WO2017222311A1 - Procédé de préparation d'une structure composite métallique dans laquelle un nanofil métallique et des particules métalliques sont soudés - Google Patents

Procédé de préparation d'une structure composite métallique dans laquelle un nanofil métallique et des particules métalliques sont soudés Download PDF

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Publication number
WO2017222311A1
WO2017222311A1 PCT/KR2017/006553 KR2017006553W WO2017222311A1 WO 2017222311 A1 WO2017222311 A1 WO 2017222311A1 KR 2017006553 W KR2017006553 W KR 2017006553W WO 2017222311 A1 WO2017222311 A1 WO 2017222311A1
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WIPO (PCT)
Prior art keywords
metal
particles
nanowires
composite structure
metal particles
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PCT/KR2017/006553
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English (en)
Korean (ko)
Inventor
박성주
이효주
홍상현
오세미
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광주과학기술원
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Publication of WO2017222311A1 publication Critical patent/WO2017222311A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
    • B23K31/02—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups relating to soldering or welding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0036—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices

Definitions

  • the present invention relates to a method for manufacturing a metal nanowire, and more particularly, to a method for manufacturing a metal composite structure formed by welding metal particles and metal nanowires.
  • Transparent electrodes are applied to various optical devices such as solar light, displays, light emitting diodes, etc., and much research is being conducted.
  • ITO transparent electrode commercialized as a transparent electrode
  • a high temperature thin film process of 300 ° C. or higher is required to form a high conductivity thin film.
  • flexible polymer substrates PET, PEN, PAR, PES
  • Amorphous ITO thin films have high sheet resistance with higher defect density than crystalline ITO.
  • there is a limit to the application to the flexible element because the durability against bending is weak.
  • transparent electrodes based on metal nanowires have been actively studied as transparent electrode materials applicable to flexible devices.
  • the metal nanowire-based transparent electrode has a problem that the electrical properties are improved when the metal nanowire density is high, but the transmittance is decreased. Therefore, a transparent electrode having high permeability and high conductivity characteristics using only a small amount of metal nanowires has been studied.
  • nano-welding technology for welding junctions between metal nanowires has been studied as a method of improving conductivity characteristics in metal nanowire-based transparent electrodes.
  • nano welding technology various methods such as a method using heat, plasma welding using light, and chemical welding using salt and reducing agent have been studied.
  • the conventional nano welding technology has a disadvantage of deteriorating the crystallinity of the metal nanowires or using additional chemicals to increase the process cost and lower the stability.
  • the problem to be solved by the present invention is to provide a method for producing a metal composite structure welded metal nanowires and metal particles as a transparent electrode material.
  • the present invention for solving the above problems, forming a metal nanowire on a conductive substrate, forming a metal particle on the conductive substrate on which the metal nanowire is formed, and by applying water to weld the metal nanowires It can provide a method for producing a metal composite structure comprising the step of.
  • the metal particles may include a method of manufacturing a metal composite structure, wherein the metal particles have a lower work function and a standard electrode potential than the metal nanowires. have.
  • the metal particle formation method may be performed by applying a solution to particles or metal particles having a core shell structure in which metal oxide particles are surrounded by vacuum deposition or metal particle surfaces. It is possible to provide a method for producing a metal composite structure, characterized in that formed using a solution process.
  • the method of manufacturing a metal composite structure further comprises adding a salt containing a metal ion or adjusting the acidity to increase the reaction rate can do.
  • the metal particles have a lower work function than the metal nanowires, and electrons separated from the metal particles move to the junction portion of the metal nanowires through the conductive substrate. can do.
  • the welding of the metal nanowires and the metal particles by coating water may provide a method of manufacturing a metal composite structure, in which water is coated on the substrate and reacted for 1 to 5 minutes.
  • the step of applying water to apply water to weld the metal nanowires and the metal particles, after the water coating reaction is a method of manufacturing a metal composite structure, characterized in that to remove the water applied on the conductive substrate with nitrogen gas It may include.
  • a metal composite structure using metal particles and metal nanowires, water is applied to weld the metal particles to the metal nanowires to form a metal composite structure is not inhibited even in the crystallinity of the metal nanowires
  • the electrical conductivity and the light transmittance can be improved without.
  • the manufactured metal composite structure can be manufactured without chemicals added to an environmentally friendly process of applying water by welding, and thus can have high economical efficiency as a material of a transparent electrode.
  • FIG. 1 is a view for explaining a method of manufacturing a metal composite structure according to an embodiment of the present invention.
  • FIG. 2 is an SEM image for explaining a metal composite structure formed according to the presence or absence of a conductive substrate according to an embodiment and a comparative example of the present invention.
  • FIG 3 is a graph for comparing the sheet resistance according to an embodiment of the present invention and a comparative example.
  • FIG. 1 is a view for explaining a method of manufacturing a metal composite structure according to an embodiment of the present invention.
  • the metal nanowires 100 are formed on the conductive substrate 10.
  • the metal particles 200 are formed on the metal nanowires 100.
  • the metal particles 200 are welded to the metal nanowires 100 to form a metal composite structure 300.
  • the metal nanowires 100 are formed on the conductive substrate 10, and the metal particles 200 are formed on the metal nanowires 100.
  • the method of forming the metal particles 200 may be formed using a vacuum deposition or a solution process of applying a solution to the particles of the core shell structure or the metal particles 200 surrounded by metal oxide particles on the surface of the metal particles 200.
  • the metal nanowires 100 and the metal particles 200 formed on the conductive substrate 10 pass current through the ohmic junction with the conductive substrate 10. Depending on the type of semiconductor and the relative work function difference between the metal and the semiconductor, current characteristics may vary and may have an ohmic junction or a rectifying junction.
  • the metal particles 200 have a lower work function and lower standard electrode potential than the metal nanowires 100, and the crystallinity and structure of the metal particles 200 are not limited.
  • the work function is a measure of the attraction force of the electrons in the metal to bond, and the energy required to excite one electron from the metal surface. That is, when the work function is low, the bonding force of the electrons is relatively low, and the electrons of the metal particles 200 having the low work function are easily separated.
  • the metal particles 200 have a lower work function than the metal nanowires 100, and electrons separated from the metal particles 200 move to the junction portion of the metal nanowires 100 through the conductive substrate 10. do.
  • water may be applied and reacted for 1 to 5 minutes.
  • salts containing metal ions may be added or acidity may be adjusted to increase the reaction rate in water.
  • the cations of the metal particles 200 dissolved in the water are combined to move to the portion having a negative charge in order to meet the standard state. Therefore, the metal particles 200 are dissolved and the metal particles 200 are welded to the metal nanowire 100 junction to form the metal composite structure 300.
  • FIG. 2 is an SEM image for explaining a metal composite structure formed according to the presence or absence of a conductive substrate according to an embodiment and a comparative example of the present invention.
  • FIG. 2 an SEM image for explaining a metal composite structure 300 formed according to the presence or absence of a conductive substrate 10 according to an embodiment of the present invention is disclosed.
  • FIG. 2A a metal composite structure 300 manufactured by the manufacturing method disclosed in FIG. 1 is disclosed.
  • the metal nanowires 100 are formed on the conductive substrate 10.
  • the metal particles 200 are formed on the metal nanowires 100.
  • the formed metal particles 200 have a lower work function and a standard electrode potential than the metal nanowires 100, and the size of the metal particles 200 is not limited.
  • the application of water initiates the reaction.
  • Water is applied onto the conductive substrate 10 and reacted for 1 to 5 minutes.
  • the metal particles 200 are welded with a metal nanowire 100 having a large work function and a standard electrode potential to form a metal composite structure 300.
  • the metal nanowires 100 are formed on the glass.
  • the metal particles 200 are formed on the metal nanowires 100.
  • the formed metal particles 200 may have a work function and a standard electrode potential smaller than those of the metal nanowires 100.
  • FIG. 2 (b) is formed by the same manufacturing method as (a) of FIG. 2, but (a) of FIG. 2 shows that the metal nanowires 100 and the metal particles 200 are formed on the conductive substrate 10. 2B is formed on the glass.
  • the metal particles 200 are not welded to the metal nanowires 100, and the metal particles 200 deposited on the glass are distributed on the front surface, and the metal nanoparticles are interposed between the metal particles 200.
  • the wire 100 is located.
  • the metal nanowires 100 intersect on parallel lines which are not equal to each other.
  • the conductive substrate 10, the metal particles 200, and the metal nanowires 100 are ohmic bonded to each other, and electrons of the metal particles 200 are transferred to the metal nanoparticles by the conductive substrate 10 due to the difference in work function and standard electrode potential.
  • the metal particles 200 are welded to the metal nanowires 100 by moving to the wire 100. However, in the case of glass, since no current flows, the movement of electrons does not occur, and thus the metal particles 200 and the metal nanowires 100 cannot be welded to each other.
  • FIG. 2C an SEM image of the metal composite structure 300 formed by welding the metal particles 200 on the SI substrate with the metal nanowires 100 is disclosed.
  • the preparation method will be described in detail in Comparative Example 2.
  • An SI substrate is used as the conductive substrate 10.
  • a metal nanowire 100 is formed on an SI substrate.
  • the metal particles 200 are formed on the metal nanowires 100.
  • the SI substrate is used as the conductive substrate 10 in (c) and water is applied to move the electrons of the metal particles 200 through the SI substrate, which is the conductive substrate 10. 100 to be welded to form a metal composite structure (300). Therefore, the kind of the conductive substrate 10 used in the manufacturing method of applying the water to the metal particles 200 by welding the metal nanowires 100 to form the metal composite structure 300 is not limited.
  • FIG 3 is a graph for comparing the sheet resistance according to an embodiment of the present invention and a comparative example.
  • 3A illustrates a sheet resistance graph according to an embodiment.
  • the first sample is a metal nanowire 100 formed on the conductive substrate 10.
  • the metal particles 200 are formed at 5 nm on the first sample.
  • the third sample was reacted for 10 minutes by applying water on the second sample and dried with nitrogen gas.
  • the fourth sample was reacted for 24 hours by applying water on the second sample and dried with nitrogen gas.
  • the first sample is a metal nanowire 100 formed on the glass.
  • the metal particles 200 are formed at 5 nm on the first sample.
  • the third sample was reacted for 10 minutes by applying water on the second sample and dried with nitrogen gas.
  • FIG. 3 shows that the metal nanowires 100 and the metal particles 200 are formed on the conductive substrate 10 to have overall low sheet resistance compared to (b) formed on the glass.
  • (b) is the metal nanowires 100 and the metal particles 200 formed on the non-conductive glass, and generally have a high sheet resistance value.
  • the sheet resistance tends to decrease.
  • the sheet resistance has a relatively high sheet resistance due to the glass, and the sheet resistance due to the formation of the metal particles 200 is greatly reduced, but when the water is applied, the sheet resistance is increased.
  • the metal nanowires 100 and the metal particles 200 are formed on the conductive substrate 10 to have a relatively low sheet resistance, and after the water is applied, the sheet resistance value is greatly reduced.
  • the fourth sample measured the sheet resistance after 24 hours of water application, the sheet resistance value similar to that of 1 to 5 minutes after the third sample water application reaction time is maintained. This is an irreversible reaction in which the metal particles 200 are dissolved and welded to the junctions of the metal nanowires 100, and thus no chemical reactions proceed.
  • the metal nanowires 100 and the metal particles 200 are formed on the conductive substrate 10 and water is coated to weld to form the metal composite structure 300 (a) and the metal nanowires on the glass ( Compared with (b) in which 100) and the metal particles 200 are not welded, (a) generally has a low sheet resistance value.
  • the metal nanowires 100 and the metal particles 200 are formed on the conductive substrate 10 to induce electron movement and the metal particles 200 are formed of the metal nanowires 100 according to the work function and the standard electrode potential difference. As a result of the welding, it can have a low sheet resistance.
  • the metal nanowires 100 and the metal particles 200 are formed on glass.
  • the metal particles 200 on the glass are not welded to the metal nanowires 100. Therefore, the remaining metal particles 200 prevent the light from being transmitted, thereby lowering the light transmittance.
  • the metal nanowires 100 and the metal particles 200 are formed on the conductive layer and the metal particles 200 are welded to the metal nanowires 100, the remaining metal particles 200 are formed.
  • the light transmittance is improved by decreasing.
  • the metal nanowires 100 and the metal particles 200 are formed on the conductive substrate 10, and the metal particles 200 are dissolved in water, so that the work function and the standard electrode potential difference are different. It is formed by welding to the metal nanowires (100).
  • the formed metal composite structure 300 does not reduce the crystallinity of the metal nanowires 100 and is welded in water, so that no additional compound for welding may be required, thereby reducing process costs.
  • the formed metal composite structure 300 may reduce sheet resistance and improve light transmittance, and thus may be used as a material of a transparent electrode.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne un procédé de préparation d'une structure composite métallique formée en utilisant une fonction de travail et une différence de potentiel d'électrode standard d'un nanofil métallique et de particules métalliques. Un nanofil métallique et des particules métalliques sont formés sur un substrat conducteur, et de l'eau est introduite de telle façon que les particules métalliques soient soudées au nanofil métallique par une fonction de travail et une différence de potentiel d'électrode standard, et une structure composite métallique est ainsi formée. La nanostructure composite métallique formée ne détériore pas la cristallinité du nanofil métallique, et peut être utilisée comme matériau d'électrode transparent en utilisant une technique de nano-soudure respectueuse de l'environnement.
PCT/KR2017/006553 2016-06-21 2017-06-21 Procédé de préparation d'une structure composite métallique dans laquelle un nanofil métallique et des particules métalliques sont soudés WO2017222311A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160077376A KR101828578B1 (ko) 2016-06-21 2016-06-21 금속 나노와이어와 금속입자가 용접된 금속복합구조체의 제조방법
KR10-2016-0077376 2016-06-21

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WO2017222311A1 true WO2017222311A1 (fr) 2017-12-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111768921A (zh) * 2019-04-02 2020-10-13 天津大学 基于金纳米颗粒自组装银纳米线柔性透明电极制作方法

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KR101465071B1 (ko) * 2013-09-27 2014-11-27 성균관대학교산학협력단 세슘을 이용한 플렉서블 투명전극필름 제조방법 및 그에 의해 제조된 플렉서블 투명전극필름
KR20150040865A (ko) * 2012-06-22 2015-04-15 시쓰리나노 인크 금속 나노 구조 네트워크 및 투명 전도성 물질
US20160032127A1 (en) * 2014-07-31 2016-02-04 C3Nano Inc. Metal nanowire inks for the formation of transparent conductive films with fused networks
US20160038909A1 (en) * 2014-08-08 2016-02-11 The University Of Hong Kong Conductive Metal Networks Including Metal Nanowires and Metal Nanoparticles and Methods of Fabricating the Same
KR101606532B1 (ko) * 2014-04-07 2016-03-25 한국전기연구원 일함수가 제어된 탄소나노소재와 금속나노와이어 하이브리드 투명전도성 필름 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150040865A (ko) * 2012-06-22 2015-04-15 시쓰리나노 인크 금속 나노 구조 네트워크 및 투명 전도성 물질
KR101465071B1 (ko) * 2013-09-27 2014-11-27 성균관대학교산학협력단 세슘을 이용한 플렉서블 투명전극필름 제조방법 및 그에 의해 제조된 플렉서블 투명전극필름
KR101606532B1 (ko) * 2014-04-07 2016-03-25 한국전기연구원 일함수가 제어된 탄소나노소재와 금속나노와이어 하이브리드 투명전도성 필름 및 그 제조방법
US20160032127A1 (en) * 2014-07-31 2016-02-04 C3Nano Inc. Metal nanowire inks for the formation of transparent conductive films with fused networks
US20160038909A1 (en) * 2014-08-08 2016-02-11 The University Of Hong Kong Conductive Metal Networks Including Metal Nanowires and Metal Nanoparticles and Methods of Fabricating the Same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111768921A (zh) * 2019-04-02 2020-10-13 天津大学 基于金纳米颗粒自组装银纳米线柔性透明电极制作方法

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KR101828578B1 (ko) 2018-03-29

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