WO2020125377A1 - 一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法 - Google Patents

一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法 Download PDF

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WO2020125377A1
WO2020125377A1 PCT/CN2019/121981 CN2019121981W WO2020125377A1 WO 2020125377 A1 WO2020125377 A1 WO 2020125377A1 CN 2019121981 W CN2019121981 W CN 2019121981W WO 2020125377 A1 WO2020125377 A1 WO 2020125377A1
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layer
self
supporting film
film
patterned
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PCT/CN2019/121981
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English (en)
French (fr)
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陈小玲
马图尔·桑贾
郭巧静
贺苗苗
郝伟珍
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太原理工大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • 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

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  • the invention belongs to the technical field of transparent conductive films, and in particular relates to a flexible transparent conductive film based on a patterned layer-by-layer assembled self-supporting film and a preparation method thereof.
  • the transparent conductive film has high transmittance and high conductivity in the visible light range, and has been widely used in antistatic coatings, electromagnetic shielding, solar cells, light emitting diodes, touch screens, sensors and actuators, smart skins, etc.
  • antistatic coatings electromagnetic shielding
  • solar cells light emitting diodes
  • touch screens touch screens
  • sensors and actuators smart skins, etc.
  • the main research work in the field of flexible transparent conductive films is roughly divided into two aspects: conductive materials and substrate materials.
  • TCO Transparent conductive oxide
  • polystyrene resin polyethylene terephthalate (PET), polycarbonate (PC), flexible polyvinyl chloride (PVC) and polymethacrylate Ester (PMMA), polyimide (PI), polyphthalamide (PPA), polydimethylsiloxane (PDMS), polymethylvinylsiloxane (PVMS), etc.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PVC flexible polyvinyl chloride
  • PMMA polymethacrylate Ester
  • PI polyimide
  • PPA polyphthalamide
  • PDMS polydimethylsiloxane
  • PVMS polymethylvinylsiloxane
  • the main problems currently facing the flexible transparent conductive film are that the adhesion between the conductive material and the substrate is not strong, the matching is not high, and the conductivity during the substrate deformation process Changes occur to weaken or distort the signal, seriously affecting the performance and life of the device.
  • the technical problem solved by the present invention is to provide a pattern-based layer for existing flexible transparent substrate materials that are not resistant to high temperatures, organic solvents, poor mechanical properties, and weak adhesion to conductive materials. Assembling self-supporting film flexible transparent conductive film and preparation method thereof.
  • a flexible transparent conductive film based on a patterned layer-by-layer assembled self-supporting film includes a layer-by-layer assembled self-supporting film with a patterned network groove on the surface and a conductive material located in the groove.
  • a method for preparing a flexible transparent conductive film based on a patterned layer-by-layer assembled self-supporting film includes the following steps:
  • the preparation of a self-supporting film with layered network grooves on the surface is assembled: the substrate is cleaned, and then the substrate is modified so that its surface is positively charged, and soaked in solution I and solution II, respectively 5 ⁇ 20min, and 2 ⁇ 3 times water washing at intervals, 1 ⁇ 2min each time, circulate for more than 2 cycles to obtain layer-by-layer assembled self-supporting membrane;
  • the NOA63 template and the layer-by-layer assembly self-supporting film are tightly attached together, stacked between two glass sheets, and then placed in the middle of the magnetic imprinting device, applying a pressure of 50-100 bar at room temperature, stored for more than 2h, and removed A template to obtain a layer-by-layer assembled self-supporting film with patterned network grooves on the surface;
  • the layers with patterned network grooves on the surface are assembled into the grooves of the self-supporting film to prepare conductive materials: the conductive material is drip-coated, spin-coated or scraped onto the surface with patterned network grooves Layer-by-layer assembly of self-supporting film, after drying or drying, a layer-by-layer assembly of self-supporting film with conductive material is obtained;
  • the layered self-supporting film with conductive material is separated from the substrate to obtain a flexible transparent conductive film based on the patterned layered self-supporting film.
  • the substrate includes a glass substrate, which is modified with poly(diallyldimethylammonium chloride) or branched polyethyleneimine.
  • the solution I includes a polyacrylic acid solution of 1 to 4 mg/ml or a mixed solution of a polyacrylic acid solution of 1 to 4 mg/ml and hyaluronic acid
  • the solution II includes a poly(allyl ammonium chloride) solution or A mixed solution of branched polyethyleneimine solution and poly(allyl ammonium chloride) solution.
  • the conductive material includes any one or two or more of transparent conductive oxide nanoparticles, metal nanoparticles, silver nanowires, copper nanowires, carbon nanotubes, graphene, or conductive polymers.
  • the method of assembling the self-supporting film with the conductive material layer by layer and separating from the substrate includes any one of a sacrificial layer method, an ion peeling method, a swelling method, or a direct peeling method.
  • the invention adopts a NOA63 flexible template to perform imprinting at room temperature, which can be expanded into a large-scale roll-to-roll imprinting method.
  • methods such as photolithography and ultraviolet imprinting can be used to achieve patterning.
  • hot pressing can be used for layer-by-layer assembly of properties similar to thermosetting or thermoplastic plastics.
  • the template can be copied from the PDMS template, and its periodic patterned structure can be optimized for design, so that the trench structure on the layer-by-layer assembly film accounts for less than 30% of the total area.
  • NOA63 flexible template has low cost and sufficient mechanical strength and toughness, which can not only ensure the high aspect ratio of the pattern, but also obtain a large area and high fidelity patterned structure.
  • Using the improved roll-to-roll room temperature embossing method a large area and continuous operation can be realized, thereby greatly shortening the preparation cycle.
  • Self-support is a relatively high standard requirement proposed and realized by the present invention.
  • the layer-by-layer assembly film is used as the interface modification layer, and the layer-by-layer assembly film is used for all other substrates.
  • the flexible transparent conductive film obtained by modifying and improving the materials should be included in the protection scope of the present invention.
  • the layer-by-layer assembly film Based on the diversity of film-forming substances and film-forming driving forces possessed by the layer-by-layer assembly film itself and the compatibility of the layer-by-layer assembly method with other film preparation technologies and interface modification methods, it is flexible and transparent to the layer-by-layer assembly film Any improvement of the conductive film is included in the protection scope of the present invention. For example, the introduction of antireflection and anti-reflection coatings on the flexible transparent conductive film based on the layer-by-layer assembly film, or changing the surface wetting properties of the flexible transparent conductive film based on the layer-by-layer assembly film.
  • Layer-by-layer assembly of films can be based on any film-forming driving forces, such as static electricity, hydrogen bonds, coordination bonds, ⁇ - ⁇ interactions, van der Waals forces, etc.
  • the film-forming substance can be any structural element, such as polyelectrolytes, nanoparticles, polymer complexes, biological macromolecules, bacteria, cells, etc.
  • Room temperature embossing does not require heating, UV exposure or etching steps, which can greatly save costs and shorten the production cycle.
  • the use of NOA63 flexible template can not only ensure the high aspect ratio of the pattern, but also obtain a large-area, high-fidelity patterned structure.
  • the layer-by-layer assembly self-supporting film has high temperature resistance, thinner thickness, stronger mechanical properties than the existing flexible transparent substrate, the composition and structure of the film can be precisely adjusted, and surface modification is easy to achieve Transmittance, anti-reflection, enhance the adhesion between the substrate and conductive materials and other purposes.
  • the self-supporting layer-by-layer self-repairing film with self-repair function can also realize self-repair of conductive function and transparency, thereby prolonging the service life of the flexible transparent conductive film.
  • the flexible transparent conductive film prepared by the present invention has the characteristics of high temperature resistance, ultra-thin thickness, ultra-strong mechanical performance, ultra-long durability, high conductivity and high transmittance of visible light.
  • PAA polyacrylic acid
  • PAH poly(allyl ammonium chloride)
  • the NOA63 template and the layer-by-layer assembled self-supporting film (PAA/PAH) n are closely attached together, stacked between two glass sheets, and then placed in the middle of the magnetic imprinting equipment, and applied with a pressure of 100 bar at room temperature for more than 2 hours , Remove the template to get the patterned layer-by-layer assembly self-supporting film (PAA/PAH) n .
  • Self-assembled patterned layer supporting film (PAA / PAH) n was heated at 150 °C ⁇ 250 °C crosslinking in a vacuum oven for 1-6 hours, cooled to room temperature.
  • PEDOT:PSS self-supporting film
  • PAA/PAH self-supporting film
  • the acid may be formic acid, phosphoric acid, hydroiodic acid, methanesulfonic acid, etc.
  • the organic solvent may be dimethyl sulfoxide, ethylene glycol, isopropyl alcohol, etc.
  • the PEDOT:PSS filled cross-linked patterned layer assembly self-supporting film (PAA/PAH) n is directly peeled from the glass substrate to obtain the aforementioned flexible transparent conductive film based on the patterned layer assembly self-supporting film.
  • the flexible transparent conductive film has extremely high mechanical strength, transparency and conductivity. The ultimate tensile strength can reach 58.7MPa, the elongation at break can reach 5.4%, the light transmittance in the visible region can reach more than 90%, and the square resistance is only 67 ⁇ sq -1 .
  • the conductive material is a conductive polymer, it has a high degree of matching with the substrate material, thereby giving the flexible transparent conductive film excellent resistance to bending, folding and stretching.
  • the glass substrate is cleaned and modified with branched polyethyleneimine (bPEI) to make its surface positively charged.
  • bPEI branched polyethyleneimine
  • HA hyaluronic acid
  • PAA&HA/bPEI&PAH layer-by-layer assembled self-supporting film
  • the NOA63 template and the layer-by-layer assembled self-supporting film (PAA&HA/bPEI&PAH) n are closely attached together, stacked between two glass sheets, and then placed in the middle of a self-made magnetic imprinting device, and 50 bar pressure is applied at room temperature for 2 hours Above, the template is removed to obtain a patterned layer-by-layer assembled self-supporting film (PAA&HA/bPEI&PAH) n .
  • the silver nanowire solution modified by polyvinylpyrrolidone (PVPON) was drip-coated, spin-coated or knife-coated on the patterned layer-assembling self-supporting film (PAA&HA/bPEI&PAH) n , and dried or dried.
  • PVPON polyvinylpyrrolidone
  • the self-supporting film (PAA&HA/bPEI&PAH) n filled with the patterned layer filled with silver nanowires is placed in a vacuum oven at 150° C. to 250° C. for 1 to 6 hours, and then cooled to room temperature.
  • the optimized cross-linking temperature and time can be used to obtain a suitable degree of cross-linking, which can not only ensure sufficient mechanical strength, but also maintain the fluidity of the molecular segments in the membrane, so as to obtain sufficient mechanical strength and self-healing function.
  • the above-mentioned self-healing high-strength conductive film in the peeling solution to separate the film from the glass substrate, and finally transfer the film to air to dry it to obtain the flexible and transparent self-supporting film based on the patterned layer assembly Conductive film.
  • the ultimate tensile strength of the flexible transparent conductive film can reach 39.8MPa, the elongation at break can reach 7.6%, the transmittance in the visible region can reach more than 89%, and the sheet resistance is only 59 ⁇ sq -1 . After repeated 3000° 180° half-folding, the electrical conductivity remained above 91%.
  • the flexible transparent conductive film can repair scratches of 20 ⁇ m wide and 4 ⁇ m deep within 20 minutes. For the damage of transparency and conductivity caused by ordinary mechanical scratches, the repair process can also be completed within 20 minutes, and the repair effect can reach more than 97%.
  • the HA in the film and the PVPON on the surface of the silver nanowire form multiple hydrogen bonds, effectively solving the problem of weak adhesion between the conductive material and the transparent substrate.
  • the flexible transparent conductive film not only has sufficient mechanical strength but also has all-round self-healing functions of mechanical properties, transparency and conductivity, which can effectively improve the bending resistance and tensile properties of the device and can greatly extend the device Service life.

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Abstract

一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法，属于透明导电膜技术领域，可解决现有柔性透明衬底材料不耐高温、不耐有机溶剂、机械性能差、与导电材料之间的黏附力弱等问题，该柔性透明导电膜主要由图案化层层组装自支持膜和导电材料组成，该方法首先用室温压印技术在层层组装膜表面制备图案化的网络状凹槽，然后在凹槽内填充导电材料，最后将层层组装膜与基底分离形成导电自支持膜。层层组装自支持膜与现有柔性透明衬底相比有耐高温、更薄的厚度，更强的机械性能，膜的组成和结构可精确调控，且易于进行表面修饰，以达到增透、减反射、增强基底与导电材料之间的黏附力等目的。

Description

一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法 技术领域
本发明属于透明导电膜技术领域，具体涉及一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法。
背景技术
透明导电膜在可见光范围内具有高的透过率和高的导电性，已广泛应用于抗静电涂层、电磁屏蔽、太阳能电池、发光二极管、触摸屏、传感器和执行器、智能皮肤等。伴随着电子器件柔性化、轻薄化的发展趋势，柔性透明导电膜的研究和开发日益受到人们的关注。目前，柔性透明导电膜领域的主要研究工作大致分为导电材料和衬底材料两个方面。
导电材料方面，最初广泛应用的ITO透明导电膜质脆、制备温度较高、膜中金属In比较稀缺且有毒，因此人们积极开发新的材料来替代ITO，如以FTO、AZO为代表的不含金属In的透明导电氧化物(TCO)、金属纳米粒子、银纳米线、铜纳米线、碳纳米管、石墨烯、导电聚合物等。
现有的柔性衬底材料多为商品化的聚合物薄膜，如聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、柔性聚氯乙烯(PVC)和聚甲基丙烯酸甲酯(PMMA)、聚酰亚胺(PI)、聚邻苯二甲酰胺(PPA)、聚二甲基硅氧烷(PDMS)和聚甲基乙烯基硅氧烷(PVMS)等。这些商品化的聚合物薄膜普遍存在不耐高温、不耐有机溶剂或透明性不高等问题。
除了导电材料和现有柔性衬底材料本身的缺陷以外，柔性透明导电膜目前面临的主要问题是导电材料与衬底之间的黏附力不强、匹配度不高，衬底形变过程中导电率发生变化使信号减弱或失真，严重影响器件的性能和使用寿命。
发明内容
本发明解决的技术问题是：针对现有柔性透明衬底材料不耐高温、不耐有机溶剂、机械性能差、与导电材料之间的黏附力弱等问题，提供了一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法。
本发明采用如下技术方案：
一种基于图案化层层组装自支持膜的柔性透明导电膜，包括表面带图案化的网络状凹槽的层层组装自支持膜和位于凹槽内的导电材料。
一种基于图案化层层组装自支持膜的柔性透明导电膜的制备方法，包括如下步骤：
第一步，表面带图案化的网络状凹槽的层层组装自支持膜的制备：清洗基底，然后对基底进行修饰，使其表面带正电荷后，分别在溶液Ⅰ和溶液Ⅱ中交替浸泡5～20min，并间隔以2～3次水洗，每次1～2min，循环2个以上周期，得到层层组装自支持膜；
将NOA63模板与层层组装自支持膜紧密贴合在一起，叠放在两个玻璃片中间，然后放置于磁力压印设备中间，在室温下施加50～100bar的压力，保存2h以上，移除模板，得到表面带图案化的网络状凹槽的层层组装自支持膜；
第二步，表面带图案化的网络状凹槽的层层组装自支持膜的凹槽内制备导电材料：将导电材料滴涂、旋涂或刮涂在表面带图案化的网络状凹槽的层层组装自支持膜上，晾干或烘干后，得到带有导电材料的层层组装自支持膜；
第三步，带有导电材料的层层组装自支持膜与基底分离，得到基于图案化层层组装自支持膜的柔性透明导电膜。
所述基底包括玻璃基底，采用聚(二烯丙基二甲基氯化铵)或枝化聚乙烯亚胺进行修饰。
第一步中所述溶液Ⅰ包括1～4mg/ml的聚丙烯酸溶液或1～4mg/ml的聚丙烯酸溶液与透明质酸的混合溶液，溶液Ⅱ包括聚(烯丙基氯化铵)溶液或支化聚乙烯亚胺溶液和聚(烯丙基氯化铵)溶液的混合溶液。
所述导电材料包括透明导电氧化物纳米粒子、金属纳米粒子、银纳米线、铜纳米线、碳纳米管、石墨烯或导电聚合物中的任意一种或两种或两种以上。
带有导电材料的层层组装自支持膜与基底分离的方法包括牺牲层法、离子剥离法、溶胀法或直接剥离法中的任意一种。
本发明采用NOA63柔性模板，在室温下进行压印，可拓展为规模化的roll-to-roll压印方法。对于含光敏成分的层层组装膜，可采用光刻、紫外压印等方法来实现图案化。对于性质类似于热固性或热塑性塑料的层层组装膜，则可采 用热压法。
该模板可由PDMS模板复制而得，其周期性图案化结构可进行优化设计，最终使层层组装膜上的沟槽结构占总面积的百分之三十以下。NOA63柔性模板与硅模板或镍模板相比，成本低，且具备足够的机械强度和韧性，从而既能保证图案的高深宽比，又可以获得大面积、高保真的图案化结构。采用改进了的roll-to-roll室温压印方法，可以实现大面积、连续化操作，从而极大地缩短了制备周期。
自支持是本发明提出并实现了的较为高标准的要求，低于此标准，不脱离本发明的基本理念，而将层层组装膜作为界面修饰层，采用层层组装膜对所有其他衬底材料进行修饰和改进从而获得的柔性透明导电膜应全部包含在本发明的保护范围内。
由层层组装膜本身所具备的成膜物质和成膜驱动力的多样性以及层层组装方法与其他膜制备技术和界面修饰方法的兼容性出发所做的对基于层层组装膜的柔性透明导电膜的任何改进均包含在本发明的保护范围内。比如，在基于层层组装膜的柔性透明导电膜上引入增透、减反射涂层，或改变基于层层组装膜的柔性透明导电膜的表面润湿性能等。
层层组装膜可以基于任意成膜驱动力，如静电、氢键、配位键、π-π相互作用、范德华力等。成膜物质可以是任意构筑基元，如聚电解质、纳米粒子、聚合物复合物、生物大分子、细菌、细胞等。
本发明的有益效果如下：
1.室温压印不需要加热、紫外曝光或刻蚀步骤，可大大节约成本，缩短生产周期。采用NOA63柔性模板，既能保证图案的高深宽比，又可以获得大面积、高保真的图案化结构。
2.层层组装自支持膜与现有柔性透明衬底相比有耐高温、更薄的厚度，更强的机械性能，膜的组成和结构可精确调控，且易于进行表面修饰，以达到增透、减反射、增强基底与导电材料之间的黏附力等目的。此外，具备自修复功能的层层组装自支持膜还可实现导电功能与透明性的自修复，从而延长柔性透明导电膜的使用寿命。
3.本发明制备的柔性透明导电膜具有耐高温、超薄的厚度，超强的机械性 能，超长耐久性，高导电性和可见光高透过率等特征。
具体实施方式
下面结合两个技术方案的具体实例对本发明作进一步阐释，本发明的保护范围不受以下实例的限制。
实施例1
首先对玻璃基底进行清洗，并用聚(二烯丙基二甲基氯化铵)(PDDA)进行修饰，使其表面带正电荷。然后分别在1～4mg/ml聚丙烯酸(PAA)溶液(pH＝2～9)和聚(烯丙基氯化铵)(PAH)溶液(pH＝2～9)中交替浸泡5～20分钟，并间隔以两到三次水洗步骤，每次1～2分钟。循环2个周期以上直至获得足够厚度的层层组装自支持膜(PAA/PAH) n(n为组装周期数)。
将NOA63模板与层层组装自支持膜(PAA/PAH) n紧密贴合在一起，叠放在两个玻璃片中间，然后放置于磁力压印设备中间，在室温下施加100bar压力保持2小时以上，移除模板得到图案化层层组装自支持膜(PAA/PAH) n。
将图案化层层组装自支持膜(PAA/PAH) n在150℃～250℃真空烘箱中加热交联1～6小时，冷却至室温。
将高导电率PEDOT:PSS滴涂、旋涂或刮涂在交联后的图案化层层组装自支持膜(PAA/PAH) n上，晾干或烘干，然后依次在酸、有机溶剂和水中浸泡处理以增强其导电性，并可有效去除凹槽外部多余的PEDOT:PSS残留。其中酸可以是甲酸、磷酸、氢碘酸、甲磺酸等，有机溶剂可以是二甲基亚砜、乙二醇、异丙醇等。
最后将填涂了PEDOT:PSS的交联图案化层层组装自支持膜(PAA/PAH) n从玻璃基底上直接撕下便得到前述基于图案化层层组装自支持膜的柔性透明导电膜。该柔性透明导电膜具备极高的机械强度、透明性和导电性。极限抗拉强度可达58.7MPa，断裂伸长率可达5.4％，可见区光透过率达90％以上，方块电阻只有67Ωsq -1。最重要的是，因导电材料是导电聚合物，与衬底材料匹配度高，从而赋予该柔性透明导电膜极佳的抗弯曲、折叠以及拉伸性能。反复3000次180°对折之后，导电性仍保持96％以上。反复进行伸长率5％的拉伸试验3000次后，导电性仍保持在91％以上，且在首次伸长率达5％时，电流改变只有0.4％。
实施例2
首先对玻璃基底进行清洗，并用枝化聚乙烯亚胺(bPEI)进行修饰，使其表面带正电荷。然后分别在1～4mg/mlPAA和透明质酸(HA)的混合溶液(pH＝2～9)以及bPEI和PAH的混合溶液(pH＝2～9)中交替浸泡5～20分钟，并间隔以两到三次水洗步骤，每次1～2分钟。循环2个周期以上直至获得足够厚度的层层组装自支持膜(PAA&HA/bPEI&PAH) n(n为组装周期数)。
将NOA63模板与层层组装自支持膜(PAA&HA/bPEI&PAH) n紧密贴合在一起，叠放在两个玻璃片中间，然后放置于自制磁力压印设备中间，在室温下施加50bar压力保持2小时以上，移除模板得到图案化层层组装自支持膜(PAA&HA/bPEI&PAH) n。
将聚乙烯基吡咯烷酮(PVPON)修饰的银纳米线溶液滴涂、旋涂或刮涂于图案化层层组装自支持膜(PAA&HA/bPEI&PAH) n上，晾干或烘干。
将上述填涂了银纳米线的图案化层层组装自支持膜(PAA&HA/bPEI&PAH) n置于150℃～250℃真空烘箱中加热交联1～6小时，冷却至室温。采用优化了的交联温度和时间可以获得合适的交联度，既能保证足够的机械强度，又能保持膜内分子链段的流动性，从而获得既具有足够机械强度又具备自修复功能的导电膜。
将上述具备自修复功能的高强度导电膜置于剥离溶液中，实现膜与玻璃基底的分离，最后将膜转移至中空气中晾干便得到前述基于图案化层层组装自支持膜的柔性透明导电膜。该柔性透明导电膜的极限抗拉强度可达39.8MPa，断裂伸长率可达7.6％，在可见区的透过率可达89％以上，方块电阻只有59Ωsq -1。反复3000次180°对折之后，导电性仍保持91％以上。反复进行伸长率5％的拉伸试验3000次后，导电性仍保持在90％以上，且在首次伸长率达5％时，电流改变只有0.3％。在80％的相对湿度下，该柔性透明导电膜可在20分钟内修复20μm宽、4μm深的划痕。对于普通机械刮擦造成的透明性和导电性的损伤，修复过程亦可在20分钟之内完成，修复效果可达97％以上。膜内的HA和银纳米线表面的PVPON形成多重氢键，有效地解决了导电材料与透明衬底之间黏附力不强的问题。另外，该柔性透明导电膜不仅具有足够的机械强度又具备机械性能、透明性和导电性全方位的自修复功能，可有效改善器件的抗弯曲性能、拉伸性能，并能极大地延长器件的使用寿命。

Claims (4)

  1. 一种基于图案化层层组装自支持膜的柔性透明导电膜的制备方法，所述基于图案化层层组装自支持膜的柔性透明导电膜包括表面带图案化的网络状凹槽的层层组装自支持膜和位于凹槽内的导电材料，其特征在于：所述制备方法，包括如下步骤：
    第一步，表面带图案化的网络状凹槽的层层组装自支持膜的制备：清洗基底，然后对基底进行修饰，使其表面带正电荷后，分别在pH为2～9、浓度为1～4mg/ml的聚丙烯酸PAA溶液和pH为2～9的聚(烯丙基氯化铵)PAH溶液中交替浸泡5～20min或分别在pH为2～9、浓度为1～4mg/ml的PAA和透明质酸HA的混合溶液以及pH为2～9的bPEI和PAH的混合溶液中交替浸泡5～20min，并间隔以2～3次水洗，每次1～2min，循环2个以上周期，得到层层组装自支持膜；
    将NOA63模板与层层组装自支持膜紧密贴合在一起，叠放在两个玻璃片中间，然后放置于磁力压印设备中间，在室温下施加100bar的压力，保存2h以上，移除模板，得到表面带图案化的网络状凹槽的层层组装自支持膜；
    第二步，表面带图案化的网络状凹槽的层层组装自支持膜的凹槽内制备导电材料：将导电材料滴涂、旋涂或刮涂在表面带图案化的网络状凹槽的层层组装自支持膜上，晾干或烘干后，得到带有导电材料的层层组装自支持膜；
    第三步，带有导电材料的层层组装自支持膜与基底分离，得到基于图案化层层组装自支持膜的柔性透明导电膜。
  2. 根据权利要求1所述的一种基于图案化层层组装自支持膜的柔性透明导电膜的制备方法，其特征在于：所述基底包括玻璃基底，采用聚(二烯丙基二甲基氯化铵)或枝化聚乙烯亚胺进行修饰。
  3. 根据权利要求1所述的一种基于图案化层层组装自支持膜的柔性透明导电膜的制备方法，其特征在于：所述导电材料包括透明导电氧化物纳米粒子、金属纳米粒子、银纳米线、铜纳米线、碳纳米管、石墨烯或导电聚合物中的任意一种或两种以上。
  4. 根据权利要求1所述的一种基于图案化层层组装自支持膜的柔性透明导电膜的制备方法，其特征在于：带有导电材料的层层组装自支持膜与基底分离的方法包括牺牲层法、离子剥离法、溶胀法或直接剥离法中的任意一种。
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