CN106486209A - A kind of patterning 3D graphene conductive film and its environment-friendly preparation method thereof and application - Google Patents
A kind of patterning 3D graphene conductive film and its environment-friendly preparation method thereof and application Download PDFInfo
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Abstract
The present invention relates to a kind of patterning 3D graphene conductive film and its environment-friendly preparation method thereof and application.Methods described includes step：1) patterning seal, graphene oxide dispersion and substrate are provided；2) graphene oxide dispersion is coated on the patterning seal, obtains coating the patterning seal of graphene oxide film；3) the patterning seal of the coating graphene oxide film is overturn in substrate, is carried out rolling process in patterning seal upper surface and is obtained graphene oxide film；4) graphene oxide film is reduced, obtains patterning 3D graphene conductive film.The preparation method has the characteristics that simple to operate, film formation time is short, with low cost, environmental friendliness, beneficial to realizing large-scale production.The patterning 3D graphene conductive film Stability Analysis of Structures, flexible strength are high, the high and pattern definition of conductance is high.
Description
Technical field
The present invention relates to conductive film material field, thin more particularly to a kind of patterning 3D graphene conductive
Film and its environment-friendly preparation method thereof and application.
Background technology
Conductive film is widely used in the electronic devices such as display, touch-screen and solar cell.At present,
Tin indium oxide prepares one of main material of conductive film due to becoming with high conductivity and high thang-kng rate.But
It is that tin indium oxide conductive film material is highly brittle, is not particularly suited for the production of following flexible electronic device.And
The two dimensional crystal structure of the uniqueness that Graphene has, imparts the performance of its uniqueness.Research discovery, graphite
Alkene has excellent electrical properties, and under normal temperature, the electron mobility of Graphene is up to 15000cm2v-1s-1, and
Resistivity is only 10-6Ω cm, therefore Graphene be expected to very much replace tin indium oxide, for develop thinner, lead
The faster flexible electronic device of electric speed.
The graphene film of patterning may be directly applied to transistor, light emitting diode, solar cell etc.
Multiple fields, the graphene film for therefore patterning are to realize the wide variety of effective way of Graphene.At present
Frequently with the preparation method of graphene pattern have：(1) with CH4For carbon source, the stone of uniformly continuous is grown
Black alkene, then pass through photoetching, the method etching away part Graphene of plasma etching, form pattern fossil
Black alkene.This method patterning degree is high, but, photoresist in its technique and developer are easily to graphite
Alkene is polluted, and plasma etch process also easily causes to damage to Graphene.(2) nano-imprint method,
Graphene is stamped where Graphene is needed using template.This method is simple to operate, but is difficult to be formed
Continuously high-quality Graphene figure, and template construct process is complicated.
Further, since Graphene is a kind of high hydrophobicity material, solubility is low in the solution, easy coagulation,
In order to obtain the Graphene ink of concentration height, stable dispersion, surface dispersant is added by a lot of research groups
Enter in graphene solution.But, the addition of surface dispersant can directly influence the electric conductivity of Graphene,
Conductance so as to cause the conductive film for preparing is greatly reduced.
In sum, a kind of continuous integration of exploitation is badly in need of in this area, damage patterns are little, flexible strength is high and
High patterning 3D graphene conductive film of conductance and preparation method thereof.
Content of the invention
It is an object of the invention to provide a kind of continuous integration, damage patterns are little, flexible strength is high and conductive
High patterning 3D graphene conductive film of rate and preparation method thereof.
A kind of a first aspect of the present invention, there is provided preparation method of patterning 3D graphene conductive film, bag
Include following steps：
1) patterning seal, graphene oxide dispersion and substrate are provided；Wherein, the graphene oxide divides
Dispersion liquid contains graphene oxide and the first solvent for disperseing the graphene oxide；
2) graphene oxide dispersion is coated on the patterning seal, treats the patterning seal
On the graphene oxide dispersion solidification after, obtain coat graphene oxide film patterning seal；
3) by step 2) gained coating graphene oxide film patterning seal overturn in substrate, in pattern
Changing seal upper surface carries out rolling process so that patterning seal and graphene oxide film physical separation, remove pattern
Change seal, obtain graphene oxide film；
4) reduction step 3) gained graphene oxide film, obtain patterning 3D graphene conductive film.
In another preference, the patterning seal includes the first bottom and on first bottom the
One concaveconvex structure, first concaveconvex structure connection integrated with first bottom, and first concaveconvex structure
Shape be selected from the group：Square, circular, triangle, bar shaped or its combination.
In another preference, the composition material of the patterning seal is preferably siloxanes.
In another preference, the siloxanes is selected from the group：Dimethyl silicone polymer, polymethyl hydrogen siloxane,
Poly- (methyl -3,3,3- trifluoropropyl siloxanes).
In another preference, the molecular weight of the siloxanes is 3000-100000, preferably 4000-80000,
It is more preferably 5000-50000.
In another preference, the size of the patterning seal is 1-1000 μm, preferably 2-500 μm,
It is more preferably 5-100 μm.
In another preference, in step 1) also comprise the steps before：Graphene oxide described in ultrasonic disperse
Dispersion liquid.
In another preference, the frequency of the ultrasonic disperse is 10-500kHz, preferably 20-300kHz,
It is more preferably 50-100kHz.
In another preference, the time of the ultrasonic disperse is 0.1-24 hour, and preferably 0.5-12 is little
When, it is more preferably 2-6 hour.
In another preference, described in the graphene oxide dispersion, the dispersion concentration of graphene oxide is
1-500g/L；And/or
The thickness of graphene oxide described in the graphene oxide dispersion is 1-1000nm.
In another preference, described in the graphene oxide dispersion, the dispersion concentration of graphene oxide is
2-300g/L, preferably 3-100g/L, are more preferably 5-50g/L.
In another preference, described in the graphene oxide dispersion, the thickness of graphene oxide is
5-500nm, preferably 10-300nm, are more preferably 15-200nm.
In another preference, graphene oxide described in the graphene oxide dispersion disperses in monolithic.
In another preference, first solvent is selected from the group：Alcohols, water or its combination.
In another preference, the alcohols is selected from the group：Ethanol, ethylene glycol, glycerine or its combination.
In another preference, the substrate is flexible substrates, and the flexible substrates are selected from the group：Polyvinyl alcohol
Film, Kapton, polyester film or paper, polyethylene terephthalate or its combination.
In another preference, the substrate is rigid basement, and the rigid basement is selected from the group：Silicon chip, two
Oxidized silicon chip, silicon carbide plate or its combination.
In another preference, the coating is selected from the group：Drop coating, spin coating, blade coating, flow coat, spraying.
In another preference, in step 3) also comprise the steps before：Substrate described in corona treatment.
In another preference, step 3) upset realized using microcontact printing techniques.
In another preference, the corona treatment is gases used to be selected from the group：Oxygen, nitrogen, argon gas,
Or its combination.
In another preference, the gases used throughput of the corona treatment is 5-1000sccm, preferably
Ground is 10-500sccm, is more preferably 20-300sccm.
In another preference, the power of the corona treatment is 10-500W, preferably 20-300W.
In another preference, the time of the corona treatment is 10-3000s, preferably 30-1000s.
In another preference, step 3) pressure that processes of the rolling is 2-100N；And/or
Step 3) described rolling number of processing be 2-20 time.
In another preference, step 3) pressure that processes of the rolling is 3-50N, preferably 5-20N.
In another preference, step 3) the rolling number of processing is 3-15 time, preferably 4-10 time.
In another preference, step 3) thickness of gained graphene oxide film is 0.01-1000 μm, relatively
It is 0.02-500 μm goodly, is more preferably 0.03-100 μm, is most preferably 0.05-10 μm.
In another preference, step 4) reduction is selected from the group：Thermal annealing is reduced, laser irradiates reduction,
Ultraviolet lighting reduction, chemical reagent reduction or its combination.
In another preference, the power of the ultraviolet lighting reduction is 50-1000W, preferably 100-500W.
In another preference, the process time of the reduction is 0.1-10 hour, preferably 0.3-5 hour.
A kind of a second aspect of the present invention, there is provided patterning prepared by method as described in the first aspect of the invention
3D graphene conductive film, the conductive film include the second bottom and positioned at second bottom surface second
Concaveconvex structure, second concaveconvex structure integrated with second bottom connection, and second concaveconvex structure with
The first concaveconvex structure physics coincide.
In another preference, the shape of second concaveconvex structure is selected from the group：Square, circular, triangle,
Bar shaped or its combination.
In another preference, the thickness of the conductive film is 0.01-1000 μm, preferably
0.02-500 μm, be more preferably 0.03-100 μm, is most preferably 0.05-10 μm..
In another preference, second concaveconvex structure in the area coverage of second bottom surface is
10-80%, preferably 20-60%, more preferably 30-50%.
In another preference, the conductive film is self-supporting.
In another preference, " self-supporting " refers to turn the conductive film from substrate surface is complete
Shifting is got off, and the conductive film has fixing shape in transfer process and after transfer.
A third aspect of the present invention, there is provided a kind of compound, the compound include：
Conductive film described in second aspect present invention；And
Graft on the polymer of the second relief structured surface of the conductive film.
In another preference, the polymer is hydrophilic polymer.
In another preference, the hydrophilic polymer is selected from the group：Polymethylacrylic acid dimethylamine ethyl ester,
Polymethyl methacrylate, poly-N-vinylcaprolactam, polyvinyl alcohol and polyacrylic acid or its combination.
A fourth aspect of the present invention, there is provided the conductive film described in a kind of second aspect present invention or the present invention
The purposes of the compound described in three aspects, for preparing electronic device.
In another preference, the electronic device is selected from the group：Display, touch-screen, solar cell,
Transistor, sensor, ultracapacitor.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and below (such as enforcement
Example) in can be combined with each other between each technical characteristic for specifically describing, so as to constitute new or preferred skill
Art scheme.As space is limited, here is no longer tired out one by one and is stated.
Description of the drawings
Fig. 1 is the knot of a typical patterning 3D graphene conductive film prepared by the method for the invention
Structure schematic diagram, wherein 1 is substrate, and 2 is patterning 3D graphene conductive film.
Fig. 2 is the partial routine schematic diagram of the method for the invention.
In Fig. 3, Fig. 3 A is the photo of obtained graphene oxide dispersion 1-2 in embodiment 1, figure
3B is the atomic force microscopy diagram of obtained graphene oxide dispersion 1-2 in embodiment 1.
Fig. 4 is the obtained SEM for being located at suprabasil patterning 3D graphene conductive film 1-2 of embodiment 1
SEM figure (the figure of figure (Fig. 4 A) and the patterning 3D graphene conductive film 1-2 shifted from substrate surface
4B).
Fig. 5 be obtained by embodiment 1 positioned at suprabasil patterning 3D graphene conductive film 1-1 (0.2
Mol/L, Fig. 5 A), the atomic force of 1-2 (0.1mol/L, Fig. 5 B) and 1-3 (0.05mol/L, Fig. 5 C)
Microscope figure.
Fig. 6 is the 3D stone with different pattern pattern obtained by the embodiment of the present invention 2 to embodiment 4
The atomic force microscopy diagram of black alkene conductive film, (A) netted (embodiment 2), (B) diamond shaped (embodiment
3), (C) strip (embodiment 4).
In Fig. 7, (a) is the atomic force microscopy diagram of graphene oxide conductive film 5 obtained by embodiment 5,
B () is the atomic force microscopy diagram of the compound 1 obtained by embodiment 5, (c) is graphene oxide conductive thin
Film 5 and the height map of compound 1, (d) for compound 1 simulation figure, (e) be by the compound 1
The scanning electron microscope (SEM) photograph stripped down from substrate, (f) are the atomic force of the compound 1 of the demoulding from substrate
Microscope figure.
Fig. 8 is the conductive capability test result of 6 gained sensor 1 of embodiment.
Specific embodiment
The present inventor prepares work through in-depth study for a long time by adopting specific raw material to combine specifically
The patterning 3D that skill prepares a kind of continuous integration, damage patterns are little, the high and conductance of flexible strength is high
Graphene conductive film.Specifically, the present inventor adopts hydrophily graphene oxide as raw material, by its point
Dispersion liquid is coated in the seal surface with different-shape, in conjunction with microcontact printing techniques and graphene oxide also
Former technology prepares a kind of pattern, and to be easy to regulation and control, pattern definition height, Stability Analysis of Structures, flexible strength excellent
And the high patterning 3D graphene conductive film of conductance.The preparation method is simple to operate, film formation time
Short, environmental friendliness, with low cost, beneficial to realize large-scale production and to products therefrom performance almost without bad
Impact.On this basis, inventor completes the present invention.
Term
As used herein, term " patterning 3D graphene conductive film ", " conductive film " or " figure
Case graphite alkene conductive film " is used interchangeably, and referring both to the conductive film includes the second bottom and be located at institute
The second concaveconvex structure of the second bottom surface is stated, second concaveconvex structure is integrated with second bottom even
Connect, and second concaveconvex structure is coincide with the first concaveconvex structure physics.
As used herein, term " patterning seal ", " template " or " seal " is used interchangeably.
Preparation method
The invention provides a kind of preparation method of patterning 3D graphene conductive film, comprises the steps：
1) patterning seal, graphene oxide dispersion and substrate are provided；Wherein, the graphene oxide divides
Dispersion liquid contains graphene oxide and the first solvent for disperseing the graphene oxide；
2) graphene oxide dispersion is coated on the patterning seal, treats the patterning seal
On the graphene oxide dispersion solidification after, obtain coat graphene oxide film patterning seal；
3) by step 2) gained coating graphene oxide film patterning seal overturn in substrate, in pattern
Changing seal upper surface carries out rolling process so that patterning seal and graphene oxide film physical separation, remove pattern
Change seal, obtain graphene oxide film；
4) reduction step 3) gained graphene oxide film, obtain patterning 3D graphene conductive film.
In the present invention, the patterning seal is not particularly limited, can according to actual needs in very large range
It is changed.
Typically, the patterning seal includes the first bottom and the first concavo-convex knot on first bottom
Structure, first concaveconvex structure connection integrated with first bottom, and the shape bag of first concaveconvex structure
Include (but being not limited to)：Square, circular, triangle, bar shaped or its combination.
It should be understood that in the present invention, the shape of first concaveconvex structure on the patterning seal surface does not have spy
Do not limit, can be changed in very large range according to actual needs.
In the present invention, the composition material of the patterning seal is not particularly limited, as long as being exposed by changing
Light time and material usage can prepare seal of different shapes.
Typically, the composition material of the patterning seal is preferably siloxanes.
Typically, the siloxanes includes (but being not limited to)：Dimethyl silicone polymer, poly- methyl hydrogen silica
Alkane, poly- (methyl -3,3,3- trifluoropropyl siloxanes).
Typically, the molecular weight of the siloxanes is 3000-100000, preferably 4000-80000, more preferably
For 5000-50000.
Typically, the size of the patterning seal is 1-1000 μm, preferably 2-500 μm, more preferably
For 5-100 μm.
In another preference, in step 1) also comprise the steps before：Graphene oxide described in ultrasonic disperse
Dispersion liquid.
In the present invention, the frequency of the ultrasonic disperse and time are not particularly limited, as long as the oxidation can be made
Graphene is realized dispersed.
Typically, the frequency of the ultrasonic disperse is 10-500kHz, preferably 20-300kHz, more preferably
For 50-100kHz.
Typically, the time of the ultrasonic disperse is 0.1-24 hour, preferably 0.5-12 hour, more preferably
Ground is 2-6 hour.
In the present invention, described in the graphene oxide dispersion, the dispersion concentration of graphene oxide is
1-500g/L；And/or
The thickness of graphene oxide described in the graphene oxide dispersion is 1-1000nm.
In another preference, described in the graphene oxide dispersion, the dispersion concentration of graphene oxide is
2-300g/L, preferably 3-100g/L, are more preferably 5-50g/L.
In another preference, described in the graphene oxide dispersion, the thickness of graphene oxide is
5-500nm, preferably 10-300nm, are more preferably 15-200nm.
In another preference, graphene oxide described in the graphene oxide dispersion disperses in monolithic.
Typically, first solvent includes (but being not limited to)：Alcohols, water or its combination.
Typically, the alcohols includes (but being not limited to)：Ethanol, ethylene glycol, glycerine or its group
Close.
In the present invention, the material of the substrate is not particularly limited, as long as surface roughness less than 5nm is
Can.
Typically, the substrate is flexible substrates, and the flexible substrates include (but being not limited to)：Polyethylene
Alcohol film, Kapton, polyester film or paper, polyethylene terephthalate or its combination.
Typically, the substrate is rigid basement, and the rigid basement includes (but being not limited to)：Silicon chip,
Titanium dioxide silicon chip, silicon carbide plate or its combination.
In the present invention, the coating includes (but being not limited to)：Drop coating, spin coating, blade coating, flow coat, spray
Apply.
In the present invention, in step 3) also comprise the steps before：Substrate described in corona treatment.
In another preference, step 3) upset realized using microcontact printing techniques.
In another preference, the corona treatment is gases used including (but being not limited to)：Oxygen,
Nitrogen, argon gas or its combination.
In another preference, the gases used throughput of the corona treatment is 5-1000sccm, preferably
Ground is 10-500sccm, is more preferably 20-300sccm.
In another preference, the power of the corona treatment is 10-500W, preferably 20-300W.
In another preference, the time of the corona treatment is 10-3000s, preferably 30-1000s.
In the present invention, step 3) described rolling process pressure be 2-100N；And/or
Step 3) described rolling number of processing be 2-20 time.
In another preference, step 3) pressure that processes of the rolling is 3-50N, preferably 5-20N.
In another preference, step 3) the rolling number of processing is 3-15 time, preferably 4-10 time.
In another preference, step 3) thickness of gained graphene oxide film is 0.01-1000 μm, relatively
It is 0.02-500 μm goodly, is more preferably 0.03-100 μm, is most preferably 0.05-10 μm.
Fig. 2 is the partial routine schematic diagram of the method for the invention.
In the present invention, step 4) mode of the reduction is not particularly limited, as long as can be by graphene oxide
Film is reduced to graphene film.
Typically, step 4) described reduction include (but being not limited to)：Thermal annealing reduction, laser irradiate also
The reduction of former, ultraviolet lighting, chemical reagent reduction or its combination.
In the present invention, by controlling the Reduction parameter such as reduction intensity and/or recovery time, controllable is aoxidized
The reducing degree of graphene film.
In another preference, the power of the ultraviolet lighting reduction is 50-1000W, preferably 100-500W.
In another preference, the process time of the reduction is 0.1-10 hour, preferably 0.3-5 hour.
It should be understood that micro-contact printing is to use to form the organic molecule of molecular self-assembled monolayer on substrate as ink,
By process of simply impressing, the class technology micro- pattern on elastomeric stamp being transferred on substrate.Micro- contact print
Brush technology is a kind of flexible, microscopic pattern method of non-lithographic class.The pattern that it is usually formed be with sub-micro
Patterning self-assembled monolayers meter-sized and that chemical functional group region is different.One point as Soft lithograph technology
, due to its have the advantages that quickly, can applied material extensively, gained pattern flexibly and need not special installation,
It is particularly suitable for common lab operation, this makes which obtain more rapidly developing compared to other Soft lithograph technology.
As microcontact printing techniques have the advantages that yield is high and printing quality is good, preparation is become flexible
A kind of effective process meanses of patterning electronic device.The present invention will be aoxidized using 3D microcontact printing techniques
Graphene film is transferred to in plasma treated substrate, being easy to prepare continuous integration, pattern and receives
Damage the high patterning 3D graphene conductive film of the high and conductance of little, flexible strength.
In the present invention, by changing the pattern for patterning seal, the concentration of graphene oxide dispersion and rolling
Pressure treatment conditions etc., can achieve the preparation of the patterning 3D graphene conductive film of different-thickness.
In the present invention, the patterning seal is not particularly limited, can be ripe using those skilled in the art
The method that knows is prepared or is commercially available from market.
A kind of preparation method of typical patterning seal is as follows：
A-1) patterning chromium plate and seal stoste are provided, wherein,
The patterning chromium plate is following preparation：
B-1) photoresist is coated in chromium plate surface, and photosensitive process is carried out to photoresist；
B-2) photosensitive region photoresist is removed using solvent orange 2 A, and solidify not photosensitive photoresist；
B-3) electron beam lithography substrate is used, and photoresist is removed using solvent B, obtain patterning chromium plate；
The seal stoste is following preparation：Component A and curing agent are mixed, and optionally mixed to gained
Closing liquid carries out bubble removing process, obtains seal stoste；
A-2) seal stoste is placed in same container with patterning chromium plate, 1-24 is placed at 45-100 DEG C
Hour, obtain patterning seal.
In another preference, the photoresist is positive photoresist, including (but being not limited to)：Diazonium
Naphthoquinones (DNQ), polymethyl methacrylate (PMMA) or its combination.
In another preference, the consumption of the photoresist is advisable so that the chromium plate surface is completely covered.
In another preference, the thickness of the photoresist is 0.1-100 μm, preferably 0.5-30 μm,
It is more preferably 0.8-10 μm.
In another preference, step b-1) the photosensitive process time is 3-120s, preferably 5-60s.
In another preference, the solvent orange 2 A includes (but being not limited to)：Acetone, n-hexane, acetic acid
Ethyl ester or its combination.
In another preference, the solvent B includes (but being not limited to)：Alcohols, water or its combination.
In another preference, the alcohols includes (but being not limited to)：Ethanol, ethylene glycol or its group
Close.
In another preference, component A includes (but being not limited to)：Dimethyl silicone polymer, poly-
The siloxanes such as methyl hydrogen siloxane, poly- (methyl -3,3,3- trifluoropropyl siloxanes).
In another preference, the curing agent includes (but being not limited to)：Epoxy resin, poly- isocyanide ester,
Or its combination.
In another preference, the volumetric usage ratio of component A and the curing agent described in the seal stoste
For 1-5：2-6.
In another preference, the bubble removing processing mode is for leading to nitrogen, and the bubble removing process time
For 5-60 minute.
Patterning 3D graphene conductive film
Present invention also offers patterning 3D graphene conductive film prepared by a kind of described method, the conduction
Film includes the second bottom and the second concaveconvex structure positioned at second bottom surface, second concaveconvex structure with
The second bottom integration connection, and second concaveconvex structure is identical with the first concaveconvex structure physics.
Typically, the shape of second concaveconvex structure includes (but being not limited to)：Square, circular, three
Angular, bar shaped or its combination.
In another preference, the thickness of the conductive film is 0.01-1000 μm, preferably
0.02-500 μm, be more preferably 0.03-100 μm, is most preferably 0.05-10 μm..
In another preference, second concaveconvex structure in the area coverage of second bottom surface is
10-80%, preferably 20-60%, more preferably 30-50%.
In the present invention, the conductive film is self-supporting.
In another preference, " self-supporting " refers to turn the conductive film from substrate surface is complete
Shifting is got off, and the conductive film has fixing shape in transfer process and after transfer.
Fig. 1 is the knot of a typical patterning 3D graphene conductive film prepared by the method for the invention
Structure schematic diagram, wherein 1 is substrate, and 2 is patterning 3D graphene conductive film.
Application
Present invention also offers a kind of compound, the compound includes：
Described conductive film；And
Graft on the polymer of the second relief structured surface of the conductive film.
In another preference, the polymer is hydrophilic polymer.
Typically, the hydrophilic polymer includes (but being not limited to)：Polymethylacrylic acid decil
Ester, polymethyl methacrylate, poly-N-vinylcaprolactam, polyvinyl alcohol and polyacrylic acid or its group
Close.
It should be understood that in the present invention, the polymer is preferably grafted on the second concavo-convex knot of the conductive film
Structure surface.
Generally, in the compound, gather in the described of the second relief structured surface grafting of the conductive film
Compound accounts for more than the 50% of the total amount of all graft polymers, and preferably more than 70%, more preferably more than 85%.
In the present invention, the polymer grafts on the conductive film (mainly described in " hair-like "
Two relief structured surface) on, and on the basis of second bottom, the grafting of the polymer is highly about described
0.5-10 times of second concaveconvex structure height, preferably 0.8-8 times, be more preferably 1-4.5 times.
In another preference, the grafting of the polymer is highly 50-1000nm, preferably 100-800nm,
It is more preferably 150-750nm.
Present invention also offers the purposes of a kind of described conductive film or described compound, for preparing electronics
Device.
Typically, the electronic device includes (but being not limited to)：Display, touch-screen, solar-electricity
Pond, transistor, sensor, ultracapacitor.
Compared with prior art, the present invention has following major advantage：
(1), using hydrophilic graphene oxide as raw material, which is dispersed good in a solvent for the preparation method
Good, it is easy to prepare high-quality patterning 3D graphene conductive film；
(2) by adjusting the concentration of graphene oxide dispersion, can prepare with diverse microcosmic appearance and not
The patterning 3D graphene conductive film of stack pile；
(3) using water and/or alcohols as solvent in the preparation method, environmentally friendly, pollution-free；
(4) by adjust the pattern of seal can be obtained be adapted to different application occasion with different macroscopic view shapes
The patterning 3D graphene conductive film of looks；
(5) preparation method to substrate material used require low, can be flexible substrates can also be rigid base
Bottom, this are greatly expanded application model of the gained patterning 3D graphene conductive film in conductive material field
Enclose；
(6) preparation method is easy to prepare continuous integration patterning 3D graphene conductive film, and prepares
Journey is less to the damage of pattern；
(7) preparation method is simple to operate, film formation time is short, with low cost, beneficial to realize large-scale production；
(8) gained patterning 3D graphene conductive film Stability Analysis of Structures, flexible strength are high, conductance is high,
Pattern definition is high.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate
The present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, leads to
Often according to normal condition or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number
Calculate by weight.
Unless otherwise defined, all specialties used in text are familiar with one skilled in the art with scientific words
Meaning identical.Additionally, any method similar or impartial to described content and material all can be applicable to the present invention
In method.Preferable implementation described in text is only presented a demonstration with material and is used.
Embodiment 1 patterns 3D graphene conductive film 1
(1) chromium plate is prepared
The polymethyl methacrylate photoresist of 5mL is spin-coated on the surface that size is 5*5 μm of chromium plate,
Then photosensitive 15s is carried out to photoresist, is then used by acetone and removes photosensitive region photoresist and solidify not photosensitive
Photoresist, finally using electron beam lithography substrate and using ethylene glycol remove photoresist obtain with required figure
The chromium plate of case.
(2) seal is prepared
The dimethyl silicone polymer (molecular weight 5000) of 20mL is added in clean beaker, Ran Houjia
Enter the epoxy resin of 20mL, stir, lead to nitrogen 15min bubble removing, subsequently by bubble-free mixing
Liquid is upside down in and is placed with the container of chromium plate, and container is positioned over 5h in 60 DEG C of environment, obtains and step (1)
Gained chromium plate has the seal of the pattern that matches.
(3) graphene oxide dispersion is prepared
Respectively the graphene oxide of 0.02g, 0.01g, 0.005g is placed in 100mL ethanol/water (v:V=2：
1) in solvent, it is ultrasonic disperse 3h under the frequency of 80kHz in power, forms the scattered oxidation of monolithic
Graphene dispersing solution 1-1,1-2 and 1-3.
(4) patterning 3D graphene conductive film is prepared
Graphene oxide dispersion 1-1,1-2 of 100mL and 1-3 drop coating are taken respectively in step (2) institute
Seal surface is obtained, after the solvent on seal surface volatilizees, seal upset is being processed (place with oxygen gas plasma
Qi-regulating flow be 100sccm, processing power be 60W, process time be 100s) cross titanium dioxide silicon substrate
The surface at bottom, is subsequently rolled in the upper surface of seal with the pressure of 6N and imprints 4 times, seal is removed, oxygen
Graphite alkene film is transferred in substrate, subsequently carries out ultraviolet lighting (200 to gained graphene oxide film
W, 0.5h) reduction obtain pattern 3D graphene conductive film 1-1,1-2 and 1-3.
As a result
In Fig. 3, Fig. 3 A is the photo of obtained graphene oxide dispersion in embodiment 1, and Fig. 3 B is
The atomic force microscopy diagram of obtained graphene oxide dispersion 1-2 in embodiment 1.Permissible from Fig. 3 A
Find out the favorable dispersibility in a solvent of graphene oxide used by the present invention.Institute of the present invention as can be seen from Figure 3B
With graphene oxide layer size than more uniform, phenomenon between each lamella, is not almost stacked.
Fig. 4 is the obtained SEM for being located at suprabasil patterning 3D graphene conductive film 1-2 of embodiment 1
SEM figure (the figure of figure (Fig. 4 A) and the patterning 3D graphene conductive film 1-2 shifted from substrate surface
4B).As can be seen from Figure 4A the homogeneous patterned Graphene film of shape can be prepared using the inventive method.
After peeling off the film from substrate as can be seen from Figure 4B, the size of Thinfilm pattern does not become
Change.
Fig. 5 be obtained by embodiment 1 positioned at suprabasil patterning 3D graphene conductive film 1-1 (0.2
Mol/L, Fig. 5 A), the atomic force of 1-2 (0.1mol/L, Fig. 5 B) and 1-3 (0.05mol/L, Fig. 5 C)
Microscope figure.Knowable to the change of Fig. 5 A-5C, gained stone can be changed by the concentration of regulation and control Graphene
The size of black alkene conductive film picture on surface, and the reduction with concentration, concaveconvex structure covering in bottom surface
Lid rate is gradually reduced (successively about 90%, 60%, 50%).
Embodiment 2 patterns 3D graphene conductive film 2
(1) chromium plate is prepared
The diazo naphthoquinone photoresist of 4mL is spin-coated on the surface that size is 5*5 μm of chromium plate, then to light
Photoresist carries out photosensitive 10s, is then used by acetone and removes photosensitive region photoresist and solidify not photosensitive photoresist,
Finally using electron beam lithography substrate and using ethylene glycol remove photoresist obtain the chromium plate with desirable pattern.
(2) seal is prepared
Poly- (methyl -3,3,3- trifluoropropyl siloxanes) (molecular weight 6000) of 25mL is added to dry
In net beaker, the epoxy resin of 15mL is subsequently adding, is stirred, lead to nitrogen 20min bubble removing,
Subsequently bubble-free mixing liquid is upside down in and is placed with the container of chromium plate, container is positioned in 60 DEG C of environment
5h, obtains the seal for having the net-like pattern for matching with step (1) gained chromium plate.
(3) graphene oxide dispersion is prepared
The graphene oxide of 0.01g is placed in 100mL ethanol/water (v:V=2：1) in solvent,
Power be 100kHz frequency under ultrasonic disperse 3h, form the scattered graphene oxide dispersion of monolithic.
(4) patterning 3D graphene conductive film is prepared
The graphene oxide dispersion drop coating of 100mL is taken in step (2) gained seal surface, when seal table
Face solvent volatilization after, by seal upset with nitrogen plasma treatment (processs throughput be 100sccm,
Processing power be 50W, process time be 80s) cross silica substrate surface, subsequently use 5N
Pressure seal upper surface roll impressing 3 times, seal is removed, graphene oxide film is transferred to
In substrate, ultraviolet lighting (200W, 0.5h) reduction is subsequently carried out to gained graphene oxide film and is obtained
Patterning 3D graphene conductive film 2.
Embodiment 3 patterns 3D graphene conductive film 3
(1) chromium plate is prepared
The polymethyl methacrylate photoresist of 5mL is spin-coated on the surface that size is 5*5 μm of chromium plate,
Then photosensitive 10s is carried out to photoresist, is then used by acetone and removes photosensitive region photoresist and solidify not photosensitive
Photoresist, finally using electron beam lithography substrate and using ethylene glycol remove photoresist obtain with required figure
The chromium plate of case.
(2) seal is prepared
In clean beaker, then the polymethyl hydrogen siloxane (molecular weight 55000) of 20mL is added to
The poly- isocyanide ester of 10mL is added, is stirred, helium injection gas 20min bubble removing, subsequently by bubble-free
Mixing liquid be upside down in and be placed with the container of chromium plate, container is positioned over 6h in 50 DEG C of environment, obtain with
Step (1) gained chromium plate has the seal of the diamond shaped pattern for matching.
(3) graphene oxide dispersion is prepared
The graphene oxide of 0.01g is placed in 100mL ethanol/water (v:V=2：1) in solvent,
Power be 80kHz frequency under ultrasonic disperse 2h, form the scattered graphene oxide dispersion of monolithic.
(4) patterning 3D graphene conductive film is prepared
The graphene oxide dispersion drop coating of 100mL is taken in step (2) gained seal surface, when seal table
Face solvent volatilization after, by seal upset with nitrogen plasma treatment (processs throughput be 100sccm,
Processing power be 50W, process time be 100s) cross silica substrate surface, subsequently use 5N
Pressure seal upper surface roll impressing 3 times, seal is removed, graphene oxide film is transferred to
In substrate, ultraviolet lighting (200W, 0.5h) reduction is subsequently carried out to gained graphene oxide film and is obtained
Patterning 3D graphene conductive film 3.
Embodiment 4 patterns 3D graphene conductive film 4
(1) chromium plate is prepared
The diazo naphthoquinone photoresist of 8mL is spin-coated on the surface that size is 5*5 μm of chromium plate, then to light
Photoresist carries out photosensitive 10s, is then used by acetone and removes photosensitive region photoresist and solidify not photosensitive photoresist,
Finally using electron beam lithography substrate and using ethylene glycol remove photoresist obtain the chromium plate with desirable pattern.
(2) seal is prepared
The dimethyl silicone polymer (molecular weight 6000) of 15mL is added in clean beaker, Ran Houjia
Enter the poly- isocyanide ester of 10mL, stir, helium injection gas 20min bubble removing, subsequently will be bubble-free
Mixing liquid is upside down in and is placed with the container of chromium plate, container is positioned over 6h in 50 DEG C of environment, is obtained and step
Suddenly (1) gained chromium plate has the seal of the strip pattern for matching.
(3) graphene oxide dispersion is prepared
The graphene oxide of 0.01g is placed in 100mL ethanol/water (v:V=2：1) in solvent,
Power be 80kHz frequency under ultrasonic disperse 2h, form the scattered graphene oxide dispersion of monolithic.
(4) patterning 3D graphene conductive film is prepared
The graphene oxide dispersion drop coating of 100mL is taken in step (2) gained seal surface, when seal table
Face solvent volatilization after, by seal upset with nitrogen plasma treatment (processs throughput be 100sccm,
Processing power be 60W, process time be 100s) cross silica substrate surface, subsequently use 8N
Pressure seal upper surface roll impressing 5 times, seal is removed, graphene oxide film is transferred to
In substrate, ultraviolet lighting (200W, 0.5h) reduction is subsequently carried out to gained graphene oxide film and is obtained
Patterning 3D graphene conductive film 4.
As a result
Fig. 6 is the 3D stone with different pattern pattern obtained by the embodiment of the present invention 2 to embodiment 4
The atomic force microscopy diagram of black alkene conductive film, (A) netted (embodiment 2), (B) diamond shaped (embodiment
3), (C) strip (embodiment 4).From fig. 6, it can be seen that from different templates, can prepare and have
The 3D graphene conductive film of different pattern.Therefore, in process of production, can according to the actual requirements,
Prepare the graphene film material with different pattern.
5 compound 1 of embodiment
(1) chromium plate is prepared
The diazo naphthoquinone photoresist of 10mL is spin-coated on the surface that size is 5*5 μm of chromium plate, then right
Photoresist carries out photosensitive 10s, is then used by acetone and removes photosensitive region photoresist and solidify not photosensitive photoetching
Glue, finally using electron beam lithography substrate and using ethylene glycol remove photoresist obtain the chromium with desirable pattern
Plate.
(2) seal is prepared
The dimethyl silicone polymer (molecular weight 8000) of 20mL is added in clean beaker, Ran Houjia
Enter the epoxy resin of 10mL, stir, helium injection gas 20min bubble removing, subsequently will be bubble-free mixed
Conjunction liquid is upside down in and is placed with the container of chromium plate, container is positioned over 6h in 50 DEG C of environment, is obtained and step
(1) gained chromium plate has the seal of the pattern for matching.
(3) graphene oxide dispersion is prepared
The graphene oxide of 0.01g is placed in 100mL ethanol/water (v:V=2：1) in solvent,
Power be 80kHz frequency under ultrasonic disperse 2h, form the scattered graphene oxide dispersion of monolithic.
(4) patterning 3D graphene conductive film is prepared
The graphene oxide dispersion drop coating of 100mL is taken in step (2) gained seal surface, when seal table
Face solvent volatilization after, by seal upset with nitrogen plasma treatment (processs throughput be 100sccm,
Processing power be 60W, process time be 100s) cross silica substrate surface, subsequently use 8N
Pressure seal upper surface roll impressing 3 times, seal is removed, graphene oxide film is transferred to
In substrate, ultraviolet lighting (200W, 0.5h) reduction is subsequently carried out to gained graphene oxide film and is obtained
Patterning 3D graphene conductive film 5.
(5) preparation of compound 1
Patterning 3D graphene conductive film 5 obtained by above-mentioned steps is placed in the metering system of 10mL
In the solution of sour dimethylamine ethyl ester, ultraviolet lighting (100W, 0.5h) is carried out, film is taken out, uses 20mL
Ethanol solution soaks 3h, dries 1h in the baking oven that film is placed in 40 DEG C, so as to metering system is obtained
Patterning 3D graphene film, the i.e. compound 1 of sour dimethylamine ethyl ester grafting.
As a result
In Fig. 7, (a) is the atomic force microscopy diagram of graphene oxide conductive film 5 obtained by embodiment 5,
B () is the atomic force microscopy diagram of the compound 1 obtained by embodiment 5, (c) is graphene oxide conductive thin
Film 5 and the height map of compound 1, (d) for compound 1 simulation figure, (e) be by the compound 1
The scanning electron microscope (SEM) photograph stripped down from substrate, (f) are the atomic force of the compound 1 of the demoulding from substrate
Microscope figure.Even if from figure 7 it can be seen that the compound 1 for being grafted polymer is de- from substrate surface
Still there is stable structure and higher intensity after getting off, rupture.
6 sensor 1 of embodiment
(1) chromium plate is prepared
The diazo naphthoquinone photoresist of 10mL is spin-coated on the surface that size is 5*5 μm of chromium plate, then right
Photoresist carries out photosensitive 10s, is then used by acetone and removes photosensitive region photoresist and solidify not photosensitive photoetching
Glue, finally using electron beam lithography substrate and using ethylene glycol remove photoresist obtain the chromium with desirable pattern
Plate.
(2) seal is prepared
The dimethyl silicone polymer (molecular weight 8000) of 20mL is added in clean beaker, Ran Houjia
Enter the poly- isocyanide ester of 10mL, stir, helium injection gas 20min bubble removing, subsequently will be bubble-free
Mixing liquid is upside down in and is placed with the container of chromium plate, container is positioned over 6h in 50 DEG C of environment, is obtained and step
Suddenly (1) gained chromium plate has the seal of the strip pattern for matching.
(3) graphene oxide dispersion is prepared
The graphene oxide of 0.01g is placed in 100mL ethanol/water (v:V=2：1) in solvent,
Power be 80kHz frequency under ultrasonic disperse 2h, form the scattered graphene oxide dispersion of monolithic.
(4) patterning 3D graphene conductive film is prepared
The graphene oxide dispersion drop coating of 100mL is taken in step (2) gained seal surface, when seal table
Face solvent volatilization after, by seal upset with nitrogen plasma treatment (processs throughput be 100sccm,
Processing power be 60W, process time be 100s) cross silica substrate surface, subsequently use 8N
Pressure seal upper surface roll impressing 3 times, seal is removed, graphene oxide film is transferred to
In substrate, ultraviolet lighting (200W, 0.5h) reduction is subsequently carried out to gained graphene oxide film and is obtained
Patterning 3D graphene conductive film 6.
(5) preparation of compound 2
Patterning 3D graphene conductive film 6 obtained in above-mentioned steps is placed in the methacrylic acid of 10mL
In the solution of dimethylamine ethyl ester, ultraviolet lighting (100W, 0.5h) is carried out, film is taken out, uses 20mL
Ethanol solution soaks 3h, dries 1h, so as to prepare metering system in the baking oven that film is placed in 40 DEG C
Patterning 3D graphene film, the i.e. compound 2 of sour dimethylamine ethyl ester grafting.
(6) sensor 1
Compound 2 is fixed on two gold electrodes using conducting resinl and sensor 1 is obtained, and which is led
Electric performance test.
As a result
Fig. 8 is the conductive capability test result of 6 gained sensor 1 of embodiment.As it can be observed in the picture that compared to
Using the sensor of existing graphene oxide film preparation, adopt with the patterned Graphene prepared by the present invention
Conductive film is that sensor prepared by substrate graft polymers gained compound either still exists in atmosphere
More excellent electric conductivity is respectively provided with water.
In sum, the patterned Graphene conductive film of the present invention not only have good mechanical stability and
Chemical stability, with more excellent electric conductivity.
The all documents referred in the present invention are all incorporated as reference in this application, just as each document
It is individually recited as reference like that.In addition, it is to be understood that after the above-mentioned instruction content for having read the present invention,
Those skilled in the art can be made various changes or modifications to the present invention, and these equivalent form of values equally fall within this Shen
Please appended claims limited range.
Claims (10)
1. a kind of preparation method of patterning 3D graphene conductive film, it is characterised in that comprise the steps：
1) patterning seal, graphene oxide dispersion and substrate are provided；Wherein, the graphene oxide divides
Dispersion liquid contains graphene oxide and the first solvent for disperseing the graphene oxide；
2) graphene oxide dispersion is coated on the patterning seal, treats the patterning seal
On the graphene oxide dispersion solidification after, obtain coat graphene oxide film patterning seal；
3) by step 2) gained coating graphene oxide film patterning seal overturn in substrate, in pattern
Changing seal upper surface carries out rolling process so that patterning seal and graphene oxide film physical separation, remove pattern
Change seal, obtain graphene oxide film；
4) reduction step 3) gained graphene oxide film, obtain patterning 3D graphene conductive film.
2. the method for claim 1, it is characterised in that the patterning seal include the first bottom and
The first concaveconvex structure on first bottom, first concaveconvex structure are integrated with first bottom even
Connect, and the shape of first concaveconvex structure is selected from the group：Square, circular, triangle, bar shaped or its combination.
3. the method for claim 1, it is characterised in that oxygen described in the graphene oxide dispersion
The dispersion concentration of graphite alkene is 1-500g/L；And/or
The thickness of graphene oxide described in the graphene oxide dispersion is 1-1000nm.
4. the method for claim 1, it is characterised in that in step 3) before also comprise the steps：
Substrate described in corona treatment.
5. the method for claim 1, it is characterised in that step 3) pressure that processes of the rolling is
2-100N；And/or
Step 3) described rolling number of processing be 2-20 time.
6. the method for claim 1, it is characterised in that step 4) reduction is selected from the group：Heat is moved back
Reduction, ultraviolet lighting reduction, chemical reagent reduction or its combination are irradiated in fire reduction, laser.
7. the patterning 3D graphene conductive film that prepared by a kind of the method for claim 1, its feature
It is, the conductive film includes the second bottom and the second concaveconvex structure positioned at second bottom surface, described
The connection integrated with second bottom of second concaveconvex structure, and second concaveconvex structure and the described first concavo-convex knot
Structure physics coincide.
8. conductive film as claimed in claim 7, it is characterised in that the conductive film is self-supporting.
9. a kind of compound, it is characterised in that the compound includes：
Conductive film described in claim 7；And
Graft on the polymer of the second relief structured surface of the conductive film.
10. the purposes of the conductive film described in a kind of claim 7 or the compound described in claim 9, its
It is characterised by, for preparing electronic device.
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| CN109411149A (en) * | 2017-08-18 | 2019-03-01 | 京东方科技集团股份有限公司 | Graphene circuit pattern and preparation method thereof, electronic product |
| CN109932867A (en) * | 2017-12-15 | 2019-06-25 | 无锡格菲电子薄膜科技有限公司 | Method for transferring and patterning graphene film simultaneously |
| CN110691823A (en) * | 2019-08-16 | 2020-01-14 | 福建华彩新材料有限公司 | Photosensitive graphene oxide coating capable of defining patterns by user and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1862379A (en) * | 2006-04-18 | 2006-11-15 | 清华大学 | Method for making polymer self-supporting nano-micron-line |
| CN102653190A (en) * | 2011-03-04 | 2012-09-05 | 国家纳米科学中心 | Method for forming graphene oxide pattern and graphene pattern |
| WO2014090661A1 (en) * | 2012-12-10 | 2014-06-19 | Ev Group E. Thallner Gmbh | Method for microcontact printing |
| CN104356740A (en) * | 2014-11-05 | 2015-02-18 | 广西师范学院 | Method for performing microcontact printing by using water-soluble porphyrin iron complex |
-
2015
- 2015-08-31 CN CN201510547598.0A patent/CN106486209A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1862379A (en) * | 2006-04-18 | 2006-11-15 | 清华大学 | Method for making polymer self-supporting nano-micron-line |
| CN102653190A (en) * | 2011-03-04 | 2012-09-05 | 国家纳米科学中心 | Method for forming graphene oxide pattern and graphene pattern |
| WO2014090661A1 (en) * | 2012-12-10 | 2014-06-19 | Ev Group E. Thallner Gmbh | Method for microcontact printing |
| CN104356740A (en) * | 2014-11-05 | 2015-02-18 | 广西师范学院 | Method for performing microcontact printing by using water-soluble porphyrin iron complex |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411149A (en) * | 2017-08-18 | 2019-03-01 | 京东方科技集团股份有限公司 | Graphene circuit pattern and preparation method thereof, electronic product |
| CN109932867A (en) * | 2017-12-15 | 2019-06-25 | 无锡格菲电子薄膜科技有限公司 | Method for transferring and patterning graphene film simultaneously |
| CN108493001A (en) * | 2018-03-17 | 2018-09-04 | 东华理工大学 | A method of simply preparing graphite high flexibility electrode and flexible super capacitor |
| CN108562621A (en) * | 2018-05-30 | 2018-09-21 | 中国农业科学院农业信息研究所 | 2- acetyl -1- pyrrolins sensitive material film and preparation method and 2- acetyl -1- pyrrolins sensing device and application |
| CN110691823A (en) * | 2019-08-16 | 2020-01-14 | 福建华彩新材料有限公司 | Photosensitive graphene oxide coating capable of defining patterns by user and preparation method thereof |
| CN110696540A (en) * | 2019-09-29 | 2020-01-17 | 东南大学 | Patterned graphene-based electronic tattoo skin and preparation method thereof |
| CN112619419A (en) * | 2020-10-23 | 2021-04-09 | 深圳前海石墨烯产业有限公司 | Composite carbon material film, composite carbon material nanofiltration membrane and preparation method |
| CN112619419B (en) * | 2020-10-23 | 2022-07-26 | 深圳前海石墨烯产业有限公司 | Composite carbon material film, composite carbon material nanofiltration membrane and preparation method |
| CN112635103A (en) * | 2020-12-18 | 2021-04-09 | 深圳先进技术研究院 | Conductive pattern, preparation method thereof and flexible electronic device |
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