WO2022142586A1 - Aluminum oxide protected silver nanowire transparent electrode, preparation method therefor and use thereof - Google Patents

Aluminum oxide protected silver nanowire transparent electrode, preparation method therefor and use thereof Download PDF

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WO2022142586A1
WO2022142586A1 PCT/CN2021/123467 CN2021123467W WO2022142586A1 WO 2022142586 A1 WO2022142586 A1 WO 2022142586A1 CN 2021123467 W CN2021123467 W CN 2021123467W WO 2022142586 A1 WO2022142586 A1 WO 2022142586A1
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silver nanowire
transparent electrode
silver
nanowire transparent
aluminum oxide
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PCT/CN2021/123467
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French (fr)
Chinese (zh)
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宁洪龙
李志航
姚日晖
陈俊龙
杨跃鑫
叶倩楠
曾璇
陈楠泓
刘泰江
彭俊彪
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华南理工大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H01B17/62—Insulating-layers or insulating-films on metal bodies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

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  • the invention belongs to the technical field of flexible transparent electrode preparation, and in particular relates to an alumina-protected silver nanowire transparent electrode and a preparation method and application thereof.
  • AMOLED Active Organic Light Emitting Diode Display
  • TCF transparent conductive film
  • the most common practice is to deposit a protective layer on the surface of silver nanowires, such as sputtering, sol-gel method and other methods to form a whole layer of inert metals, conductive oxides or organics on the surface of the film, but this The method will inevitably cause shading in the light-transmitting area without silver nanowires, which will affect the performance of the transparent conductive film.
  • the electrodeposition method using specific materials can accurately deposit the protective layer material on the surface of silver nanowires without affecting the light-transmitting area.
  • the primary purpose of the present invention is to provide a method for preparing a transparent electrode of aluminum oxide shielding silver nanowires.
  • Another object of the present invention is to provide an alumina-protected silver nanowire transparent electrode prepared by the above method.
  • Another object of the present invention is to provide the application of the above-mentioned transparent electrode for protecting silver nanowires with aluminum oxide.
  • a preparation method of aluminum oxide protective silver nanowire transparent electrode comprising the following steps:
  • the silver nanowire transparent conductive film is used as the cathode, the platinum electrode is used as the anode, the silver
  • An aluminum oxide protective layer is electrodeposited on the wire transparent conductive film, washed and annealed to obtain an aluminum oxide protective silver nanowire transparent electrode.
  • the silver nanowires in the silver nanowire solution in step (1) are prepared by a polyol method.
  • the coating method of step (1) is at least one of spin coating, spray coating, suction filtration transfer printing and blade coating.
  • the substrate is a rigid or flexible substrate
  • the rigid substrate is at least one of glass and silicon wafer
  • the flexible substrate is at least one of PI, PET, PEN and PDMS.
  • the temperature of the annealing treatment in step (1) is 100-140° C., and the time is 15-60 min.
  • the concentration of the silver nanowire solution in step (1) is 0.012-1.2 mg/mL, and the solvent is ethanol.
  • the concentration of aluminum nitrate nonahydrate (Al(NO 3 ) 3 ⁇ 9(H 2 O)) in the electrolyte in step (2) is 1-5 mmol/L.
  • the electrolyte in step (2) contains 0.05-0.2 mol/L potassium nitrate (KNO 3 ); the solvent of the electrolyte is water.
  • the volume of the electrolyte in step (2) is determined by the area of the silver nanowire transparent conductive film, and is 100-300 mL/cm 2 .
  • the temperature of the electrodeposition in step (2) is 65-85° C.
  • the voltage is -2--0.5V
  • the time is 15-60 min.
  • the washing in step (2) is rinsing with deionized water, and the rinsing time is 10-30 s.
  • the temperature of the annealing treatment in step (2) is 80-180° C., and the time is 10-30 min.
  • the thickness of the aluminum oxide protective layer in step (2) is 10-40 nm.
  • step (2) the aluminum oxide protective layer before annealing contains crystal water, which affects the performance of the transparent electrode, and the annealing treatment can remove the crystal water.
  • the quality factor of the aluminum oxide protective silver nanowire transparent electrode is higher than that of the original silver nanowire transparent electrode, and has high temperature resistance and high voltage performance, and the microscopic lower surface is flat.
  • the present invention has the following advantages and beneficial effects:
  • electrodeposited alumina can accurately deposit the protective layer material on the surface of silver nanowires without affecting the light-transmitting area, effectively improving the high temperature and high voltage resistance of silver nanowire conductive film performance.
  • Electrodeposition in constant voltage mode of three-electrode system and by using low-concentration electrolyte and prolonging the reaction time, provides a stable and controllable environment for the formation of the protective layer, which is conducive to maintaining the flatness of the surface of the deposition layer and adjusting it accurately according to requirements. Deposit thickness.
  • the alumina protection method of the present invention greatly simplifies the preparation process and the production price.
  • the aluminum oxide protective layer of the present invention has a highly flat surface and will not produce additional light absorption; and the contact interface between silver nanowires and aluminum oxide can form quasi-two-dimensional electron transport The channel promotes the conductivity to a certain extent.
  • the deposition of the aluminum oxide layer can promote the contact of silver nanowires, reduce the contact resistance and roughness at the node, and improve the quality factor of optoelectronic performance.
  • the addition of the rinsing process reduces the residue of the electrolyte on the surface of the transparent electrode, and avoids precipitation during subsequent annealing to affect the performance of the transparent electrode.
  • Fig. 1 is the three-electrode system constant voltage electrodeposition device described in the method of the present invention, wherein, electrolyte 1, platinum counter electrode 2, silver
  • FIG. 2 is a SEM image of the silver nanowire transparent electrode protected by deposition of alumina for 35 min in Example 1.
  • FIG. 2 is a SEM image of the silver nanowire transparent electrode protected by deposition of alumina for 35 min in Example 1.
  • FIG. 3 shows the withstand voltage performance of the transparent electrodes in Example 1 after different deposition times.
  • FIG. 4 shows the high temperature resistance performance of the transparent electrodes in Example 1 after different deposition times.
  • FIG. 5 is a SEM image of the silver nanowire transparent electrode protected by deposition of alumina for 60 min in Example 2.
  • FIG. 5 is a SEM image of the silver nanowire transparent electrode protected by deposition of alumina for 60 min in Example 2.
  • FIG. 6 is a SEM image of the alumina-protected silver nanowire transparent electrode prepared in Example 3.
  • FIG. 6 is a SEM image of the alumina-protected silver nanowire transparent electrode prepared in Example 3.
  • FIG. 7 is a SEM image of the alumina-protected silver nanowire transparent electrode prepared in Example 4.
  • FIG. 8 is a SEM image of the zinc oxide-protected silver nanowire transparent electrode in Comparative Example 1.
  • FIG. 9 is the roughness profile curves of the silver nanowire surfaces of Example 1 and Comparative Example 1.
  • FIG. 10 is a SEM image of the transparent electrode of aluminum oxide silver nanowires prepared in Comparative Example 2.
  • FIG. 10 is a SEM image of the transparent electrode of aluminum oxide silver nanowires prepared in Comparative Example 2.
  • the conventional conditions or the conditions suggested by the manufacturer are used.
  • the raw materials, reagents, etc., which are not specified by the manufacturer, are all conventional products that can be purchased from the market.
  • Table 1 lists the photoelectric properties of the transparent electrodes after different deposition times. It can be found that compared with the transparent electrodes without deposition treatment (deposition 0 min), the quality factor (Figure of Merit) of the transparent electrodes with the alumina protective layer is significantly improved.
  • Fig. 3 and Fig. 4 are respectively the withstand voltage and high temperature properties of transparent electrodes after different deposition times. It can be seen that the silver nanowire transparent electrodes prepared by the method of the present invention show obvious resistance to untreated transparent electrodes. The withstand voltage is doubled, and the withstand temperature is increased by more than 100 °C.
  • the aqueous solution of 200mL 2mmol/L aluminum nitrate nonahydrate and 0.15mol/L potassium nitrate was configured as electrolyte, heated to 75°C, the above-mentioned silver nanowire transparent electrode was clamped with platinum electrode as cathode, platinum electrode was used as anode, silver
  • Example 2 Use the same method as in Example 1 to prepare a transparent electrode based on silver nanowires, configure 200 mL of an aqueous solution containing 1 mmol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, and heat to 75 ° C to make the above silver nanowires transparent.
  • the electrode was clamped with platinum electrode as cathode, platinum electrode as anode, silver
  • the above electrodeposited silver nanowire transparent electrodes were immersed in deionized water at room temperature in a stirring state for 20 s, and then annealed at 150°C for 15 minutes on a hot stage to complete the transparent high-flatness silver nanowires protected by alumina as shown in Figure 6. Preparation of electrodes.
  • Example 2 Use the same method as in Example 1 to prepare a transparent electrode based on silver nanowires, configure 200 mL of an aqueous solution containing 5 mmol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, heat to 75 ° C, and make the above silver nanowires transparent.
  • the electrode was clamped with platinum electrode as cathode, platinum electrode as anode, silver
  • the above electrodeposited silver nanowire transparent electrodes were immersed in deionized water at room temperature in a stirring state for 20 s, and then annealed at 150°C for 15 minutes on a hot stage to complete the transparent high-flatness silver nanowires protected by alumina as shown in Figure 7. Preparation of electrodes.
  • Example 2 The same method as in Example 1 was used to prepare a silver nanowire-based transparent electrode of a glass substrate. Configure 200mL 2mmol/L aqueous solution of zinc nitrate hexahydrate as electrolyte, heat to 75°C, and sandwich the above-mentioned silver nanowire transparent electrode with platinum electrode as cathode, platinum electrode as anode, silver
  • Disconnect the power supply immerse the above-mentioned electrodeposited silver nanowire transparent electrode in deionized water at room temperature in a stirring state for 20s, and then anneal at 150°C for 15min on the hot stage, that is, the zinc oxide-protected silver nanowire transparent electrode on the glass substrate is completed.
  • preparation, and its SEM image is shown in Figure 8.
  • the surface is obviously rough, and the deposition area of zinc oxide is much larger than the area where the silver nanowires are located, which will have a significant impact on the transmittance of the transparent electrode. 58.4%, and the square resistance also drops to 32.03 ⁇ sq -1 , and the quality factor is only 0.14.
  • Fig. 9 compares the roughness of the zinc oxide-protected silver nanowire transparent electrode of Comparative Example 1 and the aluminum oxide-protected silver nanowire transparent electrode deposited in Example 1 by three-dimensional scanning through a laser confocal microscope, and the scanning position of the roughness profile curve is:
  • Example 2 Use the same method as in Example 1 to prepare a transparent electrode based on silver nanowires, configure 200 mL of an aqueous solution containing 0.1 mol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, and heat to 75 ° C.
  • the transparent electrode was clamped with platinum electrode as cathode, platinum electrode as anode, silver
  • the above electrodeposited silver nanowire transparent electrode was immersed in deionized water at room temperature in a stirring state, kept for 20s, and then annealed at 150°C for 15min on a hot stage to complete the electrodeposited alumina silver nanowire transparent electrode shown in Figure 10. preparation.
  • the alumina layer has expanded significantly, and the overall line width has reached 3 to 4 times that of the original silver nanowires, and some alumina particles are also deposited in the window area without nanowires, which significantly increases the film's light. Absorptivity, transmittance dropped to 64.5%.

Abstract

Disclosed are an aluminum oxide protected silver nanowire transparent electrode, a preparation method therefor and the use thereof. The method comprises: using an annealed silver nanowire transparent conductive film as a cathode, a platinum electrode as an anode, a silver/silver chloride electrode as a reference electrode and a solution containing aluminum nitrate nonahydrate as an electrolyte; electrodepositing an aluminum oxide protective layer on the silver nanowire transparent conductive film by means of the three-electrode system in a constant-voltage mode; rinsing same; and then annealing same to obtain the aluminum oxide protected silver nanowire transparent electrode. According to the present invention, the electro-deposition process is improved by controlling the reaction rate; aluminum oxide is accurately deposited on the surface of the silver nanowires without influencing a light-transmitting area; the contact between the silver nanowires is promoted by means of the deposition process; the light absorption of a coating layer is avoided via the high-flatness surface; the stability and the photoelectric properties are improved; a silver nanowire protection process is greatly simplified; the production cost of a flexible transparent electrode is greatly lowered; and the development of flexible electronics is promoted.

Description

一种氧化铝防护银纳米线透明电极及其制备方法与应用A kind of alumina protective silver nanowire transparent electrode and preparation method and application thereof 技术领域technical field
本发明属于柔性透明电极制备技术领域，具体涉及一种氧化铝防护银纳米线透明电极及其制备方法与应用。The invention belongs to the technical field of flexible transparent electrode preparation, and in particular relates to an alumina-protected silver nanowire transparent electrode and a preparation method and application thereof.
背景技术Background technique
近年来，新型显示产业发展迅速，显示器件的形态正经历着从平板显示到固定曲面显示、柔性显示的发展，并随着三星Galaxy Z Flip与华为Mate Xs等可折叠手机的上市，柔性显示的概念开始进入社会大众的脑海，并引发了新一轮的柔性显示的开发投资热潮。柔性主动有机发光二极管显示(AMOLED)是目前应用于柔性显示中最为成熟的技术，目前正处于市场成长期。在柔性显示的各组成部分中，透明导电薄膜(TCF)占据着重要的地位，是像素驱动电极，触控模组的重要组成部分。随着柔性产业的不断发展，ITO的易碎，难以低温制备与资源稀缺等缺陷愈加明显，以银纳米线为代表的新型柔性透明导电材料开始崭露头角。小尺寸纳米结构为银纳米线带来了低电阻下的高透过率，和由其组成的导电网络的优异柔性性能。然而由于纳米结构银的比表面积远大于宏观材料，所带来的高表面活泼性严重降低了银纳米线的稳定性，具体到实际应用中会面临如无法承受高加工温度，在大电压下局部热点熔融使器件失效等问题。为解决该问题，最常见的做法是在银纳米线表面沉积保护层，如通过溅射，溶胶-凝胶法等方法在薄膜表面形成一整层惰性金属、导电氧化物或有机物，但这种方法不可避免会在无银纳米线的透光区域造成遮挡，影响透明导电膜的性能。针对银纳米线导电网络的特殊结构，使用特定材料的电沉积法能够将保护层材料精确沉积在银纳米线表面，而不对透光区域产生影响。但目前报道的石墨烯保 护层仍无法回避石墨烯本身价格昂贵，处理工艺复杂等问题，而氧化锌等材料则会严重影响银纳米线的导电性能，同时由于不平整的表面形貌，会增加对光的吸收，造成光电性能的下降。因此亟需寻找一种简易低成本的银纳米线防护方法，并不对银纳米线本身性能造成影响，从而促进柔性电子行业的发展。In recent years, the new display industry has developed rapidly, and the form of display devices is undergoing development from flat-panel display to fixed curved display and flexible display. With the launch of foldable mobile phones such as Samsung Galaxy Z Flip and Huawei Mate Xs, flexible displays The concept began to enter the minds of the public, and triggered a new round of flexible display development and investment boom. Flexible Active Organic Light Emitting Diode Display (AMOLED) is currently the most mature technology used in flexible displays and is currently in the market growth stage. Among the components of the flexible display, the transparent conductive film (TCF) occupies an important position and is an important component of the pixel driving electrode and the touch module. With the continuous development of the flexible industry, the shortcomings of ITO such as brittleness, difficulty in low-temperature preparation and scarcity of resources have become more and more obvious. New flexible and transparent conductive materials represented by silver nanowires have begun to emerge. The small-scale nanostructure brings high transmittance at low resistance and excellent flexibility of the conductive network composed of silver nanowires. However, since the specific surface area of nanostructured silver is much larger than that of macroscopic materials, the high surface activity brought by it seriously reduces the stability of silver nanowires. In practical applications, it will face the problem of being unable to withstand high processing temperature and localized under high voltage. Hot spot melting causes device failure and other issues. To solve this problem, the most common practice is to deposit a protective layer on the surface of silver nanowires, such as sputtering, sol-gel method and other methods to form a whole layer of inert metals, conductive oxides or organics on the surface of the film, but this The method will inevitably cause shading in the light-transmitting area without silver nanowires, which will affect the performance of the transparent conductive film. According to the special structure of the conductive network of silver nanowires, the electrodeposition method using specific materials can accurately deposit the protective layer material on the surface of silver nanowires without affecting the light-transmitting area. However, the graphene protective layer reported so far still cannot avoid the problems of graphene itself being expensive and complicated in processing technology, while materials such as zinc oxide will seriously affect the electrical conductivity of silver nanowires. Absorption of light, resulting in a decline in optoelectronic properties. Therefore, it is urgent to find a simple and low-cost silver nanowire protection method without affecting the performance of the silver nanowire itself, thereby promoting the development of the flexible electronics industry.
发明内容SUMMARY OF THE INVENTION
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种氧化铝防护银纳米线透明电极的制备方法。In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing a transparent electrode of aluminum oxide shielding silver nanowires.
本发明的另一目的在于提供上述方法制得的一种氧化铝防护银纳米线透明电极。Another object of the present invention is to provide an alumina-protected silver nanowire transparent electrode prepared by the above method.
本发明的再一目的在于提供上述一种氧化铝防护银纳米线透明电极的应用。Another object of the present invention is to provide the application of the above-mentioned transparent electrode for protecting silver nanowires with aluminum oxide.
本发明目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种氧化铝防护银纳米线透明电极的制备方法，包括以下步骤：A preparation method of aluminum oxide protective silver nanowire transparent electrode, comprising the following steps:
(1)将银纳米线溶液涂布在基底上，退火处理后制备成银纳米线透明导电膜；(1) coating the silver nanowire solution on the substrate, and preparing a silver nanowire transparent conductive film after annealing treatment;
(2)将银纳米线透明导电膜作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，含九水合硝酸铝的溶液作为电解液，通过三电极***恒电压模式在银纳米线透明导电膜上电沉积氧化铝保护层，洗涤，退火处理，得到氧化铝防护银纳米线透明电极。(2) The silver nanowire transparent conductive film is used as the cathode, the platinum electrode is used as the anode, the silver|silver chloride electrode is used as the reference electrode, and the solution containing aluminum nitrate nonahydrate is used as the electrolyte. An aluminum oxide protective layer is electrodeposited on the wire transparent conductive film, washed and annealed to obtain an aluminum oxide protective silver nanowire transparent electrode.
优选的，步骤(1)所述银纳米线溶液中的银纳米线由多元醇法制得。Preferably, the silver nanowires in the silver nanowire solution in step (1) are prepared by a polyol method.
优选的，步骤(1)所述涂布的方法为旋涂、喷涂、抽滤转印和刮涂中的至少一种。Preferably, the coating method of step (1) is at least one of spin coating, spray coating, suction filtration transfer printing and blade coating.
优选的，步骤(1)所述基底为刚性或柔性基板，所述刚性基板为玻璃和硅片中的至少一种，所述柔性基板为PI、PET、PEN和PDMS中的至少一种。Preferably, in step (1), the substrate is a rigid or flexible substrate, the rigid substrate is at least one of glass and silicon wafer, and the flexible substrate is at least one of PI, PET, PEN and PDMS.
优选的，步骤(1)所述退火处理的温度为100～140℃，时间为15～60min。Preferably, the temperature of the annealing treatment in step (1) is 100-140° C., and the time is 15-60 min.
优选的，步骤(1)所述银纳米线溶液的浓度为0.012～1.2mg/mL，溶剂为乙醇。Preferably, the concentration of the silver nanowire solution in step (1) is 0.012-1.2 mg/mL, and the solvent is ethanol.
优选的，步骤(2)所述电解液中九水合硝酸铝(Al(NO 3) 3·9(H 2O))的浓度为1～5mmol/L。 Preferably, the concentration of aluminum nitrate nonahydrate (Al(NO 3 ) 3 ·9(H 2 O)) in the electrolyte in step (2) is 1-5 mmol/L.
优选的，步骤(2)所述电解液含0.05～0.2mol/L硝酸钾(KNO 3)；所述电解液的溶剂为水。 Preferably, the electrolyte in step (2) contains 0.05-0.2 mol/L potassium nitrate (KNO 3 ); the solvent of the electrolyte is water.
优选的，步骤(2)所述电解液的体积由银纳米线透明导电膜的面积决定，为100～300mL/cm 2。 Preferably, the volume of the electrolyte in step (2) is determined by the area of the silver nanowire transparent conductive film, and is 100-300 mL/cm 2 .
优选的，步骤(2)所述电沉积的温度为65～85℃，电压为-2～-0.5V，时间为15～60min。Preferably, the temperature of the electrodeposition in step (2) is 65-85° C., the voltage is -2--0.5V, and the time is 15-60 min.
优选的，步骤(2)所述洗涤为去离子水漂洗，漂洗的时间为10～30s。Preferably, the washing in step (2) is rinsing with deionized water, and the rinsing time is 10-30 s.
优选的，步骤(2)所述退火处理的温度为80～180℃，时间为10～30min。Preferably, the temperature of the annealing treatment in step (2) is 80-180° C., and the time is 10-30 min.
优选的，步骤(2)所述氧化铝保护层的厚度为10～40nm。Preferably, the thickness of the aluminum oxide protective layer in step (2) is 10-40 nm.
步骤(2)退火前的氧化铝保护层含结晶水，影响透明电极的性能，而退火处理可去除结晶水。In step (2), the aluminum oxide protective layer before annealing contains crystal water, which affects the performance of the transparent electrode, and the annealing treatment can remove the crystal water.
上述方法制得的一种氧化铝防护银纳米线透明电极。An alumina-protected silver nanowire transparent electrode prepared by the above method.
所述氧化铝防护银纳米线透明电极的品质因子高于原银纳米线透明电极，具备耐高温、大电压性能，且微观下表面平整。The quality factor of the aluminum oxide protective silver nanowire transparent electrode is higher than that of the original silver nanowire transparent electrode, and has high temperature resistance and high voltage performance, and the microscopic lower surface is flat.
上述一种氧化铝防护银纳米线透明电极的应用。The application of the above-mentioned aluminum oxide protective silver nanowire transparent electrode.
与现有技术相比，本发明具有以下优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
1、相比常见的制备保护膜方法，电沉积氧化铝能够将保护层材料精确沉积在银纳米线表面，而不对透光区域产生影响，有效提升了银纳米线导电膜的耐高温、高电压性能。1. Compared with the common method of preparing protective film, electrodeposited alumina can accurately deposit the protective layer material on the surface of silver nanowires without affecting the light-transmitting area, effectively improving the high temperature and high voltage resistance of silver nanowire conductive film performance.
2、以三电极***恒电压模式电沉积，并通过采用低浓度电解液与延长反应时间，为保护层形成提供了稳定可控的环境，有利于保持沉积层表面的平整度与按需求精确调整沉积层厚度。2. Electrodeposition in constant voltage mode of three-electrode system, and by using low-concentration electrolyte and prolonging the reaction time, provides a stable and controllable environment for the formation of the protective layer, which is conducive to maintaining the flatness of the surface of the deposition layer and adjusting it accurately according to requirements. Deposit thickness.
3、相比现有的电沉积石墨烯工艺，本发明的氧化铝防护法极大简化了制备工艺与生产价格。3. Compared with the existing electrodeposition graphene process, the alumina protection method of the present invention greatly simplifies the preparation process and the production price.
4、相比于氧化锌等氧化物，本发明的氧化铝保护层拥有高平整度的表面不会对光产生额外的吸收；而银纳米线与氧化铝的接触界面能够形成准二维电子运输沟道，一定程度促进了导电能力。4. Compared with oxides such as zinc oxide, the aluminum oxide protective layer of the present invention has a highly flat surface and will not produce additional light absorption; and the contact interface between silver nanowires and aluminum oxide can form quasi-two-dimensional electron transport The channel promotes the conductivity to a certain extent.
5、氧化铝层的沉积能够促进银纳米线的接触，减少节点处的接触电阻与粗糙度，提升了光电性能的品质因子。5. The deposition of the aluminum oxide layer can promote the contact of silver nanowires, reduce the contact resistance and roughness at the node, and improve the quality factor of optoelectronic performance.
6、漂洗工艺的加入减少了电解液在透明电极表面的残留，避免了在后续退火时析出影响透明电极性能。6. The addition of the rinsing process reduces the residue of the electrolyte on the surface of the transparent electrode, and avoids precipitation during subsequent annealing to affect the performance of the transparent electrode.
附图说明Description of drawings
图1为本发明方法中所述三电极***恒电压电沉积装置，其中，电解液1、铂对电极2、银|氯化银参比电极3、银纳米线工作电极4、电解池5、恒压源6。Fig. 1 is the three-electrode system constant voltage electrodeposition device described in the method of the present invention, wherein, electrolyte 1, platinum counter electrode 2, silver|silver chloride reference electrode 3, silver nanowire working electrode 4, electrolytic cell 5, Constant voltage source 6.
图2为实施例1中沉积35min氧化铝防护的银纳米线透明电极的SEM图像。FIG. 2 is a SEM image of the silver nanowire transparent electrode protected by deposition of alumina for 35 min in Example 1. FIG.
图3为实施例1中经过不同沉积时间的透明电极的耐电压性能。FIG. 3 shows the withstand voltage performance of the transparent electrodes in Example 1 after different deposition times.
图4为实施例1中经过不同沉积时间的透明电极的耐高温性能。FIG. 4 shows the high temperature resistance performance of the transparent electrodes in Example 1 after different deposition times.
图5为实施例2中沉积60min氧化铝防护的银纳米线透明电极的SEM图像。FIG. 5 is a SEM image of the silver nanowire transparent electrode protected by deposition of alumina for 60 min in Example 2. FIG.
图6为实施例3制备的氧化铝防护的银纳米线透明电极的SEM图像。FIG. 6 is a SEM image of the alumina-protected silver nanowire transparent electrode prepared in Example 3. FIG.
图7为实施例4制备的氧化铝防护的银纳米线透明电极的SEM图像。FIG. 7 is a SEM image of the alumina-protected silver nanowire transparent electrode prepared in Example 4. FIG.
图8为对比例1中氧化锌防护的银纳米线透明电极的SEM图像。FIG. 8 is a SEM image of the zinc oxide-protected silver nanowire transparent electrode in Comparative Example 1. FIG.
图9为实施例1与对比例1银纳米线表面的粗糙度轮廓曲线。FIG. 9 is the roughness profile curves of the silver nanowire surfaces of Example 1 and Comparative Example 1. FIG.
图10为对比例2制备的氧化铝银纳米线透明电极的SEM图像。FIG. 10 is a SEM image of the transparent electrode of aluminum oxide silver nanowires prepared in Comparative Example 2. FIG.
具体实施方式Detailed ways
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be described in further detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.
本发明实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。If the specific conditions are not indicated in the examples of the present invention, the conventional conditions or the conditions suggested by the manufacturer are used. The raw materials, reagents, etc., which are not specified by the manufacturer, are all conventional products that can be purchased from the market.
本申请实施例中的银纳米线的制备方法参考专利CN109346242B《一种基于银纳米线的透明电极及其制备方法》实施例1中银纳米线制备的部分(步骤1～2)。For the preparation method of silver nanowires in the examples of this application, refer to the part (steps 1-2) of silver nanowire preparation in Example 1 of Patent CN109346242B "A Transparent Electrode Based on Silver Nanowires and Its Preparation Method".
实施例1Example 1
在匀胶机上放置规格为10mm×10mm的玻璃片，将浓度为1.2mg/mL的银纳米线乙醇悬浊液旋涂于玻璃片上，具体旋涂步骤为：调节匀胶机低转速450rpm旋转，在低速旋转的过程中，取20μL银纳米线乙醇悬浊液加在玻璃片上，低速旋转10s，然后转为3000rpm高速旋转，旋转30s；重复上述在450rpm条件下加银纳米线乙醇悬浊液-低速旋转-高速旋转的旋涂步骤1次，将完成旋涂的玻璃片置于恒温平台上110℃退火30min，即完成基于银纳米线的透明电极的制备。Place a glass sheet with a size of 10mm × 10mm on the homogenizer, spin-coat the ethanol suspension of silver nanowires with a concentration of 1.2mg/mL on the glass slide, and the specific spin coating steps are as follows: adjusting the low speed of the homogenizer to rotate at 450rpm, In the process of low-speed rotation, take 20 μL of silver nanowire ethanol suspension and add it to the glass slide, rotate at low speed for 10s, then turn to 3000rpm high-speed rotation for 30s; repeat the above adding silver nanowire ethanol suspension under 450rpm condition- The spin-coating step of low-speed rotation-high-speed rotation is performed once, and the spin-coated glass sheet is placed on a constant temperature platform for annealing at 110° C. for 30 minutes, and the preparation of transparent electrodes based on silver nanowires is completed.
配置200mL含2mmol/L九水合硝酸铝与0.15mol/L硝酸钾的水溶液作为电解液，加热至75℃，将上述银纳米线透明电极用铂电极夹持作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，浸入电解液中，通过恒压源施加-1.5V工作电压，分别电沉积15min、25min、35min、45min，得到电沉积不同时间的银纳米线透明电极。断开电源，将上述电沉积后的银纳米线透明电极浸入搅拌状态的常温去离子水中，保持20s，随后在热台上150℃退火15min，即完成玻璃基板的氧化铝防护的高平整度银纳米线透明电极的制备。Configure 200 mL of an aqueous solution containing 2 mmol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, heat to 75 ° C, and sandwich the above-mentioned silver nanowire transparent electrode with a platinum electrode as a cathode, a platinum electrode as an anode, silver | As a reference electrode, the silver chloride electrode was immersed in the electrolyte, and a working voltage of -1.5V was applied through a constant voltage source, and electrodeposited for 15min, 25min, 35min, and 45min, respectively, to obtain silver nanowire transparent electrodes electrodeposited for different times. Disconnect the power supply, immerse the electrodeposited silver nanowire transparent electrodes in deionized water at room temperature in a stirring state, hold for 20s, and then anneal at 150°C for 15min on the hot stage, that is, the high-flatness silver with alumina protection of the glass substrate is completed. Preparation of nanowire transparent electrodes.
其中沉积30min氧化铝防护的高平整度银纳米线透明电极的SEM图像如图2所示，可以在银纳米线表面发现一层约22nm的高平整度的保护层。The SEM image of the high-flatness silver nanowire transparent electrode protected by deposition of alumina for 30min is shown in Figure 2, and a high-flatness protective layer of about 22 nm can be found on the surface of the silver nanowire.
表1列出了经过不同沉积时间的透明电极的光电性能，可以发现对比无沉积处理(沉积0min)的透明电极，有氧化铝保护层的透明电极的品质因子(Figure of Merit)均明显提升。图3与图4分别为经过不同沉积时间的透明电极的耐电压与耐高温性能，可以看出，经过本发明的方法制备的银纳米线透明电极相对于未处理的透明电极表现出明显的耐受性，可承受电压增加了一倍，可承受温 度提高了100℃以上。Table 1 lists the photoelectric properties of the transparent electrodes after different deposition times. It can be found that compared with the transparent electrodes without deposition treatment (deposition 0 min), the quality factor (Figure of Merit) of the transparent electrodes with the alumina protective layer is significantly improved. Fig. 3 and Fig. 4 are respectively the withstand voltage and high temperature properties of transparent electrodes after different deposition times. It can be seen that the silver nanowire transparent electrodes prepared by the method of the present invention show obvious resistance to untreated transparent electrodes. The withstand voltage is doubled, and the withstand temperature is increased by more than 100 ℃.
表1 不同沉积时间的透明电极的光电性能Table 1 Photoelectric properties of transparent electrodes with different deposition times
Figure PCTCN2021123467-appb-000001
Figure PCTCN2021123467-appb-000001
实施例2Example 2
将0.5mL浓度为1.2mg/mL的银纳米线乙醇悬浊液稀释至50mL，以孔径10μm的尼龙滤膜抽滤，随后在滤膜上放置含玻璃背板的柔性PI(规格为10mm×10mm)，开启抽气泵维持1min。将完成抽滤转移的基板置于恒温平台上110℃退火30min，即完成基于银纳米线的透明电极的制备。Dilute 0.5 mL of the silver nanowire ethanol suspension with a concentration of 1.2 mg/mL to 50 mL, filter with a nylon filter membrane with a pore size of 10 μm, and then place a flexible PI (size of 10 mm × 10 mm) with a glass back plate on the filter membrane. ), turn on the air pump for 1 min. The substrate after suction filtration transfer was placed on a constant temperature platform for annealing at 110° C. for 30 min, and the preparation of the transparent electrode based on silver nanowires was completed.
配置200mL 2mmol/L九水合硝酸铝与0.15mol/L硝酸钾的水溶液作为电解液，加热至75℃，将上述银纳米线透明电极用铂电极夹持作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，浸入电解液中，通过恒压源施加-1.5V工作电压，电沉积60min。断开电源，将上述电沉积后的银纳米线透明电极浸入搅拌状态的常温去离子水中，保持30s，随后在热台上150℃退火15min，将PI从底板剥离，即完成在柔性基板上的氧化铝防护的高平整度银纳米线透明电极的制备。图5为该透明电极的SEM图像，经过60min的沉积银纳米线表面开始***糙，但仍保持相对平整的形貌，此时透明电极透过率为85.02％，方阻为14.8Ω·sq -1，品质因子为13.3。 The aqueous solution of 200mL 2mmol/L aluminum nitrate nonahydrate and 0.15mol/L potassium nitrate was configured as electrolyte, heated to 75°C, the above-mentioned silver nanowire transparent electrode was clamped with platinum electrode as cathode, platinum electrode was used as anode, silver|chlorine The silver electrode was used as the reference electrode, immersed in the electrolyte, and the working voltage of -1.5V was applied through the constant voltage source, and the electrodeposition was carried out for 60min. Disconnect the power supply, immerse the electrodeposited silver nanowire transparent electrodes in deionized water at room temperature in a stirring state for 30s, and then anneal at 150°C for 15min on a hot stage to peel off the PI from the bottom plate, that is, complete the deposition on the flexible substrate. Preparation of alumina-protected high-flatness silver nanowire transparent electrodes. Figure 5 is the SEM image of the transparent electrode. After 60min of deposition, the surface of the silver nanowires begins to become rough, but still maintains a relatively flat morphology. At this time, the transmittance of the transparent electrode is 85.02%, and the square resistance is 14.8Ω·sq − 1 with a quality factor of 13.3.
实施例3Example 3
使用与实施1相同的方法制备基于银纳米线的透明电极，配置200mL含1mmol/L九水合硝酸铝与0.15mol/L硝酸钾的水溶液作为电解液，加热至75℃，将上述银纳米线透明电极用铂电极夹持作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，浸入电解液中，通过恒压源施加-1.5V工作电压，电沉积 35min，断开电源，将上述电沉积后的银纳米线透明电极浸入搅拌状态的常温去离子水中，保持20s，随后在热台上150℃退火15min，即完成图6所示的氧化铝防护的高平整度银纳米线透明电极的制备。Use the same method as in Example 1 to prepare a transparent electrode based on silver nanowires, configure 200 mL of an aqueous solution containing 1 mmol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, and heat to 75 ° C to make the above silver nanowires transparent. The electrode was clamped with platinum electrode as cathode, platinum electrode as anode, silver|silver chloride electrode as reference electrode, immersed in electrolyte, applied -1.5V working voltage through constant voltage source, electrodeposited for 35min, disconnected power supply, The above electrodeposited silver nanowire transparent electrodes were immersed in deionized water at room temperature in a stirring state for 20 s, and then annealed at 150°C for 15 minutes on a hot stage to complete the transparent high-flatness silver nanowires protected by alumina as shown in Figure 6. Preparation of electrodes.
实施例4Example 4
使用与实施1相同的方法制备基于银纳米线的透明电极，配置200mL含5mmol/L九水合硝酸铝与0.15mol/L硝酸钾的水溶液作为电解液，加热至75℃，将上述银纳米线透明电极用铂电极夹持作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，浸入电解液中，通过恒压源施加-1.5V工作电压，电沉积35min，断开电源，将上述电沉积后的银纳米线透明电极浸入搅拌状态的常温去离子水中，保持20s，随后在热台上150℃退火15min，即完成图7所示的氧化铝防护的高平整度银纳米线透明电极的制备。Use the same method as in Example 1 to prepare a transparent electrode based on silver nanowires, configure 200 mL of an aqueous solution containing 5 mmol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, heat to 75 ° C, and make the above silver nanowires transparent. The electrode was clamped with platinum electrode as cathode, platinum electrode as anode, silver|silver chloride electrode as reference electrode, immersed in electrolyte, applied -1.5V working voltage through constant voltage source, electrodeposited for 35min, disconnected power supply, The above electrodeposited silver nanowire transparent electrodes were immersed in deionized water at room temperature in a stirring state for 20 s, and then annealed at 150°C for 15 minutes on a hot stage to complete the transparent high-flatness silver nanowires protected by alumina as shown in Figure 7. Preparation of electrodes.
对比例1Comparative Example 1
采用与实施例1相同的方法制备玻璃基板的基于银纳米线的透明电极。配置200mL 2mmol/L的六水合硝酸锌的水溶液作为电解液，加热至75℃，将上述银纳米线透明电极用铂电极夹持作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，浸入电解液中，通过恒压源施加-1.5V工作电压，电沉积35min。断开电源，将上述电沉积后的银纳米线透明电极浸入搅拌状态的常温去离子水中，保持20s，随后在热台上150℃退火15min，即完成玻璃基板的氧化锌防护银纳米线透明电极的制备，其SEM图像如图8所示。相对于本发明的氧化铝保护层，明显表面粗糙，且氧化锌的沉积区域远大于银纳米线所在区域，这会对透明电极的透光率产生明显的影响，测试得到其透过率仅为58.4％，而方阻也下降到32.03Ω·sq -1，品质因子仅为0.14。 The same method as in Example 1 was used to prepare a silver nanowire-based transparent electrode of a glass substrate. Configure 200mL 2mmol/L aqueous solution of zinc nitrate hexahydrate as electrolyte, heat to 75°C, and sandwich the above-mentioned silver nanowire transparent electrode with platinum electrode as cathode, platinum electrode as anode, silver|silver chloride electrode as reference The electrode was immersed in the electrolyte, and a working voltage of -1.5V was applied through a constant voltage source, and electrodeposited for 35 minutes. Disconnect the power supply, immerse the above-mentioned electrodeposited silver nanowire transparent electrode in deionized water at room temperature in a stirring state for 20s, and then anneal at 150°C for 15min on the hot stage, that is, the zinc oxide-protected silver nanowire transparent electrode on the glass substrate is completed. preparation, and its SEM image is shown in Figure 8. Compared with the aluminum oxide protective layer of the present invention, the surface is obviously rough, and the deposition area of zinc oxide is much larger than the area where the silver nanowires are located, which will have a significant impact on the transmittance of the transparent electrode. 58.4%, and the square resistance also drops to 32.03Ω·sq -1 , and the quality factor is only 0.14.
图9通过激光共聚焦显微镜以三维扫描比较了对比例1的氧化锌防护银纳米线透明电极与实施例1沉积35min氧化铝防护的银纳米线透明电极的粗糙度，粗糙度轮廓曲线扫描位置为图9插图中箭头所示位置，计算得对比例1的算术平均偏差Ra与均方根偏差Rq分别为72nm与90nm，远大于实施例1中氧化铝 防护银纳米线的表面粗糙度Ra＝20nm与Rq＝24nm。Fig. 9 compares the roughness of the zinc oxide-protected silver nanowire transparent electrode of Comparative Example 1 and the aluminum oxide-protected silver nanowire transparent electrode deposited in Example 1 by three-dimensional scanning through a laser confocal microscope, and the scanning position of the roughness profile curve is: The position indicated by the arrow in the inset of Fig. 9 shows that the arithmetic mean deviation Ra and root mean square deviation Rq of Comparative Example 1 are 72 nm and 90 nm, respectively, which are much larger than the surface roughness Ra=20 nm of the alumina-protected silver nanowires in Example 1. with Rq=24nm.
对比例2Comparative Example 2
使用与实施1相同的方法制备基于银纳米线的透明电极，配置200mL含0.1mol/L九水合硝酸铝与0.15mol/L硝酸钾的水溶液作为电解液，加热至75℃，将上述银纳米线透明电极用铂电极夹持作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，浸入电解液中，通过恒压源施加-1.5V工作电压，电沉积35min，断开电源，将上述电沉积后的银纳米线透明电极浸入搅拌状态的常温去离子水中，保持20s，随后在热台上150℃退火15min，即完成图10所示的电沉积氧化铝银纳米线透明电极的制备。可以看出，氧化铝层发生了明显的扩展，总体线宽达到了原银纳米线的3～4倍，并在无纳米线的窗口区域也沉积了部分氧化铝颗粒，显著增加了薄膜的光吸收率，透过率下降到了64.5％。Use the same method as in Example 1 to prepare a transparent electrode based on silver nanowires, configure 200 mL of an aqueous solution containing 0.1 mol/L nonahydrate aluminum nitrate and 0.15 mol/L potassium nitrate as an electrolyte, and heat to 75 ° C. The transparent electrode was clamped with platinum electrode as cathode, platinum electrode as anode, silver|silver chloride electrode as reference electrode, immersed in electrolyte, applied -1.5V working voltage through constant voltage source, electrodeposited for 35min, disconnected from power supply, The above electrodeposited silver nanowire transparent electrode was immersed in deionized water at room temperature in a stirring state, kept for 20s, and then annealed at 150°C for 15min on a hot stage to complete the electrodeposited alumina silver nanowire transparent electrode shown in Figure 10. preparation. It can be seen that the alumina layer has expanded significantly, and the overall line width has reached 3 to 4 times that of the original silver nanowires, and some alumina particles are also deposited in the window area without nanowires, which significantly increases the film's light. Absorptivity, transmittance dropped to 64.5%.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.

Claims (10)

  1. 一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，包括以下步骤：A preparation method of aluminum oxide protective silver nanowire transparent electrode is characterized in that, comprises the following steps:
    (1)将银纳米线溶液涂布在基底上，退火处理后制备成银纳米线透明导电膜；(1) coating the silver nanowire solution on the substrate, and preparing a silver nanowire transparent conductive film after annealing treatment;
    (2)将银纳米线透明导电膜作为阴极，铂电极作为阳极，银|氯化银电极作为参比电极，含九水合硝酸铝的溶液作为电解液，通过三电极***恒电压模式在银纳米线透明导电膜上电沉积氧化铝保护层，洗涤，退火处理，得到氧化铝防护银纳米线透明电极。(2) The silver nanowire transparent conductive film is used as the cathode, the platinum electrode is used as the anode, the silver|silver chloride electrode is used as the reference electrode, and the solution containing aluminum nitrate nonahydrate is used as the electrolyte. An aluminum oxide protective layer is electrodeposited on the wire transparent conductive film, washed and annealed to obtain an aluminum oxide protective silver nanowire transparent electrode.
  2. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(2)所述电解液中九水合硝酸铝的浓度为1～5mmol/L；步骤(2)所述电解液含0.05～0.2mol/L硝酸钾；所述电解液的溶剂为水。A kind of preparation method of a kind of alumina protective silver nanowire transparent electrode according to claim 1, is characterized in that, the concentration of aluminum nitrate nonahydrate in the electrolyte solution described in step (2) is 1～5mmol/L; Step (2) The electrolyte contains 0.05-0.2 mol/L potassium nitrate; the solvent of the electrolyte is water.
  3. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(2)所述电沉积的温度为65～85℃，电压为-2～-0.5V，时间为15～60min。The method for preparing an alumina-protected silver nanowire transparent electrode according to claim 1, wherein the temperature of the electrodeposition in step (2) is 65-85°C, the voltage is -2--0.5V, and the time 15 to 60 minutes.
  4. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(2)所述电解液的体积由银纳米线透明导电膜的面积决定，为100～300mL/cm 2；所述氧化铝保护层的厚度为10～40nm。 The method for preparing an alumina-protected silver nanowire transparent electrode according to claim 1, wherein the volume of the electrolyte in step (2) is determined by the area of the silver nanowire transparent conductive film, which is 100-300 mL/ cm 2 ; the thickness of the aluminum oxide protective layer is 10-40 nm.
  5. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(2)所述退火处理的温度为80～180℃，时间为10～30min。The method for preparing an alumina-protected silver nanowire transparent electrode according to claim 1, wherein the temperature of the annealing treatment in step (2) is 80-180° C. and the time is 10-30 min.
  6. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(2)所述洗涤为去离子水漂洗，漂洗的时间为10～30s。The method for preparing an alumina-protected silver nanowire transparent electrode according to claim 1, wherein the washing in step (2) is rinsing with deionized water, and the rinsing time is 10-30 s.
  7. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(1)所述银纳米线溶液的浓度为0.012～1.2mg/mL，溶剂为乙醇；所述退火处理的温度为100～140℃，时间为15～60min。The method for preparing an alumina-protected silver nanowire transparent electrode according to claim 1, wherein the concentration of the silver nanowire solution in step (1) is 0.012-1.2 mg/mL, and the solvent is ethanol; The temperature of the annealing treatment is 100 to 140° C., and the time is 15 to 60 minutes.
  8. 根据权利要求1所述一种氧化铝防护银纳米线透明电极的制备方法，其特征在于，步骤(1)所述涂布的方法为旋涂、喷涂、抽滤转印和刮涂中的至少一种；所述基底为刚性或柔性基板，所述刚性基板为玻璃和硅片中的至少一种，所述柔性基板为PI、PET、PEN和PDMS中的至少一种。A kind of preparation method of alumina protective silver nanowire transparent electrode according to claim 1, is characterized in that, the coating method described in step (1) is at least one of spin coating, spray coating, suction filtration transfer printing and blade coating. One; the base is a rigid or flexible substrate, the rigid substrate is at least one of glass and silicon wafer, and the flexible substrate is at least one of PI, PET, PEN and PDMS.
  9. 权利要求1～8任一项所述方法制得的一种氧化铝防护银纳米线透明电极。A kind of alumina protective silver nanowire transparent electrode prepared by the method according to any one of claims 1 to 8.
  10. 权利要求9所述一种氧化铝防护银纳米线透明电极的应用。The application of the transparent electrode of aluminum oxide protecting silver nanowires according to claim 9.
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