WO2023116889A1 - 一种用于在基材上形成金属网格的方法和装置 - Google Patents

一种用于在基材上形成金属网格的方法和装置 Download PDF

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WO2023116889A1
WO2023116889A1 PCT/CN2022/141449 CN2022141449W WO2023116889A1 WO 2023116889 A1 WO2023116889 A1 WO 2023116889A1 CN 2022141449 W CN2022141449 W CN 2022141449W WO 2023116889 A1 WO2023116889 A1 WO 2023116889A1
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substrate
plating solution
layer
developing
copper
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PCT/CN2022/141449
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English (en)
French (fr)
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赵亚永
季成刚
严少泽
鹿轩
王钧
江建国
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浙江鑫柔科技有限公司
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3014—Imagewise removal using liquid means combined with ultrasonic means
    • 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
    • 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
    • G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material

Definitions

  • the invention belongs to the technical field of touch sensors, and more particularly relates to a method and device for forming a metal grid on a substrate.
  • the conductive material of the conductive film as a key component usually uses indium tin oxide (ITO), nano-silver wire and metal grid, among which the metal grid conductive film is low in cost and low in resistance.
  • ITO indium tin oxide
  • nano-silver wire and metal grid among which the metal grid conductive film is low in cost and low in resistance.
  • the traditional metal grid production process mainly includes coating a photoresist layer on the surface of a flexible substrate by roll-to-roll coating, in which a catalytic layer such as a metal nanoparticle catalytic layer is attached to the surface of the photoresist layer for post-processing
  • a catalytic layer such as a metal nanoparticle catalytic layer
  • Electroless copper plating after UV exposure, the substrate is then wet process (development, copper plating) to obtain a touch sensor based on copper metal grid.
  • the touch sensor produced by the traditional production process tends to form residual copper on its surface, especially near the metal grid lines. short circuit.
  • the purpose of the present invention is to solve the above-mentioned technical problems proposed, and to provide a method for forming a metal grid on a substrate. After the metal grid is formed on the substrate by this method, it is not easy to is to leave residual metal near the metal grid lines.
  • the reason for the formation of this residual copper may be: (1) in the development The catalytic layer washed away in the process is easy to stay in the developer, and re-adsorbed to the surface of the substrate after the developer accumulates a certain amount of catalytic layer components; (2) The catalytic layer is too thick, resulting in the catalytic layer not completely attached to the photoresist layer (3) the copper plating speed is too fast, and the activity of the copper bath is high; (4) the development process does not tear the bottom; and (5) the exposure is uneven.
  • the present invention provides a method for forming a metal grid on a substrate, which includes the following steps:
  • step (1) (2) exposing and developing the substrate treated in step (1) to form a predetermined pattern on the surface of the substrate;
  • step (3) performing electroless plating on the substrate treated in step (2), so as to form the metal grid on the substrate according to the predetermined pattern
  • the developing is carried out in the presence of ultrasonic waves.
  • the photoresist layer is a positive photoresist layer or a negative photoresist layer, and when the surface is a plurality of surfaces, the photoresist layers applied on the plurality of surfaces are the same or different.
  • the catalytic layer is a coating containing metal nanoparticles, preferably, the catalytic layer is a nano-palladium particle catalytic layer.
  • the method further includes applying a protective layer on the surface of the catalytic layer.
  • the exposure is UV exposure, preferably contact UV exposure.
  • the electroless plating is performed by partially or completely immersing the substrate in an electroless plating solution.
  • the electroless plating solution is selected from one or more of silver plating solution, nickel plating solution, copper plating solution, cobalt plating solution and nickel plating solution.
  • the frequency of the ultrasonic waves is 20-780KHz, preferably 40-220KHz.
  • the ultrasonic treatment time is at least 10s, preferably 10-60s, more preferably 20-40s.
  • the present invention also provides a device for implementing the above-mentioned method of the present invention to form the metal grid on the substrate, which includes:
  • a coating module configured to apply the photoresist layer and the catalytic layer, and optionally the protective layer, to one or more surfaces of the substrate;
  • an exposure module configured to perform the exposing to the substrate to cure a portion of the coating on the substrate
  • a developing module configured to include an ultrasonic wave generating device to perform the developing on the substrate in the presence of the ultrasonic wave to remove the uncured portion of the coating on the substrate;
  • An electroless plating module configured to perform electroless plating on the base material to form the metal grid on the base material.
  • the photoresist and catalyst residue near the circuit after development can be effectively removed, thereby significantly reducing the residual copper near the circuit after copper plating, and the resulting metal grid
  • the function and appearance yield of touch sensor products are significantly improved; in addition, the method and device provided by the present invention further have the effect of reducing the line width of the metal grid.
  • Fig. 1 has shown the copper grid growth situation when forming copper grid on substrate according to the method for embodiment 4 of the present invention
  • Fig. 2 has shown the copper grid growth situation when forming copper grid on substrate according to the method for embodiment 5 of the present invention
  • Fig. 3 has shown the copper grid growth situation when forming copper grid on substrate according to the method for comparative example 1 of the present invention
  • Fig. 4 has shown the copper grid growth situation when forming copper grid on substrate according to the method for embodiment 8 of the present invention
  • Fig. 5 has shown the copper grid growth situation when forming copper grid on substrate according to the method for embodiment 9 of the present invention.
  • Fig. 6 has shown the copper grid growth situation when forming copper grid on substrate according to the method for embodiment 10 of the present invention.
  • FIG. 7 shows the growth of the copper grid when the copper grid is formed on the substrate according to the method of Comparative Example 1 of the present invention.
  • the present invention provides a method for forming a metal grid on a substrate comprising the steps of:
  • step (1) (2) exposing and developing the substrate treated in step (1) to form a predetermined pattern on the surface of the substrate;
  • step (3) performing electroless plating on the substrate treated in step (2), so as to form the metal grid on the substrate according to the predetermined pattern
  • the developing is carried out in the presence of ultrasonic waves.
  • the substrate used in the present invention may be various substrates known to those skilled in the art.
  • the substrate may be highly transparent (transmittance not lower than 90% (eg, 95%) in the wavelength range of visible light).
  • the substrate can be flexible/bendable, so that it is more suitable for roll-to-roll continuous production process, which not only improves manufacturing efficiency and reduces manufacturing cost, but also can be widely used in flexible and foldable touch screens.
  • the substrate may have a UV blocking function itself and/or artificially, so that photoresist layers with different absorption wavelengths can be used on the surface of the substrate, thereby providing more choices for the types of photoresist layers.
  • the substrate can be made of, for example, polyethylene terephthalate (PET), transparent polyimide (CPI), cycloolefin polymer (COP), super retardation film (SRF), polycarbonate (PC) and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • CPI transparent polyimide
  • COP cycloolefin polymer
  • SRF super retardation film
  • PC polycarbonate
  • PEN polyethylene naphthalate
  • the photoresist layer of the present invention can be a positive photoresist layer or a negative photoresist layer, and when the surface is a plurality of surfaces, the photoresist layers applied on the plurality of surfaces can be the same or different, namely Each is independently selected from the same or different positive photoresist layer or negative photoresist layer.
  • the positive photoresist layer may preferably comprise a resin material that is soluble in a developer after exposure, thereby forming the same pattern as the mask after exposure; and the negative photoresist layer may preferably Contains a resin material that is insoluble in a developing solution after exposure, so that a pattern opposite to that of the mask is formed after exposure.
  • the catalytic layer of the present invention is used to reduce the metal ions in the electroless plating solution into metal and attach to the surface of the catalytic layer in the subsequent electroless plating stage, thereby forming a metal grid with a desired pattern, that is, the main function of the catalytic layer is Can catalyze the conversion of metal ions into metals. Therefore, based on the function of the catalytic layer, the catalytic layer may be a coating containing known various metal nanoparticles without particular limitation. In a preferred embodiment, the catalytic layer may be a nano palladium particle catalytic layer.
  • the method for forming a metal grid on a substrate according to the present invention may also include the step of forming a further protective layer on the catalytic layer.
  • the protective layer is mainly used for protecting in the subsequent exposure stage to prevent coating
  • the layer is damaged by the mask, especially when the exposure is a contact exposure, the protective layer can effectively prevent the coating from being damaged by the mask, and the protective layer can also be washed off by the developing solution later in the developing stage.
  • the protective layer material can be made using conventional protective layer materials in the art.
  • the protective layer material may be a water-soluble material, so that it can be dissolved in an aqueous developer solution during the development stage.
  • the term "exposure” refers to the step of exposing the substrate after the above coatings to light (especially ultraviolet light, i.e. UV light), and partially shielding the light through a mask during the exposure,
  • the photoresist layer exposed to light reacts with light to change its structural properties, and in the subsequent development stage, based on whether the structural properties of the photoresist layer change, a part of the photoresist layer with the same properties and formed on it
  • the catalytic layer is washed away to form the desired pattern on the substrate.
  • the exposure may be contact ultraviolet exposure.
  • the term "development” refers to a step of dissolving and washing away undesired portions other than a predetermined pattern therein by a developer, which is generally an aqueous solution containing an alkaline compound and a surfactant
  • the basic compound can be an inorganic or organic basic compound, these inorganic and organic basic compounds can be used alone or in combination of two or more; and as a surfactant, can be selected from nonionic surfactants, anionic surfactants and cationic surfactants, these surfactants may be used alone or in combination of two or more.
  • the inventors have found through research that the main reason for the formation of residual copper is that the catalyst particles cannot be completely cleaned during the developing process, so that it is easy to cause copper growth in the subsequent electroless copper plating process, so based on this
  • the reason is that the development step was optimized in a targeted manner. That is, the developing step of the present invention is performed in the presence of ultrasonic waves.
  • the frequency of the ultrasonic wave and the ultrasonic treatment time are within the predetermined range of the present invention, the effect of removing residual copper is better.
  • the frequency of the ultrasonic waves may be 20-780KHz, preferably 40-220KHz, such as 40KHz, 60KHz, 120KHz, 220KHz and so on.
  • the ultrasonic treatment time may be at least 10s, preferably 10-60s, more preferably 20-40s, such as 24s, 30s, 36s and so on. According to online experiments, there is also a risk of line drop-off when excessively increasing the ultrasound developing time.
  • electroless plating refers to the step of converting metal ions in an electroless plating solution into metals and attaching (plating) them on the surface of a substrate by chemical means, namely reduction.
  • the electroless plating is performed by partially immersing the substrate in an electroless plating solution.
  • the electroless plating is performed by fully immersing the substrate in an electroless plating solution.
  • different electroless plating solutions can be used according to the needs of different metals.
  • the electroless plating solution may be selected from one or more of silver plating solution, nickel plating solution, copper plating solution, cobalt plating solution and nickel plating solution.
  • the method of the present invention may also include the step of blackening the metal layer, so as to cover the color of the metal itself.
  • the present invention also provides a device for implementing the above-mentioned method of the present invention to form the metal grid on the substrate, which includes:
  • a coating module configured to apply the photoresist layer and the catalytic layer, and optionally the protective layer, to one or more surfaces of the substrate;
  • an exposure module configured to perform the exposing to the substrate to cure a portion of the coating on the substrate
  • a developing module configured to include an ultrasonic wave generating device to perform the developing on the substrate in the presence of the ultrasonic wave to remove the uncured portion of the coating on the substrate;
  • An electroless plating module configured to perform electroless plating on the base material to form the metal grid on the base material.
  • the photoresist and catalyst residue near the circuit after development can be effectively removed, thereby significantly reducing the residual copper near the circuit after copper plating, and the resulting metal grid
  • the function and appearance yield of touch sensor products have been significantly improved.
  • a copper grid was formed on the substrate in a manner similar to that of Example 1, except that the wavelength of the ultrasonic wave was 60 KHz. The observation results under a microscope are shown in Table 1.
  • a copper grid was formed on the substrate in a manner similar to that of Example 1, except that the wavelength of the ultrasonic waves was 120 KHz. The observation results under a microscope are shown in Table 1.
  • a copper grid was formed on the substrate in a manner similar to that of Example 1, except that the wavelength of the ultrasonic waves was 220 KHz. The observation results under a microscope are shown in Table 1 and FIG. 1 .
  • a copper grid was formed on the substrate in a manner similar to that of Example 1, except that the wavelength of the ultrasonic wave was 780 KHz. The observation results under a microscope are shown in Table 1 and FIG. 2 .
  • a copper grid was formed on the substrate in a manner similar to that of Example 1, except that ultrasonic waves were not used in the development stage, and the development time was 30 s.
  • the observation results under a microscope are shown in Table 1 and FIG. 3 .
  • adhesion level use 3M special tape for adhesion to pull out the grid area. If no grid falls off, the adhesion is F0; if the grid falls off from 0% to 20% of the test area, the adhesion is It is F1; the shedding mesh accounts for 20%-50% of the test area, then the adhesion is F2; the shedding mesh accounts for more than 50% of the test area, then the adhesion is F3.
  • a level basically no metal residue under microscope observation
  • B level slight metal residue under microscope observation, and the width is within half the line width
  • C level serious residual metal under microscope observation, and the width exceeds half the line width.
  • a copper grid was formed on the substrate in a manner similar to that of Example 6, except that the ultrasonic treatment time was 12 s.
  • the observation results under a microscope are shown in Table 2.
  • a copper grid was formed on the substrate in a manner similar to that of Example 6, except that the ultrasonic treatment time was 24s.
  • the observation results under a microscope are shown in Table 2 and FIG. 4 .
  • a copper grid was formed on the substrate in a manner similar to that of Example 6, except that the ultrasonic treatment time was 30 s.
  • the observation results under a microscope are shown in Table 2 and FIG. 5 .
  • a copper grid was formed on the substrate in a manner similar to that of Example 6, except that the ultrasonic treatment time was 38 s.
  • the observation results under a microscope are shown in Table 2 and FIG. 6 .
  • a copper grid was formed on the substrate in a manner similar to that of Example 6, except that ultrasonic waves were not used in the development stage, and the development time was 30 s.
  • the observation results under a microscope are shown in Table 2 and FIG. 7 .
  • the present application has confirmed through the comparison of the above examples and comparative examples that the method of the present application adds ultrasonic waves in the development process, which can not only effectively solve the problem of metal residue, but also achieve the effect of reducing the line width of the metal grid .

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Abstract

本发明提供了一种用于在基材上形成金属网格的方法和装置，所述方法包括以下步骤：(1)在所述基材的一个或多个表面上依次施加光阻层和催化层；(2)对经步骤(1)处理的基材进行曝光和显影，以在所述基材的表面上形成预定图案；以及(3)对经步骤(2)处理的基材进行化学镀，以按所述预定图案在所述基材上形成所述金属网格，其中所述显影在超声波的存在下进行。在通过本发明所提供的方法和装置在基材上形成金属网格时，能够有效去除显影后线路附近的光阻及催化剂残留，从而显著减少镀铜后线路附近的残铜，所得金属网格触控传感器产品功能及外观良率有明显提升，并且本发明所提供的方法和装置还进一步具有减小金属网格线宽的效果。

Description

一种用于在基材上形成金属网格的方法和装置 技术领域
本申请要求于2021年12月24日提交的申请号为202111600525.5的中国专利申请的优先权，其全部内容通过引用并入本文。
技术领域
本发明属于触控传感器技术领域，更具体地，涉及一种用于在基材上形成金属网格的方法和装置。
背景技术
目前在消费类电子触控屏行业中，作为关键部件的导电膜的导电材质通常使用氧化铟锡(ITO)、纳米银线和金属网格等，其中金属网格导电膜因其成本低、电阻最小、可应用于超薄可折叠的电子产品中等优势而受到广泛关注。
传统的金属网格生产工艺主要包括通过卷对卷涂布方式在柔性基材表面涂覆光阻层，其中光阻层表面会附上一层催化层如金属纳米颗粒催化层用于后制程中的化学镀铜，经过紫外曝光后基材再经过湿制程(显影、镀铜)后得到基于铜金属网格的触控传感器。然而，由传统生产工艺所制得的触控传感器在其表面上、特别是靠近金属网格线附近处容易形成残铜，这些留在表面的残铜不仅影响产品外观，严重时甚至会引起电路短路。
然而，目前没有相关研究报导在传统金属网格生产工艺中形成这些残铜的原因，以及如何解决这种缺陷的方法。
发明内容
本发明的目的在于解决提出的上述技术问题，提供一种用于在基材上形成金属网格的方法，通过该方法在基材上形成金属网格后，不容易在基材表面处、 特别是靠近金属网格线附近处留下残余金属。
由于在当前的研究报道中鲜有关于该技术问题的产生原因以及如何解决该技术问题的报道，发明人也因此提出了多种假设，例如该残铜形成的原因可能在于：(1)在显影工序中洗去的催化层容易停留在显影液中，在显影液积累一定的催化层组分后重新吸附到基材表面；(2)催化层过厚，导致催化层未完全附着于光阻层上，而在后续制程中吸附到基材表面；(3)镀铜速度太快，铜槽活性较高；(4)显影工序不扯底；以及(5)曝光不均匀等。
经过一系列的研究后，发明人最终发现，残铜形成的主要原因在于显影过程中有催化剂颗粒无法完全被清洗干净从而在后续的化学镀铜过程中易于引起铜生长，因此基于该原因针对性地设计了一种用于在基材上形成金属网格的方法，从而完成了本发明。
基于上述目的和发现，在一方面，本发明提供了一种用于在基材上形成金属网格的方法，其包括以下步骤：
(1)在所述基材的一个或多个表面上依次施加光阻层和催化层；
(2)对经步骤(1)处理的基材进行曝光和显影，以在所述基材的表面上形成预定图案；以及
(3)对经步骤(2)处理的基材进行化学镀，以按所述预定图案在所述基材上形成所述金属网格，
其中，所述显影在超声波的存在下进行。
在一个实施方式中，所述光阻层为正性光阻层或负性光阻层，并且当所述表面为多个表面时，所述多个表面上施加的所述光阻层相同或不同。
在另一个实施方式中，所述催化层是包含金属纳米颗粒的涂层，优选地，所述催化层为纳米钯颗粒催化层。
在另一个实施方式中，所述方法还包括在所述催化层的表面上施加保护层。
在另一个实施方式中，所述曝光为紫外曝光，优选为接触式紫外曝光。
在另一个实施方式中，所述化学镀通过将所述基材部分或全部浸没在化学镀溶液中的方式来进行。
在另一个实施方式中，所述化学镀溶液选自镀银溶液、镀镍溶液、镀铜溶液、镀钴溶液和镀镍溶液中的一种或多种。
在另一个实施方式中，在所述显影过程中，所述超声波的频率为20-780KHz，优选为40-220KHz。
在另一个实施方式中，在所述显影过程中，所述超声波的处理时间为至少10s，优选为10-60s，更优选为20-40s。
在另一方面，本发明还提供了一种用于实施本发明的上述方法以在所述基材上形成所述金属网格的装置，其包括：
涂覆模块，其配置成将所述光阻层和所述催化层、以及任选地所述保护层施加在所述基材的一个或多个表面上；
曝光模块，其配置成对所述基材进行所述曝光，以使所述基材上的涂层的一部分固化；
显影模块，其配置成包括超声波发生装置，以在所述超声波的存在下对所述基材进行所述显影，去除所述基材上的所述涂层的未固化部分；以及
化学镀模块，其配置成对所述基材进行化学镀，以在所述基材上形成所述金属网格。
在通过本发明所提供的方法和装置在基材上形成金属网格时，能够有效去除显影后线路附近的光阻及催化剂残留，从而显著减少镀铜后线路附近的残铜，所得金属网格触控传感器产品功能及外观良率有明显提升；另外本发明所提供的方法和装置还进一步具有减小金属网格线宽的效果。
附图说明
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：
图1示出了根据本发明实施例4的方法在基材上形成铜网格时的铜网格生长情况；
图2示出了根据本发明实施例5的方法在基材上形成铜网格时的铜网格生长情况；
图3示出了根据本发明比较例1的方法在基材上形成铜网格时的铜网格生长情况；
图4示出了根据本发明实施例8的方法在基材上形成铜网格时的铜网格生长情况；
图5示出了根据本发明实施例9的方法在基材上形成铜网格时的铜网格生长情况；
图6示出了根据本发明实施例10的方法在基材上形成铜网格时的铜网格生长情况；以及
图7示出了根据本发明比较例1的方法在基材上形成铜网格时的铜网格生长情况。
具体实施方式
以下对本发明的发明构思进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
除非另有定义，本文使用的所有术语(包括技术和科学术语)具有与本发明所属领域的普通技术人员通常理解的相同的含义。还应当理解，诸如在通常使用的字典中定义的那些术语应该被解释为具有与它们在相关技术的上下文中的含义一致的含义，并且不会以理想化或过度形式化的含义来解释，除非在此明确地定义。
在一方面，本发明提供了一种用于在基材上形成金属网格的方法，其包括 以下步骤：
(1)在所述基材的一个或多个表面上依次施加光阻层和催化层；
(2)对经步骤(1)处理的基材进行曝光和显影，以在所述基材的表面上形成预定图案；以及
(3)对经步骤(2)处理的基材进行化学镀，以按所述预定图案在所述基材上形成所述金属网格，
其中，所述显影在超声波的存在下进行。
本发明所使用的基材可以为本领域技术人员已知的各种基材。例如，在一个实施方式中，所述基材可以是高透性的(在可见光波长范围内的透过率不低于90％(例如95％))。在另一个实施方式中，所述基材还可以是柔性/可弯折的，从而更适用于卷对卷连续生产工艺，不仅提高制造效率、降低制备成本，而且可以广泛应用于柔性及折叠触控屏中。另外，所述基材可以本身和/或人工干预地具有UV阻隔功能，从而可以在所述基材表面上使用不同吸收波长的光阻层，从而为光阻层的种类提供更多的选择。更具体地，对于所述基材的材质，在一个实施方式中，所述基材可以由例如聚对苯二甲酸乙二酯(PET)、透明聚酰亚胺(CPI)、环烯烃聚合物(COP)、超级延迟膜(SRF)、聚碳酸酯(PC)和聚萘二甲酸乙二醇酯(PEN)中的至少一种制成。
本发明的光阻层可以为正性光阻层或负性光阻层，并且当所述表面为多个表面时，所述多个表面上施加的所述光阻层可以相同或不同，即各自独立地选自相同或不同的正性光阻层或负性光阻层。在一个实施方式中，所述正性光阻层可以优选地包含曝光后可溶于显影液的树脂材料，从而在曝光后形成与掩膜相同的图案；并且所述负光阻层可以优选地包含曝光后不溶于显影液的树脂材料，从而在曝光后形成与掩膜相反的图案。
本发明的催化层是用于在后续化学镀阶段中将化学镀溶液中的金属离子还原成金属并附着于催化层的表面，从而形成具有期望图案的金属网格，即催化层的主要功能在于能够催化金属离子转换为金属。因此，基于所述催化层的功能，所述催化层可以是包含已知的各种金属纳米颗粒的涂层，而没有特别限制。在一个优选实施方式中，所述催化层可以为纳米钯颗粒催化层。
另外，本发明的用于在基材上形成金属网格的方法还可以包括在催化层上形成进一步施加保护层的步骤，所述保护层主要用于在后续曝光阶段中起保护作用，防止涂层被掩膜损坏，特别是当所述曝光为接触式曝光时，所述保护层能够有效防止涂层被掩膜损坏，并且所述保护层能够随后在显影阶段也被显影液洗去。根据本发明，所述保护层材料可以使用本领域中常规的保护层材料来进行。在一个优选的实施方式中，所述保护层材料可以为水溶性材料，以使其能够在显影阶段溶于含水的显影液中。
如本文所用，术语“曝光”是指将施加上述各涂层后的基材暴露于光(特别是紫外光，即UV光)下的步骤，并在曝光中通过掩膜对光进行部分遮挡，使得暴露于光的光阻层与光进行反应后结构性质上发生改变，并且在后续显影阶段中基于光阻层的结构性质是否发生改变，将具有相同性质的一部分光阻层以及形成在其上的催化层洗去，从而在基材上形成期望的图案。在本发明的一个优选实施方式中，所述曝光可以为接触式紫外曝光。
如本文所用，术语“显影”是指通过显影液将预定图案以外的不期望部分溶解在其中并洗去的步骤，所述显影中使用的显影液通常是含有碱性化合物和表面活性剂的水溶液，碱性化合物可以是无机或有机碱性化合物，这些无机和有机碱性化合物可以单独使用或两种以上组合使用；而作为表面活性剂，可以使用选自由非离子表面活性剂、阴离子表面活性剂和阳离子表面活性剂所组成的组中的至少一种，这些表面活性剂可以单独使用，也可以两种以上组合使用。
特别地，如前所述，经过发明人的研究发现，残铜形成的主要原因在于显影过程中有催化剂颗粒无法完全被清洗干净从而在后续的化学镀铜过程中易于引起铜生长，因此基于该原因针对性地对显影步骤进行了优化。即，本发明的显影步骤在超声波的存在下进行。另外，经过进一步研究后发现，当所述超声波的频率和超声波处理时间在本发明预定范围内时，去除残铜形成的效果更佳。在本发明的一个优选实施方式中，所述超声波的频率可以为20-780KHz，优选为40-220KHz，例如40KHz、60KHz、120KHz、220KHz等。在本发明的另一个优选实施方式中，所述超声波的处理时间可以为至少10s，优选为10-60s，更优选为20-40s，例如24s、30s、36s等。根据在线实验，过度增加超声显影时间也存在线条脱落的风险。
如本文所用，术语“化学镀”是指通过化学方式即还原将化学镀溶液中金属离子转换为金属并附着(镀)在基材表面的步骤。在一个实施方式中，所述化学镀通过将所述基材部分浸没在化学镀溶液中的方式来进行。在另一个实施方式中，所述化学镀通过将所述基材全部浸没在化学镀溶液中的方式来进行。另外，根据对不同金属的需要，可以使用不同的化学镀溶液。例如，所述化学镀溶液可以选自镀银溶液、镀镍溶液、镀铜溶液、镀钴溶液和镀镍溶液中的一种或多种。
另外，本发明的方法还可以包括对金属层进行黑化的步骤，从而覆盖金属本身的颜色。
在另一方面，本发明还提供了一种用于实施本发明的上述方法以在所述基材上形成所述金属网格的装置，其包括：
涂覆模块，其配置成将所述光阻层和所述催化层、以及任选地所述保护层施加在所述基材的一个或多个表面上；
曝光模块，其配置成对所述基材进行所述曝光，以使所述基材上的涂层的一部分固化；
显影模块，其配置成包括超声波发生装置，以在所述超声波的存在下对所述基材进行所述显影，去除所述基材上的所述涂层的未固化部分；以及
化学镀模块，其配置成对所述基材进行化学镀，以在所述基材上形成所述金属网格。
在通过本发明所提供的方法和装置在基材上形成金属网格时，能够有效去除显影后线路附近的光阻及催化剂残留，从而显著减少镀铜后线路附近的残铜，所得金属网格触控传感器产品功能及外观良率有明显提升。
以下，将通过实施例对本发明的特定方法的效果进行详细描述。
实施例1
使用涂布线棒在柔性基材的一个表面上涂覆含有Irgacure 907的负性光刻胶涂层，然后在烘箱中于65℃的温度下干燥100秒，以得到厚度为700nm的涂层；在光刻胶膜的顶部涂一层钯纳米颗粒催化剂涂层，然后再涂一层如上制备的光 刻胶保护材料用于保护上述两个涂层，之后使用具有峰波为314nm的紫外光进行曝光；曝光后，在40KHZ超声波的存在下使用碱性显影液冲洗基材30s，以去除水溶性保护涂层及未固化的负性光刻胶涂层，所得样品浸入化学镀铜液中以生长铜网格。在显微镜下观察铜网格的生长情况，结果如表1所示。
实施例2
按照与实施例1类似的方式在基材上形成铜网格，不同的是，超声波的波长为60KHz，在显微镜下的观察结果如表1所示。
实施例3
按照与实施例1类似的方式在基材上形成铜网格，不同的是，超声波的波长为120KHz，在显微镜下的观察结果如表1所示。
实施例4
按照与实施例1类似的方式在基材上形成铜网格，不同的是，超声波的波长为220KHz，在显微镜下的观察结果如表1和图1所示。
实施例5
按照与实施例1类似的方式在基材上形成铜网格，不同的是，超声波的波长为780KHz，在显微镜下的观察结果如表1和图2所示。
比较例1
按照与实施例1类似的方式在基材上形成铜网格，不同的是，在显影阶段不使用超声波，显影时间30s，在显微镜下的观察结果如表1和图3所示。
表1
编号 超声频率 超声时间 附着力等级 1 残铜等级 2
实施例1 40KHz 30s F0 A
实施例2 60KHz 30s F0 A
实施例3 120KHz 30s F0 A
实施例4 220KHz 30s F0 A
实施例5 780KHz 30s F0 B
比较例1 无 无 F0 C
1附着力等级的定义：使用3M附着力专用胶带对网格区域拉拔测试，如无网格脱落， 则附着力为F0；脱落的网格占测试区域的0％-20％，则附着力为F1；脱落的网格占测试区域的20％-50％，则附着力为F2；脱落的网格占测试区域的50％以上，则附着力为F3.
2残铜等级的定义：A等级：显微镜观察基本无金属残留；B等级：显微镜观察轻微金属残留，宽度在一半线宽内；C等级：显微镜观察有残留金属严重，宽度超过线宽一半。
参见表1和图1至图3的结果，其中图1至图3分别示出了实施例4-5和比较例1的铜网格生长情况。可以看出，通过实施例1-5的方法形成铜网格时，相比于比较例1的残铜生长问题明显改善，特别是对于实施例1-4，其残铜等级为A，也就是说，超声波的频率对于去除金属残留的效果具有一定的影响。
实施例6
使用涂布线棒在柔性基材的一个表面上涂覆含有Irgacure 907的负性光刻胶涂层，然后在烘箱中于65℃的温度下干燥120秒，以得到厚度为550nm的涂层；在光刻胶膜的顶部涂一层钯纳米颗粒催化剂涂层，然后再涂一层如上制备的光刻胶保护材料用于保护上述两个涂层，之后样品在具有2.3μm设计线宽的光罩下使用具有峰波为314nm的紫外光进行接触式曝光，曝光能量为6mj；曝光后，在220KHZ超声波的存在下使用碱性显影液冲洗基材6s，以去除水溶性保护涂层及未固化的负性光刻胶涂层，所得样品浸入化学镀铜液中以生长铜网格。在显微镜下观察铜网格的生长情况，结果如表2所示。
实施例7
按照与实施例6类似的方式在基材上形成铜网格，不同的是，超声波的处理时间为12s，在显微镜下的观察结果如表2所示。
实施例8
按照与实施例6类似的方式在基材上形成铜网格，不同的是，超声波的处理时间为24s，在显微镜下的观察结果如表2和图4所示。
实施例9
按照与实施例6类似的方式在基材上形成铜网格，不同的是，超声波的处理时间为30s，在显微镜下的观察结果如表2和图5所示。
实施例10
按照与实施例6类似的方式在基材上形成铜网格，不同的是，超声波的处理时间为38s，在显微镜下的观察结果如表2和图6所示。
比较例2
按照与实施例6类似的方式在基材上形成铜网格，不同的是，在显影阶段不使用超声波，显影时间30s，在显微镜下的观察结果如表2和图7所示。
表2
编号 超声频率 超声时间 附着力等级 1 残铜等级 2 线宽(CD，μm)
实施例6 220KHz 6s F0 B -
实施例7 220KHz 12s F0 B -
实施例8 220KHz 24s F0 A 3.92
实施例9 220KHz 30s F0 A 3.8
实施例10 220KHz 38s F0 A 3.71
比较例2 无 无 F0 C 4.52
参见表2和图4至图7的结果，其中图4至图7分别示出了实施例8-10和比较例2的铜网格生长情况。可以看出，通过实施例6-10的方法形成铜网格时，相比于比较例2的残铜生长问题明显改善，特别是对于实施例8-10，其残铜等级为A，也就是说，超声波的处理时间对于去除金属残留的效果具有一定的影响。同时，通过对实施例8-10及比较例2的镀铜后的线宽量测可以看出，超声波的处理对减小线宽(CD)也有一定的有益效果，并且随着超声时间的增加有持续减小的趋势，而小线宽也是金属网格产品致力发展的方向之一。
综上，本申请通过上述实施例和比较例的比对已经证实了，本申请的方法在显影工序中加入超声波不仅能够有效解决金属残留问题，同时也能达到减小金属网格线宽的作用。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征， 在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

  1. 一种用于在基材上形成金属网格的方法，其包括以下步骤：
    (1)在所述基材的一个或多个表面上依次施加光阻层和催化层；
    (2)对经步骤(1)处理的基材进行曝光和显影，以在所述基材的表面上形成预定图案；以及
    (3)对经步骤(2)处理的基材进行化学镀，以按所述预定图案在所述基材上形成所述金属网格，
    其中，所述显影在超声波的存在下进行。
  2. 根据权利要求1所述的方法，其中，所述光阻层为正性光阻层或负性光阻层，并且当所述表面为多个表面时，所述多个表面上施加的所述光阻层相同或不同。
  3. 根据权利要求1所述的方法，其中，所述催化层是包含金属纳米颗粒的涂层，优选地，所述催化层为纳米钯颗粒催化层。
  4. 根据权利要求1所述的方法，其中，所述方法还包括在所述催化层的表面上施加保护层。
  5. 根据权利要求1所述的方法，其中，所述曝光为紫外曝光，优选为接触式紫外曝光。
  6. 根据权利要求1所述的方法，其中，所述化学镀通过将所述基材部分或全部浸没在化学镀溶液中的方式来进行。
  7. 根据权利要求6所述的方法，其中，所述化学镀溶液选自镀银溶液、镀镍溶液、镀铜溶液、镀钴溶液和镀镍溶液中的一种或多种。
  8. 根据权利要求1所述的方法，其中，在所述显影过程中，所述超声波的频率为20-780KHz，优选为40-220KHz。
  9. 根据权利要求1所述的方法，其中，在所述显影过程中，所述超声波的处理时间为至少10s，优选为10-60s，更优选为20-40s。
  10. 一种用于实施根据权利要求1-9中任一项所述的方法以在所述基材上形 成所述金属网格的装置，其包括：
    涂覆模块，其配置成将所述光阻层和所述催化层、以及任选地所述保护层施加在所述基材的一个或多个表面上；
    曝光模块，其配置成对所述基材进行所述曝光，以使所述基材上的涂层的一部分固化；
    显影模块，其配置成包括超声波发生装置，以在所述超声波的存在下对所述基材进行所述显影，去除所述基材上的所述涂层的未固化部分；以及
    化学镀模块，其配置成对所述基材进行化学镀，以在所述基材上形成所述金属网格。
PCT/CN2022/141449 2021-12-24 2022-12-23 一种用于在基材上形成金属网格的方法和装置 WO2023116889A1 (zh)

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