WO2020029465A1 - Flexible transparent electrode substrate and manufacturing method therefor - Google Patents

Flexible transparent electrode substrate and manufacturing method therefor Download PDF

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WO2020029465A1
WO2020029465A1 PCT/CN2018/116135 CN2018116135W WO2020029465A1 WO 2020029465 A1 WO2020029465 A1 WO 2020029465A1 CN 2018116135 W CN2018116135 W CN 2018116135W WO 2020029465 A1 WO2020029465 A1 WO 2020029465A1
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flexible transparent
polymer
transparent electrode
substrate
manufacturing
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PCT/CN2018/116135
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French (fr)
Chinese (zh)
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张霞
孙作榜
刘刚
陈孝贤
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深圳市华星光电技术有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/32051—Deposition of metallic or metal-silicide layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment

Definitions

  • the present application relates to the field of display technology, and in particular, to a flexible transparent electrode substrate and a manufacturing method thereof.
  • ITO indium zinc oxide
  • IZO indium-doped zinc oxide
  • PVD physical vapor deposition process
  • high temperature are not suitable for the resistance of transparent flexible substrates. High temperature characteristics; At the same time, films made of this oxide generally lack flexibility and are difficult to stretch, and are not suitable for flexible transparent electrodes.
  • the existing flexible transparent substrate has poor structural stability, and its manufacturing process is not suitable for the problem of the high temperature resistance of the flexible transparent substrate.
  • a method for manufacturing a flexible transparent electrode substrate including:
  • step S10 a front substrate is provided, and a peripheral wall structure of the front substrate is provided with a retaining wall structure to prevent the solution from overflowing;
  • Step S20 A flexible transparent carrier having a target pattern is formed on the front substrate, and a preparation material of the flexible transparent carrier is a polymer, and the group of the polymer includes a carboxyl group;
  • Step S30 Treat the flexible transparent support with a strong alkali solution to form a carboxylate ion capable of binding silver ions;
  • Step S40 Coating a silver nitrate solution on the flexible transparent support to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer;
  • Step S50 Treat the first polymer with a chloride solution to form silver chloride on the surface of the first polymer to form a second polymer;
  • step S60 the second polymer is subjected to light treatment to form a flexible transparent carrier and metallic silver on the surface of the flexible transparent carrier, thereby forming a flexible transparent electrode substrate.
  • the front substrate is a hydrophilic substrate
  • the hydrophobic substrate is made of one of PFA, silicon nitride, organic color resist, glass, and organic polymer.
  • the front substrate includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier.
  • the step S20 specifically includes:
  • Step S201 Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
  • Step S202 apply a polymer solution on the first substrate
  • step S203 the first substrate is heated and baked, so that the polymer gathers in the hydrophilic region, forms a front electrode pattern, and removes the solvent.
  • the molecular structural formula of the polymer is: Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
  • the step S20 specifically includes:
  • Step S201 forming a transparent photoresist solution layer on the surface of the front substrate
  • Step S202 baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
  • the composition of the transparent photoresist solution layer includes: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
  • the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, the weight percentage of the monomer is 3 to 16, the weight percentage of the resin is The percentage by weight is 3 to 16, the percentage by weight of the solvent is 50 to 90, and the percentage by weight of the auxiliary agent is 0.3 to 2.
  • the monomer is an acrylic monomer compound with a double bond
  • the resin is a polyacrylic resin
  • a flexible transparent electrode substrate is also provided, which is manufactured by using the method for manufacturing a flexible transparent electrode substrate according to claim 1;
  • the flexible transparent electrode substrate includes:
  • the flexible transparent carrier is disposed on the front substrate, a material for preparing the flexible transparent carrier is a polymer, and a group of the polymer includes a carboxyl group;
  • a flexible transparent electrode is disposed on the flexible transparent carrier and matches the flexible transparent carrier.
  • the flexible transparent electrode is prepared by in-situ reduction on the flexible transparent carrier.
  • the flexible transparent electrode is prepared by sequentially coating a silver nitrate solution and a chloride solution on the flexible transparent support, and performing light irradiation.
  • a method for manufacturing a flexible transparent electrode substrate including:
  • Step S10 Provide a front substrate
  • Step S20 A flexible transparent carrier having a target pattern is formed on the front substrate, and a preparation material of the flexible transparent carrier is a polymer, and the group of the polymer includes a carboxyl group;
  • Step S30 Treat the flexible transparent support with a strong alkali solution to form a carboxylate ion capable of binding silver ions;
  • Step S40 Coating a silver nitrate solution on the flexible transparent support to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer;
  • Step S50 Treat the first polymer with a chloride solution to form silver chloride on the surface of the first polymer to form a second polymer;
  • Step S60 The second polymer is irradiated with light to form a flexible transparent carrier and metallic silver on the surface of the flexible transparent carrier, thereby forming a flexible transparent electrode substrate.
  • the front substrate is a hydrophilic substrate
  • the hydrophobic substrate is made of one of PFA, silicon nitride, organic color resist, glass, and organic polymer.
  • the front substrate includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier.
  • the step S20 specifically includes:
  • Step S201 Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
  • Step S202 apply a polymer solution on the first substrate
  • step S203 the first substrate is heated and baked, so that the polymer is gathered in the hydrophilic region, a front electrode pattern is formed, and the solvent is removed.
  • the molecular structural formula of the polymer is: Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
  • the step S20 specifically includes:
  • Step S201 forming a transparent photoresist solution layer on the surface of the front substrate
  • Step S202 baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
  • the composition of the transparent photoresist solution layer includes: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
  • the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, the weight percentage of the monomer is 3 to 16, the weight percentage of the resin is The percentage by weight is 3 to 16, the percentage by weight of the solvent is 50 to 90, and the percentage by weight of the auxiliary agent is 0.3 to 2.
  • the monomer is an acrylic monomer compound with a double bond
  • the resin is a polyacrylic resin
  • the advantage of the present application is to provide a flexible transparent electrode substrate and a manufacturing method thereof.
  • the flexible transparent electrode uses a polymer as a flexible transparent electrode carrier, and is coated by a solution by means of an ionic bond between a carboxyl group and silver ions.
  • the flexible transparent electrode substrate is formed by light reduction, thereby improving the structural stability of the flexible transparent electrode substrate while avoiding the need to use a high temperature process, avoiding damage to the flexible transparent electrode substrate, and improving the quality of the flexible transparent electrode substrate.
  • FIG. 1 is a schematic flowchart of a method for manufacturing a flexible transparent electrode substrate according to an embodiment of the present application
  • FIGS. 2a-2e are schematic structural diagrams of a method for manufacturing a flexible transparent electrode substrate according to an embodiment of the present application
  • FIG. 3 is a schematic structural diagram of a flexible transparent electrode substrate provided by an embodiment of the present application.
  • the present application provides a flexible transparent electrode substrate and a manufacturing method thereof.
  • the existing flexible transparent substrate has poor structural stability, and its manufacturing process is not suitable for the problem of the high temperature resistance of the flexible transparent substrate. This embodiment can improve this defect. .
  • a method for manufacturing a flexible transparent electrode substrate including the following steps:
  • a front substrate 11 is provided; the front substrate is usually the carrier substrate of the flexible transparent electrode 14 and the flexible transparent carrier 13.
  • the front substrate 11 may be made of PFA, silicon nitride, organic color resist, peeling or organic polymer flexible substrate, and the surface of the front substrate has hydrophilic properties.
  • a flexible transparent carrier 13 having a target pattern is formed on the front substrate 11.
  • the material of the flexible transparent carrier 13 is a polymer, and the group of the polymer includes a carboxyl group. .
  • the front substrate 11 includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier.
  • the step S20 specifically includes:
  • Step S201 Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
  • the pattern of the photomask matches the pattern of the flexible transparent electrode 14 to form a non-hydrophilic region on the front substrate 11; the target pattern region required by the flexible transparent electrode 14 has a good Hydrophilic, non-flexible transparent electrode area has better hydrophobicity; the fluorine-containing gas contains a large amount of active ions in the low-temperature plasma, and when the front substrate 11 is processed, various substrates on the front substrate surface can be opened The chemical bonds of the groups are removed to remove the hydrophilic groups such as hydroxyl groups to achieve the purpose of hydrophobicity.
  • the treatment time for the non-hydrophilic region is from 3 minutes to 60 minutes.
  • a retaining wall structure is provided in the peripheral area of the front substrate 11 to prevent the solution from overflowing.
  • the retaining wall structure can be made of photoresist, and the thickness of the retaining wall structure can be adjusted according to actual needs. .
  • Step S202 apply a polymer solution on the first substrate
  • the molecular structure of the polymer in the polymer solution is: Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
  • step S203 the first substrate is heated and baked, so that the polymer aggregates in a hydrophilic region, forms a front electrode pattern, and removes a solvent.
  • the baking temperature is 40 ° C to 100 ° C
  • the baking time is 10 seconds to 3600 seconds.
  • the hydrophilic polymer nucleophiles with the surface of the front substrate 11 The effect is to make the polymer gather in the hydrophilic area and form a pattern matching the flexible transparent electrode.
  • the polymer is characterized in that after alkali treatment, it can form carboxylate groups with silver ions and have a certain degree of polymerization. At this time, the molecular weight of the polymer is 5000 to 34000 and the acid value is 12 to 38. After removing the solvent, a certain grid structure can be formed to form a flexible transparent carrier with a certain thickness.
  • the thickness of the flexible transparent carrier is 0.1 micrometer to 20 micrometers.
  • the step S20 specifically includes:
  • Step S201 A transparent photoresist solution layer is formed on the surface of the front substrate 11.
  • the composition of the transparent photoresist solution layer includes: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
  • the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, and the weight percentage of the monomer is 3 to 16 The weight percentage of the resin is 3 to 16, the weight percentage of the solvent is 50 to 90, and the weight percentage of the auxiliary agent is 0.3 to 2.
  • Step S202 baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
  • the monomer is an acrylic monomer compound with a double bond, which can undergo a crosslinking reaction during the light and baking stages;
  • the resin is a polyacrylic resin, and the resin has a carboxylate It will dissolve after reacting with developing solution (such as KOH solution).
  • developing solution such as KOH solution
  • the acrylic polymer has more carboxylate functional groups, and the monomer is not formed.
  • the dense film layer provides more carboxylate adsorption sites for the next combination with silver ions.
  • step S30 the flexible transparent support 13 is treated with a strong alkali (such as KOH) solution to form a carboxylate ion capable of binding silver ions;
  • a strong alkali such as KOH
  • the concentration of the strong alkali solution is 0.005 moles per liter to 20 moles per liter, and the treatment is performed by spraying, infiltration, etc., and the treatment time is 0.1 second to 30 seconds to form carboxylate ions capable of binding silver ions.
  • step S40 a silver nitrate solution is coated on the flexible transparent carrier 13 to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer.
  • the reaction equation of the reaction is as follows:
  • Step S50 The first polymer is treated with a chloride solution to form silver chloride on the surface of the first polymer to form a second polymer.
  • the reaction equation of the reaction is as follows:
  • the concentration of the chloride is 0.005 mol per liter to 0.05 mol per liter, wherein the solvent is a mixed solution of ethanol and water, and the ratio of the ethanol and water is 5: 1 to 1: 5.
  • step S60 the second polymer is irradiated with light to form a flexible transparent carrier 13 and metallic silver on the surface of the flexible transparent carrier, and then form a flexible transparent electrode substrate, where metallic silver is The flexible transparent electrode 14 in the application;
  • the reaction equation of the reaction is as follows:
  • the light is ultraviolet light.
  • the illumination time is from 1 second to 1800 seconds
  • the illumination wavelength is from 380 nanometers to 600 nanometers, preferably blue light at 460 nanometers.
  • the method further includes step S60, washing away excess chloride with water, and baking at a temperature of 80 degrees Celsius to 150 degrees Celsius for 10 seconds to 30 seconds to obtain the flexible transparent electrode substrate.
  • a flexible transparent electrode substrate is also provided, and the flexible transparent electrode substrate is manufactured by using the manufacturing method of the flexible transparent electrode substrate;
  • the flexible transparent electrode substrate includes:
  • the flexible transparent carrier 13 is disposed on the front substrate 11, and a preparation material of the flexible transparent carrier 13 is a polymer, and a group of the polymer includes a carboxyl group;
  • a flexible transparent electrode 14 is disposed on the flexible transparent carrier 13 and matched with the flexible transparent carrier 13.
  • the flexible transparent electrode is prepared by in-situ reduction on the flexible transparent carrier 13.
  • the flexible transparent electrode 14 is prepared by sequentially coating a silver nitrate solution and a chloride solution on the flexible transparent carrier 13 and performing light irradiation.
  • the working principle of the flexible transparent electrode substrate is similar to the working principle of the manufacturing method of the flexible transparent electrode substrate.
  • the working principle of the flexible transparent electrode substrate please refer to the working principle of the manufacturing method of the flexible transparent electrode substrate. Here, No longer.
  • the advantage of the present application is to provide a flexible transparent electrode substrate and a manufacturing method thereof.
  • the flexible transparent electrode uses a polymer as a flexible transparent electrode carrier, and is coated by a solution by means of an ionic bond between a carboxyl group and silver ions.
  • the flexible transparent electrode substrate is formed by light reduction, thereby improving the structural stability of the flexible transparent electrode substrate without using a high temperature process, avoiding damage to the flexible transparent electrode substrate, and improving the quality of the flexible transparent electrode substrate.

Abstract

Disclosed are a flexible transparent electrode substrate and a manufacturing method therefor, wherein the method for manufacturing the flexible transparent electrode substrate comprises: providing a front substrate (11); forming a flexible transparent carrier (13) on the front substrate (11), wherein the preparation material of the flexible transparent carrier (13) is a polymer comprising a carboxyl group; and successively treating the flexible transparent carrier (13) with a strong alkali solution, a silver nitrate solution, and a chloride solution, subjecting same to an illumination treatment, and then forming a flexible transparent electrode substrate.

Description

一种柔性透明电极及其制作方法Flexible transparent electrode and manufacturing method thereof 技术领域Technical field
本申请涉及显示技术领域，具体涉及一种柔性透明电极基板及其制作方法。The present application relates to the field of display technology, and in particular, to a flexible transparent electrode substrate and a manufacturing method thereof.
背景技术Background technique
在TFT-LCD中，柔性显示面板装置由于具有便携、可弯折等特点，进而受到广大消费者的青睐。目前，作为液晶显示装置重要组成的透明电极，仍采用透明氧化物材料，如氧化铟锌(ITO)、掺铟氧化锌(IZO)等。然而，通常采用的ITO价格昂贵，资源稀缺，还需要采用制作成本较高的物理气相沉积工艺(PVD)，并需对ITO进行高温处理工艺优化ITO晶体，但是高温不适于透明柔性基板的不耐高温特性；同时，这氧化物制作成膜一般都缺乏柔韧性，难拉伸，不适用于柔性透明电极。Among TFT-LCDs, flexible display panel devices are popular with consumers due to their portability and flexibility. Currently, as an important component of the liquid crystal display device, transparent oxide materials such as indium zinc oxide (ITO) and indium-doped zinc oxide (IZO) are still used. However, the commonly used ITO is expensive and scarce in resources. It also requires the use of a higher cost physical vapor deposition process (PVD) and a high temperature process for ITO to optimize the ITO crystal. However, high temperatures are not suitable for the resistance of transparent flexible substrates. High temperature characteristics; At the same time, films made of this oxide generally lack flexibility and are difficult to stretch, and are not suitable for flexible transparent electrodes.
因此，目前亟需一种柔性透明电极基板及其制作方法以解决上述问题。Therefore, a flexible transparent electrode substrate and a manufacturing method thereof are urgently needed to solve the above problems.
技术问题technical problem
现有柔性透明基板的结构稳定性较差，且其制程工艺不适合柔性透明基板不耐高温特性的问题。The existing flexible transparent substrate has poor structural stability, and its manufacturing process is not suitable for the problem of the high temperature resistance of the flexible transparent substrate.
技术解决方案Technical solutions
为实现上述目的，本申请提供的技术方案如下：In order to achieve the above purpose, the technical solution provided in this application is as follows:
根据本申请的一个方面，提供了一种柔性透明电极基板的制作方法，包括：According to an aspect of the present application, a method for manufacturing a flexible transparent electrode substrate is provided, including:
步骤S10、提供一前基板，所述前基板的外围区域设置有用以防止溶液外溢的挡墙结构；In step S10, a front substrate is provided, and a peripheral wall structure of the front substrate is provided with a retaining wall structure to prevent the solution from overflowing;
步骤S20、在所述前基板上形成具有目标图案的柔性透明载体，所述柔性透明载体的制备材料为聚合物，所述聚合物的基团包括羧基；Step S20: A flexible transparent carrier having a target pattern is formed on the front substrate, and a preparation material of the flexible transparent carrier is a polymer, and the group of the polymer includes a carboxyl group;
步骤S30、采用强碱溶液处理所述柔性透明载体，以形成可结合银离子的羧酸根离子；Step S30: Treat the flexible transparent support with a strong alkali solution to form a carboxylate ion capable of binding silver ions;
步骤S40、在所述柔性透明载体上涂布硝酸银溶液，以将银离子与所述聚合物表面的羧酸根离子结合，形成第一聚合物；Step S40: Coating a silver nitrate solution on the flexible transparent support to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer;
步骤S50、采用氯化物溶液处理第一聚合物，在所述第一聚合物的表面形成氯化银，形成第二聚合物；Step S50: Treat the first polymer with a chloride solution to form silver chloride on the surface of the first polymer to form a second polymer;
步骤S60、对所述第二聚合物进行照光处理，以形成柔性透明载体及所述柔性透明载体表面的金属银，进而形成柔性透明电极基板。In step S60, the second polymer is subjected to light treatment to form a flexible transparent carrier and metallic silver on the surface of the flexible transparent carrier, thereby forming a flexible transparent electrode substrate.
根据本申请一实施例，所述前基板为亲水性基板，所述疏水性基板采用PFA、氮化硅、有机色阻、玻璃和有机聚合物中的其中一者制备。According to an embodiment of the present application, the front substrate is a hydrophilic substrate, and the hydrophobic substrate is made of one of PFA, silicon nitride, organic color resist, glass, and organic polymer.
根据本申请一实施例，所述前基板包括亲水区域和非亲水区域，所述亲水区域的图案与所述柔性透明载体的图案相匹配，所述步骤S20具体包括：According to an embodiment of the present application, the front substrate includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier. The step S20 specifically includes:
步骤S201、采用含氟气体低温等离子体通过光罩对所述非亲水区域进行疏水处理，形成第一基板；Step S201: Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
步骤S202、在所述第一基板上涂布聚合物溶液；Step S202: apply a polymer solution on the first substrate;
步骤S203、加热烘烤所述第一基板，使得聚合物聚集 在亲水区域，形成前电极图案，去掉溶剂。In step S203, the first substrate is heated and baked, so that the polymer gathers in the hydrophilic region, forms a front electrode pattern, and removes the solvent.
根据本申请一实施例，所述聚合物的分子结构式为：
Figure PCTCN2018116135-appb-000001
其中，R 1为氰基、羟基、羧基、碳碳双键和碳碳三键中的至少一者，所述R 2为烷烃类取代基。 According to an embodiment of the present application, the molecular structural formula of the polymer is:
Figure PCTCN2018116135-appb-000001
Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
根据本申请一实施例，所述步骤S20具体包括：According to an embodiment of the present application, the step S20 specifically includes:
步骤S201、在所述前基板的表面形成透明光刻胶溶液层；Step S201: forming a transparent photoresist solution layer on the surface of the front substrate;
步骤S202、对所述透明光刻胶进行烘烤、光罩工艺、显示，以形成柔性透明载体。Step S202: baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
根据本申请一实施例，所述透明光刻胶溶液层的组成包括：起始剂、单体、树脂、溶剂和助剂；According to an embodiment of the present application, the composition of the transparent photoresist solution layer includes: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
其中，所述各组成在所述透明光刻胶溶液层中的重量百分率如下，所述起始剂的重量百分率为0.5至4，所述单体的重量百分率为3至16，所述树脂的重量百分率为3至16，所述溶剂的重量百分率为50至90，所述助剂的重量百分率为0.3至2。Wherein, the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, the weight percentage of the monomer is 3 to 16, the weight percentage of the resin is The percentage by weight is 3 to 16, the percentage by weight of the solvent is 50 to 90, and the percentage by weight of the auxiliary agent is 0.3 to 2.
根据本申请一实施例，所述单体为带双键的丙烯酸单体化合物，所述树脂为聚丙烯酸类树脂。According to an embodiment of the present application, the monomer is an acrylic monomer compound with a double bond, and the resin is a polyacrylic resin.
根据本申请的另一方面，还提供了一种柔性透明电极基板，采用权利要求1中所述柔性透明电极基板的制作方法制作；According to another aspect of the present application, a flexible transparent electrode substrate is also provided, which is manufactured by using the method for manufacturing a flexible transparent electrode substrate according to claim 1;
其中，所述柔性透明电极基板包括：The flexible transparent electrode substrate includes:
前基板，用以承载柔性透明载体；A front substrate for carrying a flexible transparent carrier;
所述柔性透明载体，设置在所述前基板之上，所述柔性透明载体的制备材料为聚合物，所述聚合物的基团包括羧基；The flexible transparent carrier is disposed on the front substrate, a material for preparing the flexible transparent carrier is a polymer, and a group of the polymer includes a carboxyl group;
柔性透明电极，设置在所述柔性透明载体之上，并与所述柔性透明载体匹配，所述柔性透明电极通过在所述柔性透明载体上原位还原制备而成。A flexible transparent electrode is disposed on the flexible transparent carrier and matches the flexible transparent carrier. The flexible transparent electrode is prepared by in-situ reduction on the flexible transparent carrier.
根据本申请一实施例，所述柔性透明电极通过在所述柔性透明载体上依次涂布硝酸银溶液、氯化物溶液，并进行光照后制备而成。According to an embodiment of the present application, the flexible transparent electrode is prepared by sequentially coating a silver nitrate solution and a chloride solution on the flexible transparent support, and performing light irradiation.
根据本申请的又一个方面，提供了一种柔性透明电极基板的制作方法，包括：According to another aspect of the present application, a method for manufacturing a flexible transparent electrode substrate is provided, including:
步骤S10、提供一前基板；Step S10: Provide a front substrate;
步骤S20、在所述前基板上形成具有目标图案的柔性透明载体，所述柔性透明载体的制备材料为聚合物，所述聚合物的基团包括羧基；Step S20: A flexible transparent carrier having a target pattern is formed on the front substrate, and a preparation material of the flexible transparent carrier is a polymer, and the group of the polymer includes a carboxyl group;
步骤S30、采用强碱溶液处理所述柔性透明载体，以形成可结合银离子的羧酸根离子；Step S30: Treat the flexible transparent support with a strong alkali solution to form a carboxylate ion capable of binding silver ions;
步骤S40、在所述柔性透明载体上涂布硝酸银溶液，以将银离子与所述聚合物表面的羧酸根离子结合，形成第一聚合物；Step S40: Coating a silver nitrate solution on the flexible transparent support to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer;
步骤S50、采用氯化物溶液处理第一聚合物，在所述第一聚合物的表面形成氯化银，形成第二聚合物；Step S50: Treat the first polymer with a chloride solution to form silver chloride on the surface of the first polymer to form a second polymer;
步骤S60、对所述第二聚合物进行照光处理，以形成柔性透明载体及所述柔性透明载体表面的金属银，进而形 成柔性透明电极基板。Step S60: The second polymer is irradiated with light to form a flexible transparent carrier and metallic silver on the surface of the flexible transparent carrier, thereby forming a flexible transparent electrode substrate.
根据本申请一实施例，所述前基板为亲水性基板，所述疏水性基板采用PFA、氮化硅、有机色阻、玻璃和有机聚合物中的其中一者制备。According to an embodiment of the present application, the front substrate is a hydrophilic substrate, and the hydrophobic substrate is made of one of PFA, silicon nitride, organic color resist, glass, and organic polymer.
根据本申请一实施例，所述前基板包括亲水区域和非亲水区域，所述亲水区域的图案与所述柔性透明载体的图案相匹配，所述步骤S20具体包括：According to an embodiment of the present application, the front substrate includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier. The step S20 specifically includes:
步骤S201、采用含氟气体低温等离子体通过光罩对所述非亲水区域进行疏水处理，形成第一基板；Step S201: Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
步骤S202、在所述第一基板上涂布聚合物溶液；Step S202: apply a polymer solution on the first substrate;
步骤S203、加热烘烤所述第一基板，使得聚合物聚集在亲水区域，形成前电极图案，去掉溶剂。In step S203, the first substrate is heated and baked, so that the polymer is gathered in the hydrophilic region, a front electrode pattern is formed, and the solvent is removed.
根据本申请一实施例，所述聚合物的分子结构式为：
Figure PCTCN2018116135-appb-000002
其中，R 1为氰基、羟基、羧基、碳碳双键和碳碳三键中的至少一者，所述R 2为烷烃类取代基。 According to an embodiment of the present application, the molecular structural formula of the polymer is:
Figure PCTCN2018116135-appb-000002
Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
根据本申请一实施例，所述步骤S20具体包括：According to an embodiment of the present application, the step S20 specifically includes:
步骤S201、在所述前基板的表面形成透明光刻胶溶液层；Step S201: forming a transparent photoresist solution layer on the surface of the front substrate;
步骤S202、对所述透明光刻胶进行烘烤、光罩工艺、显示，以形成柔性透明载体。Step S202: baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
根据本申请一实施例，所述透明光刻胶溶液层的组成包括：起始剂、单体、树脂、溶剂和助剂；According to an embodiment of the present application, the composition of the transparent photoresist solution layer includes: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
其中，所述各组成在所述透明光刻胶溶液层中的重量百分率如下，所述起始剂的重量百分率为0.5至4，所述单体的重量百分率为3至16，所述树脂的重量百分率为3至16，所述溶剂的重量百分率为50至90，所述助剂的重量百分率为0.3至2。Wherein, the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, the weight percentage of the monomer is 3 to 16, the weight percentage of the resin is The percentage by weight is 3 to 16, the percentage by weight of the solvent is 50 to 90, and the percentage by weight of the auxiliary agent is 0.3 to 2.
根据本申请一实施例，所述单体为带双键的丙烯酸单体化合物，所述树脂为聚丙烯酸类树脂。According to an embodiment of the present application, the monomer is an acrylic monomer compound with a double bond, and the resin is a polyacrylic resin.
有益效果Beneficial effect
本申请的优点是，提供了一种柔性透明电极基板及其制作方法，所述柔性透明电极使用聚合物为柔性透明电极载体，借助羧基与银离子之间的离子键作用，通过溶液涂布而后光照还原的方式形成柔性透明电极基板，进而在提高柔性透明电极基板结构稳定性的同时不需要采用高温工艺，避免损伤柔性透明电极基板，提高了柔性透明电极基板的品质。The advantage of the present application is to provide a flexible transparent electrode substrate and a manufacturing method thereof. The flexible transparent electrode uses a polymer as a flexible transparent electrode carrier, and is coated by a solution by means of an ionic bond between a carboxyl group and silver ions. The flexible transparent electrode substrate is formed by light reduction, thereby improving the structural stability of the flexible transparent electrode substrate while avoiding the need to use a high temperature process, avoiding damage to the flexible transparent electrode substrate, and improving the quality of the flexible transparent electrode substrate.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更清楚地说明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单介绍，显而易见地，下面描述中的附图仅仅是发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly explain the embodiments or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are merely inventions. For some embodiments, for those skilled in the art, other drawings can be obtained based on these drawings without paying creative labor.
图1为本申请实施例提供的柔性透明电极基板的制作方法的流程示意图；FIG. 1 is a schematic flowchart of a method for manufacturing a flexible transparent electrode substrate according to an embodiment of the present application; FIG.
图2a-2e为本申请实施例提供的柔性透明电极基板的制作方法的结构示意图；2a-2e are schematic structural diagrams of a method for manufacturing a flexible transparent electrode substrate according to an embodiment of the present application;
图3为本申请实施例提供的柔性透明电极基板的结构示意图。FIG. 3 is a schematic structural diagram of a flexible transparent electrode substrate provided by an embodiment of the present application.
本申请的实施方式Embodiment of the present application
以下各实施例的说明是参考附加的图示，用以例示本申请可用以实施的特定实施例。本申请所提到的方向用语，例如[上]、[下]、[前]、[后]、[左]、[右]、[内]、[外]、[侧面]等，仅是参考附加图式的方向。因此，使用的方向用语是用以说明及理解本申请，而非用以限制本申请。在图中，结构相似的单元是用以相同标号表示。The following descriptions of the embodiments are with reference to the attached drawings to illustrate specific embodiments that can be implemented by the present application. The directional terms mentioned in this application, such as [up], [down], [front], [rear], [left], [right], [in], [out], [side], etc., are for reference only. The direction of the attached schema. Therefore, the directional terms used are used to explain and understand this application, not to limit this application. In the figure, similarly structured units are denoted by the same reference numerals.
本申请提供了一种柔性透明电极基板及其制作方法，现有柔性透明基板的结构稳定性较差，且其制程工艺不适合柔性透明基板不耐高温特性的问题，本实施例能够改善该缺陷。The present application provides a flexible transparent electrode substrate and a manufacturing method thereof. The existing flexible transparent substrate has poor structural stability, and its manufacturing process is not suitable for the problem of the high temperature resistance of the flexible transparent substrate. This embodiment can improve this defect. .
下面接合附图和具体实施例对本申请做进一步的说明：The following further describes the application with reference to the accompanying drawings and specific embodiments:
如图1所示，根据本申请一实施例，提供了一种柔性透明电极基板的制作方法，包括以下步骤：As shown in FIG. 1, according to an embodiment of the present application, a method for manufacturing a flexible transparent electrode substrate is provided, including the following steps:
如图2a所示，步骤S10、提供一前基板11；所述前基板通常为所述柔性透明电极14及柔性透明载体13的承载基板。As shown in FIG. 2 a, in step S10, a front substrate 11 is provided; the front substrate is usually the carrier substrate of the flexible transparent electrode 14 and the flexible transparent carrier 13.
在一种实施例中，所述前基板11可以采用PFA、氮化 硅、有机色阻、剥离或者有机聚合物柔性基底制备，所述前基板的表面具有亲水特性。In one embodiment, the front substrate 11 may be made of PFA, silicon nitride, organic color resist, peeling or organic polymer flexible substrate, and the surface of the front substrate has hydrophilic properties.
如图2b和2c所示，步骤S20、在所述前基板11上形成具有目标图案的柔性透明载体13，所述柔性透明载体13的制备材料为聚合物，所述聚合物的基团包括羧基。As shown in FIGS. 2b and 2c, in step S20, a flexible transparent carrier 13 having a target pattern is formed on the front substrate 11. The material of the flexible transparent carrier 13 is a polymer, and the group of the polymer includes a carboxyl group. .
在一种实施例中，所述前基板11包括亲水区域和非亲水区域，所述亲水区域的图案与所述柔性透明载体的图案相匹配，所述步骤S20具体包括：In an embodiment, the front substrate 11 includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier. The step S20 specifically includes:
步骤S201、采用含氟气体低温等离子体通过光罩对所述非亲水区域进行疏水处理，形成第一基板；Step S201: Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
在一种实施例中，所述光罩的图案与所述柔性透明电极14的图案相匹配，进而在前基板11上形成非亲水区域；使柔性透明电极14所需目标图案区域具有良好的亲水性，而非柔性透明电极区域具有较好的疏水性；所述含氟气体低温等离子体中含有大量的活性离子，在对前基板11进行处理时，能够打开前基板表面的各种基团的化学键，除去羟基等亲水基团达到疏水的目的。In one embodiment, the pattern of the photomask matches the pattern of the flexible transparent electrode 14 to form a non-hydrophilic region on the front substrate 11; the target pattern region required by the flexible transparent electrode 14 has a good Hydrophilic, non-flexible transparent electrode area has better hydrophobicity; the fluorine-containing gas contains a large amount of active ions in the low-temperature plasma, and when the front substrate 11 is processed, various substrates on the front substrate surface can be opened The chemical bonds of the groups are removed to remove the hydrophilic groups such as hydroxyl groups to achieve the purpose of hydrophobicity.
在一种实施例中，对所述非亲水区域的处理时间为3分钟至60分钟。In one embodiment, the treatment time for the non-hydrophilic region is from 3 minutes to 60 minutes.
在一种实施例中，所述前基板11的外围区域设置有用以防止溶液外溢的挡墙结构，所述挡墙结构可以采用光阻制备，所述挡墙结构的厚度可根据实际需求进行调整。In one embodiment, a retaining wall structure is provided in the peripheral area of the front substrate 11 to prevent the solution from overflowing. The retaining wall structure can be made of photoresist, and the thickness of the retaining wall structure can be adjusted according to actual needs. .
步骤S202、在所述第一基板上涂布聚合物溶液；Step S202: apply a polymer solution on the first substrate;
在一种实施例中，所述聚合物溶液中的聚合物分子结 构式为：
Figure PCTCN2018116135-appb-000003
其中，R 1为氰基、羟基、羧基、碳碳双键和碳碳三键中的至少一者，所述R 2为烷烃类取代基。 In one embodiment, the molecular structure of the polymer in the polymer solution is:
Figure PCTCN2018116135-appb-000003
Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
步骤S203、加热烘烤所述第一基板，使得所述聚合物聚集在亲水区域，形成前电极图案，去掉溶剂。In step S203, the first substrate is heated and baked, so that the polymer aggregates in a hydrophilic region, forms a front electrode pattern, and removes a solvent.
具体的，烘烤温度为40℃至100摄氏度，烘烤时间为10秒至3600秒，以去除聚合物溶液中80％至98％的溶剂，亲水的聚合物与前基板11表面发生亲核作用，使得聚合物聚集在亲水区域，形成与柔性透明电极相匹配的图案。Specifically, the baking temperature is 40 ° C to 100 ° C, and the baking time is 10 seconds to 3600 seconds. In order to remove 80% to 98% of the solvent in the polymer solution, the hydrophilic polymer nucleophiles with the surface of the front substrate 11 The effect is to make the polymer gather in the hydrophilic area and form a pattern matching the flexible transparent electrode.
所述聚合物的特点为：在经过碱处理后，可形成与银离子集合的羧酸根，同时具有一定的聚合度，此时所述聚合物的分子量为5000至34000，酸价为12至38，除去溶剂后能形成一定的网格结构，形成具有一定厚度的柔性透明载体。The polymer is characterized in that after alkali treatment, it can form carboxylate groups with silver ions and have a certain degree of polymerization. At this time, the molecular weight of the polymer is 5000 to 34000 and the acid value is 12 to 38. After removing the solvent, a certain grid structure can be formed to form a flexible transparent carrier with a certain thickness.
在一种实施例中，所述柔性透明载体的厚度为0.1微米至20微米。In one embodiment, the thickness of the flexible transparent carrier is 0.1 micrometer to 20 micrometers.
在一种实施例中，所述步骤S20具体包括：In one embodiment, the step S20 specifically includes:
步骤S201、在所述前基板11的表面形成透明光刻胶溶液层。Step S201: A transparent photoresist solution layer is formed on the surface of the front substrate 11.
在一种实施例中，所述透明光刻胶溶液层的组成包括：起始剂、单体、树脂、溶剂和助剂；In one embodiment, the composition of the transparent photoresist solution layer includes: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
在一种实施例中，所述各组成在所述透明光刻胶溶液层中的重量百分率如下，所述起始剂的重量百分率为0.5 至4，所述单体的重量百分率为3至16，所述树脂的重量百分率为3至16，所述溶剂的重量百分率为50至90，所述助剂的重量百分率为0.3至2。In one embodiment, the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, and the weight percentage of the monomer is 3 to 16 The weight percentage of the resin is 3 to 16, the weight percentage of the solvent is 50 to 90, and the weight percentage of the auxiliary agent is 0.3 to 2.
步骤S202、对所述透明光刻胶进行烘烤、光罩工艺、显示，以形成柔性透明载体。Step S202: baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
在一种实施例中，所述单体为带双键的丙烯酸单体化合物，在光照和烘烤阶段，能够进行交联反应；所述树脂为聚丙烯酸类树脂，该类树脂带有羧酸根，与显影液(如KOH溶液)反应后溶解；由于经过照光、显影而未完成后烘烤的光阻中，丙烯酸脂聚合物带有较多的羧酸根官能团，同时所述单体并未形成致密膜层，为下一步与银离子的结合提供较多的羧酸根吸附点位。In one embodiment, the monomer is an acrylic monomer compound with a double bond, which can undergo a crosslinking reaction during the light and baking stages; the resin is a polyacrylic resin, and the resin has a carboxylate It will dissolve after reacting with developing solution (such as KOH solution). In the photoresist that has not been baked after irradiation and development, the acrylic polymer has more carboxylate functional groups, and the monomer is not formed. The dense film layer provides more carboxylate adsorption sites for the next combination with silver ions.
如图2d所示，步骤S30、采用强碱(如KOH)溶液处理所述柔性透明载体13，以形成可结合银离子的羧酸根离子；所述反应的反应方程式如下：As shown in FIG. 2d, in step S30, the flexible transparent support 13 is treated with a strong alkali (such as KOH) solution to form a carboxylate ion capable of binding silver ions; the reaction equation of the reaction is as follows:
Figure PCTCN2018116135-appb-000004
其中，所述强碱溶液的浓度为0.005摩尔每升至20摩尔每升，采用喷洒、浸润等方式处理，处理时间为0.1秒至30秒，以形成可结合银离子的羧酸根离子。
Figure PCTCN2018116135-appb-000004
Wherein, the concentration of the strong alkali solution is 0.005 moles per liter to 20 moles per liter, and the treatment is performed by spraying, infiltration, etc., and the treatment time is 0.1 second to 30 seconds to form carboxylate ions capable of binding silver ions.
步骤S40、在所述柔性透明载体13上涂布硝酸银溶液，以将银离子与所述聚合物表面的羧酸根离子结合，形成第一聚合物。所述反应的反应方程式如下：In step S40, a silver nitrate solution is coated on the flexible transparent carrier 13 to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer. The reaction equation of the reaction is as follows:
Figure PCTCN2018116135-appb-000005
Figure PCTCN2018116135-appb-000005
步骤S50、采用氯化物溶液处理第一聚合物，在所述第一聚合物的表面形成氯化银，形成第二聚合物；所述反应的反应方程式如下：Step S50: The first polymer is treated with a chloride solution to form silver chloride on the surface of the first polymer to form a second polymer. The reaction equation of the reaction is as follows:
Figure PCTCN2018116135-appb-000006
其中，所述氯化物的浓度为0.005摩尔每升至0.05摩尔每升，其中溶剂为乙醇和水的混合液，所述乙醇和水的比例为5：1至1：5。
Figure PCTCN2018116135-appb-000006
Wherein, the concentration of the chloride is 0.005 mol per liter to 0.05 mol per liter, wherein the solvent is a mixed solution of ethanol and water, and the ratio of the ethanol and water is 5: 1 to 1: 5.
如图2e所示，步骤S60、对所述第二聚合物进行照光处理，以形成柔性透明载体13及所述柔性透明载体表面的金属银，进而形成柔性透明电极基板，其中金属银即为本申请中的柔性透明电极14；所述反应的反应方程式如下：As shown in FIG. 2e, in step S60, the second polymer is irradiated with light to form a flexible transparent carrier 13 and metallic silver on the surface of the flexible transparent carrier, and then form a flexible transparent electrode substrate, where metallic silver is The flexible transparent electrode 14 in the application; the reaction equation of the reaction is as follows:
Figure PCTCN2018116135-appb-000007
进一步的，所述光照采用紫外线光照。
Figure PCTCN2018116135-appb-000007
Further, the light is ultraviolet light.
在一种实施例中，光照时间为1秒至1800秒，光照波长为380纳米至600纳米，优选的460纳米的蓝光。In one embodiment, the illumination time is from 1 second to 1800 seconds, and the illumination wavelength is from 380 nanometers to 600 nanometers, preferably blue light at 460 nanometers.
在一种实施例中，还包括步骤S60、采用水洗掉多余的氯化物，并采用80摄氏度至150摄氏度的温度烘烤10秒至30秒，以得到所述柔性透明电极基板。In one embodiment, the method further includes step S60, washing away excess chloride with water, and baking at a temperature of 80 degrees Celsius to 150 degrees Celsius for 10 seconds to 30 seconds to obtain the flexible transparent electrode substrate.
根据本申请的另一个方面，还提供了一种柔性透明电极基板，所述柔性透明电极基板采用所述柔性透明电极基板的制作方法制作；According to another aspect of the present application, a flexible transparent electrode substrate is also provided, and the flexible transparent electrode substrate is manufactured by using the manufacturing method of the flexible transparent electrode substrate;
在一种实施例中，所述柔性透明电极基板包括：In one embodiment, the flexible transparent electrode substrate includes:
前基板11，用以承载柔性透明载体13；A front substrate 11 for carrying a flexible transparent carrier 13;
所述柔性透明载体13，设置在所述前基板11之上，所述柔性透明载体13的制备材料为聚合物，所述聚合物的基 团包括羧基；The flexible transparent carrier 13 is disposed on the front substrate 11, and a preparation material of the flexible transparent carrier 13 is a polymer, and a group of the polymer includes a carboxyl group;
柔性透明电极14，设置在所述柔性透明载体13之上，并与所述柔性透明载体13匹配，所述柔性透明电极通过在所述柔性透明载体13上原位还原制备而成。A flexible transparent electrode 14 is disposed on the flexible transparent carrier 13 and matched with the flexible transparent carrier 13. The flexible transparent electrode is prepared by in-situ reduction on the flexible transparent carrier 13.
在一种实施例中，所述柔性透明电极14通过在所述柔性透明载体13上依次涂布硝酸银溶液、氯化物溶液，并进行光照后制备而成。In one embodiment, the flexible transparent electrode 14 is prepared by sequentially coating a silver nitrate solution and a chloride solution on the flexible transparent carrier 13 and performing light irradiation.
所述柔性透明电极基板的工作原理与所述柔性透明电极基板的制作方法的工作原理相似，所述柔性透明电极基板的工作原理具体请参考所述柔性透明电极基板的制作方法的工作原理，这里不再赘述。The working principle of the flexible transparent electrode substrate is similar to the working principle of the manufacturing method of the flexible transparent electrode substrate. For the working principle of the flexible transparent electrode substrate, please refer to the working principle of the manufacturing method of the flexible transparent electrode substrate. Here, No longer.
本申请的优点是，提供了一种柔性透明电极基板及其制作方法，所述柔性透明电极使用聚合物为柔性透明电极载体，借助羧基与银离子之间的离子键作用，通过溶液涂布而后光照还原的方式形成柔性透明电极基板，进而在提高柔性透明电极基板结构稳定性的同时不需要采用高温工艺，避免损伤柔性透明电极基板的，提高了柔性透明电极基板的品质。The advantage of the present application is to provide a flexible transparent electrode substrate and a manufacturing method thereof. The flexible transparent electrode uses a polymer as a flexible transparent electrode carrier, and is coated by a solution by means of an ionic bond between a carboxyl group and silver ions. The flexible transparent electrode substrate is formed by light reduction, thereby improving the structural stability of the flexible transparent electrode substrate without using a high temperature process, avoiding damage to the flexible transparent electrode substrate, and improving the quality of the flexible transparent electrode substrate.
综上所述，虽然本申请已以优选实施例揭露如上，但上述优选实施例并非用以限制本申请，本领域的普通技术人员，在不脱离本申请的精神和范围内，均可作各种更动与润饰，因此本申请的保护范围以权利要求界定的范围为准。In summary, although the present application has been disclosed above with preferred embodiments, the above preferred embodiments are not intended to limit the present application. Those skilled in the art can make various modifications without departing from the spirit and scope of the present application. This modification and retouching, therefore, the scope of protection of this application shall be based on the scope defined by the claims.

Claims (16)

  1. 一种柔性透明电极基板的制作方法，其包括：A method for manufacturing a flexible transparent electrode substrate includes:
    步骤S10、提供一前基板，所述前基板的外围区域设置有用以防止溶液外溢的挡墙结构；In step S10, a front substrate is provided, and a peripheral wall structure of the front substrate is provided with a retaining wall structure to prevent the solution from overflowing;
    步骤S20、在所述前基板上形成具有目标图案的柔性透明载体，所述柔性透明载体的制备材料为聚合物，所述聚合物的基团包括羧基；Step S20: A flexible transparent carrier having a target pattern is formed on the front substrate, and a preparation material of the flexible transparent carrier is a polymer, and the group of the polymer includes a carboxyl group;
    步骤S30、采用强碱溶液处理所述柔性透明载体，以形成可结合银离子的羧酸根离子；Step S30: Treat the flexible transparent support with a strong alkali solution to form a carboxylate ion capable of binding silver ions;
    步骤S40、在所述柔性透明载体上涂布硝酸银溶液，以将银离子与所述聚合物表面的羧酸根离子结合，形成第一聚合物；Step S40: Coating a silver nitrate solution on the flexible transparent support to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer;
    步骤S50、采用氯化物溶液处理所述第一聚合物，在所述第一聚合物的表面形成氯化银，形成第二聚合物；Step S50: Treat the first polymer with a chloride solution to form silver chloride on a surface of the first polymer to form a second polymer;
    步骤S60、对所述第二聚合物进行照光处理，以形成柔性透明载体及所述柔性透明载体表面的金属银，进而形成柔性透明电极基板。In step S60, the second polymer is subjected to light treatment to form a flexible transparent carrier and metallic silver on the surface of the flexible transparent carrier, thereby forming a flexible transparent electrode substrate.
  2. 根据权利要求1所述的柔性透明电极基板的制作方法，其中，所述前基板为亲水性基板，所述疏水性基板采用PFA、氮化硅、有机色阻、玻璃和有机聚合物中的其中一者制备。The method for manufacturing a flexible transparent electrode substrate according to claim 1, wherein the front substrate is a hydrophilic substrate, and the hydrophobic substrate is made of PFA, silicon nitride, organic color resist, glass, or organic polymer. One of them is prepared.
  3. 根据权利要求2所述的柔性透明电极基板的制作方法，其中，所述前基板包括亲水区域和非亲水区域，所述亲水区域的图案与所述柔性透明载体的图案相匹配，所述步骤S20具体包括：The method for manufacturing a flexible transparent electrode substrate according to claim 2, wherein the front substrate includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier, so that The step S20 includes:
    步骤S201、采用含氟气体低温等离子体通过光罩对所述非亲水区域进行疏水处理，形成第一基板；Step S201: Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
    步骤S202、在所述第一基板上涂布聚合物溶液；Step S202: apply a polymer solution on the first substrate;
    步骤S203、加热烘烤所述第一基板，使得聚合物聚集在亲水区域，形成前电极图案，去掉溶剂。In step S203, the first substrate is heated and baked, so that the polymer is gathered in the hydrophilic region, a front electrode pattern is formed, and the solvent is removed.
  4. 根据权利要求3所述的柔性透明电极基板的制作方法，其中，所述聚合物的分子结构式为：
    Figure PCTCN2018116135-appb-100001
    其中，R 1为氰基、羟基、羧基、碳碳双键和碳碳三键中的至少一者，所述R 2为烷烃类取代基。     The method for manufacturing a flexible transparent electrode substrate according to claim 3, wherein the molecular structure formula of the polymer is:
    Figure PCTCN2018116135-appb-100001
    Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
  5. 根据权利要求2所述的柔性透明电极基板的制作方法，其中，所述步骤S20具体包括：The method for manufacturing a flexible transparent electrode substrate according to claim 2, wherein the step S20 specifically comprises:
    步骤S201、在所述前基板的表面形成透明光刻胶溶液层；Step S201: forming a transparent photoresist solution layer on the surface of the front substrate;
    步骤S202、对所述透明光刻胶进行烘烤、光罩工艺、显示，以形成柔性透明载体。Step S202: baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
  6. 根据权利要求5所述的柔性透明电极基板的制作方法，其中，所述透明光刻胶溶液层的组成包括：起始剂、单体、树脂、溶剂和助剂；The method for manufacturing a flexible transparent electrode substrate according to claim 5, wherein the composition of the transparent photoresist solution layer comprises: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
    其中，所述各组成在所述透明光刻胶溶液层中的重量百分率如下，所述起始剂的重量百分率为0.5至4，所述单体的重量百分率为3至16，所述树脂的重量百分率为3至16，所述溶剂的重量百分率为50至90，所述助剂的重量百分率 为0.3至2。Wherein, the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, the weight percentage of the monomer is 3 to 16, the weight percentage of the resin is The percentage by weight is 3 to 16, the percentage by weight of the solvent is 50 to 90, and the percentage by weight of the auxiliary agent is 0.3 to 2.
  7. 根据权利要求6所述的柔性透明电极基板的制作方法，其中，所述单体为带双键的丙烯酸单体化合物，所述树脂为聚丙烯酸类树脂。The method for manufacturing a flexible transparent electrode substrate according to claim 6, wherein the monomer is an acrylic monomer compound with a double bond, and the resin is a polyacrylic resin.
  8. 一种柔性透明电极基板，其采用权利要求1中所述柔性透明电极基板的制作方法制作；A flexible transparent electrode substrate, which is manufactured by the method for manufacturing a flexible transparent electrode substrate according to claim 1;
    其中，所述柔性透明电极基板包括：The flexible transparent electrode substrate includes:
    前基板，用以承载柔性透明载体；A front substrate for carrying a flexible transparent carrier;
    所述柔性透明载体，设置在所述前基板之上，所述柔性透明载体的制备材料为聚合物，所述聚合物的基团包括羧基；The flexible transparent carrier is disposed on the front substrate, a material for preparing the flexible transparent carrier is a polymer, and a group of the polymer includes a carboxyl group;
    柔性透明电极，设置在所述柔性透明载体之上，并与所述柔性透明载体匹配，所述柔性透明电极通过在所述柔性透明载体上原位还原制备而成。A flexible transparent electrode is disposed on the flexible transparent carrier and matches the flexible transparent carrier. The flexible transparent electrode is prepared by in-situ reduction on the flexible transparent carrier.
  9. 根据权利要求8所述的柔性透明电极基板，其中，所述柔性透明电极通过在所述柔性透明载体上依次涂布硝酸银溶液、氯化物溶液，并进行光照后制备而成。The flexible transparent electrode substrate according to claim 8, wherein the flexible transparent electrode is prepared by sequentially coating a silver nitrate solution and a chloride solution on the flexible transparent carrier and performing light irradiation.
  10. 一种柔性透明电极基板的制作方法，其包括：A method for manufacturing a flexible transparent electrode substrate includes:
    步骤S10、提供一前基板；Step S10: Provide a front substrate;
    步骤S20、在所述前基板上形成具有目标图案的柔性透明载体，所述柔性透明载体的制备材料为聚合物，所述聚合物的基团包括羧基；Step S20: A flexible transparent carrier having a target pattern is formed on the front substrate, and a preparation material of the flexible transparent carrier is a polymer, and the group of the polymer includes a carboxyl group;
    步骤S30、采用强碱溶液处理所述柔性透明载体，以形成可结合银离子的羧酸根离子；Step S30: Treat the flexible transparent support with a strong alkali solution to form a carboxylate ion capable of binding silver ions;
    步骤S40、在所述柔性透明载体上涂布硝酸银溶液， 以将银离子与所述聚合物表面的羧酸根离子结合，形成第一聚合物；Step S40: coating a silver nitrate solution on the flexible transparent support to combine silver ions with carboxylate ions on the surface of the polymer to form a first polymer;
    步骤S50、采用氯化物溶液处理所述第一聚合物，在所述第一聚合物的表面形成氯化银，形成第二聚合物；Step S50: Treat the first polymer with a chloride solution to form silver chloride on a surface of the first polymer to form a second polymer;
    步骤S60、对所述第二聚合物进行照光处理，以形成柔性透明载体及所述柔性透明载体表面的金属银，进而形成柔性透明电极基板。In step S60, the second polymer is subjected to light treatment to form a flexible transparent carrier and metallic silver on the surface of the flexible transparent carrier, thereby forming a flexible transparent electrode substrate.
  11. 根据权利要求10所述的柔性透明电极基板的制作方法，其中，所述前基板为亲水性基板，所述疏水性基板采用PFA、氮化硅、有机色阻、玻璃和有机聚合物中的其中一者制备。The method for manufacturing a flexible transparent electrode substrate according to claim 10, wherein the front substrate is a hydrophilic substrate, and the hydrophobic substrate is made of PFA, silicon nitride, organic color resist, glass, or organic polymer. One of them is prepared.
  12. 根据权利要求11所述的柔性透明电极基板的制作方法，其中，所述前基板包括亲水区域和非亲水区域，所述亲水区域的图案与所述柔性透明载体的图案相匹配，所述步骤S20具体包括：The method for manufacturing a flexible transparent electrode substrate according to claim 11, wherein the front substrate includes a hydrophilic region and a non-hydrophilic region, and a pattern of the hydrophilic region matches a pattern of the flexible transparent carrier, so that The step S20 includes:
    步骤S201、采用含氟气体低温等离子体通过光罩对所述非亲水区域进行疏水处理，形成第一基板；Step S201: Use a fluorine-containing gas low-temperature plasma to perform a hydrophobic treatment on the non-hydrophilic region through a photomask to form a first substrate;
    步骤S202、在所述第一基板上涂布聚合物溶液；Step S202: apply a polymer solution on the first substrate;
    步骤S203、加热烘烤所述第一基板，使得聚合物聚集在亲水区域，形成前电极图案，去掉溶剂。In step S203, the first substrate is heated and baked, so that the polymer is gathered in the hydrophilic region, a front electrode pattern is formed, and the solvent is removed.
  13. 根据权利要求12所述的柔性透明电极基板的制作方法，其中，所述聚合物的分子结构式为：
    Figure PCTCN2018116135-appb-100002
    其中，R 1为氰基、羟基、羧基、 碳碳双键和碳碳三键中的至少一者，所述R 2为烷烃类取代基。     The method for manufacturing a flexible transparent electrode substrate according to claim 12, wherein the molecular structure formula of the polymer is:
    Figure PCTCN2018116135-appb-100002
    Wherein, R 1 is at least one of a cyano group, a hydroxyl group, a carboxyl group, a carbon-carbon double bond, and a carbon-carbon triple bond, and R 2 is an alkane-based substituent.
  14. 根据权利要求11所述的柔性透明电极基板的制作方法，其中，所述步骤S20具体包括：The method for manufacturing a flexible transparent electrode substrate according to claim 11, wherein the step S20 specifically comprises:
    步骤S201、在所述前基板的表面形成透明光刻胶溶液层；Step S201: forming a transparent photoresist solution layer on the surface of the front substrate;
    步骤S202、对所述透明光刻胶进行烘烤、光罩工艺、显示，以形成柔性透明载体。Step S202: baking, masking, and displaying the transparent photoresist to form a flexible transparent carrier.
  15. 根据权利要求14所述的柔性透明电极基板的制作方法，其中，所述透明光刻胶溶液层的组成包括：起始剂、单体、树脂、溶剂和助剂；The method for manufacturing a flexible transparent electrode substrate according to claim 14, wherein the composition of the transparent photoresist solution layer comprises: an initiator, a monomer, a resin, a solvent, and an auxiliary agent;
    其中，所述各组成在所述透明光刻胶溶液层中的重量百分率如下，所述起始剂的重量百分率为0.5至4，所述单体的重量百分率为3至16，所述树脂的重量百分率为3至16，所述溶剂的重量百分率为50至90，所述助剂的重量百分率为0.3至2。Wherein, the weight percentage of each composition in the transparent photoresist solution layer is as follows, the weight percentage of the initiator is 0.5 to 4, the weight percentage of the monomer is 3 to 16, the weight percentage of the resin is The percentage by weight is 3 to 16, the percentage by weight of the solvent is 50 to 90, and the percentage by weight of the auxiliary agent is 0.3 to 2.
  16. 根据权利要求15所述的柔性透明电极基板的制作方法，其中，所述单体为带双键的丙烯酸单体化合物，所述树脂为聚丙烯酸类树脂。The method for manufacturing a flexible transparent electrode substrate according to claim 15, wherein the monomer is an acrylic monomer compound with a double bond, and the resin is a polyacrylic resin.
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