KR20140127050A - Method of preparing transparent electrode pattern and transparent electrode prepared from the same - Google Patents

Abstract

The present invention relates to a manufacturing method of a transparent electrode and to a transparent electrode manufactured by the manufacturing method. More specifically, the present invention relates to a manufacturing method of a transparent electrode having excellent electric conductivity and transparency, wherein a silver-containing patterned electrode is formed by arranging a mask which has a fixed pattern of an opening on an organic silver (Ag) composition coating layer formed on a substrate, followed by applying a laser to the coating layer to sinter an area irradiated with the laser; and to a transparent electrode manufactured by the manufacturing method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a transparent electrode pattern,

The present invention relates to a method of manufacturing a transparent electrode pattern and a transparent electrode manufactured therefrom, and more particularly, to a method of manufacturing a transparent electrode in a fine pattern and a transparent electrode manufactured therefrom.

Nowadays, in order to realize a transparent electronic device that is receiving a great deal of attention, not only active and passive devices but also wiring and electrodes must be transparent. In general, a well-known transparent electrode is indium-doped tin oxide (ITO). Recently, attempts have been made to manufacture transparent electrodes using carbon nanotubes, conductive polymers or silver nanowires.

In the case of ITO electrodes, it is widely used in transparent electronic devices due to a transmittance of 80% or more and a low sheet resistance of 10 to 50 Ω / □. However, the scarcity of the indium material constituting the ITO and the vacuum process such as the sputtering or chemical vapor deposition are indispensable for the ITO coating, so that the manufacturing process cost is relatively high.

In order to overcome this problem, studies have been actively made to form transparent electrodes by spray coating or printing coating single-walled or double-walled carbon nanotubes, or by printing conductive polymers such as PEDOT. However, a technique using silver nanowires has been proposed to produce thin films having a conductivity of 90% or more and electric conduction properties comparable to or better than ITO.

The nanowire has a short axis width of 10 to 100 nm and a long axis length of 3 to 100 μm. Even if a small amount of silver nanowires are networked and connected to each other like a network, To 90% or more of transparency.

However, when these silver nanowires are networked and networked like a network, there is a contact between the wire and the wire, and a high resistance value is generated at the contact part. As a result, the resistance value of the silver nanowire itself is close to the bulk resistance value, but the resistance is increased in the contact region, and the more the contact region is increased, the more the resistance increases, do.

In order to solve such a problem, Korean Unexamined Patent Publication No. 2002-0092294 proposes a transparent electrode having a structure in which silver nanowires are welded. However, there is still limited improvement in electrical conductivity due to the limitation of silver nanowires.

Patent Document 1: Korean Published Patent Application No. 2012-0092294

An object of the present invention is to provide a method of producing a transparent electrode containing silver (Ag) and having excellent electrical conductivity.

It is still another object of the present invention to provide a method of manufacturing an electrode having a fine line width of an electrode pattern of nanometer level and having excellent transparency.

1. A method for manufacturing a transparent electrode, comprising: forming a silver-containing pattern electrode by disposing a mask having a predetermined pattern opening on an organic silver-silver composition coating layer formed on a substrate;

2. The method of manufacturing a transparent electrode according to 1 above, wherein the line pattern of the silver-containing pattern electrode is 1 m or less in line width.

3. The method of manufacturing a transparent electrode according to 1 above, wherein the silver-containing pattern electrode has an interval of 100 to 400 mu m.

4. The method for producing a transparent electrode according to 1 above, wherein the organic silver composition comprises a silver salt, an amine compound and an alcohol compound.

5. The method for producing a transparent electrode according to 4 above, wherein the silver salt is at least one selected from the group consisting of silver nitrate, silver oxide, silver carbonate, lactate silver, and carboxyl silver chloride.

6. The amine compound according to claim 4, wherein the amine compound is at least one selected from linear amines having 1 to 30 carbon atoms, alicyclic amine or heterocyclic amine, or arylamine or aralkylamine having 6 to 30 carbon atoms A method of manufacturing a transparent electrode.

7. The process of claim 4, wherein the alcohol compound is selected from the group consisting of a straight chain alcohol having 1 to 30 carbon atoms, an alcohol having a side chain on the straight chain, an alicyclic alcohol or a heterocyclic alcohol or an aryl alcohol or aral Wherein the transparent electrode comprises at least one of klycohols.

8. The method of claim 1, wherein the laser has an output of 30 to 70 W (Watts).

9. The method of manufacturing a transparent electrode according to 1 above, wherein the gap between the organic silver coating layer and the mask is 10 to 500 mu m.

10. A transparent electrode produced by the method according to any one of the above 1 to 9.

11. An image display apparatus comprising the above transparent electrode.

12. The image display apparatus of claim 11, wherein the image display apparatus is a touch panel, a transparent display, or a flexible display.

Unlike the case where silver nanowires are used as the electrode pattern, the gold electrode manufactured according to the manufacturing method of the present invention provides an electrode pattern having a structure in which the inside is not hollow, so that the electrical conductivity is excellent.

In addition, the transparent electrode manufactured according to the present invention is excellent in transparency since the line width of the electrode pattern is on the order of nanometers and can not be visually recognized by human eyes.

In addition, the transparent electrode manufactured according to the present invention has high flexibility since it is made of silver (Ag), which is a material having not only a fine line width but also excellent ductility.

Accordingly, the transparent electrode according to the present invention can be applied not only to a conventional image display device but also to a touch panel, a transparent display, a flexible display, and the like.

≪ Example  1>

In one embodiment of the present invention, a mask having a predetermined pattern opening is disposed on an organic silver (Ag) composition coating layer formed on a substrate, and a silver-containing pattern electrode is formed by baking the laser irradiation region by irradiating a laser, And a method of manufacturing a transparent electrode excellent in transparency.

Hereinafter, one embodiment of the present invention will be described in more detail.

The organic silver composition used in the present invention is a precursor composition for forming a transparent electrode pattern. Organic silver compositions include silver salts, amine compounds and alcohol compounds. Silver salts are mostly insoluble in water (H ₂ O) except silver nitrate, and solubility in other single solvents is very low. Accordingly, in the present invention, an organic silver compound in which a silver salt is completely dissolved using an amine compound and an alcohol compound as a solvent is used. When an amine compound and an alcohol compound are used as a solvent, an organic silver composition containing silver at a high concentration can be obtained.

Silver salts may be used alone or in combination of two or more kinds of silver nitrate, silver oxide, silver carbonate, lactate silver, and carboxyl silver chloride.

The amine compound may be, for example, a straight chain amine having from 1 to 30 carbon atoms, an alicyclic amine or a heterocyclic amine, or an aryl amine or aralkyl having from 6 to 30 carbon atoms. Amine, which may be used alone or in combination of two or more. More specific examples thereof include amines such as ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, amylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, Amine, laurylamine, stearylamine, oleylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, dilaurylamine, But are not limited to, amines such as propylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, trilaurylamine, cyclohexylamine, pyridine, piperidine, N-methylethylenediamine, N, N-dimethylethylenediamine, N-methylethylenediamine, N, N-dimethylethylenediamine, N-methylethylenediamine, , 3-propanediamine, N -Propyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, diethylenetriamine, N-dimethylethylenediamine, 3-methoxypropylamine, But is not limited thereto.

It is preferable that the amine compound is not easily vaporized in the atmosphere since it is exposed to the atmosphere when the ink is actually discharged and the image of the conductive wiring is formed, and it is preferable that the amine compound is easily removed upon heat treatment after application to the substrate. Deg.] C, preferably 10 to 150 [deg.] C, and more preferably 40 to 120 [deg.] C. And the primary amine is more preferred than the secondary or tertiary amine.

The alcohol compound may be, for example, a straight chain alcohol having 1 to 30 carbon atoms, an alcohol having a side chain on the straight chain, an alicyclic alcohol or a heterocyclic alcohol, or an aryl alcohol or an aralkyl alcohol having 6 to 30 carbon atoms , Which may be used alone or in combination of two or more.

It is preferable that the alcohol compound has a high boiling point so as not to evaporate readily at room temperature.

The organic silver compositions according to the present invention can be prepared by appropriately mixing the above components, for example, from 10 to 60% by weight of silver salts, from 20 to 70% by weight of amine compounds and from 20 to 70% by weight of alcohol compounds .

Alternatively, the organic silver compositions may further include additional organic solvents, surfactants, and the like to improve the coatability, printability, etc. of the organic silver compositions.

As the organic solvent, an alcohol, an acetone, a cellosolve, a carboxylic acid, a carbitol, an acetate, or a lactate may be used. Examples of the alcohol include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, heptanol, octanol, Diols, 1,4-octanediol; Examples of the acetone include acetone, methyl ethyl ketone, methyl butyl ketone; Examples of the cellosolve include methylcellosolve, ethylcellosolve, propylcellosolve, butylcellosolve; Examples of the carbitol include ethyl carbitol, propyl carbitol, butyl carbitol; Acetates include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate; Lactates such as lactic acid, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, and 2-ethylhexyl lactate may be used alone or in admixture of two or more. In addition, acetonitrile, tetrahydrofuran, cyclohexane, benzene, nitrobenzene, toluene, xylene, chloroform, and taphene may be used.

As the surfactant, ionic or nonionic surfactants may be used without particular limitation, and they may be used alone or in combination of two or more.

Once the organic silver composition is prepared, it is applied onto the substrate to form a coating layer. In order to form the coating layer, a drying step may be carried out if necessary. The drying process can shorten the stabilization time of the coating layer, and can be performed at 80 to 150 ° C for 3 to 20 minutes, for example.

When the coating layer of the organic silver compound is formed on the substrate, the laser is irradiated in a predetermined pattern. The organic silver compound coating layer is baked at the portion irradiated with the laser, so that the organic compound is decomposed and silvering proceeds to form a silver pattern. This silver pattern can be used as a silver electrode.

In order to irradiate the laser with a predetermined pattern, a mask having the opening of the predetermined pattern shape is used. Although the laser is advantageous in pattern formation because of its excellent linearity, it is somewhat difficult to form a pattern at the nanometer level. Accordingly, the present invention can form a pattern of a nanometer level by using a mask having a pattern. When the mask is used, the gap between the coating layer and the mask can be controlled to minimize the diffusion of the laser beam passing through the pattern opening and to form a fine pattern. For example, the distance between the organic silver coating layer and the mask may be 10 to 500 탆, and a silver electrode pattern having a line width of nanometer level in the above range can be obtained.

The laser used in the field can be used without any particular limitation, but an infrared laser is preferable considering the amount of energy to be delivered. In this respect, lasers are preferable for firing the irradiated area with the required line width, with an output of 30 to 70 W (Watts). Further, when the range of the main wavelength of the laser is in the range of 355 to 1,100 nm, the visibility and the blanking can be improved. However, even if a light source deviating from this area is used, The present invention is not limited thereto.

When the formation of the silver electrode pattern is completed by irradiating the laser, the silver electrode pattern is subjected to a cleaning step of removing the remaining unfired portions, thereby obtaining a fine patterned silver electrode pattern.

According to the present invention described above, the line width of the obtained silver electrode pattern is on the order of nanometers, for example, the line width of the pattern is 1 mu m or less. Since the linewidth of the pattern is preferably as small as possible, the lower limit is not particularly limited. When the line width of the pattern reaches the nanometer level, the transparent electrode can be realized because it is not recognized by the human eye. Therefore, the production method of the present invention is very useful for the production of transparent electrodes.

Also, the spacing between the patterns can be adjusted as needed, for example, the spacing between the patterns may be 100 to 400 mu m, but is not limited thereto.

The silver (Ag) transparent electrode thus prepared is remarkably excellent in transparency, electrical conductivity and flexibility, and can be usefully used as an electrode of an image display device such as a touch panel, a transparent display, and a flexible display.

≪ Example  2>

As another embodiment of the present invention, there is provided a method of manufacturing a transparent electrode, which comprises disposing a mask having a predetermined pattern opening on a silver-halogen photosensitive film and irradiating ultraviolet rays to form a silver-containing pattern electrode.

The silver-halogen photosensitive film to be used in the present invention can be employed in the art without any particular limitation. For example, a silver-halogen photosensitive film can be produced by coating a transparent film substrate with a photosensitive silver halide layer containing silver halide.

The transparent film may be a plastic film or the like. The plastic film is preferably a polyethylene terephthalate film or triacetylcellulose (TAC) film from the viewpoints of light transmission, heat resistance, handling, and cost.

The silver halide contained in the photosensitive silver halide layer is excellent in photo-sensing property. The silver halide can be used in a particulate state, for example, silver bromide particles, silver chlorobromide particles, or silver iodide bromide particles.

The photosensitive silver halide layer includes a binder for uniformly dispersing and binding the silver halide. The binder may be composed of a water-insoluble or water-soluble polymer, preferably a water-soluble polymer. Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharide, polyvinylamine, chitosan, polylysine, polyacrylic acid, poly Polyalginic acids, polyhyaluronic acid, and carboxyl cellulose. The binder may exhibit neutral, negative, or positive ions due to the ionic nature of the functional group.

The solvent for forming the photosensitive silver halide layer is not particularly limited and includes, for example, water, an organic solvent (e.g., alcohol such as methanol, ketone such as acetone, amide such as formamide, sulfoxide such as dimethylsulfoxide , Esters such as ethyl acetate, and ethers), and ionic liquids, which may be used alone or in combination of two or more.

When the above-described silver-halogen photosensitive film is prepared, ultraviolet rays are irradiated in a predetermined pattern. When ultraviolet rays are irradiated on the photosensitive silver halide layer of the silver-halogen photosensitive film, the silver halide photoresist film forms a silver electrode pattern through subsequent development processing.

A condensing means known in the art can be used to improve the directivity of ultraviolet rays. Such a light collecting means may be, for example, a light collecting film including a lenticular pattern, and at least one layer of the light collecting film may be laminated. When a plurality of light-condensing films including a lenticular pattern are laminated, the lenticular pattern of each light-condensing film may be a convex lenticular or a concave lenticular, and a light converging film having a convex lenticular pattern and a light converging film having a concave lenticular pattern Films may be used in combination. An ADM-JNC exposure machine available from JNC is commercially available as a product equipped with such a light condensing means. It is preferable that the line width of the ultraviolet ray passing through the light condensing means is 0.5 to 50 mu m.

Since ultraviolet light has diffusibility per se, it is somewhat difficult to form a pattern at the nanometer level. Accordingly, the present invention can form a pattern of a nanometer level by using a mask having a pattern. When the mask is used, the distance between the photosensitive silver halide layer and the mask can be adjusted to minimize the diffusion of ultraviolet rays passing through the pattern opening and to form a fine pattern. For example, the interval between the photosensitive silver halide layer and the mask may be 10 to 500 mu m, and a silver electrode pattern having a line width of nanometer level in the above range can be obtained.

The area of the photosensitive silver halide layer irradiated with ultraviolet rays is fixed to the silver electrode pattern through the development process. The developing process can be applied without limitation to a conventional developing process used for the silver salt film.

When the development is completed, the silver salt in the unexposed area is removed, and a fine silver electrode pattern can be obtained through a water washing process or the like.

The silver electrode pattern obtained according to the present invention may have a fine line width of the line width of the pattern of 1 m or less and the interval between the patterns may be 150 to 400 mu m although it can be adjusted as needed.

≪ Example  3>

As another embodiment of the present invention, the ionic property is a method of manufacturing a transparent electrode in which ink is printed in a predetermined pattern using an electro-hydro-dynamic printing method and then annealed to form a silver-containing pattern electrode to provide.

The electro-hydro-dynamic printing method is a technique of ejecting ink using an electric field. More specifically, when a constant voltage is applied between the injection nozzle and the substrate, an electric field is generated, and at the same time, charges are concentrated on the surface of the fluid near the nozzle. In this case, when the pressure of the nozzle is larger than the surface tension of the fluid due to the electric charge and electric field generated on the surface of the fluid, the spherical surface is transformed into the Taylor cone shape of 49.3 ° angle, Or spraying occurs. The formation of Taylor Cone by an electric field can generate an actual droplet or a single droplet of several hundreds nm to several micrometers in size from a relatively large nozzle of several tens to several hundreds of micrometers.

In the present invention, a silver ink printed using an electro-hydro-dynamic printing method can be printed with a line width of a nanometer level (1 탆 or less) and thereby a silver electrode pattern of a nanometer level can be manufactured have. Further, when the electric field is adjusted, the straightness of the ejected ink can be improved.

The ionic property used in the present invention is a silver ink which solidifies upon annealing at a low temperature. Such an ionic silver ink can use the organic silver compositions described in Embodiment 1 described above within the same category.

The ionicity is an annealing process after the ink is printed in a predetermined pattern. The annealing process according to the present invention is a low-temperature annealing process and is carried out at a temperature of about 80 to 100 ° C. When the annealing process is performed, the solvent is removed from the printed ink pattern and the silver is advanced to obtain a silver electrode pattern. The annealing time can be appropriately selected depending on the situation in which silver proceeds, and can be performed, for example, for 5 minutes to 1 hour.

In the present invention, if necessary, a step of drying the ink pattern printed before the annealing process at room temperature (20 to 25 ° C) may be performed in advance.

The silver electrode pattern obtained according to the present invention may also have a fine line width of the line width of the pattern of 1 m or less and the interval between the patterns may be 100 to 400 mu m although it can be adjusted if necessary.

≪ Example  4>

As another embodiment of the present invention, an electrolytic solution is printed on a substrate coated with a silver particle dispersion liquid having a negative charge on its surface in a predetermined pattern by using an electro-hydro-dynamic printing method, A method of manufacturing a transparent electrode for forming a pattern electrode is provided.

Silver particles having a negative charge on the surface are particles having a particle size on the order of nanometers, for example, 1 to 500 nm. Silver particles (hereinafter referred to as "silver nanoparticles") having a particle size on the order of nanometers usually have a negative charge on their surface charge. Therefore, the silver nanoparticles do not clump together due to the repulsive force, and when a suitable dispersion medium is used, a silver particle dispersion in which silver nanoparticles are dispersed can be obtained.

In the present invention, after the silver particle dispersion is applied to a substrate, the electrolyte solution is printed in a predetermined pattern using an electro-hydro-dynamic printing method.

The electrolyte solution is a solution containing an ionic substance, and examples of the cationic compound of the ionic substance include an ammonium cation, a pyridinium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, a cationized poly (acrylic acid) Poly (diallyldimethylammonium), and the like. However, the cationic compound may be substituted with an alkyl group having 1 to 5 carbon atoms or the like. Examples of the anionic compound include, but are not limited to, a halogen anion, BF ₄ ^- , PF ₆ ^- and the like.

The electrolyte solution is printed with a line width (1 탆 or less) at the nanometer level using an electro-hydro-dynamic printing method. When the electrolyte solution is printed on the coating layer of the silver particle dispersion, the cationic material in the ionic material of the electrolyte solution comes into contact with the nanoparticles in the negative charge on the surface of the silver nanoparticles, Is neutralized. The silver nanoparticles whose surface charges are neutralized have a property of aggregating to form agglomerates. Therefore, agglomerates of silver nanoparticles are formed at a portion where the electrolyte solution is applied in a predetermined pattern.

Silver nanoparticles are formed, silver nanoparticles aggregates are fixed, melted, and bonded by a firing process to form a silver electrode pattern. After the firing process, the silver particle dispersion coating layer on which no pattern is formed is removed.

The silver electrode pattern obtained according to the present invention may also have a fine line width of the line width of the pattern of 1 m or less and the interval between the patterns may be 100 to 400 mu m although it can be adjusted if necessary.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  One: Example  One

After applying the organic silver composition (TEC-IJ-060, InkTec) onto the substrate, a mask having a pattern of 1 mu m line width formed at intervals of 300 mu m was disposed at a position of 200 mu m above the applied composition, : 50 W).

After the laser irradiation, the substrate was cleaned to obtain a silver electrode pattern having a line width of 1 mu m.

Example  2: Example  2

A silver halide photosensitive film was placed on a substrate, and a mask having a pattern of 1 mu m line width formed at intervals of 300 mu m was placed at a position above the film at 200 mu m, and UV was irradiated using ADM-JNC (JNC).

After the UV irradiation, development was performed using an ethanol developing solution, and a silver electrode pattern with a 1 mu m line width was obtained after washing with water.

Example  3: Example  3

The ionic property was printed with a pattern of 1 mu m line width on the substrate at intervals of 300 mu m using an electrostatic jet apparatus (HIG-NP 100, manufactured by Enjet Corporation) of ink (organic silver composition, TEC-IJ-060, . After printing, the resultant was annealed at 90 DEG C for 15 minutes to obtain a silver electrode pattern having a 1 mu m line width.

Example  4: Example  4

A dispersion in which silver nanoparticles having an average particle diameter of 50 nm was dispersed in triethylene glycol was applied on a substrate and dried. An ammonium chloride aqueous solution, which is an electrolyte solution, was printed on the above-mentioned coating layer by a electrostatic jet apparatus (HIG-NP 100, manufactured by Enjet) on the substrate at intervals of 300 μm at 1 μm line width. After printing, the sheet was baked at 120 DEG C for 10 minutes to obtain a silver electrode pattern having a line width of 1 mu m.

Claims (12)

Wherein a silver-containing pattern electrode is formed by disposing a mask having a predetermined pattern opening on an organic silver silver composition coating layer formed on a substrate and irradiating a laser to sinter the laser irradiation region.
The method of manufacturing a transparent electrode according to claim 1, wherein the silver-containing pattern electrode has a line width of 1 占 퐉 or less.
The method for manufacturing a transparent electrode according to claim 1, wherein the silver-containing pattern electrode has an interval of 100 to 400 mu m.
The method of claim 1, wherein the organic silver composition comprises a silver salt, an amine compound, and an alcohol compound.
5. The method according to claim 4, wherein the silver salt is at least one selected from the group consisting of silver nitrate, silver oxide, silver carbonate, lactate silver, and carboxyl silver chloride.
[Claim 4] The method according to claim 4, wherein the amine compound is at least one selected from the group consisting of linear amines having 1 to 30 carbon atoms, alicyclic amine or heterocyclic amine, or arylamine or aralkylamine having 6 to 30 carbon atoms, ≪ / RTI >
The method according to claim 4, wherein the alcohol compound is a linear alcohol having 1 to 30 carbon atoms, an alcohol having a side chain on a straight chain, an alicyclic alcohol or a heterocyclic alcohol, or an aryl alcohol or aralkyl alcohol having 6 to 30 carbon atoms Wherein the transparent electrode comprises at least one transparent electrode.
The method according to claim 1, wherein the laser has an output of 30 to 70 W.
The method according to claim 1, wherein the gap between the organic silver coating layer and the mask is 10 to 500 탆.
A transparent electrode produced by the manufacturing method according to any one of claims 1 to 9.
10. An image display apparatus comprising the transparent electrode according to claim 10.
The image display apparatus of Claim 11 is a touch panel, a transparent display, or a flexible display.