CN110517809A - A kind of transparent graphene conductive film, preparation method and application - Google Patents
A kind of transparent graphene conductive film, preparation method and application Download PDFInfo
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Abstract
The present invention relates to conductive film production technical field more particularly to a kind of transparent graphene conductive films, preparation method and application.The present invention provides a kind of transparent graphene conductive films, comprising: flexible substrates；In the compound saturating layer of silica gel of height of the one side of the flexible substrates；The composite graphite alkene film layer in the high layer of silica gel thoroughly；In the another side Composite OC A optical adhesive layer of the flexible substrates.The cleannes and surface smoothness of transparent graphene conductive film provided by the invention are more excellent, meanwhile, preferable integrality and excellent photoelectric properties can be kept, light transmittance is more excellent.Preparation suitable for devices such as flexible capacitor, sensor, touch screen, solar battery and Organic Light Emitting Diodes.Experiment shows in the transparent graphene conductive film, and the surface resistivity of graphene film layer is no more than 630ohm/sq, and graphene film layer structural integrity, surface be smooth, clean, noresidue.
Description
Technical field
The present invention relates to conductive film production technical field more particularly to a kind of transparent graphene conductive films, its preparation
Method and application.
Background technique
Graphene (Graphene) has excellent light transmission, conduction, thermally conductive and mechanical property, as electrically conducting transparent of new generation
Film can be widely used in the neck such as sensor, capacitor, touch screen, solar battery, Organic Light Emitting Diode and sensor
Domain.Currently, chemical vapor deposition (CVD) method is to prepare the main method of large-area graphene film, but graphene is usually in gold
Belong to and being grown on foil (copper, platinum, nickel etc.) matrix, to realize its characterization and application, needs to be transferred into other matrixes (silicon wafer, glass
Glass piece, plastics etc.) on.However, the transfer processes such as existing roll-to-roll (Rollto Roll), mechanical stripping be easy to cause graphite
Alkene is damaged, seriously affects the performance of graphene after transfer.Using the method for transfer medium, this breakage can be reduced, but at present
The transfer medium used is usually the macromolecule resins such as polymethyl methacrylate (PMMA), dimethyl silicone polymer (PDMS),
Interaction with graphene is strong, is not easy to dissolve in a solvent, i.e., is cleaned using a large amount of organic solvent, in graphene table
Still there is a large amount of residual in face, not only reduces the photoelectric properties of graphene, also greatly increases the surface roughness of graphene, hinders
Its application in the fields such as photoelectric device.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of transparent graphene conductive film, its preparation
Method and application, the cleannes and surface smoothness of transparent graphene conductive film provided by the invention are more excellent, meanwhile, Ke Yibao
Hold preferable integrality and excellent photoelectric properties.
The present invention provides a kind of transparent graphene conductive films, comprising:
Flexible substrates；
In the compound saturating layer of silica gel of height of the one side of the flexible substrates；
The composite graphite alkene film layer in the high layer of silica gel thoroughly；
In the another side Composite OC A optical adhesive layer of the flexible substrates.
Preferably, the group of the flexible substrates is selected from polyethylene terephthalate, polyimides and poly- naphthalene diformazan
One or more of sour glycol ester.
Preferably, the high layer of silica gel thoroughly with a thickness of 30nm~1000 μm；
The flexible substrates with a thickness of 10~300 μm；
The OCA optical adhesive layer with a thickness of 30nm~1000 μm.
The present invention also provides a kind of preparation methods of transparent graphene conductive film, comprising the following steps:
A graphene film) is grown in the upper surface of metal foil using chemical vapour deposition technique, obtains graphene film layer；
In the high saturating silica gel of the coated on one side of flexible substrates, high layer of silica gel/flexible substrates composite layer thoroughly is obtained；
B the high layer of silica gel thoroughly is bonded with the graphene film layer), pressurizes, obtains graphene film layer/height
Saturating layer of silica gel/flexible substrates composite layer；
C it) is coated with OCA optical cement in the another side of the flexible substrates, obtains OCA optical adhesive layer；
D the metal foil) is removed by etching method or electrochemical process, obtains graphene complex, after cleaned and dry,
Obtain transparent graphene conductive film.
Preferably, step B) in, the pressure of the pressurization is 0.1~20MPa, and the time of the pressurization is 1s~30h.
Preferably, step D) in, the etching liquid that the etching method uses is the mixed solution of hydrochloric acid and hydrogen peroxide, iron chloride
Aqueous solution and one of the aqueous solution of ammonium persulfate.
Preferably, the concentration of the etching liquid is 0.1~10mol/L；
The volume ratio of the hydrochloric acid and hydrogen peroxide is 1~9:1~9.
Preferably, step D) in, the electrolyte that the electrochemical process uses includes that sulfuric acid solution, hydrochloric acid solution, nitric acid are molten
Liquid, the aqueous solution of methanesulfonic acid, the aqueous solution of citric acid, the aqueous solution of sodium hydroxide, the aqueous solution of potassium hydroxide, sodium chloride water
One of solution and the aqueous solution of potassium chloride；
The concentration of the electrolyte is 0.1~10mol/L.
Preferably, step D) in, the cleaning agent used that cleans is deionized water.
The present invention also provides a kind of transparent graphene conductive film described above or preparation method systems described above
Application of the standby transparent graphene conductive film as the transparent electrode of photoelectric device.
The present invention provides a kind of transparent graphene conductive films, comprising: flexible substrates；In the one side of the flexible substrates
The compound saturating layer of silica gel of height；The composite graphite alkene film layer in the high layer of silica gel thoroughly；It is compound in the another side of the flexible substrates
OCA optical adhesive layer.The cleannes and surface smoothness of transparent graphene conductive film provided by the invention are more excellent, meanwhile, it can be with
Preferable integrality and excellent photoelectric properties are kept, light transmittance is more excellent.Suitable for flexible capacitor, sensor, touch screen, too
The preparation of the positive energy devices such as battery and Organic Light Emitting Diode.
The present invention also provides a kind of preparation methods of transparent graphene conductive film, comprising the following steps: A) useization
It learns vapour deposition process and grows graphene film in the upper surface of metal foil, obtain graphene film layer；In the one side of flexible substrates
The high saturating silica gel of coating obtains high layer of silica gel/flexible substrates composite layer thoroughly；B) by high layer of silica gel and the graphene film thoroughly
Layer fitting, pressurizes, and obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；C) in the flexible substrates
Another side is coated with OCA optical cement, obtains OCA optical adhesive layer；D the metal foil) is removed by etching method or electrochemical process, is obtained
Graphene complex obtains transparent graphene conductive film after cleaned and dry.The present invention is that transfer is situated between with high layer of silica gel thoroughly
Matter, while the intact transfer of realization graphene film layer, the surface of graphene film layer is smooth, and no particle is residual
It stays, there are higher cleannes, the cleannes and surface smoothness of final transparent graphene conductive film obtained are more excellent, together
When, preferable integrality and excellent photoelectric properties can be kept, light transmittance is more excellent.In addition, high layer of silica gel thoroughly has automatic row
The function of bubble, applying method are easy.It is thin that preparation method provided by the invention can prepare large area, high performance electrically conducting transparent
Film has great importance for the application of graphene.
The experimental results showed that in transparent graphene conductive film prepared by the present invention, the sheet resistance of graphene film layer
Rate is no more than 630ohm/sq, and the resistivity of transparent graphene conductive film is smaller；Graphene film layer structural integrity, surface light
Sliding smooth, clean, noresidue.
Using the OLED device that transparent graphene conductive film of the invention is prepared as transparent electrode, light-emitting area is
0.4mm2；When voltage is 5V, the brightness of green light OLED device can achieve 8000cd m-2.It is led so that graphene of the invention is transparent
Conductive film is that the incident photon-to-electron conversion efficiency of the organic solar batteries of transparent electrode preparation is not less than 3.6%.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the transparent graphene conductive film that one embodiment of the present of invention provides；
Fig. 2 is the atomic force microscopy diagram of the graphene film layer of the transparent graphene conductive film of the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope of the graphene film layer of the transparent graphene conductive film of the embodiment of the present invention 1
Figure；
Fig. 4 is the visible transmission spectra of the graphene film layer of the transparent graphene conductive film of the embodiment of the present invention 1
Figure.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of transparent graphene conductive films, comprising:
Flexible substrates；
In the compound saturating layer of silica gel of height of the one side of the flexible substrates；
The composite graphite alkene film layer in the high layer of silica gel thoroughly；
In the another side Composite OC A optical adhesive layer of the flexible substrates.
The structure of the transparent graphene conductive film is as shown in Figure 1.Fig. 1 is the stone that one embodiment of the present of invention provides
The structural schematic diagram of black alkene transparent conductive film.
Transparent graphene conductive film provided by the invention includes flexible substrates.In certain embodiments of the present invention, institute
The group for stating flexible substrates is selected from one of polyethylene terephthalate, polyimides and polyethylene naphthalate
Or it is several.In certain embodiments of the present invention, the flexible substrates with a thickness of 10~300 μm.
Transparent graphene conductive film provided by the invention further includes high saturating layer of silica gel.The high layer of silica gel thoroughly is compounded in institute
State the one side of flexible substrates.In certain embodiments of the present invention, light transmittance > 90% of the high layer of silica gel thoroughly.In the present invention
Some embodiments in, the component of the high layer of silica gel thoroughly includes organic silica gel or inorganic silica gel.It can in the high layer of silica gel thoroughly
Curing agent can not also be added to add curing agent.In certain embodiments of the present invention, the group of the high layer of silica gel thoroughly is divided into
The organic silica gel of light transmittance > 90% or the inorganic silica gel of light transmittance > 90%.In certain embodiments of the present invention, described high saturating
The group of layer of silica gel is selected from organic silica gel KL-9310B.
In certain embodiments of the present invention, the high layer of silica gel thoroughly with a thickness of 30nm~1000 μm.In certain implementations
In example, the high layer of silica gel thoroughly with a thickness of 50nm~100 μm.In certain embodiments, the high layer of silica gel thoroughly with a thickness of
50 μm or 100 μm.
In certain embodiments of the present invention, the high layer of silica gel thoroughly is compounded in compound in the one side of the flexible substrates
Mode is coating.
Transparent graphene conductive film provided by the invention further includes graphene film layer.The graphene film layer is compound
In the high layer of silica gel thoroughly.
The graphene film layer can be single-layer graphene film or multi-layer graphene film.In certain realities of the invention
It applies in example, the number of plies of the multi-layer graphene film is 2 layers, 5 layers or 3 layers.In transparent graphene conductive film of the invention
Graphene film layer surface is smooth, no particle residue, cleannes with higher and surface smoothness, this is for keeping stone
The excellent photoelectric properties of black alkene transparent conductive film are very important.
The present invention has no special limitation to the thickness of the graphene film layer, can select according to actual needs corresponding
Thickness.
In certain embodiments of the present invention, the graphene film layer is compounded in the composite square in the high layer of silica gel thoroughly
Formula is pressurized adhesion.
Transparent graphene conductive film provided by the invention further includes OCA optical adhesive layer.The OCA optical adhesive layer is compounded in
The another side of the flexible substrates.The group of the OCA optical adhesive layer is divided into OCA optical cement.In certain embodiments of the present invention,
The OCA optical cement is the OCA optical cement of Shenzhen's brilliance scholar Science and Technology Ltd. production.
In certain embodiments of the present invention, the OCA optical adhesive layer with a thickness of 30nm~1000 μm.
In certain embodiments of the present invention, the OCA optical adhesive layer is compounded on the another side of the flexible substrates
Complex method is coating.
In certain embodiments of the present invention, release film is compounded in the OCA optical adhesive layer.The release film is used for
OCA optical cement surface is protected, when transfer can remove release film.
The present invention has no special limitation to the material of the release film, can be well known to those skilled in the art release
Membrane material.
The cleannes and surface smoothness of transparent graphene conductive film provided by the invention are more excellent, meanwhile, it can keep
Preferable integrality and excellent photoelectric properties.
The light transmittance of transparent graphene conductive film provided by the invention is more excellent, and light transmittance is 80~97.5%.
The present invention also provides a kind of preparation methods of transparent graphene conductive film described above, including following step
It is rapid:
A graphene film) is grown in the upper surface of metal foil using chemical vapour deposition technique, obtains graphene film layer；
In the high saturating silica gel of the coated on one side of flexible substrates, high layer of silica gel/flexible substrates composite layer thoroughly is obtained；
B the high layer of silica gel thoroughly is bonded with the graphene film layer), pressurizes, obtains graphene film layer/height
Saturating layer of silica gel/flexible substrates composite layer；
C it) is coated with OCA optical cement in the another side of the flexible substrates, obtains OCA optical adhesive layer；
D the metal foil) is removed by etching method or electrochemical process, obtains graphene complex, after cleaned and dry,
Obtain transparent graphene conductive film.
The present invention grows graphene film in the upper surface of metal foil using chemical vapour deposition technique, obtains graphene film
Layer.
The present invention has no special limitation to the specific steps and parameter of the chemical vapour deposition technique, using this field skill
Chemical vapour deposition technique known to art personnel grows graphene film in the upper surface of metal foil.In certain realities of the invention
It applies in example, the material of the metal foil includes Au, Cu, Ni, Pt or Ru.In certain embodiments of the present invention, the graphite obtained
Alkene film layer can be single-layer graphene film or multi-layer graphene film.In certain embodiments of the present invention, the multilayer
The number of plies of graphene film is 2 layers, 5 layers or 3 layers.
In the present invention, in the high saturating silica gel of the coated on one side of flexible substrates, high layer of silica gel/flexible substrates composite layer thoroughly is obtained.
The present invention has no special limitation to the source of the flexible substrates, can be general commercially available flexible substrates or soft
Property substrate.In certain embodiments of the present invention, the group of the flexible substrates is selected from polyethylene terephthalate, polyamides
One or more of imines and polyethylene naphthalate.
In certain embodiments of the present invention, the component of the high silica gel thoroughly includes organic silica gel.In the high silica gel thoroughly
Curing agent can be added or do not add curing agent.In certain embodiments of the present invention, the light transmittance of the high silica gel thoroughly >
90%.In certain embodiments of the present invention, the high silica gel thoroughly is the organic silica gel of light transmittance > 90%.In certain of the invention
In a little embodiments, the high silica gel thoroughly is organic silica gel KL-9310B.
After obtaining high layer of silica gel/flexible substrates composite layer thoroughly, by the height in the high layer of silica gel/flexible substrates composite layer thoroughly
Saturating layer of silica gel is bonded with the graphene film layer, is pressurizeed, and graphene film layer/high layer of silica gel/flexible substrates thoroughly are obtained
Composite layer.
In certain embodiments of the present invention, the pressurization specifically: added using the roller bearing or tablet press machine of laminating machine
Pressure.
In certain embodiments of the present invention, the pressure of the pressurization is 0.1~20MPa；In certain embodiments, described
The pressure of pressurization is 5~10MPa；In certain embodiments, the pressure of the pressurization is 10MPa.In certain implementations of the invention
In example, the time of the pressurization is 1s~30h；In certain embodiments, the time of the pressurization is 1s~10h；In certain realities
It applies in example, the time of the pressurization is 5h, 8h.
Layer of silica gel holds tightly together height after being overpressurized with the graphene film layer thoroughly.
After obtaining the saturating layer of silica gel/flexible substrates composite layer of graphene film layer/height, applied in the another side of the flexible substrates
Cloth OCA optical cement, obtains OCA optical adhesive layer.
In certain embodiments of the present invention, the OCA optical cement is the production of Shenzhen's brilliance scholar Science and Technology Ltd.
OCA optical cement.
After obtaining OCA optical adhesive layer, the metal foil is removed by etching method or electrochemical process, it is compound to obtain graphene
Body obtains transparent graphene conductive film after cleaned and dry.
In certain embodiments of the present invention, the etching liquid that the etching method uses is molten for the mixing of hydrochloric acid and hydrogen peroxide
One of liquid, the aqueous solution of iron chloride and aqueous solution of ammonium persulfate.In certain embodiments of the present invention, the etching liquid
Concentration be 0.1~10mol/L.In certain embodiments, the concentration of the etching liquid is 0.5~5mol/L.In certain implementations
In example, the concentration of the etching liquid is 0.5mol/L, 1mol/L, 2mol/L or 5mol/L.In certain embodiments of the present invention,
The volume ratio of the hydrochloric acid and hydrogen peroxide is 1~9:1~9.In certain embodiments, the volume ratio of the hydrochloric acid and hydrogen peroxide is
1:1.
In certain embodiments of the present invention, the electrochemical process is electrochemistry Bubbling method.The present invention is to the electrochemistry
The step of Bubbling method and parameter have no special limitation, using electrochemistry Bubbling method well known to those skilled in the art.
In certain embodiments of the present invention, the electrolyte that the electrochemical process uses includes the aqueous solution of inorganic acid, has
One of the aqueous solution of machine acid, the aqueous solution of alkali and aqueous solution of salt.In certain embodiments, the electrochemical process uses
Electrolyte includes sulfuric acid solution, hydrochloric acid solution, nitric acid solution, the aqueous solution of methanesulfonic acid, the aqueous solution of citric acid, sodium hydroxide
One of aqueous solution, the aqueous solution of potassium hydroxide, the aqueous solution of sodium chloride and aqueous solution of potassium chloride.Of the invention certain
In embodiment, the concentration of the electrolyte is 0.1~10mol/L.In certain embodiments, the concentration of the electrolyte is
1mol/L。
In certain embodiments of the present invention, the cleaning agent used that cleans is deionized water.System provided by the invention
In Preparation Method, it is described cleaning use cleaning agent without using organic solvent (such as: ethyl alcohol, ether, acetone, board-washing water, first
Benzene, dimethylbenzene, limonene, banana oil, carbon disulfide, dichloroethanes, turpentine oil, petroleum ether, gasoline), thus, the present invention provides
Preparation method it is more environmentally protective, it is pollution-free.
In certain embodiments of the present invention, the method for the drying is to be dried up using nitrogen gun.
The present invention is using high layer of silica gel thoroughly as transfer medium, while the intact transfer of realization graphene film layer, stone
The surface of black alkene film layer is smooth, no particle residue, has higher cleannes, final graphene electrically conducting transparent obtained
The cleannes and surface smoothness of film are more excellent, meanwhile, preferable integrality and excellent photoelectric properties, light transmittance can be kept
It is more excellent.In addition, high layer of silica gel thoroughly has the function of that Automatic-exhausting pickle, applying method are easy.Preparation method provided by the invention can
To prepare large area, high performance transparent conductive film, cost is relatively low, has great importance for the application of graphene.
The present invention also provides a kind of transparent graphene conductive film described above or preparation method systems described above
Application of the standby transparent graphene conductive film as the transparent electrode of photoelectric device.The applicant is the study found that system of the present invention
The cleannes and surface smoothness of standby transparent graphene conductive film are more excellent, meanwhile, preferable integrality and excellent can be kept
Different photoelectric properties, light transmittance is more excellent, therefore, it is possible to as photoelectric device such as capacitor, sensor, touch screen, solar energy
Battery (solar battery can be organic solar batteries or perovskite solar battery) and Organic Light Emitting Diode
Transparent electrode.Thus, transparent graphene conductive film or preparation method described above preparation described above is claimed
Application of the transparent graphene conductive film as the transparent electrode of photoelectric device.
In order to further illustrate the present invention, thin to a kind of graphene electrically conducting transparent provided by the invention below with reference to embodiment
Film, preparation method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Raw material used in following embodiment is general commercially available.
Embodiment 1
Using chemical vapour deposition technique in the upper surface Growing Double-Layer graphene film of copper foil, graphene film layer is obtained；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene terephthalate in group, obtains
High layer of silica gel/flexible substrates composite layer thoroughly；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the iron chloride of 0.5mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 260ohm/sq；
The light transmittance of transparent graphene conductive film is 95.1%.
The graphene film layer for the transparent graphene conductive film that embodiment 1 obtains is divided using atomic force microscope
Analysis, as a result as shown in Figure 2.Fig. 2 is the atomic force of the graphene film layer of the transparent graphene conductive film of the embodiment of the present invention 1
Microscope figure.From figure 2 it can be seen that graphene film fold is high-visible, surface is smooth, cleans without breakage, without bright
Aobvious bulky grain residual.
The graphene film layer for the transparent graphene conductive film that embodiment 1 is obtained is carried out using scanning electron microscope
Analysis, as a result as shown in Figure 3.Fig. 3 is the scanning of the graphene film layer of the transparent graphene conductive film of the embodiment of the present invention 1
Electron microscope picture.The fold of graphene film is clear that from Fig. 3, surface is smooth, cleans without breakage, without bright
Aobvious bulky grain residual.
The graphene film layer for the transparent graphene conductive film that embodiment 1 is obtained carries out visible transmission spectra point
Analysis, as a result as shown in Figure 4.Fig. 4 is the visible light of the graphene film layer of the transparent graphene conductive film of the embodiment of the present invention 1
Transmitted light spectrogram.Figure 4, it is seen that graphene film layer light transmittance with higher in visible-range.
Embodiment 2
Single-layer graphene film is grown in the upper surface of copper foil using chemical vapour deposition technique, obtains graphene film layer；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene naphthalate in group, obtains height
Saturating layer of silica gel/flexible substrates composite layer；The high layer of silica gel thoroughly with a thickness of 100 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 5MPa, institute
The time for stating pressurization is 8h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the iron chloride of 0.5mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 580ohm/sq,
Graphene film layer structural integrity, surface be smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is
97.2%.
Embodiment 3
Single-layer graphene film is grown in the upper surface of copper foil using chemical vapour deposition technique, obtains graphene film layer；
Be divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyimides in group, obtain high layer of silica gel thoroughly/
Flexible substrates composite layer；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the iron chloride of 1mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 630ohm/sq,
Graphene film layer structural integrity, surface be smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is
97.2%.
Embodiment 4
Single-layer graphene film is grown in the upper surface of copper foil using chemical vapour deposition technique, obtains graphene film layer；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene terephthalate in group, obtains
High layer of silica gel/flexible substrates composite layer thoroughly；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the ammonium persulfate of 2mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 300ohm/sq,
Graphene film layer structural integrity, surface be smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is
97.1%.
Embodiment 5
Using chemical vapour deposition technique in the upper surface Growing Double-Layer graphene film of copper foil, graphene film layer is obtained；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene terephthalate in group, obtains
High layer of silica gel/flexible substrates composite layer thoroughly；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the ammonium persulfate of 1mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 200ohm/sq,
Graphene film layer structural integrity, surface be smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is
95.2%.
Embodiment 6
5 layers of graphene film are grown in the upper surface of copper foil using chemical vapour deposition technique, obtain graphene film layer；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene terephthalate in group, obtains
High layer of silica gel/flexible substrates composite layer thoroughly；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the ammonium persulfate of 1mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 50ohm/sq, stone
Black alkene film layer structure is complete, surface is smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is 85%.
Using transparent graphene conductive film manufactured in the present embodiment as transparent electrode, it is prepared for structure are as follows: transparent electrode/tri-
Molybdenum oxide/4,4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline]/acetopyruvic acid two (2- phenylpyridine) iridium: 4,4',
4 "-three (carbazole -9- base) triphenylamine/acetopyruvic acid two (2- phenylpyridine) iridium: 1,10- phenanthrolene/1,10- neighbour's phenodiazine
Miscellaneous luxuriant and rich with fragrance/(lithium/aluminium)) green light OLED device.Through detecting, the light-emitting area of the green light OLED device is 0.4mm2；Voltage is
When 5V, the brightness of green light OLED device can achieve 8000cd m-2。
Embodiment 7
3 layers of graphene film are grown in the upper surface of copper foil using chemical vapour deposition technique, obtain graphene film layer；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene terephthalate in group, obtains
High layer of silica gel/flexible substrates composite layer thoroughly；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by etching method, obtains graphene complex；The etching liquid that the etching method uses is concentration
For the aqueous solution of the ammonium persulfate of 5mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 70ohm/sq, stone
Black alkene film layer structure is complete, surface is smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is 93%.
Using transparent graphene conductive film manufactured in the present embodiment as transparent electrode, it is prepared for structure are as follows: transparent electrode/poly-
The organic solar batteries of (3,4- ethene dioxythiophene)-polystyrolsulfon acid/poly- 3 hexyl thiophenes/PCBM (/ calcium/aluminium).Through
Detection, the incident photon-to-electron conversion efficiency of the organic solar batteries are 5.6%.
Embodiment 8
Single-layer graphene film is grown in the upper surface of copper foil using chemical vapour deposition technique, obtains graphene film layer；
It is divided into the coated on one side organic silica gel KL-9310B of the flexible substrates of polyethylene terephthalate in group, obtains
High layer of silica gel/flexible substrates composite layer thoroughly；The high layer of silica gel thoroughly with a thickness of 50 μm；
Organic silica gel KL-9310B is covered and is bonded with the graphene film layer, is added using the roller bearing of laminating machine
Pressure, so that the high layer of silica gel thoroughly holds tightly together with the graphene film layer, the pressure of the pressurization is 10MPa,
The time of the pressurization is 5h, obtains graphene film layer/high layer of silica gel/flexible substrates composite layer thoroughly；
It is coated with OCA optical cement (production of brilliance scholar Science and Technology Ltd., Shenzhen) in the another side of the flexible substrates, is obtained
To OCA optical adhesive layer；
The copper foil is removed by electrochemical process, obtains graphene complex；The electrolyte that the electrochemical process uses for
Concentration is the aqueous solution of the sodium chloride of 1mol/L；
The graphene complex is cleaned with deionized water, and is dried up with nitrogen gun, and transparent graphene conductive film is obtained.
Through detecting, in the transparent graphene conductive film, the surface resistivity of graphene film layer is 500ohm/sq,
Graphene film layer structural integrity, surface be smooth, clean, noresidue；The light transmittance of transparent graphene conductive film is
97.5%.
Using transparent graphene conductive film manufactured in the present embodiment as transparent electrode, it is prepared for structure are as follows: transparent electrode/poly-
The organic solar batteries of (3,4- ethene dioxythiophene)-polystyrolsulfon acid/poly- 3 hexyl thiophenes/PCBM (/ calcium/aluminium).Through
Detection, the incident photon-to-electron conversion efficiency of the organic solar batteries are 3.6%.
The experimental results showed that in transparent graphene conductive film prepared by the present invention, the sheet resistance of graphene film layer
Rate is no more than 630ohm/sq, and the resistivity of transparent graphene conductive film is smaller；Graphene film layer structural integrity, surface light
Sliding smooth, clean, noresidue.The light transmittance of transparent graphene conductive film is more excellent.
Using the OLED device that transparent graphene conductive film of the invention is prepared as transparent electrode, light-emitting area is
0.4mm2；When voltage is 5V, the brightness of green light OLED device can achieve 8000cd m-2.It is led so that graphene of the invention is transparent
Conductive film is that the incident photon-to-electron conversion efficiency of the organic solar batteries of transparent electrode preparation is not less than 3.6%.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of transparent graphene conductive film characterized by comprising
Flexible substrates；
In the compound saturating layer of silica gel of height of the one side of the flexible substrates；
The composite graphite alkene film layer in the high layer of silica gel thoroughly；
In the another side Composite OC A optical adhesive layer of the flexible substrates.
2. transparent graphene conductive film according to claim 1, which is characterized in that the group of the flexible substrates is selected from
One or more of polyethylene terephthalate, polyimides and polyethylene naphthalate.
3. transparent graphene conductive film according to claim 1, which is characterized in that the high layer of silica gel thoroughly with a thickness of
30nm~1000 μm；
The flexible substrates with a thickness of 10~300 μm；
The OCA optical adhesive layer with a thickness of 30nm~1000 μm.
4. a kind of preparation method of transparent graphene conductive film, comprising the following steps:
A graphene film) is grown in the upper surface of metal foil using chemical vapour deposition technique, obtains graphene film layer；Soft
Property substrate the high saturating silica gel of coated on one side, obtain high layer of silica gel/flexible substrates composite layer thoroughly；
B the high layer of silica gel thoroughly is bonded with the graphene film layer), pressurizes, obtains graphene film layer/saturating silicon of height
Glue-line/flexible substrates composite layer；
C it) is coated with OCA optical cement in the another side of the flexible substrates, obtains OCA optical adhesive layer；
D the metal foil) is removed by etching method or electrochemical process, graphene complex is obtained and is obtained after cleaned and dry
Transparent graphene conductive film.
5. the preparation method of transparent graphene conductive film according to claim 4, which is characterized in that step B) in, institute
The pressure for stating pressurization is 0.1~20MPa, and the time of the pressurization is 1s~30h.
6. the preparation method of transparent graphene conductive film according to claim 4, which is characterized in that step D) in, institute
The etching liquid that etching method uses is stated as the mixed solution of hydrochloric acid and hydrogen peroxide, the aqueous solution of iron chloride and the aqueous solution of ammonium persulfate
One of.
7. the preparation method of transparent graphene conductive film according to claim 6, which is characterized in that the etching liquid
Concentration is 0.1~10mol/L；
The volume ratio of the hydrochloric acid and hydrogen peroxide is 1~9:1~9.
8. the preparation method of transparent graphene conductive film according to claim 4, which is characterized in that step D) in, institute
The electrolyte for stating electrochemical process use includes sulfuric acid solution, hydrochloric acid solution, nitric acid solution, the aqueous solution of methanesulfonic acid, citric acid
Aqueous solution, the aqueous solution of sodium hydroxide, the aqueous solution of potassium hydroxide, the aqueous solution of sodium chloride and potassium chloride aqueous solution in one
Kind；
The concentration of the electrolyte is 0.1~10mol/L.
9. the preparation method of transparent graphene conductive film according to claim 4, which is characterized in that step D) in, institute
The cleaning agent for cleaning and using is stated as deionized water.
10. described in transparent graphene conductive film described in claims 1 to 3 any one or claim 4~9 any one
Preparation method preparation transparent graphene conductive film as photoelectric device transparent electrode application.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795619A (en) * | 2012-09-04 | 2012-11-28 | 南开大学 | Graphene thin film transferring method based on physical adsorption |
| CN104015463A (en) * | 2014-05-12 | 2014-09-03 | 中国科学院宁波材料技术与工程研究所 | Transfer method of graphene film |
| CN104129783A (en) * | 2014-08-04 | 2014-11-05 | 中国科学院金属研究所 | Low cost clean nondestructive transfer method of large area of graphene |
| CN104360778A (en) * | 2014-09-29 | 2015-02-18 | 常州二维碳素科技有限公司 | Graphene capacitive screen and manufacturing method thereof |
| CN106986334A (en) * | 2017-04-28 | 2017-07-28 | 宁波柔碳电子科技有限公司 | The transfer method and system of a kind of graphene film |
| KR20180108219A (en) * | 2017-03-24 | 2018-10-04 | 솔베이코리아 주식회사 | Hybrid electrode using graphene, preparing method of the same, and device including the same |
-
2019
- 2019-09-16 CN CN201910870735.2A patent/CN110517809A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795619A (en) * | 2012-09-04 | 2012-11-28 | 南开大学 | Graphene thin film transferring method based on physical adsorption |
| CN104015463A (en) * | 2014-05-12 | 2014-09-03 | 中国科学院宁波材料技术与工程研究所 | Transfer method of graphene film |
| CN104129783A (en) * | 2014-08-04 | 2014-11-05 | 中国科学院金属研究所 | Low cost clean nondestructive transfer method of large area of graphene |
| CN104360778A (en) * | 2014-09-29 | 2015-02-18 | 常州二维碳素科技有限公司 | Graphene capacitive screen and manufacturing method thereof |
| KR20180108219A (en) * | 2017-03-24 | 2018-10-04 | 솔베이코리아 주식회사 | Hybrid electrode using graphene, preparing method of the same, and device including the same |
| CN106986334A (en) * | 2017-04-28 | 2017-07-28 | 宁波柔碳电子科技有限公司 | The transfer method and system of a kind of graphene film |
Non-Patent Citations (1)
| Title |
|---|
| 王作智 等: "基于石墨烯透明导电薄膜的OLED 研究进展", 《表面技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437176A (en) * | 2021-01-30 | 2021-09-24 | 宣城睿晖宣晟企业管理中心合伙企业(有限合伙) | Preparation method of heterojunction battery |
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