CN108455577A - A kind of method of low liquid level tension wet method transfer graphene - Google Patents
A kind of method of low liquid level tension wet method transfer graphene Download PDFInfo
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- CN108455577A CN108455577A CN201810212644.5A CN201810212644A CN108455577A CN 108455577 A CN108455577 A CN 108455577A CN 201810212644 A CN201810212644 A CN 201810212644A CN 108455577 A CN108455577 A CN 108455577A
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- graphene
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- heptane
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Abstract
The invention discloses a kind of methods that low liquid level tension wet method shifts graphene, including have the copper foil of graphene to clean growth and dry up；Etchant solution is configured, etchant solution is added in container, so that the liquid level of etchant solution is generated protrusion, forms meniscus；Heptane is added dropwise on graphene copper foil, graphene surface is completely covered in heptane；Graphene copper foil with heptane layer is swum on the meniscus of etchant solution, copper foil is located at etchant solution on liquid level, and graphene is located on copper foil；Heptane is added dropwise in etchant solution；It waits for copper foil dissolving to finish, the oxide layer of substrate is flatly placed in above graphene；Substrate is slowly pressed into graphene, until graphene and substrate come into full contact with, graphene is attached to substrate, forms graphene-based bottom；It obtains graphene-based bottom and cleans；It is dry to obtain clean graphene-based bottom.The present invention can completely shift graphene and not introduce impurity.
Description
Technical field
The invention belongs to graphenes to shift field, and in particular to a kind of non-polymer protection wet method transfer graphene method.
Background technology
Graphene, a kind of novel two-dimensional film carbon material, because it surmounts the excellent properties of many materials so that the world
On rapidly started one graphene research overbearing tide.So far, the preparation method of graphene and its mechanics, electricity, change
The research of Xue Deng each side surface properties all achieves extraordinary progress.But graphene is wanted application and is just needed on the other devices
Growth large scale continuous graphite alkene film is obtained using CVD method, but graphene growth made from CVD method is on copper-based bottom
It cannot directly use, so needing corresponding transfer method that graphene is put into target substrate.
Traditional transfer method is also known as aqueous etching method, and specific transfer process is：1. using poly-methyl methacrylate
Ester PolymethylMethacrylate (PMMA) spin coating is on the surface of graphene to form the suitable protective layer of a layer thickness, 2.
Be heating and curing PMMA.3. the extra graphene for being removed the back side using the oxonium ion bombardment copper foil back side is penetrated into because of spin coating process
Extra PMMA.4. floaing copper foil etching copper substrate on etchant solution liquid level, graphene is made to be detached with copper-based bottom.5. utilizing glass
Glass piece will etch clean graphene below the solution and clean repeatedly 2~3 times from picking up to be put into deionized water in solution.6. making
Graphene is picked up with target substrate and is vertically dried, is slowly lost in by the moisture between graphene and substrate using gravity.7. water
Sub-control heats substrate after doing several hours, removes remaining moisture between substrate and graphene and reinforces graphene and substrate
Combination.8. using the PMMA of the good organic solvent removal graphene surface such as acetone or dichloromethane.9. cleaning sample with isopropanol
Product surface.
Aqueous etching method is primarily present following problem：Serious impurity residual, PMMA can react with etchant solution, make
It is difficult to be dissolved by an organic solvent at the PMMA in some regions, causes PMMA that cannot completely remove totally, residual is more, seriously affects
The electron mobility of graphene reduces the electric property using graphene making devices.
Invention content
The purpose of the present invention is to provide a kind of non-polymer, it can completely shift graphene and not introduce the graphite of impurity
Alkene transfer method.
A kind of method of low liquid level tension wet method transfer graphene, includes the following steps：
Step 1：There is the copper foil of graphene to clean growth and dries up；
Step 2：Etchant solution is configured, etchant solution is added in container, so that the liquid level of etchant solution is generated protrusion, is formed
Meniscus；
Step 3：Heptane is added dropwise on graphene-copper foil, graphene surface is completely covered in heptane, and graphene surface forms one
Layer heptane layer；
Step 4：Graphene-copper foil with heptane layer is swum on the meniscus of etchant solution, copper foil and corrosion are molten
In on liquid level, graphene is located on copper foil liquid level；Heptane is added dropwise in etchant solution；
Step 5：It waits for copper foil dissolving to finish, the oxide layer of substrate is flatly placed in above graphene, substrate and stone are made
Black alkene face contact；
Step 6：Substrate is slowly pressed into graphene, until graphene and substrate come into full contact with, graphene is attached to base
Bottom forms graphene-substrate；
Step 7：It obtains graphene-substrate and cleans, removal etchant solution, remaining metal and heptane；Dry acquisition is clean
Net graphene-substrate.
Further, realize that the method for meniscus is in step 2：Etchant solution is injected in container, one is floated in container
Etchant solution is added dropwise into floating frame, until there is protrusion until floating the liquid level in frame in a floating frame；Alternatively, will corrode molten
Liquid injects in container, until protrusion occurs in the liquid level in container.
Further, the etchant solution in step 2 is a concentration of 1 mole every liter of FeCl3Solution.
Further, in step 3, heptane is added dropwise on the meniscus of etchant solution.
Further, substrate is silica polished silicon wafer, and in step 5, substrate presses to graphene, substrate with the speed of 1mm/s
After submerging etchant solution, graphene comes into full contact with substrate.
Further, step 6 includes：
Step 6.1：Silica polished silicon wafer is removed from iron stand, is put into cleaning in deionized water and is remained in silica
Etchant solution in polished silicon wafer 2-3 times；
Step 6.2：Silica polished silicon wafer is put into 20：1：1 H2O：H2O2：The solution of HCl dissolves kish；
Step 6.3：Silica polished silicon wafer is put into solution 2-3 times that deionized water cleaning remains in substrate；
Step 6.4：Silica polished silicon wafer is placed to dry moisture vertically；
Step 6.5：Silica polished silicon wafer is put into cleaning remained on surface heptane in isopropanol, takes out silica polishing
Piece dries up isopropanol.
The advantage of the invention is that：The present invention greatly improves transfer efficiency, it is primary shift institute's elapsed time 1 hour with
It is interior, because not using polymer, polymer residue and doping are not had, obtains clean graphene.Entirely shifted
Journey does not do particular/special requirement to target substrate, so can theoretically be transferred in arbitrary substrate, has universality.The present invention relates to
Heptane price be 90 yuan/500ml, the PMMA relative to 5000 yuan/500ml is cheap, reduces cost of transfer.
Description of the drawings
Fig. 1 is the graphene copper foil corrosion process on meniscus.
Specific implementation mode
The present embodiment for the graphene-copper foil sample for shifting 2*2CM to illustrate, therefore the amount and holder of etchant solution
Ware selects to select by specification of 2*2CM.But it is practical not to be limited with the size described in the present embodiment.
A kind of non-polymer wet method transfer graphene method, includes the following steps：
Step 1, graphene/sample copper surfaces impurity that 2*2CM is cleaned using isopropanol, cleaning after-blow dry-eye disease surface
Isopropanol.
Step 2 is packed into a concentration of 1 mole every liter of FeCl of 40ml using the glass culture dish that capacity is 50ml3Solution.And
One floating frame of floating, the outline border size for floating frame is 3*3cm, and the inside casing size for floating frame is 2.5*2.5cm, thickness 1mm
Instrument bezel, make inside frame liquid level of solution protrusion.
1ml normal heptanes are added dropwise in the copper foil surface with graphene in step 3, and heptane is allow to cover entire graphene table
Face.
Step 4, the FeCl that graphene/copper foil that heptane is added dropwise is swum in protrusion3On liquid level of solution, as shown in Figure 1, again
2ml heptane is added dropwise, the interfacial surface tension of heptane-water is less than water-Air Interface, reduces surface tension suffered by graphene more
It destroys, it is ensured that the certain integrality of graphene, raised liquid level change the direction of surface tension so that liquid effects exist
The horizontal component of surface tension on graphene becomes smaller, and reduces damage capability of the solution to graphene.Meanwhile instrument bezel and stone
Black alkene forms an entirety, strengthens the Ability of Resisting Disturbance of graphene, reduces destruction of the external environment to graphene.
Silica polished silicon wafer after waiting for copper foil dissolving to finish, is horizontally fixed on the iron that can be lifted by step 5
On pallet, and the oxidation Plane Location of silica polished silicon wafer is made to be placed in above graphene downward and with horizontal direction parallel, protected
The various pieces for demonstrate,proving silica polished silicon wafer contact graphene increase flatness simultaneously.
Silica polished silicon wafer is pressed to graphene until solution did not had two by step 6, lifting iron stand with the speed of 1mm/s
Aoxidize it is silicon polished, ensure graphene come into full contact with silica polished silicon wafer.
Step 7 removes silica polished silicon wafer from iron stand, is put into cleaning in deionized water and remains in silica throwing
Etchant solution on mating plate 2-3 times.
Silica polished silicon wafer is put into 20 by step 8：1：1 H2O：H2O2：The solution of HCl dissolves kish.
Silica polished silicon wafer is put into solution 2-3 times that deionized water cleaning remains in substrate by step 9.
Silica polished silicon wafer is placed to dry moisture by step 10 vertically.
Silica polished silicon wafer is put into cleaning remained on surface heptane in isopropanol by step 11, takes out silica polishing
Piece dries up isopropanol.
Why to use polymer protective layer in graphene transfer process, be because simple graphene film intensity not
It is enough to resist destruction of the copper foil in corrosion process caused by the surface tension of solution.The interfacial surface tension of heptane and solution
It is low, the destructive power to graphene is directly reduced, makes its own intensity be enough to resist destruction, another aspect heptane is not mutual with solution
It is molten, it is readily volatilized not generate residual, it ensure that the cleannes of transfer result.
Floating frame and etchant solution can be reused, so the present invention is not in the case where increasing any extra cost
The quality of graphene is further improved, and reduces the difficulty of bailing graphene.
The present invention greatly improves transfer efficiency, and the primary institute's elapsed time that shifts is within 1 hour, because without using polymerization
Object obtains clean graphene so not having polymer residue and doping.Entire transfer process is not spy to target substrate
It is different to require, so can theoretically be transferred in arbitrary substrate, there is universality.Heptane price of the present invention be 90 yuan/
500ml, the PMMA relative to 5000 yuan of 500ml is cheap, reduces cost of transfer.
Claims (6)
1. a kind of method of low liquid level tension wet method transfer graphene, includes the following steps：
Step 1：There is the copper foil of graphene to clean growth and dries up；
Step 2：Etchant solution is configured, etchant solution is added in container, so that the liquid level of etchant solution is generated protrusion, forms convex liquid
Face；
Step 3：Heptane is added dropwise on graphene-copper foil, graphene surface is completely covered in heptane, and graphene surface forms one layer of heptan
Alkane layer；
Step 4：Graphene-copper foil with heptane layer is swum on the meniscus of etchant solution, copper foil and etchant solution position
In on liquid level, graphene is located on copper foil；Heptane is added dropwise in etchant solution；
Step 5：It waits for copper foil dissolving to finish, the oxide layer of substrate is flatly placed in above graphene, substrate and graphene are made
Face contacts；
Step 6：Substrate is slowly pressed into graphene, until graphene and substrate come into full contact with, graphene is attached to substrate, shape
At graphene-substrate；
Step 7：It obtains graphene-substrate and cleans, removal etchant solution, remaining metal and heptane；Dry acquisition cleaning
Graphene-substrate.
2. the method for low liquid level tension wet method transfer graphene as described in claim 1, it is characterised in that：It is realized in step 2
The method of meniscus is to inject etchant solution in container, and a floating frame is floated in container, corrosion is added dropwise into floating frame
Solution, until there is protrusion until floating the liquid level in frame；Alternatively, etchant solution is injected in container, until the liquid in container
Until there is protrusion in face.
3. the method for low liquid level tension wet method transfer graphene as claimed in claim 2, it is characterised in that：Corruption in step 2
It is a concentration of 1 mole every liter of FeCl to lose solution3Solution.
4. the method for low liquid level tension wet method transfer graphene as claimed in claim 3, it is characterised in that：In step 3, in corruption
It loses and heptane is added dropwise on the meniscus of solution.
5. the method for the low liquid level tension wet method transfer graphene as described in one of claim 1-4, it is characterised in that：Substrate is
Silica polished silicon wafer, in step 5, substrate presses to graphene with the speed of 1mm/s, after substrate submerges etchant solution, graphene
It is come into full contact with substrate.
6. the method for low liquid level tension wet method transfer graphene as claimed in claim 5, it is characterised in that：Step 6 includes：Step
Rapid 6.1：Silica polished silicon wafer is removed from iron stand, is put into cleaning in deionized water and is remained in silica polished silicon wafer
Etchant solution 2-3 times；
Step 6.2：Silica polished silicon wafer is put into 20：1：1 H2O：H2O2：The solution of HCl dissolves kish；
Step 6.3：Silica polished silicon wafer is put into solution 2-3 times that deionized water cleaning remains in substrate；
Step 6.4：Silica polished silicon wafer is placed to dry moisture vertically；
Step 6.5：Silica polished silicon wafer is put into cleaning remained on surface heptane in isopropanol, silica polished silicon wafer is taken out and blows
Dry isopropanol.
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| CN201810212644.5A CN108455577A (en) | 2018-03-15 | 2018-03-15 | A kind of method of low liquid level tension wet method transfer graphene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184835A (en) * | 2021-05-12 | 2021-07-30 | 电子科技大学 | Method for transferring graphene through pressure-assisted evaporation |
| CN114394589A (en) * | 2022-02-15 | 2022-04-26 | 浙江大学 | Method for transferring strain graphene on silicon substrate containing oxide layer |
| CN115161775A (en) * | 2022-07-01 | 2022-10-11 | 常州第六元素半导体有限公司 | Transfer method of graphene film |
-
2018
- 2018-03-15 CN CN201810212644.5A patent/CN108455577A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184835A (en) * | 2021-05-12 | 2021-07-30 | 电子科技大学 | Method for transferring graphene through pressure-assisted evaporation |
| CN113184835B (en) * | 2021-05-12 | 2022-08-12 | 电子科技大学 | Method for transferring graphene through pressure-assisted evaporation |
| CN114394589A (en) * | 2022-02-15 | 2022-04-26 | 浙江大学 | Method for transferring strain graphene on silicon substrate containing oxide layer |
| CN115161775A (en) * | 2022-07-01 | 2022-10-11 | 常州第六元素半导体有限公司 | Transfer method of graphene film |
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Application publication date: 20180828 |