KR20020007872A - Transluscent and conductive film for electric field shielding and fabrication method thereof - Google Patents

Abstract

PURPOSE: A transmission conductive film for electromagnetic shielding and a manufacturing method thereof are provided to effectively remove a harmful wave, manufacture a transmission conductive film at a reasonable price, achieve a superior film, a stable composite solution, and prevent coloration. CONSTITUTION: A composite for an upper thin film is coated on a lower thin film, dried and thermally processed in a nitrogen atmosphere or in the air, so as to form an amorphous oxide thin film. A lower thin film(32) is formed on a substrate(31). The upper thin film(33) is formed on the lower thin film(32). A stabilizer(36) contained in the upper thin film is adsorbed to a conductive particle of nano size of the lower thin film in the vicinity of an interface between the lower thin film(32) and the upper thin film(33). A surface treating agent(35) is formed on a surface of the conductive particle. When a composite for the lower thin film is manufactured, the surface treating agent is added in order to prevent cohesion of conductive powder when powder and solution are mixed.

Description

Transmissive conductive film for electromagnetic wave shield and manufacturing method therefor {TRANSLUSCENT AND CONDUCTIVE FILM FOR ELECTRIC FIELD SHIELDING AND FABRICATION METHOD THEREOF}

The present invention relates to a transparent conductive film for shielding electromagnetic waves and a method of manufacturing the same.

Low frequency leakage electromagnetic waves generated by electric fields in various display devices such as CRT TVs, monitors, plasma displays (PDP) and light emitting devices (EL or FED) are reported to cause occupational diseases that are harmful to the human body. We have a standard. Conventionally, in order to remove electromagnetic waves, a conductor such as a carbon film or a copper film is packaged in a case exterior, or an exterior case in which conductors are mixed. However, since the visible light is transmitted through the image display unit on the front face of which the image of the display device is directly visible, electromagnetic waves cannot be removed by the conventional method. Accordingly, a method of forming a transmissive conductive film on the front surface of the display device capable of eliminating harmful human waves caused by conductive loss while transmitting light has been proposed.

Since the image display unit not only generates harmful waves to the human body but also increases eye fatigue due to glare caused by external light reflection, the transparent conductive film should be made of a material having a high refractive index to prevent light reflection due to the light interference effect. For example, organic or inorganic dyes, conductive polymers, conductive oxides, metal conductors, and the like may be used as the transparent conductive film. However, dyes have a disadvantage of low conductivity, conductive polymers are difficult to form a film, low film strength and refractive index. Metal conductors have excellent conductivity but are expensive, have low transmittance, and are prone to oxidation.

The light-transmissive conductive film can be produced by a conventional sputtering method, an ion beam method, or a vacuum deposition method, but can produce a film having high electrical conductivity, but has a disadvantage in that a large amount of equipment investment is required and large size and mass production are difficult. Therefore, by a spin coating method suitable for low cost and large size, an alcohol-based or aqueous dispersion containing conductive fine powder such as tin oxide or indium oxide is coated on the substrate to form a conductive film having a thickness of 1/4 of the designed wavelength. The method of coating a low reflectivity material on it is implemented. Korean Patent Laid-Open Publication No. 1999-064113 discloses a composition for a transparent conductive film by adding hollow microfibers to tin oxide, and Korean Patent Laid-Open Publication No. 2000-009405 adds neodymium oxide to tin oxide or indium oxide. A coating solution for forming a transparent conductive photoselective absorption coating film is disclosed, and Korean Patent Laid-Open Publication No. 1997-706585 discloses a conductive powder and a coating agent mainly composed of tin oxide doped with antimony. 1 schematically shows a conventional electromagnetic shielding film for electromagnetic shielding, in which a lower thin film 12 and an upper thin film 13 are formed on a substrate 11, and conductive particles 14 are formed in the lower thin film 12. It is shown schematically.

In the prior art, a light-transmissive conductive film made of fine powder such as antimony-doped tin oxide or tin-doped indium oxide, which is a conductive metal oxide, loses conductivity due to changes in surface resistance over time due to changes in the surrounding environment such as moisture. And the electromagnetic shielding function is greatly reduced. Since the lifespan of an image display device such as a flat panel monitor is usually 10 years or more, there is a strong need for a light-transmissive conductive film to prevent the change over time.

The present invention has been made to solve the above problems, and the object of the present invention is to provide a light-transmissive conductive film that can effectively remove leakage human harmful waves since the conductivity of the light-transmissive conductive film does not decrease even after a long time at room temperature. It is still another object of the present invention to provide a transparent conductive film-transparent conductive film that is transparent and free from defects in coloration of a blue or red color due to a very stable solution composition and excellent film formation and high transmittance to visible light.

1 is a cross-sectional view showing a conventional electromagnetic shielding film for electromagnetic shielding.

2 is a schematic diagram of an apparatus for manufacturing a translucent conductive film used in the present invention.

3 is a schematic view showing a cross-sectional fine structure of the transparent conductive film prepared according to the present invention.

4 is a view showing a change in the surface resistance of the conductive film prepared according to the method of Examples 6, 7, 8 and Comparative Example 2 with time.

*** Explanation of symbols for main parts of drawing ***

31: Substrate 32: lower layer thin film

33: upper thin film 34: conductive particles

35: surface treatment agent 36: stabilizer

37: Interface

The present invention provides a thin film comprising: an underlayer thin film formed on an image display substrate and composed of conductive particles of 150 nm or less and an organic solvent; It is formed on the lower layer, the upper layer consisting of a siliceous sol-forming precursor, an organic solvent and a stabilizer; comprising, and the lower layer near the interface between the upper layer and the lower layer of the lower layer of the stabilization of the upper layer The present invention provides a light-transmitting conductive film for shielding electromagnetic waves, in which an interfacial stabilizer layer is bonded to conductive particles of the lower layer thin film, and a method of manufacturing the same.

The present invention focuses on the fact that the conductive oxide thin film, which is the lower layer thin film of the light-transmissive conductive film, has a surface resistance increased due to the change in thin film characteristics after long-term storage at room temperature, thereby reducing the electromagnetic wave blocking effect, thereby providing a stabilizer to the sol-forming precursor constituting the upper thin film. It is a main feature to form a stable layer on the surface of an underlayer thin film by adding.

In addition, the present invention has a feature that the light transmittance of the lower layer thin film is greatly improved since the lower layer thin film is formed by using nano-sized conductive particles.

The present invention consists of a double layer of a lower layer thin film containing high refractive index conductive nano-sized particles and an upper layer thin film made of a low refractive index siliceous sol compound. The present invention can be used as an electromagnetic shielding and anti-reflection film, and is generated in a cathode ray tube and a front panel of various display devices. The effect is such as to remove the harm to the human body, eye fatigue by the gloss and antistatic.

The underlayer thin film has a porous three-dimensional filling structure in which conductive nano-sized particles are in contact with each other, and the surface of the conductive particles has a surface treatment agent that prevents aggregation between particles, and a tens of nanometers that provide high refractive index and bonding strength between powders. There are meters of organic and inorganic adsorption layers.

The upper thin film is a low-temperature fired siliceous oxide layer which is a low-temperature fired film obtained by applying a solution of a siliceous precursor obtained by hydrolyzing an alkoxysilane and a stabilizer onto the lower thin film.

On the other hand, a high refractive index layer is formed at the interface between the lower thin film and the upper thin film because it has chemical affinity with the nano-sized conductive particles and the dissociated stabilizer present in the siliceous precursor solution moves to the interface. The high-refractive index layer formed at the interface improves conductivity by filling the lower surface of the porous layer and combining with the defects of the surface of the nanopowder acting as a defect source of the oxygen vacancy, thereby providing a stable conductive film in the long term without changing the surface resistance over time. Make it possible. In addition, a thin high refractive index layer is formed at the interface between the lower thin film and the upper thin film by the stabilizer to enhance the antireflection effect and to increase the hardness of the film to prevent damage due to scratches and abrasion, thereby increasing durability.

The siliceous precursor (silicone-based alkoxide or acetate salt), which is the main constituent of the upper layer, has an additional sol-forming precursor as a metal alkoxide of M (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms) and (CH ₃ CO ₂ ). One or more compounds selected from the group consisting of metal acetate salts consisting of _y M (where y is 1 to 4) can be added. Ions M of the alkoxide and acetate salts used as the precursors are silicon, indium, tin, beryllium, strontium, lanthanum, niobium, tantalum, chromium, nickel, silver, gold, cobalt, iron, copper, zinc, antimony, iridium, cerium, Europium, aluminum, and zirconium. 0.1 to 50% by weight of one or more compounds selected from the above-described precursors may be added to the silicon-based alkoxide and acetate salts, which are the main constituents of the precursor, to improve the film formation of the sol or to improve the durability of the formed film.

Substances which can be used as stabilizers of the upper thin film composition are sulfides, nitrates, chlorides and acetate compounds which are easily ionized. Indium, tin, beryllium, strontium, lanthanum, niobium, tantalum, chromium, nickel, silver, gold, cobalt, iron It is an ionic compound containing any one or more selected from the group consisting of copper, zinc, antimony, iridium, cerium, and europium. The stabilizer is mixed alone or in combination to dissolve in the siliceous precursor solution constituting the upper thin film composition.

When the stabilizer is added to the composition constituting the upper thin film and dissolved, part or all of the ion is ionized, and when added in excess, metal precipitates or promotes gelation of the upper thin film composition, resulting in poor sol stability of the upper thin film composition. Therefore, the stabilizer is preferably added at 1 × 10 ⁻⁵ to 1 × 10 ¹ molar concentration to the upper thin film composition, and particularly preferably at 1 × 10 ⁻² to 1 × 10 ⁻¹ molar concentration. When the dissociated ions of the stabilizer are reduced to the metal during the heat treatment process, the light transmittance is reduced and the refractive index of the upper thin film is increased, but when the thin film is adsorbed to the surface layer of the lower thin film to form a thin conductive oxide thin film, the surface of the conductive powder constituting the lower thin film is formed over time. Make the resistance change stable.

The method of manufacturing the electromagnetic shielding and antireflection thin film using the composition for forming a thin film according to the present invention will be described in detail below.

First, translucent conductive particles having a particle diameter of 150 nm or less are mixed with a solvent selected from alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid, isopropanol, acetic acid and butanol. And stirring to prepare a lower layer film composition. The prepared composition is then coated on a glass substrate by spin coating to form a conductive layer. 2 shows the spin coating apparatus 20 used in the present invention. The solution 26 sprayed through the nozzle 21 is applied to the rotating substrate 22 in connection with the motor 24. It can be seen that one side of the device is connected with a vacuum chamber 23, below which there is an outlet 25.

The manufacturing method of the upper thin film composition is as follows. First, a metal alkoxide or metal acetate salt is added to the siliceous precursor, and dissolved in a solvent such as alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid and isopropanol, and a siliceous sol solution. Was prepared, and nitric acid or hydrochloric acid was added to the catalyst to hydrolyze the starting material. If necessary, β-carbonyl-based acetylacetone, alkanolamine-based monoethanolamine, dimethylamine, etc. may be added as a complexing agent in order to impart storage stability of the sol solution. Stabilizers are dissolved in the sol solution either before or after the hydrolysis step.

The amorphous oxide thin film is formed by applying the prepared upper thin film composition on the lower thin film and drying the same, followed by heat treatment in air or in a nitrogen atmosphere. Fig. 3 schematically shows a light-transmissive conductive film having a multilayer structure produced by the present invention. The lower thin film 32 is formed on the substrate 31, and the upper thin film 33 is formed on the lower thin film 32. Near the interface 37 between the lower thin film 32 and the upper thin film 33, it can be seen that the stabilizer 36 contained in the upper thin film is adsorbed to the nano-sized conductive particles 34 of the lower thin film. Reference numeral 35 represents a surface treating agent formed on the surface of the conductive particles. The surface treatment agent is added to prevent aggregation of the conductive powder when preparing the composition for the lower layer film, and is added after mixing the powder and the solution, followed by stirring.

Hereinafter, specific embodiments of the present invention will be described in order to help understanding of the present invention, but the scope of the present invention is not limited to the following embodiments, and various modifications and applications are possible within the scope of the following claims.

Example 1

Upper Thin Film Composition Preparation

A mixture of 3000 g of tetraethyl orthosilicate (TEOS) and 1000 g of ethanol was mixed in a beaker and aged for 2 hours in a reactor heated to 40 ° C. to prepare a siliceous sol solution. Hydrolysis was performed by adding a catalyst to the aged siliceous solution, 77 g of the hydrolyzed siliceous sol solution and 400 g of an ethanol mixed solution containing 1.3 wt% nickel chloride were stirred and mixed for 20 hours. 300 g of isopropyl alcohol (IPA), 200 g of butanol (buthanol), 50 g of distilled water, and 1 g of 0.1 N hydrochloric acid were mixed, followed by stirring and aging for 10 hours to prepare a top coating composition. The prepared solution was refrigerated for storage stability.

Underlayer Thin Film Composition Preparation

The average particle diameter is about 75 nm, and 750 g of 6% tin doped indium oxide powder is dispersed in 14183 g of ethanol to grind the indium oxide 5 wt% solution in a ball mill for about 40 hours. In a ball mill, 5 wt% concentrated solution monodispersed in nanoparticles was diluted in a ratio of 360 g to 640 g in ethanol to prepare a 1.8 wt% lower layer composition, and then aged at room temperature for 30 hours and refrigerated.

Translucent conductive film production

First, soda-lime glass substrates were prepared for spin coating. The glass substrate was washed in the following order before coating. First, the surface of the glass substrate was removed using a general cleaning solution, the surface was polished with a ceria oxide cleaning solution, and the surface was again wiped with ethanol using gauze, and then dried at 50 ° C. in a dryer. The glass substrate heated for 30 minutes or more was placed on a spin coater and spun at 20 rpm by pouring 20 cc of the lower layer composition composition on the glass substrate while forming a lower layer. Then, 20 cc of the upper layer composition was poured on the lower layer to form a double layer. The coated glass substrate was heat treated at 180 ° C. for 30 minutes in a dryer.

Example 2

An upper thin film composition was prepared by the method of Example 1, but 30 g of silver nitrate was dissolved in ethanol. The manufacturing method, coating and heat treatment method of the lower layer thin film composition was the same as in Example 1.

Example 3

An upper thin film composition was prepared by the method of Example 1, but 30 g of zinc chloride was dissolved in ethanol. The manufacturing method, coating and heat treatment method of the lower layer thin film composition was carried out in the same manner as in Example 1.

Example 4

An upper thin film composition was prepared by the method of Example 1, but 60 g of tin chloride was dissolved in ethanol. The manufacturing method, coating and heat treatment method of the lower layer thin film composition was carried out in the same manner as in Example 1.

Example 5

An upper thin film composition was prepared by the method of Example 1, but 50 g of indium chloride was dissolved in ethanol. The manufacturing method, coating, and heat treatment method of the lower layer thin film composition were carried out in the same manner as in Example 1.

Example 6

The double coated thin film prepared by the method of Example 3 was prepared by heat treatment at 200 ℃.

Example 7

The double coated thin film prepared by the method of Example 3 was prepared by heat treatment at 300 ℃.

Example 8

The double coated thin film prepared by the method of Example 3 was prepared by heat treatment at 400 ℃.

Example 9

The double coated thin film prepared by the method of Example 3 was prepared by heat treatment at 500 ℃.

Example 10

The double coated thin film prepared by the method of Example 3 was prepared by heat treatment at 180 ° C. for 12 hours.

Example 11

An upper thin film composition was prepared by the method of Example 1, but 500 g and 100 g of tetraethyl orthosilicate (TEOS) and ethanol were mixed. The double coated thin film was prepared by heat treatment at 180 ° C. for 12 hours.

Example 12

An upper thin film composition was prepared by the method of Example 1, but 700 g and 100 g of tetraethyl orthosilicate (TEOS) and ethanol were respectively mixed. The double coated thin film was prepared by heat treatment at 180 ° C. for 12 hours.

Example 13

A double thin film coated in the same manner as in Example 7 was prepared by heat treatment at 200 ° C for 30 minutes.

Example 14

A double thin film coated in the same manner as in Example 8 was prepared by heat treatment at 200 ° C. for 30 minutes.

Example 15

A two-layer thin film coated in the same manner as in Example 9 was prepared by heat treatment at 200 ° C for 30 minutes.

Comparative Example 1

An upper thin film composition and a lower thin film composition were prepared in the same manner as in Example 1, but no stabilizer was added to the upper thin film composition.

Comparative Example 2

It was prepared by heat treatment at the same temperature as in Example 1 using the lower layer composition and the upper layer composition used in the existing monitor manufacturers. 50 nm-sized tin-doped indium oxide powder was used for the underlayer thin film composition, 597 g of ethanol, 2 g of acetone, 29.6 g of 4-hydroxy 4-methyl 2-pentanone, 84.7 g of methanol, and 2 It was prepared by dispersing in a mixed organic solvent of 181 g of 4-4-pentanedione (2,4-pentanedione), and the upper thin film composition was prepared by mixing 181 g of methanol, 330 g of ethanol, 587 g of 2-propanol in a mixed solution of tetraethoxysilane, ethanol and water 143 g of 2,4-pentanedio, 38.1 g of 4-hydroxy 4-methyl 2-pentanone, and 2.2 g of 3-penten 2-one 4-methyl were prepared by mixing.

4, Tables 1 and 2 show the characteristics of the transparent conductive film prepared from the upper thin film and the lower thin film composition according to the above Examples and Comparative Examples.

4 shows the change of surface resistance with time of the transparent conductive film formed according to Examples 6 to 8 and Comparative Example 2. As shown in FIG. 4, the light-transmissive conductive film formed according to Examples 6 to 8 has a long-term stability because the surface resistance decreases over time and remains constant, whereas the conductive film formed by Comparative Example 2 continues to have surface resistance. Increased.

Table 1 shows the surface resistance, transmittance and hardness of the transparent conductive film formed according to Examples 1 to 9 and Comparative Examples 1 and 2. It can be seen that the light-transmissive conductive films formed in Examples 1 to 9 had excellent surface properties, high transmittance and high film hardness, compared to Comparative Examples 1 and 2, respectively.

Comparison of Characteristics of Translucent Conductive Film division Heat treatment temperature (℃) Surface resistance (Ω / □) Transmittance (%) Longitude (N) Example 1 180 1.77E + 06 - - Example 2 180 5.67E + 07 - - Example 3 180 5.91E + 04 91.0 1.17 Example 4 180 2.61E + 05 - - Example 5 180 8.37E + 05 - - Example 6 200 7.00E + 04 91.5 1.17 Example 7 300 5.81E + 04 90.2 1.07 Example 8 400 3.03E + 04 88 0.98 Example 9 500 3.81E + 04 87.7 0.29 Comparative Example 1 180 1.00E + 08 - - Comparative Example 2 180 6.50E + 04 91 1.07

Table 2 shows the surface resistance measured immediately after the heat treatment and cooling of the translucent conductive films formed according to Examples 10 to 15 and Comparative Example 2 and the surface resistance measured after 5 months. The light-transmissive conductive film formed according to Examples 10 to 15 showed less change in surface resistance than the light-transmissive conductive film formed according to Comparative Example 2 and showed long-term stability.

Comparison of Characteristics of Translucent Conductive Film division Heat treatment temperature (℃) Surface resistance (Ω / □) Immediately after coating 5 months later Example 10 180 3.45E + 4 9.51E + 4 Example 11 180 3.97E + 4 9.30E + 4 Example 12 180 4.39E + 4 1.97E + 5 Example 13 200 5.16E + 4 8.62E + 4 Example 14 200 5.07E + 4 6.46E + 4 Example 15 200 5.81E + 4 9.68E + 4 Comparative Example 2 180 6.5E + 4 1.70E + 5

As can be seen from the above description, the light-transmissive conductive film of the present invention not only has a high transmittance and a low surface resistance but also maintains a low surface resistance without increasing after long-term storage. The electromagnetic wave leaking out of the cathode ray tube can be prevented continuously. In addition, since the conductive film of the present invention has a higher transmittance than the glass substrate, it is possible to provide a high quality image, and because of the high hardness of the film, an image display screen having excellent durability can be provided. In addition, the present invention is easy to manufacture the conductive film by the liquid coating method, the process is simple and does not use expensive vacuum equipment is excellent in productivity and economical. Therefore, according to the present invention, it is possible to provide an image display screen having high durability and excellent economic efficiency while simultaneously stably blocking human harmful waves leaked by an electric field for a long time.

Claims (15)

An underlayer thin film formed on an image display substrate and composed of conductive particles of 150 nm or less and an organic solvent; It is formed on the lower layer thin film, consisting of a siliceous sol forming precursor, an upper layer consisting of an organic solvent and a stabilizer; A transparent conductive film for electromagnetic shielding, wherein an interfacial stabilizer layer in which the stabilizer of the upper thin film is bonded to the conductive particles of the lower thin film is present on the lower thin film surface near the interface between the upper thin film and the lower thin film. The transparent conductive film of claim 1, wherein the conductive particles are any one of indium oxide, tin oxide, or tin coated indium oxide. The method of claim 1, wherein the organic solvent of the lower layer is selected from alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid, isopropanol, acetic acid, butanol A transparent conductive film for shielding electromagnetic waves. According to claim 1, wherein the siliceous sol-forming precursor of the upper thin film is a metal alkoxide of M (OR) ₄ (wherein R is an alkyl group having 1 to 4 carbon atoms, M is a metal ion) or (CH ₃ CO ₂ ) _y M ( Here, y is 1 to 4, M is a metal ion) The transparent conductive film for electromagnetic shielding, characterized in that it further comprises. The method of claim 4, wherein the metal ion M of the sol-forming precursor is silicon, indium, tin, beryllium, strontium, lanthanum, niobium, tantalum, chromium, nickel, silver, gold, cobalt, iron, copper, zinc, antimony, Transmissive conductive film for electromagnetic shielding, characterized in that any one or two or more selected from the group consisting of iridium, cerium, europium, aluminum, and zirconium. The method of claim 1, wherein the organic solvent of the upper thin film is any one or two or more of alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid, isopropanol. Transmissive conductive film for electromagnetic shielding. The transparent conductive film for electromagnetic shielding according to claim 1, wherein the upper thin film contains at least one material selected from β-carbonyl series acetylacetone, alkanolamine series monoethanolamine, and diethylamine. membrane. The method of claim 1, wherein the stabilizer of the upper thin film is indium, tin, beryllium, strontium, lanthanum, niobium, tartalum, chromium, nickel, silver, gold, cobalt, iron, copper, zinc, antimony, iridium, cerium, A transparent conductive film for electromagnetic shielding, characterized in that it is one or two or more substances selected from the group of ionic compounds consisting of sulfides, nitrates, chlorides and acetate compounds containing at least one of europium. The transmissive conductive film for electromagnetic shielding according to claim 8, wherein the amount of the stabilizer added is 1 × 10 ⁻⁵ to 1 × 10 ¹ molar concentration. Preparing conductive particles having a particle diameter of 150 nm or less; The conductive particles were mixed and stirred with a solvent selected from alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid, isopropanol, acetic acid and butanol to prepare a solution for a lower layer film. and, The solution is applied onto an image display substrate rotating at a constant speed in a spin coating apparatus to form a lower layer thin film, The metal alkoxide or metal acetate salt is added to the siliceous precursor and dissolved in a solvent selected from alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid and isopropanol Preparing a sol solution, Hydrolysis by adding a catalyst to the siliceous sol solution, Dissolve the stabilizer in the hydrolyzed sol solution, A sol solution in which a stabilizer is dissolved is applied onto the lower layer film in a spin coating apparatus. Method of manufacturing a transparent conductive film for electromagnetic shielding comprising the step of drying the lower layer and the upper layer formed on the substrate, the heat treatment in the atmosphere or nitrogen atmosphere. Preparing conductive particles having a particle diameter of 150 nm or less; The conductive particles were mixed and stirred with a solvent selected from alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid, isopropanol, acetic acid and butanol to prepare a solution for a lower layer film. and, The solution is applied onto an image display substrate rotating at a constant speed in a spin coating apparatus to form a lower layer thin film, The metal alkoxide or metal acetate salt is added to the siliceous precursor and dissolved in a solvent selected from alcohol, propyl alcohol, acetone, toluene, methyl ethyl ketone, methanol, formamide, ethoxyethanol, distilled water, acetic acid and isopropanol Preparing a sol solution, Dissolve a stabilizer in the siliceous sol solution, Hydrolysis by adding a catalyst to the siliceous sol solution, Hydrolyzed sol solution was applied on the lower layer film in a spin coating apparatus, Method of manufacturing a transparent conductive film for electromagnetic shielding comprising the step of drying the lower layer and the upper layer formed on the substrate, the heat treatment in the atmosphere or nitrogen atmosphere. The method of manufacturing a transparent conductive film for electromagnetic wave shielding according to claim 10 or 11, wherein the catalyst is nitric acid or hydrochloric acid. The transparent conductive film for electromagnetic shielding according to claim 10 or 11, wherein β-carbonyl-based acetylacetone, alkanolamine-based monoethanolamine or dimethylamine are added to the siliceous sol solution as a complexing agent. Manufacturing method. The method of claim 10 or 11, wherein the heat treatment step is a transparent conductive film manufacturing method for electromagnetic shielding, characterized in that carried out at 150 ℃ to 500 ℃. The method of claim 10 or 11, wherein the stabilizer is indium, tin, beryllium, strontium, lanthanum, niobium, tartalum, chromium, nickel, silver, gold, cobalt, iron, copper, zinc, antimony, iridium, cerium And one or two or more materials selected from the group consisting of ionic compounds consisting of sulfides, nitrates, chlorides, and acetate compounds containing at least one of europium.