CN110453280A - A kind of preparation method of high quality wafer level graphene monocrystalline - Google Patents
A kind of preparation method of high quality wafer level graphene monocrystalline Download PDFInfo
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- CN110453280A CN110453280A CN201810432604.1A CN201810432604A CN110453280A CN 110453280 A CN110453280 A CN 110453280A CN 201810432604 A CN201810432604 A CN 201810432604A CN 110453280 A CN110453280 A CN 110453280A
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- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- 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
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- 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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
Abstract
The present invention provides a kind of preparation method of high quality wafer level graphene monocrystalline, it include: that plasma treated metal foil is placed in reacting furnace and is passed through inert atmosphere, it then heats to after annealing temperature and is passed through hydrogen again and is made annealing treatment, the metal foil is one of copper foil, nickel foil, molybdenum foil, cobalt foil；Carbon source is imported into reacting furnace, is adjusted the growth of beginning graphene monocrystalline after annealing temperature to the growth temperature of graphene monocrystalline, is cooled to room temperature after to be grown；The atmosphere of the corona treatment is at least one of air, hydrogen, argon gas, oxygen, nitrogen, and power is 100~150W, and pressure is 400~500Pa, and the time is 1~30 minute.
Description
Technical field
The present invention relates to a kind of high quality wafer level graphene method for preparing single crystal, belong to graphene monocrystalline field.
Background technique
Since two scientists of Univ Manchester UK in 2004 have found graphenes, and so far people it is studied with
Using graphene shows immeasurable application prospect with its excellent performance.The unique crystal structure of graphene assigns it
Novel property, such as highly thermally conductive property, high mechanical strength, high mobility, high light transmittance etc..
Although graphene has a very big potential application in numerous areas, but high quality, big how is prepared in research
It still shoulders heavy responsibilities in the method for size graphite alkene monocrystalline.In existing preparation method, vapour deposition process is generally used.It should
Method is easy to operate mainly using metal as catalyst, prepares the preferable graphene monocrystalline of mass, but close due to being nucleated
Degree is high, size is small, and there are a large amount of crystal boundaries, the excellent properties of graphene monocrystalline are greatly reduced, to limit graphene
Using.
In order to reduce nucleation density, preparation high quality, big size graphene monocrystalline, so that graphene monocrystalline performance is promoted,
Give full play to its practical application value.In recent years, many researchers are made that unremitting effort in this respect, also achieve
Very big progress.For example, by copper foil doubling, the etui for being rolled into tubulose, building up sealing.Processing copper foil constitutes a closing in this way
Or semi-enclosed structure, the meltage on the inside of copper foil to carbon source is reduced, thus inhibit nucleation density, but narrow closing or half
Enclosed construction also counteracts that graphene monocrystalline is grown up, and is not convenient for shifting, and reduces the utilization rate of graphene monocrystalline[1],[2]。
In addition, grow there are also in growth phase oxygen is passed through by oxygen catalytic, be conducive to growing large-size monocrystalline, but this method
Operating difficulties, safety coefficient is low, is unfavorable for producing graphene monocrystalline in enormous quantities[3],[4].Recently, there are also on monocrystalline Cu (111)
Graphene monocrystalline is grown, method is mainly as follows, is passed through high flow capacity hydrogen, long-time environment under low pressure, or utilize high-end removable
Dynamic equipment etc. prepares monocrystalline Cu (111).The deficiencies of dangerous property of these methods, complex process, condition is harsh, time-consuming consumptive material
Place[1],[5],[6].Therefore, it seeks more excellent method and prepares large-size high-quality graphene monocrystalline with great section
Learn meaning and actual demand.
Bibliography
[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.。
Summary of the invention
On the one hand, the present invention provides a kind of preparation methods of high quality wafer level graphene monocrystalline, comprising:
Plasma treated metal foil is placed in reacting furnace and is passed through inert atmosphere, after then heating to annealing temperature
It is passed through hydrogen again to be made annealing treatment, the metal foil is one of copper foil, nickel foil, molybdenum foil, cobalt foil；
Carbon source is imported into reacting furnace, adjusts the life of beginning graphene monocrystalline after annealing temperature to the growth temperature of graphene monocrystalline
It is long, it is cooled to room temperature after to be grown；
The atmosphere of the corona treatment be at least one of air, hydrogen, argon gas, oxygen, nitrogen, power be 100~
150W, pressure are 400~500Pa, and the time is 1~30 minute.
The present invention is by carrying out corona treatment (gas to metal foil (for example, copper foil, nickel foil, molybdenum foil, cobalt foil etc.) surface
Atmosphere is at least one of air, hydrogen, argon gas, oxygen, nitrogen, and pressure is 400~500Pa, and the time is 1~30 minute), it is excellent
The flatness of copper foil surface and the oxydant on surface are changed, to effectively inhibit in the growth course of subsequent graphene monocrystalline
Graphene monocrystalline nucleation density, finally obtains high quality wafer level graphene monocrystalline.Specifically, comprising big in plasma
High energy electron, negative ions, excited state particle and the free radical with strong oxidizing property of amount, these are attached with strong oxidizing property group
In copper foil surface, have the function of low-level oxidation to metal foil.For example, the oxidizing component of copper foil is CuO.Moreover, plasma
During generation, moment high energy caused by high-frequency discharge opens the chemical energy of gas molecule enough, is allowed to decompose, therefore can
The minute impurities molecule for removing metal foil surface, improves the cleannes and flatness of metal foil surface.The oxidation of metal foil surface
Passivation is opened, nucleation is inhibited.The flatness and cleannes of copper foil surface are also for nucleation is reduced, because monocrystalline is easy at this
It is nucleated on impure point.
Preferably, the metal foil with a thickness of 25~127 μm.
Preferably, the annealing temperature is 1000~1080 DEG C, growth temperature 1000 when the metal foil is copper foil
DEG C~1080 DEG C；When the metal foil be nickel foil when, the annealing temperature be 1000~1440 DEG C, growth temperature be 1000 DEG C~
1440℃；When the metal foil is molybdenum foil, the annealing temperature is 1000~2600 DEG C, and growth temperature is 1000 DEG C~2600
℃；When the metal foil is cobalt foil, the annealing temperature is 1000~1480 DEG C, and growth temperature is 1000 DEG C~1480 DEG C.
Preferably, first carrying out electrochemical polish, the ginseng of the electrochemical polish before metal foil carries out gas ions processing
Number include: electrolyte solution be pure phosphoric acid, 1~5V of constant voltage, polishing time are 1~30 minute.
Preferably, the inert atmosphere be at least one of argon gas, nitrogen, helium, gas flow be 1~
1000sccm。
Preferably, the gas flow of hydrogen used in the annealing is 1~30sccm.
Preferably, the time of the annealing is 1~60 minute.
Preferably, the carbon source is at least one of gaseous carbon source, liquid carbon source, solid-state carbon source；Preferably, the gas
State carbon source is at least one of methane, ethane, ethylene, acetylene, propane, propine, and the liquid carbon source is methanol, ethyl alcohol, third
At least one of alcohol, acetone, the solid-state carbon source are polyethylene glycol, polyvinyl fluoride, at least one in dimethyl silicone polymer
Kind.
Preferably, being 1~20 minute from the time that graphene single crystal growth temperature is cooled to room temperature.
Preferably, the growth time of the graphene monocrystalline is 1 minute~3 hours.
Preferably, being moved back described in holding during importing carbon source when the growth temperature of annealing temperature < graphene monocrystalline
Fiery temperature is warming up to graphene single crystal growth temperature with the rate not less than 0.67 DEG C/min.Preferably, the rate is 0.67
~2.67 DEG C/min.Wherein, temperature programming growth is to speed up the speed of growth, accelerates methane cracking rate by temperature driving force,
Sufficient effective carbon source is improved for graphene crystal growth.Graphene monocrystalline is with certain point nucleation, epitaxial growth, with the increasing of size
Greatly, the demand of carbon source also increases, therefore accelerates methane cracking rate.Rate corresponds to that the time is few, and rate is excessively slow fastly, does not heat up
Effect.
On the other hand, the present invention also provides a kind of high quality wafer level graphenes prepared according to above-mentioned preparation method
Monocrystalline.High quality wafer level graphene monocrystalline prepared by the present invention, single-layer graphene single crystal domains area's size up to inch grade,
Monolayer coverage is greater than 90%, and mobility is up to 12000cm-2v-1s-1, graphene monocrystalline good quality is applicable to e-mail
Breath, the application of transparent conductive film field.
Beneficial effects of the present invention:
In the present invention, metal foil processing method is simple, and repeatability is high, and time-consuming short, consumptive material is few, clean and environmental protection；
Graphene monocrystalline nucleation density can be effectively suppressed in the present invention, is conducive to prepare high quality wafer level graphene monocrystalline；
The present invention prepares graphene single crystal domains area up to inch grade, and single-layer graphene coverage rate is greater than 90%, and mobility is
12000cm-2v-1s-1, good quality is conducive to the practical application and industrialized production of graphene；
The present invention prepares graphene monocrystalline quality height, has high mobility, is suitable for electronic information, transparent conductive film field
Using having a good application prospect, be with a wide range of applications.
Detailed description of the invention
Fig. 1 is graphene monocrystalline nucleation density SEM shape appearance figure, wherein (a) is to handle without air plasma, (b)
To be handled by air plasma；
Fig. 2 is graphene monocrystalline photo figure, wherein (a) is to grow without temperature programming, it (b) is to be grown by temperature programming；
Fig. 3 is graphene monocrystalline Ranman spectrogram prepared by embodiment 3, and wherein 2D peak intensity and G peak intensity ratio are greater than 2 in figure, by
Graphene is prepared known to this as single layer covering；
Fig. 4 is the crystal structure and the number of plies of graphene monocrystalline prepared by embodiment 3；
Fig. 5 is graphene monocrystalline photo figure prepared by embodiment 4；
Fig. 6 is the SEM figure for the graphene monocrystalline that embodiment 5 is grown on nickel foil.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the present invention, up to inch grade, monolayer coverage is greater than single-layer graphene single crystal domains area's size in graphene monocrystalline
90%, mobility is up to 12000cm-2v-1s-1, graphene monocrystalline good quality is suitable for electronic information, transparent conductive film is led
Domain application, has a good application prospect.
In an embodiment of the present invention, can by combine metal foil it is unique processing and graphene monocrystalline growing process,
The nucleation density that graphene monocrystalline can effectively be inhibited prepares high quality wafer level graphene monocrystalline.Wherein, the metal foil
It can be one of copper foil, nickel foil, molybdenum foil, cobalt foil.In an embodiment of the present invention, the unique processing energy of metal foil can be passed through
Enough nucleation densities for effectively inhibiting graphene monocrystalline, prepare high quality wafer level graphene monocrystalline.Preparation process letter of the present invention
Single, repeatability is high, is suitable for industrialization production.
With copper foil as an example, following exemplary illustrate the preparation method of high quality wafer level graphene monocrystalline.
Copper foil is put into pure phosphoric acid electrolyte solution and carries out electrochemical polish.Wherein, the condition of electrochemical polish: electrolysis
Matter solution is pure phosphoric acid, and 1~5V of constant voltage, polishing time is 1~30 minute.Then it is cleaned with deionized water, ethyl alcohol, nitrogen
Drying.
Corona treatment is carried out after copper foil after electrochemical polish is cleaned up.Specifically using plasma is set
It is standby, air valve is opened, atmosphere includes one of hydrogen, argon gas, oxygen, nitrogen and their gaseous mixtures, and power is maintained at
Between 100~150W, pressure is stablized between 400-500Pa, and the processing time is 1~30 minute.The purpose of corona treatment
It is the flatness of optimization copper foil surface, the oxydant on surface.
Plasma treated copper foil is placed in reacting furnace, inert atmosphere is passed through and is warming up to 1000~1080 DEG C,
Continue to be passed through the processing of hydrogen cycle annealing.As an example, the copper foil after corona treatment is put into CVD tube furnace,
It is passed through argon gas, gas flow is 1~1000sccm, is heated to 1000~1080 DEG C.Then cycle annealing is passed through trace hydrogen,
Annealing time is 1~60 minute.Wherein, it is passed through trace hydrogen, flow is 1~30sccm.It should be noted that annealing in above process
Temperature remains unchanged.Its annealing temperature and growth temperature are lower than the fusing point of metal foil.The biggish metal surface of annealing effect
Flatness, will affect the nano-oxide formed after corona treatment oxidized surface is the hydrogen introduced in annealing process,
There is certain corrasion.
Carbon source is imported, keeping graphene single crystal growth temperature is 1000~1080 DEG C, start the growth of graphene monocrystalline, to
It is cooled to room temperature after growth.Used carbon source includes: gaseous carbon source, liquid carbon source, solid-state carbon source.Wherein, gaseous carbon
Source preferentially selects methane, ethylene, acetylene and their mixed gas.Liquid carbon source preferentially selects methanol, ethyl alcohol, acetone and it
Mixing liquid.Solid-state carbon source preferentially selects polyethylene glycol, polyvinyl fluoride, dimethyl silicone polymer and their mixtures.It answers
When paying attention to being passed through carbon source, since there are carbon sources to be converted into gaseous state form for high temperature, flow can be 10-40sccm.Graphene monocrystalline
Growth time can be 1 minute~3 hours, in reaction process keep gas be passed through.Close carbon source after reaction, in argon gas and
It is rapidly cooled to room temperature under hydrogen shield.Wherein, cooling according to 1000~1080 DEG C of graphene single crystal growth temperature growth temperature
It is 1~20 minute to the room temperature time.When annealing temperature < graphene single crystal growth temperature, institute is kept during importing carbon source
It states annealing temperature and graphene single crystal growth temperature is warming up to the rate not less than 0.67 DEG C/min, the preferably described rate is
0.67~2.67 DEG C/min.The purpose of temperature programming growth is to speed up growth, and in certain temperature section, speed is with the time
Inverse ratio, but single crystal size is the synergistic effect of heating rate and growth time, therefore is to find equalization point, with full-size list
Growth time needed for crystalline substance is limited, and setting program heating minimum-rate cannot be below 0.67 DEG C/min.In addition, when metal foil is nickel foil
When, annealing temperature is 1000~1440 DEG C, and growth temperature is 1000 DEG C~1440 DEG C.When metal foil is molybdenum foil, annealing temperature
It is 1000~2600 DEG C, growth temperature is 1000 DEG C~2600 DEG C.When metal foil is cobalt foil, annealing temperature is 1000~1480
DEG C, growth temperature is 1000 DEG C~1480 DEG C.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Comparative example 1
Metal substrate is used as using 25 μm of copper foils (purchase is in Alpha (alfa) company, product number 46986).Copper foil is carried out
Electrochemical polish, electrolyte solution are pure phosphoric acid, and constant voltage 3V, polishing time is 1-30 minutes.Then deionized water, second are used
Alcohol cleaning, is dried with nitrogen.The clean copper foil of polishing is not plasma-treated, it is directly loadable into chemical vapour deposition reactor furnace
In, it is passed through 500sccm argon gas, is warming up to 1080 DEG C, 10sccm hydrogen is then passed to, cycle annealing 30 minutes, imports 10sccm
Methane reaction 30 minutes.Close methane, fast cooling to room temperature after reaction (cooling time is 20 minutes).Gained graphene
Monocrystalline SEM shape appearance figure shown in (a), has the nucleation density of graphene monocrystalline known to figure high, there are about five or six ten in region in figure as shown in figure 1
A graphene monocrystalline.And its graphene single crystal domains area be micron order, single-layer graphene coverage rate is low, mobility be less than
10000cm-2v-1s-1。
Embodiment 1
The present embodiment 1 is with the difference of comparative example 1: the copper foil after electrochemical polish is subjected to corona treatment again, using etc.
Gas ions equipment opens air valve, and power is adjusted to 100W, and pressure is stablized between 400-500Pa, and the processing time is 30 minutes.
Other implementation methods are identical as comparative example 1.Gained graphene monocrystalline SEM shape appearance figure shown in (b), there is graphite known to figure as shown in figure 1
The nucleation density of alkene monocrystalline is effectively reduced, and only there are two graphene monocrystalline in region in figure.Experimental comparison can obtain, copper foil by etc. from
Graphene monocrystalline nucleation number falls sharply after daughter processing, and this method demonstrates corona treatment and effectively controls graphene monocrystalline
Nucleation density.
Embodiment 2
Copper foil is subjected to electrochemical polish, electrolyte solution is pure phosphoric acid, and constant voltage 3V, polishing time is 30 minutes.Then
It is cleaned, is dried with nitrogen with deionized water, ethyl alcohol.By the copper foil using plasma processing that polishing is clean, using plasma is set
It is standby, air valve is opened, power is adjusted to 100W, and pressure is stablized between 400-500Pa, and the processing time is 30 minutes.Then it puts again
Enter in chemical vapour deposition reactor furnace, be passed through 500sccm argon gas, be warming up to 1000 DEG C, then pass to 10sccm hydrogen, constant temperature moves back
Fire 30 minutes imports 10sccm methane reaction 60 minutes.Methane, fast cooling to room temperature (cooling time are closed after reaction
It is 20 minutes).Gained graphene monocrystalline photo figure is as shown such as (a) in Fig. 2, and its graphene single crystal domains area is 1-2mm, single layer stone
Black alkene coverage rate is 93%, mobility 11000cm-2v-1s-1。
Embodiment 3
The present embodiment 3 the difference from example 2 is that: using temperature programming grow graphene monocrystalline, cycle annealing processing after,
Graphene single crystal growth temperature is warming up to 1080 DEG C (heating rate is about 1.3 DEG C/min) from 1000 DEG C and imports carbon in the process
Source, the reaction was continued, and the time is 60 minutes.Other implementation methods are same as Example 2.In gained graphene monocrystalline photo figure such as Fig. 2
(b) shown in, and its graphene single crystal domains area is about 5mm, and single-layer graphene coverage rate is 96%, mobility 12000cm-2v-1s-1.As shown in Figure 2, effectively accelerate the speed of growth of graphene monocrystalline using temperature programming growth method.In conjunction with Ranman (Fig. 3) with
And the graphene monocrystalline good crystallinity prepared known to TEM (Fig. 4), and single layer zero defect.
Embodiment 4
The present embodiment 4 is with the difference of embodiment 3: growth time in embodiment 3 being extended to 120 minutes, methane flow increases
To 30sccm.Other technological parameters are same as Example 3.The present embodiment 4 is by extension growth time and increases methane flow,
By preparing graphene single crystal size known to (Fig. 5) up to inch grade, regular appearance, coverage rate 95%, mobility is
12000cm-2v-1s-1。
Embodiment 5
The present embodiment 5 is with the difference of embodiment 2: making substrate using metal nickel foil, grows graphite after carrying out corona treatment
Alkene monocrystalline.Other implementation methods are same as Example 2.It is about 2mm that experimental result prepares graphene monocrystalline as shown in Figure 6, is covered
Lid rate is 94%, mobility 12000cm-2v-1s-1.It should be noted that plasma processing of the present invention is in other metal foil (molybdenum foils
Or cobalt foil) on can equally use, the reaction mechanism of molybdenum foil or cobalt foil and copper foil and nickel foil it is similar, have commonly used
Type.
Embodiment described above is only some experimental data of the present invention, is not intended to limit the invention, all of the invention
Made any modification within principle, equivalent replacement are improved, should be included within protection scope of the present invention.
Claims (12)
1. a kind of preparation method of high quality wafer level graphene monocrystalline characterized by comprising
Plasma treated metal foil is placed in reacting furnace and is passed through inert atmosphere, after then heating to annealing temperature
It is passed through hydrogen again to be made annealing treatment, the metal foil is one of copper foil, nickel foil, molybdenum foil, cobalt foil；
Carbon source is imported into reacting furnace, adjusts the life of beginning graphene monocrystalline after annealing temperature to the growth temperature of graphene monocrystalline
It is long, it is cooled to room temperature after to be grown；
The atmosphere of the corona treatment be at least one of air, hydrogen, argon gas, oxygen, nitrogen, power be 100~
150W, pressure are 400~500Pa, and the time is 1~30 minute.
2. preparation method according to claim 1, which is characterized in that the metal foil with a thickness of 25~127 μm.
3. preparation method according to claim 1 or 2, which is characterized in that when the metal foil is copper foil, the annealing
Temperature is 1000~1080 DEG C, and growth temperature is 1000 DEG C~1080 DEG C；When the metal foil is nickel foil, the annealing temperature
It is 1000~1440 DEG C, growth temperature is 1000 DEG C~1440 DEG C；When the metal foil is molybdenum foil, the annealing temperature is
1000~2600 DEG C, growth temperature is 1000 DEG C~2600 DEG C；When the metal foil is cobalt foil, the annealing temperature is 1000
~1480 DEG C, growth temperature is 1000 DEG C~1480 DEG C.
4. preparation method according to any one of claim 1-3, which is characterized in that carry out gas ions processing in metal foil
First carry out electrochemical polish before, the parameter of the electrochemical polish include: electrolyte solution be pure phosphoric acid, constant voltage 1~
5V, polishing time are 1~30 minute.
5. preparation method described in any one of -4 according to claim 1, which is characterized in that the inert atmosphere is argon gas, nitrogen
At least one of gas, helium, gas flow are 1~1000sccm.
6. preparation method according to any one of claims 1-5, which is characterized in that hydrogen used in the annealing
Gas flow is 1~30sccm.
7. preparation method according to claim 1 to 6, which is characterized in that the time of the annealing is 1
~60 minutes.
8. preparation method described in any one of -7 according to claim 1, which is characterized in that when annealing temperature < graphene monocrystalline
When growth temperature, the annealing temperature is kept to be warming up to stone with the rate not less than 0.67 DEG C/min during importing carbon source
Black alkene single crystal growth temperature；Preferably, the rate is 0.67~2.67 DEG C/min.
9. preparation method according to claim 1 to 8, which is characterized in that the carbon source is gaseous carbon source, liquid
At least one of state carbon source, solid-state carbon source；Preferably, the gaseous carbon source is methane, ethane, ethylene, acetylene, propane, third
At least one of alkynes, the liquid carbon source are at least one of methanol, ethyl alcohol, propyl alcohol, acetone, and the solid-state carbon source is poly-
At least one of ethylene glycol, polyvinyl fluoride, dimethyl silicone polymer.
10. preparation method described in -9 according to claim 1, which is characterized in that be cooled to room from graphene single crystal growth temperature
The time of temperature is 1~20 minute.
11. preparation method described in -10 according to claim 1, which is characterized in that the growth time of the graphene monocrystalline is 1
Minute~3 hours.
12. a kind of high quality wafer level graphene list of the preparation of preparation method described in any one of -11 according to claim 1
It is brilliant.
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| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114657635A (en) * | 2022-03-22 | 2022-06-24 | 西南交通大学 | Method for rapidly preparing single crystal graphene |
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