CN107867681A - A kind of method of electrochemical gas bubbling transfer large-area graphene - Google Patents
A kind of method of electrochemical gas bubbling transfer large-area graphene Download PDFInfo
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- CN107867681A CN107867681A CN201610855141.0A CN201610855141A CN107867681A CN 107867681 A CN107867681 A CN 107867681A CN 201610855141 A CN201610855141 A CN 201610855141A CN 107867681 A CN107867681 A CN 107867681A
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- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000012546 transfer Methods 0.000 title claims abstract description 64
- 230000005587 bubbling Effects 0.000 title claims abstract description 34
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to the transfer techniques of graphene, specially a kind of method of electrochemical gas bubbling transfer large-area graphene.Boundary layer is being formed positioned at the large-area graphene surface of initial substrate first, boundary layer forms fine and close combination with graphenic surface and has stability in the electrolytic solution；Then transfer medium layer is formed in interface layer surfaces, the adhesion between transfer medium layer and boundary layer is more than the peeling force of electrochemical gas bubbling；After being peeled off with initial substrate electrochemical gas bubbling, the graphenic surface of graphene/boundary layer/transfer medium composite membrane is combined with target substrate；Boundary layer is peeled off from graphenic surface again, realizes transfer of the graphene to target substrate；Repeat the above steps, shift multi-layer graphene.Supporting layer during using transfer medium as transfer graphene, using boundary layer improvement and the combination of graphene, structural intergrity of the large-area graphene in the stripping of electrochemical gas bubbling was both improved, has been easy to shift multi-layer graphene again.
Description
Technical field:
The present invention relates to the transfer techniques of graphene, specially a kind of electrochemical gas bubbling transfer large-area graphene
Method.
Background technology:
Graphene be by single layer of carbon atom it is tightly packed into bi-dimensional cellular shape crystal structure, be build other dimension raws material of wood-charcoal
Expect the basic structural unit of (zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).The unique crystal structure of graphene has it
There are excellent electricity, calorifics and mechanical property, such as its electron mobility is up to 200,000cm at room temperature2/ Vs, thermal conductivity are high
Up to 5300W/mk, it is expected in multi-functional nanometer electronic device, nesa coating, composite, catalysis material, energy storage material, field
The fields such as emissive material, gas sensor and gas storage obtain extensive use.In order to comprehensively utilize the numerous excellent of graphene
Characteristic, the preparation of high-quality graphene and transfers graphene in particular substrate and becomes most important.
Divided first using adhesive tape stripping method (or micromechanics stripping method) from the seminar of Univ Manchester UK in 2004
After the graphene being stabilized from acquisition, the method for much preparing graphene is developed successively, including chemical oxidation is peeled off
Method, separate out growth method and chemical vapor deposition (CVD) method.Due to relatively simple preparation process, and yield is larger, chemical oxidation
Graphene made from stripping method has been widely used for composite, flexible transparent conductive film and energy storage electrode material etc..
But chemical stripping graphene is second-rate, a large amount of faults of construction, and the size and the number of plies of unmanageable graphene be present
Etc. architectural feature.CVD method is current controllable preparation large area, the main method of high-quality graphene.By controlling temperature, carbon
The preparation condition such as source and pressure, it is possible to achieve grow large area, high-quality in a variety of substrate material surfaces (metal and nonmetallic)
The graphene of amount.For the sign of graphene, physical measurement and application study, it usually needs be placed on graphene and remove
Prepare in the particular substrate outside matrix, and it is desirable that large area, the graphene of high quality do not produce breakage in transfer process.Cause
This, development large area, the lossless transfer method of high-quality graphene have for the research or even application for promoting grapheme material
Important function and significance.
In order to reduce the cost of transfer of graphene, the lossless transfer method of matrix can be used, mainly includes direct transfer process and electricity
Chemical gas bubbling stripping method.The former utilizes the transfer medium stronger with graphene adhesion (such as：Adhesive tape, binding agent etc.) by stone
Black alkene directly strips down from matrix surface.Matrix material need not be lost in this method, also do not use with corrosivity and contaminative
Chemical reagent.But this method easily causes the breakage of graphene, therefore lossless turn of large-area graphene can not be realized
Move.The latter is inserted after graphenic surface coats transfer medium using the impetus of caused bubble and gas in electrolytic process
Layer is acted on graphene and initial substrate nondestructively peeling.The process is to graphene and its initial substrate without any destruction and damage
Consumption, and easy to operate, speed is fast, is easy to regulation and control, the pollution without metal etchants.
However, the graphene of this method transfer at present uses the polymer conducts such as polymethyl methacrylate (PMMA) film more
Transfer medium, realize transfer of the graphene to arbitrary target matrix.But PMMA is thin during large-area graphene is shifted
Film is easily damaged, so as to destroy the structural intergrity of graphene.Therefore, development is needed badly at present for large-area graphene to any
The electrochemical gas bubbling transfer techniques of target substrate transfer.
The content of the invention:
Principle transfer large-area graphene is peeled off based on electrochemical gas bubbling it is an object of the invention to provide a kind of
Method, large-area graphene can be nondestructively transferred on arbitrary target matrix.
The technical scheme is that：
A kind of method of electrochemical gas bubbling transfer large-area graphene, this method are peeled off based on electrochemical gas bubbling
Principle realize the transfer of large-area graphene；Boundary layer is being formed positioned at the large-area graphene surface of initial substrate first,
Boundary layer forms fine and close combination with graphenic surface and has stability in the electrolytic solution；Then formed and shifted in interface layer surfaces
Dielectric layer, the adhesion between transfer medium layer and boundary layer are more than the peeling force of electrochemical gas bubbling；With initial substrate electricity
After chemical gas bubbling is peeled off, by the graphenic surface of " graphene/boundary layer/transfer medium " composite membrane and target substrate knot
Close；Boundary layer is peeled off from graphenic surface again, realizes transfer of the graphene to target substrate；Repeat the above steps, transfer is more
Layer graphene.
The method of described electrochemical gas bubbling transfer large-area graphene, graphene is using chemical vapor deposition side
The graphene of method growth or the graphene of separation method growth, the average number of plies positioned at the graphene of initial substrate are individual layer, double
Layer, few layer or multilayer, the number of plies are less than 50 layers.
The method of described electrochemical gas bubbling transfer large-area graphene, initial substrate Pt, Ni, Cu, Co, Ir,
One of Ru, Au, Ag, Fe, Mo metal or its alloy or two or more composites；Or initial substrate is titanium carbide, carbonization
One of molybdenum, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, tungsten carbide or two or more composites；Or just
Primordium body is Si, SiO2、Al2O3One of semiconductor is two or more compound；Or initial substrate is both conductor and semiconductor
Composite.
The method of described electrochemical gas bubbling transfer large-area graphene, forms boundary layer in graphenic surface and turns
Moving the method for medium includes coating, fitting, the one or more of deposition.
The method of described electrochemical gas bubbling transfer large-area graphene, forms boundary layer in graphenic surface and turns
The method for moving medium is specifically included but is not limited to：It is roll coated, blade coating, bar coating, spraying, spin coating, lifting, bonding, quiet
Electro Sorb, chemical vapor deposition, physical vapour deposition (PVD), evaporation coating or sputter coating.
The method of described electrochemical gas bubbling transfer large-area graphene, interlayer materials include organic matter, metal
The combination of compound, nonmetallic and nonmetallic compound one or more, transfer medium material are high molecular polymer.
The method of described electrochemical gas bubbling transfer large-area graphene, target substrate is high molecular polymer：It is poly-
Ethylene glycol terephthalate, PEN, polysiloxanes, makrolon, polyethylene, polyvinyl chloride, polyphenyl
Ethene or polypropylene；Or target substrate is semiconductor：Silicon, silica, silicon nitride, aluminium nitride, aluminum oxide or glass；Or
Target substrate is conductor：Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo or its alloy, target substrate are shaped as plane, song
Face or wire side.
The method of described electrochemical gas bubbling transfer large-area graphene, when initial substrate and target substrate are all soft
During property material, the stripping of graphene and initial substrate and transfer to target substrate are realized using the method for volume to volume.
The present invention design philosophy be：
The present invention improves large-area graphene in electrochemistry by introducing boundary layer between transfer medium layer and graphene
Gas sparging peel off and with the structural intergrity in target substrate cohesive process.
The features of the present invention and beneficial effect are：
1. the present invention use transfer medium as transfer graphene during supporting layer, while using boundary layer improvement and
The combination of graphene, both improved large-area graphene electrochemical gas bubbling peel off and with the knot in target substrate cohesive process
Structure integrality, it is easy to shift multi-layer graphene again.
2. each processing step of the present invention is compatible with typical volume to volume rolling process, easily realizes that automation is continuous and turn
Move.
Embodiment:
The present invention is described in further detail below by embodiment.
Embodiment 1
Using metal copper foil as initial substrate, boundary layer is used as using polymethyl methacrylate (PMMA), using pressure
Sensitive tape is as transfer medium, using polyethylene terephthalate (PET) film as target substrate.Existed using CVD
(in the present embodiment, metal copper foil can change the copper sheet or copper coin of different size, monocrystalline or polycrystalline into, thick on metal copper foil
Degree is more than 10 μm, and the present embodiment is 25 μm) growth single-layer graphene.After copper foil cooling to be generated with graphene, use
The method of volume to volume blade coating is 10 μm of PMMA solution in its surface coating thickness, and volume to volume roll-in is used again after its drying
Method is by pressure sensitive adhesive tape film laminating in PMMA surface (pressure is less than 1MPa, the present embodiment 0.1MPa).Will " pressure sensitive adhesive tape/
The negative pole of the upper constant-current supply of coiled material connection of PMMA/ graphenes/copper foil " laminated film, by the use of platinized platinum as positive pole, using electrochemistry
Gas sparging method peels off graphene.In the present embodiment, electrolyte is the 1mol/L NaOH aqueous solution, by " pressure sensitive adhesive tape/PMMA/
After graphene/copper foil " web part is immersed in solution, applying 0.5 Ampere currents, electrolytic process applied voltage is 3~6 volts,
For the operation temperature of electrolytic process at 20~30 DEG C, gas caused by electrolysis is hydrogen (H2)." pressure sensitive adhesive tape/PMMA/ graphite
Alkene " first passes through water and rinses and be completely dried after being kept completely separate with copper foil, then packed up by receiving volume.Using the side of volume to volume roll-in
" pressure sensitive adhesive tape/PMMA/ graphenes " is fitted in pet sheet face by method, then is immersed in acetone soln and be completely dissolved PMMA, will be pressure-sensitive
Adhesive tape completes the transfer of graphene after being peeled off with graphene.
Embodiment 2
Difference from Example 1 is：
The heat release adhesive tape varied with temperature using cohesive force is as transfer medium.Using volume to volume hot-rolling pressure (hot pressing temperature
120 DEG C of degree, pressure 0.2MPa) method, " heat release adhesive tape/PMMA/ graphenes " is fitted in pet sheet face, then directly by
Heat release adhesive tape is peeled off with PMMA." PMMA/ graphenes " is immersed in acetone soln again and is completely dissolved PMMA, completes graphene
Transfer.
Embodiment 3
Difference from Example 1 is：
Using different materials, (in the present embodiment, metal copper foil can change the metals such as nickel, platinum, ruthenium or iridium and its alloy into
(such as：Corronil, Mo-Ni alloy or golden nickel alloy etc.) paillon foil or on silicon chip stable bond metallic film, and carbon
Change the metal carbides such as titanium, molybdenum carbide or tungsten carbide, or other semiconductors such as Si) initial substrate is used as, utilize distinct methods
In the few layer of its superficial growth or multi-layer graphene.In the present embodiment, few layer is 2~4 layers, and multilayer is 5~10 layers.
Embodiment 4
Difference from Example 1 is：
Using different materials as boundary layer (such as：Alkane type organic, esters polymer, resin, oxide or metal nitrogen
Compound etc.) and transfer medium is (such as：Hot melt adhesive film or light-curable glue film etc.).
Embodiment 5
Difference from Example 2 is：
Using low cohesive force film (such as：Silicone or esters of acrylic acid) it is used as transfer medium.
Embodiment 6
Difference from Example 1 is：
By repeatedly shifting, four layer graphenes of large area are obtained.After single-layer graphene/PET film is obtained, repeat
Above-mentioned transfer process, " pressure sensitive adhesive tape/PMMA/ graphenes " after stripping is fitted in individual layer stone by the method for volume to volume roll-in
Black alkene/PET surface, dissolving remove PMMA and obtain bilayer graphene/PET film after peeling off pressure sensitive adhesive tape.The process is repeated,
Until obtaining four layer graphenes/PET film.
Embodiment result shows that the present invention uses transfer medium to be adopted simultaneously as the supporting layer during transfer graphene
With boundary layer improvement and the combination of graphene, structural integrity of the large-area graphene in the stripping of electrochemical gas bubbling had both been improved
Property, it is easy to shift multi-layer graphene again；This method and volume to volume process compatible, it is possible to achieve scale, serialization transfer, are stone
Extensive use of the black alkene material in fields such as transparent conductive material, electronic device material and sensor materials lays the foundation.
Claims (8)
- A kind of 1. method of electrochemical gas bubbling transfer large-area graphene, it is characterised in that：This method is based on electrochemistry gas The principle that body bubbling is peeled off realizes the transfer of large-area graphene；First in the large-area graphene surface shape positioned at initial substrate Into boundary layer, boundary layer forms fine and close combination with graphenic surface and has stability in the electrolytic solution；Then in boundary layer table Face forms transfer medium layer, and the adhesion between transfer medium layer and boundary layer is more than the peeling force of electrochemical gas bubbling；With After initial substrate electrochemical gas bubbling is peeled off, by the graphenic surface and mesh of " graphene/boundary layer/transfer medium " composite membrane Matrix is marked to combine；Boundary layer is peeled off from graphenic surface again, realizes transfer of the graphene to target substrate；Repeat above-mentioned step Suddenly, multi-layer graphene is shifted.
- 2. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 1, it is characterised in that：Graphite Alkene is the graphene of the graphene or separation method growth using chemical gaseous phase depositing process growth, positioned at the graphite of initial substrate The average number of plies of alkene is that individual layer, bilayer, few layer or multilayer, the number of plies are less than 50 layers.
- 3. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 1, it is characterised in that：Initially Matrix is one of Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo metal or its alloy or two or more composites；Or Initial substrate be titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, one of tungsten carbide or two kinds with On composite；Or initial substrate Si, SiO2、Al2O3One of semiconductor is two or more compound；Or first primordium Body is the composite of both conductor and semiconductor.
- 4. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 1, it is characterised in that：In stone Black alkene surface, which forms boundary layer and the method for transfer medium, includes coating, fitting, the one or more of deposition.
- 5. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 4, it is characterised in that：In stone Black alkene surface forms boundary layer and the method for transfer medium is specifically included but is not limited to：Roll coated, blade coating, bar coating, Spraying, spin coating, lifting, bonding, Electrostatic Absorption, chemical vapor deposition, physical vapour deposition (PVD), evaporation coating or sputter coating.
- 6. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 1, it is characterised in that：Interface Layer material includes the combination of organic matter, metallic compound, nonmetallic and nonmetallic compound one or more, and transfer is situated between Material is high molecular polymer.
- 7. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 1, it is characterised in that：Target Matrix is high molecular polymer：Polyethylene terephthalate, PEN, polysiloxanes, makrolon, Polyethylene, polyvinyl chloride, polystyrene or polypropylene；Or target substrate is semiconductor：Silicon, silica, silicon nitride, nitridation Aluminium, aluminum oxide or glass；Or target substrate is conductor：Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo or its alloy, mesh Mark matrix is shaped as plane, curved surface or wire side.
- 8. the method for large-area graphene is shifted according to the electrochemical gas bubbling described in claim 1, it is characterised in that：Originally When primordium body and target substrate are all flexible material, using the method for volume to volume realize graphene and initial substrate stripping and Transfer to target substrate.
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