WO2016011794A1 - 一种透明导电电极及其制备方法、oled显示器件 - Google Patents

一种透明导电电极及其制备方法、oled显示器件 Download PDF

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WO2016011794A1
WO2016011794A1 PCT/CN2015/070291 CN2015070291W WO2016011794A1 WO 2016011794 A1 WO2016011794 A1 WO 2016011794A1 CN 2015070291 W CN2015070291 W CN 2015070291W WO 2016011794 A1 WO2016011794 A1 WO 2016011794A1
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polymer
electrode
dielectric layer
tungsten trioxide
layer
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PCT/CN2015/070291
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English (en)
French (fr)
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尤娟娟
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京东方科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates

Definitions

  • the present invention relates to the field of display technologies, and in particular, to a transparent conductive electrode, a method for fabricating the same, and an OLED display device.
  • ITO Indium Tin Oxides
  • OLED organic light emitting diode
  • a conventional OLED display device uses an ITO electrode and a metal electrode (such as silver, magnesium, aluminum, etc.) as an anode and a cathode, an anode and a cathode, respectively.
  • a metal electrode such as silver, magnesium, aluminum, etc.
  • the luminescence of the device can be observed from the transparent ITO side, and the metal cathode acts as a reflective layer.
  • ITO has a relatively good light transmittance (>90%)
  • its application also has many limitations, such as: a) poor conductivity; b) indium required for the preparation of ITO is a rare metal, in the earth's crust The distribution is relatively small and very dispersed; c) ITO has poor ductility and is not suitable for flexible substrates.
  • metal electrodes have good electrical conductivity, ductility, and a rich source, the light transmittance of metals is poor.
  • Ag silver
  • Embodiments of the present invention provide a transparent conductive electrode, a method for fabricating the same, and an OLED display device, which can solve the problem that the transparent conductive electrode in the prior art cannot simultaneously integrate electrical conductivity, light transmittance, and ductility.
  • a method of preparing a transparent conductive electrode comprising:
  • the mixed solution doped with the polymer solution is prepared by a solution method to form a doped polymer tungsten oxide dielectric layer on a substrate, including:
  • the polymer solution is doped in a tungstic acid solution to form the mixed solution; the mixed solution is applied onto the substrate by spin coating, and baked to obtain a doped polymer.
  • a tungsten trioxide dielectric layer is described.
  • the doping ratio of the polymer in the tungsten trioxide dielectric layer is 1-5 wt%.
  • the polymer is at least one of a modified polysiloxane, a fluorocarbon modified polymer, a small molecule fluorocarbon, a polymeric fluorocarbon, and an acrylate copolymer.
  • the thickness of the tungsten trioxide dielectric layer is 20 nm
  • the thickness of the Ag electrode layer is 10 nm
  • the polymer is a hydroxy-functional silicone-modified polyacrylate, and the hydroxy-functional silicone is modified.
  • the doping ratio of the polyacrylate in the tungsten trioxide dielectric layer is 3 wt%; or
  • the thickness of the tungsten trioxide dielectric layer is 20 nm, the thickness of the Ag electrode layer is 7 nm; the polymer is a fluorocarbon modified polymer, and the fluorocarbon modified polymer is in the tungsten trioxide dielectric layer
  • the doping ratio in the middle is 3 wt%.
  • a transparent conductive electrode comprising a tungsten trioxide dielectric layer and an Ag electrode layer; wherein the tungsten trioxide dielectric layer is doped with a polymer.
  • the doping ratio of the polymer in the tungsten trioxide dielectric layer is 1-5 wt%.
  • the polymer is at least one of a modified polysiloxane, a fluorocarbon modified polymer, a small molecule fluorocarbon, a polymeric fluorocarbon, and an acrylate copolymer.
  • the tungsten trioxide dielectric layer has a thickness of 20 nm, and the Ag electrode layer has a thickness of 10 nm;
  • the polymer is a hydroxy-functional silicone-modified polyacrylate, and the hydroxy-functional silicone-modified a doping ratio of the polyacrylate in the tungsten trioxide dielectric layer is 3 wt%; or
  • the thickness of the tungsten trioxide dielectric layer is 20 nm, the thickness of the Ag electrode layer is 7 nm; the polymer is a fluorocarbon modified polymer, and the fluorocarbon modified polymer is in the tungsten trioxide dielectric layer
  • the doping ratio in the middle is 3 wt%.
  • an OLED display device including a plurality of sub-pixels, each of the sub-pixels including a first electrode, an organic material functional layer, and a second electrode disposed sequentially on a substrate substrate, wherein the first The electrode is the transparent conductive electrode according to any one of the above.
  • the second electrode is an opaque metal electrode, or a transparent metal electrode, or an ITO electrode.
  • the OLED display device further includes a thin film transistor disposed between the substrate and the first electrode; wherein a drain of the thin film transistor is electrically connected to the first electrode.
  • the base substrate is a flexible base substrate.
  • An embodiment of the present invention provides a method for preparing a transparent conductive electrode, comprising: preparing a doped polymer-forming tungsten trioxide dielectric layer on a substrate by a solution solution doped with a polymer solution; The mixed solution has a surface tension of 10 to 50 mN/m; and an Ag electrode layer is formed on the tungsten trioxide dielectric layer.
  • the mixed solution has a lower surface tension, thereby The formed tungsten trioxide dielectric layer has a high surface smoothness, so that a continuous and smooth Ag electrode layer can be formed thereon, on the basis of which the formation of grain boundaries can be reduced, thereby improving the Ag electrode.
  • the conductive properties of the layer on the other hand, the smooth Ag electrode layer can reduce light scattering, thereby increasing the light transmittance; and, due to the presence of the tungsten trioxide dielectric layer doped with the polymer, it can change the Ag electrode layer.
  • the electric field can change the direction of the surface plasmon electromagnetic wave at the interface of the Ag electrode layer, thereby suppressing the light loss caused by the surface plasmon and further improving the light transmittance.
  • the transparent conductive electrode provided by the embodiment of the present invention has better ductility due to the use of the Ag electrode layer.
  • the transparent conductive electrode provided by the embodiment of the invention can solve the problem that the transparent ITO or Ag conductive electrode in the prior art cannot simultaneously integrate electrical conductivity, light transmittance and ductility.
  • FIG. 1 is a schematic flow chart of preparing a transparent conductive electrode according to an embodiment of the present invention
  • FIG. 2 is a schematic structural diagram of a transparent conductive electrode according to an embodiment of the present invention.
  • FIG. 3 is a schematic structural diagram 1 of an OLED display device according to an embodiment of the present invention.
  • FIG. 4 is a schematic structural diagram of a sub-pixel of an OLED display device according to an embodiment of the present invention.
  • 10-transparent conductive electrode 101-WO 3 dielectric layer; 102-Ag electrode layer; 20-sub-pixel; 201-first electrode; 202-organic material functional layer; 203-second electrode; 204-thin film transistor.
  • the embodiment of the invention provides a method for preparing a transparent conductive electrode. As shown in FIG. 1 , the method includes the following steps:
  • the mixed solution should include a solution capable of obtaining WO 3 in addition to the polymer solution, such as tungstic acid. Solution.
  • the WO 3 dielectric layer is prepared by a solution method, that is, the above mixed solution is applied to the substrate by spin coating, for example, and then the WO 3 dielectric doped with the polymer is formed by a related process.
  • the mixed solution has a low surface tension due to the incorporation of the polymer, and the solution molecules coated on the substrate can be avoided, resulting in the formation of the WO 3 dielectric layer being uneven, that is, The polymer improves the wetting and leveling effect of the WO 3 dielectric layer, resulting in a higher surface smoothness.
  • the polymer it may be at least one of a modified polysiloxane, a fluorocarbon modified polymer, a small molecule fluorocarbon, a polymeric fluorocarbon, and an acrylate copolymer.
  • the modified polysiloxane may be selected from a hydroxy-functional silicone-modified polyacrylate (BYK-SILCLEAN 3700) in a methoxypropyl acetate solvent, and a polyether-modified acryl-functional polydimethylene.
  • a siloxane BYK-SILCLEAN 3710
  • a polyether-modified hydroxy-functional polydimethylsiloxane BYK-SILCLEAN 3720
  • the fluorocarbon modified polymer, small molecule fluorocarbon, polymeric fluorocarbon may be selected from AFCONA-3037, AFCONA-3772, AFCONA-3777, AFCONA-3700, etc.
  • the acrylate copolymer may be selected from Wait.
  • the formation of the Ag electrode layer may be performed by vacuum thermal evaporation.
  • the substrate may be a transparent substrate that is not provided with any pattern layer, or may be a substrate on which a corresponding pattern layer is disposed on the transparent substrate, which is not limited herein.
  • the transparent substrate substrate it may be a transparent glass substrate; or may be a transparent flexible substrate substrate.
  • the flexible substrate in the process of preparing the transparent conductive electrode, the flexible substrate may be After the preparation of the transparent conductive electrode is completed, the hard carrier substrate is peeled off, which may be carried out according to actual conditions, and is not limited herein.
  • the amount of the polymer doped in, for example, a tungstic acid solution is not limited to improve the surface smoothness of the WO 3 dielectric layer, thereby improving the conductivity of the Ag electrode layer and increasing the transmittance.
  • Embodiments of the present invention provide a method for preparing a transparent conductive electrode, comprising: preparing a doped polymer-forming WO 3 dielectric layer on a substrate by a solution solution doped with a polymer solution; The surface tension of the mixed solution was 10-50 mN/m; an Ag electrode layer was formed on the WO 3 dielectric layer.
  • the mixed solution doped with the polymer is used in the process of preparing the WO 3 dielectric layer by the solution method, by doping the polymer, the mixed solution has a lower surface tension, thereby forming
  • the WO 3 dielectric layer has a high surface smoothness, so that a continuous and smooth Ag electrode layer can be formed thereon, on the basis of which the formation of grain boundaries can be reduced, thereby improving the Ag electrode layer.
  • a smooth Ag electrode layer can reduce light scattering, thereby increasing light transmittance; and, due to the presence of a WO 3 dielectric layer doped with the polymer, it can change the electric field of the Ag electrode layer, thereby The direction of the surface plasmon electromagnetic wave at the interface of the Ag electrode layer can be changed, thereby further suppressing the light loss caused by the surface plasmon and further improving the light transmittance.
  • the transparent conductive electrode provided by the embodiment of the present invention has better ductility due to the use of the Ag electrode layer.
  • the transparent conductive electrode provided by the embodiment of the invention can solve the problem that the transparent ITO or Ag conductive electrode in the prior art cannot simultaneously integrate electrical conductivity, light transmittance and ductility.
  • step S01 can be implemented by the following steps:
  • the polymer solution is doped in a solution of tungstic acid (H 2 WO 4 ) to form the mixed solution; wherein the mixed solution has a surface tension of 10 to 50 mN/m.
  • H 2 WO 4 tungstic acid
  • the H 2 WO 4 solution can be obtained by passing an aqueous solution of sodium tungstate (Na 2 WO 4 ) through a cation exchange resin such as RSO 3 Na.
  • the purpose of baking is: on the one hand, evaporating the solvent in the H 2 WO 4 solution, and decomposing H 2 WO 4 into WO 3 and water (H 2 O), and evaporating the water during the baking process.
  • the solvent in the polymer solution is evaporated; and in the process, the polymer is not affected, so that the WO 3 dielectric layer doped with the polymer can be formed.
  • the substrate coated with the mixed solution may be baked at a temperature of 150 to 200 ° C for 1-2 hours.
  • the doping ratio of the polymer in the WO 3 dielectric layer is 1-5 wt%.
  • the prepared WO 3 dielectric layer can be made to have a better surface smoothness, so that the Ag electrode layer which can be formed thereon is smoother, thereby making it have higher light transmittance and electrical conductivity.
  • the embodiment of the present invention preferably sets the thickness of the WO 3 dielectric layer to 10-50 nm, and sets the thickness of the Ag electrode layer. It is 7-25 nm.
  • the embodiments of the present invention provide several specific experiments to pass the experiments.
  • the data is used to illustrate that the transparent conductive electrode can simultaneously combine electrical conductivity and light transmittance.
  • a 7 nm Ag electrode layer was prepared by vacuum thermal evaporation, the surface roughness Rq was measured by atomic force microscopy (AFM), the surface resistance was tested by a four-probe method, and the light transmittance was measured by an optical transmittance tester. Rate, the test results are as shown in the first row of Table 1.
  • the aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and 10 mL of a 1 mol/L H 2 WO 4 solution is applied to the substrate by spin coating.
  • a 20 nm WO 3 dielectric layer was obtained, and finally a 10 nm Ag electrode layer was prepared by vacuum thermal evaporation; the surface roughness Rq was measured by atomic force microscopy, and the surface resistance was tested by a four-probe method.
  • the light transmittance was measured by an optical transmittance tester, and the test results were as shown in the second row of Table 1.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 1 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • BYK-SILCLEAN 3700 in isopropanol solution the mixed solution was applied to the substrate by spin coating, and baked at 200 ° C for 1 hour to obtain 20 nm WO 3 dielectric layer doped with 1 wt% BYK-SILCLEAN 3700.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 3 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • An isopropanol solution of BYK-SILCLEAN 3700 the mixed solution was applied to the substrate by spin coating, and baked at 200 ° C for 1 hour to obtain a 20 nm WO 3 dielectric layer doped with 3 wt% of BYK-SILCLEAN 3700.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 5 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • BYK-SILCLEAN3700 in isopropanol solution the mixed solution was applied to the substrate by spin coating, and baked at 200 ° C for 1 hour to obtain 20 nm WO 3 dielectric layer doped with 5 wt% BYK-SILCLEAN 3700.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 3 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 3 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then, in 10 mL of a 1 mol/L H 2 WO 4 solution, 2.5 g of a mass percentage of 3 wt% is blended.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 3 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • an aqueous solution of Na 2 WO 4 is passed through a strong acid type cation exchange resin to obtain a H 2 WO 4 solution, and then 2.5 g of a mass percentage of 3 wt% is blended in 10 mL of a 1 mol/L H 2 WO 4 solution.
  • Isopropanol solution the mixed solution was applied to a polyethylene terephthalate (PET) flexible substrate by spin coating, and baked at 200 ° C for 1 hour to obtain a doping of 20 nm at 3 nm.
  • PET polyethylene terephthalate
  • the WO 3 dielectric layer is finally prepared by vacuum thermal evaporation to prepare a 10 nm Ag electrode layer; the surface roughness Rq is tested by atomic force microscopy, the surface resistance is tested by the four-probe method, and the optical transmittance tester is used to test the surface resistance. Light rate, the test results are as shown in the tenth row of Table 1.
  • the third to tenth embodiments of the transparent conductive electrode provided by the embodiment of the present invention have a significantly increased light transmittance and a surface thereof.
  • the resistance is also significantly reduced, that is, the conductivity is significantly improved.
  • Embodiment 3 to Embodiment 5 it can be seen from the above-mentioned Embodiment 3 to Embodiment 5 that under the same conditions, the smaller the roughness of the transparent conductive electrode, the larger the light transmittance and the smaller the surface resistance; and the roughness is directly related to the polymer.
  • the doping ratio is related.
  • the transparent conductive electrode provided by the embodiment of the invention can have high conductivity and high light transmittance at the same time.
  • the doping ratio of the BYK-SILCLEAN 3700 in the tungsten trioxide dielectric layer is 3 wt%, and the tungsten trioxide
  • the thickness of the dielectric layer is 20 nm, and when the thickness of the Ag electrode layer is 10 nm, the transparent conductive electrode has higher light transmittance and lower sheet resistance.
  • the transparent conductive electrode has the highest permeability. Light rate and relatively low sheet resistance.
  • the embodiment of the present invention provides a transparent conductive electrode 10 prepared by the above method.
  • the transparent conductive electrode 10 includes: a WO 3 dielectric layer 101 and an Ag electrode layer 102; wherein the WO 3 dielectric layer It is doped with a polymer.
  • the polymer may be at least one of a modified polysiloxane, a fluorocarbon modified polymer, a small molecule fluorocarbon, a polymeric fluorocarbon, and an acrylate copolymer.
  • the modified polysiloxane may be selected from a hydroxy-functional silicone-modified polyacrylate (BYK-SILCLEAN 3700) in a methoxypropyl acetate solvent, and a polyether-modified acryl-functional polydimethylene.
  • a siloxane BYK-SILCLEAN 3710
  • a polyether-modified hydroxy-functional polydimethylsiloxane BYK-SILCLEAN 3720
  • the fluorocarbon modified polymer, small molecule fluorocarbon, polymeric fluorocarbon may be selected from AFCONA-3037, AFCONA-3772, AFCONA-3777, AFCONA-3700, etc.
  • the acrylate copolymer may be selected from Wait.
  • the embodiment of the present invention provides a transparent conductive electrode 10 comprising: a WO 3 dielectric layer 101 and an Ag electrode layer 102; wherein the WO 3 dielectric layer 101 is doped with a polymer.
  • the mixed solution doped with the polymer is used in the process of forming the WO 3 dielectric layer 101 by the solution method, by doping the polymer, the mixed solution has a lower surface tension, thereby The formed WO 3 dielectric layer 101 has a high surface smoothness, so that a continuous and smooth Ag electrode layer 102 can be formed thereon, on the basis of which the formation of grain boundaries can be reduced, thereby improving Ag.
  • the conductive property of the electrode layer 102 on the other hand, the smooth Ag electrode layer 102 can reduce light scattering, thereby improving light transmittance; and, due to the presence of the WO 3 dielectric layer 101 doped with the polymer, it can change Ag
  • the electric field of the electrode layer 102 can change the direction of the surface plasmon electromagnetic wave at the interface of the Ag electrode layer 102, thereby suppressing the light loss caused by the surface plasmon and further improving the light transmittance.
  • the transparent conductive electrode 10 provided by the embodiment of the present invention has better ductility due to the use of the Ag electrode layer 102.
  • the transparent conductive electrode 10 provided by the embodiment of the present invention can solve the problem that the transparent ITO or Ag conductive electrode in the prior art cannot simultaneously integrate electrical conductivity, light transmittance and ductility.
  • the doping ratio of the polymer in the WO 3 dielectric layer 101 is 1-5 wt%.
  • the prepared layer of the WO 3 dielectric 101 can have a better surface smoothness, so that the Ag electrode layer 102 formed thereon is smoother, thereby giving it higher transmittance and electrical conductivity.
  • the embodiment of the present invention preferably sets the thickness of the WO 3 dielectric layer 101 to 10 to 50 nm, and the Ag electrode layer.
  • the thickness is set to 7-25 nm.
  • the thickness of the tungsten trioxide dielectric layer is 20 nm, the thickness of the Ag electrode layer is 10 nm; the polymer is BYK-SILCLEAN 3700, and the BYK-SILCLEAN 3700 is in the tungsten trioxide dielectric layer.
  • the doping ratio was 3 wt%.
  • the thickness of the tungsten trioxide dielectric layer is 20 nm, the thickness of the Ag electrode layer is 7 nm; the polymer is a fluorocarbon modified polymer such as Said The doping ratio in the tungsten trioxide dielectric layer was 3 wt%.
  • an embodiment of the present invention further provides an OLED display device.
  • the OLED display device includes a plurality of sub-pixels 20, each of the sub-pixels including a first electrode 201 sequentially disposed above the substrate substrate, and an organic The material functional layer 202 and the second electrode 203, wherein the first electrode is the transparent conductive electrode 10 described above.
  • the WO 3 dielectric layer 101 forming the transparent conductive electrode 10 is prepared by a solution method, a mixed solution doped with a polymer is used, and by doping the polymer, the mixed solution has a lower The surface tension is such that the formed WO 3 dielectric layer 101 has a high surface smoothness, so that a continuous and smooth Ag electrode layer 102 can be formed thereon, on the one hand, the grain boundary can be reduced on the one hand.
  • the smooth Ag electrode layer 102 can reduce light scattering, thereby increasing light transmittance; and, due to the presence of the WO 3 dielectric layer 101 doped with the polymer It can change the electric field of the Ag electrode layer 102, so that the direction of the surface plasmon electromagnetic wave at the interface of the Ag electrode layer 102 can be changed, thereby suppressing the light loss caused by the surface plasmon and further improving the light transmittance.
  • the transparent conductive electrode provided by the embodiment of the present invention has better ductility due to the use of the Ag electrode layer 102.
  • the transparent conductive electrode provided by the embodiment of the invention can solve the problem that the transparent ITO or Ag conductive electrode in the prior art cannot simultaneously integrate electrical conductivity, light transmittance and ductility.
  • the organic material functional layer 202 which may include at least a light-emitting layer, in order to improve the efficiency of electron and hole injection into the light-emitting layer, the organic material functional layer 202 may further include an electron transport layer and a hole.
  • the transport layer may further include a functional layer such as an electron injection layer and a hole injection layer. Based on this, the order of forming the layers of the organic material functional layer 202 may be, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • the organic material layer of each layer of the organic material functional layer 202 may be a small molecule or a polymer material, and if it is a small molecule material, it may be formed by vacuum evaporation, and if it is a polymer material, spin coating may be used. It is formed by inkjet or screen printing.
  • the OLED display device can be classified into a bottom emission type and a double-sided emission type.
  • the second electrode 203 is an opaque metal electrode, since the light is emitted from the first electrode 201 and then through the substrate substrate side, it may be referred to as a bottom emission type;
  • the second electrode 203 is In the case of a transparent metal electrode, since light is emitted from the first electrode 201 and then through the substrate substrate side, and on the other hand, from the second electrode 203 and through the encapsulation layer disposed opposite to the substrate substrate, it can be called Double-sided light type.
  • the material of the metal electrode may be, for example, calcium, magnesium, aluminum, silver, or the like.
  • the opaque metal electrode has a thicker thickness of the metal electrode, and the transparent metal electrode has a thinner thickness of the metal electrode.
  • each layer of the organic material functional layer 202 may also be an electron injection layer.
  • the second electrode 203 is an ITO electrode.
  • the OLED display device is an inverted OLED device.
  • the OLED display device may further include a thin film transistor 204;
  • the thin film transistor 204 includes a gate electrode, a gate insulating layer, a semiconductor active layer, a source and a drain; and a drain of the thin film transistor is electrically connected to the first electrode 201.
  • the OLED display further includes a gate line electrically connected to the gate, a gate line lead (not shown), and a data line and a data line lead electrically connected to the source (in the figure) Not identified) and so on.
  • the thin film transistor 204 is a semiconductor unit having a switching characteristic, and may be a top gate type or a bottom gate type, which is not limited herein.
  • the flexible display has many advantages, such as impact resistance, strong shock resistance, light weight, small size, and more convenient carrying. Therefore, the OLED display device provided by the embodiment of the present invention may also be a flexible display device.
  • the base substrate is a flexible base substrate.
  • the material of the flexible substrate can be polyimide, polycarbonate, polyacrylate, polyetherimide, polyethersulfone, polyethylene terephthalate and polyethylene naphthalate Glycol esters and the like.

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Abstract

一种透明导电电极及其制备方法、OLED显示器件。可解决透明导电电极不能同时综合导电性、透光率及延展性的问题。该透明导电电极（10）的制备方法包括：将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂该聚合物的三氧化钨电介质层（101）；其中，该混合溶液的表面张力为10-50mN/m；在该三氧化钨电介质层（101）上制备形成Ag电极层（102）。用于透明导电电极（10）、OLED显示器件的制造。

Description

一种透明导电电极及其制备方法、OLED显示器件 技术领域
本发明涉及显示技术领域，尤其涉及一种透明导电电极及其制备方法、OLED显示器件。
背景技术
铟锡氧化物(Indium Tin Oxides，简称ITO)具有导电性和透明性，因此是透明导电电极最常用的薄膜材料。以有机发光二极管(Organic Light Emitting Diode，简称OLED)显示器件为例，传统的OLED显示器件采用ITO电极和金属电极(如：银、镁、铝等)分别作为器件的阳极和阴极，阳极和阴极之间为有机材料功能层，器件的发光可从透明的ITO一侧观察到，金属阴极起到了反射层的作用。
然而，ITO虽然具有比较好的透光率(>90％)，但其应用也存在诸多限制，例如：a)导电性比较差；b)制备ITO所需要的铟属于稀有金属，在地壳中的分布量比较小，又很分散；c)ITO延展性比较差，不适用于柔性基板。与之相反的是，金属电极虽然具有较好的导电性、延展性以及较为丰富的来源，但是金属的透光性较差。目前，比较常见的是用Ag(银)电极代替透明ITO导电电极，因为Ag的透光率在金属中是比较高的，但是为了获得较高的透光率，必须将Ag电极制备的非常薄，而Ag电极越薄，其导电性越差。
因此，如何发展同时具有高导电性、透光率及延展性的透明导电电极，是目前亟需研究的重点之一。
发明内容
本发明的实施例提供一种透明导电电极及其制备方法、OLED显示器件，可解决现有技术中透明导电电极不能同时综合导电性、透光率及延展性的问题。
为达到上述目的，本发明的实施例采用如下技术方案：
一方面，提供一种透明导电电极的制备方法，该方法包括：
将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的三氧化钨电介质层；其中，所述混合溶液的表面张力为10-50mN/m；在所述三氧化钨电介质层上制备形成Ag电极层。
例如，所述将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的三氧化钨电介质层，包括：
在钨酸溶液中掺入所述聚合物溶液，形成所述混合溶液；采用旋涂方式将所述混合溶液涂覆到所述基板上，并进行烘烤，得到掺杂所述聚合物的所述三氧化钨电介质层。
例如，所述聚合物在所述三氧化钨电介质层中的掺杂比例为1-5wt％。
基于上述，例如，所述聚合物为改性聚硅氧烷、碳氟改性聚合物、小分子碳氟化合物、聚合碳氟化合物和丙烯酸酯共聚物中的至少一种。
进一步优选的，所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为10nm；所述聚合物为羟基官能硅酮改性的聚丙烯酸酯，所述羟基官能硅酮改性的聚丙烯酸酯在所述三氧化钨电介质层中的掺杂比例为3wt％；或者，
所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为7nm；所述聚合物为碳氟改性聚合物，所述碳氟改性聚合物在所述三氧化钨电介质层中的掺杂比例为3wt％。
另一方面，提供一种透明导电电极，该透明导电电极包括三氧化钨电介质层和Ag电极层；其中，所述三氧化钨电介质层中掺杂有聚合物。
例如，所述聚合物在所述三氧化钨电介质层中的掺杂比例为1-5wt％。
基于上述，例如，所述聚合物为改性聚硅氧烷、碳氟改性聚合物、小分子碳氟化合物、聚合碳氟化合物和丙烯酸酯共聚物中的至少一种。
进一步的，所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为10nm；所述聚合物为羟基官能硅酮改性的聚丙烯酸酯，所述羟基官能硅酮改性的聚丙烯酸酯在所述三氧化钨电介质层中的掺杂比例为3wt％；或者，
所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为7nm；所述聚合物为碳氟改性聚合物，所述碳氟改性聚合物在所述三氧化钨电介质层中的掺杂比例为3wt％。
再一方面，提供一种OLED显示器件，包括多个子像素，每个所述子像素包括依次设置在衬底基板上方的第一电极、有机材料功能层和第二电极，其中，所述第一电极为上述任一项所述的透明导电电极。
可选的，所述第二电极为不透明金属电极、或透明金属电极、或ITO电极。
可选的，所述OLED显示器件还包括设置于所述衬底基板和所述第一电极之间的薄膜晶体管；其中，所述薄膜晶体管的漏极与所述第一电极电连接。
基于上述，可选的，所述衬底基板为柔性衬底基板。
本发明实施例提供了一种透明导电电极的制备方法，包括：将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的三氧化钨电介质层；其中，所述混合溶液的表面张力为10-50mN/m；在所述三氧化钨电介质层上制备形成Ag电极层。
由于在通过溶液法制备形成所述三氧化钨电介质层的过程中，采用的是掺杂有聚合物的混合溶液，而通过掺杂该聚合物，使得混合溶液具有较低的表面张力，从而使得形成的所述三氧化钨电介质层具有较高的表面平滑度，进而使得在其上可以形成连续、平滑的Ag电极层，在此基础上，一方面可以减少晶界的形成，从而提高Ag电极层的导电性能，另一方面平滑的Ag电极层可以减少光散射，从而提高透光率；并且，由于掺杂有所述聚合物的三氧化钨电介质层的存在，其可以改变Ag电极层的电场，从而可以改变Ag电极层界面处的表面等离子体电磁波的方向，进而可以抑制表面等离子体引起的光损失，进一步提高透光率。此外，相对透明ITO导电电极，本发明实施例提供的所述透明导电电极，由于使用了Ag电极层，因此其具有较好的延展性。
基于上述，本发明实施例提供的所述透明导电电极可解决现有技术中透明ITO或Ag导电电极不能同时综合导电性、透光率及延展性的问题。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲， 在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例提供的一种制备透明导电电极的流程示意图；
图2为本发明实施例提供的一种透明导电电极的结构示意图；
图3为本发明实施例提供的一种OLED显示器件的结构示意图一；
图4为本发明实施例提供的一种OLED显示器件的子像素的结构示意图。
附图标记：
10-透明导电电极；101-WO3电介质层；102-Ag电极层；20-子像素；201-第一电极；202-有机材料功能层；203-第二电极；204-薄膜晶体管。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例提供了一种透明导电电极的制备方法，如图1所示，该方法包括如下步骤：
S01、将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的三氧化钨(WO3)电介质层；其中，所述混合溶液的表面张力为10-50mN/m，所述表面张力可通过例如拉起液膜法(例如参照中国国家标准GB5549-90)测试，测试仪器例如可以是表面张力仪。
这里，由于通过上述混合溶液最终要制备得到掺杂所述聚合物的WO3电介质层，因此，所述混合溶液中除包括聚合物溶液外，还应该包括能得到WO3的溶液，例如钨酸溶液。
在此基础上，采用溶液法制备形成WO3电介质层，即为：将上述混合溶液例如采用旋涂方式涂覆到基板上，然后通过相关工艺形成掺杂有所述聚合物的WO3电介质。
其中，由于所述聚合物的掺入而使所述混合溶液具有低的表面张力，可以避免涂覆到基板上的溶液分子抱团，从而导致最终形成所述WO3电介质层不平坦，即：所述聚合物可以改善WO3电介质层的润湿和流平效果，从而使 其具有较高表面平滑度。
对于所述聚合物，其可以为改性聚硅氧烷、碳氟改性聚合物、小分子碳氟化合物、聚合碳氟化合物和丙烯酸酯共聚物中的至少一种。
其中，所述改性聚硅氧烷可以选自乙酸甲氧基丙酯溶剂中的羟基官能硅酮改性的聚丙烯酸酯(BYK-SILCLEAN 3700)，聚醚改性的丙烯酰基官能聚二甲基硅氧烷(BYK-SILCLEAN 3710)，甲氧基丙醇溶剂中的聚醚改性的羟基官能聚二甲基硅氧烷(BYK-SILCLEAN 3720)等。
所述碳氟改性聚合物、小分子碳氟化合物、聚合碳氟化合物可以选自AFCONA-3037，AFCONA-3772，AFCONA-3777，AFCONA-3700等。
所述丙烯酸酯共聚物可以选自
Figure PCTCN2015070291-appb-000002
Figure PCTCN2015070291-appb-000003
等。
S02、在所述WO3电介质层上制备形成Ag电极层。
这里，可以采用真空热蒸镀方式制备形成所述Ag电极层。
需要说明的是，第一，所述基板可以是不设置任何图案层的透明衬底基板，也可以是在透明衬底基板上设置了相应图案层的基板，在此不做限定。
其中，对于所述透明衬底基板，其可以是透明玻璃基板；也可以是透明柔性衬底基板，在此情况下，在制备所述透明导电电极的过程中，所述柔性衬底基板可以是形成在硬质承载基板上的，当完成所述透明导电电极的制备后再将硬质承载基板剥离，具体可根据实际情况进行，在此不做限定。
第二，不对掺杂在例如钨酸溶液中的所述聚合物的量进行限定，以能改善所述WO3电介质层表面平滑度，从而达到提高Ag电极层的导电性能并且提高透光率为准。
本发明实施例提供了一种透明导电电极的制备方法，包括：将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的WO3电介质层；其中，所述混合溶液的表面张力为10-50mN/m；在所述WO3电介质层上制备形成Ag电极层。
由于在通过溶液法制备形成所述WO3电介质层的过程中，采用的是掺杂有聚合物的混合溶液，而通过掺杂该聚合物，使得混合溶液具有较低的表面张力，从而使得形成的所述WO3电介质层具有较高的表面平滑度，进而使得 在其上可以形成连续、平滑的Ag电极层，在此基础上，一方面可以减少晶界的形成，从而提高Ag电极层的导电性能，另一方面平滑的Ag电极层可以减少光散射，从而提高透光率；并且，由于掺杂有所述聚合物的WO3电介质层的存在，其可以改变Ag电极层的电场，从而可以改变Ag电极层界面处的表面等离子体电磁波的方向，进而可以抑制表面等离子体引起的光损失，进一步提高透光率。此外，相对透明ITO导电电极，本发明实施例提供的所述透明导电电极，由于使用了Ag电极层，因此其具有较好的延展性。
基于上述，本发明实施例提供的所述透明导电电极可解决现有技术中透明ITO或Ag导电电极不能同时综合导电性、透光率及延展性的问题。
例如，上述步骤S01，可以通过如下步骤实现：
S011、在钨酸(H2WO4)溶液中掺入所述聚合物溶液，形成所述混合溶液；其中，所述混合溶液的表面张力为10-50mN/m。
这里，所述H2WO4溶液可以通过将钨酸钠(Na2WO4)的水溶液通过阳离子交换树脂例如RSO3Na得到。
S012、采用旋涂方式将所述混合溶液涂覆到所述基板上，并进行烘烤，得到掺杂所述聚合物的所述WO3电介质层。
这里，烘烤的目的是：一方面，使H2WO4溶液中的溶剂蒸发掉，并使H2WO4分解为WO3和水(H2O)，并且在烘烤过程中将水蒸发掉；另一方面，使所述聚合物溶液中的溶剂蒸发掉；而在此过程中，所述聚合物不受影响，从而可以形成掺杂所述聚合物的所述WO3电介质层。
其中，可以在150-200℃温度条件下，对涂覆有所述混合溶液的基板进行1-2小时的烘烤。
例如，所述聚合物在所述WO3电介质层中的掺杂比例为1-5wt％。
这样，可以使得制备的所述WO3电介质层具有更好的表面平滑度，从而使得在其上可以形成的Ag电极层更为平滑，进而使其具有更高的透光率和导电性能。
考虑到需要同时综合该透明导电电极的导电性、透光率，因此，本发明实施例优选将所述WO3电介质层的厚度设定为10-50nm，将所述Ag电极层的厚度设定为7-25nm。
基于上述，本发明实施例提供了几个具体的实验，以通过这些实验的实 验数据来说明所述透明导电电极可同时综合导电性能和透光率。
实施例一，通过真空热蒸镀方式制备一层7nm的Ag电极层，用原子力显微镜(AFM)测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第一行数值。
实施例二，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，将10mL浓度为1mol/L的H2WO4溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到20nm的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第二行数值。
实施例三，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为1wt％的BYK-SILCLEAN3700的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到20nm的掺杂有1wt％的BYK-SILCLEAN3700的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第三行数值。
实施例四，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为3wt％的BYK-SILCLEAN3700的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到20nm的掺杂有3wt％的BYK-SILCLEAN3700的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第四行数值。
实施例五，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为5wt％的BYK-SILCLEAN3700的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到20nm的掺杂有5wt％的BYK-SILCLEAN3700的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测 试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第五行数值。
实施例六，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为3wt％的
Figure PCTCN2015070291-appb-000004
的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到50nm的掺杂有3wt％的
Figure PCTCN2015070291-appb-000005
的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第六行数值。
实施例七，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为3wt％的
Figure PCTCN2015070291-appb-000006
的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到10nm的掺杂有3wt％的
Figure PCTCN2015070291-appb-000007
的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第七行数值。
实施例八，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为3wt％的
Figure PCTCN2015070291-appb-000008
的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到20nm的掺杂有3wt％的
Figure PCTCN2015070291-appb-000009
的WO3电介质层，最后再通过真空热蒸镀方式制备一层7nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第八行数值。
实施例九，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为3wt％的
Figure PCTCN2015070291-appb-000010
的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到基板上，在200℃下烘烤1小时后得到20nm的掺杂有3wt％的
Figure PCTCN2015070291-appb-000011
的WO3电介质层，最后再通过真空热蒸镀方式制备一层25nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第九行数值。
实施例十，将Na2WO4的水溶液通过强酸型阳离子交换树脂，得到H2WO4 溶液，然后在10mL浓度为1mol/L的H2WO4溶液中掺入2.5g质量百分比为3wt％的
Figure PCTCN2015070291-appb-000012
的异丙醇溶液，将混合溶液通过旋涂的方式涂覆到聚对苯二甲酸乙二醇酯(PET)柔性基板上，在200℃下烘烤1小时后得到20nm的掺杂有3wt％的
Figure PCTCN2015070291-appb-000013
的WO3电介质层，最后再通过真空热蒸镀方式制备一层10nm的Ag电极层；用原子力显微镜测试表面粗糙度Rq，用四探针法测试面电阻，用光学透过率测试仪测试透光率，测试结果如表1的第十行数值。
表1
Figure PCTCN2015070291-appb-000014
由表1中可以看出，相比实施例一和实施例二，涉及本发明实施例提供的所述透明导电电极的实施例三至实施例十，其透光率显著增大，且其面电阻也显著减小，即导电性能显著提高。
并且，由上述实施例三至实施例五可以看出，同等条件下，透明导电电极的粗糙度越小，其透光率则越大、面电阻则越小；而粗糙度直接与聚合物的掺杂比例有关。
综上所述，相比实施例一和实施例二，本发明实施例提供的所述透明导电电极，可同时具有高导电性和高透光率。
此外，基于表1中的数据可以看出，当所述聚合物为BYK-SILCLEAN3700，所述BYK-SILCLEAN3700在所述三氧化钨电介质层中的掺杂比例为3wt％，且所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为10nm时，所述透明导电电极具有更高的透光率和更低的面电阻。
当所述聚合物为碳氟改性聚合物例如
Figure PCTCN2015070291-appb-000015
所述
Figure PCTCN2015070291-appb-000016
在所述三氧化钨电介质层中的掺杂比例为3wt％，且所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为7nm时，所述透明导电电极具有最高的透光率和相对较低的面电阻。
本发明实施例提供了一种通过上述方法制备的透明导电电极10，如图2所示，该透明导电电极10包括：WO3电介质层101和Ag电极层102；其中，所述WO3电介质层中掺杂有聚合物。
这里，所述聚合物可以为改性聚硅氧烷、碳氟改性聚合物、小分子碳氟化合物、聚合碳氟化合物和丙烯酸酯共聚物中的至少一种。
其中，所述改性聚硅氧烷可以选自乙酸甲氧基丙酯溶剂中的羟基官能硅酮改性的聚丙烯酸酯(BYK-SILCLEAN 3700)，聚醚改性的丙烯酰基官能聚二甲基硅氧烷(BYK-SILCLEAN 3710)，甲氧基丙醇溶剂中的聚醚改性的羟基官能聚二甲基硅氧烷(BYK-SILCLEAN 3720)等。
所述碳氟改性聚合物、小分子碳氟化合物、聚合碳氟化合物可以选自
Figure PCTCN2015070291-appb-000017
AFCONA-3037，AFCONA-3772，AFCONA-3777，AFCONA-3700等。
所述丙烯酸酯共聚物可以选自
Figure PCTCN2015070291-appb-000018
Figure PCTCN2015070291-appb-000019
等。
本发明实施例提供了一种透明导电电极10，包括：WO3电介质层101和Ag电极层102；其中，所述WO3电介质层101中掺杂有聚合物。
由于在通过溶液法制备形成所述WO3电介质层101的过程中，采用的是掺杂有聚合物的混合溶液，而通过掺杂该聚合物，使得混合溶液具有较低的表面张力，从而使得形成的所述WO3电介质层101具有较高的表面平滑度，进而使得在其上可以形成连续、平滑的Ag电极层102，在此基础上，一方面可以减少晶界的形成，从而提高Ag电极层102的导电性能，另一方面平滑 的Ag电极层102可以减少光散射，从而提高透光率；并且，由于掺杂有所述聚合物的WO3电介质层101的存在，其可以改变Ag电极层102的电场，从而可以改变Ag电极层102界面处的表面等离子体电磁波的方向，进而可以抑制表面等离子体引起的光损失，进一步提高透光率。此外，相对透明ITO导电电极，本发明实施例提供的所述透明导电电极10，由于使用了Ag电极层102，因此其具有较好的延展性。
基于上述，本发明实施例提供的所述透明导电电极10可解决现有技术中透明ITO或Ag导电电极不能同时综合导电性、透光率及延展性的问题。
例如，所述聚合物在所述WO3电介质层101中的掺杂比例为1-5wt％。
这样，可以使得制备的所述WO3电介质101层具有更好的表面平滑度，从而使得在其上形成的Ag电极层102更为平滑，进而使其具有更高的透光率和导电性能。
例如，考虑到需要同时综合该透明导电电极10的导电性、透光率，因此，本发明实施例优选将所述WO3电介质层101的厚度设定为10-50nm，将所述Ag电极层的厚度设定为7-25nm。
进一步优选的，所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为10nm；所述聚合物为BYK-SILCLEAN3700，所述BYK-SILCLEAN3700在所述三氧化钨电介质层中的掺杂比例为3wt％。
或者，所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为7nm；所述聚合物为碳氟改性聚合物例如
Figure PCTCN2015070291-appb-000020
所述
Figure PCTCN2015070291-appb-000021
在所述三氧化钨电介质层中的掺杂比例为3wt％。
本发明实施例还提供了一种OLED显示器件，如图3所示，该OLED显示器件包括多个子像素20，每个所述子像素包括依次设置在衬底基板上方的第一电极201、有机材料功能层202和第二电极203，其中，所述第一电极为上述的透明导电电极10。
由于在通过溶液法制备形成所述透明导电电极10的WO3电介质层101的过程中，采用的是掺杂有聚合物的混合溶液，而通过掺杂该聚合物，使得混合溶液具有较低的表面张力，从而使得形成的所述WO3电介质层101具有较高的表面平滑度，进而使得在其上可以形成连续、平滑的Ag电极层102，在此基础上，一方面可以减少晶界的形成，从而提高Ag电极层102的导电 性能，另一方面平滑的Ag电极层102可以减少光散射，从而提高透光率；并且，由于掺杂有所述聚合物的WO3电介质层101的存在，其可以改变Ag电极层102的电场，从而可以改变Ag电极层102界面处的表面等离子体电磁波的方向，进而可以抑制表面等离子体引起的光损失，进一步提高透光率。此外，相对透明ITO导电电极，本发明实施例提供的所述透明导电电极，由于使用了Ag电极层102，因此其具有较好的延展性。
基于上述，本发明实施例提供的所述透明导电电极可解决现有技术中透明ITO或Ag导电电极不能同时综合导电性、透光率及延展性的问题。
对于所述有机材料功能层202，其可以至少包括发光层，在此基础上为了能够提高电子和空穴注入发光层的效率，所述有机材料功能层202进一步还可以包括电子传输层、空穴传输层，进一步的还可以包括电子注入层和空穴注入层等功能层。在此基础上，所述有机材料功能层202各层的形成顺序例如可以为空穴注入层，空穴传输层，发光层，电子传输层，电子注入层。
这里，所述有机材料功能层202各层有机材料层可分别为小分子或高分子材料，若为小分子材料，可利用真空蒸镀方式形成，若为高分子材料，则可使用旋涂、喷墨或丝网印刷等方式形成。
当向第一电极201和第二电极203施加工作电压时，第一电极201和第二电极203中的空穴和电子均会注入到所述发光层中；空穴和电子在所述发光层中相遇，二者复合在一起形成电子-空穴对、并释放出能量；该能量以光的形式发出，经过所述发光层中的不同发光分子而显示为不同颜色的光，并从所述有机材料功能层202的两侧均匀的射出。
基于此，所述OLED显示器件可以分为底发光型和双面发光型。具体的，当所述第二电极203为不透明金属电极时，由于光从第一电极201、再经衬底基底一侧出射，因此，可以称为底发光型；当所述第二电极203为透明金属电极时，由于光一方面从第一电极201、再经衬底基底一侧出射，另一方面从第二电极203、再经与衬底基底相对设置的封装层出射，因此可以称为双面发光型。
这里，所述金属电极的材质例如可以为钙、镁、铝、银等。不透明金属电极即为该金属电极的厚度较厚，透明金属电极即为金属电极的厚度较薄。
此外，所述有机材料功能层202各层的形成顺序还可以为电子注入层， 电子传输层，发光层，空穴传输层，空穴注入层，在此情况下，所述第二电极203为ITO电极，此时，所述OLED显示器件为倒置式OLED器件。
在上述基础上，如图4所示，考虑到无源矩阵应用于大尺寸显示装置时有其不足的一面，例如，本发明实施例提供的OLED显示器件还可以包括薄膜晶体管204；其中，所述薄膜晶体管204包括栅极、栅绝缘层、半导体有源层、源极和漏极；所述薄膜晶体管的漏极与所述第一电极201电连接。在此基础上，所述OLED显示器还包括与所述栅极电连接的栅线、栅线引线(图中未标识出)，与所述源极电连接的数据线、数据线引线(图中未标识出)等。
需要说明的是，所述薄膜晶体管204是一种具有开关特性的半导体单元，其可以是顶栅型，也可以是底栅型，在此不作限定。
在上述基础上，考虑到柔性显示器具有诸多优点，例如耐冲击，抗震能力强，重量轻，体积小，携带更加方便，因此，本发明实施例提供的所述OLED显示器件还可以为柔性显示器件，在此情况下，所述衬底基板为柔性衬底基板。
其中，所述柔性衬底基板的材料可以为聚酰亚胺、聚碳酸酯、聚丙烯酸酯、聚醚酰亚胺、聚醚砜、聚对苯二甲酸乙二醇酯和聚萘二甲酸乙二醇酯等。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。
本申请要求于2014年7月25日递交的中国专利申请第201410360869.7号的优先权，在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。

Claims (13)

  1. 一种制备透明导电电极的方法，包括：
    将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的三氧化钨电介质层；其中，所述混合溶液的表面张力为10-50mN/m；
    在所述三氧化钨电介质层上制备形成Ag电极层。
  2. 根据权利要求1所述的方法，其中，所述将掺杂有聚合物溶液的混合溶液通过溶液法，在基板上制备形成掺杂聚合物的三氧化钨电介质层，包括：
    在钨酸溶液中掺入所述聚合物溶液，形成所述混合溶液；
    采用旋涂方式将所述混合溶液涂覆到所述基板上，并进行烘烤，得到掺杂所述聚合物的所述三氧化钨电介质层。
  3. 根据权利要求1所述的方法，其中，所述聚合物在所述三氧化钨电介质层中的掺杂比例为1-5wt％。
  4. 根据权利要求1至3任一项所述的方法，其中，所述聚合物为改性聚硅氧烷、碳氟改性聚合物、聚合碳氟化合物和丙烯酸酯共聚物中的至少一种。
  5. 根据权利要求4所述的方法，其中，
    所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为10nm；所述聚合物为羟基官能硅酮改性的聚丙烯酸酯，所述羟基官能硅酮改性的聚丙烯酸酯在所述三氧化钨电介质层中的掺杂比例为3wt％；或者，
    所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为7nm；所述聚合物为碳氟改性聚合物，所述碳氟改性聚合物在所述三氧化钨电介质层中的掺杂比例为3wt％。
  6. 一种透明导电电极，包括三氧化钨电介质层和Ag电极层；
    其中，所述三氧化钨电介质层中掺杂有聚合物。
  7. 根据权利要求6所述的透明导电电极，其中，所述聚合物在所述三氧化钨电介质层中的掺杂比例为1-5wt％。
  8. 根据权利要求6或7所述的透明导电电极，其中，所述聚合物为改性聚硅氧烷、碳氟改性聚合物、聚合碳氟化合物和丙烯酸酯共聚物中的至少一种。
  9. 根据权利要求8所述的透明导电电极，其中，
    所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为10nm；所述聚合物为羟基官能硅酮改性的聚丙烯酸酯，所述羟基官能硅酮改性的聚丙烯酸酯在所述三氧化钨电介质层中的掺杂比例为3wt％；或者，
    所述三氧化钨电介质层的厚度为20nm，所述Ag电极层的厚度为7nm；所述聚合物为碳氟改性聚合物，所述碳氟改性聚合物在所述三氧化钨电介质层中的掺杂比例为3wt％。
  10. 一种OLED显示器件，包括多个子像素，每个所述子像素包括依次设置在衬底基板上方的第一电极、有机材料功能层和第二电极，其中，所述第一电极为权利要求6至9任一项所述的透明导电电极。
  11. 根据权利要求10所述的OLED显示器件，其中，所述第二电极为不透明金属电极、或透明金属电极、或ITO电极。
  12. 根据权利要求10所述的OLED显示器件，其中，所述OLED显示器件还包括设置于所述衬底基板和所述第一电极之间的薄膜晶体管；
    其中，所述薄膜晶体管的漏极与所述第一电极电连接。
  13. 根据权利要求10至12任一项所述的OLED显示器件，其中，所述衬底基板为柔性衬底基板。
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