CN106587030B - A kind of method that atmospheric cryochemistry vapor deposition prepares graphene film - Google Patents
A kind of method that atmospheric cryochemistry vapor deposition prepares graphene film Download PDFInfo
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- CN106587030B CN106587030B CN201710018061.4A CN201710018061A CN106587030B CN 106587030 B CN106587030 B CN 106587030B CN 201710018061 A CN201710018061 A CN 201710018061A CN 106587030 B CN106587030 B CN 106587030B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a kind of methods that atmospheric cryochemistry vapor deposition prepares graphene film, this method to metallic substrates by first carrying out the high temperature anneal, cooling annealing is carried out again, and then by chemical vapour deposition technique, graphene film is obtained in metal substrate surface.The method of the present invention improves the catalytic activity of metallic substrates, so as to reduce the growth temperature of graphene, therefore the energy consumption and cost of industrial production graphene film are reduced, compared to traditional chemical vapour deposition technique synthesizing graphite alkene film, the method of the present invention is simple for process, carbon source derives from a wealth of sources, and the graphene film quality height of preparation, the number of plies are uniform and controllable.
Description
Technical field
The present invention relates to field of preparation of graphene more particularly to a kind of utilization chemical vapour deposition technique to make under atmospheric low-temperature
The method of standby graphene film.
Background technology
Graphene is to be based on sp by single layer of carbon atom2The hexagon cellular shape two dimensional crystal of hydridization composition, since quilt in 2004
Since Andre Geim and Konstantin Novoselov et al. discovery, the extensive concern of scientific circles is attracted.Graphene exists
The excellent specific property that electricity, optics, calorifics, mechanics etc. are shown makes it in battery, flexible transparent electrode, energy storage material, electricity
There is huge potential application foreground in the fields such as catalyst, nano electron device and composite material.
At present, the preparation method of graphene film mainly has：Mechanical stripping method, reduction-oxidation graphite method, chemical vapor deposition
Area method (CVD), epitaxial growth method etc..Wherein, it is less efficient and again though mechanical stripping method can be made the graphene haveing excellent performance
Renaturation is poor；Reduction-oxidation graphite method can be prepared on a large scale graphene, but its poor quality；Graphite prepared by SiC epitaxial growth methods
Alkene is with high costs.In contrast, chemical vapour deposition technique is easy to operate, and can prepare the uniform graphene of large area, the number of plies,
Especially gaseous carbon sources can be without interruption, is to realize graphene serialization, the effective way of industrialized production.It is however, existing
CVD method growth graphene must carry out at high temperature（Usually above 1000 DEG C）, this greatly hinders the industry of graphene
Metaplasia is produced.Therefore, a kind of large-scale production of method that can prepare the controllable graphene of the number of plies at low temperature to graphene is found
It is most important with application.
Invention content
It the problem of must being carried out at high temperature present invention is generally directed to existing process for preparing graphenes by chemical vapour deposition, provides
A kind of method for preparing graphene film under atmospheric low-temperature using chemical vapour deposition technique.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of method that atmospheric cryochemistry vapor deposition prepares graphene film, includes the following steps：
（1）Metallic substrates are cleaned by ultrasonic 5 ~ 10min, and are removed metallic substrates table with hydrochloric acid, acetone, deionized water respectively
Then metallic substrates are carried out the high temperature anneal by the moisture in face, treatment conditions are：300 ~ 1000sccm of argon flow amount, hydrogen
10 ~ 100sccm of flow, temperature are 850 ~ 1050 DEG C, 10 ~ 90min of processing time；
（2）To step（1）The middle metallic substrates through the high temperature anneal carry out cooling annealing, and treatment conditions are：
200 ~ 800 DEG C are at the uniform velocity cooled under argon gas atmosphere, wherein argon flow amount is 300 ~ 1000sccm；
（3）Treat step（2）Middle metallic substrates are down to predetermined reaction temperature, are passed through gaseous carbon sources and argon gas, carry out chemical gas
Mutually deposition is to get to graphene film.
Preferably, the metallic substrates are at least one of copper foil, cobalt foil, nickel foil, iron foil or are copper film, cobalt
At least one of film, nickel film, iron film.Metallic substrates used in the present invention can pass through existing metallic film preparation method system
It is standby to obtain, such as the methods of magnetron sputtering, electrochemical deposition, vacuum evaporation.
Preferably, step（1）High temperature makes annealing treatment condition：Argon flow amount 800sccm, hydrogen flowing quantity 30sccm,
950 DEG C of temperature, processing time 50min.
Preferably, the metallic substrates are copper foil.
Preferably, step（2）Middle rate of temperature fall is 1 ~ 30 DEG C/min.
Preferably, step（2）Middle metallic substrates are at the uniform velocity cooled to 300 ~ 700 DEG C.In the present invention, step（2）It is dropped
During temperature annealing, the metallic substrates through the high temperature anneal first can also be at the uniform velocity cooled to room temperature, so under an argon atmosphere
Rise to predetermined reaction temperature again afterwards.
Preferably, step（3）Described in gaseous carbon sources be methane, ethane, acetylene, ethylene, at least one of propane.
Preferably, step（3）Middle chemical vapor deposition conditions are：Carbon-source gas 1 ~ 10sccm of flow, argon flow amount 100
~ 1000sccm, 1 ~ 20min of reaction time.
Preferably, the gaseous carbon sources are methane.
Compared with prior art, the present invention has the advantages that：
1. the present invention reduces gas by metallic substrates first being carried out with the high temperature anneal, then carry out cooling annealing
Body hydrocarbon improves the catalytic capability of metallic substrates in itself in the adsorption energy of metal substrate surface and dehydrogenation and cracking energy,
The metallic substrates with high catalytic activity have been obtained, have thus greatly reduced the growth temperature of graphene, therefore reduce industry
The energy consumption and cost of graphene film are produced, is conducive to the process of industrialization of graphene.
2. the present invention realizes and prepares individual layer continuous graphite alkene film using chemical vapour deposition technique under atmospheric low-temperature, prepare
Graphene film Raman scattering have apparent 2D peaks, and IG/I2D＜ 0.5, light transmittance is 97.1 ~ 97.3%, compared to traditional change
Vapour deposition process synthesizing graphite alkene film is learned, the method for the present invention is simple for process, and carbon source derives from a wealth of sources, the graphene film matter of preparation
Amount is high, the number of plies is uniform and controllable.
Description of the drawings
Fig. 1 is the experimental provision structure diagram that the present invention prepares graphene film use；
Fig. 2 is the optical microscope of graphene film prepared by embodiment 1；
Fig. 3 is the Raman spectrogram of graphene film prepared by embodiment 1；
Fig. 4 is the scanning electron microscope diagram of graphene film prepared by embodiment 1；
Fig. 5 is the optical microscope of graphene film prepared by embodiment 2；
Fig. 6 is the Raman spectrogram of graphene film prepared by embodiment 2；
Fig. 7 is the transmission electron microscope figure of graphene film prepared by embodiment 2.
Specific embodiment
The present invention is described in further detail in the following with reference to the drawings and specific embodiments.
Fig. 1 is the experimental provision structure diagram that the present invention prepares graphene film use, as shown in Figure 1, the device packet
Include argon gas air source 1, hydrogen source gas 2, gaseous carbon sources 3, gas Flowrate Control System and mixed gas system 4, quartz ampoule 5 and CVD tubular types
Stove 6.When preparing graphene film using the device, first metallic substrates 7 are positioned in quartz ampoule 5, and are in metallic substrates 7
The centre of tube furnace 6 after metallic substrates 7 after twice annealing process, gaseous carbon sources 3 and argon gas is passed through in quartz ampoule 5 and are carried out
Chemical vapor deposition, you can obtain graphene film on 7 surface of metallic substrates.
Embodiment 1
The present embodiment prepares graphene film under atmospheric low-temperature using chemical deposition, includes the following steps：
（1）Copper foil is cleaned by ultrasonic 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, then removes copper foil surface
Moisture, then copper foil is put into quartz ampoule, and copper foil is made to be located among tube furnace, adjusting argon flow amount are 800sccm, hydrogen stream
It measures as 30sccm, copper foil is heated to 950 DEG C under this atmosphere, re-annealing processing 50min；
（2）By step（1）The copper foil of annealed processing is at the uniform velocity cooled to 700 DEG C, wherein argon flow amount under an argon atmosphere
For 300sccm, rate of temperature fall is 28 DEG C/min；
（3）Treat step（2）When middle copper foil temperature is down to 700 DEG C, it is passed through methane and argon gas growth graphene, wherein methane stream
It measures as 2sccm, argon flow amount 500sccm, reaction time 5min；
（4）After reacting 5min, stopping is passed through methane, and copper foil is quickly down to room temperature, you can obtains stone in copper foil surface
Black alkene film.
Fig. 2 is transferred to SiO for graphene film made from the present embodiment2Optical microscope picture in/Si substrates, by scheming
2 as can be seen that graphene film thickness manufactured in the present embodiment is uniform.
Fig. 3 is the Raman collection of illustrative plates of graphene film manufactured in the present embodiment, as shown in figure 3, graphite manufactured in the present embodiment
Clearly, and the ratio at 2D peaks and G peaks is more than 2, while also has the defects of apparent peak D peaks, demonstrate,proves at the characteristic peak 2D peaks of alkene film
The single-layer graphene of better quality has been prepared in bright the present embodiment.
Fig. 4 is transferred to SiO for graphene film manufactured in the present embodiment2Scanning electron microscope diagram piece in/Si substrates,
The boundary of graphene is can clearly be seen that on the picture left side, and do not see crackle in figure, it was demonstrated that graphene manufactured in the present embodiment
It is continuous.
Embodiment 2
The present embodiment prepares graphene film under atmospheric low-temperature using chemical deposition, includes the following steps：
（1）Copper foil is cleaned by ultrasonic 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, then removes copper foil surface
Moisture, then copper foil is put into quartz ampoule, and copper foil is made to be located among tube furnace, adjusting argon flow amount are 800sccm, hydrogen stream
It measures as 30sccm, copper foil is heated to 950 DEG C under this atmosphere, re-annealing processing 50min；
（2）By step（1）The copper foil of annealed processing is at the uniform velocity cooled to 400 DEG C, wherein argon flow amount under an argon atmosphere
For 300sccm, rate of temperature fall is 30 DEG C/min；
（3）Treat step（2）When middle copper foil temperature is down to 400 DEG C, it is passed through methane and argon gas growth graphene, wherein methane stream
It measures as 10sccm, argon flow amount 500sccm, reaction time 10min；
（4）After reacting 10min, stopping is passed through methane, and copper foil is quickly down to room temperature, you can obtains stone in copper foil surface
Black alkene film.
Fig. 5 is transferred to SiO for graphene film made from the present embodiment2Optical microscope picture in/Si substrates, by scheming
2 as can be seen that graphene film thickness manufactured in the present embodiment it is uniform, can be clearly seen that SiO from rent2/ Si substrates
With the boundary of graphene.
Fig. 6 is the Raman collection of illustrative plates of graphene film manufactured in the present embodiment, as shown in figure 3, graphite manufactured in the present embodiment
Clearly, and the ratio at 2D peaks and G peaks, close to 2, compared to embodiment 1, prepared by the present embodiment at the characteristic peak 2D peaks of alkene film
Graphene film the defects of peak D peaks reduced, show that graphene quality manufactured in the present embodiment is more slightly higher than embodiment.
Fig. 7 is the transmission electron micrograph that graphene film manufactured in the present embodiment is transferred on copper mesh, can by Fig. 7
Will become apparent from graphene manufactured in the present embodiment as single-layer graphene.
Embodiment 3
The present embodiment prepares graphene film under atmospheric low-temperature using chemical deposition, includes the following steps：
（1）Using magnetron sputtering method in SiO2/ Si on pieces prepare corronil film, are then put into corronil film
In quartz ampoule, and corronil film is made to be located among tube furnace, adjusting argon flow amount is 900sccm, and hydrogen flowing quantity is
30sccm, by corronil film heating to 900 DEG C under this atmosphere, re-annealing handles 65min；
（2）By step（1）The corronil film of annealed processing, is at the uniform velocity cooled to 400 DEG C under an argon atmosphere, wherein
Argon flow amount is 400sccm, and rate of temperature fall is 25 DEG C/min；
（3）Treat step（2）When middle corronil film temperature is down to 400 DEG C, it is passed through ethane acetylene gaseous mixture and argon gas life
Long graphene, wherein mixed gas flow are 10sccm, and ethane acetylene volume ratio is 1 in gaseous mixture:2, argon flow amount is
600sccm, reaction time 15min；
（4）After reacting 15min, stopping is passed through gaseous mixture, and corronil film is quickly down to room temperature, you can in cupro-nickel
Alloy firm surface obtains graphene film.
Embodiment 4
The present embodiment prepares graphene film under atmospheric low-temperature using chemical deposition, includes the following steps：
（1）Copper-iron alloy foil is cleaned by ultrasonic 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, then removes copper and iron
The moisture on Alloy Foil surface, then copper-iron alloy foil is put into quartz ampoule, and copper-iron alloy foil is made to be located among tube furnace, it adjusts
Argon flow amount is 300sccm, hydrogen flowing quantity 15sccm, copper foil is heated to 850 DEG C under this atmosphere, re-annealing processing
10min；
（2）By step（1）The copper-iron alloy foil of annealed processing, is at the uniform velocity cooled to 300 DEG C, wherein argon under an argon atmosphere
Throughput is 600sccm, and rate of temperature fall is 3 DEG C/min；
（3）Treat step（2）When middle copper foil temperature is down to 300 DEG C, it is passed through acetylene and argon gas growth graphene, wherein acetylene stream
It measures as 5sccm, argon flow amount 1000sccm, reaction time 20min；
（4）After reacting 20min, stopping is passed through methane, and copper-iron alloy foil is quickly down to room temperature, you can in copper-iron alloy
Foil surface obtains graphene film.
Embodiment 5
The present embodiment prepares graphene film under atmospheric low-temperature using chemical deposition, includes the following steps：
（1）Copper film is cleaned by ultrasonic 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, then removes copper film surface
Moisture, then copper film is put into quartz ampoule, and copper film is made to be located among tube furnace, adjusting argon flow amount are 500sccm, hydrogen stream
It measures as 90sccm, copper foil is heated to 1050 DEG C under this atmosphere, re-annealing processing 90min；
（2）By step（1）The copper film of annealed processing is at the uniform velocity cooled to 800 DEG C, wherein argon flow amount under an argon atmosphere
For 1000sccm, rate of temperature fall is 15 DEG C/min；
（3）Treat step（2）When middle copper foil temperature is down to 800 DEG C, it is passed through ethylene and argon gas growth graphene, wherein ethylene stream
It measures as 8sccm, argon flow amount 100sccm, reaction time 1min；
（4）After reacting 1min, stopping is passed through methane, and copper film is quickly down to room temperature, you can obtains stone on copper film surface
Black alkene film.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (6)
1. a kind of method that atmospheric cryochemistry vapor deposition prepares graphene film, which is characterized in that include the following steps：
（1）Metallic substrates are cleaned by ultrasonic 5 ~ 10min, and are removed metal substrate surface with hydrochloric acid, acetone, deionized water respectively
Then metallic substrates are carried out the high temperature anneal by moisture, treatment conditions are：300 ~ 1000sccm of argon flow amount, hydrogen flowing quantity
10 ~ 100sccm, temperature are 850 ~ 950 DEG C, 10 ~ 90min of processing time；The metallic substrates are copper foil, cobalt foil, nickel foil, iron foil
At least one of or be copper film, cobalt film, nickel film, at least one of iron film；
（2）To step（1）The middle metallic substrates through the high temperature anneal carry out cooling annealing, and treatment conditions are：In argon gas
200 ~ 800 DEG C are at the uniform velocity cooled under atmosphere, wherein argon flow amount is 300 ~ 1000sccm；
（3）Treat step（2）Middle metallic substrates are down to predetermined reaction temperature, are passed through gaseous carbon sources and argon gas, carry out chemical vapor deposition
Product is to get to graphene film, the gaseous carbon sources are methane, at least one of ethane, acetylene, ethylene, propane, chemical gas
Phase sedimentary condition is：Carbon-source gas 1 ~ 10sccm of flow, 100 ~ 1000sccm of argon flow amount, 1 ~ 10min of reaction time.
2. the method that atmospheric cryochemistry vapor deposition according to claim 1 prepares graphene film, which is characterized in that
Step（1）High temperature makes annealing treatment condition：Argon flow amount 800sccm, hydrogen flowing quantity 30sccm, 950 DEG C of temperature, processing time
50min。
3. the method that atmospheric cryochemistry vapor deposition according to claim 1 prepares graphene film, which is characterized in that
The metallic substrates are copper foil.
4. the method that atmospheric cryochemistry vapor deposition according to claim 1 prepares graphene film, which is characterized in that
Step（2）Middle rate of temperature fall is 1 ~ 30 DEG C/min.
5. the method that atmospheric cryochemistry vapor deposition according to claim 1 prepares graphene film, which is characterized in that
Step（2）Middle metallic substrates are at the uniform velocity cooled to 300 ~ 700 DEG C.
6. the method that atmospheric cryochemistry vapor deposition according to claim 1 prepares graphene film, which is characterized in that
The gaseous carbon sources are methane.
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| WO2020160571A1 (en) * | 2019-02-01 | 2020-08-06 | University Of Pretoria | Graphene wool and manufacture thereof |
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| CN110775965A (en) * | 2019-12-02 | 2020-02-11 | 江苏龙汇纳米科技有限公司 | Chemical vapor deposition process for preparing high-molecular nano composite material |
| CN112126928B (en) * | 2020-09-10 | 2023-06-02 | 安徽德诠新材料科技有限公司 | Method for preparing heat pipe by vapor deposition |
| CN112919455B (en) * | 2021-02-07 | 2022-11-01 | 正大能源材料(大连)有限公司 | Method for preparing graphene film by carbon dioxide combined low-pressure chemical vapor deposition |
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| CN103303910B (en) * | 2013-06-06 | 2015-11-25 | 中国科学技术大学 | A kind ofly prepare the method for Graphene and the Graphene of preparation thereof |
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