CN104451591B - A kind of method that Graphene by copper surface CVD shifts to target substrate surface - Google Patents
A kind of method that Graphene by copper surface CVD shifts to target substrate surface Download PDFInfo
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- CN104451591B CN104451591B CN201410777633.3A CN201410777633A CN104451591B CN 104451591 B CN104451591 B CN 104451591B CN 201410777633 A CN201410777633 A CN 201410777633A CN 104451591 B CN104451591 B CN 104451591B
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- 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
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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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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Abstract
The invention discloses a kind of method that Graphene by copper surface chemical vapor deposition shifts to target substrate surface, belong to field of material technology.The method first passes through chemical gaseous phase depositing process and obtains Graphene in copper foil surface growth, then using Copper Foil as anode, as negative electrode, the agar gel of copper sulfate is as solid electrolyte for glass carbon plate, make Copper Foil slow mechanism dissolved using electrochemical method, and deposit in glassy carbon electrode surface and form copper film；Finally agar gel is dissolved in the hot water removing to obtain transferring to the graphene film on target substrate surface, obtain metal copper foil the growth in order to Graphene in glassy carbon electrode surface simultaneously.Using the present invention, the green high-efficient not only enabling Graphene in plurality of target substrate surface shifts, and recycling of metallic copper can be realized, reduce the preparation cost of graphene film, it will help promote the large-scale application in fields such as conductive films for the Graphene.
Description
Technical field
The invention belongs to field of material technology, more particularly, to a kind of by the stone of copper surface chemical vapor deposition (CVD)
The method that black alkene shifts to target substrate surface.
Background technology
2004, Univ Manchester UK professor Geim prepared Graphene first【K.S.Novoselov,
A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov,
Science 2004,306,666.】.Six side's honeycomb two-dimensional structures that Graphene is made up of monolayer carbon atom.Graphene is thin
Under film room temperature, native electronic mobility is up to 200000cm2/Vs【K.I.Bolotin, K.J.Sikes, Z.Jiang, M.Klima,
G.Fudenberg, J.Hone, P.Kim, H.L.Stormer, Solid State Communications 2008,146,
351.】, there are excellent electrical properties.Additionally, Graphene is respectively provided with high light transmittance in whole visible region, research finds
The light transmittance of single-layer graphene is close to 97%【R.R.Nair, P. Blake, A.N.Grigorenko, K.S.Novoselov,
T.J.Booth, T.Stauber, N.M.R.Peres, A.K.Geim, Science 2008,320,1308.】.
Chemical vapor deposition (CVD) method on Copper Foil is a kind of important method preparing Graphene, and the stone obtaining
Black alkene is monolayer, and defect is less【X.S.Li, W.W.Cai, J.H.An, S.Kim, J.Nah, D.X.Yang, R.Piner,
A.Velamakanni, I.Jung, E.Tutuc, S.K.Banerjee, L.Colombo, R.S.Ruoff, Science 2009,
324,1312.】.In actual application, finally need to transfer to target substrate by Graphene from copper foil surface, at present generally
Using method be PMMA thin film to be used as support in graphenic surface, by copper etchant, metal copper corrosion is removed, so
After transfer graphene to target substrate surface, final dissolving removes the PMMA thin film of graphenic surface.
Above-mentioned this transfer method not only needs using substantial amounts of PMMA and acetone equal solvent, and corrodes the copper of removing not
Can directly reuse, lead to the waste of resource and relatively costly.
Content of the invention
(1) technical problem to be solved
In view of this, present invention is primarily targeted at providing a kind of Graphene by copper surface CVD to serve as a contrast to target
The method of basal surface transfer, to realize zero use of organic solvent in transfer process and the repeatable recycling of copper, and then drops
Low cost.
(2) technical scheme
For reaching above-mentioned purpose, the invention provides a kind of Graphene by copper surface chemical vapor deposition is to target
The method of substrate surface transfer, including：
Grow Graphene in copper foil surface, and prepare the agar gel of copper electrolytes；
With glass carbon plate, graphite or ITO electro-conductive glass as negative electrode, the Copper Foil that superficial growth has Graphene is anode, cupric electrolysis
The agar gel of matter is solid electrolyte, and apply DC voltage to be electrolysed to electric current is zero, realizes dissolving and the negative electrode of anode copper
The precipitation of surface copper, obtains the complex of Graphene/agar gel/Copper Foil/negative electrode；
Target substrate is placed on the complex of Graphene/agar gel/Copper Foil/negative electrode, heating makes agar gel molten
Gel, so that tight fits between target substrate and Graphene, obtains target substrate/Graphene/agar gel/Copper Foil/negative electrode
Complex；
The complex of target substrate/Graphene/agar gel/Copper Foil/negative electrode is put into and so that agar gel is dissolved,
Surface must be arrived has the Graphene of target substrate and surface to have the negative electrode of copper film, realizes Graphene to the transfer on target substrate surface.
In such scheme, described copper foil surface grow Graphene, including：Copper Foil is put in chemical vapor deposition stove,
In hydrogen and methane atmosphere, flow is respectively 10sccm and 2sccm, utilizes chemical vapor deposition under 1000 DEG C of hot conditionss
Grow Graphene in copper foil surface.
In such scheme, described copper electrolytes are copper sulfate, copper nitrate, Schweinfurt green or copper chloride.
In such scheme, described copper electrolytes adopt copper sulfate, the agar gel of described preparation copper electrolytes, including：Point
Another name takes 10g copper sulfate and 4g agar powder, is added thereto to the deionized water of 100ml, and heated and stirred makes sol solution, will
Colloidal sol natural cooling forms the agar gel of copper sulfate.
In such scheme, it is zero that described applying DC voltage is electrolysed to electric current, is to applying 0.7V between anode and negative electrode
DC voltage, it is zero that the agar gel of copper sulfate is electrolysed to electric current.
In such scheme, described heating makes agar gel solation so that tight fits between Graphene and substrate, be
At 110 DEG C, heating makes sol-gel in 2 minutes so that tight fits between Graphene and substrate.
In such scheme, the described complex by target substrate/Graphene/agar gel/Copper Foil/negative electrode is put in hot water
So that agar gel is dissolved, be to put into the complex of target substrate/Graphene/agar gel/Copper Foil/negative electrode in 95 DEG C of hot water
Process and so that agar gel is dissolved.
In such scheme, the described complex by target substrate/Graphene/agar gel/Copper Foil/negative electrode is put in hot water
After so that agar gel is dissolved, also include：Target substrate/Graphene after agar gel being dissolved using 95 DEG C of hot water/
The complex of agar gel/Copper Foil/negative electrode is repeatedly rinsed.
In such scheme, described realize transfer from Graphene to target substrate surface while, obtaining surface has copper film
Negative electrode.The method, after must arriving surface and have the negative electrode of copper film, also includes：Peel off the copper film of cathode surface, and using peeling off
To copper film carry out the chemical vapor deposition of Graphene, realize the recycling and reuse of copper.
(3) beneficial effect
From technique scheme as can be seen that the invention has the advantages that：
1st, the side that the Graphene by copper surface chemical vapor deposition that the present invention provides shifts to target substrate surface
Method, has the characteristics that good conductivity using Graphene, is used agar gel as electrolyte, removes Graphene using electrolytic method
The copper of bottom, the deposition simultaneously realizing copper in glass carbon surface separates out, and not only achieves zero use of organic solvent in transfer process,
And so that metallic copper can be used with repetitive cycling, reduce production cost, be truly realized the green high-efficient transfer of Graphene.
2nd, the side that the Graphene by copper surface chemical vapor deposition that the present invention provides shifts to target substrate surface
Method, is a kind of transfer method of the copper foil surface CVD Graphene of green high-efficient, not only avoids employing polymethyl methacrylate
(PMMA) and acetone and other organic solvent it is achieved that copper foil surface Graphene green transfer, and dissolve copper while in the moon
Pole surface precipitating metal copper film, it is achieved that recycling of metallic copper, reduces the preparation cost of Graphene.
3rd, the side that the Graphene by copper surface chemical vapor deposition that the present invention provides shifts to target substrate surface
Method, the green high-efficient not only enabling Graphene in plurality of target substrate surface shifts, and can realize the circulation of metallic copper
Using reducing the preparation cost of graphene film, it will help promote Graphene on a large scale should in fields such as conductive films
With.
Brief description
Fig. 1 is that the Graphene by copper surface chemical vapor deposition that the present invention provides shifts to target substrate surface
Method flow diagram.
Fig. 2 is the process chart of the Graphene transfer according to the embodiment of the present invention 1.
Specific embodiment
For making the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in more detail.
The present invention is a kind of method that Graphene by copper surface chemical vapor deposition shifts to target substrate surface,
First pass through chemical gaseous phase depositing process and obtain Graphene in copper foil surface growth, then using Copper Foil as anode, glass carbon plate is made
For negative electrode, the agar gel of copper sulfate, as solid electrolyte, makes Copper Foil slow mechanism dissolved using electrochemical method, and in glass carbon electricity
Pole surface deposits and forms copper film；Finally agar gel is dissolved in the hot water removing to obtain transferring to the stone on target substrate surface
Black alkene thin film, obtains metal copper foil the growth in order to Graphene in glassy carbon electrode surface simultaneously.
As shown in figure 1, the Graphene by copper surface chemical vapor deposition that Fig. 1 is the present invention to be provided is to target substrate
The method flow diagram of surface transfer, the method comprises the following steps：
Step 1：Grow Graphene in copper foil surface, and prepare the agar gel of copper electrolytes；
In this step, grow Graphene in copper foil surface, including：Copper Foil is put in chemical vapor deposition stove, in hydrogen
In gas and methane atmosphere, flow is respectively 10sccm and 2sccm, utilizes chemical vapor deposition in copper under 1000 DEG C of hot conditionss
Paper tinsel superficial growth Graphene.
In this step, copper electrolytes can be using copper sulfate, copper nitrate, Schweinfurt green or copper chloride, when copper electrolytes are adopted
When using copper sulfate, the agar gel of preparation copper electrolytes, including：Weigh 10g copper sulfate and 4g agar powder respectively, be added thereto to
The deionized water of 100ml, and heated and stirred makes sol solution, colloidal sol natural cooling is formed the agar gel of copper sulfate.
Step 2：With glass carbon plate, graphite or ITO electro-conductive glass as negative electrode, the Copper Foil that superficial growth has Graphene is anode,
The agar gel of copper electrolytes is solid electrolyte, and applying DC voltage, to be electrolysed to electric current be zero, realize the dissolving of anode copper with
And the precipitation of cathode surface copper, obtain the complex of Graphene/agar gel/Copper Foil/negative electrode；
In this step, when copper electrolytes adopt copper sulfate, apply DC voltage to be electrolysed to electric current is zero, is to anode
Apply the DC voltage of 0.7V and negative electrode between, it is zero that the agar gel of copper sulfate is electrolysed to electric current.
Step 3：Target substrate is placed on the complex of Graphene/agar gel/Copper Foil/negative electrode, heating makes agar
Sol-gel so that tight fits between target substrate and Graphene, obtain target substrate/Graphene/agar gel/Copper Foil/
The complex of negative electrode；
In this step, target substrate can be using PET film, glass or quartz；When copper electrolytes adopt copper sulfate,
Heating makes agar gel solation so that tight fits between Graphene and substrate, is that heating makes gel molten in 2 minutes at 110 DEG C
Gel is so that tight fits between Graphene and substrate.
Step 4：The complex of target substrate/Graphene/agar gel/Copper Foil/negative electrode is put into makes agar coagulate in hot water
Peptization solution, obtaining surface has the Graphene of target substrate and surface to have the negative electrode of copper film, realizes Graphene to target substrate surface
Transfer, must arrive surface has the negative electrode of copper film simultaneously；
In this step, when copper electrolytes adopt copper sulfate, by target substrate/Graphene/agar gel/Copper Foil/the moon
The complex of pole is put into makes agar gel dissolve in hot water, be answering target substrate/Graphene/agar gel/Copper Foil/negative electrode
Compound is put into process in 95 DEG C of hot water makes agar gel dissolve for 20 minutes；By target substrate/Graphene/agar gel/copper
The complex of paper tinsel/negative electrode is put into after making agar gel dissolving in hot water, also includes：Hot water using 95 DEG C is molten to agar gel
The complex of the target substrate/Graphene/agar gel/Copper Foil/negative electrode after solution is repeatedly rinsed, and then must arrive surface and have
There is the negative electrode of copper film on the Graphene of target substrate and surface.
Step 5：Peel off the copper film of cathode surface, and carry out the chemical vapor deposition of Graphene using the copper film that stripping obtains
Long-pending, realize the recycling and reuse of copper.
Embodiment 1：Target substrate adopts PET film, and copper electrolytes adopt copper sulfate, and negative electrode adopts glass carbon plate, Ji Jiangjin
Belong to copper surface chemical vapour deposition Graphene carry out green high-efficient transfer to PET film surface, concrete steps as shown in Fig. 2
Fig. 2 shows the process chart of the Graphene transfer according to the embodiment of the present invention 1, including：
Weigh 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper sulfate；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With glass carbon plate as negative electrode, surface is given birth to
The Copper Foil that length has Graphene is anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, applies the DC voltage of 0.7V
Being electrolysed to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper；PET film is placed on surface
Have on the agar gel of Graphene, 110 DEG C of heating 2min make sol-gel in order to tight between PET film and Graphene
Suit；PET film/Graphene/gel/copper/glass carbon plate complex being put into process in 95 DEG C of hot water makes agar coagulate in 20 minutes
Peptization solution, and the hot water wash with 95 DEG C is multiple, realizes the transfer in pet sheet face for the Graphene, obtaining surface has the graphite of PET film
Alkene, obtain surface deposition has the glass carbon plate of copper film simultaneously；Peel off careful for the copper film on glass carbon plate surface and grow stone in CVD stove
Black alkene, realizes the recycling and reuse of copper.
Embodiment 2：Target substrate adopts PET film, and copper electrolytes adopt copper nitrate, and negative electrode adopts glass carbon plate, Ji Jiangjin
The Graphene belonging to copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, comprises the following steps that：
Weigh 10g copper nitrate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper nitrate；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With glass carbon plate as negative electrode, surface is given birth to
The Copper Foil that length has Graphene is anode, and the copper nitrate agar gel of above-mentioned preparation is copper electrolytes, applies the DC voltage of 0.7V
Being electrolysed to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper；PET film is placed on surface
Have on the agar gel of Graphene, 110 DEG C of heating 2min make sol-gel in order to tight between PET film and Graphene
Suit；PET film/Graphene/gel/copper/glass carbon plate complex being put into process in 95 DEG C of hot water makes agar coagulate in 20 minutes
Peptization solution, and the hot water wash with 95 DEG C is multiple, realizes the transfer in pet sheet face for the Graphene, obtaining surface has the graphite of PET film
Alkene, obtain surface deposition has the glass carbon plate of copper film simultaneously；Peel off careful for the copper film on glass carbon plate surface and grow stone in CVD stove
Black alkene, realizes the recycling and reuse of copper.
Embodiment 3：Target substrate adopts PET film, and copper electrolytes adopt Schweinfurt green, and negative electrode adopts glass carbon plate, Ji Jiangjin
The Graphene belonging to copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, comprises the following steps that：
Weigh 10g Schweinfurt green and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of Schweinfurt green；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With glass carbon plate as negative electrode, surface is given birth to
The Copper Foil that length has Graphene is anode, and the Schweinfurt green agar gel of above-mentioned preparation is copper electrolytes, applies the DC voltage of 0.7V
Being electrolysed to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper；PET film is placed on surface
Have on the agar gel of Graphene, 110 DEG C of heating 2min make sol-gel in order to tight between PET film and Graphene
Suit；PET film/Graphene/gel/copper/glass carbon plate complex being put into process in 95 DEG C of hot water makes agar coagulate in 20 minutes
Peptization solution, and the hot water wash with 95 DEG C is multiple, realizes the transfer in pet sheet face for the Graphene, obtaining surface has the graphite of PET film
Alkene, obtain surface deposition has the glass carbon plate of copper film simultaneously；Peel off careful for the copper film on glass carbon plate surface and grow stone in CVD stove
Black alkene, realizes the recycling and reuse of copper.
Embodiment 4：Target substrate adopts PET film, and copper electrolytes adopt copper chloride, and negative electrode adopts glass carbon plate, Ji Jiangjin
The Graphene belonging to copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, comprises the following steps that：
Weigh 10g copper chloride and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper chloride；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With glass carbon plate as negative electrode, surface is given birth to
The Copper Foil that length has Graphene is anode, and the copper chloride agar gel of above-mentioned preparation is copper electrolytes, applies the DC voltage of 0.7V
Being electrolysed to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper；PET film is placed on surface
Have on the agar gel of Graphene, 110 DEG C of heating 2min make sol-gel in order to tight between PET film and Graphene
Suit；PET film/Graphene/gel/copper/glass carbon plate complex being put into process in 95 DEG C of hot water makes agar coagulate in 20 minutes
Peptization solution, and the hot water wash with 95 DEG C is multiple, realizes the transfer in pet sheet face for the Graphene, obtaining surface has the graphite of PET film
Alkene, obtain surface deposition has the glass carbon plate of copper film simultaneously；Peel off careful for the copper film on glass carbon plate surface and grow stone in CVD stove
Black alkene, realizes the recycling and reuse of copper.
Embodiment 5：Target substrate adopts PET film, and copper electrolytes adopt copper sulfate, and negative electrode adopts graphite, will metal
The Graphene of copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, comprises the following steps that：
Weigh 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper sulfate；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With graphite as negative electrode, superficial growth
The Copper Foil having Graphene is anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, applies the unidirectional current piezoelectricity of 0.7V
Solution to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode graphite surface copper；PET film is placed on surface stone
On the agar gel of black alkene, 110 DEG C of heating 2min make sol-gel in order to closely cutting between PET film and Graphene
Close；PET film/Graphene/gel/copper/graphite flake complex is put into process in 95 DEG C of hot water and make agar gel in 20 minutes
Dissolving, and the hot water wash with 95 DEG C is multiple, realizes the transfer in pet sheet face for the Graphene, obtaining surface has the graphite of PET film
Alkene, obtain surface deposition has the graphite flake of copper film simultaneously；Peel off careful for the copper film on graphite flake surface and grow stone in CVD stove
Black alkene, realizes the recycling and reuse of copper.
Embodiment 6：Target substrate adopts PET film, and copper electrolytes adopt copper sulfate, and negative electrode adopts ITO electro-conductive glass, that is,
The Graphene of copper surface chemical vapor deposition is carried out green high-efficient transfer to PET film surface, comprises the following steps that：
Weigh 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper sulfate；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With ITO electro-conductive glass as negative electrode,
The Copper Foil that superficial growth has Graphene is anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, applies the straight of 0.7V
Stream potential electrolysis to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode ITO conductive glass surface copper；PET is thin
Film is placed on surface to be had on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel in order to PET film and graphite
Tight fits between alkene；PET film/Graphene/gel/copper/ITO electro-conductive glass complex is put into place in 95 DEG C of hot water
Reason makes agar gel dissolve for 20 minutes, and the hot water wash with 95 DEG C is multiple, realizes the transfer in pet sheet face for the Graphene, obtains table
There is the Graphene of PET film in face, and obtain surface deposition has the ITO electro-conductive glass of copper film simultaneously；Copper by ITO conductive glass surface
Film is careful to be peeled off and grows Graphene in CVD stove, realizes the recycling and reuse of copper.
Embodiment 7：Target substrate adopts glass, and copper electrolytes adopt copper sulfate, and negative electrode adopts glass carbon plate, will metallic copper
The Graphene of surface chemistry vapour deposition carries out green high-efficient transfer to glass surface, comprises the following steps that：
Weigh 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper sulfate；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With glass carbon plate as negative electrode, surface is given birth to
The Copper Foil that length has Graphene is anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, applies the DC voltage of 0.7V
Being electrolysed to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper；Glass is placed on surface to be had
On the agar gel of Graphene, 110 DEG C of heating 2min make sol-gel in order to the tight fits between glass and Graphene；
Glass/Graphene/gel/copper/glass carbon plate complex being put into process in 95 DEG C of hot water makes agar gel dissolve for 20 minutes, and
With 95 DEG C of hot water wash repeatedly, realize the transfer in glass surface for the Graphene, obtaining surface has the Graphene of glass, obtains simultaneously
Surface deposition has the glass carbon plate of copper film；Peel off careful for the copper film on glass carbon plate surface and grow Graphene in CVD stove, realize copper
Recycling and reuse.
Embodiment 8：Target substrate adopts copper sulfate using quartz, copper electrolytes, and negative electrode adopts glass carbon plate, will metallic copper
The Graphene of surface chemistry vapour deposition carries out green high-efficient transfer to quartz surfaces, comprises the following steps that：
Weigh 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, by it certainly
So it is cooled into the agar gel of copper sulfate；Copper Foil is put in CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere
In, utilize chemical vapor deposition under 1000 DEG C of hot conditionss in copper superficial growth Graphene；With glass carbon plate as negative electrode, surface is given birth to
The Copper Foil that length has Graphene is anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, applies the DC voltage of 0.7V
Being electrolysed to electric current is zero, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper；Quartz is placed on surface to be had
On the agar gel of Graphene, 110 DEG C of heating 2min make sol-gel in order to the tight fits between quartz and Graphene；
Quartz/Graphene/gel/copper/glass carbon plate complex being put into process in 95 DEG C of hot water makes agar gel dissolve for 20 minutes, and
With 95 DEG C of hot water wash repeatedly, realize the transfer in quartz surfaces for the Graphene, obtaining surface has the Graphene of quartz, obtains simultaneously
Surface deposition has the glass carbon plate of copper film；Peel off careful for the copper film on glass carbon plate surface and grow Graphene in CVD stove, realize copper
Recycling and reuse.
Particular embodiments described above, has carried out detailed further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail bright, be should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention, all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (9)
1. a kind of method that Graphene by copper surface chemical vapor deposition shifts to target substrate surface, its feature exists
In, including：
Grow Graphene in copper foil surface, and prepare the agar gel of copper electrolytes；
With glass carbon plate, graphite or ITO electro-conductive glass as negative electrode, the Copper Foil that superficial growth has Graphene is anode, copper electrolytes
Agar gel is solid electrolyte, and apply DC voltage to be electrolysed to electric current is zero, realizes dissolving and the cathode surface of anode copper
The precipitation of copper, obtains the complex of Graphene/agar gel/Copper Foil/negative electrode；
Target substrate is placed on the complex of Graphene/agar gel/Copper Foil/negative electrode, heating makes agar gel solation
So that tight fits between target substrate and Graphene, obtain the compound of target substrate/Graphene/agar gel/Copper Foil/negative electrode
Thing；
The complex of target substrate/Graphene/agar gel/Copper Foil/negative electrode is put into and so that agar gel is dissolved, obtain
Surface has the Graphene of target substrate and surface to have the negative electrode of copper film, realizes Graphene to the transfer on target substrate surface.
2. the Graphene by copper surface chemical vapor deposition according to claim 1 shifts to target substrate surface
Method it is characterised in that described copper foil surface grow Graphene, including：
Copper Foil is put in chemical vapor deposition stove, in hydrogen and methane atmosphere, flow is respectively 10sccm and 2sccm,
Chemical vapor deposition is utilized to grow Graphene in copper foil surface under 1000 DEG C of hot conditionss.
3. the Graphene by copper surface chemical vapor deposition according to claim 1 shifts to target substrate surface
Method is it is characterised in that described copper electrolytes are copper sulfate, copper nitrate, Schweinfurt green or copper chloride.
4. the Graphene by copper surface chemical vapor deposition according to claim 3 shifts to target substrate surface
Method it is characterised in that described copper electrolytes adopt copper sulfate, the agar gel of described preparation copper electrolytes, including：
Weigh 10g copper sulfate and 4g agar powder respectively, be added thereto to the deionized water of 100ml, and heated and stirred makes colloidal sol
Solution, colloidal sol natural cooling is formed the agar gel of copper sulfate.
5. the Graphene by copper surface chemical vapor deposition according to claim 4 shifts to target substrate surface
Method it is characterised in that it is zero that described applying DC voltage is electrolysed to electric current, be between anode and negative electrode apply 0.7V straight
Stream voltage, it is zero that the agar gel of copper sulfate is electrolysed to electric current.
6. the Graphene by copper surface chemical vapor deposition according to claim 4 shifts to target substrate surface
Method, it is characterised in that described heating makes agar gel solation so that tight fits between Graphene and substrate, is 110
At DEG C, heating makes sol-gel in 2 minutes so that tight fits between Graphene and substrate.
7. the Graphene by copper surface chemical vapor deposition according to claim 4 shifts to target substrate surface
Method is it is characterised in that the described complex by target substrate/Graphene/agar gel/Copper Foil/negative electrode is put in hot water and made
Agar gel dissolves, and is place in the hot water put into the complex of target substrate/Graphene/agar gel/Copper Foil/negative electrode 95 DEG C
Reason makes agar gel dissolve for 20 minutes.
8. the Graphene by copper surface chemical vapor deposition according to claim 4 shifts to target substrate surface
Method is it is characterised in that the described complex by target substrate/Graphene/agar gel/Copper Foil/negative electrode is put in hot water and made
After agar gel dissolving, also include：
Using 95 DEG C of hot water answering to the target substrate/Graphene/agar gel/Copper Foil/negative electrode after agar gel dissolving
Compound is repeatedly rinsed.
9. the Graphene by copper surface chemical vapor deposition according to claim 1 shifts to target substrate surface
Method is it is characterised in that the method, after must arriving surface and have the negative electrode of copper film, also includes：
The copper film of stripping cathode surface, and carry out the chemical vapor deposition of Graphene using the copper film that stripping obtains, realize copper
Recycle.
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