WO2014108015A1 - 碳纳米管透明复合电极的制备方法 - Google Patents

碳纳米管透明复合电极的制备方法 Download PDF

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WO2014108015A1
WO2014108015A1 PCT/CN2013/089463 CN2013089463W WO2014108015A1 WO 2014108015 A1 WO2014108015 A1 WO 2014108015A1 CN 2013089463 W CN2013089463 W CN 2013089463W WO 2014108015 A1 WO2014108015 A1 WO 2014108015A1
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Prior art keywords
carbon nanotube
film
transparent
composite electrode
substrate
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PCT/CN2013/089463
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English (en)
French (fr)
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郝海燕
戴雷
蔡丽菲
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北京阿格蕾雅科技发展有限公司
广东阿格蕾雅光电材料有限公司
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Priority to KR1020157017465A priority Critical patent/KR101693774B1/ko
Priority to JP2015551963A priority patent/JP5965554B2/ja
Priority to DE112013006416.2T priority patent/DE112013006416T5/de
Publication of WO2014108015A1 publication Critical patent/WO2014108015A1/zh

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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a transparent composite electrode, and more particularly to a method for preparing a carbon nanotube transparent composite electrode.
  • Display devices and photovoltaic devices such as liquid crystal panels, 0 LED panels, touch panels, electronic paper, solar cells, and transparent electrodes are indispensable parts.
  • the performance requirements of the conventional transparent electrode mainly include transmittance and resistivity, wherein the transmittance is required to be 80% or more, and the resistivity is lower than 500 Q / S qm.
  • transparent electrodes are developing toward flexibility and flexibility in addition to the requirements of transmittance and resistivity.
  • Oxidized fine tin (IT0) forms an ITO film on a glass substrate to exhibit excellent light transmittance and conductivity.
  • commercial ITO electrodes occupy a dominant position in the field of transparent electrodes.
  • transparent electrodes must have low square resistance, good transmittance in the visible range, flexibility, and a simple operation process for large-area fine coating film formation, which makes ITO
  • There are technically insurmountable problems in the expansion of thin films such as the preparation conditions of high temperature of IT0 electrodes (evaporation method or sputtering method), easy to break, difficult to reduce square resistance, poor uniformity, yellow color, difficult to transmit blue light, etc.
  • IT0 film is combined with a flexible substrate having a low melting point and can only be deposited at a low temperature, the prepared IT0 conductive film has high resistivity, poor transparency, poor adhesion to the flexible substrate, and is easily broken when bent. , causing device failure.
  • the commonly used polymer flexible substrate material is opposite to the thermal expansion coefficient of IT0.
  • IT0 conductive film will fall off due to the thermal effect of the device.
  • the indium resources used in the IT0 film are scarce, resulting in an increase in the production cost of the ⁇ film, which has also become a driving force for the development of new transparent conductive electrode materials.
  • Carbon nanotubes are carbon materials with typical lamellar hollow structure characteristics.
  • the tube body constituting carbon nanotubes is composed of hexagonal graphite carbon ring structural units, which is a special structure (radial size is nanometer order One-dimensional quantum material with an axial dimension of the order of microns.
  • Its pipe wall constitutes a coaxial pipe mainly composed of several layers to several tens of layers. The layer is maintained at a fixed distance of about 0.34 nm, and the diameter is generally 2 to 20 nm.
  • the P electrons of carbon atoms on carbon nanotubes form a wide range of delocalized IT bonds. Due to the significant conjugation effect, carbon nanotubes have some special electrical properties.
  • Carbon nanotube materials because of their high electron mobility, low resistivity and high transparency Degree, has been recognized by scientific research and industry as a transparent electrode that can replace ⁇ .
  • Wet synthesis mainly refers to the use of carbon nanotube powder uniformly dispersed in a solution for film preparation, including vacuum filtration transfer method [Green AA, Hersam M C. Colored Semitransparent Conductive Coatings Consisting of Monodisperse Metallic Single - Walled Carbon Nanotubes tJ Nano Lett. , 2008, 8 (5): 1417- 1422 ⁇ ], Spraying Method [Kang SJ, Song Y, Yi Y, et al. Work-Function Engineering of Carbon Nanotube Transparent Conductive Fi lms [J] . Carbon , 2010, 48 (2) : 520-524. ], spin coating [Meitl MA, Zhou YX, Gaur A, et al.
  • the carbon nanotube transparent electrode prepared by the wet method has the problem of uneven dispersion of the carbon nanotubes, and the prepared electrode may cause electrode failure due to local defects.
  • the current research is limited to laboratory research, and there is still a large area application. Big technical challenges.
  • the process of directly synthesizing the carbon nanotube transparent electrode by dry-aerosol is to be in a vapor deposition furnace
  • the generated carbon nanotube aerosol was column-shaped and collapsed into a flat film shape after being applied to a transparent polymeric tape.
  • the morphology and quality of the carbon nanotube transparent electrode prepared by the method are affected by many factors in the reaction process, such as the temperature of the chemical vapor deposition furnace, the flow rate of the carrier gas hydrogen, and the bypass speed of the flexible substrate.
  • the width of the deposited film is limited by the diameter at the exit of the reactor, which in turn limits the preparation of large-area carbon nanotube transparent electrodes.
  • the super-array extraction method utilizes the extensibility of carbon nanotubes to stretch carbon nanotubes into an infinitely long film. After the annealing of the super-aligned carbon nanotube array, the array direction of the CNTs changes from vertical to horizontal. When stretched, it is placed between the flexible substrate and the stretched film and pressed by two rollers.
  • the super-array extraction method has a simple process, high CNT utilization rate, low cost, high film formation quality, and can be used for industrial mass production.
  • the combination of the carbon nanotubes and the flexible substrate is only attached to the surface of the flexible substrate by mechanical extrusion, and the electrode quality is limited due to the insufficiency of the carbon nanotube film during the process. Moreover, this process is not easy to perform multiple operations on the same substrate. Summary of the invention
  • the invention develops a novel preparation method of a transparent carbon nanotube composite electrode.
  • the present invention is a super-sequential carbon nanotube film [Feng C, Liu K, Wu JS, et al. Flexible, Stretchable, Transparent Conducting Films Made from Superal igned Carbon Nanotubes [J]. Adv. Funct. Mater., 2010, 20 (6) : 885-891. ] is a conductive substrate, a conductive polymer is used as a carrier to form a layered structure of one or more layers, and the formed transparent CNT composite electrode film exhibits excellent conductivity and can be
  • the carbon nanotube transparent composite electrode can be prepared in a large area by a mechanical extrusion process at room temperature.
  • the transparent CNT composite electrode can be applied to flexible 0LED display devices, solar cells, liquid crystal displays, touch screen panels and the like.
  • the carbon nanotube transparent composite electrode comprises a transparent polymer substrate and a CNT composite film formed on the surface of the transparent substrate.
  • the CNT composite film is composed of a CNT film and a conductive polymer film, and the preparation method comprises the following steps: (1) A super-aligned carbon nanotube film is deposited on a transparent polymer substrate, and a carbon nanotube film layer of a certain width is extracted from the edge of the super-aligned carbon nanotube grown on the Si wafer, and then the film layer is flattened.
  • the minimum distance between the nips of the rolls is the thickness of the substrate.
  • the conductive polymer solution has a viscosity of 1-10 X 10 - 3 PaS.
  • the main components of the aqueous solution of the conductive polymer are: 1) polyaniline, poly 3, 4-ethylenedioxythiophene, polyethyl bromide or / and polypyrrole, 2) co-solvent: polystyrene sulfonate, camphor sulfonate Acid, dodecylbenzenesulfonic acid and salt, cetylbenzenesulfonic acid and salt or/and naphthalenesulfonic acid and salt, 3) modification aid: propylene glycol, sorbitol, dimethyl sulfoxide or/and NN dimethylformamide, ethylene glycol, 4) The rest is water.
  • the conductive polymer aqueous solution is 1.8% PEDOT: PSS aqueous solution, and the specific composition thereof is as follows: poly 3, 4-ethylenedioxythiophene PED0T 0. 5-1%,
  • a heating member is disposed inside the roller.
  • the present invention discloses a method of using a carbon nanotube (CNT) film to prepare a transparent conductive composite electrode.
  • the transparent CNT thin film electrode comprises a transparent polymer substrate and a CNT composite film formed on a surface of the transparent substrate, wherein the CNT conductive film is composed of a CNT film and a conductive polymer film.
  • a carbon nanotube array film having good adhesion to a substrate and a conductive polymer in a liquid phase are used to form a CNT composite film during mechanical extrusion.
  • the transparent CNT composite electrode exhibits excellent conductivity, and a transparent CNT composite electrode can be prepared by a wet process of mechanical extrusion at room temperature.
  • the polymer conductive film is adhered to the surface of the carbon nanotube film in the form of a solution, and the polymer conductive film has a good bonding force with the stretched film of the carbon nanotube and the substrate, and is suitable for the multilayer process operation.
  • the film formed by the present invention is a one or more composite film. Since the CNT film layer is relatively thin, the thickness of the single-layer CNT film layer is several or several tens of nanometers, so that the film layer may be partially damaged during the deposition process, in order to ensure the planar or three-dimensional conductivity of the CNT conductive layer, Can be laid in multiple layers. The process is inexpensive to prepare and can realize the preparation of a large-area transparent electrode.
  • the transparent CNT electrode can be applied to various devices requiring light transmissivity and conductivity, such as a flexible organic electroluminescent display device (OLED), a solar cell, a liquid crystal display device, a plasma display device (PDP), an image sensor, a touch screen. Panels, etc.
  • OLED organic electroluminescent display device
  • solar cell a solar cell
  • liquid crystal display device a liquid crystal display device
  • PDP plasma display device
  • image sensor a touch screen. Panels, etc.
  • the transparent CNT composite electrode can be applied to various devices that require light transmittance and conductivity, such as Electrode materials for flexible organic electroluminescent display devices (OLEDs), solar cells, liquid crystal display devices, plasma display devices (PDPs), image sensors, touch screen panels, and the like.
  • OLEDs flexible organic electroluminescent display devices
  • PDPs plasma display devices
  • image sensors touch screen panels, and the like.
  • FIG. 2 Schematic diagram of a carbon nanotube film on a transparent substrate
  • FIG. 3 Schematic diagram of preparation of carbon nanotube polymer composite film
  • FIG. 4 Schematic diagram of a carbon nanotube polymer composite film
  • FIG. 5 Schematic diagram of a multilayer carbon nanotube polymer composite film
  • 1 a transparent substrate, 2 - carbon nanotube film, 3 - carbon nanotube composite film, 4 transparent substrate with carbon nanotube film, 5 - roll, 6 - silicon, 7 - film.
  • the main technology for preparing the transparent carbon nanotube composite electrode is divided into two parts: (1) The adhesion between the carbon nanotube film and the substrate is through the surface intermolecular force bonding between the surface of the carbon nanotube film 2 and the transparent substrate 1. .
  • the specific film formation schematic is shown in Figure 1.
  • the carbon nanotube film 2 of the shape shown in FIG. 2 can be flattened in an environment of an ethanol spray for shrinkage.
  • the carbon nanotube film 2 formed after a single film is automatically shrunk in a vapor atmosphere of ethanol to form a structure composed of a stable linear carbon nanotube bundle.
  • the ethanol molecules will adsorb on the surface, modify the surface polarity, and also enhance the bonding force between the carbon nanotube film 2 and the transparent substrate 1.
  • the obtained carbon nanotube film 2 will not easily be destroyed during environmental transportation and placement. .
  • the transparent substrate 4 coated with the carbon nanotube film shown in Fig. 2 is passed through a pair of relatively rotating rolls 5. 01 ⁇ The surface roughness RaO. 02 ⁇ 0. 01 ⁇ m.
  • the minimum distance between the rolls 5 is the thickness of the transparent substrate 1.
  • a polymer aqueous solution having a viscosity of r w X 10 - 3 PaS is applied to the surface of the roll 5 . If necessary, a certain heating accessory can be added to control the temperature of the roller to ensure the viscosity of the polymer.
  • FIG. 3 is a schematic view of the preparation of the composite film 3.
  • the formed film structure is shown in Fig. 4.
  • the carbon nanotube polymer film in FIG. 4 may be repeatedly coated with a carbon nanotube film as needed, and then adhered to the conductive polymer layer, and may be operated multiple times.
  • Aqueous polymer solution 1) Polyaniline, poly 3, 4-ethylenedioxythiophene, polyethyl bromide or / and polypyrrole, 2) Cosolvent: polystyrene sulfonate, camphorsulfonic acid, dodecane Benzobenzene sulfonic acid and salt, ten Hexaalkylbenzenesulfonic acid and/or naphthalenesulfonic acid and salt, 3) modification aid: propylene glycol, sorbitol, dimethyl sulfoxide or/and NN dimethylformamide, ethylene glycol, 4) The rest is water.
  • Preparation method All components are mixed in a certain ratio in a certain solvent, and the concentration can be adjusted by adding water or a corresponding solvent.
  • Aqueous polymer aqueous solution is 1. 8% PED0T: PSS aqueous solution.
  • a transparent carbon nanotube composite electrode is prepared: a super-aligned carbon nanotube film 2 is deposited on the polymer transparent substrate 1, and the edge of the super-aligned carbon nanotubes grown on the silicon wafer 6 by the film-leading member 7 is extracted.

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Abstract

一种碳纳米管透明复合电极的制备方法，以超顺排碳纳米管薄膜（2）为导电基体，导电高分子为载体，形成一种或多种层状结构。所形成的透明CNT复合薄膜（3）显示出优异的导电性，可以在室温条件下，利用机械的工艺按照经济且简单的方式大面积制造透明CNT复合电极，该透明CNT复合电极可应用于柔性OLED显示器件、太阳能电池、液晶显示、触摸屏面板等器件。

Description

碳纳米管透明复合电极的制备方法
技术领域
本发明涉及一种透明复合电极，特别是涉及一种碳纳米管透明复合电极的制 备方法。
背景技术
液晶面板、 0LED面板、触摸屏、电子纸、太阳能电池等显示器件和光伏器件， 透明电极都是不可缺少的部分。 传统透明电极性能要求主要包括透过率和电阻 率， 其中要求透过率达到 80%以上， 电阻率低于 500 Q /Sqm以下。但随着科技的发 展及需求的增加， 透明电极除了透过率和电阻率的要求外， 正朝柔性、 可弯曲方 面发展。 氧化细锡（IT0)在玻璃基底上形成 IT0薄膜显示出优异的透光性和导电 性， 目前商业化的 IT0电极在透明电极的应用领域里占有主导地位。 然而随着透 明电极应用领域的多元化，透明电极必须具备低方阻， 可见光范围内良好的透过 率、 柔性、 可实现大面积精细涂布成膜的简单操作的工艺等要求， 这使得 ITO薄 膜的拓展应用中存在技术上难以克服的问题，如 IT0电极高温的制备工艺条件（蒸 镀法或溅镀法） 、 易破碎、 难以降低方阻、 均匀性差、 颜色泛黄、 蓝光难以透射 等， 并且如果将 IT0薄膜配合熔点低的柔性基底， 只能在低温下淀积， 所制备的 IT0导电薄膜电阻率高、 透明度差， 与柔性基底之间的附着力差， 在弯曲时易折 裂， 造成器件失效。 并且常用的高分子柔性衬底材料与 IT0的热膨胀系数相反， 在器件工作中会因为器件热效应而导致 IT0 导电薄膜脱落而失效。 再者 IT0薄膜 所用的铟资源匮乏， 导致 ιτο薄膜制备成本增高， 这也成为开发新型透明导电电 极材料的推动力。
碳纳米管是一种具有典型的层状中空结构特征的碳材料，构成碳纳米管的管 身由六边形石墨碳环结构单元组成， 是一种具有特殊结构 （径向尺寸为纳米量 级， 轴向尺寸为微米量级）的一维量子材料。 它的管壁构成主要为数层到数十层 的同轴圆管。 层与层之间保持固定的距离， 约为 0. 34nm， 直径一般为 2〜20nm 。 碳纳米管上碳原子的 P电子形成大范围的离域 IT键， 由于共轭效应显著， 碳纳米 管具有一些特殊的电学性质。 由于碳纳米管的结构与石墨的片层结构相同， 所以 具有很好的电学性能。 碳纳米管材料因为其高电子迁移率， 低电阻率及高透明 度， 已被科研和产业界认定为可代替 ιτο的透明电极。
目前制备碳纳米管透明电极的方法较多， 大致分为湿法和干法制备。
湿法合成主要指采用碳纳米管粉体均匀分散在溶液进行薄膜制备，包含真空 抽滤转移法 [Green A A, Hersam M C. Colored Semitransparent Conductive Coatings Consisting of Monodisperse Metal l ic Single -Wal led Carbon Nanotubes tJ] . Nano Lett. , 2008, 8 (5)： 1417- 1422· ]、 喷涂法 [Kang S J, Song Y, Yi Y, et al. Work-Function Engineering of Carbon Nanotube Transparent Conductive Fi lms [J] . Carbon, 2010, 48 (2) : 520-524. ]、旋涂法 [Meitl M A, Zhou Y X, Gaur A, et al. Solution Casting and Transfer Printing Single-Wal led Carbon Nanotube Fi lms [J] . Nano. Lett. , 2004, 4 (9) : 1643-1647. ] 提拉法 [Ng M H A, Hartadi L T, Tan H , et al. Efficient Coating of Transparent and Conductive Carbon Nanotube Thin Fi lms on Plastic Substrates [J] . Nanotechnology, 2008, 19 : 205703· ]、 LB法 [Li X L, Zhang L, Wang X R, et al. Langmuir-Blodgett Assembly of Densely Al igned Single-Wal led Carbon Nanotubes from Bulk Materials [J] . J. Am. Chem. Soc. , 2007, 129 (16)： 4890-4891· ]、 电泳法 [Pei S F, Du J H, Zeng Y, et al. The Fabrication of a Carbon Nanotube Transparent Conductive Fi lm by Electrophoretic Deposition and Hot-Pressing Transfer [J] . Nanotechnology, 2009, 20 : 235707. ]等； 干法制备包括气溶胶直接合成法 [Fraser I S, Motta M S, Schmidt R K, et al. Continuous Production of Flexible Carbon Nanotube-Based Transparent Conductive Fi lms [J] . Sci. Technol. Adv. Mater. , 2010, 11 (4)， 045004. ] , 超阵列提拉法 [Feng C， Liu K, Wu J S, et al. Flexible, Stretchable, Transparent Conducting Fi lms Made from Superal igned Carbon Nanotubes [J] . Adv. Funct. Mater. , 2010, 20 (6) : 885-891. ]等。
采用湿法制备的碳纳米管透明电极由于存在碳纳米管分散不均匀的问题，所 制备电极会由于局部缺陷会导致电极失效， 目前的研究局限于实验室研究， 在大 面积应用方面还存在很大的技术挑战。
采用干法 -气溶胶直接合成法碳纳米管透明电极的工艺， 是将气相沉积炉中 生成的碳纳米管气溶胶打在透明聚合胶带上后有柱状瓦解为平坦的膜状。该方法 制备的碳纳米管透明电极的形貌及质量受到反应过程中诸多因素的影响，如化学 气相沉积炉的温度、载气氢的流速、柔性基底的绕行速度等。沉积膜的宽度受到 反应炉出口处直径的限制， 进而也限制了制备大面积碳纳米管透明电极。
超阵列提拉法利用碳纳米管的可伸展性， 可将碳纳米管拉伸为无限长的薄 膜。 超顺排碳纳米管阵列在经过退火处理后， CNT的阵列方向由垂直变为水平。 在拉伸时， 将其置于柔性基底和拉伸膜之间， 通过两个滚轮将其压紧。此超阵列 提拉法与湿法合成法相比， 工艺简单， CNT 利用率高， 费用低， 成膜质量高， 可 用于工业化批量生产。但碳纳米管与柔性基底的结合只是通过机械挤压的方法附 着在柔性基底的表面，相对而言， 其工艺操作过程中由于碳纳米管膜层的不牢固 会导致电极质量受限。 并且此工艺方法不易在同一基底上进行多次操作。 发明内容
本发明开发了一种新型的透明碳纳米管复合电极的制备工艺方法。本发明以 超顺排碳纳米管薄膜 [Feng C, Liu K, Wu J S, et al. Flexible, Stretchable, Transparent Conducting Fi lms Made from Superal igned Carbon Nanotubes [J] . Adv. Funct. Mater. , 2010, 20 (6) : 885-891. ]为导电基体， 导电高分子为载体， 形成一种一层或多层的层状结构，所形成的透明 CNT 复合电极薄膜显示出优异的 导电性， 可以在室温条件下， 利用机械挤压工艺， 可大面积制备碳纳米管透明复 合电极。 该透明 CNT复合电极可应用于柔性 0LED显示器件、 太阳能电池、 液晶显 示， 触摸屏面板等器件。
碳纳米管透明复合电极，包括透明高分子基底和在透明基底的表面上形成的 CNT复合薄膜， 所述 CNT复合薄膜由 CNT薄膜和导电高分子膜组成， 其制备方法包 括如下步骤： （1 ) 在透明高分子基底上铺放超顺排的碳纳米管薄膜， 由引膜件 在 Si片上生长的超顺排碳纳米管的边缘抽出一定宽度的碳纳米管膜层，然后将此 膜层平铺在透明高分子基底表面至铺满所需区域，采用激光切割方法或者采用乙 醇收縮的方法切断碳纳米管薄膜； （2)将铺有碳纳米管薄膜的基板通过一对相对 旋转的辊筒之间，使碳纳米管薄膜的表面上粘附一层导电高分子膜， 所述一个或 两个辊筒表面涂刷有导电高分子溶液。 所述辊筒表面粗糙度 RaO. 02~0. 01 μ m。
所述辊筒之间的夹缝最小距离为基板厚度。
所述导电高分子溶液的粘度为 1-10 X 10— 3PaS。
所述导电高分子水溶液主要组成成分为： 1 ) 聚苯胺、 聚 3， 4-乙撑二氧噻 吩、 聚乙块或 /和聚吡咯， 2 ) 助溶剂： 聚苯乙烯磺酸盐、 樟脑磺酸、 十二烷基 苯磺酸及盐、 十六烷基苯磺酸及盐或 /和萘磺酸及盐， 3 )改性助剂： 丙二醇， 山 梨醇， 二甲基亚砜或 /和 N-N二甲基甲酰胺， 乙二醇， 4 ) 其余为水。
所述导电高分子水溶液为的 1. 8%PED0T: PSS水溶液， 其具体组成如下： 聚 3， 4-乙撑二氧噻吩 PED0T 0. 5-1%,
聚苯乙烯磺酸盐 PSS 0. 8- 1. 3%，
十二垸基苯磺酸钠 0. 01%-0. 05%, 乙二醇 0. 37%- 0. 44%, 水 加至 100%。
所述辊筒内部设有加热部件。
本发明公开了一种利用碳纳米管 （CNT ) 薄膜制备的透明导电复合电极的方 法。 该透明 CNT薄膜电极包括透明高分子基底和在透明基底的表面上形成的 CNT 复合薄膜， 其中， CNT导电薄膜由包含 CNT薄膜和导电高分子膜组成。本发明是采 用与基底附着力良好的碳纳米管阵列薄膜与液相的导电高分子在机械挤压时形 成一个 CNT复合薄膜。该透明 CNT复合电极显示出优异的导电性， 可以在室温条件 下利用机械挤压的湿法工艺制备透明的 CNT复合电极。 高分子导电膜是采用溶液 的形式粘附在碳纳米管薄膜表面的，高分子导电膜与碳纳米管拉伸膜及基底之间 有良好的结合力，适合于多层工艺操作。本发明形成的膜是一层或多层复合薄膜。 由于 CNT膜层本比较薄， 单层 CNT膜层厚度是几个或几十个纳米， 这样膜层在铺放 的过程中会出现局部破坏， 为了保证 CNT导电层的平面或三维的导电性， 可多层 铺设。 此工艺方法制备成本低廉， 可实现大面积透明电极的制备。 该透明 CNT电 极可应用于制造需要具有透光性和导电性的各种装置如柔性有机电致发光显示 器件 （0LED ) 、 太阳能电池、 液晶显示器件、 等离子显示器件 （PDP ) 、 图像传 感器、 触摸屏面板等。
该透明 CNT 复合电极可应用于制造需要具有透光性和导电性的各种装置如 柔性有机电致发光显示器件（0LED) 、 太阳能电池、 液晶显示器件、 等离子显示 器件 （PDP) 、 图像传感器、 触摸屏面板等的电极材料。
附图说明
图 1 Si片上碳纳米管薄膜的制备，
图 2 透明基体上碳纳米管薄膜示意图，
图 3 碳纳米管高分子复合薄膜的制备示意图，
图 4 碳纳米管高分子复合薄膜示意图，
图 5 多层碳纳米管高分子复合薄膜示意图，
其中各标号列示如下：
1一透明基底， 2—碳纳米管薄膜， 3—碳纳米管复合薄膜， 4一铺有碳纳米管薄膜 的透明基底， 5—辊筒， 6—硅片， 7—引膜件。
具体实施方式
透明碳纳米管复合电极的制备的主要技术分为两个部分： （1 ) 碳纳米管薄 膜与基底之间的附着是通过碳纳米管薄膜 2表面与透明基底 1之间的表面分子间 力结合。 具体的成膜示意图见图 1。 为保证碳纳米管薄膜 2与透明基底 1之间附 着力， 可将形如图 2的碳纳米管薄膜 2平放于乙醇喷雾的环境中进行收縮。单次 拉膜后形成的碳纳米管薄膜 2在乙醇的蒸汽环境中，会自动收縮形成稳定的线状 的碳纳米管束所组成的结构。 乙醇分子会吸附在其表面， 修饰其表面极性， 同时 也增强了碳纳米管薄膜 2与透明基体 1衬底的结合力，所得碳纳米管薄膜 2不会 轻易在环境运输及放置过程中破坏。将图 2中所示铺有碳纳米管薄膜的透明基底 4通过一对相对旋转的辊筒 5。 要求辊筒 5表面粗糙度 RaO. 02~0. 01 μ m。 辊筒 5 之间的夹缝最小距离为透明基底 1厚度。 在辊筒 5表面涂刷粘度在 rw X 10— 3PaS 的高分子水溶液。如果需要可添加一定的加热附件以实现辊筒温度的控制， 以确 保高分子体的粘度。从辊筒 5上方出来基板表面形成了带有碳纳米管的导电高分 子复合薄膜 3， 图 3是复合薄膜 3的制备示意图。 形成的薄膜结构如图 4。 可根 据需要将图 4 中的碳纳米管高分子薄膜重复铺一次碳纳米管膜后接着粘附导电 高分子层， 还可以多次操作。
导电高分子水溶液成分： 1 ) 聚苯胺、 聚 3， 4-乙撑二氧噻吩、 聚乙块或 / 和聚吡咯， 2 )助溶剂： 聚苯乙烯磺酸盐、 樟脑磺酸、 十二烷基苯磺酸及盐、 十 六烷基苯磺酸及盐或 /和萘磺酸及盐， 3 )改性助剂： 丙二醇， 山梨醇， 二甲基亚 砜或 /和 N-N二甲基甲酰胺， 乙二醇， 4 ) 其余为水。
制备方法： 是将所有组分按比例混合溶解在一定的溶剂中， 其浓度可通过添 加水或相应的溶剂来调整。
如： 导电高分子水溶液为的 1. 8%PED0T: PSS水溶液。
聚 3， 4-乙撑二氧噻吩 PED0T 0. 5-1%
聚苯乙烯磺酸盐 PSS 0. 8- 1. 3% 十二垸基苯磺酸钠 0. 01%-0. 05% 乙二醇 0. 37%- 0. 44% 水 加至 100%。 制备得到透明碳纳米管复合电极：在高分子透明基底 1上铺放超顺排的碳纳 米管薄膜 2， 由引膜件 7在硅片 6上生长的超顺排碳纳米管的边缘抽出一定宽度 的碳纳米管膜层， 然后将此膜层平铺在高分子透明基底 1表面至铺满所需区域， 采用激光切割方法或者采用乙醇收縮的方法切断碳纳米管薄膜 2 ; (2)将铺有碳 纳米管薄膜的基底 4通过一对相对旋转的辊筒 （导电高分子水溶液涂于辊筒上） 5之间， 使碳纳米管薄膜 2的表面上粘附一层导电高分子膜， 形成复合薄膜 3。

Claims

权利要求书
1、碳纳米管透明复合电极，包括透明高分子基底和在透明基底的表面上形成 的 CNT复合薄膜， 所述 CNT复合薄膜由 CNT薄膜和导电高分子膜组成， 其制备方法 包括如下步骤： （1 ) 在透明高分子基底上铺放超顺排的碳纳米管薄膜， 由引膜 件在 Si片上生长的超顺排碳纳米管的边缘抽出一定宽度的碳纳米管膜层，然后将 此膜层平铺在透明高分子基底表面至铺满所需区域，采用激光切割方法或者采用 乙醇收縮的方法切断碳纳米管薄膜； （2)将铺有碳纳米管薄膜的基板通过一对相 对旋转的辊筒之间，使碳纳米管薄膜的表面上粘附一层导电高分子膜， 所述一个 或两个辊筒表面涂刷有导电高分子水溶液。
2、 根据权利要求 1所述的碳纳米管透明复合电极， 所述辊筒表面粗糙度 RaO. 02~0· 01 μ m。
3、根据权利要求 1所述的碳纳米管透明复合电极， 所述辊筒之间的夹缝最小 距离为基板厚度。
4、根据权利要求 1所述的碳纳米管透明复合电极， 所述导电高分子水溶液的 粘度为 1-10 X 10— 3PaS。
5、根据权利要求 1所述的碳纳米管透明复合电极， 所述导电高分子水溶液主 要组成成分为： 1 ) 聚苯胺、 聚 3， 4-乙撑二氧噻吩、 聚乙块或 /和聚吡咯， 2 ) 助溶剂： 聚苯乙烯磺酸盐、 樟脑磺酸、 十二烷基苯磺酸及盐、 十六烷基苯磺酸及 盐或 /和萘磺酸及盐， 3 )改性助剂： 丙二醇， 山梨醇， 二甲基亚砜或 /和 N-N二甲 基甲酰胺， 乙二醇， 4) 其余为水。
6、根据权利要求 5所述的碳纳米管透明复合电极， 所述导电高分子水溶液为 的 1. 8%PED0T: PSS水溶液， 其具体组成如下：
聚 3， 4-乙撑二氧噻吩 0. 5-1%,
聚苯乙烯磺酸盐 0. 8- 1. 3%,
十二垸基苯磺酸钠 0. 01%- 0. 05%, 乙二醇 0. 37%- 0. 44%, 水 加至 100%。
7、根据权利要求 1所述的碳纳米管透明复合电极 所述辊筒内部设有加热部 件。
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