CN113023719A - Low-sheet-resistance and ultra-clean graphene transparent conductive film and preparation method thereof - Google Patents

Low-sheet-resistance and ultra-clean graphene transparent conductive film and preparation method thereof Download PDF

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CN113023719A
CN113023719A CN202110249209.1A CN202110249209A CN113023719A CN 113023719 A CN113023719 A CN 113023719A CN 202110249209 A CN202110249209 A CN 202110249209A CN 113023719 A CN113023719 A CN 113023719A
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graphene
substrate
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王作智
张志坤
汪伟
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention provides a low-sheet resistance and ultra-clean graphene transparent electrode and a preparation method thereof, wherein the method comprises the following steps: depositing (2-8) layers of graphene on a metal substrate by adopting a chemical vapor deposition method; processing the substrate with the graphene to obtain a processed substrate with the graphene; placing the processed substrate with the grown graphene in etching liquid for etching, cleaning, transferring the substrate into a dopant solution, transferring the substrate into a target substrate, and drying to obtain a graphene transparent electrode; the surface tension of the etching solution and the dopant solution is 0.01-1000N/m. The surface of the graphene film prepared by the method is free of any impurity; the dopant is located between the few-layer graphene and the substrate, and the few-layer graphene with few defects reduces the contact chance of the dopant with the outside, so that the sheet resistance of the doped graphene film is stable for a long time.

Description

Low-sheet-resistance and ultra-clean graphene transparent conductive film and preparation method thereof
Technical Field
The invention belongs to the technical field of graphene transparent electrodes, and particularly relates to a low-sheet-resistance ultra-clean graphene transparent conductive film and a preparation method thereof.
Background
Graphene is a material with a two-dimensional honeycomb structure composed of carbon atoms, theoretically, the sheet resistance of single-layer graphene is 30 Ω/sq, the light transmittance is as high as 97.7%, and the graphene has good flexibility and is considered as a substitute of a traditional transparent conductive material, namely indium tin oxide. However, due to the polycrystalline characteristic of the graphene thin film and the imperfect growth and transfer processes, the transferred graphene tends to have a larger sheet resistance, and still faces a larger challenge in practical application. In addition, because the single-layer graphene has a thickness of atomic level, the single-layer graphene can be relatively completely transferred to a target substrate under the protection of the supporting layer, and then the supporting layer is not completely removed due to the interaction force between the supporting layer and the graphene, the residual supporting layer causes the surface roughness of the graphene to be large, and the device is often subjected to electric leakage or short circuit, so that the clean graphene film with low sheet resistance is indispensable to the practical application of the graphene.
The traditional method for reducing the sheet resistance of graphene comprises the following steps that firstly, single-layer graphene is transferred layer by layer, although the sheet resistance of the graphene can be reduced, the process is complex, and the prepared graphene film often has larger roughness; secondly, sheet resistance is reduced by doping the surface of the graphene, the method is effective in a short time, and as time is prolonged, the problems of volatilization, desorption, cracking and the like exist when the dopant is in contact with air, so that the doping is ineffective; and thirdly, the graphene and other conductive materials form a composite electrode, although the sheet resistance of the graphene can be greatly reduced by the method, the light transmittance is seriously reduced due to the compounding of the graphene and a conductive high polymer, the graphene cannot exist stably for a long time, the roughness of the film after the film is compounded with the silver nanowires is increased, and the silver nanowires and the graphene are separated and fall off after the film is bent for several times. Therefore, obtaining a clean graphene film with low sheet resistance is a difficult problem.
Disclosure of Invention
In view of the above, the present invention provides a low sheet resistance and ultra-clean graphene transparent conductive film and a preparation method thereof.
The invention provides a preparation method of a low-sheet resistance and ultra-clean graphene transparent electrode, which comprises the following steps:
depositing multilayer graphene on a metal substrate by adopting a chemical vapor deposition method;
processing the substrate with the graphene to obtain a processed substrate with the graphene;
and placing the substrate with the graphene grown thereon in etching liquid for etching, cleaning, transferring the substrate into a solution containing a dopant, transferring the substrate to a target substrate, and drying to obtain the graphene transparent electrode.
Preferably, the metal substrate is selected from one or more of an evaporated copper substrate, a rolled copper substrate, an electrolytic copper substrate, a nickel foil substrate, and a copper-nickel alloy substrate.
Preferably, the deposition is carried out in methane, ethylene, PMMA, argon, nitrogen, argon-oxygen gas mixture or argon-methane gas mixture.
Preferably, the method for processing the substrate with the graphene comprises one or more of alcohol cotton ball erasing, oxygen plasma processing, tape tearing, laser etching, etching solution cleaning, ethanol cleaning, deionized water cleaning and dilute hydrochloric acid water solution processing.
Preferably, the etching liquid is one or more selected from ammonium persulfate aqueous solution, ferric trichloride aqueous solution, potassium chloride aqueous solution, hydrochloric acid aqueous solution, ethanol-water mixture, polyethylene glycol-water mixture and acetone-water mixture.
Preferably, the dopant in the dopant solution is selected from one or more of nitric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, ferric chloride, gold chloride, rubidium chloride, nitromethane, graphene oxide, silver nanowires, bis-trifluoromethanesulfonimide and its derivatives, ethylene glycol, N-dimethyl sulfoxide, ethanol, and water.
Preferably, the concentration of the dopant solution is 0.001-1 mol/L.
Preferably, the drying temperature is 40-140 ℃, and the drying time is 1 min-5 h.
Preferably, the number of the multilayer graphene layers is 2-8.
The invention provides a preparation method of a low-sheet resistance and ultra-clean graphene transparent electrode, which comprises the following steps: depositing (2-8) layers of graphene on a metal substrate by adopting a chemical vapor deposition method; processing the substrate with the graphene to obtain a processed substrate with the graphene; placing the processed substrate with the grown graphene in etching liquid for etching, cleaning, transferring the substrate into a dopant solution, transferring the substrate into a target substrate, and drying to obtain a graphene transparent electrode; the surface tension of the etching solution and the dopant solution is 0.01-1000N/m. The method provided by the invention prepares the multilayer graphene on the metal substrate by using a chemical vapor deposition method, realizes the transfer of the graphene under the condition of not needing a supporting layer by controlling the surface tension of an etching liquid, transfers the graphene film to a dopant solution with specific surface tension for doping after the growth substrate is etched, and transfers the graphene film to a target substrate after the doping is finished. According to the invention, due to the fact that the growing graphene has a certain number of layers and the surface tension of the etching solution and the dopant solution, the graphene film can be completely transferred to the target substrate, and the transferred graphene film has no impurities on the surface. The dopant is located between the few-layer graphene and the substrate, and the few-layer graphene with few defects reduces the contact chance of the dopant with the outside, so that the sheet resistance of the doped graphene film is stable for a long time.
Drawings
FIG. 1 is a schematic outflow diagram as used in an embodiment of the present invention;
fig. 2 is a real image (a), a scanning electron microscope image (b) and an atomic force microscope image (c) of the graphene thin film prepared in example 1 of the present invention;
fig. 3 is a result of testing doping stability of the graphene thin film electrode prepared in comparative example 5 and the graphene thin film prepared in example 2 according to the present invention;
fig. 4 shows the results of the water resistance test of the graphene thin film prepared in comparative example 5 and the graphene thin film prepared in example 3 according to the present invention.
Detailed Description
The invention provides a preparation method of a low-sheet resistance and ultra-clean graphene transparent electrode, which comprises the following steps:
depositing multilayer graphene on a metal substrate by adopting a chemical vapor deposition method;
processing the substrate with the graphene to obtain a processed substrate with the graphene;
placing the processed substrate with the grown graphene in an etching solution for etching, cleaning, transferring the substrate into a solution containing a dopant, transferring the substrate to a target substrate, and drying to obtain a graphene transparent electrode;
the surface tension of the etching solution and the dopant solution is 0.01-1000N/m.
The method provided by the invention is characterized in that 2-8 layers of graphene is prepared on a metal substrate by using a chemical vapor deposition method, the graphene is transferred under the condition of not needing a supporting layer by controlling the surface tension of an etching liquid, a graphene film is transferred into a dopant solution with specific surface tension for doping after a growth substrate is etched, and the graphene film is transferred to a target substrate after the doping is finished. According to the invention, due to the fact that the growing graphene has a certain number of layers and the surface tension of the etching solution and the dopant solution, the graphene film can be completely transferred to the target substrate, and the transferred graphene film has no impurities on the surface. The dopant is located between the few-layer graphene and the substrate, and the few-layer graphene with few defects reduces the contact chance of the dopant with the outside, so that the sheet resistance of the doped graphene film is stable for a long time.
The method adopts a chemical vapor deposition method to deposit (2-8) layers of graphene on a metal substrate. In the present invention, the metal substrate is selected from one or more of an evaporated copper substrate, a rolled copper substrate, an electrolytic copper substrate, a nickel foil substrate, and a copper-nickel alloy substrate. The deposition is carried out in methane, ethylene, PMMA, argon, nitrogen, argon-oxygen gas mixture or argon-methane gas mixture. In the present invention, the chemical vapor deposition method is performed under normal pressure; the temperature of the chemical vapor deposition method is 950-1050 ℃; in specific embodiments, the temperature is 950 ℃, 980 ℃ or 1050 ℃. Preferably, methane, hydrogen and argon are introduced into the chemical vapor deposition method; the ventilation rate of methane is 10-18 sccm, the ventilation rate of hydrogen is 60-100 sccm, and the ventilation rate of argon is 100-200 sccm.
The method comprises the step of processing a substrate with graphene to obtain the processed substrate with graphene. The method provided by the invention is used for processing the substrate with the graphene, and aims to remove the redundant graphene on the substrate without damaging the graphene to be transferred, so that the local stacking of the graphene film in the transfer process is avoided, and the cleanness and the flatness of the graphene film are ensured. The method for processing the substrate with the graphene comprises one or more of alcohol cotton ball erasing, oxygen plasma processing, adhesive tape tearing, laser etching, etching liquid cleaning, ethanol cleaning, deionized water cleaning and dilute hydrochloric acid water solution processing.
The substrate with the graphene grown thereon after treatment is placed in etching liquid for etching, is transferred to dopant solution after being cleaned, is transferred to a flexible PET substrate, and is dried to obtain the graphene transparent electrode. In the invention, the surface tension of the etching solution and the surface tension of the dopant solution are both 0.01-1000N/m. During etching, the film is prevented from being damaged or incompletely etched due to bubbles between the etching solution and the substrate. After the substrate is etched, when residual etching liquid is transferred and cleaned on the graphene film, the film and the transfer film are tightly attached and are not bonded.
In the invention, the etching liquid is preferably one or more of an ammonium persulfate aqueous solution, a ferric trichloride aqueous solution, a potassium chloride aqueous solution, a hydrochloric acid aqueous solution, an ethanol-water mixture, a polyethylene glycol-water mixture and an acetone-water mixture. The concentration of the etching liquid is preferably 0.1-3 mol/L. In the invention, the etching liquid is selected from 0.2mol/L ammonium persulfate aqueous solution; or 2mol/L ferric chloride aqueous solution. In a specific embodiment, the etching solution is selected from 0.2mol/L ammonium persulfate solution with surface tension of 78N/m or 2mol/L ferric chloride solution with surface tension of 590N/m.
The invention preferably adopts deionized water for cleaning; after several times of cleaning, no residual etching liquid exists on the surface of the graphene, and then the graphene is transferred into a dopant solution to ensure that the space between the graphene and the dopant is ensuredThe tension of graphene, the solubility of the dopant in the dopant solution, the doping time and the doping degree have important influence on the performance of graphene. In the invention, the concentration of the dopant solution is preferably 0.001-1 mmol/L. In the present invention, the dopant in the dopant solution is preferably selected from one or more of nitric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, ferric chloride, gold chloride, rubidium chloride, nitromethane, graphene oxide, silver nanowires, bis-trifluoromethanesulfonimide and its derivatives, ethylene glycol, N-dimethyl sulfoxide, ethanol, and water. Too large tension between the dopant solution and the graphene can cause damage to the graphene film; if the solute dopant is excessively adsorbed on the surface of the graphene film, the roughness of the graphene film is increased, the number of carriers is too large, the sheet resistance is increased, and the like. The surface tension of the dopant solution is preferably 0.01-1000N/m. In a specific embodiment, the dopant solution is selected from 7.5mmol/L chloroauric acid solution with surface tension of 480N/m; or 15mmol/L HNO with surface tension of 338N/m3A solution; or a 10.5mmol/L trifluoromethanesulfonic acid solution with a surface tension of 740N/m.
In a particular embodiment of the invention, the dopant in the dopant solution is selected from chloroauric acid, nitric acid or trifluoromethanesulfonic acid. The solvent in the dopant solution is selected from a mixed solvent of water and ethanol in a volume ratio of 5: 2; water; or the volume ratio is 15:2 water and ethylene glycol.
In the invention, the temperature of the solution transferred into the dopant solution is 10-30 ℃ and the time is 2-5 min; in specific embodiments, the temperature of the transfer into the dopant solution is room temperature and the time is 5min, 2min, or 3 min.
After doping is finished, the paper ink is transferred to the target substrate, then the target substrate is placed in an inclined mode, so that the residual dopant between the graphene film and the target substrate flows out, then the target substrate is dried, and close adhesion between the graphene film and the target substrate is promoted. The target substrate is preferably flexible PET. In the invention, the drying temperature is 40-140 ℃, and the drying time is 1 min-5 h; in a specific embodiment, the drying temperature is 40 ℃, 50 ℃ or 80 ℃; the drying time is 60min or 30 min.
The invention does not adopt polymer as a supporting layer, the surface roughness of the graphene film prepared by the invention is as low as 2nm,
according to the method, firstly, a chemical vapor deposition method is used for preparing few (2-8) layers of graphene, and then under the condition that a supporting layer is not needed for protection, the proportion of etching liquid is adjusted so as to adjust the surface tension between the etching liquid, and finally, the synchronous doping and transfer of the inch-level graphene film are achieved. The method has the advantages of simple process flow, low sheet resistance, high light transmittance, good flexibility, clean surface, low roughness, stable sheet resistance in a longer time and the like of the prepared graphene transparent conductive film, and can be applied to photoelectric devices such as OLED, OSC and the like.
The invention provides a low-sheet resistance and ultra-clean graphene transparent electrode which is prepared by the preparation method of the technical scheme.
In order to further illustrate the present invention, the following examples are provided to describe a low sheet resistance and ultra-clean graphene transparent conductive film and a method for preparing the same in detail, but they should not be construed as limiting the scope of the present invention.
FIG. 1 is a schematic outflow diagram as used in an embodiment of the present invention;
example 1
1. Under the condition of normal pressure, introducing 15sccm of methane, 60sccm of hydrogen and 100sccm of argon by a chemical vapor deposition method at the temperature of 950 ℃, growing for 15 minutes, and preparing the graphene with 4 layers by a rapid cooling method.
2. Then 0.2mol/L ammonium persulfate solution is used as etching liquid (the surface tension is 78N/m), and after the etching is finished, the solution is transferred into deionized water to be rinsed for 3 times and then transferred to the flexible PET substrate.
3. The method comprises the steps of doping chloroauric acid serving as a doping agent, water and ethanol in a volume ratio of 5:2 serving as a solvent in a doping agent solution (with surface tension of 480N/m) with the concentration of 7.5mmol/L for two minutes at room temperature, and transferring the doping agent solution to a flexible PET substrate to obtain a graphene/doping agent/PET sandwich structure.
4. Then heating the doped graphene in a hot bench at the temperature of 50 ℃ for 30 minutes, drying the doped graphene, wherein the sheet resistance of the doped graphene is 168 omega/□, and the light transmittance is 87.5%. After 10000 times of bending, the sheet resistance is increased by 5.4 percent compared with the original sheet resistance. The sheet resistance was 172 Ω/□ after two months, with little attenuation.
Fig. 2 is a real image (a), a scanning electron microscope image (b) and an atomic force microscope image (c) of the graphene thin film prepared in example 1 of the present invention; fig. 2 (a) is a physical diagram of the graphene film transferred to the flexible substrate, and it can be seen that the graphene film is completely transferred to the flexible substrate without any supporting layer, and no obvious breakage occurs. As can be seen from fig. 2 (b), except for the wrinkles, the surface of the graphene thin film has no significant impurities. Fig. 2 (c) is an atomic force microscope picture of the doped and transferred flexible PET surface, from which it can be seen that the graphene has very low surface roughness and no dopant residue.
Comparative example 1
In comparison with example 1, the doping treatment was not performed with the dopant solution.
The sheet resistance of the transferred graphene under the undoped condition is 380 omega/□, the light transmittance is 89%, and the sheet resistance is increased by 4.3% after 10000 times of bending test.
Example 2
1. Under the condition of normal pressure, introducing 18sccm of methane, 80sccm of hydrogen and 100sccm of argon by adopting a chemical vapor deposition method at the temperature of 980 ℃, growing for 30 minutes, and preparing the 5-layer graphene by adopting a rapid cooling method.
2. Then, the flexible PET substrate is etched by using a 2mol/L ferric chloride solution as an etching solution (the surface tension is 590N/m), rinsed three times by using deionized water and transferred to the flexible PET substrate.
3. In the presence of HNO3Mixing nitric acid and water according to the volume ratio of 2:8 as a doping agent, transferring graphene into a mixed doping agent solution (the surface tension is 338N/m) of 15mmol/L, doping for 5 minutes at room temperature, and transferring to a flexible PET substrate to obtain a graphene/doping agent/PET sandwich structure.
4. Then heating the graphene in a hot bench at the temperature of 40 ℃ for 60 minutes, drying the doped graphene, wherein the sheet resistance of the doped graphene is 108 omega/□, and the light transmittance is 85.9%. After 10000 times of bending, the sheet resistance is increased by 5.1 percent compared with the original sheet resistance. The sheet resistance is 112 omega/□ after one month, and almost no attenuation exists.
Comparative example 2
In comparison with example 2, no doping treatment was performed with the dopant solution.
The sheet resistance of the transferred graphene under the undoped condition is 330 omega/□, the light transmittance is 86%, and the sheet resistance is increased by 4.8% after 10000 times of bending tests.
Example 3
1. And under the condition of normal pressure, introducing 10sccm of methane, 100sccm of hydrogen and 200sccm of argon by adopting a chemical vapor deposition method at the temperature of 1050 ℃, growing for 30 minutes, and preparing the graphene with 4 layers by adopting a rapid cooling method.
2. Then, the copper foil is removed by using a 2mol/L ferric chloride solution (surface tension is 590N/m) as an etching solution, and the copper foil is rinsed three times by using deionized water and then transferred to a flexible PET substrate.
3. Dissolving trifluoromethanesulfonic acid serving as a dopant in a mixed solution of water and ethylene glycol in a volume ratio of 15:2, then transferring the graphene film into a 10.5mmol/L dopant solution (with surface tension of 740N/m) from deionized water, doping for 3 minutes at room temperature, and transferring to a flexible PET substrate to obtain a graphene/dopant/PET sandwich structure.
4. Then drying at normal temperature to slowly and completely volatilize residual moisture, and then heating for 30 minutes in a hot bench at the temperature of 80 ℃ to dry. The sheet resistance of the doped graphene is 138 omega/□, and the light transmittance is 87.3%. After 1000 times of bending, the sheet resistance of the material is 7.1 percent higher than the original sheet resistance. The sheet resistance is 141 omega/□ after one month, and almost no attenuation is generated.
The doped graphene film is used as a transparent electrode to be applied to the OLED, and the current efficiency of the device is up to 75cd A-1Power efficiency of 80lmW-1。
The surface roughness of the graphene film prepared in embodiment 3 of the invention is as low as 2 nm.
Comparative example 3
In comparison with example 3, no doping treatment was performed.
The sheet resistance of the transferred graphene under the undoped condition is 300 omega/□, the light transmittance is 88%, and the sheet resistance is increased by 5.4% after 10000 times of bending tests.
Comparative example 4
1. Spin-coating a layer of PMMA on the surface of the copper foil with the graphene as a supporting layer;
2. placing the supporting layer/graphene/copper foil into etching liquid to remove the copper substrate;
3. when the copper substrate disappears, transferring the supporting layer/graphene into deionized water to clean for three times;
4. transferring the transfer film/graphene to a target substrate. After residual moisture is dried, baking the transfer film/graphene/substrate on a hot table to enable the graphene to be in close contact with the substrate;
5. putting the supporting layer/graphene/substrate into a heated acetone solution to be soaked for 30min, and repeating the soaking for three times;
6. and drying the graphene/substrate.
The transfer film is used as a supporting layer, so that the surface of the graphene film prepared by the transfer film has a large number of particles with the size of 60nm due to the residue of the transfer film. This causes a serious leakage phenomenon to the light emitting device.
Comparative example 5
The preparation process of the surface-doped graphene film comprises the following steps:
1. placing the copper foil with the graphene in an etching solution to remove the copper foil substrate; 2. after the copper foil is completely removed, transferring the graphene into deionized water to remove the residual etching liquid, and repeating the steps for three times; 3. transferring the graphene to the surface of PET, and naturally airing; 4. naturally drying the obtained graphene/PET, and baking the graphene/PET at 120 ℃ for 10min on a hot bench to enable the PET to be tightly combined with the graphene; 5. and soaking the graphene/substrate in the dopant for a certain time, fishing out, and airing.
Fig. 3 is a result of testing doping stability of the graphene thin film electrode prepared in comparative example 5 and the graphene thin film prepared in example 2 according to the present invention; as can be seen from fig. 3: the sheet resistance of the graphene film prepared in the embodiment of the invention is basically unchanged within two months, while the surface-doped graphene film prepared in the comparative example 5 is easy to desorb the dopant due to the contact of the dopant and air, and is close to the sheet resistance of the graphene itself in 30 days.
Placing the graphene film into water to perform a waterproof test; fig. 4 is a result of a water resistance test of the graphene thin film prepared in comparative example 5 and the graphene thin film prepared in example 3 according to the present invention; as can be seen from fig. 4: after the graphene film prepared by the embodiment of the invention is washed by flowing water for a long time, the sheet resistance of the graphene film is slightly increased compared with the original sheet resistance; and the graphene film prepared in the comparative example 5 immediately desorbs the dopant, and the resistance is restored to the intrinsic graphene.
From the above embodiments, the invention provides a preparation method of a low sheet resistance and ultra-clean graphene transparent electrode, which includes the following steps: depositing graphene with a small number of layers on a metal substrate by adopting a chemical vapor deposition method; processing the substrate with the graphene to obtain a processed substrate with the graphene; placing the processed substrate with the grown graphene in etching liquid for etching, cleaning, transferring the substrate into a dopant solution, transferring the substrate into a target substrate, and drying to obtain a graphene transparent electrode; the surface tension of the etching solution and the dopant solution is 0.01-1000N/m. The method provided by the invention prepares the multilayer graphene on the metal substrate by using a chemical vapor deposition method, realizes the transfer of the graphene under the condition of not needing a supporting layer by controlling the surface tension of an etching liquid, transfers the graphene film to a dopant solution with specific surface tension for doping after the growth substrate is etched, and transfers the graphene film to a target substrate after the doping is finished. According to the invention, due to the fact that the growing graphene has a certain number of layers and the surface tension of the etching solution and the dopant solution, the graphene film can be completely transferred to the target substrate, and the transferred graphene film has no impurities on the surface. The dopant is located between the few-layer graphene and the substrate, and the few-layer graphene with few defects reduces the contact chance of the dopant with the outside, so that the sheet resistance of the doped graphene film is stable for a long time.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a low sheet resistance and ultra-clean graphene transparent electrode comprises the following steps:
depositing (2-8) layers of graphene on a metal substrate by adopting a chemical vapor deposition method;
processing the substrate with the graphene to obtain a processed substrate with the graphene;
placing the processed substrate with the grown graphene in etching liquid for etching, cleaning, transferring the substrate into a dopant solution, transferring the substrate into a target substrate, and drying to obtain a graphene transparent electrode;
the surface tension of the etching solution and the dopant solution is 0.01-1000N/m.
2. The production method according to claim 1, wherein the metal substrate is selected from one or more of an evaporated copper substrate, a rolled copper substrate, an electrolytic copper substrate, a nickel foil substrate, and a copper-nickel alloy substrate.
3. The method of claim 1, wherein the deposition is performed in methane, ethylene, PMMA, argon, nitrogen, an argon-oxygen mixture, or an argon-methane mixture.
4. The method of claim 1, wherein the graphene-grown substrate is treated by one or more of alcohol cotton ball wiping, oxygen plasma treatment, tape tearing, laser etching, etching solution cleaning, ethanol cleaning, deionized water cleaning, and dilute hydrochloric acid aqueous solution treatment.
5. The method according to claim 1, wherein the etching solution is one or more selected from the group consisting of an aqueous ammonium persulfate solution, an aqueous ferric chloride solution, an aqueous potassium chloride solution, an aqueous hydrochloric acid solution, an ethanol-water mixture, a polyethylene glycol-water mixture, and an acetone-water mixture.
6. The method according to claim 1, wherein the dopant in the dopant solution is selected from one or more of nitric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, ferric chloride, gold chloride, rubidium chloride, nitromethane, graphene oxide, silver nanowires, bis-trifluoromethanesulfonimide and its derivatives, ethylene glycol, N-dimethyl sulfoxide, ethanol, and water.
7. The method according to claim 1, wherein the concentration of the dopant solution is 0.001 to 1 mol/L.
8. The preparation method according to claim 1, wherein the drying temperature is 40-140 ℃ and the drying time is 1 min-5 h.
9. The method according to claim 1, wherein the number of graphene layers is 2 to 8.
10. A low sheet resistance, ultra-clean graphene transparent electrode prepared by the preparation method of any one of claims 1 to 9.
CN202110249209.1A 2021-03-08 2021-03-08 Low-sheet-resistance and ultra-clean graphene transparent conductive film and preparation method thereof Pending CN113023719A (en)

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Application publication date: 20210625