KR20000024647A - Composition for transparent conductive thin layers and method for preparing transparent conductive thin layers with low electric resistances using the same - Google Patents

Abstract

PURPOSE: A method for fabricating a transparent conductive thin film of a low resistance is provided to have an excellent adhesive property and a high corrosion resistance. CONSTITUTION: A method for fabricating a transparent conductive thin film of a low resistance comprises the steps of: providing a composition of a thin film consisting of HCL 80-120 weight%, SnCl4 15-46 weight%, SbCl3 0.5-1.5 weight%, InBr3 0.15-1.10 weight%, NaOH 0.5-4.5 weight%, HF 10-28 weight%, FeSO4 0.25-1.5 weight% and a distilled water 100 weight%; atomizing the composition through a supersonic wave vibrator(2); and spraying the atomized composition on a material surface in a range of 1-15 cc/sec while maintaining an air pressure of a nozzle in 4-6kgf/cm¬2.

Description

Composition for transparent conductive thin layers and method for preparing transparent conductive thin layers with low electric resistances using the same}

The present invention relates to a composition for a transparent conductive thin film and a method for manufacturing a low resistance transparent conductive thin film using the same, and more specifically, glass, ceramic, stone substrate or annular bead (particle size 0.3) A conductive thin film is formed on the surface of the material (mm or more) to absorb and shield radio waves, and low resistance as a heating element, and chemically. It relates to a composition for a transparent conductive thin film having mechanical durability and a low resistance transparent conductive thin film using the same.

Transparent conductive thin film is electric wave absorption and shielding, conductive powder or paint as a thin film heating element, antistatic and uninterruptible conductive treatment, electric wave absorption heating element (microwave container), electroluminescent surface light source (EL Display & Lamp Panel), flat panel display (transparent electrode) , Solar cell), surface heating heater, dew condensation, heatless heater (car, ship, aviation, architecture, refrigeration show-case), radio wave absorbing transparent glass (antenna, security device), infrared It can be used in various fields such as reflective windows, electrical and electronic parts, and energy related industries.

As a material for producing such a conductive transparent thin film, for example, metal oxides such as indium oxide-tin oxide, tin oxide-antimony oxide, zinc oxide, and the like, metals such as gold, platinum, silver, and chalcogenides ), Non-oxides such as lanthanum boride and titanium nitride are used.

For example, U. S. Patent No. 5,160, 675 discloses a method of manufacturing a conductive transparent thin film by molding and sintering the shape of the exothermic thin film using indium oxide and tin oxide as raw materials. In addition, Japanese Patent Application Laid-open No. Hei 6-4400 discloses a process of simultaneously evaporating or sputtering a plurality of kinds of thin film materials having different dopant contents to generate steam or sputtering atoms of the plurality of thin film materials; A method of forming a conductive thin film in which the content of a dopant of a thin film is partially different, including an attaching process of attaching vapor or sputtering atoms generated in the generating step to a surface of a substrate to form a thin film. Korean Patent No. 171971 discloses a metal thin film heating element consisting of ditin, fluorine, antimony and distilled water. In addition, Japanese Patent Publication No. 63-52404 discloses a method in which antimony is a main component and the remainder is composed of tin oxide, which is dissolved in an aqueous solution in which an inorganic salt is dissolved and applied onto a glass substrate by spraying.

However, the conventional technique using vacuum deposition, sputtering, etc. is excellent in homogeneity, high production cost according to expensive equipment, very difficult to produce large area, and slow growth rate of the film. In addition, the conventional spraying method and CVD has problems such as problems caused by the homogeneity and the gas generated during growth and a problem that a satisfactory film cannot be obtained. Therefore, the existing methods have the point to improve the efficiency and economical efficiency such as low cost in construction, mass production of large area, heat resistance of high temperature heat generation.

As described above, the conventional method is difficult to produce a large area due to the limitation of the vacuum apparatus, and even if the production is expensive, inevitably brings a limitation to mass production. In order to solve this problem, the present invention significantly increased the large area (2M × 2.5M) coating and film growth rate (0.4 to 4 seconds) by using a spray pyrolysis method, and uniformity, which is a weak point of the spraying method. Also in one application | coating, the structure of the spray chamber which used the ultrasonic vibrator provided constant uniformity within the defined range. In addition, in the case of a thin film made of a conventional tin compound, the maximum temperature at the time of exotherm occurs especially at low temperatures due to weak acid resistance or low Curie Point, but the composition according to the present invention has a melting point. Suitable impurities (SbCl ₃ , NaOH) are mixed with high tin and indium compounds (SnCl ₄ and InBr ₃ ) and iron sulfate and fluorine are added as reducing and oxidizing agents to ensure high melting point, high adhesion and adhesion, and high corrosion resistance. High conductivity and high electronegativity were combined with the increased material.

Accordingly, an object of the present invention is to provide a transparent conductive thin film composition which is excellent in heat resistance at the time of thin film growth and obtains a film having increased corrosion resistance due to excellent adhesiveness and fusion resistance, which cannot be compared with a conventional film even at high heat generation. .

Another object of the present invention is a method of manufacturing a low-resistance transparent conductive thin film using the composition for transparent conductive thin film having economic efficiency and import substitution effect compared to the existing production process, having a large area of application and excellent heat generation and durability. To provide.

The composition of the present invention for achieving the above object is HCl 80-120 parts by weight, SnCl ₄ 15-46 parts by weight, SbCl ₃ 0.5-1.5 parts by weight, InBr ₃ 0.15-1.10 parts by weight, NaOH 0.5-4.5 parts by weight, HF 10 to 28 parts by weight, FeSO ₄ 0.25 to 1.5 parts by weight and distilled water 100 parts by weight.

Method for producing a low-resistance transparent conductive thin film of the present invention for achieving the above another object is a method for producing a transparent conductive thin film using a spray method, HCl 80 to 120 parts by weight, SnCl ₄ 15 to 46 parts by weight, SbCl ₃ Providing a thin film composition comprising 0.5 to 1.5 parts by weight, InBr ₃ 0.15 to 1.10 parts by weight, 0.5 to 4.5 parts by weight of NaOH, 10 to 28 parts by weight of HF, 0.25 to 1.5 parts by weight of FeSO ₄ and 100 parts by weight of distilled water; Atomizing the composition through an ultrasonic vibrator; And spraying the atomized composition on the surface of the material in the range of 1 to 15 cc / sec while maintaining the air pressure of the nozzle at 4 to 6 kgf / cm ² .

1 is a schematic process diagram for forming a transparent conductive thin film according to the present invention.

2 is a schematic cross-sectional view of an electric furnace used in the present invention.

3 is a schematic view showing a state where a thin film is treated on a material surface according to the present invention.

4 is a plan view schematically illustrating a heating element in which a voltage is applied to a portion of a thin film processed according to the present invention.

※ Explanation of code about main part of drawing ※

1. Evaporator 2. Ultrasonic Oscillator

3. Valve 4. Mass Flow Controller

5. Heating heater 6. Spray nozzle

7. Coating 8. Blower

9. Heater 10. Generator

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

The transparent conductive thin film composition according to the present invention contains a tin compound as a main component. In the present invention, the most important element of the tin compound is a type of dopant and a method of forming a film. In the former, tin tetrachloride is used to form tin compound in hydrochloric acid, followed by antimony and indium. Bromine, sodium, sodium, fluorine, ferrous sulfate, and distilled water are mixed.

Since the present invention is a chemical growth method, a compound in a solution having a larger chemical reaction is more advantageous than a solution using a vacuum apparatus. In the composition of the composition according to the present invention, first, distilled water is mixed with dilute water rather than concentrated hydrochloric acid to synthesize tin. The growth rate of the film was increased by using tin chloride (IV) to increase the deposition rate than other tin compounds such as tin oxide or tin chloride (II), and antimony was added to prevent the reverse conversion of tin and low resistance. When the content of tin compound is more than 46%, the free electron concentration is increased more than necessary to decrease the infrared reflectance, and when the amount of antimony is more than necessary, the visible light transmittance is lowered. In addition, in order to increase the transmittance, the content of fluorine had to be kept boiling so that it was not lower than that of tin. Therefore, the composition ratio of the solution according to the manufacturing purposes, but can be different, and specific mixing ratio of the composition according to the invention is 80~120 parts by weight of HCl, SnCl ₄ 15~46 parts by weight, SbCl ₃ 0.5~1.5 parts by weight, InBr ₃ 0.15 ~1.10 parts by weight, and 0.5~4.5 parts by weight of NaOH, HF 10~28 parts by weight of FeSO ₄ constituted by 0.25~1.5 parts by weight of distilled water and 100 parts by weight. At this time, when the amount of SnCl ₄ is less than 15 parts by weight, the doping efficiency is lowered to increase the resistance value. When the amount of SbCl ₃ is less than 0.5 parts by weight, the electrical conductivity of the material is reduced to lower the electrical conductivity.

As described above, tin chloride (IV) is characterized by the composition of the composition as compared to other tin species such as Cl ₂ or tin oxide (II) results in an increase in the doping (doping) efficiency of the experiment results in active free electron concentration with impurities Lower resistance and higher transparency could be obtained. In addition, as a heating element, the problem of breaking a film during high heat generation was prevented by adding indium of high melting point and fluorine to increase electron affinity. In addition, compared with the conventional thin film composition, sodium sulfate was added at the same sheet resistance when exothermic to increase electrical conductivity, and iron sulfate was added to assist reduction.

This basic solution is grown by spraying in a gaseous phase that can be combined with oxygen, rather than a film of oxygen-deficient vacuum. After atomization using an ultrasonic vibrator for uniform film distribution, air is sprayed by heating through the nozzle. The heating temperature at this time is preferably maintained at 255 ~ 355 ℃ in terms of the ideal surface reaction by increasing the deposition rate. The configuration of the spray chamber and the overall configuration of the electric furnace are shown in FIGS. 1 and 2.

1 is a schematic process diagram for forming a transparent conductive thin film according to the present invention, Figure 2 is a schematic cross-sectional view of an electric furnace used in the present invention. In addition, Figure 3 is a schematic diagram showing a state of a thin film treatment on the surface of the material according to the present invention, Figure 4 is a plan view schematically showing a heating element applying a voltage to the thin film portion according to the present invention.

Meanwhile, in the present invention, a low resistance transparent conductive thin film is manufactured by spray pyrolysis. The basic chemical reaction of the spray pyrolysis method is the same as chemical vapor deposition (CVD), but the element of the material to be deposited is dissolved in an affinity solvent and then sprayed onto a material heated with fine droplets to cause pyrolysis oxidation. First, the material is heated to form a thin film, but the higher temperature inhibits side reactions and promotes crystal growth, but the present invention is different from the spray method in which the material is limited due to limitations in heat resistance and softening point. It can be implemented at low temperature (about 200 ° C). The heating temperature is 200 to 650 ° C. depending on the material, and the spray growth time of the thin film is 0.5 to 4 seconds. At this time, if the spray growth time of the thin film is less than 0.5 seconds, the oxidation reaction of the solution is weak, and if it exceeds 4 seconds, the visible light transmittance tends to be lowered.

As described above, the composition according to the present invention is extremely weak to produce by-products in the liquid phase by polymerizing the decomposition products due to the involvement of oxygen during pyrolysis, so that inert gases such as nitrogen and argon are used in pyrolysis and oxygen removal during growth. No annealing step for stabilization of the film after coating is performed, and rapid cooling may be performed. The most important film uniformity of the spraying method is to atomize the solution using an ultrasonic vibrator 2 and then to spray. At this time, the ultrasonic unit (Unit) uses a multi-frequency (20KHz ~ 70KHz), the sound intensity is preferably 10 ^-1 W / In ² or less. In addition, in order to deliver the solution in the flow pattern (Flow Pattern), the injection of the atomized solution must be heated by the heater (9), the blower (8) to adjust the air blowing amount of the spray nozzle (6). At this time, the air pressure of the nozzle is preferably in the range of 4 to ⁶ kgf / cm ² , and the spray amount is preferably in the range of 1 to 15 cc / sec. However, in order to maintain transparency due to the haze phenomenon, an exhaust hood is installed. The grown conductive thin film can mass-produce a transparent conductive thin film having a large area (maximum size 2,000 × 2500 mm), which was not expected by the conventional method.

The thin film manufactured according to the present invention has excellent heat resistance, and according to a material such as glass, ceramic, or stone substrate or annular beads (particle size of 0.3 mm or more) when voltage is applied, the exothermic temperature generates heat from room temperature to 980 ° C., and absorbs radio waves. It is a type heating element (frequency range / 2,450MHz) that generates heat up to 530 ℃ during heat generation. Thus, there is an excellent effect of forming a heat generating vessel and a radio wave absorption heat generating film using a hot plate and a microwave oven. When it is necessary to apply the exothermic property only to the selective part when used as a heating element, the conventional method is grown by local partial heating or etched after application, the manufacturing method according to the present invention silk-printed the remaining portion except the film growth portion in advance in the material And wash the print after the film growth. Subsequently, silver paste necessary for voltage application is printed and fired.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Example 1

HCl 100 parts by weight, SnCl ₄ 20 parts by weight, SbCl ₃ 1.0 parts by weight, InBr ₃ 0.5 parts by weight, NaOH 2 parts by weight, HF 15 weight parts, FeSO ₄ 1.0. FIG using a solution-part parts by weight of distilled water and 100 parts by weight It sprayed on the glass plate of 500x500x3mm in the apparatus similar to 1, and obtained the transparent conductive thin film. The electric furnace is composed of a temperature of 550 ° C on the surface of the material, a feed rate of about 250mm / sec, a pressure of about 5kgf / cm for the nozzle, a heating temperature of 300 ° C when spraying the solution, and a spray amount of about 7cc / It was set to sec. The thickness of the film was 2000 Hz, and the ultrasonic unit used was about 50 KHz, and the sound intensity was maintained at about 10 ⁻¹ W / In ² or less. The resistance measuring system measured the conductivity according to the material using MD: CMT-SR3000L for flat glass, and the results are shown in Table 1 below.

Example 2

HCl 100 parts by weight, SnCl ₄ 40 part by weight, SbCl ₃ 1.5 parts by weight, InBr ₃ 1.0 parts by weight, NaOH 2.5 part by weight, HF 35 part by weight, FeSO ₄ 1.5 parts by weight of distilled water and 100 parts by weight of also using the configured Solution 1 Spraying on glass and ceramic beads of Φ 300㎛ in the same device to obtain a transparent conductive thin film. The composition of the electric furnace is 400 ℃ temperature of the material surface, the feed speed of the material about 250mm / sec, the air pressure of the nozzle about 5kgf / cm, the heating temperature is maintained at 300 ℃ when spraying the solution, the spray amount is about 6cc / It was set to sec. The thickness of the film was 1000 Hz, and the ultrasonic unit used was about 70 KHz, and the sound intensity was maintained at about 10 ⁻¹ W / In ² or less. The resistance measuring system measured the conductivity according to the material using MD: CMT-SR3000L for flat glass, and the results are shown in Table 1 below.

Example 3

HCl 100 parts by weight, SnCl ₄ 40 parts by weight, SbCl ₃ 1.5 parts by weight, InBr ₃ 1.0 parts by weight, NaOH 2.5 part by weight, HF 35 weight parts, FeSO ₄ 1.5 parts by weight of distilled water and 100 parts by weight of also using the configured Solution 1 Spraying on a ceramic plate of Φ300㎛ in the same device to obtain a transparent conductive thin film. The electric furnace is composed of 450 ℃ of material surface, conveying speed of material about 200mm / sec, air pressure of nozzle about 5.5kgf / cm, heating temperature is 300 ℃ when spraying the solution, spray amount is about 5cc It was / sec. The thickness of the film was 2000 Hz, and the ultrasonic unit used was about 50 KHz, and the sound intensity was maintained at about 10 ⁻¹ W / In ² or less. The resistance measuring system measured the conductivity according to the material using MD: CMT-SR3000L for flat glass, and the results are shown in Table 1 below.

Yes Example 1 Example 2 Example 3 Material Glass Plate (500 × 500 × 3mm) Glass and Ceramic Beads (Φ300㎛) Ceramic Plate (Φ300㎛) Ω / ㎠ 10 300 80

The thin film grown on the glass surface as in Example 1 had high homogeneity and low resistance value, and even in the electromagnetic shielding experiment, the TCO99 standard was met by measuring instruments EFM200-ELF and VLF. When used as a radio wave (2,450MHz) absorption heating element, respectively, it generated heat to 425 ° C and 528 ° C in 5 minutes, respectively. In addition, when the voltage is applied as shown in Figure 4 when using as a heating element using a thin film distribution area of 650cm 2 it was heated to 620 ℃ in 6 minutes.

In the conventional vacuum deposition method such as CVD, the deposition time took from 1 minute to several hours, but the present invention is suitable for mass production by growing the film in about 0.5 seconds to 4 seconds. Could. In the experiment of resistance to hydrochloric acid and chlorine of the thin film, the conventional thin film was about 1 to 30 minutes, but the thin film according to the present invention obtained a robust film that can withstand 4 to 6 hours. The size of the material is not limited by the vacuum chamber size, it can grow up to 3 times the size, and compared with the existing production capacity in the same time 7 to as much as 40 times the economic efficiency and mass production was possible. The application field of the thin film was excellent in the manufacturing cost or effect in the infrared reflecting window, radio wave absorption and shielding, and the existing thin film was less than 300 ℃ in the heating temperature of the radio wave absorbing heating element and the voltage applied heating element, but the thin film according to the present invention Heated up to 980 ° C. at room temperature.

As described above, the present invention realizes the economical efficiency and the cost reduction of the coating on the large-area material surface that could not be mass-produced by using a stable composition suitable for the spraying method, and the acid resistance in terms of the performance of the film. The low resistance and the stabilization of the film showed high temperature exothermicity.

Claims (6)

HCl 80-120 parts, SnCl ₄ 15-46 parts, SbCl ₃ 0.5-1.5 parts, InBr ₃ 0.15-1.10 parts, NaOH 0.5-4.5 parts, HF 10-28 parts, FeSO ₄ 0.25-1.5 Composition for transparent conductive thin film, characterized in that consisting of parts by weight and 100 parts by weight of distilled water. In the method for producing a transparent conductive thin film using the spray method, HCl 80-120 parts, SnCl ₄ 15-46 parts, SbCl ₃ 0.5-1.5 parts, InBr ₃ 0.15-1.10 parts, NaOH 0.5-4.5 parts, HF 10-28 parts, FeSO ₄ 0.25-1.5 Providing a composition for a thin film composed of parts by weight and 100 parts by weight of distilled water; Atomizing the composition through an ultrasonic vibrator; And Spraying the atomized composition to the material surface in the range of 1 to 15 cc / sec while maintaining the air pressure of the nozzle at 4 to 6 kgf / cm ^{2 The} method of producing a low resistance transparent conductive thin film. The method of manufacturing a low resistance transparent conductive thin film according to claim 2, wherein the ultrasonic region is 20 to 70 KHz, and the sound intensity is 10 ⁻¹ W / In ² or less. The method of manufacturing a low resistance transparent conductive thin film according to claim 2, wherein the material is a glass, ceramic, stone substrate, or annular beads having a particle size of 0.3 mm or more, and a heating temperature is 200 to 650 ° C. The method of claim 2, wherein the spraying time is 0.5 to 4 seconds. The method of manufacturing a low resistance transparent conductive thin film according to claim 2, wherein a heating temperature of the atomized composition during spraying is 255 to 355 ° C.