KR20150134773A - Flexible electrode and manufacturing method thereof - Google Patents

Flexible electrode and manufacturing method thereof Download PDF

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Publication number
KR20150134773A
KR20150134773A KR1020140061994A KR20140061994A KR20150134773A KR 20150134773 A KR20150134773 A KR 20150134773A KR 1020140061994 A KR1020140061994 A KR 1020140061994A KR 20140061994 A KR20140061994 A KR 20140061994A KR 20150134773 A KR20150134773 A KR 20150134773A
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South Korea
Prior art keywords
metal
layer
nanowire layer
substrate
metal nanowire
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KR1020140061994A
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Korean (ko)
Inventor
박장웅
김미정
박지훈
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국립대학법인 울산과학기술대학교 산학협력단
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Priority to KR1020140061994A priority Critical patent/KR20150134773A/en
Publication of KR20150134773A publication Critical patent/KR20150134773A/en

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    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

The present invention relates to a stretchable electrode and a manufacturing method thereof. The stretchable electrode includes a substrate; a metal nanowire layer which is located on the substrate and has a network structure where metal nanowires are overlapped with each other; and a metal electrode layer which is located on the metal nanowire layer and is filled in a hollow space between the metal nanowires.

Description

[0001] The present invention relates to a flexible electrode and a manufacturing method thereof,

The present invention relates to a stretchable electrode and a method of manufacturing the same, and more particularly, to a stretchable electrode having elasticity and a low rate of resistance change using metal and metal nanomaterials, and a method of manufacturing the same.

2. Description of the Related Art As electronic devices are widely used, there is a growing demand for flexible electronic devices capable of overcoming the limitations of electronic devices existing on a conventional hard substrate. Electronic devices used in fields such as flexible displays, smart garments, dielectric elastomer actuators (DEA), biocompatible electrodes, in vivo electrical signal sensing, etc., require flexible and stretchable forms.

One of basic and important technologies in the field of electronic devices having such flexibility and stretchability is to form electrodes that can be stretched while maintaining conductivity.

Although materials such as metals are excellent in conductivity, they are difficult to apply to products requiring flexibility due to their unstretchable properties. When carbon nanotubes or graphene are used alone, it is also difficult to make elastic electrodes.

Examples of methods for making stretchable electrodes include a method of mixing a carbon nanotube, a transparent fluorinated polymer, and an ionic liquid into a paste form, a method of forming a paste form of a metal particle and a polyacrylic acid paste to form a pattern by an ink jet method, There has been reported an example in which a metal layer is formed on a PDMS substrate so as to have elasticity as much as the wrinkle spreads.

Korean Patent No. 10-1225143

An object of the present invention is to provide a stretchable electrode having elasticity and a low rate of resistance change using metal and metal nanomaterials, and a method for manufacturing the same.

The present invention provides a semiconductor device comprising: a substrate; A metal nanowire layer located on the substrate, the metal nanowires overlapping each other and having a network structure; And a metal electrode layer located on the metal nanowire layer and filling a space between the metal nanowires.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a substrate; Forming a metal nanowire layer having a network structure by overlapping metal nanowires on the substrate; And forming the metal electrode layer on the metal nanowire layer so as to fill an empty space between the metal nanowires.

The elastic electrode according to the present invention and its manufacturing method have the following effects.

First, the metal nanomaterial layer and the metal electrode layer are sequentially formed on the substrate, and the metal nanomaterial layer and the metal electrode layer are electrically connected to each other, so that the electrical conductivity can be improved. Particularly, the metal electrode layer connects the disconnection portion of the metal nanomaterial layer, thereby improving the electrical conductivity.

Secondly, when the metal electrode layer is formed using an inactive metal, it also acts as an oxidation preventing layer for protecting the metal nanomaterial layer, thereby preventing the metal nanomaterial layer from being oxidized over time.

Third, since the metal nanomaterial layer is formed on the substrate by spin coating and the metal nanomaterial layer is formed on the metal nanomaterial layer, it is possible to manufacture a flexible electrode having a simple manufacturing process and simple structure.

1 is a cross-sectional view illustrating the structure of a flexible electrode according to an embodiment of the present invention.
2 is a schematic view showing a method of manufacturing the flexible electrode according to FIG.
Fig. 3 shows a manufacturing process of the flexible electrode according to Fig.
FIG. 4 is a graph showing resistance test results according to a material for manufacturing the elastic electrodes and a manufacturing procedure.
5 is a graph showing resistance test results of the elastic electrodes manufactured according to FIG.
6 is an enlarged view of the elastic electrode according to an exemplary embodiment of the present invention, when the electrode is stretched by 30%.
FIG. 7 is a graph showing the resistance change rate of the elastic electrode according to FIG.

1, a stretch wire electrode according to an embodiment of the present invention is shown.

Referring to FIG. 1, an elastic electrode 100 according to an embodiment of the present invention includes a substrate 110, a metal nanowire layer 130, and a metal layer 150. The substrate 110 is formed of a polymeric material having elasticity that is deformed when an external force is applied and is restored to an initial state when the external force is removed. Although the types of the polymer compounds are very various, in the present embodiment, the substrate 110 is formed of PDMS (Polydimethylsiloxane). However, the substrate 110 is not limited to the PDMS.

 The metal nanowire layer 130 is located on the substrate 110. The metal nanowire layer 130 has a network structure by overlapping metal nanowires. In the present embodiment, the metal nanowire of the metal nanowire layer 130 is a silver nanowire (AgNW). The silver nanowires are formed in the form of short fibers. More specifically, the metal nanowire layer 130 forms a network structure of the metal nanowire layer 130 by overlapping the silver nanowires in a short fiber form. The metal nanowire layer 130 is formed by spin coating a solution containing the silver nanowires.

Meanwhile, the metal nanowire layer 130 is not limited to the metal nanowires formed by the metal nanowires, but may be a nanoparticle, a nanorod, a nanowall, a nanotube, (nanobelts) and nanorings (nanorings).

The metal electrode layer 150 is located on the metal nanowire layer 130. The metal electrode layer 150 fills an empty space between the metal nanowires of the metal nanowire layer 130 and is electrically connected to the metal nanowire layer 130. As described above, since the metal nanowire layer 130 is formed in a network structure in which the silver nanowires in a short fiber form are overlapped with each other, the metal nanowire layer 130 is superimposed among the silver nanowires forming the metal nanowire layer 130 The electrical connection may be disconnected in the unoccupied area (empty space).

When the metal electrode layer 150 is positioned on the metal nanowire layer 130, the metal electrode layer 150 is formed of silver nanowires having a short fiber shape, It is electrically connected to fill empty space. The metal electrode layer 150 is formed in the form of a flat plate. In the present embodiment, the metal electrode layer 150 is formed of gold (Au). Since the gold corresponds to an inactive metal, the gold covers the metal nanowire layer 130 as a whole, and can act as an oxidation preventing layer. Accordingly, the metal electrode layer 150 may be formed of an inert metal. After the metal electrode layer 150 is formed on the metal nanowire layer 130, a pattern may be further formed on the metal electrode layer 150 as needed.

FIGS. 2 and 3 show a method of manufacturing a flexible electrode according to an embodiment of the present invention. 2 and 3, a method of manufacturing the flexible electrode 100 according to an embodiment of the present invention includes preparing a substrate 110 (S105), forming a metal nanowire layer 130 And forming a metal electrode layer 150 (S115). The step of preparing the substrate 110 may include preparing a substrate made of a polymer having elasticity, which is a property of being deformed when an external force is applied and then restored to an initial state when the external force is removed. In particular, in this embodiment, a substrate formed of PDMS is prepared.

The step of forming the metal nanowire layer 130 is performed on the substrate 110 prepared in the previous step. The metal nanowire layer 130 is formed of the metal nanowires 130, in particular, silver nanowires in this embodiment.

The metal nanowire layer 130 is formed using a spin coating method. More specifically, the metal nanowire layer 130 is formed by spin-coating a solution mixed with the silver nanowires on the substrate 110. The spin coating is illustratively spin-coated at a speed in the range of about 100 rpm to about 3000 rpm. And the spin coating is illustratively performed for about 1 second to about 10 minutes. The metal nanowire layer 130 formed by the spin coating has a network structure by overlapping the silver nanowires.

In the present embodiment, the metal nanowire layer 130 is formed of metal nanowires, in particular, silver nanowires. However, the present invention is not limited thereto. The metal nanowire layer 130 may be formed using at least one of a nanoparticle, a nanorod, a nanowall, a nanotube, a nanobelt, and a nanorring The metal nanowire layer 130 may be formed.

The metal electrode layer 150 is formed on the metal nanowire layer 130 formed in the previous step. A metal material is deposited on the metal nanowire layer 130 to form the metal electrode layer 150. In this embodiment, gold (Au) is used as the metal material formed by the metal electrode layer 150. However, since it is limited to the present embodiment, the metal electrode layer 150 may be formed using various metal materials other than gold. Particularly, when the inactive metal material is used, the metal electrode layer 150 covers the entire metal nanowire layer 130 and may serve as an oxidation preventing layer for preventing oxidation of the metal nanowire layer 130.

When the metal electrode layer 150 is formed on the metal nanowire layer 130, the metal electrode layer 150 may fill the void space of the metal nanowire layer 130, Lt; / RTI > Since the metal nanowire layer 130 formed in the previous step has a network structure in which the silver nanowires in a short fiber shape are overlapped with each other, there may be a portion (empty space) not connected between the silver nanowires have. At this time, since the metal electrode layer 150 formed on the metal nanowire layer 130 is electrically connected to the metal nanowire layer 130, an unconnected portion between the silver nanowires is electrically connected to the metal electrode layer 150).

The metal electrode layer 150 is connected to the metal nanowire layer 130 while filling the space between the silver nanowires, thereby improving electrical conductivity of the elastic electrode 100. Meanwhile, after the metal electrode layer 150 is formed by vapor deposition as described above, a step of forming a pattern in the metal electrode layer 150 may be further performed if necessary.

The elastic electrode 100 thus manufactured forms the metal nanowire layer 130 and the metal electrode layer 150 on the substrate 110 having elasticity and the metal electrode layer 150 covers the metal Since the metal nanowire layer 130 and the metal electrode layer 150 are electrically connected to each other by filling the empty space of the nanowire layer 130, the metal nanowire layer 130 can be formed as an electrode having elasticity and flexibility. Particularly, since electrical connection is continued through the metal electrode layer 150 in a portion where the electrical connection is disconnected (empty space) in the metal nanowire layer 130 of the network structure, the electric conductivity of the elastic electrode 100 is improved .

FIGS. 4 and 5 are graphs showing the resistivity measured according to the material of the elastic electrode. Referring to FIGS. 4 and 5, it can be seen that when the elastic electrode is manufactured using gold solder, the change in resistivity according to deformation is greatest. In FIG. 4, the silver nano wire + gold and gold + silver nano wire show the difference in the production order of materials in making elastic electrodes. That is, a silver nano wire is formed by first forming a layer using silver nano wire or gold silver nano wire, and then forming a layer using gold. The gold + silver nano wire is first formed using gold, . Referring to the graph of FIG. 4, it can be seen that the resistivity of the elastic electrode fabricated by forming the layer using silver nano wire and forming the layer using gold is the lowest.

That is, when the elastic electrode is deformed, the gold + silver nano wire is formed on the gold because the silver nano wire is broken, so that the silver nano wire formed on the gold is also broken when the gold is broken. However, in the case of silver nano wire + gold, since the silver nano wire is directly formed on the elastic polymer, the change rate of the resistance is low because the silver nano wire is connected without being broken even when deformation occurs.

6 is an enlarged view showing a change in tension when the stretchable electrode according to an embodiment of the present invention is stretched at 30%

6 (a) is a photograph of a stretchable electrode formed by laminating a conductive material, gold, and silver nano wire in this order, and is an enlarged image when it is stretched up to 30%. Fig. 6 (b) is an enlarged photograph of a stretchable electrode formed by laminating conductive material, silver nano wire, and gold in this order in the same manner as when stretched to 30%. FIG. 7 is a graph showing a change in resistivity according to the number of times of stretching of the elastic electrode according to FIG.

Referring to FIG. 7, it can be seen that the resistance of the elastic electrode according to an embodiment of the present invention is not significantly changed even when the elastic electrode is stretched up to 30%. Especially, when tensile is applied up to 10000 times, the resistance value changed is only 2 ohm / sq, so that the resistance value is not greatly increased. It can be seen that the resistance value becomes smaller as the number of coatings is increased by depositing gold (Au).

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

100: elastic electrode
110: substrate 130: metal nanomaterial layer
150: metal electrode layer

Claims (9)

Board;
A metal nanowire layer located on the substrate, the metal nanowires overlapping each other and having a network structure; And
And a metal electrode layer located on the metal nanowire layer and filling a space between the metal nanowires. The method according to claim 1,
Wherein the substrate is formed of a polymer compound having elasticity. The method of claim 2,
Wherein the substrate is formed of PDMS (Polydimethylsiloxane). The method of claim 3,
Wherein the nanomaterial is silver nanowire (AgNW). The method of claim 6,
Wherein the metal electrode layer covers the metal nanowire layer as a whole to prevent oxidation of the metal nanowire layer and is formed of an inert metal. The method of claim 5,
And the metal electrode layer is formed of gold (Au). Preparing a substrate;
Forming a metal nanowire layer having a network structure by overlapping metal nanowires on the substrate; And
And forming the metal electrode layer on the metal nanowire layer so as to fill an empty space between the metal nanowires. The method of claim 7,
In the step of forming the metal nanowire layer,
Wherein the metal nanowire layer is formed by a spin coating method using a solution in which the metal nanowires are mixed. The method of claim 7,
In the step of forming the metal electrode layer,
And depositing gold on the metal nanowire layer to form the elastic electrode.
KR1020140061994A 2014-05-23 2014-05-23 Flexible electrode and manufacturing method thereof KR20150134773A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018190555A1 (en) * 2017-04-11 2018-10-18 고려대학교 산학협력단 Supercapacitor electrode and method for preparing same
CN109298044A (en) * 2018-10-23 2019-02-01 大连大学 A kind of method that flexible silver nanowires of the application based on PDMS/nanogold combination electrode detects mercury in water
CN109298039A (en) * 2018-10-23 2019-02-01 大连大学 A method of catechol is detected using AuNPs/AgNWs/PDMS ductile electrode
CN109298043A (en) * 2018-10-23 2019-02-01 大连大学 A kind of method of flexible silver nanowires of the application based on PDMS/nanogold combination electrode detection nitrite
CN109298041A (en) * 2018-10-23 2019-02-01 大连大学 A kind of method of flexible silver nanowires of the application based on PDMS/nanogold combination electrode detection hydrogen peroxide
KR20200072693A (en) * 2018-12-13 2020-06-23 충북대학교 산학협력단 Flexible substrate assembly with stretchable electrodes and fabrication method of it
KR20200099278A (en) * 2019-02-14 2020-08-24 충북대학교 산학협력단 flexible substrate assembly with stretchable electrodes and fabrication method of it
KR20210097857A (en) 2020-01-30 2021-08-10 서울대학교산학협력단 Manufacturing Method of Shape Memory Polymer Composite
KR20220081438A (en) * 2020-12-08 2022-06-16 동국대학교 산학협력단 PN Heterojunction Nano Structure Based Self-Powered Stretchable UV Sensor
KR20230104314A (en) 2021-12-30 2023-07-10 한국과학기술연구원 A stretchable electrode, a manufacturing method thereof, and a stretchable battery comprising the stretchable electrode
KR20230144184A (en) 2022-04-07 2023-10-16 원형일 A ink composition for stretchable electrode and printed circuit board having stretchable electrode manufacturing thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018190555A1 (en) * 2017-04-11 2018-10-18 고려대학교 산학협력단 Supercapacitor electrode and method for preparing same
CN109298044A (en) * 2018-10-23 2019-02-01 大连大学 A kind of method that flexible silver nanowires of the application based on PDMS/nanogold combination electrode detects mercury in water
CN109298039A (en) * 2018-10-23 2019-02-01 大连大学 A method of catechol is detected using AuNPs/AgNWs/PDMS ductile electrode
CN109298043A (en) * 2018-10-23 2019-02-01 大连大学 A kind of method of flexible silver nanowires of the application based on PDMS/nanogold combination electrode detection nitrite
CN109298041A (en) * 2018-10-23 2019-02-01 大连大学 A kind of method of flexible silver nanowires of the application based on PDMS/nanogold combination electrode detection hydrogen peroxide
KR20200072693A (en) * 2018-12-13 2020-06-23 충북대학교 산학협력단 Flexible substrate assembly with stretchable electrodes and fabrication method of it
KR20200099278A (en) * 2019-02-14 2020-08-24 충북대학교 산학협력단 flexible substrate assembly with stretchable electrodes and fabrication method of it
KR20210097857A (en) 2020-01-30 2021-08-10 서울대학교산학협력단 Manufacturing Method of Shape Memory Polymer Composite
KR20220081438A (en) * 2020-12-08 2022-06-16 동국대학교 산학협력단 PN Heterojunction Nano Structure Based Self-Powered Stretchable UV Sensor
KR20230104314A (en) 2021-12-30 2023-07-10 한국과학기술연구원 A stretchable electrode, a manufacturing method thereof, and a stretchable battery comprising the stretchable electrode
KR20230144184A (en) 2022-04-07 2023-10-16 원형일 A ink composition for stretchable electrode and printed circuit board having stretchable electrode manufacturing thereof

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