KR20130019607A - Transparent conductive layer and manufacturing method, electric device comprising the same - Google Patents

Transparent conductive layer and manufacturing method, electric device comprising the same Download PDF

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KR20130019607A
KR20130019607A KR1020110081670A KR20110081670A KR20130019607A KR 20130019607 A KR20130019607 A KR 20130019607A KR 1020110081670 A KR1020110081670 A KR 1020110081670A KR 20110081670 A KR20110081670 A KR 20110081670A KR 20130019607 A KR20130019607 A KR 20130019607A
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transparent conductive
conductive film
siloxane
substrate
manufacturing
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KR1020110081670A
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Korean (ko)
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김진욱
채기성
김태헌
김철홍
박종현
김지혜
민지혜
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엘지디스플레이 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • 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
    • 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

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  • General Physics & Mathematics (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
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Abstract

The present invention provides a transparent conductive film, a method of manufacturing the same, and an electric device having the same. The transparent conductive film according to the embodiment of the present invention includes silver nanowires and siloxane-based polymers, and is prepared by applying a silver nanowire dispersion on a substrate and applying a siloxane-based polymer on the substrate. .

Description

Transparent conductive film, manufacturing method thereof, and electric device having the same {TRANSPARENT CONDUCTIVE LAYER AND MANUFACTURING METHOD, ELECTRIC DEVICE COMPRISING THE SAME}

The present invention relates to a transparent conductive film using silver nanowires, and more particularly, to a transparent conductive film including a silver nanowire and a siloxane-based polymer, a method for manufacturing the same, and an electric device having the same.

Transparent conductive films are widely applied to plasma display panels (PDPs), organic light emitting displays (OLEDs), liquid crystal displays (LCDs), solar cells, and touch devices. With the rapid expansion of the display field and the solar cell industry, the demand for transparent conductive films is increasing rapidly. Indium Tin Oxide (ITO) has been mainly used as such a transparent conductive film material.

However, ITO is difficult to use as a transparent electrode for a flexible display because it is manufactured under process conditions suitable for a glass substrate and sputtered on a plastic substrate because of lack of flexibility of the electrode layer. Indium used for ITO is a rare metal, and is an element contained in the range of about 10 to 20 ppm when mining zinc (Zn) or lead (Pb). Given that indium reserves are 6,000 tons, indium depletion is expected in 2018.

Recently, a transparent conductive film using metal nanowires has been developed as a means to replace ITO. Silver, gold, and platinum are typical metals, but silver nanowires are in the spotlight. However, in the case of a transparent conductive film made of silver nanowires, there is a problem that it is difficult to be used for a touch device due to low hardness.

The present invention provides a low resistance and high hardness transparent conductive film, a method of manufacturing the same, and an electric device having the same by mixing silver nanowires and a siloxane polymer.

In order to achieve the above object, the transparent conductive film according to an embodiment of the present invention may include a silver nanowire and a siloxane-based polymer.

The siloxane-based polymer may be tetraethyl orthosilicate (TEOS).

The silver nanowires may be dispersed in the siloxane-based polymer.

In addition, the method of manufacturing a transparent conductive film according to an embodiment of the present invention may include the step of applying a silver nanowire dispersion on a substrate and the step of applying a siloxane-based polymer on the substrate.

The silver nanowire dispersion may be prepared by mixing and stirring silver nitrate (AgNO 3 ) in a solvent.

After applying the silver nanowire dispersion, the method may further include heating the substrate.

The siloxane-based polymer may be tetraethyl orthosilicate (TEOS).

The silver nanowire dispersion and the siloxane polymer may be applied by spin coating.

In addition, the electric device according to an embodiment of the present invention may include a transparent conductive film including a substrate and a silver nanowire and a siloxane-based polymer formed on the substrate.

The electric element may be any one of an organic light emitting display, a plasma display panel, a liquid crystal display, a field emission display, an electrophoretic display, and a touch screen.

The transparent conductive film including silver nanowires and siloxane based polymers according to an embodiment of the present invention has an advantage of improving sheet resistance and hardness. Therefore, there is an advantage in that manufacturing is easy while replacing ITO in various electric elements.

1 is a view showing the manufacturing method of the transparent conductive film according to an embodiment of the present invention by process.
2 is a view showing a display device having a touch element of the present invention.
3 is a view illustrating a structure of an electrode unit located in a touch element.
4 is an enlarged view illustrating a portion of FIG. 3 enlarged.
5 is a cross-sectional view taken along line II ′ of FIG. 4;
FIG. 6 is a diagram illustrating a method of manufacturing a display device including a touch device according to an exemplary embodiment of the present disclosure.

Hereinafter, various embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The transparent conductive film of the present invention is a transparent conductive film containing silver nanowires and a siloxane polymer. Silver nanowires used in the present invention have a cross-sectional size of 500 nm or less and an aspect ratio (length: width) of 100 or more. The silver nanowire is preferably a straight nanowire. A straight nanowire is a straight shape without a branching shape.

The silver nanowire (AGgNW) used for this invention consists of silver (Ag), and does not contain ceramics, such as an oxide of metal and nitride. The silver nanowires may have an aspect ratio (length: width) of 10 or more, and an aspect ratio of 100 nm or less may be difficult because handling becomes difficult when the aspect ratio is too large. In addition, the length of the short axis direction of the silver nanowire is 1 nm to 500 nm, the length of the short axis direction is too large to prevent the transmittance from decreasing, and the length of the short axis direction is too small to prevent the problem of synthesis. In addition, the length of the long axis direction of the silver nanowires is 1 μm to 100 μm, so that the length of the long axis direction is too short to prevent conductivity from deteriorating, and the length of the long axis direction is too long to prevent problems of handling.

In addition, the silver nanowire of this invention consists of linear nanowires. Straight nanowires mean straight nanowires without branching. However, the silver nanowires of the present invention are not limited thereto, and may be used even if they include a small number of branches or include a small angle of curvature.

The silver nanowires can be synthesized according to a known method. For example, a method of reducing silver nitrate (AgNO 3 ) in a solution, or applying an applied voltage or current from the tip of the probe to the precursor surface and eliciting the silver nanowire at the tip of the probe, the silver nano The method of forming a wire continuously, etc. are mentioned. As a method of reducing silver nitrate in the solution, specifically, a nanofiber reduction method consisting of a metal complex peptide (lipidid) fat, a polyol reduction method, an ethylene glycol reduction method, and a sodium citrate reduction method Etc. can be mentioned. Among these, ethylene glycol (ethylene glycol) reduction method is widely used because it is easy to obtain a high crystalline silver nanowire (nano wire).

The aforementioned silver nanowires are dispersed in a solvent for easy formation on a substrate. Here, the solvent may be water, alcohols, ketones, ethers, hydrocarbons or aromatic solvents such as benzene, toluene, xylene. These solvents are volatile materials with boiling points below 200 ° C. In addition, the solvent in which the silver nanowires are dispersed further includes additives such as a dispersant and a surfactant to adjust the silver nanowires to have an appropriate dispersing force in the solvent and to be easily applied onto the substrate.

In the present invention, a siloxane-based polymer is used to improve the hardness of the layer formed of silver nanowires. As a representative example of the siloxane polymer, TEOS (Tetraethyl orthosilicate) may be used. As shown in the following scheme, the polymerization mechanism of TEOS is matrixed by oxygen bonds between silicon through hydrolysis and condensation reactions. Oxygen bonding of the TEOS serves to improve the hardness of the silver nanowire network.

Figure pat00001

Hereinafter, the method of manufacturing the transparent conductive film including the silver nanowire and the siloxane polymer described above will be described. 1 is a view showing a method for manufacturing a transparent conductive film according to an embodiment of the present invention by process.

First, referring to FIG. 1A, a substrate 10 on which a transparent conductive film is to be prepared is prepared. The substrate 10 may use a substrate of various materials such as a resin film, a glass substrate, a metal substrate, and the like. When the substrate 10 is prepared, the silver nanowire dispersion described above is prepared. In the present embodiment, a method for synthesizing silver nanowires using an ethylene glycol reduction method is described. A first solution is prepared by dissolving a certain amount of EtOSO 3 (1-ethyl-3-methylimidazolium ethyl sulfate) in ethylene glycol. Manufacture. A second solution is prepared by dissolving a certain amount of silver nitrate (AgNO 3 ) in another ethylene glycol. After stirring and filtering the first solution and the second solution prepared above to obtain a solid, the solid is centrifuged with acetone and ethanol to obtain a silver nanowire. The silver nanowires thus prepared are mixed with toluene, the solvent described above, to prepare a silver nanowire dispersion. At this time, an additive such as a dispersant or a surfactant may be added to the silver nanowire dispersion.

Next, referring to FIG. 1B, the prepared silver nanowire dispersion is coated on the substrate 10. In this case, a general solution coating method may be used as a coating method of the silver nanowire dispersion, and in the present embodiment, the coating is performed by spin coating. Then, the solvent is removed by heating the substrate 10 to which the silver nanowire dispersion is applied. At this time, the temperature of the heating is carried out at a temperature of 100 ℃ to 200 ℃ for several minutes to several hours, so that all the solvent is evaporated. The silver nanowires 20 in which the solvent is evaporated are networked with each other.

Next, referring to FIG. 1C, the siloxane-based polymer 30 is coated on the substrate 10 on which the silver nanowires 20 are formed. In this case, as the siloxane-based polymer 30, the above-described TEOS can be used, and like the silver nanowire dispersion, it is applied by spin coating. Since TEOS is formed into a film while filling the silver nanowires 20, for example, when the silver nanowires 20 are formed to a thickness of 500 nm and TEOS is applied, the thickness of the TEOS film containing silver nanowires is increased. It may be formed to be 500nm.

Finally, the substrate 10 coated with the siloxane-based polymer 30 is dried at about 150 ° C. for several minutes to several hours to prepare a transparent conductive film 40. As described above, the transparent conductive film prepared according to the embodiment of the present invention includes silver nanowires and siloxane-based polymers, thereby improving the hardness of the transparent conductive film.

Hereinafter, an electric device including a transparent conductive film according to an embodiment of the present invention described above will be described. Hereinafter, a display device including a touch element will be described as an example of an electric element.

2 is a diagram illustrating a display device including a touch device according to the present invention.

Referring to FIG. 2, the display device includes a display panel PNL, a touch element TD, a scan driver SDRV, a data driver DDRV, and a detector TSC.

The display panel PNL may be configured as a flat panel display (FPD) such as an organic light emitting display panel, a liquid crystal display panel, a plasma display panel, an electrophoretic display panel, and the like. The scan driver SDRV supplies a scan signal to the subpixels included in the display panel PNL. The data driver DDRV supplies a data signal to subpixels included in the display panel PNL. The touch element TD is positioned on the display panel PNL and includes an electrode part. The sensing unit TSC is connected to the electrode unit and senses a position through the electrode unit according to the touch of the user's touch device TD. The sensing unit TSC has a capacitive type using a change in capacitance (a change in capacitance according to dielectric constant) and a resistive change using a change in resistance according to the structure of the electrode formed in the touch element TD. It is formed into a type.

3 is a diagram illustrating a structure of an electrode unit positioned in a touch device, FIG. 4 is an enlarged view of a portion of FIG. 3, and FIG. 5 is a cross-sectional view taken along line II ′ of FIG. 4.

Referring to FIG. 3, the electrode parts TPL and TPR may include first electrodes TPY arranged in the Y-axis direction of the touch element TD and second electrodes TPX arranged in the X-axis direction. Can be. The first electrodes TPY and the second electrodes TPX are patterned to be located in different regions, and the patterned electrodes TPY and TPX may be connected to each other by the bridge electrode BE.

4 and 5, the first electrodes 117 spaced apart from each other in the Y-axis direction may be disposed on the substrate 110. The first electrodes 117 may be electrically connected through the first bridge electrode 113. A portion of the first bridge electrode 113 may be exposed through the insulating layer 115 formed in a portion of the first bridge electrode 113 and the first electrodes 117 may be connected to the exposed first bridge electrode 113, respectively. have. In addition, a second bridge electrode 122 that vertically intersects between the first electrodes 117 may be located. The second bridge electrode 122 may electrically connect the second electrodes 121 arranged to be spaced apart from each other in the X-axis direction, and the insulating layer 115 and the first bridge disposed between the first electrodes 117 described above. It may be positioned perpendicular to the electrode 113. The second electrode 121 may be spaced apart from the first electrodes 117 on the substrate 110 and may be connected to the second bridge electrode 119.

In addition, the routing electrode 120 connected to the second electrode 121 may be positioned at an edge of the substrate 110. The routing electrode 120 may serve to transmit a change in capacitance due to the touch of the human body in the electrode unit. The connection pattern 119 connected to the second electrode 121 is positioned on the routing electrode 120, and the insulating layer 115 having contact holes 116 exposing a portion of the connection pattern 119 is disposed. A contact electrode 118 is disposed to cover the insulating layer 115 on the routing electrode 120 and is electrically connected to the routing electrode 120.

In the above-described touch device, the first electrode 117, the first bridge electrode 113, the second bridge electrode 122, the second electrode 121, and the connection pattern 119 are formed of silver nanowires and siloxane-based compounds of the present invention. It may be made of a transparent conductive film containing a polymer.

Hereinafter, the manufacturing method of the display device including the touch element with the transparent conductive film of the present invention described above will be described. Hereinafter, the process of forming the transparent conductive film is the same as in FIG.

6 is a diagram illustrating a method of manufacturing a display device including a touch device according to an exemplary embodiment, by process.

Referring to FIG. 6A, a display panel DP such as an organic light emitting display panel, a liquid crystal display panel, a plasma display panel, an electrophoretic display device, and the like is manufactured. Then, the routing electrode 120 is formed by stacking and patterning a low-resistance metal such as copper (Cu) or gold (Au) on the upper surface of the display panel DP.

Subsequently, the transparent conductive film including the silver nanowire and the siloxane polymer of the present invention described above is formed and patterned on the upper surface of the display panel DP on which the routing electrode 120 is formed, thereby forming the second bridge electrode 122 and the connection pattern ( 119). The second bridge electrode 122 is formed in a region spaced apart from the routing electrode 120, and the connection pattern 119 is formed on the routing electrode 120.

Next, referring to FIG. 6B, the insulating film 115 described above is formed on the upper surface of the display panel DP on which the routing electrode 120 and the connection pattern 119 are formed. In this case, the thickness of the insulating layer 115 is formed to sufficiently cover the connection pattern 119 and the second bridge electrode 122. Next, referring to FIG. 6C, a plurality of contact holes 116 are formed to pattern the insulating layer 115 by photolithography and expose the connection pattern 119.

Next, referring to FIG. 6D, the transparent conductive film including the silver nanowires and the siloxane polymer of the present invention is formed and patterned to form the first bridge electrode 113, the first electrode (not shown), and the first electrode. The second electrode 121 and the contact electrode 118 are formed. Here, the first bridge electrode 113 connects first electrodes (not shown), and the second bridge electrode 122 connects second electrodes 121. In addition, the contact electrode 118 is electrically connected to the connection patterns 119 through the contact holes 116 of the insulating layer 115. Accordingly, the display device including the touch device according to the exemplary embodiment of the present invention is manufactured by forming touch devices on the display panel DP.

In the present invention, the touch element as an electric element having a transparent conductive film has been described as an example, but the transparent conductive film of the present invention can be used in place of ITO in various electric elements. For example, the transparent conductive film of the present invention includes a pixel electrode of an organic light emitting display device, a pixel electrode or a common electrode of a liquid crystal display device, a scan electrode or a common electrode of a plasma display panel, a field emission display device, a pixel of an electrophoretic display device. It is also applicable to an electrode or a common electrode.

Hereinafter, preferred embodiments of the present invention will be described in order to help understanding of the present invention. However, the following examples are merely to illustrate the present invention is not limited to the following examples.

Comparative Example 1

ITO was deposited on the substrate to a thickness of 200 nm.

Comparative Example 2

Grayish silver nanowires were obtained using an ethylene glycol reduction method, then mixed with toluene and applied onto a substrate. The substrate was heated to remove toluene to form a transparent conductive film made of silver nanowires having a thickness of 200 nm.

Example

TEOS was applied on the transparent conductive film prepared in Comparative Example 2 by spin coating, followed by drying to form a transparent conductive film having a final thickness of 200 nm.

The sheet resistance, transmittance and hardness of the transparent conductive films prepared according to Examples and Comparative Examples 1 and 2 were measured and shown in Table 1 below.

Comparative Example 1 Comparative Example 2 Example Sheet resistance (Ω / □) 50 20 20 Transmittance (%) 91 90 90 Hardness (H) 8H 2H 8H

As shown in Table 1, the transparent conductive film according to the embodiment of the present invention exhibited a hardness and transmittance equivalent to that of ITO, while lowering the sheet resistance. In addition, the transparent conductive film according to the embodiment of the present invention was confirmed that the hardness is more improved than the transparent conductive film consisting of only silver nanowires.

As described above, the transparent conductive film including the silver nanowires and the siloxane-based polymer according to an embodiment of the present invention has an advantage of improving sheet resistance and hardness. Therefore, there is an advantage in that manufacturing is easy while replacing ITO in various electric elements.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be practiced. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all aspects. In addition, the scope of the present invention is shown by the claims below, rather than the above detailed description. Also, all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (10)

Transparent conductive film containing silver nanowires and siloxane-based polymers.
The method according to claim 1,
The siloxane-based polymer is TEOS (Tetraethyl orthosilicate) transparent conductive film.
The method according to claim 1,
The silver nanowire is a transparent conductive film dispersed in the siloxane-based polymer.
Applying a silver nanowire dispersion onto the substrate; And
Coating a siloxane-based polymer on the substrate; Method of manufacturing a transparent conductive film comprising a.
5. The method of claim 4,
The silver nanowire dispersion is a method for producing a transparent conductive film prepared by mixing and stirring silver nitrate (AgNO 3 ) in a solvent.
5. The method of claim 4,
After applying the silver nanowire dispersion, the method of manufacturing a transparent conductive film further comprising the step of heating the substrate.
5. The method of claim 4,
The siloxane-based polymer is TEOS (Tetraethyl orthosilicate) method of manufacturing a transparent conductive film.
5. The method of claim 4,
The silver nanowire dispersion and the siloxane-based polymer is a method of manufacturing a transparent conductive film is applied by a spin coating method.
Board;
An electrical device comprising a transparent conductive film comprising a silver nanowire and a siloxane-based polymer formed on the substrate.
10. The method of claim 9,
The electric device is any one of an organic light emitting display device, a plasma display panel, a liquid crystal display device, a field emission display device, an electrophoretic display device and a touch screen.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103730194A (en) * 2013-12-13 2014-04-16 中国科学院宁波材料技术与工程研究所 Multilayer structure composite transparent conducting thin film based on silver nanowires and preparation method thereof
KR20140118454A (en) * 2013-03-29 2014-10-08 코오롱인더스트리 주식회사 Transparent Conducting Film based on Nanowire and a Method for Preparing Thereof)
WO2017060572A1 (en) 2015-10-09 2017-04-13 Inkron Oy Electrically conductive siloxane particle films, and devices with the same
CN108251820A (en) * 2018-03-09 2018-07-06 无锡博硕珈睿科技有限公司 The manufacturing method and manufacturing equipment of self-heating product/material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140118454A (en) * 2013-03-29 2014-10-08 코오롱인더스트리 주식회사 Transparent Conducting Film based on Nanowire and a Method for Preparing Thereof)
CN103730194A (en) * 2013-12-13 2014-04-16 中国科学院宁波材料技术与工程研究所 Multilayer structure composite transparent conducting thin film based on silver nanowires and preparation method thereof
CN103730194B (en) * 2013-12-13 2016-02-24 中国科学院宁波材料技术与工程研究所 The preparation method of the compound transparent electricity conductive film of a kind of nano silver wire Quito Rotating fields
WO2017060572A1 (en) 2015-10-09 2017-04-13 Inkron Oy Electrically conductive siloxane particle films, and devices with the same
US11289666B2 (en) 2015-10-09 2022-03-29 Inkron Oy Electrically conductive siloxane particle films, and devices with the same
CN108251820A (en) * 2018-03-09 2018-07-06 无锡博硕珈睿科技有限公司 The manufacturing method and manufacturing equipment of self-heating product/material

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