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CN102877109A - Method for preparing grapheme transparent conducting films by electrophoretic deposition - Google Patents

Method for preparing grapheme transparent conducting films by electrophoretic deposition Download PDF

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Publication number
CN102877109A
CN102877109A CN2012103468122A CN201210346812A CN102877109A CN 102877109 A CN102877109 A CN 102877109A CN 2012103468122 A CN2012103468122 A CN 2012103468122A CN 201210346812 A CN201210346812 A CN 201210346812A CN 102877109 A CN102877109 A CN 102877109A
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graphene
film
electrophoretic deposition
copper
pmma
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姚亚东
尹光福
宫溢超
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Sichuan University
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Sichuan University
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Abstract

一种石墨烯透明导电薄膜的制备方法，以天然石墨粉为原料，在AMP(0.5-1.0vol.%)/水(0.4vol.%)/DMF溶液中超声剥离制备高浓度石墨烯分散液。然后以所制得的石墨烯分散液为电解液，采用电泳沉积法制备石墨烯导电薄膜，再将其转移至玻璃基底上。控制电泳沉积电压和沉积时间，可以制备不同厚度的石墨烯导电薄膜，再通过热处理和酸处理工艺提高其透光性和导电性。用此法制备的石墨烯导电薄膜，表面平整，缺陷较少；所制得石墨烯薄膜的透光率可达82.1%，薄膜电阻为1.0MΩ/sq。与其它制备方法相比，该方法操作简便、易于控制、成本较低、适于规模化制备等。A preparation method of a graphene transparent conductive film, using natural graphite powder as a raw material, ultrasonic stripping in AMP (0.5-1.0vol.%)/water (0.4vol.%)/DMF solution to prepare a high-concentration graphene dispersion. Then, using the prepared graphene dispersion as electrolyte, electrophoretic deposition is used to prepare a graphene conductive film, and then transfer it to a glass substrate. By controlling the electrophoretic deposition voltage and deposition time, graphene conductive films with different thicknesses can be prepared, and then the light transmittance and conductivity can be improved by heat treatment and acid treatment. The graphene conductive film prepared by this method has a smooth surface and fewer defects; the light transmittance of the prepared graphene film can reach 82.1%, and the film resistance is 1.0MΩ/sq. Compared with other preparation methods, the method is simple to operate, easy to control, low in cost, suitable for large-scale preparation and the like.

Description

Electrophoretic deposition prepares transparent graphene conductive film
Technical field
The invention belongs to the carbon material preparation field, be specifically related to a kind of method of utilizing electrophoretic deposition to prepare transparent graphene conductive film.
Background technology
As the important component part of opto-electronic device, transparent conductive film has a wide range of applications in fields such as liquid-crystal display (LCD), organic solar batteries, organic light emitting diodes (LCD).Tin indium oxide (ITO) relies on its high conductivity and light transmission, has become current main transparent conductive film material.Yet because the preparation of ITO is costly and starting material are rare and the continuous rise of price, the fragility of ITO also makes its performance requriements that can't satisfy some new application simultaneously, therefore, needs the equivalent material of exploitation ITO badly.
The electroconductibility that Graphene is good and light transmission make it that good application prospect be arranged aspect transparent conductive film.Compare with the ITO material, Graphene has higher intensity and better toughness, as transparent conductive film, can make can bending fold display device.
At present, the preparation method of transparent graphene conductive film mainly contains: CVD method and based on the method for graphene oxide or graphene dispersing solution.The CVD method can obtain the more perfect high-quality graphene of structure, yet the CVD method still exists the more high defective of equipment requirements.Be the method that raw material prepares transparent conductive film based on graphene oxide or graphene dispersing solution, because the method cost is lower, suitability is stronger etc., can satisfy the application demand of different field.
At present, the method for preparing graphene conductive film based on graphene oxide or graphene dispersing solution mainly contains: electrophoretic deposition, layer assembly method, vacuum filtration method, spin coating method, injection cladding process etc.Compare with other method, that electrophoretic deposition has is easy and simple to handle, be easy to control, cost is lower, be suitable for the advantage such as mass-producing preparation, but the method only has a small amount of report at present.
(Chem. Mater, 2009,21 (16): 3905-3916) adopt electrophoretic deposition to make level and smooth graphene film in conductive substrates such as Lee.The preparation approach comprises two kinds: the firstth, and utilize the aqueous dispersions of the graphene oxide of mechanically peel gained to be raw material, adopt electrophoretic deposition graphene oxide to be deposited on the substrate of glass of indium tin oxide coating, then it is immersed in the aqueous solution of hydrazine hydrate, thereby the graphene oxide reduction that deposits is made graphene film; Another kind then is first with graphene oxide reduction, then will reduce the Graphene electrophoretic deposition of gained to substrate.Yet there is graphene film textural defect more (due to the reduction not exclusively) in the method, waits deficiency.(Adv. Mater, 2009,21 (17): make graphene dispersing solution thereby 1756-1760) adopt the method for chemical stripping in aqueous isopropanol, to peel off synthetic graphite, then add therein Mg (NO such as Cheng 3) 26H 2O is by Mg (NO 3) 26H 2The ionization of O makes Graphene absorption Mg 2+And positively charged, with Mg 2+The absorption graphene suspension is as ionogen, and under electric field action, positively charged graphene film is towards movable cathode and be deposited in an orderly manner cathode surface, thereby obtains graphene film.But still there is charged Mg in this method 2+Be difficult to remove from graphene film, cause the problems such as the film transmittance is relatively poor.
The defective or the deficiency that prepare graphene conductive film for above-mentioned electrophoretic deposition, basic conception of the present invention is: utilize ultrasonic the peeling off of Graphite Powder 99 liquid phase to prepare in the graphene dispersing solution process, introduce 2-amino-2-methyl-1-propanol (AMP) as the additive of preparation graphene dispersing solution.AMP can ionize and be adsorbed in the Graphene surface, and adsorption charge produces electrostatic repulsion and reduces the stacking trend of absorption, thereby improves the concentration of graphene dispersing solution.Simultaneously, because AMP is easy to volatilization, after electrolytic solution electrophoretic deposition gained graphene film drying, foreign matter content is few take this dispersion liquid, and film light transmission and electroconductibility are better.The concrete technology technological line comprises: be raw material with natural graphite powder, take AMP/ water/dimethyl formamide (DMF) system as solvent, adopt the ultrasonic stripping method of liquid phase to prepare the high concentration graphene dispersion liquid.Then take prepared dispersion liquid as electrolytic solution, adopt electrophoretic deposition to prepare graphene film, again the graphene film that makes is transferred to glass or arbitrarily in other substrates.
Summary of the invention
The present invention utilizes a kind of mode of non-covalent physical adsorption to make Graphene charged, then adopts electrophoretic deposition to prepare transparent graphene conductive film.
Specifically the present invention take AMP/ water/DMF system as solvent, adopts the ultrasonic stripping method of liquid phase to prepare the high concentration graphene dispersion liquid take natural graphite powder as raw material.Then take prepared dispersion liquid as electrolytic solution, adopt electrophoretic deposition to prepare graphene film, again the graphene film that makes is transferred on the substrate of glass.
Its concrete process is as follows:
1, the preparation of graphene dispersing solution
Measuring 0.1-0.2 mLAMP and 0.08 mL deionized water joins and is configured to AMP (0.5-1.0 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mixes.Weighing 0.2-0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 24-30 h(ultrasonic power 72 W that peel off).After ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 90-120 min under 4000 rpm rotating speeds.Get centrifuge tube supernatant liquor, set aside for use with clean dropper at last.
2, the preparation of electrophoretic deposition electrode used therein
The used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing.
(1) mechanical polishing of Copper Foil is processed
Use the sand papering Copper Foil, eliminate surface film oxide.Then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect.Polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, cleans with ethanol, then dry for standby.
(2) electroplating processes of Copper Foil
Dispose saturated neutralized verdigris solution, as electrode, neutralized verdigris solution was electroplated 15 minutes under 20 mA constant current modes as ionogen with polished copper sheet, and powering at the negative electrode copper sheet plates layer of copper.Constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface.
3, electrophoretic deposition prepares graphene film
The graphene dispersing solution for preparing is diluted to 7 μ g/mL, and ultrasonic 10 min mix it.Adopt JY 600 type electrophoresis apparatuses as direct supply, between electrode, apply 80 V cm -1Steady electric field, electrophoretic deposition 30-50 s.Rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry.
4, the transfer of graphene film
(1) the anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface.
The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level.
(3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min, to remove residual etching liquid ion at every turn.Then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries.
The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn.The PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass.
5, the processing of graphene conductive film
(1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃.
(2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%.
6, the performance test of graphene film
(1) transmittance of graphene film test
Adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film.
(2) sheet resistance of graphene film test
Adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm.
What the present invention was prepared is transparent graphene conductive film.Can control by regulating electrophoretic voltage and depositing time the thickness of transparent graphene conductive film; By being heat-treated with acid treatment, the transparent graphene conductive film after shifting to improve its transmittance and electroconductibility.
Device required for the present invention is simple and cheap, mainly is comprised of two portions: Vltrasonic device, electrophoresis apparatus device.Effect and mutual relationship between two portions are as follows: 1) Vltrasonic device is used for the ultrasonic graphene dispersing solution of peeling off; 2) electrophoresis apparatus device makes graphene film in the electric field action deposit to electrode with Graphene.
The present invention compares with existing technology of preparing and synthetic route, has following advantage and beneficial effect:
1. introduce AMP as the additive of preparation graphene dispersing solution, AMP can ionize and be adsorbed in the Graphene surface, and the Graphene adsorption charge produces electrostatic repulsion and reduces the stacking trend of absorption, thereby can improve the concentration of graphene dispersing solution.Under identical ultrasound condition and ultrasonic time, peel off graphene dispersing solution with direct liquid phase and compare, adding AMP can improve 50% with the concentration of graphene dispersing solution.Simultaneously because AMP is easy to volatilization, be electrolytic solution electrophoretic deposition gained graphene film drying with this dispersion liquid after, foreign matter content is few, film light transmission and electroconductibility are better.
2. the graphene film textural defect that makes of the present invention is few, and degree of oxidation is low, and dispersion system has extraordinary stability.
3. the present invention can be by regulating the thickness of electrophoretic deposition applied voltage and depositing time control graphene conductive film, and prepared graphene film is comparatively complete, and transmittance is better.
4. technique of the present invention is simple, is suitable for the mass-producing preparation.
Embodiment
Embodiment one
1, the preparation of graphene dispersing solution
Measuring 0.2 mLAMP and 0.08 mL deionized water joins and is configured to AMP (1.0 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mixes.Weighing 0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 24 h(ultrasonic powers, 72 W that peel off).After ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 90 min under 4000 rpm rotating speeds.Get centrifuge tube supernatant liquor, set aside for use with clean dropper at last.
2, the preparation of electrophoretic deposition electrode used therein
The used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing.
(1) mechanical polishing of Copper Foil is processed
Use the sand papering Copper Foil, eliminate surface film oxide.Then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect.Polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, cleans with ethanol, then dry for standby.
(2) electroplating processes of Copper Foil
Dispose saturated neutralized verdigris solution, as electrode, neutralized verdigris solution was electroplated 15 minutes under 20 mA constant current modes as ionogen with polished copper sheet, and powering at the negative electrode copper sheet plates layer of copper.Constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface.
3, electrophoretic deposition prepares graphene film
The graphene dispersing solution for preparing is diluted to 7 μ g/mL, and ultrasonic 10 min mix it.Adopt JY 600 type electrophoresis apparatuses as direct supply, between electrode, apply 80 V cm -1Steady electric field, electrophoretic deposition 30 s.Rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry.
4, the transfer of graphene film
(1) the anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface.
The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level.
(3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min, to remove residual etching liquid ion at every turn.Then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries.
The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn.The PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass.
5, the processing of graphene conductive film
(1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃.
(2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%.
6, the performance characterization of graphene film
(1) transmittance of graphene film test
Adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film.The evaluation of transmittance index sees Table one.
(2) sheet resistance of graphene film test
Adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm.The evaluation of sheet resistance index sees Table one.
Embodiment two
1, the preparation of graphene dispersing solution
Measuring 0.1 mLAMP and 0.08 mL deionized water joins and is configured to AMP (0.5 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mixes.Weighing 0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 30 h(ultrasonic powers, 72 W that peel off).After ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 120 min under 4000 rpm rotating speeds.Get centrifuge tube supernatant liquor, set aside for use with clean dropper at last.
2, the preparation of electrophoretic deposition electrode used therein
The used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing.
(1) mechanical polishing of Copper Foil is processed
Use the sand papering Copper Foil, eliminate surface film oxide.Then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect.Polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, cleans with ethanol, then dry for standby.
(2) electroplating processes of Copper Foil
Dispose saturated neutralized verdigris solution, as electrode, neutralized verdigris solution was electroplated 15 minutes under 20 mA constant current modes as ionogen with polished copper sheet, and powering at the negative electrode copper sheet plates layer of copper.Constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface.
3, electrophoretic deposition prepares graphene film
The graphene dispersing solution for preparing is diluted to 5 μ g/mL, and ultrasonic 10 min mix it.Adopt JY 600 type electrophoresis apparatuses as direct supply, between electrode, apply 100 V cm -1Steady electric field, electrophoretic deposition 50 s.Rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry.
4, the transfer of graphene film
(1) the anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface.
The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level.
(3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min, to remove residual etching liquid ion at every turn.Then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries.
The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn.The PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass.
5, the processing of graphene conductive film
(1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃.
(2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%.
6, the performance characterization of graphene film
(1) transmittance of graphene film test
Adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film.The evaluation of transmittance index sees Table one.
(2) sheet resistance of graphene film test
Adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm.The evaluation of sheet resistance index sees Table one.
The evaluation of transparent graphene conductive film in table one example
? Embodiment Transmittance Resistance
Example one 82.1% 1.0 MΩ/sq
Example two 81.3% 1.2 MΩ/sq

Claims (1)

1.一种电泳沉积法制备石墨烯透明导电薄膜的方法，其特征在于包含以下工序步骤： 1. a method for preparing graphene transparent conductive film by electrophoretic deposition, is characterized in that comprising following operation steps: 石墨烯分散液的制备：量取0.1-0.2 mLAMP和0.08 mL去离子水加入到20 mLDMF中配置成AMP(0.5-1.0 vol.%)/水(0.4 vol.%)/DMF溶液并混合均匀，称量0.2-0.4 g石墨粉加入该混合溶液中，然后将其超声剥离24-30 h（超声功率72 W），超声完成后，将悬浮液转入离心管中，然后用800型离心机于4000 rpm转速下离心90-120 min，最后用洁净的滴管取离心管上清液，静置待用； Preparation of graphene dispersion: Measure 0.1-0.2 mL AMP and 0.08 mL deionized water into 20 mL DMF to form AMP (0.5-1.0 vol.%)/water (0.4 vol.%)/DMF solution and mix well. Weigh 0.2-0.4 g of graphite powder and add it to the mixed solution, and then ultrasonically peel it for 24-30 h (ultrasonic power 72 W). Centrifuge at 4000 rpm for 90-120 min, and finally take the supernatant of the centrifuge tube with a clean dropper, and let it stand for use; 电泳沉积所用电极的制备：电泳沉积所用阳极为机械抛光处理后的铜箔（铜箔厚度0.1 mm），电泳沉积所用阴极为先经机械抛光处理再电镀处理后的铜箔；（1）铜箔的机械抛光处理：使用砂纸打磨铜箔，消除表面氧化膜，接着使用P-1型抛光机进行进一步的机械抛光，最后达到镜面效果，将抛光好的铜箔裁剪成1.8 cm×3.5 cm的长片，用乙醇清洗，然后烘干备用；（2）铜箔的电镀处理：配置饱和的醋酸铜溶液，以抛光好的铜片作为电极，醋酸铜溶液作为电解质，在20 mA恒流模式下电镀15分钟，在阴极铜片上电镀上一层铜，用去离子水不断冲洗电镀处理后铜片以去除表面的电解质，烘干待用； Preparation of electrodes for electrophoretic deposition: the anode used for electrophoretic deposition is mechanically polished copper foil (copper foil thickness 0.1 mm), and the cathode used for electrophoretic deposition is copper foil that has been mechanically polished and then electroplated; (1) Copper foil Mechanical polishing treatment: Use sandpaper to polish the copper foil to eliminate the surface oxide film, then use a P-1 polishing machine for further mechanical polishing, and finally achieve a mirror effect, and cut the polished copper foil into a length of 1.8 cm×3.5 cm (2) Electroplating treatment of copper foil: configure saturated copper acetate solution, use polished copper sheet as electrode, copper acetate solution as electrolyte, and electroplate under 20 mA constant current mode For 15 minutes, a layer of copper was electroplated on the cathode copper sheet, and the electroplated copper sheet was continuously rinsed with deionized water to remove the electrolyte on the surface, and dried for later use; 电泳沉积法制备石墨烯薄膜：将制备好的石墨烯分散液稀释至7 μg/mL，并超声10 min使其混合均匀，采用JY 600型电泳仪作为直流电源，在电极之间施加80 V cm-1的恒定电场，电泳沉积30 s，沉积完成后迅速取出阳极铜片，在90℃下烘干； Graphene films were prepared by electrophoretic deposition: the prepared graphene dispersion was diluted to 7 μg/mL, and mixed evenly by ultrasonication for 10 min, and a JY 600 electrophoresis instrument was used as a DC power supply, and 80 V cm was applied between the electrodes. A constant electric field of -1 , electrophoretic deposition for 30 s, the anode copper sheet was quickly taken out after the deposition was completed, and dried at 90 °C; 石墨烯薄膜的转移：（1）在烘干后的阳极铜片沉积有石墨烯膜的一面涂覆上一层PMMA的苯甲醚溶液（浓度1%），在室温下让其自然晾干，即在石墨烯膜表面形成一层透明的PMMA薄膜；（2）将一面涂覆了PMMA的铜片浸泡在3 g/mL的三氯化铁水溶液中，浸泡大约12小时之后，铜完全被三氯化铁刻蚀，石墨烯/PMMA膜漂浮在液面上；（3）将石墨烯/PMMA膜取出，置于去离子水中浸泡三次，每次浸泡10 min，以去除残留的刻蚀液离子，然后将石墨烯/PMMA膜转移至清洗干净的载玻片上，自然晾干；（4）将附着石墨烯/PMMA膜的载玻片在丙酮中浸泡三次，每次浸泡12 h，PMMA膜溶于丙酮，从石墨烯表面上去除，得到附着在载玻片上的石墨烯薄膜； Transfer of graphene film: (1) Coat one layer of PMMA anisole solution (concentration 1%) on the side of the dried anode copper sheet deposited with graphene film, let it dry naturally at room temperature, That is, a transparent PMMA film is formed on the surface of the graphene film; (2) The copper sheet coated with PMMA on one side is soaked in 3 g/mL ferric chloride aqueous solution. After soaking for about 12 hours, the copper is completely covered by three Ferric chloride etching, the graphene/PMMA film floats on the liquid surface; (3) Take out the graphene/PMMA film and soak it in deionized water for three times, each time for 10 minutes, to remove the residual etching solution ions , and then transfer the graphene/PMMA film to a clean glass slide and let it dry naturally; (4) Soak the glass slide with graphene/PMMA film in acetone three times for 12 h each time, and the PMMA film dissolves In acetone, it is removed from the surface of graphene to obtain a graphene film attached to the glass slide; 石墨烯导电薄膜的处理：（1）热处理：在空气中，250℃下对得到的石墨烯薄膜热处理2 h；（2）酸处理：对热处理后的薄膜用50%的稀硝酸浸泡2 h； Treatment of graphene conductive film: (1) heat treatment: heat-treat the obtained graphene film in air at 250°C for 2 h; (2) acid treatment: soak the heat-treated film in 50% dilute nitric acid for 2 h; 石墨烯薄膜的性能测试：（1）石墨烯薄膜的透光率：采用U-3010型紫外-可见分光光度计，以空白载玻片为参照，在400-900 nm波长范围内测量石墨烯薄膜的透光率，并以在波长λ=550 nm处的透光率作为石墨烯薄膜的透光率，该石墨烯导电薄膜透光率在80-82%；（2）石墨烯薄膜的薄膜电阻：采用SB100A/2型四探针测试仪测试载玻片基材上石墨烯薄膜的薄膜电阻，探针之间的距离为3 mm，该石墨烯导电薄膜电阻在1.0-1.2 MΩ/sq。 Performance test of graphene film: (1) Light transmittance of graphene film: U-3010 UV-Vis spectrophotometer is used to measure graphene film in the wavelength range of 400-900 nm with a blank glass slide as reference The light transmittance, and the light transmittance at the wavelength λ=550 nm place as the light transmittance of the graphene film, the light transmittance of the graphene conductive film is 80-82%; (2) The sheet resistance of the graphene film : SB100A/2 type four-probe tester is used to test the sheet resistance of the graphene film on the slide substrate, the distance between the probes is 3 mm, and the resistance of the graphene conductive film is 1.0-1.2 MΩ/sq.
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