the solid carbon source is at least one of polyethylene glycol, polyvinyl fluoride and polydimethylsiloxane.
Preferably, the time for cooling from the graphene single crystal growth temperature to room temperature is 1-20 minutes.
Preferably, the growth time of the graphene single crystal is 1 minute to 3 hours.
Preferably, when the annealing temperature is less than the growth temperature of the graphene single crystal, the annealing temperature is kept to be increased to the growth temperature of the graphene single crystal at a rate of not less than 0.67 ℃/min during the introduction of the carbon source. Preferably, the rate is 0.67-2.67 ℃/min. The programmed temperature rise growth is to accelerate the growth speed, and the methane cracking rate is accelerated by the temperature driving force, so that sufficient effective carbon sources are improved for the growth of the graphene single crystals. The graphene single crystal is nucleated at a certain point and grows epitaxially, and the required amount of a carbon source is increased along with the increase of the size, so that the methane cracking rate is increased. The speed is fast, the corresponding time is short, the speed is too slow, and the temperature rise effect is not generated.
On the other hand, the invention also provides a high-quality wafer-level graphene single crystal prepared by the preparation method. According to the high-quality wafer-level graphene single crystal prepared by the invention, the size of a single-layer graphene single crystal domain can reach inch level, the single-layer coverage rate is more than 90%, and the mobility can reach 12000cm-2v-1s-1The graphene single crystal has excellent quality and can be applied to the fields of electronic information and transparent conductive films.
The invention has the beneficial effects that:
the metal foil treatment method is simple, high in repeatability, short in time consumption, low in material consumption, clean and environment-friendly;
the method can effectively inhibit the nucleation density of the graphene single crystal, and is beneficial to preparing high-quality wafer-level graphene single crystals;
the single-layer graphene domain area prepared by the method can reach inch level, the coverage rate of single-layer graphene is more than 90%, and the mobility is 12000cm-2v-1s-1The quality is excellent, and the method is beneficial to the practical application and industrial production of graphene;
the graphene single crystal prepared by the method has high quality and high mobility, is suitable for the field of electronic information and transparent conductive films, and has good application prospect and wide application prospect.
Drawings
FIG. 1 is a SEM topography of nucleation density of graphene single crystals, wherein (a) is not treated by air plasma and (b) is treated by air plasma;
FIG. 2 is a photograph of a graphene single crystal, wherein (a) is a growth without a temperature programmed process and (b) is a growth with a temperature programmed process;
fig. 3 is a raman spectrum of the graphene single crystal prepared in example 3, wherein the ratio of the 2D peak intensity to the G peak intensity in the graph is greater than 2, which indicates that the prepared graphene is single-layer covered;
fig. 4 shows the crystal structure and the number of layers of the graphene single crystal prepared in example 3;
FIG. 5 is a photograph of a graphene single crystal prepared in example 4;
fig. 6 is an SEM image of the graphene single crystal grown on the nickel foil of example 5.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the size of a single-layer graphene single-crystal domain region in the graphene single crystal can reach inch level, the single-layer coverage rate is more than 90%, and the mobility can reach 12000cm-2v-1s-1The graphene single crystal has excellent quality, is suitable for the field of electronic information and transparent conductive films, and has good application prospect.
In one embodiment of the invention, the nucleation density of the graphene single crystal can be effectively inhibited by combining the unique treatment of the metal foil and the growth process of the graphene single crystal, and the high-quality wafer-level graphene single crystal is prepared. Wherein the metal foil can be one of copper foil, nickel foil, molybdenum foil and cobalt foil. In one embodiment of the invention, the nucleation density of the graphene single crystal can be effectively inhibited through the unique treatment of the metal foil, and the high-quality wafer-level graphene single crystal is prepared. The preparation method is simple in preparation process, high in repeatability and suitable for industrial production.
Taking a copper foil as an example, a method for preparing a high-quality wafer-level graphene single crystal is exemplarily described below.
And putting the copper foil into a pure phosphoric acid electrolyte solution for electrochemical polishing. Wherein, the conditions of electrochemical polishing are as follows: the electrolyte solution is pure phosphoric acid, the constant voltage is 1-5V, and the polishing time is 1-30 minutes. Then washing with deionized water and ethanol, and drying with nitrogen.
And cleaning the copper foil subjected to electrochemical polishing, and then carrying out plasma treatment. Specifically, plasma equipment is adopted, an air valve is opened, the atmosphere comprises one of hydrogen, argon, oxygen, nitrogen and the mixture of the hydrogen, the argon, the oxygen and the nitrogen, the power is kept between 100 and 150W, the pressure is stabilized between 400 and 500Pa, and the treatment time is 1 to 30 minutes. The purpose of the plasma treatment is to optimize the flatness of the copper foil surface and the oxygen-containing composition of the surface.
And placing the copper foil subjected to the plasma treatment in a reaction furnace, introducing an inert atmosphere, heating to 1000-1080 ℃, and continuing introducing hydrogen for constant-temperature annealing treatment. As an example, the copper foil after plasma treatment is placed in a CVD tube furnace, argon gas is introduced at a gas flow rate of 1 to 1000sccm, and the copper foil is heated to 1000 to 1080 ℃. Then annealing at constant temperature, and introducing trace hydrogen for 1-60 minutes. Wherein, a small amount of hydrogen is introduced at a flow rate of 1-30 sccm. It should be noted that the annealing temperature remains unchanged during the above process. The annealing temperature and the growth temperature are lower than the melting point of the metal foil. Annealing affects the flatness of the metal surface greatly, and the nano oxide formed after the surface is oxidized by plasma treatment is hydrogen introduced in the annealing process and has a certain etching effect.
Introducing a carbon source, keeping the growth temperature of the graphene single crystal at 1000-1080 ℃, starting the growth of the graphene single crystal, and cooling to room temperature after the growth is finished. The carbon source used included: gaseous carbon source, liquid carbon source, solid carbon source. Among them, the gaseous carbon source is preferably selected from methane, ethylene, acetylene and their mixture. The liquid carbon source is preferably selected from methanol, ethanol, acetone and their mixture. The solid carbon source is preferably selected from polyethylene glycol, polyvinyl fluoride, polydimethylsiloxane and mixtures thereof. It should be noted that the carbon source may be introduced at a flow rate of 10 to 40sccm due to the transformation of the carbon source into a gaseous form at a high temperature. The growth time of the graphene single crystal can be 1 minute to 3 hours, and gas is kept introduced in the reaction process. And (4) closing the carbon source after the reaction is finished, and rapidly cooling to room temperature under the protection of argon and hydrogen. Wherein the growth temperature is 1000-1080 ℃ according to the growth temperature of the graphene single crystal, and the time for cooling to room temperature is 1-20 minutes. When the annealing temperature is less than the growth temperature of the graphene single crystal, keeping the annealing temperature to be raised to the growth temperature of the graphene single crystal at a speed of not less than 0.67 ℃/minute in the process of introducing the carbon source, and preferably, the speed is 0.67-2.67 ℃/minute. The purpose of the temperature programmed growth is to accelerate the growth, in a certain temperature interval, the speed is inversely proportional to the time, but the size of the single crystal is the synergistic effect of the temperature raising speed and the growth time, so that a balance point is found, the growth time required by the single crystal with the maximum size is taken as a limit, and the minimum speed of the temperature programmed growth cannot be lower than 0.67 ℃/min. In addition, when the metal foil is a nickel foil, the annealing temperature is 1000-1440 ℃, and the growth temperature is 1000-1440 ℃. When the metal foil is molybdenum foil, the annealing temperature is 1000-2600 ℃, and the growth temperature is 1000-2600 ℃. When the metal foil is a cobalt foil, the annealing temperature is 1000-1480 ℃, and the growth temperature is 1000-1480 ℃.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Comparative example 1
A 25 μm copper foil (purchased from alpha (alfa) corporation, product number 46986) was used as the metal substrate. And carrying out electrochemical polishing on the copper foil, wherein an electrolyte solution is pure phosphoric acid, the constant voltage is 3V, and the polishing time is 1-30 minutes. Then washing with deionized water and ethanol, and drying with nitrogen. The polished and cleaned copper foil is directly placed into a chemical vapor deposition reaction furnace without plasma treatment, 500sccm argon is introduced, the temperature is raised to 1080 ℃, 10sccm hydrogen is introduced, constant-temperature annealing is carried out for 30 minutes, and 10sccm methane is introduced for reaction for 30 minutes. After the reaction is finished, the methane is closed, and the temperature is rapidly reduced to room temperature (the cooling time is 20 minutes). The SEM topography of the obtained graphene single crystal is shown in (a) in FIG. 1, and the graph shows that the graphene isThe nucleation density of the single crystal is high, and about fifty graphene single crystals are arranged in the area of the graph. And the graphene single crystal domain area is micron-sized, the coverage rate of single-layer graphene is low, and the mobility is less than 10000cm-2v-1s-1。
Example 1
Example 1 differs from comparative example 1 in that: and carrying out plasma treatment on the copper foil after electrochemical polishing, opening an air valve by adopting plasma equipment, adjusting the power to be 100W, stabilizing the pressure to be between 400-500Pa, and treating for 30 minutes. Other implementation methods are the same as comparative example 1. The SEM topography of the obtained graphene single crystal is shown in fig. 1 (b), and it is known that the nucleation density of the graphene single crystal is effectively reduced, and the region in the figure has only two graphene single crystals. Experiments compare that the nucleation number of the graphene single crystal is sharply reduced after the copper foil is subjected to plasma treatment, and the method proves that the plasma treatment effectively controls the nucleation density of the graphene single crystal.
Example 2
And carrying out electrochemical polishing on the copper foil, wherein an electrolyte solution is pure phosphoric acid, the constant voltage is 3V, and the polishing time is 30 minutes. Then washing with deionized water and ethanol, and drying with nitrogen. The polished and cleaned copper foil is treated by plasma, a plasma device is adopted, an air valve is opened, the power is adjusted to be 100W, the pressure is stabilized between 400 and 500Pa, and the treatment time is 30 minutes. Then placing the silicon wafer into a chemical vapor deposition reaction furnace, introducing 500sccm argon, heating to 1000 ℃, then introducing 10sccm hydrogen, annealing at constant temperature for 30 minutes, and introducing 10sccm methane for reacting for 60 minutes. After the reaction is finished, the methane is closed, and the temperature is rapidly reduced to room temperature (the cooling time is 20 minutes). The obtained photo of graphene single crystal is shown in FIG. 2 (a), and the graphene single crystal domain region is 1-2mm, the single-layer graphene coverage rate is 93%, and the mobility is 11000cm-2v-1s-1。
Example 3
The present embodiment 3 differs from embodiment 2 in that: adopting temperature programming to grow graphene single crystal, and introducing a carbon source in the process of raising the growth temperature of the graphene single crystal from 1000 ℃ to 1080 ℃ (the temperature raising rate is about 1.3 ℃/min) after constant-temperature annealing treatmentThe reaction time was continued for 60 minutes. Other implementation methods are the same as example 2. The obtained photo of the graphene single crystal is shown in (b) of FIG. 2, and the graphene single crystal domain area is about 5mm, the coverage rate of single-layer graphene is 96%, and the mobility is 12000cm-2v-1s-1. As can be seen from fig. 2, the growth rate of the graphene single crystal is effectively increased by the temperature programmed growth method. The combination of Ranman (FIG. 3) and TEM (FIG. 4) shows that the prepared graphene single crystal has good crystallinity and a single layer without defects.
Example 4
This example 4 differs from example 3 in that: the growth time in example 3 was extended to 120 minutes and the methane flow was increased to 30 sccm. The other process parameters were the same as in example 3. In this example 4, by prolonging the growth time and increasing the methane flow, it can be seen from (fig. 5) that the size of the prepared graphene single crystal can reach inch level, the morphology is regular, the coverage rate is 95%, and the mobility is 12000cm-2v-1s-1。
Example 5
This example 5 differs from example 2 in that: and (3) growing the graphene single crystal after plasma treatment by using a metal nickel foil as a substrate. Other implementation methods are the same as example 2. As shown in FIG. 6, the thickness of the graphene single crystal was about 2mm, the coverage was 94%, and the mobility was 12000cm-2v-1s-1. It should be noted that the plasma treatment in the present invention can be applied to other metal foils (molybdenum foil or cobalt foil) as well, and the reaction mechanism of the molybdenum foil or cobalt foil is similar to that of the copper foil and nickel foil, and has a common application type.
The above-described embodiments are merely exemplary data of the present invention and are not intended to limit the present invention, and any modifications, equivalents, and improvements made within the principle of the present invention are included in the scope of the present invention.

Claims (10)

1. A preparation method of a high-quality wafer-level graphene single crystal is characterized by comprising the following steps:
subjecting the metal foil to electrochemical polishing and plasma treatment, wherein parameters of the electrochemical polishing comprise: the electrolyte solution is pure phosphoric acid, the constant voltage is 1-5V, and the polishing time is 1-30 minutes;
placing the metal foil subjected to plasma treatment in a reaction furnace, introducing inert atmosphere, heating to an annealing temperature, and introducing hydrogen for annealing treatment, wherein the metal foil is one of copper foil, nickel foil, molybdenum foil and cobalt foil;
introducing a carbon source into the reaction furnace, adjusting the annealing temperature to the growth temperature of the graphene single crystal, starting the growth of the graphene single crystal, growing for 30 minutes to 3 hours, and cooling to room temperature after the growth is finished;
the plasma treatment atmosphere is at least one of air, hydrogen, argon, oxygen and nitrogen, the power is 100-150W, the pressure is 400-500Pa, and the time is 1-30 minutes;
when the metal foil is a copper foil, the annealing temperature is 1000-1080 ℃, and the growth temperature is 1000-1080 ℃; when the metal foil is a nickel foil, the annealing temperature is 1000-1440 ℃, and the growth temperature is 1000-1440 ℃; when the metal foil is a molybdenum foil, the annealing temperature is 1000-2600 ℃, and the growth temperature is 1000-2600 ℃; when the metal foil is a cobalt foil, the annealing temperature is 1000-1480 ℃, and the growth temperature is 1000-1480 ℃;
the annealing temperature is less than the growth temperature of the graphene single crystal, and the annealing temperature is kept to be raised to the growth temperature of the graphene single crystal at a speed of not less than 0.67 ℃/min in the process of introducing the carbon source.
2. The method according to claim 1, wherein the metal foil has a thickness of 25 to 127 μm.
3. The method according to claim 1, wherein the inert gas atmosphere is at least one of argon, nitrogen and helium, and the gas flow rate is 1 to 1000 sccm.
4. The method as claimed in claim 1, wherein the flow rate of the hydrogen gas used for the annealing treatment is 1 to 30 sccm.
5. The method according to claim 1, wherein the annealing is performed for 1 to 60 minutes.
6. The method of claim 1, wherein the rate is 0.67 to 2.67 ℃/min.
7. The method according to claim 1, wherein the carbon source is at least one of a gaseous carbon source, a liquid carbon source, and a solid carbon source.
8. The method according to claim 7, wherein the gaseous carbon source is at least one of methane, ethane, ethylene, acetylene, propane and propyne, the liquid carbon source is at least one of methanol, ethanol, propanol and acetone, and the solid carbon source is at least one of polyethylene glycol, polyvinyl fluoride and polydimethylsiloxane.
9. The method according to any one of claims 1 to 8, wherein the time for cooling from the graphene single crystal growth temperature to room temperature is 1 to 20 minutes.
10. A high-quality wafer-level graphene single crystal produced according to the production method of any one of claims 1 to 9.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103368058A (en) * 2013-07-23 2013-10-23 上海交通大学 Saturable absorber mirror based on graphene and manufacturing method thereof
CN103643288A (en) * 2013-11-29 2014-03-19 中国科学院金属研究所 Preparation method of high-quality large-size monocrystal graphene
CN104773726A (en) * 2015-04-10 2015-07-15 武汉大学 Method for growing single-layer graphene thin film by virtue of low-temperature chemical vapor deposition
CN105018896A (en) * 2014-04-22 2015-11-04 常州二维碳素科技股份有限公司 Graphene film as well as preparation method and application thereof
CN105112999A (en) * 2015-09-09 2015-12-02 中国计量科学研究院 Method for preparing monocrystal graphene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101668691B1 (en) * 2011-08-25 2016-10-24 위스콘신 얼럼나이 리서어치 화운데이션 Barrier guided growth of microstructured and nanostructured graphene and graphite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103368058A (en) * 2013-07-23 2013-10-23 上海交通大学 Saturable absorber mirror based on graphene and manufacturing method thereof
CN103643288A (en) * 2013-11-29 2014-03-19 中国科学院金属研究所 Preparation method of high-quality large-size monocrystal graphene
CN105018896A (en) * 2014-04-22 2015-11-04 常州二维碳素科技股份有限公司 Graphene film as well as preparation method and application thereof
CN104773726A (en) * 2015-04-10 2015-07-15 武汉大学 Method for growing single-layer graphene thin film by virtue of low-temperature chemical vapor deposition
CN105112999A (en) * 2015-09-09 2015-12-02 中国计量科学研究院 Method for preparing monocrystal graphene

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