CN104451591A - Method for transferring CVD graphene on metal copper surface to target substrate surface - Google Patents

Method for transferring CVD graphene on metal copper surface to target substrate surface Download PDF

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CN104451591A
CN104451591A CN201410777633.3A CN201410777633A CN104451591A CN 104451591 A CN104451591 A CN 104451591A CN 201410777633 A CN201410777633 A CN 201410777633A CN 104451591 A CN104451591 A CN 104451591A
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graphene
copper
target substrate
agar gel
negative electrode
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CN104451591B (en
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张大勇
金智
史敬元
麻芃
王选芸
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Institute of Microelectronics of CAS
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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
    • C23C16/01—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching

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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a method for transferring chemical vapor deposition graphene on a metal copper surface to a target substrate surface, and belongs to the technical field of materials. The method comprises the following steps: firstly, growing on a copper foil surface through a chemical vapor deposition method, so as to obtain graphene; by taking a copper foil as an anode, a glassy carbon sheet as a cathode, and agar gel of copper sulfate as solid electrolyte, dissolving the copper foil by using an electrochemical method, depositing on the surface of a glassy carbon electrode and forming a copper film; and finally, dissolving and removing the agar gel in hot water to obtain a graphene film which is transferred to the target substrate surface, and obtaining the metal copper foil on the surface of the glassy carbon electrode for growth of the graphene. By using the method, green and efficient transfer of the graphene on the surfaces of a plurality of target substrates can be achieved; cyclic utilization of the metal copper can be achieved; the preparation cost of the graphene film is reduced; and large-scale application of the graphene in the fields of conductive films and the like is promoted.

Description

A kind of by the method for the Graphene of copper surface CVD to the transfer of target substrate surface
Technical field
The invention belongs to field of material technology, particularly relate to a kind of by the method for the Graphene of copper surface chemical vapour deposition (CVD) to the transfer of target substrate surface.
Background technology
2004, Univ Manchester UK professor Geim prepared Graphene [K.S.Novoselov, A.K.Geim, S.V.Morozov first, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov, Science 2004,306,666.].Graphene is by the former molecular six side's honeycomb two-dirnentional structures of monolayer carbon.Under graphene film room temperature, native electronic mobility can reach 200000cm 2/ 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 is excellent electrical properties.In addition, Graphene all has high transmittance in whole visible region, and research finds that the 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 vapour deposition (CVD) method on Copper Foil is a kind of important method preparing Graphene, and the Graphene obtained is individual layer, the less [X.S.Li of defect, 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, Graphene is finally needed to transfer to target substrate from copper foil surface, the method generally adopted at present uses PMMA film as support at graphenic surface, by copper etchant by metallic copper corrosion removing, then Graphene is transferred to target substrate surface, the final PMMA film dissolving removing graphenic surface.
Above-mentioned this transfer method not only needs to use a large amount of PMMA and acetone equal solvent, and the copper of corrosion removing can not directly reuse, and causes the waste of resource and cost is higher.
Summary of the invention
(1) technical problem that will solve
In view of this, main purpose of the present invention is to provide a kind of by the method for the Graphene of copper surface CVD to the transfer of target substrate surface, to realize zero use of organic solvent in transfer process and can recirculation using of copper, and then reduces costs.
(2) technical scheme
For achieving the above object, the invention provides a kind of by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, comprising:
At copper foil surface growing graphene, and prepare the agar gel of copper electrolytes;
With glass carbon plate, graphite or ITO conductive glass for negative electrode, surface growth has the Copper Foil of Graphene to be anode, the agar gel of copper electrolytes is solid electrolyte, applying volts DS electrolysis is zero to electric current, realize the dissolving of anode copper and the precipitation of cathode surface copper, obtain the mixture of Graphene/agar gel/Copper Foil/negative electrode;
Target substrate be placed on the mixture of Graphene/agar gel/Copper Foil/negative electrode, heating makes agar gel solation to make tight fits between target substrate and Graphene, obtains the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode;
Agar gel is dissolved by target substrate/mixture of Graphene/agar gel/Copper Foil/negative electrode puts into hot water, obtaining surface has the Graphene of target substrate and surface to have the negative electrode of copper film, realizes the transfer of Graphene to target substrate surface.
In such scheme, described at copper foil surface growing graphene, comprising: Copper Foil is put into chemical vapor deposition stove, in hydrogen and methane atmosphere, flow is respectively 10sccm and 2sccm, utilizes chemical vapour deposition at copper foil surface growing graphene under 1000 DEG C of hot conditionss.
In such scheme, described copper electrolytes is copper sulfate, cupric nitrate, neutralized verdigris or cupric chloride.
In such scheme, described copper electrolytes adopts copper sulfate, the agar gel of described preparation copper electrolytes, comprise: take 10g copper sulfate and 4g agar powder respectively, add the deionized water of 100ml wherein, and heated and stirred makes sol solution, colloidal sol naturally cooling is formed the agar gel of copper sulfate.
In such scheme, the electrolysis of described applying volts DS is zero to electric current, is the volts DS applying 0.7V between anode and negative electrode, is zero by the agar gel electrolysis of copper sulfate to electric current.
In such scheme, described heating makes agar gel solation to make tight fits between Graphene and substrate, is that heating makes sol-gel to make tight fits between Graphene and substrate for 2 minutes at 110 DEG C.
In such scheme, describedly agar gel being dissolved by target substrate/mixture of Graphene/agar gel/Copper Foil/negative electrode puts into hot water, is that the hot water process of the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode being put into 95 DEG C makes agar gel dissolve in 20 minutes.
In such scheme, the described mixture by target substrate/Graphene/agar gel/Copper Foil/negative electrode is put into hot water and is made after agar gel dissolves, also to comprise: utilize the hot water of 95 DEG C repeatedly to rinse the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode after agar gel dissolves.
In such scheme, described realize transfer from Graphene to target substrate surface while, obtain the negative electrode that there is copper film on surface.The method, after obtaining surface and having the negative electrode of copper film, also comprises: the copper film peeling off cathode surface, and utilizes and peel off the chemical vapour deposition that the copper film obtained carries out Graphene, realizes the recovery and reuse of copper.
(3) beneficial effect
As can be seen from technique scheme, the present invention has following beneficial effect:
1, provided by the invention by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, Graphene is utilized to have the feature of good conductivity, use agar gel as ionogen, adopt the copper of electrolysis process removing Graphene bottom, realize copper to separate out in the deposition of glass carbon surface simultaneously, not only achieve zero use of organic solvent in transfer process, and metallic copper can recirculation be used, reduce production cost, really achieve the green high-efficient transfer of Graphene.
2, provided by the invention by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is a kind of transfer method of copper foil surface CVD Graphene of green high-efficient, not only avoid employing polymethylmethacrylate (PMMA) and acetone and other organic solvent, achieve the green transfer of copper foil surface Graphene, and at cathode surface precipitating metal copper film while dissolved copper, achieve the recycle of metallic copper, reduce the preparation cost of Graphene.
3, provided by the invention by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, Graphene can not only be realized shift at the green high-efficient of plurality of target substrate surface, and the recycle of metallic copper can be realized, reducing the preparation cost of graphene film, promoting the large-scale application of Graphene in fields such as conductive films by contributing to.
Accompanying drawing explanation
Fig. 1 is provided by the invention by the method flow diagram of the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface.
Fig. 2 is the process flow sheet shifted according to the Graphene of the embodiment of the present invention 1.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The present invention is a kind of by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, first Graphene is obtained by chemical gaseous phase depositing process in copper foil surface growth, then using Copper Foil as anode, glass carbon plate is as negative electrode, the agar gel of copper sulfate is as solid electrolyte, utilize electrochemical method that Copper Foil is slowly dissolved, and deposit in glassy carbon electrode surface and form copper film; Finally agar gel is dissolved in the hot water removing and obtain transferring to the graphene film on target substrate surface, obtain metal copper foil and in order to the growth of Graphene in glassy carbon electrode surface simultaneously.
As shown in Figure 1, Fig. 1 is provided by the invention by the method flow diagram of the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, and the method comprises the following steps:
Step 1: at copper foil surface growing graphene, and prepare the agar gel of copper electrolytes;
In this step, at copper foil surface growing graphene, comprising: Copper Foil is put into chemical vapor deposition stove, in hydrogen and methane atmosphere, flow is respectively 10sccm and 2sccm, utilizes chemical vapour deposition at copper foil surface growing graphene under 1000 DEG C of hot conditionss.
In this step, copper electrolytes can adopt copper sulfate, cupric nitrate, neutralized verdigris or cupric chloride, when copper electrolytes adopts copper sulfate, the agar gel of preparation copper electrolytes, comprise: take 10g copper sulfate and 4g agar powder respectively, add the deionized water of 100ml wherein, and heated and stirred makes sol solution, colloidal sol naturally cooling is formed the agar gel of copper sulfate.
Step 2: with glass carbon plate, graphite or ITO conductive glass for negative electrode, surface growth has the Copper Foil of Graphene to be anode, the agar gel of copper electrolytes is solid electrolyte, applying volts DS electrolysis is zero to electric current, realize the dissolving of anode copper and the precipitation of cathode surface copper, obtain the mixture of Graphene/agar gel/Copper Foil/negative electrode;
In this step, when copper electrolytes adopts copper sulfate, applying volts DS electrolysis is zero to electric current, and being the volts DS applying 0.7V between anode and negative electrode, is zero by the agar gel electrolysis of copper sulfate to electric current.
Step 3: target substrate is placed on the mixture of Graphene/agar gel/Copper Foil/negative electrode, heating makes agar gel solation to make tight fits between target substrate and Graphene, obtains the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode;
In this step, target substrate can adopt PET film, glass or quartz; When copper electrolytes adopts copper sulfate, heating makes agar gel solation to make tight fits between Graphene and substrate, is that heating makes sol-gel to make tight fits between Graphene and substrate for 2 minutes at 110 DEG C.
Step 4: agar gel is dissolved by target substrate/mixture of Graphene/agar gel/Copper Foil/negative electrode puts into hot water, obtaining surface has the Graphene of target substrate and surface to have the negative electrode of copper film, realize the transfer of Graphene to target substrate surface, obtain the negative electrode that there is copper film on surface simultaneously;
In this step, when copper electrolytes adopts copper sulfate, agar gel being dissolved by target substrate/mixture of Graphene/agar gel/Copper Foil/negative electrode puts into hot water, is that the hot water process of the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode being put into 95 DEG C makes agar gel dissolve in 20 minutes; After the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode being put into hot water and making agar gel dissolving, also comprise: utilize the hot water of 95 DEG C repeatedly to rinse the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode after agar gel dissolves, and then obtain surface and have the Graphene of target substrate and surface to have the negative electrode of copper film.
Step 5: the copper film peeling off cathode surface, and the copper film utilizing stripping to obtain carries out the chemical vapour deposition of Graphene, realizes the recovery and reuse of copper.
Embodiment 1: target substrate adopts PET film, copper electrolytes adopts copper sulfate, negative electrode adopts glass carbon plate, Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, concrete steps as shown in Figure 2, Fig. 2 shows the process flow sheet that the Graphene according to the embodiment of the present invention 1 shifts, and comprising:
Take 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of copper sulfate; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With glass carbon plate for negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper; PET film being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between PET film and Graphene; The hot water process of PET film/Graphene/gel/copper/glass carbon plate mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene in pet sheet face, obtain the Graphene that there is PET film on surface, obtain the glass carbon plate that surface deposition has copper film simultaneously; The copper film on glass carbon plate surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 2: target substrate adopts PET film, copper electrolytes adopts cupric nitrate, and negative electrode adopts glass carbon plate, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, and concrete steps are as follows:
Take 10g cupric nitrate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of cupric nitrate; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With glass carbon plate for negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the cupric nitrate agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper; PET film being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between PET film and Graphene; The hot water process of PET film/Graphene/gel/copper/glass carbon plate mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene in pet sheet face, obtain the Graphene that there is PET film on surface, obtain the glass carbon plate that surface deposition has copper film simultaneously; The copper film on glass carbon plate surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 3: target substrate adopts PET film, copper electrolytes adopts neutralized verdigris, and negative electrode adopts glass carbon plate, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, and concrete steps are as follows:
Take 10g neutralized verdigris and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of neutralized verdigris; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With glass carbon plate for negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the neutralized verdigris agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper; PET film being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between PET film and Graphene; The hot water process of PET film/Graphene/gel/copper/glass carbon plate mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene in pet sheet face, obtain the Graphene that there is PET film on surface, obtain the glass carbon plate that surface deposition has copper film simultaneously; The copper film on glass carbon plate surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 4: target substrate adopts PET film, copper electrolytes adopts cupric chloride, and negative electrode adopts glass carbon plate, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, and concrete steps are as follows:
Take 10g cupric chloride and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of cupric chloride; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With glass carbon plate for negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the cupric chloride agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper; PET film being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between PET film and Graphene; The hot water process of PET film/Graphene/gel/copper/glass carbon plate mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene in pet sheet face, obtain the Graphene that there is PET film on surface, obtain the glass carbon plate that surface deposition has copper film simultaneously; The copper film on glass carbon plate surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 5: target substrate adopts PET film, copper electrolytes adopts copper sulfate, and negative electrode adopts graphite, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, and concrete steps are as follows:
Take 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of copper sulfate; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; Take graphite as negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode graphite surface copper; PET film being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between PET film and Graphene; The hot water process of PET film/Graphene/gel/copper/graphite flake mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene in pet sheet face, obtain the Graphene that there is PET film on surface, obtain the graphite flake that surface deposition has copper film simultaneously; The copper film on graphite flake surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 6: target substrate adopts PET film, copper electrolytes adopts copper sulfate, and negative electrode adopts ITO conductive glass, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to PET film surface, and concrete steps are as follows:
Take 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of copper sulfate; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With ITO conductive glass for negative electrode, surface growth has the Copper Foil of Graphene to be anode, the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode ITO conductive glass surface copper; PET film being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between PET film and Graphene; The hot water process of PET film/Graphene/gel/copper/ITO conductive glass mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene in pet sheet face, obtain the Graphene that there is PET film on surface, obtain the ITO conductive glass that surface deposition has copper film simultaneously; The copper film of ITO conductive glass surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 7: target substrate adopts glass, copper electrolytes adopts copper sulfate, and negative electrode adopts glass carbon plate, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to glass surface, and concrete steps are as follows:
Take 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of copper sulfate; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With glass carbon plate for negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper; Glass being placed on surface has on the agar gel of Graphene, and 110 DEG C of heating 2min make sol-gel so that tight fits between glass and Graphene; The hot water process of glass/Graphene/gel/copper/glass carbon plate mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene at glass surface, obtain the Graphene that there is glass on surface, obtain the glass carbon plate that surface deposition has copper film simultaneously; The copper film on glass carbon plate surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Embodiment 8: target substrate adopts quartz, copper electrolytes adopts copper sulfate, and negative electrode adopts glass carbon plate, and the Graphene by copper surface chemical vapour deposition carries out green high-efficient transfer to quartz surfaces, and concrete steps are as follows:
Take 10g copper sulfate and 4g agar powder, add 100ml deionized water, heated and stirred makes sol solution, its naturally cooling is formed the agar gel of copper sulfate; Copper Foil is put into CVD stove, in 10sccm hydrogen and 2sccm methane blended atmosphere, under 1000 DEG C of hot conditionss, utilize chemical vapour deposition at copper surface growth Graphene; With glass carbon plate for negative electrode, surface growth has the Copper Foil of Graphene to be anode, and the copper sulfate agar gel of above-mentioned preparation is copper electrolytes, and the volts DS electrolysis applying 0.7V is zero to electric current, realizes the dissolving of anode copper and the precipitation of negative electrode glass carbon plate surface copper; Quartz being placed on surface has on the agar gel of Graphene, 110 DEG C heating 2min make sol-gel so that quartz and Graphene between tight fits; The hot water process of quartz/Graphene/gel/copper/glass carbon plate mixture being put into 95 DEG C makes agar gel dissolve in 20 minutes, and with the hot water wash of 95 DEG C repeatedly, realize the transfer of Graphene at quartz surfaces, obtain the Graphene that there is quartz on surface, obtain the glass carbon plate that surface deposition has copper film simultaneously; The copper film on glass carbon plate surface is carefully peeled off and in CVD stove growing graphene, realize the recovery and reuse of copper.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1., by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, comprising:
At copper foil surface growing graphene, and prepare the agar gel of copper electrolytes;
With glass carbon plate, graphite or ITO conductive glass for negative electrode, surface growth has the Copper Foil of Graphene to be anode, the agar gel of copper electrolytes is solid electrolyte, applying volts DS electrolysis is zero to electric current, realize the dissolving of anode copper and the precipitation of cathode surface copper, obtain the mixture of Graphene/agar gel/Copper Foil/negative electrode;
Target substrate be placed on the mixture of Graphene/agar gel/Copper Foil/negative electrode, heating makes agar gel solation to make tight fits between target substrate and Graphene, obtains the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode;
Agar gel is dissolved by target substrate/mixture of Graphene/agar gel/Copper Foil/negative electrode puts into hot water, obtaining surface has the Graphene of target substrate and surface to have the negative electrode of copper film, realizes the transfer of Graphene to target substrate surface.
2. the method shifted to target substrate surface by the Graphene of copper surface chemical vapour deposition according to claim 1, is characterized in that, described at copper foil surface growing graphene, comprising:
Copper Foil is put into chemical vapor deposition stove, and in hydrogen and methane atmosphere, flow is respectively 10sccm and 2sccm, utilizes chemical vapour deposition at copper foil surface growing graphene under 1000 DEG C of hot conditionss.
3. according to claim 1 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, described copper electrolytes is copper sulfate, cupric nitrate, neutralized verdigris or cupric chloride.
4. according to claim 3 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, described copper electrolytes adopts copper sulfate, and the agar gel of described preparation copper electrolytes, comprising:
Take 10g copper sulfate and 4g agar powder respectively, add the deionized water of 100ml wherein, and heated and stirred makes sol solution, colloidal sol naturally cooling is formed the agar gel of copper sulfate.
5. according to claim 4 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, described applying volts DS electrolysis to electric current is zero, being the volts DS applying 0.7V between anode and negative electrode, is zero by the agar gel electrolysis of copper sulfate to electric current.
6. according to claim 4 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, described heating makes agar gel solation to make tight fits between Graphene and substrate, is that heating makes sol-gel to make tight fits between Graphene and substrate for 2 minutes at 110 DEG C.
7. according to claim 4 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, describedly agar gel being dissolved by target substrate/mixture of Graphene/agar gel/Copper Foil/negative electrode puts into hot water, is that the hot water process of the mixture of target substrate/Graphene/agar gel/Copper Foil/negative electrode being put into 95 DEG C makes agar gel dissolve in 20 minutes.
8. according to claim 4 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, the described mixture by target substrate/Graphene/agar gel/Copper Foil/negative electrode put into hot water make agar gel dissolve after, also comprise:
The mixture of the hot water of 95 DEG C to the target substrate/Graphene/agar gel/Copper Foil/negative electrode after agar gel dissolving is utilized repeatedly to rinse.
9. according to claim 1 by the Graphene of copper surface chemical vapour deposition to target substrate surface transfer method, it is characterized in that, described realize transfer from Graphene to target substrate surface while, obtain the negative electrode that there is copper film on surface.
10. according to claim 9 by the method for the Graphene of copper surface chemical vapour deposition to the transfer of target substrate surface, it is characterized in that, the method, after obtaining surface and having the negative electrode of copper film, also comprises:
Peel off the copper film of cathode surface, and the copper film utilizing stripping to obtain carries out the chemical vapour deposition of Graphene, realizes the recovery and reuse of copper.
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CN112803077A (en) * 2021-02-04 2021-05-14 凌飞 Copper-based carbon source solid battery core, battery and manufacturing method thereof
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