WO2016206158A1 - 石墨烯/pedot:pss混合溶液的制备方法及具有石墨烯/pedot:pss复合透明导电膜的基板的制备方法 - Google Patents

石墨烯/pedot:pss混合溶液的制备方法及具有石墨烯/pedot:pss复合透明导电膜的基板的制备方法 Download PDF

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WO2016206158A1
WO2016206158A1 PCT/CN2015/085101 CN2015085101W WO2016206158A1 WO 2016206158 A1 WO2016206158 A1 WO 2016206158A1 CN 2015085101 W CN2015085101 W CN 2015085101W WO 2016206158 A1 WO2016206158 A1 WO 2016206158A1
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graphene
pedot
pss
substrate
film
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French (fr)
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胡韬
李泳锐
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • H01B1/20—Conductive material dispersed in non-conductive organic material
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    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
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    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/093—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antistatic means, e.g. for charge depletion
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Definitions

  • the present invention relates to the field of display manufacturing, and in particular to a method for preparing a graphene/PEDOT:PSS mixed solution and a method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film.
  • LCDs liquid crystal displays
  • OLEDs organic light emitting diodes
  • the display panel is an important component of the LCD and the OLED.
  • the display panel of the LCD mainly consists of a Thin Film Transistor (TFT) substrate, a Color Filter (CF), and a configuration.
  • the liquid crystal layer is formed between the two substrates.
  • the working principle is to control the rotation of the liquid crystal molecules in the liquid crystal layer by applying a driving voltage on the TFT substrate and the CF substrate, and refract the light of the backlight module to generate a picture. Providing different colors through the backlight through the CF substrate.
  • the classification of liquid crystal-based modes of operation are: phase change (PC), twisted nematic (TN), super twisted nematic (STN), vertical alignment (Vertical). Alignment, VA), In Plane Switching (IPS), and the like.
  • PC phase change
  • TN twisted nematic
  • STN super twisted nematic
  • VA vertical alignment
  • VA In Plane Switching
  • VA mode is more and more widely known and widely used in various types of displays.
  • the CF substrate 10 is composed of a glass substrate 11 and a black matrix formed on the glass substrate 11.
  • the sealant is electrically connected to the conductive film on the TFT substrate to form an electric field, drive liquid crystal molecules between the CF substrate and the TFT substrate, and control liquid crystal molecules to deflect, thereby realizing display of different colors.
  • the IPS mode is widely used in a wide viewing angle liquid crystal panel. In a typical IPS display mode, as shown in FIG. 2, the structure of the CF substrate 20 is different from that of the CF substrate 10 in the VA mode.
  • the 20 is composed of a glass substrate 21, a black matrix 22, a color resist layer 23, and a transparent conductive film 24.
  • a planarization layer 25 overcoat, OC layer
  • the transparent conductive film 24 is placed on the back surface of the glass substrate 21 (the side away from the black matrix 22 and the color photoresist layer 23)
  • a back electrode is formed for venting accumulated static electricity.
  • a conventional transparent conductive film is an indium tin oxide (ITO) film prepared by a physical vapor deposition (PVD) method.
  • ITO indium tin oxide
  • PVD physical vapor deposition
  • the specific fabrication process is as follows: in the PVD device, a strong current bombards the ITO target, and a transparent conductive ITO film is deposited on the substrate.
  • the ITO film does not exhibit bending characteristics under a certain external force, which also limits its application in flexible panels and wearable devices.
  • the cost of indium has gradually increased. Therefore, it is of great significance and value to find ITO substitutes with high conductivity and light transmittance, simple preparation methods and abundant resources.
  • Graphene is a two-dimensional material with excellent electrical and mechanical properties.
  • the transmittance of single-layer graphene is about 97.7%, its electron mobility exceeds 15000 cm 2 /Vs at normal temperature, and the resistivity is as low as about 10 -8 ⁇ . m, these properties fully meet the requirements of transparent conductive films.
  • Graphene powder with the help of strong ultrasonic and water-based surfactants, can form a graphene aqueous solution with controlled concentration and uniform dispersion due to intermolecular repulsion.
  • the highly flexible PEDOT:PSS film has attracted much attention as a commonly used organic transparent conductive film coating because of its solution characteristics, a conventional wet coating can be used to prepare a PEDOT:PSS film. Compared with the ITO film, the equipment investment is greatly reduced.
  • the PEDOT:PSS film has been used in anti-static coating earlier, and the technology is relatively mature.
  • the object of the present invention is to provide a method for preparing a graphene/PEDOT:PSS mixed solution, which is prepared by using graphene and PEDOT:PSS solution to prepare a graphene/PEDOT:PSS mixed solution for preparing a transparent conductive film.
  • the material is widely available and inexpensive; the graphene/PEDOT:PSS mixed solution can be used to further fabricate a graphene/PEDOT:PSS composite transparent conductive film.
  • the object of the present invention is to provide a method for preparing a graphene/PEDOT:PSS composite transparent conductive film, which comprises graphene and PEDOT:PSS solution to prepare a graphene/PEDOT:PSS composite transparent conductive film, and has a wide range of materials and prices. Low cost, simple manufacturing method and low production cost.
  • the prepared graphene/PEDOT:PSS composite transparent conductive film has excellent performance and can be used in a color filter substrate instead of a commercial ITO conductive film in flexible devices and wearable devices. It also has great application potential.
  • the present invention provides a method for preparing a graphene/PEDOT:PSS mixed solution, comprising the following steps:
  • Step 1 According to the mass ratio of graphene powder, aqueous surfactant, and deionized water: 50 to 500: a ratio of 150 to 10000.
  • the graphene powder and the aqueous surfactant are put into deionized water and ultrasonically dispersed to obtain a graphene dispersion, and the graphene dispersion is centrifuged to obtain a supernatant to obtain graphene.
  • Step 2 mixing the graphene solution with a certain concentration of PEDOT:PSS diluted solution in a ratio of 1:100 to 100:1 by mass ratio, and obtaining a uniformly dispersed graphene/PEDOT:PSS mixed solution after sonication.
  • the aqueous surfactant is sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate or sodium tetradecyl sulfate.
  • ultrasonic dispersion is performed by using a high-power ultrasound system, the ultrasonic power is 500-900 W, and the ultrasonic time is 10-120 min; when the graphene dispersion is centrifuged, the rotation speed of the centrifuge is 2000-5000 rpm, and the centrifugation time is It is 5 to 60 minutes.
  • the content of graphene in the graphene solution obtained in the step 1 is 0.1-5 mg/ml; the PEDOT:PSS diluted solution in the step 2 is prepared by using deionized water and a PEDOT:PSS solution, and the PEDOT
  • the mass percentage of the PEDOT:PSS solution in the PSS dilution solution is from 1 to 100% by weight.
  • the invention also provides a preparation method of a substrate having a graphene/PEDOT:PSS composite transparent conductive film, comprising the following steps:
  • Step 10 preparing a graphene / PEDOT: PSS mixed solution by the preparation method according to claim 1;
  • Step 20 providing a substrate, applying the graphene/PEDOT:PSS mixed solution to the substrate by a wet coating process, and performing film formation to obtain a graphene/PEDOT:PSS film;
  • Step 30 rinsing the formed substrate with deionized water multiple times to remove the aqueous surfactant in the graphene/PEDOT:PSS film, and increasing the conductivity of the graphene/PEDOT:PSS film;
  • Step 40 Drying the graphene/PEDOT:PSS film to remove moisture in the film to obtain a dried graphene/PEDOT:PSS composite transparent conductive film on the substrate.
  • the substrate is a CF substrate, a common glass substrate, or a flexible substrate;
  • the CF substrate includes a glass substrate, a color photoresist layer disposed on the glass substrate, and a black matrix.
  • the wet coating process is spray coating, spin coating, roll coating, slit extrusion coating, dip coating, blade coating, gravure printing, inkjet printing or screen printing.
  • the step 20 is: providing a substrate, placing the substrate on a constant temperature heating plate, and spraying the graphene/PEDOT:PSS mixed solution on the substrate by spraying. Forming a film on the substrate to obtain a graphene/PEDOT:PSS film, the constant temperature heating plate having a temperature in the range of 80-120 ° C;
  • the step 20 is: providing a substrate, and coating the graphene/PEDOT:PSS mixture on the substrate. After coating, the substrate is quickly transferred to a constant temperature heating plate for baking for 3-10 minutes to form a film, and a graphene/PEDOT:PSS film is obtained, and the temperature of the constant temperature heating plate ranges from 80 to 140 °C.
  • the drying treatment process in the step 40 is natural drying, nitrogen drying or rapid drying in an environment of 80-120 ° C.
  • the graphene/PEDOT:PSS mixed solution is applied to one side of the CF substrate having the color photoresist layer or away from the side of the color photoresist layer.
  • the invention also provides a preparation method of a substrate having a graphene/PEDOT:PSS composite transparent conductive film, comprising the following steps:
  • Step 10 preparing a graphene / PEDOT: PSS mixed solution by the preparation method according to claim 1;
  • Step 20 providing a substrate, applying the graphene/PEDOT:PSS mixed solution to the substrate by a wet coating process, and performing film formation to obtain a graphene/PEDOT:PSS film;
  • Step 30 rinsing the formed substrate with deionized water multiple times to remove the aqueous surfactant in the graphene/PEDOT:PSS film, and increasing the conductivity of the graphene/PEDOT:PSS film;
  • Step 40 drying the graphene/PEDOT:PSS film to remove moisture in the film to obtain a dried graphene/PEDOT:PSS composite transparent conductive film on the substrate;
  • the substrate is a CF substrate, a common glass substrate, or a flexible substrate;
  • the CF substrate includes a glass substrate, and a color photoresist layer and a black matrix disposed on the glass substrate;
  • the wet coating process is spray coating, spin coating, roll coating, slit extrusion coating, dip coating, blade coating, gravure printing, inkjet printing or screen printing;
  • the drying treatment process in the step 40 is natural drying, nitrogen drying or rapid drying in an environment of 80-120 ° C.
  • a method for preparing a graphene/PEDOT:PSS mixed solution and a method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film provided by the present invention, using graphene and PEDOT:PSS solution A graphene/PEDOT:PSS mixed solution for preparing a transparent conductive film is prepared, which uses a wide range of materials and is inexpensive; the graphene/PEDOT:PSS mixed solution can be used to further fabricate graphene/PEDOT on a substrate.
  • a graphene/PEDOT:PSS composite transparent conductive film prepared by the invention has High conductivity and high light transmittance, which can be used in a color filter substrate instead of a commercial ITO film, as a back electrode of a color light-transmitting sheet substrate in an IPS display mode or a surface electrode of a color light-transmitting sheet substrate in a VA display mode, and Due to its excellent mechanical properties, it also has great application potential in flexible devices and wearable devices.
  • FIG. 1 is a schematic structural view of a CF substrate in a VA mode display
  • FIG. 2 is a schematic structural view of a CF substrate in an IPS mode display
  • FIG. 3 is a flow chart of a method for preparing a graphene/PEDOT:PSS mixed solution of the present invention
  • FIG. 4 is a scanning electron micrograph of a graphene/PEDOT:PSS composite transparent conductive film obtained by a first embodiment of a method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film;
  • FIG. 5 is a view showing the appearance of a graphene/PEDOT:PSS composite transparent conductive film obtained by the second embodiment of the method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film;
  • FIG. 6 is a scanning electron micrograph of a graphene/PEDOT:PSS composite transparent conductive film obtained by a second embodiment of a method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film of the present invention.
  • the present invention first provides a method for preparing a graphene/PEDOT:PSS mixed solution for preparing a transparent conductive film, comprising the following steps:
  • Step 1 The graphene powder and the aqueous surfactant are put into deionized water and ultrasonically dispersed according to a ratio of the graphene powder, the aqueous surfactant, and the deionized water in a ratio of 1:50 to 500:150 to 10,000.
  • a graphene dispersion liquid was obtained, and the graphene dispersion liquid was centrifuged to take a supernatant to obtain a graphene solution.
  • the aqueous surfactant is sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate or sodium tetradecyl sulfate.
  • the ultrasonic dispersion is performed by a high-power ultrasound system, the ultrasonic power is 500-900 W, and the ultrasonic time is 10-120 min.
  • the rotation speed of the centrifuge is 2000 to 5000 rpm, and the centrifugation time is 5 to 60 minutes.
  • the content of graphene in the graphene solution obtained in the step 1 is 0.1-5 mg/ml.
  • Step 2 the graphene solution and a certain concentration of PEDOT:PSS (poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)) diluted solution in a mass ratio of 1:100 to 100 A ratio of 1:1 was mixed, and after sonication, a uniformly dispersed graphene/PEDOT:PSS mixed solution was obtained.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)
  • the PEDOT:PSS dilution solution is prepared by using deionized water and a PEDOT:PSS solution, and the mass percentage of the PEDOT:PSS solution in the PEDOT:PSS dilution solution is 1 to 100 wt%; when the PEDOT: When the mass percentage of the PEDOT:PSS solution in the PSS dilution solution is 100% by weight, the PEDOT:PSS diluted solution is a pure PEDOT:PSS solution.
  • the PEDOT:PSS solution is an aqueous solution composed of PEDOT (poly(3,4-ethylenedioxythiophene), PSS (poly(styrenesulfonic acid)), and water, and It can be obtained by commercial purchase or laboratory preparation.
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • PSS poly(styrenesulfonic acid)
  • water water
  • the mass ratio of PSS to PEDOT in the PEDOT:PSS solution is 1-5:1, and the total amount of the two substances PEDOT and PSS is in the PEDOT.
  • the mass percentage (i.e., solid content) in the PSS solution is from 1 to 6 wt%.
  • Graphene powder and sodium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, sodium lauryl sulfate, and deionized water of 1:200:1800, and dispersed by a high-power ultrasound system.
  • Ultrasonic power is 900W, ultrasonic dispersion for 30min, the graphene dispersion is obtained, then the graphene dispersion is centrifuged, the centrifugal speed is 3000 rpm, and the centrifugation time is 30 min, and the supernatant liquid is obtained, which is a graphene solution, and the graphene solution is
  • the content of graphene is 0.5 mg/ml; a certain amount of PEDOT:PSS diluted solution is taken, and the graphene solution and the PEDOT:PSS diluted solution are mixed at a mass ratio of 50:1, and the PEDOT:PSS is diluted.
  • the mass percentage of the PEDOT:PSS solution in the solution is 50% by weight, and the mass percentages of PEDOT, PSS, and water in the PEDOT:PSS solution are 0.5 wt%, 1 wt%, and 98.5 wt%, respectively, and after sonication, uniform dispersion is obtained.
  • Graphene/PEDOT: PSS mixed solution is 50% by weight, and the mass percentages of PEDOT, PSS, and water in the PEDOT:PSS solution are 0.5 wt%, 1 wt%, and 98.5 wt%, respectively, and after sonication, uniform dispersion is obtained.
  • Graphene/PEDOT: PSS mixed solution Graphene/PEDOT: PSS mixed solution.
  • Graphene powder and sodium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, sodium lauryl sulfate and deionized water of 1:200:1050, and dispersed by high-power ultrasound system.
  • ultrasonic power is 500W
  • ultrasonic dispersion for 30min then the graphene is dispersed
  • the liquid was centrifuged, the centrifugal speed was 3000 rpm, and the centrifugation time was 30 min.
  • the supernatant liquid was obtained, which was a graphene solution.
  • the graphene content in the graphene solution was 0.8 mg/ml; a certain amount of PEDOT:PSS diluted solution was taken.
  • the graphene solution and the PEDOT:PSS diluted solution are mixed at a mass ratio of 50:1, the mass percentage of the PEDOT:PSS solution in the PEDOT:PSS diluted solution is 50 wt%, and the PEDOT:PSS solution is PEDOT
  • the mass percentages of PSS, and water were 0.5 wt%, 1.5 wt%, and 98 wt%, respectively, and after sonication, a uniformly dispersed graphene/PEDOT:PSS mixed solution was obtained.
  • Graphene powder and ammonium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, ammonium lauryl sulfate, and deionized water at a ratio of 1:50:150, and dispersed by a high-power ultrasound system.
  • ultrasonic power is 500W
  • ultrasonic dispersion for 10min to obtain a graphene dispersion
  • the graphene dispersion is centrifuged, the centrifugal speed is 2000 rpm, the centrifugation time is 60 min, and the supernatant liquid is obtained, which is a graphene solution, in the graphene solution
  • the content of graphene is 5 mg/ml; a certain amount of PEDOT:PSS diluted solution is taken, and the graphene solution and the PEDOT:PSS diluted solution are mixed at a mass ratio of 1:100, and the PEDOT:PSS diluted solution is mixed.
  • the mass percentage of the PEDOT:PSS solution is 1 wt%, and the mass percentages of PEDOT, PSS, and water in the PEDOT:PSS solution are 0.5 wt%, 2 wt%, and 97.5 wt%, respectively, and after ultrasonic treatment, uniform dispersed graphite is obtained. Alkene/PEDOT: PSS mixed solution.
  • Graphene powder and ammonium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, ammonium lauryl sulfate, and deionized water at a ratio of 1:100:9900, and dispersed by a high-power ultrasound system.
  • the content of the olefin is 0.1 mg/ml; a certain amount of PEDOT:PSS solution is taken, and the graphene solution and the PEDOT:PSS solution are mixed at a mass ratio of 100:1, and the PEDOT:PSS solution is PEDOT,
  • the mass percentages of PSS and water were 0.5 wt%, 2.5 wt%, and 97 wt%, respectively, and after sonication, a uniformly dispersed graphene/PEDOT:PSS mixed solution was obtained.
  • the present invention also provides a method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film:
  • Step 10 Prepare a graphene/PEDOT:PSS mixed solution by the above method.
  • Step 20 Providing a substrate, applying the graphene/PEDOT:PSS mixed solution onto the substrate by a wet coating process, and performing film formation to obtain a graphene/PEDOT:PSS film.
  • the substrate may be a CF substrate, a common glass substrate, or a flexible substrate.
  • the CF substrate includes a substrate, a black matrix and a color photoresist layer disposed on the substrate.
  • the flexible substrate is a PET (polyethylene terephthalate) substrate.
  • the wet coating process is spraying, spin coating, roll coating, slot-die, dip coating, knife coating, gravure printing, inkjet printing or screen printing.
  • the step 20 is: providing a substrate, placing the substrate on a constant temperature heating plate, and spraying the graphene/PEDOT:PSS mixture by spraying.
  • a film is formed on the substrate to form a graphene/PEDOT:PSS film, and the temperature of the constant temperature heating plate ranges from 80 to 120 °C.
  • the thickness of the film can be controlled by controlling the amount of the graphene/PEDOT:PSS mixture, the pressure, time, and the number of times of spraying.
  • the step 20 is: providing a substrate, and coating the graphene/PEDOT:PSS mixture on the substrate. After coating, the substrate is quickly transferred to a constant temperature heating plate for baking for 3-10 minutes to form a film, and a graphene/PEDOT:PSS film is obtained, and the temperature of the constant temperature heating plate ranges from 80 to 140 °C.
  • the thickness of the film formation is controlled by controlling the amount of the graphene/PEDOT:PSS mixture, the spin coating time, the speed, and the number of times.
  • Step 30 The film-formed substrate is washed with deionized water multiple times to remove the aqueous surfactant in the graphene/PEDOT:PSS film, and the conductivity of the graphene/PEDOT:PSS film is increased.
  • Step 40 Drying the graphene/PEDOT:PSS film to remove moisture in the film to obtain a dried graphene/PEDOT:PSS composite transparent conductive film on the substrate.
  • the drying process in the step 40 is natural drying, nitrogen drying or rapid drying in an environment of 80-140 ° C.
  • the graphite prepared in the step 40 is a surface electrode of a CF substrate in a VA display mode;
  • the graphene/PEDOT:PSS mixed solution is coated on the side of the CF substrate away from the color photoresist layer, the graphene/PEDOT prepared in the step 40
  • the PSS composite transparent conductive film is the back electrode of the CF substrate in the IPS display mode.
  • the graphene powder and sodium lauryl sulfate are put into deionized water at a mass ratio of graphene powder, sodium lauryl sulfate, and deionized water of 1:200:1800, and high power is used.
  • the ultrasonic system was dispersed, the ultrasonic power was 900 W, and the ultrasonic dispersion was performed for 30 min to obtain a graphene dispersion.
  • the graphene dispersion was centrifuged, the centrifugal speed was 3000 rpm, and the centrifugation time was 30 min to obtain a supernatant solution, which is a graphene solution.
  • the content of graphene in the graphene solution is 0.5 mg/ml; a certain amount of PEDOT:PSS diluted solution is taken, and the graphene solution and the PEDOT:PSS diluted solution are mixed at a mass ratio of 50:1.
  • the PEDOT: PSS diluted solution has a mass percentage of PEDOT:PSS solution of 50% by weight, and the PEDOT:PSS solution has a mass percentage of PEDOT, PSS, and water of 0.5 wt%, 1 wt%, and 98.5 wt%, respectively, after sonication.
  • a uniformly dispersed graphene/PEDOT:PSS mixed solution was obtained.
  • the 10 cm*10 cm color filter substrate After cleaning the 10 cm*10 cm color filter substrate, it was placed on a spin coater, and 3 ml of the above graphene/PEDOT:PSS mixed solution was uniformly coated on the side of the color filter substrate having the color photoresist layer. After spin coating, the color filter substrate was transferred to a constant temperature heating plate at 80 ° C for 10 minutes, and then a graphene/PEDOT:PSS film was obtained, and then the graphene was washed repeatedly with deionized water. /PEDOT: Sodium lauryl sulfate remaining in the PSS film, followed by drying with nitrogen, to obtain a graphene/PEDOT:PSS composite transparent conductive film on a color filter substrate.
  • Example 4 is a scanning electron microscope (SEM) image of the graphene/PEDOT:PSS composite transparent conductive film obtained in Example 1. It is observed that the film surface is uniform.
  • the surface resistance of the graphene/PEDOT:PSS composite transparent conductive film was measured by a four-probe method to be 204 ⁇ /sq, and the light transmittance at a wavelength of 550 nm was measured by a visible spectrophotometer at room temperature of 85%. .
  • the graphene powder and sodium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, sodium lauryl sulfate, and deionized water of 1:500:750, and dispersed by a high-power ultrasound system.
  • the ultrasonic power is 500W
  • the ultrasonic dispersion is 30min
  • the graphene dispersion is centrifuged
  • the centrifugal speed is 3000rpm
  • the centrifugation time is 30min
  • the supernatant liquid is obtained, which is a graphene solution
  • the graphene content in the graphene solution is 0.8.
  • Fig. 6 is a scanning electron micrograph of the graphene/PEDOT:PSS composite transparent conductive film obtained in Example 2. It is observed that the film surface is uniform and there is no obvious protrusion.
  • the surface resistance of the graphene/PEDOT:PSS composite transparent conductive film was measured by a four-probe method to be 207 ⁇ /sq, and the light transmittance at a wavelength of 550 nm was measured by a visible spectrophotometer at room temperature to be 91%. .
  • Graphene powder and ammonium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, ammonium lauryl sulfate, and deionized water at a ratio of 1:50:150, and dispersed by a high-power ultrasound system.
  • ultrasonic power is 500W
  • ultrasonic dispersion for 10min to obtain a graphene dispersion
  • the graphene dispersion is centrifuged, the centrifugal speed is 2000 rpm, the centrifugation time is 60 min, and the supernatant liquid is obtained, which is a graphene solution, in the graphene solution
  • the content of graphene is 5 mg/ml; a certain amount of PEDOT:PSS diluted solution is taken, and the graphene solution and the PEDOT:PSS diluted solution are mixed at a mass ratio of 1:100, and the PEDOT:PSS diluted solution is mixed.
  • the mass percentage of the PEDOT:PSS solution is 1 wt%, and the mass percentages of PEDOT, PSS, and water in the PEDOT:PSS solution are 0.5 wt%, 2 wt%, and 97.5 wt%, respectively, and after ultrasonic treatment, uniform dispersed graphite is obtained. Alkene/PEDOT: PSS mixed solution.
  • Graphene powder and ammonium lauryl sulfate were put into deionized water at a mass ratio of graphene powder, ammonium lauryl sulfate, and deionized water at a ratio of 1:100:9900, and dispersed by a high-power ultrasound system.
  • the content of the olefin is 0.1 mg/ml; a certain amount of PEDOT:PSS solution is taken, and the graphene solution and the PEDOT:PSS solution are mixed at a mass ratio of 100:1, and the PEDOT:PSS solution is PEDOT,
  • the mass percentages of PSS and water were 0.5 wt%, 2.5 wt%, and 97 wt%, respectively, and after sonication, a uniformly dispersed graphene/PEDOT:PSS mixed solution was obtained.
  • the present invention provides a method for preparing a graphene/PEDOT:PSS mixed solution and a method for preparing a substrate having a graphene/PEDOT:PSS composite transparent conductive film, which are prepared by using graphene and PEDOT:PSS solution.
  • a graphene/PEDOT:PSS mixed solution for preparing a transparent conductive film which uses a wide range of materials and is inexpensive; the graphene/PEDOT:PSS mixed solution can be used to further produce graphene/PEDOT on a substrate:
  • the PSS composite transparent conductive film adopts a low-cost, high-efficiency wet coating process when preparing the graphene/PEDOT:PSS composite transparent conductive film, thereby avoiding expensive PVD equipment used in preparing the ITO film and reducing the production cost;
  • the graphene/PEDOT:PSS composite transparent conductive film prepared by the invention has high conductivity and high light transmittance, and can be used for replacing the commercial ITO film in the color filter substrate, and is used as the color transparent substrate in the IPS display mode.
  • the back electrode or the surface electrode of the color light-transmitting sheet substrate in the VA display mode and because of its excellent mechanical properties, has great application potential in flexible devices and wearable devices.

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Abstract

采用石墨烯与PEDOT:PSS溶液来制备一种用于制备透明导电膜的石墨烯/PEDOT:PSS混合溶液，所使用的材料来源广泛、价格低廉；石墨烯/PEDOT:PSS混合溶液可用于进一步在基板上制作石墨烯/PEDOT:PSS复合透明导电膜，由于制备石墨烯/PEDOT:PSS复合透明导电膜时采用低成本、高效率的湿法涂布工艺，避免了制备ITO膜时使用的昂贵的PVD设备，降低了生产成本；制备的石墨烯/PEDOT:PSS复合透明导电膜具有高导电性和高透光率，可用于彩色滤光片基板中取代商用ITO膜，并且由于其机械性能优良，在柔性器件、可穿戴设备中也具有很大的应用潜力。

Description

石墨烯/PEDOT:PSS混合溶液的制备方法及具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法 技术领域
本发明涉及显示器制造领域，尤其涉及一种石墨烯/PEDOT:PSS混合溶液的制备方法及具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法。
背景技术
在显示技术领域，液晶显示器(Liquid Crystal Display，LCD)与有机发光二极管显示器(Organic Light Emitting Diode，OLED)等平板显示器已经逐步取代CRT显示器，广泛的应用于液晶电视、手机、个人数字助理、数字相机、计算机屏幕或笔记本电脑屏幕等。
显示面板是LCD、OLED的重要组成部分，以LCD的显示面板为例，其主要是由一薄膜晶体管(Thin Film Transistor，TFT)基板、一彩色滤光片基板(Color Filter，CF)、以及配置于两基板间的液晶层(Liquid Crystal Layer)所构成，其工作原理是通过在TFT基板与CF基板上施加驱动电压来控制液晶层中液晶分子的旋转，将背光模组的光线折射出来产生画面，通过背光透过CF基板来提供不同的颜色。
在LCD显示器中，基于液晶的运作模式的分类有：相变(phase change，PC)、扭转向列(twisted nematic，TN)、超扭转向列(super twisted nematic，STN)、垂直配向型(Vertical Alignment，VA)、横向电场切换型(In plane Switching，IPS)等。当前，VA模式越来越多被人们所熟知，广泛应用于各类显示器中，通常VA模式显示器中，如图1所示，CF基板10由玻璃基板11，形成于玻璃基板11上的黑色矩阵12，形成于黑色矩阵12上的RGB彩色光阻层13，和形成于RGB彩色光阻层13上的透明导电膜14构成，其中透明导电膜14的作用是通过掺有导电金球(Au ball)的框胶与TFT基板上的导电膜导通，形成电场，驱动CF基板和TFT基板之间的液晶分子，控制液晶分子偏转，从而实现不同颜色的显示。而IPS模式在广视角液晶面板中得到了广泛的应用，在典型的IPS显示模式中，如图2所示，CF基板20的构造与VA模式中CF基板10的构造有所不同，该CF基板20除了由玻璃基板21，黑色矩阵22，彩色光阻层23，透明导电膜24构成以外， 在RGB彩色光阻层上有一层平坦化层25(over coat，OC层)，另外，透明导电膜24被置于玻璃基板21的背面(远离黑色矩阵22及彩色光阻层23的一侧)形成背面电极，用于泄放积累的静电。
目前，传统的透明导电膜是由物理气相溅射(PVD)的方法制备出的氧化铟锡(ITO)薄膜。具体制作过程为：在PVD装置中，强电流轰击ITO靶材，在基板上沉积得到透明导电ITO薄膜。但是由于ITO本身氧化物的物理特性，ITO薄膜并不能在一定外力作用下展现弯折特性，这也限制了其在柔性面板，可穿戴设备上的应用。另一方面，随着国家政策的导向，铟的成本也逐渐涨高。所以寻找高导电性和透光率、制备方法简单、资源丰富的ITO替代品具有重要的意义和价值。
石墨烯是具有优异的电导性和机械性能的二维材料，单层石墨烯的透光率约97.7％，常温下其电子迁移率超过15000cm2/V.s，而电阻率低至约10-8Ω·m，这些性能完全满足透明导电膜的要求。石墨烯粉末在强力超声和水系表面活性剂协助下，由于分子间斥力作用，能够形成浓度可控、分散均匀的石墨烯水溶液。另一方面，高柔性的PEDOT:PSS膜作为常用的有机透明导电膜涂料已经备受材料界关注，因为其溶液特性，可以使用常见的湿法涂布来制备PEDOT:PSS薄膜。相对于ITO膜，设备投入大幅降低，另外，PEDOT:PSS薄膜已经较早使用在防静电涂层，技术比较成熟。
发明内容
本发明的目的在于提供一种石墨烯/PEDOT:PSS混合溶液的制备方法，采用石墨烯与PEDOT:PSS溶液来制备一种用于制备透明导电膜的石墨烯/PEDOT:PSS混合溶液，所使用的材料来源广泛、价格低廉；所述石墨烯/PEDOT:PSS混合溶液可用于进一步制作石墨烯/PEDOT:PSS复合透明导电膜。
本发明的目的还在于提供一种具有石墨烯/PEDOT:PSS复合透明导电膜的制备方法，采用石墨烯与PEDOT:PSS溶液来制备石墨烯/PEDOT:PSS复合透明导电膜，材料来源广泛、价格低廉，且制作方法简单，降低了生产成本，所制备的石墨烯/PEDOT:PSS复合透明导电膜性能优异，可用于彩色滤光片基板中取代商用ITO导电膜，在柔性器件、可穿戴设备中也具有很大的应用潜力。
为实现上述目的，本发明提供一种石墨烯/PEDOT:PSS混合溶液的制备方法，包括以下步骤：
步骤1、按照石墨烯粉末、水系表面活性剂、及去离子水的质量比为1： 50～500：150～10000的比例将石墨烯粉末与水系表面活性剂投入去离子水中并进行超声分散，得到石墨烯分散液，对所述石墨烯分散液进行离心取上清液，得到石墨烯溶液；
步骤2、将所述石墨烯溶液与一定浓度的PEDOT:PSS稀释溶液按质量比为1：100至100：1的比例混合，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
所述步骤1中，所述水系表面活性剂为十二烷基硫酸钠、十二烷基硫酸铵、十二烷基磺酸钠、十二烷基苯磺酸钠或十四烷基硫酸钠。
所述步骤1中，采用高功率超声仪进行超声分散，超声功率为500～900W，超声时间为10～120min；对所述石墨烯分散液进行离心时离心机的转速为2000～5000rpm，离心时间为5～60min。
所述步骤1得到的石墨烯溶液中石墨烯的含量为0.1～5mg/ml；所述步骤2中所述PEDOT:PSS稀释溶液由去离子水与PEDOT:PSS溶液配制而成，且所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为1～100wt％。
本发明还提供一种具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，包括以下步骤：
步骤10、采用如权利要求1所述的制备方法制备石墨烯/PEDOT:PSS混合溶液；
步骤20、提供基板，采用湿法涂布工艺将所述石墨烯/PEDOT:PSS混合溶液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜；
步骤30、将成膜后的基板使用去离子水多次冲洗，以去除石墨烯/PEDOT:PSS薄膜内的水系表面活性剂，增加石墨烯/PEDOT:PSS薄膜的导电性；
步骤40、对所述石墨烯/PEDOT:PSS薄膜进行干燥处理，将薄膜内的水分去除，得到位于基板上的干燥的石墨烯/PEDOT:PSS复合透明导电膜。
所述步骤20中，所述基板为CF基板、普通玻璃基板、或者柔性基板；所述CF基板包括玻璃基板、及设于玻璃基板上的彩色光阻层和黑色矩阵。
所述步骤20中，所述湿法涂布工艺为喷涂、旋涂、辊涂、狭缝挤压涂布、浸涂、刮涂、凹版印刷、喷墨打印或者丝网印刷。
当所述湿法涂布工艺为喷涂时，所述步骤20为：提供基板，将所述基板放置在恒温加热板上，采用喷涂方式将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-120℃；
当所述湿法涂布工艺为旋涂、辊涂或者狭缝挤压涂布时，所述步骤20为：提供基板，将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，涂布后迅速将基板转移到恒温加热板上烘烤3-10min，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-140℃。
所述步骤40中的干燥处理工艺为自然干燥、氮气吹干或者在80-120℃环境中快速烘干。
所述步骤20中提供的基板为CF基板时，将石墨烯/PEDOT:PSS混合溶液涂布于CF基板上具有彩色光阻层的一侧或远离彩色光阻层的一侧。
本发明还提供一种具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，包括以下步骤：
步骤10、采用如权利要求1所述的制备方法制备石墨烯/PEDOT:PSS混合溶液；
步骤20、提供基板，采用湿法涂布工艺将所述石墨烯/PEDOT:PSS混合溶液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜；
步骤30、将成膜后的基板使用去离子水多次冲洗，以去除石墨烯/PEDOT:PSS薄膜内的水系表面活性剂，增加石墨烯/PEDOT:PSS薄膜的导电性；
步骤40、对所述石墨烯/PEDOT:PSS薄膜进行干燥处理，将薄膜内的水分去除，得到位于基板上的干燥的石墨烯/PEDOT:PSS复合透明导电膜；
其中，所述步骤20中，所述基板为CF基板、普通玻璃基板、或者柔性基板；所述CF基板包括玻璃基板、及设于玻璃基板上的彩色光阻层和黑色矩阵；
其中，所述步骤20中，所述湿法涂布工艺为喷涂、旋涂、辊涂、狭缝挤压涂布、浸涂、刮涂、凹版印刷、喷墨打印或者丝网印刷；
其中，所述步骤40中的干燥处理工艺为自然干燥、氮气吹干或者在80-120℃环境中快速烘干。
本发明的有益效果：本发明提供的一种石墨烯/PEDOT:PSS混合溶液的制备方法及具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，采用石墨烯与PEDOT:PSS溶液来制备一种用于制备透明导电膜的石墨烯/PEDOT:PSS混合溶液，所使用的材料来源广泛、价格低廉；所述石墨烯/PEDOT:PSS混合溶液可用于进一步在基板上制作石墨烯/PEDOT:PSS复合透明导电膜，由于制备石墨烯/PEDOT:PSS复合透明导电膜时采用低成本、高效率的湿法涂布工艺，避免了制备ITO膜时使用的昂贵的PVD设备，降低了生产成本；本发明制备的一种石墨烯/PEDOT:PSS复合透明导电膜具有 高导电性和高透光率，可用于彩色滤光片基板中取代商用ITO膜，作为IPS显示模式中彩色透光片基板的背面电极或者VA显示模式中彩色透光片基板的面电极，并且由于其机械性能优良，在柔性器件、可穿戴设备中也具有很大的应用潜力。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为VA模式显示器中CF基板的结构示意图；
图2为IPS模式显示器中CF基板的结构示意图；
图3为本发明的石墨烯/PEDOT:PSS混合溶液的制备方法的流程图；
图4为本发明的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法的第一实施例所得到的石墨烯/PEDOT:PSS复合透明导电膜的扫描电镜图；
图5为本发明的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法的第二实施例所得到的石墨烯/PEDOT:PSS复合透明导电膜的外观图片；
图6为本发明的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法的第二实施例所得到的石墨烯/PEDOT:PSS复合透明导电膜的扫描电镜图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
请参阅图3，本发明首先提供一种用于制备透明导电膜的石墨烯/PEDOT:PSS混合溶液的制备方法，包括以下步骤：
步骤1、按照石墨烯粉末、水系表面活性剂、及去离子水的质量比为1：50～500：150～10000的比例将石墨烯粉末与水系表面活性剂投入去离子水中并进行超声分散，得到石墨烯分散液，对所述石墨烯分散液进行离心取上清液，得到石墨烯溶液。
具体的，所述水系表面活性剂为十二烷基硫酸钠、十二烷基硫酸铵、十二烷基磺酸钠、十二烷基苯磺酸钠或十四烷基硫酸钠。
具体的，采用高功率超声仪进行超声分散，超声功率为500～900W，超声时间为10～120min。
具体的，对所述石墨烯分散液进行离心时离心机的转速为2000～5000rpm，离心时间为5～60min。
具体的，所述步骤1得到的石墨烯溶液中石墨烯的含量为0.1～5mg/ml。
步骤2、将所述石墨烯溶液与一定浓度的PEDOT:PSS(聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸))稀释溶液按质量比为1：100至100：1的比例混合，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
具体的，所述PEDOT:PSS稀释溶液由去离子水与PEDOT:PSS溶液配制而成，且所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为1～100wt％；当所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为100wt％时，所述PEDOT:PSS稀释溶液即为纯的PEDOT:PSS溶液。
具体的，所述PEDOT:PSS溶液为一种水溶液，由PEDOT(聚(3,4-亚乙二氧基噻吩)、PSS(聚(苯乙烯磺酸))、和水三种物质构成，其可以通过商业购买或者实验室配制获得，一般情况下，所述PEDOT:PSS溶液中PSS与PEDOT的质量比为1～5:1，且所述PEDOT与PSS两种物质的总量在所述PEDOT：PSS溶液中的质量百分比(即固含量)为1～6wt％。
本发明的石墨烯/PEDOT:PSS混合溶液的制备方法的具体实施例1：
按照石墨烯粉末、十二烷基硫酸钠、及去离子水的质量比为1：200：1800的比例将石墨烯粉末与十二烷基硫酸钠投入去离子水中，采用高功率超声仪进行分散，超声功率为900W，超声分散30min，得到石墨烯分散液，然后将石墨烯分散液离心，离心转速3000rpm，离心时间为30min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为0.5mg/ml；取一定量的PEDOT:PSS稀释溶液，将所述石墨烯溶液与PEDOT:PSS稀释溶液按质量比为50:1的比例进行混合，所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为50wt％，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、1wt％、98.5wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
本发明的石墨烯/PEDOT:PSS混合溶液的制备方法的具体实施例2：
按照石墨烯粉末、十二烷基硫酸钠、及去离子水的质量比为1：200：1050的比例将石墨烯粉末与十二烷基硫酸钠投入去离子水中，采用高功率超声仪进行分散，超声功率为500W，超声分散30min，然后将石墨烯分散 液离心，离心转速3000rpm，离心时间为30min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为0.8mg/ml；取一定量的PEDOT:PSS稀释溶液，将所述石墨烯溶液与PEDOT:PSS稀释溶液按质量比为50:1的比例进行混合，所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为50wt％，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、1.5wt％、98wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
本发明的石墨烯/PEDOT:PSS混合溶液的制备方法的具体实施例3：
按照石墨烯粉末、十二烷基硫酸铵、及去离子水的质量比为1：50：150的比例将石墨烯粉末与十二烷基硫酸铵投入去离子水中，采用高功率超声仪进行分散，超声功率为500W，超声分散10min，得到石墨烯分散液，然后将石墨烯分散液离心，离心转速2000rpm，离心时间为60min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为5mg/ml；取一定量的PEDOT:PSS稀释溶液，将所述石墨烯溶液与PEDOT:PSS稀释溶液按质量比为1:100的比例进行混合，所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为1wt％，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、2wt％、97.5wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
本发明的石墨烯/PEDOT:PSS混合溶液的制备方法的具体实施例4：
按照石墨烯粉末、十二烷基硫酸铵、及去离子水的质量比为1：100：9900的比例将石墨烯粉末与十二烷基硫酸铵投入去离子水中，采用高功率超声仪进行分散，超声功率900W，超声分散120min，得到石墨烯分散液，然后将石墨烯分散液离心，离心转速5000rpm，离心时间为5min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为0.1mg/ml；取一定量的PEDOT:PSS溶液，将所述石墨烯溶液与PEDOT:PSS溶液按质量比为100:1的比例进行混合，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、2.5wt％、97wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
基于上述石墨烯/PEDOT:PSS混合溶液的制备方法，本发明还提供一种具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法：
步骤10、采用上述方法制备石墨烯/PEDOT:PSS混合溶液。
步骤20、提供基板，采用湿法涂布工艺将所述石墨烯/PEDOT:PSS混合溶液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜。
具体的，所述基板可以为CF基板、普通玻璃基板、或者柔性基板。具 体的，所述CF基板包括基板、及设于基板上的黑色矩阵和彩色光阻层。
优选的，所述柔性基板为PET(聚对苯二甲酸乙二醇酯)基板。
具体的，所述湿法涂布工艺为喷涂、旋涂、辊涂、狭缝挤压涂布(slot-die)、浸涂、刮涂、凹版印刷、喷墨打印或者丝网印刷等方式。
具体地，当所述湿法涂布工艺为喷涂时，所述步骤20为：提供基板，将所述基板放置在恒温加热板上，采用喷涂方式将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-120℃。
具体的，采用喷涂工艺时，可以通过控制石墨烯/PEDOT:PSS混合液的用量，喷涂压力、时间和次数等因素来控制成膜的厚度。
当所述湿法涂布工艺为旋涂、辊涂或者狭缝挤压涂布时，所述步骤20为：提供基板，将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，涂布后迅速将基板转移到恒温加热板上烘烤3-10min，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-140℃。
具体的，采用旋涂工艺时，通过控制石墨烯/PEDOT:PSS混合液的用量，旋涂时间、速度和次数等因素来控制成膜的厚度。
步骤30、将成膜后的基板使用去离子水多次冲洗，以去除石墨烯/PEDOT:PSS薄膜内的水系表面活性剂，增加石墨烯/PEDOT:PSS薄膜的导电性。
步骤40、对所述石墨烯/PEDOT:PSS薄膜进行干燥处理，将薄膜内的水分去除，得到位于基板上的干燥的石墨烯/PEDOT:PSS复合透明导电膜。
具体的，所述步骤40中的干燥处理工艺为自然干燥、氮气吹干或者在80-140℃环境中快速烘干。
具体的，当所述步骤20中提供的基板为CF基板，并且将石墨烯/PEDOT:PSS混合溶液涂布于CF基板上具有彩色光阻层的一侧时，所述步骤40制得的石墨烯/PEDOT:PSS复合透明导电膜为VA显示模式中CF基板的面电极；
当所述步骤20中提供的基板为CF基板，并且将石墨烯/PEDOT:PSS混合溶液涂布于CF基板上远离彩色光阻层的一侧时，所述步骤40制得的石墨烯/PEDOT:PSS复合透明导电膜为IPS显示模式中CF基板的背面电极。
本发明的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法的具体实施例1：
按照石墨烯粉末、十二烷基硫酸钠、及去离子水的质量比为1：200：1800的比例将石墨烯粉末与十二烷基硫酸钠投入去离子水中，采用高功率 超声仪进行分散，超声功率为900W，超声分散30min，得到石墨烯分散液，然后将石墨烯分散液离心，离心转速3000rpm，离心时间为30min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为0.5mg/ml；取一定量的PEDOT:PSS稀释溶液，将所述石墨烯溶液与PEDOT:PSS稀释溶液按质量比为50:1的比例进行混合，所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为50wt％，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、1wt％、98.5wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。将10cm*10cm的彩色滤光片基板清洗干净后，置于旋涂机上，将3ml上述石墨烯/PEDOT:PSS混合溶液均匀涂布在彩色滤光片基板上具有彩色光阻层的一侧，开始旋涂，旋涂后将此彩色滤光片基板转移到80℃的恒温加热板上，烘干10分钟后，得到石墨烯/PEDOT:PSS薄膜，再使用去离子水多次冲洗去除石墨烯/PEDOT:PSS薄膜内残留的十二烷基硫酸钠，接着再用氮气吹干，即得到在彩色滤光片基板上的石墨烯/PEDOT:PSS复合透明导电膜。
图4为本实施例1所得到的石墨烯/PEDOT:PSS复合透明导电膜的扫描电镜(SEM)图，观察可知其膜表面均匀。用四探针法量测得该石墨烯/PEDOT:PSS复合透明导电膜的面电阻为204Ω/sq，用可见分光光度计在室温下量测其在550nm波长下的光透过率为85％。
本发明的具有石墨烯/PEDOT:PSS复合透明导电膜基板的的制备方法的具体实施例2：
按照石墨烯粉末、十二烷基硫酸钠、及去离子水的质量比为1：500：750的比例将石墨烯粉末与十二烷基硫酸钠投入去离子水中，采用高功率超声仪进行分散，超声功率为500W，超声分散30min，然后将石墨烯分散液离心，离心转速3000rpm，离心时间为30min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为0.8mg/ml；取一定量的PEDOT:PSS稀释溶液，将所述石墨烯溶液与PEDOT:PSS稀释溶液按质量比为50:1的比例进行混合，所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为50wt％，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、1.5wt％、98wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。将10cm*10cm的玻璃基板清洗干净后，置于旋涂机上，开始旋涂，将3ml上述混合溶液均匀涂布在玻璃基板上，旋涂后将此玻璃基板转移到140℃的恒温加热板上，烘干3分钟后，得到石墨烯/PEDOT:PSS薄膜，再使用去离子水多次冲洗去除石墨烯/PEDOT:PSS薄膜内残留的十二烷基硫酸钠，接着在空气中自然干燥，即得到在玻璃基板上 的石墨烯/PEDOT:PSS复合透明导电膜，其外观呈淡蓝色，图5为其外观图片。
图6为本实施例2所得到的石墨烯/PEDOT:PSS复合透明导电膜的扫描电镜图，观察可知其膜表面均匀，无明显凸起。用四探针法量测得该石墨烯/PEDOT:PSS复合透明导电膜的面电阻为207Ω/sq，用可见分光光度计在室温下量测其在550nm波长下的光透过率为91％。
本发明的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法的具体实施例3：
按照石墨烯粉末、十二烷基硫酸铵、及去离子水的质量比为1：50：150的比例将石墨烯粉末与十二烷基硫酸铵投入去离子水中，采用高功率超声仪进行分散，超声功率为500W，超声分散10min，得到石墨烯分散液，然后将石墨烯分散液离心，离心转速2000rpm，离心时间为60min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为5mg/ml；取一定量的PEDOT:PSS稀释溶液，将所述石墨烯溶液与PEDOT:PSS稀释溶液按质量比为1:100的比例进行混合，所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为1wt％，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、2wt％、97.5wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。将10cm*10cm的玻璃基板清洗干净后，转移到80℃的恒温加热板上，使用喷涂机对玻璃基板进行喷涂，将5ml上述混合溶液均匀喷涂在玻璃基板上，烘干后，得到石墨烯/PEDOT:PSS薄膜，再使用去离子水多次冲洗去除石墨烯/PEDOT:PSS薄膜内残留的十二烷基硫酸铵，接着在80℃环境中快速烘干，即得到在玻璃基板上的石墨烯/PEDOT:PSS复合透明导电膜。
本发明的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法的具体实施例4：
按照石墨烯粉末、十二烷基硫酸铵、及去离子水的质量比为1：100：9900的比例将石墨烯粉末与十二烷基硫酸铵投入去离子水中，采用高功率超声仪进行分散，超声功率900W，超声分散120min，得到石墨烯分散液，然后将石墨烯分散液离心，离心转速5000rpm，离心时间为5min，得到上清液，即为石墨烯溶液，所述石墨烯溶液中石墨烯的含量为0.1mg/ml；取一定量的PEDOT:PSS溶液，将所述石墨烯溶液与PEDOT:PSS溶液按质量比为100:1的比例进行混合，所述PEDOT:PSS溶液中PEDOT、PSS、及水的质量百分比分别为0.5wt％、2.5wt％、97wt％，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。将10cm*10cm的玻璃基板清洗干净后， 转移到120℃的恒温加热板上，使用喷涂机对玻璃基板进行喷涂，将5ml上述混合溶液均匀喷涂在玻璃基板上，烘干后，得到石墨烯/PEDOT:PSS薄膜，使用去离子水多次冲洗去除石墨烯/PEDOT:PSS薄膜内残留的十二烷基硫酸铵，然后在140℃环境中快速烘干，即得到在玻璃基板上的石墨烯/PEDOT:PSS复合透明导电膜。
综上所述，本发明提供的一种石墨烯/PEDOT:PSS混合溶液的制备方法及具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，采用石墨烯与PEDOT:PSS溶液来制备一种用于制备透明导电膜的石墨烯/PEDOT:PSS混合溶液，所使用的材料来源广泛、价格低廉；所述石墨烯/PEDOT:PSS混合溶液可用于进一步在基板上制作石墨烯/PEDOT:PSS复合透明导电膜，由于制备石墨烯/PEDOT:PSS复合透明导电膜时采用低成本、高效率的湿法涂布工艺，避免了制备ITO膜时使用的昂贵的PVD设备，降低了生产成本；本发明制备的一种石墨烯/PEDOT:PSS复合透明导电膜具有高导电性和高透光率，可用于彩色滤光片基板中取代商用ITO膜，作为IPS显示模式中彩色透光片基板的背面电极或者VA显示模式中彩色透光片基板的面电极，并且由于其机械性能优良，在柔性器件、可穿戴设备中也具有很大的应用潜力。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (13)

  1. 一种石墨烯/PEDOT:PSS混合溶液的制备方法，包括以下步骤：
    步骤1、按照石墨烯粉末、水系表面活性剂、及去离子水的质量比为1：50～500：150～10000的比例将石墨烯粉末与水系表面活性剂投入去离子水中并进行超声分散，得到石墨烯分散液，对所述石墨烯分散液进行离心取上清液，得到石墨烯溶液；
    步骤2、将所述石墨烯溶液与一定浓度的PEDOT:PSS稀释溶液按质量比为1：100至100：1的比例混合，超声处理后，得到分散均匀的石墨烯/PEDOT:PSS混合溶液。
  2. 如权利要求1所述的石墨烯/PEDOT:PSS混合溶液的制备方法，其中，所述步骤1中，所述水系表面活性剂为十二烷基硫酸钠、十二烷基硫酸铵、十二烷基磺酸钠、十二烷基苯磺酸钠或十四烷基硫酸钠。
  3. 如权利要求1所述的石墨烯/PEDOT:PSS混合溶液的制备方法，其中，所述步骤1中，采用高功率超声仪进行超声分散，超声功率为500～900W，超声时间为10～120min；对所述石墨烯分散液进行离心时离心机的转速为2000～5000rpm，离心时间为5～60min。
  4. 如权利要求1所述的石墨烯/PEDOT:PSS混合溶液的制备方法，其中，所述步骤1得到的石墨烯溶液中石墨烯的含量为0.1～5mg/ml；所述步骤2中所述PEDOT:PSS稀释溶液由去离子水与PEDOT:PSS溶液配制而成，且所述PEDOT:PSS稀释溶液中PEDOT:PSS溶液的质量百分比为1～100wt％。
  5. 一种具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，包括以下步骤：
    步骤10、采用如权利要求1所述的制备方法制备石墨烯/PEDOT:PSS混合溶液；
    步骤20、提供基板，采用湿法涂布工艺将所述石墨烯/PEDOT:PSS混合溶液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜；
    步骤30、将成膜后的基板使用去离子水多次冲洗，以去除石墨烯/PEDOT:PSS薄膜内的水系表面活性剂，增加石墨烯/PEDOT:PSS薄膜的导电性；
    步骤40、对所述石墨烯/PEDOT:PSS薄膜进行干燥处理，将薄膜内的水分去除，得到位于基板上的干燥的石墨烯/PEDOT:PSS复合透明导电膜。
  6. 如权利要求5所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，所述步骤20中，所述基板为CF基板、普通玻璃基板、或者柔性基板；所述CF基板包括玻璃基板、及设于玻璃基板上的彩色光阻层和黑色矩阵。
  7. 如权利要求5所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，所述步骤20中，所述湿法涂布工艺为喷涂、旋涂、辊涂、狭缝挤压涂布、浸涂、刮涂、凹版印刷、喷墨打印或者丝网印刷。
  8. 如权利要求7所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，当所述湿法涂布工艺为喷涂时，所述步骤20为：提供基板，将所述基板放置在恒温加热板上，采用喷涂方式将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-120℃；
    当所述湿法涂布工艺为旋涂、辊涂或者狭缝挤压涂布时，所述步骤20为：提供基板，将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，涂布后迅速将基板转移到恒温加热板上烘烤3-10min，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-140℃。
  9. 如权利要求5所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，所述步骤40中的干燥处理工艺为自然干燥、氮气吹干或者在80-120℃环境中快速烘干。
  10. 如权利要求5所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，所述步骤20中提供的基板为CF基板时，将石墨烯/PEDOT:PSS混合溶液涂布于CF基板上具有彩色光阻层的一侧或远离彩色光阻层的一侧。
  11. 一种具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，包括以下步骤：
    步骤10、采用如权利要求1所述的制备方法制备石墨烯/PEDOT:PSS混合溶液；
    步骤20、提供基板，采用湿法涂布工艺将所述石墨烯/PEDOT:PSS混合溶液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜；
    步骤30、将成膜后的基板使用去离子水多次冲洗，以去除石墨烯/PEDOT:PSS薄膜内的水系表面活性剂，增加石墨烯/PEDOT:PSS薄膜的导电性；
    步骤40、对所述石墨烯/PEDOT:PSS薄膜进行干燥处理，将薄膜内的水分去除，得到位于基板上的干燥的石墨烯/PEDOT:PSS复合透明导电膜；
    其中，所述步骤20中，所述基板为CF基板、普通玻璃基板、或者柔性基板；所述CF基板包括玻璃基板、及设于玻璃基板上的彩色光阻层和黑色矩阵；
    其中，所述步骤20中，所述湿法涂布工艺为喷涂、旋涂、辊涂、狭缝挤压涂布、浸涂、刮涂、凹版印刷、喷墨打印或者丝网印刷；
    其中，所述步骤40中的干燥处理工艺为自然干燥、氮气吹干或者在80-120℃环境中快速烘干。
  12. 如权利要求11所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，当所述湿法涂布工艺为喷涂时，所述步骤20为：提供基板，将所述基板放置在恒温加热板上，采用喷涂方式将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-120℃；
    当所述湿法涂布工艺为旋涂、辊涂或者狭缝挤压涂布时，所述步骤20为：提供基板，将所述石墨烯/PEDOT:PSS混合液涂布于所述基板上，涂布后迅速将基板转移到恒温加热板上烘烤3-10min，进行成膜，得到石墨烯/PEDOT:PSS薄膜，所述恒温加热板的温度范围为80-140℃。
  13. 如权利要求11所述的具有石墨烯/PEDOT:PSS复合透明导电膜的基板的制备方法，其中，所述步骤20中提供的基板为CF基板时，将石墨烯/PEDOT:PSS混合溶液涂布于CF基板上具有彩色光阻层的一侧或远离彩色光阻层的一侧。
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* Cited by examiner, † Cited by third party
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* Cited by examiner, † Cited by third party
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CN112151768B (zh) * 2020-09-11 2021-10-08 成都新柯力化工科技有限公司 一种挤出压延制备硅碳负极电极片的方法及电极片
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KR20250010239A (ko) * 2023-07-12 2025-01-21 엘지디스플레이 주식회사 표시패널용 모기판과 이를 이용한 표시패널

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110090398A (ko) * 2010-02-03 2011-08-10 삼성테크윈 주식회사 그래핀 패턴 형성 방법
CN103903818A (zh) * 2014-04-08 2014-07-02 国家纳米科学中心 一种大面积石墨烯透明导电膜的制备方法
CN104593130A (zh) * 2014-12-29 2015-05-06 北京航空航天大学 一种原位制备石墨烯水基润滑剂的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7449133B2 (en) * 2006-06-13 2008-11-11 Unidym, Inc. Graphene film as transparent and electrically conducting material
WO2012108371A1 (ja) * 2011-02-09 2012-08-16 株式会社インキュベーション・アライアンス 多層グラフェン被覆基板の製造方法
US8858776B2 (en) * 2011-06-28 2014-10-14 Academia Sinica Preparation of graphene sheets
TWI457409B (zh) * 2011-12-28 2014-10-21 Taiwan Textile Res Inst 透明導電塗佈液／薄膜及其製備方法
GB201218952D0 (en) * 2012-10-22 2012-12-05 Cambridge Entpr Ltd Functional inks based on layered materials and printed layered materials
WO2014076259A1 (en) * 2012-11-15 2014-05-22 Solvay Sa Film forming composition comprising graphene material and conducting polymer
CN103365004B (zh) * 2013-07-26 2016-04-13 深圳市华星光电技术有限公司 透明导电层、具有该透明导电层的cf基板及其制备方法
CN103943790B (zh) * 2014-04-23 2016-03-30 福州大学 一种石墨烯复合柔性透明电极及其制备方法
CN104291328B (zh) * 2014-09-25 2017-04-12 深圳粤网节能技术服务有限公司 石墨烯材料的分级分离方法
CN104465993A (zh) * 2014-10-28 2015-03-25 南昌大学 一种碳基复合透明电极及制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110090398A (ko) * 2010-02-03 2011-08-10 삼성테크윈 주식회사 그래핀 패턴 형성 방법
CN103903818A (zh) * 2014-04-08 2014-07-02 国家纳米科学中心 一种大面积石墨烯透明导电膜的制备方法
CN104593130A (zh) * 2014-12-29 2015-05-06 北京航空航天大学 一种原位制备石墨烯水基润滑剂的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721282A (zh) * 2019-02-18 2019-05-07 中山市君泽科技有限公司 一种基于石墨烯的水性浆料制备方法
CN118299185A (zh) * 2024-05-28 2024-07-05 南京星梵电子科技有限公司 一种高压稳定的固态电解电容器及其制备方法

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