CN104843694A - Preparation method for multilayered graphene film - Google Patents
Preparation method for multilayered graphene film Download PDFInfo
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- CN104843694A CN104843694A CN201510257911.7A CN201510257911A CN104843694A CN 104843694 A CN104843694 A CN 104843694A CN 201510257911 A CN201510257911 A CN 201510257911A CN 104843694 A CN104843694 A CN 104843694A
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Abstract
The invention provides a preparation method for a multilayered graphene film, which includes the following steps: (S1) a polymer supporting layer is formed on a graphene film growing on the surface of a metal layer; (S2) the metal layer is dissolved, and the polymer supporting layer/graphene film is doped; (S3) another graphene film growing on the surface of a metal layer is covered by the polymer supporting layer/graphene film; (S4) metal layer dissolution and doping are carried out again; (S5) a target substrate is covered by the polymer supporting layer/graphene film, and the polymer supporting layer is removed. By flexibly controlling the frequency of repeating the steps S3 and S4, the graphene film with a needed layer number which is located on the target substrate can be obtained. By repetitively utilizing the polymer supporting layer formed in one step in the process of transfer, the preparation method prevents polymer from remaining among the layers of graphene; moreover, since chemical doping is carried out in the layer-by-layer transfer process, doped ions are located among the layers of graphene, and cannot easily separate from the graphene film, and thereby the doping effect is prolonged.
Description
Technical field
The present invention relates to material and prepare manufacture field, relate to a kind of preparation method of multi-layer graphene film.
Background technology
Graphene is a kind of monoatomic layer two dimensional crystal material be made up of with honeycomb type lattice carbon atom.Due to crystalline network and the two-dimensional characteristics of Graphene uniqueness, this material has the character of numerous excellences such as high light transmittance, high mechanical strength, high carrier mobility, high thermal conductivity coefficient and high-specific surface area.Many aspects such as scene effect transistor, flexible transparent electrode, touch-screen, printed electronic, energy storage device all have a wide range of applications.Therefore, the technology such as the domestic and international growth to graphene film, transfer and application in recent years produces to know clearly and studies interest widely.
Chemical vapour deposition (CVD) method is considered to one of technology being best suited for scale operation graphene film.This method utilizes the gas such as methane or acetylene as carbon source, by the tinsel such as copper or nickel as catalyzer, by heat, the molecule of gaseous carbon sources is decomposed at catalyst surface, wherein carbon atom is deposited on metal foil surface and forms continuous print graphene film.
Graphene film prepared by current CVD method is based on single-layer graphene, although carrier mobility is very high, carrier concentration is on the low side.In order to the requirement making graphene film adapt to various flexible electronic device, need to regulate and control the physical propertys such as its carrier concentration, square resistance, energy gap and work function.The number of plies controlling Graphene is the Main Means regulating and controlling its performance with doping.Therefore, develop suitable multi-layer graphene successively to shift with doping techniques for promoting that the practical and industrialization of graphene film is significant.
At present graphene film is stripped down from metallic catalyst surfaces; transfer to the main method in silicon chip, glass or polymer substrate; be utilize the polymkeric substance such as polymethylmethacrylate (PMMA) or polydimethylsiloxane (PDMS) to form one deck protection supporting layer at graphenic surface, then the tinsel that graphene film adheres to is eroded.The polymer/graphene duplicature obtained like this is transferred in target substrate, finally falls polymeric support layer with organic solvent dissolution.When this method is used for the successively transfer of multi-layer graphene, processing step is comparatively loaded down with trivial details, and the graphene film surface of every layer of transfer can exist a small amount of polymer residues, be difficult to remove, the character of multi-layer graphene film and subsequent device made and causes disadvantageous effect.
And mainly in the solution such as hydrochloric acid, nitric acid, sulfuric acid or gold trichloride, certain hour is soaked the graphene film after transfer to the method that graphene film carries out surface doping, the ion in solution is made to be attached to graphenic surface, by the Charger transfer between attachment ion and Graphene, in graphene film, form the doping effect of particular carrier.But this method also has following shortcoming: during immersion, graphene film easily comes off from substrate; And after doping, the ion of graphenic surface attachment is exposed in external environment, surface can be departed from gradually, make doping effect pass in time and obviously weaken.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of preparation method of multi-layer graphene film, the successively transfer of multi-layer graphene is not suitable for, the problem that doping effect is passed in time and weakened for solving graphene film transfer method in prior art.
For achieving the above object and other relevant objects, the invention provides a kind of preparation method of multi-layer graphene film, comprise the following steps:
S1: form polymeric support layer on the graphene film being grown on layer on surface of metal;
S2: dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S3: polymeric support layer/graphene film is covered another and is grown on the graphene film of layer on surface of metal;
S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S5: polymeric support layer/graphene film is covered in target substrate, more described polymeric support layer is removed, obtain the multi-layer graphene film be formed in target substrate.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, the preparation method of described multi-layer graphene film comprises the following steps:
S1: form polymeric support layer on the graphene film being grown on layer on surface of metal;
S2: dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S3: polymeric support layer/graphene film is covered another and is grown on the graphene film of layer on surface of metal;
S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
Polymeric support layer/graphene film at least one times, then covers in target substrate by S5: repeating step S3 ~ S4, then is removed by described polymeric support layer, obtains the multi-layer graphene film be formed in target substrate.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S2 or step S4, polymeric support layer/graphene film is put into doped solution and carry out doping and comprise the steps:
Polymeric support layer/graphene film is put into deionized water rinsing 1 ~ 5 time;
Polymeric support layer/graphene film is put into doped solution to soak 1 ~ 10 minute.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S3, polymeric support layer/graphene film is covered on another graphene film being grown on layer on surface of metal and comprise the steps:
With surface growth, polymeric support layer/graphene film picks up by the metal level of Graphene from doped solution;
Dry surface-moisture, polymeric support layer/graphene film and layer on surface of metal are fitted tightly.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S5, polymeric support layer/graphene film is covered in target substrate and comprises the steps:
By described target substrate, polymeric support layer/graphene film is picked up from doped solution;
Dry surface-moisture, polymeric support layer/graphene film and described target substrate are fitted tightly.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, when drying surface-moisture, storing temperature scope is 100 ~ 180 DEG C, and baking time is 5 ~ 30 minutes.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S1, the one in Best-Effort request, spin coating, scraper, spraying, wet coating, silk screen printing, roller coating or board-like coating is adopted to prepare described polymeric support layer.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, described polymeric support layer also comprises the step that thermal treatment realizes solidification after application.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, the process slurry forming described polymeric support layer adopts acetone, Virahol, methyl-phenoxide, at least one in chlorine benzene,toluene,xylene as solvent.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S5, the method that described polymeric support layer is removed is comprised in organic solvent soak, in reducing atmosphere annealing in one.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, described organic solvent comprises at least one in acetone, Virahol, acetic acid, methyl-phenoxide, chlorine benzene,toluene,xylene.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, described reducing atmosphere comprises the one in the mixed atmosphere of the mixed atmosphere of hydrogen, hydrogen and nitrogen, hydrogen and argon gas.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, the temperature range of annealing in reducing atmosphere is 400 ~ 600 DEG C.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, the material of described polymeric support layer comprises the one in polymethylmethacrylate, polycarbonate, polydimethylsiloxane, poly-(4-vinyl pyridine), polyhutadiene, polyvinyl chloride, transparent fluoro-resin.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, the thickness range of described polymeric support layer is 300 ~ 800 nanometers.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, the material of described metal level comprises the one in monometallic Au, Pt, Pd, Ir, Ru, Co, Ni, Cu, or at least two kinds of alloy materials formed in described monometallic.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S2 or step S4, the solution dissolving described metal level comprises at least one in iron(ic) chloride, iron nitrate, ammonium persulphate, sulfuric acid, nitric acid, hydrochloric acid.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, described doped solution comprises at least one in sulfuric acid, nitric acid, hydrochloric acid, gold trichloride.
As a kind of preferred version of the preparation method of multi-layer graphene film of the present invention, in described step S1 or step S3, described in be grown on layer on surface of metal graphene film be single or multiple lift Graphene.
As mentioned above, the preparation method of multi-layer graphene film of the present invention, there is following beneficial effect: the preparation method of multi-layer graphene film of the present invention, by being recycled by the polymeric support layer once formed in transfer process, avoids the polymer residue between each layer graphene; Simultaneously in successively transfer process, carry out chemical doping, dopant ion is between each layer graphene, not easily departs from from graphene film, extend the effect of doping.
Accompanying drawing explanation
Fig. 1 is shown as the process flow sheet of the preparation method of multi-layer graphene film of the present invention.
Fig. 2 is shown as the structural representation of the graphene film being grown on layer on surface of metal.
Fig. 3 is shown as the schematic diagram forming polymeric support layer on the graphene film being grown on layer on surface of metal.
Fig. 4 is shown as the schematic diagram dissolved by the metal level of polymeric support layer/graphene film attachment with solution.
Fig. 5 is shown as schematic diagram polymeric support layer/graphene film put into doped solution and carry out adulterating.
Fig. 6 is shown as and polymeric support layer/graphene film is covered another and be grown on schematic diagram on the graphene film of layer on surface of metal.
Fig. 7 is shown as again with the schematic diagram that the metal level of polymeric support layer/graphene film attachment dissolves by solution.
Fig. 8 is shown as the schematic diagram covered by polymeric support layer/graphene film in target substrate.
Fig. 9 is shown as and is removed by described polymeric support layer, obtains the schematic diagram of the multi-layer graphene film be formed in target substrate.
Element numbers explanation
S1 ~ S5 step
101,105 graphene films
102,106 metal levels
103 polymeric support layer
104 doped solution
107 target substrate
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to Fig. 1 to Fig. 9.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
Embodiment one
The invention provides a kind of preparation method of multi-layer graphene film, refer to Fig. 1, be shown as the process flow sheet of the method, comprise the following steps:
S1: form polymeric support layer on the graphene film being grown on layer on surface of metal;
S2: dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S3: polymeric support layer/graphene film is covered another and is grown on the graphene film of layer on surface of metal;
S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S5: polymeric support layer/graphene film is covered in target substrate, more described polymeric support layer is removed, obtain the multi-layer graphene film be formed in target substrate.
First refer to Fig. 2 ~ Fig. 3, perform step S1: on the graphene film 101 being grown on metal level 102 surface, form polymeric support layer 103.
Concrete, described metal level 102 is as the catalytic substrate of graphene film, and its material comprises the one in monometallic Au, Pt, Pd, Ir, Ru, Co, Ni, Cu, or at least two kinds of alloy materials formed in described monometallic.Certainly, described metal level 102 also can be other suitable catalytic substrate, should too not limit the scope of the invention herein.
Concrete, chemical vapour deposition (CVD) method can be adopted on described metal level 102 to prepare described graphene film 101, in the present embodiment, described metal level 102 is for Copper Foil, detailed process is: Copper Foil is cut into suitable size, put into beaker, use each ultrasonic cleaning of deionized water, acetone and Virahol 10 minutes successively.The Copper Foil cleaned is put into acetic acid to soak 10 minutes, take out and use deionized water rinsed clean.With nitrogen, Copper Foil is dried up, put into tube furnace.With mechanical pump, boiler tube internal gas pressure is extracted into below 5Pa, passes into hydrogen, flow 10 ~ 100sccm.Be warming up to 950 ~ 1050 DEG C, after temperature-stable, pass into methane, flow 0.1 ~ 10sccm.After 1 ~ 10 minute, stop passing into methane, close heating power supply, tube furnace is down to room temperature.Stop passing into hydrogen, take out the surface growth Copper Foil of graphene film 101, as shown in Figure 2.Can see, the upper and lower surface of Copper Foil all grows and has graphene film 101, in the present invention, only needs to choose graphene film 101 on one of them surface as research object.In the present embodiment, be grown on the graphene film 101 on described metal level 102 surface for single-layer graphene.
The mode of spin coating can be adopted in the present embodiment to prepare described polymeric support layer 103, certainly, in other embodiments, the technique that Best-Effort request, scraper, spraying, wet coating, silk screen printing, roller coating or board-like coating etc. also can be adopted suitable is to prepare described polymeric support layer 103.Exemplarily, the detailed process adopting the method for spin coating to prepare described polymeric support layer 103 is: be first dissolved in by polymethylmethacrylate (PMMA) in solvent (at least one in acetone, Virahol, methyl-phenoxide, chlorine benzene,toluene,xylene), formation process slurry, afterwards at described graphene film 101 surperficial spin coating one deck PMMA slurry, the concentration of PMMA is 10 ~ 80mg/ml, rotating speed 2000 ~ 8000 revs/min, 20 ~ 60 seconds time.
Concrete, described polymeric support layer 103 also comprises the step that thermal treatment realizes solidification after application.Exemplarily, detailed process is as follows: sample is put into baking oven, storing temperature 120 ~ 180 DEG C, and 5 ~ 20 minutes time, to solidify PMMA.As shown in Figure 3, the thickness of the polymeric support layer 103 of acquisition is in 300 ~ 800 nanometer range.In other embodiments, the material of described polymeric support layer 103 can also be polycarbonate, polydimethylsiloxane, poly-(4-vinyl pyridine), polyhutadiene, polyvinyl chloride, transparent fluoro-resin etc.
Then refer to Fig. 4 ~ Fig. 5, perform step S2: dissolve with the metal level of solution by the attachment of polymeric support layer/graphene film, and polymeric support layer/graphene film is put into doped solution 104 adulterate.
Detailed process is: the sample that described step S1 obtains is put into the FeCl that concentration is 0.1 ~ 1mol/L
3floating in the aqueous solution.After 1 ~ 5 hour, Copper Foil is completely dissolved.Then polymeric support layer/graphene film is put into deionized water rinsing 1 ~ 5 time, the hydrochloric acid again polymeric support layer/graphene film being put into 5 ~ 30% afterwards adulterates 1 ~ 10 minute.
In other embodiments, the solution dissolving described metal level 102 can also be at least one in iron nitrate, ammonium persulphate, sulfuric acid, nitric acid, hydrochloric acid etc.Described doped solution 104 can also be at least one in sulfuric acid, nitric acid, gold trichloride etc.For hydrochloric acid, sulfuric acid or nitric acid doped solution, mainly utilize the effect of acid ion wherein; For gold trichloride doped solution, mainly utilize the effect of gold ion wherein.
Then refer to Fig. 6, perform step S3: covered by polymeric support layer/graphene film on another graphene film 105 being grown on metal level 106 surface.
Concrete, described metal level 106 is as the catalytic substrate of graphene film, and its material includes but not limited to the one in monometallic Au, Pt, Pd, Ir, Ru, Co, Ni, Cu, or at least two kinds of alloy materials formed in described monometallic.In the present embodiment, described metal level 106 is also for Copper Foil, and its epontic graphene film 105 is single-layer graphene.Described graphene film 101 superposes with described graphene film 105, forms bilayer graphene (one of multi-layer graphene).
Concrete, polymeric support layer/graphene film is covered on another graphene film being grown on layer on surface of metal and comprise the steps:
1) with surface growth, polymeric support layer/graphene film picks up by the metal level 106 of Graphene 105 from doped solution 104;
2) dry surface-moisture, polymeric support layer/graphene film and metal level 106 intimate surface are fitted.
Refer to Fig. 7 again, perform step S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated.
Concrete, adopt the method substantially identical with step S2 to dissolve described metal level 106, and polymeric support layer/graphene film is adulterated.Because described graphene film 101 and described graphene film 105 are respectively through doping, dopant ion are between each layer graphene, not easily depart from from graphene film, extend the effect of doping.
Finally refer to Fig. 8 ~ Fig. 9, perform step S5: covered in target substrate 107 by polymeric support layer/graphene film, then removed by described polymeric support layer 103, obtain the multi-layer graphene film be formed in target substrate 107.
Concrete, polymeric support layer/graphene film is covered in target substrate 107 and comprise the steps:
1) by described target substrate 107, polymeric support layer/graphene film is picked up from doped solution;
2) dry surface-moisture, polymeric support layer/graphene film and described target substrate 107 are fitted tightly.
Exemplarily, when drying surface-moisture, storing temperature scope is 100 ~ 180 DEG C, and baking time is 5 ~ 30 minutes.
Concrete, the method removed by described polymeric support layer 103 can be soaked in organic solvent, or in reducing atmosphere high temperature annealing.
According to the method for soaking in organic solution, described organic solvent includes but not limited at least one in acetone, Virahol, acetic acid, methyl-phenoxide, chlorine benzene,toluene,xylene.Exemplarily, the sample after drying is put into acetone immersion 1 ~ 5 hour, removes PMMA.
According to the method for high temperature annealing in reducing atmosphere, described reducing atmosphere includes but not limited to the one in the mixed atmosphere of the mixed atmosphere of hydrogen, hydrogen and nitrogen, hydrogen and argon gas.Exemplarily, the temperature range of annealing in reducing atmosphere is 400 ~ 600 DEG C.
So far, target substrate obtains bilayer graphene film, the preparation method of multi-layer graphene film of the present invention, by being recycled by the polymeric support layer once formed in transfer process, avoids the polymer residue between each layer graphene; Simultaneously in successively transfer process, carry out chemical doping, dopant ion is between each layer graphene, not easily departs from from graphene film, extend the effect of doping.
Embodiment two
The present embodiment adopts substantially identical technical scheme with embodiment one, and difference is, in embodiment one, only performs described step S2 ~ S3 once, the obtained bilayer graphene film being positioned at target substrate surface; And in the present embodiment after execution of step S4, repeating step S3 ~ S4 at least one times, obtained three layers that are positioned at target substrate surface or more layer graphene films.
Concrete, as shown in Figure 1, the preparation method of described multi-layer graphene film comprises the following steps:
S1: form polymeric support layer on the graphene film being grown on layer on surface of metal;
S2: dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S3: polymeric support layer/graphene film is covered another and is grown on the graphene film of layer on surface of metal;
S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
Polymeric support layer/graphene film at least one times, then covers in target substrate by S5: repeating step S3 ~ S4, then is removed by described polymeric support layer, obtains the multi-layer graphene film be formed in target substrate.
The detailed process of each step see embodiment one, can repeat no more herein above.
In the present embodiment, by controlling the number of times of repeating step S3 ~ S4 flexibly, the graphene film of the required number of plies can be obtained, and in transfer process, the polymeric support layer once formed recycled, avoiding the polymer residue between each layer graphene; Simultaneously in successively transfer process, carry out chemical doping, dopant ion is between each layer graphene, not easily departs from from graphene film, extend the effect of doping.Exemplarily, repeating step S3 ~ S4 once, obtains the three layer graphene films be formed in target substrate.
Through test, the double doping layer graphene film square resistance obtained in embodiment one is 300 ~ 400 Ω/, the three layers of doped graphene film rectangular resistance obtained in the present embodiment are 200 ~ 300 Ω/, and its square resistance can keep one month and not have considerable change, doping successful is more stable than existing method.
Embodiment three
The present embodiment adopts substantially identical technical scheme with embodiment one or embodiment two, difference is, in embodiment one and embodiment two, in described step S1 or step S3, the described graphene film being grown on layer on surface of metal is single-layer graphene, and the multi-layer graphene film be positioned in target substrate finally obtained is formed by stacking by multiple single-layer graphene through doping; And in the present embodiment, in described step S1 or step S3, described in be grown on layer on surface of metal graphene film both can be single-layer graphene, also can be multi-layer graphene (comprising bilayer graphene).
In the present embodiment, the multi-layer graphene film be positioned in target substrate finally obtained both by multiple single-layer graphene through doping and can be formed by stacking through the multi-layer graphene of doping, also can be formed by stacking by multiple multi-layer graphene through doping, although there is no dopant ion between some layer graphene film, but the dopant ion between other layer still can play a role, and not easily depart from from graphene film, the doping effect of multi-layer graphene can be extended equally., in transfer process, the polymeric support layer once formed is recycled meanwhile, avoid the polymer residue between each layer graphene.
In sum, the preparation method of multi-layer graphene film of the present invention, by being recycled by the polymeric support layer once formed in transfer process, avoids the polymer residue between each layer graphene; Simultaneously in successively transfer process, carry out chemical doping, dopant ion is between each layer graphene, not easily departs from from graphene film, extend the effect of doping.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (19)
1. a preparation method for multi-layer graphene film, is characterized in that, comprises the following steps:
S1: form polymeric support layer on the graphene film being grown on layer on surface of metal;
S2: dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S3: polymeric support layer/graphene film is covered another and is grown on the graphene film of layer on surface of metal;
S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S5: polymeric support layer/graphene film is covered in target substrate, more described polymeric support layer is removed, obtain the multi-layer graphene film be formed in target substrate.
2. the preparation method of multi-layer graphene film according to claim 1, is characterized in that: comprise the following steps:
S1: form polymeric support layer on the graphene film being grown on layer on surface of metal;
S2: dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
S3: polymeric support layer/graphene film is covered another and is grown on the graphene film of layer on surface of metal;
S4: again dissolve with the metal level of solution by polymeric support layer/graphene film attachment, and polymeric support layer/graphene film is put into doped solution and adulterated;
Polymeric support layer/graphene film at least one times, then covers in target substrate by S5: repeating step S3 ~ S4, then is removed by described polymeric support layer, obtains the multi-layer graphene film be formed in target substrate.
3. the preparation method of multi-layer graphene film according to claim 1, is characterized in that: in described step S2 or step S4, polymeric support layer/graphene film is put into doped solution and carries out doping and comprise the steps:
Polymeric support layer/graphene film is put into deionized water rinsing 1 ~ 5 time;
Polymeric support layer/graphene film is put into doped solution to soak 1 ~ 10 minute.
4. the preparation method of multi-layer graphene film according to claim 1, is characterized in that: in described step S3, is covered by polymeric support layer/graphene film on another graphene film being grown on layer on surface of metal and comprises the steps:
With surface growth, polymeric support layer/graphene film picks up by the metal level of Graphene from doped solution;
Dry surface-moisture, polymeric support layer/graphene film and layer on surface of metal are fitted tightly.
5. the preparation method of multi-layer graphene film according to claim 1, is characterized in that: in described step S5, is covered in target substrate by polymeric support layer/graphene film and comprises the steps:
By described target substrate, polymeric support layer/graphene film is picked up from doped solution;
Dry surface-moisture, polymeric support layer/graphene film and described target substrate are fitted tightly.
6. the preparation method of multi-layer graphene film according to claim 5, is characterized in that: when drying surface-moisture, storing temperature scope is 100 ~ 180 DEG C, and baking time is 5 ~ 30 minutes.
7. the preparation method of multi-layer graphene film according to claim 1, it is characterized in that: in described step S1, adopt the one in Best-Effort request, spin coating, scraper, spraying, wet coating, silk screen printing, roller coating or board-like coating to prepare described polymeric support layer.
8. the preparation method of multi-layer graphene film according to claim 7, is characterized in that: described polymeric support layer also comprises the step that thermal treatment realizes solidification after application.
9. the preparation method of multi-layer graphene film according to claim 1, is characterized in that: the process slurry forming described polymeric support layer adopts acetone, Virahol, methyl-phenoxide, at least one in chlorine benzene,toluene,xylene as solvent.
10. the preparation method of multi-layer graphene film according to claim 1, is characterized in that: in described step S5, the method that described polymeric support layer is removed is comprised in organic solvent soak, in reducing atmosphere annealing in one.
The preparation method of 11. multi-layer graphene films according to claim 10, is characterized in that: described organic solvent comprises at least one in acetone, Virahol, acetic acid, methyl-phenoxide, chlorine benzene,toluene,xylene.
The preparation method of 12. multi-layer graphene films according to claim 10, is characterized in that: described reducing atmosphere comprises the one in the mixed atmosphere of the mixed atmosphere of hydrogen, hydrogen and nitrogen, hydrogen and argon gas.
The preparation method of 13. multi-layer graphene films according to claim 10, is characterized in that: the temperature range of annealing in reducing atmosphere is 400 ~ 600 DEG C.
The preparation method of 14. multi-layer graphene films according to claim 1, is characterized in that: the material of described polymeric support layer comprises the one in polymethylmethacrylate, polycarbonate, polydimethylsiloxane, poly-(4-vinyl pyridine), polyhutadiene, polyvinyl chloride, transparent fluoro-resin.
The preparation method of 15. multi-layer graphene films according to claim 1, is characterized in that: the thickness range of described polymeric support layer is 300 ~ 800 nanometers.
The preparation method of 16. multi-layer graphene films according to claim 1, it is characterized in that: the material of described metal level comprises the one in monometallic Au, Pt, Pd, Ir, Ru, Co, Ni, Cu, or at least two kinds of alloy materials formed in described monometallic.
The preparation method of 17. multi-layer graphene films according to claim 1, it is characterized in that: in described step S2 or step S4, the solution dissolving described metal level comprises at least one in iron(ic) chloride, iron nitrate, ammonium persulphate, sulfuric acid, nitric acid, hydrochloric acid.
The preparation method of 18. multi-layer graphene films according to claim 1, is characterized in that: described doped solution comprises at least one in sulfuric acid, nitric acid, hydrochloric acid, gold trichloride.
The preparation method of 19. multi-layer graphene films according to claim 1, is characterized in that: in described step S1 or step S3, described in be grown on layer on surface of metal graphene film be single or multiple lift Graphene.
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CN105752965A (en) * | 2016-01-26 | 2016-07-13 | 无锡格菲电子薄膜科技有限公司 | Etching method for directly forming multi-layer graphene film in graphene prepared through CVD method |
CN106158144A (en) * | 2016-06-23 | 2016-11-23 | 无锡格菲电子薄膜科技有限公司 | A kind of preparation method of ultra-thin super Flexible graphene conductive film |
CN107673327A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of graphene transfer and doping method |
CN108101027A (en) * | 2017-12-29 | 2018-06-01 | 重庆墨希科技有限公司 | Large area CVD graphenes adulterate transfer method |
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CN110963484A (en) * | 2019-12-23 | 2020-04-07 | 中国科学院长春光学精密机械与物理研究所 | Doping layer-assisted large-area high-quality graphene nondestructive transfer method |
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CN102938373A (en) * | 2012-10-22 | 2013-02-20 | 西安电子科技大学 | Laminated transfer technology for graphene transparent conducting thin film and manufactured device thereby |
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CN105752965A (en) * | 2016-01-26 | 2016-07-13 | 无锡格菲电子薄膜科技有限公司 | Etching method for directly forming multi-layer graphene film in graphene prepared through CVD method |
CN106158144A (en) * | 2016-06-23 | 2016-11-23 | 无锡格菲电子薄膜科技有限公司 | A kind of preparation method of ultra-thin super Flexible graphene conductive film |
CN107673327A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of graphene transfer and doping method |
CN108101027A (en) * | 2017-12-29 | 2018-06-01 | 重庆墨希科技有限公司 | Large area CVD graphenes adulterate transfer method |
CN108101027B (en) * | 2017-12-29 | 2020-01-31 | 重庆墨希科技有限公司 | Large-area CVD graphene doping transfer method |
CN109950001A (en) * | 2019-03-28 | 2019-06-28 | 合肥工业大学 | A kind of preparation method of multi-layer graphene farmland area flexible transparent electrode |
CN109965868A (en) * | 2019-04-08 | 2019-07-05 | 清华大学 | It is tatooed formula electrode preparation method and device based on multi-layer graphene |
CN110327484A (en) * | 2019-06-10 | 2019-10-15 | 浙江大学 | A kind of multiple layer polymer of medical degradable/graphene film material and preparation method thereof |
CN110963484A (en) * | 2019-12-23 | 2020-04-07 | 中国科学院长春光学精密机械与物理研究所 | Doping layer-assisted large-area high-quality graphene nondestructive transfer method |
CN113406732A (en) * | 2021-06-10 | 2021-09-17 | 南京大学深圳研究院 | Protective device, manufacturing method thereof and method for expelling microorganisms |
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