WO2018098853A1 - Nano-indium ink for flexible electronic devices, preparation method therefor and application thereof - Google Patents

Nano-indium ink for flexible electronic devices, preparation method therefor and application thereof Download PDF

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WO2018098853A1
WO2018098853A1 PCT/CN2016/109956 CN2016109956W WO2018098853A1 WO 2018098853 A1 WO2018098853 A1 WO 2018098853A1 CN 2016109956 W CN2016109956 W CN 2016109956W WO 2018098853 A1 WO2018098853 A1 WO 2018098853A1
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indium
nano
ink
surfactant
nano indium
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PCT/CN2016/109956
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French (fr)
Chinese (zh)
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潘毅
周洁
曹辰辉
虞磊
孔令宇
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南京大学
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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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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

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  • the invention belongs to the technical field of inkjet printing inks, and particularly relates to a nano indium ink for a transparent conductive film and a preparation method and application thereof.
  • the touch screen has become the fastest growing technology with the excellent human-computer communication.
  • the touch screen allows people to communicate with the machine in a more friendly and direct way, making the use of personal electronic products more humane.
  • resistive and capacitive touch screens require the use of a transparent conductive film.
  • the material of the transparent conductive film needs to have both flexibility, transparency, and conductivity.
  • the transparent conductive film needs to be subjected to etching, printing, pressing, and the like to form a touch screen.
  • the nano indium compound can be dissolved in the organic solution, and thus the nano indium compound can be printed and prepared into a transparent conductive film using a normal temperature and normal pressure process. Based on the excellent compatibility between the nano metal particle/organic polymer interface, the nano indium material can significantly reduce the surface contact resistance of the device, reduce the material defects between the metal electrode and the organic film, thereby improving device reliability and photoelectric conversion efficiency. .
  • the present invention provides a nano indium ink for flexible electronic device and preparation thereof Methods and applications.
  • Nano indium ink calculated by weight percentage, includes the following components: nano indium particles: 40-60%; ink carrier: 40-60%; the ink carrier comprises the following components by weight percentage: solvent 40 ⁇ 70%, surfactant 10-25%, wetting agent 1-20% and adhesive 1-15%; the solvent is hexane or ethanol; the surfactant is stearic acid, triethanolamine, lauric acid or polyoxygen Vinyl ether; the wetting agent is diethylene glycol, diethylene glycol butyl ether, glycerin; the adhesive is a phenolic resin or an acrylic resin.
  • the nano indium particles have a diameter of 10 nm to 30 nm, and the nano indium particles are encapsulated by organic molecules, and the organic molecules are alkyl mercaptans.
  • the preparation method of the nano indium ink is: dissolving indium chloride in hydrochloric acid under magnetic stirring, wherein the mass ratio of HCl to indium chloride is 170-200:1, and then adding n-hexane, chlorine
  • the mass ratio of indium to n-hexane is 1: (2.5 to 4), and then tetraethylene glycol monolauryl ether as a nonionic surfactant is added to the above solution, wherein tetraethylene glycol monolaurate and chlorine
  • the mass ratio of indium is 0.15:1 to 0.25:1, and a microemulsion molecule group containing water molecules, a surfactant, an organic solvent and In 3+ is formed by stirring; then, hexyl mercaptan is added to stir, hexyl mercaptan and In The molar ratio of 3+ is 0.125-5:1, and the indium thiocarbonate encapsulated nano-indium particles obtained by using excess sodium boro
  • Indium Nanoparticles be regulated by the size and the molar ratio of alkyl mercaptan of In 3+, and when the molar ratio of alkyl mercaptan In 3+ of 0.125 to 5: 1, indium nanometer size between 10 ⁇ 30nm and with As the amount of alkyl mercaptan increases, the size of the nano indium particles gradually decreases.
  • the above nano indium ink is used in the preparation of flexible electronic devices.
  • the present invention solves the problem of excessive curing sintering temperature and compatibility of metal nanoparticles with a matrix.
  • the nano indium particles are thiol encapsulated nano indium particles, and the use of the thiol can increase the compatibility between the metal particles and the substrate, and can also be used as a dispersing agent for the ink system.
  • the ink can be widely used in printers of various nozzle sizes, and can print fine electronic circuits and large areas.
  • the printing of metal electrodes of optoelectronic devices is in preparation.
  • Figure 1 is a scanning electron micrograph of the present invention.
  • Conductive ink of the present invention shown for transmission electron microscopy (TEM) at 90 ° C The structure of the surface of the conductive indium film after sintering for 2 hours;
  • TEM transmission electron microscopy
  • Indium has its melting point lower than that of silver, gold and other metals due to its own nature, while the melting point of nano indium is lower.
  • the curing temperature of nano indium ink is generally 80-100 ° C, which is much lower than the curing temperature of conductive silver ink.
  • the indium ink of the present invention is printed and baked and sintered in an oven at 90 ° C for 2 hours, and naturally cooled to room temperature to form a uniform conductive film. A continuous and uniform distribution on the surface of the substrate material shows better compatibility with the substrate material.
  • the obtained indium particle size is controlled to about 10 nm (Fig. 1 a) .
  • the surface resistance measured by the four-probe method was 0.3 m ⁇ / ⁇ .
  • Hexyl mercaptan (1:8 molar ratio of hexyl mercaptan and In 3+ ) was added, and 1.0 g of sodium borohydride was added to reduce the metal indium to obtain organic indium encapsulated nano indium particles.
  • the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature.
  • the sintered product was observed by scanning electron microscopy.
  • the indium particles were connected to one surface on the surface of the glass carrier; the size of the nano indium was changed by adjusting the molar ratio of alkyl mercaptan and In 3+ , when hexyl mercaptan and In 3+ were When the molar ratio is 1:8, the obtained indium particle size is controlled to be about 30 nm (b in Fig. 1).
  • the surface resistance measured by the four-probe method was 0.4 m ⁇ / ⁇ .
  • indium chloride is dissolved in hydrochloric acid, wherein the mass ratio of HCl to indium chloride is 170:1, and then n-hexane is added, and the mass ratio of indium chloride to n-hexane is 1:2.5, and then A nonionic surfactant tetraethylene glycol monolauryl ether is added to the solution, wherein the mass ratio of tetraethylene glycol monolaurate and indium chloride is 0.15:1, and the mixture is formed to contain water molecules, surfactants, Organic solvent and In 3+ microemulsion micelles; then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan to In 3+ is 0.125:1, and the thiol obtained by reducing the metal indium using an excess of sodium borohydride The nano-indium particles of the capsule, the molar ratio of sodium borohydride to indium chloride is 1:1.
  • Nano indium particles (mass percent): 40%; ink carrier (mass percent): 60%; ink carrier composition as follows (mass percentage): ethanol (solvent, 70%), stearic acid (surfactant, 25%) , Diethylene glycol butyl ether (wetting agent, 1%), acrylic resin (adhesive, 4%).
  • the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature.
  • the surface resistance measured by the four-probe method was 0.45 m ⁇ / ⁇ .
  • indium chloride is dissolved in hydrochloric acid, wherein the mass ratio of HCl to indium chloride is 190:1, and then n-hexane is added, and the mass ratio of indium chloride to n-hexane is 1:3.3, and then A nonionic surfactant tetraethylene glycol monolauryl ether is added to the solution, wherein the mass ratio of tetraethylene glycol monolaurate and indium chloride is 0.2:1, and the mixture is formed to contain water molecules, surfactants, Organic solvent and In 3+ microemulsion micelles; then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan to In 3+ is 2:1, and the thiol obtained by reducing the metal indium using an excess of sodium borohydride
  • the nano-indium particles of the capsules have a molar ratio of sodium borohydride to indium chloride of 1.5:1.
  • Nano indium particles 50%; ink carrier (mass percent): 50%.
  • the composition of the ink carrier is as follows (mass percentage): ethanol (solvent, 60%), triethanolamine (surfactant, 15%), diethylene glycol (wetting agent, 15%), phenolic Resin (adhesive, 10%).
  • indium chloride is dissolved in hydrochloric acid, wherein the mass ratio of HCl to indium chloride is 200:1, and then n-hexane is added, and the mass ratio of indium chloride to n-hexane is 1:4, and then A nonionic surfactant tetraethylene glycol monolauryl ether is added to the solution, wherein the mass ratio of tetraethylene glycol monolaurate to indium chloride is 0.25:1, and the mixture is formed to contain water molecules, surfactants, Organic solvent and In 3+ microemulsion micelles; then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan to In 3+ is 5:1, and the thiol obtained by reducing the metal indium using an excess of sodium borohydride
  • the encapsulated nano indium particles have a molar ratio of sodium borohydride to indium chloride of 2:1.
  • Nano indium particles encapsulated in hexyl mercaptan are dissolved in a solvent, and a surfactant, a wetting agent and an adhesive are added, and the mixture is uniformly stirred to obtain an emulsion.
  • the emulsion is filtered using a 0.45 ⁇ m mixed cellulose filter to obtain a conductive ink.
  • the composition of the ink carrier is as follows (mass percentage): hexane (solvent, 40%), lauric acid (surfactant, 25%), diethylene glycol butyl ether (wetting agent, 20%), phenolic resin (Adhesive, 15%).
  • the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature.
  • the surface resistance measured by the four-probe method was 0.35 m ⁇ / ⁇ .

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

A nano-indium ink for flexible electronic devices, a preparation method therefor and an application thereof. The nano-indium ink comprises the following components in percentage by weight: 40-60% of indium nanoparticles and 40-60% of ink carrier; the ink carrier comprises the following components in percentage by weight: 40-70% of a solvent, 10-25% of a surfactant, 1-20% of a wetting agent, and 1-15% of a tackifier; the solvent is hexane or ethanol; the surfactant is stearic acid, triethanolamine, lauric acid, or polyoxyethylene ether; the wetting agent is diethylene glycol, diethylene glycol monobutyl ether, or glycerol; the tackifier is phenolic resin or fatty amine. The ink can be widely applied to printers with a variety of different sizes of nozzles, can print fine electronic circuits, and can be used for printing metal electrodes of large-area optoelectronic devices.

Description

用于柔性电子器件的纳米铟墨水及其制备方法和应用Nano indium ink for flexible electronic device and preparation method and application thereof 技术领域Technical field
本发明属于喷墨打印墨水技术领域，具体涉及用于透明导电膜的纳米铟墨水及其制备方法和应用。The invention belongs to the technical field of inkjet printing inks, and particularly relates to a nano indium ink for a transparent conductive film and a preparation method and application thereof.
背景技术Background technique
新型有机聚合物材料为基础的微电子器件(Organic Electronics)的迅速发展代表的一个崭新行业的掘起。英国著名的IDTechex公司预测，新型有机电子器件的全球销量在2018年将达到约470亿美元/年，到2028年，这个数字将会突飞猛进到约3800亿美元/年。在整个产业的产值分配中，有大约50％-60％是来自各类配套材料，其中金属电极材料大约占8％-10％左右。The rapid development of new organic polymer-based microelectronic devices (Organic Electronics) represents a new industry. The famous IDTechex company in the UK predicts that global sales of new organic electronic devices will reach approximately US$47 billion/year in 2018. By 2028, this number will advance rapidly to approximately US$380 billion/year. About 50%-60% of the output distribution of the whole industry comes from various supporting materials, of which metal electrode materials account for about 8%-10%.
随着计算机工业的发展，人机界面的沟通成了计算机技术的一个热点，触摸屏凭着优秀的人机沟通方式，成为了当今发展最快的技术。触控屏幕可使人与机器间以更友善直接的方式沟通，使个人电子产品的使用更加人性化。其中，电阻式和电容式触摸屏需要使用到透明导电膜。透明导电膜的材料需要同时具备柔性、透明性和导电性。透明导电膜需要经过蚀刻、印刷线路、压合等工序后才能形成触摸屏。With the development of the computer industry, the communication of human-machine interface has become a hot spot of computer technology. The touch screen has become the fastest growing technology with the excellent human-computer communication. The touch screen allows people to communicate with the machine in a more friendly and direct way, making the use of personal electronic products more humane. Among them, resistive and capacitive touch screens require the use of a transparent conductive film. The material of the transparent conductive film needs to have both flexibility, transparency, and conductivity. The transparent conductive film needs to be subjected to etching, printing, pressing, and the like to form a touch screen.
在全面商用产业化的进程中，有机电子还存在着许多有待突破的技术难点，其中包括合成和制备有机聚合物薄膜表面上的金属电极材料。半导体有机聚合物薄膜要求与其功函数(Work Function)相匹配的金属电极。这类金属电极大多以金和银等金属化合物为主，通过真空镀膜的方式制备到有机聚合物薄膜表面上。可是这种金属镀膜工艺一般需要200-300℃的高温退火。这个温度范围对于很多有机聚合物薄膜来说是无法承受的。这样的高温工艺会导致在有机聚合物薄膜和金属电极的界面上产生需多缺陷，从而大大降低器件的光电转换效率和使用寿命。而且，真空镀膜的工艺技术无法同印刷技术匹配来制造大面积和超大面积的薄膜光电池和柔性电子器件。因此开发一类专门用于各类有机柔性光电子器件的、适合大面积印刷工艺在常温常压下制造的薄膜金属电极材料有着巨大的技术价值和经济效益。In the process of comprehensive commercial industrialization, there are still many technical difficulties to be solved in organic electronics, including the synthesis and preparation of metal electrode materials on the surface of organic polymer films. Semiconductor organic polymer films require metal electrodes that are matched to their work function. Most of such metal electrodes are mainly made of a metal compound such as gold or silver, and are prepared by vacuum coating on the surface of the organic polymer film. However, this metal coating process generally requires a high temperature annealing of 200-300 °C. This temperature range is unacceptable for many organic polymer films. Such a high temperature process results in a large number of defects at the interface between the organic polymer film and the metal electrode, thereby greatly reducing the photoelectric conversion efficiency and the service life of the device. Moreover, vacuum coating process technology cannot be matched to printing technology to produce large-area and ultra-large-area thin film photovoltaic cells and flexible electronic devices. Therefore, the development of a class of thin film metal electrode materials suitable for various types of organic flexible optoelectronic devices suitable for large-area printing processes at normal temperature and pressure has great technical and economic benefits.
纳米铟化物可以溶解于有机溶液中，因此可以使用常温常压工艺，将纳米铟化物印刷并制备成透明的导电膜。基于纳米金属颗粒/有机聚合物界面之间的优良兼容性，纳米铟化物材料可以显著降低器件的表面接触电阻，降低金属电极和有机薄膜之间的材料缺陷，从而提高器件可靠性和光电转换效率。 The nano indium compound can be dissolved in the organic solution, and thus the nano indium compound can be printed and prepared into a transparent conductive film using a normal temperature and normal pressure process. Based on the excellent compatibility between the nano metal particle/organic polymer interface, the nano indium material can significantly reduce the surface contact resistance of the device, reduce the material defects between the metal electrode and the organic film, thereby improving device reliability and photoelectric conversion efficiency. .
发明内容Summary of the invention
解决的技术问题：为了解决透明导电膜制备过程中出现的固化烧结温度过高和金属纳米颗粒与基体相容性的问题，本发明提供了一种用于柔性电子器件的纳米铟墨水及其制备方法和应用。Technical problem to be solved: In order to solve the problem of excessive curing sintering temperature and compatibility of metal nanoparticles with a matrix which occurs during preparation of a transparent conductive film, the present invention provides a nano indium ink for flexible electronic device and preparation thereof Methods and applications.
技术方案：纳米铟墨水，按重量百分比计算，包括如下组份：纳米铟颗粒：40～60％；墨水载体：40～60％；所述墨水载体按重量百分比计算包括以下组份：溶剂40～70％、表面活性剂10～25％、润湿剂1～20％和胶粘剂1～15％；所述溶剂为己烷或乙醇；表面活性剂为硬脂酸、三乙醇胺、月桂酸或聚氧乙烯醚；润湿剂为二甘醇、二乙二醇丁醚、丙三醇；胶粘剂为酚醛树脂或丙烯酸树脂。Technical Solution: Nano indium ink, calculated by weight percentage, includes the following components: nano indium particles: 40-60%; ink carrier: 40-60%; the ink carrier comprises the following components by weight percentage: solvent 40~ 70%, surfactant 10-25%, wetting agent 1-20% and adhesive 1-15%; the solvent is hexane or ethanol; the surfactant is stearic acid, triethanolamine, lauric acid or polyoxygen Vinyl ether; the wetting agent is diethylene glycol, diethylene glycol butyl ether, glycerin; the adhesive is a phenolic resin or an acrylic resin.
上述纳米铟颗粒的直径为10nm～30nm，且纳米铟颗粒被有机分子囊包，所述的有机分子为烷基硫醇。The nano indium particles have a diameter of 10 nm to 30 nm, and the nano indium particles are encapsulated by organic molecules, and the organic molecules are alkyl mercaptans.
纳米铟墨水的制备方法，纳米铟的制备步骤为：在磁力搅拌下，将氯化铟溶于盐酸中，其中HCl与氯化铟的质量比为170～200:1，再加入正己烷，氯化铟和正己烷的质量比为1：(2.5～4)，然后将作为非离子表面活性剂的四聚乙二醇单月桂醚加入上述溶液中，其中四聚乙二醇单月桂醚和氯化铟的质量比为0.15:1～0.25:1，搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团；然后，加入己硫醇搅拌，己硫醇和In3+的摩尔比例为0.125～5:1，使用过量的硼氢化钠将金属铟还原出来得到的己硫醇囊包的纳米铟颗粒，硼氢化钠和氯化铟的摩尔比为1:1～2:1。The preparation method of the nano indium ink, the preparation step of the nano indium is: dissolving indium chloride in hydrochloric acid under magnetic stirring, wherein the mass ratio of HCl to indium chloride is 170-200:1, and then adding n-hexane, chlorine The mass ratio of indium to n-hexane is 1: (2.5 to 4), and then tetraethylene glycol monolauryl ether as a nonionic surfactant is added to the above solution, wherein tetraethylene glycol monolaurate and chlorine The mass ratio of indium is 0.15:1 to 0.25:1, and a microemulsion molecule group containing water molecules, a surfactant, an organic solvent and In 3+ is formed by stirring; then, hexyl mercaptan is added to stir, hexyl mercaptan and In The molar ratio of 3+ is 0.125-5:1, and the indium thiocarbonate encapsulated nano-indium particles obtained by using excess sodium borohydride to reduce the metal indium, the molar ratio of sodium borohydride and indium chloride is 1:1. 2:1.
纳米铟的尺寸通过烷基硫醇和In3+的摩尔比例来调控，当烷基硫醇和In3+的摩尔比例为0.125～5:1时，纳米铟的尺寸在10～30nm之间并且随着烷基硫醇用量增加，纳米铟颗粒的尺寸逐渐减小。Indium Nanoparticles be regulated by the size and the molar ratio of alkyl mercaptan of In 3+, and when the molar ratio of alkyl mercaptan In 3+ of 0.125 to 5: 1, indium nanometer size between 10 ~ 30nm and with As the amount of alkyl mercaptan increases, the size of the nano indium particles gradually decreases.
上述纳米铟墨水在制备柔性电子器件中应用。The above nano indium ink is used in the preparation of flexible electronic devices.
有益效果：本发明解决了固化烧结温度过高和金属纳米颗粒与基体相容性的问题。纳米铟颗粒是硫醇囊包的纳米铟颗粒，硫醇的使用即可以增加金属颗粒和基材之间的相容性，也可作为墨水体系的分散剂使用。此外，通过调控烷基硫醇和In3+的摩尔比例来改变纳米铟的尺寸，使得该墨水可以广泛用于各种不同尺寸喷嘴的打印机，既可以打印精细的电子电路，又可以用于大面积光电子器件的金属电极的打印制备中。Advantageous Effects: The present invention solves the problem of excessive curing sintering temperature and compatibility of metal nanoparticles with a matrix. The nano indium particles are thiol encapsulated nano indium particles, and the use of the thiol can increase the compatibility between the metal particles and the substrate, and can also be used as a dispersing agent for the ink system. In addition, by adjusting the molar ratio of alkylthiol to In 3+ to change the size of nano indium, the ink can be widely used in printers of various nozzle sizes, and can print fine electronic circuits and large areas. The printing of metal electrodes of optoelectronic devices is in preparation.
附图说明DRAWINGS
图1为本发明的扫描电镜图。(a)为透射电镜(TEM)展示的本发明导电墨水在90℃ 烧结2小时后导电铟膜表面的结构；(b)为透射电镜(TEM)展示的本发明导电墨水在80℃烧结2小时后导电铟膜表面的结构。Figure 1 is a scanning electron micrograph of the present invention. (a) Conductive ink of the present invention shown for transmission electron microscopy (TEM) at 90 ° C The structure of the surface of the conductive indium film after sintering for 2 hours; (b) The structure of the surface of the conductive indium film after the conductive ink of the present invention exhibited by transmission electron microscopy (TEM) was sintered at 80 ° C for 2 hours.
具体实施方式detailed description
以上实例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人是能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。The above examples are only intended to illustrate the technical concept and the features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the present invention and to implement the present invention, and the scope of the present invention is not limited thereto. Equivalent transformations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention.
实施例1：Example 1:
称取5.0g的氯化铟固体，溶于12.5mL的0.06M的盐酸中，加入25.0mL的正己烷，形成混合溶液，搅拌均匀后加入1.0mL的四聚乙二醇单月桂醚作为非离子表面活性剂。搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团。加入己硫醇(己硫醇和In3+的摩尔比例为5:1)，加入1.25g的硼氢化钠将金属铟还原出来，得到有机分子囊包的纳米铟颗粒。Weigh 5.0g of indium chloride solid, dissolve it in 12.5mL of 0.06M hydrochloric acid, add 25.0mL of n-hexane to form a mixed solution, stir evenly and add 1.0mL of tetraethylene glycol monolaurate as non-ion Surfactant. Stirring forms a microemulsion molecule cluster containing water molecules, surfactants, organic solvents, and In 3+ . Hexyl mercaptan (5:1 molar ratio of hexyl mercaptan and In 3+ ) was added, and 1.25 g of sodium borohydride was added to reduce the metal indium to obtain organic indium encapsulated nano indium particles.
称取1.5g有机分子囊包的纳米铟颗粒溶于2.0mL的己烷中，加入0.23g三乙醇胺作为表面活性剂，加入0.4g二甘醇作为润湿剂，加入0.3g的酚醛树脂作为胶粘剂，搅拌30min，使用0.45μm的混合纤维素滤膜过滤乳液即得到可打印的墨水。1.5 g of organic molecular capsules were weighed into 2.0 mL of hexane, 0.23 g of triethanolamine was added as a surfactant, 0.4 g of diethylene glycol was added as a wetting agent, and 0.3 g of phenolic resin was added as an adhesive. After stirring for 30 min, the emulsion was filtered using a 0.45 μm mixed cellulose filter to obtain a printable ink.
铟由于自身性质决定了它的熔点比银，金等金属低，而纳米铟的熔点更低，纳米铟墨水的固化温度一般在80～100℃，远低于导电银墨水的固化温度。本发明的铟墨水经过打印，在90℃烘箱内加热烧结2h，自然冷却到室温形成均匀的导电薄膜。在基底材料表面连续和均匀的分布显示了和基底材料较好的相容性。通过调控烷基硫醇和In3+的摩尔比例来改变纳米铟的尺寸，当己硫醇和In3+的摩尔比例为5:1时，得到的铟颗粒尺寸控制在10nm左右(图1中a)。经四探针法测得表面电阻是0.3mΩ/□。Indium has its melting point lower than that of silver, gold and other metals due to its own nature, while the melting point of nano indium is lower. The curing temperature of nano indium ink is generally 80-100 ° C, which is much lower than the curing temperature of conductive silver ink. The indium ink of the present invention is printed and baked and sintered in an oven at 90 ° C for 2 hours, and naturally cooled to room temperature to form a uniform conductive film. A continuous and uniform distribution on the surface of the substrate material shows better compatibility with the substrate material. By adjusting the molar ratio of alkylthiol to In 3+ to change the size of nano indium, when the molar ratio of hexyl mercaptan to In 3+ is 5:1, the obtained indium particle size is controlled to about 10 nm (Fig. 1 a) . The surface resistance measured by the four-probe method was 0.3 mΩ/□.
实施例2：Example 2:
称取约4.0g的氯化铟固体，溶于10.0mL的0.06M的盐酸中，磁力搅拌，然后加入20mL的正己烷，形成混合溶液，搅拌几分钟后加入0.8mL的四聚乙二醇单月桂醚作为非离子表面活性剂。搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团。加入己硫醇(己硫醇和In3+的摩尔比例为1:8)，加入1.0g的硼氢化钠将金属铟还原出来，得到有机分子囊包的纳米铟颗粒。Weigh about 4.0 g of indium chloride solid, dissolve it in 10.0 mL of 0.06 M hydrochloric acid, stir with magnetic force, then add 20 mL of n-hexane to form a mixed solution. After stirring for a few minutes, add 0.8 mL of tetraethylene glycol alone. Laurel ether is used as a nonionic surfactant. Stirring forms a microemulsion molecule cluster containing water molecules, surfactants, organic solvents, and In 3+ . Hexyl mercaptan (1:8 molar ratio of hexyl mercaptan and In 3+ ) was added, and 1.0 g of sodium borohydride was added to reduce the metal indium to obtain organic indium encapsulated nano indium particles.
称取2.0g纳米铟颗粒溶于3mL的己烷中，加入0.3g硬脂酸作为表面活性剂，加入0.4 g丙三醇作为润湿剂，加入0.32g的丙烯酸树脂作为胶粘剂，搅拌30min，使用0.45μm的混合纤维素滤膜过滤乳液即得到可打印的墨水。Weigh 2.0g of nano-indium particles in 3mL of hexane, add 0.3g of stearic acid as surfactant, add 0.4 g glycerol was used as a wetting agent, 0.32 g of an acrylic resin was added as an adhesive, and the mixture was stirred for 30 minutes, and the emulsion was filtered using a 0.45 μm mixed cellulose filter to obtain a printable ink.
此墨水经打印后，在80℃烘箱内加热烧结2h，自然冷却到室温。烧结产品使用扫描电镜观察得知：烧结后，铟颗粒在玻璃载体表面已连成一片；通过调控烷基硫醇和In3+的摩尔比例来改变纳米铟的尺寸，当己硫醇和In3+的摩尔比例为1:8时，得到的铟颗粒尺寸控制在30nm左右(图1中b)。经四探针法测得表面电阻是0.4mΩ/□。After printing, the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature. The sintered product was observed by scanning electron microscopy. After sintering, the indium particles were connected to one surface on the surface of the glass carrier; the size of the nano indium was changed by adjusting the molar ratio of alkyl mercaptan and In 3+ , when hexyl mercaptan and In 3+ were When the molar ratio is 1:8, the obtained indium particle size is controlled to be about 30 nm (b in Fig. 1). The surface resistance measured by the four-probe method was 0.4 mΩ/□.
实施例3Example 3
在磁力搅拌下，将氯化铟溶于盐酸中，其中HCl与氯化铟的质量比为170:1，再加入正己烷，氯化铟和正己烷的质量比为1：2.5，然后将作为非离子表面活性剂的四聚乙二醇单月桂醚加入溶液中，其中四聚乙二醇单月桂醚和氯化铟的质量比为0.15:1，搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团；然后，加入己硫醇搅拌，己硫醇和In3+的摩尔比例为0.125:1，使用过量的硼氢化钠将金属铟还原出来得到的硫醇囊包的纳米铟颗粒，硼氢化钠和氯化铟的摩尔比为1:1。Under magnetic stirring, indium chloride is dissolved in hydrochloric acid, wherein the mass ratio of HCl to indium chloride is 170:1, and then n-hexane is added, and the mass ratio of indium chloride to n-hexane is 1:2.5, and then A nonionic surfactant tetraethylene glycol monolauryl ether is added to the solution, wherein the mass ratio of tetraethylene glycol monolaurate and indium chloride is 0.15:1, and the mixture is formed to contain water molecules, surfactants, Organic solvent and In 3+ microemulsion micelles; then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan to In 3+ is 0.125:1, and the thiol obtained by reducing the metal indium using an excess of sodium borohydride The nano-indium particles of the capsule, the molar ratio of sodium borohydride to indium chloride is 1:1.
将己硫醇囊包的纳米铟颗粒溶于溶剂中，加入表面活性剂、润湿剂和胶粘剂后搅拌均匀得到乳液，使用0.45μm的混合纤维素滤膜过滤乳液即得到导电的墨水。纳米铟颗粒(质量百分比)：40％；墨水载体(质量百分比)：60％；墨水载体的成分如下(质量百分比)：乙醇(溶剂，70％)，硬脂酸(表面活性剂，25％)，二乙二醇丁醚(润湿剂，1％)，丙烯酸树脂(胶粘剂，4％)。此墨水经打印后，在80℃烘箱内加热烧结2h，自然冷却到室温。经四探针法测得表面电阻是0.45mΩ/□。The nano-indium particles encapsulated in hexyl mercaptan are dissolved in a solvent, and a surfactant, a wetting agent and an adhesive are added, and the mixture is uniformly stirred to obtain an emulsion. The emulsion is filtered using a 0.45 μm mixed cellulose filter to obtain a conductive ink. Nano indium particles (mass percent): 40%; ink carrier (mass percent): 60%; ink carrier composition as follows (mass percentage): ethanol (solvent, 70%), stearic acid (surfactant, 25%) , Diethylene glycol butyl ether (wetting agent, 1%), acrylic resin (adhesive, 4%). After printing, the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature. The surface resistance measured by the four-probe method was 0.45 mΩ/□.
实施例4Example 4
在磁力搅拌下，将氯化铟溶于盐酸中，其中HCl与氯化铟的质量比为190:1，再加入正己烷，氯化铟和正己烷的质量比为1:3.3，然后将作为非离子表面活性剂的四聚乙二醇单月桂醚加入溶液中，其中四聚乙二醇单月桂醚和氯化铟的质量比为0.2:1，搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团；然后，加入己硫醇搅拌，己硫醇和In3+的摩尔比例为2:1，使用过量的硼氢化钠将金属铟还原出来得到的硫醇囊包的纳米铟颗粒，硼氢化钠和氯化铟的摩尔比为1.5:1。Under magnetic stirring, indium chloride is dissolved in hydrochloric acid, wherein the mass ratio of HCl to indium chloride is 190:1, and then n-hexane is added, and the mass ratio of indium chloride to n-hexane is 1:3.3, and then A nonionic surfactant tetraethylene glycol monolauryl ether is added to the solution, wherein the mass ratio of tetraethylene glycol monolaurate and indium chloride is 0.2:1, and the mixture is formed to contain water molecules, surfactants, Organic solvent and In 3+ microemulsion micelles; then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan to In 3+ is 2:1, and the thiol obtained by reducing the metal indium using an excess of sodium borohydride The nano-indium particles of the capsules have a molar ratio of sodium borohydride to indium chloride of 1.5:1.
将己硫醇囊包的纳米铟颗粒溶于溶剂中，加入表面活性剂、润湿剂和胶粘剂后搅拌均匀得到乳液，使用0.45μm的混合纤维素滤膜过滤乳液即得到导电的墨水。纳米铟颗粒(质量百分比)：50％；墨水载体(质量百分比)：50％。其中，墨水载体的成分如下(质量百分比)：乙醇(溶剂，60％)，三乙醇胺(表面活性剂，15％)，二甘醇(润湿剂，15％)，酚醛 树脂(胶粘剂，10％)。此墨水经打印后，在80℃烘箱内加热烧结2h，自然冷却到室温。经四探针法测得表面电阻是0.47mΩ/□。The nano-indium particles encapsulated in hexyl mercaptan are dissolved in a solvent, and a surfactant, a wetting agent and an adhesive are added, and the mixture is uniformly stirred to obtain an emulsion. The emulsion is filtered using a 0.45 μm mixed cellulose filter to obtain a conductive ink. Nano indium particles (mass percent): 50%; ink carrier (mass percent): 50%. Among them, the composition of the ink carrier is as follows (mass percentage): ethanol (solvent, 60%), triethanolamine (surfactant, 15%), diethylene glycol (wetting agent, 15%), phenolic Resin (adhesive, 10%). After printing, the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature. The surface resistance measured by the four-probe method was 0.47 mΩ/□.
实施例5Example 5
在磁力搅拌下，将氯化铟溶于盐酸中，其中HCl与氯化铟的质量比为200:1，再加入正己烷，氯化铟和正己烷的质量比为1：4，然后将作为非离子表面活性剂的四聚乙二醇单月桂醚加入溶液中，其中四聚乙二醇单月桂醚和氯化铟的质量比为0.25:1，搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团；然后，加入己硫醇搅拌，己硫醇和In3+的摩尔比例为5:1，使用过量的硼氢化钠将金属铟还原出来得到的硫醇囊包的纳米铟颗粒，硼氢化钠和氯化铟的摩尔比为2:1。Under magnetic stirring, indium chloride is dissolved in hydrochloric acid, wherein the mass ratio of HCl to indium chloride is 200:1, and then n-hexane is added, and the mass ratio of indium chloride to n-hexane is 1:4, and then A nonionic surfactant tetraethylene glycol monolauryl ether is added to the solution, wherein the mass ratio of tetraethylene glycol monolaurate to indium chloride is 0.25:1, and the mixture is formed to contain water molecules, surfactants, Organic solvent and In 3+ microemulsion micelles; then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan to In 3+ is 5:1, and the thiol obtained by reducing the metal indium using an excess of sodium borohydride The encapsulated nano indium particles have a molar ratio of sodium borohydride to indium chloride of 2:1.
将己硫醇囊包的纳米铟颗粒溶于溶剂中，加入表面活性剂、润湿剂和胶粘剂后搅拌均匀得到乳液，使用0.45μm的混合纤维素滤膜过滤乳液即得到导电的墨水。纳米铟颗粒(质量百分比)：60％；墨水载体(质量百分比)：40％。其中，墨水载体的成分如下(质量百分比)：己烷(溶剂，40％)，月桂酸(表面活性剂，25％)，二乙二醇丁醚作(润湿剂，20％)，酚醛树脂(胶粘剂，15％)。此墨水经打印后，在80℃烘箱内加热烧结2h，自然冷却到室温。经四探针法测得表面电阻是0.35mΩ/□。 The nano-indium particles encapsulated in hexyl mercaptan are dissolved in a solvent, and a surfactant, a wetting agent and an adhesive are added, and the mixture is uniformly stirred to obtain an emulsion. The emulsion is filtered using a 0.45 μm mixed cellulose filter to obtain a conductive ink. Nano indium particles (mass percent): 60%; ink carrier (mass percent): 40%. The composition of the ink carrier is as follows (mass percentage): hexane (solvent, 40%), lauric acid (surfactant, 25%), diethylene glycol butyl ether (wetting agent, 20%), phenolic resin (Adhesive, 15%). After printing, the ink was heated and sintered in an oven at 80 ° C for 2 h, and naturally cooled to room temperature. The surface resistance measured by the four-probe method was 0.35 mΩ/□.

Claims (7)

  1. 纳米铟墨水，其特征在于按重量百分比计算，包括如下组份：纳米铟颗粒：40～60％；墨水载体：40～60％；所述墨水载体按重量百分比计算包括以下组份：溶剂40～70％、表面活性剂10～25％、润湿剂1～20％和胶粘剂1～15％；所述溶剂为己烷或乙醇；表面活性剂为硬脂酸、三乙醇胺、月桂酸或聚氧乙烯醚；润湿剂为二甘醇、二乙二醇丁醚、丙三醇；胶粘剂为酚醛树脂或丙烯酸树脂。The nano indium ink is characterized by weight percentage, comprising the following components: nano indium particles: 40-60%; ink carrier: 40-60%; and the ink carrier comprises the following components by weight percentage: solvent 40~ 70%, surfactant 10-25%, wetting agent 1-20% and adhesive 1-15%; the solvent is hexane or ethanol; the surfactant is stearic acid, triethanolamine, lauric acid or polyoxygen Vinyl ether; the wetting agent is diethylene glycol, diethylene glycol butyl ether, glycerin; the adhesive is a phenolic resin or an acrylic resin.
  2. 根据权利要求1所述的纳米铟墨水，其特征在于所述纳米铟颗粒的直径为10nm～30nm。The nano indium ink according to claim 1, wherein the nano indium particles have a diameter of 10 nm to 30 nm.
  3. 根据权利要求1所述的纳米铟墨水，其特征在于所述纳米铟颗粒被有机分子囊包。The nano indium ink according to claim 1, wherein the nano indium particles are encapsulated by organic molecules.
  4. 根据权利要求3所述的纳米铟墨水，其特征在于所述的有机分子为烷基硫醇。The nano indium ink according to claim 3, wherein the organic molecule is an alkyl mercaptan.
  5. 根据权利要求1～4任一所述纳米铟墨水的制备方法，其特征在于纳米铟的制备步骤为：在磁力搅拌下，将氯化铟溶于盐酸中，其中HCl与氯化铟的质量比为170～200:1，再加入正己烷，氯化铟和正己烷的质量比为1：(2.5～4)，然后将作为非离子表面活性剂的四聚乙二醇单月桂醚加入上述溶液中，其中四聚乙二醇单月桂醚和氯化铟的质量比为0.15:1～0.25:1，搅拌形成了含有水分子、表面活性剂、有机溶剂和In3+的微乳胶束分子团；然后，加入己硫醇搅拌，己硫醇和In3+的摩尔比例为0.125～5:1，使用过量的硼氢化钠将金属铟还原出来得到的己硫醇囊包的纳米铟颗粒，硼氢化钠和氯化铟的摩尔比为1:1～2:1。The method for preparing a nano indium ink according to any one of claims 1 to 4, wherein the preparation step of the nano indium is: dissolving indium chloride in hydrochloric acid under magnetic stirring, wherein the mass ratio of HCl to indium chloride 170-200:1, further adding n-hexane, the mass ratio of indium chloride to n-hexane is 1: (2.5-4), and then adding tetraethylene glycol monolauryl ether as a nonionic surfactant to the above solution The mass ratio of tetraethylene glycol monolaurate and indium chloride is 0.15:1 to 0.25:1, and a microemulsion molecule group containing water molecules, a surfactant, an organic solvent and In 3+ is formed by stirring. Then, adding hexyl mercaptan to stir, the molar ratio of hexyl mercaptan and In 3+ is 0.125 to 5:1, and the indium thiocarbonate encapsulated nano indium particles obtained by using excess sodium borohydride to reduce the metal indium, hydroboration The molar ratio of sodium to indium chloride is 1:1 to 2:1.
  6. 根据权利要求5所述的纳米铟墨水的制备方法，其特征在于纳米铟的尺寸通过烷基硫醇和In3+的摩尔比例来调控；当烷基硫醇和In3+的摩尔比例为0.125～5:1时，纳米铟的尺寸在10～30nm之间并且随着烷基硫醇用量增加，纳米铟颗粒的尺寸逐渐减小。The production method of claim 5 nano ink of claim indium, indium wherein the nano size be regulated by a molar ratio of alkyl mercaptan and In 3+; as alkyl mercaptans and a molar ratio of In 3+ 0.125 to 5 When the temperature is 1, the size of the nano indium is between 10 and 30 nm and the size of the nano indium particles gradually decreases as the amount of the alkyl mercaptan increases.
  7. 权利要求1～4任一所述纳米铟墨水在制备柔性电子器件中应用。 The nano indium ink according to any one of claims 1 to 4 for use in the preparation of a flexible electronic device.
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