WO2016024743A1

WO2016024743A1 - Method for forming transparent electrode and transparent electrode laminate

Info

Publication number: WO2016024743A1
Application number: PCT/KR2015/008059
Authority: WO
Inventors: 이정열; 안민석; 변자훈; 이승준; 차영철; 홍우성; 박성연; 정재훈; 배민영; 김동민
Original assignee: 주식회사 동진쎄미켐
Priority date: 2014-08-13
Filing date: 2015-07-31
Publication date: 2016-02-18
Also published as: TW201623694A; KR20160020230A; KR102243747B1; CN106575552A; TWI683039B

Abstract

The present invention relates to a method for forming a transparent electrode capable of more stably forming a transparent electrode pattern having a finer line width and a great aspect ratio, and a transparent electrode laminate formed thereby. The method for forming a transparent electrode comprises the steps of: forming, on a substrate, a transparent electrode layer including one or more conductive materials selected from a group consisting of a conductive polymer, a conductive carbon-based material, a metal nanostructure, and a conductive metal oxide; forming, on the transparent electrode layer, a protection layer including one or more materials selected from a group consisting of a polysiloxane-based polymer, an acrylic polymer, and an urethane-based polymer; forming a photoresist pattern on the protection layer; and making the transparent electrode layer non-conductive by surface-treating, with an oxidizer, the protection layer and the transparent electrode layer in a region which has been opened by the photoresist pattern.

Description

【Specification】

[Name of invention]

Formation method of transparent electrode and projection mesh laminated body

Technical Field

The present invention relates to a method of forming a transparent electrode having a finer line width and capable of more stably forming a transparent electrode pattern having a larger aspect ratio, and a transparent electrode laminate formed therefrom.

Background technology

Transparent electrodes are defined as thin films that are transparent and electrically conductive to visible light, and are used in various fields such as plasma display panels, liquid crystal display devices, light emitting diode devices, organic electroluminescent devices, touch panels, and solar cells. Recently, as various devices or touch panels become ultra fine and highly sensitive, a transparent electrode pattern having a finer line width and a larger aspect ratio, for example, a line and space type having a thinner line width and a larger height The formation of the transparent electrode pattern is desired.

Conventionally, after forming a transparent conductive material on a substrate, the method of etching and patterning the transparent conductive material through a photolithography process of exposure, development and etching using a photoresist pattern, mainly having a line & space form It was common to form a transparent electrode pattern. However, according to the conventional method, a problem such as damage to the upper or lower portion of the transparent electrode pattern having a fine line width occurs due to the margin of the etching process using the photoresist pattern as a mask, which is excellent. It was difficult to form a transparent electrode pattern having conductivity. This problem is more prominent as the transparent electrode pattern has a finer line width, has a larger aspect ratio, and worse, the transparent electrode pattern collapses.

Due to the problems of the prior art, there is a continuous need for a method of more stably and satisfactorily forming a transparent electrode pattern having a finer line width and having a more aspect ratio.

[Content of invention]

[Problem to solve] Accordingly, the present invention provides a method for forming a transparent electrode, which can more stably form a transparent electrode pattern having a finer line width and a large aspect ratio.

The present invention also provides a transparent electrode laminate including a transparent electrode pattern formed on a substrate through the method of forming the transparent electrode.

[Solution of problem]

Accordingly, the present invention comprises the steps of forming a transparent electrode layer on the substrate comprising at least one conductive material selected from the group consisting of a conductive polymer, a conductive carbon-based material, a metal nanostructure and a conductive metal oxide; Forming a protective layer on the transparent electrode layer, the protective layer including at least one selected from the group consisting of a polysiloxane polymer, an acrylic polymer, and a urethane polymer; Forming a photoresist pattern on the protective layer; And non-conducting the transparent electrode layer by surface-treating the protective layer and the transparent electrode layer in the area opened by the photoresist pattern with an oxidant.

The present invention also includes at least one selected from the group consisting of polysiloxane polymers, acrylic polymers and urethane polymers, and includes a protective layer formed on the transparent electrode layer, wherein the first region of the transparent electrode layer is non-conductive. The remaining second region maintains conductivity to provide a transparent electrode laminate that defines a transparent electrode pattern.

Hereinafter, a method of forming a transparent electrode and a transparent electrode laminate formed therefrom according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the invention, forming a transparent electrode layer comprising at least one conductive material selected from the group consisting of a conductive polymer, a conductive carbon-based material, a metal nanostructure and a conductive metal oxide on a substrate; Forming a protective layer on the transparent electrode layer, the protective layer including at least one selected from the group consisting of a polysiloxane polymer, an acrylic polymer, and a urethane polymer; Forming a photoresist pattern on the protective layer; And non-conducting the transparent electrode layer by surface-treating the protective layer and the transparent electrode layer in the area opened by the photoresist pattern with an oxidant. In the forming method of this embodiment, after forming a transparent electrode layer including a predetermined conductive material, and then forming a predetermined protective layer, a photoresist pattern defining a transparent electrode pattern on the protective layer is photographed and etched. Form by. Thereafter, the photoresist pattern is used as a mask, and the protective layer and the transparent electrode layer of the open area are surface-treated with an oxidant, instead of removing the transparent electrode layer or the like in the open area.

In this surface treatment, the oxidant can pass through the protective layer to selectively oxidize the conductive material of the transparent electrode layer, and as a result, it is possible to unconvert the transparent electrode layer in the area opened by the photoresist pattern (so-called chemical ON / OFF process). As a result of this process, between the transparent electrode layer of the non-conducted region, a transparent electrode layer of the remaining region that maintains the conductivity can be formed, and the transparent electrode layer that maintains the conductivity can form a transparent electrode pattern as a whole. have.

According to the method of this embodiment, since the transparent electrode layer and the protective layer remain intact even in the non-conductive region between the transparent electrode patterns, the risk of damaging the transparent electrode pattern or deteriorating its electrical characteristics by etching is minimized. Even if a transparent electrode pattern having a finer line width and a larger aspect ratio is formed, there is no fear that the transparent electrode pattern will collapse. Therefore, a transparent electrode pattern having a finer line width and excellent electrical characteristics can be formed well, and this can be applied to a touch panel, various display elements, or solar cells.

Hereinafter, with reference to the accompanying drawings, a transparent electrode forming method of an embodiment will be described for each process. FIG. 1 is a process flowchart schematically illustrating an example of a method of forming a transparent electrode according to an embodiment.

Referring to the first drawing of FIG. 1, in one embodiment, a transparent electrode layer including at least one conductive material selected from the group consisting of a conductive polymer, a conductive carbon-based material, a metal nanostructure, and a conductive metal oxide is formed on a substrate. To form.

In this case, in consideration of the type of the device, etc. to which the transparent electrode forming method of the present invention is applied, all of the conventional substrates can be applied without particular limitations. For example, any glass substrate, resin substrate, etc. which show transparency and transparency to visible light can be used.

In addition, the transparent electrode layer is formed according to a conventional electrode forming method including the above conductive material, after forming a solution or dispersion containing the at least one conductive material, an organic solvent or an aqueous solvent, and then apply it to a transparent substrate and It can be dried and formed. At this time, if necessary, depending on the type of the conductive material, the solution or dispersion may further include a suitable dispersant or binder.

The transparent electrode layer is formed using any conductive material known to be able to form a transparent electrode, for example, a conductive polymer, a conductive carbon-based material, a metal nanostructure or a conductive metal oxide, without any particular limitation. can do. Specific examples of such conductive materials include conductive polymers such as polyaniline polymers, polypyrrole polymers or polythiophene polymers; Conductive carbon-based materials such as carbon nanotubes or graphene; Metal nanostructures such as silver nanowires (AgNw) or copper nanoparticles; Conductive metal oxides such as indium tin oxide or antimony tin oxide, and the like, and the transparent electrode may be formed using various conductive materials.

In addition, the transparent electrode layer may have a thickness of about 0.03 urn to 0.5 im, or about 0.05 m to 0.3. When the thickness of the transparent electrode layer is too thin, the effective sheet resistance may also be greatly reduced, resulting in uneven sheet resistance, and when the thickness of the transparent electrode layer is too thick, transparency or optical characteristics may be degraded.

The transparent electrode layer may have a sheet resistance of about 80i) / sq to 400 Ω / sq, or about 150il / sq to 280 O / sq.

On the other hand, after the transparent electrode layer is formed, a protective layer containing at least one selected from the group consisting of a polysiloxane polymer, an acrylic polymer and a urethane polymer may be formed on the transparent electrode layer. Such a protective layer can protect a transparent electrode layer and can suppress that a transparent electrode layer is removed by the said oxidant in the surface treatment using the oxidizing agent mentioned later and the nonelectroconductive process by this, a transparent electrode layer. That is, by forming such a protective layer, the transparent electrode layer in a certain region is not removed, and only the oxidant passes through the protective layer and then reflects with the transparent electrode layer to make the transparent. Only selective oxidation and non-conduction of the electrode layer can proceed. As a result, the effect of suppressing the collapse of the transparent electrode pattern and the like, which the method of one embodiment is intended, can be achieved. In consideration of the role of the protective layer, the protective layer may be formed using a polysiloxane polymer, an acrylic polymer or a urethane polymer, and among these, a polysiloxane polymer may be more suitably used. Such polysiloxane-based polymers may exhibit better surface properties when treated with the oxidizing agent, and when formed as a protective layer, minimize the insulation effect related to conductivity, and also have excellent water resistance and chemical resistance as the original purpose, and the photo above It is because it can show high coating property and adhesiveness also with respect to a resist pattern.

The polysiloxane-based polymer and the protective layer including the same include an alkyloxy silane monomer, an amino silane monomer, a vinyl silane monomer, an epoxy silane monomer, a methacryloxy silane monomer, an isocyanate silane monomer, and a fluorine silane monomer. It may include one polymer or two or more co-polymers selected from.

Specifically, the polysiloxane-based polymer and the protective layer are tetraethyloxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, and Υ-methacryloxypropyltrimethoxysilane ， Β- (3, 4-epoxycyclonucleosilane) ethyltrimethoxysilane, _γ -glycidoxy propyltrimethoxysilane, _γ -mercaptopropyltrimethoxysilane, _γ -aminopropyltrieoxysilane, Ν --(Aminoethyl) aminopropyltrimethoxysilane, _γ -euraidpropyltrioxysilane, phenyltriethyloxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide modified silane monomers, ply It may comprise one polymer or two or more copolymers selected from the group consisting of methylethoxysiloxane and nuxamethyldisirazine.

Furthermore, in order to secure a low sheet resistance while the protective layer including the polysiloxane polymer has a higher bonding strength or adhesion to another neighboring layer, the polysiloxane polymer and the protective layer may be about 60 to 90 weight of tetraethyloxysilane. ⁰ / 。; and vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclonucleosilane) ethyl Trimethoxysilane, glycidoxypropyltrimethoxysilane, Υ- mercaptopropyltrimethoxysilane, aminopropyltriethyl silane Ν- β-(aminoethyl)- Aminopropyltrimethoxysilane, Euraid propyltrioxysilane, Phenyltrioxysilane, Methyltriethoxysilane, Methyltrimethoxysilane, Polyethyleneoxide Modified Silane Monomer / Polymethylethoxysiloxane and Nuxamethyldicy at least one compound selected from the group consisting of piperazine for about 10 to 40 parts by weight ^_0/0; And hepatic copolymers.

If the content of tetraethyloxysilane is less than about 60 wt. In addition, when the content of tetraethyloxysilane in the monomer is greater than about 90% by weight ⁰ /., The density of the protective layer may be excessively high or surface cracking may occur and the moisture resistance may be greatly reduced.

Meanwhile, in addition to the polysiloxane polymer, the protective layer may be used using an acrylic polymer or a urethane polymer, and specific examples thereof are not particularly limited, and any of those known to be usable as a protective layer or a coating layer of a conductive layer has been known. Both acrylic polymers or urethane polymers can be used without any particular limitation.

The protective layer may have a thickness of about 0.05 urn to 0.4 urn, or about 0.12 urn to 0.35 kPa. In addition, as described above, the transparent electrode layer having such a protective layer may have a sheet resistance of about 80 Q / sq to 400 Ω / sq, or about 150 £ l / sq to 280 Ω / sq. As a result, in the surface treatment of the oxidizing agent and the transparent electrode layer nonconducting step of the region to be described later, it is possible to selectively nonconductive while appropriately protecting the lower transparent electrode layer, and the finally formed transparent electrode pattern and the laminate can exhibit excellent electrical properties. have.

After the transparent electrode layer and the protective layer are sequentially formed, a photoresist pattern defining a region in which the transparent electrode pattern is to be formed may be formed on the protective layer, as shown in FIG. 1.

Such photoresist patterns may be formed by performing exposure and development processes using commonly known photosensitive resin compositions or photoresist compositions, and the progress conditions and methods of such exposure and development processes may be determined by those skilled in the art according to the type of each photoresist composition. Since it is well known, further description thereof will be omitted. The photoresist composition for forming the photoresist pattern may include a positive photoresist composition including an alkali-soluble resin; Or a monomer or oligomer and a photoinitiator containing one or more anti-male functional _group, the negative photoresist composition comprising; may be used, it is possible to more suitably use the positive-working photoresist composition.

The photoresist pattern may be formed through a conventional exposure and development process after the photoresist composition layer is formed to have a thickness of about 1 / m to 5 Ά, or about 2 kPa to 4. If the thickness of the photoresist composition layer is too thin, staining or appearance damage may occur in the photoresist composition layer (pattern) and / or the protective insect during exposure and development, and a cloudy appearance may occur. If the thickness of the photoresist composition layer is too thick, the exposure may not be easy and development may not occur sufficiently or mismatch of line width may occur.

On the other hand, after forming the above-described photoresist pattern, as shown in Figure 1, the step of non-conducting the transparent electrode layer by surface treatment of the protective layer and the transparent electrode layer of the area opened by the photoresist pattern with an oxidant Proceed. In this process, the oxidant passes through the protective layer, thereby selectively oxidizing and non-conducting the transparent electrode layer thereunder. As a result, the transparent electrode layer may remain unconducted in the region opened and oxidized by the photoresist pattern, and the transparent electrode layer may be formed while the transparent electrode layer remains conductive in the remaining regions.

As the oxidizing agent for such a surface treatment, without substantially removing or damaging the protective layer and the transparent electrode layer (for example, the protective layer thickness change before and after the surface treatment: about 200 nm or less), through the protective layer Any material capable of selectively oxidizing and nonconducting the transparent electrode layer may be used. More specific examples of such oxidizing agents include hypochlorous acid or salts thereof (e.g. hypochlorous acid in the form of a mixture with acids such as hypochlorite or acetic acid), dichloromethane or salts thereof (e.g. alkali metal salts such as potassium salts). ), Permanganic acid or salts thereof (e.g., alkali metal salts such as potassium salts), strong acids having oxidative properties such as hydrogen peroxide, nitric acid or hydrochloric acid, and mixtures of copper chloride and acids (e.g. hydrochloric acid, etc.) One selected, black may include two or more combinations selected for these diseases, and various other oxidizing agents may be used.

Among them, the above-mentioned hypochlorous acid or a salt thereof may be further considered in consideration of the characteristic of selectively oxidizing and non-converting the transparent electrode worm and not causing defects such as stains or turbidity on the protective layer and the transparent electrode layer. It can use suitably. Further, the oxidizing agent can be used more suitably as a hypochlorous acid form (see Example 2 described later) in which hypochlorite and a weak acid such as acetic acid are mixed. As a result, the transparent electrode can be more effectively oxidized and nonconducted without further causing defects in the protective layer.

In addition, the surface treatment process using the oxidant may proceed by a method of diluting such an oxidant component to an appropriate concentration in the liquid phase to apply or spray the surface.

Meanwhile, after the oxidant surface treatment step described above, the step of removing the photoresist pattern may be further performed, and the removing of the photoresist pattern may be performed according to a stripping process of a conventional photoresist pattern.

After the process of the above-described embodiment, a substrate; A transparent electrode layer including at least one conductive material selected from the group consisting of a conductive polymer, a conductive carbon-based material, a metal nanostructure, and a conductive metal oxide, and formed on a substrate; And at least one member selected from the group consisting of polysiloxane polymers, acrylic polymers, and urethane polymers, the protective layer being formed on the transparent electrode layer, wherein the first region of the transparent electrode layer is non-conductive. The second region may have a transparent electrode stack that maintains conductivity to define a transparent electrode pattern.

In this transparent electrode stack, the transparent electrode layer of the first region can remain on the substrate in an unconducted state with a sheet resistance of 150 C} / sq to 280 Ω / sq, and the transparent electrode layer of the remaining second region. Silver can maintain the excellent conductivity originally possessed by a conductive material. Accordingly, the fine transparent electrode pattern can be formed, but the transparent electrode layer and the protective layer of the non-conducted first region remain intact, whereby a finer transparent electrode pattern can be better formed without collapse of the pattern. . Through the transparent electrode forming method of the above-described embodiment, various types of transparent electrode patterns may be formed, and typically, a plurality of lines may be formed by forming the transparent electrode layer of the non-conducted first region and the transparent electrode layer of the remaining second region. The transparent electrode pattern of the line & space form which has the pattern form alternately arranged can be formed suitably. This makes it possible to form a line and space-shaped transparent electrode pattern having a very fine line width and a large aspect ratio without sacrificing such a pattern. 【Effects of the Invention】

According to the present invention, in the process of performing a conventional photolithography process, the transparent electrode pattern may be damaged or the electrical characteristics thereof may be degraded, and the transparent electrode pattern having a finer line width and a larger aspect ratio may be transparent. A transparent electrode forming method substantially free of the possibility of collapse of the electrode pattern, and a transparent electrode laminate formed through this can be provided.

Therefore, by applying the present invention, it is possible to form a transparent electrode pattern having a finer line width and excellent electrical properties with good, it can be applied to a touch panel, various display elements or solar cells very preferably.

[Brief Description of Drawings]

FIG. 1 is a process flowchart schematically illustrating an example of a method of forming a transparent electrode according to an embodiment, for each process sequence.

FIG. 2 is a view showing electron micrographs before and after surface treatment (after removing to a photoresist pattern) in Example 2. FIG.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

[Formation of electrode layer]

A dispersion of conductive polymer PEDOT: PSS [Poly (3,4-ethylenedioxythiophene) Polystyrene sulfonate, solids 1wt%], and a dispersion of silver nanowai solids 1wt%] were obtained by IPA (isopropylene alcohol), MeOH (methanol) and It manufactured using the mixed solvent of this ISO (dimethyl sulfoxide). The conductive polymer dispersion and silver nanowiser The dispersions were mixed at a weight ratio of 1: 1, which was coated on a 100-thick PET substrate with a coating liquid thickness of 6.86 // m using a bar coater. Thereafter, hot air was dried under the condition of 120 ^° C./1 min to form a transparent electrode layer. The sheet resistance of this transparent electrode layer was found to be 80 Q / sq.

Example 1

In order to form a protective coating liquid on the electrode layer, first, 16.08 parts by weight of TEOS (tetraethyloxysilane), 4.02 parts by weight of PTMS (phenyltrimethoxysilane), 23.55 parts by weight of water, 54.95 parts by weight of IPA (isopropyl alcohol), 1.4 parts by weight of acetic acid were mixed and sol-gel reacted at 70 ^° C. for 3 hours to form a polysiloxane-based polymer. As a result, 100 g of a sol-gel reaction solution was obtained. In this case, the solid content was 7.8wt ⁰ /.. This was diluted 1: 4 by weight ratio using isopropyl alcohol as a diluent to prepare 500 g of a protective layer coating solution. Solid content at this time was 1.56 wt%.

This protective coating material was coated with a bar coater on a substrate on which the electrode layer was formed to a thickness of 11.43 / im, and then hot-air dried under the condition of 120 ^° C / 10 min. As a result, a protective layer was formed to a thickness of 0.178 um, and the sheet resistance was found to be 90 Q / sq.

Then, Dongjin Semichem photoresist (Positive Type) SJ-631 (10cP, solid content 23wt%) was applied to the formed protective layer using a bar coating, dried for 1 minute at 120 ^° C temperature of about 2.5 βνΆ thickness photo The resist was formed, and after the 50mJ exposure with the SUSS Microtec MA-6 exposure apparatus, development was carried out at room temperature for 25 seconds using a developer DPD-200 of Dongjin Semichem to form a photoresist pattern.

Then, dilute hypochlorite (Hypochroite Salt, 12%) in distilled water,

After preparing an aqueous hypochlorite solution at a concentration of 3%, the protective layer and the transparent electrode layer in the area opened by the photoresist pattern were surface treated.

Example 2

Hypochlorite (12%) and acetic acid were mixed at a content of 1: 1 to prepare 6% of the mixture. The appearance at this time was found to be acidic and take the form of hypochlorous acid. By using the photoresist pattern Example, except that the protective layer and the transparent electrode layer of the open area is surface-treated

In the same manner as in 1, a transparent electrode laminate and a pattern were formed. Example 3

Aqueous chemical PED-2102 (solid content 30wt%), which is a water-dispersible urethane polymer, was diluted in a weight ratio of 1: 9 using isopropyl alcohol as a diluent to prepare 500 g of a protective layer coating solution. Solid content at this time was 3 wt%.

The protective layer coating solution was coated on the crawfish on which the electrode layer was formed to a thickness of 11.43 using a bar coater, and then hot air dried under a condition of 120 ^° C./10 min. As a result, a protective layer was formed to a thickness of 0.34 um, and the surface resistance was confirmed as ΙΙΟ Ω / sq. Thereafter, the process was performed in the same manner as in Example 2 to form a photoresist pattern, and the protective layer and the transparent electrode layer in the area opened by the photoresist pattern were treated with an aqueous hypochlorite solution. Example 4

Takamatsh oil & fat co., Ltd., a water-dispersible acrylic ester polymer, was diluted to 1: 9 by weight ratio of PESRESIN A-645GH (solid content 30wt%) using isopropyl alcohol, a diluent, and a protective layer coating solution. 500 g was prepared. Solid content at this time was 3 wt%.

This protective layer coating liquid is applied to the substrate on which the electrode layer is formed using a bar coater

It was coated with a thickness of 11 .43 and then hot air dried under a condition of 120 ^° C./10 min. As a result, a protective layer was formed to a thickness of 0.33 um, and the surface resistance was confirmed as ΙΙΟ Ω / sq. Thereafter, the process was performed in the same manner as in Example 2 to form a photoresist pattern, and the protective layer and the transparent electrode layer of the area opened by the photoresist pattern were treated with an aqueous hypochlorite solution. First, in Example 2, electron micrographs before and after the surface treatment using hypochlorous acid and after the surface treatment (after removing the photoresist pattern) are respectively shown in FIG. 2. In addition, the characteristics of the transparent electrode patterns of Examples 1, 2, 3, and 4 were evaluated under the following criteria, and the evaluation results are shown in Table 1 below.

(1) Surface property evaluation: Based on the following criteria, it was evaluated whether or not there were chemical changes in the protective layer and the transparent electrode layer before and after the surface treatment.

0: by the color difference meter, the amount of front and rear change is ΔEab <3, Haze <0.5

Δ: The color difference meter satisfies only one change amount before and after "0" (that is, only one of A Eab <3 or Haze <0.5).

X ： The amount of front and rear change by the color difference meter is ΔEab> 3, Haze> 0.5

(2) Evaluation of defect occurrence on the surface of the transparent electrode: According to the following criteria, the degree of defect occurrence was evaluated on the surfaces of the protective layer and the transparent electrode layer after the surface treatment. ^' ᄋ: When there are no defects such as 100% foreign matters on the transparent electrode pattern of line and space; .

Δ: when there are no defects such as foreign matters over 80% of the observed parameters for the transparent electrode patterns of the line and the space;

X ： Observation on transparent electrode patterns of line and space.

(3) Evaluation of disconnection: On the basis of the following criteria, it was evaluated whether electrical disconnection of the transparent electrode layer between the surface-treated region and the untreated region was performed after the surface treatment.

0: measurement parameter 100% electrical disconnection for transparent electrode patterns of line and space;

Δ: electrical disconnection of more than 80% of the length parameter for the transparent electrode patterns of line and space;

X ： When the measurement parameter is 60% or more for the transparent electrode pattern of line and space

TABLE 1

Example 1 Example 2 Example 3 Example 4 Surface property evaluation Δ 0 0 0 Defect generation evaluation 0 0 0 0 Open circuit evaluation 0 0 0 O Referring to FIG. 2 and Table 1, it was confirmed by Examples 1 and 2 that a good transparent electrode pattern electrically disconnected between the surface treated region and the untreated region was formed. In addition, referring to Examples 3 and 4, even when the protective layer is formed of a urethane-based polymer or an acrylic polymer, it was confirmed that a good transparent electrode pattern can be formed, similarly to Examples 1 and 2.

In addition, it was confirmed that the formation of such a transparent electrode pattern was caused by a phenomenon in which the transparent electrode layer ^' was oxidized (chemically changed) and unconverted in the surface treated region. In addition, it was confirmed that the protective layer and the transparent electrode layer maintained their thickness substantially without physical damage even in the surface treated region, and almost no defects occurred in the protective layer and the transparent electrode layer as a whole, thereby providing good surface characteristics. It was confirmed that it was maintained.

Claims

[Patent Claims]

[Claim 1]

Forming a transparent electrode layer on the substrate, the transparent electrode layer comprising at least one conductive material selected from the group consisting of a conductive polymer, a conductive carbonaceous material, a metal nanostructure, and a conductive metal oxide;

Forming a protective layer on the transparent electrode layer, the protective layer including at least one selected from the group consisting of a polysiloxane polymer, an acrylic polymer, and a urethane polymer;

Forming a photoresist pattern on the protective layer; And ^'

And surface-treating the protective layer and the transparent electrode layer in the area opened by the photoresist pattern with an oxidant to thereby non-convert the transparent electrode layer.

[Claim 2]

The method of claim 1, wherein the conductive material is a polyaniline-based polymers, polypyrrole-based polymers, ^{polythiophene-based,} polymer, carbon nanotubes, graphene, the nanowire (AgNw), copper nanoparticles, indium tin oxide (Indium Tin Oxide And at least one transparent electrode selected from the group consisting of antimony tin oxide.

[Claim 3]

The method of claim 1, wherein the polysiloxane polymer is 60 to 90% by weight of tetraethyloxysilane; And vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, methacryloxypropyltrimethoxysilane, 13- (3,

4-epoxycyclonucleosilane) ethyltrimethoxysilane, Υ-glycidoxypropyltrimethoxysilane, -mercaptopropyltrimethoxysilane, Υ-aminopropyltriethoxysilane Ν-β-(aminoethyl) _-γ -Aminopropyltrimethoxysilane, Υ-euraidpropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide modified silane monomer, polymethylethoxysiloxane and nuxamethyl DC l of at least one member selected from the group consisting of compounds 10 to 40 parts by weight ^_0/0; A method of forming a transparent electrode comprising a copolymer of liver. [Claim 4]

The method for forming a transparent electrode according to claim 1, wherein the transparent electrode layer has a thickness of 0.03 to 0.5; win and a sheet resistance of 80 Q / sq to 400 Q / sq.

[Claim 5]

The method of claim 1, wherein the protective layer has a thickness of 0.05 to 0.40 mm 3.

[Claim 6]

The transparent oxidizing agent of claim 1, wherein the oxidizing agent comprises at least one selected from the group consisting of hypochlorous acid or salts thereof, dichromic acid or salts thereof, permanganic acid or salts thereof, hydrogen peroxide, nitric acid, hydrochloric acid, and copper chloride and a mixture of acids. Method of forming the electrode.

[Claim 7]

The method of claim 1, wherein the transparent electrode layer of the non-conductive region and the transparent electrode layer of the remaining region have a pattern in which a plurality of lines are alternately arranged.

[Claim 8]

The method of claim 1, further comprising removing the photoresist pattern after the oxidant surface treatment step.

[Claim 9]

Board;

A transparent electrode layer including at least one conductive material selected from the group consisting of a conductive polymer, a conductive carbon-based material, a metal nanostructure, and a conductive metal oxide, and formed on a substrate; And At least one selected from the group consisting of polysiloxane polymers, acrylic polymers and urethane polymers, and includes a protective layer formed on the transparent electrode layer,

A transparent electrode laminate, in which the first region of the transparent electrode layer is unconducted, and the remaining second region maintains conductivity to define a transparent electrode pattern.

[Claim 10]

The transparent electrode stack of claim 1, wherein the non-conducted transparent electrode layer in the first region has a sheet resistance of 150i / sq to 280 £ l / sq.

[Claim 11]

The method of claim 1 wherein ^"a transparent electrode stacked body having the first area and the transparent electrode layer pattern forms a plurality of lines alternating arrangement of the second area.