WO2014059798A1 - Nano-copper ink and copper conductive film preparation method - Google Patents

Nano-copper ink and copper conductive film preparation method Download PDF

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Publication number
WO2014059798A1
WO2014059798A1 PCT/CN2013/078180 CN2013078180W WO2014059798A1 WO 2014059798 A1 WO2014059798 A1 WO 2014059798A1 CN 2013078180 W CN2013078180 W CN 2013078180W WO 2014059798 A1 WO2014059798 A1 WO 2014059798A1
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copper
nano
ink
conductive film
hydroxycarboxylic acid
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PCT/CN2013/078180
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French (fr)
Chinese (zh)
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邓吨英
肖斐
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复旦大学
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Publication of WO2014059798A1 publication Critical patent/WO2014059798A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature

Definitions

  • the present invention relates to the field of printed electronics, and more particularly to a method for preparing a nano copper ink for stabilizing printed electrons using a short chain hydroxycarboxylic acid as a reducing agent and a dispersing agent, and a method for producing a copper conductive film using the nano copper ink.
  • Gold, silver and copper nanoparticles are considered to be promising functional materials for use on conductive inks because of their high electrical conductivity (10 5 S/cm), operational stability, and low temperature process capability.
  • Gold and silver are much more expensive than copper, so the preparation of copper nano-inks has attracted widespread attention in recent years.
  • the surface is easily oxidized to form a thin oxide layer and there is a potential for further oxidation during post-treatment processes such as ink preparation, printing and annealing.
  • the copper surface oxide layer will raise the firing temperature and reduce the electrical conductivity.
  • the nano copper is usually coated on the surface of the nano copper by using materials such as graphene, polyvinylpyrrolidone, oleic acid or alkyl mercaptan (6-18 carbons) in the process of preparing nano copper or directly
  • materials such as graphene, polyvinylpyrrolidone, oleic acid or alkyl mercaptan (6-18 carbons) in the process of preparing nano copper or directly
  • the Cu-Ag core-shell nano-particles are dispersed in a solvent and then ink-jet printed on the surface of the substrate to be sintered into a conductive line.
  • Graphene, polyvinylpyrrolidone, oleic acid and long-chain aliphatic materials are difficult to completely remove during the sintering process, and the residual in the copper circuit will affect the conductivity; the preparation of Cu-Ag core-shell nanoparticles, the process is more complicated, and use Ag, will increase the cost.
  • a reducing substance alcohol, aldehyde or carboxylic acid, etc.
  • a direct hydrogen gas in a carrier gas.
  • the reducing substance is heated and then introduced into the calcining apparatus through nitrogen bubbling with nitrogen gas.
  • the calcining apparatus needs to be equipped with a venting system, including a heater, a flow rate controller, and a reducing substance accumulator, etc., which will make the roasting process more complicated. Thereby increasing the cost. And if hydrogen is used, there is a higher requirement for safety.
  • the object of the present invention is to provide a method for preparing a nano copper ink and a copper conductive film, which makes the preparation process of the nano copper ink and the nano copper ink are easily oxidized during the process of preparing the copper conductive film by post-processing steps such as printing and baking. Can be solved.
  • an embodiment of the present invention provides a method for preparing a nano copper ink, comprising the following steps:
  • the short-chain hydroxycarboxylic acid reacts with the nano-copper surface oxide layer to form copper hydroxycarboxylate, and the copper hydroxycarboxylate and the excess hydroxycarboxylic acid after the reaction are attached to the surface of the nano-copper.
  • Embodiments of the present invention also provide a method for preparing a copper conductive film, comprising the following steps Preparing a nano copper ink by using the method for preparing a nano copper ink according to any one of claims 1 to 6; applying the prepared nano copper ink to a surface of a substrate to form a nano copper ink layer; The nano copper ink layer is vacuum dried and calcined in an inert atmosphere or in a vacuum to form the copper conductive film; wherein the copper hydroxycarboxylate coated on the surface of the nano copper is reduced to metallic copper, and the excess hydroxycarboxylic acid is Remove.
  • Embodiments of the present invention by dispersing nano copper in ethanol, ethylene glycol containing a short-chain hydroxycarboxylic acid or a mixed solution of ethanol and ethylene glycol, and then applying it to a surface of a substrate, relative to the prior art A high-conductivity copper circuit is formed after firing at a low temperature.
  • the short-chain hydroxycarboxylic acid can react with the surface-oxidized nano-copper to form an organic carboxylic acid copper salt, and the organic copper salt and the excess hydroxycarboxylic acid are coated on the surface of the nano-copper to prevent further oxidation of the nano-copper;
  • the formed organic copper salt can be reduced to copper, wherein the hydroxycarboxylic acid can inhibit the oxidation of the nano copper during the calcination process, and the excess short-chain hydroxycarboxylic acid is easily present due to the relatively low boiling point and decomposition temperature. It is removed during the calcination process, so the addition of short-chain hydroxycarboxylic acid effectively solves the problem that nano-copper is easily oxidized during post-treatment such as dispersion, printing and baking.
  • FIG. 1 is a flow chart of a method for preparing a copper conductive film according to a second embodiment of the present invention
  • FIG. 2 is a transmission electron micrograph (TEM) of nano copper dispersed in a lactic acid-containing ethanol solution
  • FIG. 3 is an initial nano copper.
  • XRD X-ray diffraction analysis
  • a first embodiment of the present invention relates to a method for preparing a nano-copper ink, which comprises dispersing nano-copper particles in a solvent containing a short-chain hydroxycarboxylic acid by ultrasonication to obtain a nano-copper ink; wherein, the nano-copper
  • the weight percentage concentration is 5% to 30.
  • the concentration of the short-chain hydroxycarboxylic acid is 1% to 10%
  • the short-chain hydroxycarboxylic acid may be lactic acid, glycolic acid or citric acid
  • the solvent may be ethanol, ethylene glycol or ethanol.
  • a mixed solution of ethylene glycol, the nano copper may be commercially available nano copper or nano copper prepared by any method.
  • the short-chain hydroxycarboxylic acid reacts with the surface copper oxide layer to form copper hydroxycarboxylate, and the copper hydroxycarboxylate and the excess hydroxycarboxylic acid adhered to the surface of the nano-copper after the reaction can prevent further oxidation of the nano-copper.
  • the stable anti-oxidation nano-copper ink is produced as follows:
  • lactic acid reacts with the oxidized nano-copper to form copper lactate, and the resulting copper acrylate and excess lactic acid can coat the surface of the nano-copper to prevent further oxidation of the nano-copper.
  • lactic acid-stabilized nano-copper inks can not only help redisperse nano-copper, but also lactic acid can react with oxidized nano-copper surface to form copper lactate, which can be reduced during roasting. Copper metal, the resulting copper conductive pattern High quality and good electrical conductivity.
  • a short-chain hydroxycarboxylic acid such as glycolic acid or citric acid instead of lactic acid, and the preparation process is similar, and will not be described herein.
  • a second embodiment of the present invention relates to a method for preparing a copper conductive film.
  • the flow is shown in FIG. 1.
  • the specific steps are as follows: Step 101: A nano copper ink is prepared, and the preparation method thereof is the method described in the first embodiment.
  • Step 102 applying the prepared nano copper ink to the surface of the substrate by drop coating, spin coating, pulling, screen printing or inkjet printing to form a nano copper ink layer; wherein the substrate may be silicon wafer, glass, Polyimide or polyester film.
  • Step 103 vacuum drying the nano copper ink layer, and baking in an inert atmosphere or vacuum to form a copper conductive film;
  • the inert atmosphere may be a nitrogen atmosphere and an argon atmosphere;
  • the baking method may be electric heating, wave heating or Laser-assisted heating, calcination temperature between 100 and 250 ° C, within 1 hour.
  • the copper hydroxycarboxylate coated on the surface of the nano-copper can be reduced to metallic copper, wherein the hydroxycarboxylic acid can also inhibit the oxidation of the nano-copper during the calcination process, and the excess hydroxycarboxylic acid can be removed.
  • a nano-copper ink prepared by dispersing nano-copper particles having a particle diameter of less than 10 nm in a solvent containing lactic acid, and a TEM of the dispersed transmission electron microscope photograph is shown in FIG. 2, which shows that nano-copper can be in a solution containing lactic acid in ethanol. Very well dispersed; the nano-copper ink was applied to the glass surface at 200. After calcination for 0.5 hour, the resistivity of the formed copper film was 1.4 x 10 -5 ohm.cm (Q.cm). Please refer to FIG.
  • FIG. 3 which is an X-ray diffraction analysis (XRD) diagram of the initial copper nanoparticle a, the copper film prepared by the nano copper ink before baking b and the calcination c.
  • XRD X-ray diffraction analysis
  • the present invention disperses nano copper in ethanol, ethylene glycol containing a short-chain hydroxycarboxylic acid or a mixed solution of ethanol and ethylene glycol, and then applies it to the surface of the substrate at a low temperature. A high conductivity copper circuit is formed after the lower firing.
  • the short-chain hydroxycarboxylic acid can react with the oxidized nano-copper to form an organic carboxylic acid copper salt, and the organic copper salt and excess hydroxycarboxylic acid are coated on the surface of the nano-copper to prevent further oxidation of the nano-copper; roasting During the process, the formed organic copper salt can be reduced to copper, wherein the hydroxycarboxylic acid can inhibit the oxidation of the nano copper during the calcination process, and the excess short-chain hydroxycarboxylic acid is easily removed during the calcination process due to the relatively low boiling point.
  • the addition of the short-chain hydroxycarboxylic acid effectively solves the problem that the nano-copper is easily oxidized during post-treatment such as dispersion, printing, and baking.
  • the steps of the above various methods are divided for the sake of clear description.
  • the implementation may be combined into one step or split into certain steps and decomposed into multiple steps. As long as the same logical relationship is included, it is within the protection scope of this patent. Adding insignificant modifications to an algorithm or process, or introducing an insignificant design, without changing the core design of its algorithms and processes, is covered by this patent.
  • a person skilled in the art can understand that the above embodiments are specific embodiments for implementing the present invention, and various changes can be made in the form and details without departing from the spirit and scope of the present invention. range.

Abstract

A nano-copper ink and copper conductive film preparation method, comprising: dispersing nano-copper in ethanol containing short-chain hydroxyl carboxylic acid, or in ethylene glycol or in the mixed solution of the ethanol and the ethylene glycol to obtain the nano-copper ink; then coating the nano-copper ink onto the surface of a substrate; and baking at a low temperature to form the copper conductive film. The addition of the short-chain hydroxyl carboxylic acid solves the problem of the nano-copper being likely to be oxidized in the dispersing, printing and baking process.

Description

说 明 书  Description
纳米铜油墨和铜导电薄膜的制备方法 技术领域  Method for preparing nano copper ink and copper conductive film
本发明涉及印制电子技术领域， 特别涉及一种用短链羟基羧酸作为还原 剂和分散剂稳定印制电子用纳米铜油墨的制备方法以及以该纳米铜油墨制作 铜导电薄膜的方法。  The present invention relates to the field of printed electronics, and more particularly to a method for preparing a nano copper ink for stabilizing printed electrons using a short chain hydroxycarboxylic acid as a reducing agent and a dispersing agent, and a method for producing a copper conductive film using the nano copper ink.
背景技术 Background technique
近年来， 印制电子技术在射频识别标签、 可穿戴电子产品、 有机发光二 极管和有机太阳能材料的应用上引起极大关注。 传统的印制电路工业使用光 刻技术， 然而这一方法涉及许多步驟， 如刻蚀、 金属沉积和电镀等， 这些过 程伴随着大量的有毒化学廈弃物的产生。 因此许多的研究者开始关注直接的 喷墨印刷技术， 因为这一方法不需要额外的刻蚀以及金属沉积过程， 仅仅一 步就能在各种基质上制备要求的导电模式。 与传统的光刻技术相比， 喷墨印 刷技术不仅工艺简单、 成本低， 灵活的导电图案变换以及能够在大面积区域 印刷是其最大的优势。  In recent years, printed electronics has attracted a great deal of attention in the use of radio frequency identification tags, wearable electronics, organic light-emitting diodes and organic solar materials. The conventional printed circuit industry uses lithography, but this approach involves many steps, such as etching, metal deposition, and electroplating, which are accompanied by the production of a large number of toxic chemical wastes. As a result, many researchers have begun to focus on direct inkjet printing because it requires no additional etching and metal deposition processes to produce the desired conductive pattern on a variety of substrates in just one step. Compared to conventional lithography, inkjet printing technology is not only simple in process, low in cost, flexible in conductive pattern change, and printing in large areas is its greatest advantage.
金、 银和铜纳米粒子被认为是前景很好的用在导电油墨上的功能材料， 因为它们具有高的导电性（105S/cm ) 、 操作稳定性以及低温过程能力。 金和 银比铜贵很多， 因而在近几年铜纳米油墨的制备引起广泛关注。 然而， 因为 铜纳米粒子的高度活性， 表面容易被氧化形成一层薄的氧化层， 并且在后处 理过程 （比如油墨制备、 印刷和退火）有进一步氧化的可能。 铜表面氧化层 将使焙烧温度升高， 并且降低电导性。 Gold, silver and copper nanoparticles are considered to be promising functional materials for use on conductive inks because of their high electrical conductivity (10 5 S/cm), operational stability, and low temperature process capability. Gold and silver are much more expensive than copper, so the preparation of copper nano-inks has attracted widespread attention in recent years. However, because of the high activity of the copper nanoparticles, the surface is easily oxidized to form a thin oxide layer and there is a potential for further oxidation during post-treatment processes such as ink preparation, printing and annealing. The copper surface oxide layer will raise the firing temperature and reduce the electrical conductivity.
为了解决此问题， 通常在制备纳米铜过程中通过使用石墨烯、 聚乙烯吡 咯烷酮、 油酸或者烷基硫醇 (6-18 个碳)等材料包覆在纳米铜表面或者直接制 备 Cu-Ag核壳结构的纳米粒子， 纳米粒子分散于溶剂中后通过喷墨印刷于基 质表面， 烧结成导电线路。 石墨烯、 聚乙烯吡咯烷酮、 油酸以及长链脂肪族 材料在烧结过程中难以完全除去，残留在铜线路中将影响导电性；制备 Cu-Ag 核壳结构的纳米粒子， 过程更加复杂， 并且使用 Ag, 将增加成本。 另外， 为了避免喷墨印刷后的纳米铜膜在焙烧过程中被氧化， 往往在焙 烧环境中使用氮气作载气引入还原性物质 （醇、 醛或羧酸等） 或者直接通入 氢气， 液态的还原性物质被加热后通过氮气鼓泡随氮气一起通入焙烧装置， 焙烧装置需要配有通气***， 包括加热器、 流速控制器以及还原性物质储液 器等， 这将使焙烧过程更加复杂， 从而使成本增加。 而如果使用氢气， 对安 全性有更高要求。 In order to solve this problem, it is usually coated on the surface of the nano copper by using materials such as graphene, polyvinylpyrrolidone, oleic acid or alkyl mercaptan (6-18 carbons) in the process of preparing nano copper or directly The Cu-Ag core-shell nano-particles are dispersed in a solvent and then ink-jet printed on the surface of the substrate to be sintered into a conductive line. Graphene, polyvinylpyrrolidone, oleic acid and long-chain aliphatic materials are difficult to completely remove during the sintering process, and the residual in the copper circuit will affect the conductivity; the preparation of Cu-Ag core-shell nanoparticles, the process is more complicated, and use Ag, will increase the cost. In addition, in order to prevent the nano-copper film after inkjet printing from being oxidized during the roasting process, it is often used in a roasting environment to introduce a reducing substance (alcohol, aldehyde or carboxylic acid, etc.) or a direct hydrogen gas in a carrier gas. The reducing substance is heated and then introduced into the calcining apparatus through nitrogen bubbling with nitrogen gas. The calcining apparatus needs to be equipped with a venting system, including a heater, a flow rate controller, and a reducing substance accumulator, etc., which will make the roasting process more complicated. Thereby increasing the cost. And if hydrogen is used, there is a higher requirement for safety.
发明内容 Summary of the invention
本发明的目的在于提供一种纳米铜油墨和铜导电薄膜的制备方法， 使得 纳米铜油墨的制备过程以及纳米铜油墨通过印刷以及焙烧等后处理步驟制作 铜导电薄膜的过程中容易被氧化的问题得以解决。  The object of the present invention is to provide a method for preparing a nano copper ink and a copper conductive film, which makes the preparation process of the nano copper ink and the nano copper ink are easily oxidized during the process of preparing the copper conductive film by post-processing steps such as printing and baking. Can be solved.
为解决上述技术问题， 本发明的实施方式提供了一种纳米铜油墨的制备 方法， 包含以下步驟：  In order to solve the above technical problem, an embodiment of the present invention provides a method for preparing a nano copper ink, comprising the following steps:
将纳米铜粒子均勾分散在含有短链羟基羧酸的溶剂中， 得到所述纳米铜 油墨； 其中， 所述纳米铜的重量百分比浓度为 5%至 30 所述短链羟基羧酸 的重量百分比浓度为 1%至 10 %;  Dispersing the nano copper particles in a solvent containing a short-chain hydroxycarboxylic acid to obtain the nano-copper ink; wherein the nano-copper has a concentration by weight of 5% to 30% by weight of the short-chain hydroxycarboxylic acid The concentration is from 1% to 10%;
所述短链羟基羧酸与纳米铜表面氧化层反应形成羟基羧酸铜， 所述羟基 羧酸铜和所述反应之后多余的羟基羧酸附着在纳米铜表面。 本发明的实施方式还提供了一种铜导电薄膜的制备方法， 包含以下步 驟： 采用如权利要求 1至 6任一项所述的纳米铜油墨的制备方法制备纳米铜 油墨； 将所述制备得到的纳米铜油墨施于基材表面， 形成纳米铜油墨层； 对所述纳米铜油墨层进行真空干燥， 并在惰性气氛或者真空中进行焙 烧， 形成所述铜导电薄膜； 其中， 包覆在纳米铜表面的羟基羧酸铜被还原成金属铜， 多余的羟基羧 酸被除去。 本发明实施方式相对于现有技术而言， 通过将纳米铜分散于含有短链羟 基羧酸的乙醇、 乙二醇或者乙醇和乙二醇的混合溶液中， 然后将其涂覆于基 材表面， 在低温下焙烧后形成高导电性的铜电路。 在纳米铜分散的过程中， 短链羟基羧酸能与表面被氧化的纳米铜反应生成有机羧酸铜盐， 有机铜盐以 及多余的羟基羧酸包覆在纳米铜表面防止纳米铜进一步氧化； 焙烧过程中， 生成的有机铜盐能被还原成铜， 其中羟基羧酸在焙烧过程中能抑制纳米铜被 氧化， 而且多余的短链羟基羧酸由于相对低的沸点和分解温度， 很容易在焙 烧过程中被除去， 因此通过短链羟基羧酸的加入， 有效的解决了纳米铜在分 散、 印刷以及焙烧等后处理过程中容易被氧化的问题。 The short-chain hydroxycarboxylic acid reacts with the nano-copper surface oxide layer to form copper hydroxycarboxylate, and the copper hydroxycarboxylate and the excess hydroxycarboxylic acid after the reaction are attached to the surface of the nano-copper. Embodiments of the present invention also provide a method for preparing a copper conductive film, comprising the following steps Preparing a nano copper ink by using the method for preparing a nano copper ink according to any one of claims 1 to 6; applying the prepared nano copper ink to a surface of a substrate to form a nano copper ink layer; The nano copper ink layer is vacuum dried and calcined in an inert atmosphere or in a vacuum to form the copper conductive film; wherein the copper hydroxycarboxylate coated on the surface of the nano copper is reduced to metallic copper, and the excess hydroxycarboxylic acid is Remove. Embodiments of the present invention, by dispersing nano copper in ethanol, ethylene glycol containing a short-chain hydroxycarboxylic acid or a mixed solution of ethanol and ethylene glycol, and then applying it to a surface of a substrate, relative to the prior art A high-conductivity copper circuit is formed after firing at a low temperature. In the process of nano-copper dispersion, the short-chain hydroxycarboxylic acid can react with the surface-oxidized nano-copper to form an organic carboxylic acid copper salt, and the organic copper salt and the excess hydroxycarboxylic acid are coated on the surface of the nano-copper to prevent further oxidation of the nano-copper; During the calcination process, the formed organic copper salt can be reduced to copper, wherein the hydroxycarboxylic acid can inhibit the oxidation of the nano copper during the calcination process, and the excess short-chain hydroxycarboxylic acid is easily present due to the relatively low boiling point and decomposition temperature. It is removed during the calcination process, so the addition of short-chain hydroxycarboxylic acid effectively solves the problem that nano-copper is easily oxidized during post-treatment such as dispersion, printing and baking.
附图说明 DRAWINGS
图 1是根据本发明第二实施方式的铜导电薄膜的制备方法的流程图； 图 2是纳米铜在含乳酸的乙醇溶液中分散后的透射电镜照片 （TEM ) ； 图 3是初始的纳米铜粒子 (a)、纳米铜油墨制作的铜膜在焙烧前 (b)和焙烧 后 (c)的 X射线衍射分析 （ XRD ) 图。 具体实施方式 为使本发明的目的、 技术方案和优点更加清楚， 下面将结合附图对本发 明的各实施方式进行详细的阐述。 然而， 本领域的普通技术人员可以理解， 在本发明各实施方式中， 为了使读者更好地理解本申请而提出了许多技术细 节。但是， 即使没有这些技术细节和基于以下各实施方式的种种变化和修改， 也可以实现本申请各权利要求所要求保护的技术方案。 1 is a flow chart of a method for preparing a copper conductive film according to a second embodiment of the present invention; FIG. 2 is a transmission electron micrograph (TEM) of nano copper dispersed in a lactic acid-containing ethanol solution; FIG. 3 is an initial nano copper. X-ray diffraction analysis (XRD) pattern of copper film prepared by particle (a) and nano copper ink before (b) and after firing (c). DETAILED DESCRIPTION OF THE EMBODIMENTS In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it will be apparent to those skilled in the art that, in the various embodiments of the present invention, numerous technical details are set forth to provide a better understanding of the present application. However, the technical solutions claimed in the claims of the present application can be implemented without these technical details and various changes and modifications based on the following embodiments.
本发明的第一实施方式涉及一种纳米铜油墨的制备方法， 该方法将纳米 铜粒子通过超声作用均勾分散在含有短链羟基羧酸的溶剂中， 得到纳米铜油 墨； 其中， 纳米铜的重量百分比浓度为 5%至 30 短链羟基羧酸的重量百 分比浓度为 1%至 10 % , 短链羟基羧酸可以为乳酸、 羟基乙酸或者柠檬酸， 溶剂可以为乙醇、 乙二醇或者乙醇和乙二醇的混合溶液， 纳米铜可以为市售 的纳米铜或者任何一种方法制备的纳米铜。 在超声分散过程中， 短链羟基羧酸与纳米铜表面氧化层反应形成羟基羧 酸铜， 羟基羧酸铜和反应之后多余的羟基羧酸附着在纳米铜表面， 可以阻止 纳米铜的进一步氧化。 以乳酸为例， 稳定的抗氧化的纳米铜油墨制作过程如下：  A first embodiment of the present invention relates to a method for preparing a nano-copper ink, which comprises dispersing nano-copper particles in a solvent containing a short-chain hydroxycarboxylic acid by ultrasonication to obtain a nano-copper ink; wherein, the nano-copper The weight percentage concentration is 5% to 30. The concentration of the short-chain hydroxycarboxylic acid is 1% to 10%, the short-chain hydroxycarboxylic acid may be lactic acid, glycolic acid or citric acid, and the solvent may be ethanol, ethylene glycol or ethanol. A mixed solution of ethylene glycol, the nano copper may be commercially available nano copper or nano copper prepared by any method. In the ultrasonic dispersion process, the short-chain hydroxycarboxylic acid reacts with the surface copper oxide layer to form copper hydroxycarboxylate, and the copper hydroxycarboxylate and the excess hydroxycarboxylic acid adhered to the surface of the nano-copper after the reaction can prevent further oxidation of the nano-copper. Taking lactic acid as an example, the stable anti-oxidation nano-copper ink is produced as follows:
乙醇、 乙二醇或者乙醇和乙二醇的混合溶液中， 其中， 纳米铜的重量百分比 浓度为 5-30 %, 乳酸的重量百分比浓度为 1-10 %, 超声分散的时间为 1-2小 时。 超声过程中， 乳酸能和被氧化的纳米铜反应生成乳酸铜， 并且生成的乳 酸铜和多余的乳酸能包覆在纳米铜表面阻止纳米铜的进一步氧化。 Ethanol, ethylene glycol or a mixed solution of ethanol and ethylene glycol, wherein the concentration of nano copper is 5-30% by weight, the concentration by weight of lactic acid is 1-10%, and the time of ultrasonic dispersion is 1-2 hours. . During the ultrasonic process, lactic acid reacts with the oxidized nano-copper to form copper lactate, and the resulting copper acrylate and excess lactic acid can coat the surface of the nano-copper to prevent further oxidation of the nano-copper.
通过在纳米铜分散过程中加入乳酸， 解决了纳米铜的团聚以及后处理过 程中被氧化的问题。 相对于其它表面活性剂稳定的纳米铜油墨， 乳酸稳定的 纳米铜油墨不仅能帮助纳米铜再分散， 而且乳酸能与被氧化的纳米铜表面反 应生成乳酸铜， 乳酸铜在焙烧过程中能被还原成金属铜， 得到的铜导电图形 的质量高， 导电性好。 使用羟基乙酸、柠檬酸等短链羟基羧酸可以代替乳酸，获得同样的效果， 其制备过程类似， 在此不再赘述。 本发明的第二实施方式涉及一种铜导电薄膜的制备方法， 流程如图 1所 示， 具体步驟如下： 步驟 101 , 制备纳米铜油墨， 其制备方法是第一实施方式里描述的方法。 步驟 102, 将制备得到的纳米铜油墨通过滴涂、 旋涂、 提拉、 丝网印刷 或者喷墨印刷施于基材表面， 形成纳米铜油墨层； 其中， 基材可以为硅片、 玻璃、 聚酰亚胺或者聚酯薄膜。 步驟 103 , 对纳米铜油墨层进行真空干燥， 并在惰性气氛或者真空中进 行焙烧， 形成铜导电薄膜； 其中， 惰性气氛可以为氮气氛和氩气氛等； 焙烧 方式可以是电加热、 波加热或者激光辅助加热，焙烧的温度在 100至 250°C 之间， 时间在 1小时之内。 在焙烧过程中， 包覆在纳米铜表面的羟基羧酸铜能被还原成金属铜， 其 中羟基羧酸在焙烧过程中还能抑制纳米铜被氧化，多余的羟基羧酸能被除去。 将粒径小于 10 nm 的纳米铜粒子分散在含乳酸的溶剂中制备纳米铜油 墨， 其分散后的透射电镜照片 TEM如图 2所示， 该图说明纳米铜在含有乳 酸的乙醇溶液中能被很好的分散；将该纳米铜油墨涂敷于玻璃表面，于 200。C 焙烧 0.5小时后， 形成的铜膜电阻率为 1.4x10— 5欧姆.厘米 （Q.cm ) 。 请参阅图 3 , 是初始的纳米铜粒子 a、 纳米铜油墨制作的铜膜在焙烧前 b 和焙烧后 c的 X射线衍射分析（ XRD )图， 图中横坐标是衍射角， 单位为度； 纵坐标是衍射强度， 单位为任意单位， 只要所有数据都是按照相同的处理方 式得到即可。 由图中可以看到， 即使初始的纳米铜表面有轻微氧化， 但在乳 酸乙醇溶液中分散制作成油墨并涂覆成膜焙烧后， 进行 X射线衍射分析， 可 见原来的氧化亚铜 （Cu20 ) 的衍射峰消失， 即图中曲线 a存在的 （111 )衍 射峰， 在曲线 b和 c上没有出现， 说明 Cu20已被还原成铜。 与现有技术相比， 本发明通过将纳米铜分散于含有短链羟基羧酸的乙 醇、 乙二醇或者乙醇和乙二醇的混合溶液中， 然后将其涂覆于基材表面， 在 低温下焙烧后形成高导电性的铜电路。 在纳米铜分散的过程中， 短链羟基羧 酸能与被氧化的纳米铜反应生成有机羧酸铜盐， 有机铜盐以及多余的羟基羧 酸包覆在纳米铜表面防止纳米铜进一步氧化； 焙烧过程中， 生成的有机铜盐 能被还原成铜， 其中羟基羧酸在焙烧过程中能抑制纳米铜被氧化， 而且多余 的短链羟基羧酸由于相对低的沸点， 很容易在焙烧过程中被除去， 因此通过 短链羟基羧酸的加入， 有效的解决了纳米铜在分散、 印刷以及焙烧等后处理 过程中容易被氧化的问题。 上面各种方法的步驟划分， 只是为了描述清楚， 实现时可以合并为一个 步驟或者对某些步驟进行拆分，分解为多个步驟， 只要包含相同的逻辑关系， 都在本专利的保护范围内； 对算法中或者流程中添加无关紧要的修改或者引 入无关紧要的设计， 但不改变其算法和流程的核心设计都在该专利的保护范 围内。 本领域的普通技术人员可以理解， 上述各实施方式是实现本发明的具体 实施例， 而在实际应用中， 可以在形式上和细节上对其作各种改变， 而不偏 离本发明的精神和范围。 By adding lactic acid during the dispersion of nano-copper, the problem of agglomeration of nano-copper and oxidation during post-treatment is solved. Compared with other surfactant-stabilized nano-copper inks, lactic acid-stabilized nano-copper inks can not only help redisperse nano-copper, but also lactic acid can react with oxidized nano-copper surface to form copper lactate, which can be reduced during roasting. Copper metal, the resulting copper conductive pattern High quality and good electrical conductivity. The same effect can be obtained by using a short-chain hydroxycarboxylic acid such as glycolic acid or citric acid instead of lactic acid, and the preparation process is similar, and will not be described herein. A second embodiment of the present invention relates to a method for preparing a copper conductive film. The flow is shown in FIG. 1. The specific steps are as follows: Step 101: A nano copper ink is prepared, and the preparation method thereof is the method described in the first embodiment. Step 102, applying the prepared nano copper ink to the surface of the substrate by drop coating, spin coating, pulling, screen printing or inkjet printing to form a nano copper ink layer; wherein the substrate may be silicon wafer, glass, Polyimide or polyester film. Step 103, vacuum drying the nano copper ink layer, and baking in an inert atmosphere or vacuum to form a copper conductive film; wherein, the inert atmosphere may be a nitrogen atmosphere and an argon atmosphere; the baking method may be electric heating, wave heating or Laser-assisted heating, calcination temperature between 100 and 250 ° C, within 1 hour. During the calcination process, the copper hydroxycarboxylate coated on the surface of the nano-copper can be reduced to metallic copper, wherein the hydroxycarboxylic acid can also inhibit the oxidation of the nano-copper during the calcination process, and the excess hydroxycarboxylic acid can be removed. A nano-copper ink prepared by dispersing nano-copper particles having a particle diameter of less than 10 nm in a solvent containing lactic acid, and a TEM of the dispersed transmission electron microscope photograph is shown in FIG. 2, which shows that nano-copper can be in a solution containing lactic acid in ethanol. Very well dispersed; the nano-copper ink was applied to the glass surface at 200. After calcination for 0.5 hour, the resistivity of the formed copper film was 1.4 x 10 -5 ohm.cm (Q.cm). Please refer to FIG. 3 , which is an X-ray diffraction analysis (XRD) diagram of the initial copper nanoparticle a, the copper film prepared by the nano copper ink before baking b and the calcination c. In the figure, the abscissa is the diffraction angle, and the unit is degree; The ordinate is the diffraction intensity, and the unit is arbitrary. As long as all the data is obtained in the same way. It can be seen from the figure that even if the initial nano-copper surface is slightly oxidized, it can be X-ray diffraction analysis after being dispersed into an ink in a lactate ethanol solution and coated into a film for baking. It is seen that the diffraction peak of the original cuprous oxide (Cu 2 0) disappears, that is, the (111) diffraction peak existing in the curve a in the figure does not appear on the curves b and c, indicating that Cu 2 0 has been reduced to copper. Compared with the prior art, the present invention disperses nano copper in ethanol, ethylene glycol containing a short-chain hydroxycarboxylic acid or a mixed solution of ethanol and ethylene glycol, and then applies it to the surface of the substrate at a low temperature. A high conductivity copper circuit is formed after the lower firing. In the process of nano-copper dispersion, the short-chain hydroxycarboxylic acid can react with the oxidized nano-copper to form an organic carboxylic acid copper salt, and the organic copper salt and excess hydroxycarboxylic acid are coated on the surface of the nano-copper to prevent further oxidation of the nano-copper; roasting During the process, the formed organic copper salt can be reduced to copper, wherein the hydroxycarboxylic acid can inhibit the oxidation of the nano copper during the calcination process, and the excess short-chain hydroxycarboxylic acid is easily removed during the calcination process due to the relatively low boiling point. Therefore, the addition of the short-chain hydroxycarboxylic acid effectively solves the problem that the nano-copper is easily oxidized during post-treatment such as dispersion, printing, and baking. The steps of the above various methods are divided for the sake of clear description. The implementation may be combined into one step or split into certain steps and decomposed into multiple steps. As long as the same logical relationship is included, it is within the protection scope of this patent. Adding insignificant modifications to an algorithm or process, or introducing an insignificant design, without changing the core design of its algorithms and processes, is covered by this patent. A person skilled in the art can understand that the above embodiments are specific embodiments for implementing the present invention, and various changes can be made in the form and details without departing from the spirit and scope of the present invention. range.

Claims

权 利 要 求 书 Claim
1. 一种纳米铜油墨的制备方法， 其特征在于， 包含以下步驟： 将纳米铜粒子均勾分散在含有短链羟基羧酸的溶剂中 ,得到所述纳米铜 油墨； 其中， 所述纳米铜的重量百分比浓度为 5%至 30 %, 所述短链羟基羧酸 的重量百分比浓度为 1%至 10 %; A method for preparing a nano copper ink, comprising the steps of: dispersing nano copper particles in a solvent containing a short chain hydroxycarboxylic acid to obtain the nano copper ink; wherein the nano copper The weight percentage concentration is 5% to 30%, and the concentration of the short-chain hydroxycarboxylic acid is from 1% to 10% by weight;
所述短链羟基羧酸与纳米铜表面氧化层反应形成羟基羧酸铜，所述羟基 羧酸铜和所述反应之后多余的羟基羧酸附着在纳米铜表面。  The short-chain hydroxycarboxylic acid reacts with the nano-copper surface oxide layer to form copper hydroxycarboxylate, and the copper hydroxycarboxylate and the excess hydroxycarboxylic acid after the reaction adhere to the surface of the nano-copper.
2. 根据权利要求 1所述的纳米铜油墨的制备方法， 其特征在于， 所述 纳米铜的粒径小于 100 纳米。 The method for preparing a nano copper ink according to claim 1, wherein the nano copper has a particle diameter of less than 100 nm.
3. 根据权利要求 1所述的纳米铜油墨的制备方法， 其特征在于， 所述 短链羟基羧酸为乳酸、 羟基乙酸或者柠檬酸。 The method for producing a nano copper ink according to claim 1, wherein the short-chain hydroxycarboxylic acid is lactic acid, glycolic acid or citric acid.
4. 根据权利要求 1所述的纳米铜油墨的制备方法， 其特征在于， 所述 溶剂为乙醇、 乙二醇或者乙醇和乙二醇的混合溶液。 The method for producing a nano copper ink according to claim 1, wherein the solvent is ethanol, ethylene glycol or a mixed solution of ethanol and ethylene glycol.
5. 根据权利要求 1 所述的纳米铜油墨的制备方法， 其特征在于， 在所 述将纳米铜粒子均勾分散在含有短链羟基羧酸的溶剂中的步驟中，采用超声 作用进行分散。 The method for producing a nano-copper ink according to claim 1, wherein in the step of uniformly dispersing the nano-copper particles in a solvent containing a short-chain hydroxycarboxylic acid, dispersion is carried out by ultrasonic action.
6. 根据权利要求 5 所述的纳米铜油墨的制备方法， 其特征在于， 所述 超声分散的时间为 1小时至 2小时。  The method for producing a nano copper ink according to claim 5, wherein the ultrasonic dispersion is performed for 1 hour to 2 hours.
7. 一种铜导电薄膜的制备方法， 其特征在于， 包含以下步驟： 采用如权利要求 1至 6任一项所述的纳米铜油墨的制备方法制备纳米铜 油墨； 将所述制备得到的纳米铜油墨施于基材表面， 形成纳米铜油墨层； 对所述纳米铜油墨层进行真空干燥， 并在惰性气氛或者真空中进行焙 烧， 形成所述铜导电薄膜； A method for preparing a copper conductive film, comprising the steps of: preparing a nano copper ink by using the method for preparing a nano copper ink according to any one of claims 1 to 6; The copper ink is applied to the surface of the substrate to form a nano copper ink layer; Performing vacuum drying on the nano copper ink layer, and baking in an inert atmosphere or in a vacuum to form the copper conductive film;
其中，在制备纳米铜油墨过程中包覆在纳米铜表面的羟基羧酸铜在焙烧 时被还原成金属铜， 多余的羟基羧酸被除去。  Among them, copper hydroxycarboxylate coated on the surface of the nano copper during the preparation of the nano copper ink is reduced to metallic copper upon firing, and excess hydroxycarboxylic acid is removed.
8. 根据权利要求 7所述的铜导电薄膜的制备方法， 其特征在于， 所述 基材为硅片、 玻璃、 聚酰亚胺或者聚酯薄膜。  The method of producing a copper conductive film according to claim 7, wherein the substrate is a silicon wafer, a glass, a polyimide or a polyester film.
9. 根据权利要求 7 所述的铜导电薄膜的制备方法， 其特征在于， 在将 所述制备得到的纳米铜油墨施于基材表面的步驟中，通过滴涂、旋涂、提拉、 丝网印刷或者喷墨印刷方法将所述制备得到的纳米铜油墨施于基材表面。 The method for preparing a copper conductive film according to claim 7, wherein in the step of applying the prepared nano copper ink to the surface of the substrate, by spin coating, spin coating, pulling, and wire The prepared nano copper ink is applied to the surface of the substrate by a screen printing or inkjet printing method.
10. 根据权利要求 7所述的铜导电薄膜的制备方法， 其特征在于， 在惰 性气氛或者真空中进行焙烧的步驟中， 所述焙烧方式是电加热、 电加热辅以 紫外光照、 微波加热或者激光辅助加热。  The method for preparing a copper conductive film according to claim 7, wherein in the step of performing baking in an inert atmosphere or in a vacuum, the baking method is electric heating, electric heating, ultraviolet light irradiation, microwave heating or Laser assisted heating.
11. 根据权利要求 7所述的铜导电薄膜的制备方法， 其特征在于， 在惰 性气氛或者真空中进行焙烧的步驟中，所述焙烧的温度在 100至 250°C之间 , 时间在 1小时之内。  The method for producing a copper conductive film according to claim 7, wherein in the step of performing the calcination in an inert atmosphere or in a vacuum, the calcination temperature is between 100 and 250 ° C for 1 hour. within.
12. 根据权利要求 7所述的铜导电薄膜的制备方法， 其特征在于， 在惰 性气氛或者真空中进行焙烧的步驟中， 所述惰性气氛为氮气氛和氩气氛。  The method of producing a copper conductive film according to claim 7, wherein in the step of baking in an inert atmosphere or in a vacuum, the inert atmosphere is a nitrogen atmosphere and an argon atmosphere.
PCT/CN2013/078180 2012-10-16 2013-06-27 Nano-copper ink and copper conductive film preparation method WO2014059798A1 (en)

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